Method for forming thin film of perovskite compound and method for manufacturing solar cell by using same

Abstract

The present invention provides a method for forming a thin film of a perovskite compound, the method comprising a step of reacting i) at least one compound selected from the group consisting of an amine-based compound, an amine-based iodide, an amine-based bromide, an amine-based chloride, an amidine-based compound, an amidine-based iodide, an amidine-based bromide, and an amidine-based chloride, ii) an organometallic compound containing a divalent cation, represented by R1(CH3)4 or R1(CH2H5)4 (where R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl.

Description

Method for forming a thin film of a perovskite compound and method for manufacturing a solar cell using the same

[0001] The present invention relates to a method for forming a thin film of a perovskite compound and a method for manufacturing a solar cell using the same.

[0002] Traditionally, a solution process has been primarily used to manufacture solar cells using perovskite compounds. The solution process involves dissolving the perovskite compound in a predetermined solvent and applying the liquid perovskite compound onto a substrate using methods such as spin coating, spray coating, or slot die.

[0003] This solution process has no problem when applying a perovskite compound to a substrate with a flat surface, but when applying a perovskite compound to a crystalline silicon substrate with pyramidal irregularities to form a tandem solar cell, the step-wise application property is poor, making it difficult to form a thin film with a uniform thickness.

[0004] The present invention has been designed to solve the above-mentioned conventional problems, and the purpose of the present invention is to provide a method for forming a thin film of a perovskite compound, which is capable of forming a thin film of uniform thickness by improving step application properties through manufacturing using a deposition process, and a method for manufacturing a solar cell using the same.

[0005] In order to achieve the above object, the present invention provides a method for forming a thin film of a perovskite compound, comprising a process of reacting i) at least one compound selected from the group consisting of amine-based compounds, amine-based iodides, amine-based bromides, amine-based chlorides, amidine-based compounds, amidine-based iodides, amidine-based bromides, and amidine-based chlorides, ii) an organometallic compound including a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl.

[0006] The perovskite compound comprises a compound of ABX3, wherein A is composed of a monovalent organic cation of at least one compound selected from the group consisting of the amine series compound, the amine series iodide, the amine series bromide, the amine series chloride, the amidine series compound, the amidine series iodide, the amidine series bromide, and the amidine series chloride, wherein B is composed of the divalent cation, and wherein X may be composed of at least one halogen compound.

[0007] The compound of ABX3 can be obtained through a process of reacting ii) an organometallic compound containing a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl to obtain a compound of BX3, and reacting the obtained BX3 with at least one compound selected from the group consisting of i) an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride.

[0008] The present invention also provides a method for forming a thin film of a perovskite compound, comprising a process of reacting i) at least one alkali metal series compound represented by CH(R2)O2 (wherein R2 is an alkali metal), ii) at least one compound selected from the group consisting of amine series compounds, amine series iodides, amine series bromides, amine series chlorides, amidine series compounds, amidine series iodides, amidine series bromides, and amidine series chlorides, iii) an organometallic compound including a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iv) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl.

[0009] The perovskite compound comprises a compound of CABX3, wherein C is composed of at least one alkali metal, A is composed of a monovalent organic cation of at least one compound selected from the group consisting of an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride, B is composed of the divalent cation, and X may be composed of at least one halogen compound.

[0010] The compound of the above CABX3 is obtained by reacting at least one alkali metal series compound represented by the above i) CH(R2)O2 (wherein R2 is an alkali metal), the above iii) an organometallic compound including a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi and Ba), and iv) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl to obtain a compound of CBX3, and reacting the obtained CBX3 with the above ii) an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride. It can be obtained through a process of reacting at least one compound selected from the group consisting of:

[0011] The present invention also provides a method for manufacturing a solar cell, comprising: a step of forming a first electrode on a substrate; a step of forming a first conductive charge transfer layer on the first electrode; a step of forming a light-absorbing layer on the first conductive charge transfer layer; a step of forming a second conductive charge transfer layer on the light-absorbing layer; and a step of forming a second electrode on the second conductive charge transfer layer, wherein the step of forming the light-absorbing layer includes the method for forming a thin film of a perovskite compound as described above.

