阅读说明：本技术 功能元件和功能元件的制造方法以及电子设备 (Functional element, method for manufacturing functional element, and electronic device ) 是由 佐藤能久 米泽元 阿部昇平 高桥祐一 岛津武仁 鱼本幸 于 2018-12-26 设计创作，主要内容包括：根据本公开的实施例的功能元件包括：第一基板；第二基板,布置成与所述第一基板对置；以及缓冲层,设置在所述第一基板和所述第二基板之间,并且具有在层的厚度方向上变化的金属元素的浓度分布。(The functional elements according to embodiments of the present disclosure include: a first substrate; a second substrate disposed to be opposed to the first substrate; and a buffer layer provided between the first substrate and the second substrate and having a concentration distribution of a metal element that varies in a thickness direction of the layer.)

1. A functional element, comprising:

a first substrate;

a second substrate disposed to be opposed to the first substrate; and

a buffer layer provided between the first substrate and the second substrate, the buffer layer having a concentration distribution of a metal element in a layer thereof that varies in a film thickness direction.

2. The functional element according to claim 1, wherein the buffer layer has a concentration distribution of the metal element in a layer thereof that decreases toward an interface with the first substrate and with the second substrate.

3. The functional element according to claim 1, wherein the buffer layer has a concentration distribution of the metal element in a layer thereof that decreases from an interface with the first substrate toward an interface with the second substrate.

4. The functional element according to claim 1, wherein the buffer layer has optical transparency and electrical insulation.

5. The functional element according to claim 1, wherein the buffer layer comprises an oxygen supply material.

6. The functional element according to claim 1, wherein the buffer layer comprises at least any one of an inorganic oxide, an inorganic nitride, an inorganic oxynitride, and an inorganic fluoride.

7. The functional element according to claim 6, wherein the metal element has a higher ability to bind oxygen than a binding ability of the inorganic oxide, the inorganic nitride, the inorganic oxynitride, and the inorganic fluoride.

8. The functional element according to claim 1, further comprising a functional layer at least one of between the first substrate and the buffer layer and between the second substrate and the buffer layer.

9. A method of manufacturing a functional element, the method comprising

A first substrate and a second substrate are bonded, and a buffer layer having a concentration distribution of a metal element that varies in a film thickness direction in a layer thereof is formed between the first substrate and the second substrate.

10. The method for manufacturing a functional element according to claim 9, wherein

Forming a first metal film on the first substrate, the first metal film having a first buffer layer including at least any one of an inorganic oxide, an inorganic nitride, an inorganic oxynitride, and an inorganic fluoride, and a microcrystalline structure,

forming a second metal film on the second substrate, the second metal film having a second buffer layer and a microcrystalline structure, the second buffer layer including at least any one of an inorganic oxide, an inorganic nitride, an inorganic oxynitride, and an inorganic fluoride, and

forming the buffer layer by performing heat treatment after bonding the first metal film and the second metal film.

11. The manufacturing method of a functional element according to claim 10, wherein the first metal film and the second metal film are formed and bonded under vacuum conditions.

12. The manufacturing method of a functional element according to claim 11, wherein the first metal film and the second metal film are further formed and bonded in the same device.

13. The method of manufacturing a functional element according to claim 10, wherein the first metal film and the second metal film are oxidized by placing the bonded first substrate and second substrate in an environment of 100 ℃ or higher and 800 ℃ or lower as the heat treatment.

14. The method for manufacturing a functional element according to claim 9, wherein

Forming a first metal film on the first substrate, the first metal film having a first buffer layer including at least any one of an inorganic oxide, an inorganic nitride, an inorganic oxynitride, and an inorganic fluoride, and a microcrystalline structure,

forming a second metal film on the second substrate, the second metal film having a microcrystalline structure, an

Forming the buffer layer by performing heat treatment after bonding the first metal film and the second metal film.

15. An electronic device comprises

Functional element comprising

A first substrate having a first surface and a second surface,

a second substrate arranged to be opposed to the first substrate, an

A buffer layer provided between the first substrate and the second substrate, the buffer layer having a concentration distribution of a metal element in a layer thereof that varies in a film thickness direction.

Technical Field

The present disclosure relates to a functional element including, for example, two or more light-transmitting substrates stuck together, a manufacturing method thereof, and an electronic device including the functional element.

Background

In the case of bonding a light-transmitting substance, the following method is generally used: wherein these substances are stuck together with an adhesive comprising an acrylic polymer as a material, and then bonded by irradiating with ultraviolet rays. However, the cured adhesive is known to change its properties and deteriorate due to ultraviolet rays or the like. To cope with such a situation, for example, patent document 1 discloses a structure including two substances as members to be joined. By using the atomic diffusion bonding method, two substances are bonded without an adhesive.

CITATION LIST

Patent document

Patent document 1: japanese unexamined patent application publication No.2010-46696

Disclosure of Invention

Incidentally, the joining of the light-transmitting members to be joined requires high light-transmissivity of the joined portion in addition to resistance to deterioration of the joining between the members to be joined.

It is desirable to provide a functional element that makes it possible to improve reliability, a manufacturing method of the functional element, and an electronic apparatus including the functional element.

The functional elements according to embodiments of the present disclosure include: a first substrate; a second substrate disposed to be opposed to the first substrate; and a buffer layer disposed between the first substrate and the second substrate. The buffer layer has a concentration distribution of a metal element in its layer. The distribution varies in the film thickness direction.

A manufacturing method of a functional element according to an embodiment of the present disclosure includes: bonding the first substrate and the second substrate; and forming a buffer layer between the first substrate and the second substrate. The buffer layer has a concentration distribution of a metal element in its layer. The distribution varies in the film thickness direction.

