CN113571640A - Perovskite solar cell containing superposed composite transmission layer and preparation method thereof - Google Patents
Perovskite solar cell containing superposed composite transmission layer and preparation method thereof Download PDFInfo
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- CN113571640A CN113571640A CN202010351511.3A CN202010351511A CN113571640A CN 113571640 A CN113571640 A CN 113571640A CN 202010351511 A CN202010351511 A CN 202010351511A CN 113571640 A CN113571640 A CN 113571640A
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- perovskite
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- 230000005540 biological transmission Effects 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 145
- 239000010408 film Substances 0.000 claims abstract description 126
- 239000010409 thin film Substances 0.000 claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 56
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 59
- -1 alkyl fullerene Chemical compound 0.000 claims description 54
- 229910052799 carbon Inorganic materials 0.000 claims description 52
- 238000002207 thermal evaporation Methods 0.000 claims description 47
- 238000012545 processing Methods 0.000 claims description 45
- 230000005525 hole transport Effects 0.000 claims description 42
- 238000005566 electron beam evaporation Methods 0.000 claims description 34
- 229910003472 fullerene Inorganic materials 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 24
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 24
- 238000005507 spraying Methods 0.000 claims description 24
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 23
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 20
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000011135 tin Substances 0.000 claims description 18
- 229910052718 tin Inorganic materials 0.000 claims description 18
- 229910003437 indium oxide Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 15
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 238000001017 electron-beam sputter deposition Methods 0.000 claims description 12
- 229910001369 Brass Inorganic materials 0.000 claims description 10
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 10
- 239000010951 brass Substances 0.000 claims description 10
- 239000002019 doping agent Substances 0.000 claims description 10
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 10
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 10
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 8
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000906 Bronze Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010974 bronze Substances 0.000 claims description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000010956 nickel silver Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 2
- 229940006165 cesium cation Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002892 organic cations Chemical class 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- NCCSSGKUIKYAJD-UHFFFAOYSA-N rubidium(1+) Chemical compound [Rb+] NCCSSGKUIKYAJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000005416 organic matter Substances 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 238000004544 sputter deposition Methods 0.000 abstract description 16
- 230000000903 blocking effect Effects 0.000 abstract description 5
- 238000010923 batch production Methods 0.000 abstract description 2
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- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 description 7
- 229920000144 PEDOT:PSS Polymers 0.000 description 6
- FWXNJWAXBVMBGL-UHFFFAOYSA-N 9-n,9-n,10-n,10-n-tetrakis(4-methylphenyl)anthracene-9,10-diamine Chemical compound C1=CC(C)=CC=C1N(C=1C2=CC=CC=C2C(N(C=2C=CC(C)=CC=2)C=2C=CC(C)=CC=2)=C2C=CC=CC2=1)C1=CC=C(C)C=C1 FWXNJWAXBVMBGL-UHFFFAOYSA-N 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000011368 organic material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 229910021438 complex inorganic oxide Inorganic materials 0.000 description 1
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- 239000012044 organic layer Substances 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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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
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
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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
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
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- H—ELECTRICITY
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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
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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- H—ELECTRICITY
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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
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K85/60—Organic compounds having low molecular weight
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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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
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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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
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Abstract
The invention relates to a perovskite solar cell containing a superposed composite transmission layer, wherein the internal structure of the perovskite solar cell comprises a transparent substrate, a first electrode layer, a transmission layer, a perovskite layer, a superposed composite transmission layer and a back electrode layer in sequence from the front side to the back side of the cell, and the structural form of the superposed composite transmission layer is A0+ n (BA) type, zero layer of film layer A0And a thin film layer A on the n-th layernRespectively an organic transmission layer, the preparation material is an organic hole transmission material or an organic electron transmission material, and the thin film layer B is positioned on the nth layernIs an organic insulating layer, and the preparation material is an organic insulating/blocking material. The invention also discloses a preparation method of the perovskite solar cell. The invention solves the problems of perovskite solar cell and sputtering using organic transmission layer structureThe problem of unmatched coating process enables the preparation of the perovskite solar cell back electrode layer to be improved in material selection type and quantity, coating speed, coating quality and batch production capacity.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cell preparation, and particularly relates to a perovskite solar cell containing a superposed composite transmission layer and a preparation method thereof.
