JP2011205086A - Photoelectric conversion element manufacturable by method suitable for mass production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion element that can attain photoelectric conversion efficiency with good reproducibility without depending on a vacuum process of high manufacturing cost and is suitable for CIS solar cells or the like.SOLUTION: The photoelectric conversion element includes at least a metal oxide semiconductor layer and a buffer layer made of InS, wherein the buffer layer is formed on the metal oxide semiconductor layer by the spray method and its thickness is 0.2 to 1.0 μm.

Description

  The present invention relates to a photovoltaic device that can be manufactured by a method suitable for mass production and can obtain high photoelectric conversion efficiency.

From the viewpoint of global warming, finite fossil fuel reserves, etc., energy resources have been reviewed, and as one of them, solar power generation, which is a clean power generation technology, has attracted attention. Solar energy is inexhaustible, there is no fear of exhaustion like fossil fuels, and there is no increase in CO ₂ . However, silicon solar cells, which are currently mainstream, have high production costs and are difficult to depreciate against the current cost of electricity, so product development based on a free economy has not yet been made. Accordingly, there is a demand for a lower cost and higher efficiency solar cell, a thin film silicon solar cell with reduced silicon usage, a chalcogenide thin film solar cell (CIS solar cell) such as Cu (In, Ga) Se ₂ , CuInS _2, etc. ), Organic solar cells such as dye-sensitized solar cells are being developed. Among them, chalcogenide-based thin film solar cells such as Cu (In, Ga) Se ₂ and CuInS ₂ have been widely studied as solar cells that have high potential to replace silicon solar cells. However, since most of the thin film fabrication used in current CIS solar cells uses vacuum processes such as vapor deposition, sputtering, ALD, and CVD, it is difficult to reduce costs in terms of equipment and production efficiency, resulting in a large area. Not applicable to

  Thus, electrodeposition methods, screen printing methods, spray pyrolysis methods, and the like can be cited as film forming methods that are inexpensive and capable of increasing the area without relying on a vacuum process. CdTe solar cells are produced by First Solar in the United States as solar cells manufactured by the low-cost process as described above. Currently, First Solar is the world's top solar cell manufacturer. This solar cell has a module conversion efficiency of 10%, which is very low compared to the conversion efficiency of about 15% of other solar cell modules, but the cost is 100 yen / W, and other solar cells It is about 2/5 of the battery. In other words, consumers have found that cost is the biggest concern. Therefore, it is clear that the cost is a very big factor in production and sales.

  From the above, the most important point in the production of solar cells is the cost. However, the spray pyrolysis method is known as a film formation method for a large area, and if it can be applied to CIS solar cell production, the power generation cost is reduced. It is an attractive film forming method that can be greatly reduced. Sufficient photoelectric conversion efficiency and reproducibility are important for commercial production of CIS solar cells by spray pyrolysis.

  However, Non-Patent Document 1 reports 9% conversion efficiency by spray pyrolysis, but does not describe detailed optimization and reproducibility.

T. T. John, et al., Solar Energy Materials & Solar Cells 89 (2005) 27-36.

  An object of this invention is to provide the photoelectric conversion element suitable for a CIS solar cell etc. from which high photoelectric conversion efficiency is obtained with high reproducibility without relying on the vacuum process with a high manufacturing cost.

