CN117255572A - Improve FA 0.75 MA 0.25 SnI 3 Method for stabilizing perovskite film and FA prepared by method 0.75 MA 0.25 SnI 3 Perovskite thin film and application - Google Patents
Improve FA 0.75 MA 0.25 SnI 3 Method for stabilizing perovskite film and FA prepared by method 0.75 MA 0.25 SnI 3 Perovskite thin film and application Download PDFInfo
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- CN117255572A CN117255572A CN202311155071.4A CN202311155071A CN117255572A CN 117255572 A CN117255572 A CN 117255572A CN 202311155071 A CN202311155071 A CN 202311155071A CN 117255572 A CN117255572 A CN 117255572A
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- 239000010408 film Substances 0.000 title claims abstract description 77
- 239000010409 thin film Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 76
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 29
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 239000012296 anti-solvent Substances 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 15
- 238000004528 spin coating Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 150000002222 fluorine compounds Chemical class 0.000 description 7
- 230000005525 hole transport Effects 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VOWZMDUIGSNERP-UHFFFAOYSA-N carbamimidoyl iodide Chemical compound NC(I)=N VOWZMDUIGSNERP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JAHFQMBRFYOPNR-UHFFFAOYSA-N iodomethanamine Chemical compound NCI JAHFQMBRFYOPNR-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
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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
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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
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
- C03C2217/948—Layers comprising indium tin oxide [ITO]
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a method for improving FA 0.75 MA 0.25 SnI 3 Method for stabilizing perovskite film and FA prepared by method 0.75 MA 0.25 SnI 3 Perovskite thin film and application, the method is that in FA 0.75 MA 0.25 SnI 3 The surface of the perovskite film is added with a fluoride layer of isopropanol. The invention is realized by the method in FA 0.75 MA 0.25 SnI 3 The surface of the perovskite film is added with a fluoride layer of isopropanol, so that the hydrophobic property of the perovskite film is enhanced, and the perovskite film is improvedResistance to water attack, reduced damage to perovskite film from water and oxygen, and improved FA 0.75 MA 0.25 SnI 3 The perovskite film has stability, can be widely applied to the photoelectric field, such as perovskite solar cells, perovskite light-emitting devices and the like, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to an improvement of FA 0.75 MA 0.25 SnI 3 Method for stabilizing perovskite film and FA prepared by method 0.75 MA 0.25 SnI 3 PerovskiteFilms and applications.
Background
In recent years, lead (Pb) -based perovskite solar cells have been rapidly developed, but they may bring about environmental pollution problems that prevent commercialization of the same. In this case, tin (Sn) -based perovskite is attracting attention from a large number of perovskite materials because of its environmental friendliness and excellent performance. At present, FA 0.75 MA 0.25 SnI 3 Perovskite is a material with excellent photoelectric performance in tin-based perovskite materials, and has good application prospect in the field of perovskite solar cells.
Although perovskite solar cells have high energy conversion efficiency, the stability problem has been the main reason limiting commercialization, and the stability of many perovskite solar cells cannot meet the requirements of standard stability tests at present. The main reason for influencing the stability is that the perovskite layer of the perovskite solar cell is a perovskite film, and water vapor and oxygen are easy to diffuse and permeate into the perovskite film, so that the perovskite film is rapidly degraded and the stability is poor, and therefore, the stability of the perovskite film seriously influences the stability of the perovskite solar cell. In the prior art, various hydrophobic materials can protect the perovskite film from being contacted with water vapor, such as fluorine compounds have excellent steam resistance and heat resistance, but not all fluorine compounds can be used for improving the stability of the perovskite film, some fluorine compounds can dissolve perovskite and damage the perovskite film, some fluorine compounds have insulativity, and after the fluorine compounds are coated on the surface of the perovskite film to protect the perovskite film, the perovskite film cannot be used for perovskite solar cells, and the stability of the perovskite film cannot be improved.
