JP2012256781A - Method for manufacturing semiconductor layer, method for manufacturing photoelectric conversion device, and semiconductor layer forming solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To further improve photoelectric conversion efficiency of a photoelectric conversion device.SOLUTION: A method for manufacturing a semiconductor layer comprises the steps of: preparing a first compound containing a first chalcogen element-containing organic compound, a Lewis base, a group I-B element, and a first group III-B element; preparing a second compound containing a second chalcogen element-containing organic compound, a second group III-B element, and ammonium ions; producing a semiconductor layer forming solution containing the first compound, the second compound, and an organic solvent; and forming a semiconductor layer containing a group I-III-VI compound using the semiconductor layer forming solution.

Description

  The present invention relates to a method for producing a semiconductor layer containing an I-III-VI group compound, a method for producing a photoelectric conversion device using the same, and a solution for forming a semiconductor layer.

  As a solar cell, there is a solar cell using a photoelectric conversion device including a light absorption layer containing a chalcopyrite-based I-III-VI group compound such as CIGS. Such a photoelectric conversion device has a substrate containing soda lime glass. On this substrate, for example, a first electrode layer containing Mo, which becomes a back electrode, is formed. A first semiconductor layer containing an I-III-VI group compound is formed as a light absorption layer on the first electrode layer. Further, a second semiconductor layer selected from ZnS, CdS, and the like is formed as a buffer layer on the first semiconductor layer. Further, a transparent second electrode layer containing ZnO or the like is formed on the second semiconductor layer.

  As a manufacturing method for forming such a first semiconductor layer, the following method is disclosed.

In Patent Document 1, a single source precursor (Single Source Precursor) that is a compound in which Cu, Se, and In or Ga are present in one organic compound is used, and Cu (In, Ga) Se is used. _The formation of _two semiconductor layers is described.

US Pat. No. 6,992,202

  However, in the manufacturing method using the single source precursor, it is difficult to control the composition of the first semiconductor layer, that is, the molar ratio of Cu / (In + Ga), and there is a limit in improving the photoelectric conversion efficiency. Therefore, an object of the present invention is to further improve the photoelectric conversion efficiency of the photoelectric conversion device.

  The manufacturing method of the semiconductor layer which concerns on one Embodiment of this invention is a process of preparing the 1st compound containing a 1st chalcogen element containing organic compound, a Lewis base, a IB group element, and a 1st III-B group element. And a step of preparing a second compound containing a second chalcogen element-containing organic compound, a second group III-B element and an ammonium ion, and forming a semiconductor layer containing the first compound, the second compound and an organic solvent And a step of producing a semiconductor layer containing a group I-III-VI compound using the solution for forming a semiconductor layer.

  A method for manufacturing a photoelectric conversion device according to an embodiment of the present invention includes a step of manufacturing a first semiconductor layer by the above-described method for manufacturing a semiconductor layer, and being electrically connected to the first semiconductor layer. And a step of producing a second semiconductor layer having a conductivity type different from that of the first semiconductor layer.

  A solution for forming a semiconductor layer according to an embodiment of the present invention includes a first compound containing a first chalcogen element-containing organic compound, a Lewis base, a group IB element, and a first group III-B element, and a second compound. A chalcogen element-containing organic compound, a second compound containing a second group III-B element and an ammonium ion, and an organic solvent.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to improve the photoelectric conversion efficiency of a photoelectric conversion apparatus.

It is a perspective view which shows an example of embodiment of a photoelectric conversion apparatus. It is sectional drawing of the photoelectric conversion apparatus of FIG.

  Hereinafter, a semiconductor layer manufacturing method, a photoelectric conversion device manufacturing method, and a semiconductor forming solution according to an embodiment of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a perspective view illustrating an example of a photoelectric conversion device manufactured using the method for manufacturing a semiconductor layer according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view thereof. The photoelectric conversion device 11 includes a substrate 1, a first electrode layer 2, a first semiconductor layer 3 that is a semiconductor layer containing an I-III-VI group compound, a second semiconductor layer 4, and a second semiconductor layer 4. And an electrode layer 5. However, the present invention is not limited to this, and the second semiconductor layer 4 may be a semiconductor layer containing an I-III-VI group compound.

