Method for manufacturing perovskite solar cells

Abstract

This invention provides a method for manufacturing perovskite solar cells that improves power generation efficiency. [Solution] The method for manufacturing a perovskite solar cell is to form a first electrode layer 21, a first carrier transport layer 31, a perovskite layer 40, a second carrier transport layer 32, and a second electrode layer 22 on a substrate 10 in this order, wherein in the step of forming the perovskite layer 40, an AX material containing an organic atom A, a metal atom B, or a halogen atom X is mixed with a BX material, and a solution of which a poor solvent is added is applied to cause a chemical reaction between the AX material and the BX material, thereby forming a perovskite layer 40 which is a compound having a perovskite structure of ABX3 and also contains unreacted BX or B from before the chemical reaction. The poor solvent is anisole, chloroanisole, or phenethole.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a perovskite solar cell.

Background Art

[0002] Perovskite solar cells using a perovskite layer as a photoelectric conversion layer are known. Patent Documents 1 and 2 disclose such perovskite solar cells.

[0003] Such a perovskite solar cell includes, sequentially formed on a base material such as glass or a resin film, a first electrode layer (an anode electrode or a cathode electrode), a first carrier transport layer (a hole transport film or an electron transport film), a perovskite layer, a second carrier transport layer (an electron transport film or a hole transport film), and a second electrode layer (a cathode electrode or an anode electrode).

[0004] As a method for forming the perovskite layer, a method is known in which a spin coating method (coating method) is used to apply a solution in which the material of the perovskite layer is dissolved, while a poor solvent (a solvent with low solubility) for the perovskite compound is added dropwise to perform film formation, drying and crystallization of the perovskite layer. Thereby, the power generation efficiency of the perovskite solar cell can be improved.

[0005] Further, Patent Document 1 discloses, as a different method of using the poor solvent, immersing the applied film in the poor solvent after applying the solution containing the material of the perovskite layer. Further, Patent Document 2 discloses, as a different method of using the poor solvent, allowing an adjacent layer to be laminated after applying the solution containing the material of the perovskite layer to contain the poor solvent.

Related Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

[0007] The present inventor proposes yet another method of using a poor solvent to improve the power generation efficiency of perovskite solar cells.

[0008] The present invention aims to provide a method for manufacturing a perovskite solar cell that improves power generation efficiency. [Means for solving the problem]

[0009] The present invention relates to a method for manufacturing a perovskite solar cell, comprising forming a first electrode layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, and a second electrode layer on a substrate in this order, wherein in the step of forming the perovskite layer, an AX material containing an organic atom A, a metal atom B, or a halogen atom X is mixed with a BX material, and a solution obtained by further mixing in a poor solvent is applied to the mixture to chemically react the AX material and the BX material, thereby forming a perovskite layer which is a compound having a perovskite structure of ABX3 and further contains unreacted BX or B from before the chemical reaction. The poor solvent is anisole, chloroanisole, or phenethole. [Effects of the Invention]

[0010] According to the present invention, the power generation efficiency of a perovskite solar cell can be improved. [Brief explanation of the drawing]

[0011] [Figure 1] This is a cross-sectional view showing an example of a solar cell according to this embodiment. [Figure 2] This is a cross-sectional view showing another example of a solar cell according to this embodiment. [Figure 3] This figure shows the observation results of the cross-section in the stacking direction of the perovskite layer in Example 1. [Figure 4] This figure shows the observation results of the cross-section in the stacking direction of the perovskite layer of Comparative Example 1. [Figure 5] This figure shows the observation results of the cross-section in the stacking direction of the perovskite layer of Comparative Example 2. [Modes for carrying out the invention]

[0012] An example of an embodiment of the present invention will be described below with reference to the attached drawings. In each drawing, the same or corresponding parts will be denoted by the same reference numerals. Also, for convenience, hatching and component reference numerals may be omitted, in which case refer to other drawings.

