Method for forming electron transfer layer for perovskite solar cell and method for manufacturing perovskite solar cell

Abstract

The present invention relates to a method for forming an electron transfer layer for a perovskite solar cell, the method comprising: a first step for preparing an atomic layer deposition process chamber including a substrate therein; a second step for introducing a laminate into the atomic layer deposition process chamber and positioning the laminate on the upper part of the substrate; a third step for injecting a material for forming an electron transport layer into the atomic layer deposition process chamber; and a fourth step for performing an atomic layer deposition process to form an electron transport layer on the upper part of the laminate, wherein condition (1): A > B is satisfied. (In the condition (1), A represents the temperature inside the atomic layer deposition process chamber, and B represents the temperature of the substrate included in the atomic layer deposition process chamber.)

Description

Method for forming an electron transport layer for a perovskite solar cell and method for manufacturing a perovskite solar cell

[0001] The present invention relates to a method for forming an electron transport layer for a perovskite solar cell by performing an atomic layer deposition process under specific temperature conditions and a method for manufacturing a perovskite solar cell.

[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] At this time, one of the methods for forming an electron transport layer is to perform an atomic layer deposition (ALD) process. Generally, the ALD process is performed at a temperature of 100°C or higher. However, when forming an electron transport layer through such a high-temperature ALD process, there was a problem in that the lower organic layer was deteriorated due to the high-temperature reaction and chemical bonding of the source and reactant.

[0010] In addition, when forming an electron transport layer through an atomic layer deposition process at temperatures below 100°C to avoid such problems, there was a problem in that the photoelectric conversion efficiency was reduced due to changes in the density and band gap of the formed electron transport layer, which resulted in a decrease in the characteristics and charge transfer characteristics of the electron transport layer.

[0011]

[0012] The present invention has been devised to overcome the above-described problems, and provides a method for forming an electron transport layer for a perovskite solar cell and a method for manufacturing a perovskite solar cell, which not only minimizes heat damage and prevents deterioration occurring at the interface by forming an electron transport layer through an atomic layer deposition process under specific temperature conditions, but also minimizes a decrease in the performance of the perovskite solar cell and ensures stability.

[0013]

[0014] In order to solve the above-described problem, the method for forming an electron transport layer for a perovskite solar cell of the present invention may include a first step of preparing an atomic layer deposition process chamber including a substrate therein, a second step of introducing a laminate into the atomic layer deposition process chamber and positioning the laminate on top of the substrate, a third step of injecting a material for forming an electron transport layer into the atomic layer deposition process chamber, and a fourth step of performing an atomic layer deposition process to form an electron transport layer on top of the laminate.

[0015] As a preferred embodiment of the present invention, the method for forming an electron transport layer for a perovskite solar cell of the present invention can satisfy the following condition (1).

[0016] (1) A > B

[0017] In the above condition (1), A represents the temperature inside the chamber for the atomic layer deposition process, and B represents the temperature of the substrate included inside the chamber for the atomic layer deposition process.

[0018] As a preferred embodiment of the present invention, the atomic layer deposition process of the fourth step of the method for forming an electron transport layer for a perovskite solar cell of the present invention can be performed under conditions in which the temperature inside the chamber for the atomic layer deposition process is 85 to 150°C and the temperature of the substrate included inside the chamber for the atomic layer deposition process is 80°C or lower.

[0019] As a preferred embodiment of the present invention, the atomic layer deposition process of the fourth step of the method for forming an electron transport layer for a perovskite solar cell of the present invention can be performed under conditions in which the temperature inside the chamber for the atomic layer deposition process is 85 to 120°C and the temperature of the substrate included inside the chamber for the atomic layer deposition process is 40 to 70°C.

[0020] As a preferred embodiment of the present invention, the laminate has a structure in which a hole transport layer and a perovskite light-absorbing layer are sequentially laminated, and an electron transport layer can be formed on top of the perovskite light-absorbing layer.

[0021] As a preferred embodiment of the present invention, the laminate has a structure in which a hole transport layer, a perovskite light-absorbing layer, and an intermediate layer are sequentially laminated, and an electron transport layer can be formed on top of the intermediate layer.

[0022] As a preferred embodiment of the present invention, the intermediate layer may include a fullerene-based organic material.

[0023] As a preferred embodiment of the present invention, the fullerene-based organic material is C 60 , C 70 , may include one or more selected from PC60BM and PC70BM.

[0024] As a preferred embodiment of the present invention, the electron transport layer may have an average thickness of 3 to 20 nm.

[0025] As a preferred embodiment of the present invention, the material for forming the electron transport layer is tin oxide (SnOx), nickel oxide (NiOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), hafnium oxide (HfO x ), zirconium oxide (ZrO x ), vanadium oxide (VO x) and niobium pentoxide (Nb2O5).

[0026] Meanwhile, the method for manufacturing a perovskite solar cell of the present invention may include a first step of manufacturing a laminate by forming a perovskite light-absorbing layer on top of a hole transport layer, a second step of forming an electron transport layer on top of the perovskite light-absorbing layer through an atomic layer deposition process, and a third step of sequentially forming a transparent electrode and a metal electrode on top of the electron transport layer.

[0027] As a preferred embodiment of the present invention, the atomic layer deposition process of the second step of the method for manufacturing a perovskite solar cell of the present invention may be performed by including a step 2-1 of preparing an atomic layer deposition process chamber including a substrate therein, a step 2-2 of introducing a laminate into the atomic layer deposition process chamber and positioning the laminate on top of the substrate, a step 2-3 of injecting a material for forming an electron transport layer into the atomic layer deposition process chamber, and a step 2-4 of performing an atomic layer deposition process to form an electron transport layer on top of the perovskite light-absorbing layer.

[0028] Furthermore, the method for manufacturing a perovskite solar cell of the present invention may include a first step of manufacturing a laminate by sequentially forming a perovskite light-absorbing layer and an intermediate layer on top of a hole transport layer, a second step of forming an electron transport layer on top of the intermediate layer through an atomic layer deposition process, and a third step of sequentially forming a transparent electrode and a metal electrode on top of the electron transport layer.

