阅读说明：本技术 半导体器件的制造方法、衬底处理装置及程序 (Method for manufacturing semiconductor device, substrate processing apparatus, and program ) 是由 出贝求 中谷公彦 芦原洋司 于 2018-07-17 设计创作，主要内容包括：提供能够选择性地在衬底上形成膜的技术。具有下述工序：在将在表面具有第1区域和与所述第1区域不同的第2区域的衬底的温度根据所述第1区域的组成进行调节的同时,向所述衬底供给具有有机配体的吸附控制剂,使所述第1区域有机封端的工序；和向所述衬底供给堆积气体,使膜选择生长于所述第2区域的工序。(Provided is a technique capable of selectively forming a film on a substrate. Comprises the following steps: supplying an adsorption control agent having an organic ligand to a substrate having a 1 st region and a 2 nd region different from the 1 st region on the surface thereof while adjusting the temperature of the substrate in accordance with the composition of the 1 st region, thereby organically capping the 1 st region; and supplying a deposition gas to the substrate to selectively grow a film in the 2 nd region.)

1. A method for manufacturing a semiconductor device, comprising the steps of:

supplying an adsorption control agent having an organic ligand to a substrate having a 1 st region and a 2 nd region different from the 1 st region on the surface thereof while adjusting the temperature of the substrate in accordance with the composition of the 1 st region, thereby organically capping the 1 st region; and

and supplying a deposition gas to the substrate to selectively grow a film in the 2 nd region.

2. The method for manufacturing a semiconductor device according to claim 1, wherein the organic ligand contains an alkyl group.

3. The method for manufacturing a semiconductor device according to claim 1, wherein the organic ligand is an alkylamine.

4. The method for manufacturing a semiconductor device according to claim 1, wherein the 1 st region is a silicon layer and a silicon oxide layer, and wherein the temperature of the substrate is adjusted so as to be 100 ℃ or higher and 250 ℃ or lower in the step of organically capping the 1 st region.

5. The method for manufacturing a semiconductor device according to claim 1, wherein the 1 st region is a silicon layer, the 2 nd region is a silicon oxide layer and a silicon nitride layer, and the temperature of the substrate is adjusted so as to be 300 ℃ to 500 ℃ in the step of organically capping the 1 st region.

6. The method for manufacturing a semiconductor device according to claim 1, wherein the ligand contained in the stacking gas and the organic ligand are each selected from electronegative ligands.

7. A method for manufacturing a semiconductor device, comprising the steps of:

a step of adjusting the temperature of a substrate having a 1 st region and a 2 nd region different from the 1 st region on the surface thereof in accordance with the composition of the 1 st region, and supplying a pretreatment gas having a ligand adsorbed to the 1 st region to the substrate without adsorbing the deposition gas, thereby adsorbing the ligand to the 1 st region; and

and supplying the deposition gas to the substrate to selectively grow a film only in the 2 nd region.

8. A method for manufacturing a semiconductor device, comprising the steps of:

supplying an adsorption control agent having an organic ligand to a substrate having a 1 st region and a 2 nd region different from the 1 st region on a surface thereof, and organically capping the 1 st region; and

supplying a deposition gas to the substrate to selectively grow a film in the 2 nd region,

in the method, in the step of organically capping the 1 st region, the type of the organic ligand is selected according to the composition of the 1 st region.

9. A substrate processing apparatus, comprising:

a processing chamber for accommodating a substrate;

a heating system that heats the processing chamber;

a 1 st gas supply system that supplies an adsorption control agent having an organic ligand to the process chamber;

a 2 nd gas supply system for supplying a deposition gas to the process chamber; and

a control unit configured to control the 1 st gas supply system, the 2 nd gas supply system, and the heating system to perform: a process of supplying the adsorption control agent to the process chamber housing a substrate having a 1 st domain and a 2 nd domain different from the 1 st domain on the surface thereof while adjusting the temperature of the process chamber according to the composition of the 1 st domain, thereby organically terminating the 1 st domain; and a process of supplying the deposition gas to the process chamber to selectively grow a film in the 2 nd region.

10. A program for causing a substrate processing apparatus to execute, by a computer, the steps of:

a step of supplying an adsorption control agent having an organic ligand to organically terminate the 1 st region while adjusting the temperature of a substrate, which is accommodated in a processing chamber of the substrate processing apparatus and has a 1 st region and a 2 nd region different from the 1 st region on the surface, according to the composition of the 1 st region; and

and supplying a deposition gas to the substrate to selectively grow a film in the 2 nd region.

Technical Field

The invention relates to a method for manufacturing a semiconductor device, a substrate processing apparatus and a program.

Background

Miniaturization of patterning technology has been progressing along with miniaturization of Large Scale Integrated circuits (hereinafter referred to as LSIs). As the patterning technique, for example, a hard mask or the like is used, but it is difficult to apply a method of dividing an etched region and a non-etched region by exposing a resist to light because of miniaturization of the patterning technique. Therefore, an epitaxial film of silicon (Si), silicon germanium (SiGe), or the like is selectively grown and formed on a substrate of a silicon (Si) wafer or the like (for example, see patent documents 1 and 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2003-100746

Patent document 2: japanese patent laid-open publication No. 2015-122481

Disclosure of Invention

Problems to be solved by the invention

An object of the present invention is to provide a technique capable of selectively forming a film on a substrate.

Means for solving the problems

According to one aspect of the present invention, there is provided a technique including the steps of:

supplying an adsorption control agent having an organic ligand to a substrate having a 1 st region and a 2 nd region different from the 1 st region on the surface thereof while adjusting the temperature of the substrate in accordance with the composition of the 1 st region, thereby organically capping the 1 st region; and

and supplying a deposition gas to the substrate to selectively grow a film in the 2 nd region.

Effects of the invention

According to the present invention, a film can be selectively formed on a substrate.

Drawings

Fig. 1 is a schematic vertical sectional view showing a processing furnace of a substrate processing apparatus according to an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view taken along line A-A of the treatment furnace shown in FIG. 1.

Fig. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus according to an embodiment of the present invention, and a control system of the controller is shown as a block diagram.

Fig. 4 is a diagram showing the timing of gas supply in the embodiment of the present invention.

FIG. 5 (A) shows the Si layer, SiN layer and SiO layer before exposure using HMDSN gas₂A model view of a condition of a wafer surface of a layer; (B) is a model diagram showing a state immediately after the wafer surface is exposed with HMDSN gas; (C) is a model diagram showing the wafer surface after exposure using HMDSN gas.

FIG. 6 (A) shows that TiCl has just been fed₄A model diagram of the state of the wafer surface after the gas treatment; (B) shows the use of TiCl₄A model view of the state of the wafer surface after gas exposure; (C) is to show that NH has just been supplied₃Model diagram of the wafer surface state after gassing.