[0013] (Solar cells) Figure 1 is a cross-sectional view showing an example of a solar cell according to this embodiment, and Figure 2 is a cross-sectional view showing another example of a solar cell according to this embodiment. The solar cell 1 shown in Figures 1 and 2 is a perovskite solar cell using a perovskite layer as the photoelectric conversion layer. The solar cell 1 comprises a substrate 10, a first electrode layer 21, a first carrier transport layer 31, a perovskite layer 40, a second carrier transport layer 32, and a second electrode layer 22.

[0014] Note that the polarity differs between the solar cell 1 shown in Figure 1 and the solar cell 1 shown in Figure 2. Specifically, in the solar cell 1 shown in Figure 1, the first carrier transport layer 31 and the second carrier transport layer 32 are the hole transport layer (HTL) and the electron transport layer (ETL), respectively, and the first electrode layer 21 and the second electrode layer 22 are the anode and the cathode, respectively. On the other hand, in the solar cell 1 shown in Figure 2, the first carrier transport layer 31 and the second carrier transport layer 32 are the electron transport layer (ETL) and the hole transport layer (HTL), respectively, and the first electrode layer 21 and the second electrode layer 22 are the cathode and the anode, respectively.

[0015] Further, in the solar cell 1 shown in FIG. 1 and FIG. 2, the base material 10 side, that is, the first electrode layer 21 side may be the light-receiving surface, or the side opposite to the base material 10, that is, the second electrode layer 22 side may be the light-receiving surface. Alternatively, both the base material 10 side and the side opposite to the base material 10, that is, both the first electrode layer 21 side and the second electrode layer 22 side may function as light-receiving surfaces.

[0016] The base material 10 may be an insulating and light-transmissive transparent substrate, or may be a flexible transparent film. Examples of the transparent substrate include substrates composed of materials such as glass or resin. Examples of the transparent film include resin films composed of materials such as polyimide, polyethylene naphthalate, and polyethylene terephthalate.

[0017] The first electrode layer 21 is formed on the base material 10, and functions as an anode (FIG. 1) or a cathode (FIG. 2). The first electrode layer 21 is made of a conductive and light-transmissive transparent conductive film (Transparent Conductive Oxides: TCO). As the material of the first electrode layer 21, transparent conductive metal oxides, for example, indium oxide, tin oxide, zinc oxide, titanium oxide, and composite oxides thereof and the like are used. Among these, indium-based composite oxides containing indium oxide as a main component are preferable. From the viewpoint of high conductivity and transparency, indium oxide is particularly preferable. Furthermore, in order to ensure reliability or higher conductivity, it is preferable to add a dopant to indium oxide. Examples of the dopant include Sn, W, Zn, Ti, Ce, Zr, Mo, Al, Ga, Ge, As, Si, or S and the like. Among these, ITO (Indium Tin Oxide) in which tin (Sn) is added to indium oxide is particularly preferable.

[0018] When the substrate 10 side, that is, the first electrode layer 21 side, is the light-receiving surface, the first electrode layer 21 may include a grid-shaped or slit-shaped metal electrode layer. Alternatively, when the side opposite to the substrate 10, that is, the second electrode layer 22 side, is the light-receiving surface, the first electrode layer 21 may include, for example, a planar metal electrode layer on the substrate 10 side. Examples of the material for the metal electrode layer include Ag, Au, Cu, and the like.

[0019] The first carrier transport layer 31 is formed on the first electrode layer 21, and functions as a hole transport layer (HTL) (Figure 1) or an electron transport layer (ETL) (Figure 2). The first carrier transport layer 31 is made of a light-transmissive semiconductor material.

[0020] Specifically, in Figure 1, the first carrier transport layer 31 functions as a hole transport layer (HTL) that transports holes (first carriers) among the carriers generated by photoelectric conversion in the perovskite layer 40 to the first electrode layer 21. Examples of the main material of the first carrier transport layer 31 serving as the hole transport layer (HTL) include nickel oxide (NiO), copper oxide (Cu₂O), PTAA (Poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine)), Spiro-MeOTAD, and the like.