Therefore, how to improve the stability of the perovskite thin film and further improve the stability of the perovskite solar cell is a key technical problem to be solved urgently.
Disclosure of Invention
The invention provides a method for improving FA (FA) in order to overcome the defect and the defect of poor stability of perovskite solar cells caused by poor stability of the existing perovskite thin film 0.75 MA 0.25 SnI 3 Method for improving FA by perovskite film stability 0.75 MA 0.25 SnI 3 Stability of perovskite thin films.
A second object of the present invention is to provide an FA 0.75 MA 0.25 SnI 3 Perovskite thin films.
A third object of the present invention is to provide an FA 0.75 MA 0.25 SnI 3 A method for preparing perovskite thin film.
A fourth object of the present invention is to provide an FA 0.75 MA 0.25 SnI 3 Perovskite solar cell.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention provides a method for improving FA 0.75 MA 0.25 SnI 3 A method for stabilizing perovskite film, which is characterized in that FA 0.75 MA 0.25 SnI 3 The surface of the perovskite film is added with a fluoride layer of isopropanol.
The invention is applied to FA 0.75 MA 0.25 SnI 3 The fluoride layer of isopropanol is added on the surface of the perovskite film, and the unexpected discovery that the hydrophobic property of the perovskite film is enhanced, the water erosion resistance of the perovskite film is improved, the damage of water and oxygen to the perovskite film is reduced, and the FA is improved 0.75 MA 0.25 SnI 3 Stability of perovskite thin films.
Further, the fluoride layer of isopropanol is prepared from hexafluoroisopropanol or 1, 1-trifluoroisopropanol.
The invention provides an FA 0.75 MA 0.25 SnI 3 Perovskite thin film, FA 0.75 MA 0.25 SnI 3 The perovskite film is made of FA 0.75 MA 0.25 SnI 3 The perovskite film comprises a perovskite film base layer and an isopropyl alcohol fluoride layer which is covered on the surface of the base layer.
The invention provides an FA 0.75 MA 0.25 SnI 3 The preparation method of the perovskite thin film comprises the following steps:
s1, taking FA 0.75 MA 0.25 SnI 3 Coating perovskite precursor solution on a substrate, and applying FA to the coated substrate 0.75 MA 0.25 SnI 3 Adding an antisolvent on a substrate of the perovskite precursor solution, and obtaining the FA by using an antisolvent method 0.75 MA 0.25 SnI 3 A perovskite initial thin film;
s2, FA in step S1 0.75 MA 0.25 SnI 3 Coating fluoride of isopropanol on perovskite initial film to obtain FA 0.75 MA 0.25 SnI 3 Perovskite thin films.
Further, the FA in step S1 0.75 MA 0.25 SnI 3 The perovskite precursor solution is prepared by dissolving iodoformamidine, iodomethylamine and stannous iodide in a molar ratio of 0.75:0.25:1 in a solvent.
Further, the FA 0.75 MA 0.25 SnI 3 After the perovskite initial film is coated with fluoride of isopropanol, annealing or drying treatment is also needed.
Further, the FA in step S1 0.75 MA 0.25 SnI 3 The volume ratio of the perovskite precursor solution to the fluoride of isopropanol in S2 is 1: (2-2.5).
FA 0.75 MA 0.25 SnI 3 FA when the volume ratio of the perovskite precursor solution and the fluoride of isopropyl alcohol is within this range 0.75 MA 0.25 SnI 3 The perovskite film has the best stability effect.
Preferably, the fluoride of isopropyl alcohol in step S2 is hexafluoroisopropyl alcohol.
Still further, the solvent is dimethyl sulfoxide (DMSO) and/or Dimethylformamide (DMF).
Further, the antisolvent in step S1 is one of chlorobenzene, toluene, ethyl acetate, diethyl ether, dichloromethane, anisole.
The invention provides the FA prepared by the method 0.75 MA 0.25 SnI 3 Perovskite thin films.
