Perovskite solar cell and manufacturing method therefor

Abstract

The present invention relates to a perovskite solar cell comprising a passivation layer of a specific material, and a manufacturing method therefor.

Description

Perovskite solar cell and method for manufacturing the same

[0001] The present invention relates to a perovskite solar cell comprising a passivation layer of a specific material and a method for manufacturing the same.

[0002]

[0003] In order to address the depletion of fossil fuels and the global environmental problems caused by their use, research on renewable and clean alternative energy sources such as solar, wind, and hydroelectric power is actively underway.

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

[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 they are being used in actual solar power generation. There are also solar cells using compound semiconductors such as gallium arsenide (GaAs), which have even better conversion efficiency. However, these inorganic semiconductor-based solar cells require materials purified to a very high degree of purity to achieve high efficiency, so a large amount of energy is consumed in purifying the raw materials. Furthermore, expensive process equipment is required to process the raw materials into single crystals or thin films, which limits the ability to lower the manufacturing cost of solar cells and has been a stumbling block to large-scale utilization.

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

[0007] Recently, perovskite solar cells using (NH3CH3)PbX3 (X=I, Br, Cl), a halogen compound with a perovskite structure, as a photoactive material have been developed, and research for commercialization is underway. The general structural formula of a perovskite structure is ABX3, in which an anion is located at the X site, a large cation is located at the A site, and a small cation is located at the B site.

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

[0009] Furthermore, there is a technique for forming a passivation layer on the surface of a perovskite light-absorbing layer to improve the efficiency of perovskite solar cells. Conventional passivation layers are generally formed by vacuum deposition, and lithium fluoride (LiF) is generally used as the forming material.

[0010] However, lithium fluoride (LiF) has a fatal disadvantage in that it has low lattice energy, which causes problems with the reliability of perovskite solar cells.

[0011]

[0012] The present invention has been devised to overcome the aforementioned problems and aims to provide a perovskite solar cell and a method for manufacturing the same, which not only possesses excellent power conversion efficiency but also ensures excellent reliability by using a metal oxide as the material for the passivation layer formed on the surface of the perovskite light-absorbing layer.

[0013] In addition, by applying a thermal evaporation method instead of the vacuum deposition method generally used to form a passivation layer on the surface of a perovskite light-absorbing layer, we aim to provide a perovskite solar cell capable of not only having excellent power conversion efficiency but also ensuring excellent reliability, and a method for manufacturing the same.

[0014]

[0015] To solve the above-mentioned problem, the perovskite solar cell of the present invention comprises a laminate in which a perovskite light absorption layer, a passivation layer, and an electron transport layer are sequentially stacked, and the passivation layer may comprise a metal oxide.

[0016] As a preferred embodiment of the present invention, the metal oxide may include one or more selected from lead monoxide (PbO), lead dioxide (PbO2), tin monoxide (SnO), tin oxide (SnO2), cesium monoxide (Cs2O), rubidium monoxide (Rb2O), aluminum oxide (Al2O3), aluminum monoxide (AlO), magnesium oxide (MgO), manganese monoxide (MnO), and manganese dioxide (MnO2).

[0017] As a preferred embodiment of the present invention, the passivation layer may have a thickness of 0.3 to 2 nm.

[0018] As a preferred embodiment of the present invention, the electron transport layer may include a fullerene-based organic material.

[0019] As a preferred embodiment of the present invention, the perovskite light-absorbing layer may include a perovskite material represented by the following chemical formula 1.

[0020] [Chemical Formula 1]

[0021] CMX3

[0022] In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X is a monovalent anion.

[0023] Meanwhile, the tandem perovskite solar cell of the present invention comprises a stack in which a solar cell, a transparent conductive layer, a hole transport layer, a perovskite light absorption layer, a passivation layer, and an electron transport layer are sequentially stacked, and the passivation layer may include a metal oxide.

[0024] As 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 dye-sensitized solar cell, or a group 3-5 compound solar cell.

[0025] Furthermore, the method for manufacturing a perovskite solar cell according to the present invention may include a first step of forming a perovskite light-absorbing layer on top of a hole transport layer, a second step of forming a passivation layer by depositing a metal oxide on top of the perovskite light-absorbing layer through a deposition process, and a third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the passivation layer.