  The first semiconductor layer 3 and the second semiconductor layer 4 have different conductivity types and are electrically connected. Thereby, the photoelectric conversion body which can take out an electric charge favorably is formed. For example, if the first semiconductor layer 3 is p-type, the second semiconductor layer 4 is n-type. A high-resistance buffer layer may be interposed between the first semiconductor layer 3 and the second semiconductor layer 4. In the present embodiment, an example is shown in which the first semiconductor layer 3 is a one-conductivity type light absorption layer, and the second semiconductor layer 4 serves both as a buffer layer and the other conductivity-type semiconductor layer.

  Moreover, although the photoelectric conversion apparatus 11 in this embodiment assumes what light enters from the 2nd electrode layer 5 side, it is not limited to this, Light enters from the board | substrate 1 side. There may be.

  1 and 2, a plurality of photoelectric conversion cells 10 are arranged and electrically connected to each other to constitute a photoelectric conversion device 11. The photoelectric conversion cell 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. 1 and 2, the third electrode layer 6 is obtained by extending the first electrode layer 2 of the adjacent photoelectric conversion cell 10. With this configuration, adjacent photoelectric conversion cells 10 are connected in series. In one photoelectric conversion cell 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 cell 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 contains a I-III-VI group compound. An I-III-VI group compound is a group consisting of 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, has a chalcopyrite structure, and is called a chalcopyrite compound (also called a CIS compound). Examples of the I-III-VI group compound include Cu (In, Ga) Se ₂ (also referred to as CIGS), Cu (In, Ga) (Se, S) ₂ (also referred to as CIGSS), and CuInSe ₂ (also referred to as CIS). Say). Incidentally, Cu (In, Ga) and Se ₂ refers mainly a compound containing Cu and In, Ga and Se. Cu (In, Ga) (Se, S) ₂ refers to a compound mainly containing Cu, In, Ga, Se, and S. Such an I-III-VI group compound has high photoelectric conversion efficiency, and an effective electromotive force can be obtained even when used as a thin layer of 10 μm or less.

  Such a first semiconductor layer 3 is manufactured as follows. First, a solution for forming a semiconductor layer for forming the first semiconductor layer 3 is prepared. Then, a film is formed using the semiconductor layer forming solution, and the film is heat-treated to form the first semiconductor layer 3. Such a solution for forming a semiconductor layer is prepared by a step of preparing a first compound, a step of preparing a second compound, and a step of preparing a solution for forming a semiconductor layer. Each step will be described in detail below.

<< Step of Preparing First Compound >>
The first compound contains a first chalcogen element-containing organic compound, a Lewis base, a group IB element, and a first group III-B element in one complex molecule. That is, the 1st compound contains all the IB group element, the III-B group element, and the VI-B group element which are the elements which comprise an I-III-VI group compound. And I-III-VI group compound can be formed by the chemical reaction of these elements. Thus, the first compound is sometimes referred to as a single source precursor.

  The chalcogen element-containing organic compound is an organic compound having a chalcogen element (the chalcogen element is S, Se, or Te among VI-B group elements), and an organic compound having a covalent bond between a carbon element and a chalcogen element It is. Examples of the chalcogen element-containing organic compound include thiol, sulfide, disulfide, thiophene, sulfoxide, sulfone, thioketone, sulfonic acid, sulfonic acid ester, sulfonic acid amide, selenol, selenide, diselenide, selenoxide, selenone, tellurol, telluride, ditelluride, etc. There is. In particular, thiol, sulfide, disulfide, selenol, selenide, diselenide, tellurol, telluride, ditelluride may be used from the viewpoint of high coordination power and easy formation of a stable complex with a metal element.

