High-transmittance perovskite photoelectric device and manufacturing method therefor

Abstract

The present invention relates to a perovskite photoelectric device having high light transmittance and photoelectric conversion efficiency and a method for manufacturing the perovskite photoelectric device, the method comprising: (S1) a charge transport layer complex preparation step of stacking an intermediate layer containing an intermediate layer compound on a charge transport layer; and (S2) a step of stacking a perovskite thin film on the intermediate layer, wherein the intermediate layer compound contains a repeating unit satisfying chemical formula 1 below. (Chemical formula 1) (In chemical formula 1, Z is at least one selected from the group consisting of phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and n is a positive integer of 1 or greater.)

Description

High-transmittance perovskite photovoltaic device and method for manufacturing the same

[0001] The present invention relates to a perovskite photoelectric device having high light transmittance and photoelectric conversion efficiency and a method for manufacturing the perovskite photoelectric device.

[0002]

[0003] Recently, organic-inorganic hybrid perovskite materials have been highlighted as key materials for next-generation photovoltaic devices due to their advantages such as high light absorbance, high external quantum efficiency (EQE), fast charge transfer rate, and solution processability. Over the past decade, extensive research has been conducted on perovskite materials, focusing on solar cells, and commercialization is imminent with a peak photoelectric conversion efficiency of 25%. However, many challenges remain for the commercialization of perovskite solar cells, such as improving stability against light, heat, and moisture, improving charge transfer efficiency, reducing toxic substances, and developing low-cost, large-area perovskite thin film manufacturing methods. Therefore, active research is being actively conducted.

[0004] Meanwhile, research on semitransparent perovskite solar cells has recently been conducted. Perovskite thin films have easily tunable optical bandgaps, enabling them to reflect light across a wide spectrum. Therefore, high average visible transmittance (AVT) can be achieved through various strategies. Furthermore, when the average visible transmittance exceeds 30%, the aesthetic appearance of the target structure can be maintained, making them a subject of active research.

[0005] Among the various strategies mentioned above, there are strategies such as patterning the microstructure of the device or controlling the band gap of the perovskite thin film, but these methods require complex processes or have problems such as low light absorption due to the wide band gap.

[0006] In addition, there is a strategy to achieve high average visible light transmittance by controlling the thickness of the perovskite thin film, but thin perovskite thin films less than 200 nm have problems such as difficulty in controlling nucleation and nucleus growth of perovskite crystals and significantly low efficiency in exciton generation, etc. Specifically, thin perovskite thin films less than 200 nm have small crystal sizes and many grain boundaries, which cause problems such as carrier recombination occurring at the grain boundaries or acting as carrier defects. In addition, as the thickness of the perovskite thin film decreases, the surface roughness increases, making it difficult to conformally coat the substrate.

[0007]

[0008] The purpose of the present invention is to provide a perovskite photovoltaic device having high light transmittance and high photoelectric conversion efficiency, and a method for manufacturing the same.

[0009] Another object of the present invention is to provide a charge transfer layer composite capable of preventing nonradiative recombination at the interface between a perovskite thin film and a charge transfer layer included in a perovskite photovoltaic device.

[0010]

[0011] The present invention provides a method for manufacturing a perovskite photovoltaic device, the method for manufacturing a perovskite photovoltaic device comprising: (S1) a charge transfer layer composite manufacturing step of laminating an intermediate layer including an intermediate layer compound on a charge transfer layer; and (S2) a step of laminating a perovskite thin film on the intermediate layer; wherein the intermediate layer compound includes a repeating unit satisfying the following chemical formula 1.

[0012] (Chemical formula 1)

[0013]

[0014] (In chemical formula 1, Z is one or more selected from the group including phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and n is a positive integer greater than or equal to 1.)

[0015] In the method for manufacturing a perovskite photovoltaic device according to the present invention, Z in the intermediate layer compound satisfying the chemical formula 1 may be phosphorus (P).

[0016] In the method for manufacturing a perovskite photovoltaic device according to the present invention, n of the intermediate layer compound satisfying the chemical formula 1 may be 2.

[0017] In the method for manufacturing a perovskite photovoltaic device according to the present invention, the intermediate layer compound may include a pyrophosphate salt.

[0018] In the method for manufacturing a perovskite photovoltaic device according to the present invention, the intermediate layer compound may include potassium pyrophosphate.

[0019] In the method for manufacturing a perovskite photovoltaic device according to the present invention, the charge transfer layer may include an oxide.

[0020] In the method for manufacturing a perovskite photovoltaic device according to the present invention, the charge transfer layer is a transition metal oxide (M x O y ) may be included.

[0021] In the method for manufacturing a perovskite photovoltaic device according to the present invention, the charge transfer layer is tin oxide (SnO x , 0 <x≤2)을 포함할 수 있다.

[0022] In the method for manufacturing a perovskite photovoltaic device according to the present invention, the thickness of the perovskite thin film may be 10 to 250 nm.

[0023] In the method for manufacturing a perovskite photovoltaic device according to the present invention, the thickness of the intermediate layer may be 0.1 to 10 nm.

[0024] In the method for manufacturing a perovskite photoelectric device according to the present invention, the perovskite thin film may include a perovskite crystal satisfying the following chemical formula 2 or chemical formula 3.

[0025] (Chemical formula 2)

[0026] ABX3

[0027] (Chemical formula 3)

[0028] A2BX4

[0029] (In the above chemical formulas 2 and 3, A is a monovalent alkylammonium cation; a monovalent amidinium cation; Li + ; Na + ; K + ; Rb + ; Cs + ; Fr + ; Cu(I) + ; Ag(I) + and Au(I) + A compound comprising one or more monovalent cations selected from the group consisting of a combination of, B is a divalent metal cation, and X is I - , Br - , Cl - or a combination of these halogen anions.)

[0030] The present invention provides a charge transfer layer complex, wherein the charge transfer layer complex comprises: a charge transfer layer; and an intermediate layer positioned on the charge transfer layer and containing an intermediate layer compound; wherein the intermediate layer compound comprises a repeating unit satisfying the following chemical formula 1.

[0031] (Chemical formula 1)

[0032]

[0033] (In chemical formula 1, Z is one or more selected from the group including phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and n is a positive integer greater than or equal to 1.)

[0034] In the charge transfer layer complex according to the present invention, Z in the intermediate layer compound satisfying the chemical formula 1 may be phosphorus (P).

[0035] In the charge transfer layer complex according to the present invention, n of the intermediate layer compound satisfying the chemical formula 1 may be 2.

[0036] In the charge transfer layer complex according to the present invention, the intermediate layer compound may include a pyrophosphate salt.

[0037] In the charge transfer layer complex according to the present invention, the intermediate layer compound may include potassium pyrophosphate.

[0038] In the charge transfer layer complex according to the present invention, the charge transfer layer may include an oxide.

[0039] In the charge transfer layer complex according to the present invention, the charge transfer layer is a transition metal oxide (M x O y ) may be included.

[0040] In the charge transfer layer complex according to the present invention, the charge transfer layer is tin oxide (SnO x , 0 <x≤2)을 포함할 수 있다.

[0041] In the charge transfer layer complex according to the present invention, the thickness of the intermediate layer may be 0.1 to 10 nm.

[0042] In the charge transfer layer complex according to the present invention, when the charge transfer layer complex is measured by Fourier-transform infrared spectroscopy (FT-IR), 913±10 cm -1 and 1148+10 cm -1 can have a peak at the location of .

[0043] In the charge transfer layer complex according to the present invention, the charge transfer layer complex can satisfy the following relational expression 1.

