Semiconductor photoelectrode and method for producing the same

Abstract

The present invention provides a semiconductor photoelectrode 1 which performs a catalytic function when irradiated with light, thereby causing an oxidation-reduction reaction. This semiconductor photoelectrode 1 comprises: a conductive or insulating substrate 11; a semiconductor thin film 12 that is arranged on the front surface of the substrate 11; a catalyst layer 14 that is arranged on the front surface of the semiconductor thin film 12; a light-transmitting layer 15 that is arranged in a grid-like pattern on the front surface of the catalyst layer 14; and a protective layer 16 that is arranged so as to cover the back surface of the substrate 11 and the lateral surfaces of the substrate 11 and the semiconductor thin film 12. Another configuration of this semiconductor photoelectrode 1 comprises a second semiconductor thin film 13 between the semiconductor thin film 12 and the catalyst layer 14.

Description

[Technical field]

[0001] The present invention relates to a semiconductor photoelectrode and a method for producing a semiconductor photoelectrode. [Background technology]

[0002] The water splitting reaction using a photocatalyst consists of a water oxidation reaction and a proton reduction reaction.

[0003] Oxidation reaction: 2H2O+4h + →O2+4H + Reduction reaction: 4H + +4e - →2H2

[0004] When light is irradiated onto an n-type photocatalytic material, electrons and holes are generated and separated within the photocatalyst. The holes move to the surface of the photocatalytic material and contribute to the reduction reaction of protons. Meanwhile, the electrons move to the reduction electrode and contribute to the reduction reaction of protons. Ideally, this type of oxidation-reduction reaction proceeds, resulting in a water splitting reaction.

[0005] Conventional water splitting devices have an oxidation tank and a reduction tank connected via a proton exchange membrane, with an aqueous solution and an oxidation electrode placed in the oxidation tank, and an aqueous solution and a reduction electrode placed in the reduction tank. Protons generated in the oxidation tank diffuse into the reduction tank via the proton exchange membrane. The oxidation electrode and reduction electrode are electrically connected by a conductor, and electrons move from the oxidation electrode to the reduction electrode. The water splitting reaction is caused by irradiating the oxidation electrode with light of a wavelength that can be absorbed by the material that makes up the oxidation electrode from a light source. [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] S. Yotsuhashi, et al., “CO2Conversion with Light and Water by GaN Photoelectrode”, Japanese Journal of Applied Physics 51 (2012) 02BP07 Summary of the Invention [Problem to be solved by the invention]

[0007] For example, when a gallium nitride thin film grown on a sapphire substrate is used as an oxidation electrode, oxygen is generated on the gallium nitride surface when the gallium nitride thin film is irradiated with light in an aqueous solution. The process by which oxygen is generated mainly consists of (1) adsorption of water to the reaction site, (2) dissociation of the O-H bond, (3) bonding of the adsorbed oxygen, and (4) removal of oxygen from the reaction site. To improve the reaction efficiency, it is necessary to improve the reaction rate of each of steps (1) to (4). To promote the oxygen generation reaction, a catalyst material such as NiO is formed on the semiconductor surface, but most catalyst materials only contribute little to the promotion of step (4). There was a problem that the oxygen finally generated does not leave the surface and covers the reaction site, hindering the efficiency improvement by catalyst formation.

[0008] The present invention has been made in view of the above, and has an object to improve the light energy conversion efficiency of a semiconductor photoelectrode that causes an oxidation-reduction reaction when irradiated with light. [Means for solving the problem]

