Perovskite solar cell and method for producing same

Abstract

The present invention relates to a perovskite solar cell comprising a novel perovskite compound in a perovskite light-absorbing layer, and a method for producing same.

Description

Perovskite solar cell and method for manufacturing the same

[0001] The present invention relates to a perovskite solar cell comprising a novel perovskite compound in a perovskite light-absorbing layer and a method for manufacturing the same.

[0002]

[0003] To address the depletion of fossil fuels and the global environmental problems caused by their use, research is actively being conducted on renewable and clean alternative energy sources such as solar energy, wind power, and hydropower.

[0004] Among these, interest in solar cells, which directly convert sunlight into electrical energy, is growing significantly. Here, a solar cell refers to a cell that generates current and voltage by utilizing the photovoltaic effect, which generates electrons and holes by absorbing light energy from sunlight.

[0005] Currently, it is possible to manufacture np diode-type silicon (Si) single crystal-based solar cells with a light energy conversion efficiency of over 20%, and these are actually being used for solar power generation. There are also solar cells using compound semiconductors such as gallium arsenide (GaAs) with even better conversion efficiencies. However, these inorganic semiconductor-based solar cells require highly purified materials to achieve high efficiency, so a lot of energy is consumed in refining the raw materials. In addition, expensive processing equipment is required in the process of forming single crystals or thin films using the raw materials, which limits the cost of lowering the manufacturing cost of solar cells, and this has been an obstacle to large-scale utilization.

[0006] Accordingly, in order to manufacture solar cells at low cost, it is necessary to drastically reduce the cost of materials or manufacturing processes used as core components of solar cells, and research is being conducted on perovskite solar cells that can be manufactured using low-cost materials and processes as an alternative to inorganic semiconductor-based solar cells.

[0007] Recently, perovskite solar cells using (NH3CH3)PbX3 (X=I, Br, Cl), a halogen compound with a perovskite structure, as a photoactive agent have been developed, and research is being conducted toward commercialization. The general structural formula of the perovskite structure is the ABX3 structure, where anions are located in the X position, large cations are located in the A position, and small cations are located in the B position.

[0008] Meanwhile, perovskite solar cells are being developed in the structure of a PIN perovskite single solar cell or a two-terminal perovskite / silicon tandem solar cell. In the case of a two-terminal perovskite / silicon tandem solar cell, a transparent conductive layer is formed on top of a lower silicon solar cell, and then a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a transparent electrode, and a metal electrode are sequentially formed to manufacture it.

[0009] When fabricating two-terminal perovskite / silicon tandem solar cells, tuning the wide bandgap of the perovskite light-absorbing layer is essential to achieve maximum efficiency when combined with the underlying silicon solar cell. However, the perovskite compounds used to form the perovskite light-absorbing layer have narrow bandgaps, preventing them from achieving maximum efficiency.

[0010]

[0011] The present invention has been devised to overcome the above-described problems, and provides a perovskite solar cell and a method for manufacturing the same, which can improve the performance of a perovskite solar cell by including a novel perovskite compound having a wide bandgap in a perovskite light-absorbing layer.

[0012]

[0013] In order to solve the above-described problem, the perovskite solar cell of the present invention is a perovskite solar cell including a perovskite light-absorbing layer, and the perovskite light-absorbing layer may include a compound represented by the following chemical formula 1.

[0014] [Chemical Formula 1]

[0015] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0016] In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X, X 1 and X 2 is a monovalent anion, a is 0.1 to 0.9, and y is 0.6 to 0.95.

[0017] As a preferred embodiment of the present invention, X, X of the compound represented by chemical formula 1 1 and X 2 can be different monovalent anions.

[0018] In a preferred embodiment of the present invention, in the compound represented by Chemical Formula 1, C is formamidinium (FA), methylammonium (MA), FAMA, CsFAMA, CsFA or N(R)4 + It could be.

[0019] As a preferred embodiment of the present invention, in the compound represented by Chemical Formula 1, R may be the same or different groups, and may be a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, or an alkyl halide.

[0020] As a preferred embodiment of the present invention, in the compound represented by chemical formula 1, M may include one or two selected from Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Eu, and Zr.

[0021] As a preferred embodiment of the present invention, in the compound represented by chemical formula 1, X, X 1 and X 2 It may include one or more halide elements or group 16 anions selected from Cl, Br and I as different monovalent anions.

[0022] As a preferred embodiment of the present invention, in the compound represented by chemical formula 1, a may be 0.3 to 0.7.

[0023] As a preferred embodiment of the present invention, in the compound represented by chemical formula 1, y may be 0.74 to 0.86.

[0024] As a preferred embodiment of the present invention, in the compound represented by Chemical Formula 1, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.45 to 0.55, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y can be 0.76 to 0.79.

[0025] As a preferred embodiment of the present invention, the perovskite solar cell of the present invention may be a pin structure type perovskite solar cell, a nip inverse structure type perovskite solar cell, a tandem type perovskite solar cell, or a tandem type silicon / perovskite heterojunction solar cell.

[0026] Meanwhile, the method for forming a perovskite light-absorbing layer for a perovskite solar cell of the present invention may include a step of applying a perovskite solution on top of a hole transport layer through a solution process and then performing a heat treatment to form a perovskite light-absorbing layer having a perovskite crystal structure.

[0027] As a preferred embodiment of the present invention, the perovskite solution may be prepared by adding and dissolving a perovskite mixture in a solvent.

[0028] As a preferred embodiment of the present invention, the perovskite mixture may be a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4.

[0029] [Chemical Formula 2]

[0030] CMX3

[0031] In the above chemical formula 2, C may be a monovalent cation, M may be a divalent cation, and X may be a monovalent anion.

[0032] [Chemical Formula 4]

[0033] CsPbX 1 (3-a) (X 2 ) a

[0034] In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a can be 0.1 to 0.9.

[0035] As a preferred embodiment of the present invention, in the compound represented by chemical formula 2, C may be formamidinium (FA), M may be lead (Pb), and X may be iodine (I).

[0036] As a preferred embodiment of the present invention, in the compound represented by chemical formula 4, a is 0.45 to 0.55, and X 1 is bromine (Br), and X 2 may be chlorine (Cl).

[0037] As a preferred embodiment of the present invention, the perovskite mixture may be a mixture of 60 to 95 mol% of the compound represented by the above chemical formula 2 and 5 to 40 mol% of the perovskite compound represented by the above chemical formula 4, based on the total mol%.

[0038] As a preferred embodiment of the present invention, the perovskite mixture may be a mixture of 76 to 79 mol% of the compound represented by the chemical formula 2 and 21 to 24 mol% of the perovskite compound represented by the chemical formula 4, based on the total mol%.

[0039] As a preferred embodiment of the present invention, the perovskite compound represented by Chemical Formula 4 may be manufactured through a step of preparing a first precursor aqueous solution by dissolving a cesium halide compound in ultrapure water (DI water), preparing a second precursor solution by dissolving a lead halide compound in dimethylformamide (DMF), adding the first precursor aqueous solution dropwise to the second precursor solution, performing a reaction while stirring, then allowing to stand to form a precipitate, filtering the precipitate to obtain the precipitate, and purifying the precipitate, filtering the precipitate to obtain a powder, and drying the powder to obtain the perovskite compound represented by Chemical Formula 4.

[0040] As a preferred embodiment of the present invention, the cesium halide compound may include cesium bromide (CsBr) and cesium chloride (CsCl).

[0041] As a preferred embodiment of the present invention, the lead halide compound may include a compound represented by the following chemical formula 3.

[0042] [Chemical Formula 3]

[0043] PbX 1 (3-a)

[0044] In the above chemical formula 3, X 1 is bromine (Br), and a can be 0.5 to 2.5.

[0045] As a preferred embodiment of the present invention, the cesium halide compound may include cesium bromide (CsBr) and cesium chloride (CsCl) in a weight ratio of 1:0.48 to 0.73.

[0046] Furthermore, the perovskite solar cell of the present invention includes a laminate in which a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a transparent electrode, and a metal electrode are sequentially laminated, and the perovskite light-absorbing layer may include a compound represented by the following chemical formula 1.

[0047] [Chemical Formula 1]

[0048] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0049] In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X, X 1 and X 2 is a monovalent anion, a is 0.1 to 0.9, and y is 0.6 to 0.95.

[0050] As a preferred embodiment of the present invention, an inter layer may be formed between the perovskite light-absorbing layer and the electron transport layer.

[0051] As a preferred embodiment of the present invention, an anti-reflective layer may be formed on the upper portion of the metal electrode.

[0052] Meanwhile, the tandem perovskite solar cell of the present invention is a tandem perovskite solar cell in which a solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a transparent electrode, and a metal electrode are sequentially laminated, and the perovskite light-absorbing layer may include a compound represented by the following chemical formula 1.

[0053] [Chemical Formula 1]

[0054] (CMX3) y (CsPbX 1(3-a) (X 2 ) a ) 1-y

[0055] In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X, X 1 and X 2 is a monovalent anion, a is 0.1 to 0.9, and y is 0.6 to 0.95.

