Perovskite photoelectric conversion element, perovskite solar cell including the same, and method for manufacturing the same

Abstract

The present invention relates to a perovskite photoelectric conversion element in which an intermediate layer is introduced onto one surface of a perovskite light absorbing layer by a thermal evaporation process, a perovskite solar cell including the same, and a method for manufacturing the same.

Description

[Technical Field]

[0001] The present invention relates to a perovskite photoelectric conversion element in which an intermediate layer is introduced onto one surface of a perovskite light absorbing layer by a thermal evaporation process, a perovskite solar cell including the same, and a method for manufacturing the same. [Background technology]

[0002] A solar cell converts solar energy into electrical energy, and generates electrical energy by absorbing solar energy and generating electrons and holes using the photovoltaic effect.

[0003] Various methods have been proposed for such solar cells, and among them, solar cells that use perovskite material, known to have the same crystal structure as calcium titanium oxide (CaTiO3), as a light absorption layer are attracting attention.

[0004] Perovskite solar cells are third-generation solar cells that combine thin-film technology and have high absorption coefficients, tunable bandgaps, and rapidly increasing properties compared to other solar cells. In addition, perovskite solar cells are superior to silicon solar cells in terms of price, rigidity, weight, and increased efficiency.

[0005] The perovskite used in solar cells generally has a three-dimensional crystal structure, and the perovskite with such a crystal structure is used in the light-absorbing layer. Solar cells generally have a structure in which an electron transport layer and a hole transport layer are disposed on both sides of the perovskite light-absorbing layer having a three-dimensional crystal structure.

[0006] The perovskite light absorbing layer, which has a three-dimensional crystal structure, is generally formed into a thin film by applying a solution process or a vapor deposition process. The surface and / or top of the perovskite thus formed is doped with Pb + A defect occurs and the voltage of the solar cell element (V OC) is reduced. In addition, in a specific device structure, the C applied to the top of the perovskite 60 There is a problem of energy mismatch with the material, which reduces the fill factor (FF) of the solar cell element. To solve this problem, previous research has attempted to solve the problem by applying an ammonium-based material, which is an A-site material that can form 2D perovskite, to the surface of the perovskite using a solution process to remove defects on the top and / or surface. In the structure of nip-type perovskite solar cells, this method reduces the voltage (V OC ), and fill factor (FF) could be improved. However, in the structure of pin-type perovskite solar cells, the formed 2D perovskite material and the next layer, the electron transport layer (ETL), C 60 The short circuit current density (J SC ) and other problems occur in that the fill factor (FF) decreases.

[0007] Therefore, the C applied to the top of the pin-type perovskite 60 To improve the energy matching mismatch with the material, a LiF layer was applied between the perovskite light absorbing layer and the electron transport layer to increase the voltage (V OC ), improved fill factor (FF), but did not improve defect removal on the perovskite surface, resulting in the conversion of LiF material to Li + The problem was that ions separated, reducing the stability of the solar cell elements.

[0008] To overcome this, lead oxysalts (C8H) can be formed on the upper surface of the perovskite, as shown in Figure 1. 17 A thin film was formed by applying NH3)2SO4 solvent, and Pb + Defects and pin structure in perovskite and C 60 The energy level matching problem was solved, but Pb + reacts with SO4 2- Unreacted outside the substance (C8H17 NH3) 2+ There are problems such as surface contamination by residues, coverage of the solution process, and uneven thickness uniformity. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been devised to overcome the above-mentioned problems, and aims to provide a perovskite photoelectric conversion device, a perovskite solar cell including the same, and a manufacturing method thereof, which can solve the coverage problems, limitations in thickness control, and problems of residual unreacted materials that occur in solution processes by adopting a thermal evaporation process to introduce an intermediate insertion layer on top of a perovskite light absorption layer.

[0010] The present invention also provides a perovskite photoelectric conversion element having excellent photoelectric conversion efficiency and durability, a perovskite solar cell including the same, and a method for manufacturing the same. [Means for solving the problem]

[0011] To solve the above problems, a method for manufacturing a perovskite photoelectric conversion device according to the present invention may include a first step of forming a hole transport layer on a first electrode, a second step of forming a perovskite light absorbing layer on the hole transport layer, a third step of forming an interlayer on the perovskite light absorbing layer by a thermal evaporation process, a fourth step of forming an electron transport layer on the interlayer, and a fifth step of forming a second electrode on the electron transport layer.

[0012] In a preferred embodiment of the present invention, the interlayer may comprise one or more selected from lead sulfate (PbSO), lead phosphate (Pb(PO), lead carbonate (PbCO), lead chromate (PbCrO), and lead oxalate (PbCO).

[0013] In one preferred embodiment of the present invention, the interlayer may include lead sulfate (PbSO4).