[0044] (Relationship 1)

[0045] D1> D2

[0046] (In equation 1, D1 is the transition metal oxide (M) of the charge transfer layer single thin film measured by extended X-ray absorption fine structure (EXAFS) x O y ) is the peak position (Å) for the distance between metal (M) and oxygen (O) included in the charge transfer layer complex thin film, and D2 is the transition metal oxide (M) of the charge transfer layer complex thin film measured by X-ray absorption fine structure. x O y ) is the peak position (Å) for the distance between metal (M) and oxygen (O) contained in the compound.

[0047] In the charge transfer layer complex according to the present invention, the charge transfer layer complex can satisfy the following relational expression 2 or the following relational expression 3.

[0048] (Relationship 2)

[0049] E1> E2

[0050] (In equation 2, E1 is the transition metal oxide (M) of the single thin film of the charge transfer layer x O y 3d of metal (M) contained in 3 / 2 is the peak position (eV) of the binding energy, and E2 is the 3d of the metal included in the transition metal oxide of the charge transfer layer composite thin film. 3 / 2 (This is the peak position of binding energy.)

[0051] (Relationship 3)

[0052] G1> G2

[0053] (In equation 3, G1 is the transition metal oxide (M) of the single thin film of the charge transfer layer x O y 3d of metal (M) contained in 5 / 2is the peak position (eV) of the binding energy, and G2 is the 3d of the metal included in the transition metal oxide of the charge transfer layer complex thin film. 5 / 2 (This is the peak position of binding energy.)

[0054] The present invention provides a perovskite photovoltaic device, comprising: a first electrode; the above-described charge transport layer complex positioned on the first electrode; a perovskite thin film positioned on the charge transport layer complex; and a second electrode positioned on the perovskite thin film.

[0055] In the perovskite photovoltaic device according to the present invention, the perovskite thin film may include a perovskite crystal satisfying the following chemical formula 2 or chemical formula 3.

[0056] (Chemical formula 2)

[0057] ABX3

[0058] (Chemical formula 3)

[0059] A2BX4

[0060] (In the above chemical formulas 2 and 3, A is a monovalent alkylammonium cation; a monovalent amidinium cation; Li + ; Na + ; K + ; Rb + ; Cs + ; Fr + ; Cu(I) + ; Ag(I) + and Au(I) + A compound comprising one or more monovalent cations selected from the group consisting of a combination of, B is a divalent metal cation, and X is I - , Br - , Cl - or a combination of these halogen anions.)

[0061] In the perovskite photovoltaic device according to the present invention, the thickness of the perovskite thin film may be 10 to 250 nm.

[0062] In the perovskite photovoltaic device according to the present invention, the average visible transmittance (AVT) of the thin film including the charge transfer layer complex and the perovskite thin film may be 30% or more.

[0063] In the perovskite photovoltaic device according to the present invention, the power conversion efficiency (PCE) of the perovskite photovoltaic device may be 14% or more.

[0064] In the perovskite photovoltaic device according to the present invention, the perovskite photovoltaic device is heated at 25°C, 1 atm, and 100 mW / cm 2 The photoelectric conversion efficiency when left for 300 hours in an environment under visible light irradiation can be more than 90% of the initial photoelectric conversion efficiency.

[0065]

[0066] The charge transfer layer composite according to the present invention can increase the photoelectric conversion efficiency of a perovskite photovoltaic device by reducing nonradiative recombination between interfaces, defect concentration, and surface roughness of the perovskite photovoltaic device.

[0067] The perovskite photovoltaic device according to the present invention can have high light transmittance and high photoelectric conversion efficiency.

[0068] The method for manufacturing a perovskite photovoltaic device according to the present invention can manufacture a perovskite photovoltaic device with a low manufacturing cost and high yield and efficiency.

[0069]

[0070] FIG. 1 is a diagram schematically illustrating part of a method for manufacturing a perovskite photovoltaic device according to one embodiment of the present invention.

[0071] FIG. 2 is a diagram illustrating peaks measured using Fourier-transform infrared spectroscopy (FT-IR) of a single substance of potassium pyrophosphate (KPP Powder), a charge transfer layer composite (SnO2 / KPP) of Example 1, and a tin oxide charge transfer layer (SnO2) of Comparative Example 1.

[0072] FIG. 3 is a drawing illustrating the results of measuring the tin oxide charge transfer layer (SnO2) according to Comparative Example 1 and the charge transfer layer composite (SnO2 / KPP) according to Example 1 using extended X-ray absorption fine structure (EXAFS) analysis.

[0073] FIG. 4 is a drawing showing the results of measuring the binding energy of a tin oxide charge transfer layer (SnO2) according to Comparative Example 1 and a charge transfer layer composite (SnO2 / KPP) according to Example 1 using X-ray photoelectron spectroscopy (XPS).

[0074] FIG. 5 is a drawing showing surface images of a tin oxide charge transfer layer / perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and a charge transfer layer composite / perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1, using a scanning electron microscope (SEM).

[0075] FIG. 6 is a cross-sectional image of a tin oxide charge transfer layer / perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and a charge transfer layer composite / perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1, obtained using a scanning electron microscope (SEM).

[0076] FIG. 7 is a drawing showing the X-ray diffraction peaks of a perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and a perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1 measured using X-ray diffraction (XRD).

[0077] FIG. 8 is a drawing showing the results of measuring photoluminescence (PL) of a perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and a perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1.

[0078] FIG. 9 is a diagram illustrating the carrier lifetime of a perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and a perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1 measured using Time-Correlated Single Photon Counting (TCSPC).

[0079] FIG. 10 is a drawing showing the results of measuring the optical transmittance of a tin oxide / perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and a charge transfer layer complex / perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1.

[0080] FIG. 11 is a diagram showing a short-circuit current density-open circuit voltage graph under visible light of AM 1.5G of a perovskite photovoltaic device according to Comparative Example 3 (Reference) and a perovskite photovoltaic device according to Example 3 (KPP).

[0081] FIG. 12 is a diagram showing the stability of a perovskite photovoltaic device (KPP) according to Example 3 and a perovskite photovoltaic device (Reference) according to Comparative Example 3 against an external environment.

[0082]

[0083] The embodiments described herein may be modified in various different forms, and the technology according to one embodiment is not limited to the embodiments described below. In addition, the embodiments of one embodiment are provided to more completely explain the present disclosure to a person with average knowledge in the relevant technical field. In this case, unless there is a different definition for the technical and scientific terms used, they have the meaning commonly understood by a person with ordinary skill in the technical field to which this invention belongs, and in the following description and the attached drawings, descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted.

[0084] Additionally, the singular forms used in this specification and the appended claims are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0085] Additionally, in this specification and the appended claims, the terms first, second, etc. are not used in a limiting sense, but are used for the purpose of distinguishing one component from another.

[0086] Additionally, in this specification and the appended claims, when a part such as a film (layer), region or component is said to be located “on,” “above,” “upper,” “below,” “lower,” or “lower” another part, this includes not only cases where one part is in contact with another part, but also cases where another part exists between the two parts.

[0087] In addition, the terms "about," "substantially," and the like used in this specification and the appended claims are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings stated are presented, and are used to prevent unscrupulous infringers from unfairly utilizing the disclosure in which exact or absolute values ​​are stated to aid in the understanding of this specification and the appended claims.

[0088] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes.

[0089] Furthermore, in this specification and the appended claims, terms such as “include” or “have” mean that a feature or component described in the specification is present, and unless specifically limited, do not preclude the possibility that one or more other features or components may be added.

[0090] Hereinafter, the manufacturing method of the perovskite photovoltaic device of the present invention, the charge transfer layer complex, and the perovskite photovoltaic device will be described in detail.