[0026] As a preferred embodiment of the present invention, the deposition process may be a thermal evaporation process.

[0027] 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, a hole transport layer, and a perovskite light absorption layer on top of a solar cell; a second step of forming a passivation layer by depositing a metal oxide on top of the perovskite light absorption layer through a deposition process; and a third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the passivation layer.

[0028]

[0029] The perovskite solar cell and the method for manufacturing the same according to the present invention not only have excellent power conversion efficiency but can also ensure excellent reliability.

[0030]

[0031] Figure 1 is an image taken with a field emission scanning electron microscope (FE-SEM, JSM-7900F, JEOL) of the perovskite light absorption layer prepared in Preparation Example 1, the perovskite light absorption layer with a passivation layer prepared in Example 1 and Comparative Example 1, after forming a thin film and storing it for 8 days.

[0032] Figure 2 is a graph showing the results of UPS analysis performed on the perovskite light-absorbing layer prepared in Preparation Example 1, and the perovskite light-absorbing layer with passivation layer prepared in Example 1 and Comparative Example 1, using Ultraviolet Photoelectron Spectroscopy (UPS).

[0033]

[0034] The present invention will be described in more detail below.

[0035] Perovskite solar cells are being developed in the form of PIN perovskite single solar cells or two-terminal perovskite / silicon tandem solar cells. In the case of two-terminal perovskite / silicon tandem solar cells, a transparent conductive layer is formed on top of a lower silicon solar cell, and then a hole transport layer, a perovskite light absorption layer, an electron transport layer, a transparent electrode, and a metal electrode are sequentially formed to manufacture the cells.

[0036] Meanwhile, there is a technique for forming a passivation layer on the surface of a perovskite light-absorbing layer to improve the efficiency of perovskite solar cells. Conventional passivation layers are generally formed by vacuum deposition, and lithium fluoride (LiF) is generally used as the forming material. Lithium fluoride (LiF) has a fatal disadvantage in that it has low lattice energy, which causes problems with the reliability of perovskite solar cells.

[0037] To solve this, the present invention uses a metal oxide as the material for the passivation layer formed on the surface of a perovskite light-absorbing layer, thereby not only having excellent power conversion efficiency but also ensuring excellent reliability. Furthermore, by applying a thermal evaporation method instead of the vacuum deposition method generally used when forming the passivation layer on the surface of the perovskite light-absorbing layer, it is possible to not only have excellent power conversion efficiency but also ensure excellent reliability.

[0038]

[0039] The perovskite solar cell of the present invention may include a laminate in which a perovskite light absorption layer, a passivation layer, and an electron transport layer are sequentially stacked.

[0040] The perovskite light-absorbing layer may include a general perovskite material applied to the light-absorbing layer of a solar cell, and as a preferred example, it may include a perovskite material represented by the following chemical formula 1.

[0041] [Chemical Formula 1]

[0042] CMX3

[0043] In the above Formula 1, C is a monovalent cation and may include an amine, ammonium, a Group 1 metal, a Group 2 metal, and / or other cation or cation-like compound, preferably formamidinium (FA), methylammonium (MA), FAMA, CsFAMA, CsFA, or N(R)4 + (Here, R may be the same or different group, and R may be a straight-chain alkyl group having 1 to 5 carbon atoms, a branched-chain alkyl group having 3 to 5 carbon atoms, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, or an alkyl halide.)

[0044] In addition, M of Chemical Formula 1 is a divalent cation and may include one or two types selected from Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Eu, and Zr.

[0045] In addition, X of 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, and in a preferred example, X is I x Br 3-x (0 ≤ x ≤ 3) can be.

[0046] And, as a preferred embodiment of Chemical Formula 1, FAPbI x Br 3-x (0 ≤ x ≤ 3), MAPbI x Br 3-x (0 ≤ x ≤ 3), CSFAPbI x Br 3-x (0 ≤ x ≤ 3), CSMAFAPbI x Br 3-x (0 ≤ x ≤ 3), CH3NH3PbX3(X= Cl, Br, I, BrI2, or Br2I), CH3NH3SnX3(X= Cl, Br or I), CH(=NH)NH3PbX3(X= Cl, Br, I, BrI2, or Br2I) or CH(=NH)NH3SnX3(X= Cl, Br or I).

