CN114373871A - Preparation method of high-open-voltage wide-band-gap perovskite top battery for laminated battery - Google Patents

Preparation method of high-open-voltage wide-band-gap perovskite top battery for laminated battery Download PDF

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CN114373871A
CN114373871A CN202210024662.7A CN202210024662A CN114373871A CN 114373871 A CN114373871 A CN 114373871A CN 202210024662 A CN202210024662 A CN 202210024662A CN 114373871 A CN114373871 A CN 114373871A
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李跃龙
亓文静
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Nankai University
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    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a preparation method of a high-open-voltage wide-band-gap perovskite top battery for a tandem cell, and belongs to the field of solar cells. The laminated cell structure comprises a narrow-band gap bottom cell, a tunneling layer and a wide-band gap perovskite top cell. The band gap of the high-open-voltage wide-band-gap perovskite battery is adjusted by changing the molar ratio of metal halide in a solution, the wide-band-gap perovskite absorption layer is prepared by a two-step method, firstly, a metal halide thin film is obtained, then, an organic halide thin film is prepared on the metal halide thin film and reacts with the organic halide thin film to prepare the wide-band-gap perovskite absorption layer, and the surface interface defect of the wide-band-gap perovskite absorption layer is eliminated by adopting an organic halide passivator on the upper interface and the lower interface of the perovskite or in the body of the perovskite, so that a high-open-voltage and high-performance wide-band-gap perovskite solar battery device is obtained, and a foundation is laid for the application of a transparent single-junction solar battery or a high-efficiency multi-junction laminated solar battery, a large-area solar battery corresponding to the transparent single-junction solar battery and other photoelectric devices such as a light emitting diode, a photoelectric detector and a laser.

Description

Preparation method of high-open-voltage wide-band-gap perovskite top battery for laminated battery
Technical Field
The invention belongs to the field of perovskite solar cells, and particularly relates to a preparation method of a high-open-voltage wide-band-gap perovskite top cell for a tandem cell.
Technical Field
The metal halide perovskite material is widely researched by scientific researchers in various countries due to the high light absorption coefficient, adjustable band gap, high carrier mobility and longer carrier diffusion length. With the continuous progress of perovskite cell preparation technology and technology, the photoelectric conversion efficiency of the perovskite cell is rapidly improved from the initial 3.8% to 25.5%. However, in order to break through the theoretical limit of the scherrer-quinetiser, the multi-junction solar cell is produced and becomes an important way for improving the conversion efficiency of the photovoltaic device, and the conversion efficiency of the device is hopefully improved greatly on the basis of the crystalline silicon solar cell technology which is already applied commercially in a large scale by combining perovskite with low cost and crystalline silicon with mature technology. In order to stack with crystalline silicon to obtain higher conversion efficiency, it is most critical to prepare high-performance wide-bandgap perovskite solar cells, however, the surface interface of the high-bromine-content wide-bandgap perovskite thin film has higher defect state density, which causes serious open-circuit voltage loss problem, and thus the performance is far less than expected. The perovskite solar cell is prepared by adopting a two-step method, the prepared film has more controllable appearance, the crystal grains of the perovskite are larger and more uniform, a high-quality wide-band-gap perovskite film can be obtained, the defects in the wide-band-gap perovskite film are reduced by combining a proper passivator, and the non-radiative recombination induced by the defects is reduced, so that the open-circuit voltage loss is further reduced. Therefore, the search for more sophisticated process conditions and passivating agents is an effective means to improve the performance of wide bandgap perovskite solar cells as well as tandem cells.