[0021] On the other hand, in Figure 2, the first carrier transport layer 31 functions as an electron transport layer (ETL) that transports electrons (first carriers) among the carriers generated by photoelectric conversion in the perovskite layer 40 to the first electrode layer 21. Examples of the main material of the first carrier transport layer 31 serving as the electron transport layer (ETL) include titanium oxide (TiO₂), zinc oxide (ZnO), tin oxide (SnO₂), fullerene, and the like.

[0022] Examples of fullerenes include C60, C70, their hydrides, oxides, metal complexes, alkyl groups, and derivatives, such as PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester). By forming the second carrier transport layer 32 from a material containing a fullerene encapsulating lithium Li, the electron transport efficiency can be improved.

[0023] Furthermore, the first carrier transport layer 31 may be a self-assembled monolayer (SAM) formed from, for example, 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid), MeO-2PACz ([2-(3,6-Dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic Acid), Me-4PACz ([4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid), etc. Also, the first carrier transport layer 31 may have a multilayer structure.

[0024] The perovskite layer 40 is formed on the first carrier transport layer 31 and functions as a photoelectric conversion layer. The main material (main component) of the perovskite layer 40 is a compound represented by the following formula containing an organic atom A, a metal atom B, and a halogen atom X, and having a perovskite structure. ABX3 Examples of A include organic atoms containing at least one of the monovalent organic ammonium ions and amidinium-based ions. Examples of B include metal atoms containing divalent metal ions. Examples of X include halogen atoms containing at least one of the iodide ions (I), bromide ions (Br), chloride ions (Cl), and fluoride ions (F).

[0025] Examples of the main material (main component) of the perovskite layer 40 include methylammonium lead halide MAPbX3 (CH3NH3PbX3), such as MAPbI3, MAPbBr3, MAPbCl3, and formamidinium lead halide FAPbX3 (CH(NH2)2PbX3), such as FAPbI3, FAPbBr3, FAPbCl3, etc. Note that multiple types of halogen atoms X may be included. For example, if iodide I and other halogen atoms X are included, the main material (main component) of the perovskite layer 40 may be methylammonium lead halide MAPbI y X (3-y) (CH3NH3PbI y X (3-y) ), for example MAPbI y Br (3-y) MAPbI y Cl (3-y) Examples include (where y is any positive integer).

[0026] Furthermore, the perovskite layer 40 contains unreacted BX or B prior to the chemical reaction to ABX3. For example, the metal atom B includes at least one of Pb, Sn, Bi, and Cs, and the halogen atom X includes at least one of I, Br, Cl, and F. More specifically, for example, the unreacted BX or B is CsPbI or Pb, etc.

[0027] The content of unreacted substances BX and B in the perovskite layer 40 is 0.5% or less. For example, as shown in Figures 1 and 2, the content of unreacted substances BX and B is the content of unreacted substances BX and B in a predetermined region R in the cross-section of the perovskite layer 40 in the stacking direction, for example, a region R of 650 nm × 2490 nm, and may be the average value of the content of unreacted substances BX and B in multiple regions R in the plane direction intersecting the stacking direction.

[0028] The proportions of unreacted substances BX and B can be confirmed using a transmission electron microscope (TEM).

[0029] The second carrier transport layer 32 is formed on the perovskite layer 40 and functions as an electron transport layer (ETL) (Figure 1) or a hole transport layer (HTL) (Figure 2). The second carrier transport layer 32 is made of a light-transmitting semiconductor material.

[0030] Specifically, in Figure 1, the second carrier transport layer 32 functions as an electron transport layer (ETL) that transports electrons (second carriers) from the carriers generated by photoelectric conversion in the perovskite layer 40 to the second electrode layer 22. Examples of main materials for the second carrier transport layer 32 as an electron transport layer (ETL) include titanium oxide (TiO2), zinc oxide (ZnO), tin oxide (SnO2), or fullerene.

