WO2024039134A1 - Cellule solaire en pérovskite comprenant une couche d'interface et son procédé de fabrication - Google Patents

Cellule solaire en pérovskite comprenant une couche d'interface et son procédé de fabrication Download PDF

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WO2024039134A1
WO2024039134A1 PCT/KR2023/011816 KR2023011816W WO2024039134A1 WO 2024039134 A1 WO2024039134 A1 WO 2024039134A1 KR 2023011816 W KR2023011816 W KR 2023011816W WO 2024039134 A1 WO2024039134 A1 WO 2024039134A1
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solar cell
layer
perovskite solar
perovskite
transport layer
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Korean (ko)
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전남중
신성식
유정완
김영윤
김범수
홍순일
박은영
이진원
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한국화학연구원
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a perovskite solar cell including an interfacial layer and a method of manufacturing the same.
  • the present invention relates to a perovskite solar cell including an interfacial layer and a heat treatment process for forming a perovskite light absorption layer.
  • the present invention relates to a perovskite solar cell that can be heat treated even at high temperatures without deteriorating efficiency, thereby improving durability and photoelectric conversion efficiency, and a method of manufacturing the same.
  • Organometallic halides with a perovskite structure also referred to as organic-inorganic perovskite compounds or organometal halide perovskite compounds, contain an organic cation (A), a metal cation (M), and a halogen anion. It is composed of (X) and is a substance represented by the chemical formula of AMX3.
  • Perovskite compounds have high absorbance in the visible light range and can generate sufficient charge even in thin films. In addition, electrons and holes can be effectively separated due to the high extinction coefficient and small exciton binding energy, and it can be manufactured through a low-temperature process, which is economically advantageous.
  • titanium oxide was mainly used as the electron transport layer of perovskite solar cells, but tin oxide has a wider band gap than titanium oxide, high light transmittance in visible light, high electron mobility, excellent stability, non-toxicity, and perovskite. It is attracting attention as a material for the electron transport layer of high-efficiency perovskite solar cells because it has the advantages of better energy alignment with the layer and low-temperature processing.
  • the purpose is to provide a method for manufacturing a low-level solar cell.
  • the perovskite solar cell according to the present invention contains tin oxide as an electron transport layer, has an interface layer containing a pyrophosphate compound or a residue derived therefrom on the electron transport layer, and contains a perovskite compound.
  • the light absorption layer is located on the interface layer.
  • the pyrophosphate compound may have the composition of Formula 1.
  • R is independently selected from alkali metal and hydrogen, and at least one R is an alkali metal.
  • the pyrophosphate compound may have the composition of Formula 2 below.
  • the X-ray photoelectron spectroscopy (XPS) spectrum of the interface layer may include a peak of phosphorus (P) detected at a binding energy of 185 eV to 190 eV. there is.
  • the phosphorus (P) content in the interface layer may be 0.5 to 1.2 atomic%.
  • the thickness of the interfacial layer may be less than 5 nm.
  • a perovskite solar cell according to an embodiment of the present invention can satisfy Equation 1 below.
  • PCE 1 is the photoelectric conversion efficiency of the perovskite solar cell including the interface layer
  • PCE 0 refers to the photoelectric conversion efficiency of the perovskite solar cell not including the interface layer.
  • a perovskite solar cell according to an embodiment of the present invention can satisfy Equation 2 below in the linear attenuation section of time-resolved fluorescence spectroscopy (TCSPC, time-correlated single photon counting).
  • Equation 2 ⁇ 1 refers to the carrier life of a perovskite solar cell including an interface layer, and ⁇ 0 refers to the carrier life of a perovskite solar cell not including an interface layer.
  • the perovskite compound may have an AMX3 composition, A may be a monovalent cation, M may be a divalent cation, and X may be a halide anion.
  • the perovskite solar cell according to the present invention includes a hole transport layer located on top of the light absorption layer; A first electrode connected to the lower part of the electron transport layer; and a second electrode connected to the top of the hole transport layer.
  • the present invention includes a method for manufacturing the above-described perovskite solar cell.
  • the method of manufacturing a perovskite solar cell according to the present invention includes forming an interface layer containing a pyrophosphate compound or a residue derived therefrom on an electron transport layer containing tin oxide; Forming a first material layer by applying and drying a perovskite precursor solution on the interface layer; and heat-treating the first material layer to form a perovskite light absorption layer.
  • the heat treatment temperature of the first material layer may be 130°C or higher.
  • the method of manufacturing an interface layer includes applying a solution containing a pyrophosphate compound on the electron transport layer; and heat treatment.