Disclosure of Invention
The invention aims to further improve the quality of the wide-bandgap perovskite thin film and reduce the defect state density of the wide-bandgap perovskite thin film, thereby improving the open-circuit voltage and the performance of the wide-bandgap perovskite solar cell and laying a foundation for the application of a transparent single-junction solar cell or a high-efficiency multi-junction laminated solar cell, a large-area solar cell corresponding to the transparent single-junction solar cell and other photoelectric devices such as a light emitting diode, a photoelectric detector and a laser. The preparation method of the wide-band-gap perovskite absorption layer is a two-step method, the band gap of the high-open-pressure wide-band-gap perovskite battery is adjusted by changing the addition molar ratio of metal halide in a solution, the wide-band-gap perovskite absorption layer is prepared by the two-step method, firstly, a metal halide thin film is obtained, then, an organic halide thin film is prepared on the metal halide thin film, the metal halide thin film and the organic halide thin film are reacted to prepare the wide-band-gap perovskite absorption layer, and the surface interface defects of the wide-band-gap perovskite absorption layer are eliminated by adopting an organic halide passivator on the upper interface and the lower interface of the perovskite or in the body of the perovskite, so that the high-open-pressure and high-performance wide-band-gap perovskite solar battery device is obtained. The film prepared by the two-step method is more controllable in morphology, the crystal grains of the perovskite are larger and more uniform, the halogen vacancy defect is effectively filled by combining passivators such as organic halide salts such as phenethyl ammonium iodide, phenethyl ammonium bromide, phenethyl ammonium chloride and the like, the high-quality perovskite film with reduced defect density and reduced non-radiative recombination loss is obtained, the open-circuit voltage loss of a wide-bandgap perovskite device is further reduced, and therefore the wide-bandgap perovskite solar cell with obviously enhanced open-circuit voltage and photoelectric conversion efficiency is obtained. The invention effectively solves the problem of serious open-circuit voltage loss of the wide-band gap perovskite device, and lays a foundation for the application of the transparent single-junction solar cell or the high-efficiency multi-junction laminated solar cell, the large-area solar cell corresponding to the transparent single-junction solar cell and other photoelectric devices such as a light emitting diode, a photoelectric detector and a laser.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the high-open-pressure wide-band-gap perovskite top battery for the laminated battery is characterized in that the structure of the laminated battery based on the high-open-pressure wide-band-gap perovskite top battery is shown in figure 1, and the structure of the perovskite battery comprises the following steps: 1) a transparent conductive substrate; 2) an electron transport layer; 3) a perovskite absorption layer; 4) a passivation layer; 5) a hole transport layer; 6) and a metal electrode. The substrate may be at least one of a flexible or rigid substrate such as, but not limited to, glass, metal, silicon wafer, fabric, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), Polyimide (PI), polybutylene terephthalate (PBT), Polydimethylsiloxane (PDMS), and derivatives thereof, and the substrate has a thickness of 0.7 mm to 3 mm; the transparent conductive film may be, but is not limited to, at least one of oxide thin films of Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), Indium Cerium Oxide (ICO), etc., and the thickness is generally 100 nm to 400 nm; the electron transport layer can be, but is not limited to, titanium dioxide (TiO)2) Tin dioxide (SnO)2) At least one of zinc oxide (ZnO), polystyrene sulfonate (such as PSSA), fullerene derivative (such as PCBM), poly (3-hexylthiophene-2, 5-diyl), graphene, zinc tin oxide, metal phthalocyanine molecular material, fullerene and the like, and the thickness is generally 5-500 nm; the hole transport layer may be, but is not limited to, 4-butylenePoly-N, N-diphenylaniline homopolymer (Poly-TPD), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanodimethyl-p-benzoquinone, Poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA), 2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD), nickel oxide (NiO)x) Molybdenum oxide (MoO)x) Tungsten oxide (WO)x) Vanadium pentoxide (V)2Ox) At least one of cuprous thiocyanate (CuSCN), poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate (such as PEDOT: PSS), copper thiocyanate, cuprous iodide, zinc sulfide, key disulfide, chromium oxide, key oxide, polyvinylcarbazole, etc., with a thickness of 5-500 nm; the perovskite absorption layer can be at least one of inorganic perovskite material, organic-inorganic hybrid perovskite material and the like, and is formed by organic-inorganic hybrid ABX3Perovskite materials of the structure are taken as examples, wherein A site cation is at least one of lithium, sodium, potassium, rubidium, cesium, amino, amidino and guanidino compounds, and B site cation is Pb2+、Sn2+、Ge2+、Sb2+、Bi3+Equispaced in at least one of the elements of the fourth, fifth and sixth etc. main groups, the X-anion being I-、Cl-、Br-At least one of halogen elements; the passivation layer comprises phenethyl ammonium iodide (PEAI), phenethyl ammonium bromide (PEABr), phenethyl ammonium chloride (PEACl), Ethylene Diamine Tetraacetic Acid (EDTA), choline chloride, polymethyl methacrylate (PMMA) and the like with-COOH, -OH and-NH2One or more compounds of alkane, aromatic hydrocarbon, pyridine, fullerene, graphene and the like with terminal functional groups of, -SH, -CN, -SCN and the like and derivatives thereof, or Al2O3、SiNx、SiO2、a-Si:H、a-SiOxH, one or more inorganic materials with the thickness of 1-100 nanometers; the metal electrode may be, but is not limited to, at least one of various metals such as Au, Ag, Al, Cu, Ti, etc.