[0031] As mentioned above, examples of fullerenes include C60, C70, their hydrides, oxides, metal complexes, alkyl groups, and derivatives, such as PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester). By forming the second carrier transport layer 32 from a material containing a fullerene encapsulating lithium Li, the electron transport efficiency can be improved.

[0032] Furthermore, if the second carrier transport layer 32 is an electron transport layer (ETL), a hole blocking layer may be provided between the second carrier transport layer 32 and the second electrode layer 22, or between the second carrier transport layer 32 and the perovskite layer 40. Examples of materials for the hole blocking layer include bathocproine (BCP) and SnO formed by atomic layer deposition (ALD), which causes relatively little damage to the deposited layer.

[0033] Furthermore, if the second carrier transport layer 32 is an electron transport layer (ETL), an electron extraction layer may be provided between the second carrier transport layer 32 and the second electrode layer 22, or between the second carrier transport layer 32 and the perovskite layer 40. Examples of materials for the electron extraction layer include lithium (Li) and lithium fluoride (LiF).

[0034] On the other hand, in Figure 2, the second carrier transport layer 32 functions as a hole transport layer (HTL) that transports holes (second carriers) from the carriers generated by photoelectric conversion in the perovskite layer 40 to the second electrode layer 22. Examples of main materials for the second carrier transport layer 32 as a hole transport layer (HTL) include nickel oxide (NiO), copper oxide (Cu2O), PTAA (Poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine)), or Spiro-MeOTAD.

[0035] The second electrode layer 22 is formed on the second carrier transport layer 32 and functions as a cathode (Figure 1) or anode (Figure 2). When the substrate 10 side, i.e., the first electrode layer 21 side, is the light-receiving surface, the second electrode layer 22 may include, for example, a planar metal electrode layer on the substrate 10 side. Alternatively, when the side opposite to the substrate 10, i.e., the second electrode layer 22 side, is the light-receiving surface, the second electrode layer 22 may include a transparent conductive oxide (TCO) that is conductive and light-transmitting, and may also include a grid-like or slit-like metal electrode layer.

[0036] As materials for the transparent conductive film TCO, transparent conductive metal oxides such as indium oxide, tin oxide, zinc oxide, titanium oxide, and composite oxides thereof can be used. Among these, indium-based composite oxides mainly composed of indium oxide are preferred. Indium oxide is particularly preferred from the viewpoint of high conductivity and transparency. Furthermore, to ensure reliability or higher conductivity, it is preferable to add a dopant to the indium oxide. Examples of dopants include Sn, W, Zn, Ti, Ce, Zr, Mo, Al, Ga, Ge, As, Si, or S. Examples of materials for the metal electrode layer include Ag, Au, and Cu.

[0037] With this configuration, the solar cell 1 generates a current corresponding to the light incident from the substrate 10 side, i.e., the first electrode layer 21 side, or the side opposite to the substrate 10, i.e., the second electrode layer 22 side, and outputs it to the first electrode layer 21 and the second electrode layer 22.

[0038] (Method of manufacturing solar cells) Next, the manufacturing method of the solar cell according to this embodiment will be described with reference to Figures 1 and 2.

[0039] First, a transparent conductive film is formed on the substrate 10 as the first electrode layer 21 (first electrode layer formation step). The method for forming the transparent conductive film is not particularly limited, but methods such as CVD (chemical vapor deposition), RPD (reactive plasma deposition), or sputtering using a vacuum chamber can be used.

[0040] Next, a first carrier transport layer 31 is formed on the first electrode layer 21 (first carrier transport layer formation step). The method for forming the first carrier transport layer 31 is not particularly limited, but examples include dry processes such as CVD, PVD, or sputtering, or wet processes such as coating or printing. Among these, sputtering is preferred from the viewpoint of forming a dense film.