FIG. 7 (A) shows the use of NH₃A model view of the state of the wafer surface after gas exposure; (B) the figure shows a wafer surface after a substrate processing step according to an embodiment of the present invention is performed.

Fig. 8 (a) is a model diagram showing a state immediately after the wafer surface is exposed with HMDSN gas; (B) is a model diagram showing the wafer surface after exposure of the wafer surface using HMDSN gas; (C) is a model diagram showing the wafer surface after (B) exposing the wafer surface with HMDSN gas.

FIG. 9 (A) shows the Si layer, SiN layer and SiO layer at a treatment temperature of 200 deg.C₂A graph showing the relationship between the number of film formation cycles of a TiN film formed on a layer and the film thickness; (B) is shown at a process temperature of 200 ℃ in the Si layer, SiN layer and SiO₂Model diagram of the state of the wafer surface after 100 cycles of the TiN film formed on the layer.

FIG. 10 (A) shows the Si layer, SiN layer and SiO layer at a processing temperature of 350 deg.C₂A graph showing the relationship between the number of film formation cycles of a TiN film formed on a layer and the film thickness; (B) is shown at a process temperature of 350 ℃ in the Si layer, SiN layer and SiO layer₂Model diagram of the state of the wafer surface after 100 cycles of the TiN film formed on the layer.

Detailed Description

Next, preferred embodiments of the present invention will be described.

Fig. 1 is a vertical sectional view of a substrate processing apparatus (hereinafter, simply referred to as a substrate processing apparatus 10) for carrying out a method for manufacturing a semiconductor device.

The following description will be made with reference to fig. 1 to 4. The substrate processing apparatus 10 is an example of an apparatus used in a manufacturing process of a semiconductor device. In the following description, a silicon (Si) layer, a silicon nitride (SiN) layer, and silicon oxide (SiO) layer are formed on the surface as a base film₂) A case where a titanium nitride (TiN) film is formed as a thin film on the wafer 200 of layers will be described.

(1) Constitution of substrate processing apparatus

The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as a heating means (heating mechanism, heating system). The heater 207 has a cylindrical shape and is vertically mounted by being supported by a heater base (not shown) as a holding plate.

An outer tube 203 constituting a reaction vessel (processing vessel) is disposed concentrically with the heater 207 inside the heater 207. The outer tube 203 is formed of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end. A manifold (inlet flange) 209 is disposed below the outer tube 203 concentrically with the outer tube 203. The manifold 209 is formed of a metal such as stainless steel (SUS), and is formed in a cylindrical shape with upper and lower ends open. An O-ring 220a as a sealing member is provided between the upper end of the manifold 209 and the outer tube 203. The manifold 209 is supported by the heater base, and the outer tube 203 is vertically assembled.

An inner tube 204 constituting a reaction vessel is disposed inside the outer tube 203. The inner tube 204 is made of, for example, quartz (SiO)₂) And silicon carbide (SiC), and is formed into a cylindrical shape with its upper end closed and its lower end open. The processing vessel (reaction vessel) is mainly composed of an outer tube 203, an inner tube 204, and a manifold 209. A processing chamber 201 is formed in a hollow portion of the processing container (inside the inner tube 204).

The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate in a horizontal posture and in a state of being arranged in a plurality of stages in a vertical direction by a boat 217 described later.

In the processing chamber 201, the nozzles 410, 420, and 430 are provided so as to penetrate the side wall of the manifold 209 and the inner tube 204. The nozzles 410, 420, and 430 are connected to gas supply pipes 310, 320, and 330, respectively. However, the treatment furnace 202 of the present embodiment is not limited to the above embodiment.

Mass Flow Controllers (MFCs) 312, 322, and 332 as flow rate controllers (flow rate control portions) are provided in the gas supply pipes 310, 320, and 330 in this order from the upstream side. Further, the gas supply pipes 310, 320, and 330 are provided with valves 314, 324, and 334, respectively, which are on/off valves. Gas supply pipes 510, 520, and 530 for supplying an inert gas are connected to the gas supply pipes 310, 320, and 330 on the downstream side of the valves 314, 324, and 334, respectively. MFCs 512, 522, and 532 serving as flow rate controllers (flow rate control units) and valves 514, 524, and 534 serving as on-off valves are provided in the gas supply pipes 510, 520, and 530 in this order from the upstream side.

Nozzles 410, 420, and 430 are coupled to the distal ends of the gas supply pipes 310, 320, and 330, respectively. The nozzles 410, 420, and 430 are L-shaped nozzles, and the horizontal portions thereof are provided so as to penetrate the side wall of the manifold 209 and the inner pipe 204. The vertical portions of the nozzles 410, 420, and 430 are provided inside the preliminary chamber 201a having a channel shape (groove shape) that protrudes radially outward from the inner tube 204 and extends in the vertical direction, and are provided in the preliminary chamber 201a so as to extend upward (upward in the arrangement direction of the wafers 200) along the inner wall of the inner tube 204.

The nozzles 410, 420, and 430 are provided to extend from a lower region of the process chamber 201 to an upper region of the process chamber 201, and a plurality of gas supply holes 410a, 420a, and 430a are provided at positions facing the wafer 200, respectively. Thereby, the process gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430, respectively. The plurality of gas supply holes 410a, 420a, and 430a are provided in the range from the lower portion to the upper portion of the inner tube 204, have the same opening area, and are further provided at the same opening pitch. However, the gas supply holes 410a, 420a, and 430a are not limited to the above-described embodiments. For example, the opening area may be gradually increased from the lower portion of the inner tube 204 toward the upper portion. This makes it possible to further uniformize the flow rates of the gases supplied from the gas supply holes 410a, 420a, and 430 a.

The gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 are provided in plural numbers at a height position from a lower portion to an upper portion of the boat 217, which will be described later. Therefore, the process gas supplied into the process chamber 201 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 is supplied over the entire range of the wafers 200 stored in the wafer boat 217 from the lower portion to the upper portion. The nozzles 410, 420, and 430 may be provided to extend from the lower region to the upper region of the process chamber 201, but are preferably provided to extend to the vicinity of the ceiling of the boat 217.

As the pretreatment gas, a treatment gas having an organic ligand is supplied from the gas supply pipe 310 into the treatment chamber 201 through the MFC312, the valve 314, and the nozzle 410. As the process gas having an organic ligand, a process gas (having an alkyl ligand) containing an alkyl group such as dialkylamine and having an alkylamine as a ligand can be used, and as an example thereof, a Hexamethyldisilazane (HMDSN) gas containing a methyl group can be used. The process gas having the organic ligand is used as an adsorption control agent (adsorption inhibitor) for controlling the film formation of the deposition gas supplied thereafter.

As a process gas, a source gas as a deposition gas is supplied from the gas supply pipe 320 into the process chamber 201 through the MFC322, the valve 324, and the nozzle 420. As the raw material gas, a Cl-containing gas containing chlorine (Cl) as a raw material molecule not adsorbed to the alkyl ligand and having an electronegative ligand such as halogen, etc. can be used, and titanium tetrachloride (TiCl) can be used as an example thereof₄) A gas.