[0029] As a preferred embodiment of the present invention, the atomic layer deposition process of the second step of the method for manufacturing a perovskite solar cell of the present invention may be performed by including a step 2-1 of preparing an atomic layer deposition process chamber including a substrate therein, a step 2-2 of introducing a laminate into the atomic layer deposition process chamber and positioning the laminate on top of the substrate, a step 2-3 of injecting a material for forming an electron transport layer into the atomic layer deposition process chamber, and a step 2-4 of performing an atomic layer deposition process to form an electron transport layer on top of the intermediate layer.

[0030] As a preferred embodiment of the present invention, the method for manufacturing a perovskite solar cell of the present invention can satisfy the following condition (1).

[0031] (1) A > B

[0032] In the above condition (1), A represents the temperature inside the chamber for the atomic layer deposition process, and B represents the temperature of the substrate included inside the chamber for the atomic layer deposition process.

[0033] As a preferred embodiment of the present invention, the atomic layer deposition process of steps 2-4 of the method for manufacturing a perovskite solar cell of the present invention can be performed under conditions in which the temperature inside the chamber for the atomic layer deposition process is 85 to 150°C and the temperature of the substrate included inside the chamber for the atomic layer deposition process is 80°C or lower.

[0034] Meanwhile, the method for manufacturing a tandem perovskite solar cell of the present invention may include a first step of manufacturing a laminate by sequentially forming a transparent conductive layer, a hole transport layer, and a perovskite light-absorbing layer on top of a solar cell, a second step of forming an electron transport layer on top of the perovskite light-absorbing layer through an atomic layer deposition process, and a third step of sequentially forming a transparent electrode and a metal electrode on top of the electron transport layer.

[0035] As a preferred embodiment of the present invention, the atomic layer deposition process of the second step of the method for manufacturing a tandem perovskite solar cell of the present invention may be performed by including a step 2-1 of preparing an atomic layer deposition process chamber including a substrate therein, a step 2-2 of introducing a laminate into the atomic layer deposition process chamber and positioning the laminate on top of the substrate, a step 2-3 of injecting a material for forming an electron transport layer into the atomic layer deposition process chamber, and a step 2-4 of performing an atomic layer deposition process to form an electron transport layer on top of the perovskite light-absorbing layer.

[0036] Furthermore, the method for manufacturing a tandem perovskite solar cell of the present invention may include a first step of manufacturing a laminate by sequentially forming a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, and an intermediate layer on top of a solar cell, a second step of forming an electron transport layer on top of the intermediate layer through an atomic layer deposition process, and a third step of sequentially forming a transparent electrode and a metal electrode on top of the electron transport layer.

[0037] As a preferred embodiment of the present invention, the atomic layer deposition process of the second step of the method for manufacturing a tandem perovskite solar cell of the present invention may be performed by including a step 2-1 of preparing an atomic layer deposition process chamber including a substrate therein, a step 2-2 of introducing a laminate into the atomic layer deposition process chamber and positioning the laminate on top of the substrate, a step 2-3 of injecting a material for forming an electron transport layer into the atomic layer deposition process chamber, and a step 2-4 of performing an atomic layer deposition process to form an electron transport layer on top of the intermediate layer.

[0038] As a preferred embodiment of the present invention, the method for manufacturing a tandem perovskite solar cell of the present invention can satisfy the following condition (1).

[0039] (1) A > B

[0040] In the above condition (1), A represents the temperature inside the chamber for the atomic layer deposition process, and B represents the temperature of the substrate included inside the chamber for the atomic layer deposition process.

[0041] As a preferred embodiment of the present invention, the atomic layer deposition process of steps 2-4 of the method for manufacturing a tandem perovskite solar cell of the present invention can be performed under conditions in which the temperature inside the chamber for the atomic layer deposition process is 85 to 150°C and the temperature of the substrate included inside the chamber for the atomic layer deposition process is 80°C or lower.

[0042] 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.

[0043]

[0044] The method for forming an electron transport layer for a perovskite solar cell and the method for manufacturing a perovskite solar cell of the present invention can induce stabilization of an interface and improve charge transfer characteristics through better aligned energy levels and hole block characteristics, thereby improving voltage characteristics and fill factor characteristics, thereby increasing power conversion efficiency.

[0045]

[0046] FIG. 1 is a schematic diagram showing a chamber for an atomic layer deposition process according to a preferred embodiment of the present invention.

[0047] Figure 2 is an FE-SEM image of the electron transport layer surface of a tandem silicon / perovskite heterojunction solar cell manufactured in Example 1.

[0048] Figure 3 is an FE-SEM image of the electron transport layer surface of a tandem silicon / perovskite heterojunction solar cell manufactured in Comparative Example 1.

[0049]

[0050] Hereinafter, the present invention will be described in more detail.

[0051] 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.

[0052] At this time, one of the methods for forming an electron transport layer is to perform an atomic layer deposition (ALD) process. Generally, the ALD process is performed at a temperature of 100°C or higher. However, when forming an electron transport layer through such a high-temperature ALD process, there was a problem in that the lower organic layer was deteriorated due to the high-temperature reaction and chemical bonding of the source and reactant.

[0053] In addition, when forming an electron transport layer through an atomic layer deposition process at temperatures below 100°C to avoid such problems, there was a problem in that the photoelectric conversion efficiency was reduced due to changes in the density and band gap of the formed electron transport layer, which resulted in a decrease in the characteristics and charge transfer characteristics of the electron transport layer.

[0054] Accordingly, the present invention relates to a method for forming an electron transport layer for a perovskite solar cell, which can prevent deterioration occurring at an interface by minimizing heat damage by forming an electron transport layer through an atomic layer deposition process under specific temperature conditions, and a method for manufacturing a perovskite solar cell, which can minimize a decrease in the performance of a perovskite solar cell and ensure stability.

[0055]

[0056] The method for forming an electron transport layer for a perovskite solar cell of the present invention comprises steps 1 to 4.

[0057] 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.

[0058] First, referring to FIG. 1, the first step of the method for forming an electron transport layer for a perovskite solar cell of the present invention may be to prepare a chamber (10) for an atomic layer deposition (ALD) process including a substrate (2) therein.