[0009] A semiconductor photoelectrode according to one embodiment of the present invention is a semiconductor photoelectrode that exhibits a catalytic function by irradiation with light to cause an oxidation-reduction reaction, and includes a conductive or insulating substrate, a semiconductor thin film disposed on a surface of the substrate, a catalyst layer disposed on the surface of the semiconductor thin film, a light-transmitting layer disposed in an uneven pattern on the surface of the catalyst layer, and a protective layer disposed so as to cover the back surface of the substrate and the side surfaces of the substrate and the semiconductor thin film. The catalyst layer is made of one or more metals selected from the group consisting of Ni, Co, Cu, W, Ta, Pd, Ru, Fe, Zn, and Nb, or an oxide of such metal. . A semiconductor photoelectrode according to one embodiment of the present invention is a semiconductor photoelectrode that exhibits a catalytic function when irradiated with light to cause an oxidation-reduction reaction, and includes a conductive or insulating substrate, a semiconductor thin film disposed on a surface of the substrate, a catalyst layer disposed on the surface of the semiconductor thin film, a light-transmitting layer disposed in an uneven pattern on the surface of the catalyst layer, a protective layer disposed so as to cover the rear surface of the substrate and the side surfaces of the substrate and the semiconductor thin film, and a second semiconductor thin film disposed between the semiconductor thin film and the catalyst layer.

[0010] A manufacturing method for a semiconductor photoelectrode according to one embodiment of the present invention is a manufacturing method for a semiconductor photoelectrode that exhibits catalytic function when irradiated with light to cause an oxidation-reduction reaction, and includes the steps of forming a semiconductor thin film on the surface of a conductive or insulating substrate, forming a catalyst layer on the surface of the semiconductor thin film, heat-treating the semiconductor thin film and the catalyst layer, forming a light-transmitting layer with an uneven pattern on the surface of the catalyst layer, and forming a protective layer so as to cover the back surface of the substrate and the side surfaces of the substrate and the semiconductor thin film. Effect of the Invention

[0011] According to the present invention, it is possible to improve the light energy conversion efficiency of a semiconductor photoelectrode in which an oxidation-reduction reaction occurs upon irradiation with light. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a cross-sectional view showing an example of the configuration of a semiconductor photoelectrode of this embodiment. [Diagram 2] FIG. 2 is a top view showing an example of the shape of the light transmitting layer. [Diagram 3] FIG. 3 is a flowchart showing an example of a method for manufacturing the semiconductor photoelectrode of FIG. [Figure 4] FIG. 4 is a cross-sectional view showing an example of another configuration of the semiconductor photoelectrode of the present embodiment. [Diagram 5] FIG. 5 is a flowchart showing an example of a method for manufacturing the semiconductor photoelectrode of FIG. [Figure 6] FIG. 6 is a cross-sectional view showing an example of the configuration of a semiconductor photoelectrode of a comparative example. [Figure 7] FIG. 7 is a cross-sectional view showing an example of the configuration of a semiconductor photoelectrode of a comparative example. [Figure 8] FIG. 8 is a cross-sectional view showing an example of the configuration of a semiconductor photoelectrode of a comparative example. [Figure 9] FIG. 9 is a cross-sectional view showing an example of the configuration of a semiconductor photoelectrode of a comparative example. [Figure 10] FIG. 10 is a diagram showing an example of an apparatus for performing an oxidation-reduction reaction test. [Figure 11A] FIG. 11A is a diagram showing gas generation on a flat surface. [Figure 11B] FIG. 11B is a diagram showing how gas is generated and released from an uneven surface. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiment described below, and modifications may be made without departing from the spirit of the present invention.

[0014] [Configuration of semiconductor photoelectrode] 1 is a cross-sectional view showing an example of the configuration of a semiconductor photoelectrode 1 of this embodiment. When irradiated with light in an aqueous solution, the semiconductor photoelectrode 1 exerts a catalytic function to cause an oxidation-reduction reaction. The semiconductor photoelectrode 1 shown in the figure includes an insulating or conductive substrate 11, a semiconductor thin film 12 disposed on the surface of the substrate 11, a catalyst layer 14 disposed on the surface of the semiconductor thin film 12, a light-transmitting layer 15 disposed in a lattice pattern on the surface of the catalyst layer 14, and a protective layer 16 formed so as to cover the back surface of the substrate 11 and the side surfaces of the substrate 11 and the semiconductor thin film 12.

[0015] The substrate 11 may be, for example, an insulating or conductive substrate such as a sapphire substrate, a GaN substrate, a glass substrate, or a Si substrate.