  • an interfacial layer containing a pyrophosphate compound or a residue derived therefrom is located at the interface between an electron transport layer containing tin oxide and a light absorption layer containing a perovskite compound.
  • the thermal instability of the perovskite solar cell can be resolved by increasing the heat treatment temperature without reducing efficiency, resulting in excellent durability and improved stability and efficiency.
  • Figure 1 is a diagram showing a current density-voltage graph according to the heat treatment temperature of the first material layer when manufacturing a perovskite solar cell according to Comparative Example 2.
  • Figure 2 is a diagram showing a current density-voltage graph of perovskite solar cells manufactured according to Example 1, Comparative Example 1, and Comparative Example 2.
  • Figure 3 shows the open-circuit voltage (V OC ), short-circuit current density (J SC ), fill factor (FF), and photoelectric conversion efficiency of perovskite solar cells manufactured according to Example 1, Comparative Example 1, and Comparative Example 2 ( This is a diagram showing PCE).
  • FIG. 4 is a graph showing changes in time-correlated single photon counting (TCSPC) of perovskite solar cells manufactured according to Example 1, Comparative Example 1, and Comparative Example 2.
  • TCSPC time-correlated single photon counting
  • Figure 5 is a diagram showing the XPS analysis spectrum of the interfacial layer in the perovskite solar cell manufactured according to Example 1 and Comparative Example 2.
  • a perovskite solar cell providing an interfacial layer containing a pyrophosphate compound or a residue derived therefrom according to the present invention and a method for manufacturing the same will be described in detail.
  • the terms used in this specification are general terms that are currently widely used as much as possible while considering the function of the present invention, but this may vary depending on the intention or precedent of a technician working in the related field, the emergence of new technology, etc. Unless otherwise defined, the technical and scientific terms used may have meanings commonly understood by those skilled in the art in the technical field to which this invention belongs.
  • the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified in the specification of the present invention, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.
  • the efficiency refers to photoelectric conversion efficiency (Power Conversion Efficiency, PCE).
  • the present invention provides a perovskite solar cell, wherein the perovskite solar cell includes an electron transport layer containing tin oxide; An interface layer located on the electron transport layer; A light absorption layer located on the interface layer and containing a perovskite compound, wherein the interface layer includes a pyrophosphate compound or a residue derived therefrom.
  • the perovskite compound of the light absorption layer refers to an organic metal halide with a perovskite structure.
  • perovskite compounds can satisfy the chemical formula of AMX 3 based on monovalent organic cations (A), divalent metal cations (M), and halogen anions (X), but AMX 4 , A 2 MX 4 , A 3 Examples that satisfy chemical formulas such as MX 5 are not excluded.
  • perovskite compounds can have a three-dimensional structure in which A combines with 12 That is not the case.
  • the perovskite compound satisfies the formula AMX 3 , wherein A is a monovalent organic cation, M is a divalent metal ion, and X is selected from I - , Br - , F - and Cl - There may be one or two or more types.
  • M, a divalent metal ion include Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr 2+ , Pd 2+ , Cd 2+ , Ge 2+ , Sn 2+ , Pb
  • One or two or more types selected from 2+ and Yb 2+ may be mentioned, but are not limited thereto.
  • A may be an amidinium group ion, an organic ammonium ion, or an amidinium group ion and an organic ammonium ion.
  • A may be represented by the formula of (R 1 -NH 3 + )X, where R 1 is C1-C24 alkyl, C3-C20 cycloalkyl, or C6 - C20 aryl, and It means one or more halogen anions selected from Br - , F - and I - .
  • R 2 -C 3 H 3 N 2 + -R 3 )X where R 2 is C1-C24 alkyl, C3-C20 cycloalkyl, or C6-C20 aryl.
  • R 3 is hydrogen or C1-C24 alkyl
  • X means one or more halogen anions selected from Cl - , Br - , F - and I - .
  • R 1 may be C1-C24 alkyl, preferably C1-C7 alkyl, and more preferably methyl.
  • R 2 may be C1-C24 alkyl
  • R 3 may be hydrogen or C1-C24 alkyl, preferably R 2 may be C1-C7 alkyl and R 3 may be hydrogen or C1-C7 alkyl, , more preferably, R 2 may be methyl and R 3 may be hydrogen.
  • A is a monovalent organic ion that contains both organic ammonium ions and amidinium ions
  • A is A ⁇ 1-x A ⁇ x
  • a ⁇ x (A ⁇ is the monovalent organic ammonium ion described above, and A ⁇ is It is an amidinium-based ion, and x can satisfy the real number 0 ⁇ x ⁇ 1, preferably a real number 0.05 ⁇ x ⁇ 0.3).