Background
The conventional perovskite solar cell generally adopts a transparent conductive electrode-hole transport layer-perovskite-electron transport layer-back electrode structure (an inverse structure) or a transparent conductive electrode-electron transport layer-perovskite-hole transport layer-back electrode structure (a positive structure); further, in order to improve the carrier extraction efficiency, some researchers have optimized the above structure by adding an insulating layer (or called a hole blocking layer) between the transport layer far from the light incident surface and the back electrode, such as an electron transport layer of an inverted structure, or adding an electron blocking layer in addition to the hole transport layer of a positive structure, and forming a structure of a transparent conductive electrode-hole transport layer-perovskite-electron transport layer-insulating layer (hole blocking layer) -back electrode, or a transparent conductive electrode-electron transport layer-perovskite-hole transport layer-insulating layer (electron blocking layer) -back electrode; other researchers regulate and control the transmission layer by adopting a mode of gradually changing energy levels to form a multi-layer transmission layer to improve the carrier extraction capability, the positive perovskite solar cell is structurally a transparent conductive electrode-electron transmission layer-perovskite-hole transmission layer 1-hole transmission layer 2- … -hole transmission layer n-back electrode, the negative perovskite solar cell is structurally a transparent conductive electrode-hole transmission layer-perovskite-electron transmission layer 1-electron transmission layer 2 … electron transmission layer n-back electrode, wherein the energy levels of the multi-layer hole transmission layer or electron transmission layer are gradually changed, but the structure of the multi-layer hole transmission layer or electron transmission layer in the device is continuous, and other functional layers are not inserted in the middle; some researchers add a functional layer between the transmission layer close to the light incident surface and the perovskite layer, and play a role in energy level matching through the action of electric dipole moment and the like; there are also some special perovskite cell structures in which a structure without a hole transport layer is adopted, and the cell structure is simply expressed as a transparent conductive electrode-an electron transport layer-a perovskite layer-a back electrode.
In the above structure, although there are theoretically various methods for preparing the back electrode, such as thermal evaporation, electron beam evaporation, pulsed laser evaporation, vacuum ion plating, vacuum sputtering, chemical deposition, etc., in actual practice, most of the perovskite solar cell back electrodes are prepared by thermal evaporation due to the manufacturing cost limit, the manufacturing equipment limit, and the balance of the manufacturing speed and the manufacturing effect. Sputtering coating is a mature technology widely used in the field of coating of photoelectric devices, and is considered to be one of the most suitable technologies for preparing back electrodes due to the remarkable advantages of high coating speed, high coating quality, rich coating types, relatively low equipment investment, convenience for large-scale production coating and the like. However, this coating technique has met with challenges in the application of perovskite back electrode coatings. In the case of high performance perovskite solar cells, it is generally necessary to use at least one layer of organic transport layer material to achieve energy level matching, such as a positive cell using a spiro-OMeTAD between the perovskite and the back electrode, or in an inverted cell, PCBM between the perovskite and the back electrode. Because the principle of sputtering coating is to use charged particles (usually positive ions of inert gas) to bombard the surface of a solid target material so as to cause atoms or molecules on the surface of the target material to escape to a sample to be coated, when the sputtering coating is used for preparing a back electrode of a perovskite solar cell, high-energy particles can generate large damage on the surface when contacting the surface of a perovskite organic thin film layer (including perovskite is also an easily damaged inorganic-organic hybrid material), so that the interface performance is seriously influenced, and further the overall performance of the solar cell is influenced. The existing solution is to prepare an inorganic oxide layer on the organic transport layer for protecting organic materials and perovskite materials from the damage of sputtered particles, which are generally referred to as sacrificial or protective layers in the literature. In this case, the perovskite solar cell forms the following structure: transparent conductive electrode-transmission layer-perovskite-organic transmission layer-inorganic oxide sacrifice/protection layer-back electrode. There are some very significant drawbacks with this approach: (1) the preparation method of the inorganic oxide sacrificial layer is very limited, atomic layer vapor deposition is generally adopted, and the method is low in coating speed, high in large-scale production cost and difficult to realize on a large scale; (2) the preparation method of the inorganic oxide sacrificial layer is greatly different from the preparation method of the common functional layer of the