[0047] Meanwhile, the perovskite light-absorbing layer may be a single layer composed of the same perovskite material, or a multilayer structure in which multiple layers composed of different perovskite materials are stacked, and may include a different type of perovskite material different from the one type of perovskite material having a pillar shape, plate shape, needle shape, wire shape, rod shape, etc. within the light-absorbing layer composed of one type of perovskite material.

[0048] In addition, methods for forming a perovskite light-absorbing layer may include deposition processes and solution processes. The deposition process may be any general deposition process used in the industry, such as thermal evaporation, vacuum deposition, atomic layer deposition (ALD), chemical vapor deposition (CVD), or physical vapor deposition (PVD). The solution process may be any general solution process used in the industry, such as spin coating, slot die coating, blade coating, printing coating, gravure coating, or spray coating.

[0049] In addition, there is no separate limit on the thickness of the perovskite light absorption layer, but it can preferably have a thickness of 50 nm to 800 nm, and more preferably 300 nm to 600 nm.

[0050]

[0051] The passivation layer serves to align energy levels between the perovskite light absorption layer and the electron transport layer, and may include metal oxides.

[0052] Specifically, the metal oxide may include one or more selected from lead monoxide (PbO), lead dioxide (PbO2), tin monoxide (SnO), tin oxide (SnO2), cesium monoxide (Cs2O), rubidium monoxide (Rb2O), aluminum oxide (Al2O3), aluminum monoxide (AlO), magnesium oxide (MgO), manganese monoxide (MnO), and manganese dioxide (MnO2), and preferably may include lead monoxide (PbO).

[0053] In addition, the passivation layer may have a thickness of 0.3 to 2 nm, preferably 0.3 to 1.3 nm, and more preferably 0.7 to 1.3 nm; if the thickness is less than 0.3 nm, there may be a problem where the open-circuit voltage decreases due to insufficient defect passivation caused by insufficient coverage, and if it exceeds 1.3 nm, the series resistance (R) is significantly increased due to the insulating layer effect. s There may be a problem with ) increasing.

[0054] In addition, a deposition process can be performed as a method for forming the passivation layer. Any general deposition process used in the industry, such as thermal evaporation, vacuum deposition, atomic layer deposition (ALD), chemical vapor deposition (CVD), or physical vapor deposition (PVD), can be performed, and preferably, a thermal evaporation process can be performed.

[0055]

[0056] The electron transporting layer (ETL, or electron transport layer) is a layer that transports electrons formed in the perovskite light-absorbing layer while simultaneously blocking the movement of holes.

[0057] The electron transport layer may include one or more 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).

[0058] In addition, the electron transport layer may include inorganic and / or organic materials.

[0059] At this time, the inorganic material may include one or more 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.

[0060] In addition, organic 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 (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 one or more selected from 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.

[0061] In addition, the electron transport layer may include fullerene-based organic materials. In this case, the fullerene-based organic material is C 60 , C 70 It may include one or more selected from PC60BM and PC70BM.

[0062] In addition, deposition processes and solution processes can be performed as methods for forming the electron transport layer. The deposition process can be any general deposition process used in the industry, such as thermal evaporation, vacuum deposition, atomic layer deposition (ALD), chemical vapor deposition (CVD), and physical vapor deposition (PVD). The solution process can be any general solution process used in the industry, such as spin coating, slot die coating, blade coating, printing coating, gravure coating, and spray coating.

[0063] In addition, there is no separate limit on the thickness of the electron transport layer, but preferably it can have an average thickness of 3 to 300 nm, and more preferably 5 to 200 nm.

[0064]

[0065] In addition, the perovskite solar cell of the present invention may include a laminate in which a hole transport layer, a perovskite light absorption layer, a passivation layer, and an electron transport layer are sequentially stacked. In this case, the perovskite light absorption layer, the passivation layer, and the electron transport layer are each as described above.

[0066] A hole transport layer (HTL, or hole transport layer) is a layer that transports holes formed in a perovskite light-absorbing layer while simultaneously blocking the movement of electrons, and may include inorganic and / or organic hole transport materials.