  • the tin oxide of the electron transport layer may be tin oxide (SnO2), and the thickness of the thin film may be 10 nm to 500 nm, but the present invention is not limited by the thickness of the electron transport layer.
  • a perovskite solar cell is manufactured by forming an electron transport layer containing tin oxide and then forming a light absorption layer containing a perovskite compound, followed by heat treatment.
  • Heat treatment at a high temperature of 130°C or higher is preferred to suppress defects in the light absorption layer and improve PCE.
  • defects such as oxygen vacancies are generated at the interface between the electron transport layer and the light absorption layer. It acts as a trap to confine charges and does not prevent holes from moving toward the electron transport layer, causing recombination of electrons and holes.
  • an electron transport layer containing tin oxide is formed, and then a perovskite precursor solution is applied and dried to form a light absorption layer, and then heat treatment is performed at a low temperature of 100°C or lower.
  • the low-temperature heat treatment process inevitably causes defects in the light absorption layer, which may lead to a decrease in PCE performance.
  • the pyrophosphate compound included in the interface layer may be represented by the following formula (1).
  • R is independently selected from alkali metal and hydrogen, and at least one R is an alkali metal.
  • the alkali metal may be one or more selected from the group including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). It may be potassium (K).
  • the pyrophosphate compound is included in the interface layer between the electron transport layer and the light absorption layer, and as subsequent heat treatment is performed, the structure of the pyrophosphate compound is not maintained in the interface layer, but is converted to the form of a residue derived from the pyrophosphate compound. It can exist.
  • the residue derived from the pyrophosphate compound essentially includes phosphorus (P), but may optionally have a structure in which oxygen (O) or an oxygen-containing ligand (OR) is covalently bonded to phosphorus.
  • the interface layer has a clear interface between the electron transport layer and the light absorption layer and may not necessarily exist.
  • at least a portion of the pyrophosphate compound penetrates into the interface between the electron transport layer and the light absorption layer, so that the pyrophosphate compound or a residue derived therefrom has the highest concentration in the interface layer, and the electron transport layer in the interface layer
  • the light absorption layer may be a layer that exists with a concentration gradient in the form of a concentration decrease due to mutual diffusion as the distance in each direction increases.
  • the pyrophosphate compound penetrates both the electron transport layer and the light absorption layer, so that the interface layer in which only the pyrophosphate compound exists is substantially absent, and the pyrophosphate compound penetrates into both the electron transport layer and the light absorption layer at a certain depth of the electron transport layer and the light absorption layer in the thickness direction. It may be a layer in which a pyrophosphate compound exists with a concentration gradient.
  • this does not mean that the pyrophosphate compound of the interfacial layer or a residue derived therefrom penetrates into the entire volume of the electron transport layer and the light absorption layer, and does not mean that the thickness direction of the entire volume of each layer of the electron transport layer and the light absorption layer This means that it penetrates only through a portion of the thickness and has a concentration gradient due to mutual diffusion.
  • the pyrophosphate compound may be represented by the following formula (2).
  • the pyrophosphate compound is selected as the potassium pyrophosphate salt represented by Formula 2, the generation of defects such as oxygen vacancies can be effectively suppressed and the photoelectric conversion efficiency can be further improved through high temperature heat treatment of 130°C or higher.
  • the X-ray photoelectron spectroscopy (XPS) spectrum of the interface layer may include a peak of phosphorus (P) detected at a binding energy of 185 eV to 190 eV. Specifically, a peak for 2S phosphorus (P) can be detected at about 188 eV.
  • the content of phosphorus (P) in the interface layer may be 0.5 atomic% to 1.2 atomic%, specifically 0.6 atomic% to 1.1 atomic%, and more specifically 0.7 atomic% to 1.0 atomic%.
  • it may be 0.5 atomic% or more, 0.6 atomic% or more, or 0.7 atomic% or more, and the upper limit may be 1.2 atomic% or less, 1.1 atomic% or less, 1.0 atomic% or less, and 0.9 atomic% or less, and may be substantially 0.8 atomic%.
  • analyzing the materials and element concentrations contained in the interface layer through X-ray photoelectron spectroscopy (XPS), it can be confirmed that the interface layer containing phosphorus (P) was formed with a concentration gradient.
  • XPS X-ray photoelectron spectroscopy
  • the thickness of the interfacial layer may be less than 5 nm, specifically less than 3 nm, and more specifically less than 1 nm, and may exist with a concentration gradient at a partial thickness without substantially having a clear interface.