[0091] The present invention provides a method for manufacturing a perovskite photovoltaic device, the method for manufacturing a perovskite photovoltaic device comprising: (S1) a charge transfer layer composite manufacturing step of laminating an intermediate layer including an intermediate layer compound on a charge transfer layer; and (S2) a step of laminating a perovskite thin film on the intermediate layer; wherein the intermediate layer compound includes a repeating unit satisfying the following chemical formula 1.

[0092]

[0093] (Chemical formula 1)

[0094]

[0095] (In chemical formula 1, Z is one or more selected from the group including phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and n is a positive integer greater than or equal to 1.)

[0096]

[0097] According to one embodiment, the intermediate layer compound including a repeating unit satisfying the above chemical formula 1 may be such that Z in the above chemical formula 1 is phosphorus (P).

[0098] In addition, according to one embodiment, the intermediate layer compound including a repeating unit satisfying the chemical formula 1 may have n in the chemical formula 1 as 2.

[0099] Specifically, in the intermediate layer compound comprising a repeating unit satisfying the above chemical formula 1 according to one embodiment, n may be 1, 2, 4, 6, 8, 10, 12 or 14, and Z may be selected from the group consisting of phosphorus (P), arsenic (As), antimony (Sb) and bismuth (Bi), but as an advantageous example, the intermediate layer compound may be a compound in which n is 2 and Z is phosphorus (P), i.e., a pyrophosphate salt. When the intermediate layer compound is a pyrophosphate salt, the process cost of the method for manufacturing the perovskite photovoltaic device may be low and the photoelectric conversion efficiency of the perovskite photovoltaic device may be high, which may be advantageous. The advantageous effects when the intermediate layer compound is a pyrophosphate salt are described in detail in the charge transfer layer composite and perovskite photovoltaic device described below.

[0100] According to one embodiment, the intermediate compound may include potassium pyrophosphate. As described above, the intermediate compound may be a pyrophosphate salt. The cation that binds to the pyrophosphate group may be selected from a group including various chemical species, for example, sodium (Na), potassium (K), magnesium (Mg), and calcium (Ca). However, when the cation that binds to the pyrophosphate group is potassium (K), the pyrophosphate salt may be easily dissolved in a solvent, and there may be no chemical reaction with other components included in the perovskite photovoltaic device, which may be advantageous.

[0101] According to one embodiment, the intermediate compound may also be selected from the group comprising potassium chloride (KCl), potassium fluoride (KF), and ammonium chloride (NH4Cl). The intermediate compound described above has an effect similar to that of potassium pyrophosphate and can be used as the intermediate compound.

[0102] According to one embodiment, the charge transport layer may be a hole transport layer or an electron transport layer. The charge transport layer may be a layer laminated to separate excitons generated when light is irradiated on the perovskite thin film into electrons and holes.

[0103] As a non-limiting example, the electron transport layer may include an electron-conductive organic or inorganic material. Specifically, it may include, but is not limited to, an electron-conductive organic thin film such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), or a metal oxide such as titanium oxide, zinc oxide, indium oxide, tin oxide, tungsten oxide, niobium oxide, molybdenum oxide, magnesium oxide, zirconium oxide, strontium oxide, lanthanum oxide, vanadium oxide, aluminum oxide, yttrium oxide, gallium oxide, or a composite thereof, and may include a material commonly used for electron conduction in a conventional perovskite photovoltaic device.

[0104] In addition, as a non-limiting example, the hole transport layer may include a hole-conducting organic or inorganic material. Specifically, it may include a hole-conducting organic thin film such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) or copper phthalocyanine (CuPc), or a metal oxide such as tungsten oxide, molybdenum oxide, vanadium oxide, nickel oxide, or a composite thereof, but is not limited thereto, and may be a material layer commonly used for hole conduction in a conventional perovskite photovoltaic device.

[0105] As a preferred example, the charge transfer layer may include an oxide. As a more preferred example, the charge transfer layer may include a transition metal oxide (M x O y ) may be included. The transition metal oxide may be a non-stoichiometric transition metal oxide having an oxygen vacancy. The transition metal oxide may be an oxide in which x and y are appropriately selected from positive real numbers depending on the oxidation number of the transition metal (M).

[0106] As a non-limiting and advantageous example, the transition metal oxide included in the charge transfer layer is tin oxide (SnO x , 0 <x≤2)일 수 있다. 상기 주석산화물을 포함하는 전하전달층은 상기 중간층 화합물과 조합되어 페로브스카이트 광전소자의 높은 광전변환효율의 달성에 유리한 효과를 제공할 수 있다. 상기 유리한 효과는 하술할 실시예 및 실험예에서 상세히 서술한다. 한편, 상기 주석산화물(SnO x , 0 <x≤2)은 상기 주석(Sn)의 산화수가 4일 수 있음에 따라, 상기 산소 빈자리(oxygen vacancy)의 함유 정도에 따라 상기 x가 양의 실수에서 적절하게 선택될 수 있다.

[0107] According to one embodiment, the thickness of the perovskite thin film may be 10 to 250 nm. The thickness of the perovskite thin film may be 5 nm or more, 10 nm or more, 50 nm or more, or 100 nm or more, and an upper limit may be 1,000 nm or less, 500 nm or less, 250 nm or less, or 200 nm or less. Specifically, the thickness of the perovskite thin film may be 5 to 1,000 nm, 10 to 500 nm, or 50 to 250 nm, and advantageously, 100 to 200 nm. When the thickness of the perovskite thin film is excessively thick, the size of the perovskite crystal included in the perovskite thin film may be large and the grain boundary may be small, thereby allowing high photoelectric conversion efficiency, but the light transmittance of the perovskite photovoltaic device may be low. In addition, if the thickness of the perovskite thin film is excessively thin, the perovskite crystals included in the perovskite photovoltaic device may have small crystal sizes and excessively many crystal boundaries when irradiated with light, making it difficult to generate excitons, which may significantly reduce the photoelectric conversion efficiency. Therefore, the thickness of the perovskite thin film is advantageously appropriately selected from 100 to 200 nm, and combined with the charge transfer layer complex, high light transmittance and high photoelectric conversion efficiency can be achieved simultaneously.

[0108] According to one embodiment, the thickness of the intermediate layer may be 0.1 to 10 nm. The thickness of the intermediate layer may be 0.1 nm or more, 0.5 nm or more, 1 nm or more, or 2 nm or more, and an upper limit may be 20 nm or less, 10 nm or less, 5 nm or less, or 3 nm or less. Specifically, the thickness of the intermediate layer may be 0.1 to 20 nm, 0.5 to 10 nm, 1 to 5 nm, or 2 to 3 nm. The intermediate layer may interact with the charge transfer layer and / or the perovskite to achieve high photoelectric conversion efficiency, but the intermediate layer is a material having significantly low charge transfer ability, i.e., hole mobility or electron mobility. Accordingly, the intermediate layer may have a thin thickness within the above-described range to maintain interaction with the charge transfer layer and / or the perovskite and facilitate the transfer of electrons or holes extracted from the perovskite thin film. The electrons or holes may pass through the intermediate layer due to a tunneling effect, or may pass through a gap created when the intermediate layer is not partially applied on the charge transfer layer.

[0109] According to one embodiment, the perovskite thin film includes a perovskite crystal, and the perovskite crystal may be a three-dimensional perovskite structure satisfying the following chemical formula 2 of ABX3, or a two-dimensional planar perovskite structure satisfying the following chemical formula 3 of A2BX4.

[0110]

[0111] (Chemical formula 2)

[0112] ABX3

[0113] (Chemical formula 3)

[0114] A2BX4

[0115] (In the above chemical formulas 2 and 3, A is a monovalent alkylammonium cation; a monovalent amidinium cation; Li+ ; Na + ; K + ; Rb + ; Cs + ; Fr + ; Cu(I) + ; Ag(I) + and Au(I) + A compound comprising one or more monovalent cations selected from the group consisting of a combination of, B is a divalent metal cation, and X is I - , Br - , Cl - or a combination of these halogen anions.)

