JP2011249560A - Semiconductor layer manufacturing method and photoelectric conversion device manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide, using a simple method, a semiconductor layer having a large crystal grain size and a photoelectric conversion device having a high photoelectric conversion efficiency.SOLUTION: A semiconductor layer manufacturing method includes: a step for forming a material coating by applying a material solution containing group III-VI compound semiconductor particles and group I-III-VI compound semiconductor particles having a hexagonal crystal system structure onto a substrate; and a step for producing a group I-III-VI compound semiconductor layer having a tetragonal crystal system structure by heating the material coating to thereby cause a reaction between the group III-VI compound semiconductor particles and the group I-III-VI compound semiconductor particles.

Description

  The present invention relates to a method for manufacturing a semiconductor layer and a method for manufacturing a photoelectric conversion device using the same.

  Some solar cells use a photoelectric conversion device including a light absorption layer made of a chalcopyrite-based I-III-VI group compound semiconductor such as CIGS. In this photoelectric conversion device, for example, a first electrode layer made of, for example, Mo is formed on a substrate made of soda-lime glass, and the I-III-VI group compound is formed on the first electrode layer. A light absorption layer made of a semiconductor is formed. Further, a transparent second electrode layer made of ZnO or the like is formed on the light absorption layer via a buffer layer made of ZnS, CdS or the like.

  As a manufacturing method for forming such a semiconductor layer constituting the light absorption layer, various methods aimed at lowering cost can be used instead of a high-cost manufacturing method using a vacuum system such as a sputtering method that has been conventionally used. Manufacturing methods are being developed.

For example, in Patent Document 1, a metal chalcogenide such as Cu ₂ S is dissolved in hydrazine (N ₂ H ₄ ) to form a metal hydrazinium-based precursor solution, and this solution is added to a substrate having an electrode layer. A technique is disclosed in which a metal chalcogenide film (compound semiconductor layer) can be obtained by coating on the electrode to form a precursor layer and then heat-treating the precursor layer.

US Pat. No. 7,341,917

  However, a compound semiconductor layer manufactured using a metal hydrazinium precursor as shown in Patent Document 1 has a problem that the crystal grain size is small and the photoelectric conversion efficiency is low.

  The present invention has been completed in view of the above-described conventional problems, and an object thereof is to provide a semiconductor layer having a large crystal grain size and a photoelectric conversion device having high photoelectric conversion efficiency by a simple method.

  A method for producing a semiconductor layer according to an embodiment of the present invention includes applying a raw material solution containing III-VI compound semiconductor particles and a hexagonal structure I-III-VI compound semiconductor particle on a substrate, Forming a film; and heating the raw material film to react the group III-VI compound semiconductor particles with the group I-III-VI compound semiconductor particles to form a group I-III-VI having a tetragonal structure And a step of producing a compound semiconductor layer.

  A method for manufacturing a photoelectric conversion device according to an embodiment of the present invention includes a step of producing the group I-III-VI compound semiconductor layer on a substrate by the method for manufacturing a semiconductor layer, and the group I-III-VI. And a step of forming a semiconductor layer having a conductivity type different from that of the I-III-VI group compound semiconductor layer on the compound semiconductor layer.

  According to the method for producing a semiconductor layer of the present invention, a semiconductor layer having a large crystal grain size can be produced by a simple method.

  Moreover, according to the manufacturing method of the photoelectric converting layer of this invention, a photoelectric conversion apparatus with high photoelectric conversion efficiency is producible with a simple method.

It is a perspective view showing an example of an embodiment of a photoelectric conversion device using a semiconductor layer. It is sectional drawing of the photoelectric conversion apparatus of FIG.

  FIG. 1 is a perspective view illustrating an example of an embodiment of a photoelectric conversion device manufactured using the method for manufacturing a semiconductor layer of the present invention, and FIG. 2 is a cross-sectional view thereof. The photoelectric conversion device 10 includes a substrate 1, a first electrode layer 2, a first semiconductor layer 3, a second semiconductor layer 4, and a second electrode layer 5. In this embodiment, an example in which the first semiconductor layer 3 is a light absorption layer and the second semiconductor layer 4 is a buffer layer bonded to the first semiconductor layer 3 is shown, but the present invention is not limited to this.