[0059] Next, in the second step of the method for forming an electron transport layer for a perovskite solar cell of the present invention, the laminate (20) can be placed inside the chamber (10) for the atomic layer deposition process prepared in the first step, and the laminate (20) can be positioned on top of the substrate (2).

[0060] Next, the third step of the method for forming an electron transport layer for a perovskite solar cell of the present invention can be to inject a material for forming an electron transport layer into a chamber (10) for an atomic layer deposition process.

[0061] At this time, the material for forming the electron transport layer is a material that forms the electron transport layer through an atomic layer deposition process, such as tin oxide (SnOx), nickel oxide (NiOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), and hafnium oxide (HfO). x ), zirconium oxide (ZrO x ), vanadium oxide (VO x ) and niobium pentoxide (Nb2O5), and preferably tin oxide (SnO2).

[0062] Finally, the fourth step of the method for forming an electron transport layer for a perovskite solar cell of the present invention can form an electron transport layer on top of a laminate (20) placed inside a chamber (10) for an atomic layer deposition process by performing an atomic layer deposition process.

[0063] Meanwhile, the laminate (20) may have a structure in which a hole transport layer and a perovskite light-absorbing layer are sequentially laminated, and an electron transport layer may be formed on top of the perovskite light-absorbing layer through the fourth step of the method for forming an electron transport layer for a perovskite solar cell.

[0064] In addition, the laminate (20) may have a structure in which a hole transport layer, a perovskite light-absorbing layer, and an inter layer are sequentially laminated, and an electron transport layer may be formed on top of the inter layer through the fourth step of the method for forming an electron transport layer for a perovskite solar cell.

[0065] Meanwhile, the method for forming an electron transport layer for a perovskite solar cell of the present invention can satisfy the following condition (1).

[0066] (1) A > B

[0067] In the above condition (1), A represents the temperature inside (1) of the chamber (10) for the atomic layer deposition process, and B represents the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process.

[0068] In this way, by satisfying condition (1) of the present invention and forming an electron transport layer, not only is heat damage minimized and deterioration occurring at the interface prevented, but also the performance reduction of the perovskite solar cell is minimized and stability is secured.

[0069] Specifically, the atomic layer deposition process of the fourth step of the method for forming an electron transport layer for a perovskite solar cell of the present invention can be performed under the conditions that the temperature inside the chamber (10) for the atomic layer deposition process (1) is 85 to 150°C, preferably 85 to 120°C, and the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process is 80°C or less, preferably 40°C to 70°C, more preferably 57°C to 63°C, and by forming the electron transport layer while satisfying these temperature conditions, not only can heat damage be minimized to prevent deterioration occurring at the interface, but also the performance reduction of the perovskite solar cell can be minimized and stability can be secured.

[0070] Furthermore, the electron transport layer formed through the method for forming an electron transport layer for a perovskite solar cell of the present invention may have an average thickness of 3 to 20 nm, preferably an average thickness of 4 to 15 nm, and more preferably an average thickness of 4 to 8 nm. If the average thickness is less than 3 nm, it may be difficult to form a layer with a uniform thickness, which may cause a problem of reduced electron transport characteristics, and if it exceeds 20 nm, not only may the electron transport characteristics decrease, but there may also be a problem of increased series resistance.

[0071]

[0072] The hole transport layer (HTL) included in the laminate (20) is a layer that transports holes formed in the perovskite light-absorbing layer while simultaneously blocking the movement of electrons, and may include an inorganic and / or organic hole transport material.

[0073] 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.

[0074] 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.

[0075] In addition, methods for forming a hole transport layer include a coating method and a vacuum deposition method, and methods for applying the hole transport layer include a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, and a die coat method.

[0076] 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.

[0077]

[0078] The perovskite light-absorbing layer included in the laminate (20) may include a general perovskite material applied to the light-absorbing layer of a solar cell, and as a preferred example, may include a perovskite material represented by the following chemical formula 1.

[0079] [Chemical Formula 1]

[0080] CMX3

[0081] 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, 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.)

[0082] In addition, M in chemical formula 1 is a divalent cation and may include one or two selected from Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Eu, and Zr.

[0083] In addition, X in chemical formula 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 a preferred example is I x Br 3-x (0 ≤ x ≤ 3) may be.

[0084] 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).

[0085] 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.

[0086] In addition, methods for forming a perovskite light-absorbing layer include a coating method and a vacuum deposition method, and methods for applying the layer include a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, an inkjet coating method, and a die coat method.

[0087] 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 600 nm.

[0088]

[0089] The intermediate layer included in the laminate (20) may include a fullerene series organic material. At this time, the fullerene series organic material is C 60 , C 70 , may include at least one selected from PC60BM and PC70BM, preferably C 60 second may include. In addition, the intermediate layer included in the laminate (20) may further include lithium fluoride (LiF).

[0090] In addition, the intermediate layer may have an average thickness of 3 to 30 nm, preferably an average thickness of 5 to 20 nm, and more preferably an average thickness of 11 to 17 nm. If the average thickness is less than 3 nm, there may be a problem of reduced charge transfer capability due to failure to form uniformly on the rough surface of the perovskite light-absorbing layer, and if it exceeds 30 nm, there may be a problem of reduced characteristics of the solar cell due to absorption of light that should be absorbed by the perovskite light-absorbing layer, thereby hindering the light-receiving characteristics of the perovskite light-absorbing layer.

[0091]

[0092] Meanwhile, the method for manufacturing a perovskite solar cell of the present invention includes steps 1 to 3.

[0093] First, in the first step of the method for manufacturing a perovskite solar cell of the present invention, a laminate can be manufactured by forming a perovskite light-absorbing layer on top of a hole transport layer. At this time, the hole transport layer and the perovskite light-absorbing layer are as described above.

[0094] Next, in the second step of the method for manufacturing a perovskite solar cell of the present invention, an electron transport layer can be formed on top of the perovskite light-absorbing layer formed in the first step through an atomic layer deposition process. As described above, the electron transporting layer (ETL) is a layer that transports electrons formed in the perovskite light-absorbing layer while simultaneously blocking the movement of holes.

[0095] Specifically, the atomic layer deposition process of the second step of the method for manufacturing a perovskite solar cell of the present invention includes steps 2-1 to 2-4.

