CN113471364B - Preparation method of perovskite solar cell - Google Patents
Preparation method of perovskite solar cell Download PDFInfo
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- CN113471364B CN113471364B CN202110647655.8A CN202110647655A CN113471364B CN 113471364 B CN113471364 B CN 113471364B CN 202110647655 A CN202110647655 A CN 202110647655A CN 113471364 B CN113471364 B CN 113471364B
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- perovskite
- hole transport
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- transport layer
- passivation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 70
- 230000005525 hole transport Effects 0.000 claims abstract description 50
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000002161 passivation Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 238000004528 spin coating Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000031700 light absorption Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 claims description 6
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 claims description 6
- RTLUPHDWSUGAOS-UHFFFAOYSA-N 4-iodopyridine Chemical compound IC1=CC=NC=C1 RTLUPHDWSUGAOS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
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- 238000005893 bromination reaction Methods 0.000 claims description 4
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- 238000005859 coupling reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000005118 spray pyrolysis Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- -1 niobium pentoxide metal oxide Chemical class 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 83
- 238000006243 chemical reaction Methods 0.000 description 72
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000010410 layer Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 28
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- 239000010408 film Substances 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 18
- 229940125904 compound 1 Drugs 0.000 description 16
- 229940125782 compound 2 Drugs 0.000 description 16
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 16
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 16
- 239000003480 eluent Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000741 silica gel Substances 0.000 description 13
- 229910002027 silica gel Inorganic materials 0.000 description 13
- 239000010409 thin film Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 150000002220 fluorenes Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004896 high resolution mass spectrometry Methods 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XTAALASUYSUXDX-UHFFFAOYSA-N n-(4-methoxyphenyl)-9,9-dimethylfluoren-2-amine Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(C=2C(=CC=CC=2)C2(C)C)C2=C1 XTAALASUYSUXDX-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JKSIBASBWOCEBD-UHFFFAOYSA-N N,N-bis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-1-amine Chemical compound COc1ccc(cc1)N(c1ccc(OC)cc1)c1cccc2-c3ccccc3C3(c4ccccc4-c4ccccc34)c12 JKSIBASBWOCEBD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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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
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H—ELECTRICITY
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- 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
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
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- 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
- H10K30/88—Passivation; Containers; Encapsulations
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- 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
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- 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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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- 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
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- Y02E10/549—Organic PV cells
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Abstract
The invention belongs to the technical field of solar cells, and discloses a preparation method of a high-efficiency stable perovskite solar cell. A functional material CZ-Py with carbazole As a core structure is introduced to the surface of perovskite As a passivation layer, and an organic micromolecular material CZ-As is adopted As a hole transport material, so that a perovskite solar cell device is assembled. Firstly, the introduction of the passivation layer can passivate the defects of the perovskite surface and the grain boundary, effectively improve the charge transmission performance, isolate the contact of perovskite with water vapor and oxygen, inhibit the degradation of perovskite, and further improve the stability of the device; secondly, the energy levels of the hole transport material, the passivation material and the perovskite material are arranged in a step shape, so that the energy level matching is reasonable, and the extraction and the transmission of charges are facilitated; in addition, the passivation material and the hole transport material have the advantages of simple synthesis, low cost, high hole mobility and conductivity, good thermal stability and chemical stability and the like, and are suitable for being used in the perovskite solar cell preparation process on a large scale.
Description
Technical Field
The invention belongs to the technical field of solar cells, and relates to a preparation method of a high-efficiency stable perovskite solar cell.
Background
In the past decade, the Photoelectric Conversion Efficiency (PCE) of organic-inorganic lead halide Perovskite Solar Cells (PSC) has increased significantly from the first 3.8% to 25% or more, gaining widespread attention by many scholars (J.J.Yoo, G.Seo, M.R.Chua, T.G.Park, Y.Lu, F.Rotermund, Y.K.Kim, C.S.Moon, N.J.Jeon, J.P.Correa-Baena, V.Bulovic, S.S.Shin, M.G.Bawendi, J.Seo, nature 2021,590,587-593). The high efficiency of perovskite solar cells results from the excellent photovoltaic properties of perovskite materials, such as higher light absorption coefficient, higher carrier mobility, lower exciton binding energy, and tunable direct band gap, etc. (s. De Wolf, J.Holovsky, S.J.Moon, P.Loper, B.Niesen, M.Ledinsky, F.J.Haug, J.H.Yum, C.Ballif, J.Phys.Chem.Lett.2014,5, 1035-1039.). Nevertheless, further improvements in efficiency and long-term stability of the device still limit the large-scale production and commercial applications of perovskite solar cells. One of the main factors adversely affecting cell efficiency and stability is from defects in the perovskite material bulk phase and at the surface interface. Perovskite thin films prepared by solution processes are generally polycrystalline, and rapid crystal growth imparts disorder to the structure of the perovskite layer, which disorder distribution can produce grain boundary defects and crystal defects. These defects not only lead to a reduction in crystal quality, severely affecting carrier transport, but also accelerate moisture/oxygen permeation, accelerating degradation of the perovskite, and thus adversely affecting the efficiency and long-term stability of the perovskite solar cell (H.Li, J.Shi, J.Deng, Z.Chen, Y.Li, W.Zhao, J.Wu, H.Wu, Y.Luo, D.Li, Q.Meng, adv.Mater.2020,32, e 1907396.). On the other hand, currently efficient perovskite solar cells mostly use 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-ome) and poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA) as Hole Transport Materials (HTM), but complicated synthetic routes and purification steps of Spiro-ome and PTAA make them high cost materials, limiting their large scale application in future commercialization (E.H.Jung, N.J.Jeon, E.Y.Park, C.S.Moon, T.J.Shin, t. -Y.Yang, J.H.Noh, J.Seo, nature 2019,567,511-515; n.j.jeon, h.g.lee, y.c. kim, j.seo, j.h.noh, j.lee, s.i.seok, j.am.chem.soc.2014,136,7837-7840. Therefore, to further improve the efficiency and stability of the battery, on one hand, an effective interface passivation strategy needs to be proposed to reduce the defects of the perovskite surface interface; on the other hand, development of a novel low-cost and high-efficiency hole transport material is needed, and the preparation cost of the novel low-cost and high-efficiency hole transport material is greatly reduced while the charge extraction and transport efficiency is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to develop a preparation method of a high-efficiency stable perovskite solar cell, which comprises the specific steps of introducing a functional material CZ-Py taking carbazole As a core structure to the surface of perovskite As a passivation layer, adopting an organic micromolecular material CZ-As As a hole transport material, and further assembling the perovskite solar cell device. The passivation material and the hole transport material both take carbazole as a core structure, take diphenylamine derivatives or fluorene derivatives as end groups, and take 4-methoxybenzene or pyridine groups as N-site substituents. On one hand, the introduction of the passivation layer can passivate the defects of the perovskite surface and the grain boundary, effectively improve the charge transmission performance, and simultaneously isolate the perovskite from contact with water vapor and oxygen, inhibit the degradation of the perovskite, and further improve the stability of the device; on the other hand, the energy levels of the hole transport material, the passivation material and the perovskite material are arranged in a step shape, so that the energy level matching is reasonable, and the extraction and the transport of charges are facilitated; in addition, the passivation material and the hole transport material have the advantages of simple synthesis, low cost, high hole mobility and conductivity, good thermal stability and chemical stability and the like, are suitable for being applied to the perovskite solar cell preparation process in a large scale, and are beneficial to commercial application. Therefore, the invention not only can improve the photoelectric performance of the perovskite solar cell and enhance the stability of the cell, but also can reduce the manufacturing cost of the cell.
The invention adopts the technical scheme that: the preparation method of the perovskite solar cell is characterized by comprising the following steps of: introducing a carbazole functional material CZ-Py containing pyridine groups into an antisolvent solution in the preparation process of the perovskite solar cell, dripping the carbazole functional material CZ-Py onto the surface of perovskite, and carrying out passivation treatment on a perovskite layer; subsequently, a hole transport material CZ-As is spin-coated on the perovskite thin film.
The perovskite solar cell consists of a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a surface passivation layer, a hole transport layer and a metal electrode, and the specific preparation steps are as follows:
(1) Cutting a transparent conductive substrate into fixed sizes, etching, sequentially ultrasonically cleaning the etched conductive substrate in different solvents, and then performing ultraviolet ozone sterilization treatment;
(2) Preparing an electron transport layer on the transparent conductive substrate treated in the step (1) by a spray pyrolysis method or a spin coating method;
(3) Transferring the conductive substrate coated with the electron transport layer into a glove box, spin-coating the perovskite precursor liquid onto the electron transport layer by a spin-coating method, and dropwise adding chlorobenzene anti-solvent containing 0.1-3 mg/mL passivation material CZ-Py in the process of spin-coating the perovskite precursor liquid, wherein the dropwise adding amount is 100-300 mu L, so as to form a perovskite light absorption layer with a passivated surface;
(4) Covering a hole transport layer solution containing a hole transport material CZ-As on the perovskite light absorption layer prepared in the step (3) by a spin coating method or a vacuum evaporation method to form a hole transport layer; the dosage of the hole transport layer solution is 30-60 mu L, and the concentration is 30-60 mg/mL;
(5) The metal electrode is deposited onto the hole transport layer by vacuum evaporation.
In the step (1), the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or transparent flexible conductive substrate; the solvent is deionized water, acetone and ethanol in sequence;
in the step (2), the electron transport layer is one of metal oxides such as titanium dioxide, tin dioxide, zinc oxide or niobium pentoxide;
in the step (3), the perovskite light absorption layer is FA X MA 1-X Pb(I X Br 1-X ) 3 、CH 3 NH 3 PbI 3-x Cl x Or all-inorganic perovskite CsPbI 3 、CsPbBr 3 One of the following; wherein FA is CH 2 ＝CHNH 3 MA is CH 3 NH 3 ，0≤x≤1；
The passivation material CZ-Py has the structural characteristics that: carbazole groups are used as a core structure, two ends of the carbazole groups are directly connected with fluorene derivatives or diphenylamine derivatives electron donor groups, N-site substituents are pyridine groups, and the carbazole groups have the following chemical structural general formula (I):
in the formula (I), R is a fluorene derivative or a diphenylamine derivative electron donor group respectively, and specifically is one of the following structures:
the synthesis method of the passivation material CZ-Py comprises the following steps: the carbazole and 4-iodopyridine undergo Buchwald-Hartwig reaction to obtain an intermediate 1; intermediate 1 undergoes bromination reaction to obtain intermediate 2; the intermediate 2 and RH undergo Buchwald carbon nitrogen coupling reaction to obtain a final product CZ-Py, and the specific steps are as follows:
(i) Adding carbazole, 4-iodopyridine, palladium acetate, tri-tert-butyl phosphorus, sodium tert-butoxide and toluene serving as a solvent into a dry reaction container, stirring uniformly at room temperature under the protection of nitrogen, heating to 110-120 ℃ for reaction for 24-48 hours, cooling to room temperature after the reaction is finished, adding methylene dichloride into a reaction liquid, washing with water for several times, collecting an organic layer, removing an organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain a compound 1;
(ii) Compound 1 was dissolved in tetrahydrofuran solvent, the reaction solution was cooled to 0-5 ℃, then N-bromosuccinimide (NBS) was added to the reaction solution in several portions, and after the addition of NBS, the reaction was completed for 8-12 hours. After the reaction is finished, 50mL of dichloromethane is added into the reaction liquid, the reaction liquid is washed three times with 150mL of water, an organic layer is collected, the solvent is removed under reduced pressure, the remainder is separated and purified by a silica gel chromatographic column, petroleum ether/dichloromethane (1:4vol/vol) is used as eluent, and the compound 2 is obtained by vacuum drying;
(iii) Adding a compound 2, RH, palladium acetate, tri-tert-butyl phosphorus, potassium tert-butoxide and a solvent toluene into a dry reaction container, stirring uniformly at room temperature under the protection of nitrogen, heating to 110-120 ℃ for reaction for 18-24h, cooling to room temperature after the reaction is finished, adding dichloromethane into a reaction liquid, washing with water for several times, collecting an organic layer, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the compound CZ-Py.