  • the thickness of the interface layer satisfies the above range, it effectively contributes to the suppression of defect generation, and the pyrophosphate compound of the interface layer or residues derived therefrom do not excessively penetrate into the entire volume of the electron transport layer and light absorption layer, thereby preventing photoelectric energy. This can be particularly advantageous in terms of conversion efficiency.
  • equation 1 may be satisfied.
  • PCE 1 is the photoelectric conversion efficiency of the perovskite solar cell including the interface layer
  • PCE 0 refers to the photoelectric conversion efficiency of the perovskite solar cell not including the interface layer.
  • Advantageously PCE 1 /PCE 0 may be at least 1.5, at least 1.6, at least 1.7 or at least 1.8, and without limitation, at most 2.0.
  • a perovskite precursor solution is applied and dried without including an interface layer to form a light absorption layer, and then heat treated at 150°C, pyrophosphate
  • an interface layer containing is further included and heat treated at 150° C., both open-circuit voltage and fill factor are improved, and photoelectric conversion efficiency can be significantly improved.
  • Equation 2 can be satisfied in the linear attenuation section of time-correlated single photon counting (TCSPC).
  • Equation 2 ⁇ 1 refers to the carrier life of a perovskite solar cell including an interface layer, and ⁇ 0 refers to the carrier life of a perovskite solar cell not including an interface layer.
  • the time-resolved fluorescence spectral characteristics (TCSPC, Time-correlated single photon counting) of the perovskite solar cell can be measured by Edinburgh Instruments, FL920, and the sample was excited at 470 nm and the PL decay was at 800 nm. It was detected.
  • Carrier lifetime ( ⁇ ) refers to a value calculated by measuring the slope of the attenuation section through a mono-exponential fit based on time-resolved fluorescence spectral characteristics.
  • the carrier life of the perovskite solar cell according to the present invention may be 2000 nsec or more, specifically 2500 nsec or more, or 2800 nsec or more, and may be indefinitely 3000 nsec or less.
  • the perovskite solar cell according to the present invention may further include a hole transport layer on top of the light absorption layer, and may further include a first electrode below the electron transport layer and a second electrode on top of the hole transport layer. That is, the perovskite solar cell according to one embodiment includes a first electrode; An electron transport layer located on the first electrode; An interfacial layer located on the electron transport layer; A light absorption layer located on the interface layer; A hole transport layer located on the light absorption layer; And it may include a second electrode located on the hole transport layer.
  • the first electrode may be a transparent conductive electrode that is ohmic bonded to the electron transport layer.
  • the materials of the transparent conductive electrode include fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), ZnO, carbon nanotube, and graphene. ) and complexes thereof may be any one or two or more selected from the group, but are not limited thereto.
  • a transparent substrate (support) that is a rigid substrate (support) or a flexible substrate (support) may be located below the first electrode.
  • a transparent substrate is polyethylene terephthalate (PET). ), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene (PP), triacetylcellulose (TAC), or polyethersulfone (PES) substrate, etc., but the present invention is applicable to the substrate. It is not limited to concrete materials.
  • the hole transport layer may be an organic hole transport layer, and the organic hole transport material of the organic hole transport layer may be a single molecule or a high molecule organic hole transport material.
  • Non-limiting examples of single to low molecule organic hole transport materials include pentacene, coumarin 6, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin), ZnPC (zinc phthalocyanine), CuPC(copper phthalocyanine), TiOPC(titanium oxide phthalocyanine), Spiro-MeOTAD(2,2',7,7'-tetrakis(N,N-p-dimethoxyphenylamino)-9,9'-spirobifluorene), F16CuPC(copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine), SubPc (boron subphthalocyanine chloride) and N3( One or more substances selected from cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dica
  • the organic hole transport material is a polymer (hole conductive polymer), which not only ensures stable operation of the solar cell, but also allows for improved power generation efficiency through energy matching with the light absorber.
  • the hole-conducting polymer may include one or a combination of two or more selected from the group consisting of thiophene-based polymers, paraphenylenevinylene-based polymers, carbazole-based polymers, and triphenylamine-based polymers, and thiophene-based polymers or Triphenylamine-based polymers are preferred, and more preferably, triphenylamine-based polymers may be used.
  • Non-limiting examples of polymeric organic hole transport materials include 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-octylthiophene)), POT(poly(octylthiophene)), P3DT( poly(3-decyl thiophene)), P3DDT(poly(3-dodecyl thiophene)), PPV(poly(p-phenylene vinylene)), TFB(poly(9,9'-dioctylfluorene-co-N-(4-butylphenyl) )diphen
  • the hole transporter may be a thin film of an organic hole transport material, and the thickness of the thin film may be 10 nm to 500 nm, but the present invention is not limited thereto.