The invention provides fluoride of isopropanol to increase FA 0.75 MA 0.25 SnI 3 Perovskite thin film stability or FA production 0.75 MA 0.25 SnI 3 Use in perovskite thin films.
The invention provides fluoride of isopropanol to increase FA 0.75 MA 0.25 SnI 3 Perovskite solar cell stability or FA production 0.75 MA 0.25 SnI 3 Application in perovskite solar cell, FA 0.75 MA 0.25 SnI 3 Perovskite solar cell containing FA 0.75 MA 0.25 SnI 3 Perovskite thin film, FA 0.75 MA 0.25 SnI 3 The perovskite thin film is coated with fluoride of isopropyl alcohol.
The invention provides FA 0.75 MA 0.25 SnI 3 Use of perovskite thin films in the photovoltaic field, said FA 0.75 MA 0.25 SnI 3 The perovskite thin film is coated with fluoride of isopropyl alcohol.
Further, the photoelectric field is the fields of perovskite solar cells, perovskite light emitting devices and the like.
The invention provides an FA 0.75 MA 0.25 SnI 3 Perovskite solar cell, the FA 0.75 MA 0.25 SnI 3 Perovskite solar cell containing FA 0.75 MA 0.25 SnI 3 Perovskite thin film, FA 0.75 MA 0.25 SnI 3 The perovskite thin film is coated with fluoride of isopropyl alcohol.
Further, the FA 0.75 MA 0.25 SnI 3 Perovskite solar cell comprising cathode layer, hole blocking layer, electron transport layer, FA 0.75 MA 0.25 SnI 3 Perovskite layer, hole transport layer and ITO anode substrate, the FA 0.75 MA 0.25 SnI 3 The perovskite layer is formed by the FA 0.75 MA 0.25 SnI 3 Perovskite thin film composition.
The invention uses fluoride of isopropanol to make FA 0.75 MA 0.25 SnI 3 Perovskite thin film is treated to improveFA 0.75 MA 0.25 SnI 3 The stability of the perovskite film is further improved, and FA with high stability is obtained 0.75 MA 0.25 SnI 3 Perovskite solar cell.
Further, the cathode layer is a metal cathode layer, and the material of the cathode layer can be copper or silver.
Further, the hole transport layer is made of PEDOT: PSS.
Compared with the prior art, the invention has the beneficial effects that:
(1) Improve FA 0.75 MA 0.25 SnI 3 A method for stabilizing perovskite film, which is characterized in that FA 0.75 MA 0.25 SnI 3 The surface of the perovskite film is added with a fluoride layer of isopropanol, and the fluoride of isopropanol is used for FA 0.75 MA 0.25 SnI 3 The perovskite film is treated, the hydrophobic property of the perovskite film is enhanced, the water erosion resistance of the perovskite film is improved, the damage of water and oxygen to the perovskite film is reduced, and the FA is improved 0.75 MA 0.25 SnI 3 Stability of perovskite thin films.
(2) Containing FA 0.75 MA 0.25 SnI 3 FA of perovskite thin film 0.75 MA 0.25 SnI 3 The stability of the perovskite solar cell is also obviously improved; utilizing FA 0.75 MA 0.25 SnI 3 FA prepared by coating perovskite thin film with isopropanol 0.75 MA 0.25 SnI 3 The perovskite thin film can be widely applied to the photoelectric field, such as perovskite solar cells, perovskite light-emitting devices and the like.
Drawings
FIG. 1 is a diagram of FA obtained in example 1 0.75 MA 0.25 SnI 3 Surface topography of perovskite thin films.
FIG. 2 is a diagram of FA obtained in example 1 and comparative example 1 0.75 MA 0.25 SnI 3 A contact angle comparison graph of perovskite thin films;
FIG. 2 a shows the FA in example 1 0.75 MA 0.25 SnI 3 Contact angle of perovskite thin film; b represents FA in comparative example 1 0.75 MA 0.25 SnI 3 Contact angle of perovskite thin film.