[0056] In a preferred embodiment of the present invention, the solar cell may be a polycrystalline silicon solar cell, a crystalline silicon solar cell, a perovskite solar cell, a gallium arsenide (GaAs) solar cell, a cadmium telluride (CdTe) solar cell, a CIGS (CuInGaSe) solar cell, a CZTS (Cu2ZnSnS4) solar cell, an organic solar cell, a fuel-sensitized solar cell, or a group 3-5 compound solar cell.

[0057] Furthermore, the method for manufacturing a perovskite solar cell of the present invention includes a first step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then performing a heat treatment, and a second step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the perovskite light-absorbing layer, wherein the perovskite solution is prepared by introducing and dissolving a perovskite mixture in a solvent, and the perovskite mixture may be a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4.

[0058] [Chemical Formula 2]

[0059] CMX3

[0060] In the above chemical formula 2, C may be a monovalent cation, M may be a divalent cation, and X may be a monovalent anion.

[0061] [Chemical Formula 4]

[0062] CsPbX 1 (3-a) (X 2 )a

[0063] In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a can be 0.1 to 0.9.

[0064] Meanwhile, the method for manufacturing a perovskite solar cell of the present invention includes a first step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then heat-treating the perovskite solution, and a second step of sequentially forming an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer on top of the perovskite light-absorbing layer, wherein the perovskite solution is prepared by introducing and dissolving a perovskite mixture in a solvent, and the perovskite mixture may be a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4.

[0065] [Chemical Formula 2]

[0066] CMX3

[0067] In the above chemical formula 2, C may be a monovalent cation, M may be a divalent cation, and X may be a monovalent anion.

[0068] [Chemical Formula 4]

[0069] CsPbX 1 (3-a) (X 2 ) a

[0070] In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a can be 0.1 to 0.9.

[0071] Furthermore, the method for manufacturing a tandem perovskite solar cell of the present invention includes a first step of sequentially forming a transparent conductive layer and a hole transport layer on top of a solar cell, a second step of applying a perovskite solution on top of the hole transport layer through a solution process and then heat-treating it to form a perovskite light-absorbing layer having a perovskite crystal structure, and a third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the perovskite light-absorbing layer, wherein the perovskite solution is prepared by introducing and dissolving a perovskite mixture in a solvent, and the perovskite mixture may be a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4.

[0072] [Chemical Formula 2]

[0073] CMX3

[0074] In the above chemical formula 2, C may be a monovalent cation, M may be a divalent cation, and X may be a monovalent anion.

[0075] [Chemical Formula 4]

[0076] CsPbX 1 (3-a) (X 2 ) a

[0077] In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a can be 0.1 to 0.9.

[0078] Meanwhile, the method for manufacturing a tandem perovskite solar cell of the present invention includes a first step of sequentially forming a transparent conductive layer and a hole transport layer on top of a solar cell, a second step of applying a perovskite solution on top of the hole transport layer through a solution process and then heat treating it to form a perovskite light-absorbing layer having a perovskite crystal structure, and a third step of sequentially forming an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer on top of the perovskite light-absorbing layer, wherein the perovskite solution is prepared by introducing and dissolving a perovskite mixture in a solvent, and the perovskite mixture may be a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4.

[0079] [Chemical Formula 2]

[0080] CMX3

[0081] In the above chemical formula 2, C may be a monovalent cation, M may be a divalent cation, and X may be a monovalent anion.

[0082] [Chemical Formula 4]

[0083] CsPbX 1 (3-a) (X 2 ) a

[0084] In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a can be 0.1 to 0.9.

[0085]

[0086] The perovskite solar cell of the present invention and its manufacturing method can improve the performance of the perovskite solar cell by including a novel perovskite compound having a wide bandgap in the perovskite light-absorbing layer.

[0087]

[0088] Figure 1 is a graph showing the absorbance according to wavelength of each perovskite film manufactured in Examples 1 to 6 using UV-Vis Spectroscopy.

[0089] Figure 2 is an XRD graph showing XRD analysis performed on each of the perovskite films manufactured in Examples 1 to 6 using X-ray diffraction (XRD).

[0090]

[0091] Hereinafter, the present invention will be described in more detail.

[0092] Perovskite solar cells are being developed in the structure of a PIN perovskite single solar cell or a two-terminal perovskite / silicon tandem solar cell. In the case of a two-terminal perovskite / silicon tandem solar cell, a transparent conductive layer is formed on top of a lower silicon solar cell, and then a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a transparent electrode, and a metal electrode are sequentially formed to manufacture it.

[0093] When fabricating two-terminal perovskite / silicon tandem solar cells, tuning the wide bandgap of the perovskite light-absorbing layer is essential to achieve maximum efficiency when combined with the underlying silicon solar cell. However, the perovskite compounds used to form the perovskite light-absorbing layer have narrow bandgaps, preventing them from achieving maximum efficiency.

[0094]

[0095] The perovskite solar cell of the present invention includes a perovskite light-absorbing layer.

[0096] At this time, the perovskite light-absorbing layer may include a compound represented by the following chemical formula 1.

[0097] [Chemical Formula 1]

[0098] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0099] In the above chemical formula 1, C is a monovalent cation, which may include amine, ammonium, a group 1 metal, a group 2 metal, and / or other cations or cation-like compounds, and preferably formamidinium (FA), methylammonium (MA), FAMA, CsFAMA, CsFA or N(R)4. + (Here, R may be the same or different groups, and R may be a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, or an alkyl halide.) Most preferably, C may be formamidinium (FA).

[0100] In addition, in the above chemical formula 1, M is a divalent cation and may include one or two selected from Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Eu, and Zr. Most preferably, M may be lead (Pb).

[0101] In addition, X in chemical formula 1 is a monovalent anion and may include one or more halide elements selected from F, Cl, Br, and I and / or a Group 16 anion.

[0102] Also, X of chemical formula 1 1 is a monovalent anion, and may include one or more halide elements selected from F, Cl, Br, and I and / or a Group 16 anion.

[0103] Also, X of chemical formula 1 2 is a monovalent anion, and may include one or more halide elements selected from F, Cl, Br, and I and / or a Group 16 anion.

[0104] Meanwhile, X, X of chemical formula 1 1 and X 2 can be different monovalent anions. Most preferably, X is iodine (I), and X 1 is bromine (Br), and X 2 may be chlorine (Cl).

[0105] Additionally, a in chemical formula 1 may be 0.1 to 0.9, preferably 0.3 to 0.7, and more preferably 0.45 to 0.55.

[0106] Additionally, y in chemical formula 1 may be 0.6 to 0.95, preferably 0.74 to 0.86, more preferably 0.76 to 0.82, and even more preferably 0.76 to 0.79.

[0107] Meanwhile, the perovskite light-absorbing layer may be a single layer composed of the same perovskite material, or may be a multilayer structure in which multiple layers composed of different perovskite materials are stacked, and may include a heterogeneous perovskite material other than the one type of perovskite material having a pillar shape such as a columnar shape, a plate shape, a needle shape, a wire shape, or a rod shape within the light-absorbing layer composed of one type of perovskite material.

[0108] In addition, as a method for forming a perovskite light-absorbing layer, a deposition process and a solution process can be performed, and the deposition process can be any general deposition process used in the art, such as a thermal evaporation process, a vacuum deposition process, an atomic layer deposition (ALD) process, a chemical vapor deposition (CVD) process, and a physical vapor deposition (PVD) process, and the solution process can be any general solution process used in the art, such as a spin coating process, a slot die coating process, a blade coating process, a printing coating process, a gravure coating process, and a spray coating process.

[0109] In addition, the thickness of the perovskite light-absorbing layer is not particularly limited, but may preferably have a thickness of 50 nm to 800 nm, more preferably 300 nm to 800 nm.

[0110] Specifically, the method for forming a perovskite light-absorbing layer for a perovskite solar cell of the present invention may include a step of applying a perovskite solution on top of a hole transport layer through a solution process and then performing a heat treatment to form a perovskite light-absorbing layer having a perovskite crystal structure.

[0111] At this time, the perovskite solution may be prepared by adding and dissolving a perovskite mixture in a solvent.

[0112] Any solvent commonly used in the art can be used as the solvent, and preferably, a solvent in which dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) are mixed in a volume ratio of 8 to 10:1 can be used.

[0113] The perovskite mixture may be a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4.

[0114] [Chemical Formula 2]

[0115] CMX3

[0116] In the above chemical formula 2, C is a monovalent cation, which may include amine, ammonium, a group 1 metal, a group 2 metal, and / or other cations or cation-like compounds, and preferably formamidinium (FA), methylammonium (MA), FAMA, CsFAMA, CsFA or N(R)4. + (Here, R may be the same or different groups, and R may be a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, or an alkyl halide.) Most preferably, C may be formamidinium (FA).

[0117] In the above chemical formula 2, M is a divalent cation and may include one or two selected from Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Eu, and Zr. Most preferably, M may be lead (Pb).