[0096] Referring to FIG. 1, step 2-1 of the method for manufacturing a perovskite solar cell of the present invention can prepare a chamber (10) for an atomic layer deposition (ALD) process including a substrate (2) therein.

[0097] Next, in the second step of the method for manufacturing a perovskite solar cell of the present invention, the laminate (20) can be placed inside the chamber (10) for the atomic layer deposition process prepared in the first step, and the laminate (20) can be positioned on top of the substrate (2).

[0098] Next, in the second and third steps of the method for manufacturing a perovskite solar cell of the present invention, a material for forming an electron transport layer can be injected into the chamber (10) for an atomic layer deposition process.

[0099] At this time, the material for forming the electron transport layer is a material that forms the electron transport layer through an atomic layer deposition process, such as tin oxide (SnOx), nickel oxide (NiOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), and hafnium oxide (HfO). x ), zirconium oxide (ZrO x ), vanadium oxide (VO x ) and niobium pentoxide (Nb2O5), and preferably tin oxide (SnO2).

[0100] Finally, in the second to fourth steps of the method for manufacturing a perovskite solar cell of the present invention, an atomic layer deposition process is performed to form an electron transport layer on top of a laminate (20) placed inside a chamber (10) for an atomic layer deposition process.

[0101] Meanwhile, the laminate (20) may have a structure in which a hole transport layer and a perovskite light-absorbing layer are sequentially laminated, and an electron transport layer may be formed on top of the perovskite light-absorbing layer through steps 2-4 of the method for manufacturing a perovskite solar cell of the present invention.

[0102] In addition, the method for manufacturing a perovskite solar cell of the present invention can satisfy the following condition (1).

[0103] (1) A > B

[0104] In the above condition (1), A represents the temperature inside (1) of the chamber (10) for the atomic layer deposition process, and B represents the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process.

[0105] In this way, by satisfying condition (1) of the present invention and forming an electron transport layer, not only is heat damage minimized and deterioration occurring at the interface prevented, but also the performance reduction of the perovskite solar cell is minimized and stability is secured.

[0106] Specifically, the atomic layer deposition process of the second to fourth steps of the method for manufacturing a perovskite solar cell of the present invention can be performed under the conditions that the temperature inside the chamber (10) for the atomic layer deposition process (1) is 85 to 150°C, preferably 85 to 120°C, and the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process is 80°C or less, preferably 40°C to 70°C, more preferably 57°C to 63°C, and by forming an electron transport layer while satisfying these temperature conditions, not only can heat damage be minimized to prevent deterioration occurring at the interface, but also the performance reduction of the perovskite solar cell can be minimized and stability can be secured.

[0107] Furthermore, the electron transport layer formed through the second step of the method for manufacturing a perovskite solar cell of the present invention may have an average thickness of 3 to 20 nm, preferably an average thickness of 4 to 15 nm, and more preferably an average thickness of 4 to 8 nm. If the average thickness is less than 3 nm, it may be difficult to form a layer with a uniform thickness, which may cause a problem of reduced electron transport characteristics, and if it exceeds 20 nm, not only may the electron transport characteristics decrease, but there may also be a problem of increased series resistance.

[0108] Next, in the third step of the method for manufacturing a perovskite solar cell of the present invention, a transparent electrode and a metal electrode can be sequentially formed on top of the electron transport layer formed in the second step.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115]

[0116] Meanwhile, as another method, the method for manufacturing a perovskite solar cell of the present invention includes steps 1 to 3.

[0117] First, in the first step of the method for manufacturing a perovskite solar cell of the present invention, a laminate can be manufactured by sequentially forming a perovskite light-absorbing layer and an intermediate layer on top of a hole transport layer. At this time, the hole transport layer, perovskite light-absorbing layer, and intermediate layer are as described above.

[0118] Next, in the second step of the method for manufacturing a perovskite solar cell of the present invention, an electron transport layer can be formed on top of the intermediate layer formed in the first step through an atomic layer deposition process. As described above, 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.

[0119] Specifically, the atomic layer deposition process of the second step of the method for manufacturing a perovskite solar cell of the present invention includes steps 2-1 to 2-4.

[0120] Referring to FIG. 1, step 2-1 of the method for manufacturing a perovskite solar cell of the present invention can prepare a chamber (10) for an atomic layer deposition (ALD) process including a substrate (2) therein.

[0121] Next, in the second step of the method for manufacturing a perovskite solar cell of the present invention, the laminate (20) can be placed inside the chamber (10) for the atomic layer deposition process prepared in the first step, and the laminate (20) can be positioned on top of the substrate (2).

[0122] Next, in the second and third steps of the method for manufacturing a perovskite solar cell of the present invention, a material for forming an electron transport layer can be injected into the chamber (10) for an atomic layer deposition process.

[0123] At this time, the material for forming the electron transport layer is a material that forms the electron transport layer through an atomic layer deposition process, such as tin oxide (SnOx), nickel oxide (NiOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), and hafnium oxide (HfO). x ), zirconium oxide (ZrO x ), vanadium oxide (VO x ) and niobium pentoxide (Nb2O5), and preferably tin oxide (SnO2).

[0124] Finally, in the second to fourth steps of the method for manufacturing a perovskite solar cell of the present invention, an atomic layer deposition process is performed to form an electron transport layer on top of a laminate (20) placed inside a chamber (10) for an atomic layer deposition process.

[0125] Meanwhile, the laminate (20) may have a structure in which a hole transport layer, a perovskite light-absorbing layer, and an intermediate layer are sequentially laminated, and an electron transport layer may be formed on top of the intermediate layer through steps 2-4 of the method for manufacturing a perovskite solar cell of the present invention.

[0126] In addition, the method for manufacturing a perovskite solar cell of the present invention can satisfy the following condition (1).

[0127] (1) A > B

[0128] In the above condition (1), A represents the temperature inside (1) of the chamber (10) for the atomic layer deposition process, and B represents the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process.

[0129] In this way, by satisfying condition (1) of the present invention and forming an electron transport layer, not only is heat damage minimized and deterioration occurring at the interface prevented, but also the performance reduction of the perovskite solar cell is minimized and stability is secured.