perovskite solar cell, so that the complexity of large-scale production is further increased, and the yield and the like are uncontrollable; (3) once the inorganic oxide sacrificial layer is used, the integrity and the energy level matching degree of the original battery structure are influenced, so that the transmission of holes/electrons is influenced, and the efficiency is reduced; (4) the surface energy of the organic transmission layer is less than that of the inorganic oxide sacrificial/protective layer, so that the inorganic oxide sacrificial/protective layer prepared on the transmission layer has low adhesion and poor bonding force, the mechanical strength of an interface is low, and the battery performance is extremely easily degraded and even stripped in the processes of cold and hot circulation and the like. These factors have led to the inability of the sputtering process described above to be used to prepare the back electrode of perovskite solar cells.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a perovskite solar cell containing a superposed composite transmission layer and a preparation method thereof, which solve the problem that the perovskite solar cell using an organic transmission layer structure is not matched with a sputtering coating process, and can prepare a back electrode layer of the perovskite solar cell by using the sputtering coating process on the premise of not introducing a complex inorganic oxide sacrifice/protection layer, so that the preparation of the back electrode layer of the perovskite solar cell is improved in material selection type and quantity, coating speed, coating quality and batch production capacity.
The invention is realized by providing a perovskite solar cell containing a superposed composite transmission layer, wherein the internal structure of the perovskite solar cell comprises a transparent substrate, a first electrode layer, a transmission layer, a perovskite layer, a superposed composite transmission layer and a back electrode layer from a light incident surface (the front surface of the cell) to the back surface of the cell in sequence, and the structural form of the superposed composite transmission layer is A0+ n (ba) type, where n =1, 2, 3, …, film layer a located at zero layer0And a thin film layer A on the n-th layernRespectively an organic transmission layer and a thin film layer B arranged on the n-th layernA thin film layer A of an organic insulating layer, zero layer0The preparation material and the thin film layer A of the n-th layernThe preparation material is organic hole transport material or organic electron transport material, and the thin film layer B of the n-th layernThe preparation material of (a) is an organic insulating/barrier material.
The invention is realized by providing the preparation method of the perovskite solar cell containing the superposed composite transmission layer, which is as described above, and the structural form A of the superposed composite transmission layer0N =1 in + n (ba) type,namely the structural form of the superposed composite transmission layer is A0B1A1Preparing a zero-layer film layer A0The material is selected from alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester or alkyl fullerene phenyl-carbon 72-butyric acid-methyl ester (PCBM), and the film layer B of the 1 st layer is prepared1The material is selected from 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (BCP), and a film layer A of a 1 st layer is prepared1The material is selected from carbon 60 or carbon 70, and the method specifically comprises the following steps:
step 11, the transparent substrate adopts glass coated with an indium tin oxide conducting layer, the glass surface is an illumination incidence surface, and the surface coated with the indium tin oxide conducting layer is used as a first electrode layer;
step 12, preparing a hole transport layer on the first electrode layer, wherein the preparation method of the hole transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering, and the material for preparing the hole transport layer comprises nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), cuprous thiocyanate (CuSCN), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), 2',7,7' -tetra (N, N-P-methoxyanilino) -9,9' -spirobifluorene (Spiro-MeOTAD)), 3, 4-Ethylenedioxythiophene (EDOT), poly (3-hexylthiophene-2, 5-diyl) (P3 HT), At least one hole transport layer material of poly [ bis (4-phenyl) (4-butylphenyl) amine ] (poly TPD), the thickness of which is 5nm to 50 nm;
step 13, preparing a perovskite layer on the hole transport layer, wherein the method for preparing the perovskite layer comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness of the film is 300 nm-2 μm;
step 14, preparing a superposed composite transmission layer on the perovskite layer, wherein the method for preparing the superposed composite transmission layer comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer0A film layer B of the 1 st layer1And film layer A of layer 11(ii) a Wherein, the film layer A of the zero layer0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm;
and step 15, preparing a back electrode layer on the superposed composite transmission layer, wherein the method for preparing the back electrode layer comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes, the material for preparing the back electrode layer comprises any one of metals or any one of alloys of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and the thickness of the back electrode layer is 20 nm-1000 nm.