[0016] The semiconductor thin film 12 has a photocatalytic function that causes a reaction of a target substance when irradiated with light. For the semiconductor thin film 12, for example, metal oxides such as gallium nitride (GaN), titanium oxide (TiO2), tungsten oxide (WO3), and gallium oxide (Ga2O3), or compound semiconductors such as tantalum nitride (Ta3N5), and cadmium sulfide (CdS) can be used.

[0017] The catalyst layer 14 uses a material that functions as a promoter for the semiconductor thin film 12. For example, the catalyst layer 14 can use one or more metals selected from the group consisting of Ni, Co, Cu, W, Ta, Pd, Ru, Fe, Zn, and Nb, or an oxide of such a metal. The thickness of the catalyst layer 14 is preferably 1 nm to 10 nm, and more preferably 1 nm to 3 nm, which allows sufficient light transmission. The catalyst layer 14 may cover the entire exposed surface of the semiconductor thin film 12, or may cover only a portion of it.

[0018] The light transmitting layer 15 is a concave-convex structure arranged on the surface of the catalyst layer 14. In this embodiment, as shown in FIG. 2, the light transmitting layer 15 is in a lattice shape with a 5 μm square and a pitch of 10 μm. In order to obtain a desorption effect in consideration of the typical bubble size of the generated gas, it is preferable to set the pitch to 20 μm or less (the interval of the lattice is 10 μm or less). The film thickness of the light transmitting layer 15 is preferably in a range (5-50 nm) that does not inhibit the transmission of light and forms a continuous film. If the film thickness of the light transmitting layer 15 is 5 nm or less, the density and uniformity of the layer become insufficient, and the semiconductor thin film 12 deteriorates due to contact between the aqueous solution and the semiconductor thin film 12. On the other hand, if the film thickness of the light transmitting layer 15 is 50 nm or more, the light of the wavelength absorbed by the semiconductor in the lower layer is not sufficiently transmitted. The shape of the concave-convex structure of the light transmitting layer 15 is not limited to a lattice, and it is sufficient if the width and depth of the recesses can obtain the desorption effect of the bubbles of the generated gas.

[0019] For example, SiO2 can be used for the light transmitting layer 15. The light transmitting layer 15 may be made of any material that transmits light of a wavelength that is absorbed by the semiconductor layer below.

[0020] The protective layer 16 is intended to prevent deterioration of the substrate 11 and the semiconductor thin film 12 due to contact with the aqueous solution. The protective layer 16 is made of an insulating material, such as an epoxy resin, that does not react with the aqueous solution, the substrate 11, and the semiconductor thin film 12.

[0021] Next, with reference to FIG. 3, a method for manufacturing the semiconductor photoelectrode 1 of FIG. 1 will be described.

[0022] In step S 1 , a semiconductor thin film 12 is grown on a substrate 11 .

[0023] In step S2, catalyst layer 14 is formed on the surface of semiconductor thin film 12. Catalyst layer 13 may be formed so as to cover the entire surface of semiconductor thin film 12, or may be formed so as to cover only a portion of the surface of semiconductor thin film 12.

[0024] In step S3, the sample in which the semiconductor thin film 12 and the catalyst layer 13 are formed on the substrate 11 is heat-treated. The heat treatment may be performed on a hot plate or in an electric furnace.

[0025] In step S4, the light transmitting layer 15 is vacuum-deposited using a mask so that the light transmitting layer 15 has a predetermined geometric pattern.

[0026] In step S 5 , a protective layer 16 is formed so as to cover the rear and side surfaces of the substrate 11 and the side surfaces of the semiconductor thin film 12 .

[0027] Next, with reference to FIG. 4, another configuration of the semiconductor photoelectrode 1 of the present embodiment will be described.

[0028] 4 includes an insulating or conductive substrate 11, a semiconductor thin film 12 disposed on the surface of the substrate 11, a second semiconductor thin film 13 disposed on the surface of the semiconductor thin film 12, a catalyst layer 14 disposed on the surface of the second semiconductor thin film 13, a light transmitting layer 15 disposed in a lattice pattern on the surface of the catalyst layer 14, and a protective layer 16 formed so as to cover the back surface of the substrate 11 and the side surfaces of the substrate 11 and the semiconductor thin films 12 and 13. It differs from the semiconductor photoelectrode 1 of the first embodiment in that the second semiconductor thin film 13 is disposed between the semiconductor thin film 12 and the catalyst layer 14.