[0014] In one preferred embodiment of the present invention, lead sulfate may be produced by reacting lead nitrate (Pb(NO3)2) with sodium sulfate (Na2SO4).

[0015] In a preferred embodiment of the present invention, lead sulfate may be produced by reacting lead nitrate (Pb(NO3)2) and sodium sulfate (Na2SO4) in a molar ratio of 1:0.8 to 1.2.

[0016] In a preferred embodiment of the present invention, the perovskite light-absorbing layer and the intermediate insertion layer may have a thickness ratio of 1:0.0005 to 0.005.

[0017] In a preferred embodiment of the present invention, the perovskite light-absorbing layer may include a compound represented by Chemical Formula 1.

[0018] [ka] In the above chemical formula 1, A is a monovalent organic cation, a monovalent metal cation, or a mixture thereof, B is a divalent metal cation, and X is at least one anion.

[0019] The electron transport layer may include a fullerene-based organic material.

[0020] In one preferred embodiment of the present invention, the fullerene-based organic material is C 60 , C 70 , PC60BM, and PC70BM.

[0021] The method for manufacturing a perovskite photoelectric conversion device of the present invention may include a first step of forming a hole transport layer on a first electrode, a second step of forming an organic interface layer on the hole transport layer, a third step of forming a perovskite light absorbing layer on the organic interface layer, a fourth step of forming an interlayer on the perovskite light absorbing layer by a thermal evaporation process, a fifth step of forming an electron transport layer on the interlayer, and a sixth step of forming a second electrode on the electron transport layer.

[0022] The perovskite photoelectric conversion element of the present invention includes a laminate in which a first electrode, a hole transport layer, a perovskite light absorption layer, an interlayer, an electron transport layer, and a second electrode are stacked in this order, and the interlayer may include one or more selected from lead sulfate (PbSO), lead phosphate (Pb(PO)), lead carbonate (PbCO), lead chromate (PbCrO), and lead oxalate (PbC0).

[0023] In one preferred embodiment of the present invention, the interlayer may include lead sulfate (PbSO4).

[0024] In a preferred embodiment of the present invention, the perovskite light-absorbing layer and the intermediate insertion layer may have a thickness ratio of 1:0.0005 to 0.005.

[0025] In one preferred embodiment of the present invention, the electron transport layer may comprise a fullerene-based organic material.

[0026] In one preferred embodiment of the present invention, the fullerene-based organic material is C 60 , C 70 , PC60BM, and PC70BM.

[0027] In one preferred embodiment of the present invention, the stack may further comprise an organic interfacial layer between the hole transport layer and the perovskite light absorbing layer.

[0028] The perovskite solar cell of the present invention includes the perovskite photoelectric conversion element of the present invention.

[0029] Furthermore, the tandem silicon / perovskite heterojunction solar cell of the present invention may include the perovskite photoelectric conversion element of the present invention. [Effects of the Invention]

[0030] The perovskite photoelectric conversion element, the perovskite solar cell including the same, and the method for manufacturing the same of the present invention have excellent photoelectric conversion efficiency and long-term stability due to the improved interfacial characteristics between the perovskite light absorption layer and the electron transport layer, which are achieved by introducing an intermediate layer between the perovskite light absorption layer and the electron transport layer through a thermal evaporation process. [Brief explanation of the drawings]

[0031] [Figure 1] FIG. 1 is a schematic diagram showing a solution process in which a (C8H17NH3)2SO4 solvent is applied to the surface of perovskite, which can form lead oxysalts. [Figure 2] FIG. 2 is a schematic diagram showing the formation of an intermediate layer by thermal evaporation on top of a perovskite photoactive layer in the method for producing a perovskite photoelectric conversion device of the present invention. [Figure 3] FIG. 3 is a graph showing the XRD pattern (top graph) of the reactant prepared in Preparative Example 1 of the present invention (bottom graph is theoretical data). DETAILED DESCRIPTION OF THE INVENTION

[0032] The present invention will now be described in more detail.

[0033] C applied on top of conventional pin-type perovskite 60 To improve the energy matching mismatch with the material, a LiF layer was applied between the perovskite light absorbing layer and the electron transport layer to increase the voltage (V OC ), improved fill factor (FF), but did not improve defect removal on the perovskite surface, resulting in the conversion of LiF material to Li + The problem was that ions separated, reducing the stability of the solar cell elements.

[0034] To overcome this, lead oxysalts (C8H) can be formed on the upper surface of the perovskite. 17 By applying NH3)2SO4 solvent, a thin film is formed and Pb + Defects and pin structure in perovskite and C 60 The energy level matching problem was solved, but Pb + reacts with SO4 2- Unreacted outside the substance (C8H 17 NH3) 2+ There are problems such as surface contamination by residues, coverage of the solution process, and uneven thickness uniformity.

