Perovskite solar cell and method for producing same

Abstract

The present invention relates to: a perovskite solar cell having an electron transport layer comprising a fullerene-based organic material and a naphthalene diimide derivative, or a fullerene-based organic material and a perylene diimide derivative; and a method for producing same.

Description

Perovskite solar cell and method for manufacturing the same

[0001] The present invention relates to a perovskite solar cell having an electron transport layer comprising a fullerene-based organic material and a naphthalene diimide derivative or a fullerene-based organic material and a perylene diimide derivative, and a method for manufacturing the same.

[0002]

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

[0004] 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 operation.

[0005] 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.

[0006] 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.

[0007] Meanwhile, for perovskite solar cells to exhibit excellent efficiency, they must effectively transport electrons and perform the function of suppressing charge recombination by preventing holes from crossing over into the electron transport layer.

[0008] To this end, C as a material for the conventional electron transport layer 60 Although fullerenes were widely used, C 60 Fullerenes had limited charge transport performance, lacked passivation effects, and had limitations in work function regulation.

[0009]

[0010] The present invention has been devised to overcome the aforementioned problems and aims to provide a perovskite solar cell with high efficiency and stability and a method for manufacturing the same, which prevents damage to the perovskite light absorption layer, improves charge mobility, maximizes the interfacial defect passivation effect, and improves work function control performance.

[0011]

[0012] To solve the above-mentioned problem, the perovskite solar cell of the present invention comprises a laminate in which a perovskite light-absorbing layer and an electron-transfer layer are sequentially stacked, and the electron-transfer layer may include a first electron-transfer layer formed on top of the perovskite light-absorbing layer and a second electron-transfer layer formed on top of the first electron-transfer layer.

[0013] As a preferred embodiment of the present invention, the first electron transport layer may include a naphthalene diimide derivative and a fullerene-based organic material.

[0014] As a preferred embodiment of the present invention, the first electron transport layer may include a perylene diimide derivative and a fullerene-based organic material.

[0015] As a preferred embodiment of the present invention, the second electron transport layer may include an inorganic material.

[0016] As a preferred embodiment of the present invention, the naphthalene diimide derivative may include a compound represented by the following chemical formula 1.

[0017] [Chemical Formula 1]

[0018]

[0019] In the above chemical formula 1, R1 and R2 are each independently, , , , , , , , , , , , , , , , , or And, the above R3 to R8 are each independently -H, a C1 to C20 straight-chain alkyl group or a C3 to C20 branched-chain alkyl group.

[0020] As a preferred embodiment of the present invention, the naphthalene diimide derivative and the fullerene-based organic material may have a mass ratio of 1:1.5 to 10.

[0021] As a preferred embodiment of the present invention, the perylene diimide derivative may include a compound represented by the following chemical formula 2.

[0022] [Chemical Formula 2]

[0023]

[0024] In the above chemical formula 2, R9 and R 10 Each independently, , , , , , , , , , , , , , , , , or And, the above R3 to R8 are each independently -H, a C1 to C20 straight-chain alkyl group or a C3 to C20 branched-chain alkyl group.

[0025] As a preferred embodiment of the present invention, the perylene diimide derivative and the fullerene-based organic material may have a mass ratio of 1:1.5 to 10.

[0026] As a preferred embodiment of the present invention, the first electron transfer layer can be formed through a double co-deposition process.

[0027] As a preferred embodiment of the present invention, the inorganic material is tin oxide (SnOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), niobium pentoxide (Nb2O5), nickel oxide (NiOx), copper thiocyanate (CuSCN), copper chromium oxide (CuCrO2), cuprous iodide (CuI), copper oxide (CuOx), copper sulfide (CuS), copper phthalocyanine (CuPc), copper gallium oxide (CuGaO2), lead sulfide (PbS), molybdenum oxide (MoOx), aluminum oxide (AlOx), copper aluminum oxide (CuAlOx), aluminum oxide nanoparticles, silica nanoparticles, nickel oxide nanoparticles, hafnium nanoparticles, and It may include one or more selected from vanadium oxide (V2O5).

[0028] As a preferred embodiment of the present invention, the first electron transport layer and the second electron transport layer may have a thickness ratio of 1:0.1 to 2.0.

[0029] 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.

[0030] [Chemical Formula 1]

[0031] CMX3

[0032] In the above chemical formula 1, C is a monovalent cation, M is a divalent cation, and X is a monovalent anion.

[0033] Meanwhile, the tandem perovskite solar cell of the present invention comprises a stack in which a solar cell, a recombination layer, a hole transport layer, a perovskite light absorption layer, and an electron transport layer are sequentially stacked, and the electron transport layer may include a first electron transport layer formed on top of the perovskite light absorption layer and a second electron transport layer formed on top of the first electron transport layer.

[0034] 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.

[0035] Furthermore, the method for manufacturing a perovskite solar cell according to the present invention may include a first step of preparing a laminate comprising a perovskite light-absorbing layer, a second step of forming a first electron transport layer on top of the perovskite light-absorbing layer through a double co-deposition process, and a third step of forming a second electron transport layer on top of the first electron transport layer.

[0036] As a preferred embodiment of the present invention, the first electron transport layer can be formed by simultaneously depositing a naphthalene diimide derivative and a fullerene-based organic material.

[0037] As a preferred embodiment of the present invention, the first electron transport layer can be formed by simultaneously depositing a perylene diimide derivative and a fullerene-based organic material.

[0038] Meanwhile, the method for manufacturing a tandem perovskite solar cell according to the present invention may include a first step of preparing a laminate in which a solar cell, a recombination layer, a hole transport layer, and a perovskite light absorption layer are sequentially stacked, a second step of forming a first electron transport layer on top of the perovskite light absorption layer through a double co-deposition process, and a third step of forming a second electron transport layer on top of the first electron transport layer.

[0039]

[0040] The perovskite solar cell of the present invention and the method for manufacturing the same can improve the electron transport capability of the electron transport layer.

[0041] In addition, the perovskite solar cell and the method for manufacturing the same according to the present invention do not cause the problem of molecular aggregation in the electron transport layer.

[0042] In addition, the perovskite solar cell and the method for manufacturing the same according to the present invention can not only improve the work function of the electron transport layer but also enhance stability.

[0043] In addition, the perovskite solar cell of the present invention and the method for manufacturing the same can prevent damage to the perovskite light absorption layer caused by the electron transport layer.

[0044] In addition, the perovskite solar cell and the method for manufacturing the same according to the present invention have a simple process, so a high-quality thin film can be formed in a single process.

[0045]

[0046] The present invention will be described in more detail below.

[0047] For perovskite solar cells to exhibit excellent efficiency, they must effectively transport electrons and perform the function of suppressing charge recombination by preventing holes from crossing into the electron transport layer.