The synthetic route is as follows:
in step (i), carbazole: 4-iodopyridine: palladium acetate: tri-tert-butyl phosphorus: the molar ratio of the sodium tert-butoxide is 1:1.1:0.05:0.1:3; the reaction concentration of carbazole is 0.04-0.08 mol/L; the volume ratio of the reaction solution to the dichloromethane is 1:1-2.
In step (ii), compound 1: the molar ratio of NBS is 1:2; the reaction concentration of the compound 1 is 0.02-0.04 mol/L.
In step (iii), compound 2: RH: palladium acetate: tri-tert-butyl phosphorus: the molar ratio of the sodium tert-butoxide is 1:2.3:0.1:0.2:6; the reaction concentration of the compound 2 is 0.04-0.08 mol/L.
In the step (4), the hole transport layer solution further comprises an additive; the additive is one or more of LiTFSI, tert-butylpyridine or FK 209; the addition concentrations are respectively as follows: liTFSI is 20-30mmol/L, tert-butylpyridine is 200-300mmol/L, FK209 is 1.0-2.0mmol/L.
The structural characteristics of the hole transport material CZ-As are As follows: carbazole is used as a core structure, two ends of the carbazole are directly connected with fluorene derivative groups, and an N-site substituent is a 4-methoxy phenyl group, and the carbazole has the following chemical structural general formula (II):
the synthesis method of the hole transport material CZ-As comprises the following steps: the carbazole and 4-iodoanisole undergo Buchwald-Hartwig reaction to obtain an intermediate 1'; bromination reaction is carried out on the intermediate 1 'to obtain an intermediate 2'; the intermediate 2' and fluorene derivative undergo Buchwald carbon nitrogen coupling reaction to obtain a final product CZ-As, which comprises the following specific steps:
(i) Adding carbazole, 4-iodoanisole, palladium acetate, tri-tert-butyl phosphorus, sodium tert-butoxide and solvent toluene into a dry reaction container, stirring uniformly at room temperature under the protection of nitrogen, heating to 110-120 ℃ for reaction for 24-48h, cooling to room temperature after the reaction is finished, adding dichloromethane into the reaction liquid, washing with water for several times, collecting an organic layer, removing an organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain a compound 1';
(ii) Compound 1' was dissolved in tetrahydrofuran solvent, the reaction solution was cooled to 0-5 ℃, then N-bromosuccinimide (NBS) was added to the reaction solution in several portions, and after the addition of NBS, the reaction was carried out for 8-12 hours. After the reaction is finished, 50mL of dichloromethane is added into the reaction liquid, the reaction liquid is washed three times with 150mL of water, an organic layer is collected, the solvent is removed under reduced pressure, the remainder is separated and purified by a silica gel chromatographic column, petroleum ether/dichloromethane (1:4vol/vol) is used as an eluent, the obtained solid is separated and purified by vacuum drying, and the compound 2' is obtained by vacuum drying;
(iii) Adding a compound 2', fluorene derivative, palladium acetate, tri-tert-butyl phosphorus, potassium tert-butoxide and solvent toluene into a dry reaction container, stirring uniformly at room temperature under the protection of nitrogen, heating to 110-120 ℃ for reaction for 18-24 hours, cooling to room temperature after the reaction is finished, adding dichloromethane into the reaction liquid, washing with water for several times, collecting an organic layer, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the compound CZ-As.
The synthetic route is as follows:
in step (i), carbazole: 4-iodoanisole: palladium acetate: tri-tert-butyl phosphorus: the molar ratio of the sodium tert-butoxide is 1:1.1:0.05:0.1:3; the reaction concentration of carbazole is 0.04-0.08 mol/L; the volume ratio of the reaction solution to the dichloromethane is 1:1-2.
In step (ii), compound 1: the molar ratio of NBS is 1:2; the reaction concentration of the compound 1 is 0.02-0.04 mol/L.
In step (iii), compound 2: fluorene derivative: palladium acetate: tri-tert-butyl phosphorus: the molar ratio of the sodium tert-butoxide is 1:2.3:0.1:0.2:6; the reaction concentration of the compound 2 is 0.04-0.08 mol/L.
In the step (5), the metal electrode is one of gold, silver or copper.
The invention has the following advantages:
(1) The preparation process of the perovskite solar cell provided by the invention can effectively passivate the defects of the perovskite surface and grain boundaries, improves the charge transmission performance, and can isolate the perovskite from contact with water vapor and oxygen, inhibit the degradation of the perovskite and further improve the stability of the device.