  A Lewis base is a compound having an unshared electron pair. As the Lewis base, an organic compound having a functional group including a VB group element having an unshared electron pair (also referred to as a Group 15 element) or a VI-B group element having an unshared electron pair is used. Used.

An example of the first compound is shown in Structural Formula 1. In the formula, R′-E ′ is a first chalcogen element-containing organic compound (R ′ is an organic compound, and E ′ is a chalcogen element). L is the first Lewis base. ^MI is an IB group element. M ^III ′ is a first group III-B element.

  Such a first compound is prepared as follows. The production method of the first compound includes a production process of the first complex solution, a production process of the second complex solution, and a production process of the precipitate having the first compound. Each step will be described in detail below.

<Process for producing first complex solution>
First, the 1st complex solution in which the 1st complex containing a Lewis base and an IB group element exists is produced. As the Lewis base, an organic compound containing a VB group element (also referred to as a Group 15 element) such as P (C ₆ H ₅ ) ₃ , As (C ₆ H ₅ ) ₃ , and N (C ₆ H ₅ ) ₃ is used. May be used. As the raw material of the I-B group _element, Cu (CH 3 _CN) organometallic complex such as 4 · PF ₆ and the like. As the organic ligand used in the organometallic complex, those having weaker basicity than the above Lewis base are preferable. Moreover, acetonitrile, acetone, methanol, ethanol, isopropanol etc. are mentioned as an organic solvent of a 1st complex solution.

The Lewis base is L, the organometallic complex of the group IB element is [M ^I R ¹ _m ] ⁺ (X ¹ ) ^−, and the first complex is [L _n M ^I R ¹ _(mn) ] ⁺ ( When X ¹ ) ^— , the reaction for forming the first complex is represented by Reaction Formula 1. In this case, ^{M I} is I-B group element, ^{R 1} is any organic ligand, ^{(X 1) -} shows the any anion.

As a specific example of Reaction Formula 1, for example, Lewis base L is P (C ₆ H ₅ ) ₃ , organometallic complex [M′R ′ _m ] ⁺ (X ′) ^{− of} group IB element is Cu (CH ₃ CN) ₄ · PF ₆ , the first complex [L _n M′R ′ _(mn) ] ⁺ (X ′) ⁻ is {P (C ₆ H ₅ ) ₃ } ₂ Cu (CH ₃ CN) _2. Generated as PF ₆ .

<Process for producing second complex solution>
A second complex solution in which a second complex containing the first chalcogen element-containing organic compound and the first group III-B element is present is produced. As the first chalcogen element-containing organic compound, phenyl selenol, diphenyl diselenide, or the like may be used. In addition, examples of the material of the first group III-B element include metal salts such as InCl ₃ and GaCl ₃ . Moreover, methanol, ethanol, propanol etc. are mentioned as an organic solvent of a 2nd complex solution.

The chalcogen element is E ′, the metal salt of the first chalcogen element-containing organic compound is A (E′R ′), the metal salt of the first group III-B element is M ^III ′ (X ² ) ₃ , When the second complex is A ⁺ [M ^III ′ (E′R ′) ₄ ] ⁻ , the reaction for forming the second complex is represented by reaction formula 2. At this time, R ′ represents an organic compound, A represents an arbitrary cation, M ^III ′ represents a first group III-B element, and X ² represents an arbitrary anion. In addition, the metal salt A (E′R ′) of the first chalcogen element-containing organic compound is a metal alkoxide such as NaOCH ₃ and a first chalcogen element-containing organic compound such as phenyl selenol (HSeC ₆ H ₅ ). It is obtained by reacting.