The preparation method of the high-open-pressure wide-band-gap perovskite top cell for the laminated cell is characterized in that the wide-band-gap perovskite absorption layer of the high-open-pressure wide-band-gap perovskite cell is prepared by a two-step method, firstly, a metal halide thin film is obtained, then, an organic halide thin film is prepared on the metal halide thin film, the organic halide thin film and the metal halide thin film are reacted to prepare the wide-band-gap perovskite absorption layer, and a passivating agent is adopted to eliminate the surface interface defect of the wide-band-gap perovskite absorption layer so as to obtain the high-open-pressure and high-performance wide-band-gap perovskite solar cell device, wherein the band gap range of the perovskite absorption layer prepared by the method can be, but is not limited to: 1.6eV to 2.9 eV; the metal halide thin film is characterized in that the metal halide thin film is prepared by at least one of lead iodide, lead bromide, lead chloride, cesium iodide, cesium chloride, cesium bromide and the like. Different band gaps are obtained by adjusting the addition molar ratio of the halides in the solution; the solvent for dissolving the metal halide may be, but is not limited to, at least one of organic solvents such as N, N-dimethylformamide, dimethyl sulfoxide, a mixed methylamine/alcohol solution, acetonitrile, 2-methoxyethanol, and the like; or at least one of methylamine, formamidine and other gases; or at least one of ionic liquids such as methylamine acetate, methylamine formate and formamidine acetate; for example, the solvent ratio of N, N-dimethylformamide to dimethylsulfoxide may be, but is not limited to, 1:9 to 9:1, and preferably 3:1 to 5:1, when dissolved in N, N-dimethylformamide and dimethylsulfoxide. The metal halide solution can be obtained by dissolving a plurality of substances together, or can be obtained by mixing the plurality of substances according to a certain molar concentration ratio after being dissolved separately; the preferred preparation method is that lead iodide and lead bromide are respectively dissolved into a solution A and a solution B, then the two are dissolved according to the volume ratio of 5:1-1:5 to obtain a solution C, cesium iodide or cesium bromide and the like are separately dissolved to obtain a solution D, and then the solution C and the solution D are mixed according to the volume ratio (20:1-10:1) to obtain a solution E for preparing the metal halide film. The concentration range of solution A, B, C, D, E includes, but is not limited to, 0.5 moles/liter to 1.7 moles/liter; wherein the organic halide includes but is not limited to at least one of formamidine iodine (FAI), formamidine bromine (FABr), formamidine chlorine (FACl), methylamine iodine (MAI), methylamine iodine (MABr), methylamine iodine (MACl), etc.; the solvent that dissolves the above substances includes, but is not limited to, at least one of organic solvents that do not dissolve the perovskite material, such as isopropyl alcohol (IPA), chlorobenzene, toluene, and methylene chloride. The organic halide solution concentration includes, but is not limited to, 50 mg/ml to 150 mg/ml, with a preferred range being 90 mg/ml to 120 mg/ml.