[0035] Therefore, the present invention provides excellent photoelectric conversion efficiency and long-term stability by introducing an interlayer between the perovskite light absorbing layer and the electron transport layer through a thermal evaporation process, thereby improving the interface characteristics between the perovskite light absorbing layer and the electron transport layer.

[0036] The method for producing a perovskite photoelectric conversion element of the present invention includes first to fifth steps.

[0037] First, in the first step of the method for manufacturing a perovskite photoelectric conversion device of the present invention, a hole transport layer may be formed on the first electrode.

[0038] The first electrode may include a conductive transparent substrate, which 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).

[0039] The thickness of the first electrode is not particularly limited, but may preferably be 50 nm to 200 nm, and more preferably 100 nm to 170 nm.

[0040] The hole transport layer (HTL) is a layer that transports holes formed in the perovskite light-absorbing layer described below and simultaneously blocks the movement of electrons, and may contain an inorganic and / or organic hole transport material.

[0041] In this case, the inorganic hole transport material may include at least one selected from nickel oxide (NiOx), CuSCN, CuCrO2, CuI, MoO, and V2O5.

[0042] Examples of 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), and TiOPC (titanium oxide). phthalocyanine), Spiro-MeOTAD(2,2′,7,7′-tetrakis(N,Np-dimethoxyphenylamino)-9,9′-spirobifluorene), F16CuP C(copper(II)1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H, 31H-phthalocyanine), SubPc(boron 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)、ポリアニリン(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(9,9′-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 It may contain one or more selected from poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), PTAA (poly(triarylamine)), 2-PACz, MeO-2PACz, Br-2PACz, Me-4PACz, MeO-4PACz, and 6-PACz.

[0043] The hole transport layer can be formed by coating or vacuum deposition, and the coating method can be gravure coating, bar coating, printing, spraying, spin coating, dipping, or die coating.

[0044] The thickness of the hole transport layer is not particularly limited, but may preferably be 5 nm to 50 nm, and more preferably 10 nm to 40 nm.

[0045] Next, in the second step of the method for producing a perovskite photoelectric conversion element of the present invention, a perovskite light absorbing layer can be formed on top of the hole transport layer.

[0046] The perovskite light-absorbing layer may contain a common perovskite material that is used in light-absorbing layers of solar cells, and the perovskite having a three-dimensional crystal structure may contain a perovskite material that absorbs light at a wavelength of 300 to 800 nm. As a preferred example, it may contain a compound represented by the following chemical formula 1:

[0047] [ka] In the above chemical formula 1, A is a monovalent organic cation, a monovalent metal cation, or a mixture thereof, B is a divalent metal cation, and X is at least one anion.

[0048] Specifically, A may include amines, ammonium, Group 1 metals, Group 2 metals, and / or other cations or cation-like compounds, preferably formamidinium (FA), methylammonium (MA), FAMA, CsFAMA, CsFA, or N(R)4. + (wherein R may be the same or different groups, and R may be a linear 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).

[0049] Furthermore, B may contain one or two elements selected from Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Eu, and Zr.

[0050] Furthermore, X may contain one or more halide elements and / or Group 16 anions selected from F, Cl, Br, and I. In a preferred example, X is I x Br 3-x (0≦x≦3).

[0051] The perovskite light-absorbing layer may be a single layer made of the same perovskite material, or may have a multilayer structure in which multiple layers made of different perovskite materials are stacked.The light-absorbing layer made of one type of perovskite material may contain a different type of perovskite material that has a pillar shape, such as a columnar, plate, needle, wire, or rod, different from the one type of perovskite material.

[0052] Furthermore, examples of methods for forming the perovskite light-absorbing layer include coating methods and vacuum deposition methods. Examples of coating methods include gravure coating, bar coating, printing, spraying, spin coating, dipping, inkjet coating, and die coating.

[0053] Next, in the third step of the method for manufacturing a perovskite photoelectric conversion device of the present invention, an interlayer 20 can be formed on top of the perovskite light absorbing layer 10 by a thermal evaporation process, as shown in Figure 2. By introducing the interlayer by a thermal evaporation process, the present invention has the advantage of not only eliminating defects on the surface of the perovskite light absorbing layer, but also properly guiding energy matching with the electron transport layer, which will be described later.

[0054] Specifically, the intermediate layer may contain one or more selected from lead sulfate (PbSO), lead phosphate (Pb(PO)), lead carbonate (PbCO), lead chromate (PbCrO), and lead oxalate (PbC0), and preferably contains lead sulfate (PbSO).

[0055] In this case, lead sulfate may be produced by reacting lead nitrate (Pb(NO3)2) with sodium sulfate (Na2SO4), preferably in a molar ratio of 1:0.9 to 1.1, more preferably 1:0.95 to 1.05. If the molar ratio is less than 1:0.9, there may be a problem of reduced yield, and if it exceeds 1:1.1, there may be a problem of extracting a high-purity final reaction product.