  1 and 2, a plurality of photoelectric conversion devices 10 are formed side by side. The photoelectric conversion device 10 includes a third electrode layer 6 provided on the substrate 1 side of the first semiconductor layer 3 so as to be separated from the first electrode layer 2. The second electrode layer 5 and the third electrode layer 6 are electrically connected by the connection conductor 7 provided in the first semiconductor layer 3. The third electrode layer 6 is integrated with the first electrode layer 2 of the adjacent photoelectric conversion device 10. With this configuration, adjacent photoelectric conversion devices 10 are connected in series. In one photoelectric conversion device 10, the connection conductor 7 is provided so as to penetrate the first semiconductor layer 3 and the second semiconductor layer 4, and the first electrode layer 2 and the second electrode layer are provided. The first semiconductor layer 3 and the second semiconductor layer 4 sandwiched between 5 and 5 perform photoelectric conversion.

  The substrate 1 is for supporting the photoelectric conversion device 10. Examples of the material used for the substrate 1 include glass, ceramics, resin, and metal.

  The first electrode layer 2 and the third electrode layer 6 are made of a conductor such as Mo, Al, Ti, or Au, and are formed on the substrate 1 by a sputtering method or a vapor deposition method.

The first semiconductor layer 3 is a group I-III-VI compound semiconductor having a chalcopyrite structure belonging to the tetragonal system. The group I-III-VI compound semiconductor is a group IB element (also referred to as a group 11 element), a group III-B element (also referred to as a group 13 element), and a group VI-B element (also referred to as a group 16 element). It is a compound semiconductor. Examples of the I-III-VI group compound semiconductor include Cu (In, Ga) Se ₂ (also referred to as CIGS), Cu (In, Ga) (Se, S) ₂ (also referred to as CIGSS), and CuInS ₂ (CIS). Also called). Cu (In, Ga) Se ₂ refers to a compound mainly composed of Cu, In, Ga, and Se. Cu (In, Ga) (Se, S) ₂ refers to a compound mainly composed of Cu, In, Ga, Se, and S.

  Such a first semiconductor layer 3 is manufactured as follows. First, a raw material solution containing III-VI group compound semiconductor particles and hexagonal I-III-VI group compound semiconductor particles is applied onto a substrate 1 having a first electrode layer 2 as a precursor. The raw material film is formed. These raw material films may be a plurality of laminated bodies having different compositions.

The group III-VI compound semiconductor particles are particles containing a compound semiconductor of a group III-B element and a group VI-B element. Examples of such a material include In ₂ Se, Ga ₂ Se, In ₂ S, and Ga ₂ S. As such III-VI group compound semiconductor particles, those having an average particle diameter of 0.1 μm or less are used from the viewpoint of improving the reactivity and favorably producing the first semiconductor layer 3 having large crystal grains. It is desirable. More preferably, the thickness is preferably 50 to 300 nm from the viewpoint of increasing the reactivity with the hexagonal structure I-III-VI group compound semiconductor particles.

  The hexagonal structure I-III-VI group compound semiconductor particles are particles having a hexagonal structure including a compound semiconductor of a group I-B element, a group III-B element, and a group VI-B element. Since the I-III-VI group compound semiconductor is more stable in the tetragonal structure than in the hexagonal structure, the hexagonal structure shows higher activity. Therefore, by heat-treating such a highly active hexagonal structure I-III-VI group compound semiconductor particle together with the III-VI group compound semiconductor particle, crystallization is promoted and the crystal grain size is large. The first semiconductor layer 3 made of an I-III-VI group compound semiconductor can be formed.

  In addition, such an I-III-VI group compound semiconductor particle has an average particle size of 0.1 μm or less from the viewpoint of improving the reactivity and satisfactorily producing the first semiconductor layer 3 having large crystal grains. It is desirable to use those. More preferably, the thickness is preferably 50 to 300 nm from the viewpoint of increasing the reactivity.

  The group III-B element of the III-VI compound semiconductor particle and the group III-B element of the hexagonal I-III-VI compound semiconductor particle may be the same element or different. May be. Similarly, the VI-B group element of the III-VI group compound semiconductor particle and the VI-B group element of the I-III-VI group compound semiconductor particle having a hexagonal structure may be the same element or different. It may be a thing. By combining these, the formed first semiconductor layer 3 can easily have a desired composition ratio. That is, there is a limit in controlling the composition ratio of each element only with the hexagonal structure I-III-VI group compound semiconductor particles, but the hexagonal structure I-III-VI group compound semiconductor particles and III- By reacting with the group VI compound semiconductor particles, the composition ratio of the first semiconductor layer 3 to be formed can be easily changed over a wide range.