(2) In the perovskite solar cell prepared by the method, energy levels of the hole transport material, the passivation material and the perovskite material are arranged in a step shape, the energy level matching is reasonable, and the extraction and the transmission of charges are facilitated.
(3) The passivation material and the hole transport material used in the process have the advantages of simple synthesis, low cost, high hole mobility and conductivity, good thermal stability and chemical stability and the like, are suitable for being applied to the perovskite solar cell preparation process on a large scale, and are beneficial to commercial application.
Therefore, the invention not only can effectively improve the photoelectric performance of the perovskite solar cell and enhance the stability of the cell, but also can reduce the manufacturing cost of the cell.
Drawings
FIG. 1 is a schematic diagram of the structure of a perovskite solar cell;
FIG. 2 is a schematic molecular structure of passivation materials CZ-Py-1, CZ-Py-2 and hole transport materials CZ-As used in examples 1 and 2 of the present invention.
FIG. 3 (a) is a cross-sectional scanning electron microscope image of a perovskite solar cell using CZ-Py-1 As a passivation material and CZ-As As a hole transport material in example 1 of the present invention; (b) And (c), (d), (e) and (f) are respectively the morphology patterns of the perovskite film, the perovskite film after CZ-Py-1 passivation, the hole transport material CZ-As film coated on the perovskite surface after CZ-Py-1 passivation, the perovskite film after CZ-Py-2 passivation and the hole transport material CZ-As film coated on the perovskite surface after CZ-Py-2 passivation.
FIG. 4 shows XRD patterns of perovskite thin films and CZ-Py-1, CZ-Py-2 modified perovskite thin films.
Fig. 5 (a) and (b) are J-V diagrams of perovskite solar cells based on perovskite thin films modified by CZ-Py-1 and CZ-Py-2, respectively, using CZ-As a hole transport material.
Detailed Description
The invention will be further described with reference to specific examples for a better understanding of the invention by those skilled in the art, but the scope of the invention is not limited to the following examples, which are set forth in the claims.
Example 1:
the preparation method and the process of the perovskite solar cell adopting CZ-Py-1 As a passivation material and CZ-As As a hole transport material comprise the following steps:
the perovskite solar cell has a cell structure of FTO/c-TiO 2 /m-TiO 2 The preparation process of the Perovskite solar cell comprises the following steps of:
(1) FTO (fluorine doped tin dioxide) conductive glass was cut into 15mm x 15mm sized glass substrates and etched using an etcher. And sequentially ultrasonically cleaning the etched glass substrate in deionized water, acetone and ethanol for 30min, and then placing the glass substrate in an ultraviolet ozone machine for 30min.
(2) Spraying isopropanol solution of 0.2M titanium tetraisopropoxide and 2M acetylacetone onto FTO glass substrate heated to 500 deg.C by spray pyrolysis to form a thin layer of TiO 2 A dense layer; 150mg/ml nano TiO 2 Is coated on TiO by spin coating ethanol solution 2 On the dense layer, the revolution was controlled at 5000rpm, spin-coating time was 30s, and then it was dried on a heating plate at 100℃for 15min, and sintered at 500℃for 60min.
(3) Lead iodide (PbI) 2 ) Formamidino iodinated amine (FAI) Lead bromide (PbBr) 2 ) Methyl amine bromide (MABr) (molar ratio 1.1:1:0.2:0.2) was dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide (volume ratio 4:1) with stirring at room temperature. The prepared 31 mu L perovskite solution is spin-coated on TiO by a spin coater 2 On the film, the revolution was controlled at 1000rpm, the spin-coating time was controlled at 10s, then the revolution was controlled at 5000rpm, the spin-coating time was controlled at 30s, in this process, 200. Mu.L of CZ-Py-1 chlorobenzene containing 1mg/mL was dropped onto the film, and the perovskite film was annealed and calcined at 100℃for 30min. Then, the mixture was left in the glove box for 1 hour and cooled.
(4) After 45. Mu.L of a hole transport layer solution (40 mg CZ-As, 125. Mu.L of t-butylpyridine, 17.5. Mu.L of LiTFSI dissolved in 1mL of chlorobenzene) was spin-coated on the surface of the perovskite thin film by spin coating, the spin-coating time was 30s at 4500 rpm.
(5) Finally, 100nm of Au is deposited on the device film by a vacuum evaporation method.
(3) The operation steps (4) were all completed in a glove box filled with nitrogen.
In the step (3), the synthetic route and specific steps of the passivation material CZ-Py-1 are as follows:
(i) Carbazole (0.335 g,2.0 mmol), 4-iodopyridine (0.457 g,2.2 mmol), palladium acetate (0.023 g,0.1 mmol), tri-tert-butylphosphorus (0.040 g,0.2 mmol), sodium tert-butoxide (0.577 g,6.0 mmol) and toluene (50 ml) were added to the dry reaction vessel, stirred uniformly under nitrogen at room temperature, and then heated to 110-120℃for reaction for 12-24 hours. After the reaction was completed, it was cooled to room temperature, 50mL of methylene chloride was added to the reaction solution, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by separation on a silica gel column, petroleum ether/ethyl acetate (1:3 vol/vol) as an eluent, and dried in vacuo to give compound 1 (0.442 g, yield 85%) as a yellow oil. 1 H NMR(400MHz,CDCl 3 ):δ8.83(d,2H,J＝6.0Hz),8.13(d,2H,J＝7.6Hz),7.54-7.58(m,4H),7.43(t,2H,J＝7.6Hz),7.33(t,2H,J＝7.2Hz).