[0029] The second semiconductor thin film 13 may be made of a compound semiconductor such as indium gallium nitride (InGaN) or aluminum gallium nitride (AlGaN).

[0030] Next, with reference to FIG. 5, a method for manufacturing the semiconductor photoelectrode 1 of FIG. 1 will be described.

[0031] In step S1, a semiconductor thin film 12 is grown on a substrate 11, and in step S1-2, a second semiconductor thin film 13 is grown on the semiconductor thin film 12.

[0032] Thereafter, similarly to steps S2 to S5 in FIG. 2, the catalyst layer 14, the light transmitting layer 15, and the protective layer 16 are formed.

[0033] [Example of semiconductor photoelectrode] Semiconductor photoelectrodes of Examples 1-6 were fabricated by changing the configuration of the semiconductor photoelectrode, the material of the substrate, and the material of the second semiconductor thin film, and the redox reaction test described below was carried out. The semiconductor photoelectrodes of Examples 1-6 will be described below.

[0034] <Example 1> The semiconductor photoelectrode of Example 1 is a semiconductor photoelectrode having the configuration shown in Fig. 1. A sapphire substrate was used.

[0035] In step S1, an n-GaN thin film was epitaxially grown on a sapphire substrate by metalorganic chemical vapor deposition (MOCVD) to form a semiconductor thin film as a light absorption layer (a layer that absorbs light and generates electrons and holes). Ammonia gas and trimethylgallium were used as growth materials. Hydrogen was used as the carrier gas sent into the growth furnace. The thickness of the n-GaN thin film was 2 μm, which is sufficient to absorb light. The carrier density was 3×10 18 cm -3 It was.

[0036] In step S2, Ni was deposited on the surface of the n-GaN thin film by evaporation to a thickness of 1 nm.

[0037] In step S3, the sample was heat-treated in air at 300 degrees Celsius for 1 hour to form a NiO layer. TEM observation of the sample cross section revealed that the NiO film thickness was 2 nm.

[0038] In step S4, a SiO2 film with a thickness of about 50 nm was vacuum-deposited on the surface of the NiO layer using a mask to form a lattice pattern with a 5 μm square and a pitch of 10 μm as shown in Figure 2. From the shape of the pattern, the surface area of ​​the NiO layer was determined to be about 0.75 cm2. 2 The surface area of ​​the SiO2 layer is approximately 0.25 cm 2 The surface area of ​​the sample was approximately 1 cm 2 It is.

[0039] In step S5, a protective layer was formed using epoxy resin so as to cover the rear surface of the sapphire substrate (the surface on which the n-GaN thin film was not formed) and the side surfaces of the sapphire substrate and the n-GaN thin film.

[0040] Through the above steps, the semiconductor photoelectrode of Example 1 was obtained. In the redox reaction test described below, the n-GaN surface was scribed, a conductor wire was connected to part of the surface, soldered using In, and covered with epoxy resin so that the indium surface was not exposed, and then the resulting electrode was set as an oxidation electrode.

[0041] <Example 2> The semiconductor photoelectrode of Example 2 is a semiconductor photoelectrode having the configuration shown in Fig. 4. A sapphire substrate was used, and indium gallium nitride was used as the material for the second semiconductor thin film 13.

[0042] In step S1, an n-GaN thin film was epitaxially grown on a sapphire substrate by MOCVD. Ammonia gas and trimethylgallium were used as growth materials. Hydrogen was used as the carrier gas sent into the growth furnace. The thickness of the n-GaN thin film was 2 μm. The carrier density was 3×10 18 cm -3 It was.

[0043] In step S1-2, an indium gallium nitride (InGaN) thin film with an indium composition ratio of 5% was grown on the n-GaN thin film. Ammonia gas, trimethylgallium, and trimethylindium were used as growth materials. Hydrogen was used as the carrier gas sent into the growth furnace. The thickness of the InGaN thin film was set to 100 nm, which is sufficient to absorb light.