As a process gas, a reaction gas that reacts with a source gas, which is a deposition gas, is supplied into the process chamber 201 through the MFC332, the valve 334, and the nozzle 430. As the reaction gas, for example, an N-containing gas containing nitrogen (N) can be used, and as an example thereof, ammonia (NH) can be used₃) A gas.

As an inert gas, from a gas supply pipe510. 520, 530 supply, for example, nitrogen (N) into the processing chamber 201 via the MFCs 512, 522, 532, valves 514, 524, 534, and nozzles 410, 420, 430, respectively₂) A gas. Hereinafter, N is used as the inert gas pair₂Examples of gases are illustrated, but as the inert gas, except for N₂In addition to the gas, a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas may be used.

The process gas supply system is mainly constituted by the gas supply pipes 310, 320, 330, the MFCs 312, 322, 332, the valves 314, 324, 334, and the nozzles 410, 420, 430, but only the nozzles 410, 420, 430 may be regarded as the process gas supply system. The process gas supply system may also be referred to simply as a gas supply system. When the adsorption control agent is flowed in from the gas supply pipe 310, the 1 st gas supply system for supplying the adsorption control agent having the organic ligand is mainly configured by the gas supply pipe 310, the MFC312, and the valve 314, but it is also conceivable that the nozzle 410 is included in the 1 st gas supply system. Further, the gas supply pipes 320 and 330, the MFCs 322 and 332, the valves 324 and 334, and the nozzles 420 and 430 constitute the 2 nd gas supply system for supplying the deposition gas, but only the nozzles 420 and 430 may be regarded as the 2 nd gas supply system. In the case where the source gas is introduced from the gas supply pipe 320, the source gas supply system is mainly constituted by the gas supply pipe 320, the MFC322, and the valve 324, but it is also conceivable to include the nozzle 420 in the source gas supply system. In addition, when the reaction gas is flowed from the gas supply pipe 330, the reaction gas supply system is mainly constituted by the gas supply pipe 330, the MFC332, and the valve 334, but it is also conceivable to include the nozzle 430 in the reaction gas supply system. When the nitrogen-containing gas is supplied as the reaction gas from the gas supply pipe 330, the reaction gas supply system may be referred to as a nitrogen-containing gas supply system. The gas supply pipes 510, 520, and 530, the MFCs 512, 522, and 532, and the valves 514, 524, and 534 constitute an inert gas supply system.

In the method of supplying gas in the present embodiment, gas is supplied through the nozzles 410, 420, and 430 disposed in the annular preliminary chamber 201a in the vertically long space defined by the inner wall of the inner tube 204 and the end portions of the plurality of wafers 200. Then, the gas is ejected into the inner pipe 204 from the plurality of gas supply holes 410a, 420a, and 430a provided at positions facing the wafer of the nozzles 410, 420, and 430. More specifically, the source gas and the like are ejected in a direction parallel to the surface of the wafer 200 through the gas supply holes 410a of the nozzle 410, the gas supply holes 420a of the nozzle 420, and the gas supply holes 430a of the nozzle 430.

The exhaust hole (exhaust port) 204a is a through hole formed in the side wall of the inner tube 204 at a position facing the nozzles 410, 420, and 430, and is, for example, a slit-shaped through hole elongated in the vertical direction. The gas supplied into the process chamber 201 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 and flowing on the surface of the wafer 200 flows into the exhaust passage 206 formed by the gap formed between the inner tube 204 and the outer tube 203 via the exhaust hole 204 a. The gas flowing into the exhaust passage 206 flows into the exhaust pipe 231 and is exhausted to the outside of the processing furnace 202.

The exhaust hole 204a is provided at a position facing the plurality of wafers 200, and the gas supplied from the gas supply holes 410a, 420a, and 430a into the processing chamber 201 in the vicinity of the wafers 200 flows in the horizontal direction and then flows into the exhaust passage 206 through the exhaust hole 204 a. The exhaust hole 204a is not limited to a slit-shaped through hole, and may be formed by a plurality of holes.

The manifold 209 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. A Pressure sensor 245 as a Pressure detector (Pressure detecting unit) for detecting the Pressure in the processing chamber 201, an APC (automatic Pressure Controller) valve 243, and a vacuum pump 246 as a vacuum exhaust device are connected to the exhaust pipe 231 in this order from the upstream side. The APC valve 243 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve in a state where the vacuum pump 246 is operated, and can adjust the pressure in the processing chamber 201 by adjusting the valve opening degree in a state where the vacuum pump 246 is operated. The exhaust system is mainly constituted by the exhaust hole 204a, the exhaust passage 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. It is also contemplated that the vacuum pump 246 may be included in the exhaust system.

A seal cap 219 serving as a furnace opening cover capable of hermetically sealing the lower end opening of the manifold 209 is provided below the manifold 209. The seal cap 219 is configured to abut against the lower end of the manifold 209 from the lower side in the vertical direction. The seal cap 219 is formed of a metal such as SUS, and is formed in a disk shape. An O-ring 220b as a sealing member is provided on the upper surface of the seal cap 219 to be in contact with the lower end of the manifold 209. A rotation mechanism 267 for rotating the boat 217 containing the wafers 200 is provided on the side of the seal cap 219 opposite to the process chamber 201. The rotary shaft 255 of the rotary mechanism 267 penetrates the seal cover 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically lifted by a boat lifter 115 as a lifting mechanism provided vertically outside the outer tube 203. The boat elevator 115 is configured to move the boat 217 into and out of the process chamber 201 by moving the seal cap 219 up and down. The boat elevator 115 is configured as a conveying device (conveying mechanism) that conveys the boat 217 and the wafers 200 contained in the boat 217 into and out of the processing chamber 201.

The boat 217 as a substrate support is configured such that a plurality of, for example, 25 to 200 wafers 200 are horizontally oriented and aligned with each other at intervals in the vertical direction. The boat 217 is made of a heat-resistant material such as quartz or SiC. A heat shield plate 218 made of a heat-resistant material such as quartz or SiC is supported in a horizontal posture at a lower portion of the boat 217 in a plurality of stages (not shown). With this configuration, heat from the heater 207 is less likely to be transmitted to the seal cap 219. However, the present embodiment is not limited to the above embodiment. For example, instead of providing the heat insulating plate 218 on the lower portion of the boat 217, a heat insulating cylinder formed as a cylindrical member made of a heat-resistant material such as quartz or SiC may be provided.

As shown in fig. 2, a temperature sensor 263 as a temperature detector is provided in the inner tube 204, and the amount of current to the heater 207 is adjusted based on temperature information detected by the temperature sensor 263, so that the temperature in the processing chamber 201 has a desired temperature distribution. The temperature sensor 263 is formed in an L-shape like the nozzles 410, 420, and 430, and is provided along the inner wall of the inner tube 204.