  In the I-III-VI group compound semiconductor particles having a hexagonal structure, the atomic ratio of the III-B group element to the IB group element forms a chalcopyrite-structured I-III-VI group compound semiconductor satisfactorily. From the viewpoint, it is preferably 1.0 to 1.3 times. Further, from the viewpoint of enhancing the reactivity, the III-VI group compound semiconductor particles and the hexagonal I-III-VI group compound semiconductor particles are the III-B group semiconductor elements of the III-VI group compound semiconductor particles. The total number of group III-B elements in the hexagonal structure I-III-VI compound semiconductor particles is equal to the number of atoms in the group I-B elements in the hexagonal structure I-III-VI compound semiconductor particles. It is preferable to mix so that it may become 1.1 to 1.3 times.

  The hexagonal structure I-III-VI group compound semiconductor particles can be produced, for example, as follows. First, a mixed solvent containing a chalcogen element-containing organic compound and a Lewis basic organic compound (hereinafter referred to as a chalcogen element-containing organic compound) and a group I-B element such as Cu and a group III-B element such as Ga or In. A mixed solvent containing a Lewis basic organic compound is simply dissolved in the mixed solvent S) to prepare a solution. Note that a VI-B group element such as Se may be further dissolved in this solution. Next, this solution is heated under a temperature condition of 150 to 200 ° C. for 1 minute to 20 hours, whereby I-III-VI group compound semiconductor particles having a hexagonal structure can be precipitated.

Here, the chalcogen element-containing organic compound is an organic compound containing a chalcogen element.
A chalcogen element means S, Se, and Te among VI-B group elements. When the chalcogen element is S, examples of the chalcogen element-containing organic compound include thiol, sulfide, disulfide, thiophene, sulfoxide, sulfone, thioketone, sulfonic acid, sulfonic acid ester, and sulfonic acid amide. Preferably, thiol, sulfide, disulfide and the like are preferable from the viewpoint that a metal solution can be favorably produced by forming a complex with a metal. In particular, those having a phenyl group are preferred from the viewpoint of enhancing the coating property. As what has such a phenyl group, thiophenol, diphenyl sulfide, etc. and derivatives thereof are mentioned, for example.

  When the chalcogen element is Se, examples of the chalcogen element-containing organic compound include selenol, selenide, diselenide, selenoxide, and selenone. Preferably, from the viewpoint that a metal solution can be satisfactorily formed by forming a complex with a metal, serer, selenide, diselenide and the like are preferable. In particular, those having a phenyl group are preferred from the viewpoint of enhancing the coating property. Examples of those having such a phenyl group include phenyl selenol, phenyl selenide, diphenyl diselenide and the like and derivatives thereof.

  When the chalcogen element is Te, examples of the chalcogen element-containing organic compound include tellurol, telluride, ditelluride, and the like.

  The Lewis basic organic compound is an organic compound having a functional group that can be a Lewis base with respect to an IB group element or an III-B group element. The functional group that can be a Lewis base includes a functional group having a VB group element having an unshared electron pair (also referred to as a Group 15 element) and a functional group having a VI-B group element having an unshared electron pair. Are preferable, and examples thereof include an amino group (any of primary amine to tertiary amine), a carbonyl group, a cyano group, and the like. Specific examples of Lewis basic organic compounds include pyridine, aniline, triphenylphosphine, 2,4-pentanedione, 3-methyl-2,4-pentanedione, triethylamine, triethanolamine, acetonitrile, benzyl, benzoin and the like. And derivatives thereof. Nitrogen-containing organic compounds are particularly preferable from the viewpoint of increasing the solubility of metal elements. Further, from the viewpoint of improving the coating property, those having a boiling point of 100 ° C. or higher are preferable.

  The above mixed solvent S is preferably a combination that becomes liquid at room temperature from the viewpoint of handleability. The chalcogen element-containing organic compound is preferably 1 to 250 mol% with respect to the Lewis basic organic compound. Thereby, a chemical bond between each raw material element and the chalcogen element-containing organic compound and a chemical bond between the chalcogen element-containing organic compound and the Lewis basic organic compound can be satisfactorily formed, and the hexagonal structure I-III- Group VI compound semiconductor particles can be produced satisfactorily.