The preparation method of the high-open-pressure wide-band-gap perovskite roof battery for the laminated battery is characterized in that the two-step method comprises at least one or more methods selected from the preparation methods of a spin coating method, a thermal evaporation method, a blade coating method, a slit coating method, a roll coating method, a spray coating method and the like; taking a spin coating method as an example, a metal halide film is prepared by dripping 30-100 microliter of solution on a substrate, then spin-coating at the rotation speed of 1000-3000 r/min for 30 seconds, after annealing at 70-100 ℃ for 1-5 minutes, dripping 30-100 microliter of organic halide solution, then spin-coating at the rotation speed of 1000-3000 r/min for 30 seconds, and after annealing at 100-160 ℃ for 10-20 minutes, obtaining the wide-bandgap perovskite absorption layer.
The preparation method of the high-open-voltage wide-band-gap perovskite roof battery for the laminated battery is characterized in that organic halide salts such as phenethyl ammonium iodide, phenethyl ammonium bromide, phenethyl ammonium chloride and the like are used as passivators, and the adding position of the passivator can be at least one of the positions between the perovskite absorption layer and the electron transport layer, between the perovskite absorption layer and the hole transport layer and between the perovskite absorption layers. The preparation method of the passivating agent added between the perovskite absorption layer and the electron transport layer comprises the following steps: firstly, preparing a passivating agent solution with the concentration of 1-10 mg/ml, wherein the solvent is at least one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbons, such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, gamma-butyrolactone, acetonitrile, chlorobenzene, toluene and isopropanol, and depositing the passivating agent solution on the electron transport layer by a spin coating method without annealing; the preparation method of the passivating agent added between the perovskite absorption layer and the hole transport layer comprises the following steps: firstly, preparing a passivating agent solution with the concentration of 1-10 mg/ml, wherein the solvent is at least one of isopropanol, chlorobenzene, toluene, dichloromethane and other organic solvents which do not dissolve the perovskite material, and the passivating agent solution is deposited on the perovskite absorption layer by a spin coating method without further annealing; the preparation steps of the passivating agent added into the perovskite absorption layer comprise: adding 1-10 mg/ml of passivating agent into the lead iodide solution, and forming a film along with the perovskite precursor solution.
The invention has the beneficial effects that: the high-open-voltage wide-band-gap perovskite solar cell is prepared by a two-step method, firstly, a metal halide film is obtained, then, an organic halide film is prepared on the metal halide film and reacts with the metal halide film to prepare a wide-band-gap perovskite absorption layer, and the defects of the surface interface of the wide-band-gap perovskite absorption layer are eliminated by adopting an organic halide passivator on the upper interface and the lower interface of the perovskite or in the body of the perovskite, so that the high-open-voltage and high-performance wide-band-gap perovskite solar cell device is obtained. The prepared film is more controllable in appearance, crystal grains of perovskite are larger and more uniform, organic halide salts such as phenethyl ammonium iodide, phenethyl ammonium bromide, phenethyl ammonium chloride and the like are used as passivators to act on the upper surface, the lower surface and the inner part of the wide-bandgap perovskite film, the high-quality perovskite film with reduced defect density and reduced non-radiative recombination loss can be obtained, the problem that the open-circuit voltage loss of the wide-bandgap perovskite solar cell is serious is effectively solved, the high-open-voltage, high-efficiency and stable wide-bandgap perovskite solar cell is prepared, and a foundation is laid for the application of a transparent single-junction solar cell or a high-efficiency multi-junction laminated solar cell, a large-area solar cell corresponding to the solar cell, and other photoelectric devices such as a light emitting diode, a photoelectric detector and a laser.
Drawings
Fig. 1 is a schematic structural diagram of the high open-voltage wide band gap perovskite top battery for the laminate battery provided by the invention.
FIG. 2 is a graph showing absorption and fluorescence spectra of a wide band gap perovskite thin film according to embodiment 1 of the present invention.
Figure 3 is a current density-voltage curve for a wide bandgap perovskite solar cell after phenethyl ammonium iodide treatment in example 3 of the invention.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are further described in detail with reference to the accompanying drawings and specific embodiments, but the described embodiments are only a part of all possible embodiments of the present invention, and are not limited thereto.
Example 1
1) ITO/glass is used as a substrate, and is subjected to ultrasonic cleaning and ozone treatment for 20 minutes after being cleaned by a cleaning agent, deionized water, acetone and isopropanol.