[0048] However, conventional materials had a problem in that they could not achieve maximum efficiency even when placed in the appropriate location or on the appropriate thin film layer of perovskite solar cells.

[0049] Accordingly, the present invention aims to provide a naphthalene diimide-based compound for a perovskite solar cell that can not only prevent electron recombination but also secure thin film stability and secure an energy level suitable for electron transport characteristics, a perovskite solar cell containing the same, and a method for manufacturing the same.

[0050]

[0051] Meanwhile, the perovskite solar cell of the present invention may include a laminate in which a perovskite light-absorbing layer and an electron transport layer are sequentially stacked. Additionally, the perovskite solar cell of the present invention may include a laminate in which a hole transport layer, a perovskite light-absorbing layer, and an electron transport layer are sequentially stacked. Furthermore, the perovskite solar cell of the present invention may further include an organic interface layer between the hole transport layer and the perovskite light-absorbing layer. Additionally, the perovskite solar cell of the present invention may further include a transparent electrode formed on one surface of the electron transport layer. Additionally, the perovskite solar cell of the present invention may further include a metal electrode formed on one surface of the transparent electrode.

[0052]

[0053] 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.

[0054] At this time, the inorganic hole transport material may include one or more selected from nickel oxide (NiOx), CuSCN, CuCrO2, CuI, MoO, and V2O5.

[0055] 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.

[0056] In addition, methods for forming a hole transport layer include coating methods and vacuum deposition methods, and coating methods include gravure coating, bar coating, printing, spraying, spin coating, dip coating, and die coating.

[0057] In addition, there is no separate limitation 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.

[0058]

[0059] The organic interface layer may include a non-covalent electron pair-holding compound for perovskite solar cells represented by the following chemical formula 5. In this case, the organic interface layer may be a layer capable of inducing intermolecular hydrogen bonding to improve intermolecular interactions and securing an energy level suitable for hole transport.

[0060] [Chemical Formula 5]

[0061]

[0062] In the above chemical formula 5, A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and A 4" Each is independently carbon (C) or nitrogen (N). However, at least one of A1, A2, A3, and A4 is nitrogen (N), and A 1' , A 2' , A 3' and A 4' At least one of them is nitrogen (N), and A 1" , A 2" , A 3" and A 4" At least one of them is nitrogen (N). As an example, A2, A3, A4, A 2' , A 3' , A 4' , A 2" , A 3" and A 4" If each is carbon (C), then A1, A 1' and A 1" is nitrogen (N).

[0063] In addition, in the above Chemical Formula 5, R1, R2, R3, R4, R 1' , R 2' , R 3' , R 4' , R 1" , R 2" , R 3" and R 4" Each is independently -H, a C1–C20 straight-chain alkyl group or a C3–C20 branched alkyl group. However, A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and / or A 4"If this is nitrogen (N), then A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and / or A 4" R1, R2, R3, R4, R combined with 1' , R 2' , R 3' , R 4' , R 1" , R 2" , R 3" and / or R 4" is a non-shared electron pair.

[0064] In addition, in the above chemical formula 5, B1, B2, and B3 are each independently a single bond, a C6 to C18 arylene group, or a C5 to C18 heteroarylene group.

[0065] In addition, in the above chemical formula 5, X1, X2 and X3 are each independently a dihydroxyphosphoryl group (-P=O(OH)2), a carboxyl group (-COOH), a sulfo group (-SO3H), a boronic acid group (-B(OH)2), a trihalogenated silyl group (-SiX3) or a trialkoxysilyl group (-Si(OR5)3).

[0066] Additionally, the organic interface layer may include a second reactant and a reactant of bromotrimethylsilane. In this case, the second reactant may be a reactant of a compound represented by the following chemical formula 4, sodium hydride, and diethyl(3-bromopropyl)phosphonate.

[0067] [Chemical Formula 4]

[0068]

[0069] In the above chemical formula 4, A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and A 4" Each is independently carbon (C) or nitrogen (N). However, at least one of A1, A2, A3, and A4 is nitrogen (N), and A 1' , A 2' , A 3' and A 4' At least one of them is nitrogen (N), and A 1" , A 2" , A 3" and A 4" At least one of them is nitrogen (N). As an example, A2, A3, A4, A 2' , A 3' , A 4' , A 2" , A 3" and A 4" If each is carbon (C), then A1, A 1' and A 1" is nitrogen (N).

[0070] In addition, in the above Chemical Formula 4, R1, R2, R3, R4, R 1' , R 2' , R 3' , R 4' , R 1" , R 2" , R 3" and R 4" Each is independently -H, a C1–C20 straight-chain alkyl group or a C3–C20 branched alkyl group. However, A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and / or A 4"If this is nitrogen (N), then A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and / or A 4" R1, R2, R3, R4, R combined with 1' , R 2' , R 3' , R 4' , R 1" , R 2" , R 3" and / or R 4" is a non-shared electron pair.

[0071] In addition, the compound represented by the above chemical formula 4 may include the reaction product of the compound represented by the following chemical formula 3 and phosphoryl chloride.

[0072] [Chemical Formula 3]

[0073]

[0074] In the above chemical formula 3, A1, A2, A3, and A4 are each independently carbon (C) or nitrogen (N). However, at least one of A1, A2, A3, and A4 is nitrogen (N).

[0075] In addition, in the above formula 3, R1, R2, R3, and R4 are each independently -H, a C1-C20 straight-chain alkyl group or a C3-C20 branched-chain alkyl group. However, if A1, A2, A3, and / or A4 is nitrogen (N), R1, R2, R3, and / or R4 bonded to A1, A2, A3, and / or A4 are non-covalent electron pairs.

[0076] In addition, the non-covalent electron pair possessing compound for a perovskite solar cell represented by the above chemical formula 5 may be a non-covalent electron pair possessing compound for a perovskite solar cell represented by the following chemical formula 5-5.

[0077] [Chemical Formula 5-5]

[0078]

[0079] In the above chemical formula 5-5, A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and A 4" Each is independently carbon (C) or nitrogen (N). However, at least one of A1, A2, A3, and A4 is nitrogen (N), and A 1' , A 2' , A 3' and A 4' At least one of them is nitrogen (N), and A 1" , A 2" , A 3" and A 4" At least one of them is nitrogen (N).

[0080] In addition, in the above chemical formula 5-5, R1, R2, R3, R4, R 1' , R 2' , R 3' , R 4' , R 1" , R 2" , R 3" and R 4" Each is independently -H, a C1–C20 straight-chain alkyl group or a C3–C20 branched alkyl group. However, A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and / or A 4" If this is nitrogen (N), then A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and / or A 4" R1, R2, R3, R4, R combined with 1' , R 2' , R 3' , R 4' , R 1" , R 2" , R 3" and / or R 4" is a non-shared electron pair.