[0041] Next, a perovskite layer 40 is formed on the first carrier transport layer 31 (perovskite layer formation step). An AX material containing an organic atom A, a metal atom B, or a halogen atom X is mixed with a BX material, and a solution of this mixture, further mixed with anisole, chloroanisole, or phenethole as a poor solvent, is applied to the mixture to chemically react the AX material and the BX material. This forms a perovskite layer that is a compound having the perovskite structure of ABX3 and further contains unreacted BX or B from before the chemical reaction. For example, a perovskite layer 40 is formed by mixing a methylammonium iodide (MAI) material with a lead iodide (PbI2) material, and then applying a solution of this mixture, further mixed with anisole, chloroanisole, or phenethole as a poor solvent, to chemically react the MAI material and the PbI2 material.

[0042] The proportion of the poor solvent to the solution is 3% by weight or more and 30% by weight or less. While not particularly limited, examples of solvents in the solution include organic solvents such as DMF and NMP. The method for forming the perovskite layer 40 is not particularly limited, but examples include wet processes such as printing, coating, or solution methods.

[0043] Next, a second carrier transport layer 32 is formed on the perovskite layer 40 (second carrier transport layer formation step). The method for forming the second carrier transport layer 32 is not particularly limited, but examples include dry processes such as CVD, PVD, or sputtering, or vapor deposition, or wet processes such as coating or printing.

[0044] Next, a second electrode layer 22 is formed on the second carrier transport layer 32 (second electrode layer formation step). The method for forming the second electrode layer 22 is not particularly limited, but examples include dry processes such as CVD, PVD, or sputtering using a vacuum chamber, or evaporation, or wet processes such as printing or coating. Among these, sputtering is preferred. Based on the above, the perovskite solar cell 1 of this embodiment, as shown in Figure 1 or Figure 2, can be obtained.

[0045] As described above, according to the solar cell 1 and solar cell manufacturing method of this embodiment, when forming the perovskite layer 40, the AX material and the BX material are mixed, and a solution containing anisole, chloroanisole, or phenethole as a poor solvent is applied to cause a chemical reaction between the AX material and the BX material. As a result, the perovskite layer 40 is a compound having the perovskite structure of ABX3, and further contains unreacted BX or B before the chemical reaction to ABX3, and the content of unreacted material can be reduced to 0.5% or less. As a result, the power generation efficiency of the solar cell 1 can be improved.

[0046] Although embodiments of the present invention have been described above, the present invention is not limited to the embodiments described above, and various modifications and variations are possible. For example, the embodiments described above can also be applied to the manufacture of perovskite solar cells in so-called tandem (also called multi-junction) solar cells, which combine crystalline silicon solar cells or amorphous silicon thin-film solar cells with perovskite solar cells. [Examples]

[0047] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples.

[0048] (Example 1) Using the solar cell manufacturing method of this embodiment, the solar cell shown in Figure 1 was fabricated as Example 1. The main features of the solar cell manufacturing method of Example 1 are as follows.

[0049] <Method of manufacturing solar cells> The precursor solution and drying conditions for the perovskite layer in the perovskite layer formation process are as follows: <<Precursor solution>> Perovskite layer materials: MACL, FAI, PbI, CsI +Solvent: DMF / NMP +Additive (poor solvent): Anisole, 3% by weight <<Drying conditions>> Vacuum drying was followed by heat drying. Vacuum drying time: 5 minutes Heat drying temperature: 150 degrees Heat drying time: 10 minutes

[0050] (Example 2) In Example 2, a solar cell was fabricated using the same manufacturing method as in Example 1, except that the amount of additive (poor solvent) mixed into the perovskite layer precursor solution during the perovskite layer formation process was different. <<Precursor solution>> Perovskite layer materials: MACL, FAI, PbI, CsI +Solvent: DMF / NMP +Additive (poor solvent): Anisole, 30% by weight <<Drying conditions>> Vacuum drying was followed by heat drying. Vacuum drying time: 5 minutes Heat drying temperature: 150 degrees Heat drying time: 10 minutes