[0130] Specifically, the atomic layer deposition process of the second to fourth steps of the method for manufacturing a perovskite solar cell of the present invention can be performed under the conditions that the temperature inside the chamber (10) for the atomic layer deposition process (1) is 85 to 150°C, preferably 85 to 120°C, and the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process is 80°C or less, preferably 40°C to 70°C, more preferably 57°C to 63°C, and by forming an electron transport layer while satisfying these temperature conditions, not only can heat damage be minimized to prevent deterioration occurring at the interface, but also the performance reduction of the perovskite solar cell can be minimized and stability can be secured.

[0131] Furthermore, the electron transport layer formed through the second step of the method for manufacturing a perovskite solar cell of the present invention may have an average thickness of 3 to 20 nm, preferably an average thickness of 4 to 15 nm, and more preferably an average thickness of 4 to 8 nm. If the average thickness is less than 3 nm, it may be difficult to form a layer with a uniform thickness, which may cause a problem of reduced electron transport characteristics, and if it exceeds 20 nm, not only may the electron transport characteristics decrease, but there may also be a problem of increased series resistance.

[0132] Next, in the third step of the method for manufacturing a perovskite solar cell of the present invention, a transparent electrode and a metal electrode can be sequentially formed on top of the electron transport layer formed in the second step. At this time, the transparent electrode and the metal electrode are as described above.

[0133]

[0134] Furthermore, the method for manufacturing a tandem perovskite solar cell of the present invention includes steps 1 to 3.

[0135] First, in the first step of the method for manufacturing a tandem perovskite solar cell of the present invention, a laminate can be manufactured by sequentially forming a transparent conductive layer, a hole transport layer, and a perovskite light-absorbing layer on top of a solar cell. At this time, the hole transport layer and the perovskite light-absorbing layer are as described above.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] Next, in the second step of the method for manufacturing a tandem perovskite solar cell of the present invention, an electron transport layer can be formed on top of the perovskite light-absorbing layer formed in the first step through an atomic layer deposition process. As described above, the electron transporting layer (ETL) is a layer that transports electrons formed in the perovskite light-absorbing layer while simultaneously blocking the movement of holes.

[0142] Specifically, the atomic layer deposition process of the second step of the method for manufacturing a tandem perovskite solar cell of the present invention includes steps 2-1 to 2-4.

[0143] Referring to FIG. 1, the second step of the method for manufacturing a tandem perovskite solar cell of the present invention can prepare a chamber (10) for an atomic layer deposition (ALD) process including a substrate (2) therein.

[0144] Next, in the second step of the method for manufacturing a tandem perovskite solar cell of the present invention, the laminate (20) can be placed inside the chamber (10) for the atomic layer deposition process prepared in the first step, and the laminate (20) can be positioned on top of the substrate (2).

[0145] Next, in the second and third steps of the method for manufacturing a tandem perovskite solar cell of the present invention, a material for forming an electron transport layer can be injected into the chamber (10) for an atomic layer deposition process.

[0146] At this time, the material for forming the electron transport layer is a material that forms the electron transport layer through an atomic layer deposition process, such as tin oxide (SnOx), nickel oxide (NiOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), and hafnium oxide (HfO). x ), zirconium oxide (ZrO x ), vanadium oxide (VO x ) and niobium pentoxide (Nb2O5), and preferably tin oxide (SnO2).

[0147] Finally, in the second to fourth steps of the method for manufacturing a tandem perovskite solar cell of the present invention, an atomic layer deposition process is performed to form an electron transport layer on top of a laminate (20) placed inside a chamber (10) for an atomic layer deposition process.

[0148] Meanwhile, the laminate (20) may have a structure in which a solar cell, a transparent conductive layer, a hole transport layer, and a perovskite light-absorbing layer are sequentially laminated, and an electron transport layer may be formed on top of the perovskite light-absorbing layer through steps 2-4 of the method for manufacturing a tandem perovskite solar cell of the present invention.

[0149] In addition, the method for manufacturing a tandem perovskite solar cell of the present invention can satisfy the following condition (1).

[0150] (1) A > B

[0151] In the above condition (1), A represents the temperature inside (1) of the chamber (10) for the atomic layer deposition process, and B represents the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process.

[0152] In this way, by satisfying condition (1) of the present invention and forming an electron transport layer, not only is heat damage minimized and deterioration occurring at the interface prevented, but also the performance reduction of the perovskite solar cell is minimized and stability is secured.

[0153] Specifically, the atomic layer deposition process of the second to fourth steps of the method for manufacturing a tandem perovskite solar cell of the present invention can be performed under the conditions that the temperature inside the chamber (10) for the atomic layer deposition process (1) is 85 to 150°C, preferably 85 to 120°C, and the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process is 80°C or less, preferably 40°C to 70°C, more preferably 57°C to 63°C, and by forming an electron transport layer while satisfying these temperature conditions, not only can heat damage be minimized to prevent deterioration occurring at the interface, but also the performance reduction of the perovskite solar cell can be minimized and stability can be secured.

[0154] Furthermore, the electron transport layer formed through the second step of the method for manufacturing a tandem perovskite solar cell of the present invention may have an average thickness of 3 to 20 nm, preferably an average thickness of 4 to 15 nm, and more preferably an average thickness of 4 to 8 nm. If the average thickness is less than 3 nm, it may be difficult to form a layer with a uniform thickness, which may cause a problem of reduced electron transport characteristics, and if it exceeds 20 nm, not only may the electron transport characteristics decrease, but there may also be a problem of increased series resistance.

[0155] Next, in the third step of the method for manufacturing a tandem perovskite solar cell of the present invention, a transparent electrode and a metal electrode can be sequentially formed on top of the electron transport layer formed in the second step. At this time, the transparent electrode and the metal electrode are as described above.

[0156]

[0157] Furthermore, as another method, the method for manufacturing a tandem perovskite solar cell of the present invention includes steps 1 to 3.

[0158] First, in the first step of the method for manufacturing a tandem perovskite solar cell of the present invention, a laminate can be manufactured by sequentially forming a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, and an intermediate layer on top of a solar cell. At this time, the solar cell, the transparent conductive layer, the hole transport layer, the perovskite light-absorbing layer, and the intermediate layer are as described above.