[0056] The perovskite light-absorbing layer 10 and intermediate layer 20 of the present invention may have a thickness ratio of 1:0.0005 to 0.005, preferably 1:0.001 to 0.003. If the thickness ratio is less than 0.0005, problems may arise in energy matching and coverage with the electron transport layer described below. If the thickness ratio exceeds 0.005, problems may arise in that the insulating properties are increased and the current of the solar cell is reduced.

[0057] Next, in the fourth step of the method for manufacturing a perovskite photoelectric conversion device of the present invention, an electron transport layer may be formed on the intermediate insertion layer.

[0058] The electron transporting layer (ETL) is a layer that transports electrons formed in the perovskite light absorbing layer and blocks the movement of holes, and may contain a fullerene-based organic material. In this case, the fullerene-based organic material is C 60 , C 70 , PC60BM and PC70BM, and preferably C 60 may include:

[0059] The electron transport layer can be formed by coating and / or vacuum deposition, and examples of the coating method include gravure coating, bar coating, printing, spraying, spin coating, dipping, and die coating.

[0060] The thickness of the electron transport layer is not particularly limited, but may preferably be 5 to 30 nm, more preferably 10 to 15 nm.

[0061] Finally, in the fifth step of the method for producing a perovskite photoelectric conversion device of the present invention, a second electrode can be formed on top of the electron transport layer.

[0062] The second electrode may be formed by depositing a metal material through a deposition process, preferably a thermal evaporation process.

[0063] In this case, the metal substance may include one or more selected from Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C, and conductive polymers.

[0064] The thickness of the second electrode is not particularly limited, but may preferably be 50 nm to 2.5 μm, and more preferably 80 nm to 150 nm.

[0065] Another method for manufacturing a perovskite photoelectric conversion element of the present invention may include a first step of forming a hole transport layer on a first electrode, a second step of forming an organic interface layer on the hole transport layer, a third step of forming a perovskite light absorbing layer on the organic interface layer, a fourth step of forming an interlayer on the perovskite light absorbing layer by a thermal evaporation process, a fifth step of forming an electron transport layer on the interlayer, and a sixth step of forming a second electrode on the electron transport layer.

[0066] Specifically, unlike the method for manufacturing a perovskite photoelectric conversion element of the present invention described above, an organic interface layer may be formed between the hole transport layer and the perovskite light absorption layer, and the organic interface layer can improve hole transport ability while preventing recombination.

[0067] The organic interface layer may include an aromatic compound having an aromatic structure with a double bond, and preferably includes one or more selected from pyridine, aniline, carbazole, phenazine, phenoxazine, and phenothiazine. In addition, pyridine, aniline, carbazole, phenazine, phenoxazine, or phenothiazine may have other alkyl groups connected to the carbon, oxygen, or nitrogen positions, and the last part of the alkyl group may be carboxylic acid, phosphorous acid, or R4N. + Groups such as halide anion groups (where R can be H or C), sulfonate, etc. may be included.

[0068] In addition, examples of methods for forming the organic interface layer include coating methods and / or vacuum deposition methods, and examples of coating methods include gravure coating methods, bar coating methods, printing methods, spraying methods, spin coating methods, dipping methods, and die coating methods.

[0069] The thickness of the organic interface layer is not particularly limited, but may preferably be 1 to 10 nm, more preferably 1 to 3 nm.

[0070] Furthermore, the perovskite photoelectric conversion device of the present invention may include a laminate in which a first electrode, a hole transport layer, a perovskite light absorbing layer, an interlayer, an electron transport layer, and a second electrode are sequentially laminated, where the first electrode, the hole transport layer, the perovskite light absorbing layer, the interlayer, the electron transport layer, and the second electrode are as described above.

[0071] The intermediate layer may also contain one or more selected from lead sulfate (PbSO4), lead phosphate (Pb3(PO4)2), lead carbonate (PbCO3), lead chromate (PbCrO4) and lead oxalate (PbC2O4), and preferably contains lead sulfate (PbSO4).

[0072] The perovskite light-absorbing layer and intermediate insertion layer of the present invention may have a thickness ratio of 1:0.0005 to 0.005, preferably 1:0.001 to 0.003.

[0073] The electron transport layer may also contain a fullerene-based organic material, preferably C 60 , C 70 , PC60BM, and PC70BM.

[0074] The stack may also further include an organic interfacial layer between the hole transport layer and the perovskite light absorbing layer, the organic interfacial layer being as described above.

[0075] The perovskite solar cell of the present invention may include the perovskite photoelectric conversion element of the present invention.

[0076] Furthermore, the tandem silicon / perovskite heterojunction solar cell of the present invention may include the perovskite photoelectric conversion element of the present invention.