An electronic device according to an embodiment of the present disclosure includes the above-described functional elements according to an embodiment of the present disclosure.

In the functional element according to the embodiment of the present disclosure and the manufacturing method of the functional element according to the embodiment and the electronic apparatus according to the embodiment, the first substrate and the second substrate are bonded across the buffer layer having the concentration distribution of the metal element in the layer thereof. The distribution varies in the film thickness direction. This allows the first substrate and the second substrate to be bonded without an adhesive, and makes it possible to improve the light transmittance of the bonded portion.

According to the functional element, the manufacturing method of the functional element, and the electronic apparatus according to the embodiments of the present disclosure, the first substrate and the second substrate are bonded across the buffer layer having the concentration distribution of the metal element in the layer thereof, thereby forming the bonding portion that does not include the adhesive and has high light transmittance. The distribution varies in the film thickness direction. Therefore, a functional element with high reliability can be provided.

It is to be noted that the effects described herein are not necessarily limited, but may include any of the effects described in the present disclosure.

Drawings

Fig. 1 is a schematic cross-sectional view of a configuration of functional elements according to an embodiment of the present disclosure.

Fig. 2 is a graph showing an example of a change in concentration of a metal element in the buffer layer shown in fig. 1.

Fig. 3 is a graph illustrating another example of a change in concentration of a metal element in the buffer layer illustrated in fig. 1.

Fig. 4A is a schematic cross-sectional view illustrating an example of a manufacturing method of the functional element illustrated in fig. 1.

Fig. 4B is a schematic sectional view showing a process subsequent to fig. 4A.

Fig. 4C is a schematic sectional view showing a process subsequent to fig. 4B.

Fig. 5A is a characteristic diagram showing the concentration distribution of the metal element in each layer shown in fig. 4C before the annealing treatment.

Fig. 5B is a characteristic diagram showing the concentration distribution of the metal element in each layer shown in fig. 4C after the annealing treatment.

Fig. 6A is a schematic cross-sectional view illustrating another example of the manufacturing method of the functional element illustrated in fig. 1.

Fig. 6B is a schematic sectional view showing a process subsequent to fig. 6A.

Fig. 6C is a schematic sectional view showing a process subsequent to fig. 6B.

Fig. 7A is a characteristic diagram showing the concentration distribution of the metal element in each layer shown in fig. 6C before the annealing treatment.

Fig. 7B is a characteristic diagram showing the concentration distribution of the metal element in each layer shown in fig. 6C after the annealing treatment.

Fig. 8 is a schematic cross-sectional view of the configuration of a functional element according to a modified example of the present disclosure.

Fig. 9 is a schematic sectional view showing an example of an application example.

Fig. 10 is a characteristic diagram showing a relationship between the transmittance of the joint portion and the thickness of the Ti film in each of experimental examples 1-1 and 1-2.

Fig. 11 is a characteristic diagram showing a relationship between the transmittance of the joint portion and the thickness of the Ti film in each of experimental examples 1-3 and 1-4.

Fig. 12 is a characteristic diagram showing a relationship between the strength of the joint and the thickness of the Ti film in each of experimental examples 1-1 and 1-2.

Fig. 13 is a characteristic diagram showing a relationship between the strength of the joint and the thickness of the Ti film in each of experimental examples 1-3 and 1-4.

Fig. 14 is a graph showing each spectral characteristic in experimental examples 2-1 and 2-2.

Detailed Description

Embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. The following description is a specific example of the present disclosure, but the present disclosure is not limited to the following modes. In addition, the present disclosure is not limited to the disposition, size ratio, etc. of the respective components shown in the drawings thereof. Note that the description is given in the following order.

1. Example (example of a buffer layer having a concentration distribution of a metal element varying in the film thickness direction in the layer thereof as a functional element of a junction)

1-1. arrangement of functional elements

1-2. method for manufacturing functional element

1-3. work and Effect

2. Modified example (example of functional element including functional layer between substrates arranged to be opposed to each other)

3. Application example

4. Working examples

<1. example >

Fig. 1 shows a sectional configuration of a functional element (functional element 1) according to an embodiment of the present disclosure. This functional element 1 has a stacked structure in which two or more members to be joined are stuck together, and is included in an optical element used in a projector or the like, for example (see fig. 9, for example). The functional element 1 according to the present embodiment has the following configuration: in which a substrate 11 (first substrate) and a substrate 21 (second substrate) are bonded across a buffer layer 12, the buffer layer 12 has a concentration distribution of a metal element that varies in the stacking direction (film thickness direction; e.g., Y-axis direction). The substrate 11 (first substrate) and the substrate 21 (second substrate) are members to be joined.

(1-1. configuration of functional element)

The substrates 11 and 21 are not particularly limited as long as the substrates 11 and 21 have flat bonding surfaces; for example, the substrate 11 and the substrate 21 each include an inorganic material, a metal material, a plastic material, or some other material. Examples of the inorganic material include silicon (Si), silicon oxide (SiO)_x) Silicon nitride (SiN)_x) Aluminum oxide (AlO)_x) YAG (yttrium aluminum garnet), silicon carbide (SiC), diamond, and the like. Examples of silicon oxide include glass, spin-on glass (SOG), and the like. Examples of the metal material include aluminum (Al), nickel (Ni), stainless steel, and the like. Examples of the plastic material include Polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), and the like. The substrate 11 and the substrate 21 may be light-transmissive substrates, or may be non-light-transmissive substrates. Examples of the light-transmitting substrate include a glass or quartz substrate and the like.

