阅读说明：本技术 半导体装置以及半导体装置的制造方法 (Semiconductor device and method for manufacturing semiconductor device ) 是由 山崎舜平 神保安弘 石川纯 手塚祐朗 掛端哲弥 于 2019-10-17 设计创作，主要内容包括：提供一种具有良好的电特性的半导体装置。该半导体装置包括第一氧化物、第一氧化物上的第一导电体及第二导电体、第一导电体上的第一绝缘体、第二导电体上的第二绝缘体、第一绝缘体及第二绝缘体上的第三绝缘体、在第一氧化物上配置在第一导电体与第二导电体之间的第二氧化物、第二氧化物上的第四绝缘体、第四绝缘体上的第三导电体、接触于第三绝缘体的顶面、第二氧化物的顶面、第四绝缘体的顶面及第三导电体的顶面的第五绝缘体、嵌入到形成在第一绝缘体、第三绝缘体及第五绝缘体中的开口中且与第一导电体接触的第四导电体、以及嵌入到形成在第二绝缘体、第三绝缘体及第五绝缘体的开口中且与第二导电体接触的第五导电体,其中,第三绝缘体在与第四导电体的界面附近及与第五导电体的界面附近具有其氮浓度高于第三绝缘体的其他区域的区域。(A semiconductor device having excellent electrical characteristics is provided. The semiconductor device includes a first oxide, a first conductor and a second conductor on the first oxide, a first insulator on the first conductor, a second insulator on the second conductor, a third insulator on the first insulator and the second insulator, a second oxide disposed between the first conductor and the second conductor on the first oxide, a fourth insulator on the second oxide, a third conductor on the fourth insulator, a fifth insulator in contact with a top surface of the third insulator, a top surface of the second oxide, a top surface of the fourth insulator, and a top surface of the third conductor, a fourth conductor embedded in an opening formed in the first insulator, the third insulator, and the fifth insulator and in contact with the first conductor, and a fifth conductor embedded in an opening formed in the second insulator, the third insulator, and the fifth insulator and in contact with the second conductor, wherein the third insulator has a region having a higher nitrogen concentration than other regions of the third insulator in the vicinity of the interface with the fourth conductor and in the vicinity of the interface with the fifth conductor.)

1. A semiconductor device, comprising:

a first oxide;

a first conductor and a second conductor over the first oxide;

a first insulator on the first conductor;

a second insulator on the second conductor;

a third insulator on the first insulator and the second insulator;

a second oxide provided over the first oxide between the first conductor and the second conductor;

a fourth insulator on the second oxide;

a third electrical conductor on the fourth insulator;

a fifth insulator in contact with a top surface of the third insulator, a top surface of the second oxide, a top surface of the fourth insulator, and a top surface of the third conductor;

a fourth conductor embedded in openings formed in the first insulator, the third insulator, and the fifth insulator and in contact with the first conductor; and

a fifth conductor embedded in openings formed in the second insulator, the third insulator, and the fifth insulator and in contact with the second conductor,

wherein the third insulator has a region having a higher nitrogen concentration than other regions of the third insulator in the vicinity of an interface with the fourth conductor and in the vicinity of an interface with the fifth conductor.

2. The semiconductor device according to claim 1, wherein the first and second electrodes are formed on a substrate,

wherein the first conductive body has a region having a higher nitrogen concentration than other regions of the first conductive body in the vicinity of an interface with the fourth conductive body,

and the second conductor has a region having a higher nitrogen concentration than other regions of the second conductor in the vicinity of an interface with the fifth conductor.

3. A semiconductor device, comprising:

a first insulator;

a first conductor on the first insulator;

a second insulator on the first conductor;

a first oxide over the second insulator;

a second conductor and a third conductor over the first oxide;

a third insulator on the second conductor;

a fourth insulator on the third conductor;

a fifth insulator on the third insulator and the fourth insulator;

a second oxide provided over the first oxide and between the second conductor and the third conductor;

a sixth insulator on the second oxide;

a fourth electrical conductor on the sixth insulator;

a seventh insulator in contact with a top surface of the fifth insulator, a top surface of the second oxide, a top surface of the sixth insulator, and a top surface of the fourth conductor;

An eighth insulator contacting a top surface and a side surface of the seventh insulator, a side surface of the fifth insulator, a side surface of the second insulator, and a top surface of the first insulator;

a fifth conductor embedded in openings formed in the third insulator, the fifth insulator, the seventh insulator, and the eighth insulator and in contact with the second conductor; and

a sixth conductor embedded in an opening formed in the fourth insulator, the fifth insulator, the seventh insulator, and the eighth insulator and in contact with the third conductor,

wherein the fifth insulator has regions in which a nitrogen concentration is higher than other regions of the fifth insulator in the vicinity of an interface with the fifth conductor, in the vicinity of an interface with the sixth conductor, and in the vicinity of an interface with the eighth insulator.

4. The semiconductor device according to claim 3, wherein the first and second semiconductor layers are stacked,

wherein the second conductive body has a region having a higher nitrogen concentration than other regions of the second conductive body in the vicinity of an interface with the fifth conductive body,

and the third conductor has a region having a higher nitrogen concentration than other regions of the third conductor in the vicinity of an interface with the sixth conductor.

5. A method for manufacturing a semiconductor device including first to fifth conductors, first to fifth insulators, and first and second oxides, comprising the steps of:

forming the first oxide, a first conductor layer over the first oxide, and a first insulator layer over the first conductor layer over a substrate;

forming the third insulator on the first insulator layer;

forming an opening in the third insulator to the first insulator layer;

removing the first conductor layer and the first insulator layer from the region overlapping the opening to form the first conductor, the second conductor, the first insulator, and the second insulator;

forming a first oxide film so as to be in contact with the first oxide between the first conductor and the second conductor;

forming a first insulating film over the first oxide film;

forming a first conductive film over the first insulating film;

removing a part of the first oxide film, a part of the first insulating film, and a part of the first conductive film until a top surface of the third insulator is exposed, thereby forming the second oxide, the fourth insulator, and the third conductor;

Forming the fifth insulator on the third insulator, the second oxide, the fourth insulator, and the third conductor;

forming openings in the first insulator, the third insulator, and the fifth insulator to the first conductor, and forming openings in the second insulator, the third insulator, and the fifth insulator to the second conductor;

performing microwave treatment in a nitrogen-containing atmosphere; and

a fourth conductor is formed so as to be fitted into an opening reaching the first conductor, and a fifth conductor is formed so as to be fitted into an opening reaching the second conductor.

6. The method for manufacturing a semiconductor device according to claim 5,

wherein the microwave treatment is performed under reduced pressure.

7. A method for manufacturing a semiconductor device including first and second conductors, first to seventh insulators, and first and second oxides, comprising the steps of:

forming the first insulator on a substrate;

forming the first conductor on the first insulator;

forming the second insulator on the first conductor;

forming the third insulator on the second insulator;

Forming the first oxide over the third insulator;

forming a fourth insulator on the first oxide;

forming a first opening in the fourth insulator to the first oxide;

forming a first oxide film in the first opening so as to be in contact with the first oxide and the fourth insulator;

forming a first insulating film over the first oxide film;

forming a first conductive film over the first insulating film;

removing a part of the first oxide film, a part of the first insulating film, and a part of the first conductive film until a top surface of the fourth insulator is exposed, thereby forming the second oxide, the fifth insulator, and the second conductor;

forming the sixth insulator so as to be in contact with the fourth insulator, the second oxide, the fifth insulator, and the second conductor;

removing a portion of the sixth insulator, a portion of the fourth insulator, a portion of the third insulator, and a portion of the second insulator to form a second opening to the first insulator; and

the seventh insulator in contact with the first insulator in the second opening is formed so as to cover the sixth insulator, the fourth insulator, the third insulator, and the second insulator,

Wherein the third insulator, the fourth insulator, and the first insulating film are formed using a gas containing molecules including silicon atoms,

and, in the molecule containing silicon atoms, each silicon atom has three or less hydrogen atoms.

8. The method for manufacturing a semiconductor device according to claim 7,

wherein the microwave treatment is performed under a nitrogen-containing atmosphere after the second opening is formed.

9. The method for manufacturing a semiconductor device according to claim 7 or 8,

wherein the silicon atom-containing molecule has no hydrogen atom.

10. The method for manufacturing a semiconductor device according to any one of claims 7 to 9,

wherein the gas having molecules containing silicon atoms does not have hydrogen atoms.

11. The method for manufacturing a semiconductor device according to any one of claims 7 to 10,

wherein the first insulator and the seventh insulator are less permeable to hydrogen than the fourth insulator.

12. The method for manufacturing a semiconductor device according to any one of claims 7 to 11,

wherein the fourth insulator is formed by a PECVD method or an APCVD method.

13. The method for manufacturing a semiconductor device according to any one of claims 7 to 12,

Wherein the first insulating film is formed by a PEALD method or a thermal ALD method.

Technical Field

One embodiment of the present invention relates to a semiconductor device and a method for manufacturing the semiconductor device. One embodiment of the present invention relates to a semiconductor wafer, a module, and an electronic device.

Note that in this specification and the like, a semiconductor device refers to all devices which can operate by utilizing semiconductor characteristics. In addition to a semiconductor element such as a transistor, a semiconductor circuit, an arithmetic device, or a memory device is also one embodiment of a semiconductor device. A display device (a liquid crystal display device, a light-emitting display device, or the like), a projection device, an illumination device, an electro-optical device, a power storage device, a memory device, a semiconductor circuit, an imaging device, an electronic apparatus, or the like may include a semiconductor device.

Note that one embodiment of the present invention is not limited to the above-described technical field. One embodiment of the invention disclosed in this specification and the like relates to an object, a method, or a manufacturing method. In addition, one embodiment of the present invention relates to a process (process), a machine (machine), a product (manufacture), or a composition (machine).

Background

In recent years, semiconductor devices have been developed, and LSI, CPU, and memory have been mainly used. The CPU is an aggregate of semiconductor elements including a semiconductor integrated circuit (including at least a transistor and a memory) separated from a semiconductor wafer and formed with an electrode as a connection terminal.

Semiconductor circuits (IC chips) such as LSIs, CPUs, memories, etc. are mounted on circuit boards such as printed wiring boards, and are used as one of components of various electronic devices.

In addition, attention is paid to a technique for forming a transistor by using a semiconductor thin film formed over a substrate having an insulating surface. Such a transistor is widely used in electronic devices such as Integrated Circuits (ICs) and image display devices (also simply referred to as display devices). As a semiconductor thin film which can be applied to a transistor, a silicon-based semiconductor material is widely known. As other materials, oxide semiconductors are attracting attention.

In addition, it is known that a transistor using an oxide semiconductor has extremely small leakage current in a non-conductive state. For example, a low power consumption CPU and the like using a transistor using an oxide semiconductor and having a characteristic of a small leakage current have been disclosed (see patent document 1). In addition, for example, a memory device or the like has been disclosed which achieves long-term retention of memory contents by utilizing a characteristic that a transistor using an oxide semiconductor has low leakage current (see patent document 2).

In recent years, with the miniaturization and weight reduction of electronic devices, demands for further densification of integrated circuits have been increasing. In addition, there is a demand for improving the productivity of semiconductor devices including integrated circuits.

[ Prior Art document ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. 2012 and 257187

[ patent document 2] Japanese patent application laid-open No. 2011-

Disclosure of Invention

Technical problem to be solved by the invention

An object of one embodiment of the present invention is to provide a semiconductor device having excellent electrical characteristics. Another object of one embodiment of the present invention is to provide a semiconductor device having normally-off electrical characteristics. Another object of one embodiment of the present invention is to provide a semiconductor device with high reliability. Another object of one embodiment of the present invention is to provide a semiconductor device with a large on-state current. Another object of one embodiment of the present invention is to provide a semiconductor device having high frequency characteristics. Another object of one embodiment of the present invention is to provide a semiconductor device which can be miniaturized or highly integrated. Another object of one embodiment of the present invention is to provide a semiconductor device with high productivity.

An object of one embodiment of the present invention is to provide a semiconductor device capable of holding data for a long period of time. An object of one embodiment of the present invention is to provide a semiconductor device with a high data writing speed. An object of one embodiment of the present invention is to provide a semiconductor device with a high degree of freedom in design. An object of one embodiment of the present invention is to provide a semiconductor device in which power consumption can be suppressed. An object of one embodiment of the present invention is to provide a novel semiconductor device.

Note that the description of these objects does not hinder the existence of other objects. Note that one mode of the present invention is not required to achieve all the above-described objects. Objects other than the above are apparent from and can be extracted from the description of the specification, drawings, claims, and the like.

Means for solving the problems

One embodiment of the present invention is a semiconductor device including a first oxide, a first conductor and a second conductor over the first oxide, a first insulator over the first conductor, a second insulator over the second conductor, a third insulator over the first insulator and the second insulator, a second oxide disposed between the first conductor and the second conductor over the first oxide, a fourth insulator over the second oxide, a third conductor over the fourth insulator, a fifth insulator in contact with a top surface of the third insulator, a top surface of the second oxide, a top surface of the fourth insulator, and a top surface of the third conductor, a fourth conductor embedded in an opening formed in the first insulator, the third insulator, and the fifth insulator and in contact with the first conductor, and a fifth conductor embedded in an opening formed in the second insulator, the third insulator, and the fifth insulator and in contact with the second conductor, wherein the third insulator has a region having a higher nitrogen concentration than other regions of the third insulator in the vicinity of the interface with the fourth conductor and in the vicinity of the interface with the fifth conductor.

In the semiconductor device, it is preferable that the first conductor has a region having a higher nitrogen concentration than other regions of the first conductor in the vicinity of an interface with the fourth conductor, and the second conductor has a region having a higher nitrogen concentration than other regions of the second conductor in the vicinity of an interface with the fifth conductor.

Another aspect of the present invention is a semiconductor device including a first insulator, a first conductor on the first insulator, a second insulator on the first conductor, a first oxide on the second insulator, a second conductor and a third conductor on the first oxide, a third insulator on the second conductor, a fourth insulator on the third conductor, a fifth insulator on the third insulator and the fourth insulator, a second oxide disposed between the second conductor and the third conductor on the first oxide, a sixth insulator on the second oxide, a fourth conductor on the sixth insulator, a seventh insulator in contact with a top surface of the fifth insulator, a top surface of the second oxide, a top surface of the sixth insulator and a top surface of the fourth conductor, an eighth insulator in contact with a top surface and side surfaces of the seventh insulator, side surfaces of the fifth insulator, side surfaces of the second insulator and a top surface of the first insulator, and a seventh insulator, And a sixth conductor embedded in the openings formed in the fourth insulator, the fifth insulator, the seventh insulator, and the eighth insulator and in contact with the third conductor, wherein the fifth insulator has a region having a higher nitrogen concentration than other regions of the fifth insulator in the vicinity of an interface with the fifth conductor, in the vicinity of an interface with the sixth conductor, and in the vicinity of an interface with the eighth insulator.

In the semiconductor device, it is preferable that the second conductor has a region having a higher nitrogen concentration than other regions of the second conductor in the vicinity of the interface with the fifth conductor, and the third conductor has a region having a higher nitrogen concentration than other regions of the third conductor in the vicinity of the interface with the sixth conductor.

Another embodiment of the present invention is a method for manufacturing a semiconductor device including first to fifth conductors, first to fifth insulators, and first and second oxides, including the steps of: forming a first oxide over a substrate, a first conductor layer over the first oxide, and a first insulator layer over the first conductor layer; forming a third insulator on the first insulator layer; forming an opening in the third insulator layer to the first insulator layer; removing the area overlapping the opening in the first conductor layer and the first insulator layer to form a first conductor, a second conductor, a first insulator and a second insulator; forming a first oxide film between the first conductor and the second conductor so as to be in contact with the first oxide; forming a first insulating film over the first oxide film; forming a first conductive film over the first insulating film; removing a part of the first oxide film, a part of the first insulating film, and a part of the first conductive film until a top surface of the third insulator is exposed to form a second oxide, a fourth insulator, and a third conductor; forming a fifth insulator on the third insulator, the second oxide, the fourth insulator, and the third conductor; forming openings reaching the first conductor in the first insulator, the third insulator, and the fifth insulator, and forming openings reaching the second conductor in the second insulator, the third insulator, and the fifth insulator; performing microwave treatment in a nitrogen-containing atmosphere; and forming a fourth conductor so as to be fitted into the opening reaching the first conductor, and forming a fifth conductor so as to be fitted into the opening reaching the second conductor.

In the above method for manufacturing a semiconductor device, the microwave treatment is preferably performed under reduced pressure.

One embodiment of the present invention is a method for manufacturing a semiconductor device including first and second conductors, first to seventh insulators, and first and second oxides, including the steps of: forming a first insulator on a substrate; forming a first conductor on the first insulator; forming a second insulator on the first conductor; forming a third insulator on the second insulator; forming a first oxide over the third insulator; forming a fourth insulator on the first oxide; forming a first opening reaching the first oxide in the fourth insulator; forming a first oxide film in the first opening so as to be in contact with the first oxide and the fourth insulator; forming a first insulating film over the first oxide film; forming a first conductive film over the first insulating film; removing a part of the first oxide film, a part of the first insulating film, and a part of the first conductive film until a top surface of the fourth insulator is exposed to form a second oxide, a fifth insulator, and a second conductor; forming a sixth insulator so as to be in contact with the fourth insulator, the second oxide, the fifth insulator, and the second conductor; removing a portion of the sixth insulator, a portion of the fourth insulator, a portion of the third insulator, and a portion of the second insulator to form a second opening reaching the first insulator; and a seventh insulator formed in the second opening so as to cover the sixth insulator, the fourth insulator, the third insulator, and the second insulator, the seventh insulator being in contact with the first insulator, wherein the third insulator, the fourth insulator, and the first insulating film are formed using a gas containing a molecule containing a silicon atom, and the molecule containing a silicon atom contains three or less hydrogen atoms per silicon atom.

In the above method for manufacturing a semiconductor device, it is preferable that the microwave treatment is performed in a nitrogen-containing atmosphere after the second opening is formed.

In the above method for manufacturing a semiconductor device, the molecule containing silicon atoms preferably does not contain hydrogen atoms. In addition, the gas having molecules containing silicon atoms preferably does not have hydrogen atoms.

In the above method for manufacturing a semiconductor device, it is preferable that the first insulator and the seventh insulator are less permeable to hydrogen than the fourth insulator.

In the above method for manufacturing a semiconductor device, the fourth insulator is preferably formed by a PECVD method or an APCVD method. In the above method for manufacturing a semiconductor device, the first insulating film is preferably formed by a PEALD method or a thermal ALD method.

Effects of the invention

According to one embodiment of the present invention, a semiconductor device having excellent electrical characteristics can be provided. Further, according to one embodiment of the present invention, a semiconductor device having normally-off electrical characteristics can be provided. Further, according to an embodiment of the present invention, a semiconductor device with high reliability can be provided. Further, according to one embodiment of the present invention, a semiconductor device with a large on-state current can be provided. Further, according to an embodiment of the present invention, a semiconductor device having high frequency characteristics can be provided. Further, according to one embodiment of the present invention, a semiconductor device which can be miniaturized or highly integrated can be provided. Further, according to one embodiment of the present invention, a semiconductor device with high productivity can be provided.

Further, a semiconductor device capable of holding data for a long period can be provided. Further, a semiconductor device with a high data writing speed can be provided. Further, a semiconductor device with a high degree of freedom in design can be provided. Further, a semiconductor device capable of suppressing power consumption can be provided. Further, a novel semiconductor device can be provided.

Note that the description of these effects does not hinder the existence of other effects. Note that one mode of the present invention is not required to achieve all the above-described effects. Effects other than the above effects are apparent from the description of the specification, the drawings, the claims, and the like, and can be extracted from the description.

Brief description of the drawings

Fig. 1A, 1B, 1C, and 1D are a top view and a cross-sectional view of a semiconductor device according to one embodiment of the present invention.

Fig. 2A, 2B, 2C, and 2D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 3A, 3B, 3C, and 3D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 4A, 4B, 4C, and 4D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention.

Fig. 5A, 5B, 5C, and 5D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 6A, 6B, 6C, and 6D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 7A, 7B, 7C, and 7D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention.

Fig. 8A, 8B, 8C, and 8D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention.

Fig. 9A, 9B, 9C, and 9D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 10A, 10B, 10C, and 10D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 11A, 11B, 11C, and 11D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to an embodiment of the present invention.

Fig. 12A, 12B, 12C, and 12D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 13A, 13B, 13C, and 13D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 14A, 14B, 14C, and 14D are a plan view and a cross-sectional view illustrating a method for manufacturing a semiconductor device according to one embodiment of the present invention.

Fig. 15 is a plan view illustrating a microwave processing apparatus according to an embodiment of the present invention.

Fig. 16 is a sectional view illustrating a microwave processing apparatus according to one embodiment of the present invention.

Fig. 17 is a sectional view illustrating a microwave processing apparatus according to one embodiment of the present invention.

Fig. 18A, 18B, 18C, and 18D are a top view and a cross-sectional view of a semiconductor device according to one embodiment of the present invention.

Fig. 19A, 19B, 19C, and 19D are a top view and a cross-sectional view of a semiconductor device according to one embodiment of the present invention.

Fig. 20A, 20B, 20C, and 20D are a top view and a cross-sectional view of a semiconductor device according to one embodiment of the present invention.

Fig. 21A and 21B are cross-sectional views of a semiconductor device according to one embodiment of the present invention.

Fig. 22 is a sectional view showing a structure of a memory device according to one embodiment of the present invention.

Fig. 23 is a sectional view showing a structure of a memory device according to one embodiment of the present invention.

Fig. 24A and 24B are block diagrams of examples of the structure of a memory device according to an embodiment of the present invention.

Fig. 25A, 25B, 25C, 25D, 25E, 25F, 25G, and 25H are circuit diagrams of examples of the structure of a memory device according to one embodiment of the present invention.

Fig. 26A and 26B are schematic views of a semiconductor device according to one embodiment of the present invention.

Fig. 27A, 27B, 27C, 27D, and 27E are schematic diagrams of a memory device according to an embodiment of the present invention.

Fig. 28A, 28B, 28C, 28D, 28E1, 28E2, and 28F are diagrams illustrating an electronic device according to one embodiment of the present invention.

Fig. 29 is a schematic diagram showing the structure of a sample according to an embodiment of the present invention.

Fig. 30A, 30B, and 30C are diagrams showing STEM images of a sample according to an embodiment of the present invention.

Fig. 31 is a graph illustrating EDX analysis results of a sample according to an embodiment of the present invention.

Fig. 32A, 32B, and 32C are graphs showing the results of SIMS analysis of samples according to an embodiment of the present invention.

Fig. 33A, 33B are graphs showing the resistivity of the samples according to the embodiment of the present invention.

Fig. 34A, 34B are graphs showing the results of SIMS analysis of samples according to an embodiment of the present invention.

Fig. 35 is a schematic diagram showing the structure of a sample according to an embodiment of the present invention.

Fig. 36 is a graph illustrating the results of SIMS analysis of a sample according to an embodiment of the present invention.

Modes for carrying out the invention

The following describes embodiments with reference to the drawings. Note that a person skilled in the art can easily understand the fact that the embodiments can be implemented in a plurality of different forms, and the modes and details can be changed into various forms without departing from the spirit and the scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments shown below.

In the drawings, the size, thickness of layers, or regions may be exaggerated for clarity. Therefore, the present invention is not limited to the dimensions in the drawings. In addition, in the drawings, ideal examples are schematically shown, and therefore the present invention is not limited to the shapes, numerical values, and the like shown in the drawings. For example, in an actual manufacturing process, a layer, a resist mask, or the like may be unintentionally etched by a process such as etching, but for ease of understanding, the layer, the resist mask, or the like may not be reflected in the drawings. In the drawings, the same reference numerals are used in common between different drawings to denote the same portions or portions having the same functions, and a repetitive description thereof will be omitted. In addition, the same hatching is sometimes used when parts having the same function are indicated, and no reference numeral is particularly attached.

In particular, in a plan view (also referred to as a plan view), a perspective view, or the like, some of the components may not be described to facilitate understanding of the present invention. In addition, a description of a partial hidden line or the like may be omitted.

Note that, in this specification and the like, first and second ordinal numbers are added for convenience, and do not indicate the order of steps or the order of stacking. Therefore, for example, "first" may be replaced with "second" or "third" as appropriate to describe the present invention. In addition, ordinal numbers described in this specification and the like may not coincide with ordinal numbers for specifying one embodiment of the present invention.

For convenience, in this specification and the like, terms indicating arrangement such as "upper" and "lower" are used to describe positional relationships of constituent elements with reference to the drawings. Further, the positional relationship of the components is changed as appropriate in accordance with the direction in which each component is described. Therefore, the words are not limited to the words described in the specification, and the words may be appropriately changed depending on the case.

For example, in the present specification and the like, when it is explicitly described that "X and Y are connected", the following is meant: x is electrically connected with Y; x is functionally linked to Y; x and Y are directly connected. Therefore, the connection relationships are not limited to the predetermined connection relationships such as those shown in the drawings or described herein, and connection relationships other than those shown in the drawings or described herein are also disclosed in the drawings or described herein.

Here, X and Y are objects (for example, devices, elements, circuits, wirings, electrodes, terminals, conductive films, layers, and the like).

In addition, when transistors having different polarities are used, or when the direction of current flow during circuit operation changes, the functions of the source and the drain may be interchanged. Therefore, in this specification and the like, the source and the drain may be interchanged with each other.

In this specification and the like, depending on the structure of a transistor, the actual channel width (hereinafter, also referred to as "effective channel width") in a region where a channel is formed may be different from the channel width (hereinafter, also referred to as "apparent channel width") shown in a plan view of the transistor. For example, when the gate electrode covers the side surface of the semiconductor, the influence of the effective channel width may not be ignored because the effective channel width is larger than the apparent channel width. For example, in a transistor which is miniaturized and has a gate electrode covering a side surface of a semiconductor, a proportion of a channel formation region formed on the side surface of the semiconductor may be increased. In this case, the effective channel width is larger than the apparent channel width.

In such a case, it may be difficult to estimate the effective channel width by actual measurement. For example, in order to estimate the effective channel width from the design value, it is necessary to know the assumption of the shape of the semiconductor in advance. Therefore, when the shape of the semiconductor is not determined, it is difficult to accurately measure the effective channel width.

In this specification, when simply described as "channel width", it sometimes means channel width in appearance. Alternatively, in the present specification, when simply indicating "channel width", it may sometimes indicate effective channel width. Note that values of the channel length, the channel width, the effective channel width, the apparent channel width, and the like can be determined by analyzing a cross-sectional TEM image or the like.

Note that the impurity of the semiconductor refers to, for example, an element other than a main component of the semiconductor. For example, an element having a concentration of less than 0.1 atomic% can be said to be an impurity. The inclusion of impurities may increase the DOS (Density of States) of a semiconductor, thereby lowering the crystallinity. When the semiconductor is an oxide semiconductor, examples of impurities that change the characteristics of the semiconductor include group 1 elements, group 2 elements, group 13 elements, group 14 elements, group 15 elements, and transition metals other than the main component of the oxide semiconductor. For example, hydrogen, lithium, sodium, silicon, boron, phosphorus, carbon, nitrogen, and the like. When the semiconductor is an oxide semiconductor, water may also function as an impurity. In addition, when the semiconductor is an oxide semiconductor, oxygen vacancies may be generated due to, for example, the entry of impurities. In addition, when the semiconductor is silicon, as impurities that change the semiconductor characteristics, for example, oxygen, group 1 elements other than hydrogen, group 2 elements, group 13 elements, group 15 elements, and the like are given.

Note that in this specification and the like, silicon oxynitride refers to a substance having an oxygen content larger than a nitrogen content. Further, silicon oxynitride refers to a substance having a nitrogen content greater than an oxygen content.

Note that in this specification and the like, "insulator" may be referred to interchangeably as "insulating film" or "insulating layer". In addition, the "conductive body" may be referred to as a "conductive film" or a "conductive layer" instead. In addition, the "semiconductor" may be referred to as a "semiconductor film" or a "semiconductor layer" instead.

In the present specification and the like, "parallel" means a state in which an angle formed by two straight lines is-10 ° or more and 10 ° or less. Therefore, the state where the angle is-5 ° or more and 5 ° or less is also included. "substantially parallel" means a state in which the angle formed by two straight lines is-30 ° or more and 30 ° or less. The term "perpendicular" refers to a state in which the angle between two straight lines is 80 ° or more and 100 ° or less. Therefore, the angle is 85 ° or more and 95 ° or less. "substantially perpendicular" means a state in which an angle formed by two straight lines is 60 ° or more and 120 ° or less.

Note that in this specification, a barrier film refers to a film having a function of suppressing permeation of impurities such as water and hydrogen and oxygen, and when the barrier film has conductivity, the barrier film is sometimes referred to as a conductive barrier film.

In this specification and the like, a metal oxide (metal oxide) refers to an oxide of a metal in a broad sense. The metal Oxide is classified into an Oxide insulator, an Oxide conductor (including a transparent Oxide conductor), an Oxide Semiconductor (which may also be simply referred to as OS), and the like. For example, when a metal oxide is used for a semiconductor layer of a transistor, the metal oxide is sometimes referred to as an oxide semiconductor. In other words, the OS FET or the OS transistor may be referred to as a transistor including a metal oxide or an oxide semiconductor.