[0081] In addition, in the above chemical formula 5-5, B1, B2, and B3 are each independently -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, , or am.

[0082] In addition, in the above chemical formula 5-5, X1, X2 and X3 are each independently a dihydroxyphosphoryl group (-P=O(OH)2), a carboxyl group (-COOH), or a boronic acid group (-B(OH)2).

[0083] In addition, the non-covalent electron pair possessing compound for a perovskite solar cell represented by the above chemical formula 5 may be a non-covalent electron pair possessing compound for a perovskite solar cell represented by the following chemical formula 5-6.

[0084] [Chemical Formula 5-6]

[0085]

[0086] In the above chemical formulas 5-6, A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A3" and A 4" Each is independently carbon (C) or nitrogen (N). However, at least one of A1, A2, A3, and A4 is nitrogen (N), and A 1' , A 2' , A 3' and A 4' At least one of them is nitrogen (N), and A 1" , A 2" , A 3" and A 4" At least one of them is nitrogen (N).

[0087] In addition, in the above chemical formulas 5-6, R1, R2, R3, R4, R 1' , R 2' , R 3' , R 4' , R 1" , R 2" , R 3" and R 4" Each is independently -H, a C1–C20 straight-chain alkyl group or a C3–C20 branched alkyl group. However, A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and / or A 4" If this is nitrogen (N), then A1, A2, A3, A4, A 1' , A 2' , A 3' , A 4' , A 1" , A 2" , A 3" and / or A 4" R1, R2, R3, R4, R combined with 1' , R 2' , R 3' , R 4' , R 1" , R2" , R 3" and / or R 4" is a non-shared electron pair.

[0088] In addition, in the above chemical formulas 5-6, B1, B2 and B3 are each independently -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-.

[0089] In addition, in the above chemical formulas 5-6, X1, X2, and X3 are each dihydroxyphosphoryl groups (-P=O(OH)2).

[0090] Specifically, the non-covalent electron pair possessing compound for a perovskite solar cell represented by the above chemical formula 5 may be a non-covalent electron pair possessing compound for a perovskite solar cell represented by the following chemical formula 5-1.

[0091] [Chemical Formula 5-1]

[0092]

[0093] In the above chemical formula 5-1, A2, A3, A4, A 2' , A 3' , A 4' , A 2" , A 3" and A 4" are each carbon (C), and A1, A 1' and A 1" Each is nitrogen (N).

[0094] In the above chemical formula 5-1, R2, R3, R4, R 2' , R 3' , R 4' , R 2" , R 3" and R 4" Each is independently -H, a C1-C20 straight-chain alkyl group or a C3-C20 branched-chain alkyl group.

[0095] In the above chemical formula 5-1, B1, B2 and B3 are each independently -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-.

[0096] In the above chemical formula 5-1, X1, X2, and X3 are each a dihydroxyphosphoryl group (-P=O(OH)2).

[0097] In addition, specifically, the non-covalent electron pair possessing compound for a perovskite solar cell represented by the above chemical formula 5 may be a non-covalent electron pair possessing compound for a perovskite solar cell represented by the following chemical formula 5-2.

[0098] [Chemical Formula 5-2]

[0099]

[0100] In the above chemical formula 5-2, A1, A3, A4, A 1' , A 3' , A 4' , A 1" , A 3" and A 4" are each carbon (C), and A2, A 2' and A 2" Each is nitrogen (N).

[0101] In addition, in the above chemical formula 5-2, R1, R3, R4, R 1' , R 3' , R 4' , R 1" , R 3" and R 4" Each is independently -H, a C1-C20 straight-chain alkyl group or a C3-C20 branched-chain alkyl group.

[0102] In addition, in the above chemical formula 5-2, B1, B2 and B3 are each independently -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-.

[0103] In addition, in the above chemical formula 5-2, X1, X2, and X3 are each dihydroxyphosphoryl groups (-P=O(OH)2).

[0104] In addition, specifically, the non-covalent electron pair possessing compound for a perovskite solar cell represented by the above chemical formula 5 may be a non-covalent electron pair possessing compound for a perovskite solar cell represented by the following chemical formula 5-3.

[0105] [Chemical Formula 5-3]

[0106]

[0107] In the above chemical formula 5-3, A1, A2, A4, A 1' , A 2' , A 4' , A 1" , A 2" and A 4" are each carbon (C), and A3, A 3' and A 3" Each is nitrogen (N).

[0108] In addition, in the above chemical formula 5-3, R1, R2, R4, R 1' , R 2' , R 4' , R 1" , R 2" and R 4" Each is independently -H, a C1-C20 straight-chain alkyl group or a C3-C20 branched-chain alkyl group.

[0109] In addition, in the above chemical formula 5-3, B1, B2 and B3 are each independently -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-.

[0110] In addition, in the above chemical formula 5-3, X1, X2, and X3 are each dihydroxyphosphoryl groups (-P=O(OH)2).

[0111] In addition, specifically, the non-covalent electron pair possessing compound for a perovskite solar cell represented by the above chemical formula 5 may be a non-covalent electron pair possessing compound for a perovskite solar cell represented by the following chemical formula 5-4.

[0112] [Chemical Formula 5-4]

[0113]

[0114] In the above chemical formula 5-4, A1, A2, A3, A 1' , A 2' , A 3' , A 1" , A 2" and A 3" are each carbon (C), and A4, A 4' and A 4" Each is nitrogen (N).

[0115] In addition, in the above chemical formula 5-4, R1, R2, R3, R 1' , R 2' , R 3' , R 1" , R 2" and R 3" Each is independently -H, a C1-C20 straight-chain alkyl group or a C3-C20 branched-chain alkyl group.

[0116] In addition, in the above chemical formula 5-4, B1, B2 and B3 are each independently -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-.

[0117] In addition, in the above chemical formula 5-4, X1, X2, and X3 are each dihydroxyphosphoryl groups (-P=O(OH)2).

[0118] In addition, methods for forming an organic interface layer include coating methods and vacuum deposition methods, and coating methods include gravure coating, bar coating, printing, spraying, spin coating, dip coating, and die coating.

[0119] In addition, there is no separate limitation on the thickness of the organic interface layer, but preferably it can have a thickness of 0.5 nm to 10 nm, and more preferably 1 nm to 5 nm.

[0120]

[0121] The perovskite light-absorbing layer may include a perovskite material represented by the following chemical formula 1.

[0122] [Chemical Formula 1]

[0123] CMX3

[0124] 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.)

[0125] 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.

[0126] 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.

[0127] 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).

[0128] 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.

[0129] 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.

[0130] In addition, there is no separate limit on the thickness of the perovskite light absorption layer, but preferably it can have a thickness of 50 nm to 800 nm, and more preferably 300 nm to 600 nm.

[0131]

[0132] 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.

[0133] 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.