[0118] In the above chemical formula 2, X is a monovalent anion and may include one or more halide elements selected from F, Cl, Br, and I and / or a Group 16 anion.

[0119] [Chemical Formula 4]

[0120] CsPbX 1 (3-a) (X 2 ) a

[0121] In the above chemical formula 4, X 1 is a monovalent anion, and may include one or more halide elements selected from F, Cl, Br, and I and / or a Group 16 anion.

[0122] In the above chemical formula 4, X 2 is a monovalent anion, and may include one or more halide elements selected from F, Cl, Br, and I and / or a Group 16 anion.

[0123] In the above chemical formula 4, a may be 0.1 to 0.9, preferably 0.3 to 0.7, and more preferably 0.45 to 0.55.

[0124] Also, X, X 1 and X 2 can be different monovalent anions. Most preferably, X is iodine (I), and X 1 is bromine (Br), and X 2 may be chlorine (Cl).

[0125] Specifically, the perovskite mixture may be a mixture of 60 to 95 mol%, preferably 74 to 86 mol%, more preferably 76 to 82 mol%, and even more preferably 76 to 79 mol% of the compound represented by the above chemical formula 2 and 5 to 40 mol%, preferably 14 to 26 mol%, more preferably 18 to 24 mol%, and even more preferably 21 to 24 mol% of the perovskite compound represented by the above chemical formula 4, based on the total mol%, and by satisfying this mol% range, the manufactured perovskite solar cell may exhibit excellent performance.

[0126] Meanwhile, the perovskite compound represented by the above chemical formula 4 may be manufactured through a step of preparing a first precursor aqueous solution by dissolving a cesium halide compound in ultrapure water (DI water), preparing a second precursor solution by dissolving a lead halide compound in dimethylformamide (DMF), adding the first precursor aqueous solution dropwise to the second precursor solution, performing a reaction while stirring, then allowing to stand to form a precipitate, filtering the precipitate to obtain the precipitate, and purifying the precipitate, filtering the precipitate to obtain a powder, and drying the powder to obtain the perovskite compound represented by the above chemical formula 4.

[0127] At this time, the cesium halogenated compound may include cesium bromide (CsBr) and cesium chloride (CsCl), and preferably, cesium bromide (CsBr) and cesium chloride (CsCl) in a weight ratio of 1:0.48 to 0.73, more preferably, 1:0.54 to 0.67.

[0128] Additionally, the lead halide compound may include a compound represented by the following chemical formula 3.

[0129] [Chemical Formula 3]

[0130] PbX 1 (3-a)

[0131] In the above chemical formula 3, X 1 is a monovalent anion, and may include one or more halide elements and / or Group 16 anions selected from F, Cl, Br and I, and preferably may be bromine (Br).

[0132] In the above chemical formula 3, a may be 0.5 to 2.5, preferably 0.6 to 2.0, more preferably 0.8 to 1.5, and even more preferably 0.8 to 1.2.

[0133]

[0134] Furthermore, the perovskite solar cell of the present invention may be a pin structure type perovskite solar cell, a nip inverse structure type perovskite solar cell, a tandem type perovskite solar cell, or a tandem type silicon / perovskite heterojunction solar cell.

[0135]

[0136] Meanwhile, the perovskite solar cell of the present invention may include a laminate in which a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a transparent electrode, and a metal electrode are sequentially laminated. In this case, the perovskite light-absorbing layer is as described above.

[0137] A hole transport layer (HTL) is a layer that transports holes formed in a perovskite light-absorbing layer while simultaneously blocking the movement of electrons, and may include an inorganic and / or organic hole transport material.

[0138] At this time, the inorganic hole transport material may include at least one selected from nickel oxide (NiOx), CuSCN, CuCrO2, CuI, CuOx, CuS, CuI, CuPc, CIS, CuGaO2, PbS, MoOx, AlOx (aluminum oxide), CuAlOx, aluminum oxide nanoparticles, silica nanoparticles, nickel oxide nanoparticles, hafnium nanoparticles, and V2O5.

[0139] In addition, organic hole transport materials include carbazole derivatives, polyarylalkane derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorene derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidine compounds, porphyrin compounds, phthalocyanine compounds, polythiophene derivatives, polypyrrole derivatives, polyparaphenylenevinylene derivatives, pentacene, coumarin 6 (coumarin 6, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin), ZnPC (zinc phthalocyanine), CuPC (copper phthalocyanine), TiOPC (titanium oxide phthalocyanine), Spiro-MeOTAD(2,2',7,7'-tetrakis(N,Np-dimethoxyphenylamino)-9,9'-spirobifluorene), F16CuPC(copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine), SubPc (boron subphthalocyanine chloride) and N3(cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II), P3HT(poly[3-hexylthiophene]), MDMO-PPV(poly[2-methoxy-5-(3',7'-dimethyloctyloxyl)]-1,4-phenylene vinylene), MEH-PPV(poly[2-methoxy-5-(2''-ethylhexyloxy)-p-phenylene vinylene]), P3OT(poly(3-octyl thiophene)), POT(poly(octyl thiophene)), P3DT(poly(3-decyl thiophene)),P3DDT(poly(3-dodecyl thiophene), PPV(poly(p-phenylene vinylene)), TFB(poly(9,9'-dioctylfluorene-co-N-(4-butylphenyl)diphenyl amine), 폴리아닐린(Polyaniline), Spiro-MeOTAD([2,22′,7,77′-tetrkis (N,N-di-pmethoxyphenyl amine)-9,9,9′-spirobi fluorine]), PCPDTBT(Poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl-4H-cyclopenta [2,1-b:3,4-b']dithiophene-2,6-diyl]], Si-PCPDTBT(poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]), PBDTTPD(poly((4,8-diethylhexyloxyl), PFDTBT(poly[2,7-(9-(2-ethylhexyl)-9-hexyl-fluorene)-alt-5,5-(4', 7, -di-2-thienyl-2',1', 3'-benzothiadiazole)]), PFO-DBT(poly[2,7-.9,9-(dioctyl-fluorene)-alt-5,5-(4',7'-di-2-.thienyl-2', 1', 3'-benzothiadiazole)]), PSiFDTBT(poly[(2,7-dioctylsilafluorene)-2,7-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl]), PCDTBT(Poly [[9-(1-octylnonyl)-9H-carbazole-2,7-diyl] -2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]), PFB(poly(9,It may include at least one selected from among 9′-dioctylfluorene-co-bis(N,N′-(4,butylphenyl))bis(N,N′-phenyl-1,4-phenylene)diamine), F8BT(poly(9,9′-dioctylfluorene-cobenzothiadiazole), PEDOT (poly(3,4-ethylenedioxythiophene)), PEDOT:PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), PTAA (poly(triarylamine)), 2-PACz, MeO-2PACz, Br-2PACz, Me-4PACz, MeO-4PACz and 6-PACz.

[0140] In addition, a deposition process and a solution process can be performed as a method for forming a hole transport layer, and the deposition process can be any general deposition process used in the art, such as a thermal evaporation process, a vacuum deposition process, an atomic layer deposition (ALD) process, a chemical vapor deposition (CVD) process, and a physical vapor deposition (PVD) process, and the solution process can be any general solution process used in the art, such as a spin coating process, a slot die coating process, a blade coating process, a printing coating process, a gravure coating process, and a spray coating process.

[0141] In addition, the thickness of the hole transport layer is not particularly limited, but may preferably have a thickness of 5 nm to 40 nm, more preferably 10 nm to 30 nm.

[0142] The electron transport layer (ETL) is a layer that transports electrons formed in the perovskite light-absorbing layer while simultaneously blocking the movement of holes.

[0143] The electron transport layer may include at least one selected from tin oxide (SnOx), nickel oxide (NiOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), and niobium pentoxide (Nb2O5).

[0144] Additionally, the electron transport layer may include inorganic and / or organic materials.

[0145] At this time, the inorganic material may include at least one selected from nickel oxide (NiOx), CuSCN, CuCrO2, CuI, CuOx, CuS, CuI, CuPc, CIS, CuGaO2, PbS, MoOx, AlOx (aluminum oxide), CuAlOx, aluminum oxide nanoparticles, silica nanoparticles, nickel oxide nanoparticles, hafnium nanoparticles, and V2O5.