As a specific example of Reaction Formula 2, for example, the metal salt A (E′R ′) of the first chalcogen element-containing organic compound is NaSeC ₆ H ₅ , and the metal salt M ^III ′ (X ² ) When ₃ is InCl ₃ or GaCl ₃ , the second complex A ⁺ [M ^III ′ (E′R ′) ₄ ] ⁻ is Na ⁺ [In (SeC ₆ H ₅ ) ₄ ] ⁻ or Na ^+. It is generated as [Ga (SeC ₆ H ₅ ) ₄ ] ⁻ .

  In addition, the 1st III-B group element contained in a 2nd complex solution is not restricted to one type, Multiple types may be contained. For example, both In and Ga may be included in the second complex solution. Such a second complex solution is prepared by using a mixture of a plurality of types of metal salts of the first group III-B elements as a raw material of the second complex solution. Alternatively, a second complex solution containing one kind of first group III-B element may be prepared for each first group III-B element and mixed together.

<Preparation Step of Precipitate Having First Compound>
By mixing the first complex solution and the second complex solution prepared as described above, the first complex reacts with the second complex, and an IB group element such as Cu, In, Ga, etc. And a first compound containing a first compound containing a first group III-B element and a chalcogen element such as Se. A reaction for forming such a first compound [L _n M ^I (E′R ′) ₂ M ^III ′ (E′R ′) ₂ ] is represented by Reaction Scheme 3.

Specific examples of Scheme 3, the first complex is _{{P (C 6 H 5)} 3} 2 Cu (CH 3 CN) 2 · PF 6, second complex is _{^{Na + [M III '(SeC}} 6 H 5) ₄ ] ⁻ (M ^III ′ is In and / or Ga), the first compound is {P (C ₆ H ₅ ) ₃ } ₂ Cu (SeC ₆ H ₅ ) ₂ M ^III ′ (SeC ₆ H ₅ ) Generate as ₂ .

  Then, the precipitate containing the first compound is separated from the solution above the precipitate, and the solution portion is discharged and dried, whereby the precipitate containing the first compound is taken out.

  The temperature set in the reaction between the first complex and the second complex is, for example, 0 to 30 ° C. Moreover, the time of this reaction is 1 to 5 hours, for example. The precipitate generated by the reaction may be washed using a technique such as centrifugation or filtration in order to remove impurities such as Na and Cl.

<< Step of Preparing Second Compound >>
Next, the process of preparing a 2nd compound is shown. The second compound contains a second chalcogen element-containing organic compound, a second group III-B element, and ammonium ions. That is, the second compound is an ammonium salt of a complex in which the second chalcogen element-containing organic compound is coordinated to the second group III-B element, and is represented by, for example, Structural Formula 2. In Structural Formula 2, M ^III ″ is a second group III-B element, R ″ -E ″ is a chalcogen element-containing organic compound (R ″ is an organic compound, and E ″ is a chalcogen element. ). Specific examples of the second complex include those in which MIII ″ is In or Ga and R ″ -E ″ is phenyl selenol or diphenyl diselenide.

  The second chalcogen element-containing organic compound may be the same as or different from the first chalcogen element-containing organic compound. The second group III-B element may be the same as or different from the first group III-B element.

  Such a 2nd compound is produced when a III-B group element is melt | dissolved in the solvent containing the ammonium salt of a chalcogen element containing organic compound. As said solvent, the organic solvent which can melt | dissolve the ammonium salt of a chalcogen element containing organic compound is used, For example, methanol is mentioned. The group III-B element is dissolved in a solvent in which the ammonium salt of the chalcogen element-containing organic compound is dissolved in a metal state, a metal salt state, or an organometallic complex in which an organic ligand is coordinated. And a 2nd compound precipitates by adding a nonpolar solvent or a low polarity solvent to this solution. As the nonpolar solvent or low polarity solvent used for the precipitation of the second compound, a nonpolar solvent such as hexane, heptane, carbon tetrachloride, benzene or the like may be used, or a solvent that dissolves the second compound may be used. Alternatively, a low polarity solvent with low polarity may be used.