[0134] The electron transport layer may include a first electron transport layer formed on top of a perovskite light absorption layer and a second electron transport layer formed on top of the first electron transport layer.

[0135] The first electron transport layer may include a naphthalene diimide derivative and a fullerene-based organic material.

[0136] In addition, the first electron transport layer may include a perylene diimide derivative and a fullerene-based organic material.

[0137] Fullerene series organic materials are C 60 Fullerene, C 70 It may include one or more selected from fullerene, PC60BM and PC70BM.

[0138] Naphthalene diimide derivatives may include compounds represented by the following chemical formula 1.

[0139] [Chemical Formula 1]

[0140]

[0141] In the above chemical formula 1, R1 and R2 are each independently, , , , , , , , , , , , , , , , , or And, the above R3 to R8 are each independently -H, a C1 to C20 straight-chain alkyl group or a C3 to C20 branched-chain alkyl group.

[0142] Perylene diimide derivatives may include compounds represented by the following chemical formula 2.

[0143] [Chemical Formula 2]

[0144]

[0145] In the above chemical formula 2, R9 and R 10 Each independently, , , , , , , , , , , , , , , , , or And, the above R3 to R8 are each independently -H, a C1 to C20 straight-chain alkyl group or a C3 to C20 branched-chain alkyl group.

[0146] In addition, naphthalene diimide derivatives and fullerene-based organic materials may have a mass ratio of 1:1.5 to 10, preferably 1:1.5 to 7, and more preferably 1:1.7 to 3. If the mass ratio is less than 1:1.5, there may be a problem with molecular aggregation, and if it exceeds 1:10, there may be a problem with degraded charge transport properties.

[0147] In addition, perylene diimide derivatives and fullerene-based organic materials may have a mass ratio of 1:1.5 to 10, preferably 1:1.5 to 7, and more preferably 1:1.7 to 3. If the mass ratio is less than 1:1.5, there may be a problem with molecular aggregation, and if it exceeds 1:10, there may be a problem with degraded charge transport properties.

[0148] In addition, the first electron transport layer can be formed through a double co-deposition process.

[0149] The second electron transport layer may include inorganic materials.

[0150] The inorganic material is selected from tin oxide (SnOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), niobium pentoxide (Nb2O5), nickel oxide (NiOx), copper thiocyanate (CuSCN), copper chromium oxide (CuCrO2), cuprous iodide (CuI), copper oxide (CuOx), copper sulfide (CuS), copper phthalocyanine (CuPc), copper gallium oxide (CuGaO2), lead sulfide (PbS), molybdenum oxide (MoOx), aluminum oxide (AlOx), copper-aluminum oxide (CuAlOx), aluminum oxide nanoparticles, silica nanoparticles, nickel oxide nanoparticles, hafnium nanoparticles, and vanadium oxide (V2O5). It may include one or more types, and preferably may include tin oxide (SnO2).

[0151] In addition, as a method for forming the second electron 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.

[0152] Meanwhile, the first electron transport layer and the second electron transport layer may have a thickness ratio of 1:0.1 to 2.0, preferably 1:0.1 to 1.5, more preferably 1:0.2 to 1.0, and even more preferably 1:0.3 to 0.7. If the thickness ratio is less than 1:0.1, there may be a problem with leakage current generation, and if it exceeds 1:2.0, there may be a problem with increased resistance value.

[0153]

[0154] A transparent electrode can be formed 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.

[0155] In addition, the transparent electrode may be a transparent thin film deposited 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).

[0156] In addition, there is no separate limit on the thickness of the transparent electrode, but preferably it can have a thickness of 50 to 200 nm, and more preferably 60 to 140 nm.

[0157]

[0158] A metal electrode can be formed by patterning a metal material on one side of a transparent electrode. Specifically, the patterning process is largely composed 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 removing unnecessary parts. Additionally, the patterning process can be performed using a screen printing method with a metal paste containing a metal material. More specifically, the metal electrode may be composed of a plurality of bus bar electrodes arranged in a horizontal direction and a plurality of finger electrodes arranged in a vertical direction relative to the bus bar electrodes.

[0159] In addition, the metallic material may include one or more selected from Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C, and conductive polymers.

[0160] 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 15 µm.

[0161]

[0162] Meanwhile, the tandem perovskite solar cell of the present invention may include a laminate in which a solar cell, a recombination layer, a hole transport layer, a perovskite light absorption layer, and an electron transport layer are sequentially stacked. Additionally, the tandem perovskite solar cell of the present invention may further include an organic interface layer between the hole transport layer and the perovskite light absorption layer. Furthermore, the tandem perovskite solar cell of the present invention may further include a transparent electrode formed on one surface of the electron transport layer. Additionally, the tandem perovskite solar cell of the present invention may further include a metal electrode formed on one surface of the transparent electrode. In this case, the hole transport layer, the organic interface layer, the perovskite light absorption layer, the electron transport layer, the transparent electrode, and the metal electrode are each as described above.

[0163] 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.

[0164] In addition, there is no separate limit on the thickness of the solar cell, but preferably it can have a thickness of 140 to 250 μm, and more preferably 160 to 200 μm.

[0165] In addition, when using silicon solar cells doped with n or p-type impurities as solar cells, the silicon solar cells doped with n or p-type impurities can be used after removing the SiOx oxide film by treating them with hydrofluoric acid and then removing the residual hydrofluoric acid using ultrapure water.

[0166] The recombination 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 deposited 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).

[0167] In addition, as an example of forming a recombination layer, a recombination layer can be formed on one surface of a solar cell through a sputtering process.

[0168] In addition, there is no separate limitation on the thickness of the recombination layer, but it can preferably have a thickness of 5 nm to 50 nm, and more preferably 15 nm to 25 nm.

[0169]

[0170] Furthermore, the method for manufacturing a perovskite solar cell according to the present invention comprises steps 1 to 3.

[0171] The first step of the method for manufacturing a perovskite solar cell according to the present invention may prepare a laminate comprising a perovskite light-absorbing layer. Additionally, the first step of the method for manufacturing a perovskite solar cell according to the present invention may prepare a laminate in which a hole transport layer and a perovskite light-absorbing layer are sequentially stacked. Furthermore, the first step of the method for manufacturing a perovskite solar cell according to the present invention may prepare a laminate in which a hole transport layer, an organic interface layer, and a perovskite light-absorbing layer are sequentially stacked. At this time, the hole transport layer, the organic interface layer, and the perovskite light-absorbing layer are each as described above.

[0172] The second step of the method for manufacturing a perovskite solar cell of the present invention can form a first electron transport layer on top of a perovskite light absorption layer through a double co-deposition process.