As shown in fig. 3, the controller 121 serving as a control unit (control means) is configured as a computer including a cpu (central Processing unit)121a, a RAM (Random Access Memory)121b, a storage device 121c, and an I/O port 121 d. The RAM121b, the storage device 121c, and the I/O port 121d are configured to be able to exchange data with the CPU121a via an internal bus. An input/output device 122 configured as a touch panel, for example, is connected to the controller 121.

The storage device 121c is configured by, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process procedure in which steps, conditions, and the like of a method for manufacturing a semiconductor device, which will be described later, are described is stored so as to be readable. The process steps are combined so that the controller 121 can perform each step (each step) in the method for manufacturing a semiconductor device described later to obtain a predetermined result, and function as a program. Hereinafter, the process, control program, and the like are also collectively referred to as a program. When the term "program" is used in the present specification, there are cases where only a process is included, only a control program is included, or a combination of a process and a control program is included. The RAM121b is configured as a memory area (work area) that temporarily holds programs, data, and the like read by the CPU121 a.

The I/O port 121d is connected to the MFCs 312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, the pressure sensor 245, the APC valve 243, the vacuum pump 246, the heater 207, the temperature sensor 263, the rotation mechanism 267, the boat elevator 115, and the like.

The CPU121a is configured to read and execute a control program from the storage device 121c, and read a process or the like from the storage device 121c in response to input of an operation command or the like from the input/output device 122. The CPU121a is configured to control flow rate adjustment operations of various gases by the MFCs 312, 322, 332, 512, 522, 532, opening and closing operations of the valves 314, 324, 334, 514, 524, 534, opening and closing operations of the APC valve 243, pressure adjustment operations by the pressure sensor 245 by the APC valve 243, temperature adjustment operations of the heater 207 by the temperature sensor 263, start and stop of the vacuum pump 246, rotation and rotation speed adjustment operations of the boat 217 by the rotation mechanism 267, lifting and lowering operations of the boat 217 by the boat lifter 115, accommodation operations of the wafers 200 into the boat 217, and the like, in accordance with the read contents of the process.

The controller 121 can be configured by installing the above-described program stored in the external storage device 123 (for example, a magnetic disk such as a magnetic tape, a flexible disk, and a hard disk, an optical disk such as a CD and a DVD, an optical magnetic disk such as an MO, a USB memory, and a semiconductor memory such as a memory card) into a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, the above members are also collectively referred to as a recording medium. In this specification, the recording medium may include only the storage device 121c, only the external storage device 123, or both of them. The program may be provided to the computer by using a communication means such as the internet or a dedicated line without using the external storage device 123.

(2) Substrate processing procedure

As one step of the manufacturing process of the semiconductor device (device), using fig. 4, a Si layer and SiO layer having a plurality of regions, for example, the 1 st region on the surface as the base film are treated₂An example of selectively growing a TiN film on a layer and a SiN layer on the wafer 200 as the SiN layer of the 2 nd region will be described. This process is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. In the following description, the operations of the respective parts constituting the substrate processing apparatus 10 are controlled by the controller 121.

The substrate processing step (semiconductor device manufacturing step) of the present embodiment includes the steps of:

a Si layer, a SiN layer and SiO layer on the surface₂Temperature of the layer wafer 200 depends on the Si layer and SiO₂While the composition of the layer is adjusted, HMDSN gas as an adsorption control agent having an organic ligand is supplied to the wafer 200 to form an Si layer and SiO₂A step of capping the layer with an organic cap; and

TiCl as a source gas is supplied to the wafer 200 as a deposition gas₄Gas and NH as reaction gas₃And a step of selectively growing a TiN film on the SiN layer by using a gas.

The Si layer and SiO layer are formed₂The process of organically capping the layers may also be performed a plurality of times, respectively. The Si layer and SiO layer are formed₂The process of organically capping the layer is referred to as pretreatment. The process of selectively growing a TiN film on the SiN layer is referred to as a film formation process.

When the term "wafer" is used in the present specification, the term "wafer" may be used to indicate a "wafer itself" or a "laminate of a wafer and a predetermined layer, film, or the like formed on the surface of the wafer". In the present specification, the term "surface of a wafer" is used, and there are cases where "surface of wafer" and "surface of a predetermined layer, film, or the like formed on a wafer" are indicated. The term "substrate" used in this specification is also the same as the term "wafer".

(wafer handling)

When a plurality of wafers 200 are loaded into the boat 217 (wafer loading), as shown in fig. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the process chamber 201 (boat loading). In this state, the seal cap 219 closes the lower end opening of the reaction tube 203 via the O-ring 220.

(pressure control and temperature control)

The processing chamber 201 is evacuated by a vacuum pump 246 to a desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and feedback control (pressure adjustment) of the APC valve 243 is performed based on the measured pressure information. The vacuum pump 246 is maintained in operation at least until the process for the wafer 200 is completed. In addition, the inside of the processing chamber 201 is heated by the heater 207 to a desired temperature. At this time, the amount of current supplied to the heater 207 is feedback-controlled (temperature-adjusted) based on the temperature information detected by the temperature sensor 263 so that a desired temperature distribution is achieved in the processing chamber 201. The heating in the processing chamber 201 by the heater 207 is continued at least until the processing for the wafer 200 is completed.

A. Organic end-capping procedure (pretreatment)

First, as a pretreatment, a Si layer and SiO layer are formed on the wafer 200₂Organic end caps are generated on the layers.

A-1: [ adsorption control agent supplying step ]

(HMDSN gas supply)

The valve 314 is opened to allow HMDSN gas as an adsorption control agent to flow into the gas supply pipe 310. The HMDSN gas is supplied into the process chamber 201 from the gas supply hole 410a of the nozzle 410 while being flow-regulated by the MFC312, and is exhausted from the exhaust pipe 231. HMDSN gas is supplied to the wafer 200 at this time. In parallel, valve 514 is opened, N₂An inert gas such as a gas flows into the gas supply pipe 510. N flowing in the gas supply pipe 510₂The gas is supplied into the processing chamber 201 together with the HMDSN gas by adjusting the flow rate of the gas by the MFC512, and is exhausted from the exhaust pipe 231. At this time, to prevent the HMDSN gas from entering the nozzles 420 and 430, the valves 524 and 534 are opened to allow N to enter₂The gas flows into the gas supply pipes 520, 530. N is a radical of₂The gas is supplied into the processing chamber 201 through the gas supply pipes 320 and 330 and the nozzles 420 and 430, and is exhausted from the exhaust pipe 231.