  • the hole transport layer is TBP (tertiary butyl pyridine), LiTFSI (Lithium Bis(Trifluoro methanesulfonyl)Imide), HTFSI (bis(trifluoromethane)sulfonimide), 2,6-lutidine, and Tris(2-(1H -pyrazol-1-yl)pyridine. ) Of course, it may further contain known additives such as cobalt(III).
  • the second electrode may be a conductive electrode that is ohmic bonded to the hole transporter, and any material commonly used as the electrode material for the front or back electrode in solar cells can be used.
  • the second electrode when the second electrode is the electrode material of the back electrode, the second electrode is one of gold, silver, platinum, palladium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide, and composites thereof. It may be any material selected above.
  • the material of the second electrode may be fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), ZnO, or CNT.
  • FTO fluorine-doped tin oxide
  • ITO indium-doped tin oxide
  • ZnO or CNT.
  • It may be an inorganic conductive electrode such as (carbon nanotube) or graphene, or it may be an organic conductive material such as PEDOT:PSS.
  • the materials, structures, shapes, and sizes of the first electrode, second electrode, electron transport layer, light absorption layer, interface layer, and hole transport layer are the perovskite described above.
  • the manufacturing method of the perovskite solar cell according to the present invention includes all the contents previously described for the perovskite solar cell.
  • the method for manufacturing a perovskite solar cell according to the present invention includes forming an interface layer containing a pyrophosphate compound or a residue derived therefrom on an electron transport layer containing tin oxide; Forming a first material layer by applying and drying a perovskite precursor solution on the interface layer; and heat-treating the first material layer to form a perovskite light absorption layer.
  • Methods for forming an electron transport layer containing tin oxide include spin coating, bar coating, gravure coating, blade coating and roll coating, spray coating, chemical solution growth method, slot-die coating, chemical solution deposition method, atomic layer deposition method, and thermal evaporation method. , may be performed by one or more selected from the group including electron beam evaporation, magnetron sputtering, and pulse laser deposition.
  • tin oxide precursor may be manufactured by applying a solution containing a tin oxide precursor onto the first electrode and heat treating it.
  • Precursors such as tin salt (SnCl2, SnCl4) or tin hydrate (SnCl2 ⁇ 2H2O, SnCl4 ⁇ 5H2O) or tin nanoparticles are dissolved in a polar solvent such as deionized water, ethanol, or isopropanol for spin coating, bar coating, gravure coating, and blade.
  • a polar solvent such as deionized water, ethanol, or isopropanol for spin coating, bar coating, gravure coating, and blade.
  • the electron transport layer can be formed by applying a tin oxide precursor solution using coating, roll coating, spray coating, and slot-die coating methods and heat treating it.
  • an electron transport layer containing tin oxide can be manufactured by chemical bath deposition (CBD).
  • CBD chemical bath deposition
  • the solution used in CBD to deposit tin oxide is one from the group containing a tin precursor in deionized water and urea, mercaptoic acid, and hydrochloric acid, which act as a binder and stabilizer, respectively. It can be prepared by adding a specific acid selected above.
  • An electron transport layer containing tin oxide may be formed through a chemical reaction by immersing the first electrode in the prepared solution.
  • the electron transport layer can be manufactured by heat treatment below °C.
  • a thermal evaporation method in which liquid or solid tin is evaporated under high vacuum and a high temperature of 1630°C or higher and deposited on the first electrode, and a high-voltage electron beam is irradiated to a tin oxide target to deposit the evaporated tin oxide on the first electrode.
  • the tin oxide electron transport layer can be manufactured by one or more methods selected from the pulse laser deposition method for forming a tin thin film, but the present invention is not limited by the method of manufacturing the electron transport layer.
  • a step of forming an interface layer may be performed.
  • a solution containing a pyrophosphate compound is applied on the electron transport layer by methods such as spin coating, bar coating, gravure coating, blade coating, roll coating, spray coating, chemical solution growth method, and slot-die coating, It can be manufactured by heat treatment, but the present invention is not limited by the method of applying the solution.
  • the light absorption layer can be manufactured by spontaneous crystallization (self-assembly) as the solvent is removed from a solution (hereinafter referred to as perovskite solution) containing the ions that make up the perovskite compound and the desired additive(s). Accordingly, the above-described perovskite compound film can be manufactured using a solution application method conventionally used to prepare perovskite compounds.