[0067] At this time, the inorganic hole transport material may include one or more 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.

[0068] In addition, organic hole transporters include carbazole derivatives, polyarylalkane derivatives, phenylenediamine derivatives, arylamines, 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 (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 one or more selected from 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.

[0069] In addition, as a method for forming a hole transport layer, deposition processes and solution processes can be performed. The deposition process can be any general deposition process used in the industry, such as thermal evaporation, vacuum deposition, atomic layer deposition (ALD), chemical vapor deposition (CVD), and physical vapor deposition (PVD). The solution process can be any general solution process used in the industry, such as spin coating, slot die coating, blade coating, printing coating, gravure coating, and spray coating.

[0070] In addition, there is no separate limit on the thickness of the hole transport layer, but preferably it can have a thickness of 5 nm to 40 nm, and more preferably 10 nm to 30 nm.

[0071]

[0072] In addition, in the perovskite solar cell of the present invention, a transparent electrode and a metal electrode may be sequentially stacked on top of the electron transport layer.

[0073] A transparent electrode can be formed on top of an electron transport layer through a deposition process. At this time, the deposition can be performed using a general deposition process used in the industry, and preferably, the deposition process can be performed using a sputtering method.

[0074] In addition, the transparent electrode may be a transparent thin film with 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) deposited thereon.

[0075] In addition, there is no separate limit on the thickness of the transparent electrode, but it can preferably have a thickness of 50 to 200 nm, and more preferably 60 to 140 nm.

[0076]

[0077] A metal electrode can be formed by patterning a metal material on top of a transparent electrode. Specifically, the patterning process consists mainly of deposition, lithography, and etching. A metal electrode can be formed on top of a transparent electrode by laying a metal material in the form of a thin film on one side of a substrate, printing a pattern by exposure, and then removing the unnecessary parts. Additionally, the patterning process can be performed using a screen printing method with a metal paste containing a metal material.

[0078] At this time, the metal material may include one or more selected from Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C, and conductive polymers.

[0079] In addition, there is no separate limit on the thickness of the metal electrode, but preferably, it can have a thickness of 50 nm to 2.5 µm.

[0080]

[0081] Meanwhile, the tandem perovskite solar cell of the present invention may include a laminate in which a solar cell, a transparent conductive layer, a hole transport layer, a perovskite light absorption layer, a passivation layer, and an electron transport layer are sequentially stacked. In this case, the hole transport layer, the perovskite light absorption layer, the passivation layer, and the electron transport layer are each as described above, and a transparent electrode and a metal electrode may be sequentially stacked on top of the electron transport layer, and the transparent electrode and the metal electrode are each as described above.

[0082] 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 dye-sensitized solar cell, or a group 3-5 compound solar cell.

[0083] In addition, there is no separate limit on the thickness of the solar cell, but it can preferably have a thickness of 140 to 250 μm, and more preferably 160 to 200 μm.

[0084] The transparent conductive layer is a layer that induces the recombination of electrons and holes generated in the solar cell and the perovskite light absorption layer, and may be a transparent thin film with deposited 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).

[0085] 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 can be treated with hydrofluoric acid to remove the SiOx oxide film, and then the residual hydrofluoric acid can be removed using ultrapure water, after which a transparent conductive layer can be formed on top of the silicon solar cell from which the oxide film has been removed through a sputtering process.

[0086] In addition, there is no separate limit on the thickness of the transparent conductive layer, but preferably it can have a thickness of 5 nm to 50 nm, and more preferably 15 nm to 25 nm.

[0087]

[0088] Furthermore, the method for manufacturing a perovskite solar cell according to the present invention may include a first step of forming a perovskite light-absorbing layer on top of a hole transport layer, a second step of forming a passivation layer by depositing a metal oxide on top of the perovskite light-absorbing layer through a deposition process, and a third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the passivation layer. At this time, the hole transport layer, the perovskite light-absorbing layer, the passivation layer, the electron transport layer, the transparent electrode, and the metal electrode are each as described above.