[0077] The present invention will be described in more detail below based on examples. However, the following examples should not be construed as limiting the scope of the present invention, but as being intended to aid in understanding the present invention.

[0078] Preparation Example 1: Preparation of composition for forming intermediate insertion layer A 250ml flask was charged with 25g (75.48mmol) of lead nitrate (Pb(NO3)2), 10.72g (75.48mmol) of sodium sulfate (Na2SO4), and 50ml of distilled water, and the mixture was stirred for 1 hour to produce a reactant. The reactant was filtered using a pressure filter and washed three times with 100ml of distilled water. XRD analysis of the washed reactant confirmed that lead sulfate (PbSO4) had been produced as the reactant, as shown in Figure 3, with a yield of 96%.

[0079] Example 1: Production of perovskite photoelectric conversion element (1) An ITO conductive transparent substrate measuring 2.5 cm wide x 2.5 cm long x 100 nm thick was prepared as the first electrode. The prepared ITO conductive transparent substrate was placed in a sodium hydroxide cleaning solution and ultrasonically cleaned for 1 hour. It was then washed again with distilled water and ethanol and dried using nitrogen gas. After the cleaning and drying process, the ITO conductive transparent substrate was partially etched with an IR laser, and a 30 nm thick hole transport layer (NiOx) was formed on top of the ITO conductive transparent substrate using sputtering vacuum deposition.

[0080] (2) Next, 200 μl of the organic interface layer-forming solution was dropped onto the hole transport layer, spin-coated at 3000 rpm for 30 seconds, and then heat-treated at 100° C. for 20 minutes to form an organic interface layer with a thickness of 2 nm. The organic interface layer-forming solution used was ethanol containing Me-4PACz:[4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid at a concentration of 1 mM.

[0081] (3) Next, a perovskite crystal structure (Cs) was formed on top of the organic interfacial layer. 0.2 FA0.8 Pb(I 0.8 Br 0.2 100 μl of a 1.3 M perovskite precursor solution containing 3) was dropped onto the substrate, spin-coated at 5000 rpm for 30 seconds in a 99% pure nitrogen environment, and then heat-treated at 100°C for 20 minutes to form a 500 nm thick perovskite light-absorbing layer.

[0082] (4) Next, an intermediate layer having a thickness of 1 nm was formed on the perovskite light absorption layer by a thermal evaporation process using a thermal evaporation apparatus. In this case, lead sulfate (PbSO4) prepared in Preparation Example 1 was used as the intermediate layer forming material.

[0083] (5) Next, C is deposited on the top of the intermediate layer by a vacuum deposition process. 60 Fullerene (C 60 fullerene) was evaporated to form an electron transport layer with an average thickness of 13 nm.

[0084] (6) Next, 200 μL of a solution of 1 mg of bathocuproine dissolved in 1 mL of isopropyl alcohol was dropped onto the top of the electron transport layer, spin-coated at 4000 rpm for 30 seconds, and heat-treated at 100°C for 20 minutes to form an exciton blocking layer.

[0085] (7) Finally, a second electrode (Ag) with a thickness of 100 nm was formed on the exciton blocking layer by a thermal evaporation process using a thermal evaporation device, thereby manufacturing a perovskite photoelectric conversion element.

[0086] Comparative Example 1: Production of perovskite photoelectric conversion element (1) An ITO conductive transparent substrate measuring 2.5 cm wide x 2.5 cm long x 100 nm thick was prepared as the first electrode. The prepared ITO conductive transparent substrate was placed in a sodium hydroxide cleaning solution and ultrasonically cleaned for 1 hour. It was then washed again with distilled water and ethanol and dried using nitrogen gas. After the cleaning and drying process, the ITO conductive transparent substrate was partially etched with an IR laser, and a 30 nm thick hole transport layer (NiOx) was formed on top of the ITO conductive transparent substrate using sputtering vacuum deposition.

[0087] (2) Next, 200 μl of the organic interface layer-forming solution was dropped onto the hole transport layer, spin-coated at 3000 rpm for 30 seconds, and then heat-treated at 100° C. for 20 minutes to form an organic interface layer with a thickness of 2 nm. The organic interface layer-forming solution used was ethanol containing Me-4PACz:[4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid at a concentration of 1 mM.

[0088] (3) Next, a perovskite crystal structure (Cs) was formed on top of the organic interfacial layer. 0.2 FA 0.8 Pb(I 0.8 Br 0.2 100 μl of a 1.3 M perovskite precursor solution containing 3) was dropped onto the substrate, spin-coated at 5000 rpm for 30 seconds in a 99% pure nitrogen environment, and then heat-treated at 100°C for 20 minutes to form a 500 nm thick perovskite light-absorbing layer.

[0089] (4) Next, an intermediate layer having a thickness of 1 nm was formed on the upper surface of the perovskite light absorbing layer by a thermal evaporation process using a thermal evaporation apparatus. In this case, lithium fluoride (LiF) was used as the intermediate layer forming material.