  • the perovskite solution contains amidinium group ions, organic ammonium ions, or monovalent organic cations containing both amidinium group ions and organic ammonium ions, Cu 2+ , Ni 2+ , and Co 2+ , Fe 2+ , Mn 2+ , Cr 2+ , Pd 2+ , Cd 2+ , Ge 2+ , Sn 2+ , Pb 2+ and Yb 2+ , one or more types of divalent metal ions selected from It can be prepared by mixing a perovskite compound containing one or more monovalent halogen anions selected from I - , Br - , F -, and Cl - with a polar organic solvent.
  • the perovskite solution may contain additives commonly used to improve the film quality of the perovskite compound being produced or to improve the interface properties between the perovskite compound and other components such as electron transporters.
  • additives commonly used to improve the film quality of the perovskite compound being produced or to improve the interface properties between the perovskite compound and other components such as electron transporters.
  • the present invention cannot be limited by the specific type and content of the additive.
  • the solvent of the perovskite solution may be a polar organic solvent in which the ion source and additives are easily dissolved and can be easily volatilized and removed when dried.
  • the solvent is gamma-butyrolactone, formamide, N,N-dimethylformamide, diformamide, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, diethylene glycol, 1-methyl-2- Pyrrolidone, N,N-dimethylacetamide, acetone, ⁇ -terpineol, ⁇ -terpineol, dihydro terpineol, 2-methoxy ethanol, acetylacetone, methanol, ethanol, propanol, butanol, It may be one or two or more selected from pentanol, hexanol, ketone, methyl isobutyl ketone, etc., but the present invention is not limited by the specific substance of the solvent.
  • the perovskite solution can be done through inkjet printing, microcontact printing, imprinting, gravure printing, gravure-offset printing, flexography printing, offset printing, reverse offset printing, slot die coating, bar coating, blade coating, and spray coating. , dip coating, roll coating, etc., but is not limited thereto.
  • the perovskite compound film can be manufactured using a solution application method of applying a perovskite solution, and further, solvent-non-solvent application by sequentially applying a perovskite solution and a non-solvent. It can be manufactured using this method.
  • solution application methods and solvent-non-solvent application methods can be performed with reference to the applicant's Korean Patent No. 10-1547877 or 10-1547870.
  • a step of forming a perovskite light absorption layer by heat treating the first material layer may be further performed.
  • the heat treatment temperature may be 130°C or higher, 135°C or higher, 140°C or higher, 145°C or higher, or 150°C or higher, and may be substantially 200°C or lower.
  • the hole transport layer may be formed by applying and drying a solution containing an organic hole transport material on the light absorption layer.
  • the solvent used to form the hole transport layer may be any solvent that dissolves the organic hole transport material and does not chemically react with the perovskite compound and the materials of the electron transport layer.
  • the solvent used to form the hole transport layer may be a non-polar solvent, but is not limited thereto.
  • the first electrode and the second electrode may be formed through a deposition process such as physical vapor deposition or chemical vapor deposition.
  • FTO substrate first electrode
  • FTO substrate first electrode
  • the FTO substrate was cleaned by sonication in Hellmanex solution, deionized water, acetone, and isopropyl alcohol (IPA) for 10 minutes each.
  • CBD solution reaction solution
  • reaction solution was prepared by mixing 625 mg of urea, 625 ⁇ L of HCl, 12.5 ⁇ L of thioglycolic acid (TGA), and 137.5 mg of SnCl 2 ⁇ 2H 2 O per 50 mL of deionized water.
  • TGA thioglycolic acid
  • SnCl 2 ⁇ 2H 2 O per 50 mL of deionized water.
  • one edge of the cleaned FTO substrate was taped with Kapton tape.
  • the taped FTO substrate and CBD solution were loaded into a glass reaction vessel (Hellendahl staining dish, ⁇ 170 mL vessel volume) and reacted at 90°C for 4 hours to form tin oxide.
  • the FTO substrate on which the tin oxide layer was formed by chemical solution growth was annealed at 170°C for 60 minutes at 15-30% relative humidity, and then spin-coated with deionized water containing 10mM KCl dissolved at 3000 rpm for 30 seconds.
  • An electron transport layer was prepared by heat treatment again at 100°C for 10 minutes.
  • a solution was prepared by dissolving 10 mg of potassium pyrophosphate in 1 ml of water and quantifying it. This was applied on the electron transport layer, spin-coated at 3000 rpm for 30 seconds, and then heat-treated at 100°C for 3 minutes to form an interface layer. did.