[0089] Meanwhile, the method for manufacturing a tandem perovskite solar cell according to the present invention may include a first step of sequentially forming a transparent conductive layer, a hole transport layer, and a perovskite light absorption layer on top of a solar cell; a second step of forming a passivation layer by depositing a metal oxide on top of the perovskite light absorption layer through a deposition process; and a third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the passivation layer. At this time, the solar cell, the transparent conductive layer, the hole transport layer, the perovskite light absorption layer, the passivation layer, the electron transport layer, the transparent electrode, and the metal electrode are each as described above.

[0090]

[0091] The present invention will be explained in more detail below through examples, but the following examples are not intended to limit the scope of the invention and should be interpreted as being for the purpose of aiding understanding of the invention.

[0092]

[0093] Preparation Example 1: Preparation of a Perovskite Light Absorbing Layer

[0094] A washed glass substrate is prepared, a yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is formed on the prepared glass substrate via spin coating, and a perovskite light-absorbing layer (CSFAPbI) having a 400 nm thick perovskite crystal structure is heat-treated at 150°C for 10 minutes. x Br 3-X (0 ≤ x ≤ 3)) was formed.

[0095]

[0096] Example 1: Preparation of a perovskite light-absorbing layer with a passivation layer

[0097] (1) A washed glass substrate is prepared, and a yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is formed on the prepared glass substrate by spin coating, and a perovskite light-absorbing layer (CSFAPbI) having a perovskite crystal structure with a thickness of 400 nm is formed by heat treatment at 150°C for 10 minutes. x Br 3-X (0 ≤ x ≤ 3)) was formed.

[0098] (2) Next, a 1 nm thick layer of lead monoxide (PbO) was deposited on the perovskite light-absorbing layer through an evaporator process to form a passivation layer on the perovskite light-absorbing layer.

[0099]

[0100] Comparative Example 1: Preparation of a perovskite light-absorbing layer with a passivation layer

[0101] (1) A washed glass substrate is prepared, and a yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is formed on the prepared glass substrate by spin coating, and a perovskite light-absorbing layer (CSFAPbI) having a perovskite crystal structure with a thickness of 400 nm is formed by heat treatment at 150°C for 10 minutes. x Br 3-X (0 ≤ x ≤ 3)) was formed.

[0102] (2) Next, a 1 nm thick lithium fluoride (LiF) layer was deposited on top of the perovskite light-absorbing layer through an evaporator process to form a passivation layer on top of the perovskite light-absorbing layer.

[0103]

[0104] Experimental Example 1: SEM imaging

[0105] Figure 1 is an image taken with a field emission scanning electron microscope (FE-SEM, JSM-7900F, JEOL) of the perovskite light absorption layer prepared in Preparation Example 1, the perovskite light absorption layer with a passivation layer prepared in Example 1 and Comparative Example 1, after forming a thin film and storing it for 8 days.

[0106] As can be seen in Fig. 1, compared to the perovskite light-absorbing layer prepared in Preparation Example 1, it was confirmed that no damage occurred at the grain surface and grain boundary of the perovskite light-absorbing layer with a passivation layer prepared in Example 1, whereas it was confirmed that surface damage occurred in the black area at the grain surface and grain boundary of the perovskite light-absorbing layer with a passivation layer prepared in Comparative Example 1. From these results, it was confirmed that the perovskite light-absorbing layer with a passivation layer prepared in Example 1 is more advantageous in terms of stability than the perovskite light-absorbing layer with a passivation layer prepared in Comparative Example 1.

[0107]

[0108] Experimental Example 2: UPS Analysis

[0109] Using Ultraviolet Photoelectron Spectroscopy (UPS), UPS analysis was performed on the perovskite light-absorbing layer prepared in Preparation Example 1, and the perovskite light-absorbing layer with passivation layer formed in Example 1 and Comparative Example 1, and the resulting graph is shown in FIG. 2 (the graph on the right in FIG. 2 shows the shape of the UPS graph near the secondary electron cut-off, and the graph on the left in FIG. 2 shows the shape of the UPS graph near the secondary valence band).