[0044] In step S2, Ni was deposited to a thickness of 1 nm on the surface of the InGaN thin film by evaporation.

[0045] In step S3, the sample was heat-treated in air at 300 degrees Celsius for 1 hour to form a NiO layer. TEM observation of the sample cross section revealed that the NiO film thickness was 2 nm.

[0046] In step S4, SiO2 was vacuum-deposited to a thickness of about 50 nm on the surface of the NiO layer using a mask so as to form a lattice pattern of 5 μm squares and a pitch of 10 μm as shown in FIG.

[0047] In step S5, a protective layer was formed using epoxy resin so as to cover the rear surface of the sapphire substrate and the side surfaces of the sapphire substrate, the n-GaN thin film, and the InGaN thin film.

[0048] Through the above steps, a semiconductor photoelectrode of Example 2 was obtained. In the redox reaction test described later, the InGaN surface was scribed to expose the n-GaN, a conductor was connected to a part of the n-GaN surface, soldered using In, and covered with epoxy resin so that the indium surface was not exposed, and this was set as an oxidation electrode.

[0049] <Example 3> The semiconductor photoelectrode of Example 3 is a semiconductor photoelectrode having the configuration shown in Fig. 4. A sapphire substrate was used, and aluminum gallium nitride was used as the material for the second semiconductor thin film 13.

[0050] In step S1, an n-GaN thin film was epitaxially grown on a sapphire substrate by MOCVD. Ammonia gas and trimethylgallium were used as growth materials. Hydrogen was used as the carrier gas sent into the growth furnace. The thickness of the n-GaN thin film was 2 μm. The carrier density was 3×10 18 cm -3 It was.

[0051] In step S1-2, an aluminum gallium nitride (AlGaN) thin film with an aluminum composition ratio of 10% was grown on the n-GaN thin film. Ammonia gas, trimethylgallium, and trimethylaluminum were used as growth materials. Hydrogen was used as the carrier gas sent into the growth furnace. The thickness of the AlGaN thin film was set to 100 nm, which is sufficient to absorb light.

[0052] The steps from step S2 onwards were carried out in the same manner as in Example 2.

[0053] <Example 4> The semiconductor photoelectrode of Example 4 is a semiconductor photoelectrode having the configuration shown in Fig. 1. It differs from Example 1 in that an n-GaN substrate is used.

[0054] In step S1, an n-GaN thin film was epitaxially grown on an n-GaN substrate by MOCVD. Ammonia gas and trimethylgallium were used as growth materials. Hydrogen was used as the carrier gas sent into the growth furnace. The thickness of the n-GaN thin film was 2 μm. The carrier density was 3×10 18 cm -3 It was.

[0055] The steps from step S2 onwards were carried out in the same manner as in the first embodiment.

[0056] <Example 5> The semiconductor photoelectrode of Example 5 is a semiconductor photoelectrode having the configuration shown in Fig. 4. It differs from Example 2 in that an n-GaN substrate is used.

[0057] In step S1, an n-GaN thin film was epitaxially grown on an n-GaN substrate by MOCVD. Ammonia gas and trimethylgallium were used as growth materials. Hydrogen was used as the carrier gas sent into the growth furnace. The thickness of the n-GaN thin film was 2 μm. The carrier density was 3×10 18 cm -3 It was.

[0058] The steps from step S1-2 onwards were carried out in the same manner as in Example 2.

[0059] <Example 6> The semiconductor photoelectrode of Example 6 is a semiconductor photoelectrode having the configuration shown in Fig. 4. It differs from Example 2 in that an n-GaN substrate is used.

[0060] In step S1, an n-GaN thin film was epitaxially grown on an n-GaN substrate by MOCVD. Ammonia gas and trimethylgallium were used as growth materials. Hydrogen was used as the carrier gas sent into the growth furnace. The thickness of the n-GaN thin film was 2 μm. The carrier density was 3×10 18 cm -3 It was.