2) SnO with a concentration of 2.5 wt.%is used2The electron transport layer was prepared from the solution and spin coated at 4000 revolutions for 30 seconds and annealed at 150 degrees.
3) At SnO2And preparing the perovskite absorption layer on the transmission layer by adopting a two-step spin coating method. Firstly PbI2、PbBr2The solution dissolved separately from the CsI and then mixed together was spin-coated at 1500 rpm for 30 seconds and annealed at 70 ℃. Then, an organic salt solution is dripped, spin-coated for 30 seconds at the rotation speed of 1800 revolutions and annealed at 150 ℃ to prepare the perovskite thin film. The absorption and fluorescence spectra of the wide band gap perovskite thin film are shown in FIG. 2, and the band gap of the perovskite prepared by the method is about 1.65 eV.
4) A Spiro-OMeTAD hole transport layer was prepared on the passivation layer, and the Spiro-OMeTAD solution was spin-coated at 4000 revolutions for 30 seconds.
5) Depositing 80 nanometer Au as a metal electrode.
Example 2
1) ITO/glass is used as a substrate, and is subjected to ultrasonic cleaning and ozone treatment for 20 minutes after being cleaned by a cleaning agent, deionized water, acetone and isopropanol.
2) SnO with a concentration of 2.5 wt.%is used2The electron transport layer was prepared from the solution and spin coated at 4000 revolutions for 30 seconds and annealed at 150 degrees.
3) At SnO2And preparing the perovskite absorption layer on the transmission layer by adopting a two-step spin coating method. Firstly PbI2、PbBr2The solution dissolved with CsI was spin coated at 1500 rpm for 30 seconds and annealed at 70 degrees. Then, an organic salt solution is dripped, spin-coated for 30 seconds at the rotation speed of 1800 revolutions and annealed at 150 ℃ to prepare the perovskite thin film.
4) A NiOx hole transport layer was prepared on the perovskite layer, and the NiOx solution was spin-coated at 4000 revolutions for 30 seconds.
5) Depositing 80 nanometer Au as a metal electrode.
Example 3
1) ITO/glass is used as a substrate, and is subjected to ultrasonic cleaning and ozone treatment for 20 minutes after being cleaned by a cleaning agent, deionized water, acetone and isopropanol.
2) SnO with a concentration of 2.5 wt.%is used2The electron transport layer was prepared from the solution and spin coated at 4000 revolutions for 30 seconds and annealed at 150 degrees.
3) At SnO2And preparing the perovskite absorption layer on the transmission layer by adopting a two-step spin coating method. Firstly PbI2、PbBr2The solution dissolved separately from the CsI and then mixed together was spin-coated at 1500 rpm for 30 seconds and annealed at 70 ℃. Then, an organic salt solution is dripped, spin-coated for 30 seconds at the rotation speed of 1800 revolutions and annealed at 150 ℃ to prepare the perovskite thin film.
4) And preparing a phenethyl ammonium iodide passivation layer on the perovskite absorption layer. The phenethyl ammonium iodide solution had a solubility of 4 mg/ml, the solvent was isopropanol, and spin-coated at 5000 revolutions for 30 seconds.
5) A PTAA hole transport layer was prepared on the passivation layer, and the PTAA solution was spin-coated at 4000 revolutions for 30 seconds.
6) Depositing 80 nanometer Au as a metal electrode.
7) The current density-voltage curve of the wide-bandgap perovskite solar cell treated by phenethyl ammonium iodide is shown in fig. 3, the maximum efficiency of the wide-bandgap perovskite solar cell treated by phenethyl ammonium iodide is 21.06%, and the specific parameters are as follows: short-circuit current density: 22.03mA/cm2Open circuit voltage: 1.258V, fill factor: 75.96 percent.
Example 4
1) FTO/glass is used as a substrate, and is subjected to ultrasonic cleaning and ozone treatment for 20 minutes after being cleaned by a cleaning agent, deionized water, acetone and isopropanol.
2) SnO with a concentration of 3 wt.%is used2The electron transport layer was prepared from the solution and spin coated at 4000 revolutions for 30 seconds and annealed at 150 degrees.