[0110] As can be seen in Figure 2, compared to the perovskite light-absorbing layer prepared in Preparation Example 1, the perovskite light-absorbing layer with the passivation layer prepared in Example 1 showed a significant decrease in work function as an n-type, whereas the perovskite light-absorbing layer with the passivation layer prepared in Comparative Example 1 showed a smaller decrease in work function as an n-type. From these results, it was confirmed that the perovskite light-absorbing layer with the passivation layer prepared in Example 1 was more advantageous in terms of electron transport than the perovskite light-absorbing layer with the passivation layer prepared in Comparative Example 1.

[0111]

[0112] Preparation Example 1: Preparation of a tandem silicon / perovskite heterojunction solar cell

[0113] (1) A silicon solar cell (thickness: 180 μm) doped with n or p-type impurities was prepared, and the SiOx oxide film was removed by treating it with hydrofluoric acid, and the remaining hydrofluoric acid was removed using ultrapure water. Then, a transparent conductive layer (ITO) with a thickness of 20 nm was formed on the silicon solar cell from which the oxide film had been removed through a sputtering process.

[0114] (2) Next, a 20 nm thick nickel oxide (NiOx) was deposited on the transparent conductive layer by sputtering vacuum deposition, and a 5 nm thick Me-4PACz was coated on the deposited nickel oxide by spin coating to form a hole transport layer.

[0115] (3) Next, a yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is formed on top of the hole transport layer by spin coating, and a perovskite light-absorbing layer (CSFAPbI) having a 400 nm thick perovskite crystal structure is formed by heat treatment at 150°C for 10 minutes. x Br 3-X (0 ≤ x ≤ 3)) was formed.

[0116] (4) Next, a 1 nm thick layer of lead monoxide (PbO) was deposited on the perovskite light-absorbing layer through an evaporator process to form a passivation layer on the perovskite light-absorbing layer.

[0117] (5) Next, an electron transport layer (C) with an average thickness of 10 nm is formed on top of the passivation layer through an atomic layer deposition (ALD) process. 60 formed ).

[0118] (6) Next, a transparent electrode (ITO) with a thickness of 75 nm was formed on top of the electron transport layer through a sputtering process.

[0119] (7) Finally, silver (Ag) is placed on top of the transparent electrode in a 1×10⁻¹⁰ manner. -7 A tandem silicon / perovskite heterojunction solar cell was fabricated by sequentially stacking a silicon solar cell, a transparent conductive layer, a hole transport layer, a perovskite light absorption layer, a passivation layer, an electron transport layer, a transparent electrode, and a metal electrode by forming a metal electrode by depositing at a pressure of 100 nm at a pressure of torr.

[0120]

[0121] Preparation Example 2: Preparation of a tandem silicon / perovskite heterojunction solar cell

[0122] A tandem silicon / perovskite heterojunction solar cell was prepared using the same method as in Preparation Example 1. However, unlike Preparation Example 1, the passivation layer was not formed with a thickness of 1 nm, but with a thickness of 0.5 nm, thereby finally preparing a tandem silicon / perovskite heterojunction solar cell.

[0123]

[0124] Preparation Example 3: Preparation of a tandem silicon / perovskite heterojunction solar cell

[0125] A tandem silicon / perovskite heterojunction solar cell was prepared using the same method as in Preparation Example 1. However, unlike Preparation Example 1, the passivation layer was not formed with a thickness of 1 nm, but with a thickness of 1.5 nm, thereby finally preparing a tandem silicon / perovskite heterojunction solar cell.

[0126]

[0127] Experimental Example 3: Measurement of Solar Cell Performance

[0128] For each of the tandem silicon / perovskite heterojunction solar cells prepared in Preparation Examples 1 to 3, the efficiency was measured using a photovoltaic simulation device and a JV Keithley device, and the initial JV curve was used and is shown in Table 1 below.

[0129]

[0130] As can be seen in Table 1, it was confirmed that the tandem silicon / perovskite heterojunction solar cell prepared in Preparation Example 1 not only has superior power conversion efficiency compared to the tandem silicon / perovskite heterojunction solar cells prepared in Preparation Examples 2 and 3, but also possesses superior reliability.

[0131] Specifically, it was confirmed that the open-circuit voltage of the tandem silicon / perovskite heterojunction solar cell prepared in Preparation Example 2 decreased due to a defect passivation phenomenon caused by insufficient coverage, and it was confirmed that the series resistance (Rs) of the tandem silicon / perovskite heterojunction solar cell prepared in Preparation Example 3 increased significantly due to the insulating layer effect.