[0051] (Example 3) In Example 3, a solar cell was fabricated using the same manufacturing method as in Example 1, except that the additive (poor solvent) mixed into the perovskite layer precursor solution during the perovskite layer formation process was different. <<Precursor solution>> Perovskite layer materials: MACL, FAI, PbI, CsI +Solvent: DMF / NMP +Additive (poor solvent): Chloroanisole, 3% by weight <<Drying conditions>> Vacuum drying was followed by heat drying. Vacuum drying time: 5 minutes Heat drying temperature: 150 degrees Heat drying time: 10 minutes

[0052] (Example 4) In Example 4, a solar cell was fabricated using the same manufacturing method as in Example 1, except that the additive (poor solvent) mixed into the perovskite layer precursor solution during the perovskite layer formation process was different. <<Precursor solution>> Perovskite layer materials: MACL, FAI, PbI, CsI +Solvent: DMF / NMP +Additive (poor solvent): Phenetol, 3% by weight <<Drying conditions>> Vacuum drying was followed by heat drying. Vacuum drying time: 5 minutes Heat drying temperature: 150 degrees Heat drying time: 10 minutes

[0053] (Comparative Example 1) In Comparative Example 1, a solar cell was fabricated using the same manufacturing method as in Example 1, except that a poor solvent was not mixed into the perovskite layer precursor solution during the perovskite layer formation process, and no poor solvent was added dropwise after coating. <<Precursor solution>> Perovskite layer materials: MACL, FAI, PbI, CsI +Solvent: DMF / NMP <<Drying conditions>> Vacuum drying was followed by heat drying. Vacuum drying time: 5 minutes Heat drying temperature: 150 degrees Heat drying time: 10 minutes

[0054] (Comparative Example 2) In Comparative Example 2, a solar cell was fabricated using the same manufacturing method as in Example 1, except that the poor solvent mixed into the perovskite layer precursor solution during the perovskite layer formation process was different. <<Precursor solution>> Perovskite layer materials: MACL, FAI, PbI, CsI +Solvent: DMF / NMP +Additive (poor solvent): Chlorobenzene, 3% by weight <<Drying conditions>> Vacuum drying was followed by heat drying. Vacuum drying time: 5 minutes Heat drying temperature: 150 degrees Heat drying time: 10 minutes

[0055] (Comparative Example 3) In Comparative Example 3, we attempted to fabricate a solar cell as Comparative Example 3 using the same manufacturing method as in Example 1, except that the poor solvent mixed into the perovskite layer precursor solution during the perovskite layer formation process was different. <<Precursor solution>> Perovskite layer materials: MACL, FAI, PbI, CsI +Solvent: DMF / NMP +Additive (poor solvent): Toluene, 3% by weight However, after adding the poor solvent, a precipitate formed in the solution, making it impossible to form a perovskite layer (coating and drying), and therefore evaluation was not possible.

[0056] (Comparative Example 4) In Comparative Example 4, we attempted to fabricate a solar cell using the same manufacturing method as in Example 1, except that the poor solvent and its proportion mixed into the perovskite layer precursor solution during the perovskite layer formation process were different. <<Precursor solution>> Perovskite layer materials: MACL, FAI, PbI, CsI +Solvent: DMF / NMP +Additive (poor solvent): Anisole, 40% by weight However, after adding the poor solvent, a precipitate formed in the solution, making it impossible to form a perovskite layer (coating and drying), and therefore evaluation was not possible.