Note that, in this specification and the like, normally closed means: the current flowing through the transistor at 1 μm per channel width when no potential is applied to the gate or a ground potential is applied to the gate is 1 × 10 at room temperature^-20A is 1X 10 at 85 deg.C^-18A is less than or equal to 1X 10 at 125 DEG C^-16A is below.

(embodiment mode 1)

An example of a semiconductor device including the transistor 200 according to one embodiment of the present invention and a manufacturing method thereof are described below.

< example of Structure of semiconductor device >

Fig. 1A, 1B, 1C, and 1D are a top view and a cross-sectional view of a transistor 200 and a periphery of the transistor 200 according to one embodiment of the present invention.

Fig. 1A is a top view of a semiconductor device including a transistor 200. Fig. 1B and 1C are cross-sectional views of the semiconductor device. Here, fig. 1B is a cross-sectional view of a portion indicated by a chain line a1-a2 in fig. 1A, and is also a cross-sectional view in the channel length direction of the transistor 200. Fig. 1C is a cross-sectional view of a portion indicated by a chain line A3-a4 in fig. 1A, and is also a cross-sectional view in the channel width direction of the transistor 200. FIG. 1D is a cross-sectional view of the portion indicated by the dashed line A5-A6 in FIG. 1A. Note that in the plan view of fig. 1A, some components are omitted to make the drawing more clear.

A semiconductor device according to one embodiment of the present invention includes an insulator 212 over a substrate (not shown), an insulator 214 over the insulator 212, a transistor 200 over the insulator 214, an insulator 280 over the transistor 200, an insulator 282 over the insulator 280, an insulator 283 over the insulator 282, and an insulator 274 over the insulator 283. The insulator 212, the insulator 214, the insulator 280, the insulator 282, the insulator 283, and the insulator 274 serve as interlayer films. Further, a conductor 240 (a conductor 240a and a conductor 240b) serving as a plug electrically connected to the transistor 200 is provided. Further, a conductor 246 (a conductor 246a and a conductor 246b) serving as a wiring electrically connected to the conductor 240 is provided on the insulator 274 and the conductor 240.

Further, the conductor 240 is provided with a first conductor and a second conductor inside. Here, the height of the top surface of the conductive body 240 and the height of the top surface of the insulator 274 may be substantially equal. In the transistor 200, a first conductor of the conductors 240 and a second conductor of the conductors 240 are stacked, but the present invention is not limited to this. For example, the conductor 240 may have a single-layer structure or a stacked-layer structure of three or more layers. When the structure has a stacked structure, the structures may be distinguished by giving ordinal numbers in the order of formation.

As shown in fig. 1, the transistor 200 of this embodiment mode is preferably formed over the insulator 212, and the top surface and the side surfaces thereof are preferably covered with the insulator 283. Further, it is preferable that the transistor 200 be sealed with the insulator 283 and the insulator 212 in such a structure that the insulator 283 and the insulator 212 are in contact with each other outside the transistor 200 in a plan view.

[ transistor 200]

As shown in fig. 1, the transistor 200 includes: insulator 216 on insulator 214; a conductor 205 (a conductor 205a and a conductor 205b) disposed so as to be embedded in the insulator 216; an insulator 222 on the insulator 216 and on the conductor 205; an insulator 224 on insulator 222; oxide 230a on insulator 224; oxide 230b over oxide 230 a; oxide 243a and oxide 243b on oxide 230 b; conductor 242a over oxide 243 a; a conductor 242b over oxide 243 b; an insulator 272a on conductor 242 a; an insulator 272b on the conductor 242 b; oxide 230c over oxide 230 b; insulator 250 over oxide 230 c; and a conductor 260 (conductor 260a and conductor 260b) overlapping the oxide 230c on the insulator 250. Further, the oxide 230c is in contact with the side surface of the oxide 243a, the side surface of the oxide 243b, the side surface of the conductor 242a, and the side surface of the conductor 242b, respectively. The conductor 260 includes a conductor 260a and a conductor 260b, and the conductor 260a is disposed so as to surround the bottom surface and the side surface of the conductor 260 b. Here, as shown in fig. 1B, the top surface of the conductor 260 is arranged to substantially coincide with the top surface of the insulator 250 and the top surface of the oxide 230 c. In addition, insulator 282 contacts the top surfaces of conductor 260, insulator 250, oxide 230c, and insulator 280, respectively.

Note that the oxide 243a and the oxide 243b are hereinafter sometimes collectively referred to as the oxide 243. The conductors 242a and 242b may be collectively referred to as the conductors 242. The conductors 242a and 242b may be collectively referred to as the conductors 242. The insulator 272a and the insulator 272b may be collectively referred to as an insulator 272.

In the transistor 200, the conductor 260 functions as a gate of the transistor, and the conductors 242a and 242b function as a source electrode and a drain electrode, respectively. In the transistor 200, the conductor 260 serving as a gate is formed in a self-aligned manner so as to fill an opening formed of the insulator 280 or the like. By forming the conductor 260 in this manner, the conductor 260 can be reliably disposed without alignment in the region between the conductor 242a and the conductor 242 b.

At least one of the insulator 212, the insulator 214, the insulator 222, the insulator 272 (hereinafter, the insulator 272a and the insulator 272b may be collectively referred to as "insulator 272"), the insulator 282, and the insulator 283 preferably has a function of suppressing diffusion of hydrogen (for example, at least one of a hydrogen atom, a hydrogen molecule, and the like) or water molecules. In particular, the insulator 212 and the insulator 283 are preferably capable of efficiently suppressing diffusion of hydrogen (for example, at least one of hydrogen atoms, hydrogen molecules, and the like) or water molecules. At least one of the insulator 212, the insulator 214, the insulator 222, the insulator 272, the insulator 282, and the insulator 283 preferably has a function of suppressing oxygen (for example, at least one of oxygen atoms, oxygen molecules, and the like) from diffusing. For example, at least one of the insulator 212, the insulator 214, the insulator 222, the insulator 272, the insulator 282, and the insulator 283 preferably has lower permeability to one or both of oxygen and hydrogen than the insulator 224. At least one of the insulator 212, the insulator 214, the insulator 222, the insulator 272, the insulator 282, and the insulator 283 preferably has lower permeability to one or both of oxygen and hydrogen than the insulator 250. At least one of the insulator 212, the insulator 214, the insulator 222, the insulator 272, the insulator 282, and the insulator 283 preferably has lower permeability to one or both of oxygen and hydrogen than the insulator 280.

As the insulator 212, the insulator 214, the insulator 222, the insulator 272, the insulator 282, and the insulator 283, for example, aluminum oxide, hafnium oxide, gallium oxide, indium gallium zinc oxide, silicon nitride, silicon oxynitride, or the like can be used. In particular, silicon nitride or silicon oxynitride having a higher hydrogen barrier property is preferably used for the insulator 212 and the insulator 283.

As shown in fig. 1, in one embodiment of the semiconductor device of this embodiment mode, the insulator 214, the insulator 216, the insulator 222, the insulator 224, the insulator 280, and the insulator 282 are patterned and covered with an insulator 283. That is, insulator 283 contacts the top and side surfaces of insulator 282, the side surfaces of insulator 280, the side surfaces of insulator 224, the side surfaces of insulator 222, the side surfaces of insulator 216, the side surfaces of insulator 214, and the top surface of insulator 212. Thus, in addition to the oxide 230 and the like, the insulator 214, the insulator 216, the insulator 222, the insulator 224, the insulator 280, and the insulator 282 are also separated from the outside by the insulator 283 and the insulator 212.

Additionally, oxide 230 preferably includes oxide 230a on insulator 224, oxide 230b on oxide 230a, and oxide 230c disposed on oxide 230b with at least a portion thereof in contact with a top surface of oxide 230 b. Here, the oxide 230c is preferably provided so that the side surfaces thereof are in contact with the oxide 243a, the oxide 243b, the conductor 242a, the conductor 242b, the insulator 272a, the insulator 272b, and the insulator 280.

Note that in the transistor 200, three layers of oxide 230a, oxide 230b, and oxide 230c are stacked in the channel formation region and the vicinity thereof, but the present invention is not limited thereto. For example, a single layer of the oxide 230b, a two-layer structure of the oxide 230b and the oxide 230a, a two-layer structure of the oxide 230b and the oxide 230c, or a stacked-layer structure of four or more layers may be provided. For example, the oxide 230c may have a two-layer structure to form a four-layer stacked structure.

In the transistor 200, a metal oxide (hereinafter also referred to as an oxide semiconductor) used as an oxide semiconductor is preferably used as the oxide 230 (the oxide 230a, the oxide 230b, and the oxide 230c) including a channel formation region. For example, a metal oxide used as an oxide semiconductor has an energy gap of 2eV or more, preferably 2.5eV or more. By using a metal oxide having a wide energy gap in this manner, the leakage current (off-state current) in the non-conductive state of the transistor 200 can be made extremely small. By using such a transistor, a semiconductor device with low power consumption can be provided.

For example, as the oxide 230, a metal oxide such as an In-M-Zn oxide (the element M is one or more selected from aluminum, gallium, yttrium, tin, copper, vanadium, beryllium, boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, magnesium, and the like) is preferably used. In particular, aluminum, gallium, yttrium or tin can be used as element M. Further, as the oxide 230, an In-M oxide, an In-Zn oxide, or an M-Zn oxide may be used.

Oxide 230 includes oxide 230a, oxide 230b on oxide 230a, and oxide 230c on oxide 230 b. When the oxide 230a is included under the oxide 230b, diffusion of impurities from a structure formed under the oxide 230a to the oxide 230b can be suppressed. When the oxide 230c is included over the oxide 230b, diffusion of impurities from a structure formed over the oxide 230c to the oxide 230b can be suppressed.

The oxide 230 preferably has a stacked-layer structure of oxides having different atomic number ratios of metal atoms. Specifically, the atomic number ratio of the element M in the constituent elements of the metal oxide used for the oxide 230a is preferably larger than the atomic number ratio of the element M in the constituent elements of the metal oxide used for the oxide 230 b. In addition, the atomic number ratio of the element M with respect to In the metal oxide for the oxide 230a is preferably larger than the atomic number ratio of the element M with respect to In the metal oxide for the oxide 230 b. In addition, the atomic number ratio of In with respect to the element M In the metal oxide used for the oxide 230b is preferably larger than the atomic number ratio of In with respect to the element M In the metal oxide used for the oxide 230 a. In addition, as the oxide 230c, a metal oxide which can be used for the oxide 230a or the oxide 230b can be used.

Specifically, as the oxide 230a, In: ga: 1, Zn: 3: 4[ atomic number ratio ] or 1: 1: 0.5[ atomic number ratio ]. In addition, as the oxide 230b, In: ga: zn is 4: 2: 3[ atomic number ratio ] or 1: 1: 1[ atomic number ratio ]. In addition, as the oxide 230c, In: ga: 1, Zn: 3: 4[ atomic number ratio ], Ga: zn is 2: 1[ atomic number ratio ] or Ga: zn is 2: 5[ atomic number ratio ]. Specific examples of the case where the oxide 230c has a stacked-layer structure include In: ga: zn is 4: 2: 3[ atomic number ratio ] and In: ga: 1, Zn: 3: 4[ atomic number ratio ], Ga: zn is 2: 1[ atomic number ratio ] and In: ga: zn is 4: 2: 3[ atomic number ratio ], Ga: zn is 2: 5[ atomic number ratio ] and In: ga: zn is 4: 2: 3[ atomic number ratio ], gallium oxide, and In: ga: zn is 4: 2: a laminated structure of 3[ atomic number ratio ], and the like.

In addition, the oxide 230b preferably has crystallinity. For example, the following CAAC-OS (c-axis aligned crystalline oxide semiconductor) is preferably used. An oxide having crystallinity such as CAAC-OS has a highly crystalline and dense structure with few impurities and defects (oxygen vacancies). Therefore, the source electrode or the drain electrode can be suppressed from extracting oxygen from the oxide 230 b. Thus, even if the heat treatment is performed, the amount of oxygen extracted from the oxide 230b can be reduced, and therefore the transistor 200 is stable against a high temperature (so-called thermal budget) in the manufacturing process.

In addition, the energy of the conduction band bottom of oxide 230a and oxide 230c is preferably higher than that of oxide 230 b. That is, the electron affinity of the oxide 230a and the oxide 230c is preferably smaller than that of the oxide 230 b.

Here, the electron affinity or the conduction band bottom level Ec can be calculated from the ionization potential Ip of the difference between the vacuum level and the valence band top level Ev, and the energy gap Eg. The ionization potential Ip can be measured, for example, by means of an Ultraviolet Photoelectron Spectroscopy (UPS: Ultraviolet Photoelectron Spectroscopy) apparatus. The energy gap Eg can be measured, for example, with a spectroscopic ellipsometer.

Here, the energy level of the conduction band bottom changes gently at the junction of the oxide 230a, the oxide 230b, and the oxide 230 c. In other words, the above case can be expressed as a case where the energy levels of the conduction band bottoms of the junctions of the oxide 230a, the oxide 230b, and the oxide 230c are continuously changed or continuously joined. For this reason, it is preferable to reduce the defect state density of the mixed layer formed at the interface between the oxide 230a and the oxide 230b and the interface between the oxide 230b and the oxide 230 c.

At this time, the main path of the carriers is oxide 230 b. By providing the oxide 230a and the oxide 230c with the above structure, the defect state density at the interface between the oxide 230a and the oxide 230b and the interface between the oxide 230b and the oxide 230c can be reduced. Therefore, the influence of the interface scattering on the carrier conduction is reduced, and the transistor 200 can obtain a high-pass current and high-frequency characteristics.

In addition, an oxide semiconductor with a low carrier concentration is preferably used for the oxide 230 (for example, the oxide 230 b). In order to reduce the carrier concentration of the oxide semiconductor, the impurity concentration in the oxide semiconductor may be reduced to reduce the defect state density. In this specification and the like, a state in which the impurity concentration is low and the defect state density is low is referred to as high-purity intrinsic or substantially high-purity intrinsic. Examples of the impurities in the oxide semiconductor include hydrogen, nitrogen, alkali metals, alkaline earth metals, iron, nickel, and silicon.

In particular, hydrogen contained in the oxide semiconductor reacts with oxygen bonded to a metal atom to generate water, and thus oxygen vacancies (also referred to as V) are sometimes formed in the oxide semiconductor_O: oxygen vacacy). Further, there are cases where hydrogen enters a defect in an oxygen vacancy (hereinafter, also referred to as "V" in some cases)_OH) Is used as a donor to generate electrons as carriers. Sometimes due to partial reaction of hydrogen withOxygen bonded to the metal atom bonds, generating electrons as carriers. Therefore, a transistor using an oxide semiconductor containing a large amount of hydrogen easily has a normally-on characteristic. Further, since hydrogen in the oxide semiconductor is likely to move due to stress such as heat or an electric field, when the oxide semiconductor contains a large amount of hydrogen, reliability of the transistor may be lowered.

V_OH may be used as a donor of the oxide semiconductor. However, it is difficult to quantitatively evaluate the defect. Therefore, in the oxide semiconductor, evaluation may be performed not by the donor concentration but by the carrier concentration. Thus, in this specification and the like, as a parameter of the oxide semiconductor, a carrier concentration in a state where an electric field is not applied may be used instead of the donor concentration. That is, the "carrier concentration" described in this specification and the like may be referred to as "donor concentration".

From the above, when an oxide semiconductor is used as the oxide 230, it is preferable to reduce V in the oxide 230 as much as possible_OH to render the oxide 230 highly intrinsic or substantially highly intrinsic. In order to obtain such a V_OAn oxide semiconductor in which H is sufficiently reduced, and it is important that: removing impurities such as moisture and hydrogen in the oxide semiconductor (sometimes referred to as dehydration and dehydrogenation treatment); and supplying oxygen to the oxide semiconductor to fill the oxygen vacancy (sometimes also referred to as an oxidation treatment). By mixing V_OAn oxide semiconductor in which impurities such as H are sufficiently reduced is used for a channel formation region of a transistor, and stable electrical characteristics can be provided.

However, even if the oxide semiconductor is formed so as to reduce the hydrogen concentration, hydrogen may be absorbed from the conductor 240 in contact with the oxide semiconductor. The conductor 240 is a conductor used as a through hole (via), and is disposed so as to be embedded in openings formed in the insulator 274 and the insulator 280. Here, the insulator 274 and the insulator 280 are insulating films used as interlayer films, and insulators containing silicon such as silicon oxide and silicon oxynitride are preferably used. In forming the insulators 274 and 280, SiH is often used as a source gas₄And the like. Containing SiH₄The source gas of the silicon hydride is decomposed at the time of film formation, and thus there is a concern that: a large amount of highly reactive hydrogen (e.g., hydrogen radicals) is generated and a large amount of hydrogen is absorbed by the insulators 274 and 280 formed. A part of a large amount of hydrogen absorbed in the insulators 274 and 280 may diffuse into the conductor 240 serving as a through hole by heat treatment or the like in the manufacturing process of the transistor 200. Also, the hydrogen may diffuse into the oxide 230 through the conductive body 240. In this manner, it is possible to increase the hydrogen concentration in the oxide semiconductor through the conductive body 240.

In contrast, in the transistor 200 shown in this embodiment, the region 241 in which the nitrogen concentration is higher than that in the other regions is formed in the vicinity of the interface with the conductor 240a and the vicinity of the interface with the conductor 240b between the insulator 274 and the insulator 280, whereby the contamination of hydrogen from the insulator 274 and the insulator 280 into the conductor 240 is reduced.

In the present embodiment, as shown in fig. 1, the region 241 may be referred to separately as a region 241a formed near the interface with the conductor 240a in the insulator 280, a region 241b formed near the interface with the conductor 240b in the insulator 280, and a region 241c formed near the interfaces with the conductors 240a and 240b in the insulator 274. In addition, as shown in fig. 1, a region 241c is sometimes formed near the top surface of the insulator 274.

The region 241 is preferably formed to have a thickness of, for example, 1nm or more, more preferably 1.5nm or more, in the insulator 274 and the insulator 280. The thickness of the region 241 may be 50nm or less, 20nm or less, or 10nm or less in the insulator 274 and the insulator 280, for example.

Region 241 is a region having a higher nitrogen concentration than the other regions of insulator 274 and insulator 280. The nitrogen concentration of the regions 241a and 241b is higher than at least a portion of the other regions of the insulator 280. In addition, the region 241c has a higher nitrogen concentration than at least a portion of the other regions of the insulator 274. The oxygen concentration in the region 241 may be lower than that in other regions of the insulator 274 and the insulator 280.

The region 241 can be formed by solid-phase nitriding the surfaces of the insulator 274 and the insulator 280 in a state where the conductor 240 is not provided and the openings are formed in the insulator 272, the insulator 280, the insulator 282, the insulator 283, and the insulator 274. The solid-phase nitridation of the insulators 274 and 280 can be performed by performing plasma treatment in a nitrogen-containing atmosphere. Hereinafter, such a process is sometimes referred to as a nitrogen plasma process. In the nitrogen plasma treatment, nitrogen gas is converted into plasma by high frequency such as microwave or RF, and the nitrogen plasma is applied to the vicinity of the surfaces of the insulator 280 and the insulator 274, whereby the vicinity of the surfaces of the insulator 280 and the insulator 274 can be nitrided in a solid phase.

For the nitrogen plasma treatment, for example, a device including a power source for generating high-density plasma using microwaves is preferably used. Hereinafter, a plasma process using microwaves is sometimes referred to as a microwave process and an apparatus including a power supply for generating high-density plasma using microwaves is sometimes referred to as a microwave processing apparatus. Further, the microwave processing apparatus may also include a power supply that applies RF to one side of the substrate. By using high-density plasma under a nitrogen-containing atmosphere, nitrogen radicals can be generated at a high density. By applying RF to the substrate side, ions generated by high-density plasma can be efficiently introduced into the insulator 274 and the insulator 280. The microwave treatment in the nitrogen-containing atmosphere is preferably performed under reduced pressure, and the pressure may be 400Pa or less, preferably 200Pa or less, more preferably 60Pa or less, and still more preferably 12Pa or less. At a nitrogen flow rate ratio (N) of 50% or less₂/(N₂+ Ar)), preferably at a nitrogen flow rate ratio of 10% to 30%. The treatment temperature may be, for example, about 400 ℃. Note that in this specification and the like, the term "processing temperature" includes not only the substrate temperature at the time of processing but also a set temperature of the processing apparatus.

The region 241 as described above has a function of suppressing diffusion of hydrogen (for example, at least one of hydrogen atoms, hydrogen molecules, and the like). Region 241 is preferably less permeable to hydrogen than insulator 274 or insulator 280, for example. By forming such a region 241 between the conductor 240 and the insulators 274 and 280, it is possible to reduce the mixing of hydrogen contained in the insulators 274 and 280 into the conductor 240. Therefore, the amount of hydrogen diffused from the conductor 240 into the conductor 242 and the oxide 230 can be reduced. Further, the region 241 preferably has a function of suppressing oxygen diffusion.

By providing the region 241 between the insulator 280 and the conductor 240, the hydrogen concentration in the oxide 230 can be reduced. For example, in the oxide 230b, the hydrogen concentration measured by Secondary Ion Mass Spectrometry (SIMS) may be less than 1X 10²⁰atoms/cm³Preferably less than 1X 10¹⁹atoms/cm³More preferably less than 5X 10¹⁸atoms/cm³More preferably less than 1X 10¹⁸atoms/cm³. By using the oxide 230 in which impurities such as hydrogen are sufficiently reduced in the channel formation region of the transistor 200, normally-off characteristics can be realized, stable electrical characteristics can be obtained, and reliability can be improved.

In addition, when an oxide semiconductor is used as the oxide 230, it is preferable that the carrier concentration of the oxide semiconductor in a region serving as a channel formation region is 1 × 10 ¹⁸cm^-3Below, more preferably less than 1 × 10¹⁷cm^-3More preferably less than 1X 10¹⁶cm^-3More preferably less than 1X 10¹³cm^-3Further preferably less than 1X 10¹²cm^-3. The lower limit of the carrier concentration of the oxide semiconductor in the region serving as the channel formation region is not particularly limited, and may be set to 1 × 10, for example^-9cm^-3。

In addition, when the region 241 is formed, the nitrogen plasma treatment is performed in a state where the opening reaching the conductor 242a and the opening reaching the conductor 242b are formed in the insulator 272, the insulator 280, the insulator 282, the insulator 283, and the insulator 274. Thus, a region 244a having a higher nitrogen concentration than the other region of the conductor 242a is formed in the vicinity of the interface between the conductor 242a and the conductor 240a (in the vicinity of the surface of the conductor 242a when formed), and a region 244b having a higher nitrogen concentration than the other region of the conductor 242b is formed in the vicinity of the interface between the conductor 242b and the conductor 240b (in the vicinity of the surface of the conductor 242b when formed). Note that the region 244a and the region 244b may be collectively referred to as a region 244 in the following.

When a metal nitride, for example, tantalum nitride is used as the conductor 242, the region 244 preferably has a resistivity approximately equal to that of the other regions of the conductor 242. For example, the resistivity of the region 244 is preferably 130% or less of the resistivity of the other regions of the conductor 242. As such, the region 244 does not significantly affect the conductivity of the conductor 242 used as a source electrode or a drain electrode. Therefore, even if the region 241 is formed by the nitrogen plasma treatment, the conductor 242 does not need to be subjected to a special post-treatment. Further, by providing the region 244 having a higher nitrogen concentration than the other region of the conductor 242, the amount of hydrogen diffused from the conductor 240 into the conductor 242 may be further reduced.

In addition, a region 245 having a higher nitrogen concentration than other regions of the insulator 280, the insulator 224, and the insulator 216 may be formed in the vicinity of the interface with the insulator 283 among the insulator 280, the insulator 224, and the insulator 216. As shown in fig. 1, region 245 is formed on the sides of insulator 280, insulator 224, and insulator 216. The region 245 preferably has the same structure as the region 241. The region 245 as described above has a function of suppressing diffusion of hydrogen (for example, at least one of hydrogen atoms, hydrogen molecules, and the like). Region 245 preferably has a lower hydrogen permeability than, for example, insulator 280, insulator 224, and insulator 216. In addition, the region 245 can be formed by nitrogen plasma treatment as in the region 241. Therefore, the structure and the forming method of the region 245 can be described in detail with reference to the region 241.

By forming such a region 245 between the insulator 280, the insulator 224, and the insulator 216 and the insulator 283, it is possible to reduce the mixing of hydrogen contained in the insulator 274 into the insulator 280 and the like. Therefore, the amount of hydrogen diffused into the oxide 230 from the insulator 280 and the like can be further reduced.

By forming the region 245 on the side surfaces of the insulator 280, the insulator 224, and the insulator 216 before forming the insulator 283, even when a CVD method or the like in which a large amount of hydrogen is generated in a process chamber is used to form the insulator 283, the hydrogen can be prevented from being mixed into the insulator 280, the insulator 224, and the insulator 216. Thus, the insulator 283 can be formed by a film formation method having good step coverage such as a CVD method when the insulator 283 is formed, so that no disconnection or pin hole is formed in the step of the insulator 280 or the like. Thus, the transistor 200 can be sealed with the insulator 283 and the insulator 212.

Further, since the conductor 240 penetrates the insulator 283 and the region 241 is in contact with the conductor 240 as described above, hydrogen mixed into the inside of the insulator 283 through the conductor 240 can be reduced. This method can more firmly seal the transistor 200 with the insulator 283, the insulator 212, and the region 241, thereby reducing the contamination of impurities such as hydrogen in the insulator 274 and the like from the outside of the insulator 283.

Further, by forming the interlayer insulating film (the insulator 216, the insulator 274, the insulator 280, and the like) and the gate insulating film (the insulator 224, the insulator 250, and the like) using a source gas containing no hydrogen atoms or a small amount of hydrogen atoms, the concentration of hydrogen contained in the insulating films can be reduced to reduce hydrogen mixed into the channel formation region of the oxide semiconductor.

In forming the insulating film, a gas having a molecule containing a silicon atom is mainly used as a film formation gas. In order to reduce the hydrogen contained in the insulating film, the silicon atom-containing molecule preferably has a small number of hydrogen atoms, and more preferably the silicon atom-containing molecule does not have a hydrogen atom. Of course, the film forming gas other than the gas containing molecules of silicon atoms preferably contains a small amount of hydrogen atoms, and more preferably contains no hydrogen atoms.

In the presence of Si_x-R_yWhen the functional group R represents a molecule containing a silicon atom, for example, an isocyanate group (-N ═ C ═ O), an cyanate group (-O-C ≡ N), a cyano group (-C ≡ N), or a diazo group (═ N ≡ N) can be used as the functional group R₂) Azido (-N)₃) Nitroso (-NO) and nitro (-NO)₂) At least one of (a). For example, 1. ltoreq. x.ltoreq.3 and 1. ltoreq. y.ltoreq.8 can be set. Examples of the molecule containing a silicon atom include tetraisocyanatosilane, tetracyanosilane, hexaisocyanatosilane, octaisocyanatosilane, and the like. The example shows the bonding of a silicon atom to a functional group of the same kindHowever, the present embodiment is not limited to this. The silicon atom may also be bonded to different kinds of functional groups.

Further, for example, as the functional group R, halogen (Cl, Br, I, or F) may also be used. For example, 1. ltoreq. x.ltoreq.2 and 1. ltoreq. y.ltoreq.6 can be set. Examples of the molecule containing a silicon atom include tetrachlorosilane (SiCl)₄) Hexachlorodisilane (Si)₂Cl₆) And the like. While chlorine is shown as an example of the functional group, halogens other than chlorine, such as bromine, iodine, and fluorine, may be used as the functional group. In addition, the silicon atom may be bonded to a different kind of halogen.

The insulator 216, the insulator 274, the insulator 280, the insulator 224, and the insulator 250 can be formed by a Chemical Vapor Deposition (CVD) method using the gas containing molecules including silicon atoms. The CVD method is suitable for forming the thick insulators 280, 274, and 216 because the film formation rate is high.

As the CVD method, a Plasma CVD (PECVD: Plasma Enhanced CVD) method using Plasma or a Thermal CVD (TCVD: Thermal CVD) method using heat is preferably used. When the thermal CVD method is used, an Atmospheric Pressure CVD (APCVD) method in which a film is formed under Atmospheric Pressure or a Low Pressure CVD (LPCVD) method in which a film is formed under a reduced Pressure lower than Atmospheric Pressure may be used.

When the insulators 216, 274, 280, 224, and 250 are formed by CVD, an oxidizing agent is preferably used. As the oxidizing agent, O is preferably used₂、O₃、NO、NO₂、N₂O、N₂O₃、N₂O₄、N₂O₅、CO、CO₂And the like do not contain hydrogen atoms.

In addition, the insulator 216, the insulator 274, the insulator 280, the insulator 224, and the insulator 250 may be formed by an ALD (Atomic Layer Deposition) method. In the ALD method, a first source gas (hereinafter, referred to as a precursor, which may be referred to as a precursor or a metal precursor) and a second source gas (hereinafter, referred to as a reactant or a non-metal precursor) for reaction are alternately introduced into a process chamber, and such source gases are repeatedly introduced to perform film formation.