[0090] (5) Next, C is deposited on the top of the intermediate layer by a vacuum deposition process. 60 Fullerene (C 60 fullerene) was evaporated to form an electron transport layer with an average thickness of 13 nm.

[0091] (6) Next, 200 μL of a solution of 1 mg of bathocuproine dissolved in 1 mL of isopropyl alcohol was dropped onto the top of the electron transport layer, spin-coated at 4000 rpm for 30 seconds, and heat-treated at 100°C for 20 minutes to form an exciton blocking layer.

[0092] (7) Finally, a second electrode (Ag) with a thickness of 100 nm was formed on the exciton blocking layer by a thermal evaporation process using a thermal evaporation device, thereby manufacturing a perovskite photoelectric conversion element.

[0093] Comparative Example 2: Production of perovskite photoelectric conversion element (1) An ITO conductive transparent substrate measuring 2.5 cm wide x 2.5 cm long x 100 nm thick was prepared as the first electrode. The prepared ITO conductive transparent substrate was placed in a sodium hydroxide cleaning solution and ultrasonically cleaned for 1 hour. It was then washed again with distilled water and ethanol and dried using nitrogen gas. After the cleaning and drying process, the ITO conductive transparent substrate was partially etched using an IR laser, and a 30 nm thick hole transport layer (NiOx) was then formed on top of the ITO conductive transparent substrate using sputtering vacuum deposition.

[0094] (2) Next, 200 μl of the organic interface layer-forming solution was dropped onto the hole transport layer, spin-coated at 3000 rpm for 30 seconds, and then heat-treated at 100° C. for 20 minutes to form an organic interface layer with a thickness of 2 nm. The organic interface layer-forming solution used was ethanol containing Me-4PACz:[4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid at a concentration of 1 mM.

[0095] (3) Next, a perovskite crystal structure (Cs) was formed on top of the organic interfacial layer. 0.2 FA 0.8 Pb(I 0.8 Br 0.2100 μl of a 1.3 M perovskite precursor solution containing 3) was dropped onto the substrate, spin-coated at 5000 rpm for 30 seconds in a 99% pure nitrogen environment, and then heat-treated at 100°C for 20 minutes to form a 500 nm thick perovskite light-absorbing layer.

[0096] (4) Next, a 2 mM solution was prepared by diluting octylamine and hydroperoxide (H2O4) in chloroform. 200 μl of the prepared 2 mM solution was dropped onto the top of the organic interface layer, spin-coated at 3000 rpm for 30 seconds, and then heat-treated at 100°C for 20 minutes to form a 1 nm thick lead oxysalt intercalation layer.

[0097] (5) Next, C is deposited on the top of the intermediate layer by a vacuum deposition process. 60 Fullerene (C 60 fullerene) was evaporated to form an electron transport layer with an average thickness of 13 nm.

[0098] (6) Next, 200 μL of a solution of 1 mg of bathocuproine dissolved in 1 mL of isopropyl alcohol was dropped onto the top of the electron transport layer, spin-coated at 4000 rpm for 30 seconds, and heat-treated at 100°C for 20 minutes to form an exciton blocking layer.

[0099] (7) Finally, a second electrode (Ag) with a thickness of 100 nm was formed on the exciton blocking layer by a thermal evaporation process using a thermal evaporation device, thereby manufacturing a perovskite photoelectric conversion element.

[0100] Comparative Example 3: Production of perovskite photoelectric conversion element (1) An ITO conductive transparent substrate measuring 2.5 cm wide x 2.5 cm long x 100 nm thick was prepared as the first electrode. The prepared ITO conductive transparent substrate was placed in a sodium hydroxide cleaning solution and ultrasonically cleaned for 1 hour. It was then washed again with distilled water and ethanol and dried using nitrogen gas. After the cleaning and drying process, the ITO conductive transparent substrate was partially etched with an IR laser, and a 30 nm thick hole transport layer (NiOx) was formed on top of the ITO conductive transparent substrate using sputtering vacuum deposition.

[0101] (2) Next, 200 μl of the organic interface layer-forming solution was dropped onto the hole transport layer, spin-coated at 3000 rpm for 30 seconds, and then heat-treated at 100° C. for 20 minutes to form an organic interface layer with a thickness of 2 nm. The organic interface layer-forming solution used was ethanol containing Me-4PACz:[4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid at a concentration of 1 mM.

[0102] (3) Next, a perovskite crystal structure (Cs) was formed on top of the organic interfacial layer. 0.2 FA 0.8 Pb(I 0.8 Br 0.2 100 μl of a 1.3 M perovskite precursor solution containing 3) was dropped onto the substrate, spin-coated at 5000 rpm for 30 seconds in a 99% pure nitrogen environment, and then heat-treated at 100°C for 20 minutes to form a 500 nm thick perovskite light-absorbing layer.