[0146] In addition, organic substances include carbazole derivatives, polyarylalkane derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorene derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidine compounds, porphyrin compounds, phthalocyanine compounds, polythiophene derivatives, polypyrrole derivatives, polyparaphenylenevinylene derivatives, pentacene, coumarin 6 (coumarin 6, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin), ZnPC (zinc phthalocyanine), CuPC (copper phthalocyanine), TiOPC (titanium oxide phthalocyanine), Spiro-MeOTAD(2,2',7,7'-tetrakis(N,Np-dimethoxyphenylamino)-9,9'-spirobifluorene), F16CuPC(copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine), SubPc (boron subphthalocyanine chloride) and N3(cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II), P3HT(poly[3-hexylthiophene]), MDMO-PPV(poly[2-methoxy-5-(3',7'-dimethyloctyloxyl)]-1,4-phenylene vinylene), MEH-PPV(poly[2-methoxy-5-(2''-ethylhexyloxy)-p-phenylene vinylene]), P3OT(poly(3-octyl thiophene)), POT(poly(octyl thiophene)), P3DT(poly(3-decyl thiophene)),P3DDT(poly(3-dodecyl thiophene), PPV(poly(p-phenylene vinylene)), TFB(poly(9,9'-dioctylfluorene-co-N-(4-butylphenyl)diphenyl amine), 폴리아닐린(Polyaniline), Spiro-MeOTAD([2,22′,7,77'-tetrkis (N,N-di-pmethoxyphenyl amine)-9,9,9′'-spirobi fluorine]), PCPDTBT(Poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl-4H-cyclopenta [2,1-b:3,4-b']dithiophene-2,6-diyl]], Si-PCPDTBT(poly[(4,4′'-bis(2-ethylhexyl)dithieno[3,2-b:2′',3′'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]), PBDTTPD(poly((4,8-diethylhexyloxyl), PFDTBT(poly[2,7-(9-(2-ethylhexyl)-9-hexyl-fluorene)-alt-5,5-(4', 7, -di-2-thienyl-2',1', 3'-benzothiadiazole)]), PFO-DBT(poly[2,7-.9,9-(dioctyl-fluorene)-alt-5,5-(4',7'-di-2-.thienyl-2', 1', 3'-benzothiadiazole)]), PSiFDTBT(poly[(2,7-dioctylsilafluorene)-2,7-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′'-diyl]), PCDTBT(Poly [[9-(1-octylnonyl)-9H-carbazole-2,7-diyl] -2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]), PFB(poly(9,It may include at least one selected from among 9′'-dioctylfluorene-co-bis(N,N′'-(4,butylphenyl))bis(N,N′'-phenyl-1,4-phenylene)diamine), F8BT(poly(9,9′'-dioctylfluorene-cobenzothiadiazole), PEDOT (poly(3,4-ethylenedioxythiophene)), PEDOT:PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), PTAA (poly(triarylamine)), 2-PACz, MeO-2PACz, Br-2PACz, Me-4PACz, MeO-4PACz and 6-PACz.

[0147] Additionally, the electron transport layer may include a fullerene-based organic material. At this time, the fullerene-based organic material may include at least one selected from C60, C70, PC60BM, and PC70BM.

[0148] In addition, as a method for forming an electron transport layer, a deposition process and a solution process can be performed, and the deposition process can be any general deposition process used in the art, such as a thermal evaporation process, a vacuum deposition process, an atomic layer deposition (ALD) process, a chemical vapor deposition (CVD) process, and a physical vapor deposition (PVD) process, and the solution process can be any general solution process used in the art, such as a spin coating process, a slot die coating process, a blade coating process, a printing coating process, a gravure coating process, and a spray coating process.

[0149] In addition, the thickness of the electron transport layer is not particularly limited, but may preferably have an average thickness of 3 to 300 nm, more preferably 5 to 200 nm.

[0150] A transparent electrode can be formed on top of the electron transport layer through a deposition process. The deposition process can be performed using a typical deposition process used in the art, and preferably, a sputtering process can be used.

[0151] In addition, the transparent electrode may be a transparent thin film on which ITO (Indium Tin Oxide), FTO (Fluorine doped Tin Oxide), ATO (Sb2O3 doped Tin Oxide), GTO (Gallium doped Tin Oxide), ZTO (tin doped zinc oxide), ZTO:Ga (gallium doped ZTO), IGZO (Indium gallium zinc oxide), IZO (Indium doped zinc oxide), or AZO (Aluminum doped zinc oxide) is deposited.

[0152] In addition, the thickness of the transparent electrode has no separate limitation, but may preferably have a thickness of 50 to 200 nm, more preferably 60 to 140 nm.

[0153] A metal electrode can be formed by patterning a metal material on top of a transparent electrode. Specifically, the patterning process is largely composed of deposition, exposure (lithography), and etching. A metal electrode can be formed on top of a transparent electrode by spreading a metal material in the form of a thin film on one surface of a substrate, printing a pattern by exposure, and then removing unnecessary portions. In addition, the patterning process can also be performed through a screen printing method using a metal paste containing a metal material.

[0154] At this time, the metal material may include at least one selected from Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C, and a conductive polymer.

[0155] Additionally, there is no separate limitation on the thickness of the metal electrode, but it may preferably have a thickness of 50 nm to 2.5 μm.

[0156]

[0157] Meanwhile, the perovskite solar cell of the present invention may have an inter layer formed between the perovskite light-absorbing layer and the electron transport layer.

[0158] The intermediate layer may contain a fullerene-based organic material. In this case, the fullerene-based organic material is C 60 Fullerene, C 70 Fullerene, PC 60 BM and PC 70 It may include one or more selected from BM, preferably C 60 May contain fullerenes.

[0159] Additionally, the intermediate layer may further comprise lithium fluoride (LiF).

[0160] In addition, as a method for forming an intermediate layer, a deposition process and a solution process can be performed, and the deposition process can be any general deposition process used in the art, such as a thermal evaporation process, a vacuum deposition process, an atomic layer deposition (ALD) process, a chemical vapor deposition (CVD) process, and a physical vapor deposition (PVD) process, and the solution process can be any general solution process used in the art, such as a spin coating process, a slot die coating process, a blade coating process, a printing coating process, a gravure coating process, and a spray coating process.

[0161] In addition, the thickness of the intermediate layer has no separate limitation, but may preferably have an average thickness of 3 to 50 nm, more preferably 5 to 30 nm.

[0162]

[0163] Furthermore, the perovskite solar cell of the present invention may have an anti-reflective layer formed on top of the metal electrode.

[0164] The antireflection layer may include lithium fluoride (LiF).

[0165] In addition, as a method for forming an anti-reflection layer, a deposition process and a solution process can be performed, and the deposition process can be any general deposition process used in the art, such as a thermal evaporation process, a vacuum deposition process, an atomic layer deposition (ALD) process, a chemical vapor deposition (CVD) process, and a physical vapor deposition (PVD) process, and the solution process can be any general solution process used in the art, such as a spin coating process, a slot die coating process, a blade coating process, a printing coating process, a gravure coating process, and a spray coating process.

[0166] In addition, the thickness of the antireflection layer is not particularly limited, but preferably has an average thickness of 3 to 500 nm, more preferably 100 to 300 nm.

[0167]

[0168] Meanwhile, the tandem perovskite solar cell of the present invention may be one in which a solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a transparent electrode, and a metal electrode are sequentially laminated. In this case, the hole transport layer, the perovskite light-absorbing layer, the electron transport layer, the transparent electrode, and the metal electrode are each as described above.

[0169] In addition, the tandem perovskite solar cell of the present invention may have an inter layer formed between the perovskite light-absorbing layer and the electron transport layer, and an anti-reflective layer formed on top of the metal electrode, and the inter layer and the anti-reflective layer are as described above, respectively.

[0170] The solar cell may be a polycrystalline silicon solar cell, a crystalline silicon solar cell, a perovskite solar cell, a gallium arsenide (GaAs) solar cell, a cadmium telluride (CdTe) solar cell, a CIGS (CuInGaSe) solar cell, a CZTS (Cu2ZnSnS4) solar cell, an organic solar cell, a fuel-sensitized solar cell, or a group III-V compound solar cell.

[0171] In addition, there is no separate limitation on the thickness of the solar cell, but it may preferably have a thickness of 140 to 250 μm, more preferably 160 to 200 μm.

[0172] The transparent conductive layer is a layer that induces recombination of electrons and holes generated in a solar cell and a perovskite light-absorbing layer, and may be a transparent thin film on which ITO (Indium Tin Oxide), FTO (Fluorine doped Tin Oxide), ATO (Sb2O3 doped Tin Oxide), GTO (Gallium doped Tin Oxide), ZTO (tin doped zinc oxide), ZTO:Ga (gallium doped ZTO), IGZO (Indium gallium zinc oxide), IZO (Indium doped zinc oxide), or AZO (Aluminum doped zinc oxide) is deposited.

[0173] In addition, as an example of forming a transparent conductive layer, when using a silicon solar cell doped with n- or p-type impurities as a solar cell, the silicon solar cell doped with n- or p-type impurities is treated with hydrofluoric acid to remove the SiOx oxide film, and then the remaining hydrofluoric acid is removed using ultrapure water. Then, a transparent conductive layer can be formed on the top of the silicon solar cell from which the oxide film has been removed through a sputtering process.

[0174] In addition, the thickness of the transparent conductive layer is not particularly limited, but may preferably have a thickness of 5 nm to 50 nm, more preferably 15 nm to 25 nm.