In the ALD method, atoms of each layer are deposited by utilizing self-regulation of atomic properties by performing film formation while switching source gases. Thus, by the ALD method, a film having an extremely small thickness can be formed, a film can be formed with a high aspect ratio structure, a film having few defects such as pinholes can be formed, and a film having excellent coverage can be formed. Therefore, the ALD method is suitable for formation of the insulator 250 and the insulator 224.

As the ALD method, a thermal ALD (thermal ALD) method in which a reaction of a precursor and a reactant is performed only by thermal energy, or a peald (plasma Enhanced ALD) method in which a reactant is plasma-Enhanced may be used.

In the case of the ALD method, the gas having a molecule containing a silicon atom may be used as a precursor, and the oxidizing agent may be used as a reactant. This can significantly reduce the amount of hydrogen introduced into the insulators 216, 274, 280, 224, and 250.

Note that although the above shows an example in which a molecule containing a silicon atom does not contain a hydrogen atom, this embodiment is not limited to this, and a structure in which a part of a functional group bonded to a silicon atom in the molecule containing a silicon atom is replaced with a hydrogen atom may be employed. However, the above-mentioned molecule containing a silicon atom preferably has less hydrogen atoms than Silane (SiH) ₄). That is, in the above-described molecule containing silicon atoms, one silicon atom preferably has three or less hydrogen atoms. In addition, in the gas having the molecule containing silicon atoms, it is more preferable that one silicon atom has three or less hydrogen atoms.

As described above, by forming at least one of the insulator 216, the insulator 274, the insulator 280, the insulator 224, and the insulator 250 by a film formation method using a gas in which hydrogen atoms are reduced or removed, the amount of hydrogen in these insulating films can be reduced. In particular, it is preferable that the oxide 230 and the insulators 216, 224, 280, and 250 formed in the region sealed by the insulator 283 and the insulator 212 are formed by the above method, because the concentration of hydrogen in the sealed region can be reduced, and thus the incorporation of hydrogen from the outside can be further reduced by the insulator 283, the insulator 212, and the region 241.

As shown in fig. 1B, 1C, and 1D, the transistor 200 has a structure in which the insulator 282 and the insulator 250 are in direct contact with each other. By adopting such a structure, oxygen contained in the insulator 280 is not easily absorbed by the conductor 260. Therefore, oxygen contained in the insulator 280 can be efficiently supplied to the oxide 230a and the oxide 230b through the oxide 230c, and oxygen vacancies in the oxide 230a and the oxide 230b can be reduced, thereby improving the electrical characteristics and reliability of the transistor 200. Further, since impurities such as hydrogen in the insulator 280 can be suppressed from being mixed into the insulator 250, the hydrogen concentration of the insulator 250 and the oxide 230 can be further reduced. This can suppress adverse effects on the electrical characteristics and reliability of the transistor 200. As the insulator 282, silicon nitride, silicon oxynitride, aluminum oxide, or hafnium oxide can be used.

As described above, it is possible to provide a semiconductor device in which variations in electrical characteristics are suppressed, stable electrical characteristics are obtained, and reliability is improved. In addition, a semiconductor device having normally-off electrical characteristics can be provided. In addition, a semiconductor device including a transistor with a large on-state current can be provided. In addition, a semiconductor device having a transistor with high frequency characteristics can be provided. In addition, a semiconductor device having a transistor with a small off-state current can be provided.

Next, a detailed structure of a semiconductor device including the transistor 200 according to one embodiment of the present invention will be described.

The conductor 205 is disposed so as to overlap with the oxide 230 and the conductor 260. The conductor 205 is preferably embedded in the insulators 214 and 216.

Here, the conductive body 260 sometimes serves as a first gate (also referred to as a top gate) electrode. In addition, the conductive body 205 sometimes functions as a second gate (also referred to as a bottom gate) electrode. In this case, the Vth of the transistor 200 can be controlled by independently changing the potential supplied to the conductor 205 without interlocking with the potential applied to the conductor 260. In particular, by applying a negative potential to the conductive body 205, Vth of the transistor 200 can be made larger than 0V, and off-state current can be reduced. Therefore, when a negative potential is applied to the conductor 205, the drain current when the potential applied to the conductor 260 is 0V can be reduced as compared with the case where a negative potential is not applied to the conductor 205.

As shown in fig. 1A, the conductor 205 is preferably larger than the region of the oxide 230 that does not overlap with the conductors 242a and 242 b. In particular, as shown in fig. 1C, the conductive body 205 preferably extends to a region outside the end portion of the oxide 230 that intersects the channel width direction. That is, it is preferable that the conductor 205 and the conductor 260 overlap each other with an insulator interposed therebetween outside the side surface of the oxide 230 in the channel width direction. Alternatively, by making the conductive body 205 large, local charging (also referred to as charge accumulation) may be alleviated in a process using plasma in a manufacturing process after the conductive body 205 is formed. However, one embodiment of the present invention is not limited to this. As long as the conductive body 205 overlaps at least the oxide 230 between the conductive body 242a and the conductive body 242 b.

Further, the bottom surface of the conductor 260 in the region where the oxide 230a, the oxide 230b, and the conductor 260 do not overlap is preferably located lower than the bottom surface of the oxide 230b, based on the bottom surface of the insulator 224. The difference between the height of the bottom surface of the region of the conductor 260 not overlapping the oxide 230b and the height of the bottom surface of the oxide 230b is 0nm to 100nm, preferably 3nm to 50nm, and more preferably 5nm to 20 nm.

In this way, the conductor 260 used as a gate covers the side surfaces and the top surface of the oxide 230b in the channel formation region with the oxide 230c and the insulator 250 interposed therebetween, and this structure facilitates the electric field of the conductor 260 to act on the entire oxide 230b in the channel formation region. Therefore, the on-state current (on-state current) of the transistor 200 can be increased to improve the frequency characteristics. In this specification, a structure of a transistor in which a channel formation region is electrically surrounded by electric fields of a first gate and a second gate is referred to as a "surrounded channel (S-channel) structure".

The conductor 205a is preferably a conductor that suppresses permeation of impurities such as water and hydrogen and oxygen. For example, titanium nitride, tantalum, or tantalum nitride may be used. In addition, the conductive body 205b is preferably made of a conductive material containing tungsten, copper, or aluminum as a main component. Although the conductor 205 has a two-layer structure, the conductor 205 may have a multilayer structure of three or more layers.

Here, it is preferable that different types of films be formed continuously without exposure to the air as an oxide semiconductor, an insulator or a conductor located in a lower layer of the oxide semiconductor, and an insulator or a conductor located in an upper layer of the oxide semiconductor, so that an oxide semiconductor film having substantially high purity and intrinsic in which the concentration of impurities (particularly, hydrogen and water) is reduced can be formed.

At least one of the insulator 212, the insulator 214, the insulator 222, the insulator 272, the insulator 282, and the insulator 283 is preferably used as a barrier insulating film which suppresses impurities such as water or hydrogen from being mixed into the transistor 200 from the substrate side or from above. Therefore, at least one of the insulator 212, the insulator 214, the insulator 222, the insulator 272, the insulator 282, and the insulator 283 is preferably a material having a hydrogen atom, a hydrogen molecule, a water molecule, a nitrogen atom, a nitrogen molecule, and a nitrogen oxide molecule (N) suppressed therein₂O、NO、NO₂Etc.), copper atoms, etc., and functions to diffuse impurities such as copper atoms (the impurities are not easily permeated). Further, it is preferable to use an insulating material having a function of suppressing diffusion of oxygen (for example, at least one of oxygen atoms, oxygen molecules, and the like) (which is less likely to allow the oxygen to permeate).

For example, silicon nitride, silicon oxynitride, or the like is preferably used for the insulator 212 and the insulator 283, and aluminum oxide, hafnium oxide, or the like is preferably used for the insulator 214, the insulator 222, the insulator 272, and the insulator 282. This can prevent impurities such as water and hydrogen from diffusing from the substrate side to the transistor 200 side through the insulator 212 and the insulator 214. Alternatively, oxygen in the insulator 224 or the like can be suppressed from diffusing to the substrate side through the insulator 212 and the insulator 214. Further, diffusion of impurities such as water and hydrogen from the insulator 274 and the like disposed above the insulator 272, the insulator 282, and the insulator 283 to the transistor 200 side can be suppressed. In this manner, it is preferable to adopt a structure in which the transistor 200 is surrounded by the insulator 212, the insulator 214, the insulator 222, the insulator 272, the insulator 282, and the insulator 283, which have a function of suppressing diffusion of impurities such as water and hydrogen, and oxygen.

In addition, the resistivity of the insulator 212 and the insulator 283 is preferably low in some cases. For example, the resistivity of the insulator 212 and the insulator 283 is set to about 1 × 10¹³Ω cm, in the process of manufacturing a semiconductor device using plasma or the like, the insulator 212 and the insulator 283 may reduce charge accumulation in the conductor 205, the conductor 242, or the conductor 260. The resistivity of the insulator 212 and the insulator 283 is preferably 1 × 10¹⁰1 × 10 at least omega cm¹⁵Omega cm or less.

The dielectric constants of the insulator 216, the insulator 280, and the insulator 274 are preferably lower than the dielectric constant of the insulator 214. By using a material having a low dielectric constant for the interlayer film, parasitic capacitance generated between wirings can be reduced. For example, as the insulator 216, the insulator 280, and the insulator 274, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, silicon oxide to which fluorine is added, silicon oxide to which carbon and nitrogen are added, silicon oxide having a hole, or the like can be used as appropriate.

The insulators 222 and 224 function as gate insulators.

Here, the insulator 224 in contact with the oxide 230 is preferably heated to release oxygen. In this specification, oxygen desorbed by heating is sometimes referred to as excess oxygen. For example, silicon oxide, silicon oxynitride, or the like can be used as the insulator 224. By providing an insulator containing oxygen in contact with the oxide 230, oxygen vacancies in the oxide 230 can be reduced, and thus the reliability of the transistor 200 can be improved.

Specifically, as the insulator 224, an oxide material in which part of oxygen is desorbed by heating is preferably used. The oxide which is freed from oxygen by heating is analyzed by Thermal Desorption Spectroscopy (TDS)Spectroscopy) analysis) the amount of oxygen molecules released was 1.0X 10¹⁸molecules/cm³Above, preferably 1.0X 10¹⁹molecules/cm³The above is more preferably 2.0 × 10¹⁹molecules/cm³Above, or 3.0 × 10²⁰molecules/cm³The above oxide film. The surface temperature of the membrane when TDS analysis is performed is preferably in the range of 100 ℃ to 700 ℃ or more, or 100 ℃ to 400 ℃ or less.

The insulator 222 is preferably used as a barrier insulating film which suppresses impurities such as water and hydrogen from entering the transistor 200 from the substrate side. For example, insulator 222 preferably has a lower hydrogen permeability than insulator 224. By surrounding the insulator 224, the oxide 230, and the like with the insulator 222 and the insulator 283, impurities such as water and hydrogen can be suppressed from entering the transistor 200 from the outside.

Further, the insulator 222 preferably has a function of suppressing diffusion of oxygen (for example, at least one of oxygen atoms, oxygen molecules, and the like) (the oxygen is not easily permeated). For example, insulator 222 preferably has a lower oxygen permeability than insulator 224. It is preferable that the insulator 222 has a function of suppressing diffusion of oxygen or impurities, because diffusion of oxygen contained in the oxide 230 to the lower side of the insulator 222 can be reduced. Further, the reaction of the conductor 205 with oxygen contained in the insulator 224 and the oxide 230 can be suppressed.

As the insulator 222, an insulator containing an oxide of one or both of aluminum and hafnium is preferably used as an insulating material. As the insulator containing an oxide of one or both of aluminum and hafnium, aluminum oxide, hafnium oxide, an oxide containing aluminum and hafnium (hafnium aluminate), or the like is preferably used. When the insulator 222 is formed using such a material, the insulator 222 is used as a layer which suppresses release of oxygen from the oxide 230 or entry of impurities such as hydrogen into the oxide 230 from the peripheral portion of the transistor 200.

Alternatively, for example, alumina, bismuth oxide, germanium oxide, niobium oxide, silicon oxide, titanium oxide, tungsten oxide, yttrium oxide, or zirconium oxide may be added to the insulator. Alternatively, the insulator may be subjected to nitriding treatment. Alternatively, silicon oxide, silicon oxynitride, or silicon nitride may be stacked over the insulator.

Further, as the insulator 222, for example, a single layer or a stacked layer including aluminum oxide, hafnium oxide, tantalum oxide, zirconium oxide, lead zirconate titanate (PZT), and strontium titanate (SrTiO) may be used₃) Or (Ba, Sr) TiO₃(BST) and the like. When miniaturization and high integration of a transistor are performed, a problem of leakage current or the like may occur due to the thinning of a gate insulator. By using a high-k material as an insulator used as a gate insulator, the gate potential at the time of operation of the transistor can be reduced while maintaining the physical thickness.

The insulators 222 and 224 may have a stacked structure of two or more layers. In this case, the stacked structure is not limited to the stacked structure formed of the same material, and may be formed of different materials.

Further, an oxide 243 (an oxide 243a and an oxide 243b) may be provided between the oxide 230b and the conductor 242 (the conductor 242a and the conductor 242b) serving as the source electrode or the drain electrode. Since the conductive body 242 does not contact the oxide 230, the conductive body 242 can be inhibited from absorbing oxygen of the oxide 230. That is, by preventing the oxidation of the conductor 242, the decrease in the conductivity of the conductor 242 can be suppressed. Therefore, the oxide 243 preferably has a function of suppressing oxidation of the conductor 242.

Thus, the oxide 243 preferably has a function of suppressing oxygen permeation. When the oxide 243 having a function of suppressing oxygen permeation is disposed between the conductor 242 serving as the source electrode or the drain electrode and the oxide 230b, the resistance between the conductor 242 and the oxide 230b is preferably decreased. With such a structure, the electric characteristics of the transistor 200 and the reliability of the transistor 200 can be improved.

As the oxide 243, a metal oxide having the element M may also be used. In particular, aluminum, gallium, yttrium or tin is preferably used as the element M. The concentration of the element M in the oxide 243 is preferably higher than that of the oxide 230 b. In addition, gallium oxide can also be used as the oxide 243. Further, as the oxide 243, a metal oxide such as In-M-Zn oxide can be used. Specifically, the atomic number ratio of the element M with respect to In the metal oxide for the oxide 243 is preferably larger than the atomic number ratio of the element M with respect to In the metal oxide for the oxide 230 b. The thickness of the oxide 243 is preferably 0.5nm or more and 5nm or less, and preferably 1nm or more and 3nm or less. In addition, the oxide 243 preferably has crystallinity. When the oxide 243 has crystallinity, oxygen release from the oxide 230 can be more suppressed. For example, when the oxide 243 has a crystal structure of hexagonal crystals or the like, oxygen release from the oxide 230 may be sometimes suppressed.

In addition, the oxide 243 is not necessarily provided. In this case, the conductor 242 (the conductor 242a and the conductor 242b) may be oxidized because the conductor 242 contacts the oxide 230 and oxygen in the oxide 230 diffuses into the conductor 242. The possibility that the conductivity of the conductor 242 decreases due to oxidation becomes high. Note that the diffusion of oxygen in the oxide 230 to the conductor 242 may be referred to as the absorption of oxygen in the oxide 230 by the conductor 242.

Further, when oxygen in the oxide 230 diffuses into the conductor 242 (the conductor 242a and the conductor 242b), another layer may be formed between the conductor 242a and the oxide 230b and between the conductor 242b and the oxide 230 b. Since the other layer contains more oxygen than the conductor 242, the other layer is assumed to have insulating properties. In this case, the three-layer structure of the conductor 242, the other layer, and the oxide 230b may be a three-layer structure composed of a Metal-Insulator-Semiconductor, and may be referred to as a MIS (Metal-Insulator-Semiconductor) structure or a diode structure mainly including a MIS structure.

Note that the above-described another layer is not limited to being formed between the conductor 242 and the oxide 230b, and for example, another layer may be formed between the conductor 242 and the oxide 230c or between the conductor 242 and the oxide 230b and between the conductor 242 and the oxide 230 c.

Conductors 242 (conductors 242a and 242b) serving as source and drain electrodes are provided over the oxide 243. The thickness of the conductor 242 may be, for example, 1nm to 50nm, and preferably 2nm to 25 nm.

As the conductor 242, a metal element selected from aluminum, chromium, copper, silver, gold, platinum, tantalum, nickel, titanium, molybdenum, tungsten, hafnium, vanadium, niobium, manganese, magnesium, zirconium, beryllium, indium, ruthenium, iridium, strontium, and lanthanum, an alloy containing the above metal element as a component, an alloy combining the above metal elements, or the like is preferably used. For example, tantalum nitride, titanium nitride, tungsten, a nitride containing titanium and aluminum, a nitride containing tantalum and aluminum, ruthenium oxide, ruthenium nitride, an oxide containing strontium and ruthenium, an oxide containing lanthanum and nickel, or the like is preferably used. Tantalum nitride, titanium nitride, a nitride containing titanium and aluminum, a nitride containing tantalum and aluminum, ruthenium oxide, ruthenium nitride, an oxide containing strontium and ruthenium, and an oxide containing lanthanum and nickel are preferable because they are conductive materials which are not easily oxidized or materials which absorb oxygen and maintain conductivity.

An insulator 272 is provided in contact with the top surface of the conductive body 242, and the insulator 272 preferably serves as a barrier. With this structure, the conductor 242 can be prevented from absorbing the excess oxygen contained in the insulator 280. Further, by suppressing oxidation of the conductive body 242, increase in contact resistance between the transistor 200 and the wiring can be suppressed. This can provide the transistor 200 with excellent electrical characteristics and reliability.

Therefore, the insulator 272 preferably has a function of suppressing oxygen diffusion. For example, the insulator 272 preferably has a function of suppressing diffusion of oxygen from the insulator 280. As the insulator 272, for example, an insulator containing an oxide of one or both of aluminum and hafnium is preferably formed. Further, as the insulator 272, for example, an insulator containing aluminum nitride can be used.

Note that although the insulator 272 is in contact with only the top surface of the conductor 242 in fig. 1B, 1C, and 1D, the present embodiment is not limited thereto. For example, the insulator 272 may be in contact with the top and side surfaces of the conductor 242, the side surfaces of the oxide 243, the side surfaces of the oxide 230b, and the side surfaces of the oxide 230 a.

Insulator 250 is used as a gate insulator. Insulator 250 is preferably disposed in contact with the top surface of oxide 230 c. As the insulator 250, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, silicon oxide to which fluorine is added, silicon oxide to which carbon and nitrogen are added, or silicon oxide having pores can be used. In particular, silicon oxide and silicon oxynitride are preferable because they have thermal stability.

As the insulator 224, the insulator 250 is preferably formed using an insulator which releases oxygen by heating. By providing an insulator that releases oxygen by heat addition as the insulator 250 so as to be in contact with the top surface of the oxide 230c, oxygen can be efficiently supplied to the channel formation region of the oxide 230 b. Similarly to the insulator 224, it is preferable to reduce the concentration of impurities such as water and hydrogen in the insulator 250. The thickness of the insulator 250 is preferably 1nm or more and 20nm or less.

Further, a metal oxide may be provided between the insulator 250 and the conductor 260. The metal oxide preferably inhibits oxygen diffusion from the insulator 250 to the electrical conductor 260. By providing a metal oxide that suppresses diffusion of oxygen, diffusion of oxygen from the insulator 250 to the conductor 260 can be suppressed. In other words, a decrease in the amount of oxygen supplied to the oxide 230 can be suppressed. In addition, the oxidation of the conductive body 260 due to oxygen in the insulator 250 can be suppressed.

In addition, the metal oxide is sometimes used as part of the gate insulator. Therefore, when silicon oxide, silicon oxynitride, or the like is used for the insulator 250, a metal oxide which is a high-k material having a high relative dielectric constant is preferably used as the metal oxide. By providing the gate insulator with a stacked structure of the insulator 250 and the metal oxide, a stacked structure having thermal stability and a high relative dielectric constant can be formed. Therefore, the gate potential applied at the time of the transistor operation can be reduced while maintaining the physical thickness of the gate insulator. In addition, the Equivalent Oxide Thickness (EOT) of the insulator used as the gate insulator can be reduced.

Specifically, a metal oxide containing one or two or more selected from hafnium, aluminum, gallium, yttrium, zirconium, tungsten, titanium, tantalum, nickel, germanium, magnesium, and the like can be used. In particular, aluminum oxide, hafnium oxide, an oxide containing aluminum and hafnium (hafnium aluminate), and the like are preferably used as insulators containing an oxide of one or both of aluminum and hafnium.

Alternatively, the metal oxide is sometimes used as part of the gate. In this case, it is preferable that a conductive material containing oxygen be provided on the channel formation region side. By providing a conductive material containing oxygen on the channel formation region side, oxygen desorbed from the conductive material is easily supplied to the channel formation region.

In particular, as a conductor used for a gate electrode, a conductive material containing a metal element contained in a metal oxide forming a channel and oxygen is preferably used. In addition, a conductive material containing the metal element and nitrogen may be used. In addition, indium tin oxide, indium oxide containing tungsten oxide, indium zinc oxide containing tungsten oxide, indium oxide containing titanium oxide, indium tin oxide containing titanium oxide, indium zinc oxide, indium tin oxide to which silicon is added can be used. In addition, indium gallium zinc oxide containing nitrogen may also be used. By using the above materials, hydrogen contained in the metal oxide forming the channel may be trapped. Alternatively, hydrogen mixed from an external insulator or the like may be trapped.

Although the electric conductor 260 has a two-layer structure in fig. 1, it may have a single-layer structure or a stacked-layer structure of three or more layers.

The conductor 260a is preferably a conductor having a function of suppressing hydrogen atoms, hydrogen molecules, water molecules, nitrogen atoms, nitrogen molecules, and nitrogen oxide molecules (N)₂O、NO、NO₂Etc.), copper atoms, etc. In addition, it is preferable to use a conductive material having a function of suppressing diffusion of oxygen (for example, at least one of oxygen atoms, oxygen molecules, and the like).

Further, when the conductor 260a has a function of suppressing diffusion of oxygen, it is possible to suppress a decrease in conductivity due to oxidation of the conductor 260b by oxygen contained in the insulator 250. As the conductive material having a function of suppressing oxygen diffusion, for example, tantalum nitride, ruthenium oxide, or the like is preferably used.

In addition, a conductive material containing tungsten, copper, or aluminum as a main component is preferably used for the conductor 260 b. Further, since the conductor 260 is also used as a wiring, a conductor having high conductivity is preferably used. For example, a conductive material containing tungsten, copper, or aluminum as a main component can be used. The conductor 260b may have a laminated structure, for example, a laminated structure of titanium or titanium nitride and the above-described conductive material.

As the insulator 280, for example, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon oxide to which fluorine is added, silicon oxide to which carbon and nitrogen are added, silicon oxide having a void, or the like is preferably used. By performing the above-described nitrogen plasma treatment using a silicon-based oxide as the insulator 280, the regions 241 and 245 nitrided in a solid phase can be formed. In particular, silicon oxide and silicon oxynitride are preferable because they have thermal stability. In particular, silicon oxide, silicon oxynitride, silicon oxide having pores, or the like is preferable because a region having oxygen desorbed by heating can be easily formed. The insulator 280 may be formed by stacking the above materials, for example, a stacked structure in which silicon oxynitride formed by a CVD method is stacked over silicon oxide formed by a sputtering method. Further, silicon nitride may be further stacked on the stack layer.

The concentration of impurities such as water or hydrogen in the insulator 280 is preferably reduced. In addition, the top surface of the insulator 280 may also be planarized.

Note that although the region 245 is formed in the vicinity of the interface between the insulator 280 and the insulator 283 in fig. 1B, 1C, and 1D, the present embodiment is not limited to this. For example, when the insulator 283 is formed, the region 245 may not be formed in the insulator 280, for example, when the atmosphere containing excess hydrogen is not present. The same applies to the insulators 224 and 216, and the region 245 may not be formed. In this case, it is preferable to form an insulating film having a high hydrogen barrier property similar to the insulator 272 so as to cover the insulator 216, the insulator 222, the insulator 224, the insulator 280, and the insulator 282, instead of forming the region 245. As such an insulating film having a high hydrogen barrier property, for example, a silicon nitride film or a silicon oxynitride film may be used. When a silicon nitride film is used, the silicon nitride film may be formed by a PEALD method, a PECVD method, or the like using a gas in which hydrogen atoms are reduced or removed. When the PEALD method is employed, nitrogen radicals obtained by converting nitrogen gas into plasma may be used as the reactant.

The insulator 282 and the insulator 283 preferably have a function of suppressing impurities such as water and hydrogen from being mixed into the barrier insulating film of the insulator 280 from above. The insulator 282 and the insulator 283 preferably function as a barrier insulating film that suppresses oxygen permeation. As the insulator 282 and the insulator 283, for example, an insulator such as aluminum oxide, silicon nitride, or silicon oxynitride can be used. For example, alumina having a high barrier property against oxygen may be used for the insulator 282, and silicon nitride or silicon oxynitride having a high barrier property against hydrogen may be used for the insulator 283.

Further, an insulator 274 serving as an interlayer film is preferably provided over the insulator 283. The insulator 274 and the insulator 224 preferably have a reduced concentration of impurities such as water and hydrogen in the film.

The conductors 240a and 240b are preferably made of a conductive material containing tungsten, copper, or aluminum as a main component. The conductors 240a and 240b may have a laminated structure. In fig. 1A, the conductors 240a and 240b are circular in plan view, but the present invention is not limited thereto. For example, the conductors 240a and 240b may have a substantially circular shape such as an ellipse, a polygonal shape such as a quadrangle, or an arc shape at the corner of a polygonal shape such as a quadrangle in a plan view.

When the conductor 240 has a stacked-layer structure, a conductive material having a function of suppressing permeation of impurities such as water and hydrogen and oxygen is preferably used as a conductor in contact with the region 241. For example, tantalum nitride, titanium nitride, ruthenium oxide, or the like is preferably used. Further, a conductive material having a function of suppressing permeation of impurities such as water and hydrogen and oxygen may be used in a single layer or a stacked layer. By using such a conductive material, it is possible to further reduce the mixing of impurities such as water and hydrogen diffused from the insulator 280 and the like into the oxide 230 through the conductors 240a and 240 b. Further, oxygen added to the insulator 280 can be prevented from being absorbed into the conductor 240a and the conductor 240 b. Further, since the region 241 has a high barrier property against oxygen, the absorption of oxygen into the conductor 240a and the conductor 240b can be further reduced.

The conductor 246 (the conductor 246a and the conductor 246b) used as a wiring may be disposed so as to be in contact with the top surface of the conductor 240a and the top surface of the conductor 240 b. The conductive body 246 is preferably made of a conductive material containing tungsten, copper, or aluminum as a main component. The conductor may have a laminated structure, for example, a laminated structure of titanium or titanium nitride and the conductive material. The conductor may be formed to be embedded in an opening provided in the insulator.

< materials for Forming semiconductor devices >

Hereinafter, constituent materials that can be used for the semiconductor device will be described.

< substrate >

As a substrate for forming the transistor 200, an insulator substrate, a semiconductor substrate, or a conductor substrate can be used, for example. Examples of the insulator substrate include a glass substrate, a quartz substrate, a sapphire substrate, a stabilized zirconia substrate (e.g., a yttria-stabilized zirconia substrate), and a resin substrate. Examples of the semiconductor substrate include a semiconductor substrate made of silicon, germanium, or the like, and a compound semiconductor substrate made of silicon carbide, silicon germanium, gallium arsenide, indium phosphide, zinc oxide, gallium oxide, or the like. Further, a semiconductor substrate having an Insulator region in the semiconductor substrate may be mentioned, and examples thereof include an SOI (Silicon On Insulator) substrate and the like. Examples of the conductive substrate include a graphite substrate, a metal substrate, an alloy substrate, and a conductive resin substrate. Alternatively, a substrate including a metal nitride, a substrate including a metal oxide, or the like can be given. Further, an insulating substrate provided with a conductor or a semiconductor, a semiconductor substrate provided with a conductor or an insulator, a conductor substrate provided with a semiconductor or an insulator, and the like can be given. Alternatively, a substrate provided with an element over such a substrate may be used. Examples of the element provided over the substrate include a capacitor, a resistor, a switching element, a light-emitting element, a memory element, and the like.

< insulators >

Examples of the insulator include insulating oxides, nitrides, oxynitrides, metal oxides, metal oxynitrides, and metal oxynitrides.

For example, when miniaturization and high integration of a transistor are performed, a problem of leakage current or the like may occur due to the thinning of a gate insulator. By using a high-k material as an insulator used as a gate insulator, a low voltage can be achieved during operation of the transistor while maintaining a physical thickness. On the other hand, by using a material having a low relative permittivity for the insulator used as the interlayer film, parasitic capacitance generated between wirings can be reduced. Therefore, it is preferable to select the material according to the function of the insulator.

Examples of the insulator having a high relative dielectric constant include gallium oxide, hafnium oxide, zirconium oxide, an oxide containing aluminum and hafnium, an oxynitride containing aluminum and hafnium, an oxide containing silicon and hafnium, an oxynitride containing silicon and hafnium, or a nitride containing silicon and hafnium.