[0012] The present invention also provides a method for manufacturing a solar cell, comprising: a step of forming a crystalline solar cell; a step of forming a buffer layer on the crystalline solar cell; a step of forming a perovskite solar cell on the buffer layer; and a step of forming a first electrode on the crystalline solar cell and a second electrode on the perovskite solar cell, wherein the step of forming the perovskite solar cell comprises: a step of forming a first conductive charge transfer layer on the buffer layer; a step of forming a light-absorbing layer on the first conductive charge transfer layer; and a step of forming a second conductive charge transfer layer on the light-absorbing layer, wherein the step of forming the light-absorbing layer comprises a method for forming a thin film of a perovskite compound as described above.

[0013] According to the present invention as described above, the following effects are achieved.

[0014] According to one embodiment of the present invention, a perovskite compound is manufactured by reacting i) at least one compound selected from the group consisting of an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride, ii) an organometallic compound including a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl through a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. Therefore, the step spreadability is improved, enabling the formation of a thin film of uniform thickness.

[0015] According to one embodiment of the present invention, since a thin film can be formed through a chemical vapor deposition (CVD) process or atomic layer deposition (ALD) at a temperature of room temperature to 200°C or lower, preferably 50 to 150°C, organic substances in the finally obtained perovskite compound can be prevented from being decomposed during the CVD process or ALD.

[0016] According to one embodiment of the present invention, the band gap of the finally obtained perovskite compound can be controlled depending on the type of the hydrogen halide.

[0017] According to another embodiment of the present invention, the instability of monovalent organic cations that are vulnerable to moisture, heat, and plasma can be compensated for by adding at least one alkali metal series compound to the reactants.

[0018] Figures 1a to 1f are manufacturing process diagrams of a solar cell according to one embodiment of the present invention.

[0019] FIGS. 2A to 2D are process cross-sectional views illustrating a method for manufacturing a solar cell according to another embodiment of the present invention.

[0020] The advantages and features of the present invention, and the methods for achieving them, will become clearer with reference to the embodiments described in detail below together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms. These embodiments are provided solely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined solely by the scope of the claims.

[0021] The shapes, sizes, ratios, angles, numbers, etc. disclosed in the drawings for explaining embodiments of the present invention are illustrative and are not limited to the matters illustrated in the drawings. Like reference numerals refer to like components throughout the specification. In addition, in describing the present invention, if a detailed description of a related known technology is judged to unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. When the terms “includes,” “has,” and “consists of” are used in this specification, other parts may be added unless “only” is used. When a component is expressed in the singular, it includes a case where the plural is included unless there is a specifically explicit description.

[0022] When interpreting a component, it is interpreted as including the error range even if there is no separate explicit description.

[0023] When describing a positional relationship, for example, when the positional relationship between two parts is described as 'on top of', 'upper part of', 'lower part of', 'next to', etc., one or more other parts may be located between the two parts, unless 'right away' or 'directly' is used.

[0024] When describing a temporal relationship, for example, when the temporal continuity is described as 'after', 'following', 'next to', 'before', etc., it can also include cases where it is not continuous, as long as 'right away' or 'directly' is not used.

[0025] While terms like "first" and "second" are used to describe various components, these components are not limited by these terms. These terms are merely used to distinguish one component from another. Therefore, a "first" component referred to below may also be a "second" component within the technical scope of the present invention.

[0026] The features of each of the various embodiments of the present invention can be partially or wholly combined or combined with each other, and various technical connections and operations are possible, and each embodiment can be implemented independently of each other or implemented together in a related relationship.

[0027] Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the drawings.

[0028] A thin film of a perovskite compound according to one embodiment of the present invention is obtained through a process of forming a compound of ABX3 by reacting i) at least one compound selected from the group consisting of an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride, ii) an organometallic compound including a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl.

[0029] In the above ABX3, the A may be formed of a monovalent organic cation of at least one compound selected from the group consisting of the amine series compound, the amine series iodide, the amine series bromide, the amine series chloride, the amidine series compound, the amidine series iodide, the amidine series bromide, and the amidine series chloride.