  As a method of dissolving a group I-B element such as Cu and a group III-B element such as Ga or In in the mixed solution S, a group I-B element and a group III-B element (if necessary, VI -B group element) may be dissolved in the mixed solvent S in the form of a simple substance or an alloy, or in the form of an organometallic salt. Preferably, the group I-B element and the group III-B element (and the group VI-B element as necessary) are directly dissolved in the form of a simple substance or an alloy. Thereby, it can suppress effectively that an unnecessary organic component remains in the 1st semiconductor layer 3, and can perform crystallization favorably.

For example, when the first semiconductor layer 3 is CIGS, Cu as the IB group element, In and Ga as the III-B group element, phenyl selenol and Lewis base as the chalcogen element-containing organic compound 50 to 30 dispersed in the solution by dissolving in a mixed solvent S with aniline as a soluble organic compound and heating this solution at 150 to 200 ° C. for 1 to 20 hours
Fine particles containing 0 nm hexagonal CIGS can be formed. Then, by removing the fine particles by centrifugation or the like, I-III-VI group compound semiconductor particles (CIGS particles) having a hexagonal structure can be isolated. This crystal structure can be specified by the Rietveld method.

  The first semiconductor layer 3 is prepared by dispersing the hexagonal structure I-III-VI group compound semiconductor particles prepared as described above together with the III-VI group compound semiconductor particles in an organic solvent such as pyridine or aniline. It can be set as the raw material solution for forming.

  The raw material solution is applied to the surface of the substrate 1 having the first electrode 2 by using a spin coater, screen printing, dipping, spraying, or a die coater, and dried to form a raw material film. Drying is desirably performed in a reducing atmosphere. The temperature at the time of drying is 50-300 degreeC, for example.

And the I-III-VI group compound semiconductor of the chalcopyrite structure which belongs to a tetragonal system can be produced by 1.0-2.5 micrometers thickness by heat-processing the said raw material film | membrane. The heat treatment is preferably performed in a reducing atmosphere in order to prevent oxidation and form a good semiconductor layer. In particular, the reducing atmosphere in the heat treatment is preferably any one of a nitrogen atmosphere, a forming gas atmosphere, and a hydrogen atmosphere. The heat treatment temperature is, for example, 400 ° C to 600 ° C. In this heat treatment, from the viewpoint of satisfactorily crystallizing the first semiconductor layer 3, a chalcogen element may be mixed in the atmosphere in a state such as Se vapor or H ₂ Se.

The photoelectric conversion device 10 uses the first semiconductor layer 3 as a light absorption layer, and the second semiconductor layer 4 as a buffer layer is formed on the first semiconductor layer 3 with a thickness of 10 to 200 nm. The second semiconductor layer 4 is a semiconductor layer having a conductivity type different from that of the first semiconductor layer 3 and performing a heterojunction with the light absorption layer 3. For example, when the first semiconductor layer 3 is a p-type semiconductor, the second semiconductor layer 4 is an n-type semiconductor or an i-type semiconductor. Preferably, from the viewpoint of reducing leakage current, the second semiconductor layer is a layer having a resistivity of 1 Ω · cm or more. Examples of the second semiconductor layer 4 include CdS, ZnS, ZnO, In ₂ Se ₃ , In (OH, S), (Zn, In) (Se, OH), and (Zn, Mg) O. For example, it is formed by a chemical solution deposition (CBD) method or the like. In (OH, S) refers to a compound mainly composed of In, OH, and S. (Zn, In) (Se, OH) refers to a compound mainly composed of Zn, In, Se, and OH. (Zn, Mg) O refers to a compound mainly composed of Zn, Mg and O. In order to increase the absorption efficiency of the first semiconductor layer 3, the second semiconductor layer 4 preferably has a light transmittance with respect to the wavelength region of light absorbed by the first semiconductor layer 3.

  The second electrode layer 5 is a 0.05 to 3.0 μm transparent conductive film such as ITO or ZnO. The second electrode layer 5 is preferably made of a semiconductor having a conductivity type different from that of the first semiconductor layer 3 in order to improve translucency and conductivity. The second electrode layer 5 is formed by sputtering, vapor deposition, chemical vapor deposition (CVD), or the like. The second electrode layer 5 is a layer having a resistivity lower than that of the second semiconductor layer 4, and is for taking out charges generated in the first semiconductor layer 3. From the viewpoint of taking out charges well, it is preferable that the resistivity of the second electrode layer 5 is less than 1 Ω · cm and the sheet resistance is 50 Ω / □ or less.