(ii) Compound 1 (0.520 g,2.0 mmol) was dissolved in 50mL of tetrahydrofuran solvent, the reaction solution was cooled to 0-5℃and then N-bromosuccinimide (NBS, 0.712g,4.0 mmol) was added to the reaction solution in several portions for reaction for 8-12 hours. After the completion of the reaction, 50mL of methylene chloride was added to the reaction mixture, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by chromatography on silica gel, with petroleum ether/methylene chloride (1:4 vol/vol) as an eluent, and dried in vacuo to give Compound 2 (0.772 g, yield 96%) as a yellow powder. 1 H NMR(400MHz,DMSO)δ8.62(d,J＝1.9Hz,2H),7.77(dd,J＝4.7,1.4Hz,2H),7.64(dd,J＝8.8,2.0Hz,2H),7.56(d,J＝8.8Hz,2H).
(iii) To a dry reaction vessel were added compound 2 (0.480 g,1.2 mmol), N- (4-methoxyphenyl) -9, 9-dimethyl-9H-fluoren-2-amine (0.882 g,2.8 mmol), palladium acetate (0.028 g,0.12 mmol), tri-tert-butylphosphorus (0.049 g,0.24 mmol), sodium tert-butoxide (0.692 g,7.2 mmol) and solvent toluene (50 ml), stirred uniformly under nitrogen protection at room temperature, and then heated to 110-120℃for reaction for 18-24H. After the reaction was completed, cooled to room temperature, 50mL of methylene chloride was added to the reaction solution, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by separation on a silica gel column, petroleum ether/ethyl acetate (6:1 vol/vol) as an eluent, and dried in vacuo to give CZ-Py-1 (0.731 g, yield 70%) as a yellow powder. 1 H NMR (400 MHz, DMSO). Delta.8.81 (dd, J=13.9, 6.1Hz, 2H), 7.90 (d, J=2.0 Hz, 2H), 7.73 (ddd, J=11.2, 4.7,1.5Hz, 2H), 7.59 (ddd, J=16.9, 14.6,7.8Hz, 6H), 7.47-7.38 (m, 2H), 7.29-7.14 (m, 6H), 7.12-6.99 (m, 6H), 6.89 (dd, J=25.1, 9.0Hz, 4H), 6.73 (dd, J=8.3, 2.1Hz, 2H), 3.72 (d, J=20.6 Hz, 6H), 1.1.20 (m, 12H). HR-MS calculated: C 61 H 50 N 4 O 2 870.3943, found 870.3928.
In the step (4), the synthesis route and specific steps of the hole transport material CZ-As are As follows:
(i) Carbazole (0.335 g,2 mmol), 4-iodoanisole (0.515 g,2.2 mmol), palladium acetate (0.023 g,0.1 mmol), tri-tert-butyl phosphorus (0.040 g,0.2 mmol), sodium tert-butoxide (0.577 g,6.0 mmol) and toluene (50 ml) were added to the dry reaction vessel, stirred uniformly under nitrogen at room temperature, and then heated to 110-120℃for reaction for 12-24h. After the reaction was completed, cooled to room temperature, 50mL of methylene chloride was added to the reaction solution, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by separation on a silica gel column, petroleum ether/methylene chloride (1:10 vol/vol) was used as an eluent, and dried in vacuo to give compound 1' (0.442 g, yield 81%) as a white powder. 1 H NMR(400MHz,CDCl 3 )δ,8.15(d,J＝8.0Hz,2H),7.46(d,J＝8.8Hz,2H),7.40(td,J＝8.4,0.8Hz,2H),7.32(d,J＝8.4Hz,2H),7.28(td,J＝8.0,0.8Hz,2H),7.12(d,J＝8.8Hz,2H),3.93(s,3H).
(ii) Compound 1 (0.540 g,2 mmol) was dissolved in 50mL of tetrahydrofuran solvent, the reaction mixture was cooled to 0-5℃and then N-bromosuccinimide (NBS, 0.712g,4 mmol) was added to the reaction mixture in several portions for reaction for 8-12 hours. After the completion of the reaction, 50mL of methylene chloride was added to the reaction mixture, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by separation using a silica gel column, petroleum ether/methylene chloride (1:10 vol/vol) as an eluent, and dried in vacuo to give compound 2' (0.802 g, yield 93%) as a white powder. 1 H NMR(400MHz,CDCl 3 )δ,8.19(dd,J＝2.0,0.8Hz,2H),7.48(dd,J＝8.4,2.0Hz,2H),7.38(d,J＝8.8Hz,2H),7.17(dd,J＝8.4,0.8Hz,2H),7.10(d,J＝8.8Hz,2H),3.92(s,3H).