Preferably, the bonding surfaces of the substrate 11 and the substrate 21 have smoothness. Specifically, the bonding surface between the substrate 11 and the substrate 21 preferably has an arithmetic average roughness (Ra) of, for example, 0.5nm or less; however, for example, in the case of an inorganic material in which it is difficult to plastically deform and closely adhere the joining surfaces by applying pressure at the time of joining, the joining surfaces of the substrate 11 and the substrate 21 only have to have an arithmetic average roughness (Ra) of, for example, 1nm or less.

The buffer layer 12 is a bonding portion that bonds the substrate 11 and the substrate 21, and as described above, the buffer layer 12 has, in its layer, a concentration distribution of a metal element that varies in the film thickness direction (Y-axis direction). For example, the buffer layer 12 has the following configuration: wherein oxygen supply layers (oxygen supply layers 13 and 22) each containing an oxygen supply material are provided on both the substrate 11 side and the substrate 21 side across the oxide layer of the metal material (metal oxide layer). The metal oxide layer is formed, for example, by oxidation of the metal films 14 and 23, which will be described later, by oxygen supplied from the oxygen supply layers 13 and 22. The concentration distribution of the above-described metal element is formed between the metal oxide layer and the oxygen supply layers 13 and 22.

Fig. 2 shows an example of the change in the concentration of the metal element in the buffer layer 12. In fig. 2, the horizontal axis indicates the position in the film thickness direction in the buffer layer 12; for example, Y₀Represents an interface with the substrate 11, and Y₁Showing the interface with the substrate 21. The vertical axis indicates the concentration of the metal element in the buffer layer 12. For example, as shown in fig. 2, the buffer layer 12 has, for example, a concentration distribution that continuously decreases within a predetermined range from the inside of the buffer layer 12 toward the interface with the substrate 11 and the substrate 21.

Further, the concentration distribution of the metal element in the buffer layer 12 is not limited thereto. For example, although details are described later, the buffer layer 12 may have an oxygen supply layer containing an oxygen supply material formed only on one side (for example, on the substrate 21 side) of one of the substrates arranged to oppose each other. In this case, in the buffer layer 12, as shown in fig. 3, a concentration distribution is formed that continuously decreases, for example, within a predetermined range from the substrate 11 side toward the substrate 21, for example. The concentration distribution of the metal element in the buffer layer 12 shown in fig. 2 and 3 is formed in a process of bonding the substrate 11 and the substrate 21 described later.

Examples of the metal material contained In the buffer layer 12 include aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), indium (In), tin (Sn), hafnium (Hf), tantalum (Ta), and the like. The above-described metal materials are metal elements each forming the above-described concentration distribution in the buffer layer 12, and are used as materials of metal films 14 and 23 which will be described later. That is, the metal element forming the concentration distribution in the buffer layer 12 is derived from the metal films 14 and 23.

The oxygen supplying material contained in the buffer layer 12 may be any material as long as it allows the metal films 14 and 23 to be oxidized after the metal film 14 and the metal film 23, which will be described later, are bonded. As such a material, for example, an inorganic material or a metal material chemically bonded to oxygen can be used. Further, a material that allows oxygen to be physically adsorbed and contained in the voids formed by the grain boundaries or the like in the oxygen supply layers 13 and 22 may be used. As the oxygen supplying material, either material is preferably a material having a lower ability to bind oxygen than each of the metal materials used as the metal films 14 and 23. Examples of the oxygen supplying material include inorganic oxides (e.g., SiO)_x) Metal oxide (e.g., aluminum oxide (Al)₂O₃) Inorganic nitrides (e.g., SiN), inorganic oxynitrides (e.g., SiON), inorganic fluorides (e.g., SiF)_x) And the like.

Here, the ability to bind oxygen is defined as follows. For example, titanium (Ti) is used as the metal material contained in the metal films 14 and 23In the case of the material, the oxygen binding capacity of each metal material contained in the metal films 14 and 23 is the capacity to chemically bind titanium atoms to oxygen atoms. In addition, silicon oxide (SiO)₂) In the case of using as the oxygen supplying material, the oxygen binding ability of the oxygen supplying material includes the ability to chemically bind silicon atoms to oxygen atoms and the ability to chemically bind silicon oxide (SiO)₂) The ability to bind to non-covalent, trapped oxygen. It is noted that non-covalent, captured oxygen includes oxygen captured by water and oxygen captured in the membrane.

It is to be noted that the metal material and the oxygen supplying material may be crystalline solids, or may be glassy solids (amorphous solids).

The buffer layer 12 preferably has optical transparency in the case where the functional element 1 is used as an optical element such as a polarization conversion element in, for example, an optical device or some other device, and the buffer layer 12 preferably has electrical insulation in the case where the functional element 1 is used in, for example, an electrical device such as MEMS. In this case, as the metal material and the oxygen supplying material contained in the buffer layer 12, materials each having high light transmittance or materials each having high electrical insulation are preferably used. In the present embodiment, as described above, a part or all of the metal material contained in the buffer layer 12 is oxidized by oxygen supplied from the oxygen supply layers 13 and 22 and becomes an oxide, and constitutes a metal oxide layer. This increases the light transmittance and electrical insulation of the buffer layer 12.

(1-2. method for producing functional element)

Such a functional element 1 can be manufactured, for example, in the following manner.

First, as shown in fig. 4A, the oxygen supplying layer 13 (first buffer layer) having a thickness of, for example, 2nm or more and 20 μm or less is formed on the bonding surface of the substrate 11 using, for example, a vacuum deposition method using an electron beam. It is to be noted that, in addition to the vacuum Deposition method, an Ion Assisted Deposition (IAD) method, a sputtering method, an Ion plating method, a Chemical Vapor Deposition (CVD) method, or the like may be used for forming the oxygen supplying layer 13. Then, a metal film (first metal film) 14 having a microcrystalline structure is formed on the oxygen supply layer 13.