[0030] For example, if the above A contains the monovalent organic cation of the above amine series compound in an x ​​ratio and the monovalent organic cation of the above amidine series compound in a y ratio, the above x and the above y are each greater than 0, and x+y=1.

[0031] The above amine series compound may be selected from the group consisting of methylamine, ethylamine, and phenethylamine.

[0032] The above amidine series compound may be composed of formamidine.

[0033] In the above ABX3, the B is composed of the divalent cation.

[0034] In the above ABX3, X is composed of at least one halogen compound.

[0035] The above i) at least one compound selected from the group consisting of amine series compounds, amine series iodides, amine series bromides, amine series chlorides, amidine series compounds, amidine series iodides, amidine series bromides, and amidine series chlorides, the above ii) an organometallic compound including a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and the above iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl is composed of a substance that vaporizes at a temperature in the range of room temperature to 200°C, and preferably a substance that vaporizes at a temperature in the range of 50°C to 150°C. Accordingly, the process for manufacturing the compound of ABX3 can be performed at a temperature of 200°C or lower, preferably 150°C or lower, through a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD), so that organic substances in the final compound of ABX3 can be prevented from being decomposed during the CVD or ALD process. Meanwhile, it is also possible to apply plasma when performing the CVD or ALD process.

[0036] According to another embodiment of the present invention, a perovskite compound comprises: i) at least one alkali metal series compound represented by CH(R2)O2 (wherein R2 is an alkali metal), ii) at least one compound selected from the group consisting of an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride, iii) an organometallic compound including a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iv) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl to form CABX3. Obtained through a process of forming a compound.

[0037] In the above CABX3, the C may be composed of at least one alkali metal.

[0038] In the above CABX3, the A may be formed of a monovalent organic cation of at least one compound selected from the group consisting of the amine series compound, the amine series iodide, the amine series bromide, the amine series chloride, the amidine series compound, the amidine series iodide, the amidine series bromide, and the amidine series chloride.

[0039] For example, when the CA contains a monovalent organic cation of the amine series compound in a ratio x, a monovalent organic cation of the amidine series compound in a ratio y, and a monovalent cation of the alkali metal in a ratio z, x, y, and z are each greater than 0, and x+y+z=1.

[0040] In the above CABX3, the B is composed of the divalent cation.

[0041] In the above CABX3, X is composed of at least one halogen compound.

[0042] According to another embodiment of the present invention, the instability of monovalent organic cations that are vulnerable to moisture, heat, and plasma can be compensated for by adding at least one alkali metal series compound to the reactant.

[0043] According to one embodiment of the present invention, a thin film of a perovskite compound can be formed by a CVD or ALD process.

[0044] The following reaction schemes 1 to 4 are reaction schemes for obtaining CBX3 according to one embodiment of the present invention. Specifically, it is a process for forming a compound of CBX3 by reacting i) at least one alkali metal series compound represented by CH(R2)O2 (wherein R2 is an alkali metal), iii) an organometallic compound including a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), iv) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl, and hydrogen.

[0045] Reaction formulas 5 and 6 below are reaction formulas for obtaining CABX3 from CBX3 according to one embodiment of the present invention. Specifically, it is a process for forming a compound of CABX3 by reacting the obtained CBX3 with ii) at least one compound selected from the group consisting of amine series compounds, amine series iodides, amine series bromides, amine series chlorides, amidine series compounds, amidine series iodides, amidine series bromides, and amidine series chlorides.

[0046] Reaction Scheme 1

[0047] CHCsO2+ Pb(CH3)4+ 3HI + 4H2→ CsPbI3+ 5CH4+ 2H2O

[0048] Reaction Scheme 2

[0049] CHCsO2+ Pb(CH3)4+ 3HI + 4H2→ CsPbI3+ 5CH4+ 2H2+ O2

[0050] Reaction Scheme 3

[0051] CHCsO2+ Pb(C2H5)4+ 3HI + 4H2→ CsPbI3+ CH4+ 2H2O + 4C2H6

[0052] Reaction Scheme 4

[0053] CHCsO2+ Pb(C2H5)4+ 3HI + 4H2→ CsPbI3+ CH4+ 2H2+ O2+ 4C2H6

[0054] Reaction Scheme 5

[0055] 2CsPbI3+ 2NH2CHNH + H2→ 2CsNH2CHNH2PbI3

[0056] Reaction Scheme 6

[0057] 2CsPbI3+ 2NH2CHNH2I + H2→ 2CsNH2CHNH2PbI3+ 2HI

[0058] ii) an organometallic compound containing a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl, thereby forming a compound of BX3, and the obtained BX3 may be reacted with i) at least one compound selected from the group consisting of an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride, thereby forming a compound of ABX3.