(iii) To a dry reaction vessel were added compound 2' (0.515 g,1.2 mmol), N- (4-methoxyphenyl) -9, 9-dimethyl-9H-fluoren-2-amine (0.882 g,2.8 mmol), palladium acetate (0.028 g,0.12 mmol), tri-tert-butylphosphorus (0.049 g,0.24 mmol), sodium tert-butoxide (0.692 g,7.2 mmol) and solvent toluene (50 ml), stirred uniformly under nitrogen protection at room temperature, and then heated to 110-120 ℃ for reaction for 18-24H. After the reaction was completed, the mixture was cooled to room temperature, 50mL of methylene chloride was added to the reaction mixture, and the mixture was washed three times with 150mL of water, followed by collectionThe organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/ethyl acetate (6:1 vol/vol) As eluent and dried in vacuo to give CZ-As (0.961 g, 89% yield) As a yellow powder. 1 H NMR (400 mhz, dmso) delta 7.94 (d, j=2.0 hz, 2H), 7.62 (d, j=7.5 hz, 2H), 7.56 (dd, j=8.6, 2.8hz, 4H), 7.43 (d, j=7.3 hz, 2H), 7.30-7.16 (m, 10H), 7.06 (t, j=6.2 hz, 4H), 6.99 (d, j=2.1 hz, 2H), 6.89 (d, j=9.0 hz, 4H), 6.73 (dd, j=8.3, 2.1hz, 2H), 3.88 (d, j=10.2 hz, 3H), 3.72 (s, 6H), 1.30-1.25 (m, 12H) HR-MS calculated as C 63 H 53 N 3 O 3 899.4081, found 899.4071.
Example 2:
the preparation method and the process of the perovskite solar cell adopting CZ-Py-2 As a passivation material and CZ-As As a hole transport material comprise the following steps:
the perovskite solar cell has a cell structure of FTO/c-TiO 2 /m-TiO 2 The preparation process of the Perovskite solar cell comprises the following steps of:
(1) FTO (fluorine doped tin dioxide) conductive glass was cut into 15mm x 15mm sized glass substrates and etched using an etcher. And respectively ultrasonically cleaning the etched glass substrate in deionized water, acetone and ethanol for 30min, and then placing the glass substrate in an ultraviolet ozone machine for 30min.
(2) Spraying isopropanol solution of 0.2M titanium tetraisopropoxide and 2M acetylacetone onto FTO glass substrate heated to 500 deg.C by spray pyrolysis to form a thin layer of TiO 2 A dense layer; 150mg/ml nano TiO 2 Is coated on TiO by spin coating ethanol solution 2 On the dense layer, the revolution was controlled at 5000rpm, spin-coating time was 30s, and then it was dried on a heating plate at 100℃for 15min, and sintered at 500℃for 60min.
(3) Lead iodide (PbI) 2 ) Formamidino iodinated amine (FAI), lead bromide (PbBr) 2 ) Methyl amine bromide (MABr) (molar ratio 1.1:1:0.2:0.2) was dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide (volume ratio 4:1) with stirring at room temperature. 31 mu L of prepared calcium was applied by spin coaterSpin coating of titanium ore solution on TiO 2 On the film, the revolution was controlled at 1000rpm, the spin-coating time was controlled at 10s, then the revolution was controlled at 5000rpm, the spin-coating time was controlled at 30s, in this process, 150. Mu.L of CZ-Py-2 chlorobenzene containing 2mg/mL was dropped onto the film, and then the perovskite film was annealed and calcined at 100℃for 30min. Then, the mixture was left in the glove box for 1 hour and cooled.
(4) After 60. Mu.L of a hole transport layer solution (60 mg CZ-As, 125. Mu.L of t-butylpyridine, 17.5. Mu.L of LiTFSI dissolved in 1mL of chlorobenzene) was spin-coated on the surface of the perovskite thin film by spin coating, the spin-coating time was 30s at 4500 rpm.
(5) Finally, 100nm of Au is deposited on the device film by a vacuum evaporation method.
(3) The operation steps (4) were all completed in a glove box filled with nitrogen.
In the step (3), the synthetic route and specific steps of the passivation material CZ-Py-2 are as follows:
(i) Carbazole (0.335 g,2.0 mmol), 4-iodopyridine (0.457 g,2.2 mmol), palladium acetate (0.023 g,0.1 mmol), tri-tert-butylphosphorus (0.040 g,0.2 mmol), sodium tert-butoxide (0.577 g,6.0 mmol) and toluene (50 ml) were added to the dry reaction vessel, stirred uniformly under nitrogen at room temperature, and then heated to 110-120℃for reaction for 12-24 hours. After the reaction was completed, it was cooled to room temperature, 50mL of methylene chloride was added to the reaction solution, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by separation on a silica gel column, petroleum ether/ethyl acetate (1:3 vol/vol) as an eluent, and dried in vacuo to give compound 1 (0.442 g, yield 85%) as a yellow oil. 1 H NMR(400MHz,CDCl 3 ):δ8.83(d,2H,J＝6.0Hz),8.13(d,2H,J＝7.6Hz),7.54-7.58(m,4H),7.43(t,2H,J＝7.6Hz),7.33(t,2H,J＝7.2Hz).
(ii) Compound 1 (0.520 g,2.0 mmol) was dissolved in 50mL of tetrahydrofuran solvent, the reaction solution was cooled to 0-5℃and then N-bromosuccinimide (NBS, 0.710 g,4.0 mmol) was separatedAdding a plurality of batches into the reaction liquid for reaction for 8-12h. After the completion of the reaction, 50mL of methylene chloride was added to the reaction mixture, and the mixture was washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by chromatography on silica gel, with petroleum ether/methylene chloride (1:4 vol/vol) as an eluent, and dried in vacuo to give Compound 2 (0.772 g, yield 96%) as a yellow powder. 1 H NMR(400MHz,DMSO)δ8.62(d,J＝1.9Hz,2H),7.77(dd,J＝4.7,1.4Hz,2H),7.64(dd,J＝8.8,2.0Hz,2H),7.56(d,J＝8.8Hz,2H).