3) The perovskite absorption layer is prepared by a two-step method. First, Pb is first introducedI2、PbBr2The solution dissolved separately from CsI and then mixed together was used to prepare a thin film by roll coating, and in the second step, an organic salt solution was deposited on the thin film of the first step by slit coating to prepare a perovskite layer.
4) A Spiro-OMeTAD hole transport layer was prepared on the perovskite layer, and the Spiro-OMeTAD solution was spin-coated at 4000 revolutions for 30 seconds.
5) Depositing 80 nanometer Au as a metal electrode.
Example 5
1) A crystal silicon bottom cell with sputtered ITO as a tunneling layer is used as a substrate.
2) SnO with a concentration of 2.5 wt.%is used2The solution is used for preparing an electron transport layer by a spin coating method, and is subjected to spin coating for 30 seconds at the rotating speed of 4000 revolutions and 150-degree annealing.
3) At SnO2On the transmission layer, a perovskite absorption layer is prepared by adopting a two-step method. Firstly PbI2、PbBr2The solution dissolved separately from the CsI and then mixed together was spin-coated at 1500 rpm for 30 seconds and annealed at 70 ℃. Then, an organic salt solution is dripped, spin-coated for 30 seconds at the rotation speed of 1800 revolutions and annealed at 150 ℃ to prepare the perovskite thin film.
4) A Spiro-OMeTAD hole transport layer was prepared on the perovskite layer, and the Spiro-OMeTAD solution was spin-coated at 4000 revolutions for 30 seconds.
5) The 10 nm MoOx was deposited by thermal evaporation.
6) Depositing 200nm IZO by sputtering.
7) Thermally evaporating Ag grid line electrodes with the thickness of 200 nm.
8) A 140nm thick LiF antireflective layer was thermally evaporated.
Example 6
1) A crystal silicon bottom battery of sputtering IZO is used as a substrate.
2) The NiOx solution was spin-coated at 2000 revolutions for 30 seconds and annealed at 150 degrees to prepare a hole transport layer.
3) On the NiOx transmission layer, a perovskite absorption layer is prepared by adopting a two-step method. Firstly PbI2、PbBr2Solutions separately dissolved and then mixed with CsI were spun at 1500 rpmSpin coating for 30 seconds and 70 degree annealing. Then, an organic salt solution is dripped, spin-coated for 30 seconds at the rotation speed of 1800 revolutions and annealed at 150 ℃ to prepare the perovskite thin film.
4) A PCBM electron transport layer was prepared on the perovskite layer and the PCBM solution was spin coated for 30 seconds at 1000 revolutions.
5) And depositing 10 nm SnOx by atomic layer deposition.
6) 100 nm ITO was deposited by sputtering.
7) Thermally evaporating Ag grid line electrodes with the thickness of 200 nm.
8) Thermal evaporation of 150nm thick MgF2And (4) antireflection layer.
Although the present invention has been described in detail with reference to the embodiments, it will be apparent to those skilled in the art that changes and substitutions can be made in the embodiments described above, and any changes and modifications made based on the principles of the present invention and the non-inventive work therein shall fall within the scope of the present invention.

Claims (10)

1. The preparation method of the high-open-pressure wide-band-gap perovskite roof battery for the laminated battery is characterized in that the wide-band-gap perovskite absorption layer of the high-open-pressure wide-band-gap perovskite battery is prepared through a two-step method, firstly, a metal halide thin film is obtained, then, an organic halide thin film is prepared on the metal halide thin film, the organic halide thin film and the metal halide thin film react to prepare the wide-band-gap perovskite absorption layer, and a surface interface defect of the wide-band-gap perovskite absorption layer is eliminated through a passivating agent, so that a high-open-pressure and high-performance wide-band-gap perovskite solar battery device is obtained, and a foundation is laid for application of a transparent single-junction solar battery or a high-efficiency multi-junction laminated solar battery.