[0173] In this case, the first electron transport layer can be formed by simultaneously depositing a naphthalene diimide derivative and a fullerene-based organic material. Additionally, the first electron transport layer can be formed by simultaneously depositing a perylene diimide derivative and a fullerene-based organic material. Furthermore, the naphthalene diimide derivative, the perylene diimide derivative, and the fullerene-based organic material are as described above.

[0174] The third step of the method for manufacturing a perovskite solar cell of the present invention may form a second electron transport layer on top of the first electron transport layer. At this time, the second electron transport layer is as described above.

[0175] Additionally, the method for manufacturing a perovskite solar cell of the present invention may form a transparent electrode on the upper part of a second electron transport layer and may form a metal electrode on the upper part of the transparent electrode, and the transparent electrode and the metal electrode are as described above.

[0176]

[0177] Meanwhile, the method for manufacturing a tandem perovskite solar cell of the present invention includes steps 1 to 3.

[0178] The first step of the method for manufacturing a tandem perovskite solar cell according to the present invention may prepare a laminate in which a solar cell, a recombination layer, a hole transport layer, and a perovskite light absorption layer are sequentially stacked. Additionally, the first step of the method for manufacturing a tandem perovskite solar cell according to the present invention may prepare a laminate in which a solar cell, a recombination layer, a hole transport layer, an organic interface layer, and a perovskite light absorption layer are sequentially stacked. At this time, the solar cell, the recombination layer, the hole transport layer, the organic interface layer, and the perovskite light absorption layer are each as described above.

[0179] The second step of the method for manufacturing a tandem perovskite solar cell of the present invention can form a first electron transport layer on top of a perovskite light absorption layer through a double co-deposition process.

[0180] In this case, the first electron transport layer can be formed by simultaneously depositing a naphthalene diimide derivative and a fullerene-based organic material. Additionally, the first electron transport layer can be formed by simultaneously depositing a perylene diimide derivative and a fullerene-based organic material. Furthermore, the naphthalene diimide derivative, the perylene diimide derivative, and the fullerene-based organic material are as described above.

[0181] The third step of the method for manufacturing a tandem perovskite solar cell of the present invention may form a second electron transport layer on top of the first electron transport layer. At this time, the second electron transport layer is as described above.

[0182] Additionally, the method for manufacturing a tandem perovskite solar cell of the present invention may form a transparent electrode on the upper part of a second electron transport layer and may form a metal electrode on the upper part of the transparent electrode, and the transparent electrode and the metal electrode are as described above.

[0183]

[0184] 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.

[0185]

[0186] Preparation Example 1: Preparation of a non-covalent electron pair-bearing compound for perovskite solar cells

[0187] (1) 223.65 mmol of the compound represented by the chemical formula 3-1 below was added to 50 ml of phosphoryl chloride, and the first reaction product was prepared by reflux stirring at a temperature of 150°C for 24 hours.

[0188] (2) The first reaction product prepared was neutralized with sodium hydroxide to obtain a precipitate, which was then filtered to obtain a filtrate. The obtained filtrate was then purified through silica gel column chromatography (solvent: dichloromethane) to prepare a purified product.

[0189] (3) After concentrating the purified product under reduced pressure, the compound represented by the following chemical formula 4-1 was prepared by recrystallizing it with acetone.

[0190] (4) A compound represented by the following chemical formula 4-1 was dissolved in 300 ml of dimethylformamide anhydrous, sodium hydride was added, and the mixture was stirred at a temperature of 20°C for 10 minutes to prepare a mixture. At this time, the compound represented by the following chemical formula 4-1 and sodium hydride were added in a molar ratio of 1:3.

[0191] (5) Diethyl(3-bromopropyl)phosphonate was added to the prepared mixture and stirred at a temperature of 100°C for 10 hours to prepare a second reaction product. At this time, the diethyl(3-bromopropyl)phosphonate was added in such a molar ratio of 1:3 to the compound represented by the chemical formula 4-1 below.

[0192] (6) The second reaction product prepared was extracted with dichloromethane, and the organic phase of the extract was concentrated under reduced pressure to prepare a concentrate. Then, the concentrate was purified by silica gel chromatography and dried to obtain a dried product.

[0193] (7) After dissolving the obtained dried product in dichloromethane, bromotrimethylsilane was added and stirred and reacted at a temperature of 20°C for 24 hours to produce a third reaction product, and the prepared third reaction product was recrystallized using methanol to produce a non-covalent electron pair-holding compound for perovskite solar cells represented by the following chemical formula 5-1. At this time, bromotrimethylsilane was added such that the ratio of the compound represented by the following chemical formula 4-1 and the bromotrimethylsilane was 1:5 molar ratio.

[0194] [Chemical Formula 3-1]

[0195]

[0196] In the above chemical formula 3-1, A2, A3 and A4 are each carbon (C), A1 is nitrogen (N), and R2, R3 and R4 are each -H.

[0197] [Chemical Formula 4-1]

[0198]

[0199] In the above chemical formula 4-1, A2, A3, A4, A 2' , A 3' , A 4' , A 2" , A 3" and A 4" are each carbon (C), and A1, A 1' and A 1" are each nitrogen (N), and R2, R3, R4, R 2' , R 3' , R 4' , R 2" , R 3" and R 4" are each -H.

[0200] [Chemical Formula 5-1]

[0201]

[0202] In the above chemical formula 5-1, A2, A3, A4, A 2' , A 3' , A 4' , A 2" , A 3" and A 4" are each carbon (C), and A1, A 1' and A 1" are each nitrogen (N), and R2, R3, R4, R 2' , R 3' , R 4' , R 2" , R 3" and R 4" Each is -H, B1, B2 and B3 are each -CH2CH2CH2-, and X1, X2 and X3 are each dihydroxyphosphoryl groups (-P=O(OH)2).

[0203]

[0204] Example 1: Preparation of a Perovskite Solar Cell

[0205] (1) An ITO (Indium tin oxide) conductive transparent substrate (thickness: 180 μm) was prepared, and a 20 nm thick recombination layer (ITO) was formed on the prepared transparent substrate through a sputtering process.

[0206] (2) A hole transport layer was formed by depositing a 20 nm thick nickel oxide (NiOx) on top of the recombination layer using a sputter vacuum deposition method.

[0207] (3) A solution for forming an organic interface layer was prepared by mixing the non-covalent electron pair-bearing compound for a perovskite solar cell prepared in Preparation Example 1 with ethanol, and the solution for forming an organic interface layer was prepared by spin-coating the prepared solution for forming an organic interface layer on top of a hole transport layer at a speed of 3000 rpm for 30 seconds, and then heat-treating at a temperature of 100°C for 20 minutes to form an organic interface layer with a thickness of 2 nm.

[0208] (4) A yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) on top of an organic interface layer is formed 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.