The oxygen supplying layer 13 contains the oxygen supplying material described above. As described above, the oxygen supplying layer 13 is preferably formed to have a thickness of, for example, 2nm or more and 20 μm or less; however, the thickness of the oxygen supply layer 13 is not limited thereto. For example, if the surface roughness of the oxygen supplying layer 13 is reduced by, for example, mirror polishing, the oxygen supplying layer 13 having a thickness of 20 μm or more can be formed.

The metal film 14 has a microcrystalline structure, and contains the above-described metal material or semimetal material. The metal film 14 preferably has a thickness that allows oxygen generated by the oxygen supply layer 13 to sufficiently oxidize the metal material contained in the metal film 14, and is desirably sufficiently thinner than the oxygen supply layer 13. In the present embodiment, as described later, the substrate 11 and the substrate 21 are bonded with the metal film 14 and the metal film 23 overlapped using an atomic diffusion bonding method. At this time, if the respective surfaces of the oxygen supplying layers 13 and 22 are smooth, bonding can be performed although the metal films 14 and 23 each have a thickness of an ultra-thin film of, for example, 0.2 nm. Meanwhile, in the case where each of the oxygen supply layers 13 and 22 has a high surface roughness, or in the case where an oxidation reaction layer is formed at each interface between the metal films 14 and 23 and the oxygen supply layers 13 and 22 when the metal films 14 and 23 are formed, it is necessary to make the metal films 14 and 22 thicker. However, the bonding strength increases as the oxidation of the metal film proceeds. In addition, the thickness of the metal films 14 and 23 is important for imparting light transmissivity and insulation to the buffer layer 12. Therefore, the metal film 14 is preferably thin and, for example, 0.2nm or more and 10nm or less.

The metal film 14 is formed, for example, using the following method first, for example, at 1 × 10 having a high degree of vacuum^-4To 1 × 10^-8In the vacuum chamber of extreme vacuum of Pa, for example, a Ti film having a thickness of, for example, 0.2nm or more and 10nm or less is formed using a Physical Vapor Deposition (PVD) method such as a sputtering method or an ion plating method, a CVD method, or any of various Vapor Deposition methods. It is to be noted that, in the case of using a metal material having a relatively low diffusion rate, it is preferable to perform film formation using a vacuum film formation method or a sputtering method in which formation is made so that the shape can be increasedThe film formation is performed under the plasma of the internal stress of the formed metal film 14.

The pressure in the vacuum chamber at the time of forming the metal film 14 only has to be a limiting vacuum of 1 × 10^-4To 1 × 10^-8A vacuum atmosphere of Pa; however, a lower pressure (higher vacuum) is more preferable. This makes it possible, for example, to use a material that is easily oxidized, such as Al.

In the case of forming the metal film 14 by a sputtering method, the pressure of an inert gas (usually argon (Ar)) at the time of film formation is preferably a dischargeable region (for example, 0.01Pa or more). However, since there is a possibility that the bonding may not be performed at a pressure exceeding 30Pa (300 μ bar), it is preferable to set the upper limit to 30Pa (300 μ bar) or less. This is because an increase in Ar gas pressure increases the surface roughness of the metal film 14 to be formed.

Then, similarly to the above-described method, the oxygen supplying layer 22 and the metal film 23 are sequentially formed on the substrate 21. The oxygen supplying layer 22 and the metal film 23 contain the oxygen supplying material and the metal material, respectively, as in the oxygen supplying layer 13 and the metal film 14 described above.

Note that the oxygen supplying layers 13 and 22 may be formed in different devices; however, it is desirable to form the metal films 14 and 23 under vacuum conditions in the same apparatus and bond the metal film 14 to the metal film 23 as described later. This reduces oxidation of the surfaces of the metal films 14 and 23, and thus enables good bonding to be achieved.

Then, as shown in fig. 4B, the metal film 14 provided on the substrate 11 and the metal film 23 provided on the substrate 21 are arranged to be opposed to each other, and as shown in fig. 4C, the substrate 11 and the substrate 21 are bonded with the metal film 14 and the metal film 23 overlapped using, for example, an atomic diffusion bonding method. This allows atomic diffusion to occur at the bonding interface between the metal film 14 and the metal film 23 and the grain boundary, and allows strain relaxation bonding.

Finally, the bonded substrates 11 and 21 are placed as an annealing treatment in an environment of, for example, 100 ℃ or higher and 800 ℃ or lower. This forms the buffer layer 12 having the concentration distribution of the metal element in its layer between the substrate 11 and the substrate 21. As described above, the functional element 1 shown in fig. 1 is completed.

Note that the annealing treatment may be performed under the same conditions as those for the formation of the metal films 14 and 23 and the bonding of the metal film 14 and the metal film 23, or may be performed in an atmosphere outside the apparatus, for example. Further, 100 ℃ which is the temperature of the lower limit of the annealing treatment is an example of a temperature equal to or higher than the ambient temperature in which the functional element 1 is used. The 800 ℃ temperature, which is the upper limit of the annealing treatment, is based on the softening point of the optical glass and the melting point of the light metal used in the substrates 11 and 21 and the oxygen supplying layers 13 and 22 in the case where the functional element 1 is used as an optical element. Therefore, the temperature of the annealing treatment is not limited to the above range; for example, when a metal oxide film which is stable even in the range of the ambient temperature in which the functional element 1 is used is formed, the treatment at 100 ℃ or lower is preferable. For example, in the case of joining the low melting point glasses having a thermal expansion coefficient or the substrates 11 and 21, the annealing treatment is preferably performed in an environment of, for example, 300 ℃ or less, and more preferably, the annealing treatment is performed, for example, 100 ℃ or less. For example, depending on the film formation process and the film formation material, placing the metal films 14 and 23 at normal temperature enables oxidation. In addition, decreasing the density of the oxygen donor layers 13 and 22 to increase the voids in the layers increases the amount of water that is physically adsorbed. This results in supplying more oxygen from the oxygen supply layer, accelerating the oxidation of the metal films 14 and 23 at normal temperature.