In order to increase the absorption efficiency of the first semiconductor layer 3, it is preferable that the second electrode layer 5 has optical transparency with respect to the absorbed light of the first semiconductor layer 3. The second electrode layer 5 has a thickness of 0.05 to 0.5 μm from the viewpoint of enhancing the light transmittance and at the same time enhancing the light reflection loss prevention effect and the light scattering effect and further transmitting the current generated by the photoelectric conversion. Thickness is preferred. Also,
From the viewpoint of preventing light reflection loss at the interface between the second electrode layer 5 and the second semiconductor layer 4, the refractive indexes of the second electrode layer 5 and the second semiconductor layer 4 are preferably equal.

  A plurality of photoelectric conversion devices 10 can be arranged and electrically connected to form a photoelectric conversion module. In order to easily connect adjacent photoelectric conversion devices 10 in series, as shown in FIGS. 1 and 2, the photoelectric conversion device 10 is connected to the first electrode layer 2 on the substrate 1 side of the first semiconductor layer 3. A third electrode layer 6 is provided so as to be spaced apart. The second electrode layer 5 and the third electrode layer 6 are electrically connected by the connection conductor 7 provided in the first semiconductor layer 3.

  The connection conductor 7 is preferably formed and integrated at the same time when the second electrode layer 5 is formed. Thereby, the process can be simplified and the reliability of electrical connection with the second electrode layer 5 can be improved.

  The connection conductor 7 connects the second electrode layer 5 and the third electrode layer 6 and is formed so as to penetrate each first semiconductor layer 3 of the adjacent photoelectric conversion device 10. With such a configuration, photoelectric conversion can be performed satisfactorily in the adjacent light absorption layers 3 and current can be taken out in series connection.

  As shown in FIGS. 1 and 2, a collecting electrode 8 may be formed on the second electrode layer 5. The collecting electrode 8 is for reducing the electric resistance of the second electrode layer 5. From the viewpoint of increasing light transmittance, the thickness of the second electrode layer 5 is preferably as thin as possible, but if it is thin, the conductivity is lowered. However, since the current collecting electrode 8 is provided on the second electrode layer 5, the current generated in the first semiconductor layer 3 can be taken out efficiently. As a result, the power generation efficiency of the photoelectric conversion device 10 can be increased.

  For example, as shown in FIG. 1, the collector electrode 8 is formed in a linear shape from one end of the photoelectric conversion device 10 to the connection conductor 7. Thereby, the current generated by the photoelectric conversion of the first semiconductor layer 3 is collected to the current collecting electrode 8 via the second electrode layer 5, and this current is collected to the adjacent photoelectric conversion device 10 via the connection conductor 7. It can conduct well. Therefore, by providing the current collecting electrode 8, the current generated in the first semiconductor layer 3 can be efficiently taken out even if the second electrode layer 5 is thinned. As a result, power generation efficiency can be increased.

  The collector electrode 8 preferably has a width of 50 to 400 μm from the viewpoint of suppressing light from being blocked to the first semiconductor layer 3 and having good conductivity. The current collecting electrode 8 may have a plurality of branched portions.

  The collector electrode 8 can be formed, for example, by printing a metal paste in which a metal powder such as Ag is dispersed in a resin binder or the like in a pattern and curing it.

  The manufacturing method of the semiconductor layer and the manufacturing method of the photoelectric conversion device of the present invention were evaluated as follows.

  Phenylselenol was dissolved in aniline so as to be 100 mol% to prepare a mixed solvent S. Next, copper, indium, gallium and selenium of bullion are directly dissolved in the mixed solvent S, and 5 mol of copper, indium, gallium and selenium are each dissolved in the mixed solvent S. %, 3 mol%, 2 mol%, and 10 mol%.

  Then, this solution was heated at 185 ° C. for 20 hours with stirring to form CIGS fine particles having an average particle diameter of 50 nm, and the CIGS fine particles were taken out by centrifugation. The average particle size was measured by analyzing the fine particles with an SEM image. Moreover, when the produced CIGS microparticles | fine-particles were analyzed by the Rietveld method, it turned out that it has a hexagonal crystal structure. Moreover, when the produced CIGS microparticles | fine-particles were analyzed by ICP method, it turned out that the atomic ratio of Cu, In, Ga, and Se is 10: 6: 4: 20.

Next, 3.6 g of the CIGS fine particles and 0.4 g of In ₂ Se particles having an average particle diameter of 50 nm were dispersed in 16 g of aniline to prepare a raw material paste.