[0209] (5) Naphthalene diimide derivative and C through a double co-deposition process on top of the perovskite light-absorbing layer 60 A fullerene was deposited to form a first electron transport layer with an average thickness of 20 nm. At this time, a naphthalene diimide derivative and C 60 Fullerene was deposited in a mass ratio of 1:2, and a compound represented by the following chemical formula 1-1 was used as a naphthalene diimide derivative.

[0210] [Chemical Formula 1-1]

[0211]

[0212] In the above chemical formula 1-1, R1 and R2 are respectively am.

[0213] (6) A second electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the first electron transport layer through an atomic layer deposition (ALD) process.

[0214] (7) A transparent electrode (IZO) with a thickness of 75 nm was formed on the second electron transport layer through a sputtering process.

[0215] (8) Silver (Ag) is applied to the top of the transparent electrode through a screen printing process, 1 10 times -7 A perovskite solar cell was fabricated by sequentially stacking a transparent substrate, a recombination layer, a hole transport layer, an organic interface layer, a perovskite light absorption layer, an electron transport layer, a transparent electrode, and a metal electrode by forming a metal electrode with a thickness of 100 nm by depositing at a pressure of torr.

[0216]

[0217] Example 2: Preparation of a Perovskite Solar Cell

[0218] A perovskite solar cell was prepared using the same method as in Example 1. However, unlike Example 1, the first electron transport layer was a naphthalene diimide derivative and C 60 A perovskite solar cell was finally fabricated by depositing fullerene in a mass ratio of 1:5.

[0219]

[0220] Example 3: Preparation of a Perovskite Solar Cell

[0221] A perovskite solar cell was prepared using the same method as in Example 1. However, unlike Example 1, the first electron transport layer was a naphthalene diimide derivative and C 60A perovskite solar cell was finally fabricated by depositing fullerene in a mass ratio of 1:8.

[0222]

[0223] Example 4: Preparation of a Perovskite Solar Cell

[0224] A perovskite solar cell was prepared using the same method as in Example 1. However, unlike Example 1, the first electron transport layer was a naphthalene diimide derivative and C 60 A perovskite solar cell was finally fabricated by depositing fullerene in a 1:1 mass ratio.

[0225]

[0226] Example 5: Preparation of a Perovskite Solar Cell

[0227] (1) An ITO (Indium tin oxide) conductive transparent substrate (thickness: 180 μm) was prepared, and a 20 nm thick recombination layer (ITO) was formed on the prepared transparent substrate through a sputtering process.

[0228] (2) A hole transport layer was formed by depositing a 20 nm thick nickel oxide (NiOx) on top of the recombination layer using a sputter vacuum deposition method.

[0229] (3) A solution for forming an organic interface layer was prepared by mixing the non-covalent electron pair-bearing compound for a perovskite solar cell prepared in Preparation Example 1 with ethanol, and the solution for forming an organic interface layer was prepared by spin-coating the prepared solution for forming an organic interface layer on top of a hole transport layer at a speed of 3000 rpm for 30 seconds, and then heat-treating at a temperature of 100°C for 20 minutes to form an organic interface layer with a thickness of 2 nm.

[0230] (4) A yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) on top of an organic interface layer is formed 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.

[0231] (5) Perylene diimide derivative and C through a double co-deposition process on top of the perovskite light-absorbing layer 60 A fullerene was deposited to form a first electron transport layer with an average thickness of 20 nm. At this time, a perylene diimide derivative and C 60 Fullerene was deposited in a mass ratio of 1:2, and a compound represented by the following chemical formula 2-1 was used as a perylene diimide derivative.

[0232] [Chemical Formula 2-1]

[0233]

[0234] In the above chemical formula 2-1, R9 and R 10 are each am.

[0235] (6) A second electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the first electron transport layer through an atomic layer deposition (ALD) process.

[0236] (7) A transparent electrode (IZO) with a thickness of 75 nm was formed on the second electron transport layer through a sputtering process.

[0237] (8) Silver (Ag) is applied to the top of the transparent electrode through a screen printing process, 1 10 times -7A perovskite solar cell was fabricated by sequentially stacking a transparent substrate, a recombination layer, a hole transport layer, an organic interface layer, a perovskite light absorption layer, an electron transport layer, a transparent electrode, and a metal electrode by forming a metal electrode with a thickness of 100 nm by depositing at a pressure of torr.

[0238]

[0239] Example 6: Preparation of a Perovskite Solar Cell

[0240] A perovskite solar cell was prepared using the same method as in Example 5. However, unlike Example 5, the first electron transport layer was a perylene diimide derivative and C 60 A perovskite solar cell was finally fabricated by depositing fullerene in a mass ratio of 1:5.

[0241]

[0242] Example 7: Preparation of a Perovskite Solar Cell

[0243] A perovskite solar cell was prepared using the same method as in Example 5. However, unlike Example 5, the first electron transport layer was a perylene diimide derivative and C 60 A perovskite solar cell was finally fabricated by depositing fullerene in a mass ratio of 1:8.

[0244]

[0245] Example 8: Preparation of a Perovskite Solar Cell

[0246] A perovskite solar cell was prepared using the same method as in Example 5. However, unlike Example 5, the first electron transport layer was a perylene diimide derivative and C 60 A perovskite solar cell was finally fabricated by depositing fullerene in a 1:1 mass ratio.

[0247]

[0248] Comparative Example 1: Preparation of a Perovskite Solar Cell

[0249] (1) An ITO (Indium tin oxide) conductive transparent substrate (thickness: 180 μm) was prepared, and a 20 nm thick recombination layer (ITO) was formed on the prepared transparent substrate through a sputtering process.

[0250] (2) A hole transport layer was formed by depositing a 20 nm thick nickel oxide (NiOx) on top of the recombination layer using a sputter vacuum deposition method.

[0251] (3) A solution for forming an organic interface layer was prepared by mixing the non-covalent electron pair-bearing compound for a perovskite solar cell prepared in Preparation Example 1 with ethanol, and the solution for forming an organic interface layer was prepared by spin-coating the prepared solution for forming an organic interface layer on top of a hole transport layer at a speed of 3000 rpm for 30 seconds, and then heat-treating at a temperature of 100°C for 20 minutes to form an organic interface layer with a thickness of 2 nm.

[0252] (4) A yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) on top of an organic interface layer is formed 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.

[0253] (5) C on top of the perovskite light absorption layer through a sequential deposition process 60 After depositing fullerene to an average thickness of 10 nm, a naphthalene diimide derivative was deposited to an average thickness of 10 nm to form a first electron transport layer with an average thickness of 20 nm. At this time, a compound represented by the chemical formula 1-1 above was used as the naphthalene diimide derivative.

[0254] (6) A second electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the first electron transport layer through an atomic layer deposition (ALD) process.

[0255] (7) A transparent electrode (IZO) with a thickness of 75 nm was formed on the second electron transport layer through a sputtering process.