The concentration distribution of the metal element in the layer of the buffer layer 12 is formed as follows. Fig. 5A shows the concentration distribution of the metal element in each layer shown in fig. 4C before the annealing treatment. Fig. 5B shows the concentration distribution of the metal element in each layer shown in fig. 4C after the annealing treatment. In the functional element 1 in which the metal film 14 and the metal film 23 are bonded using the atomic diffusion bonding method, oxygen is diffused from the oxygen supply layer 13 and the oxygen supply layer 22 to the metal film 14 and the metal film 23 by the annealing treatment, and the metal material contained in the metal films 14 and 23 is oxidized, which forms a metal oxide layer. This forms a transparent bonding interface having electrical insulation between the substrate 11 and the substrate 21. At this time, in the metal films 14 and 23, metal atoms are oxidized, and this allows oxygen atoms to enter between the metal atoms. This increases the distance between metal atoms and decreases the density of the metal element per unit volume. Therefore, as shown in fig. 5B, the distribution width of the metal element increases from the metal films 14 and 23 toward the oxygen supplying layers 13 and 22. As described above, the concentration of the metal element in the layer of the buffer layer 12 between the substrate 11 and the substrate 21 changes from fig. 5A to fig. 5B, and a concentration distribution of the metal element that continuously decreases toward each interface with the substrate 11 and the substrate 21, for example, as shown in fig. 2, is formed in the layer of the buffer layer 12.

Note that, in the case where the annealing treatment is performed at a higher temperature, the interdiffusion between the metal oxide layer and the oxygen supply layers 13 and 22 is further accelerated; however, the metal atoms in the metal oxide are less likely to move, and therefore a concentration distribution of the metal element is formed in the buffer layer 12.

Further, the concentration distribution of the metal element in the buffer layer 12 can be observed by, for example, an Energy Dispersive X-ray analysis (EDX) method, an Electron Energy Loss Spectroscopy (EELS) method, a Secondary Ion Mass Spectroscopy (SUMS) method, TOF-SIMS analysis, or the like.

Furthermore, the functional element 1 can be manufactured, for example, in the following manner. In the above manufacturing method, an example is given in which the oxygen supplying layers 13 and 22 are provided on both the substrate 11 and the substrate 21; however, only one substrate may be provided with an oxygen supplying layer to join the two substrates.

First, as shown in fig. 6A, for example, the oxygen supplying layer 22 is formed on the bonding surface of the substrate 21. Then, a metal film 23 having a microcrystalline structure is formed on the oxygen supply layer 22. A metal film 14 is directly formed on the bonding surface of the substrate 11 in a vacuum atmosphere.

Then, as shown in fig. 6B, the surface of the substrate 21 on which the oxygen supply layer 22 and the metal film 23 are formed and the surface of the substrate 11 on which the metal film 14 is formed are arranged to be opposed to each other, and as shown in fig. 6C, the substrate 11 and the substrate 21 are bonded with the metal film 14 and the metal film 23 overlapped using, for example, an atomic diffusion bonding method.

Finally, the bonded substrates 11 and 21 are placed as an annealing treatment in an environment of, for example, 100 ℃ or higher and 800 ℃ or lower. This forms the buffer layer 12 having the concentration distribution of the metal element in its layer between the substrate 11 and the substrate 21. As described above, the functional element 1 shown in fig. 1 is completed.

As described above, in the case where the oxygen supplying layer is formed only on one substrate, as shown in fig. 7A (before the annealing treatment) and fig. 7B (after the annealing treatment), the concentration distribution of the metal element in each layer changes before and after the annealing treatment, and the concentration distribution of the metal element that continuously decreases from the substrate 11 side toward the substrate 21 as shown in fig. 3, for example, is formed in the layer of the buffer layer 12.

Note that the metal films 14 and 23 may be bonded using a method other than the above-described atomic diffusion bonding method. For example, in the case where a metal film is formed in advance on one or both surfaces of two substrates arranged to oppose each other, activation of the surface of the previously formed metal film by, for example, plasma etching or the like in a vacuum chamber makes it possible to bond the metal film to another metal film. Further, as a process of accelerating the oxidation of the metal films 14 and 23, laser or electromagnetic heating may be used, and local heating may be possible.

(1-3. work and Effect)

As described above, the light transmitting substance is generally bonded using an adhesive including an acrylic polymer as a material. However, the cured adhesive is known to change its properties and deteriorate due to ultraviolet rays or the like. Particularly in the case where the members to be joined are used as optical components, for example, the adhesive may deteriorate due to high-luminance light output from the light source section, and thus a technique of joining the members to be joined without the adhesive is required.

As a method of joining members to be joined without an adhesive, for example, there are frit joining and fusion joining. However, the joining strength is low in the frit bonding, and high-temperature heat treatment is performed in the fusion bonding; unfortunately, this is difficult to achieve in industrial terms. In contrast, the atomic diffusion bonding method is a technique of forming thin metal microcrystalline films on respective surfaces of two substrates to be bonded and bringing the metal microcrystalline films into contact with each other to bond the two substrates at room temperature. At the interface between the metal microcrystal films in contact with each other, atomic diffusion (atomic rearrangement) occurs due to the large surface energy on the metal surface and the high atomic diffusion capability of the metal microcrystal film, thereby bonding the substrates.