As a result of intensive investigations in view of the above object, by forming a buffer layer made of In ₂ S ₃ having a thickness of 0.2 to 1.0 μm on the metal oxide semiconductor layer by a spray method, the manufacturing cost can be reduced. The inventors have found that high photoelectric conversion efficiency can be obtained with high reproducibility without depending on a high vacuum process, and the present invention has been completed. That is, the present invention has the following configuration.
Item 1. At least a metal oxide semiconductor layer and a buffer layer made of a compound containing indium and sulfur,
The buffer layer is a photoelectric conversion element formed on a metal oxide semiconductor layer by a spray method and having a thickness of 0.2 to 1.0 μm.
Item 2. Item 2. The photoelectric conversion element according to Item 1, wherein the compound containing indium and sulfur is In ₂ S ₃ .
Item 3. Item 3. The photoelectric conversion element according to Item 1 or 2, wherein the metal oxide semiconductor layer has a porous structure.
Item 4. The metal oxide semiconductor layer is at least one selected from the group consisting of titanium oxide, tungsten oxide, zinc oxide, niobium oxide, tantalum oxide, and strontium titanate, The photoelectric conversion element as described.
Item 5. Item 5. The photoelectric conversion element according to any one of Items 1 to 4, further comprising a light absorption layer made of a chalcopyrite semiconductor formed on the buffer layer by a spray method.
Item 6. Furthermore, the photoelectric conversion element in any one of claim | item 1 -5 provided with a translucent conductive layer on a metal oxide semiconductor layer.
Item 7. The translucent conductive layer is at least one transparent conductive oxide selected from the group consisting of fluorine-doped tin oxide, indium-doped tin oxide, gallium-doped tin oxide, aluminum-doped tin oxide and niobium-doped tin oxide Item 7. The photoelectric conversion element according to any one of Items 1 to 6.
Item 8. Item 8. The photoelectric conversion element according to any one of Items 1 to 7, further comprising a translucent substrate on the translucent conductive layer and a back electrode on the light absorption layer.
Item 9. Item 9. The photoelectric conversion element according to Item 8, wherein the translucent substrate is made of glass or plastic.
Item 10. Item 10. The photoelectric conversion element according to Item 8 or 9, wherein the back electrode is made of at least one selected from the group consisting of molybdenum, gold, silver, aluminum, carbon, and platinum.
Item 11. At least a step of forming a buffer layer by spraying a raw material solution containing InCl ₃ and CS (NH ₂ ) ₂ in air on a metal oxide semiconductor layer having a spray surface heated to 150 to 350 ° C. The manufacturing method of the photoelectric conversion element in any one of claim | item 1 -10.
Item 12. A step of forming a light absorption layer by spraying a raw material solution containing CuCl ₂ , InCl ₃ and CS (NH ₂ ) ₂ in air on at least a buffer layer whose spray surface is heated to 250 to 310 ° C. The manufacturing method of the photoelectric conversion element in any one of claim | item 5-10 provided.

  ADVANTAGE OF THE INVENTION According to this invention, the photoelectric conversion element suitable for a CIS solar cell etc. from which high photoelectric conversion efficiency is obtained with high reproducibility without relying on a vacuum process with a high manufacturing cost can be provided.

It is a schematic cross section which shows the one aspect | mode of the photoelectric conversion element of this invention in case a metal oxide semiconductor layer has a smooth structure. It is a schematic cross section which shows the one aspect | mode of the photoelectric conversion element of this invention in case a metal oxide semiconductor layer has a porous structure. It is a graph which shows the relationship between the open circuit voltage of Example 1 and Comparative Example 1, and a short circuit current density.

1. Photoelectric Conversion Element The photoelectric conversion element of the present invention includes at least a metal oxide semiconductor layer and a buffer layer made of In ₂ S ₃ , and the buffer layer is formed on the metal oxide semiconductor layer by a spray method. And the thickness is 0.2 to 1.0 μm. Thereby, high photoelectric conversion efficiency with high reproducibility can be realized.

<Metal oxide semiconductor layer>
In the present invention, the metal oxide semiconductor layer may have a smooth structure or a porous structure. The porous structure is not particularly limited as long as it is a collection of metal oxide semiconductors such as granular bodies, linear bodies (linear bodies: needles, tubes, columns, etc.). Good. If the metal oxide semiconductor layer has a porous structure, it is nanoscale, so the active surface area of the light absorption layer described later formed by the spray method is remarkably increased, the photoelectric conversion efficiency is improved, and the metal is excellent in electron collection. An oxide semiconductor layer can be formed.