[0061] The steps from step S1-2 onwards were carried out in the same manner as in the third embodiment.

[0062] Next, Comparative Example 1-4 will be described.

[0063] <Comparative Example 1> 6, Comparative Example 1 has a configuration in which a light transmitting layer is not formed in the semiconductor photoelectrode of Example 1. The semiconductor photoelectrode 5 of Comparative Example 1 in FIG.

[0064] For the semiconductor photoelectrode of Comparative Example 1, the process of step S4 in Example 1 was not carried out. The surface area of ​​the NiO layer (semiconductor thin film 52) of Comparative Example 1 was set to about 0.75 cm 2 The area of ​​the reaction field was set to be the same as in Example 1. Other points were the same as in Example 1.

[0065] <Comparative Example 2> 7, Comparative Example 2 has a configuration in which a light transmitting layer is not formed in the semiconductor photoelectrode of Example 2. The semiconductor photoelectrode 5 of Comparative Example 2 in FIG.

[0066] For the semiconductor photoelectrode of Comparative Example 2, the process of step S4 in Example 2 was not carried out. 2 The area of ​​the reaction field was set to be the same as in Example 2. Other points were the same as in Example 2.

[0067] <Comparative Example 3> As shown in Fig. 8, Comparative Example 3 has a configuration in which a light-shielding layer is formed on the SiO2 layer of the semiconductor photoelectrode of Example 1. The semiconductor photoelectrode 5 of Comparative Example 3 in Fig. 8 includes a substrate 51, a semiconductor thin film 52, a catalyst layer 54, a light-transmitting layer 55, and a protective layer 56, and further includes a light-shielding layer 57 on the light-shielding layer 55.

[0068] The semiconductor photoelectrode of Comparative Example 3 was prepared by forming a 40 nm SiO2 layer in step S4 of Example 1, and then depositing Ni to a thickness of 10 nm on the SiO2 layer using the same mask.

[0069] <Comparative Example 4> As shown in Fig. 9, Comparative Example 4 has a configuration in which a light-shielding layer is formed on the SiO2 layer of the semiconductor photoelectrode of Example 2. The semiconductor photoelectrode 5 of Comparative Example 4 in Fig. 9 includes a substrate 51, a semiconductor thin film 52, a second semiconductor thin film 53, a catalyst layer 54, a light transmitting layer 55, and a protective layer 56, and further includes a light-shielding layer 57 on the light-shielding layer 55.

[0070] The semiconductor photoelectrode of Comparative Example 4 was prepared by forming a 40 nm SiO2 layer in step S4 of Example 2, and then depositing Ni to a thickness of 10 nm on the SiO2 layer using the same mask.

[0071] [Oxidation-reduction reaction test] An oxidation-reduction reaction test was carried out for Examples 1-6 and Comparative Examples 1-4 using the device shown in FIG.

[0072] 10 includes an oxidation tank 110 and a reduction tank 120. An aqueous solution 111 is placed in the oxidation tank 110, and the semiconductor photoelectrode 1 of Example 1-4 or the semiconductor photoelectrode 5 of Comparative Example 1-4 is placed in the aqueous solution 111 as the oxidation electrode 1. An aqueous solution 121 is placed in the reduction tank 120, and a reduction electrode 122 is placed in the aqueous solution 121.

[0073] A 1 mol / l aqueous sodium hydroxide solution was used as the aqueous solution 111 in the oxidation bath 110. An aqueous potassium hydroxide solution or hydrochloric acid may also be used as the aqueous solution 111. When the oxidation electrode 1 is made of gallium nitride, an alkaline aqueous solution is preferable.

[0074] A 0.5 mol / l aqueous potassium hydrogen carbonate solution was used as the aqueous solution 121 in the reduction tank 120. As the aqueous solution 121, an aqueous sodium hydrogen carbonate solution, an aqueous potassium chloride solution, or an aqueous sodium chloride solution may also be used.

[0075] Platinum (manufactured by Nilaco) was used for the reduction electrode 122. The reduction electrode 122 may be a metal or a metal compound. For example, nickel, iron, gold, silver, copper, indium, or titanium may be used for the reduction electrode 122.