  • An amidinium-based perovskite compound layer was formed on the tin oxide layer using a perovskite solution on the prepared interface layer.
  • the composition of lead iodide is excessive by about 9 mol% compared to the stoichiometric ratio (ABX 3 standard stoichiometric ratio), and methylammonium chloride (MACl) is used to stabilize the intermediate phase and improve the orientation of the perovskite compound. ; Methylammonium Chloride) was used as an additive.
  • the perovskite solution is a mixture of dimethylformamide and dimethyl sulfoxide in an 8:1 (V/V) ratio, 1.53M lead iodide (PbI 2) , and 1.4M formamidinium aiodide. It was prepared by mixing 0.0122M (0.8 mol%) methylammonium lead bromide (MAPbBr3; methylammonium lead bromide) with (FAI; formamidinium iodide) and 0.5M methylammonium chloride (MACl; Methylammonium Chloride). The prepared perovskite solution was spin-coated at 1000 rpm for 10 seconds, followed by 5000 rpm for 30 seconds.
  • MAPbBr3 methylammonium lead bromide
  • FAI formamidinium iodide
  • MACl Methylammonium Chloride
  • Measurement conditions To measure the current-voltage characteristics of the manufactured solar cell, an artificial solar device (ORIEL class A solar simulator, Newport, model 91195A) and a source-meter (source-meter, Kethley, model 2420) were used. Illumination was set to AM 1.5G and calibrated to 100 mW/cm 2 using a calibrated silicon reference cell. The step voltage was 10mV and the delay time was 50ms. Measurements of time correlated single photon counting (TCSPC) were performed by Edinburgh Instruments, FL920.
  • ORIEL class A solar simulator Newport, model 91195A
  • source-meter source-meter
  • TCSPC time correlated single photon counting
  • a perovskite solar cell containing no interface layer was manufactured in the same manner as Example 1, except that the interface layer was not formed on the electron transport layer.
  • An interface layer was prepared in the same manner as in Example 1, except that the solution containing the pyrophosphate compound was not applied to the electron transport layer, but a solution of potassium chloride dissolved in water was applied to the electron transport layer to form the interface layer.
  • a perovskite solar cell was manufactured.
  • a perovskite solar cell was manufactured in the same manner as in Example 1, but without forming an interface layer on the electron transport layer, and by adding phosphoric acid when manufacturing the electron transport layer containing tin oxide. did. Specifically, 7.4 at% phosphoric acid was added to the tin oxide precursor solution (sol), spin-coated at 5000 rpm for 30 seconds, dried at 100°C for 10 minutes, and then heat treated at 180°C for 30 minutes under nitrogen to form an electron transport layer. did. Afterwards, formamidinium lead iodide (FAPbI3) and methylammonium lead bromide (MAPbBr3) were spin-coated at a molar ratio of 0.85:0.15 to form a light absorption layer.
  • a perovskite solar cell containing a pyrophosphoric acid compound was manufactured by depositing an 80 nm thick silver electrode on the hole transport layer containing Spiro-OMeTAD to form a second electrode.
  • Table 1 shows the open-circuit voltage (V OC ), short-circuit current density (J SC ), fill factor (FF), and This is a summary of the photoelectric conversion efficiency (PCE).
  • Example 1 As can be seen in Table 1, it can be seen that the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of Example 1 are all significantly improved compared to Comparative Examples 1 and 2.
  • the interface layer containing potassium pyrophosphate of Example 1 it is possible to provide the effect of preventing deterioration of the perovskite light-absorbing layer even when heat-treated at 150°C.
  • crystal defects in the perovskite layer are alleviated, providing a perovskite solar cell with improved stability and durability.
  • Comparative Example 3 which provides a perovskite solar cell doped with phosphoric acid in the tin oxide electron transport layer rather than the interface layer
  • the performance may be improved to some extent compared to Comparative Examples 1 and 2, but the performance of Example 1 It can be seen that the degree of improvement is not significant compared to the perovskite solar cell manufactured using this method.
  • Figure 1 is a diagram showing current density-voltage graphs when the heat treatment temperature of the first material layer is 100°C and 150°C when manufacturing perovskite by the method of Comparative Example 2.
  • the efficiency did not decrease, showing an open circuit voltage of 1.2V.
  • the open circuit voltage decreased to 1V due to a defect in the electron transport layer, indicating a decrease in efficiency. You can check it.
  • Figure 2 is a diagram showing a current density-voltage graph of perovskite solar cells manufactured according to Example 1, Comparative Example 1, and Comparative Example 2 when heat treatment of the first material layer is performed at 150°C.