The metal oxide semiconductor used for the metal oxide semiconductor layer is not particularly limited as long as it is an n-type semiconductor having a band gap of about 2 to 5 eV. For example, titanium (Ti), zinc (Zn), tin (Sn), niobium (Nb), indium (In), yttrium (Y), lanthanum (La), zirconium (Zr), tantalum (Ta), hafnium (Hf) ), Strontium (Sr), barium (Ba), vanadium (V), a metal oxide containing at least one selected from the group consisting of metal elements such as tungsten (W) is preferable. Further, it contains at least one selected from the group consisting of non-metallic elements such as nitrogen (N), carbon (C), fluorine (F), sulfur (S), chlorine (Cl), phosphorus (P) and the like. Also good. Specifically, titanium oxide, tungsten oxide, zinc oxide, niobium oxide, tantalum oxide, strontium titanate, and the like are more preferable, and titanium oxide is more preferable. In particular, an n-type semiconductor whose conduction band is lower than the conduction band of In ₂ S ₃ used for the buffer layer in the electron energy level is preferable. Note that in the case where a perovskite oxide semiconductor is used as the metal oxide semiconductor, a donor may be doped. By forming a metal oxide semiconductor layer made of these metal oxide semiconductors, the metal oxide semiconductor layer becomes a window layer for introducing light into a light absorption layer described later, and from a buffer layer described later. It can be set as the n-type semiconductor layer which plays the role which collects these electrons. In addition, these metal oxide semiconductors may be used independently and may be used in combination of 2 or more type.

  When titanium oxide is employed as the metal oxide semiconductor used for the metal oxide semiconductor layer, it is preferable to use an anatase type crystal structure.

  The thickness of the metal oxide semiconductor layer is preferably about 10 to 2000 nm, and more preferably about 20 to 300 nm. By setting the thickness of the metal oxide semiconductor layer to this level, it is possible to more reliably suppress leakage current and collect electrons from a buffer layer described later.

<Buffer layer>
In the present invention, the buffer layer is made of a compound containing indium and sulfur. Specific examples of such a compound containing indium and sulfur include InS and In ₂ S _3. In ₂ S ₃ is preferable from the viewpoint of photoelectric conversion efficiency. Further, elements constituting the light absorption layer, elements for doping the light absorption layer, and the like may be diffused in the buffer layer.

  Examples of the material for the buffer layer include CdS. In addition to safety concerns, a decrease in the spectral response in the blue region is observed in light absorption. Therefore, in the present invention, a compound containing indium and sulfur is used.

  The buffer layer of the present invention is formed on the above-described metal oxide semiconductor layer by a spray method. Thereby, since a vacuum process is not used, manufacturing cost can be reduced.

  In the present invention, the buffer layer has a thickness of about 0.2 to 1.0 μm, preferably about 0.4 to 0.8 μm. If the thickness of the buffer layer is too thin, it is difficult to obtain a photoelectric conversion element capable of obtaining highly reproducible photoelectric conversion efficiency. If the buffer layer is too thick, the transmitted light to the light absorption layer is reduced and the conversion efficiency is lowered.

In the case where a porous metal oxide semiconductor layer is employed as the metal oxide semiconductor layer, a buffer layer having a thickness of 0.2 to 1.0 μm is formed on the metal oxide semiconductor layer. For example, In ₂ S ₃ having a thickness of 0.2 to 1.0 μm is formed on the surface of a metal oxide semiconductor such as a granular body or a linear body (linear body: needle shape, tube shape, columnar shape, etc.) In addition, a combination of these may be used as a metal oxide semiconductor layer and a buffer layer.

<Light absorption layer>
In the present invention, it is preferable to form a light absorption layer on the buffer layer (on the side opposite to the metal oxide semiconductor layer).

This light absorption layer is preferably made of a chalcopyrite semiconductor. Examples of the chalcopyrite semiconductor that can be used for the light absorption layer include CuInS ₂ , CuIn (S, Se) ₂ , and CuZnSnS ₂ .