[0076] The oxidation tank 110 and the reduction tank 120 are connected via a proton membrane 130. Protons generated in the oxidation tank 110 diffuse into the reduction tank 120 via the proton membrane 130. Nafion (registered trademark) was used for the proton membrane 130. Nafion is a perfluorocarbon material composed of a hydrophobic Teflon skeleton made of carbon and fluorine and a perfluoro side chain having a sulfonic acid group.

[0077] The oxidation electrode 1 and the reduction electrode 122 are electrically connected by a conductor 132 , and electrons move from the oxidation electrode 1 to the reduction electrode 122 .

[0078] The light source 140 was a 300 W high-pressure xenon lamp (illuminance 5 mW / cm 2) was used. The light source 140 may irradiate light of a wavelength that can be absorbed by the material constituting the semiconductor photoelectrode installed as the oxidation electrode. For example, an oxidation electrode made of gallium nitride can absorb wavelengths of 365 nm or less. The light source 140 may be a xenon lamp, a mercury lamp, a halogen lamp, a solar simulant light source, or sunlight, or a combination of these light sources.

[0079] In the redox reaction test, nitrogen gas was flowed at 10 ml / min in each reaction chamber, and the light irradiation area of ​​the sample was set to 1 cm 2 (In the case of Example 1, the surface area is 1.5 cm 2 ) and the aqueous solutions 111 and 121 were stirred at the center of the bottom of each reaction vessel at a rotation speed of 250 rpm using a stirring bar and a stirrer.

[0080] After the atmosphere inside the reaction vessel was sufficiently replaced with nitrogen gas, the light source 140 was fixed so as to face the surface of the semiconductor photoelectrode to be tested on which NiO was formed, and the semiconductor photoelectrode was uniformly irradiated with light.

[0081] After 10 hours of light irradiation, the gas in each reaction tank was sampled and the reaction products were analyzed by gas chromatography. As a result, it was confirmed that oxygen was produced in the oxidation tank 110 and hydrogen was produced in the reduction tank 120. By changing the metal of the reduction electrode to, for example, Ni, Fe, Au, Pt, Ag, Cu, In, Ti, Co, or Ru, or by changing the atmosphere in the cell, it is also possible to produce carbon compounds through the reduction reaction of carbon dioxide and ammonia through the reduction reaction of nitrogen.

[0082] [Test Results] The amounts of oxygen and hydrogen gas produced versus light irradiation time in Examples 1-6 and Comparative Examples 1-4 are shown in Table 1. The amounts of each gas produced are shown normalized by the surface area of ​​the semiconductor photoelectrode.

[0083] [Table 1]

[0084] It was found that both Examples 1-6 and Comparative Examples 1-4 produced oxygen and hydrogen upon irradiation with light.

[0085] Example 2 produced more gas than Example 1. This is because the InGaN thin film of the light absorption layer has a wider wavelength range that can be absorbed than the GaN thin film. Example 3 also produced more gas than Example 1. This is because the use of AlGaN in the light absorption layer formed an AlGaN / GaN heterostructure, which generated a large electric field in the AlGaN and promoted charge separation. The same is true when comparing Example 4 with Example 5 and Example 4 with Example 6.

[0086] Even though the area of ​​the reaction field was the same, Example 1 produced more gas than Comparative Example 1. As shown in Figures 11A and 11B, this is believed to be because Example 1 was provided with light transmitting layer 15, which reduced the surface tension and promoted the release of the generated gas, rather than having a flat surface. The same is true when comparing Example 2 and Comparative Example 2.

[0087] However, between Example 1 and Comparative Example 1, Example 1 has a larger light absorption area, which may have influenced the increase in the amount of gas generated. Therefore, Comparative Example 3 and Comparative Example 1 are compared. Comparative Example 3 has the same light absorption area and reaction field area as Comparative Example 1 by blocking light from the light transmission layer 55 with the light shielding layer 57. Comparative Example 3 generated more gas than Comparative Example 1. It is considered that the amount of gas generated increased because the surface of the semiconductor photoelectrode was made uneven, reducing the surface tension and promoting the desorption of the generated gas. The same is true when Comparative Example 2 and Comparative Example 4 are compared.