[0103] (4) Next, a 4 mM solution was prepared by diluting octylamine and hydroperoxide (H2O4) in chloroform. 200 μl of the prepared 4 mM solution was dropped onto the top of the organic interface layer, spin-coated at 3000 rpm for 30 seconds, and then heat-treated at 100°C for 20 minutes to form a 1 nm thick lead oxysalt intercalation layer.

[0104] (5) Next, C is deposited on the top of the intermediate layer by a vacuum deposition process. 60 Fullerene (C60 fullerene) was evaporated to form an electron transport layer with an average thickness of 13 nm.

[0105] (6) Next, 200 μL of a solution of 1 mg of bathocuproine dissolved in 1 mL of isopropyl alcohol was dropped onto the top of the electron transport layer, spin-coated at 4000 rpm for 30 seconds, and heat-treated at 100°C for 20 minutes to form an exciton blocking layer.

[0106] (7) Finally, a second electrode (Ag) with a thickness of 100 nm was formed on the exciton blocking layer by a thermal evaporation process using a thermal evaporation device, thereby manufacturing a perovskite photoelectric conversion element.

[0107] Experimental example 1: Performance measurement of perovskite photoelectric conversion elements For each of the perovskite photoelectric conversion elements produced in Example 1 and Comparative Examples 1 to 3, the efficiency was measured using a sunlight simulator and a JV Keithley device and the initial JV curve, and the results are shown in Table 1 below.

[0108] [Table 1]

[0109] As can be seen from Table 1, the photoelectric conversion device manufactured in Example 1, in which a PbSO4 interlayer was formed as a uniform thin film on the surface of the perovskite by a thermal evaporation process, was found to be improved in all efficiency parameters compared to the photoelectric conversion devices manufactured in Comparative Examples 1 to 3.

[0110] Comparative Example 4: Production of perovskite photoelectric conversion element (1) An ITO conductive transparent substrate measuring 2.5 cm wide x 2.5 cm long x 100 nm thick was prepared as the first electrode. The prepared ITO conductive transparent substrate was placed in a sodium hydroxide cleaning solution and ultrasonically cleaned for 1 hour. It was then washed again with distilled water and ethanol and dried using nitrogen gas. After the cleaning and drying process, the ITO conductive transparent substrate was partially etched with an IR laser, and a 30 nm thick hole transport layer (NiOx) was formed on top of the ITO conductive transparent substrate using sputtering vacuum deposition.

[0111] (2) Next, 200 μl of the organic interface layer-forming solution was dropped onto the hole transport layer, spin-coated at 3000 rpm for 30 seconds, and then heat-treated at 100° C. for 20 minutes to form an organic interface layer with a thickness of 2 nm. The organic interface layer-forming solution used was ethanol containing Me-4PACz:[4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid at a concentration of 1 mM.

[0112] (3) Next, a perovskite crystal structure (Cs) was formed on top of the organic interfacial layer. 0.2 FA 0.8 Pb(I 0.8 Br 0.2 100 μl of a 1.3 M perovskite precursor solution containing 3) was dropped onto the substrate, spin-coated at 5000 rpm for 30 seconds in a 99% pure nitrogen environment, and then heat-treated at 100°C for 20 minutes to form a 500 nm thick perovskite light-absorbing layer.

[0113] (4) Next, C is deposited on top of the perovskite light-absorbing layer by a vacuum deposition process. 60 Fullerene (C 60 fullerene) was evaporated to form an electron transport layer with an average thickness of 13 nm.

[0114] (5) Next, 200 μL of a solution of 1 mg of bathocuproine dissolved in 1 mL of isopropyl alcohol was dropped onto the top of the electron transport layer, spin-coated at 4000 rpm for 30 seconds, and heat-treated at 100°C for 20 minutes to form an exciton blocking layer.

[0115] (6) Finally, a second electrode (Ag) with a thickness of 100 nm was formed on the exciton blocking layer by a thermal evaporation process using a thermal evaporation apparatus, thereby manufacturing a perovskite photoelectric conversion element.

[0116] Experimental Example 2: Measurement of the work function of a perovskite photoelectric conversion element The work function of the perovskite light-absorbing layer surface of the perovskite photoelectric conversion element produced in Comparative Example 4 and the work function of the intermediate layer of the perovskite photoelectric conversion element produced in Example 1 were measured by XPS analysis and are shown in Table 2 below.

[0117] [Table 2]

[0118] As can be seen from Table 2, the introduction of the intercalation layer reduces the work function (WF) of the perovskite by approximately 0.5 eV. This reduction in the work function is due to the 60 It was confirmed that the energy matching with the electron transport layer made of fullerene was guided in the correct direction.