FIG. 3 is the FA obtained in example 7 and comparative examples 4-5 0.75 MA 0.25 SnI 3 Stability comparison graph of perovskite solar cell.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
Example 1
FA (FA) 0.75 MA 0.25 SnI 3 The perovskite thin film is prepared by the following method:
s1, 70 mu LFA is used 0.75 MA 0.25 SnI 3 Dripping perovskite precursor solution on ITO (Indium Tin Oxide) glass substrate, spin-coating at 4000rpm for 60s, continuously and uniformly dripping 120 mu L chlorobenzene anti-solvent on the surface of perovskite film in the spin-coating process at 13s after the spin-coating is started, and spin-coating FA after the spin-coating is finished 0.75 MA 0.25 SnI 3 Placing the substrate of perovskite precursor solution on a heat table at 100 ℃ for annealing for 11min to obtain FA 0.75 MA 0.25 SnI 3 Annealing at 100 ℃ of the perovskite initial film can remove the solvent and facilitate the formation of large-sized grains.
Wherein, FA 0.75 MA 0.25 SnI 3 The preparation method of the perovskite precursor solution comprises the following steps: FAI (129 mg), MAI (40 mg) and SnI 2 (373 mg) was added to 1mL of a mixed solvent of dimethyl sulfoxide and dimethylformamide (volume ratio: 1:4) and mixed uniformly to give FA 0.75 MA 0.25 SnI 3 Precursor solution.
S2, FA in step S1 0.75 MA 0.25 SnI 3 Spin-coating 150 μL hexafluoroisopropanol on perovskite initial film at 3500rpm for 30s, spin-coating knotsFA coated with hexafluoroisopropanol by annealing for 11min on a hot bench at 35 ℃ after beam 0.75 MA 0.25 SnI 3 Drying the perovskite initial film to obtain FA 0.75 MA 0.25 SnI 3 Perovskite thin films. The FA 0.75 MA 0.25 SnI 3 The perovskite film is made of FA 0.75 MA 0.25 SnI 3 FA of perovskite initial film composition 0.75 MA 0.25 SnI 3 A perovskite film base layer and a fluoride layer of isopropanol composed of isopropanol and hexafluoroisopropanol.
Example 2
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film, substantially the same as in example 1, differing in that: 140. Mu.L hexafluoroisopropanol was spin coated.
Example 3
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film, substantially the same as in example 1, differing in that: 175 μl of hexafluoroisopropanol was spin coated.
Example 4
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film, substantially the same as in example 1, differing in that: hexafluoroisopropanol was replaced with 1, 1-trifluoroisopropanol.
Example 5
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film, substantially the same as in example 1, differing in that: 70 μl of hexafluoroisopropanol was spin coated.
Example 6
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film, substantially the same as in example 1, differing in that: 300. Mu.L hexafluoroisopropanol was spin coated.
Comparative example 1
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film, substantially the same as in example 1, differing in that: no hexafluoroisopropanol to FA 0.75 MA 0.25 SnI 3 The perovskite initial film is treated.
Comparative example 2
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film, substantially the same as in example 1, differing in that: 150 μl of hydrofluoric acid was spin coated.
Comparative example 3
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film, substantially the same as in example 1, differing in that: 150. Mu.L of pentafluorobenzene was spin-coated.