Examples of the insulator having a low relative permittivity include silicon oxide, silicon oxynitride, silicon nitride oxide, silicon oxide to which fluorine is added, silicon oxide to which carbon and nitrogen are added, silicon oxide having pores, resin, or the like.

Further, by surrounding a transistor using an oxide semiconductor with an insulator having a function of suppressing permeation of impurities such as hydrogen and oxygen, electric characteristics of the transistor can be stabilized. As the insulator having a function of suppressing permeation of impurities such as hydrogen and oxygen, for example, an insulator containing boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum may be used in a single layer or a stacked layer. Specifically, as the insulator having a function of suppressing permeation of impurities such as hydrogen and oxygen, a metal oxide such as aluminum oxide, magnesium oxide, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide, or a metal nitride such as aluminum nitride, aluminum titanium nitride, silicon oxynitride, or silicon nitride can be used.

Further, the insulator used as the gate insulator is preferably an insulator having a region containing oxygen desorbed by heating. For example, by using a structure in which silicon oxide or silicon oxynitride having a region containing oxygen which is desorbed by heating is in contact with the oxide 230, oxygen vacancies contained in the oxide 230 can be filled.

< electric conductor >

As the conductor, a metal element selected from aluminum, chromium, copper, silver, gold, platinum, tantalum, nickel, titanium, molybdenum, tungsten, hafnium, vanadium, niobium, manganese, magnesium, zirconium, beryllium, indium, ruthenium, iridium, strontium, lanthanum, or the like, an alloy containing the above metal element as a component, an alloy combining the above metal elements, or the like is preferably used. For example, tantalum nitride, titanium nitride, tungsten, a nitride containing titanium and aluminum, a nitride containing tantalum and aluminum, ruthenium oxide, ruthenium nitride, an oxide containing strontium and ruthenium, an oxide containing lanthanum and nickel, or the like is preferably used. Further, tantalum nitride, titanium nitride, a nitride containing titanium and aluminum, a nitride containing tantalum and aluminum, ruthenium oxide, ruthenium nitride, an oxide containing strontium and ruthenium, and an oxide containing lanthanum and nickel are conductive materials which are not easily oxidized or materials which absorb oxygen and maintain conductivity, and thus are preferable. Further, a semiconductor having high conductivity typified by polycrystalline silicon containing an impurity element such as phosphorus, or a silicide such as nickel silicide can be used.

Further, a plurality of conductive layers formed of the above materials may be stacked. For example, a stacked-layer structure in which a material containing the above-described metal element and a conductive material containing oxygen are combined may also be employed. Further, a stacked-layer structure in which a material containing the above-described metal element and a conductive material containing nitrogen are combined may also be employed. Further, a stacked-layer structure in which a material containing the above-described metal element, a conductive material containing oxygen, and a conductive material containing nitrogen are combined may also be employed.

In addition, in the case where an oxide is used for a channel formation region of a transistor, a stacked-layer structure in which a material containing the above-described metal element and a conductive material containing oxygen are combined is preferably used as a conductor used for a gate. In this case, it is preferable that a conductive material containing oxygen be provided on the channel formation region side. By providing a conductive material containing oxygen on the channel formation region side, oxygen desorbed from the conductive material is easily supplied to the channel formation region.

In particular, as a conductor used for a gate electrode, a conductive material containing a metal element contained in a metal oxide forming a channel and oxygen is preferably used. In addition, a conductive material containing the metal element and nitrogen may be used. For example, a conductive material containing nitrogen such as titanium nitride or tantalum nitride may be used. In addition, indium tin oxide, indium oxide containing tungsten oxide, indium zinc oxide containing tungsten oxide, indium oxide containing titanium oxide, indium tin oxide containing titanium oxide, indium zinc oxide, indium tin oxide to which silicon is added can be used. In addition, indium gallium zinc oxide containing nitrogen may also be used. By using the above materials, hydrogen contained in the metal oxide forming the channel may be trapped. Alternatively, hydrogen entering from an insulator or the like on the outside may be trapped.

Metal oxide

As the oxide 230, a metal oxide used as an oxide semiconductor is preferably used. Hereinafter, a metal oxide that can be used for the oxide 230 according to the present invention will be explained.

The metal oxide preferably contains at least indium or zinc. Particularly preferably indium and zinc. In addition, aluminum, gallium, yttrium, tin, or the like is preferably contained. Alternatively, one or more of boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, magnesium, or the like may be contained.

Here, a case where the metal oxide is an In-M-Zn oxide containing indium, an element M, and zinc is considered. Note that the element M is aluminum, gallium, yttrium, tin, or the like. As other elements which can be used as the element M, there are boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, magnesium and the like. Note that as the element M, a plurality of the above elements may be combined.

Note that in this specification and the like, a metal oxide containing nitrogen is also sometimes referred to as a metal oxide (metal oxide). In addition, a metal oxide containing nitrogen may also be referred to as a metal oxynitride (metal oxynitride).

[ Structure of Metal oxide ]

Oxide semiconductors (metal oxides) are classified into single crystal oxide semiconductors and non-single crystal oxide semiconductors. Examples of the non-single crystal oxide semiconductor include CAAC-OS, polycrystalline oxide semiconductor, nc-OS (nanocrystalline oxide semiconductor), a-like OS (amorphous oxide semiconductor), and amorphous oxide semiconductor.

CAAC-OS has c-axis orientation, and a plurality of nanocrystals are connected in the a-b plane direction, and the crystal structure is distorted. The distortion is a portion in which the direction of lattice alignment changes between a region in which lattice alignments coincide and a region in which other lattice alignments coincide among regions in which a plurality of nanocrystals are connected.

The nanocrystals are substantially hexagonal in shape, but are not limited to regular hexagonal shapes, and sometimes non-regular hexagonal shapes. In addition, the nanocrystals may have a lattice arrangement such as a pentagonal or heptagonal shape in distortion. In the CAAC-OS, it is difficult to observe a clear grain boundary (also referred to as grain boundary) even in the vicinity of the distortion. That is, it is found that the formation of grain boundaries can be suppressed due to the distortion of the lattice arrangement. This is because CAAC-OS can contain distortion due to low density of oxygen atom arrangement in the a-b plane direction, or due to change in bonding distance between atoms caused by substitution of metal elements.

CAAC-OS tends to have a layered crystal structure (also referred to as a layered structure) In which a layer containing indium and oxygen (hereinafter referred to as an In layer) and a layer containing the elements M, zinc, and oxygen (hereinafter referred to as an (M, Zn) layer) are stacked. In addition, indium and the element M may be substituted for each other, and In the case where the element M In the (M, Zn) layer is substituted with indium, the layer may be represented as an (In, M, Zn) layer. In addition, In the case where indium In the In layer is replaced with the element M, the layer may be represented as an (In, M) layer.

CAAC-OS is a metal oxide with high crystallinity. On the other hand, in CAAC-OS, it is not easy to observe a clear grain boundary, and therefore, a decrease in electron mobility due to the grain boundary does not easily occur. Further, the crystallinity of the metal oxide may be lowered by the entry of impurities, the formation of defects, or the like, and therefore, CAAC-OS may be said to be impurities orDefect (oxygen vacancy (also referred to as V)_O(oxygen vaccy)), etc.). Therefore, the metal oxide including CAAC-OS is stable in physical properties. Therefore, the metal oxide having the CAAC-OS has heat resistance and high reliability.

In nc-OS, the atomic arrangement in a minute region (for example, a region of 1nm to 10nm, particularly 1nm to 3 nm) has periodicity. In addition, no regularity in crystallographic orientation was observed between different nanocrystals for nc-OS. Therefore, orientation was not observed in the entire film. Therefore, sometimes nc-OS does not differ from a-like OS or amorphous oxide semiconductor in some analytical methods.

In addition, indium-gallium-zinc oxide (hereinafter, IGZO), which is one of metal oxides including indium, gallium, and zinc, may have a stable structure when composed of the above-described nanocrystal. In particular, IGZO tends to be less likely to undergo crystal growth in the atmosphere, and therefore, it is sometimes structurally stable when IGZO is formed of small crystals (for example, the nanocrystals described above) as compared with when IGZO is formed of large crystals (here, crystals of several mm or crystals of several cm).

The a-like OS is a metal oxide having a structure between nc-OS and an amorphous oxide semiconductor. The a-like OS contains holes or low density regions. That is, the crystallinity of a-like OS is lower than that of nc-OS and CAAC-OS.

Oxide semiconductors (metal oxides) have various structures and various characteristics. The oxide semiconductor according to one embodiment of the present invention may include two or more of an amorphous oxide semiconductor, a polycrystalline oxide semiconductor, an a-like OS, nc-OS, and CAAC-OS.

Note that in the semiconductor device according to one embodiment of the present invention, the structure of the oxide semiconductor (metal oxide) is not particularly limited, and the oxide semiconductor preferably has crystallinity. For example, the oxide 230 may have a CAAC-OS structure and the oxide 243 may have a hexagonal crystal structure. By forming the oxide 230 and the oxide 243 to have the above crystal structures, a semiconductor device with high reliability can be provided. In addition, the oxide 230a, the oxide 230c, and the oxide 243 can have substantially the same composition.

[ impurities ]

Here, the influence of each impurity in the metal oxide will be described.

In addition, when the metal oxide contains an alkali metal or an alkaline earth metal, a defect level may be formed to form a carrier. Therefore, a transistor using a metal oxide containing an alkali metal or an alkaline earth metal as a channel formation region easily has a normally-on characteristic. Thus, the concentration of the alkali metal or alkaline earth metal in the metal oxide is preferably reduced. Specifically, the concentration of alkali metal or alkaline earth metal in the metal oxide (concentration measured by SIMS) is set to 1X 10 ¹⁸atoms/cm³Hereinafter, 2 × 10 is preferable¹⁶atoms/cm³The following.

Hydrogen contained in the metal oxide reacts with oxygen bonded to the metal atom to generate water, and thus oxygen defects are sometimes formed. When hydrogen enters the oxygen defect, electrons are sometimes generated as carriers. In addition, a part of hydrogen is bonded to oxygen bonded to a metal atom, and electrons as carriers are generated in some cases. Therefore, a transistor using a metal oxide containing hydrogen easily has a normally-on characteristic. Thus, it is preferable to reduce hydrogen in the metal oxide as much as possible.

As a metal oxide used for a semiconductor of a transistor, a thin film with high crystallinity is preferably used. The stability or reliability of the transistor can be improved by using the thin film. Examples of the thin film include a single crystal metal oxide thin film and a polycrystalline metal oxide thin film. However, forming a single crystal metal oxide thin film or a polycrystalline metal oxide thin film on a substrate requires a step of heating at high temperature or with a laser. Therefore, the cost of the manufacturing process becomes high and the throughput is reduced.

< method for manufacturing semiconductor device >

Next, a method for manufacturing the semiconductor device including the transistor 200 according to the present invention shown in fig. 1 is described with reference to fig. 2 to 14. In fig. 2 to 14, a in each drawing shows a top view. In addition, B in each drawing shows a sectional view along a portion of the chain line a1-a2 in a, which corresponds to a sectional view in the channel length direction of the transistor 200. C in each drawing shows a sectional view along a portion of the chain line A3-a4 in a, which corresponds to a sectional view in the channel width direction of the transistor 200. D in each figure shows a cross-sectional view along the portion of dotted line A5-A6 in A. For the sake of clarity, some constituent elements are omitted in the top view of a in each drawing.

First, a substrate (not shown) is prepared, and the insulator 212 is formed over the substrate. The insulator 212 can be formed by a sputtering method, a Chemical Vapor Deposition (CVD) method, a Molecular Beam Epitaxy (MBE) method, a Pulsed Laser Deposition (PLD) method, an ald (atomic Layer Deposition) method, or the like.

Note that the CVD method can be classified into a Plasma CVD (PECVD: Plasma Enhanced CVD) method using Plasma, a Thermal CVD (TCVD: Thermal CVD) method using heat, a photo CVD (photo CVD) method using light, and the like. The CVD method can be classified into a Metal CVD (MCVD) method and a Metal Organic CVD (MOCVD) method according to the source gas used. The CVD method can be classified into an Atmospheric Pressure CVD (APCVD) method in which film formation is performed under Atmospheric Pressure and a Low Pressure CVD (LPCVD) method in which film formation is performed under a reduced Pressure state lower than Atmospheric Pressure, depending on the Pressure at the time of film formation.

By using the plasma CVD method, a high-quality film can be obtained at a relatively low temperature. In addition, the thermal CVD method is a film formation method capable of reducing plasma damage to the object to be processed, because plasma is not used. For example, wirings, electrodes, elements (transistors, capacitors, and the like) and the like included in a semiconductor device may receive charges from plasma, and charge up may occur. At this time, wirings, electrodes, elements, and the like included in the semiconductor device may be damaged by the accumulated charges. On the other hand, in the case of the thermal CVD method not using plasma, the plasma damage described above is not generated, so that the yield of the semiconductor device can be improved. In addition, in the thermal CVD method, plasma damage does not occur during film formation, and therefore a film with few defects can be obtained.

As the ALD method, a thermal ALD (thermal ALD) method in which a precursor and a reactant are reacted only by thermal energy, a peald (plasma Enhanced ALD) method in which a reactant excited by plasma is used, or the like is used.

The ALD method can deposit atoms of each layer by utilizing self-controllability, which is a property of atoms, and has effects of enabling formation of an extremely thin film, formation of a film with a high aspect ratio, formation of a film with few defects such as pinholes, formation of a film with excellent coverage, formation of a film at a low temperature, and the like. In the PEALD method, film formation can be performed at a lower temperature by using plasma, and thus, such a method is preferable in some cases. Note that the precursor used in the ALD method may contain impurities such as carbon. Therefore, a film formed by the ALD method may contain impurities such as carbon more than a film formed by another film forming method. In addition, the quantification of impurities can be carried out by X-ray Photoelectron Spectroscopy (XPS: X-ray photon Spectroscopy).

The CVD method and the ALD method are film forming methods for forming a film by a reaction on the surface of a target, unlike a film forming method for depositing particles released from a target or the like. Therefore, the film formed by the CVD method and the ALD method is less susceptible to the shape of the object to be processed and has good step coverage. In particular, since a film formed by the ALD method has excellent step coverage and thickness uniformity, the ALD method is suitably used in a case where the surface of an opening portion having a high aspect ratio is to be covered. Note that the ALD method is relatively slow in film formation rate, and therefore may be preferably used in combination with another film formation method having a high film formation rate such as a CVD method.

The CVD method and the ALD method can control the composition of the obtained film by adjusting the flow ratio of the source gas. For example, when the CVD method or the ALD method is used, a film having an arbitrary composition can be formed by adjusting the flow ratio of the source gases. In addition, for example, when the CVD method and the ALD method are used, a film whose composition changes continuously can be formed by performing film formation while changing the flow ratio of the source gases. When film formation is performed while changing the flow ratio of the source gases, since the time required for transferring and adjusting the pressure is not required, the film formation time can be shortened as compared with the case of performing film formation using a plurality of film formation chambers. Therefore, the productivity of the semiconductor device may be improved.

In this embodiment, silicon nitride is formed as the insulator 212 by a CVD method. By using an insulator such as silicon nitride which does not easily allow copper to penetrate therethrough as the insulator 212 in this manner, even if a metal such as copper which easily diffuses is used as a conductor of a layer (not shown) below the insulator 212, diffusion of the metal through the insulator 212 to an upper layer can be suppressed. Further, by using an insulator through which water, hydrogen, or other impurities such as silicon nitride do not easily penetrate, diffusion of water, hydrogen, or other impurities from a lower layer of the insulator 212 can be prevented.

Next, an insulator 214 is formed on the insulator 212. The insulator 214 can be formed by sputtering, CVD, MBE, PLD, ALD, or the like. In this embodiment, alumina is used as the insulator 214.

Next, an insulator 216 is formed on the insulator 214. The insulator 216 can be formed by sputtering, CVD, MBE, PLD, ALD, or the like. In this embodiment mode, silicon oxide or silicon oxynitride is used as the insulator 216. The insulator 216 is preferably formed by the above-described film formation method using a gas in which hydrogen atoms are reduced or removed. Thereby, the hydrogen concentration of the insulator 216 can be reduced.

Next, an opening reaching the insulator 214 is formed in the insulator 216. The openings comprise, for example, slots or slits or the like. The region where the opening is formed may be referred to as an opening. In forming the opening, a wet etching method may be used, but a dry etching method is more preferable for micro-fabrication. As the insulator 214, an insulator which functions as an etching stopper film when the insulator 216 is etched to form a groove is preferably selected. For example, when a silicon oxide film or a silicon oxynitride film is used as the insulator 216 for forming the groove, a silicon nitride film, an aluminum oxide film, or a hafnium oxide film is preferably used as the insulator 214.

After the opening is formed, a conductive film to be the conductor 205a is formed. The conductive film preferably contains an electric conductor having a function of inhibiting oxygen transmission. For example, tantalum nitride, tungsten nitride, titanium nitride, or the like can be used. Alternatively, a stacked film of the conductor and tantalum, tungsten, titanium, molybdenum, aluminum, copper, or a molybdenum-tungsten alloy may be used. The conductive film to be the conductor 205a can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

In this embodiment, a conductive film serving as the conductor 205a has a multilayer structure. First, tantalum nitride is deposited by sputtering, and titanium nitride is stacked on the tantalum nitride. By using such a metal nitride as the lower layer of the conductor 205b, even when a metal such as copper which is easily diffused is used as a conductive film which is to be the conductor 205b described later, the diffusion of the metal from the conductor 205a to the outside can be suppressed.

Next, a conductive film to be the conductor 205b is formed. The conductive film can be formed by a plating method, a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. In this embodiment, a low-resistance conductive material such as copper is formed as a conductive film to be the conductor 205 b.

Next, a CMP process (Chemical Mechanical Polishing) is performed to remove a part of the conductive film to be the conductor 205a and a part of the conductive film to be the conductor 205b, thereby exposing the insulator 216. As a result, the conductor 205a and the conductor 205b remain only in the opening. Thereby, the conductor 205 having a flat top surface can be formed. Note that a part of the insulator 216 may be removed by the CMP process (see fig. 2).

In addition, although the conductor 205 is formed to be embedded in the opening of the insulator 216 in the above description, the present embodiment is not limited thereto. For example, the conductor 205 may be formed on the insulator 214, the insulator 216 may be formed on the conductor 205, and a part of the insulator 216 may be removed by CMP processing of the insulator 216 to expose the surface of the conductor 205.

Next, an insulator 222 is formed over the insulator 216 and the conductor 205. The insulator 222 is preferably formed of an oxide containing one or both of aluminum and hafnium. As the insulator containing an oxide of one or both of aluminum and hafnium, aluminum oxide, hafnium oxide, an oxide containing aluminum and hafnium (hafnium aluminate), or the like is preferably used. An insulator containing an oxide of one or both of aluminum and hafnium has a barrier property against oxygen, hydrogen, and water. When the insulator 222 has a barrier property against hydrogen and water, hydrogen and water contained in a structural body provided around the transistor 200 can be suppressed from diffusing through the insulator 222 to the inside of the transistor 200, and generation of oxygen vacancies in the oxide 230 can be suppressed.

The insulator 222 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, an insulator 224 is formed on the insulator 222. The insulator 224 can be formed by sputtering, CVD, MBE, PLD, ALD, or the like. In this embodiment mode, silicon oxide or silicon oxynitride is used as the insulator 224. The insulator 224 is preferably formed by the above-described film formation method using a gas in which hydrogen atoms are reduced or removed. This can reduce the hydrogen concentration in the insulator 224. Since the insulator 224 is in contact with the oxide 230a in a later step, the hydrogen concentration is preferably reduced as described above.

Next, heat treatment is preferably performed. The heat treatment may be performed at 250 ℃ to 650 ℃, preferably at 300 ℃ to 500 ℃, and more preferably at 320 ℃ to 450 ℃. The heat treatment is performed in a nitrogen or inert gas atmosphere or an atmosphere containing 10ppm or more, 1% or more, or 10% or more of an oxidizing gas. The heat treatment may be performed under reduced pressure. Alternatively, the heat treatment may be performed in an atmosphere of nitrogen or an inert gas, and then performed in an atmosphere containing 10ppm or more, 1% or more, or 10% or more of an oxidizing gas in order to compensate for the released oxygen.

In this embodiment, the treatment is performed at a temperature of 400 ℃ for 1 hour in a nitrogen atmosphere, and then the treatment is continuously performed at a temperature of 400 ℃ for 1 hour in an oxygen atmosphere. By performing this heating treatment, impurities such as water and hydrogen contained in the insulator 224 can be removed.

Further, the insulator 222 may be formed and then subjected to heat treatment. The heat treatment may be performed under the conditions of the heat treatment described above.

Here, in order to form an excess oxygen region in the insulator 224, plasma treatment containing oxygen may be performed in a reduced pressure state. The plasma treatment containing oxygen preferably employs, for example, an apparatus including a power supply for generating a high-density plasma using microwaves. Alternatively, a power supply for applying a high frequency such as RF to the substrate side may be included. High-density oxygen radicals can be generated by using high-density plasma, and oxygen radicals generated by high-density plasma can be efficiently introduced into the insulator 224 by applying RF to the substrate side. Alternatively, after the plasma treatment using the apparatus, the plasma treatment including the inert gas may be performed, and then the plasma treatment including the oxygen may be performed to fill the desorbed oxygen. Further, by appropriately selecting the conditions of the plasma treatment, impurities such as water and hydrogen contained in the insulator 224 can be removed. In this case, the heat treatment may not be performed.

Here, for example, alumina may be formed on the insulator 224 by a sputtering method, and CMP may be performed on the alumina until the alumina reaches the insulator 224. By performing this CMP, the surface of the insulator 224 can be planarized and the surface of the insulator 224 can be smoothed. By performing CMP by disposing this alumina on the insulator 224, the end point of CMP can be easily detected. In addition, although a part of the insulator 224 may be polished by CMP to reduce the thickness of the insulator 224, the thickness may be adjusted at the time of forming the insulator 224. By flattening and smoothing the surface of the insulator 224, it is possible to prevent a decrease in the coverage of the oxide to be deposited below and a decrease in the yield of the semiconductor device. Further, aluminum oxide is preferably formed on the insulator 224 by a sputtering method, since oxygen can be added to the insulator 224.

Next, oxide film 230A and oxide film 230B are sequentially formed on insulator 224 (see fig. 2). The oxide film is preferably formed continuously without exposure to the atmospheric environment. By forming the oxide film so as not to be exposed to the atmosphere, it is possible to prevent impurities or moisture from the atmospheric environment from adhering to the oxide films 230A and 230B, and therefore, the vicinity of the interface between the oxide film 230A and the oxide film 230B can be kept clean.

The oxide film 230A and the oxide film 230B can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

For example, in the case of forming the oxide film 230A and the oxide film 230B by a sputtering method, oxygen or a mixed gas of oxygen and a rare gas is used as a sputtering gas. By increasing the ratio of oxygen contained in the sputtering gas, the excess oxygen in the formed oxide film can be increased. In addition, when the oxide film is formed by a sputtering method, for example, the In-M-Zn oxide target can be used.

In particular, when the oxide film 230A is formed, a part of oxygen included in the sputtering gas may be supplied to the insulator 224. Therefore, the oxygen content in the sputtering gas for the oxide film 230A may be 70% or more, preferably 80% or more, and more preferably 100%.

In the case where the oxide film 230B is formed by a sputtering method, when the film is formed in a state where the ratio of oxygen contained in the sputtering gas is set to 1% or more and 30% or less, preferably 5% or more and 20% or less, an oxygen-deficient oxide semiconductor is formed. A transistor using an oxygen-deficient oxide semiconductor for a channel formation region can have high field-effect mobility. Further, by forming the film while heating the substrate, the crystallinity of the oxide film can be improved. Note that one embodiment of the present invention is not limited to this. When the oxide film 230B is formed by the sputtering method, the oxide film 230B is formed so that the ratio of oxygen contained in the sputtering gas is set to be more than 30% and 100% or less, preferably 70% or more and 100% or less, whereby an oxygen-excess oxide semiconductor is formed. A transistor using an oxygen-excess type oxide semiconductor for a channel formation region has high reliability.

In this embodiment, In: ga: 1, Zn: 1: 0.5[ atomic number ratio ] (2: 2: 1[ atomic number ratio ]) or 1: 3: the target of 4[ atomic number ratio ] forms the oxide film 230A. In addition, In: ga: zn is 4: 2: 4.1[ atomic number ratio ] or 1: 1: the oxide film 230B is formed with a target of 1[ atomic number ratio ]. The oxide film can be formed by appropriately selecting film formation conditions and the atomic number ratio in accordance with the characteristics required for the oxide 230.

Subsequently, a heat treatment may be performed. As the conditions of the heat treatment, the above-mentioned heat treatment conditions can be used. By performing the heat treatment, impurities such as water and hydrogen in the oxide films 230A and 230B can be removed. In this embodiment, the treatment is performed at a temperature of 400 ℃ for 1 hour in a nitrogen atmosphere, and then the treatment is continuously performed at a temperature of 400 ℃ for 1 hour in an oxygen atmosphere.

Next, an oxide film 243A is formed on oxide film 230B (see fig. 2). The oxide film 243A can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. The atomic number ratio of Ga to In the oxide film 243A is preferably larger than the atomic number ratio of Ga to In the oxide film 230B. In this embodiment, In: ga: 1, Zn: 3: the target of 4[ atomic number ratio ] forms the oxide film 243A.

Next, a conductive film 242A is formed over the oxide film 243A (see fig. 2). The conductive film 242A can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, an insulating film 272A is formed over the conductive film 242A (see fig. 2). The insulating film 272A can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. The insulating film 272A is preferably an insulating film having a function of suppressing oxygen permeation. For example, aluminum oxide, silicon nitride, silicon oxide, or gallium oxide can be formed by a sputtering method or an ALD method.

Next, the oxide film 230A, the oxide film 230B, the oxide film 243A, the conductive film 242A, and the insulating film 272A are processed into island shapes by photolithography, whereby the oxide 230A, the oxide 230B, the oxide layer 243B, the conductor layer 242B, and the insulator layer 272B are formed (see fig. 3). Here, the oxide 230a, the oxide 230B, the oxide layer 243B, the conductor layer 242B, and the insulator layer 272B are formed so that at least a part thereof overlaps with the conductor 205. In addition, dry etching or wet etching may be used for this processing. The processing by the dry etching method is suitable for microfabrication. In this step, the insulator 224 may have a reduced thickness in a region not overlapping with the oxide 230 a.

In addition, in the photolithography method, the resist is first exposed through a mask. Next, a resist mask is formed by removing or leaving the exposed region using a developing solution. Next, an etching process is performed through the resist mask to process a conductor, a semiconductor, an insulator, or the like into a desired shape. For example, a resist mask can be formed by exposing a resist to light using a KrF excimer laser, an ArF excimer laser, an EUV (Extreme Ultraviolet) light, or the like. Further, a liquid immersion technique may be used in which exposure is performed in a state where a space between the substrate and the projection lens is filled with a liquid (e.g., water). In addition, an electron beam or an ion beam may be used instead of the light. Note that no mask is required when using an electron beam or an ion beam. In addition, when removing the resist mask, dry etching treatment such as ashing treatment or wet etching treatment may be performed, or wet etching treatment may be performed after dry etching treatment, or dry etching treatment may be performed after wet etching treatment.

Alternatively, a hard mask made of an insulator or a conductor may be used instead of the resist mask. When a hard mask is used, an insulating film or a conductive film which is a hard mask material may be formed over the conductive film 242A, a resist mask may be formed thereover, and then the hard mask material may be etched to form a hard mask having a desired shape. The etching of the conductive film 242A and the like may be performed after the removal of the resist mask, or may be performed without removing the resist mask. In the latter case, the resist mask may disappear when etching is performed. The hard mask may be removed by etching after etching of the conductive film 242A or the like. On the other hand, in the case where the hard mask material does not affect or can be used in a post process, the hard mask does not necessarily have to be removed.

As the dry etching apparatus, a Capacitively Coupled Plasma (CCP) etching apparatus including parallel plate-shaped electrodes can be used. The capacitively coupled plasma etching apparatus including the parallel plate type electrodes may be configured to apply high-frequency power to one of the parallel plate type electrodes. Alternatively, a configuration may be adopted in which a plurality of different high-frequency powers are applied to one of the parallel flat plate electrodes. Alternatively, a configuration may be adopted in which high-frequency power having the same frequency is applied to each of the parallel flat plate electrodes. Alternatively, a configuration may be adopted in which high-frequency power having different frequencies is applied to each of the parallel flat plate electrodes. Alternatively, a dry etching apparatus having a high-density plasma source may be used. For example, as a dry etching apparatus having a high-density Plasma source, an Inductively Coupled Plasma (ICP) etching apparatus or the like can be used.

Here, the insulator layer 272B is used as a mask for the conductor layer 242B, and as shown in fig. 3C and 3D, the conductor layer 242B does not have a curved surface between the side surface and the top surface. Thus, the end portions of the conductors 242a and 242b shown in fig. 1 where the side surfaces and the top surface intersect are formed in an angular shape. When the end portion where the side surface of the conductor 242 intersects the top surface is formed in an angular shape, the cross-sectional area of the conductor 242 is increased as compared with the case where the end portion has a curved surface. This reduces the resistance of the conductor 242, thereby increasing the on-state current of the transistor 200.