[0159] Next, in the second step of the method for manufacturing a tandem perovskite solar cell of the present invention, an electron transport layer can be formed on top of the intermediate layer formed in the first step through an atomic layer deposition process. As described above, 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.

[0160] Specifically, the atomic layer deposition process of the second step of the method for manufacturing a tandem perovskite solar cell of the present invention includes steps 2-1 to 2-4.

[0161] Referring to FIG. 1, the second step of the method for manufacturing a tandem perovskite solar cell of the present invention can prepare a chamber (10) for an atomic layer deposition (ALD) process including a substrate (2) therein.

[0162] Next, in the second step of the method for manufacturing a tandem perovskite solar cell of the present invention, the laminate (20) can be placed inside the chamber (10) for the atomic layer deposition process prepared in the first step, and the laminate (20) can be positioned on top of the substrate (2).

[0163] Next, in the second and third steps of the method for manufacturing a tandem perovskite solar cell of the present invention, a material for forming an electron transport layer can be injected into the chamber (10) for an atomic layer deposition process.

[0164] At this time, the material for forming the electron transport layer is a material that forms the electron transport layer through an atomic layer deposition process, such as tin oxide (SnOx), nickel oxide (NiOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), and hafnium oxide (HfO). x ), zirconium oxide (ZrO x ), vanadium oxide (VO x ) and niobium pentoxide (Nb2O5), and preferably tin oxide (SnO2).

[0165] Finally, in the second to fourth steps of the method for manufacturing a tandem perovskite solar cell of the present invention, an atomic layer deposition process is performed to form an electron transport layer on top of a laminate (20) placed inside a chamber (10) for an atomic layer deposition process.

[0166] Meanwhile, the laminate (20) may have a structure in which a solar cell, a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, and an intermediate layer are sequentially laminated, and an electron transport layer may be formed on the upper portion of the intermediate layer through steps 2-4 of the method for manufacturing a tandem perovskite solar cell of the present invention.

[0167] In addition, the method for manufacturing a tandem perovskite solar cell of the present invention can satisfy the following condition (1).

[0168] (1) A > B

[0169] In the above condition (1), A represents the temperature inside (1) of the chamber (10) for the atomic layer deposition process, and B represents the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process.

[0170] In this way, by satisfying condition (1) of the present invention and forming an electron transport layer, not only is heat damage minimized and deterioration occurring at the interface prevented, but also the performance reduction of the perovskite solar cell is minimized and stability is secured.

[0171] Specifically, the atomic layer deposition process of the second to fourth steps of the method for manufacturing a tandem perovskite solar cell of the present invention can be performed under the conditions that the temperature inside the chamber (10) for the atomic layer deposition process (1) is 85 to 150°C, preferably 85 to 120°C, and the temperature of the substrate (2) included inside the chamber (10) for the atomic layer deposition process is 80°C or less, preferably 40°C to 70°C, more preferably 57°C to 63°C, and by forming an electron transport layer while satisfying these temperature conditions, not only can heat damage be minimized to prevent deterioration occurring at the interface, but also the performance reduction of the perovskite solar cell can be minimized and stability can be secured.

[0172] Furthermore, the electron transport layer formed through the second step of the method for manufacturing a tandem perovskite solar cell of the present invention may have an average thickness of 3 to 20 nm, preferably an average thickness of 4 to 15 nm, and more preferably an average thickness of 4 to 8 nm. If the average thickness is less than 3 nm, it may be difficult to form a layer with a uniform thickness, which may cause a problem of reduced electron transport characteristics, and if it exceeds 20 nm, not only may the electron transport characteristics decrease, but there may also be a problem of increased series resistance.

[0173] Next, in the third step of the method for manufacturing a tandem perovskite solar cell of the present invention, a transparent electrode and a metal electrode can be sequentially formed on top of the electron transport layer formed in the second step. At this time, the transparent electrode and the metal electrode are as described above.

[0174]

[0175] 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.

[0176]

[0177] Example 1: Fabrication of a tandem silicon / perovskite heterojunction solar cell

[0178] (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.

[0179] (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.

[0180] (3) Next, a yellow light-absorbing layer solution dissolved in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) was formed on top of the hole transport layer by spin coating, and a perovskite light-absorbing layer (CSFAPbI) having a perovskite crystal structure with a thickness of 400 nm was formed by heat-treating at 150°C for 10 minutes. x Br 3-X (0 ≤ x ≤ 3)) was formed.

[0181] (4) Next, lithium fluoride (LiF) with an average thickness of 1 nm is deposited on the perovskite light-absorbing layer through a vacuum deposition process, and C with an average thickness of 15 nm is deposited on top of the lithium fluoride deposited through the vacuum deposition process. 60 Fullerene (C 60 A laminate was manufactured by depositing a fullerene to form an interlayer.

[0182] (5) An atomic layer deposition (ALD) process chamber (10) including a substrate (2) inside as illustrated in FIG. 1 was prepared, and a laminate (20) was placed inside the ALD process chamber (10). At this time, the laminate (20) was positioned on the substrate (2) so that the silicon solar cell of the laminate (20) and the substrate (2) were in contact. An electron transport layer forming material was injected into the ALD process chamber (10), and the atomic layer deposition process was performed for 15 minutes, thereby forming an electron transport layer with an average thickness of 6 nm on the laminate (20). At this time, the ALD process was performed under the conditions that the temperature inside the ALD process chamber (10) was 110°C, and the temperature of the substrate (2) was 60°C. In addition, tin oxide (SnO2) was used as the electron transport layer forming material.

[0183] (6) Next, a 75 nm thick transparent electrode (ITO) was formed on top of the electron transport layer through a sputtering process.

[0184] (7) Finally, 1X10 silver (Ag) is added to the top of the transparent electrode. -7 A tandem silicon / perovskite heterojunction solar cell was fabricated 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, and a metal electrode sequentially stacked by depositing the metal electrode at a thickness of 100 nm at a pressure of 10 torr.

[0185]

[0186] Example 2: Fabrication of a tandem silicon / perovskite heterojunction solar cell

[0187] A tandem silicon / perovskite heterojunction solar cell was manufactured using the same method as in Example 1. However, unlike Example 1, when forming an electron transport layer using an atomic layer deposition process chamber, the atomic layer deposition process was performed under conditions where the temperature inside the atomic layer deposition process chamber was 110°C and the temperature of the substrate was 75°C.