[0057] (Rating 1) A transmission electron microscope (TEM) was used to observe the cross-section of the perovskite layer 40 in the stacking direction of the examples and comparative examples. The observation results for Example 1 are shown in Figure 3, the observation results for Comparative Example 1 are shown in Figure 4, and the observation results for Comparative Example 2 are shown in Figure 5.

[0058] Furthermore, the content ratio of unreacted CsPbI and Pb in the perovskite layer 40 was determined. As shown in Figures 1 and 2, the content ratio of unreacted CsPbI and Pb is the average value of the content ratio of unreacted CsPbI and Pb in five regions R in the plane direction intersecting the stacking direction of the perovskite layer 40, with a length of 650 nm × 2490 nm in the cross section in the stacking direction.

[0059] As shown in Figure 4, in Comparative Example 1, the perovskite crystal layer was formed using a crystallization technique in which the organic solvent in the precursor solution was evaporated by vacuum drying during the perovskite layer formation process. This made it difficult to control nucleation and crystal growth rates in a short time, resulting in the generation of unreacted materials CsPbI, Pb, and voids. The content of unreacted materials CsPbI and Pb was 10%.

[0060] In contrast, as shown in Figure 3, in Example 1, the amount of unreacted CsPbI and Pb was reduced by mixing anisole as a poor solvent into the precursor solution during the perovskite layer formation process. The content of unreacted CsPbI and Pb was 0.5%. In Examples 2, 3, and 4, the content of unreacted CsPbI and Pb was also 0.5%.

[0061] As shown in Figure 5, in Comparative Example 2, when chlorobenzene was mixed as a poor solvent in the precursor solution during the perovskite layer formation process, a relatively large amount of unreacted CsPbI and Pb was present. The content of unreacted CsPbI and Pb was 5%.

[0062] Furthermore, in Comparative Example 3, when toluene was mixed as a poor solvent in the precursor solution, precipitates derived from CsPbI and Pb were generated in the solution, preventing the formation of a perovskite layer, and thus evaluation was not possible.

[0063] Furthermore, in Comparative Example 4, when too much anisole (40% by weight) was mixed as a poor solvent in the precursor solution, precipitates derived from CsPbI and Pb were generated in the solution, preventing the formation of a perovskite layer, and thus making evaluation impossible.

[0064] (Rating 2) The power generation efficiency of the examples and comparative examples was measured. Taking the power generation efficiency of Comparative Example 1 as 100%, the power generation efficiency of Examples 1 and 2 improved to 130%, and the power generation efficiency of Examples 3 and 4 also improved to 130%. However, the power generation efficiency of Comparative Example 2 decreased to 50%. [Explanation of Symbols]

[0065] 1. Perovskite solar cells 10 Base material 21. First electrode layer (anode or cathode) 22. Second electrode layer (cathode or anode) 31. First carrier transport layer (hole transport layer or electron transport layer) 32. Second carrier transport layer (electron transport layer or hole transport layer) 40 Perovskite layer

Claims

1. A method for manufacturing a perovskite solar cell, comprising forming a first electrode layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, and a second electrode layer on a substrate in this order, In the process of forming the perovskite layer, By mixing an AX material containing organic atom A, metal atom B, or halogen atom X with a BX material, and then applying a solution containing a poor solvent, the AX material and the BX material are subjected to a chemical reaction. ABX ３ A compound having a perovskite structure, further forming the perovskite layer containing unreacted BX or B before the chemical reaction, The poor solvent is anisole, chloroanisole, or phenethole. A method for manufacturing perovskite solar cells.

2. The method for producing a perovskite solar cell according to claim 1, wherein the proportion of the poor solvent to the solution is 3% by weight or more and 30% by weight or less.

3. The metal atom B comprises at least one of Pb, Sn, Bi, and Cs. The halogen atom X comprises at least one of I, Br, Cl, and F. A method for manufacturing a perovskite solar cell according to claim 1.

4. The method for manufacturing a perovskite solar cell according to claim 1, wherein the unreacted substance BX or B is CsPbI or Pb.

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