The side surfaces of oxide 230a, oxide 230B, oxide layer 243B, conductor layer 242B, and insulator layer 272B are preferably substantially perpendicular to the top surface of insulator 222. When the side surfaces of the oxide 230a, the oxide 230B, the oxide layer 243B, the conductor layer 242B, and the insulator layer 272B are substantially perpendicular to the top surface of the insulator 222, a small area and high density can be achieved when a plurality of transistors 200 are provided. However, the present invention is not limited to this, and the side surfaces of oxide layer 230a, oxide layer 230B, oxide layer 243B, conductor layer 242B, and insulator layer 272B may form a small angle with the top surface of insulator 222.

Next, an insulator 280 is formed over the insulator 224, the oxide 230a, the oxide 230B, the oxide layer 243B, the conductor layer 242B, and the insulator layer 272B (see fig. 4). The insulating film to be the insulator 280 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For example, as the insulator 280, a silicon oxide film can be formed by a sputtering method, and a silicon oxide film can be formed thereon by a PEALD method or a thermal ALD method. The insulator 280 is preferably formed by the above-described film formation method using a gas in which hydrogen atoms are reduced or removed. Thereby, the hydrogen concentration of the insulator 280 can be reduced.

Next, the insulator 280 is subjected to CMP to form the insulator 280 having a flat top surface (see fig. 4). Similarly to the insulator 224, for example, alumina may be formed on the insulator 280 by sputtering, and CMP may be performed on the alumina until the alumina reaches the insulator 280.

Next, the insulator 280, the oxide 230b, and the oxide 230a may be irradiated with high frequency such as microwave or RF. The irradiated microwave or RF or the like penetrates into the insulator 280, the oxide 230b and the oxide 230a to remove hydrogen therein. In particular, in the oxide 230a and the oxide 230b, V occurs_OReaction in which H bond is cleaved, in other words, "V" occurs_OH→V_OAnd + H "to dehydrogenate it. Some of the hydrogen generated at this time may be bonded to oxygen to form H₂The morphology of O is removed from oxide 230 and insulator 280. In addition, a part of hydrogen may be gettered by the conductive material 242. In this manner, by irradiation with high frequency such as microwave or RF, the hydrogen concentration in the insulator 280, the oxide 230b, and the oxide 230a can be reduced. Note that irradiation with a high frequency such as microwave or RF may be performed before the CMP process.

Alternatively, oxygen gas may be converted into plasma using high frequency such as microwave or RF to form oxygen radicals. That is, the insulator 280, the oxide 230b, and the oxide 230a may be subjected to plasma treatment in an atmosphere containing oxygen. Hereinafter, this treatment is sometimes referred to as oxygen plasma treatment. Further, oxygen can be supplied to the insulator 280, the oxide 230b, and the oxide 230a from the formed oxygen radicals. When the insulator 280, the oxide 230b, and the oxide 230a are subjected to plasma treatment in an atmosphere containing oxygen, a structure in which high frequency such as microwave or RF is not easily irradiated to the oxide 230 may be employed.

For the oxygen plasma treatment, for example, a microwave treatment apparatus including a power source for generating high-density plasma using microwaves is preferably used. Further, the microwave processing apparatus may also include a power supply that applies RF to one side of the substrate. By using high-density plasma, high-density oxygen radicals can be generated. By applying RF to the substrate side, oxygen ions generated by high density plasma can be efficiently introduced into the insulator 280 and the oxide 230. The oxygen plasma treatment is preferably performed under reduced pressure, and the pressure is 60Pa or more, preferably 133Pa or more, more preferably 200Pa or more, and further preferably 400Pa or more. At an oxygen flow rate (O) of 50% or less₂/O₂+ Ar), preferably at an oxygen flow rate ratio of 10% to 30%. The treatment temperature may be 750 ℃ or less, preferably 500 ℃ or less, for example, about 400 ℃. After the oxygen plasma treatment, the heating treatment may be continuously performed without being exposed to the atmosphere. The heat treatment temperature may be 750 ℃ or lower, preferably 500 ℃ or lower.

Further, the nitrogen plasma treatment may be continuously performed without being exposed to the atmosphere after the oxygen plasma treatment. The oxygen plasma treatment and the nitrogen plasma treatment may be performed in the same chamber, or may be performed in different chambers of a multi-chamber processing apparatus. This makes it possible to form a solid-phase nitrided region on the surface of the insulator 280, similar to the region 241, and to reduce the possibility of hydrogen being re-mixed into the insulator 280 in which the hydrogen concentration is reduced by the oxygen plasma treatment.

Next, a part of insulator 280, a part of insulator layer 272B, and parts of conductor layer 242B and oxide layer 243B are processed to form an opening reaching oxide 230B (see fig. 5). The opening is preferably formed to overlap with the conductive body 205. By forming the openings, oxide 243a, oxide 243b, conductor 242a, conductor 242b, insulator 272a, and insulator 272b are formed.

The processing of a portion of insulator 280, a portion of insulator layer 272B, conductor layer 242B, and a portion of oxide layer 243B may be performed using a dry etching method or a wet etching method. The process using the dry etching method is suitable for microfabrication. The processing may be performed under different conditions. For example, a portion of insulator 280 may be processed by a dry etching method, a portion of insulator layer 272B may be processed by a wet etching method, and portions of oxide layer 243B and conductor layer 242B may be processed by a dry etching method.

By performing the above-described dry etching or the like, impurities caused by an etching gas or the like may be attached to or diffused in the surface or the inside of the oxide 230a, the oxide 230b, or the like. Examples of the impurities include fluorine and chlorine.

Washing is performed to remove the impurities and the like. Examples of the washing method include wet washing using a washing liquid or the like, plasma treatment using plasma, washing using heat treatment, and the like, and the above-mentioned washing methods may be combined as appropriate.

As the wet cleaning, an aqueous solution obtained by diluting oxalic acid, phosphoric acid, ammonia water, hydrofluoric acid, or the like with carbonated water or pure water may be used for the cleaning treatment. Alternatively, ultrasonic washing may be performed using pure water or carbonated water.

The heat treatment may be performed after the etching or the washing. For example, the heat treatment is performed at 100 ℃ or higher and 450 ℃ or lower, and more preferably at 350 ℃ or higher and 400 ℃ or lower. The heat treatment is performed in an atmosphere of nitrogen gas or inert gas, or an atmosphere containing 10ppm or more, 1% or more, or 10% or more of oxidizing gas. For example, the heat treatment is preferably performed under an oxygen atmosphere. Thereby, oxygen is supplied to the oxide 230a and the oxide 230b, and the oxygen vacancy V can be reduced_O. Further, the heat treatment may be performed in a reduced pressure state. Alternatively, the heat treatment may be performed in an oxygen atmosphere and then continuously in a nitrogen atmosphere without exposure to the atmosphere.

Next, an oxide film 230C is formed (see fig. 6). Alternatively, a heat treatment may be performed before the oxide film 230C is formed, and the heat treatment may be performed under reduced pressure, so that the oxide film 230C is continuously formed without being exposed to the atmosphere. Further, the heat treatment is preferably performed under an atmosphere containing oxygen. By performing such a treatment, moisture and hydrogen adhering to the surface of the oxide 230b and the like can be removed, and the moisture concentration and the hydrogen concentration in the oxide 230a and the oxide 230b can be reduced. The temperature of the heat treatment is preferably 100 ℃ or more and 400 ℃ or less, and more preferably 150 ℃ or more and 350 ℃ or less. In the present embodiment, the temperature of the heat treatment is 200 ℃ and the heat treatment is performed under reduced pressure.

Here, the oxide film 230C is preferably provided so as to be in contact with at least a part of the side surface of the oxide 230a, a part of the side surface and a part of the top surface of the oxide 230b, a part of the side surface of the oxide 243, a part of the side surface of the conductor 242, a part of the side surface of the insulator 272, and a side surface of the insulator 280. Since the conductor 242 is surrounded by the oxide 243, the insulator 272, and the oxide film 230C, a decrease in conductivity due to oxidation of the conductor 242 can be suppressed in a subsequent step.

The oxide film 230C can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. The atomic number ratio of Ga to In the oxide film 230C is preferably larger than the atomic number ratio of Ga to In the oxide film 230B. In this embodiment, as the oxide film 230C, In: ga: 1, Zn: 3: 4[ atomic number ratio ] of the target material.

Further, the oxide film 230C may be a laminate. For example, In: ga: zn is 4: 2: 4.1[ atomic number ratio ] of the target material, and then successively using In: ga: 1, Zn: 3: 4[ atomic number ratio ] of the target material.

When the oxide film 230C is formed, part of oxygen included in the sputtering gas may be supplied to the oxide 230a and the oxide 230 b. Alternatively, when the oxide film 230C is formed, a part of oxygen contained in the sputtering gas is supplied to the insulator 280. Therefore, the oxygen content in the sputtering gas for the oxide film 230C may be 70% or more, preferably 80% or more, and more preferably 100%.

Subsequently, a heat treatment may be performed. The heat treatment may also be performed under reduced pressure, and in which the insulating film 250A is continuously formed without being exposed to the atmosphere. By performing this heating treatment, moisture and hydrogen adhering to the surface of the oxide film 230C and the like can be removed, and the moisture concentration and the hydrogen concentration in the oxide 230a, the oxide 230b, and the oxide film 230C can be reduced. The temperature of the heat treatment is preferably 100 ℃ or higher and 400 ℃ or lower. In the present embodiment, the temperature of the heat treatment is 200 ℃.

Next, an insulating film 250A is formed on the oxide film 230C (see fig. 6). The insulating film 250A can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. The insulating film 250A is preferably formed by the above-described film formation method using a gas in which hydrogen atoms are reduced or removed. This can reduce the hydrogen concentration in the insulating film 250A. Since the insulating film 250A serves as the insulator 250 which is in contact with the oxide 230c in a later step, it is preferable to reduce the hydrogen concentration thereof as described above. After the insulating film 250A is formed, high-frequency irradiation such as microwave or RF, or oxygen plasma treatment may be performed after the insulator 280 is formed.

Next, conductive films 260Aa and 260Ab are formed (see fig. 7). The conductive films 260Aa and 260Ab can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For example, a CVD method is preferably used. In this embodiment, the conductive film 260Aa is formed by an ALD method, and the conductive film 260Ab is formed by a CVD method.

Next, the oxide film 230C, the insulating film 250A, the conductive film 260Aa, and the conductive film 260Ab are polished by CMP until the insulator 280 is exposed, thereby forming an oxide 230C, an insulator 250, and a conductor 260 (a conductor 260A and a conductor 260b) (see fig. 8).

Subsequently, a heat treatment may be performed. In this embodiment, the treatment is performed at a temperature of 400 ℃ for 1 hour under a nitrogen atmosphere. By this heating treatment, the moisture concentration and the hydrogen concentration in the insulator 250 and the insulator 280 can be reduced. After the heat treatment, the insulator 282 may be formed continuously without being exposed to the atmosphere.

Next, an insulator 282 is formed over the conductor 260, oxide 230c, insulator 250, and insulator 280. The insulator 282 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like (see fig. 9). As the insulator 282, for example, alumina is preferably formed by a sputtering method. By forming the insulator 282 by a sputtering method in an atmosphere containing oxygen, oxygen can be added to the insulator 280 at the same time as film formation. At this time, it is preferable to form the insulator 280 while performing substrate heating. It is preferable that the insulator 282 be formed in contact with the top surface of the conductor 260, because absorption of oxygen contained in the insulator 280 by the conductor 260 can be suppressed in the subsequent heating process.

Next, a part of the insulator 282, a part of the insulator 280, a part of the insulator 224, a part of the insulator 222, a part of the insulator 216, and a part of the insulator 214 are processed to form an opening reaching the insulator 212 (see fig. 10). The opening is sometimes formed in a manner to surround the transistor 200. Alternatively, the opening may be formed so as to surround the plurality of transistors 200. Therefore, in the opening, a part of the side surface of the insulator 282, a part of the side surface of the insulator 280, a part of the side surface of the insulator 224, a part of the side surface of the insulator 222, a part of the side surface of the insulator 216, and a part of the side surface of the insulator 214 are exposed.

A portion of insulator 282, a portion of insulator 280, a portion of insulator 224, a portion of insulator 222, a portion of insulator 216, and a portion of insulator 214 may be processed using a dry or wet etch process. The processing by the dry etching method is suitable for microfabrication. The processing may be performed under different conditions.

Next, nitrogen plasma treatment is performed, whereby a region 245 having a higher nitrogen concentration than other regions of the insulator 280, the insulator 224, and the insulator 216 is formed on the exposed side surfaces of the insulator 280, the insulator 224, and the insulator 216 (see fig. 10). In the nitrogen plasma treatment, nitrogen gas is converted into plasma by high frequency such as microwave or RF, and the nitrogen plasma is applied to the vicinity of the side surfaces of the insulator 280, the insulator 224, and the insulator 216, whereby the vicinity of the side surfaces of the insulator 280, the insulator 224, and the insulator 216 can be nitrided in a solid phase. In the nitrogen plasma treatment, it is preferable to introduce a rare gas such as argon in addition to the nitrogen gas.

Further, as the nitrogen plasma treatment, for example, a microwave treatment in which nitrogen gas is converted into plasma by a microwave is preferably performed. In the microwave treatment under a nitrogen-containing atmosphere, it is preferable to generate high-density plasma using the following microwave treatment apparatus. Further, the microwave processing apparatus may also include a power supply that applies RF to one side of the substrate. By using high-density plasma under a nitrogen-containing atmosphere, nitrogen radicals can be generated at a high density. Further, by applying RF to the substrate side, ions generated by high-density plasma can be efficiently introduced into the insulator 280, the insulator 224, and the insulator 216. The microwave treatment in the nitrogen-containing atmosphere is preferably performed under reduced pressure, and the pressure may be 400Pa or less, preferably 200Pa or less, more preferably 60Pa or less, and still more preferably 12Pa or less. At a nitrogen flow rate ratio (N) of 50% or less ₂/(N₂+ Ar)), preferably at a nitrogen flow rate ratio of 10% to 30%. The treatment temperature may be, for example, about 400 ℃.

At this time, the insulator 280 or the like may be irradiated with a high frequency such as microwave or RF. The irradiated microwave, RF, or the like penetrates the insulator 280, the oxide 230b, the oxide 230a, and the like, and hydrogen therein can be removed. For example, in oxide 230a and oxide 230b, V occurs_OReaction in which H bond is cleaved, in other words, "V" occurs_OH→V_OAnd + H "to dehydrogenate it. Some of the hydrogen generated at this time may be bonded to oxygen to form H₂The morphology of O is removed from oxide 230 and insulator 280. In addition, a part of hydrogen may be gettered by the conductive material 242.

Although not shown, the side surfaces of the openings of the insulator 214, the insulator 222, and the insulator 282 may be solid-phase nitrided by the nitrogen plasma treatment of the formation region 245.

Next, an insulator 283 is formed so as to cover the insulator 282, the insulator 280, the insulator 224, the insulator 222, the insulator 216, and the insulator 214 (see fig. 11). As shown in fig. 11, the insulator 283 contacts the insulator 212 at the bottom of the opening. That is, the top and side surfaces of the transistor 200 are surrounded by the insulator 283, and the bottom surface is surrounded by the insulator 212. In this manner, the transistor 200 is surrounded by the insulator 283 and the insulator 212 having high barrier properties, whereby moisture and hydrogen can be prevented from entering from the outside.

The insulator 283 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. As described above, by forming the region 245 on the side surfaces of the insulator 280, the insulator 224, and the insulator 216 before forming the insulator 283, even when the insulator 283 is formed by a film formation method in which a large amount of hydrogen is generated in the process chamber, the hydrogen can be prevented from being mixed into the insulator 280, the insulator 224, and the insulator 216. Thus, the insulator 283 can be formed by a film formation method having good step coverage such as a PECVD method, so that the insulator 283 can be formed without forming a break or a pinhole in the step of the insulator 280 or the like.

Subsequently, a heat treatment may be performed. In this embodiment, the treatment is performed at 400 ℃ for 1 hour under a nitrogen atmosphere. By this heat treatment, oxygen added when the insulator 282 is formed can be diffused into the insulator 280, and the oxygen can be supplied to the oxide 230a and the oxide 230b via the oxide 230 c. In this manner, the oxygen vacancy in the oxide 230 (oxide 230b) can be filled with oxygen by subjecting the oxide 230 to an oxidation treatment, that is, "V" can be promoted_O+ O → null "reaction. Further, hydrogen remaining in the oxide 230 may be reacted with supplied oxygen to convert the hydrogen into H ₂The form of O is removed (dehydration). This can suppress the recombination of hydrogen remaining in the oxide 230 and oxygen vacancies to form V_OH. The heat treatment is not limited to the heat treatment performed after the insulator 283 is formed, and may be performed after the insulator 282 is formed.

Next, an insulator 274 is formed over the insulator 283 (see fig. 12). The insulator 274 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Further, the insulator 274 is preferably formed by the film formation method using the gas in which hydrogen atoms are reduced or removed. Thereby, the hydrogen concentration of the insulator 274 can be reduced.

Next, the insulator 274 is subjected to CMP processing to form the insulator 274 having a flat top surface (see fig. 12).

Next, an opening 255a reaching the conductor 242a is formed in the insulator 272a, the insulator 280, the insulator 282, the insulator 283, and the insulator 274, and an opening 255b reaching the conductor 242b is formed in the insulator 272b, the insulator 280, the insulator 282, the insulator 283, and the insulator 274 (see fig. 12). The opening may be formed using photolithography. In fig. 12A, the openings 255a and 255b are circular in plan view, but the present invention is not limited to this. For example, the openings 255a and 255b may have a substantially circular shape such as an ellipse, a polygonal shape such as a quadrangle, or a shape having a curved corner portion of a polygonal shape such as a quadrangle in plan view.

Next, nitrogen plasma treatment is performed, whereby a region 241 in which the nitrogen concentration is higher than that in the other regions of the insulator 274 and the insulator 280 is formed on the exposed top and side surfaces of the insulator 274 and the insulator 280 (see fig. 13). The region 241a is formed in the inner wall of the opening 255a of the insulator 280, the region 241b is formed in the inner wall of the opening 255b of the insulator 280, and the region 241c is formed in the top surface of the insulator 274, the inner wall of the opening 255a, and the inner wall of the opening 255 b. In the nitrogen plasma treatment, nitrogen gas is converted into plasma by microwaves, RF, or other high frequency, and the nitrogen plasma is applied to the vicinity of the exposed top surface and the vicinity of the exposed side surface of the insulator 274 and the insulator 280, whereby the vicinity of the exposed top surface and the vicinity of the exposed side surface of the insulator 274 and the insulator 280 can be nitrided in a solid phase. In the nitrogen plasma treatment, it is preferable to introduce a rare gas such as argon in addition to the nitrogen gas.

Further, as the nitrogen plasma treatment, for example, a microwave treatment in which nitrogen gas is converted into plasma by a microwave is preferably performed. In the microwave treatment under a nitrogen-containing atmosphere, it is preferable to generate high-density plasma using the following microwave treatment apparatus. Further, the microwave processing apparatus may also include a power supply that applies RF to one side of the substrate. By using high-density plasma under a nitrogen-containing atmosphere, nitrogen radicals can be generated at a high density. Ions generated by the high-density plasma are efficiently introduced into the insulator 274 and the insulator 280 by applying RF to the substrate side. In addition, microwave treatment under nitrogen-containing atmosphere Preferably, the reaction is carried out under reduced pressure, and the pressure may be 400Pa or less, preferably 200Pa or less, more preferably 60Pa or less, and further preferably 12Pa or less. At a nitrogen flow rate ratio (N) of 50% or less₂/N₂+ Ar), preferably at a nitrogen flow ratio of 10% to 30%. The treatment temperature may be, for example, about 400 ℃.

The region 241 as described above has a function of suppressing diffusion of hydrogen (for example, at least one of hydrogen atoms, hydrogen molecules, and the like). By forming such a region 241 between the conductor 240 and the insulators 274 and 280, it is possible to reduce the mixing of hydrogen contained in the insulators 274 and 280 into the conductor 240. Therefore, the amount of hydrogen diffused from the conductor 240 into the conductor 242 and the oxide 230 can be reduced. By using the oxide 230 in which impurities such as hydrogen are sufficiently reduced in the channel formation region of the transistor 200, normally-on characteristics can be realized, stable electrical characteristics can be obtained, and reliability can be improved.

In addition, the insulator 274, the insulator 280, and the like may be irradiated with high frequency such as microwave or RF during the nitrogen plasma treatment. The irradiated microwave, RF, or the like penetrates into the insulator 274, the insulator 280, the oxide 230b, the oxide 230a, and the like, and hydrogen therein can be removed.

In the nitrogen plasma treatment, the conductor 242a and the conductor 242b are exposed on the bottom surface of the opening 255a and the bottom surface of the opening 255b, respectively. Thus, a region 244a having a higher nitrogen concentration than the other region of the conductor 242a is formed near the surface of the conductor 242a, and a region 244b having a higher nitrogen concentration than the other region of the conductor 242b is formed near the surface of the conductor 242 b. Region 244 preferably has a resistivity approximately equal to the other regions of conductive body 242. Therefore, the region 244 does not significantly affect the conductivity of the conductor 242 used as a source electrode or a drain electrode. Therefore, even if the region 241 is formed by the nitrogen plasma treatment, the conductor 242 does not need to be subjected to a special post-treatment.

When an insulating film corresponding to the region 241 is formed by a CVD method or the like, the insulating film is also formed on the conductor 242, and therefore, a step of removing only the insulating film at the bottom of the opening 255a and the opening 255b is required. However, as described in this embodiment, the region 241 used as a barrier film is formed only on the side surfaces of the opening 255a and the opening 255b by the nitrogen plasma treatment, and an extra removal process is not required, so that the productivity of the semiconductor device can be improved.

Although not shown, the side surfaces of the openings of the insulator 272a, the insulator 272b, the insulator 282, and the insulator 283 other than the region 244 may be solid-phase nitrided by the nitrogen plasma treatment for forming the region 241.

Next, a conductive film to be the conductor 240a and the conductor 240b is formed. The conductive films serving as the conductors 240a and 240b are preferably a stacked structure including a conductor having a function of suppressing permeation of impurities such as water and hydrogen. For example, a stack of tantalum nitride, titanium nitride, or the like, and tungsten, molybdenum, copper, or the like may be used. The conductive film to be the conductor 240 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, CMP is performed to remove a part of the conductive film which becomes the conductor 240a and the conductor 240b, and expose the top surface of the insulator 274 (which may be referred to as a region 241 c). As a result, the conductive film remains only in the openings 255a and 255b, whereby the conductors 240a and 240b having flat top surfaces can be formed (see fig. 14). Note that a part of the top surface of the insulator 274 is sometimes removed due to this CMP process, and the region 241c formed in the vicinity of the top surface of the insulator 274 at this time is also removed.

Next, a conductive film to be the conductor 246 is formed. The conductive film to be the conductor 246 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, a conductive film to be the conductor 246 is processed by photolithography to form a conductor 246a in contact with the top surface of the conductor 240a and a conductor 246b in contact with the top surface of the conductor 240b (see fig. 1).

Through the above steps, a semiconductor device including the transistor 200 shown in fig. 1 can be manufactured. As shown in fig. 2 to 14, a transistor 200 can be manufactured by using the method for manufacturing a semiconductor device shown in this embodiment mode.

< microwave treatment apparatus >

A microwave processing apparatus that can be used in the above-described method for manufacturing a semiconductor device will be described below.

First, the structure of a manufacturing apparatus in which impurities are less mixed when manufacturing a semiconductor device or the like will be described with reference to fig. 15, 16, and 17.

Fig. 15 schematically illustrates a top view of a single-wafer multi-chamber manufacturing apparatus 2700. The manufacturing apparatus 2700 includes: an atmosphere-side substrate supply chamber 2701 including a cassette 2761 for housing a substrate and an aligner 2762 for aligning the substrate; an atmosphere-side substrate transfer chamber 2702 that transfers a substrate from the atmosphere-side substrate supply chamber 2701; a load lock chamber 2703a in which a substrate is loaded and the pressure in the chamber is switched from atmospheric pressure to reduced pressure or from reduced pressure to atmospheric pressure; an unload lock chamber 2703b for carrying out the substrate and switching the pressure in the chamber from a reduced pressure to an atmospheric pressure or from the atmospheric pressure to a reduced pressure; a transfer chamber 2704 in which transfer of the substrate is performed in vacuum; the process chamber 2706 a; the process chamber 2706 b; the process chamber 2706 c; and process chamber 2706 d.

The atmospheric substrate transfer chamber 2702 is connected to the load lock chamber 2703a and the unload lock chamber 2703b, the load lock chamber 2703a and the unload lock chamber 2703b are connected to the transfer chamber 2704, and the transfer chamber 2704 is connected to the process chamber 2706a, the process chamber 2706b, the process chamber 2706c, and the process chamber 2706 d.

Gate valves GV are provided at the connections between the chambers, whereby the chambers can be independently kept in a vacuum state except for the atmosphere-side substrate supply chamber 2701 and the atmosphere-side substrate transfer chamber 2702. A transfer robot 2763a is provided in the atmosphere-side substrate transfer chamber 2702, and a transfer robot 2763b is provided in the transfer chamber 2704. The substrate can be transferred in the manufacturing apparatus 2700 by using the transfer robot 2763a and the transfer robot 2763 b.

The back pressure (full pressure) of the transfer chamber 2704 and each processing chamber is, for example, 1X 10^-4Pa or less, preferably 3X 10^-5Pa or less, more preferably 1X 10^-5Pa or less. The partial pressure of gas molecules (atoms) having a mass-to-charge ratio (m/z) of 18 in the transfer chamber 2704 and the process chambers is, for example, 3X 10^-5Pa or less, preferably 1X 10^-5Pa or less, more preferably 3X 10^-6Pa or less. Further, the partial pressure of gas molecules (atoms) in the transfer chamber 2704 and each processing chamber, where m/z is 28, is, for example, 3X 10 ^-5Pa or less, preferably 1X 10^-5Pa or less, more preferably 3X 10^-6Pa or less. The partial pressure of gas molecules (atoms) in the transfer chamber 2704 and each processing chamber, which m/z is 44, is, for example, 3X 10^-5Pa or less, preferably 1X 10^-5Pa or less, more preferably 3X 10^-6Pa or less.

The total and partial pressures in the transfer chamber 2704 and the various processing chambers can be measured using a mass analyzer. For example, a quadrupole mass analyzer (also referred to as Q-mass) square CGM-051 manufactured by ULVAC, inc.

The transfer chamber 2704 and the processing chambers preferably have a structure with less external leakage or internal leakage. For example, the leakage rate of the transfer chamber 2704 and each processing chamber is 3 × 10^-6Pa·m³Less than s, preferably 1X 10^-6Pa·m³The ratio of the water to the water is less than s. Further, for example, the leakage rate of gas molecules (atoms) having m/z of 18 is set to 1X 10^-7Pa·m³Is preferably set to 3X 10 or less per s^{- 8}Pa·m³The ratio of the water to the water is less than s. Further, for example, the leakage rate of gas molecules (atoms) having an m/z of 28 is set to 1X 10^-5Pa·m³Is preferably set to 1X 10 or less per s^-6Pa·m³The ratio of the water to the water is less than s. Further, for example, the leakage rate of gas molecules (atoms) having an m/z of 44 is set to 3X 10^-6Pa·m³Is preferably set to 1X 10 or less per s^-6Pa·m³The ratio of the water to the water is less than s.

The leakage rate can be calculated from the total and partial pressures measured by the mass analyzer. The leakage rate depends on the external leakage and the internal leakage. The external leakage is a phenomenon in which gas flows from the outside of the vacuum system due to a minute hole, a poor seal, or the like. The internal leakage is caused by leakage from a diaphragm such as a valve in the vacuum system or by released gas from internal components. In order to set the leak rate to the above value or less, it is necessary to take measures from both the external leak and the internal leak.

For example, the transfer chamber 2704 and the opening/closing portion of each processing chamber are preferably sealed with a metal gasket. The metal gasket preferably uses a metal covered with iron fluoride, aluminum oxide, or chromium oxide. The metal gasket is more tight than the O-ring and thus reduces external leakage. By covering the passive metal with iron fluoride, aluminum oxide, chromium oxide, or the like, the off-gas containing impurities released from the metal gasket can be suppressed, whereby the internal leakage can be reduced.

As the members constituting the manufacturing apparatus 2700, aluminum, chromium, titanium, zirconium, nickel, or vanadium containing impurities and having a small amount of released gas is used. Further, the member may be covered with an alloy containing iron, chromium, nickel, or the like. Alloys containing iron, chromium, nickel, and the like are rigid, heat resistant, and suitable for processing. Here, by reducing the unevenness on the member surface by performing polishing or the like to reduce the surface area, the released gas can be reduced.

Alternatively, the members of the manufacturing apparatus 2700 may be covered with iron fluoride, aluminum oxide, chromium oxide, or the like.