Example 7
FA (FA) 0.75 MA 0.25 SnI 3 The perovskite solar cell sequentially comprises a cathode layer, a hole blocking layer, an electron transport layer and FA from top to bottom 0.75 MA 0.25 SnI 3 The cathode layer is made of Ag, the hole blocking layer is made of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), and the electron transport layer is made of C 60 ，FA 0.75 MA 0.25 SnI 3 The perovskite layer is FA 0.75 MA 0.25 SnI 3 The perovskite film and the hole transport layer are made of PEDOT: PSS, and are prepared by the following method:
s1, cleaning an ITO anode substrate: scrubbing an ITO anode substrate by sequentially using acetone and ethanol, sequentially ultrasonically cleaning the substrate by using acetone, ethanol and deionized water for 15min, and drying the substrate in a baking oven at 120 ℃ after ultrasonic treatment;
s2, preparing a hole transport layer: the PEDOT-PSS solution with the aperture of 0.45 mu m is filtered twice by a water-based filter, spin-coated for 45s on an ITO anode substrate to which the anode modification layer is applied at 3500rpm, and dried in an oven at 120 ℃ for 40min to obtain a 40nm hole transport layer PEDOT-PSS;
s3, preparing FA 0.75 MA 0.25 SnI 3 Perovskite layer: preparation of FA by one-step antisolvent method 0.75 MA 0.25 SnI 3 Perovskite layer, FAI (129 mg), MAI (40 mg), snI 2 (373 mg) was added to 1mL of a mixed solvent of dimethyl sulfoxide and dimethylformamide (volume ratio: 1:4) and mixed uniformly to give FA 0.75 MA 0.25 SnI 3 Precursor solution70 mu LFA 0.75 MA 0.25 SnI 3 Dropwise adding perovskite precursor solution onto the hole transport layer, spin-coating at 4000rpm for 60s, continuously and uniformly dropwise adding 120 mu L of chlorobenzene anti-solvent onto the surface of the perovskite film in the spin-coating process at 13s after the spin-coating is started, and spin-coating FA after the spin-coating is finished 0.75 MA 0.25 SnI 3 Placing the substrate of perovskite precursor solution on a heat table at 100 ℃ for annealing for 11min to obtain FA 0.75 MA 0.25 SnI 3 Perovskite initial thin film. At FA 0.75 MA 0.25 SnI 3 150 mu L of hexafluoroisopropanol is spin-coated on the perovskite initial film at 4000rpm, and annealed at 100 ℃ for 11min after spin-coating is finished to obtain 170nm FA 0.75 MA 0.25 SnI 3 A perovskite layer;
s4, FA described in S3 0.75 MA 0.25 SnI 3 Vacuum evaporation of 35nm electron transport layer C on perovskite layer 60 8nm hole blocking layer BCP, 90nm cathode layer Ag.
Comparative example 4
FA (FA) 0.75 MA 0.25 SnI 3 A perovskite solar cell, substantially identical to example 7, differs in that: no hexafluoroisopropanol to FA 0.75 MA 0.25 SnI 3 Performing aftertreatment on the perovskite initial film, and performing FA (FA) 0.75 MA 0.25 SnI 3 The perovskite layer is FA 0.75 MA 0.25 SnI 3 Perovskite initial thin film.
Comparative example 5
The method of example 7 is referred to, except that in step S3, the FA is 0.75 MA 0.25 SnI 3 150. Mu.L of pentafluorobenzene was coated on the perovskite starting film at 4000rpm to prepare a battery.
Experimental example 1 scanning electron microscope test
1. Experimental method
For FA prepared in example 1 0.75 MA 0.25 SnI 3 The perovskite thin film was subjected to Scanning Electron Microscope (SEM) test to test FA prepared in example 1 0.75 MA 0.25 SnI 3 Whether the perovskite film surface is damaged or not. The testing method comprises the following steps: FA is set up 0.75 MA 0.25 SnI 3 The perovskite film is placed in a Scanning Electron Microscope (SEM) cavity and FA is bombarded with high-energy incident electrons 0.75 MA 0.25 SnI 3 Perovskite thin film surface by utilizing electrons and FA 0.75 MA 0.25 SnI 3 Interaction of perovskite, obtaining FA 0.75 MA 0.25 SnI 3 Surface morphology image of perovskite film, and further observation of FA 0.75 MA 0.25 SnI 3 Variation in perovskite thin film quality.