[0116]

[0117] The perovskite crystal having the structure and composition described above can exhibit a photoelectric effect when irradiated with light of a specific wavelength band depending on the band gap of the perovskite crystal, and a photoelectric device can be implemented using this.

[0118] The present invention provides a charge transfer layer complex, wherein the charge transfer layer complex comprises: a charge transfer layer; and an intermediate layer positioned on the charge transfer layer and containing an intermediate layer compound; wherein the intermediate layer compound comprises a repeating unit satisfying the following chemical formula 1.

[0119]

[0120] (Chemical formula 1)

[0121]

[0122] (In chemical formula 1, Z is one or more selected from the group including phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and n is a positive integer greater than or equal to 1.)

[0123]

[0124] In describing the above charge transfer layer complex, the charge transfer layer, the intermediate layer compound, and the charge transfer layer complex are the same as or similar to the contents described above in the method for manufacturing a perovskite photoelectric device described above, and therefore the charge transfer layer complex according to the present invention includes all the contents described above in the method for manufacturing a perovskite photoelectric device described above.

[0125] Hereinafter, the charge transfer layer complex of the present invention will be described in more detail.

[0126] According to one embodiment, when the charge transfer layer complex was measured by Fourier-transform infrared spectroscopy (FT-IR), it had a wavelength of 913±10 cm -1 and 1148+10 cm -1 It can have a peak at the location of .

[0127] In detail, as a non-limiting example, the charge transfer layer included in the charge transfer layer complex is tin oxide (SnO x , 0 <x≤2)일 수 있고, 상기 중간층은 피로인산(pyrophosphate)염을 포함할 수 있다. 이 때, 상기 피로인산염이 포함하는 P-O 및 P=O와 같은 결합이 상기 주석산화물과 상호작용하여 상기 피로인산염 단일 물질에 해당하는 피크가 나타나지 않고 상기 주석산화물 피크 위치와도 상이한 913±10 cm -1 and 1148+10 cm -1 Peaks may occur at locations.

[0128] According to one embodiment, in addition to the non-limiting example above, the position of the peak may vary depending on whether the chemical species constituting the charge transfer layer complex is different.

[0129] Accordingly, it should be understood that the charge transfer layer complex according to the present invention may generate a peak that is different from the peak position measured for the charge transfer layer single material using Fourier transform infrared spectroscopy; and the peak position measured for the intermediate layer using Fourier transform infrared spectroscopy; due to the interaction between the charge transfer layer and the intermediate layer.

[0130] According to one embodiment, the charge transfer layer complex can satisfy the following relationship 1.

[0131]

[0132] (Relationship 1)

[0133] D1> D2

[0134] (In equation 1, D1 is the transition metal oxide (M) of the charge transfer layer single thin film measured by extended X-ray absorption fine structure (EXAFS) x O y ) is the peak position (Å) for the distance between metal (M) and oxygen (O) included in the charge transfer layer complex thin film, and D2 is the transition metal oxide (M) of the charge transfer layer complex thin film measured by X-ray absorption fine structure. x O y ) is the peak position (Å) for the distance between metal (M) and oxygen (O) contained in the compound.

[0135]

[0136] What the above relational expression 1 means is that the transition metal oxide (M) contained in the charge transfer layer complex x O y ) may mean that the number of defects, such as oxygen vacancies, contained in the charge transfer layer is less than that of the single thin film.

[0137] Specifically, when the intermediate layer is positioned on the single thin film of the charge transfer layer and the charge transfer layer and the intermediate layer come into contact, the intermediate layer compound included in the intermediate layer can coordinate to the under-coordinated portion of the charge transfer layer to remove defects such as the oxygen vacancy. Therefore, the charge transfer layer complex may have fewer defects than the charge transfer layer and may have high charge transfer characteristics and / or high optoelectronic properties. Accordingly, the charge transfer layer complex may satisfy the above relational expression 1, thereby enabling the perovskite photovoltaic device to have high photoelectric conversion efficiency.

[0138] According to one embodiment, the charge transfer layer complex can satisfy the following relationship 2 or the following relationship 3.

[0139]

[0140] (Relationship 2)

[0141] E1> E2

[0142] (In equation 2, E1 is the transition metal oxide (M) of the single thin film of the charge transfer layer x O y 3d of metal (M) contained in 3 / 2 is the peak position (eV) of the binding energy, and E2 is the 3d of the metal included in the transition metal oxide of the charge transfer layer composite thin film. 3 / 2 (This is the peak position of binding energy.)

[0143]

[0144] (Relationship 3)

[0145] G1> G2

[0146] (In equation 3, G1 is the transition metal oxide (M) of the single thin film of the charge transfer layer x O y 3d of metal (M) contained in 5 / 2is the peak position (eV) of the binding energy, and G2 is the 3d of the metal included in the transition metal oxide of the charge transfer layer complex thin film. 5 / 2 (This is the peak position of binding energy.)

[0147]

[0148] What the above equations 2 and 3 mean is that the charge transfer layer complex includes a transition metal oxide (M x O y ) may mean that the transition metal (M) contained in it has a high oxidation number.

[0149] As a non-limiting example, the transition metal oxide is tin oxide (SnO x , 0 <x≤2)일 수 있다. 또한, 상기 주석산화물이 포함하는 주석 원자의 산화수는 산소 빈자리(oxygen vacancy)로 인하여 +2 또는 +4일 수 있다. 이 때, 상기 전하전달층 복합체가 포함하는 +4가 주석 원자 / +2가 주석원자의 비(Sn 4+ / Sn 2+ ); is the ratio of +4-valent tin atoms / +2-valent tin atoms contained in the single thin film of the charge transfer layer (Sn 4+ / Sn 2+ ); may be greater. This may be an effect generated by the charge transfer layer interacting with the intermediate layer. Therefore, the charge transfer layer complex may have fewer defects than the charge transfer layer and may have high charge transfer characteristics and / or high optoelectronic properties. Therefore, the charge transfer layer complex may satisfy the above equation 2 or equation 3, thereby enabling the perovskite photoelectric element to have high photoelectric conversion efficiency. The equation 2 or equation 3 may be the transition metal oxide (M x O y ) can be satisfied by appropriately selecting either equation 2 or equation 3 depending on the chemical species of the transition metal included.

[0150] The present invention provides a perovskite photovoltaic device, comprising: a first electrode; the above-described charge transport layer complex positioned on the first electrode; a perovskite thin film positioned on the charge transport layer complex; and a second electrode positioned on the perovskite thin film.

[0151] In describing the above perovskite photoelectric device, the charge transfer layer complex and the perovskite thin film are the same as or similar to the contents described above in the method for manufacturing a perovskite photoelectric device and the charge transfer layer complex, and therefore the perovskite photoelectric device according to the present invention includes all contents described above in the method for manufacturing a perovskite photoelectric device and the charge transfer layer complex.

[0152] Hereinafter, the perovskite photovoltaic device of the present invention will be described in more detail.

[0153] According to one embodiment, the first electrode may be a conductive electrode that is ohmic-bonded with the perovskite thin film and / or the charge transfer layer complex. As a non-limiting example, the first electrode may be a transparent conductive electrode, and the transparent conductive electrode may be at least one selected from the group consisting of fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), zinc oxide, carbon nanotubes, graphene, and combinations thereof, but the present invention is not limited thereto.