  Since the second compound is an ammonium salt, even when the semiconductor layer is formed using the second compound as a raw material, ammonium ions are easily vaporized as ammonia or the like, and it is effective that impurities remain in the semiconductor layer. Can be reduced.

<< Process for Producing Semiconductor Layer Forming Solution >>
By dissolving the first compound and the second compound described above in an organic solvent, a semiconductor layer forming solution is prepared. Thus, by mixing the first compound and the second compound, the molar ratio of the IB group element and the III-B group element can be easily adjusted, and the first photoelectric conversion efficiency is high. The semiconductor layer 3 can be easily manufactured.

  In addition, the second compound has higher affinity with the first compound due to the presence of the second chalcogen element-containing organic compound so as to surround the second group III-B element. Therefore, when a film is formed using such a solution for forming a semiconductor layer, the first compound and the second compound approach each other well, and the first compound and the second compound do not undergo phase separation. , Well dispersed. Further, the presence of the second chalcogen element-containing organic compound so as to surround the second group III-B element facilitates chalcogenization of the second group III-B element. As a result, when the film is heat-treated, the IB group element, III-B group element and VI-B group element contained in the first compound, and the III-B group element and VI- The group B element reacts satisfactorily to form a group I-III-VI group.

  As the organic solvent used for preparing the semiconductor layer forming solution, a solvent capable of dissolving the first compound and the second compound is used. Examples of such an organic solvent include pyridine and acetone.

  The solution for forming a semiconductor layer produced as described above 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. A film is formed. Drying may be performed in a reducing atmosphere. The temperature during drying may be, for example, 50 to 300 ° C.

  And the said membrane | film | coat is heat-processed and the 1st semiconductor layer 3 with a thickness of 1-2.5 micrometers is produced. The heat treatment may be performed in a reducing atmosphere in order to prevent oxidation and obtain a good first semiconductor layer 3. The reducing atmosphere in the heat treatment may be any of a nitrogen atmosphere, a forming gas atmosphere, a hydrogen atmosphere, and the like. The heat treatment temperature may be, for example, 400 ° C to 600 ° C.

  In the heat treatment, a metal element in the film can react with a chalcogen element contained as a chalcogen element-containing organic compound in the film to form an I-III-VI group compound. In addition, in order to further promote chalcogenization of the metal element, a chalcogen element may be separately dissolved in the semiconductor layer forming solution in addition to the first compound and the second compound. Further, when the film is heat-treated, a chalcogen element may be contained in the atmosphere. As a result, a chalcogen element that is easily deficient due to evaporation or the like is sufficiently supplied, and the first semiconductor layer 3 having a desired composition ratio is easily formed.

  By using the semiconductor layer forming solution as described above, the first semiconductor layer 3 having a desired composition ratio can be easily formed. The photoelectric conversion of the photoelectric conversion device including the first semiconductor layer 3 Efficiency can be increased.

  In the photoelectric conversion device 10, a second semiconductor layer 4 having a conductivity type different from that of the first semiconductor layer 3 is formed on the first semiconductor layer 3. The first semiconductor layer 3 and the second semiconductor layer 4 have different conductivity types, one being n-type and the other being p-type, and these are pn-junctioned. Alternatively, the first semiconductor layer 3 may be p-type and the second semiconductor layer 4 may be n-type, or the reverse relationship may be used. The pn junction by the first semiconductor layer 3 and the second semiconductor layer 4 is not limited to the one in which the first semiconductor layer 3 and the second semiconductor layer 4 are directly joined. For example, another semiconductor layer having the same conductivity type as that of the first semiconductor layer 3 or another semiconductor layer having the same conductivity type as that of the second semiconductor layer 4 may be further provided therebetween. Further, a pin junction having an i-type semiconductor layer may be provided between the first semiconductor layer 3 and the second semiconductor layer 4.

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. In this case, the second semiconductor layer 4 is formed with a thickness of 10 to 200 nm by, for example, a chemical bath deposition (CBD) method or the like. In (OH, S) refers to a compound mainly containing In, OH, and S. (Zn, In) (Se, OH) refers to a compound mainly containing Zn, In, Se, and OH. (Zn, Mg) O refers to a compound mainly containing Zn, Mg and O.