  The light absorption layer is preferably formed by a spray method. Thereby, since a vacuum process is not used, manufacturing cost can be reduced.

  In the present invention, the thickness of the light absorption layer can be made thinner than that of the dye-sensitized solar cell, preferably about 0.8 to 2.5 μm, and more preferably about 1.0 to 2.0 μm. By setting the thickness of the light absorption layer within the above range, pinholes are not generated in the light absorption layer, a certain strength can be maintained, and light can be absorbed more efficiently.

<Translucent conductive layer>
In the present invention, it is preferable to provide a translucent conductive layer on the metal oxide semiconductor layer (on the side opposite to the buffer layer).

  The light-transmitting conductive layer may be made of, for example, a transparent conductive oxide. For example, fluorine-doped tin oxide (FTO), indium tin oxide (ITO), gallium-doped zinc oxide, aluminum-doped zinc What consists of an oxide, niobium dope titanium oxide, etc. is preferable, and what consists of ITO among these is more preferable. Thereby, a translucent conductive layer becomes a window layer for introducing into a light absorption layer, and the electric power obtained from the light absorption layer can be taken out efficiently.

  The thickness of the translucent conductive layer is preferably about 0.01 to 10.0 μm, and more preferably about 0.3 to 1.0 μm. By setting the thickness of the translucent conductive layer within the above range, the sheet resistance can be reduced, and as a result, the series resistance of the photoelectric conversion device can be reduced, so that the fill factor characteristic can be maintained.

<Translucent substrate>
In the present invention, it is preferable to provide a translucent substrate on the translucent conductive layer (on the side opposite to the metal oxide semiconductor layer).

  Although it does not restrict | limit especially as a translucent board | substrate, For example, what is necessary is just to comprise from glass, a plastics, etc. Thereby, it can become a window layer for introducing light into the light absorption layer.

  Although the thickness of a translucent board | substrate is not specifically limited, What is necessary is just to be about 0.1-5.0 mm.

  For example, a substrate with a transparent conductive film such as a glass with an ITO film or a glass with an FTO film may be used as the light-transmitting substrate and the light-transmitting conductive layer.

<Back electrode>
In the present invention, a back electrode is preferably provided on the light absorption layer (on the side opposite to the buffer layer).

  Although it does not restrict | limit especially as a back electrode, For example, a metal electrode, especially molybdenum, gold | metal | money, silver, aluminum, carbon, platinum etc. are preferable. Also, alloys of these metals are preferably used.

  The thickness of the back electrode is not particularly limited, but may be about 0.1 to 2.0 μm.

<Specific embodiment>
Specific embodiments of the photoelectric conversion element of the present invention described above will be described in more detail with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view illustrating one embodiment of the photoelectric conversion element of the present invention when the metal oxide semiconductor layer has a smooth structure.

  The photoelectric conversion element 1 can be formed with, for example, a super straight structure, and a translucent substrate 2 is disposed on the lower surface side as one main surface, and a translucent conductive layer 3 and a smooth metal oxide are formed thereon. The physical semiconductor layer 4, the buffer layer 5, the light absorption layer 6, and the back electrode 7 are laminated in this order. By adopting such a configuration, high photoelectric conversion efficiency can be realized with high reproducibility.

  The materials, thicknesses, and the like of the translucent substrate 2, the translucent conductive layer 3, the smooth metal oxide semiconductor layer 4, the buffer layer 5, the light absorption layer 6, and the back electrode 7 are as described above.

  The translucent conductive layer 3 may be formed on the translucent substrate 2 by a CVD method, a sputtering method, a spray method, or the like. The spray method is preferable in consideration of manufacturing cost, easy area enlargement, and stable quality. Commercially available glass with a transparent conductive film or the like can also be used as the translucent substrate 2 and the translucent conductive layer 3.