At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 10 to 1000 Pa. The supply flow rate of the HMDSN gas controlled by MFC312 is set to a flow rate in the range of, for example, 10 to 1000 sccm. N controlled by MFCs 512, 522, 532₂The supply flow rate of the gas is, for example, in the range of 20 to 2000 sccm. In this case, the temperature of the heater 207 is set so that the temperature of the wafer 200 is, for example, in the range of 100 to 250 ℃, preferably 150 to 250 ℃, and more preferably 180 to 220 ℃. In the present specification, the expression of a numerical range of "100 to 250 ℃ means that the lower limit value and the upper limit value are included in the range. Thus, "100 to 250 ℃ means" 100 ℃ to 250 ℃. Other numerical ranges are also the same.

That is, the temperature of the heater 207 at this time is such that the organic ligand contained in the HMDSN gas is adsorbed on the Si layer and the SiO layer₂On the layer without adsorbing on the SiN layer to make the Si layer and SiO layer₂Temperature of organic end-capping of the surface of the layer.

The gases flowing into the process chamber 201 are now HMDSN gas and N₂A gas. By supplying the HMDSN gas, the organic ligand contained in the HMDSN gas is mixed with the Si layer and SiO layer of the wafer 200₂The surface of the layer is bonded to effect organic end-capping.

Here, the Si layer and SiO layer on the wafer surface₂The types (compositions) of the layer and the SiN layer, and the temperature at which the adsorption-controlling agent starts to adsorb, desorb, and decompose are different. In particular, on the Si layer, and on SiO₂The adsorption-controlling agent is more easily adsorbed on the layer and the SiN layer, and the temperature at which the adsorption-controlling agent starts to be desorbed and decomposed is higher. In addition, it is in SiO₂On the layer, the adsorption-controlling agent is not adsorbed until 80 ℃ is reached, but adsorption is started from about 100 ℃. And, with the temperature rise, the adsorption rate is accelerated, and is fastest at about 200 ℃. However, when the temperature is increased to about 250 ℃, self-decomposition starts. That is, if the temperature is lower than 100 ℃, an Si layer and SiO layer are present₂When the layer does not adsorb the adsorption-controlling agent, the adsorption-controlling agent is self-decomposed at a temperature higher than 250 ℃ and the organic ligand (methyl group or the like) is at least separated from SiO₂Case of separation/detachment on a layer. That is, the Si layer and SiO layer are formed₂The surface of the layer is organically terminated, and the temperature of the heater 207 is adjusted so that the temperature of the wafer 200 is, for example, 100 to 250 ℃, preferably 180 to 220 ℃, and more preferably 190 to 210 ℃.

That is, by controlling the temperature of the wafer 200 when the adsorption control agent is exposed, the kind of the surface of the wafer 200 to which the organic ligand contained in the adsorption control agent is adsorbed can be made different, and film formation can be performed according to the kind of the surface of the wafer. That is, the type of the surface of the wafer 200 to be selectively grown can be controlled.

The organic ligand contained in the HMDSN gas is adsorbed on the Si layer to make the Si layerThe temperature of the surface organic end-capping is within the range of 100-500 ℃, preferably 150-400 ℃, and further preferably 180-350 ℃. In addition, organic ligands contained in the HMDSN gas adsorb to SiO₂On the layer to make SiO₂The temperature of the organic end-capping on the surface of the layer is 150 to 250 ℃, preferably 180 to 220 ℃, and further preferably 190 to 210 ℃.

After a predetermined time has elapsed after the start of the supply of the HMDSN gas, the valve 314 of the gas supply pipe 310 is closed to stop the supply of the HMDSN gas.

FIG. 5 shows such a Si layer and SiO₂The surface of the layer is organically terminated. FIG. 5 (A) shows the Si layer, SiN layer and SiO layer before exposure using HMDSN gas₂Fig. 5 (B) is a model diagram showing a state immediately after the surface of the wafer 200 is exposed by using HMDSN gas, and fig. 5 (C) is a model diagram showing a state after the surface of the wafer 200 is exposed by using HMDSN gas. In the diagrams shown in fig. 5 (B), 5 (C) and later, Me represents a methyl group (CH)₃)。

Referring to fig. 5 (B) and 5 (C), the surface of the wafer 200 exposed to the HMDSN gas is adsorbed on the Si layer and SiO on the surface by the HMDSN gas₂The H molecules on the layer bond with the N molecules of the HMDSN gas to form NH₃And is disengaged. And Si (Me) containing a methyl group as an organic ligand₃Adsorption after H molecule detachment, Si layer and SiO₂The surface of the layer is organically end-capped.

A-2: [ purging step ]

(residual gas removal)

Next, when the supply of the HMDSN gas is stopped, a purge process for exhausting the gas in the process chamber 201 is performed. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, and the inside of the process chamber 201 is evacuated by the vacuum pump 246 to remove unreacted HMDSN gas, Si layer, and SiO remaining in the process chamber 201₂HMDSN gas that has organically terminated the surface of the layer is exhausted from the process chamber 201. At this time, the valves 514, 524, 534 remain open, maintaining N₂Gas into the processing chamber 201And (4) supplying. N is a radical of₂The gas functions as a purge gas, and the effect of removing unreacted HMDSN gas remaining in the process chamber 201 or HMDSN gas from the process chamber 201 can be improved.

(number of execution times)

The cycle of sequentially performing the adsorption control agent supply step and the purge step is performed 1 or more times (predetermined number of times (n times)), thereby forming an Si layer and SiO layer on the wafer 200₂The surface of the layer is organically terminated.

In the pretreatment step, the HMDSN gas is supplied and exhausted alternately. If HMDSN gas and Si layer and SiO as base film₂By-products (for example, HMDSN) generated by the layer reaction remain on the wafer 200, and these by-products may prevent the Cl-containing gas contained in the source gas from reaching the SiN layer of the wafer 200. Therefore, such by-products are exhausted. This prevents adverse effects due to by-products.

B. Selective growth step (film formation treatment)

Next, the Si layer and SiO layer are formed by pretreatment₂The surface of the layer is organically capped and a TiN film is generated on the surface of the SiN layer on the wafer 200.

B-1: [ step 1 ]

(TiCl₄Gas supply)

The valve 324 was opened to let TiCl as the raw material gas₄The gas flows into the gas supply pipe 320. TiCl (titanium dioxide)₄The gas is supplied into the processing chamber 201 from the gas supply hole 420a of the nozzle 420 by adjusting the flow rate of the gas by the MFC322, and is exhausted from the exhaust pipe 231. At this time, TiCl is supplied to the wafer 200₄A gas. In parallel, valve 524 is opened, N₂An inert gas such as a gas flows into the gas supply pipe 520. N flowing in the gas supply pipe 520₂Gas flow regulation by MFC522 with TiCl₄The gases are supplied into the processing chamber 201 and exhausted from the exhaust pipe 231. At this time, to prevent TiCl₄Gas is introduced into the nozzles 410, 430, and the valves 514, 534 are opened to thereby control N₂The gas flows into the gas supply pipes 510, 530.N₂The gas is supplied into the processing chamber 201 through the gas supply pipes 310 and 330 and the nozzles 410 and 430, and is exhausted from the exhaust pipe 231.