(iii) In a dry reaction vessel, compound 2 (0.480 g,1.2 mmol), 4' -dimethoxydiphenylamine (0.640 g,2.8 mmol), palladium acetate (0.028 g,0.12 mmol), tri-tert-butylphosphorus (0.049 g,0.24 mmol), sodium t-butoxide (0.692 g,7.2 mmol) and toluene (50 ml) were added and stirred uniformly under nitrogen at room temperature, and then heated to 110-120℃for reaction for 18-24 hours. After the reaction was completed, cooled to room temperature, 50mL of methylene chloride was added to the reaction solution, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by separation on a silica gel column, petroleum ether/ethyl acetate (6:1 vol/vol) as an eluent, and dried in vacuo to give CZ-Py-2 (0.578 g, yield 69%) as a yellow powder. 1 H NMR (400 MHz, DMSO). Delta.8.81 (ddd, J=12.4, 4.7,1.5Hz, 2H), 7.72-7.66 (m, 4H), 7.52 (d, J=8.9 Hz, 2H), 7.14-7.03 (m, 2H), 6.99-6.90 (m, 1H), 6.90-6.79 (m, 15H), 3.71 (d, J=12.6 Hz, 12H). HR-MS calculated as C 45 H 38 N 4 O 4 698.2888, found 698.2871
In the step (4), the synthesis route and specific steps of the hole transport material CZ-As are As follows:
(i) Carbazole (0.335 g,2 mmol), 4-iodoanisole (0.515 g,2.2 mmol), palladium acetate (0.023 g,0.1 mmol), tri-tert-butyl phosphorus (0.040 g,0.2 mmol), sodium tert-butoxide (0.577 g,6.0 mmol) and toluene (50 ml) were added to the dry reaction vessel, stirred uniformly under nitrogen at room temperature, and then heated to 110-120℃for reaction for 12-24h. After the reaction is finishedAfter cooling to room temperature, 50mL of methylene chloride was added to the reaction solution, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by chromatography on silica gel column with petroleum ether/methylene chloride (1:10 vol/vol) as eluent, and dried in vacuo to give compound 1' (0.442 g, yield 81%) as a white powder. 1 H NMR(400MHz,CDCl 3 )δ,8.15(d,J＝8.0Hz,2H),7.46(d,J＝8.8Hz,2H),7.40(td,J＝8.4,0.8Hz,2H),7.32(d,J＝8.4Hz,2H),7.28(td,J＝8.0,0.8Hz,2H),7.12(d,J＝8.8Hz,2H),3.93(s,3H).
(ii) Compound 1 (0.540 g,2 mmol) was dissolved in 50mL of tetrahydrofuran solvent, the reaction mixture was cooled to 0-5℃and then N-bromosuccinimide (NBS, 0.712g,4 mmol) was added to the reaction mixture in several portions for reaction for 8-12 hours. After the completion of the reaction, 50mL of methylene chloride was added to the reaction mixture, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by separation using a silica gel column, petroleum ether/methylene chloride (1:10 vol/vol) as an eluent, and dried in vacuo to give compound 2' (0.802 g, yield 93%) as a white powder. 1 H NMR(400MHz,CDCl 3 )δ,8.19(dd,J＝2.0,0.8Hz,2H),7.48(dd,J＝8.4,2.0Hz,2H),7.38(d,J＝8.8Hz,2H),7.17(dd,J＝8.4,0.8Hz,2H),7.10(d,J＝8.8Hz,2H),3.92(s,3H).
(iii) To a dry reaction vessel were added compound 2' (0.515 g,1.2 mmol), N- (4-methoxyphenyl) -9, 9-dimethyl-9H-fluoren-2-amine (0.882 g,2.8 mmol), palladium acetate (0.028 g,0.12 mmol), tri-tert-butylphosphorus (0.049 g,0.24 mmol), sodium tert-butoxide (0.692 g,7.2 mmol) and solvent toluene (50 ml), stirred uniformly under nitrogen protection at room temperature, and then heated to 110-120 ℃ for reaction for 18-24H. After the reaction was completed, cooled to room temperature, 50mL of methylene chloride was added to the reaction solution, and washed three times with 150mL of water, the organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by separation on a silica gel column, petroleum ether/ethyl acetate (6:1 vol/vol) As an eluent, and dried in vacuo to give CZ-As (0.961 g, yield 89%) As a yellow powder. 1 H NMR(400MHz,DMSO)δ7.94(d,J＝2.0Hz,2H),7.62(d,J＝7.5Hz,2H),7.56(dd,J＝8.6,2.8Hz,4H),7.43(d,J＝7.3Hz,2H),7.30-7.16(m,10H),7.06(t,J＝6.2Hz,4H),6.99(d,J＝2.1Hz,2H)6.89 (d, J=9.0 Hz, 4H), 6.73 (dd, J=8.3, 2.1Hz, 2H), 3.88 (d, J=10.2 Hz, 3H), 3.72 (s, 6H), 1.30-1.25 (m, 12H). HR-MS: calculated C 63 H 53 N 3 O 3 899.4081, found 899.4071.
FIG. 2 is a schematic molecular structure of passivation materials CZ-Py-1, CZ-Py-2 and hole transport materials CZ-As used in examples 1 and 2 of the present invention.
FIG. 3 (a) is a scanning electron microscope image of a cross section of a perovskite solar cell using CZ-Py-1 As a passivation material and CZ-As As a hole transport material in example 1 of the present invention; (b) And (c), (d), (e) and (f) are respectively the morphology patterns of the perovskite film, the perovskite film after CZ-Py-1 passivation, the hole transport material CZ-As film coated on the perovskite surface after CZ-Py-1 passivation, the perovskite film after CZ-Py-2 passivation and the hole transport material CZ-As film coated on the perovskite surface after CZ-Py-2 passivation. As can be seen from the graph, the perovskite surface after passivation treatment with CZ-Py-1, CZ-Py-2 is smoother and PbI compared with the unmodified perovskite film 2 Less crystallization; meanwhile, the hole transport layer based on CZ-As can completely cover the surface of the perovskite light absorption layer, and a layer of compact and uniform film is formed on the surface of the perovskite light absorption layer.