The members of the manufacturing apparatus 2700 are preferably made of metal as much as possible, and when an observation window (viewing window) made of quartz or the like is provided, for example, it is preferable to cover the surface of the observation window with iron fluoride, aluminum oxide, chromium oxide, or the like having a small thickness in order to suppress outgassing.

The deposits existing in the transfer chamber 2704 and the respective processing chambers adhere to the inner wall and the like without affecting the pressure of the transfer chamber 2704 and the respective processing chambers, but the deposits cause gas release generated when the transfer chamber 2704 and the respective processing chambers are exhausted. Therefore, although the leak rate is not related to the exhaust rate, it is important to use a pump having a high exhaust capacity to remove the deposits existing in the transfer chamber 2704 and each processing chamber as much as possible and exhaust the deposits in advance. The transfer chamber 2704 and the respective processing chambers may be baked to promote the detachment of the attached matter. By baking, the speed of detaching the attached matter can be increased to about 10 times. Baking at 100-450 deg.C. At this time, by removing the deposits while introducing the inert gas into the transfer chamber 2704 and each processing chamber, the speed of separation of water or the like which is not easily separated only by the exhaust gas can be further increased. Further, the speed of detaching the deposit can be further increased by heating the introduced inert gas at a temperature approximately equal to the baking temperature. Here, as the inert gas, a rare gas is preferably used.

It is preferable that the pressure in the transfer chamber 2704 and each processing chamber is increased by introducing an inert gas such as a heated rare gas, oxygen, or the like, and the transfer chamber 2704 and each processing chamber are exhausted again after a predetermined time has elapsed. By introducing the heated gas, the deposits in the transfer chamber 2704 and the processing chambers can be removed, and thereby the impurities in the transfer chamber 2704 and the processing chambers can be reduced. It is effective to repeat the treatment 2 or more and 30 or less times, preferably 5 or more and 15 or less times. Specifically, the pressure in the transfer chamber 2704 and each processing chamber may be set to 0.1Pa to 10kPa, preferably 1Pa to 1kPa, more preferably 5Pa to 100Pa by introducing an inert gas or oxygen at 40 ℃ to 400 ℃, preferably 50 ℃ to 200 ℃, and the like, and the period of holding the pressure may be set to 1 minute to 300 minutes, preferably 5 minutes to 120 minutes. Then, the transfer chamber 2704 and each processing chamber are evacuated for 5 minutes to 300 minutes, preferably 10 minutes to 120 minutes.

Next, the processing chambers 2706b and 2706c will be described with reference to the cross-sectional schematic diagram shown in fig. 16.

The processing chambers 2706b and 2706c are processing chambers capable of performing microwave processing on an object to be processed, for example. Note that the processing chamber 2706b is different from the processing chamber 2706c only in the atmosphere when the microwave processing is performed. The other structures of the processing chambers 2706b and 2706c are the same, and therefore, the following description is also given.

The processing chambers 2706b and 2706c include slot antenna plates 2808, dielectric plates 2809, substrate holders 2812, and exhaust ports 2819. Further, a gas supply source 2801, a valve 2802, a high-frequency generator 2803, a waveguide 2804, a mode converter 2805, a gas pipe 2806, a waveguide 2807, a matching box (matching box)2815, a high-frequency power source 2816, a vacuum pump 2817, and a valve 2818 are provided outside the processing chamber 2706b and the processing chamber 2706 c.

The high-frequency generator 2803 is connected to a mode converter 2805 via a waveguide 2804. The mode converter 2805 is connected to a slot antenna plate 2808 via a waveguide 2807. The slot antenna plate 2808 is disposed in contact with the dielectric plate 2809. Further, a gas supply source 2801 is connected to a mode converter 2805 through a valve 2802. Then, gas is introduced into the processing chambers 2706b and 2706c through the gas pipe 2806 passing through the mode converter 2805, the waveguide 2807, and the dielectric plate 2809. The vacuum pump 2817 has a function of exhausting gas and the like from the processing chambers 2706b and 2706c through the valve 281 and the exhaust port 2819. A high-frequency power source 2816 is connected to the substrate holder 2812 via an adapter 2815.

The substrate holder 2812 can hold a substrate 2811. For example, the substrate holder 2812 has a function of performing electrostatic chuck or mechanical chuck on the substrate 2811. The substrate holder 2812 functions as an electrode to which power is supplied from a high-frequency power supply 2816. Further, the substrate holder 2812 includes a heating mechanism 2813 in its inside and has a function of heating the substrate 2811.

As the vacuum pump 2817, for example, a dry pump, a mechanical booster pump, an ion pump, a titanium sublimation pump, a cryopump, a turbo molecular pump, or the like can be used. Further, a cryotrap may be used in addition to vacuum pump 2827. It is particularly preferable that the cryopump and the cryopump discharge water efficiently.

As the heating means 2813, for example, a heating means for heating by a resistance heating element or the like may be used. Alternatively, a heating mechanism that heats by heat conduction or heat radiation of a medium such as heated gas may be used. For example, RTA (Rapid Thermal Annealing) such as GRTA (Gas Rapid Thermal Annealing) or LRTA (Lamp Rapid Thermal Annealing) can be used. GRTA is heat treated with high temperature gas. An inert gas is used as the gas.

Further, the gas supply source 2801 may be connected to the refiner through a mass flow controller. As the gas, a gas having a dew point of-80 ℃ or lower, preferably-100 ℃ or lower is preferably used. For example, oxygen gas, nitrogen gas, and rare gas (argon gas or the like) can be used.

As the dielectric plate 2809, for example, silicon oxide (quartz), aluminum oxide (alumina), yttrium oxide (yttria), or the like may be used. Further, another protective layer may be further formed on the surface of the dielectric plate 2809. As the protective layer, magnesium oxide, titanium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silicon oxide, aluminum oxide, yttrium oxide, or the like can be used. Since the dielectric plate 2809 is exposed to a particularly high-density region of high-density plasma 2810 described later, damage can be reduced by providing a protective layer. As a result, the increase of particles and the like during the treatment can be suppressed.

The high-frequency generator 2803 has a function of generating microwaves of, for example, 0.3GHz to 3.0GHz, 0.7GHz to 1.1GHz, or 2.2GHz to 2.8 GHz. The microwaves generated by the high-frequency generator 2803 are transmitted to the mode converter 2805 through the waveguide 2804. In the mode converter 2805, the transmitted TE mode microwaves are converted into TEM mode microwaves. Then, the microwave is transmitted to a slot antenna plate 2808 through a waveguide 2807. A plurality of slots are provided in the slot antenna plate 2808, and microwaves are transmitted through the slots and the dielectric plate 2809. Then, an electric field is generated below the dielectric plate 2809, whereby high-density plasma 2810 can be generated. The high-density plasma 2810 includes ions and radicals according to the kind of gas supplied from the gas supply source 2801. For example, the high-density plasma 2810 includes oxygen radicals, nitrogen radicals, or the like.

At this time, the quality of a film or the like over the substrate 2811 can be improved by using ions and radicals generated in the high-density plasma 2810. Further, it is sometimes preferable to apply a bias voltage to the substrate 2811 side using the high-frequency power supply 2816. As the high-Frequency power source 2816, for example, a Radio Frequency (RF) power source having a Frequency of 13.56MHz, 27.12MHz, or the like can be used. By applying a bias voltage to the substrate side, ions in the high-density plasma 2810 can be efficiently made to reach a deep portion of an opening portion of a film or the like on the substrate 2811.

For example, oxygen radical treatment using the high density plasma 2810 can be performed in the processing chamber 2706b by introducing oxygen from the gas supply source 2801, and nitrogen radical treatment using the high density plasma 2810 can be performed in the processing chamber 2706c by introducing nitrogen from the gas supply source 2801.

Next, the processing chambers 2706a and 2706d will be described with reference to a cross-sectional schematic diagram shown in fig. 17.

The processing chambers 2706a and 2706d are processing chambers capable of irradiating an object to be processed with electromagnetic waves, for example. Note that the processing chamber 2706a is different from the processing chamber 2706d only in the kind of the electromagnetic wave. The other structures of the processing chambers 2706a and 2706d are the same, and therefore, the following description is also given.

The processing chambers 2706a and 2706d include one or more lamps 2820, substrate holders 2825, gas inlets 2823, and gas outlets 2830. Further, a gas supply source 2821, a valve 2822, a vacuum pump 2827, and a valve 2829 are provided outside the processing chamber 2706a and the processing chamber 2706 d.

The gas supply source 2821 is connected to the gas inlet 2823 through a valve 2822. Vacuum pump 2828 is connected to exhaust 2830 through valve 2829. The lamp 2820 is disposed opposite to the substrate holder 2825. The substrate holder 2825 has a function of holding the substrate 2824. Further, the substrate holder 2825 includes a heating mechanism 2826 in its inside and has a function of heating the substrate 2824.

As the lamp 2820, for example, a light source having a function of emitting electromagnetic waves such as visible light or ultraviolet light can be used. For example, a light source having a function of emitting an electromagnetic wave having a peak in a wavelength region of 10nm or more and 2500nm or less, 500nm or more and 2000nm or less, or 40nm or more and 340nm or less may be used.

For example, as the lamp 2820, a light source such as a halogen lamp, a metal halide lamp, a xenon arc lamp, a carbon arc lamp, a high-pressure sodium lamp, or a high-pressure mercury lamp can be used.

For example, a part or all of the electromagnetic waves emitted from the lamp 2820 are sucked by the substrate 2824, whereby the quality of a film or the like on the substrate 2824 can be improved. For example, defects may be generated or reduced, or impurities may be removed. Further, in the case where defects are generated or reduced or impurities are removed while heating the substrate 2824, the defects can be generated or reduced or the impurities can be removed efficiently.

Alternatively, for example, the substrate 2824 may be heated by heating the substrate holder 2825 using electromagnetic waves emitted from the lamp 2820. In this case, it is not necessary to include the heating mechanism 2826 inside the substrate holder 2825.

The vacuum pump 2827 can refer to the description of the vacuum pump 2817. The heating means 2826 can refer to the description of the heating means 2813. In addition, the gas supply source 2821 may refer to the description of the gas supply source 2801.

By using the above-described manufacturing apparatus, it is possible to suppress the mixing of impurities into the object to be processed and to improve the film quality.

< modified example of semiconductor device >

Next, an example of a semiconductor device including a transistor 200 according to one embodiment of the present invention, which is different from the semiconductor device described in < example of structure of semiconductor device > above, will be described with reference to fig. 18 to 21. Note that in the semiconductor devices shown in fig. 18 to 21, the same reference numerals are given to structures having the same components as those constituting the semiconductor device (see fig. 1) shown in < example of the structure of the semiconductor device >. In this section, as a constituent material of the transistor 200, a material described in detail in < structural example of semiconductor device > can be used.

< modified example 1 of semiconductor device >

Fig. 18A is a top view of a semiconductor device including the transistor 200. Here, fig. 18B is a sectional view corresponding to a portion indicated by a chain line a1-a2 in fig. 18A, and is also a sectional view in the channel length direction of the transistor 200. Fig. 18C is a sectional view corresponding to a portion indicated by a chain line A3-a4 in fig. 18A, and is also a sectional view in the channel width direction of the transistor 200. Fig. 18D is a sectional view corresponding to the portion indicated by the chain line a5-a6 in fig. 18A. Note that in the plan view of fig. 18A, some components are omitted to make the figure more clear.

The transistor 200 shown in fig. 18 is different from the transistor 200 shown in fig. 1 in that: insulator 224, insulator 280, and insulator 282 are patterned and encapsulated by insulator 283 and insulator 222. In other words, the insulator 283 contacts the top and side surfaces of the insulator 282, the side surfaces of the insulator 280, the side surfaces of the insulator 224, and the top surface of the insulator 222. Thus, region 245 is also formed in insulator 280 and insulator 224. Thus, the insulator 224, the insulator 280, and the insulator 282 are separated from the outside by the insulator 222 and the insulator 283, in addition to the oxide 230 and the like.

With this structure, the insulator 214, the insulator 216, and the insulator 222 do not need to be patterned, and therefore, the process can be simplified and the productivity of the semiconductor device can be improved.

< modified example 2 of semiconductor device >

Fig. 19A is a top view of a semiconductor device including the transistor 200. Here, fig. 19B is a sectional view corresponding to a portion indicated by a chain line a1-a2 in fig. 19A, and is also a sectional view in the channel length direction of the transistor 200. Fig. 19C is a sectional view corresponding to a portion indicated by a chain line A3-a4 in fig. 19A, and is also a sectional view in the channel width direction of the transistor 200. Fig. 19D is a sectional view corresponding to the portion indicated by the chain line a5-a6 in fig. 19A. Note that in the plan view of fig. 19A, some components are omitted to make the figure more clear.

The transistor 200 shown in fig. 19 is different from the transistor 200 shown in fig. 1 in that: insulator 214, insulator 216, insulator 222, insulator 224, insulator 280, and insulator 282 are not patterned. Since insulator 280, insulator 224, and insulator 216 are not patterned in transistor 200 shown in fig. 19, region 245 is not formed.

With this structure, it is not necessary to pattern the insulator 214, the insulator 216, the insulator 222, the insulator 224, the insulator 280, and the insulator 282, and therefore, the process can be simplified and the productivity of the semiconductor device can be improved.

In addition, an insulator 272 is provided so as to cover the insulator 224, the oxide 230a, the oxide 230b, the oxide 243, and the conductor 242 instead of the insulator 272a and the insulator 272 b. The insulator 272 can be formed using the same insulating film as the insulator 272a and the insulator 272 b.

Since the top and side surfaces of the conductor 242, the side surfaces of the oxide 243, the side surfaces of the oxide 230a, and the side surfaces of the oxide 230b are covered with the insulator 272, diffusion of impurities such as hydrogen and water and oxygen into the conductor 242 from the side surfaces of the conductor 242 and the top surface of the conductor 242 can be suppressed. Further, since the bottom surface of the conductor 242 is in contact with the oxide 243, oxygen in the oxide 230b is blocked by the oxide 243, and diffusion of the oxygen into the conductor 242 is suppressed. Therefore, diffusion of oxygen from the periphery of the conductor 242 to the conductor 242 can be suppressed, and thus oxidation of the conductor 242 can be suppressed. Further, diffusion of impurities such as hydrogen and water into the oxide 230a and the oxide 230b from the side surfaces of the oxide 230a and the oxide 230b can be suppressed.

< modification example 3 of semiconductor device >

Fig. 20A is a top view of a semiconductor device including the transistor 200. Here, fig. 20B is a sectional view corresponding to a portion indicated by a chain line a1-a2 in fig. 20A, and is also a sectional view in the channel length direction of the transistor 200. Fig. 20C is a sectional view corresponding to a portion indicated by a chain line A3-a4 in fig. 20A, and is also a sectional view in the channel width direction of the transistor 200. Fig. 20D is a sectional view corresponding to the portion indicated by the chain line a5-a6 in fig. 20A. Note that in the plan view of fig. 20A, some components are omitted to make the drawing more clear.

The transistor 200 shown in fig. 20 is different from the transistor 200 shown in fig. 1 in that: insulator 214, insulator 216, insulator 222, insulator 224, and insulator 280 are patterned and encapsulated by insulator 282 and insulator 222. In other words, insulator 282 contacts the top and side surfaces of insulator 280, the side surfaces of insulator 224, the side surfaces of insulator 222, the side surfaces of insulator 216, the side surfaces of insulator 214, and the top surface of insulator 212. Here, the insulator 283 is formed on the insulator 282.

In the case of forming the transistor 200 shown in fig. 20, after the conductor 260 and the like are formed as shown in fig. 8, the process shown in fig. 10 is performed without forming the insulator 282, and a part of the insulator 280, a part of the insulator 224, a part of the insulator 222, a part of the insulator 216, and a part of the insulator 214 are processed to form an opening reaching the insulator 212. Then, nitrogen plasma treatment is performed, thereby forming a region 245 having a higher nitrogen concentration than other regions of the insulator 280, the insulator 224, and the insulator 216 on the exposed top and side surfaces of the insulator 280, the exposed side surfaces of the insulator 224, and the exposed side surfaces of the insulator 216. Next, an insulator 283 is formed covering the insulator 280, the insulator 224, the insulator 222, the insulator 216, and the insulator 214. The subsequent steps may be performed in the same manner as the steps shown in fig. 11 and later.

By thus forming the transistor 200, unlike the transistor 200 shown in fig. 1, the region 245 is also formed on the top surface of the insulator 280 in the transistor 200 shown in fig. 20. In addition to oxide 230 and the like, insulator 214, insulator 216, insulator 222, insulator 224, and insulator 280 are also separated from the outside by insulator 212, insulator 282, and insulator 283.

Modified example of semiconductor device 4

Fig. 21A and 21B show a structure in which the plurality of transistors 200_1 to 200 — n are sealed with insulators 283 and 212 surrounding them. Fig. 21A and 21B show that the transistors 200_1 to 200 — n are arranged along the channel length direction, but are not limited thereto. The transistors 200_1 to 200 — n may be arranged in the channel width direction, may be arranged in a matrix, or may be arranged irregularly.

As shown in fig. 21A, an insulator 283 is formed outside the transistors 200_1 to 200 — n so as to be in contact with the insulator 212 (hereinafter, may be referred to as a sealing portion 265). A sealing portion 265 is formed so as to surround the plurality of transistors 200_1 to 200 — n. By adopting such a structure, the plurality of transistors 200_1 to 200 — n can be surrounded by the insulator 283 and the insulator 212. In other words, the sides and the top of the four sides of the plurality of transistors 200_1 to 200_ n may be surrounded by the insulator 283, and the bottom thereof may be surrounded by the insulator 212. In this manner, a plurality of transistor groups surrounded by the sealing portion 265 are provided over the substrate.

A region 245 is formed on the side surfaces of the insulator 280, the insulator 224, and the insulator 216 in the vicinity of the sealing portion 265, and the transistor group surrounded by the sealing portion 265 is also surrounded by the region 245.

Further, a cut line (sometimes referred to as a dividing line, or a cutting line) may be provided so as to overlap the seal portion 265. Since the substrate is divided by the dicing lines, the transistor group surrounded by the sealing portion 265 is taken out as one chip.

An example in which the plurality of transistors 200_1 to 200 — n are surrounded by one sealing portion 265 is shown in fig. 21A, but is not limited thereto. As shown in fig. 21B, the plurality of transistors 200_1 to 200 — n may be surrounded by a plurality of sealing portions. In fig. 21B, the plurality of transistors 200_1 to 200_ n are surrounded by a sealing portion 265a, and the transistors are also surrounded by an outer sealing portion 265B.

As described above, when the plurality of transistors 200_1 to 200 — n are surrounded by the plurality of sealing portions, the insulator 283 and the insulator 212 contact each other in a larger number of portions, and thus the adhesiveness between the insulator 283 and the insulator 212 can be further improved. Thereby, the plurality of transistors 200_1 to 200 — n can be more firmly sealed.

In this case, a cutting line may be provided overlapping with the sealing portion 265a or the sealing portion 265b or between the sealing portion 265a and the sealing portion 265 b.

According to one embodiment of the present invention, a semiconductor device having excellent electrical characteristics can be provided. In addition, according to one embodiment of the present invention, a semiconductor device having normally-off electrical characteristics can be provided. In addition, according to one embodiment of the present invention, a semiconductor device with high reliability can be provided. According to one embodiment of the present invention, a semiconductor device with a large on-state current can be provided. In addition, according to one embodiment of the present invention, a semiconductor device having high frequency characteristics can be provided. According to one embodiment of the present invention, a semiconductor device which can be miniaturized or highly integrated can be provided. In addition, according to one embodiment of the present invention, a semiconductor device with a small off-state current can be provided. In addition, according to one embodiment of the present invention, a semiconductor device with reduced power consumption can be provided. In addition, according to one embodiment of the present invention, a semiconductor device with high productivity can be provided.

(embodiment mode 2)

In this embodiment, an embodiment of a semiconductor device will be described with reference to fig. 22 and 23.

[ storage device 1]

Fig. 22 shows an example of a semiconductor device (memory device) using a capacitor which is one embodiment of the present invention. In the semiconductor device according to one embodiment of the present invention, the transistor 200 is provided above the transistor 300, and the capacitor 100 is provided above the transistor 300 and the transistor 200. Note that the transistor 200 described in the above embodiment mode can be used as the transistor 200.

The transistor 200 is a transistor whose channel is formed in a semiconductor layer including an oxide semiconductor. Since the off-state current of the transistor 200 is small, the memory content can be maintained for a long period of time by using it for a memory device. In other words, since the refresh operation is not necessary or the frequency of the refresh operation is extremely low, the power consumption of the memory device can be sufficiently reduced.

In the semiconductor device shown in fig. 22, a wiring 1001 is electrically connected to a source of the transistor 300, and a wiring 1002 is electrically connected to a drain of the transistor 300. Further, a wiring 1003 is electrically connected to one of a source and a drain of the transistor 200, a wiring 1004 is electrically connected to a first gate of the transistor 200, and a wiring 1006 is electrically connected to a second gate of the transistor 200. The gate of the transistor 300 and the other of the source and the drain of the transistor 200 are electrically connected to one electrode of the capacitor 100, and the wiring 1005 is electrically connected to the other electrode of the capacitor 100.

The memory device shown in fig. 22 is arranged in a matrix to form a memory cell array.

< transistor 300>

The transistor 300 is provided over a substrate 311, and includes: a conductor 316 serving as a gate; an insulator 315 serving as a gate insulator; a semiconductor region 313 formed of a part of the substrate 311; and a low-resistance region 314a and a low-resistance region 314b functioning as a source region or a drain region. The transistor 300 may be of a p-channel type or an n-channel type.

Here, in the transistor 300 shown in fig. 22, a semiconductor region 313 (a part of the substrate 311) where a channel is formed has a convex shape. Further, a conductor 316 is provided so as to cover the side surface and the top surface of the semiconductor region 313 with an insulator 315 interposed therebetween. In addition, a material for adjusting the work function can be used for the conductive body 316. Such a transistor 300 is also referred to as a FIN type transistor because a convex portion of a semiconductor substrate is used. Further, the insulator may have a mask for forming the convex portion so as to be in contact with the upper surface of the convex portion. Although the case where a part of the semiconductor substrate is processed to form the convex portion is described here, a semiconductor film having a convex portion may be formed by processing an SOI substrate.

Note that the structure of the transistor 300 shown in fig. 22 is merely an example, and is not limited to the above structure, and an appropriate transistor may be used depending on a circuit structure or a driving method.

< capacitor 100>

The capacitor 100 is disposed above the transistor 200. The capacitor 100 includes a conductive body 110 serving as a first electrode, a conductive body 120 serving as a second electrode, and an insulator 130 serving as a dielectric.

For example, the conductor 112 and the conductor 110 provided on the conductor 246 may be formed at the same time. Further, the conductive body 112 functions as a plug or a wiring electrically connected to the capacitor 100, the transistor 200, or the transistor 300.

In fig. 22, the conductors 112 and 110 have a single-layer structure, but the structure is not limited to this, and may have a laminated structure of two or more layers. For example, a conductor having high adhesion to a conductor having barrier properties and a conductor having high conductivity may be formed between the conductor having barrier properties and the conductor having high conductivity.

Further, the insulator 130 can be formed using, for example, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, aluminum oxide, aluminum oxynitride, aluminum nitride oxide, aluminum nitride, hafnium oxide, hafnium oxynitride, hafnium nitride oxide, hafnium nitride, or the like, and can be formed using a stacked layer or a single layer.

For example, the insulator 130 preferably has a stacked-layer structure of a material having high dielectric strength such as silicon oxynitride and a material having a high dielectric constant (high-k). With this configuration, the capacitor 100 can include an insulator having a high dielectric constant (high-k) to ensure sufficient capacitance, and can include an insulator having a high dielectric withstand voltage to increase the dielectric withstand voltage, thereby suppressing electrostatic breakdown of the capacitor 100.

Note that as an insulator of a high dielectric constant (high-k) material (a material having a high relative dielectric constant), gallium oxide, hafnium oxide, zirconium oxide, an oxide having aluminum and hafnium, an oxynitride having aluminum and hafnium, an oxide having silicon and hafnium, an oxynitride having silicon and hafnium, a nitride having silicon and hafnium, or the like is available.

On the other hand, as a material having high insulation withstand voltage (a material having a low relative dielectric constant), there are silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, silicon oxide to which fluorine is added, silicon oxide to which carbon and nitrogen are added, silicon oxide having a void, resin, or the like.

< Wiring layer >

Wiring layers including interlayer films, wirings, plugs, and the like may be provided between the structures. Further, the wiring layer may be provided as a plurality of layers according to design. Here, in a conductor having a function of a plug or a wiring, a plurality of structures may be denoted by the same reference numeral. In this specification and the like, a wiring and a plug electrically connected to the wiring may be one component. That is, a part of the conductor is sometimes used as a wiring, and a part of the conductor is sometimes used as a plug.

For example, an insulator 320, an insulator 322, an insulator 324, and an insulator 326 are stacked in this order as interlayer films on the transistor 300. Conductors 328, 330, and the like electrically connected to the capacitor 100 or the transistor 200 are embedded in the insulator 320, the insulator 322, the insulator 324, and the insulator 326. The conductor 328 and the conductor 330 are used as plugs or wires.

Further, the insulator serving as the interlayer film may be used as a planarizing film covering the concave-convex shape thereunder. For example, in order to improve the flatness of the top surface of the insulator 322, planarization may be performed by a planarization process using a Chemical Mechanical Polishing (CMP) method or the like.

Further, a wiring layer may be provided over the insulator 326 and the conductor 330. For example, in fig. 22, an insulator 350, an insulator 352, and an insulator 354 are stacked in this order. Further, a conductor 356 is formed in the insulator 350, the insulator 352, and the insulator 354. Electrical conductor 356 serves as a plug or wiring.

Similarly, a conductor 218, a conductor (conductor 205) constituting the transistor 200, and the like are embedded in the insulator 210, the insulator 212, the insulator 214, and the insulator 216. Further, the conductor 218 is used as a plug or a wiring electrically connected to the capacitor 100 or the transistor 300. Further, an insulator 150 is provided on the conductor 120 and the insulator 130.

Here, it is preferable that the region 217 of the solid-phase nitrided region is formed in contact with the side surface of the conductor 218, similarly to the region 241 shown in the above embodiment. Region 217 is formed near the inner walls of the openings formed in insulator 210 and insulator 216. In other words, the region 217 is disposed between the conductor 218 and the insulators 210 and 216. Since the conductor 205 can be formed in parallel with the conductor 218, the region 217 may be formed so as to be in contact with the side surface of the conductor 205.

Since the region 217 is formed in the vicinity of the side surfaces of the insulator 210 and the insulator 216, impurities such as water and hydrogen can be prevented from being mixed into the oxide 230 from the insulator 210, the insulator 216, and the like through the conductor 218. In addition, by forming the region 217, oxygen contained in the insulator 210 or the insulator 216 can be prevented from being absorbed by the conductor 218.

The region 217 can be formed in the same manner as the region 241. For example, the region 217 may be formed by forming an opening into which the conductor 218 is inserted, and then performing nitrogen plasma treatment to solid-phase nitridize the side surfaces of the insulator 210 and the insulator 216. When the oxidation resistance of the conductor 218 is sufficiently high and the hydrogen concentration of the insulator 216 or the like is sufficiently reduced, the region 217 may not be provided.

As an insulator which can be used as the interlayer film, there are an oxide, a nitride, an oxynitride, a metal oxide, a metal oxynitride, and the like which have insulating properties.

For example, by using a material having a relatively low dielectric constant for the insulator of the interlayer film, parasitic capacitance generated between wirings can be reduced. Therefore, it is preferable to select the material according to the function of the insulator.

For example, the insulators 150, 210, 352, 354, and the like preferably have low relative dielectric constants. For example, the insulator preferably contains silicon oxynitride, silicon nitride, silicon oxide to which fluorine is added, silicon oxide to which carbon and nitrogen are added, silicon oxide having pores, resin, or the like. Alternatively, the insulator preferably has a stacked-layer structure of silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, silicon oxide to which fluorine is added, silicon oxide to which carbon and nitrogen are added, or silicon oxide having a void and a resin. Since silicon oxide and silicon oxynitride have thermal stability, a stacked structure having thermal stability and a low relative dielectric constant can be realized by combining them with a resin. Examples of the resin include polyester, polyolefin, polyamide (nylon, aramid, etc.), polyimide, polycarbonate, and acrylic.

Further, by surrounding a transistor using an oxide semiconductor with an insulator having a function of suppressing permeation of impurities such as hydrogen and oxygen, electric characteristics of the transistor can be stabilized. Therefore, as the insulator 214, the insulator 212, the insulator 350, and the like, an insulator having a function of suppressing permeation of impurities such as hydrogen and oxygen may be used.

As the insulator having a function of suppressing permeation of impurities such as hydrogen and oxygen, for example, an insulator containing boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum may be used in a single layer or a stacked layer. Specifically, as the insulator having a function of suppressing permeation of impurities such as hydrogen and oxygen, metal oxides such as aluminum oxide, magnesium oxide, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, and tantalum oxide, silicon oxynitride, silicon nitride, and the like can be used.