[0154] According to one embodiment, the second electrode may be a conductive electrode that is ohmic-contacted with the perovskite thin film, and may have a different work function from the first electrode so that electrons and holes generated by the photoelectric effect in the perovskite thin film can be transferred to the first electrode and the second electrode, respectively, to generate a photocurrent. As a non-limiting example, the second electrode may be at least one selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), copper (Cu), aluminum (Al), carbon, cobalt sulfide, copper sulfide, nickel oxide, and combinations of these compounds, but the present invention is not limited thereto.

[0155] According to one embodiment, the first electrode and the second electrode may be transparent conductive electrodes. The perovskite photovoltaic device according to the present invention may have a high average visible transmittance (AVT), and therefore, the first electrode and the second electrode may also be configured as transparent conductive electrodes, so that the visible light transmittance of the entire perovskite photovoltaic device may be high.

[0156] According to one embodiment, the average visible transmittance (AVT) of a thin film including the charge transfer layer complex; and the perovskite thin film; may be 30% or more. The thin film including the charge transfer layer complex; and the perovskite thin film; refers to a composite thin film in which the perovskite thin film is positioned on the charge transfer layer complex. The average visible transmittance of the composite thin film may be 20% or more, 25% or more, 30% or more, or 35% or more, and an upper limit may be 80% or less, 70% or less, 60% or less, or 50% or less. Specifically, the average visible transmittance of the composite thin film may be 20 to 80%, 25 to 70%, 30 to 60%, or 35 to 50%. The composite thin film may include the charge transfer layer complex described above; and thin perovskite films; can have high visible light transmittance.

[0157] The above visible light may refer to light in the wavelength band of 380 to 780 nm, and specifically, may refer to light in the wavelength band of 400 to 700 nm.

[0158] According to one embodiment, the power conversion efficiency (PCE) of the perovskite photovoltaic device may be 14% or more. The power conversion efficiency of the perovskite photovoltaic device may vary depending on the thickness of the perovskite thin film included in the perovskite photovoltaic device, the chemical species included in the perovskite thin film, and the chemical species included in the charge transfer layer complex. However, the perovskite photovoltaic device may have a high average visible transmittance (AVT) within the above-described range, and at the same time, the power conversion efficiency may be 14% or more, 15% or more, or 16% or more, and an upper limit may be 30% or less, 25% or less, or 20% or less. Specifically, the perovskite photovoltaic device may have a high visible light transmittance within the above-described range and a photoelectric conversion efficiency of 14 to 30%, 15 to 25%, or 16 to 20%.

[0159] According to one embodiment, when the perovskite photovoltaic device is left in an environment of 25°C, 1 atm, and 100 mW / cm2 of visible light irradiation for 300 hours, the power conversion efficiency (PCE) may be 90% or more of the initial photovoltaic efficiency. The perovskite photovoltaic device may have a high average visible transmittance (AVT) within the above-described range, and at the same time, the photovoltaic efficiency under the above-described conditions may be 70% or more, 80% or more, or 90% or more of the initial photovoltaic efficiency, and an upper limit may be 99% or less, 98% or less, or 95% or less. Specifically, the perovskite photovoltaic device may have a high visible light transmittance within the above-described range, and at the same time, the photoelectric conversion efficiency under the above-described conditions may be 70 to 99%, 80 to 98%, or 90 to 95% of the initial photoelectric conversion efficiency. The perovskite photovoltaic device according to one embodiment may have high external environmental stability by combining the charge transfer layer complex and the perovskite thin film described above. The external environment may be stability against temperature, humidity, and light irradiation.

[0160] According to one embodiment, a second charge transfer layer may be further laminated on the upper portion of the perovskite thin film included in the perovskite photovoltaic device; and on the lower portion of the second electrode. The second charge transfer layer may include a material that extracts and moves carriers different from the charge transfer layer included in the charge transfer layer complex.

[0161] As a non-limiting example, when the charge transfer layer included in the charge transfer layer complex is a hole transport layer, the second charge transfer layer may be an electron transport layer. Furthermore, as a non-limiting example, when the charge transfer layer included in the charge transfer layer complex is an electron transport layer, the second charge transfer layer may be a hole transport layer.

[0162] According to one embodiment, the second charge transfer layer can separate excitons generated when light is irradiated on the perovskite thin film and extract electrons or holes more quickly, thereby further increasing the power conversion efficiency (PCE) of the perovskite photovoltaic device. In addition, the second charge transfer layer can also encapsulate the charge transfer layer complex and / or the perovskite thin film to increase the external environmental stability of the perovskite photovoltaic device.

[0163] According to one embodiment, the electron transport layer included in the second charge transport layer may be an electron-conductive organic or inorganic material. Specifically, it may be an electron-conductive organic thin film such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), or a metal oxide thin film such as titanium oxide, zinc oxide, indium oxide, tin oxide, tungsten oxide, niobium oxide, molybdenum oxide, magnesium oxide, zirconium oxide, strontium oxide, lanthanum oxide, vanadium oxide, aluminum oxide, yttrium oxide, gallium oxide, or a composite thereof, but is not limited thereto, and any material layer commonly used for electron conduction in a conventional perovskite photovoltaic device may suffice.

[0164] According to one embodiment, the hole transport layer included in the second charge transport layer may be a hole-conducting organic or inorganic material. Specifically, it may be a hole-conducting organic thin film such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) or copper phthalocyanine (CuPc), or a metal oxide thin film such as tungsten oxide, molybdenum oxide, vanadium oxide, nickel oxide, or a composite thereof, but is not limited thereto, and any material layer commonly used for hole conduction in a conventional perovskite photovoltaic device may suffice.

[0165] According to one embodiment, the second charge transfer layer may be formed of an appropriate chemical species or have a thickness that can be adjusted to satisfy the average visible transmittance (AVT) of the perovskite photovoltaic device described above.

[0166] According to one embodiment, the photoelectric device may be any of various photoelectric devices used in the art as photoelectric devices, such as a solar cell, a photodetector, a photodetector, and a phototransistor. As an advantageous example, the photoelectric device may be a solar cell.

[0167]

[0168] Hereinafter, specific examples and experimental examples will be described. However, the examples and experimental examples described below are only illustrative, and the technology described in this specification is not limited thereto.

[0169]

[0170] (Example 1)

[0171] A 2.5 cm x 2.5 cm glass substrate with an indium tin oxide (ITO) electrode was used as the substrate. The substrate was cleaned with a glass cleaner (HELLMANEX_ll, Hellma GmbH & Co. KG), acetone, and isopropyl alcohol (IPA), and surface-treated using argon plasma (Ar plasma) for 15 minutes.

[0172] A tin oxide solution was prepared by dissolving tin chloride hydrate (SnCl22H2O) in deionized water (DI-water) at a concentration of 2.5 wt%. The tin oxide solution was dropped onto the substrate, spin-coated at 3000 rpm for 30 seconds, and heat-treated at 150°C for 1 hour to prepare a tin oxide charge transfer layer on the indium tin oxide electrode.

[0173] A 13 mM intermediate layer compound solution was prepared by dissolving 4 mg of potassium pyrophosphate (KPP) in 1 ml of deionized water (DI-water). The intermediate layer compound solution was dropped onto the tin oxide charge transfer layer, spin-coated at 3000 rpm for 30 seconds, and heat-treated at 100°C for 3 minutes to laminate the intermediate layer, thereby laminating a charge transfer layer composite, which is a charge transfer layer-intermediate layer composite thin film.

[0174] A perovskite precursor solution was prepared by dissolving 800 mg of formamidinium lead iodide (FAPbI3), 300 mg of methylammonium chloride (MACl), and 300 mg of methylammonium lead bromide (MAPbBr3) in a mixed solvent of 0.8 ml of dimethylformamide (N-dimethylformamide; DMF) and 0.1 ml of dimethylsulfoxide (DMSO), and then diluting the solution in a 1:3 ratio in a mixed solvent of 0.8 ml of dimethylformamide and 0.1 ml of dimethylsulfoxide. That is, the perovskite precursor solution used was 3.2 ml of dimethylformamide and 0.4 ml of dimethylsulfoxide.