[0175]

[0176] Furthermore, the method for manufacturing a perovskite solar cell of the present invention may include a first step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then heat-treating the solution, and a second step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the perovskite light-absorbing layer. At this time, the hole transport layer, the perovskite solution, the perovskite light-absorbing layer, the electron transport layer, the transparent electrode, and the metal electrode are each as described above.

[0177]

[0178] Meanwhile, the method for manufacturing a perovskite solar cell of the present invention may include a first step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then heat-treating the perovskite solution, and a second step of sequentially forming an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer on top of the perovskite light-absorbing layer. At this time, the hole transport layer, the perovskite solution, the perovskite light-absorbing layer, the intermediate electron transport layer, the transparent electrode, the metal electrode, and the antireflection layer are each as described above.

[0179]

[0180] Furthermore, the method for manufacturing a tandem perovskite solar cell of the present invention may include a first step of sequentially forming a transparent conductive layer and a hole transport layer on top of a solar cell, a second step of applying a perovskite solution on top of the hole transport layer through a solution process and then heat treating it to form a perovskite light-absorbing layer having a perovskite crystal structure, and a third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the perovskite light-absorbing layer. At this time, the solar cell, the transparent conductive layer, the hole transport layer, the perovskite solution, the perovskite light-absorbing layer, the electron transport layer, the transparent electrode, and the metal electrode are each as described above.

[0181]

[0182] Meanwhile, the method for manufacturing a tandem perovskite solar cell of the present invention may include a first step of sequentially forming a transparent conductive layer and a hole transport layer on top of a solar cell, a second step of applying a perovskite solution on top of the hole transport layer through a solution process and then heat treating it to form a perovskite light-absorbing layer having a perovskite crystal structure, and a third step of sequentially forming an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer on top of the perovskite light-absorbing layer. At this time, the solar cell, the transparent conductive layer, the hole transport layer, the perovskite solution, the perovskite light-absorbing layer, the intermediate electron transport layer, the transparent electrode, the metal electrode, and the antireflection layer are each as described above.

[0183]

[0184] Hereinafter, the present invention will be described in more detail through examples, but the following examples do not limit the scope of the present invention, and should be interpreted as helping to understand the present invention.

[0185]

[0186] Preparation Example 1: Preparation of perovskite compound

[0187] (1) A first precursor aqueous solution with a concentration of 1.3 M was prepared by dissolving 13.8 g of cesium bromide (CsBr) powder, which is a cesium halide compound, and 8.4 g of cesium chloride (CsCl) powder in ultrapure water (DI water).

[0188] (2) 3.6 g of lead halide compound powder, which is a compound represented by the following chemical formula 3-1, was dissolved in dimethylformamide (DMF) to prepare a second precursor solution having a concentration of 0.27 M.

[0189] [Chemical Formula 3-1]

[0190] PbX 1 (3-a)

[0191] In the above chemical formula 3-1, X 1 is bromine (Br), and a is 1.

[0192] (3) At a temperature of 23℃ and atmospheric pressure (1 atm), the second precursor solution was slowly stirred, and the first precursor aqueous solution was added dropwise to the second precursor solution. The reaction was performed while stirring for an additional 2 hours, and then the mixture was allowed to stand to form a precipitate, which was then filtered to obtain an orange precipitate. At this time, the reaction molar ratio of the first precursor solution and the second precursor solution was 1:1.

[0193] (4) The obtained precipitate was purified three times with acetone, filtered again to obtain a powder, and then placed in a thermal drying oven to perform a drying process, thereby producing 3.0249 g of a perovskite compound represented by the following chemical formula 4-1.

[0194] [Chemical Formula 4-1]

[0195] CsPbX 1 (3-a) (X 2 ) a

[0196] In the above chemical formula 4-1, a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl).

[0197]

[0198] Example 1: Preparation of perovskite film

[0199] (1) A solvent containing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1 was prepared, and a perovskite mixture was added and dissolved in the prepared solvent to prepare a yellow perovskite solution. At this time, the perovskite mixture was used in a mixture of 70 mol% of the compound represented by the following chemical formula 2-1 and 30 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 based on the total mol%.

[0200] [Chemical Formula 2-1]

[0201] CMX3

[0202] In the above chemical formula 2-1, C is formamidinium (FA), M is lead (Pb), and X is iodine (I).

[0203] (2) A washed glass substrate was prepared, and the yellow perovskite solution was spin-coated on top of the prepared glass substrate, followed by a first heat treatment at 150°C for 10 minutes and a second heat treatment at 100°C for 20 minutes, thereby producing a perovskite film including a compound represented by the following chemical formula 1-1 having a perovskite crystal structure with a thickness of 600 nm.

[0204] [Chemical Formula 1-1]

[0205] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0206] In the above chemical formula 1-1, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.7.

[0207]

[0208] Example 2: Preparation of perovskite film

[0209] (1) A solvent containing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1 was prepared, and a perovskite mixture was added and dissolved in the prepared solvent to prepare a yellow perovskite solution. At this time, the perovskite mixture was used in a mixture of 75 mol% of the compound represented by the chemical formula 2-1 and 25 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 based on the total mol%.

[0210] (2) A washed glass substrate was prepared, and the yellow perovskite solution was spin-coated on the prepared glass substrate, followed by a first heat treatment at 150°C for 10 minutes and a second heat treatment at 100°C for 20 minutes, thereby producing a perovskite film including a compound represented by the following chemical formula 1-2 having a perovskite crystal structure with a thickness of 600 nm.

[0211] [Chemical Formula 1-2]

[0212] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0213] In the above chemical formula 1-2, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.75.

[0214]

[0215] Example 3: Preparation of perovskite film

[0216] (1) A solvent containing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1 was prepared, and a perovskite mixture was added and dissolved in the prepared solvent to prepare a yellow perovskite solution. At this time, the perovskite mixture was used in a mixture of 77.5 mol% of the compound represented by the chemical formula 2-1 and 22.5 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 based on the total mol%.

[0217] (2) A washed glass substrate was prepared, and the yellow perovskite solution was spin-coated on the prepared glass substrate, followed by a first heat treatment at 150°C for 10 minutes and a second heat treatment at 100°C for 20 minutes, thereby producing a perovskite film including a compound represented by the following chemical formula 1-3 having a perovskite crystal structure with a thickness of 600 nm.

[0218] [Chemical Formula 1-3]

[0219] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0220] In the above chemical formula 1-3, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.775.

[0221]

[0222] Example 4: Preparation of perovskite film

[0223] (1) A solvent containing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1 was prepared, and a perovskite mixture was added and dissolved in the prepared solvent to prepare a yellow perovskite solution. At this time, the perovskite mixture was used in a mixture of 80 mol% of the compound represented by the chemical formula 2-1 and 20 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 based on the total mol%.

[0224] (2) A washed glass substrate was prepared, and the yellow perovskite solution was spin-coated on the prepared glass substrate, followed by a first heat treatment at 150°C for 10 minutes and a second heat treatment at 100°C for 20 minutes, thereby producing a perovskite film including a compound represented by the following chemical formula 1-4 having a perovskite crystal structure with a thickness of 600 nm.

[0225] [Chemical Formula 1-4]

[0226] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0227] In the above chemical formula 1-4, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.8.

[0228]

[0229] Example 5: Preparation of perovskite film

[0230] (1) A solvent containing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1 was prepared, and a perovskite mixture was added and dissolved in the prepared solvent to prepare a yellow perovskite solution. At this time, the perovskite mixture was used in a mixture of 85 mol% of the compound represented by the chemical formula 2-1 and 15 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 based on the total mol%.

[0231] (2) A washed glass substrate was prepared, and the yellow perovskite solution was spin-coated on top of the prepared glass substrate, followed by a first heat treatment at 150°C for 10 minutes and a second heat treatment at 100°C for 20 minutes, thereby producing a perovskite film including a compound represented by the following chemical formula 1-5 having a perovskite crystal structure with a thickness of 600 nm.

[0232] [Chemical Formula 1-5]

[0233] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0234] In the above chemical formula 1-5, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.85.

[0235]

[0236] Example 6: Preparation of perovskite film

[0237] (1) A solvent containing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1 was prepared, and a perovskite mixture was added and dissolved in the prepared solvent to prepare a yellow perovskite solution. At this time, the perovskite mixture was used in a mixture of 90 mol% of the compound represented by the chemical formula 2-1 and 10 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 based on the total mol%.

[0238] (2) A washed glass substrate was prepared, and the yellow perovskite solution was spin-coated on the prepared glass substrate, followed by a first heat treatment at 150°C for 10 minutes and a second heat treatment at 100°C for 20 minutes, thereby producing a perovskite film including a compound represented by the following chemical formula 1-6 having a perovskite crystal structure with a thickness of 600 nm.

[0239] [Chemical Formula 1-6]

[0240] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0241] In the above chemical formula 1-6, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.9.

[0242]

[0243] Experimental Example 1: Absorbance Measurement

[0244] Using UV-Vis Spectroscopy, the absorbance of each perovskite film manufactured in Examples 1 to 6 according to wavelength was measured, and the results are shown in Figure 1.