2. The method of claim 1, wherein the wide band gap perovskite absorber layer has a band gap range selected from the group consisting of: 1.6eV to 2.9 eV. The wide-band-gap perovskite absorption layer material has ABX3The structure is shown in the specification, wherein the A-site cation is at least one of lithium, sodium, potassium, rubidium, cesium, amido, amidino and guanidino compounds; the cation at the B position is Pb2+、Sn2+、Ge2+、Sb2+、Bi3+At least one of the fourth, fifth and sixth etc. main group elements, etc.; the anion X is I-、Cl-、Br-And the like.
3. The method of manufacturing a high-open-pressure wide-bandgap perovskite-roof battery for a laminate battery as claimed in claim 1, wherein the metal halide thin film is manufactured by at least one of lead iodide, lead bromide, lead chloride, cesium iodide, cesium chloride, cesium bromide, and the like. Different band gaps are obtained by adjusting the addition molar ratio of the halides in the solution; the solvent for dissolving the metal halide may be, but is not limited to, at least one of organic solvents such as N, N-dimethylformamide, dimethyl sulfoxide, a mixed methylamine/alcohol solution, acetonitrile, 2-methoxyethanol, and the like; or at least one of methylamine, formamidine and other gases; or at least one of ionic liquids such as methylamine acetate, methylamine formate and formamidine acetate; taking the solvent dissolved in N, N-dimethylformamide and dimethyl sulfoxide as an example, the ratio of the N, N-dimethylformamide to the dimethyl sulfoxide can be, but is not limited to, 1:9-9:1, and preferably ranges from 3:1 to 5: 1. The metal halide solution can be obtained by dissolving a plurality of substances together, or can be obtained by mixing the plurality of substances according to a certain molar concentration ratio after being dissolved separately; the preferred preparation method is that lead iodide and lead bromide are respectively dissolved into a solution A and a solution B, then the two are dissolved according to the volume ratio of 5:1-1:5 to obtain a solution C, cesium iodide or cesium bromide and the like are separately dissolved to obtain a solution D, and then the solution C and the solution D are mixed according to the volume ratio (20:1-10:1) to obtain a solution E for preparing the metal halide film. The concentration range of solution A, B, C, D, E includes, but is not limited to, 0.5 moles/liter to 1.7 moles/liter.
4. The method of claim 1, wherein the organic halide includes, but is not limited to, at least one of formamidine iodide (FAI), formamidine bromide (FABr), formamidine chloride (FACl), methylamine iodide (MAI), methylamine iodide (MABr), methylamine iodide (MACl), etc.; the solvent that dissolves the above substances includes, but is not limited to, at least one of organic solvents that do not dissolve the perovskite material, such as isopropyl alcohol (IPA), chlorobenzene, toluene, and methylene chloride. The organic halide solution concentration includes, but is not limited to, 50 mg/ml to 150 mg/ml, with a preferred range being 90 mg/ml to 120 mg/ml.
5. The method for manufacturing a high-open-pressure wide-bandgap perovskite roof battery for a laminate battery as claimed in claim 1, wherein the two-step process includes at least one or more methods selected from but not limited to spin coating, thermal evaporation, blade coating, slit coating, roll coating, spray coating, etc; taking a spin coating method as an example, a metal halide film is prepared by dripping 30-100 microliter of solution on a substrate, then spin-coating at the rotation speed of 1000-3000 r/min for 30 seconds, after annealing at 70-100 ℃ for 1-5 minutes, dripping 30-100 microliter of organic halide solution, then spin-coating at the rotation speed of 1000-3000 r/min for 30 seconds, and after annealing at 100-160 ℃ for 10-20 minutes, obtaining the wide-bandgap perovskite absorption layer.
6. The method for preparing a high-open-voltage wide-bandgap perovskite-roof battery for a tandem cell as claimed in claim 1, wherein the passivation method comprises adding at least one of organic halide salts such as phenethyl ammonium iodide, phenethyl ammonium bromide and phenethyl ammonium chloride as a passivating agent to at least one of the perovskite absorption layer and the electron transport layer, the perovskite absorption layer and the hole transport layer, or the perovskite absorption layer to obtain a perovskite thin film with less non-radiative recombination defects and reduce open-circuit voltage loss.