[0059] Figures 1a to 1f are manufacturing process diagrams of a solar cell according to one embodiment of the present invention.

[0060] First, as can be seen in Fig. 1a, a first electrode (20) is formed on a substrate (10).

[0061] The above substrate (10) may be made of a material known in the art, such as glass or plastic.

[0062] The first electrode (20) may be formed of a conductive oxide such as ITO, but is not necessarily limited thereto. The first electrode (20) may be formed by a deposition process such as ALD (Atomic Layer Deposition). The first electrode (20) may function as an anode or a cathode.

[0063] Next, as can be seen in Fig. 1b, a first conductive charge transfer layer (30) is formed on the first electrode (20).

[0064] The above first conductive charge transport layer (30) may be formed as a hole transport layer or an electron transport layer.

[0065] The above hole transport layer can be formed by including various P-type organic materials known in the art, such as Spiro-MeO-TAD, Spiro-TTB, polyaniline, polypyrrolidone, poly-3,4-ethylenedioxythiophene-polystyrenesulfonate (PEDOT-PSS), or poly-[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA), Poly(3-hexylthiophene-2,5-diyl) (P3HT), various P-type metal oxides known in the art, such as Ni oxide, Mo oxide or V oxide, W oxide, Cu oxide, and various other P-type organic or inorganic materials known in the art.

[0066] The electron transport layer may be formed by including an N-type organic material such as BCP (Bathocuproine), C60, or PCBM (Phenyl-C61-butyric acid methyl ester), various N-type metal oxides known in the art such as ZnO, c-TiO2 / mp-TiO2, SnO2, or IZO, and various other N-type organic or inorganic materials known in the art.

[0067] The above first conductive charge transport layer (30) may be composed of a plurality of hole transport layers or a plurality of electron transport layers.

[0068] The above first conductive charge transfer layer (30) can be formed by a deposition process such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).

[0069] Next, as can be seen in Fig. 1c, a light absorption layer (40) is formed on the first conductive charge transfer layer (30).

[0070] The above light absorption layer (40) may be formed of the aforementioned ABX3 or CABX3 using a deposition process such as CVD or ALD.

[0071] Next, as can be seen in FIG. 1d, a second conductive charge transfer layer (50) is formed on the light absorption layer (40).

[0072] The above second conductive charge transfer layer (50) may be formed as an electron transfer layer or a hole transfer layer.

[0073] When the first conductive charge transfer layer (30) is formed as a hole transfer layer, the second conductive charge transfer layer (50) is formed as an electron transfer layer, and when the first conductive charge transfer layer (30) is formed as an electron transfer layer, the second conductive charge transfer layer (50) is formed as a hole transfer layer.

[0074] Next, as can be seen in FIG. 1e, a transparent conductive layer (60) is formed on the second conductive charge transfer layer (50).

[0075] The transparent conductive layer (60) may be formed of, but is not necessarily limited to, ITO or IZO. The transparent conductive layer (60) may be formed by a deposition process such as ALD. The transparent conductive layer (60) may be omitted.

[0076] Next, as can be seen in FIG. 1f, a second electrode (70) is formed on the transparent conductive layer (60).

[0077] The second electrode (70) may be made of a metal material such as Ag. The second metal (70) may be patterned into a predetermined shape to allow sunlight to enter the cell. The second electrode (70) may function as a cathode or an anode.

[0078] FIGS. 2A to 2D are process cross-sectional views illustrating a method for manufacturing a solar cell according to another embodiment of the present invention.

[0079] First, as can be seen in Fig. 2a, a crystalline solar cell (100) is manufactured.