[0245] As can be seen in Fig. 1, as the molar % of the perovskite compound represented by Chemical Formula 4-1 prepared in Preparation Example 1 included in the perovskite mixture increases, it can be confirmed that the absorption position constantly changes toward a shorter wavelength.

[0246] In addition, the optical band gap of each perovskite film manufactured in Examples 1 to 6 was calculated using the Tauc. Plot using the measured results, and is shown in Table 1 below.

[0247]

[0248] As can be seen in Table 1, it was confirmed that the optical band gap increased linearly as the molar % of the perovskite compound represented by Chemical Formula 4-1 prepared in Preparation Example 1 included in the perovskite mixture increased.

[0249]

[0250] Experimental Example 2: XRD Analysis

[0251] Using X-ray diffraction analysis (XRD), the XRD graphs for each of the perovskite films manufactured in Examples 1 to 6 are shown in Fig. 2.

[0252] As can be seen in Fig. 2, it was confirmed that as the molar % of the perovskite compound represented by Chemical Formula 4-1 prepared in Preparation Example 1 included in the perovskite mixture increased, a certain ratio shifted to a high angle was observed.

[0253]

[0254] Experimental Example 3: XPS Analysis

[0255] The component ratios of the perovskite films manufactured in Examples 2 to 5 were analyzed using X-ray photoelectron spectroscope (XPS), and the results are shown in Table 2 below.

[0256]

[0257] As can be seen in Table 2, as the molar % of the perovskite compound represented by Chemical Formula 4-1 prepared in Preparation Example 1 included in the perovskite mixture increases, the proportion of chlorine (Cl) increases, and the proportions of cesium (Cs) and bromine (Br) also show the same trend.

[0258] From these results, it was confirmed that all elements constituting the perovskite compound represented by Chemical Formula 4-1 manufactured in Preparation Example 1 remained the same until a perovskite film was manufactured using the compound, thereby directly affecting the change in the band gap of the perovskite.

[0259]

[0260] Manufacturing Example 1: Manufacturing of a tandem silicon / perovskite heterojunction solar cell

[0261] (1) A silicon solar cell (thickness: 180 ㎛) doped with n or p type impurities was prepared, and the SiOx oxide film was removed by hydrofluoric acid treatment. Then, the remaining hydrofluoric acid was removed using ultrapure water. A 20 nm thick transparent conductive layer (ITO) was formed on the top of the silicon solar cell from which the oxide film was removed through a sputtering process.

[0262] (2) Next, nickel oxide (NiOx) with a thickness of 20 nm was deposited on top of the transparent conductive layer through a sputter vacuum deposition method, and Me-4PACz with a thickness of 5 nm was coated on top of the nickel oxide deposited through spin coating to form a hole transport layer.

[0263] (3) Next, a yellow perovskite solution was spin-coated on top of the hole transport layer, and a first heat treatment was performed at 150°C for 10 minutes, and a second heat treatment was performed at 100°C for 20 minutes, thereby forming a perovskite light-absorbing layer including a compound represented by the following chemical formula 1-1 having a perovskite crystal structure with a thickness of 600 nm. At this time, the yellow perovskite solution was prepared by mixing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1, and adding and dissolving the perovskite mixture in the prepared solvent. The perovskite mixture was prepared by mixing 70 mol% of the compound represented by the chemical formula 2-1 and 30 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 with respect to the total mol%.

[0264] [Chemical Formula 1-1]

[0265] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0266] In the above chemical formula 1-1, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.7.

[0267] (4) Next, lithium fluoride (LiF) with a thickness of 10 nm is deposited on top of the perovskite light-absorbing layer through a thermal evaporation process, and C is deposited on top of the lithium fluoride (LiF) deposited through the thermal evaporation process. 60 Fullerene (C 60 By depositing fullerene, an intermediate layer with an average thickness of 15 nm was formed.

[0268] (5) Next, an electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the protective layer through an ALD (atomic layer deposition) process.

[0269] (6) Next, a 75 nm thick transparent electrode (IZO) was formed on top of the electron transport layer through a sputtering process.

[0270] (7) Next, silver (Ag) is added to the upper part of the transparent electrode at 1X10 -7 A metal electrode was formed by depositing it with a thickness of 100 nm at a pressure of 10 torr.

[0271] (8) Finally, a tandem silicon / perovskite heterojunction solar cell was manufactured in the form of a silicon solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer sequentially stacked by forming an antireflection layer (LiF) with a thickness of 200 nm on top of the metal electrode through a thermal deposition process.

[0272]

[0273] Manufacturing Example 2: Manufacturing of a tandem silicon / perovskite heterojunction solar cell

[0274] (1) A silicon solar cell (thickness: 180 ㎛) doped with n or p type impurities was prepared, and the SiOx oxide film was removed by hydrofluoric acid treatment. Then, the remaining hydrofluoric acid was removed using ultrapure water. A 20 nm thick transparent conductive layer (ITO) was formed on the top of the silicon solar cell from which the oxide film was removed through a sputtering process.

[0275] (2) Next, nickel oxide (NiOx) with a thickness of 20 nm was deposited on top of the transparent conductive layer through a sputter vacuum deposition method, and Me-4PACz with a thickness of 5 nm was coated on top of the nickel oxide deposited through spin coating to form a hole transport layer.

[0276] (3) Next, a yellow perovskite solution was spin-coated on top of the hole transport layer, and a first heat treatment was performed at 150°C for 10 minutes, and a second heat treatment was performed at 100°C for 20 minutes, thereby forming a perovskite light-absorbing layer including a compound represented by the following chemical formula 1-2 having a perovskite crystal structure with a thickness of 600 nm. At this time, the yellow perovskite solution was prepared by mixing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1, and adding and dissolving the perovskite mixture in the prepared solvent. The perovskite mixture was prepared by mixing 75 mol% of the compound represented by the chemical formula 2-1 and 25 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 with respect to the total mol%.

[0277] [Chemical Formula 1-2]

[0278] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0279] In the above chemical formula 1-2, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.75.

[0280] (4) Next, lithium fluoride (LiF) with a thickness of 10 nm is deposited on top of the perovskite light-absorbing layer through a thermal evaporation process, and C is deposited on top of the lithium fluoride (LiF) deposited through the thermal evaporation process. 60 Fullerene (C 60 By depositing fullerene, an intermediate layer with an average thickness of 15 nm was formed.

[0281] (5) Next, an electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the protective layer through an ALD (atomic layer deposition) process.

[0282] (6) Next, a 75 nm thick transparent electrode (IZO) was formed on top of the electron transport layer through a sputtering process.

[0283] (7) Next, silver (Ag) is added to the upper part of the transparent electrode at 1X10 -7 A metal electrode was formed by depositing it with a thickness of 100 nm at a pressure of 10 torr.

[0284] (8) Finally, a tandem silicon / perovskite heterojunction solar cell was manufactured in the form of a silicon solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer sequentially stacked by forming an antireflection layer (LiF) with a thickness of 200 nm on top of the metal electrode through a thermal deposition process.

[0285]

[0286] Manufacturing Example 3: Manufacturing of a tandem silicon / perovskite heterojunction solar cell

[0287] (1) A silicon solar cell (thickness: 180 ㎛) doped with n or p type impurities was prepared, and the SiOx oxide film was removed by hydrofluoric acid treatment. Then, the remaining hydrofluoric acid was removed using ultrapure water. A 20 nm thick transparent conductive layer (ITO) was formed on the top of the silicon solar cell from which the oxide film was removed through a sputtering process.

[0288] (2) Next, nickel oxide (NiOx) with a thickness of 20 nm was deposited on top of the transparent conductive layer through a sputter vacuum deposition method, and Me-4PACz with a thickness of 5 nm was coated on top of the nickel oxide deposited through spin coating to form a hole transport layer.

[0289] (3) Next, a yellow perovskite solution was spin-coated on top of the hole transport layer, and a first heat treatment was performed at 150°C for 10 minutes, and a second heat treatment was performed at 100°C for 20 minutes, thereby forming a perovskite light-absorbing layer including a compound represented by the following chemical formula 1-3 having a perovskite crystal structure with a thickness of 600 nm. At this time, the yellow perovskite solution was prepared by preparing a solvent in which dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) were mixed in a volume ratio of 9:1, and then adding and dissolving the perovskite mixture in the prepared solvent. The perovskite mixture was prepared by mixing 77.5 mol% of the compound represented by the chemical formula 2-1 and 22.5 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 with respect to the total mol%.

[0290] [Chemical Formula 1-3]

[0291] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0292] In the above chemical formula 1-3, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.775.

[0293] (4) Next, lithium fluoride (LiF) with a thickness of 10 nm is deposited on top of the perovskite light-absorbing layer through a thermal evaporation process, and C is deposited on top of the lithium fluoride (LiF) deposited through the thermal evaporation process. 60 Fullerene (C 60 By depositing fullerene, an intermediate layer with an average thickness of 15 nm was formed.

[0294] (5) Next, an electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the protective layer through an ALD (atomic layer deposition) process.