[0175] The perovskite precursor solution was applied by spin coating onto the intermediate layer. The spin coating was performed sequentially at 500 rpm for 5 seconds, 1000 rpm for 8 seconds, and 5000 rpm for 2 seconds. The time required to reach the spin coating rotation speeds of 500 rpm and 1000 rpm was 1 second, and the time required to reach the spin coating rotation speed of 5000 rpm was 2 seconds. 17 seconds after the start of the spin coating, i.e., immediately after the spin coating rotation speed reached 5000 rpm; and onto the perovskite precursor solution positioned on the intermediate layer; 0.5 ml of ethyl acetate was dropped during the spin coating and spin coating was completed. Thereafter, the perovskite precursor solution was heat-treated at 150°C for 5 minutes to complete the deposition of a perovskite thin film on the intermediate layer. The thickness of the perovskite thin film was confirmed to be 150 nm.

[0176] A second charge transfer layer mixture solution was prepared by dissolving 100 mg of spiro-OMeTAD (2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene), 23 μL of lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) (1.8 M in acetonitrile), 39 μL of tetrabutylpyridine (4-tert-butylpyridine; tBP), and 10 μL of 4 Co(III) TFSI solution (0.25 M in acetonitrile) in 1.1 mL of chlorobenzene.

[0177] The second charge transfer layer mixture solution was dropped onto the perovskite thin film, and then spin-coated at 3000 rpm for 30 seconds to deposit the second charge transfer layer on the perovskite thin film.

[0178] Molybdenum oxide (MoO) on the second charge transfer layer x , 0 <x≤3) 10 nm를 물리기상증착(physical vapor deposition; PVD)법을 사용하여 증착하여 상기 제2전하전달층 상에 몰리브덴산화물층을 적층하였다.

[0179] A perovskite photovoltaic device was manufactured by depositing 150 nm of indium tin oxide (ITO) on the molybdenum oxide layer using a sputtering method.

[0180]

[0181] (Example 2)

[0182] In Example 1, 10 mg of poly(triaryl amine); PTAA (Mw 110 kDa, MS solution, MSS-E03112-N22) and 2.5 mg of alkylammonium bis(trifluoromethylsulfonyl)imide; OA-TFSI were dissolved in 1 ml of toluene to prepare a second charge transfer layer mixture solution, and the second charge transfer layer mixture solution was dropped onto the perovskite thin film, followed by spin-coating at 3000 rpm for 30 seconds to deposit the second charge transfer layer on the perovskite thin film, with the exception that a perovskite photovoltaic device was manufactured in the same manner as in Example 1.

[0183]

[0184] (Example 3)

[0185] In Example 1, a perovskite photovoltaic device was manufactured using the same method as in Example 1, except that gold (Au) was deposited 80 nm thick on the molybdenum oxide layer using a physical vapor deposition (PVD) method instead of indium tin oxide.

[0186]

[0187] (Example 4)

[0188] In Example 2, a perovskite photovoltaic device was manufactured in the same manner as in Example 2, except that gold (Au) was deposited 80 nm thick on the molybdenum oxide layer by physical vapor deposition (PVD) instead of indium tin oxide.

[0189]

[0190] (Comparative Example 1)

[0191] In Example 1, a perovskite photovoltaic device was manufactured in the same manner as in Example 1, except that a perovskite thin film was deposited directly on the tin oxide electron transport layer without depositing a potassium pyrophosphate (KPP) intermediate layer.

[0192]

[0193] (Comparative Example 2)

[0194] In Example 2, a perovskite photovoltaic device was manufactured in the same manner as in Example 2, except that a perovskite thin film was deposited directly on the tin oxide electron transport layer without depositing a potassium pyrophosphate (KPP) intermediate layer.

[0195]

[0196] (Comparative Example 3)

[0197] In Example 3, a perovskite photovoltaic device was manufactured in the same manner as in Example 3, except that a perovskite thin film was deposited directly on the tin oxide electron transport layer without depositing a potassium pyrophosphate (KPP) intermediate layer.

[0198]

[0199] (Comparative Example 4)

[0200] In Example 4, a perovskite photovoltaic device was manufactured in the same manner as in Example 4, except that a perovskite thin film was deposited directly on the tin oxide electron transport layer without depositing a potassium pyrophosphate (KPP) intermediate layer.

[0201]

[0202] (Experimental Example 1)

[0203] Using Fourier-transform infrared spectroscopy (FT-IR), the peaks of potassium pyrophosphate (KPP Powder) single substance, the charge transfer layer composite (SnO2 / KPP) of Example 1, and the tin oxide charge transfer layer (SnO2) of Comparative Example 1 were measured and shown in Fig. 2.

[0204] Referring to Figure 2, the potassium pyrophosphate single substance (KPP Powder) has a wavelength of 900±10 to 1100±10 cm when measured by Fourier transform infrared spectroscopy. -1 PO4 at the location of 3- With a vibration peak of 500±10 to 800±10 cm -1 P2O7 at the location 4- It has a vibration peak of 709±10 cm -1 It was confirmed that the POP bridge had a vibration peak at the location.

[0205] In addition, when the tin oxide charge transfer layer (SnO2) according to Comparative Example 1 was measured using Fourier transform infrared spectroscopy, it was confirmed to have a peak as shown in Fig. 2.

[0206] On the other hand, the charge transfer layer composite (SnO2 / KPP) according to Example 1 showed almost no peak corresponding to potassium pyrophosphate when measured by Fourier transform infrared spectroscopy and showed a peak at 913 cm -1 and 1146 cm -1 It was confirmed that a peak appeared in (* in the right image of Figure 2).

[0207] This is thought to be because the bonding groups such as PO and / or P=O of the potassium pyrophosphate interact with the tin oxide charge transfer layer (SnO2) to stabilize the vibrational modes existing in the potassium pyrophosphate single material. Accordingly, it can be seen that the potassium pyrophosphate is bonded to the tin oxide charge transfer layer, and it is thought that the potassium pyrophosphate is coordinately or covalently bonded to the oxygen vacancy and / or defect included in the tin oxide.

[0208]

[0209] (Experimental Example 2)

[0210] The tin oxide charge transfer layer (SnO2) according to Comparative Example 1 and the charge transfer layer composite (SnO2 / KPP) according to Example 1 were measured using extended X-ray absorption fine structure (EXAFS) analysis, and the results are shown in FIG. 3.

[0211] Referring to FIG. 3, the radial distance (Sn-O) between tin and oxygen of the tin oxide charge transfer layer (SnO2) according to Comparative Example 1 was found to be 2.06 Å, but the radial distance (Sn-O) between tin and oxygen of the charge transfer layer composite (SnO2 / KPP) according to Example 1 was confirmed to be 1.90 Å.

[0212] This is the ratio of SnO2 / SnO in the tin oxide charge transfer layer structure included in the charge transfer layer composite according to Example 1, i.e., Sn 4+ / Sn 2+ The ratio of SnO2 / SnO of the single thin film of tin oxide charge transfer layer according to Comparative Example 1, i.e., Sn 4+ / Sn 2+This means that the ratio is higher than that of the intermediate layer compound. Therefore, it is thought that the intermediate layer compound coordinates to the oxygen vacancy and / or defect of the tin oxide charge transfer layer to improve the optoelectronic properties of the device.

[0213]

[0214] (Experimental Example 3)

[0215] The binding energy of the tin oxide charge transfer layer (SnO2) according to Comparative Example 1 and the charge transfer layer composite (SnO2 / KPP) according to Example 1 was measured using X-ray photoelectron spectroscopy (XPS), and the results are shown in Fig. 4.