[0080] The above crystalline solar cell (100) is manufactured through a process of forming a rough structure by etching one side and the other side of a semiconductor substrate (110) such as a wafer, doping a predetermined dopant on one side of the semiconductor substrate (110) to form a first semiconductor layer (120), and doping a predetermined dopant on the other side of the semiconductor substrate (110) to form a second semiconductor layer (130).

[0081] As one side and the other side of the semiconductor substrate (110) are formed with a rough structure, the first semiconductor layer (120) and the second semiconductor layer (130) are formed in a shape corresponding to the rough structure.

[0082] Meanwhile, it is not necessarily limited thereto, and one of the one side and the other side of the semiconductor substrate (110) may be formed with a rough structure and the other side may be formed as a plane. In some cases, both the one side and the other side of the semiconductor substrate (110) may be formed as a plane.

[0083] The semiconductor substrate (110) may be formed of a P-type or N-type wafer, the first semiconductor layer (120) may be doped with a dopant having a different polarity from that of the semiconductor substrate (110), and the second semiconductor layer (130) may be doped with a dopant having the same polarity as that of the semiconductor substrate (110). For example, the semiconductor substrate (110) may be formed of a P-type wafer, the first semiconductor layer (120) may be doped with an N-type dopant, and the second semiconductor layer (130) may be doped with a P-type dopant to form a P+ layer.

[0084] Next, as can be seen in Fig. 2b, a buffer layer (200) is formed on the crystalline solar cell (100).

[0085] The above buffer layer (200) is formed on the first semiconductor layer (120). As the first semiconductor layer (120) is formed in a rough structure, the buffer layer (200) is formed in a shape corresponding to the rough structure.

[0086] The above buffer layer (200) is provided between the crystalline solar cell (100) and the perovskite solar cell, so that the solar cell according to one embodiment of the present invention forms a tandem solar cell structure through tunnel junction.

[0087] The buffer layer (200) is preferably made of a material that allows long-wavelength light penetrating the perovskite solar cell to be incident on the crystalline solar cell (100) without loss. For example, the buffer layer (200) may be made of a transparent conductive oxide, a carbonaceous conductive material, a metallic material, or a conductive polymer, and in some cases, the material may be doped with an n-type or p-type dopant.

[0088] Next, as can be seen in Fig. 2c, a perovskite solar cell is formed on the buffer layer (200).

[0089] The above perovskite solar cell may include a first conductive charge transfer layer (30) provided on the buffer layer (200), a light absorption layer (40) provided on the first conductive charge transfer layer (30), a second conductive charge transfer layer (50) provided on the light absorption layer (40), and a transparent conductive layer (60) provided on the second conductive charge transfer layer (50).

[0090] The first conductive charge transfer layer (30), the light absorption layer (40), the second conductive charge transfer layer (50), and the transparent conductive layer (60) are the same as those in the above-described embodiment, so a repeated description will be omitted.

[0091] Next, as can be seen in FIG. 2d, a first electrode (20) is formed on the lower surface of the crystalline solar cell (100), and a seventh electrode (70) is formed on the upper surface of the perovskite solar cell, for example, on the transparent conductive layer (60).

[0092] The first electrode (20) and the second electrode (70) can be configured to be patterned in a predetermined shape so that sunlight or its reflected light can be incident into the interior of the solar cell.

[0093] Although not shown, a passivation layer with a rough structure can be additionally formed on the second electrode (70). At this time, a portion of the passivation layer is etched so that the second electrode (70) can be exposed.

[0094] By forming the above passivation layer into a rough structure, the amount of light incident on the perovskite solar cell (300) can increase.

[0095] The above passivation layer may be made of polydimethylsiloxane, and when the polydimethylsiloxane is formed on the perovskite solar cell (300), a micropyramid-shaped uneven structure can be obtained. The passivation layer may be formed of various materials such as SiO, SiON, SiN, Al2O3, or MgF.

[0096] Such solar cells can be applied in a variety of ways, including in transportation, automobiles, aircraft, ships, and trains.