  Next, a glass substrate 1 on which a first electrode layer 2 made of Mo was formed was prepared, and the raw material solution was applied by a blade method and dried to form a film. After a total of two coatings by this blade method, heat treatment was performed in an atmosphere of hydrogen gas and Se vapor. The heat treatment was performed by raising the temperature to 525 ° C. over 5 minutes and holding at 525 ° C. for 1 hour, followed by natural cooling to produce the first semiconductor layer 3 made of CIGS as a sample having a thickness of 2 μm.

Moreover, the semiconductor layer and the photoelectric converting layer as a comparative example were produced as follows. First, CuI was dissolved in pyridine at 5 mol%, InI ₃ at 3 mol%, and GaI ₃ at 2 mol%. Next, Na ₂ Se was dissolved in methanol so as to be 10 mol%. Then, these solutions were mixed and stirred to form CIGS fine particles having an average particle diameter of 70 nm, and the CIGS fine particles were taken out by centrifugation. When the produced CIGS fine particles were analyzed by the Rietveld method, it was found to have a tetragonal structure. Moreover, when the produced CIGS microparticles | fine-particles were analyzed by ICP method, it turned out that the atomic ratio of Cu, In, Ga, and Se is 0.99: 0.76: 0.17: 2.00.

  When the cross-section observation (cross-section perpendicular to the first semiconductor layer 3) of the sample manufactured in this manner and the first semiconductor layer 3 made of CIGS as a comparative example was performed by SEM, the first example as a comparative example was obtained. The average crystal grain size of one semiconductor layer is 1200 nm, whereas the average crystal grain size of the first semiconductor layer as a sample is 80 nm, and it is observed that the crystal grain size of the sample is larger It was done.

  Cadmium acetate and thiourea were dissolved in 2.5 M aqueous ammonia, and the substrate 1 on which the first semiconductor layer 3 made of the above-mentioned sample and CIGS as a comparative example was formed was immersed in each of the first semiconductor layers 3. A second semiconductor layer 4 made of CdS having a thickness of 50 nm was formed thereon. Further, a transparent second electrode layer 5 made of an Al-doped zinc oxide film was formed on the second semiconductor layer 4 by a sputtering method. Finally, an aluminum electrode (extraction electrode) was formed by vapor deposition, and a photoelectric conversion device 10 was produced as a sample and a comparative example.

And about these photoelectric conversion apparatuses, the photoelectric conversion efficiency was measured, respectively. In addition, about photoelectric conversion efficiency, what is called a stationary light solar simulator is used, and the irradiation intensity of the light with respect to the light-receiving surface of the photoelectric conversion apparatus 10 is 100 mW / cm < ² >, and AM (air mass) is 1.5. The conversion efficiency was measured.

  As a result of the measurement, it was found that the photoelectric conversion efficiency of the photoelectric conversion device as a comparative example was 9%, whereas the photoelectric conversion efficiency of the photoelectric conversion device as a sample was 13%.

1: Substrate 2: First electrode layer 3: First semiconductor layer 4: Second semiconductor layer 5: Second electrode layer 6: Third electrode layer 7: Connection conductor 8: Current collecting electrode 10: Photoelectric Conversion device

Claims (4)

Applying a raw material solution containing III-VI compound semiconductor particles and hexagonal I-III-VI compound semiconductor particles on a substrate to form a raw material film;
A step of producing a I-III-VI group compound semiconductor layer having a tetragonal structure by heating the raw material film and reacting the III-VI group compound semiconductor particles with the I-III-VI group compound semiconductor particles. A method for producing a semiconductor layer, comprising:   The method for producing a semiconductor layer according to claim 1, further comprising a chalcogen element-containing organic compound in the raw material solution. In the I-III-VI group compound semiconductor particles, Cu is used as a group I element, at least one of In and Ga is used as a group III element, and Se is used as a group VI element.
In the group III-VI compound semiconductor particles, using at least one of In and Ga as a group III element and Se as a group VI element,
The method for producing a semiconductor layer according to claim 1 or 2, wherein in the I-III-VI group compound semiconductor layer, the group I element is Cu, the group III element is In and Ga, and the group VI element is Se. A step of producing the I-III-VI group compound semiconductor layer on the substrate by the method of producing a semiconductor layer according to claim 1;
A process for producing a semiconductor layer having a conductivity type different from that of the I-III-VI group compound semiconductor layer on the I-III-VI group compound semiconductor layer.

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