[0188]

[0189] Example 3: Fabrication of a tandem silicon / perovskite heterojunction solar cell

[0190] A tandem silicon / perovskite heterojunction solar cell was manufactured using the same method as in Example 1. However, unlike Example 1, when forming the electron transport layer using an atomic layer deposition process chamber, the electron transport layer was formed to have an average thickness of 10 nm.

[0191]

[0192] Example 4: Fabrication of a tandem silicon / perovskite heterojunction solar cell

[0193] A tandem silicon / perovskite heterojunction solar cell was manufactured using the same method as in Example 2. However, unlike Example 2, when forming the electron transport layer using an atomic layer deposition process chamber, the electron transport layer was formed to have an average thickness of 10 nm.

[0194]

[0195] Comparative Example 1: Fabrication of a Tandem Silicon / Perovskite Heterojunction Solar Cell

[0196] A tandem silicon / perovskite heterojunction solar cell was manufactured using the same method as in Example 1. However, unlike Example 1, when forming an electron transport layer using an atomic layer deposition process chamber, the atomic layer deposition process was performed under conditions where the temperature inside the atomic layer deposition process chamber was 110°C and the temperature of the substrate was 110°C.

[0197]

[0198] Experimental Example 1: Surface SEM image analysis of the electron transport layer included in a solar cell.

[0199] In Example 1, when manufacturing a tandem silicon / perovskite heterojunction solar cell, immediately after forming the electron transport layer, the surface of the electron transport layer was photographed using a field emission scanning electron microscope, and the photographed FE-SEM image is shown in Fig. 2. In addition, in Comparative Example 1, when manufacturing a tandem silicon / perovskite heterojunction solar cell, immediately after forming the electron transport layer, the surface of the electron transport layer was photographed using a field emission scanning electron microscope, and the photographed FE-SEM image is shown in Fig. 3.

[0200] As can be seen in FIGS. 2 and 3, it was confirmed that similar grains were observed in the electron transport layer of Example 1 and the electron transport layer of Comparative Example 1, and through this, when forming the electron transport layer using the chamber for the atomic layer deposition process, it was confirmed that the electron transport layer was formed similarly to the condition where the temperature inside the chamber for the atomic layer deposition process was 110°C and the temperature of the substrate was 60°C, even when the temperature inside the chamber for the atomic layer deposition process was 110°C and the temperature of the substrate was 110°C.

[0201]

[0202] Experimental Example 2: Analysis of Surface Chemical Properties of the Electron Transport Layer

[0203] The surface chemical properties of the electron transport layer of each of the tandem silicon / perovskite heterojunction solar cells manufactured in Example 1 and Comparative Example 1 were analyzed using XPS (Exchange-Position Spectroscopy), and are shown in Table 1 below.

[0204]

[0205] As can be seen in Table 1 above, the tandem silicon / perovskite heterojunction solar cell manufactured in Example 1 had an increased valence band maximum (VBM), a decreased work function (WF), and an increased O / Sn ratio compared to the tandem silicon / perovskite heterojunction solar cell manufactured in Comparative Example 1. As the valence band maximum (VBM) increased and the work function (WF) decreased, the energy level matching and electron transport characteristics became favorable, which could improve the power conversion efficiency through an improvement in the open circuit voltage. In addition, it was confirmed that the oxygen (O) ratio increased and the defect states above the valence band maximum (VBM) decreased, which could enhance the hole block characteristics.

[0206]

[0207] Experimental Example 3: Measuring Solar Cell Performance

[0208] For each of the tandem silicon / perovskite heterojunction solar cells manufactured in Examples 1 to 4 and Comparative Example 1, the efficiency was measured using a solar simulation device and a JV Keithley device, and the initial JV curve was used. After storing the cells in a desiccator for 9 days, the JV curve was measured to measure the change in solar cell characteristics after aging, which is shown in Table 2 below.

[0209]

[0210] As can be seen in Table 2 above, it was confirmed that the tandem silicon / perovskite heterojunction solar cell manufactured in Example 1 exhibited the best power conversion efficiency.

[0211]

[0212] 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. A first step of preparing a chamber for an atomic layer deposition process including a substrate inside; A second step of placing a laminate into a chamber for the atomic layer deposition process and positioning the laminate on top of the substrate; A third step of injecting a material for forming an electron transport layer into the chamber for the atomic layer deposition process; and A fourth step of forming an electron transport layer on top of the laminate by performing an atomic layer deposition process; A method for forming an electron transport layer for a perovskite solar cell, characterized in that the following condition (1) is satisfied. (1) A > B In the above condition (1), A represents the temperature inside the chamber for the atomic layer deposition process, and B represents the temperature of the substrate included inside the chamber for the atomic layer deposition process.

2. In paragraph 1, A method for forming an electron transport layer for a perovskite solar cell, characterized in that the atomic layer deposition process of the fourth step is performed under the conditions that the temperature inside the atomic layer deposition process chamber is 85 to 150°C and the temperature of the substrate included inside the atomic layer deposition process chamber is 80°C or lower.

3. In paragraph 2, A method for forming an electron transport layer for a perovskite solar cell, characterized in that the atomic layer deposition process of the fourth step is performed under the conditions that the temperature inside the atomic layer deposition process chamber is 85 to 120°C and the temperature of the substrate included inside the atomic layer deposition process chamber is 40 to 70°C.

4. In paragraph 1, The above laminate has a structure in which a hole transport layer and a perovskite light absorbing layer are sequentially laminated. A method for forming an electron transport layer for a perovskite solar cell, characterized by forming an electron transport layer on top of the perovskite light-absorbing layer.

5. In paragraph 1, The above laminate has a structure in which a hole transport layer, a perovskite light-absorbing layer, and an intermediate layer are sequentially laminated. A method for forming an electron transport layer for a perovskite solar cell, characterized by forming an electron transport layer on top of the intermediate layer.

6. In paragraph 5, A method for forming an electron transport layer for a perovskite solar cell, characterized in that the intermediate layer comprises a fullerene series organic material.