As the conductor that can be used for wiring and plugs, a material containing at least one metal element selected from aluminum, chromium, copper, silver, gold, platinum, tantalum, nickel, titanium, molybdenum, tungsten, hafnium, vanadium, niobium, manganese, magnesium, zirconium, beryllium, indium, ruthenium, and the like is preferably used. Further, a semiconductor having high conductivity typified by polycrystalline silicon containing an impurity element such as phosphorus, or a silicide such as nickel silicide can be used.

For example, as the conductors 328, 330, 356, 218, 112, and the like, a conductive material such as a metal material, an alloy material, a metal nitride material, or a metal oxide material, which is formed of the above-described materials, may be used in a single layer or a stacked layer. High melting point materials such as tungsten and molybdenum having both heat resistance and conductivity are preferably used, and tungsten is particularly preferably used. Alternatively, it is preferably formed using a low-resistance conductive material such as aluminum or copper. Wiring resistance can be reduced by using a low-resistance conductive material.

< plug provided with layer of oxide semiconductor >

As in the above-described embodiment, the region 241 is preferably formed so as to be in contact with the side surface of the conductor 240 serving as a plug. Region 241 is formed near the inner walls of the openings formed in insulator 224, insulator 280, and insulator 274. In other words, the region 241 is disposed between the conductive body 240 and the insulator 224, the insulator 280, and the insulator 274. Further, in the case where the top surface of the insulator 274 is exposed when the region 241 is formed, the region 241 is also formed near the top surface of the insulator 274.

Since the region 241 is formed in the vicinity of the side surfaces of the insulator 224, the insulator 280, and the insulator 274, impurities such as water and hydrogen can be prevented from being mixed into the oxide 230 from the insulator 224, the insulator 280, the insulator 274, and the like through the conductor 240. Further, by forming the region 241, oxygen contained in the insulator 224, the insulator 280, and the insulator 274 can be prevented from being absorbed by the conductor 240. Therefore, the amount of hydrogen diffused from the conductor 240 into the conductor 242 and the oxide 230 can be reduced.

For example, after forming an opening into which the conductor 240 is inserted, the side surfaces of the insulator 224, the insulator 280, and the insulator 274 may be solid-phase nitrided to form the region 241 by performing nitrogen plasma treatment.

In addition, as in the above-described embodiment, the transistor 200 is preferably sealed by the insulator 283 and the insulator 212. Further, a region 245 is preferably formed in the vicinity of the interface with the insulator 283 among the insulator 216, the insulator 224, and the insulator 280. By forming the region 245 between the insulator 280, the insulator 224, and the insulator 216 and the insulator 283, it is possible to reduce the hydrogen in the insulator 274 from being mixed into the insulator 280 and the like.

Here, although the insulator 283 is penetrated by the conductor 240 and the insulator 212 is penetrated by the conductor 218, the region 241 is provided so as to be in contact with the conductor 240 and the region 217 is provided so as to be in contact with the conductor 218 as described above. Therefore, hydrogen mixed into the inside of the insulator 283 and the insulator 212 through the conductor 240 and the conductor 218 can be reduced. By this method, the transistor 200 can be more firmly sealed by the insulator 283, the insulator 212, the region 241, and the region 217, whereby impurities such as hydrogen in the insulator 274 and the like can be reduced from being mixed into the outside of the insulator 283.

As described in the above embodiments, the insulators 216, 224, 280, 250, and 274 are preferably formed by a film formation method using a gas in which hydrogen atoms are reduced or removed. This can reduce the hydrogen concentration in the insulator 216, the insulator 224, the insulator 280, the insulator 250, and the insulator 274.

As shown in fig. 22, the insulator 216, the insulator 224, the insulator 280, and the insulator 274 are provided with the conductor 240 and the conductor 218, which are through holes, connected to the conductor 242. As described above, by reducing the hydrogen concentration in the insulator 216, the insulator 224, the insulator 280, and the insulator 274, the amount of hydrogen diffused into the conductor 242 and the oxide 230 through the conductor 240 and the conductor 218 can be further reduced.

This method can reduce the hydrogen concentration in the silicon-based insulating film near the transistor 200, thereby reducing the hydrogen concentration in the oxide 230.

Cutting line

Next, a description will be given of scribe lines (also referred to as dividing lines, or cutting lines) provided when a large-area substrate is divided into a plurality of semiconductor devices each having a chip shape for each semiconductor element. As a dividing method, for example, there are cases where a groove (dicing line) for dividing a semiconductor element is first formed in a substrate, and then the substrate is divided at the dicing line to obtain a plurality of divided (divided) semiconductor devices.

Here, for example, as shown in fig. 22, the scribe line is preferably designed to overlap a region where the insulator 283 and the insulator 212 are in contact with each other. That is, openings are provided in the insulator 280, the insulator 224, the insulator 222, the insulator 216, and the insulator 214 in the vicinity of a region to be a cutting line provided at an edge of a memory cell including the plurality of transistors 200.

That is, the insulator 212 is in contact with the insulator 283 in the openings provided in the insulator 280, the insulator 224, the insulator 222, the insulator 216, and the insulator 214 described above. For example, in this case, the insulator 212 and the insulator 283 may be formed using the same material and the same method. By forming the insulator 212 and the insulator 283 using the same material and the same method, the adhesion can be improved. For example, silicon nitride is preferably used.

With this structure, the transistor 200 can be surrounded by the insulator 212 and the insulator 283. Since the insulators 212 and 283 have a function of suppressing diffusion of oxygen, hydrogen, and water, even if the substrate is divided into a plurality of chips for each circuit region where a semiconductor element is formed as in this embodiment mode, impurities such as hydrogen and water can be prevented from being mixed and diffused into the transistor 200 from the side surface direction of the divided substrate.

With this structure, the excessive oxygen in the insulator 280 and the insulator 224 can be prevented from diffusing to the outside. Therefore, the excess oxygen in the insulator 280 and the insulator 224 is efficiently supplied into the oxide forming the channel in the transistor 200. By this oxygen, oxygen vacancies in the oxide forming the channel in the transistor 200 can be reduced. Thus, the oxide forming the channel in the transistor 200 can be an oxide semiconductor having low defect density and stable characteristics. That is, the reliability can be improved while suppressing the variation in the electrical characteristics of the transistor 200.

The above is a description of structural examples. With this structure, it is possible to suppress variations in electrical characteristics and improve reliability in a semiconductor device using a transistor including an oxide semiconductor. Further, a transistor including an oxide semiconductor with a large on-state current can be provided. Further, a transistor including an oxide semiconductor with small off-state current can be provided. Further, a semiconductor device with reduced power consumption can be provided.

[ storage device 2]

Fig. 23 shows an example of a memory device using a semiconductor device which is one embodiment of the present invention. The memory device shown in fig. 23 includes a transistor 400 in addition to the semiconductor devices of the transistor 200, the transistor 300, and the capacitor 100 shown in fig. 22.

The transistor 400 may control the second gate voltage of the transistor 200. For example, a structure is adopted in which the first gate and the second gate of the transistor 400 are diode-connected to the source and the source of the transistor 400 is connected to the second gate of the transistor 200. When the negative potential of the second gate of the transistor 200 is held in this structure, the voltage between the first gate and the source and the voltage between the second gate and the source of the transistor 400 become 0V. In the transistor 400, since the drain current when the second gate voltage and the first gate voltage are 0V is very small, the negative potential of the second gate of the transistor 200 can be maintained for a long time even if power is not supplied to the transistor 200 and the transistor 400. Thus, the memory device including the transistor 200 and the transistor 400 can retain memory contents for a long period of time.

Therefore, in fig. 23, the wiring 1001 is electrically connected to the source of the transistor 300, and the wiring 1002 is electrically connected to the drain of the transistor 300. Further, a wiring 1003 is electrically connected to one of a source and a drain of the transistor 200, a wiring 1004 is electrically connected to a gate of the transistor 200, and a wiring 1006 is electrically connected to a back gate of the transistor 200. The gate of the transistor 300 and the other of the source and the drain of the transistor 200 are electrically connected to one electrode of the capacitor 100, and the wiring 1005 is electrically connected to the other electrode of the capacitor 100. A wiring 1007 is electrically connected to a source of the transistor 400, a wiring 1008 is electrically connected to a gate of the transistor 400, a wiring 1009 is electrically connected to a back gate of the transistor 400, and a wiring 1010 is electrically connected to a drain of the transistor 400. Here, the wiring 1006, the wiring 1007, the wiring 1008, and the wiring 1009 are electrically connected.

The memory device shown in fig. 23 can be configured as a memory cell array by arranging the memory device in a matrix like the memory device shown in fig. 22. Note that one transistor 400 may control the second gate voltage of the plurality of transistors 200. Therefore, the number of transistors 400 is preferably smaller than that of the transistors 200. In the memory device shown in fig. 23, the transistor 200 and the transistor 400 can be sealed with the insulator 212 and the insulator 283, similarly to the memory device shown in fig. 22.

< transistor 400>

Transistor 400 is formed in the same layer as transistor 200 and can be fabricated in parallel. The transistor 400 includes a conductor 460 (a conductor 460a and a conductor 460b) functioning as a first gate, a conductor 405 (a conductor 405a and a conductor 405b) functioning as a second gate, an insulator 222 and an insulator 450 functioning as a gate insulating layer, an oxide 430c including a channel formation region, a conductor 442a, an oxide 443a, an oxide 431a, and an oxide 431b functioning as a source, a conductor 442b, an oxide 443b, an oxide 432a, and an oxide 432b functioning as a drain, a conductor 440 (a conductor 440a and a conductor 440b) functioning as a plug, and an insulator 472 (an insulator 472a and an insulator 472b) functioning as a barrier insulating film of the conductor 442. In addition, a part of the region 241 formed in the insulator 280 and the insulator 274 is used as a barrier layer of the conductor 440.

In the transistor 400, the conductive body 405 and the conductive body 205 are the same layer. Oxide 431a and oxide 432a are the same layer as oxide 230a, and oxide 431b and oxide 432b are the same layer as oxide 230 b. Conductor 442 is the same layer as conductor 242. The oxide 443 is the same layer as the oxide 243. Oxide 430c is the same layer as oxide 230 c. Insulator 450 is the same layer as insulator 250. Electrical conductor 460 is the same layer as electrical conductor 260. Conductor 440 is the same layer as conductor 240. Insulator 472 is the same layer as insulator 272.

Note that the structures formed in the same layer may be formed simultaneously. For example, the oxide 430c can be formed by processing an oxide film to be the oxide 230 c.

Similarly to the oxide 230 and the like, in the oxide 430c used as an active layer of the transistor 400, oxygen vacancies and impurities such as hydrogen and water are reduced. Therefore, the threshold voltage of the transistor 400 can be made larger than 0V, the off-state current can be reduced, and the drain currents when the second gate voltage and the first gate voltage are 0V can be made very small.

The structures, methods, and the like described in this embodiment can be used in combination with the structures, methods, and the like described in other embodiments and other examples as appropriate.

(embodiment mode 3)

In this embodiment, a memory device (hereinafter, sometimes referred to as an OS memory device) using a transistor in which an oxide is used for a semiconductor (hereinafter, sometimes referred to as an OS transistor) and a capacitor according to one embodiment of the present invention will be described with reference to fig. 24 and 25. The OS memory device is a memory device including at least a capacitor and an OS transistor that controls charging and discharging of the capacitor. The OS memory device has excellent retention characteristics because the off-state current of the OS transistor is extremely small, and thus can be used as a nonvolatile memory.

< example of memory device construction >

Fig. 24A shows an example of the structure of the OS storage device. The memory device 1400 includes peripheral circuitry 1411 and a memory cell array 1470. The peripheral circuit 1411 includes a row circuit 1420, a column circuit 1430, an output circuit 1440, and a control logic circuit 1460.

The column circuit 1430 includes, for example, a column decoder, a precharge circuit, a sense amplifier, a write circuit, and the like. The precharge circuit has a function of precharging the wiring. The sense amplifier has a function of amplifying a data signal read out from the memory cell. Note that the above-described wirings are wirings connected to memory cells included in the memory cell array 1470, and details thereof are described below. The amplified data signal is output to the outside of the memory device 1400 through the output circuit 1440 as a data signal RDATA. Further, the row circuit 1420 includes, for example, a row decoder, a word line driver circuit, and the like, and can select a row to be accessed.

A low power supply Voltage (VSS) as a power supply voltage, a high power supply Voltage (VDD) for the peripheral circuit 1411, and a high power supply Voltage (VIL) for the memory cell array 1470 are supplied to the memory device 1400 from the outside. Control signals (CE, WE, RE), address signals ADDR, and data signals WDATA are externally input to the memory device 1400. Address signal ADDR is input to a row decoder and a column decoder, and data signal WDATA is input to a write circuit.

The control logic circuit 1460 processes input signals (CE, WE, RE) from the outside to generate control signals for the row decoder and the column decoder. CE is a chip enable signal, WE is a write enable signal, and RE is a read enable signal. The signal processed by the control logic circuit 1460 is not limited to this, and another control signal may be input as needed.

The memory cell array 1470 includes a plurality of memory cells MC arranged in rows and columns and a plurality of wirings. Note that the number of wirings connecting the memory cell array 1470 and the row circuit 1420 depends on the structure of the memory cells MC, the number of memory cells MC included in one column, and the like. In addition, the number of wirings connecting the memory cell array 1470 and the column circuit 1430 depends on the structure of the memory cells MC, the number of memory cells MC included in one row, and the like.

In addition, although an example in which the peripheral circuit 1411 and the memory cell array 1470 are formed on the same plane is shown in fig. 24A, the embodiment is not limited thereto. For example, as shown in fig. 24B, the memory cell array 1470 may be provided so as to overlap with a part of the peripheral circuit 1411. For example, a structure may be employed in which a sense amplifier is provided so as to overlap the memory cell array 1470.

An example of a structure of a memory cell that can be suitably used for the above-described memory cell MC is illustrated in fig. 25.

[DOSRAM]

Fig. 25A to 25C show circuit configuration examples of memory cells of a DRAM. In this specification and the like, a DRAM using a 1OS transistor 1 capacitor type memory cell is sometimes referred to as a dosram (dynamic Oxide Semiconductor Random Access memory). The memory cell 1471 shown in fig. 25A includes a transistor M1 and a capacitor CA. In addition, the transistor M1 includes a gate (sometimes referred to as a front gate) and a back gate.

A first terminal of the transistor M1 is connected to a first terminal of the capacitor CA, a second terminal of the transistor M1 is connected to the wiring BIL, a gate of the transistor M1 is connected to the wiring WOL, and a back gate of the transistor M1 is connected to the wiring BGL. The second terminal of the capacitor CA is connected to the wiring CAL.

The wiring BIL is used as a bit line, and the wiring WOL is used as a word line. The wiring CAL is used as a wiring for applying a predetermined potential to the second terminal of the capacitor CA. In writing and reading data, it is preferable to apply a low-level potential to the wiring CAL. The wiring BGL is used as a wiring for applying a potential to the back gate of the transistor M1. By applying an arbitrary potential to the wiring BGL, the threshold voltage of the transistor M1 can be increased or decreased.

In addition, the memory cell MC is not limited to the memory cell 1471, and the circuit configuration thereof may be changed. For example, the memory cell MC may have a structure in which the back gate of the transistor M1 is connected to the wiring WOL instead of the wiring BGL, as in the memory cell 1472 shown in fig. 25B. For example, the memory cell MC may be a memory cell including a transistor having a single gate structure, that is, a transistor M1 not including a back gate, as in the memory cell 1473 shown in fig. 25C.

In the case where the semiconductor device shown in the above embodiment mode is used for the memory cell 1471 or the like, the transistor 200 can be used as the transistor M1, and the capacitor 100 can be used as the capacitor CA. By using an OS transistor as the transistor M1, the leakage current of the transistor M1 can be made extremely low. In other words, since the written data can be held by the transistor M1 for a long time, the refresh frequency of the memory cell can be reduced. Further, the refresh operation of the memory cell may not be performed. Further, since the leakage current is extremely low, multi-valued data or analog data can be held in the memory cell 1471, the memory cell 1472, and the memory cell 1473.

In the case of the dorams in which the sense amplifiers are provided so as to overlap the memory cell array 1470 as described above, the bit lines can be shortened. Thereby, the bit line capacitance is reduced, so that the storage capacitance of the memory cell can be reduced.

[NOSRAM]

Fig. 25D to 25H show circuit configuration examples of the gain unit type memory cell of the 2-transistor 1 capacitor. The memory cell 1474 shown in fig. 25D includes a transistor M2, a transistor M3, and a capacitor CB. The transistor M2 includes a front gate (sometimes simply referred to as a gate) and a back gate. In this specification and the like, a memory device including a gain cell type memory cell using an OS transistor for the transistor M2 is sometimes referred to as an nosram (nonvolatile Oxide Semiconductor ram).

A first terminal of the transistor M2 is connected to a first terminal of the capacitor CB, a second terminal of the transistor M2 is connected to the wiring WBL, a gate of the transistor M2 is connected to the wiring WOL, and a back gate of the transistor M2 is connected to the wiring BGL. A second terminal of the capacitor CB is connected to the wiring CAL. A first terminal of the transistor M3 is connected to the wiring RBL, a second terminal of the transistor M3 is connected to the wiring SL, and a gate of the transistor M3 is connected to a first terminal of the capacitor CB.

The wiring WBL is used as a write bit line, the wiring RBL is used as a read bit line, and the wiring WOL is used as a word line. The wiring CAL is used as a wiring for applying a prescribed potential to the second terminal of the capacitor CB. In writing, holding, and reading of data, a low-level potential is preferably applied to the wiring CAL. The wiring BGL is used as a wiring for applying a potential to the back gate of the transistor M2. By applying an arbitrary potential to the wiring BGL, the threshold voltage of the transistor M2 can be increased or decreased.

Further, the memory cell MC is not limited to the memory cell 1474, and the circuit configuration thereof may be appropriately changed. For example, the memory cell MC may have a structure in which the back gate of the transistor M2 is connected to the wiring WOL instead of the wiring BGL, as in the memory cell 1475 shown in fig. 25E. For example, the memory cell MC may be a memory cell including a transistor having a single gate structure, that is, a transistor M2 not including a back gate, as in the memory cell 1476 shown in fig. 25F. For example, the memory cell MC may have a structure in which the wiring WBL and the wiring RBL are combined into one wiring BIL as in the memory cell 1477 shown in fig. 25G.

In the case where the semiconductor device shown in the above embodiment mode is used for the memory cell 1474 or the like, the transistor 200 can be used as the transistor M2, the transistor 300 can be used as the transistor M3, and the capacitor 100 can be used as the capacitor CB. By using an OS transistor as the transistor M2, the leakage current of the transistor M2 can be made extremely low. Thus, since the written data can be held for a long time by the transistor M2, the refresh frequency of the memory cell can be reduced. Further, the refresh operation of the memory cell may not be performed. Further, since the leakage current is extremely low, multi-valued data or analog data can be held in the memory cell 1474. The same applies to the memory units 1475 to 1477.

The transistor M3 may be a transistor including silicon in a channel formation region (hereinafter, sometimes referred to as a Si transistor). The conductivity type of the Si transistor may be an n-channel type or a p-channel type. The field effect mobility of Si transistors is sometimes higher than that of OS transistors. Therefore, as the transistor M3 serving as a readout transistor, a Si transistor may also be used. Further, by using a Si transistor for the transistor M3, the transistor M2 can be provided so as to be stacked over the transistor M3, whereby the occupied area of the memory cell can be reduced, and high integration of the memory device can be achieved.

Further, the transistor M3 may be an OS transistor. When OS transistors are used for the transistors M2 and M3, a circuit can be formed using only n-type transistors in the memory cell array 1470.

Fig. 25H shows an example of a gain cell type memory cell of a 3-transistor 1 capacitor. The memory cell 1478 shown in FIG. 25H includes transistors M4-M6 and a capacitor CC. The capacitor CC may be appropriately set. Memory cell 1478 is electrically connected to wirings BIL, RWL, WWL, BGL, and GNDL. The wiring GNDL is a wiring for supplying a low-level potential. Further, the memory cell 1478 may be electrically connected to the wirings RBL and WBL, but not electrically connected to the wiring BIL.

The transistor M4 is an OS transistor including a back gate, which is electrically connected to the wiring BGL. Further, the back gate and the gate of the transistor M4 may be electrically connected to each other. Alternatively, the transistor M4 may not include a back gate.

Further, the transistors M5, M6 may be an n-channel type Si transistor or a p-channel type Si transistor, respectively. Alternatively, the transistors M4 to M6 are all OS transistors. In this case, a circuit can be formed using only n-type transistors in the memory cell array 1470.

In the case where the semiconductor device shown in the above embodiment mode is used for the memory cell 1478, the transistor 200 can be used as the transistor M4, the transistor 300 can be used as the transistors M5 and M6, and the capacitor 100 can be used as the capacitor CC. By using an OS transistor as the transistor M4, the leakage current of the transistor M4 can be made extremely low.

Note that the structures of the peripheral circuit 1411, the memory cell array 1470, and the like described in this embodiment are not limited to the above structures. Further, the arrangement or the function of these circuits, wirings connected to the circuits, circuit elements, and the like may be changed, removed, or added as necessary.

The structures, methods, and the like described in this embodiment can be used in combination with the structures, methods, and the like described in other embodiments and other examples as appropriate.

(embodiment mode 4)

In this embodiment, an example of a chip 1200 on which a semiconductor device of the present invention is mounted will be described with reference to fig. 26. A plurality of circuits (systems) are mounted on the chip 1200. As described above, a technology in which a plurality of circuits (systems) are integrated on one Chip is sometimes called a System on Chip (SoC).

As shown in fig. 26A, the chip 1200 includes a Central Processing Unit (CPU) 1211, a Graphics Processing Unit (GPU) 1212, one or more analog operation units 1213, one or more memory controllers 1214, one or more interfaces 1215, one or more network circuits 1216, and the like.

The chip 1200 is provided with a bump (not shown) connected to a first surface of a Printed Circuit Board (PCB) 1201 as shown in fig. 26B. Further, the rear surface of the first surface of the PCB1201 is provided with a plurality of bumps 1202, and the bumps 1202 are connected to the motherboard 1203.

The motherboard 1203 may be provided with a memory device such as a DRAM1221 or a flash memory 1222. For example, the dossram shown in the above embodiment mode can be applied to the DRAM 1221. Further, for example, the nossram shown in the above embodiment mode can be applied to the flash memory 1222.

CPU1211 preferably has a plurality of CPU cores. Further, the GPU1212 preferably has multiple GPU cores. Further, the CPU1211 and the GPU1212 may have memories for temporarily storing data, respectively. Alternatively, the chip 1200 may be provided with a memory used in common by the CPU1211 and the GPU 1212. The above-described nossram or DOSRAM may be applied to the memory. Further, the GPU1212 is suitable for parallel computation of multiple data, which may be used for image processing or product-sum operations. By providing an image processing circuit or a product-sum operation circuit using the oxide semiconductor of the present invention as the GPU1212, image processing and product-sum operation can be performed with low power consumption.

Further, since the CPU1211 and the GPU1212 are provided on the same chip, it is possible to shorten the wiring between the CPU1211 and the GPU1212, and to perform data transfer from the CPU1211 to the GPU1212, data transfer between the memories included in the CPU1211 and the GPU1212, and transfer of the operation result from the GPU1212 to the CPU1211 after the operation in the GPU1212 is completed at high speed.

The analog operation unit 1213 includes one or both of an analog/digital (a/D) conversion circuit and a digital/analog (D/a) conversion circuit. The analog operation unit 1213 may be provided with the product-sum operation circuit.

The memory controller 1214 has a circuit functioning as a controller of the DRAM1221 and a circuit functioning as an interface of the flash memory 1222.

The interface 1215 has interface circuits with externally connected devices such as a display device, speaker, microphone, image capture device, controller, etc. The controller includes a mouse, a keyboard, a controller for a game machine, and the like. As the Interface, a Universal Serial Bus (USB), a High-Definition Multimedia Interface (HDMI) (registered trademark), or the like can be used.

The Network circuit 1216 has a Network circuit such as a Local Area Network (LAN). In addition, a network security circuit may be provided.

The circuits (systems) described above may be formed on the chip 1200 through the same manufacturing process. Thus, even if the number of circuits required for the chip 1200 is increased, the chip 1200 can be manufactured at low cost without increasing the number of manufacturing steps.

Motherboard 1203 including PCB1201 provided with chip 1200 having GPU1212, DRAM1221, and flash memory 1222 may be referred to as GPU module 1204.

GPU module 1204 may reduce its size by having chip 1200 using SoC technology. Further, the GPU module 1204 is suitable for use in portable electronic devices such as smart phones, tablet terminals, laptop personal computers, portable (portable) game machines, and the like because of having high image processing capability. Further, by using a product-sum operation circuit using the GPU1212, operations of a Deep Neural Network (DNN), a Convolutional Neural Network (CNN), a Recurrent Neural Network (RNN), an auto encoder, a Deep Boltzmann Machine (DBM), a Deep Belief Network (DBN), and the like can be performed, whereby the chip 1200 can be used as an AI chip, or the GPU module 1204 can be used as an AI system module.

The structures, methods, and the like described in this embodiment can be used in combination with the structures, methods, and the like described in other embodiments and other examples as appropriate.

(embodiment 5)

In this embodiment, an application example of a memory device using the semiconductor device described in the above embodiment will be described. The semiconductor device described in the above embodiment can be applied to, for example, a storage device of various electronic devices (for example, an information terminal, a computer, a smartphone, an electronic book reader terminal, a digital camera (including a video camera), a video recording and reproducing device, a navigation system, and the like). Note that here, the computer includes a tablet computer, a notebook computer, a desktop computer, and a mainframe computer such as a server system. Alternatively, the semiconductor device described in the above embodiment mode is applied to various removable storage devices such as a memory card (e.g., an SD card), a USB memory, and an SSD (solid state disk). Fig. 27 schematically shows several structural examples of the removable storage device. For example, the semiconductor device shown in the above embodiments is processed into a packaged memory chip and used for various memory devices or removable memories.

FIG. 27A is a schematic diagram of a USB memory. USB memory 1100 includes housing 1101, cover 1102, USB connector 1103, and substrate 1104. A substrate 1104 is accommodated in the housing 1101. For example, a memory chip 1105 and a controller chip 1106 are mounted on the substrate 1104. The semiconductor device described in the above embodiment mode can be mounted on a memory chip 1105 or the like over a substrate 1104.

Fig. 27B is an external view of the SD card, and fig. 27C is an internal structure of the SD card. SD card 1110 includes housing 1111, connector 1112, and substrate 1113. The substrate 1113 is accommodated in the housing 1111. For example, a memory chip 1114 and a controller chip 1115 are mounted on the substrate 1113. By providing the memory chip 1114 also on the back side of the substrate 1113, the capacity of the SD card 1110 can be increased. A wireless chip having a wireless communication function may be provided over the substrate 1113. Thus, data can be read from and written to the memory chip 1114 by wireless communication between the host device and the SD card 1110. The semiconductor device described in the above embodiment mode can be mounted on a memory chip 1114 or the like over a substrate 1113.

Fig. 27D is an external view of the SSD, and fig. 27E is a schematic view of an internal structure of the SSD. SSD1150 includes housing 1151, connector 1152, and substrate 1153. The substrate 1153 is accommodated in a housing 1151. For example, a memory chip 1154, a memory chip 1155, and a controller chip 1156 are mounted on the substrate 1153. The memory chip 1155 is a working memory of the controller chip 1156, and for example, a DOSRAM chip may be used. By providing the memory chip 1154 also on the back surface side of the substrate 1153, the capacity of the SSD1150 can be increased. The semiconductor device shown in the above embodiment modes can be mounted on a memory chip 1154 or the like over a substrate 1153.

The structures, methods, and the like described in this embodiment can be used in combination with the structures, methods, and the like described in other embodiments and other examples as appropriate.

(embodiment mode 6)

In this embodiment, a specific example of an electronic device which can be used for a semiconductor device which is one embodiment of the present invention will be described with reference to fig. 28.

Specifically, the semiconductor device according to one embodiment of the present invention can be applied to a processor or a chip such as a CPU or a GPU. Fig. 28 shows a specific example of an electronic device having a processor or a chip such as a CPU, a GPU, or the like according to an embodiment of the present invention.

< electronic apparatus and System >

A GPU or a chip according to an embodiment of the present invention can be mounted on a variety of electronic devices. Examples of the electronic devices include electronic devices having a large screen such as a television set, a desktop or notebook personal computer, a display for a computer or the like, a large-sized game machine such as a Digital Signage (Digital signal) or a pachinko, and a Digital camera, a Digital video camera, a Digital photo frame, a mobile phone, a portable game machine, a portable information terminal, an audio reproducing device, and the like. Further, by providing the integrated circuit or the chip according to one embodiment of the present invention in an electronic device, the electronic device can be provided with artificial intelligence.

The electronic device according to one embodiment of the present invention may include an antenna. By receiving the signal through the antenna, an image, information, or the like can be displayed on the display unit. Further, when the electronic device includes an antenna and a secondary battery, the antenna may be used for non-contact power transmission.