[0097] Although the embodiments of the present invention have been described in more detail with reference to the attached drawings, the present invention is not necessarily limited to these embodiments, and various modifications may be implemented without departing from the technical spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain it, and the scope of the technical spirit of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not restrictive. The protection scope of the present invention should be interpreted by the claims, and all technical ideas within a scope equivalent thereto should be interpreted as being included in the scope of the rights of the present invention.

Claims

1. A method for forming a thin film of a perovskite compound, comprising a process of reacting at least one compound selected from the group consisting of amine-based compounds, amine-based iodides, amine-based bromides, amine-based chlorides, amidine-based compounds, amidine-based iodides, amidine-based bromides, and amidine-based chlorides, ii) an organometallic compound containing a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl.

2. In paragraph 1, The above perovskite compound comprises a compound of ABX3, The above A is composed of a monovalent organic cation of at least one compound selected from the group consisting of the above amine series compound, the above amine series iodide, the above amine series bromide, the above amine series chloride, the above amidine series compound, the above amidine series iodide, the above amidine series bromide, and the above amidine series chloride, The above B is composed of the above divalent cations, The above X is a method for forming a thin film of a perovskite compound composed of at least one halogen compound.

3. In paragraph 2, The compound of ABX3 is obtained by reacting ii) an organometallic compound containing a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iii) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl, to obtain a compound of BX3, A method for forming a thin film of a perovskite compound obtained through a process of reacting the obtained BX3 with at least one compound selected from the group consisting of i) an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride.

4. A method for forming a thin film of a perovskite compound, comprising a process of reacting at least one alkali metal series compound represented by i) CH(R2)O2 (wherein R2 is an alkali metal), ii) at least one compound selected from the group consisting of amine series compounds, amine series iodides, amine series bromides, amine series chlorides, amidine series compounds, amidine series iodides, amidine series bromides, and amidine series chlorides, iii) an organometallic compound containing a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iv) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl.

5. In paragraph 4, The above perovskite compound comprises a compound of CABX3, The above C is composed of at least one alkali metal, The above A is composed of a monovalent organic cation of at least one compound selected from the group consisting of the above amine series compound, the above amine series iodide, the above amine series bromide, the above amine series chloride, the above amidine series compound, the above amidine series iodide, the above amidine series bromide, and the above amidine series chloride, The above B is composed of the above divalent cations, The above X is a method for forming a thin film of a perovskite compound composed of at least one halogen compound.

6. In paragraph 5, The compound of CABX3 is obtained by reacting i) at least one alkali metal series compound represented by CH(R2)O2 (wherein R2 is an alkali metal), iii) an organometallic compound containing a divalent cation represented by R1(CH3)4 or R1(CH2H5)4 (wherein R1 includes a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba), and iv) at least one hydrogen halide selected from the group consisting of HI, HBr, Hf, and HCl, to obtain a compound of CBX3, A method for forming a thin film of a perovskite compound obtained through a process of reacting the obtained CBX3 with at least one compound selected from the group consisting of ii) an amine series compound, an amine series iodide, an amine series bromide, an amine series chloride, an amidine series compound, an amidine series iodide, an amidine series bromide, and an amidine series chloride.

7. Process of forming a first electrode on a substrate; A process for forming a first conductive charge transfer layer on the first electrode; A process of forming a light absorption layer on the first conductive charge transfer layer; A process of forming a second conductive charge transfer layer on the light absorbing layer; and A process for forming a second electrode on the second conductive charge transfer layer is included, A method for manufacturing a solar cell, wherein the process for forming the light-absorbing layer comprises a method for forming a thin film of a perovskite compound according to any one of claims 1 to 6 described above.

8. Process for forming crystalline solar cells; A process for forming a buffer layer on the above crystalline solar cell; A process for forming a perovskite solar cell on the buffer layer; and A process for forming a first electrode on the crystalline solar cell and a process for forming a second electrode on the perovskite solar cell, The process of forming the above perovskite solar cell is: A process of forming a first conductive charge transfer layer on the buffer layer; A process of forming a light absorption layer on the first conductive charge transfer layer; and A process for forming a second conductive charge transfer layer on the above light absorbing layer is included, A method for manufacturing a solar cell, wherein the process for forming the light-absorbing layer comprises a method for forming a thin film of a perovskite compound according to any one of claims 1 to 6 described above.

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