[0256] (8) Silver (Ag) is applied to the top of the transparent electrode through a screen printing process, 1 10 times -7 A perovskite solar cell was fabricated by sequentially stacking a transparent substrate, a recombination layer, a hole transport layer, an organic interface layer, a perovskite light absorption layer, an electron transport layer, a transparent electrode, and a metal electrode by forming a metal electrode with a thickness of 100 nm by depositing at a pressure of torr.

[0257]

[0258] Comparative Example 2: Preparation of a Perovskite Solar Cell

[0259] (1) An ITO (Indium tin oxide) conductive transparent substrate (thickness: 180 μm) was prepared, and a 20 nm thick recombination layer (ITO) was formed on the prepared transparent substrate through a sputtering process.

[0260] (2) A hole transport layer was formed by depositing a 20 nm thick nickel oxide (NiOx) on top of the recombination layer using a sputter vacuum deposition method.

[0261] (3) A solution for forming an organic interface layer was prepared by mixing the non-covalent electron pair-bearing compound for a perovskite solar cell prepared in Preparation Example 1 with ethanol, and the solution for forming an organic interface layer was prepared by spin-coating the prepared solution for forming an organic interface layer on top of a hole transport layer at a speed of 3000 rpm for 30 seconds, and then heat-treating at a temperature of 100°C for 20 minutes to form an organic interface layer with a thickness of 2 nm.

[0262] (4) A yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) on top of an organic interface layer is formed 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.

[0263] (5) After depositing a naphthalene diimide derivative with an average thickness of 10 nm on top of the perovskite light-absorbing layer through a sequential deposition process, C 60 Fullerene was deposited to an average thickness of 10 nm to form a first electron transport layer with an average thickness of 20 nm. At this time, a compound represented by the above chemical formula 1-1 was used as a naphthalene diimide derivative.

[0264] (6) A second electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the first electron transport layer through an atomic layer deposition (ALD) process.

[0265] (7) A transparent electrode (IZO) with a thickness of 75 nm was formed on the second electron transport layer through a sputtering process.

[0266] (8) Silver (Ag) is applied to the top of the transparent electrode through a screen printing process, 1 10 times -7 A perovskite solar cell was fabricated by sequentially stacking a transparent substrate, a recombination layer, a hole transport layer, an organic interface layer, a perovskite light absorption layer, an electron transport layer, a transparent electrode, and a metal electrode by forming a metal electrode with a thickness of 100 nm by depositing at a pressure of torr.

[0267]

[0268] Comparative Example 3: Preparation of a Perovskite Solar Cell

[0269] (1) An ITO (Indium tin oxide) conductive transparent substrate (thickness: 180 μm) was prepared, and a 20 nm thick recombination layer (ITO) was formed on the prepared transparent substrate through a sputtering process.

[0270] (2) A hole transport layer was formed by depositing a 20 nm thick nickel oxide (NiOx) on top of the recombination layer using a sputter vacuum deposition method.

[0271] (3) A solution for forming an organic interface layer was prepared by mixing the non-covalent electron pair-bearing compound for a perovskite solar cell prepared in Preparation Example 1 with ethanol, and the solution for forming an organic interface layer was prepared by spin-coating the prepared solution for forming an organic interface layer on top of a hole transport layer at a speed of 3000 rpm for 30 seconds, and then heat-treating at a temperature of 100°C for 20 minutes to form an organic interface layer with a thickness of 2 nm.

[0272] (4) A yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) on top of an organic interface layer is formed 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.

[0273] (5) C on top of the perovskite light absorption layer through a sequential deposition process 60 After depositing fullerene to an average thickness of 10 nm, a perylene diimide derivative was deposited to an average thickness of 10 nm to form a first electron transport layer with an average thickness of 20 nm. At this time, a compound represented by the chemical formula 2-1 above was used as the perylene diimide derivative.

[0274] (6) A second electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the first electron transport layer through an atomic layer deposition (ALD) process.

[0275] (7) A transparent electrode (IZO) with a thickness of 75 nm was formed on the second electron transport layer through a sputtering process.

[0276] (8) Silver (Ag) is applied to the top of the transparent electrode through a screen printing process, 1 10 times -7 A perovskite solar cell was fabricated by sequentially stacking a transparent substrate, a recombination layer, a hole transport layer, an organic interface layer, a perovskite light absorption layer, an electron transport layer, a transparent electrode, and a metal electrode by forming a metal electrode with a thickness of 100 nm by depositing at a pressure of torr.

[0277]

[0278] Comparative Example 4: Preparation of Perovskite Solar Cells

[0279] (1) An ITO (Indium tin oxide) conductive transparent substrate (thickness: 180 μm) was prepared, and a 20 nm thick recombination layer (ITO) was formed on the prepared transparent substrate through a sputtering process.

[0280] (2) A hole transport layer was formed by depositing a 20 nm thick nickel oxide (NiOx) on top of the recombination layer using a sputter vacuum deposition method.

[0281] (3) A solution for forming an organic interface layer was prepared by mixing the non-covalent electron pair-bearing compound for a perovskite solar cell prepared in Preparation Example 1 with ethanol, and the solution for forming an organic interface layer was prepared by spin-coating the prepared solution for forming an organic interface layer on top of a hole transport layer at a speed of 3000 rpm for 30 seconds, and then heat-treating at a temperature of 100°C for 20 minutes to form an organic interface layer with a thickness of 2 nm.

[0282] (4) A yellow light-absorbing layer solution formed by dissolving in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) on top of an organic interface layer is formed 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.

[0283] (5) After depositing a perylene diimide derivative with an average thickness of 10 nm on top of the perovskite light-absorbing layer through a sequential deposition process, C 60 Fullerene was deposited to an average thickness of 10 nm to form a first electron transport layer with an average thickness of 20 nm. At this time, a compound represented by the chemical formula 2-1 above was used as a perylene diimide derivative.

[0284] (6) A second electron transport layer (SnO2) with an average thickness of 10 nm was formed on top of the first electron transport layer through an atomic layer deposition (ALD) process.

[0285] (7) A transparent electrode (IZO) with a thickness of 75 nm was formed on the second electron transport layer through a sputtering process.

[0286] (8) Silver (Ag) is applied to the top of the transparent electrode through a screen printing process, 1 10 times -7 A perovskite solar cell was fabricated by sequentially stacking a transparent substrate, a recombination layer, a hole transport layer, an organic interface layer, a perovskite light absorption layer, an electron transport layer, a transparent electrode, and a metal electrode by forming a metal electrode with a thickness of 100 nm by depositing at a pressure of torr.

[0287]

[0288] Experimental Example 1: Measurement of Solar Cell Performance

[0289] For each of the perovskite solar cells prepared in Examples 1 to 8 and Comparative Examples 1 to 4, 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.