The electronic device according to one embodiment of the present invention may further include a sensor (the sensor has a function of measuring a force, a displacement, a position, a velocity, an acceleration, an angular velocity, a rotational speed, a distance, light, liquid, magnetism, a temperature, a chemical substance, sound, time, hardness, an electric field, a current, a voltage, electric power, radiation, a flow rate, humidity, inclination, vibration, odor, or infrared rays).

An electronic device according to one embodiment of the present invention can have various functions. For example, the following functions may be provided: a function of displaying various information (still images, moving pictures, character images, and the like) on the display unit; a function of a touch panel; a function of displaying a calendar, date, time, or the like; functions of executing various software (programs); a function of performing wireless communication; a function of reading out a program or data stored in a storage medium; and the like. Fig. 28 shows an example of an electronic apparatus.

[ Mobile telephone ]

Fig. 28A shows a mobile phone (smartphone) which is one of the information terminals. The information terminal 5500 includes a housing 5510 and a display unit 5511, the display unit 5511 includes a touch panel as an input interface, and the housing 5510 is provided with buttons.

By applying the chip of one embodiment of the present invention to the information terminal 5500, an application using artificial intelligence can be executed. Examples of the application program using artificial intelligence include an application program that recognizes a conversation and displays the content of the conversation on the display unit 5511, an application program that recognizes characters or graphics input by a user to a touch panel provided in the display unit 5511 and displays the characters or graphics on the display unit 5511, and an application program that performs biometric recognition such as a fingerprint or a voiceprint.

[ information terminal 1]

Fig. 28B illustrates a desktop information terminal 5300. The desktop information terminal 5300 includes an information terminal main body 5301, a display 5302, and a keyboard 5303.

Similarly to the information terminal 5500 described above, by applying the chip according to one embodiment of the present invention to the desktop information terminal 5300, an application program using artificial intelligence can be executed. Examples of the application using artificial intelligence include design support software, article collation software, and menu automatic generation software. Further, by using the desktop information terminal 5300, novel artificial intelligence can be developed.

Note that, although fig. 28A and 28B show examples of a smartphone and a desktop information terminal as electronic devices in the above examples, information terminals other than a smartphone and a desktop information terminal may be applied. Examples of information terminals other than smartphones and desktop information terminals include PDAs (Personal Digital assistants), notebook information terminals, and workstations.

[ electric products ]

Fig. 28C shows an electric refrigerator-freezer 5800 as an example of an electric product. The electric refrigerator-freezer 5800 includes a housing 5801, a refrigerator compartment door 5802, a freezer compartment door 5803, and the like.

By applying the chip according to one embodiment of the present invention to the electric refrigerator-freezer 5800, the electric refrigerator-freezer 5800 having artificial intelligence can be realized. By using artificial intelligence, the electric refrigerator-freezer 5800 can be provided with a function of automatically creating a menu based on the food stored in the electric refrigerator-freezer 5800 or the expiration date of the food, and a function of automatically adjusting the temperature of the electric refrigerator-freezer 5800 according to the stored food.

In the above examples, the electric refrigerator-freezer is described as an electric appliance, but examples of other electric appliances include a vacuum cleaner, a microwave oven, an electric cooker, a water heater, an IH cooker, a water fountain, a cooling and heating machine including an air conditioner, a washing machine, a clothes dryer, and an audio-visual device.

[ Game machine ]

Fig. 28D shows a portable game machine 5200 as an example of a game machine. The portable game machine includes a housing 5201, a display portion 5202, buttons 5203, and the like.

By applying the GPU or the chip according to one embodiment of the present invention to the portable game machine 5200, the portable game machine 5200 with low power consumption can be realized. Further, by virtue of low power consumption, heat generation from the circuit can be reduced, whereby adverse effects on the circuit itself, peripheral circuits, and modules due to heat generation can be reduced.

In addition, by applying the GPU or the chip according to one embodiment of the present invention to the portable game machine 5200, the portable game machine 5200 having artificial intelligence can be realized.

Although the progress of the game, the language of a living being appearing in the game, and the expression of a phenomenon occurring in the game are originally defined by the program of the game, the artificial intelligence applied to the portable game device 5200 can realize the expression of the program not limited to the game. For example, it is possible to realize expression of the contents of questions asked by the game player, the progress of the game, the time, the change in language of characters appearing on the game, and the like.

Further, when a game requiring a plurality of persons is played using the portable game machine 5200, an anthropomorphic game player can be constructed using artificial intelligence, whereby the artificial intelligence game player can be regarded as an opponent and one person can also play a game played by a plurality of persons.

Although fig. 28D shows a portable game machine as an example of a game machine, a game machine to which a GPU or a chip according to an embodiment of the present invention is applied is not limited to this. Examples of a game machine to which the GPU or chip according to an embodiment of the present invention is applied include a home-use stationary game machine, a arcade game machine installed in an entertainment facility (a game center, an amusement park, or the like), a ball shooting machine for ball hitting practice installed in a sports facility, and the like.

[ moving body ]

The GPU or the chip according to one embodiment of the present invention can be applied to an automobile as a moving object and the vicinity of a driver's seat of the automobile.

Fig. 28E1 is a diagram showing an automobile 5700 as an example of a moving object, and fig. 28E2 is a diagram showing the periphery of a front windshield in an automobile cabin. Fig. 28E2 shows a dashboard-mounted display panel 5701, a display panel 5702, a display panel 5703, and a pillar-mounted display panel 5704.

The display panels 5701 to 5703 may display speedometers, tachometers, travel distances, fuel gauges, gear states, settings of air conditioners to provide various information. In addition, the user can change the display content and layout displayed on the display panel according to the preference, thereby improving the design. The display panels 5701 to 5703 can also be used as lighting devices.

By displaying an image captured by an imaging device (not shown) provided in the automobile 5700 on the display panel 5704, a view (blind spot) blocked by the pillar can be supplemented. That is, by displaying an image captured by an imaging device provided outside the automobile 5700, a blind spot can be compensated, and safety can be improved. In addition, by displaying an image that complements an invisible portion, safety can be confirmed more naturally and comfortably. The display panel 5704 can also be used as a lighting device.

Since the GPU or the chip according to one embodiment of the present invention can be used as a component of artificial intelligence, the chip can be used in an automatic driving system of the automobile 5700, for example. The chip can also be used in systems for navigation, risk prediction, etc. In addition, information such as navigation and risk prediction can be displayed on the display panels 5701 to 5704.

Although an automobile is described as an example of the moving body in the above example, the moving body is not limited to an automobile. For example, the moving body may be an electric train, a monorail, a ship, a flying object (a helicopter, an unmanned plane (drone), an airplane, a rocket), or the like, and the chip according to one embodiment of the present invention may be applied to the moving body to provide a system using artificial intelligence.

[ broadcast television System ]

The GPU or the chip of one embodiment of the present invention can be applied to a broadcast television system.

Fig. 28F schematically shows data transfer in the broadcast television system. Specifically, fig. 28F shows a path along which a radio wave (broadcast television signal) transmitted from a broadcast station 5680 reaches a television receiver (TV)5600 for each home. The TV5600 includes a receiver (not shown), and thus a broadcast television signal received by the antenna 5650 is input to the TV5600 via the receiver.

Although an Ultra High Frequency (UHF) antenna is shown as the antenna 5650 in fig. 28F, a BS and 110-degree CS antenna, a CS antenna, or the like may be used as the antenna 5650.

Radio wave 5675A and radio wave 5675B are terrestrial broadcast television signals, and radio wave tower 5670 amplifies received radio wave 5675A and transmits radio wave 5675B. By receiving the radio wave 5675B with the antenna 5650, each household can watch terrestrial TV broadcasting with the TV 5600. Further, the broadcast television system may be a satellite broadcast television using an artificial satellite, a data broadcast television using an optical route, or the like without being limited to the terrestrial broadcast television shown in fig. 28F.

Further, the chip according to one embodiment of the present invention may be applied to the broadcast television system to form a broadcast television system using artificial intelligence. Compression of broadcast television data is performed using an encoder when the broadcast television data is transmitted from the broadcast station 5680 to the TV5600 of each home; when the antenna 5650 receives the broadcast television data, recovery of the broadcast television data is performed by a decoder of a receiver included in the TV 5600. By using artificial intelligence, for example, a display model contained in a display image can be identified in a motion-compensated prediction of one of the compression methods of the encoder. Further, intra prediction using artificial intelligence or the like may be performed. For example, when the TV5600 receives low-resolution broadcast television data and performs high-resolution display, image supplement processing such as up-conversion may be performed in restoring the broadcast television data by the decoder.

The above-described broadcast television system using artificial intelligence is suitable for ultra high definition television (UHDTV: 4K, 8K) playback in which the broadcast television data volume is increased.

As an application of artificial intelligence on the TV5600 side, for example, a video recording apparatus having artificial intelligence may be provided in the TV 5600. By adopting the structure, the video recording device with artificial intelligence can learn the hobbies of the user, and can automatically record the television programs according with the hobbies of the user.

The electronic device, the function of the electronic device, the application example of the artificial intelligence, the effect thereof, and the like described in this embodiment can be implemented in combination with the description of another electronic device as appropriate.

The structures, methods, and the like described in this embodiment can be used in combination with the structures, methods, and the like described in other embodiments and other examples as appropriate.

[ example 1]

In this example, the results of manufacturing and analyzing samples 1A, 1B, and 1C having the structures shown in fig. 29 will be described.

The structure shown in fig. 29 includes a silicon substrate 10, a silicon oxide film 12 on the silicon substrate 10, a silicon oxynitride film 14 on the silicon oxide film 12, a silicon oxynitride film 18 on the silicon oxynitride film 14, and a silicon oxynitride film 20 on the silicon oxynitride film 18. Here, a nitride region 16 is formed in the vicinity of the interface with the silicon oxynitride film 18 in the silicon oxynitride film 14. In addition, the silicon oxynitride film 20 contains heavy hydrogen D. Note that the nitrided region 16 was not formed in sample 1A. In sample 1B and sample 1C, the nitrided region 16 is formed, but the method of forming the nitrided region 16 is different.

First, methods for producing samples 1A, 1B, and 1C will be described.

First, the silicon substrate 10 was thermally oxidized in the samples 1A, 1B, and 1C, and the silicon oxide film 12 having a target thickness of 100nm was formed on the surface of the silicon substrate 10.

Next, in samples 1A, 1B, and 1C, the silicon oxynitride film 14 having a target thickness of 150nm was formed by a PECVD method. SiH is used as a film forming gas₄Gas 5sccm and N₂O gas was 1000sccm, the film formation pressure was 133.3Pa, the film formation power was 45W (13.56MHz), the substrate temperature was 325 ℃, and the inter-electrode distance was 20 mm.

Next, the samples 1B and 1C were subjected to microwave treatment using a microwave treatment apparatus. In the microwave treatment, Ar gas 1000sccm and N was used as the treatment gas₂The gas was 200sccm, the pressure was 12Pa, the power was 1200W, and the treatment temperature was 400 ℃. Here, the processing time of sample 1B was 300 seconds, and the processing time of sample 1C was 1800 seconds. Thereby, the nitrided region 16 is formed in the vicinity of the surface of the silicon oxynitride film 14 of sample 1B and sample 1C. Note that, since the microwave treatment was not performed on the sample 1A, the nitrided region 16 was not formed in this sample.

Next, in sample 1A, sample 1B, and sample 1C, the silicon oxynitride film 18 having a target thickness of 50nm was formed under the same film formation conditions as those of the silicon oxynitride film 14.

Subsequently, PEC was used in samples 1A, 1B and 1CThe VD method forms the silicon oxynitride film 20 with a target thickness of 50 nm. SiH is used as a film forming gas₄Gas 2sccm, N₂O gas 800sccm and D₂The dilution gas was 200sccm, the film formation pressure was 200Pa, the film formation power was 150W (60MHz), the substrate temperature was 160 ℃, and the inter-electrode distance was 35 mm. Note that D₂The diluent gas being Ar gas-based D₂The gas is diluted to 5% gas.

For the manufactured samples 1A to 1C, "HD-2700" manufactured by Hitachi high tech Co., Ltd., Japan was used, and the imaging of the cross-sectional STEM image and the analysis by Energy Dispersive X-ray spectroscopy (EDX) were performed with the acceleration voltage set to 200 kV.

Fig. 30A to 30C show cross-sectional STEM images of the vicinity of the interface between the silicon oxynitride film 14 and the silicon oxynitride film 18 of samples 1A to 1C. As shown in fig. 30A, the nitrided region 16 was not observed in the vicinity of the interface of the silicon oxynitride film 14 of sample 1A that was not subjected to the microwave treatment. In contrast, in fig. 30B and 30C, the nitrided region 16 is observed in the vicinity of the interface between the silicon oxynitride films 14 of the samples 1B and 1C subjected to the microwave treatment. The thickness of the nitrided region 16 in sample 1B was about 1.7nm, and the thickness of the nitrided region 16 in sample 1C was about 1.8 nm. That is, the thickness of the nitrided region 16 is the same regardless of the time of the microwave treatment.

Next, fig. 31 shows EDX analysis results of the silicon oxynitride film 14(1A to 14) of sample 1A, the nitrided regions (1B to 16) of sample 1B, the silicon oxynitride film 14(1B to 14) of sample 1B, the nitrided regions (1C to 16) of sample 1C, and the silicon oxynitride film 14(1C to 14) of sample 1C. Fig. 31 is a bar graph showing the quantitative value of nitrogen [ atomic% ].

In sample 1B and sample 1C, the nitrogen concentration of the nitrided region 16 is higher than that of the silicon oxynitride film 14, and it is known that the surface of the silicon oxynitride film 14 is nitrided by the microwave treatment. This tendency is remarkably exhibited by sample 1C, which has a long microwave treatment time, as compared with sample 1B.

Next, samples 1D to 1F having the same structure as samples 1A to 1C and subjected to heat treatment at 400 ℃ for 1 hour under a nitrogen atmosphere were manufactured.

SIMS analysis was performed on the samples 1A to 1F thus produced to examine the diffusion of the heavy hydrogen D contained in the silicon oxynitride film 20. FIG. 32A shows the concentration [ atoms/cm ] of deuterium D in samples 1A and 1D³]FIG. 32B shows the concentration of deuterium D [ atoms/cm ] in samples 1B and 1E³]FIG. 32C shows the concentration [ atoms/cm ] of deuterium D in sample 1C and sample 1F³]. Note that SIMS analysis measurement is performed from the silicon substrate 10 side for samples 1A to 1F, and an adhesive is formed on the silicon oxynitride film 20. In addition, the broken line of the SIMS charts shown in fig. 32A to 32C indicates the measurement lower limit. The quantitative layers are a silicon oxynitride film 14, a silicon oxynitride film 18, and a silicon oxynitride film 20.

As shown in fig. 32A, in samples 1A and 1D, heavy hydrogen D diffuses into the silicon oxynitride film 14, and is particularly significant in sample 1D subjected to heat treatment. In contrast, as shown in fig. 32B and 32C, in sample 1B, sample 1C, sample 1E, and sample 1F, the concentration of heavy hydrogen D at the interface between silicon oxynitride film 18 and silicon oxynitride film 14, that is, in nitrided region 16, is significantly reduced. That is, it can be seen that the heavy hydrogen D contained in the silicon oxynitride film 20 is blocked by the nitrided region 16 in these samples.

As described above, by forming a nitrided region in the silicon oxynitride film by microwave treatment, a layer having a barrier property against hydrogen can be formed. By using such a layer as in the above embodiment mode, hydrogen diffusion into the oxide semiconductor can be reduced. In this manner, by using an oxide semiconductor in which impurities such as hydrogen are sufficiently reduced in a channel formation region of a transistor, a normally-on characteristic can be achieved, and reliability can be improved while stable electric characteristics can be provided.

[ example 2]

In this example, the results of measuring the resistivity of samples 2A to 2I each subjected to microwave treatment under a nitrogen-containing atmosphere for a tantalum nitride film formed on a silicon substrate are explained.

First, the methods for producing samples 2A to 2I are explained.

First, a silicon substrate was thermally oxidized in samples 2A to 2I, and a silicon oxide film having a target thickness of 100nm was formed on the surface of the silicon substrate.

Next, in samples 2A to 2I, a tantalum nitride film with a target thickness of 20nm was formed using a DC sputtering method. In the formation of the tantalum nitride film, a tantalum target was used, and as a film formation gas, 50sccm of argon gas and 10sccm of nitrogen gas were used, the film formation pressure was 0.6Pa, the film formation power was 1000W, the substrate temperature was room temperature, and the distance between the target and the substrate was 60 mm.

Next, samples 2B to 2I were subjected to microwave treatment using a microwave treatment apparatus. In the microwave treatment, Ar gas 1000sccm and N was used as the treatment gas₂The gas was 200sccm, the power was 1200W, and the process temperature was 400 ℃. Here, the pressure and the treatment time of the microwave treatment of samples 2B to 2I were set to the conditions shown in table 1 below.

[ Table 1]

2B

2C

2D

2E

2F

2G

2H

2I

Pressure of

12Pa

60Pa

133Pa

400Pa

667Pa

12Pa

12Pa

12Pa

Time of treatment

5 minutes

5 minutes

5 minutes

5 minutes

5 minutes

1 minute

10 minutes

30 minutes

Fig. 33A and 33B show the results of sheet resistance measurement of tantalum nitride films for the manufactured samples 2A to 2I. Fig. 33A is a graph comparing samples 2A to 2F having different pressure conditions with the treatment time fixed at 5 minutes, and fig. 33B is a graph comparing samples 2A, 2G, 2B, 2H, and 2I having different treatment time conditions with the pressure fixed at 12 Pa. The vertical axes of both FIG. 33A and FIG. 33B show the resistivity [ Ω cm ] ]. In addition, 2.0 × 10 in fig. 33A and 33B^-3A dashed line is drawn at Ω cm, which is a value that is a target value of the resistivity of the source electrode and the drain electrode of the transistor shown in the above embodiment.

As shown in fig. 33A, the resistivity was somewhat increased in samples 2B to 2F subjected to the microwave treatment as compared with sample 2A not subjected to the microwave treatment, but was approximately the same level. In addition, no pressure dependence of the microwave treatment of the resistivity was observed in samples 2B to 2F.

As shown in fig. 33B, samples 2G, 2B, 2H, and 2I subjected to microwave treatment tended to have higher resistivity with the passage of time. However, the resistivity ratios of samples 2G, 2B, 2H and 2I were 2.0X 10^-3Omega cm is much lower.

As described above, it is found that even when the source electrode and the drain electrode are subjected to microwave treatment when the nitrided region is formed in the silicon oxynitride film, the resistivity of tantalum nitride used as the source electrode and the drain electrode is not increased so much. By using such a conductive film as the source electrode and the drain electrode, it is not necessary to perform special post-treatment on the source electrode and the drain electrode after the nitride region is formed in the silicon oxynitride film, and thus the productivity of the semiconductor device can be improved.

[ example 3]

In this example, the results of manufacturing samples 3A to 3H having the structures shown in fig. 29 in example 1 and analyzing these samples are explained. The samples 3A to 3H are different from the samples 1A to 1F in the formation condition of the nitrided region 16.

The structure shown in fig. 29 includes a silicon substrate 10, a silicon oxide film 12 on the silicon substrate 10, a silicon oxynitride film 14 on the silicon oxide film 12, a silicon oxynitride film 18 on the silicon oxynitride film 14, and a silicon oxynitride film 20 on the silicon oxynitride film 18, similarly to embodiment 1. Here, a nitride region 16 is formed in the vicinity of the interface with the silicon oxynitride film 18 in the silicon oxynitride film 14. In addition, the silicon oxynitride film 20 contains heavy hydrogen D. Note that the nitrided region 16 was not formed in samples 3A and 3E. In samples 3B, 3C, 3D, 3F, 3G, and 3H, the nitrided region 16 is formed, but the conditions for forming the nitrided region 16 are different.

First, the methods for producing samples 3A to 3H are explained.

First, the silicon substrate 10 was thermally oxidized in samples 3A to 3H, and the silicon oxide film 12 having a target thickness of 100nm was formed on the surface of the silicon substrate 10.

Next, a silicon oxynitride film 14 having a target thickness of 150nm was formed in samples 3A to 3H by a PECVD method. SiH is used as a film forming gas ₄Gas 5sccm and N₂O gas of 1000sccm, film formation pressure of 133.3Pa,the film formation power was 45W (13.56MHz), the substrate temperature was 325 ℃ and the electrode-to-electrode distance was 20 mm.

Next, samples 3B, 3C, 3D, 3F, 3G, and 3H were subjected to microwave treatment using a microwave treatment apparatus. In the microwave treatment, Ar gas 1000sccm and N was used as the treatment gas₂The gas was at 200sccm, the power was 1200W, the process temperature was 400 deg.C, and the process time was 300 seconds. Here, the pressure of the samples 3B and 3F was 12Pa, the pressure of the samples 3C and 3G was 60Pa, and the pressure of the samples 3D and 3H was 400 Pa. Thereby, the nitrided region 16 is formed in the vicinity of the surface of the silicon oxynitride film 14 in sample 3B, sample 3C, sample 3D, sample 3F, sample 3G, and sample 3H. Note that, since the microwave treatment was not performed on samples 3A and 3E, the nitrided region 16 was not formed in the samples.

Next, in samples 3A to 3H, the silicon oxynitride film 18 having a target thickness of 50nm was formed under the same film formation conditions as the silicon oxynitride film 14.

Next, in samples 3A to 3H, the silicon oxynitride film 20 with a target thickness of 50nm was formed using the PECVD method. SiH is used as a film forming gas ₄Gas 2sccm, N₂O gas 800sccm and D₂The dilution gas was 200sccm, the film formation pressure was 200Pa, the film formation power was 150W (60MHz), the substrate temperature was 160 ℃, and the inter-electrode distance was 35 mm. D₂The diluent gas being Ar gas-based D₂The gas is diluted to 5% gas.

Subsequently, samples 3E, 3F, 3G and 3H were subjected to heat treatment at 400 ℃ for 8 hours under a nitrogen atmosphere.

SIMS analysis was performed on the samples 3A to 3H thus produced to examine the diffusion of the heavy hydrogen D contained in the silicon oxynitride film 20. FIG. 34A shows the concentration of deuterium D [ atoms/cm ] of samples 3A to 3D³]FIG. 34B shows the concentration of deuterium D [ atoms/cm ] of samples 3E to 3H³]. Note that SIMS analysis measurement was performed from the silicon substrate 10 side for samples 3A to 3H, and an adhesive was formed on the silicon oxynitride film 20. The broken line in the SIMS charts shown in fig. 34A and 34B indicates the lower limit of measurement. The quantitative layer is a silicon oxide film 12,Silicon oxynitride film 14, silicon oxynitride film 18, and silicon oxynitride film 20.

As shown in fig. 34A, in samples 3B to 3D in which high-temperature heat treatment was not performed for a long time, heavy hydrogen D contained in the silicon oxynitride film 20 was blocked by the nitrided region 16 without depending on the pressure of the microwave treatment. On the other hand, as shown in fig. 34B, in samples 3F to 3H in which high-temperature heat treatment was performed for a long time, heavy hydrogen D contained in the silicon oxynitride film 20 was blocked by the nitrided region 16 as compared with sample 3E in which the nitrided region 16 was not formed, but the hydrogen blocking property thereof had pressure dependency of the microwave treatment. That is, the diffusion of the deuterium D in the sample 3G at a pressure of 60Pa was suppressed as compared with the sample 3H at a pressure of 400Pa, and the diffusion of the deuterium D in the sample 3F at a pressure of 12Pa was suppressed as compared with the sample 3G at a pressure of 60 Pa.

As described above, by reducing the pressure at the time of microwave treatment and forming a nitrided region in the silicon oxynitride film, the barrier property against hydrogen can be improved. By using such a nitrided region as in the above embodiment, even if a high-temperature heat treatment is performed for a long time in the manufacturing process of the semiconductor device, hydrogen diffused into the oxide semiconductor can be reduced. In this manner, by using an oxide semiconductor in which impurities such as hydrogen are sufficiently reduced in a channel formation region of a transistor, a normally-on characteristic can be achieved, and reliability can be improved while stable electric characteristics can be provided.

[ example 4]

In this example, the results of manufacturing samples 4A and 4B having the structures shown in fig. 35 and analyzing these samples will be described.

The structure shown in fig. 35 includes a silicon substrate 30, a silicon oxide film 32 on the silicon substrate 30, a silicon oxide film 34 on the silicon oxide film 32, and a silicon nitride film 38 on the silicon oxide film 34. Here, in sample 4B, a nitride region 36 is formed in the silicon oxide film 34 in the vicinity of the interface with the silicon nitride film 38. Note that the nitrided region 36 was not formed in sample 4A.

First, the method for producing samples 4A and 4B will be described.

First, the silicon substrate 30 is thermally oxidized in the samples 4A and 4B, and the silicon oxide film 32 having a target thickness of 100nm is formed on the surface of the silicon substrate 30.

Next, in samples 4A and 4B, the silicon oxide film 34 with a target thickness of 100nm was formed by the RF sputtering method. SiO is used for forming the silicon oxide film 34₂(Anhydrous synthetic quartz) target. 50sccm of oxygen gas was used as a film forming gas, the film forming pressure was 0.7Pa (measured by a small vacuum gauge MG-2 manufactured by Canon-Annawa, Japan), the film forming power was 1500W, the substrate temperature was 170 ℃, and the distance between the target and the substrate was 60 mm.

Next, sample 4B was subjected to microwave treatment using a microwave treatment apparatus. In the microwave treatment, Ar gas 1000sccm and N was used as the treatment gas₂The gas was at 200sccm, the power was 1200W, the treatment temperature was 400 deg.C, the pressure was 12Pa, and the treatment time was 300 seconds. Thereby, a nitrided region 36 is formed in the vicinity of the surface of the silicon oxide film 34 of sample 4B. Note that, since the sample 4A was not subjected to the microwave treatment, the nitrided region 36 was not formed in this sample.

Next, in samples 4A and 4B, a silicon nitride film 38 with a target thickness of 20nm was formed by a PECVD method. SiH is used as a film forming gas₄Gas 5sccm and N₂The gas was 2500sccm, the film formation pressure was 100Pa, the film formation power was 250W (13.56MHz), the substrate temperature was 350 ℃, and the electrode-to-electrode distance was 20 mm. In this step, the samples 4A and 4B are exposed to a large amount of hydrogen generated in the process chamber.

SIMS analysis was performed on the thus-produced samples 4A and 4B to confirm whether or not hydrogen diffused into the silicon oxide film 34 when the silicon nitride film 38 was formed. FIG. 36 shows the concentrations of Hydrogen H [ atoms/cm ] of samples 4A and 4B³]. Note that in samples 4A and 4B, SIMS analysis measurement was performed from the silicon substrate 30 side, and a binder was formed on the silicon nitride film 38. In addition, the broken line of the SIMS chart shown in fig. 36 indicates the lower limit of measurement. The quantitative layer is a silicon oxide film 34.

As shown in fig. 36, in sample 4A, hydrogen H diffuses into the silicon oxide film 34. In contrast, in sample 4B, the concentration of hydrogen H in the interface between the silicon nitride film 38 and the silicon oxide film 34, i.e., the nitrided region 36, is significantly reduced. That is, it is found that hydrogen in the formation of the silicon nitride film 38 in sample 4B is reduced in the nitride region 36.

As described above, by forming the nitrided region by the microwave treatment, even if a film formation method such as a PECVD method in which a large amount of hydrogen is generated in the processing chamber in a state where the nitrided region is exposed is used, the hydrogen diffused into the inside of the nitrided region can be reduced. By using such a nitrided region as described above, hydrogen diffusion into the oxide semiconductor can be reduced. In this manner, by using an oxide semiconductor in which impurities such as hydrogen are sufficiently reduced in a channel formation region of a transistor, a normally-on characteristic can be achieved, and reliability can be improved while stable electric characteristics can be provided.

As described above, the structure, the method, and the like described in this embodiment can be used in combination with the structures, the methods, and the like described in other embodiments and other examples as appropriate.

[ description of symbols ]

200: transistor, 200 — n: transistor, 200_ 1: transistor, 205: conductor, 205 a: conductor, 205 b: conductor, 210: insulator, 212: insulator, 214: insulator, 216: insulator, 217: region, 218: conductor, 222: insulator, 224: insulator, 230: oxide, 230 a: oxide, 230A: oxide film, 230 b: oxide, 230B: oxide film, 230 c: oxide, 230C: oxide film, 240: conductor, 240 a: conductor, 240 b: conductor, 241: region, 241 a: region, 241 b: region, 241 c: region, 242: conductor, 242 a: conductor, 242A: conductive film, 242 b: conductor, 242B: conductor layer, 243: oxide, 243 a: oxide, 243A: oxide film, 243 b: oxide, 243B: oxide layer, 244: region, 244 a: region, 244 b: region, 245: region, 246: electrical conductor, 246 a: conductor, 246 b: conductor, 250: insulator, 250A: insulating film, 255 a: opening, 255 b: opening, 260: conductor, 260 a: conductor, 260 Aa: conductive film, 260 Ab: conductive film, 260 b: electrical conductor, 265: sealing portion, 265 a: sealing portion 265 b: sealing portion, 272: insulator, 272 a: insulator, 272A: insulating film, 272 b: insulator, 272B: insulator layer, 274: insulator, 280: insulator, 281: valve, 282: insulator, 283: insulator