The atomic diffusion bonding method is allowed to be even about a fewThe thin metal films of (a) join substrates each containing any material at room temperature. Therefore, the transparent substrates can be bonded while maintaining the light transmittance of the transparent substrates; unfortunately, however, the light transmittance is reduced due to the metal film used for bonding. In addition, the use is about a fewIn the case of joining substrates with a thin metal film of (2), some electrical insulation can be imparted to the joining interface, but unfortunately, electrical conductivity is slightly maintained due to the residual metal.

In general, many metal oxides have high light transmittance and insulation properties. Therefore, if the metal film for bonding can be oxidized after bonding, a bonding interface having high light transmittance and insulation can be realized.

To cope with this, in the present embodiment, an oxygen supply layer (for example, the oxygen supply layer 13) is formed on at least one of the substrate 11 or the substrate 21, and a metal film (metal films 14 and 23) having a microcrystalline structure is formed on each of the substrates 11 and 21. The substrate 11 and the substrate 21 are bonded using an atomic diffusion bonding method, and then the substrate 11 and the substrate 21 are heated at a low temperature (for example, 100 ℃ or higher and 800 ℃ or lower). Therefore, the annealing treatment after the bonding moves oxygen from the oxygen supply layer to the metal film, and oxidizes the metal film. This increases the transparency of the bonding interface and eliminates the conductivity of the bonding interface. That is, the substrate 11 and the substrate 21 can be bonded without an adhesive, and the light transmittance and the electrical insulation of the bonded portion (the buffer layer 12) can also be increased. In addition, a concentration distribution of a metal element that changes in the film thickness direction is formed in the layer of the buffer layer 12 between the substrate 11 and the substrate 21.

As described above, in the present embodiment, the oxygen supplying layer and the metal film having the microcrystalline structure are formed on at least one of the substrate 11 or the substrate 21. The substrate 11 and the substrate 21 are bonded using an atomic diffusion bonding method, and then the substrate 11 and the substrate 21 are heated at a low temperature. This forms a buffer layer 12 between the substrate 11 and the substrate 21. The buffer layer 12 has, in its layer, a concentration distribution of a metal element that varies in the film thickness direction, and also has high light transmittance and electrical insulation. That is, a bonding portion having high bonding strength, high light transmittance, and electrical insulation can be formed between the substrate 11 and the substrate 21 without using an adhesive. Therefore, the functional element 1 with high reliability can be provided.

Described below are modified examples of the above-described embodiments. In the following description, the same components as those of the above-described embodiment are denoted by the same reference numerals, and the description of the same components is omitted as appropriate.

<2. modified example >

Fig. 8 shows a sectional configuration of a functional element (functional element 2) according to a modified example of the present disclosure. As in the above-described embodiment, this functional element 2 has a stacked structure in which two or more members to be joined are stuck together, and is incorporated in, for example, an optical element used in a projector or the like (see, for example, fig. 9). The functional element 2 according to the present modified example is different from the above-described embodiment in that the functional element 2 has the functional layer 15 between the substrate 11 and the buffer layer 12.

The functional layer 15 has an optical function such as a polarization separation film that separates light incident on the functional element 2 into S-polarized light and P-polarized light, a dichroic filter that reflects light having a predetermined wavelength and transmits light having another wavelength, an antireflection film, a film that generates a phase difference, and the like. A plurality of functional layers 15 having different functions may be provided between the substrate 11 and the substrate 21, and in this case, the functional layers 15 may be arranged between the substrate 21 and the buffer layer 12.

<3. application example >

Subsequently, application examples of the functional elements (functional elements 1 and 2) described in the above-described embodiment and modified examples are described. However, the configuration described below is merely an example, and the configuration may be changed as appropriate.

Fig. 9 schematically shows a cross-sectional configuration of an optical element (e.g., prism 3) as one of specific examples of the functional element. The prism 3 has a shape of, for example, a triangular prism, and includes, in order from the substrate 110 side, a functional layer 150, a buffer layer 12, and a functional layer 240 between the substrate 110 and the substrate 210 arranged to oppose each other. The substrate 110 and the substrate 210 each include, for example, transparent optical glass having a triangular pyramid shape. The functional layer 150 and the functional layer 240 are, for example, so-called polarization beam splitters each enabling S-polarized light and P-polarized light of the light to be separated and combined. The functional layers 150 and 240 each have a structure in which, for example, titanium oxide (TiO) is repeatedly stacked in order₂) Silicon oxide (SiO)₂) And alumina (Al)₂O₃) The configuration of (2). For example, 11 TiO are stacked₂Film, 10 SiO₂Film and 10 Al₂O₃And (3) a membrane. The buffer layer 12 includes titanium (Ti) as a metal material. The buffer layer 12 further includes silicon oxide (SiO)₂) And has a Ti concentration distribution in its layer. At least a part of Ti contained in the buffer layer 12 is titanium oxide (TiO)₂) Are present.

It is noted that the SiO is typically formed using an Ion Assisted Deposition (IAD) method or a vacuum deposition method₂A film; however, SiO formed using an IAD method or a vacuum deposition method₂The flatness of the film is low and typically has an arithmetic average roughness (Ra) of about 0.5nm after being polished. As mentioned above, in the reaction of SiO₂The film serves as the functional layer (e.g., the functional layer 150) and the buffer layer 12 and uses a material that allows formation of SiO having flatness corresponding to an arithmetic average roughness (Ra) of about 0.5nm₂Method of forming a film to form SiO₂In the case of a film, SiO on the outermost surface of the functional layer 150 may be applied₂The film serves as an oxygen supplying layer (for example, oxygen supplying layer 13).