At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, a pressure in the range of 10 to 1000Pa, for example, 50 Pa. TiCl controlled by MFC322₄The supply flow rate of the gas is, for example, in the range of 0.01 to 1 slm. N controlled by MFCs 512, 522, 532₂The supply flow rates of the gases are, for example, in the range of 0.1 to 2 slm. TiCl is supplied to the wafer 200₄The gas time is, for example, in the range of 0.1 to 100 seconds. In this case, the temperature of the heater 207 is set so that the temperature of the wafer 200 is, for example, in the range of 150 to 500 ℃, preferably 200 to 400 ℃, and more preferably 200 to 350 ℃.

The gas flowing into the processing chamber 201 is TiCl at this time₄Gas and N₂A gas. TiCl (titanium dioxide)₄The gas is not adsorbed on the Si layer and SiO blocked by organic on the surface in the pretreatment₂On the layer and adsorbed on the SiN layer. This is due to TiCl₄Halogen (Cl) contained in gas, Si layer and SiO₂The organic ligands on the layer are all electronegative ligands, and therefore, they become repulsive factors and are not easily adsorbed.

Here, when a thin film is selectively formed on a specific wafer surface, the raw material gas may be adsorbed on the wafer surface on which the film is not desired to be formed, and an undesired film formation may occur. This is a selective failure (the Japanese sky-gravity center disruption れ). This selective failure is likely to occur when the probability of adsorption of the source gas molecules to the wafer is high. That is, the reduction of the adsorption probability of the source gas molecules to the wafer on which film deposition is not desired is directly related to the improvement of the selectivity.

The adsorption of the source gas on the wafer surface is caused by the source gas staying on the wafer surface for a certain time due to the electrical interaction of the source molecules with the wafer surface. That is, the adsorption probability depends on both the exposure density of the source gas or its decomposition product to the wafer and the electrochemical factor possessed by the wafer itself. Here, the electrochemical factor possessed by the wafer itself means, for example, surface defects at an atomic level, and electrification due to polarization, an electric field, and the like in many cases. That is, it can be said that adsorption occurs easily if the electrochemical factor on the wafer surface and the source gas are in a relationship of being easily attracted to each other.

In a conventional semiconductor film formation process, a selective film formation process is realized by reducing the pressure of a source gas on the source gas side, increasing the gas flow rate, and the like to suppress as much as possible the stagnation thereof at a site where adsorption of the source gas onto a wafer is likely. However, as the surface area of semiconductor devices increases due to the progress of miniaturization and three-dimensionality, technological advances tend to increase the amount of exposure of the source gas to the wafer. In recent years, a method of obtaining high step coverage even for a fine pattern having a large surface area by alternately supplying gas has become the mainstream. That is, it is difficult to achieve the purpose of selective film formation by taking measures against the source gas side.

In addition, in the semiconductor device, Si, SiO are used₂Control of selective growth properties of various thin films such as a film, a SiN film, and a metal film, particularly, a SiO film (which is one of the most widely used materials) is useful for improving the margin and the degree of freedom in device processing.

Since the methyl group as the alkyl ligand contained in the HMDSN gas as the adsorption control agent in the present embodiment is electronegative, the raw material molecules are mutually repulsive and hardly bonded to each other if they are negativity. For example, adsorption on Si layer and SiO₂Methyl (Me-) on the layer with TiCl₄Halogens (Cl-) contained in the gas are negative to each other and are difficult to bond. That is, it can be said that the material having the alkyl ligand has selectivity controllability for halogen. Thereby, in the Si layer and SiO₂On the layer, the latency is longer, and the Si layer and SiO layer can be formed₂A TiN film is selectively grown on the surface of the SiN layer other than the layer. Here, the latency is a time until a film starts to grow on the wafer surface.

That is, the adsorption control agent is supplied before the deposition gas is supplied to the surface of the wafer 200, so that the growth of a thin film on the wafer 200, on which film deposition is not desired, can be suppressed. In other words, the adsorption control agent is adsorbed on the surface of the wafer 200, thereby inhibiting the surface adsorption of the raw material molecules contained in the raw material gas.

B-2: [ 2 nd step ]

(residual gas removal)

After the Ti containing layer is formed, the valve 324 is closed and TiCl is stopped₄And (3) supplying gas.

Then, the residual unreacted TiCl remaining in the processing chamber 201 or participating in the formation of the Ti-containing layer₄Gases and reaction by-products are exhausted from the processing chamber 201.

B-3: [ 3 rd step ]

(NH₃Gas supply)

After the residual gas in the processing chamber 201 is removed, the valve 334 is opened to make the gas NH as the reaction gas₃The gas flows into the gas supply pipe 330. NH (NH)₃The gas is supplied into the processing chamber 201 from the gas supply hole 430a of the nozzle 430 while being flow-regulated by the MFC332, and is exhausted from the exhaust pipe 231. At this time, NH is supplied to the wafer 200₃A gas. In parallel, valve 534 is opened, N₂The gas flows into the gas supply pipe 530. N flowing in the gas supply pipe 530₂The gas is flow regulated by MFC 532. N is a radical of₂Gas and NH₃The gases are supplied into the processing chamber 201 at a time and exhausted from the exhaust pipe 231. At this time, to prevent NH₃The gas enters the nozzles 410, 420, and the valves 514, 524 are opened to allow N to flow₂The gas flows into the gas supply pipes 510, 520. N is a radical of₂The gas is supplied into the processing chamber 201 through the gas supply pipes 310 and 320 and the nozzles 410 and 420, and is exhausted from the exhaust pipe 231.

At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 10 to 2000Pa, for example, 100 Pa. NH controlled by MFC332₃The supply flow rate of the gas is, for example, in the range of 0.1 to 2 slm. N controlled by MFCs 512, 522, 532₂The supply flow rates of the gases are, for example, in the range of 0.2 to 3 slm. NH supply to the wafer 200₃The gas time is, for example, in the range of 1 to 200 seconds. The temperature of the heater 207 at this time is set to be equal to TiCl₄The gas supply step is at the same temperature.

At this time, the gas flowing into the processing chamber 201 is only NH₃Gas and N₂A gas. NH (NH)₃The gas performs a substitution reaction with at least a part of the Ti-containing layer formed on the SiN layer of the wafer 200 in the above-described step 1. Ti and NH contained in the Ti-containing layer at the time of substitution reaction₃N contained in the gas bonds to form a TiN film containing Ti and N on the SiN layer on the wafer 200. I.e., the Si layer and SiO layer on the wafer 200₂No TiN film was formed on the layer.

B-4: [ 4 th step ]

(residual gas removal)

After the TiN film is formed, the valve 334 is closed to stop NH₃And (3) supplying gas.