  • the open-circuit voltage is only about 1V, whereas when potassium pyrophosphate is included in the interface layer (Example 1 ), it can be seen that the open-circuit voltage has significantly improved to 1.2V.
  • Figure 3 shows the open-circuit voltage (V OC ), short-circuit current density (J SC ), fill factor (FF), and photoelectric conversion efficiency of perovskite solar cells prepared according to Example 1, Comparative Example 1, and Comparative Example 2 ( This is a diagram showing the characteristics of PCE measured as a box and whisker plot (center line, average; box limit, standard deviation; whisker, outlier).
  • Ref is a perovskite solar cell manufactured by the method of Comparative Example 1
  • KCl is a perovskite solar cell manufactured by the method of Comparative Example 2
  • KPP is a perovskite solar cell manufactured by the method of Example 1. This refers to a perovskite solar cell manufactured by .
  • the open-circuit voltage was about 1.01V
  • the short-circuit current density was about 24.42mA/cm2
  • the fill factor was about 64%
  • the photoelectric conversion efficiency was about 15.8%.
  • potassium chloride was included in the interface layer (Comparative Example 2)
  • the open-circuit voltage was about 1.02V
  • the short-circuit current density was about 24.42mA/cm2
  • the fill factor was about 74%
  • the photoelectric conversion efficiency was about 18.5%.
  • Figure 4 is a graph showing changes in time-correlated single photon counting (TCSPC) of perovskite solar cells manufactured according to Example 1, Comparative Example 1, and Comparative Example 2, and carrier life (carrier life). Lifetime, ⁇ ) may be calculated through a mono-exponential fit based on time-resolved fluorescence spectral characteristics. As shown in Figure 4, when the interface layer is not included (Comparative Example 1), the carrier life is 366 nsec, when potassium chloride is added (Comparative Example 2), the carrier life is 150 nsec, and when potassium pyrophosphate is added (Example 1) ) It can be seen that the carrier life is significantly increased when a compound containing potassium pyrophosphate is applied to the interface layer at 2825 nsec.
  • TCSPC time-correlated single photon counting
  • Figure 5 shows an XPS analysis spectrum (blue dotted line) of the interfacial layer of the perovskite solar cell prepared according to Example 1.
  • a peak was detected at 185 to 190 eV that was not detected in the XPS spectrum (black dotted line) of the interfacial layer of the perovskite solar cell prepared according to Comparative Example 2.
  • P phosphorus

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Abstract

La présente invention concerne une cellule solaire en pérovskite et son procédé de fabrication, la cellule solaire comprenant : une couche de transport d'électrons contenant de l'oxyde d'étain ; une couche d'interface positionnée sur la couche de transport d'électrons ; et une couche d'absorption de lumière, qui est positionnée sur la couche d'interface et contient un composé de pérovskite, la couche d'interface comprenant un composé pyrophosphate et un résidu dérivé de celui-ci. Pendant un processus de traitement thermique pour former une couche d'absorption de lumière en pérovskite, l'efficacité ne diminue pas même pendant un traitement thermique à haute température de telle sorte que l'instabilité thermique d'une cellule solaire en pérovskite est résolue et ainsi une excellente durabilité est fournie et la stabilité et l'efficacité peuvent être améliorées.
PCT/KR2023/011816 2022-08-18 2023-08-10 Cellule solaire en pérovskite comprenant une couche d'interface et son procédé de fabrication WO2024039134A1 (fr)

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KR102106643B1 (ko) * 2019-03-20 2020-05-04 한국전력공사 페로브스카이트 태양전지의 제조 방법 및 이를 이용한 페로브스카이트 태양전지
KR102228799B1 (ko) * 2019-10-18 2021-03-18 울산과학기술원 고효율 대면적 페로브스카이트 태양전지 및 이의 제조방법

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KR20190110268A (ko) * 2018-03-20 2019-09-30 주식회사 엘지화학 유-무기 복합 태양전지
KR20200020435A (ko) * 2018-08-17 2020-02-26 국민대학교산학협력단 광전변환효율 및 장기안정성이 향상된 페로브스카이트 태양전지 및 이의 제조 방법
KR102106643B1 (ko) * 2019-03-20 2020-05-04 한국전력공사 페로브스카이트 태양전지의 제조 방법 및 이를 이용한 페로브스카이트 태양전지
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118265314A (zh) * 2024-05-28 2024-06-28 上海电气集团恒羲光伏科技(南通)有限公司 一种太阳能电池及其制备方法

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