[0295] (6) Next, a 75 nm thick transparent electrode (IZO) was formed on top of the electron transport layer through a sputtering process.

[0296] (7) Next, silver (Ag) is added to the upper part of the transparent electrode at 1X10 -7 A metal electrode was formed by depositing it with a thickness of 100 nm at a pressure of 10 torr.

[0297] (8) Finally, a tandem silicon / perovskite heterojunction solar cell was manufactured in the form of a silicon solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer sequentially stacked by forming an antireflection layer (LiF) with a thickness of 200 nm on top of the metal electrode through a thermal deposition process.

[0298]

[0299] Manufacturing Example 4: Manufacturing of a tandem silicon / perovskite heterojunction solar cell

[0300] (1) A silicon solar cell (thickness: 180 ㎛) doped with n or p type impurities was prepared, and the SiOx oxide film was removed by hydrofluoric acid treatment. Then, the remaining hydrofluoric acid was removed using ultrapure water. A 20 nm thick transparent conductive layer (ITO) was formed on the top of the silicon solar cell from which the oxide film was removed through a sputtering process.

[0301] (2) Next, nickel oxide (NiOx) with a thickness of 20 nm was deposited on top of the transparent conductive layer through a sputter vacuum deposition method, and Me-4PACz with a thickness of 5 nm was coated on top of the nickel oxide deposited through spin coating to form a hole transport layer.

[0302] (3) Next, a yellow perovskite solution was spin-coated on top of the hole transport layer, and a first heat treatment was performed at 150°C for 10 minutes, and a second heat treatment was performed at 100°C for 20 minutes, thereby forming a perovskite light-absorbing layer including a compound represented by the following chemical formula 1-4 having a perovskite crystal structure with a thickness of 600 nm. At this time, the yellow perovskite solution was prepared by mixing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1, and adding and dissolving the perovskite mixture in the prepared solvent. The perovskite mixture was prepared by mixing 80 mol% of the compound represented by the chemical formula 2-1 and 20 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 with respect to the total mol%.

[0303] [Chemical Formula 1-4]

[0304] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0305] In the above chemical formula 1-4, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.8.

[0306] (4) Next, lithium fluoride (LiF) with a thickness of 10 nm is deposited on top of the perovskite light-absorbing layer through a thermal evaporation process, and C is deposited on top of the lithium fluoride (LiF) deposited through the thermal evaporation process. 60 Fullerene (C 60 By depositing fullerene, an intermediate layer with an average thickness of 15 nm was formed.

[0307] (5) Next, an electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the protective layer through an ALD (atomic layer deposition) process.

[0308] (6) Next, a 75 nm thick transparent electrode (IZO) was formed on top of the electron transport layer through a sputtering process.

[0309] (7) Next, silver (Ag) is added to the upper part of the transparent electrode at 1X10 -7 A metal electrode was formed by depositing it with a thickness of 100 nm at a pressure of 10 torr.

[0310] (8) Finally, a tandem silicon / perovskite heterojunction solar cell was manufactured in the form of a silicon solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer sequentially stacked by forming an antireflection layer (LiF) with a thickness of 200 nm on top of the metal electrode through a thermal deposition process.

[0311]

[0312] Manufacturing Example 5: Manufacturing of a tandem silicon / perovskite heterojunction solar cell

[0313] (1) A silicon solar cell (thickness: 180 ㎛) doped with n or p type impurities was prepared, and the SiOx oxide film was removed by hydrofluoric acid treatment. Then, the remaining hydrofluoric acid was removed using ultrapure water. A 20 nm thick transparent conductive layer (ITO) was formed on the top of the silicon solar cell from which the oxide film was removed through a sputtering process.

[0314] (2) Next, nickel oxide (NiOx) with a thickness of 20 nm was deposited on top of the transparent conductive layer through a sputter vacuum deposition method, and Me-4PACz with a thickness of 5 nm was coated on top of the nickel oxide deposited through spin coating to form a hole transport layer.

[0315] (3) Next, a yellow perovskite solution was spin-coated on top of the hole transport layer, and a first heat treatment was performed at 150°C for 10 minutes, and a second heat treatment was performed at 100°C for 20 minutes, thereby forming a perovskite light-absorbing layer including a compound represented by the following chemical formula 1-5 having a perovskite crystal structure with a thickness of 600 nm. At this time, the yellow perovskite solution was prepared by mixing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1, and adding and dissolving the perovskite mixture in the prepared solvent. The perovskite mixture was prepared by mixing 85 mol% of the compound represented by the chemical formula 2-1 and 15 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 based on the total mol%.

[0316] [Chemical Formula 1-5]

[0317] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0318] In the above chemical formula 1-5, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.85.

[0319] (4) Next, lithium fluoride (LiF) with a thickness of 10 nm is deposited on top of the perovskite light-absorbing layer through a thermal evaporation process, and C is deposited on top of the lithium fluoride (LiF) deposited through the thermal evaporation process. 60 Fullerene (C 60 By depositing fullerene, an intermediate layer with an average thickness of 15 nm was formed.

[0320] (5) Next, an electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the protective layer through an ALD (atomic layer deposition) process.

[0321] (6) Next, a 75 nm thick transparent electrode (IZO) was formed on top of the electron transport layer through a sputtering process.

[0322] (7) Next, silver (Ag) is added to the upper part of the transparent electrode at 1X10 -7 A metal electrode was formed by depositing it with a thickness of 100 nm at a pressure of 10 torr.

[0323] (8) Finally, a tandem silicon / perovskite heterojunction solar cell was manufactured in the form of a silicon solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer sequentially stacked by forming an antireflection layer (LiF) with a thickness of 200 nm on top of the metal electrode through a thermal deposition process.

[0324]

[0325] Manufacturing Example 6: Manufacturing of a tandem silicon / perovskite heterojunction solar cell

[0326] (1) A silicon solar cell (thickness: 180 ㎛) doped with n or p type impurities was prepared, and the SiOx oxide film was removed by hydrofluoric acid treatment. Then, the remaining hydrofluoric acid was removed using ultrapure water. A 20 nm thick transparent conductive layer (ITO) was formed on the top of the silicon solar cell from which the oxide film was removed through a sputtering process.

[0327] (2) Next, nickel oxide (NiOx) with a thickness of 20 nm was deposited on top of the transparent conductive layer through a sputter vacuum deposition method, and Me-4PACz with a thickness of 5 nm was coated on top of the nickel oxide deposited through spin coating to form a hole transport layer.

[0328] (3) Next, a yellow perovskite solution was spin-coated on top of the hole transport layer, and a first heat treatment was performed at 150°C for 10 minutes, and a second heat treatment was performed at 100°C for 20 minutes, thereby forming a perovskite light-absorbing layer including a compound represented by the following chemical formula 1-6 having a perovskite crystal structure with a thickness of 600 nm. At this time, the yellow perovskite solution was prepared by mixing dimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (N-Methyl-2-Pyrrolidone, NMP) in a volume ratio of 9:1, and adding and dissolving the perovskite mixture in the prepared solvent. The perovskite mixture was prepared by mixing 90 mol% of the compound represented by the chemical formula 2-1 and 10 mol% of the perovskite compound represented by the chemical formula 4-1 prepared in Preparation Example 1 with respect to the total mol%.

[0329] [Chemical Formula 1-6]

[0330] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y

[0331] In the above chemical formula 1-6, C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.5, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.9.

[0332] (4) Next, lithium fluoride (LiF) with a thickness of 10 nm is deposited on top of the perovskite light-absorbing layer through a thermal evaporation process, and C is deposited on top of the lithium fluoride (LiF) deposited through the thermal evaporation process. 60 Fullerene (C 60 By depositing fullerene, an intermediate layer with an average thickness of 15 nm was formed.

[0333] (5) Next, an electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the protective layer through an ALD (atomic layer deposition) process.

[0334] (6) Next, a 75 nm thick transparent electrode (IZO) was formed on top of the electron transport layer through a sputtering process.

[0335] (7) Next, silver (Ag) is added to the upper part of the transparent electrode at 1X10 -7 A metal electrode was formed by depositing it with a thickness of 100 nm at a pressure of 10 torr.

[0336] (8) Finally, a tandem silicon / perovskite heterojunction solar cell was manufactured in the form of a silicon solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer sequentially stacked by forming an antireflection layer (LiF) with a thickness of 200 nm on top of the metal electrode through a thermal deposition process.

[0337]

[0338] Experimental Example 3: Measuring Solar Cell Performance

[0339] For each of the tandem silicon / perovskite heterojunction solar cells manufactured in Manufacturing Examples 3 to 6, the efficiency was measured using a solar simulation device and a JV Keithley device, and the initial JV curve was used, and the results are shown in Table 3 below.

[0340]

[0341] As can be seen in Table 3, it was confirmed that the tandem silicon / perovskite heterojunction solar cell manufactured in Manufacturing Example 3 had a better power conversion efficiency than the tandem silicon / perovskite heterojunction solar cell manufactured in Manufacturing Examples 4 to 6.