[0216] Referring to Fig. 4, Sn 3d of the tin oxide charge transfer layer (SnO2) according to Comparative Example 1 3 / 2 (495±0.5 eV) and Sn 3d 5 / 2 (468±0.5 eV) compared to the binding energy of Sn 3d of the charge transfer layer composite (SnO2 / KPP) according to Example 1 5 / 2 and Sn 3d 5 / 2 It was confirmed that the binding energy increased (shifted).

[0217] As described above, this is Sn within the tin oxide charge transfer layer structure included in the charge transfer layer complex. 4+ / Sn 2+ The ratio of the Sn to the tin oxide charge transfer layer single thin film 4+ / Sn 2+ This means that the ratio is higher than that of the tin oxide charge transfer layer. Therefore, it is thought that the intermediate layer compound improves the optoelectronic properties of the device by coordinating to the oxygen vacancy and / or defect of the tin oxide charge transfer layer.

[0218]

[0219] (Experimental Example 4)

[0220] Surface images and cross-sectional images of the tin oxide charge transfer layer / perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and the charge transfer layer composite / perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1 were obtained using a scanning electron microscope (SEM) and are shown in FIGS. 5 and 6, respectively.

[0221] Referring to FIG. 5, it was confirmed that the perovskite thin film laminated on the tin oxide charge transfer layer according to Comparative Example 1 had perovskite crystals formed in a small size of 200 to 400 nm, thereby creating numerous grain boundaries.

[0222] On the other hand, it was confirmed that the crystal grain size of the perovskite thin film laminated on the charge transfer layer composite according to Example 1 was larger than that of the perovskite thin film laminated on the tin oxide charge transfer layer according to Comparative Example 1.

[0223] Referring to FIG. 6, it was confirmed that the perovskite thin film laminated on the charge transfer layer composite according to Example 1 had a lower perovskite surface roughness than the perovskite thin film laminated on the tin oxide charge transfer layer according to Comparative Example 1. This is thought to be because, in addition to the carrier movement of the perovskite thin film itself, the carrier movement at the interface of the second charge transfer layer or the second electrode in contact with the perovskite thin film also becomes smooth, which is the cause of the improvement in the photoelectric conversion efficiency of the perovskite photovoltaic device.

[0224]

[0225] (Experimental Example 5)

[0226] The X-ray diffraction peaks of the perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and the perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1 were measured using X-ray diffraction (XRD) analysis, and are shown in Fig. 7.

[0227] The diffraction peak of the perovskite crystal appeared at 14±0.1°, and the peak of non-crystallized lead iodide (PbI2) appeared at 11.4±0.1°.

[0228] Referring to FIG. 7, it was confirmed that the intensity of the X-ray diffraction peak of the perovskite crystal of the perovskite thin film according to Example 1 was about 5 times greater than that of the perovskite thin film according to Comparative Example 1. In addition, it was confirmed that the perovskite thin film according to Example 1 exhibited a larger lead iodide (PbI2) peak than that of the perovskite thin film according to Comparative Example 1.

[0229] This is thought to be because the perovskite thin film according to Example 1 has improved crystallinity due to a larger grain size and fewer crystal defects. In addition, the lead iodide peak is thought to be a result of the intermediate compound, potassium pyrophosphate, preventing the formation of lead iodide by preventing thermal decomposition that occurs during the heat treatment of the perovskite thin film.

[0230]

[0231] (Experimental Example 6)

[0232] The photoluminescence (PL) of the perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and the perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1 was measured and shown in Fig. 8. The photoluminescence refers to steady-state photoluminescence (ssPL).

[0233] Referring to FIG. 8, it was confirmed that the photoluminescence peak of the perovskite thin film according to Example 1 was about 3 times higher than the photoluminescence peak of the perovskite thin film according to Comparative Example 1.

[0234] This is thought to be a result of the perovskite thin film according to Example 1 reducing carrier loss through prevention of nonradiative recombination and maintaining a higher carrier generation density compared to the perovskite thin film according to Comparative Example 1.

[0235]

[0236] (Experimental Example 7)

[0237] The carrier lifetimes of the perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and the perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1 were measured using Time-Correlated Single Photon Counting (TCSPC), and the results are shown in Fig. 9.

[0238] Referring to FIG. 9, it was confirmed that the perovskite thin film according to Example 1 had a carrier lifetime that was increased by more than three times at low fluence compared to the perovskite thin film according to Comparative Example 1.

[0239] This is thought to be a result of the perovskite thin film according to Example 1 having a reduced nonradiative recombination channel compared to the perovskite thin film according to Comparative Example 1.

[0240]

[0241] (Experimental Example 8)

[0242] The optical transmittance of the tin oxide / perovskite thin film (SnO2 / Perovskite) according to Comparative Example 1 and the charge transfer layer complex / perovskite thin film (SnO2 / KPP / Perovskite) according to Example 1 was measured and is shown in Fig. 10.

[0243] Due to the extremely thin thickness of the potassium pyrophosphate, the difference in transmittance between the two samples was extremely minimal. Furthermore, due to the thin thickness of the perovskite film, the average visible transmittance (AVT) in the visible light range of 400 to 700 nm was confirmed to be approximately 39% for both samples.

[0244]

[0245] (Experimental Example 9)

[0246] The short-circuit current density-open circuit voltage graphs of the perovskite photovoltaic device according to Comparative Example 3 (Reference) and the perovskite photovoltaic device according to Example 3 (KPP) under visible light of AM 1.5G are shown in Fig. 11. Fo represents forward voltage application (forward scan), and Re represents reverse voltage application (reverse scan). In addition, the average reverse-forward performance indices of the perovskite photovoltaic device are shown in Table 1 below.

[0247]

[0248] Short-circuit current density (J sc )(mA / cm 2 ) Open circuit voltage (V) oc )(V)Fill factor(FF)(%)Photoelectric conversion efficiency(PCE)(%)Example 116.71.1880.015.8Comparative example 114.81.0679.812.5

[0249]

[0250] Referring to FIG. 11 and Table 1, the perovskite photovoltaic device according to Example 1 has a higher open circuit voltage (V) compared to the perovskite photovoltaic device according to Comparative Example 1. oc ) was confirmed. This is thought to be an effect that occurs due to the suppression of nonradiative recombination of the perovskite photovoltaic device according to Example 1. In addition, as described above in the experimental example, the short circuit current density (J) was increased due to the increase in carrier lifespan, photoluminescence efficiency, and decrease in surface roughness. sc ) and fill factor (FF) increased, thereby increasing the power conversion efficiency (PCE).

[0251] In addition, the reason why the perovskite photovoltaic device according to Example 1 exhibits a high fill factor (FF) and low hysteresis is thought to be because the nucleation of the perovskite thin film is smoothly performed by the charge transfer layer complex, resulting in low surface roughness and a decrease in interfacial resistance between each thin film.

[0252]

[0253] (Experimental Example 9)

[0254] The stability of the perovskite photovoltaic device (KPP) according to Example 3 and the perovskite photovoltaic device (Reference) according to Comparative Example 3 to the external environment was measured and shown in Fig. 12. Each perovskite photovoltaic device was continuously irradiated with light of AM 1.5 in an open atmosphere at a temperature of 35 to 40°C, and the change in power conversion efficiency (PCE) was measured.

[0255] Referring to Fig. 12, the perovskite photovoltaic device according to Comparative Example 1 maintained 83% of the initial photoelectric conversion efficiency after 300 hours, but the perovskite photovoltaic device according to Example 1 maintained 95% of the initial photoelectric conversion efficiency, confirming excellent stability.