  The smooth metal oxide semiconductor layer 4 may be formed on the translucent conductive layer 3 by a CVD method, a sputtering method, a spray method, or the like. The spray method is preferable in consideration of manufacturing cost, easy area enlargement, and stable quality.

The buffer layer 5 is formed on the smooth metal oxide semiconductor layer 4 by a spray method. For example, on the smooth metal oxide semiconductor layer 4 whose spray surface is heated to 150 to 350 ° C., a raw material solution containing InCl ₃ and CS (NH ₂ ) ₂ (concentrations are InCl ₃ : 1 mM to 500 mM, and CS (NH ₂ ) ₂ : 1 mM to 500 mM) may be sprayed in air to form a buffer layer. At this time, if the spray surface of the smooth metal oxide semiconductor layer 4 is too low, sufficient thermal decomposition reaction cannot be obtained, and the target buffer layer 5 cannot be obtained. Moreover, if the spray surface of the smooth metal oxide semiconductor layer 4 is too high, it is difficult to increase the thickness of the buffer layer 5.

The light absorption layer 6 is formed on the buffer layer 5 by a spray method. For example, a raw material solution containing CuCl ₂ , InCl ₃ and CS (NH ₂ ) ₂ on the buffer layer 5 whose spray surface is heated to 250 to 310 ° C., preferably 280 to 300 ° C. (concentrations are each CuCl ₂ : The light absorption layer 6 may be formed by spraying 1 mM to 500 mM, InCl ₃ : 1 mM to 500 mM, and CS (NH ₂ ) ₂ : 1 mM to 1000 mM in the air. At this time, if the spray surface of the buffer layer 5 is too low, a sufficient thermal decomposition reaction cannot be obtained. Further, the photoelectric conversion efficiency of the buffer layer 5 is remarkably deteriorated. The CuCl ₂ used may be a hydrate (CuCl ₂ .2H ₂ O), and the CS (NH ₂ ) ₂ may be CS (NHCH ₃ ) ₂ .

  In addition, although an example was shown about the formation method of the buffer layer 5 and the light absorption layer 6 above, it is not limited to this, It can produce with various compositions and conditions.

  The back electrode 7 may be formed on the light absorption layer 6 by a CVD method, a sputtering method, a screen printing method, or the like.

  On the other hand, FIG. 2 is a schematic cross-sectional view showing one embodiment of the photoelectric conversion element of the present invention when the metal oxide semiconductor layer has a porous structure.

In FIG. 2, the translucent substrate 2 is disposed on the lower surface side as one main surface, and the translucent conductive layer 3, the smooth metal oxide semiconductor layer 4, and the back electrode 7 are laminated in this order. Further, between the smooth metal oxide semiconductor layer 4 and the back electrode 7, semiconductor fine particles 8 are covered with In ₂ S ₃ 9 which is a material of the buffer layer, and the gap is a material of the light absorption layer. A layer containing CuInS ₂ 10 is formed.

  The photoelectric conversion element 1 having this configuration can be manufactured, for example, by the following method.

  The translucent substrate 2, the translucent conductive layer 3, and the smooth metal oxide semiconductor layer 4 are formed in the same manner as in the embodiment of FIG.

  Next, a porous semiconductor layer made of semiconductor fine particles 8 is formed on the metal oxide semiconductor layer 4. For example, when the porous semiconductor layer is made of titanium oxide, a chelating agent such as acetylacetone, acetic acid or citric acid is added to anatase-type titanium oxide and then kneaded with deionized water, and a surfactant such as Triton X-100 is added. In addition, using a titanium oxide paste that has been stabilized by stirring, it is applied by spin coating, screen printing, or the like, and is 300 to 600 ° C., preferably 400 to 500 ° C. in air, for 10 to 60 minutes. Preferably, the porous semiconductor layer can be easily formed by heat treatment for 20 to 40 minutes. The specific composition is not limited to this, but anatase-type titanium oxide (6 g), acetylacetone (0.2 mL), deionized water (8 mL), Triton X-100 (poly (oxyethylene) = Octylphenyl ether; Roche Diagnostics Co., Ltd.) (0.2 mL).