2. Experimental results
The test results are shown in FIG. 1, and FIG. 1 is the FA obtained in example 1 0.75 MA 0.25 SnI 3 As can be seen from the surface topography of the perovskite film, FIG. 1 shows FA after hexafluoroisopropanol treatment 0.75 MA 0.25 SnI 3 The morphology of the perovskite film is almost unchanged, and the surface is uniform and has no damage, so that the hexafluoroisopropanol can be proved to not cause damage to FA 0.75 MA 0.25 SnI 3 The perovskite thin film causes damage.
Experimental example 2 contact angle test of perovskite thin film
1. Experimental method
FA prepared in examples 1 to 6 and comparative examples 1 to 3 was measured using a contact angle tester 0.75 MA 0.25 SnI 3 The contact angle of the perovskite thin film was tested. The testing method comprises the following steps: FA is set up 0.75 MA 0.25 SnI 3 The perovskite film is placed on a platform of a contact angle tester, pure deionized water slowly falls on the surface of the perovskite film through the arrangement of the tester, the tester performs full-scale photography, the change condition of the contact angle during monitoring is monitored, and then the related data of the contact angle are obtained.
2. Experimental results
As shown in Table 1, the results of the test are shown in Table 1, and it is clear from Table 1 that FA after treatment with hexafluoroisopropanol or 1, 1-trifluoroisopropanol 0.75 MA 0.25 SnI 3 The perovskite thin film contact angle increases significantly and when theFA 0.75 MA 0.25 SnI 3 The ratio of the amount of the fluoride of the perovskite precursor solution and the isopropyl alcohol is 1: (2-2.5) the contact angle is large; and other fluorides or fluorides without isopropanol are used, so that the contact angle is smaller, and the water erosion resistance of the perovskite film is lower. As shown in FIG. 2, FA obtained in example 1 and comparative example 1 0.75 MA 0.25 SnI 3 The contact angle of the perovskite thin film is compared with that of FIG. 2, and it can be seen that FA after hexafluoroisopropanol treatment 0.75 MA 0.25 SnI 3 The water contact angle of the perovskite film is obviously increased, which indicates that the water erosion resistance of the perovskite film is improved.
TABLE 1 contact angle results for examples 1-6 and comparative examples 1-3
Experimental example 3FA 0.75 MA 0.25 SnI 3 Perovskite solar cell stability test
1. Experimental method
FA prepared in example 7 and comparative examples 4 to 5 0.75 MA 0.25 SnI 3 Perovskite solar cells were tested for stability. The testing method comprises the following steps: FA is set up 0.75 MA 0.25 SnI 3 Perovskite solar cells were placed in air at intervals using a standard simulated solar simulator (AM 1.5g,100mw/cm 2 ) At the beginning of being filled with N 2 Atmosphere (O) 2 <1ppm and H 2 O<0.1 ppm) of Parafa in glove box 0.75 MA 0.25 SnI 3 The perovskite solar cell is subjected to a Current Density-Voltage (J-V) characteristic test (under the irradiation of standard sunlight), so that the photoelectric conversion efficiency is measured, the aging condition of the perovskite solar cell is analyzed, and further, the relevant data of stability are obtained.
2. Experimental results
The test results are shown in FIG. 3, and FIG. 3 shows the FA obtained in example 7 and comparative examples 4 and 5 0.75 MA 0.25 SnI 3 Comparison of the stability of perovskite solar cell, it can be seen from the graph that FA prepared in example 7 was obtained at the same time 0.75 MA 0.25 SnI 3 The photoelectric conversion efficiency of the perovskite solar cell was higher than that of the FA prepared in comparative example 4 and comparative example 5 0.75 MA 0.25 SnI 3 Perovskite solar cell. From this, it was found that FA after hexafluoroisopropanol post-treatment 0.75 MA 0.25 SnI 3 FA prepared from perovskite thin film 0.75 MA 0.25 SnI 3 The stability of the perovskite solar cell is improved.