7. In paragraph 6, The above fullerene series organic material is C 60 , C 70 A method for forming an electron transport layer for a perovskite solar cell, characterized in that it comprises at least one selected from PC60BM and PC70BM.

8. In paragraph 1, A method for forming an electron transport layer for a perovskite solar cell, characterized in that the electron transport layer has an average thickness of 3 to 20 nm.

9. In paragraph 1, The materials for forming the above electron transport layer are tin oxide (SnOx), nickel oxide (NiOx), and tin oxide (SnO). 2 ), titanium dioxide (TiO 2 ), zinc oxide (ZnO), barium tin oxide (BaSnO 3 ), niobium hydroxide (NbOH), hafnium oxide (HfO x ), zirconium oxide (ZrO x ), vanadium oxide (VO x ) and niobium pentoxide (Nb 2 O 5 ) is characterized by including at least one selected from among.

10. A first step of manufacturing a laminate by forming a perovskite light-absorbing layer on top of a hole transport layer; A second step of forming an electron transport layer through an atomic layer deposition process on top of the perovskite light-absorbing layer; and A third step of sequentially forming a transparent electrode and a metal electrode on the upper portion of the electron transport layer; The above atomic layer deposition process Step 2-1 of preparing a chamber for an atomic layer deposition process including a substrate inside; Step 2-2 of placing a laminate inside a chamber for the atomic layer deposition process and positioning the laminate on top of the substrate; Step 2-3 of injecting a material for forming an electron transport layer into the chamber for the atomic layer deposition process; and Step 2-4 of forming an electron transport layer on top of the perovskite light-absorbing layer by performing an atomic layer deposition process; including; A method for manufacturing a perovskite solar cell, characterized in that the following condition (1) is satisfied. (1) A > B In the above condition (1), A represents the temperature inside the chamber for the atomic layer deposition process, and B represents the temperature of the substrate included inside the chamber for the atomic layer deposition process.

11. A first step of manufacturing a laminate by sequentially forming a perovskite light-absorbing layer and an intermediate layer on top of a hole transport layer; A second step of forming an electron transport layer through an atomic layer deposition process on top of the intermediate layer; and A third step of sequentially forming a transparent electrode and a metal electrode on the upper portion of the electron transport layer; The above atomic layer deposition process Step 2-1 of preparing a chamber for an atomic layer deposition process including a substrate inside; Step 2-2 of placing a laminate inside a chamber for the atomic layer deposition process and positioning the laminate on top of the substrate; Step 2-3 of injecting a material for forming an electron transport layer into the chamber for the atomic layer deposition process; and Step 2-4 of forming an electron transport layer on top of the intermediate layer by performing an atomic layer deposition process; including; A method for manufacturing a perovskite solar cell, characterized in that the following condition (1) is satisfied. (1) A > B In the above condition (1), A represents the temperature inside the chamber for the atomic layer deposition process, and B represents the temperature of the substrate included inside the chamber for the atomic layer deposition process.

12. In clause 10 or 11, A method for manufacturing a perovskite solar cell, characterized in that the atomic layer deposition process of steps 2 to 4 is performed under the conditions that the temperature inside the atomic layer deposition process chamber is 85 to 150°C and the temperature of the substrate included inside the atomic layer deposition process chamber is 80°C or lower.

13. A first step of manufacturing a laminate by sequentially forming a transparent conductive layer, a hole transport layer, and a perovskite light-absorbing layer on top of a solar cell; A second step of forming an electron transport layer through an atomic layer deposition process on top of the perovskite light-absorbing layer; and A third step of sequentially forming a transparent electrode and a metal electrode on the upper portion of the electron transport layer; The above atomic layer deposition process Step 2-1 of preparing a chamber for an atomic layer deposition process including a substrate inside; Step 2-2 of placing a laminate inside a chamber for the atomic layer deposition process and positioning the laminate on top of the substrate; Step 2-3 of injecting a material for forming an electron transport layer into the chamber for the atomic layer deposition process; and Step 2-4 of forming an electron transport layer on top of the perovskite light-absorbing layer by performing an atomic layer deposition process; including; A method for manufacturing a tandem perovskite solar cell, characterized in that the following condition (1) is satisfied. (1) A > B In the above condition (1), A represents the temperature inside the chamber for the atomic layer deposition process, and B represents the temperature of the substrate included inside the chamber for the atomic layer deposition process.

14. A first step of manufacturing a laminate by sequentially forming a transparent conductive layer, a hole transport layer, a perovskite light-absorbing layer, and an intermediate layer on top of a solar cell; A second step of forming an electron transport layer through an atomic layer deposition process on top of the intermediate layer; and A third step of sequentially forming a transparent electrode and a metal electrode on the upper portion of the electron transport layer; The above atomic layer deposition process Step 2-1 of preparing a chamber for an atomic layer deposition process including a substrate inside; Step 2-2 of placing a laminate inside a chamber for the atomic layer deposition process and positioning the laminate on top of the substrate; Step 2-3 of injecting a material for forming an electron transport layer into the chamber for the atomic layer deposition process; and Step 2-4 of forming an electron transport layer on top of the intermediate layer by performing an atomic layer deposition process; including; A method for manufacturing a tandem perovskite solar cell, characterized in that the following condition (1) is satisfied. (1) A > B In the above condition (1), A represents the temperature inside the chamber for the atomic layer deposition process, and B represents the temperature of the substrate included inside the chamber for the atomic layer deposition process.

15. In paragraph 13 or 14, A method for manufacturing a tandem perovskite solar cell, characterized in that the atomic layer deposition process of steps 2 to 4 is performed under the conditions that the temperature inside the atomic layer deposition process chamber is 85 to 150°C and the temperature of the substrate included inside the atomic layer deposition process chamber is 80°C or lower.

16. In paragraph 13 or 14, The above solar cells are polycrystalline silicon solar cells, crystalline silicon solar cells, perovskite solar cells, gallium arsenide (GaAs) solar cells, cadmium telluride (CdTe) solar cells, CIGS (CuInGaSe) solar cells, CZTS (Cu 2 ZnSnS 4 ) A method for manufacturing a tandem perovskite solar cell, characterized in that the tandem perovskite solar cell is a solar cell, an organic solar cell, a fuel-sensitized solar cell or a group 3-5 compound solar cell.

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