Further, the prism 3 is an example of an application example of the functional element according to the present disclosure, and is applicable to any electronic apparatus including two or more members to be joined with an adhesive. For example, the functional element and the manufacturing method thereof according to the present disclosure can be applied to an optical device of a projector, specifically, an optical element such as a phase difference element (phase difference plate) or a polarization conversion element (PS converter). In addition, the functional element and the manufacturing method thereof can be applied to, for example, a light source device. Examples of the bonding in the light source device include: bonding of a collimating lens of an LD (laser diode); bonding of nonlinear crystals such as YAG-YAG used in high-output lasers; bonding of YAG-sapphire substrates for increasing cooling efficiency; bonding to YAG ceramic phosphor on a wheel substrate used in a projector, and the like. In addition, the functional element and the manufacturing method thereof can also be applied to an electric device. Examples of bonding in electrical devices include MEMS (micro electro mechanical systems), stacked TSV (through silicon via) bonding in 3D NAND-based memories and CMOS image sensors, and stacked bonding in SAW (surface acoustic wave) filters, and the like.

<4. working examples >

Next, working examples of the present disclosure are described.

(experiment 1: evaluation of transmittance and bonding strength of a bonding portion according to the thickness of Ti film as a metal film)

First, as experimental example 1-1, a sample was produced by forming a Ti film as a microcrystalline structure thin film (metal film) on each of the respective bonding surfaces of two pieces of quartz glass, and then bonding the metal films to each other. In addition, various samples having different thicknesses of metal films were produced, and the transmittance and bonding strength of the bonding portion were measured. The respective transmittances of the joints measured in this experiment each exhibited an average transmittance at a wavelength of 400 to 700nm, which is a visible light range.

In addition, experimental examples 1-2 to 1-4 were made. As experimental example 1-2, except that SiO was formed to a thickness of 5 μm on each of the respective bonding surfaces of two pieces of quartz glass₂The film is used as an oxygen supply layer and is formed on the SiO₂A method similar to that of the above-described Experimental example 1-1 was used except that a Ti film was formed as a metal film on the filmVarious samples were made in which the thickness of the metal film was different. As experimental examples 1 to 3, metal films were bonded to each other using a method similar to that of experimental example 1 to 1, and then subjected to an annealing treatment at 300 ℃ for 10 hours. As experimental examples 1 to 4, metal films were bonded to each other using a method similar to that of experimental examples 1 to 2, and then subjected to an annealing treatment at 300 ℃ for 10 hours. Table 1 summarizes the compositions and annealing conditions of the respective samples fabricated as experimental examples 1-1 to 1-4.

[ Table 1]

Fig. 10 shows a relationship between the transmittance of the joint and the thickness of the Ti film in each of experimental examples 1-1 and 1-2. Fig. 11 shows the relationship between the transmittance of the joint and the thickness of the Ti film in each of experimental examples 1 to 3 and 1 to 4. Fig. 10 and 11 each plot the transmittance of the joint on the vertical axis and the thickness of the Ti film on the horizontal axis.

The results of fig. 10 show that the transmittance of the joint portion decreases as the thickness of the Ti film increases. Further, the results of fig. 11 indicate that, in experimental example 1-3 in which the oxygen supplying layer was not formed as in experimental example 1-1, the transmittance of the joint portion was decreased as the thickness of the Ti film was increased, and the annealing treatment hardly caused a change in transmittance. Meanwhile, in experimental examples 1 to 4 in which the oxygen supplying layer was formed on the quartz glass, the transmittance was almost 100% regardless of the thickness of the Ti film. That is, it was shown that the transmittance of the joint portion was increased by forming an oxygen supplying layer in the lower layer of the Ti film and performing an annealing treatment after the joining.

Fig. 12 shows the relationship between the strength of the joint and the thickness of the Ti film in each of experimental examples 1-1 and 1-2. Fig. 13 shows the relationship between the strength of the joint and the thickness of the Ti film in each of experimental examples 1-3 and 1-4. Fig. 12 and 13 each plot the strength of the joint on the vertical axis and the thickness of the Ti film on the horizontal axis. Note that the bonding strength was found using the doctor blade method.

The results of fig. 12 show that the strength of the joint portion increases as the thickness of the Ti film increases. Further, the results of fig. 13 indicate that experimental examples 1 to 3 in which the oxygen supplying layer was not formed provided almost the same results as those of experimental example 1 to 1, and a large change was not seen in the change in the bonding strength caused by the annealing treatment. Meanwhile, it was found that, in experimental examples 1 to 4 in which the oxygen supplying layer was formed on the quartz glass, the bonding strength was increased regardless of the thickness of the Ti film. That is, it is shown that the bonding strength is increased by forming an oxygen supplying layer in the lower layer of the Ti film and performing an annealing treatment after bonding.

As described above, the result of experiment 1 shows that, in the functional element according to the present disclosure, providing the oxygen supplying layer on each member to be bonded, forming the metal film on the oxygen supplying layer, and further performing the annealing treatment after the members to be bonded are bonded, makes it possible to form the bonding portion (buffer layer) capable of achieving both high transmittance and high bonding strength regardless of the thickness of the metal film having the microcrystalline structure.

(experiment 2: evaluation of transmittance of junction part according to each wavelength)

First, as experimental example 2-1, two pieces of transparent optical glass (PBH 56 available from OHARA inc.) were prepared, and a functional layer was formed on each of the respective bonding surfaces. The functional layer has the following configuration: in which titanium oxide (TiO) is repeatedly stacked in order₂) Silicon oxide (SiO)₂) And alumina (Al)₂O₃) And 11 TiO are stacked₂Film, 10 SiO₂Film and 10 Al₂O₃And (3) a membrane. Next, by forming SiO with a thickness of 5 μm on each functional layer₂The film is used as an oxygen supply layer and then on SiO₂A Ti film of about 0.1nm to 1.0nm was formed as a metal film on the film, and the metal films were joined to each other to make a sample, and the spectral transmittance was measured.