In summary, the present invention provides for increasing FA 0.75 MA 0.25 SnI 3 Method for perovskite film stability by using hexafluoroisopropanol to react FA 0.75 MA 0.25 SnI 3 The perovskite initial film is subjected to post-treatment, hexafluoroisopropanol is gathered on the surface of the perovskite initial film, so that the crystallization quality of the perovskite film is improved, the hydrophobic property of the perovskite film is enhanced, the water erosion resistance of the perovskite film is improved, the damage of water and oxygen to the perovskite film is reduced, and the FA is improved 0.75 MA 0.25 SnI 3 The stability of the perovskite film is improved, and the FA is further improved 0.75 MA 0.25 SnI 3 Stability of perovskite solar cells.
It is to be understood that the above examples of the present invention are provided by way of illustration only and are not intended to limit the scope of the invention. It will be appreciated by persons skilled in the art that other variations or modifications may be made in the various forms based on the description above. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. ImproveFA 0.75 MA 0.25 SnI 3 A method for stabilizing perovskite thin film, characterized in that, in FA 0.75 MA 0.25 SnI 3 The surface of the perovskite film is added with a fluoride layer of isopropanol.
2. The method according to claim 1, wherein the fluoride layer of isopropyl alcohol is made of hexafluoroisopropyl alcohol or 1, 1-trifluoroisopropyl alcohol.
3. FA (FA) 0.75 MA 0.25 SnI 3 A perovskite thin film characterized in that the FA 0.75 MA 0.25 SnI 3 The perovskite film is made of FA 0.75 MA 0.25 SnI 3 The perovskite film comprises a perovskite film base layer and an isopropyl alcohol fluoride layer which is covered on the surface of the base layer.
4. FA (FA) 0.75 MA 0.25 SnI 3 The preparation method of the perovskite thin film is characterized by comprising the following steps of:
s1, taking FA 0.75 MA 0.25 SnI 3 Coating perovskite precursor solution on a substrate, and applying FA to the coated substrate 0.75 MA 0.25 SnI 3 Adding an antisolvent on a substrate of the perovskite precursor solution, and obtaining the FA by using an antisolvent method 0.75 MA 0.25 SnI 3 A perovskite initial thin film;
s2, FA in step S1 0.75 MA 0.25 SnI 3 Coating fluoride of isopropanol on perovskite initial film to obtain FA 0.75 MA 0.25 SnI 3 Perovskite thin films.
5. The process according to claim 4, wherein the antisolvent in step S1 is one of chlorobenzene, toluene, ethyl acetate, diethyl ether, dichloromethane, anisole.
6. The method according to claim 4, wherein the FA in step S1 is selected from the group consisting of 0.75 MA 0.25 SnI 3 The ratio of the amount of the perovskite precursor solution to the fluoride of isopropyl alcohol in step S2 is 1: (2-2.5).
7. A FA prepared by the method according to any one of claims 4 to 6 0.75 MA 0.25 SnI 3 Perovskite thin films.
8. Fluoride of isopropanol to increase FA 0.75 MA 0.25 SnI 3 Perovskite thin film stability or FA production 0.75 MA 0.25 SnI 3 Use in perovskite thin films.
9.FA 0.75 MA 0.25 SnI 3 Use of perovskite thin film in the field of optoelectronics, characterized in that the FA 0.75 MA 0.25 SnI 3 The perovskite thin film is coated with fluoride of isopropyl alcohol.
10. FA (FA) 0.75 MA 0.25 SnI 3 Perovskite solar cell, characterized in that the FA 0.75 MA 0.25 SnI 3 Perovskite solar cell containing FA 0.75 MA 0.25 SnI 3 Perovskite thin film, FA 0.75 MA 0.25 SnI 3 The perovskite thin film is coated with fluoride of isopropyl alcohol.
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