FIG. 4 shows XRD patterns of perovskite thin films and CZ-Py-1, CZ-Py-2 modified perovskite thin films. As is clear from the graph, the crystal peak intensity of the perovskite thin film after the CZ-Py-1, CZ-Py-2 passivation treatment is increased and attributed to PbI as compared with the unmodified perovskite thin film 2 The XRD peaks of (C) were significantly reduced, indicating that CZ-Py-1, CZ-Py-2 can react with Pb in the perovskite 2+ Coordination is carried out, the perovskite surface is effectively passivated, and PbI is inhibited 2 Is generated.
Fig. 5 (a) and (b) are J-V diagrams of perovskite solar cells based on perovskite thin films modified by CZ-Py-1 and CZ-Py-2, respectively, using CZ-As a hole transport material. As can be seen from FIG. 5 (a), the device using CZ-As As hole transport material obtained 23.5% (V) after the CZ-Py-1 passivation treatment oc ＝1.15V,J sc ＝25.2mA·cm -2 and ff=81.2%) of photoelectric conversion efficiency; as can be seen from FIG. 5 (b), a device using CZ-As As a hole transport material was obtained by performing a CZ-Py-2 passivation treatment18.24% (V) is obtained oc ＝1.07V,J sc ＝22.9mA·cm -2 Ff=74.4%); and the battery has no obvious hysteresis phenomenon under the working condition.
Claims (10)
1. The preparation method of the perovskite solar cell is characterized in that the perovskite solar cell consists of a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a surface passivation layer, a hole transport layer and a metal electrode, and comprises the following specific preparation steps:
(1) Cutting the transparent conductive substrate into fixed sizes, etching, sequentially ultrasonically cleaning the etched transparent conductive substrate in different solvents, and then performing ultraviolet ozone sterilization treatment;
(2) Preparing an electron transport layer on the transparent conductive substrate treated in the step (1) by a spray pyrolysis method or a spin coating method;
(3) Transferring the transparent conductive substrate coated with the electron transport layer into a glove box, spin-coating the perovskite precursor liquid onto the electron transport layer by a spin-coating method, and dropwise adding a chlorobenzene anti-solvent containing a passivation material CZ-Py in the spin-coating process of the perovskite precursor liquid to form a perovskite light absorption layer with a passivated surface; wherein, the structural formula of the passivation material CZ-Py is as follows:
wherein R is a fluorene derivative or a diphenylamine derivative electron donor group respectively; specifically, one of the following structures is adopted:
(4) Covering a hole transport layer solution containing a hole transport material CZ-As on the perovskite light absorption layer prepared in the step (3) by a spin coating method to form a hole transport layer; wherein, the chemical structural formula of the hole transport material CZ-As is As follows:
(5) The metal electrode is deposited onto the hole transport layer by vacuum evaporation.
2. The method of manufacturing of claim 1, wherein in step (1), the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass, or transparent flexible conductive substrate; the solvent is deionized water, acetone and ethanol in turn.
3. The method of claim 1, wherein in step (2), the electron transport layer is one of titanium dioxide, tin dioxide, zinc oxide or niobium pentoxide metal oxide.
4. The method of claim 1, wherein in step (3), the perovskite light absorbing layer is FA X MA 1-X Pb(I X Br 1-X ) 3 、CH 3 NH 3 PbI 3-x Cl x Or all-inorganic perovskite CsPbI 3 、CsPbBr 3 One of the following; wherein FA is CH 2 ＝CHNH 3 MA is CH 3 NH 3 ，0≤x≤1。
5. The method according to claim 1, wherein in the step (3), the amount of the anti-solvent for chlorobenzene containing the passivation material CZ-Py added is 100 to 300 μl, wherein the concentration of the passivation material is 0.1 to 3mg/mL.
6. The method of claim 1, wherein the passivation material CZ-Py is synthesized by: the carbazole and 4-iodopyridine undergo Buchwald-Hartwig reaction to obtain an intermediate 1; intermediate 1 undergoes bromination reaction to obtain intermediate 2; and performing Buchwald carbon-nitrogen coupling reaction on the intermediate 2 and RH to obtain a final product CZ-Py.
7. The method according to claim 1, wherein in the step (4), the hole transport layer solution is used in an amount of 30 to 60. Mu.L and at a concentration of 30 to 60mg/mL.
8. The method of claim 1, wherein in step (4), the hole transport layer solution further comprises an additive; the additive is one or more of LiTFSI, tert-butylpyridine or FK 209; the addition concentrations are respectively as follows: liTFSI is 20-30mmol/L, tert-butylpyridine is 200-300mmol/L, FK209 is 1.0-2.0mmol/L.
9. The method of claim 1, wherein the method of synthesizing the hole transport material CZ-As comprises: the carbazole and 4-iodoanisole undergo Buchwald-Hartwig reaction to obtain an intermediate 1'; bromination reaction is carried out on the intermediate 1 'to obtain an intermediate 2'; and (3) carrying out Buchwald carbon-nitrogen coupling reaction on the intermediate 2' and fluorene derivatives to obtain a final product CZ-As.
10. The method of claim 1, wherein in step (5), the metal electrode is one of gold, silver, or copper.
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