[0119] The above describes one embodiment of the present invention, but the concept of the present invention is not limited to the embodiment described in this specification. A person skilled in the art who understands the concept of the present invention can easily propose other embodiments by adding, changing, deleting, or adding components within the scope of the same concept, and these can also be said to fall within the scope of the concept of the present invention.

Claims

1. a first step of forming a hole transport layer on a first electrode; a second step of forming a perovskite light absorbing layer on top of the hole transport layer; a third step of forming an interlayer on the perovskite light absorbing layer by a thermal deposition process; a fourth step of forming an electron transport layer on the intermediate insertion layer; a fifth step of forming a second electrode on the electron transport layer; A method for producing a perovskite photoelectric conversion element, comprising:

2. The intermediate layer is made of lead sulfate (PbSO ４ ), lead phosphate (Pb ３ (P.O. ４ ) ２ ), lead carbonate (PbCO ３ ), lead chromate (PbCrO ４ ) and lead oxalate (PbC ２ O ４ 2. The method for producing a perovskite photoelectric conversion element according to claim 1, wherein the perovskite photoelectric conversion element contains one or more selected from the group consisting of:

3. The intermediate layer is made of lead sulfate (PbSO ４ 3. The method for producing a perovskite photoelectric conversion element according to claim 2, further comprising:

4. The lead sulfate is lead nitrate (Pb(NO ３ ) ２ ) and sodium sulfate (Na ２ SO ４ 4. The method for producing a perovskite photoelectric conversion element according to claim 3, wherein the element is produced by reacting

5. The lead sulfate is lead nitrate (Pb(NO ３ ) ２ ) and sodium sulfate (Na ２ SO ４ 5. The method for producing a perovskite photoelectric conversion element according to claim 4, wherein the perovskite photoelectric conversion element is produced by reacting the above-mentioned compounds in a molar ratio of 1:0.8 to 1.

2.

6. 2. The method for manufacturing a perovskite photoelectric conversion element according to claim 1, wherein the perovskite light-absorbing layer and the intermediate layer have a thickness ratio of 1:0.0005 to 0.

005.

7. The method for manufacturing a perovskite photoelectric conversion element according to claim 1 , wherein the perovskite light-absorbing layer contains a compound represented by Chemical Formula 1. 【Chemistry 1】 In the above formula 1, A is a monovalent organic cation, a monovalent metal cation, or a mixture thereof, B is a divalent metal cation, and X is at least one anion.

8. The method for manufacturing a perovskite photoelectric conversion device according to claim 1, wherein the electron transport layer contains a fullerene-based organic material.

9. The fullerene-based organic material is C ６０ , C ７０ 9. The method for producing a perovskite photoelectric conversion element according to claim 8, wherein the perovskite photoelectric conversion element contains one or more selected from the group consisting of PC60BM, PC60BM, and PC70BM.

10. a first step of forming a hole transport layer on a first electrode; a second step of forming an organic interfacial layer on top of the hole transport layer; a third step of forming a perovskite light-absorbing layer on top of the organic interfacial layer; a fourth step of forming an interlayer on the perovskite light absorbing layer by a thermal deposition process; a fifth step of forming an electron transport layer on the intermediate insertion layer; a sixth step of forming a second electrode on the electron transport layer; A method for producing a perovskite photoelectric conversion element, comprising:

11. The device includes a stacked structure in which a first electrode, a hole transport layer, a perovskite light absorbing layer, an interlayer, an electron transport layer, and a second electrode are stacked in order; The intermediate layer is made of lead sulfate (PbSO ４ ), lead phosphate (Pb ３ (P.O. ４ ) ２ ), lead carbonate (PbCO ３ ), lead chromate (PbCrO ４ ) and lead oxalate (PbC ２ O ４ ) a perovskite photoelectric conversion element characterized by containing one or more selected from the group consisting of

12. The intermediate layer is made of lead sulfate (PbSO ４ 12. The perovskite photoelectric conversion element according to claim 11, comprising:

13. 12. The perovskite photoelectric conversion element according to claim 11, wherein the perovskite light-absorbing layer and the intermediate insertion layer have a thickness ratio of 1:0.0005 to 0.

005.

14. The perovskite photoelectric conversion device according to claim 11, wherein the electron transport layer comprises a fullerene-based organic material.

15. The fullerene-based organic material is C ６０ , C ７０ 15. The perovskite photoelectric conversion element according to claim 14, characterized in that it contains one or more selected from the group consisting of PC60BM, PC60BM, and PC70BM.

16. The perovskite photoelectric conversion element according to claim 15, wherein the stack further comprises an organic interface layer between the hole transport layer and the perovskite light absorption layer.

17. A perovskite solar cell comprising the perovskite photoelectric conversion element according to claim 11.

18. A tandem silicon / perovskite heterojunction solar cell comprising the perovskite photoelectric conversion element according to claim 11.

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