[0132]

[0133] Specific embodiments have been illustrated and described above. However, the invention is not limited to the aforementioned embodiments, and those skilled in the art may make various modifications without departing from the essence of the technical concept of the invention as described in the following claims.

Claims

1. A laminate comprising a perovskite light absorption layer, a passivation layer, and an electron transport layer stacked sequentially, and The above passivation layer comprises a metal oxide, perovskite solar cell.

2. In Paragraph 1, A perovskite solar cell comprising one or more selected from the group consisting of lead monoxide (PbO), lead dioxide (PbO2), tin monoxide (SnO), tin oxide (SnO2), cesium monoxide (Cs2O), rubidium monoxide (Rb2O), aluminum oxide (Al2O3), aluminum monoxide (AlO), magnesium oxide (MgO), manganese monoxide (MnO), and manganese dioxide (MnO2).

3. In Paragraph 1, The above passivation layer has a thickness of 0.3 to 2 nm, and is a perovskite solar cell.

4. In Paragraph 1, A perovskite solar cell in which the electron transport layer comprises a fullerene-based organic material.

5. In Paragraph 1, A perovskite solar cell in which the perovskite light-absorbing layer comprises a perovskite material represented by the following chemical formula 1. [Chemical Formula 1] CMX3 In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X is a monovalent anion.

6. A laminate comprising a solar cell, a transparent conductive layer, a hole transport layer, a perovskite light absorption layer, a passivation layer, and an electron transport layer stacked sequentially, and The above passivation layer comprises a metal oxide, in a tandem perovskite solar cell.

7. In Paragraph 6, A tandem perovskite solar cell comprising one or more metal oxides selected from lead monoxide (PbO), lead dioxide (PbO2), tin monoxide (SnO), tin oxide (SnO2), cesium monoxide (Cs2O), rubidium monoxide (Rb2O), aluminum oxide (Al2O3), aluminum monoxide (AlO), magnesium oxide (MgO), manganese monoxide (MnO), and manganese dioxide (MnO2).

8. In Paragraph 7, 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 dye-sensitized solar cell, or a group 3-5 compound solar cell.

9. A first step of forming a perovskite light absorption layer on top of a hole transport layer; A second step of forming a passivation layer by depositing a metal oxide on the upper surface of the perovskite light-absorbing layer through a deposition process; and A third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the passivation layer; A method for manufacturing a perovskite solar cell comprising 10. In Paragraph 9, A method for manufacturing a perovskite solar cell, wherein the metal oxide comprises one or more selected from lead monoxide (PbO), lead dioxide (PbO2), tin monoxide (SnO), tin oxide (SnO2), cesium monoxide (Cs2O), rubidium monoxide (Rb2O), aluminum oxide (Al2O3), aluminum monoxide (AlO), magnesium oxide (MgO), manganese monoxide (MnO), and manganese dioxide (MnO2).

11. In Paragraph 9, A method for manufacturing a perovskite solar cell, wherein the above deposition process is a thermal evaporation process.

12. A first step of sequentially forming a transparent conductive layer, a hole transport layer, and a perovskite light absorption layer on top of a solar cell; A second step of forming a passivation layer by depositing a metal oxide on the upper surface of the perovskite light-absorbing layer through a deposition process; and A third step of sequentially forming an electron transport layer, a transparent electrode, and a metal electrode on top of the passivation layer; A method for manufacturing a tandem perovskite solar cell comprising 13. In Paragraph 12, A method for manufacturing a tandem perovskite solar cell, wherein the metal oxide comprises one or more selected from lead monoxide (PbO), lead dioxide (PbO2), tin monoxide (SnO), tin oxide (SnO2), cesium monoxide (Cs2O), rubidium monoxide (Rb2O), aluminum oxide (Al2O3), aluminum monoxide (AlO), magnesium oxide (MgO), manganese monoxide (MnO), and manganese dioxide (MnO2).

14. In Paragraph 12, A method for manufacturing a tandem perovskite solar cell, wherein the deposition process is a thermal evaporation process.

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