[0342]

[0343] The above illustrates and describes specific embodiments. However, the invention is not limited to the aforementioned embodiments, and those skilled in the art will readily appreciate that various modifications and implementations can be made without departing from the spirit and scope of the invention as set forth in the claims below.

Claims

1. In a perovskite solar cell including a perovskite light-absorbing layer, A perovskite solar cell, wherein the perovskite light-absorbing layer comprises a compound represented by the following chemical formula 1. [Chemical Formula 1] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X, X 1 and X 2 is a monovalent anion, a is 0.1 to 0.9, and y is 0.6 to 0.

95.

2. In paragraph 1, X, X of the compound represented by the above chemical formula 1 1 and X 2 Perovskite solar cells, which are monovalent anions with different valences.

3. In the first paragraph, in the compound represented by the chemical formula 1 C is formamidinium (FA), methylammonium (MA), FAMA, CsFAMA, CsFA or N(R)4 + , R may be the same or different groups, and is a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group, an alkylphenyl group, an alkoxyphenyl group or an alkyl halide, M may include one or two selected from Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Eu and Zr, and X, X 1 and X 2 A perovskite solar cell, wherein the perovskite solar cell may include one or more halide elements or group 16 anions selected from Cl, Br, and I as different monovalent anions, a is 0.3 to 0.7, and y is 0.74 to 0.

86.

4. In the third paragraph, in the compound represented by the chemical formula 1 C is formamidinium (FA), M is lead (Pb), X is iodine (I), a is 0.45 to 0.55, and X 1 is bromine (Br), and X 2 is chlorine (Cl), and y is 0.76 to 0.79, perovskite solar cell.

5. In any one of the clauses 1 to 4, The above perovskite solar cell is a perovskite solar cell that is a pin structure type perovskite solar cell, a nip inverse structure type perovskite solar cell, a tandem type perovskite solar cell, or a tandem type silicon / perovskite heterojunction solar cell.

6. A step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then performing a heat treatment; The above perovskite solution is prepared by adding and dissolving a perovskite mixture in a solvent, A method for forming a perovskite light-absorbing layer for a perovskite solar cell, wherein the perovskite mixture is a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4. [Chemical Formula 2] CMX3 [Chemical Formula 4] CsPbX 1 (3-a) (X 2 ) a In the above chemical formula 2, C is a monovalent cation, M is a divalent cation, X is a monovalent anion, In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a is 0.1 to 0.

9.

7. In paragraph 6, In the compound represented by the above chemical formula 2, C is formamidinium (FA), M is lead (Pb), X is iodine (I), In the compound represented by the above chemical formula 4, a is 0.45 to 0.55, and X 1 is bromine (Br), and X 2 A method for forming a perovskite light-absorbing layer for a perovskite solar cell, wherein the perovskite layer is chlorine (Cl).

8. In paragraph 6, A method for forming a perovskite light-absorbing layer for a perovskite solar cell, wherein the perovskite mixture is a mixture of 60 to 95 mol% of the compound represented by the chemical formula 2 and 5 to 40 mol% of the perovskite compound represented by the chemical formula 4, based on the total mol%.

9. In paragraph 8, A method for forming a perovskite light-absorbing layer for a perovskite solar cell, wherein the perovskite mixture is mixed with 76 to 79 mol% of the compound represented by the chemical formula 2 and 21 to 24 mol% of the perovskite compound represented by the chemical formula 4, based on the total mol%.

10. In the 6th paragraph, the perovskite compound represented by the chemical formula 4 is A step of preparing a first precursor aqueous solution by dissolving a cesium halide compound in ultrapure water (DI water), and preparing a second precursor solution by dissolving a lead halide compound in dimethylformamide (DMF); A step of adding a first precursor aqueous solution dropwise to the second precursor solution, performing a reaction while stirring, allowing the mixture to settle to form a precipitate, and then filtering the precipitate to obtain the precipitate; and A step of purifying the above precipitate, filtering it to obtain a powder, and drying it to prepare a perovskite compound represented by the above chemical formula 4; A method for forming a perovskite light-absorbing layer for a perovskite solar cell, the method comprising:

11. In paragraph 10, The above cesium halide compounds include cesium bromide (CsBr) and cesium chloride (CsCl), A method for forming a perovskite light-absorbing layer for a perovskite solar cell, wherein the lead halide compound comprises a compound represented by the following chemical formula 3. [Chemical Formula 3] PbX 1 (3-a) In the above chemical formula 3, X 1 is bromine (Br), and a is 0.5 to 2.

5.

12. In paragraph 11, A method for forming a perovskite light-absorbing layer for a perovskite solar cell, wherein the above cesium halide compound comprises cesium bromide (CsBr) and cesium chloride (CsCl) in a weight ratio of 1:0.48 to 0.

73.

13. A laminate comprising a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a transparent electrode, and a metal electrode sequentially laminated, A perovskite solar cell, wherein the perovskite light-absorbing layer comprises a compound represented by the following chemical formula 1. [Chemical Formula 1] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X, X 1 and X 2 is a monovalent anion, a is 0.1 to 0.9, and y is 0.6 to 0.

95.

14. In paragraph 13, An interlayer is formed between the perovskite light-absorbing layer and the electron transport layer, A perovskite solar cell in which an anti-reflective layer is formed on the upper surface of the metal electrode.

15. A tandem perovskite solar cell in which a solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a transparent electrode, and a metal electrode are sequentially laminated, A tandem perovskite solar cell, wherein the perovskite light-absorbing layer comprises a compound represented by the following chemical formula 1. [Chemical Formula 1] (CMX3) y (CsPbX 1 (3-a) (X 2 ) a ) 1-y In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X, X 1 and X 2 is a monovalent anion, a is 0.1 to 0.9, and y is 0.6 to 0.

95.

16. In paragraph 15, A method for manufacturing a tandem perovskite solar cell, wherein the solar cell is a polycrystalline silicon solar cell, a crystalline silicon solar cell, a perovskite solar cell, a gallium arsenide (GaAs) solar cell, a cadmium telluride (CdTe) solar cell, a CIGS (CuInGaSe) solar cell, a CZTS (Cu2ZnSnS4) solar cell, an organic solar cell, a fuel-sensitized solar cell, or a group 3-5 compound solar cell.

17. A first step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then performing a heat treatment; and A second step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the perovskite light-absorbing layer; The above perovskite solution is prepared by adding and dissolving a perovskite mixture in a solvent, A method for manufacturing a perovskite solar cell, wherein the perovskite mixture is a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4. [Chemical Formula 2] CMX3 [Chemical Formula 4] CsPbX 1 (3-a) (X 2 ) a In the above chemical formula 2, C is a monovalent cation, M is a divalent cation, X is a monovalent anion, In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a is 0.1 to 0.

9.

18. A first step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then performing a heat treatment; and A second step of sequentially forming an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer on top of the perovskite light-absorbing layer; The above perovskite solution is prepared by adding and dissolving a perovskite mixture in a solvent, A method for manufacturing a perovskite solar cell, wherein the perovskite mixture is a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4. [Chemical Formula 2] CMX3 [Chemical Formula 4] CsPbX 1 (3-a) (X 2 ) a In the above chemical formula 2, C is a monovalent cation, M is a divalent cation, X is a monovalent anion, In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a is 0.1 to 0.

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19. The first step of sequentially forming a transparent conductive layer and a hole transport layer on top of the solar cell; A second step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then heat-treating the solution; and A third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the perovskite light-absorbing layer; The above perovskite solution is prepared by adding and dissolving a perovskite mixture in a solvent, A method for manufacturing a tandem perovskite solar cell, wherein the perovskite mixture is a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4. [Chemical Formula 2] CMX3 [Chemical Formula 4] CsPbX 1 (3-a) (X 2 ) a In the above chemical formula 2, C is a monovalent cation, M is a divalent cation, X is a monovalent anion, In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a is 0.1 to 0.

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20. The first step of sequentially forming a transparent conductive layer and a hole transport layer on top of the solar cell; A second step of forming a perovskite light-absorbing layer having a perovskite crystal structure by applying a perovskite solution on top of a hole transport layer through a solution process and then heat-treating the solution; and A third step of sequentially forming an intermediate layer, an electron transport layer, a transparent electrode, a metal electrode, and an antireflection layer on top of the perovskite light-absorbing layer; The above perovskite solution is prepared by adding and dissolving a perovskite mixture in a solvent, A method for manufacturing a tandem perovskite solar cell, wherein the perovskite mixture is a mixture of a compound represented by the following chemical formula 2 and a perovskite compound represented by the following chemical formula 4. [Chemical Formula 2] CMX3 [Chemical Formula 4] CsPbX 1 (3-a) (X 2 ) a In the above chemical formula 2, C is a monovalent cation, M is a divalent cation, X is a monovalent anion, In the above chemical formula 4, X 1 and X 2 is a monovalent anion, and a is 0.1 to 0.9.

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