[0290]

[0291] As can be seen in Table 1, it was confirmed that the perovskite solar cells prepared in Examples 1 to 3 and Examples 5 to 7 had the best photoelectric conversion efficiency.

[0292]

[0293] 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 and an electron transport layer stacked sequentially, and The electron transport layer comprises a first electron transport layer formed on top of a perovskite light absorption layer and a second electron transport layer formed on top of the first electron transport layer, and The first electron transport layer comprises a naphthalene diimide derivative and a fullerene-based organic material, and The above second electron transport layer comprises an inorganic material, perovskite solar cell.

2. A laminate comprising a perovskite light absorption layer and an electron transport layer stacked sequentially, and The electron transport layer comprises a first electron transport layer formed on top of a perovskite light absorption layer and a second electron transport layer formed on top of the first electron transport layer, and The first electron transport layer comprises a perylene diimide derivative and a fullerene-based organic material, and The above second electron transport layer comprises an inorganic material, perovskite solar cell.

3. In Paragraph 1, The above naphthalene diimide derivative comprises a compound represented by the following chemical formula 1, a perovskite solar cell. [Chemical Formula 1] In the above chemical formula 1, R1 and R2 are each independently, , , , , , , , , , , , , , , , , or And, the above R3 to R8 are each independently -H, a C1 to C20 straight-chain alkyl group or a C3 to C20 branched-chain alkyl group.

4. In Paragraph 1, A perovskite solar cell having a mass ratio of 1:1.5 to 10 of the above naphthalene diimide derivative and fullerene-based organic material.

5. In Paragraph 2, The above perylene diimide derivative comprises a compound represented by the following chemical formula 2, a perovskite solar cell. [Chemical Formula 2] In the above chemical formula 2, R9 and R 10 Each independently, , , , , , , , , , , , , , , , , or And, the above R3 to R8 are each independently -H, a C1 to C20 straight-chain alkyl group or a C3 to C20 branched-chain alkyl group.

6. In Paragraph 2, A perovskite solar cell having a mass ratio of 1:1.5 to 10 for the above perylene diimide derivative and fullerene-based organic material.

7. In Paragraph 1 or 2, A perovskite solar cell in which the first electron transport layer is formed through a double co-deposition process.

8. In Paragraph 1 or 2, The above inorganic material is selected from tin oxide (SnOx), tin oxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), barium tin oxide (BaSnO3), niobium hydroxide (NbOH), niobium pentoxide (Nb2O5), nickel oxide (NiOx), copper thiocyanate (CuSCN), copper chromium oxide (CuCrO2), cuprous iodide (CuI), copper oxide (CuOx), copper sulfide (CuS), copper phthalocyanine (CuPc), copper gallium oxide (CuGaO2), lead sulfide (PbS), molybdenum oxide (MoOx), aluminum oxide (AlOx), copper-aluminum oxide (CuAlOx), aluminum oxide nanoparticles, silica nanoparticles, nickel oxide nanoparticles, hafnium nanoparticles, and vanadium oxide (V2O5). A perovskite solar cell comprising one or more types.

9. In Paragraph 1 or 2, A perovskite solar cell in which the first electron transport layer and the second electron transport layer have a thickness ratio of 1:0.1 to 2.

0.

10. In Paragraph 1 or 2, 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.

11. A laminate comprising a solar cell, a recombination layer, a hole transport layer, a perovskite light absorption layer, and an electron transport layer stacked sequentially, and The electron transport layer comprises a first electron transport layer formed on top of a perovskite light absorption layer and a second electron transport layer formed on top of the first electron transport layer, and The first electron transport layer comprises a naphthalene diimide derivative and a fullerene-based organic material, and A tandem perovskite solar cell in which the second electron transport layer comprises an inorganic material.

12. A laminate comprising a solar cell, a recombination layer, a hole transport layer, a perovskite light absorption layer, and an electron transport layer stacked sequentially, and The electron transport layer comprises a first electron transport layer formed on top of a perovskite light absorption layer and a second electron transport layer formed on top of the first electron transport layer, and The first electron transport layer comprises a perylene diimide derivative and a fullerene-based organic material, and A tandem perovskite solar cell in which the second electron transport layer comprises an inorganic material.

13. In Paragraph 11, The above naphthalene diimide derivative comprises a compound represented by the following chemical formula 1, a tandem perovskite solar cell. [Chemical Formula 1] In the above chemical formula 1, R1 and R2 are each independently, , , , , , , , , , , , , , , , , or And, the above R3 to R8 are each independently -H, a C1 to C20 straight-chain alkyl group or a C3 to C20 branched-chain alkyl group.

14. In Paragraph 12, The above perylene diimide derivative comprises a compound represented by the following chemical formula 2, a tandem perovskite solar cell. [Chemical Formula 2] In the above chemical formula 2, R9 and R 10 Each independently, , , , , , , , , , , , , , , , , or And, the above R3 to R8 are each independently -H, a C1 to C20 straight-chain alkyl group or a C3 to C20 branched-chain alkyl group.

15. In Paragraph 11 or 12, The above solar cell is a tandem perovskite solar cell, which 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.

16. A first step of preparing a laminate including a perovskite light-absorbing layer; A second step of forming a first electron transport layer on top of the perovskite light absorption layer through a double co-deposition process; and A third step of forming a second electron transport layer on top of the first electron transport layer; comprising, A method for manufacturing a perovskite solar cell, wherein the first electron transport layer is formed by simultaneously depositing a naphthalene diimide derivative and a fullerene-based organic material.

17. A first step of preparing a laminate including a perovskite light-absorbing layer; A second step of forming a first electron transport layer on top of the perovskite light absorption layer through a double co-deposition process; and A third step of forming a second electron transport layer on top of the first electron transport layer; comprising, A method for manufacturing a perovskite solar cell, wherein the first electron transport layer is formed by simultaneously depositing a perylene diimide derivative and a fullerene-based organic material.

18. A first step of preparing a laminate in which a solar cell, a recombination layer, a hole transport layer, and a perovskite light absorption layer are sequentially stacked; A second step of forming a first electron transport layer on top of the perovskite light absorption layer through a double co-deposition process; and A third step of forming a second electron transport layer on top of the first electron transport layer; comprising, A method for manufacturing a tandem perovskite solar cell, wherein the first electron transport layer is formed by simultaneously depositing a naphthalene diimide derivative and a fullerene-based organic material.

19. A first step of preparing a laminate in which a solar cell, a recombination layer, a hole transport layer, and a perovskite light absorption layer are sequentially stacked; A second step of forming a first electron transport layer on top of the perovskite light absorption layer through a double co-deposition process; and A third step of forming a second electron transport layer on top of the first electron transport layer; comprising, A method for manufacturing a tandem perovskite solar cell, wherein the first electron transport layer is formed by simultaneously depositing a perylene diimide derivative and a fullerene-based organic material.

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