Further, on the surface of the formed porous semiconductor layer, for example, TiCl ₄ treatment, that is, a laminate in which the porous semiconductor layer is formed is immersed in a TiCl ₄ aqueous solution at about 5 to 95 ° C. for about 1 to 100 minutes. After washing with water, if baking treatment is performed at about 300 to 650 ° C. for about 1 to 100 minutes, the conductivity can be further improved and the photoelectric conversion efficiency can be improved.

Thereafter, the raw material solution of the buffer layer 5 and the raw material solution of the light absorption layer 6 are sprayed in order as in the embodiment of FIG. As a result, the semiconductor fine particles 8 are covered with In ₂ S ₃ 9 which is a material of the buffer layer, and a layer in which CuInS ₂ 10 which is the material of the light absorption layer enters the gap is formed. Thereby, the active area of the light absorption layer 6 can be enlarged and photoelectric conversion efficiency can be improved.

  Further, a back electrode may be formed thereon in the same manner as in the embodiment shown in FIG.

2. Application of photoelectric conversion element The photoelectric conversion element of the present invention can be applied to various applications by using the photoelectric conversion element of the present invention as a power generation means and supplying the generated power of the power generation means to a load. Specifically, the photoelectric conversion device of the present invention, a photoelectric conversion device having a configuration including an inverter device that converts a direct current output from the photoelectric conversion device of the present invention into an alternating current, an electric motor, a lighting device, and the like can do. As its application, for example, it can be used as a CIS type solar cell installed on the roof, wall surface, etc. of a building.

  The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

Example 1
The photoelectric conversion element of the aspect of FIG. 1 was produced as follows.

As the translucent substrate 2 having the translucent conductive layer 3, a translucent conductive layer made of SnO ₂ : F layer (fluorine-doped SnO ₂ layer) having a sheet resistance of 10Ω / □ (square) and a thickness of about 0.5 μm. A metal oxide semiconductor layer 4 made of titanium oxide was laminated on a glass substrate having a main surface of about 200 nm in thickness. The spraying method is used as the laminating method, the surface temperature of the light-transmitting conductive layer is about 400 to 450 ° C., and the precursor solution is a TAA solution (a solution of titanium (IV) isopropoxide and acetylacetone = 1: 2 (molar ratio)). 50 ml of an ethanol solution diluted 10-fold, and sprayed for 50 minutes.

A buffer layer 5 having a thickness of about 0.7 μm was formed on the metal oxide semiconductor layer 4 by a spray method. The surface temperature of the metal oxide semiconductor layer 4 was set to about 200 ° C., and 50 ml of an aqueous solution in which 10 mM InCl ₃ and 20 mM CS (NH ₂ ) ₂ were mixed as a precursor solution was sprayed for 50 minutes.

Next, a light absorption layer 6 having a thickness of about 1 μm was laminated on the buffer layer 5 by a spray method. At that time, the surface temperature on the buffer layer 5 is set to about 300 ° C., and 30 ml of a mixed solution of 30 mM CuCl ₂ .2H ₂ O, 24 mM InCl ₃ and 120 mM CS (NH ₂ ) ₂ is used as the precursor solution. For 30 minutes.

Finally, molybdenum was deposited as a back electrode 7 on the light absorption layer 6 to a thickness of about 100 nm by a sputtering method, and the photoelectric conversion element 1 was manufactured. The photoelectric conversion element 1 was 5 mm square (= 25 mm ² ), and six photoelectric conversion elements 1 having the same structure were produced.

Comparative Example 1
As a comparative example for improving reproducibility and photoelectric conversion efficiency, a photoelectric conversion element 1 was produced in the same manner as in Example 1 except that the thickness of the buffer layer 5 was less than 0.2 μm.

  Specifically, the buffer layer 5 was formed by using 10 ml of the same precursor solution as in Example 1 and spraying for 30 minutes.