Then, the remaining unreacted NH or NH participating in the formation of the TiN film in the processing chamber 201 is treated by the same process as the step 1₃Gases and reaction by-products are exhausted from the processing chamber 201.

Fig. 6 (a) to 6 (C) and 7 (a) show the case where such a TiN film is formed on the SiN layer. FIG. 6 (A) shows that TiCl has just been fed₄Model diagram of the wafer surface state after the gas treatment, and FIG. 6 (B) is a diagram showing the use of TiCl₄Model diagram of the state of the wafer surface after gas exposure, and (C) of FIG. 6 is a diagram showing the state immediately after NH is supplied₃Model diagram of the wafer surface state after gassing. FIG. 7 (A) shows the use of NH₃Model diagram of the state of the wafer surface after gas exposure.

Referring to FIG. 7A, on the surface of the wafer 200, the Si layer and SiO layer on the wafer 200₂The surface of the layer is capped with an organic ligand (organic capping). Further, a TiN film containing Ti and N was formed on the SiN layer surface on the wafer 200. That is, the Si layer and SiO layer were found₂The layer surface was organically end-capped without forming a TiN film.

(number of execution times)

In addition, TiCl is used as the raw material gas₄Gas and NH as reaction gas₃Gas is supplied alternately without mixing with each other, and the above-mentioned 1 st to 4 th steps are sequentially performedThe cycle is performed 1 or more times (predetermined number of times (n times)), and a TiN film having a predetermined thickness (for example, -nm) is formed on the SiN layer of the wafer 200 as shown in fig. 7 (B). Preferably, the above cycle is repeated a plurality of times.

In the above-described pretreatment, the configuration in which the adsorption-control-agent supply step (HMDSN gas supply) and the purge step (residual gas removal) are alternately performed a plurality of times by pulse supply was described, but the above-described film formation process may be performed in the process chamber 201 after the adsorption-control-agent supply step (HMDSN gas supply) and the purge step (residual gas removal) are continuously performed 1 time each in sequence in the process chamber 201.

(post purge and atmospheric pressure recovery)

N is supplied into the processing chamber 201 from the gas supply pipes 510, 520, 530, respectively₂And the gas is discharged from the gas discharge pipe 231. N is a radical of₂The gas functions as a purge gas, and thus the inside of the processing chamber 201 is purged with an inert gas, and the gas and by-products remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 (post-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure recovery).

(wafer carrying-out)

Thereafter, the sealing cap 219 is lowered by the boat elevator 115 to open the lower end of the reaction tube 203. The processed wafers 200 are carried out from the lower end of the reaction tube 203 to the outside of the reaction tube 203 (boat unloading) while being supported by the boat 217. After that, the processed wafer 200 is taken out from the boat 217 (wafer take-out).

(3) Effect of one embodiment of the invention

In this embodiment, first, HMDSN gas is supplied to the surface of the wafer 200 to expose the surface, thereby forming an Si layer and SiO layer₂Organic capping of the layers. Thus, the raw material molecules are adsorbed only on the SiN layer not subjected to the organic capping. That is, the Si layer and SiO adsorbed with the organic ligand contained in the HMDSN gas₂On the layer, adsorption of raw material molecules becomes difficult, and a TiN film can not be formed. In addition, the raw material molecules are adsorbed on HMDSN gasThe organic ligand contained in (1) can selectively grow a TiN film on the SiN layer not adsorbed by the organic ligand.

That is, by controlling the temperature of the wafer 200 when the adsorption control agent is exposed, the type of the surface of the wafer 200 to which the organic ligand contained in the adsorption control agent is adsorbed can be made different, and film formation can be performed according to the type of the surface of the wafer. That is, the type of the surface of the wafer 200 to be selectively grown can be controlled.

As a result, according to the present embodiment, a technique capable of forming a semiconductor device in which a film is selectively formed on the wafer 200 can be provided.

(4) Other embodiments

Next, another embodiment in which film formation is performed in accordance with the type of the wafer surface by controlling the temperature of the wafer 200 when exposed to the adsorption control agent will be described. Here, the Si layer as the 1 st region and SiO layer as the 2 nd region are provided on the surface as the base film₂SiO on wafer 200 of layers and SiN layers₂An example of selectively growing a TiN film on the layer and the SiN layer will be described.

The substrate processing step (semiconductor device manufacturing step) in the present embodiment includes the steps of:

a Si layer, a SiN layer and SiO layer on the surface₂A step of supplying HMDSN gas as an adsorption control agent having an organic ligand to the wafer 200 while adjusting the temperature of the wafer 200 of the layer in accordance with the composition of the Si layer, thereby organically capping the Si layer; and

TiCl as a source gas is supplied to the wafer 200 as a deposition gas₄Gas and NH as reaction gas₃Gas, allowing TiN film to selectively grow on SiO₂And a step of forming a layer and a SiN layer.

Fig. 8 shows a case where the surface of such a Si layer is organically end-capped. FIG. 8A shows a structure in which a Si layer, a SiN layer and SiO are formed₂A model diagram of the wafer 200 surface immediately after exposure using HMDSN gas, FIG. 8 (B) is a model diagram showing the wafer 200 surface after exposure using HMDSN gas, and FIG. 8 (C) is a model diagram showing the wafer 200 surface after exposure using HMD gasFig. 8 (B) is a schematic view showing the surface of the wafer 200 after SN gas exposure.

Referring to fig. 8 (a) and 8 (B), the HMDSN gas adsorbs on the Si layer and SiO on the surface of the wafer 200 exposed to the HMDSN gas₂The H molecules on the layer bond with the N molecules of the HMDSN gas to form NH₃And detached. And Si (Me) containing a methyl group as an organic ligand₃Adsorption after H molecule separation, so that the Si layer and SiO₂Organic end capping is carried out on the surface of the layer. However, it adsorbs to SiO at a temperature in the range of 300 to 500 deg.C₂Si (Me) on the layer₃Detachment/detachment from the surface as shown in fig. 8 (C). Alternatively, the organic ligand contained in the HMDSN gas is not adsorbed on the SiN layer and SiO from the beginning₂And (3) a layer. Thus, only SiO not organically capped₂The layer and the SiN layer adsorb raw material molecules. That is, adsorption of raw material molecules on the Si layer to which the organic ligand contained in the HMDSN gas is adsorbed is difficult, and it is possible to prevent formation of a TiN film. In addition, SiO which does not adsorb organic ligands contained in HMDSN gas₂On the layer and the SiN layer, the raw material molecules are adsorbed, so that the TiN film can be selectively grown.