[0256] This is thought to be a result of potassium pyrophosphate preventing the formation of lead oxide (PbO), which can affect the long-term stability of perovskite photovoltaic devices, while maintaining a strong interaction between the tin oxide charge transfer layer (SnO2) and the perovskite thin film.

[0257]

[0258] Although the present invention has been described in this specification with specific details and limited examples, these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on this description.

[0259] Therefore, the ideas described in this specification should not be limited to the described embodiments, and all things that are equivalent or equivalent to the claims described below as well as the claims are considered to fall within the scope of the ideas described in this specification.

Claims

1. (S1) A charge transfer layer complex manufacturing step of laminating an intermediate layer including an intermediate layer compound on a charge transfer layer; and (S2) a step of laminating a perovskite thin film on the intermediate layer; including; A method for manufacturing a perovskite photovoltaic device, wherein the intermediate layer compound comprises a repeating unit satisfying the following chemical formula 1. (Chemical formula 1) (In chemical formula 1, Z is one or more selected from the group including phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and n is a positive integer greater than or equal to 1.) 2. In paragraph 1, A method for manufacturing a perovskite photovoltaic device, wherein Z in the intermediate layer compound satisfying the above chemical formula 1 is phosphorus (P).

3. In paragraph 1, A method for manufacturing a perovskite photoelectric element, wherein n of the intermediate layer compound satisfying the above chemical formula 1 is 2.

4. In paragraph 1, A method for manufacturing a perovskite photovoltaic device, wherein the intermediate layer compound comprises a pyrophosphate salt.

5. In paragraph 1, A method for manufacturing a perovskite photovoltaic device, wherein the intermediate layer compound comprises potassium pyrophosphate.

6. In paragraph 1, A method for manufacturing a perovskite photovoltaic device, wherein the charge transfer layer comprises an oxide.

7. In paragraph 1, The above charge transfer layer is a transition metal oxide (M x O y ) and a method for manufacturing a perovskite photovoltaic device.

8. In paragraph 1, The above charge transfer layer is tin oxide (SnO x , 0 <x≤2)을 포함하는, 페로브스카이트 광전소자의 제조방법.

9. In paragraph 1, A method for manufacturing a perovskite photovoltaic device, wherein the thickness of the perovskite thin film is 10 to 250 nm.

10. In paragraph 1, A method for manufacturing a perovskite photovoltaic device, wherein the thickness of the intermediate layer is 0.1 to 10 nm.

11. In paragraph 1, A method for manufacturing a perovskite photoelectric device, wherein the perovskite thin film comprises a perovskite crystal satisfying the following chemical formula 2 or chemical formula 3. (Chemical formula 2) ABX3 (Chemical formula 3) A2BX4 (In the above chemical formulas 2 and 3, A is a monovalent alkylammonium cation; a monovalent amidinium cation; Li + ; Na + ; K + ; Rb + ; Cs + ; Fr + ; Cu(I) + ; Ag(I) + and Au(I) + A compound comprising one or more monovalent cations selected from the group consisting of a combination of, B is a divalent metal cation, and X is I - , Br - , Cl - or a combination of these halogen anions.) 12. A charge transfer layer; and an intermediate layer positioned on the charge transfer layer and containing an intermediate layer compound; A charge transfer layer complex, wherein the intermediate layer compound comprises a repeating unit satisfying the following chemical formula 1. (Chemical formula 1) (In chemical formula 1, Z is one or more selected from the group including phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and n is a positive integer greater than or equal to 1.) 13. In paragraph 12, A charge transfer layer complex, wherein Z in the intermediate layer compound satisfying the above chemical formula 1 is phosphorus (P).

14. In paragraph 12, A charge transfer layer complex, wherein n is 2 in the intermediate layer compound satisfying the above chemical formula 1.

15. In paragraph 12, The above intermediate layer compound is a charge transfer layer complex comprising a pyrophosphate salt.

16. In paragraph 12, A charge transfer layer complex wherein the intermediate layer compound comprises potassium pyrophosphate.

17. In paragraph 12, A charge transfer layer complex, wherein the charge transfer layer comprises an oxide.

18. In paragraph 12, The above charge transfer layer is a transition metal oxide (M x O y ) comprising a charge transfer layer complex.

19. In paragraph 12, The above charge transfer layer is tin oxide (SnO x , 0 <x≤2)을 포함하는, 전하전달층 복합체.

20. In paragraph 12, A charge transfer layer complex, wherein the thickness of the intermediate layer is 0.1 to 10 nm.

21. In paragraph 12, When the charge transfer layer complex was measured by Fourier-transform infrared spectroscopy (FT-IR), 913±10 cm -1 and 1148+10 cm -1 A charge transfer layer complex having a peak at the position of .

22. In paragraph 18, The above charge transfer layer complex is a charge transfer layer complex that satisfies the following relational expression 1. (Relationship 1) D1> D2 (In equation 1, D1 is the transition metal oxide (M) of the charge transfer layer single thin film measured by extended X-ray absorption fine structure (EXAFS) x O y ) is the peak position (Å) for the distance between metal (M) and oxygen (O) included in the charge transfer layer composite thin film, and D2 is the transition metal oxide (M) of the charge transfer layer composite thin film measured by X-ray absorption fine structure. x O y ) is the peak position (Å) for the distance between metal (M) and oxygen (O) contained in the compound.

23. In paragraph 18, The above charge transfer layer complex is a charge transfer layer complex that satisfies the following relational expression 2 or the following relational expression 3. (Relationship 2) E1> E2 (In equation 2, E1 is the transition metal oxide (M) of the single thin film of the charge transfer layer x O y 3d of metal (M) contained in 3 / 2 is the peak position (eV) of the binding energy, and E2 is the 3d of the metal included in the transition metal oxide of the charge transfer layer composite thin film. 3 / 2 (This is the peak position of binding energy.) (Relationship 3) G1> G2 (In equation 3, G1 is the transition metal oxide (M) of the single thin film of the charge transfer layer x O y 3d of metal (M) contained in 5 / 2 is the peak position (eV) of the binding energy, and G2 is the 3d of the metal included in the transition metal oxide of the charge transfer layer complex thin film. 5 / 2 (This is the peak position of binding energy.) 24. First electrode; A charge transfer layer complex according to any one of claims 12 to 23 positioned on the first electrode; A perovskite thin film positioned on the charge transfer layer complex; and A perovskite photovoltaic device comprising a second electrode positioned on the perovskite thin film.

25. In paragraph 24, A perovskite photovoltaic device, wherein the perovskite thin film comprises a perovskite crystal satisfying the following chemical formula 2 or chemical formula 3. (Chemical formula 2) ABX3 (Chemical formula 3) A2BX4 (In the above chemical formulas 2 and 3, A is a monovalent alkylammonium cation; a monovalent amidinium cation; Li + ; Na + ; K + ; Rb + ; Cs + ; Fr + ; Cu(I) + ; Ag(I) + and Au(I) + A compound comprising one or more monovalent cations selected from the group consisting of a combination of, B is a divalent metal cation, and X is I - , Br - , Cl - or a combination of these halogen anions.) 26. In paragraph 24, A perovskite photovoltaic device, wherein the thickness of the perovskite thin film is 10 to 250 nm.

27. In paragraph 24, A perovskite photovoltaic device, wherein the average visible transmittance (AVT) of the thin film including the charge transfer layer complex and the perovskite thin film is 30% or more.

28. In paragraph 27, A perovskite photovoltaic device having a power conversion efficiency (PCE) of 14% or more.

29. In paragraph 27, The above perovskite photovoltaic device was subjected to a test at 25°C, 1 atm, and 100 mW / cm 2 A perovskite photovoltaic device whose photoelectric conversion efficiency is more than 90% of the initial photoelectric conversion efficiency when left in an environment under visible light irradiation for 300 hours.

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