In addition, as experimental example 2-2, metal films were bonded to each other using a method similar to that of the above experimental example 2-1, and then an annealing treatment was performed at 300 ℃ for 48 hours to make a sample, and the spectral transmittance was measured. Table 2 summarizes the compositions and annealing conditions of the respective samples fabricated as experimental examples 2-1 to 2-2.

[ Table 2]

Note that the functional layers fabricated in this experiment correspond to the functional layers 150 and 240 of the prism 3 described in the above application example.

Fig. 14 shows the transmittance of the joint according to each wavelength obtained as a result by measuring the spectral transmittance of each of the experimental example 2-1 and the experimental example 2-2. Fig. 14 plots the transmittance of the junction on the vertical axis and the wavelength on the horizontal axis. The results of fig. 14 show that even if another layer (functional layer) is formed between the members to be joined and the buffer layer, the transmittance of the joined portion is increased by performing the annealing treatment after the joining.

Although the present disclosure has been described above with reference to the embodiments, the modification examples, and the working examples, the present disclosure is not limited to the aspects described in the above-described embodiments and the like, and may be modified in various ways. For example, all the components described in the above-described embodiments and the like are not necessarily provided, and any other components may be further included. In addition, the materials and thicknesses of each of the above-described components are merely examples, and are not limited to those described herein.

Further, in the above-described embodiment and modified examples, an example is provided in which the two substrates 11 and 21 are joined; however, another substrate may be further bonded to the surface of the substrate 11 or 21 on the side opposite to the bonding surface using the method according to the present disclosure.

It is noted that the effects described herein are merely examples, and are not limiting. In addition, other effects are possible.

Note that the present disclosure may have the following configuration.

(1) A functional element, comprising:

a first substrate;

a second substrate disposed to be opposed to the first substrate; and

a buffer layer provided between the first substrate and the second substrate, the buffer layer having a concentration distribution of a metal element in a layer thereof that varies in a film thickness direction.

(2) The functional element according to (1), wherein the buffer layer has a concentration distribution of the metal element in a layer thereof that decreases toward an interface with the first substrate and with the second substrate.

(3) The functional element according to (1), wherein the buffer layer has a concentration distribution of the metal element in a layer thereof that decreases from an interface with the first substrate toward an interface with the second substrate.

(4) The functional element according to any one of (1) to (3), wherein the buffer layer has light transmittance and electrical insulation.

(5) The functional element according to any one of (1) to (4), wherein the buffer layer includes an oxygen supplying material.

(6) The functional element according to any one of (1) to (5), wherein the buffer layer includes at least any one of an inorganic oxide, an inorganic nitride, an inorganic oxynitride, and an inorganic fluoride.

(7) The functional element according to (6), wherein the metal element has a higher ability to bind oxygen than a binding ability of the inorganic oxide, the inorganic nitride, the inorganic oxynitride, and the inorganic fluoride.

(8) The functional element according to any one of (1) to (7), further comprising a functional layer at least one of between the first substrate and the buffer layer and between the second substrate and the buffer layer.

(9) A method of manufacturing a functional element, the method comprising

A first substrate and a second substrate are bonded, and a buffer layer having a concentration distribution of a metal element that varies in a film thickness direction in a layer thereof is formed between the first substrate and the second substrate.

(10) The method for producing a functional element according to (9), wherein

Forming a first metal film on the first substrate, the first metal film having a first buffer layer including at least any one of an inorganic oxide, an inorganic nitride, an inorganic oxynitride, and an inorganic fluoride, and a microcrystalline structure,

forming a second metal film on the second substrate, the second metal film having a second buffer layer and a microcrystalline structure, the second buffer layer including at least any one of an inorganic oxide, an inorganic nitride, an inorganic oxynitride, and an inorganic fluoride, and

forming the buffer layer by performing heat treatment after bonding the first metal film and the second metal film.

(11) The method of manufacturing a functional element according to (10), wherein the first metal film and the second metal film are formed and bonded under vacuum conditions.

(12) The method of manufacturing a functional element according to (11), wherein the first metal film and the second metal film are further formed and bonded in the same device.

(13) The method of manufacturing a functional element according to any one of (10) to (12), wherein the first metal film and the second metal film are oxidized by placing the bonded first substrate and second substrate in an environment of 100 ℃ or higher and 800 ℃ or lower as the heat treatment.

(14) The method for manufacturing a functional element according to any one of (9) or (11) to (13), wherein

Forming a first metal film on the first substrate, the first metal film having a first buffer layer including at least any one of an inorganic oxide, an inorganic nitride, an inorganic oxynitride, and an inorganic fluoride, and a microcrystalline structure,

forming a second metal film on the second substrate, the second metal film having a microcrystalline structure, an

Forming the buffer layer by performing heat treatment after bonding the first metal film and the second metal film.

(15) An electronic device comprises

Functional element comprising

A first substrate having a first surface and a second surface,

a second substrate arranged to be opposed to the first substrate, an

A buffer layer provided between the first substrate and the second substrate, the buffer layer having a concentration distribution of a metal element in a layer thereof that varies in a film thickness direction.

Priority is claimed for this application based on japanese patent application No.2018-004115 filed on the sun of the patent office on day 1, 15, 2018, the entire contents of which are incorporated herein by reference.

It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and alterations may be made depending on design requirements and other factors as long as they are within the scope of the appended claims or their equivalents.