That is, the temperature of the wafer 200 when exposed to the HMDSN gas in the present embodiment is such that the organic ligands contained in the HMDSN gas are adsorbed only to the Si layer and not to the SiO layer₂The temperature of the layer and the SiN layer at which only the surface of the Si layer is organically sealed is, for example, in the range of 300 to 500 ℃, preferably 300 to 400 ℃, and more preferably 330 to 350 ℃. If the temperature is lower than 300 ℃, organic ligands (methyl group and the like) contained in HMDSN gas remain adsorbed to SiO as well₂State of layer and SiO₂The case where the layer is difficult to adsorb the raw material molecules. If the temperature is higher than 500 ℃, there is a case where the organic ligand contained in the HMDSN gas is not adsorbed on SiO₂The layer is not adsorbed to the Si layer, or is detached/detached from the surface even if adsorbed.

That is, the substrate selectivity of adsorption of the adsorption-controlling agent can be changed by changing the temperature of the wafer when exposed to the adsorption-controlling agent, whereby the selection of film formation can be changedAnd (4) sex. For example, HMDSN gas is used as the adsorption control agent, and methyl groups contained in the HMDSN gas are adsorbed on the Si layer and SiO layer₂At a low wafer temperature (100 to 250 ℃) on the Si layer without adsorbing on the SiN layer, only the Si layer and SiO layer₂The layer and the SiN layer are formed on the SiN layer, and methyl contained in HMDSN gas is adsorbed only to Si but not to SiO₂The Si layer and SiO layer can be formed at a high wafer temperature (300 to 500 ℃ C.) of the layer and SiN₂SiO in layer and SiN layer₂A layer and a SiN layer are formed.

That is, as a pretreatment, the adsorption control agent is exposed to the surface of the wafer 200 to organically terminate the surface of the specific type of wafer 200. Thus, only the surface of the specific type of wafer 200 that is not subjected to the organic termination is adsorbed with the raw material molecules. Thus, adsorption of the raw material molecules on the surface of the specific type of wafer 200 having the adsorption control agent adsorbed thereon becomes difficult, and a film can be formed on the surface of the specific type of wafer 200 having the adsorption control agent adsorbed thereon. Further, the raw material molecules are adsorbed on the surface of the specific kind of wafer 200 not adsorbing the adsorption control agent, and selective growth can be performed on the surface of the specific kind of wafer 200 not adsorbing the adsorption control agent.

In the above embodiment, the case where the methyl group contained in the HMDSN gas as the adsorption control agent is used has been described, but the present invention is not limited to this case. The adsorption control agent may be any gas having an alkylamine in the ligand, and when the alkylamine is desired to be densely packed, a methyl group having a small ligand is more effective than other groups such as an ethyl group, and when the heat resistance is desired to be further improved, a ligand such as an ethyl group is large and is less volatile, and therefore, is more effective. Further, as the adsorption control agent, a composition containing an Si layer or SiO having an adsorption probability to the surface of the wafer 200 dependent on the adsorption probability is used₂A layer, a SiN layer, and the like.

That is, by changing the ligand having substrate selectivity of the adsorption control agent, the substrate selectivity at which the adsorption control agent is adsorbed can be changed, and thus the selectivity of film formation can be changed. For example, by incorporating an adsorption control agentThe ligand having substrate selectivity is dialkylamine, so that the adsorption control agent can be selectively adsorbed to SiO₂Layer and Si layer, thereby can be excluded from SiO₂Forming a film on the layer and the Si layer.

Similarly, in the above embodiment, the case where the TiN film is selectively grown by the deposition gas has been described, but the present invention is not limited to this case. The present invention can be similarly applied to the case of selectively growing a film type for forming a film at a low temperature, for example, an ultra-low temperature SiO film.

In the above embodiment, the case where the pretreatment as the organic capping step and the film formation treatment as the selective growth step are performed in 1 processing chamber 201 was described, but the present invention is not limited to this case. For example, the present invention can be similarly applied to a case where each process is performed in different process chambers using a cluster type apparatus having a plurality of process chambers. In this case, the transport system and the control unit may be shared. The present invention can be similarly applied to a case where each process is performed by a different substrate processing apparatus using a substrate processing system having a plurality of substrate processing apparatuses.

In the above-described embodiment, the case where the film is formed using the batch-type processing furnace that processes a plurality of wafers at a time has been described, but the present invention is not limited to this case. For example, the present invention can be similarly applied to the case of forming a film using a single-wafer processing furnace that processes 1 or several wafers at a time. The processing chambers included in the cluster tool and the substrate processing system may be all batch processing furnaces or all single-wafer processing furnaces, and the present invention can be similarly applied to a combination of both.

While various exemplary embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be appropriately combined and used.

(5) Examples of the embodiments

Next, the following description will be made based on fig. 9 and 10: in the form of a base filmRespectively forming a Si layer and SiO₂When a TiN film is formed on a wafer having a layer and a SiN layer by using the substrate processing apparatus 10 described above and the substrate processing step described in fig. 4, there is a difference in film thickness of the TiN film formed depending on the wafer temperature. Fig. 9 (a) and 9 (B) show the results of selective deposition of TiN films at a wafer temperature of 200 ℃, and fig. 10 (a) and 10 (B) show the results of selective deposition of TiN films at a wafer temperature of 350 ℃.

As shown in fig. 9 (a), it was confirmed that a TiN film was formed in accordance with the number of cycles immediately after the film formation treatment was started on the SiN layer at a wafer temperature of 200 ℃. On the other hand, it was confirmed that in SiO₂If the above-described film formation process is not repeated for 100 cycles or more, the TiN film shown in fig. 9 (B) cannot be formed on the layer and the Si layer. The reason for this is believed to be that at a wafer temperature of 200 deg.C, SiO occurs with less than 100 cycles₂The layer surface and the Si layer surface are organically end-capped, while the SiN layer is not organically end-capped. I.e. if in SiO₂Before starting film formation on the surface of the layer and the surface of the Si layer (in SiO)₂Before desorption and decomposition of the adsorption control agent occurs on the surface of the layer and the surface of the Si layer) the film formation process is terminated, so that a TiN film can be selectively formed on the SiN layer.

In addition, as shown in FIG. 10 (A), it was confirmed that SiO and SiN layers were present on the wafer at a wafer temperature of 350 ℃₂On the layer, a TiN film was formed in accordance with the number of cycles immediately after the start of the film formation process. On the other hand, it was confirmed that the TiN film shown in fig. 10 (B) was not formed on the Si layer unless the above-described film formation process was repeated for 100 cycles or more. The reason for this is believed to be that the Si layer surface is organically end-capped at a wafer temperature of 350 c before reaching around 100 cycles. That is, if the film formation process is stopped before the film formation on the surface of the Si layer is started (before the adsorption control agent on the surface of the Si layer starts to be desorbed and decomposed), the SiN layer and the SiO layer can be selectively formed on the SiN layer and the SiO layer₂A TiN film is formed on the layer.

From the above results, it is understood that the selectivity can be changed according to the film formation temperature by supplying the adsorption control agent before supplying the deposition gas to make the organic end capping of the surface of the base film.

Description of the reference numerals

10 substrate processing apparatus

121 controller

200 wafer (substrate)

201 processing chamber