  The second electrode layer 5 is a 0.05 to 3 μm transparent conductive film such as ITO or ZnO. In order to improve translucency and conductivity, the second electrode layer 5 may be made of a semiconductor having the same conductivity type as the second semiconductor layer 4. 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, the resistivity of the second electrode layer 5 may be less than 1 Ω · cm and the sheet resistance may be 50 Ω / □ or less.

  The second electrode layer 5 may have optical transparency with respect to the light absorbed by the first semiconductor layer 3 in order to increase the absorption efficiency of the first semiconductor layer 3. The second electrode layer 5 may have a thickness of 0.05 to 0.5 μm from the viewpoint of improving the light transmittance and transmitting the current generated by the photoelectric conversion satisfactorily. Further, from the viewpoint of reducing light reflection at the interface between the second electrode layer 5 and the second semiconductor layer 4, even if the refractive index difference between the second electrode layer 5 and the second semiconductor layer 4 is small. Good.

  A plurality of photoelectric conversion cells 10 are arranged and electrically connected to form a photoelectric conversion device 11. In order to easily connect adjacent photoelectric conversion cells 10 in series, as shown in FIG. 1, the photoelectric conversion cell 10 is separated from the first electrode layer 2 on the substrate 1 side of the first semiconductor layer 3. A third electrode layer 6 is provided. 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.

  In FIG. 1, the connection conductor 7 is formed by filling a conductor such as a conductive paste in a groove that penetrates the first semiconductor layer 3, the second semiconductor layer 4, and the second electrode layer 5. . The connection conductor 7 is not limited to this, and may be formed by extending the second electrode layer 5.

  Further, 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. For example, as shown in FIG. 1, the collector electrode 8 is formed in a linear shape from one end of the photoelectric conversion cell 10 to the connection conductor 7. As a result, the current generated by the photoelectric conversion of the first semiconductor layer 3 is collected by the current collecting electrode 8 via the second electrode layer 5, and is favorably applied to the adjacent photoelectric conversion cell 10 via the connection conductor 7. Conducted. Therefore, the current generated in the first semiconductor layer 3 is provided even if the second electrode layer 5 is thinned in order to increase the light transmittance to the first semiconductor layer 3 by providing the collecting electrode 8. Can be taken out efficiently. As a result, the photoelectric conversion efficiency can be increased.

  The collector electrode 8 may have a width of 50 to 400 μm from the viewpoint of increasing the light transmittance 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 is 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.

  It should be noted that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the present invention.

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 11: Photoelectric Conversion device

Claims (4)

Providing a first compound comprising a first chalcogen element-containing organic compound, a Lewis base, a group IB element, and a first group III-B element;
Preparing a second compound containing a second chalcogen element-containing organic compound, a second group III-B element and ammonium ions;
Producing a semiconductor layer forming solution containing the first compound, the second compound and an organic solvent;
And a step of producing a semiconductor layer containing an I-III-VI group compound using the solution for forming a semiconductor layer.   In the step of preparing the second compound, the second compound precipitated by adding a low-polarity solvent to a solution containing ammonium ions, the second chalcogen element-containing organic compound, and the second group III-B element. The method for producing a semiconductor layer according to claim 1, which is a step of taking out. Producing a first semiconductor layer by the method for producing a semiconductor layer according to claim 1 or 2,
And a step of producing a second semiconductor layer having a conductivity type different from that of the first semiconductor layer so as to be electrically connected to the first semiconductor layer. Production method. A first compound comprising a first chalcogen element-containing organic compound, a Lewis base, a group IB element and a first group III-B element;
A second compound containing a second chalcogen element-containing organic compound, a second group III-B element and ammonium ions;
A solution for forming a semiconductor layer containing an organic solvent.

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