[0088] The desorption of the generated gas depends on the surface tension of the semiconductor photoelectrode surface. Since surface tension can be reduced by the structure of the semiconductor photoelectrode surface, we were able to increase the efficiency of the amount of hydrogen and oxygen produced by the water splitting reaction (light energy conversion efficiency) by making the surface structure of the semiconductor photoelectrode uneven and promoting the desorption of the generated gas.

[0089] As described above, the semiconductor photoelectrode 1 of this embodiment has a conductive or insulating substrate 11, a semiconductor thin film 12 disposed on the surface of the substrate 11, a catalyst layer 14 disposed on the surface of the semiconductor thin film 12, a light transmitting layer 15 disposed in a lattice pattern on the surface of the catalyst layer 14, and a protective layer 16 disposed so as to cover the back surface of the substrate 11 and the side surfaces of the substrate 11 and the semiconductor thin film 12. Providing the light transmitting layer 15 with an uneven pattern on the surface of the semiconductor photoelectrode 1 promotes the desorption of the generated gas from the surface of the semiconductor photoelectrode 1, thereby increasing the amount of gas generated by the oxidation-reduction reaction, i.e., improving the light energy conversion efficiency. [Explanation of symbols]

[0090] 1...Semiconductor photoelectrode 11...Substrate 12, 13...Semiconductor thin film 14...Catalyst layer 15...Light transmission layer 16...Protective layer

Claims

1. A semiconductor photoelectrode that exhibits a catalytic function by irradiation with light to cause an oxidation-reduction reaction, A conductive or insulating substrate; a semiconductor thin film disposed on a surface of the substrate; a catalyst layer disposed on a surface of the semiconductor thin film; a light transmitting layer arranged in a concave-convex pattern on the surface of the catalyst layer; a protective layer disposed so as to cover the rear surface of the substrate and the side surfaces of the substrate and the semiconductor thin film; The catalyst layer is made of one or more metals selected from the group consisting of Ni, Co, Cu, W, Ta, Pd, Ru, Fe, Zn, and Nb, or an oxide of such a metal. Semiconductor photoelectrode.

2. A semiconductor photoelectrode that exhibits catalytic function when irradiated with light to cause an oxidation-reduction reaction, A conductive or insulating substrate; a semiconductor thin film disposed on a surface of the substrate; a catalyst layer disposed on a surface of the semiconductor thin film; a light transmitting layer arranged in a concave-convex pattern on the surface of the catalyst layer; a protective layer disposed so as to cover a rear surface of the substrate and side surfaces of the substrate and the semiconductor thin film; A second semiconductor thin film is disposed between the semiconductor thin film and the catalyst layer. Semiconductor photoelectrode.

3. 3. The semiconductor photoelectrode according to claim 1, The semiconductor thin film is an n-type semiconductor. Semiconductor photoelectrode.

4. 4. The semiconductor photoelectrode according to claim 1, The uneven pattern is a lattice pattern. Semiconductor photoelectrode.

5. A method for producing a semiconductor photoelectrode that exhibits a catalytic function by light irradiation to cause an oxidation-reduction reaction, comprising the steps of: forming a semiconductor thin film on a surface of a conductive or insulating substrate; forming a catalyst layer on a surface of the semiconductor thin film; heat-treating the semiconductor thin film and the catalyst layer; forming a light transmitting layer with a concave-convex pattern on a surface of the catalyst layer; forming a protective layer so as to cover the rear surface of the substrate and the side surfaces of the substrate and the semiconductor thin film; A method for producing a semiconductor photoelectrode.

6. A method for producing a semiconductor photoelectrode according to claim 5, comprising the steps of: forming a second semiconductor thin film on a surface of the semiconductor thin film after the step of forming the semiconductor thin film; The step of forming a catalyst layer includes forming the catalyst layer on a surface of the second semiconductor thin film. A method for producing a semiconductor photoelectrode.

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