7. The preparation step of the passivating agent added between the perovskite absorption layer and the electron transport layer according to claim 6, comprising: firstly, preparing a passivating agent solution with the concentration of 1-10 mg/ml, wherein the solvent is at least one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbons, such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, gamma-butyrolactone, acetonitrile, chlorobenzene, toluene and isopropanol, and depositing the passivating agent solution on the electron transport layer by a spin coating method without annealing; the preparation method of the passivating agent added between the perovskite absorption layer and the hole transport layer comprises the following steps: firstly, preparing a passivating agent solution with the concentration of 1-10 mg/ml, wherein the solvent is at least one of isopropanol, chlorobenzene, toluene, dichloromethane and other organic solvents which do not dissolve the perovskite material, and the passivating agent solution is deposited on the perovskite absorption layer by a spin coating method without annealing; the preparation steps of the passivating agent added into the perovskite absorption layer comprise: and adding 1-10 mg/ml of passivating agent into the lead iodide solution, and forming a film together with the perovskite precursor solution.
8. The method for manufacturing a high open-voltage wide band gap perovskite-top cell for a stacked cell as claimed in claim 1, wherein the substrate may be at least one of flexible or rigid substrates such as but not limited to glass, metal, silicon wafer, fabric, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyimide (PI), Polydimethylsiloxane (PDMS), and derivatives thereof; the transparent conductive film may be, but is not limited to, at least one of oxide thin films of Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), Indium Cerium Oxide (ICO), and the like; the metal electrode can be but is not limited to at least one of various metals such as Au, Ag, Al, Cu, Ti and the like.
9. The method of claim 1, wherein the electron transport layer is selected from the group consisting of titanium dioxide (TiO)2) Tin dioxide (SnO)2) Zinc oxide (ZnO), polystyrene sulfonate (e.g., PSSA), fullerene derivatives (e.g., PSSA)At least one of PCBM), poly (3-hexylthiophene-2, 5-diyl), graphene, zinc tin oxide, a metal phthalocyanine molecular material, fullerene and the like; the hole transport layer may be, but is not limited to, nickel oxide (NiO)x) Molybdenum oxide (MoO)x) Tungsten oxide (WO)x) Vanadium pentoxide (V)2Ox) Copper thiocyanate (CuSCN), Poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate (e.g., PEDOT: PSS), copper thiocyanate, copper iodide, zinc sulfide, key disulfide, chromium oxide, key oxide, polyvinylcarbazole, 4-butyl-N, N-diphenylaniline homopolymer (Poly-TPD), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane, Poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA), 2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]9,9' -spirobifluorene (Spiro-OMeTAD) and the like.
10. The method for preparing a high-open-voltage wide-band-gap perovskite roof cell for a tandem cell as claimed in claim 1, wherein the method is applicable to at least one of a single-junction wide-band-gap perovskite solar cell, a perovskite/crystalline silicon multi-junction tandem solar cell, a perovskite/perovskite multi-junction tandem solar cell, and a corresponding large-area solar cell and other photoelectric devices such as a light emitting diode, a photoelectric detector, a laser and the like.
CN202210024662.7A 2022-01-07 2022-01-07 Preparation method of high-open-voltage wide-band-gap perovskite top battery for laminated battery Pending CN114373871A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115084395A (en) * 2022-08-22 2022-09-20 中国华能集团清洁能源技术研究院有限公司 Perovskite absorption layer/hole transport layer interface processing method and perovskite solar cell
CN115867054A (en) * 2022-11-25 2023-03-28 江苏振宁半导体研究院有限公司 Super-conformal metal halide perovskite photoelectric detector array

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115084395A (en) * 2022-08-22 2022-09-20 中国华能集团清洁能源技术研究院有限公司 Perovskite absorption layer/hole transport layer interface processing method and perovskite solar cell
CN115084395B (en) * 2022-08-22 2022-11-15 中国华能集团清洁能源技术研究院有限公司 Perovskite absorption layer/hole transport layer interface processing method and perovskite solar cell
CN115867054A (en) * 2022-11-25 2023-03-28 江苏振宁半导体研究院有限公司 Super-conformal metal halide perovskite photoelectric detector array

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