Example 2
The same procedure as in Example 1 was performed except that the metal oxide semiconductor layer 4 made of WO ₃ was formed.

First, WCl ₆ was dissolved in ethanol so as to be 100 mM, and stirred with a magnetic stirrer for 1 hour to prepare a solution.

  Subsequently, the solution was dropped on an FTO glass substrate with a 1 mL dropper, and spin coating was performed. Thereafter, it was dried at 125 ° C. for 3 minutes. Then, the substrate was sufficiently cooled (about 7 to 8 minutes at room temperature).

This operation was repeated 20 times, and finally sintered at 600 ° C. for 3 hours to obtain a WO ₃ layer having a thickness of about 200 nm.

Test Example The photoelectric exchange elements of Example 1 and Comparative Example 1 were irradiated with AM1.5 solar simulator light (100 mW / cm ² ) to measure photoelectric characteristics.

  The photoelectric conversion element of Comparative Example 1 had a low photoelectric conversion efficiency of 0.6 ± 0.4% and a large variation. On the other hand, the photoelectric conversion efficiency of the photoelectric conversion element of Example 1 in which the buffer layer of about 0.7 μm was laminated was 1.0 ± 0.3%, the photoelectric conversion efficiency was improved, and the variation was reduced. (Figure 3).

1 photoelectric conversion element 2 a transparent substrate 3 transparent conductive layer 4 metal oxide semiconductor layer 5 buffer layer 6 light absorbing layer 7 back electrode 8 semiconductor fine particles 9 an In ₂ S ₃
10 CuInS ₂
S sunlight

Claims (12)

At least a metal oxide semiconductor layer and a buffer layer made of a compound containing indium and sulfur,
The buffer layer is a photoelectric conversion element formed on a metal oxide semiconductor layer by a spray method and having a thickness of 0.2 to 1.0 μm. The photoelectric conversion element according to claim 1, wherein the compound containing indium and sulfur is In ₂ S ₃ . The photoelectric conversion element according to claim 1, wherein the metal oxide semiconductor layer has a porous structure. The metal oxide semiconductor layer is at least one selected from the group consisting of titanium oxide, tungsten oxide, zinc oxide, niobium oxide, tantalum oxide, and strontium titanate. The photoelectric conversion element as described in 2. Furthermore, the photoelectric conversion element in any one of Claims 1-4 provided with the light absorption layer which consists of a chalcopyrite type | system | group semiconductor formed by the spray method on the buffer layer. Furthermore, the photoelectric conversion element in any one of Claims 1-5 provided with a translucent conductive layer on a metal oxide semiconductor layer. The translucent conductive layer is at least one transparent conductive oxide selected from the group consisting of fluorine-doped tin oxide, indium-doped tin oxide, gallium-doped tin oxide, aluminum-doped tin oxide and niobium-doped tin oxide The photoelectric conversion element according to claim 1, comprising: Furthermore, the photoelectric conversion element in any one of Claims 1-7 provided with a translucent board | substrate on a translucent conductive layer, and provided with a back electrode on a light absorption layer. The photoelectric conversion element according to claim 8, wherein the translucent substrate is made of glass or plastic. The photoelectric conversion element according to claim 8 or 9, wherein the back electrode is made of at least one selected from the group consisting of molybdenum, gold, silver, aluminum, carbon, and platinum. At least a step of forming a buffer layer by spraying a raw material solution containing InCl ₃ and CS (NH ₂ ) ₂ in air on a metal oxide semiconductor layer having a spray surface heated to 150 to 350 ° C. The manufacturing method of the photoelectric conversion element in any one of Claims 1-10. A step of forming a light absorption layer by spraying a raw material solution containing CuCl ₂ , InCl ₃ and CS (NH ₂ ) ₂ in air on at least a buffer layer whose spray surface is heated to 250 to 310 ° C. The manufacturing method of the photoelectric conversion element in any one of Claims 5-10 provided.

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