The invention is realized by providing the preparation method of the perovskite solar cell containing the superposed composite transmission layer, which is as described above, and the structural form A of the superposed composite transmission layer0N =2 in + n (ba) type, i.e. the structural form of the superimposed composite transport layer is a0B1A1B2A2Preparing a zero-layer film layer A0Layer 1, thin film layer A1And film layer A of layer 22All the materials are poly [ bis (4-phenyl) (4-butylphenyl) amine](polytPD) preparation of layer 1 film layer B1And film layer B of layer 22The material is Polyethyleneimine (PEI), and specifically comprises the following steps:
step 21, the transparent substrate adopts glass coated with an Indium Tin Oxide (ITO) conducting layer, the glass surface is an illumination incidence surface, and the surface coated with the ITO conducting layer is used as a first electrode layer;
step 22 of forming on the first electrode layerPreparing an electron transport layer, wherein the preparation method of the electron transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes, and the material for preparing the electron transport layer comprises titanium dioxide (TiO)2) Tin dioxide (SnO)2) Zinc oxide (ZnO), Di-PDI, ITCPTC-Th, carbon 60(C60), carbon 70(C70), alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester (PC)61BM), alkyl fullerene phenyl-C72-butyric acid-methyl ester (PC)72BM), PCBM and novel indene and C60 double adduct (IC)60BA) or a variant of the fullerene-based organic substance and any one of the dopants as an electron transport layer material, wherein the thickness of the electron transport layer material is 5nm to 50 nm;
step 23, preparing a perovskite layer on the electron transport layer, wherein the method for preparing the perovskite layer comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness of the film is 300 nm-2 μm;
step 24, preparing a superposed composite transmission layer on the perovskite layer, wherein the method for preparing the superposed composite transmission layer comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer0A film layer B of the 1 st layer1Layer 1, thin film layer A1A 2 nd thin film layer B2And film layer A of layer 22Wherein, the film layer A of the zero layer0Layer 1, layerFilm layer A of1And film layer A of layer 22The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1And film layer B of layer 22The thickness of (a) is 1 nm-20 nm;
and 25, preparing a back electrode layer on the superposed composite transmission layer, wherein the method for preparing the back electrode layer comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes, the material for preparing the back electrode layer comprises any one of metals or any one of alloys of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and the thickness of the back electrode layer is 20 nm-1000 nm.
The invention is realized by providing the preparation method of the perovskite solar cell containing the superposed composite transmission layer, which is as described above, and the structural form A of the superposed composite transmission layer0N =1 in + n (ba) type, i.e. the structural form of the superimposed composite transport layer is a0B1A1Preparing a zero-layer film layer A0And film layer A of layer 11Is carbon 60 or carbon 70, respectively, to prepare the thin film layer B of the 1 st layer1The material is selected from 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the method specifically comprises the following steps:
step 31, the transparent substrate adopts glass coated with an Indium Tin Oxide (ITO) conducting layer, the glass surface is an illumination incidence surface, and the surface coated with the ITO conducting layer is used as a first electrode layer;
step 32, preparing a hole transport layer on the first electrode layer, wherein the preparation method of the hole transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes, the material for preparing the hole transport layer comprises at least one of nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), cuprous thiocyanate (CuSCN), and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), and the thickness of the hole transport layer is 5 nm-50 nm;
step 33, preparing a perovskite layer on the hole transport layer, wherein the method for preparing the perovskite layer comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness of the film is 300 nm-2 μm;
step 34, preparing a superposed composite transmission layer on the perovskite layer, wherein the method for preparing the superposed composite transmission layer comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer0A film layer B of the 1 st layer1And film layer A of layer 11(ii) a Wherein, the film layer A of the zero layer0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm;
and step 35, preparing a back electrode layer on the superposed composite transmission layer, wherein the method for preparing the back electrode layer comprises any one of processing modes of magnetron sputtering, plasma enhanced chemical vapor deposition and monoatomic layer deposition, and the material for preparing the back electrode layer comprises any one of Indium Tin Oxide (ITO), aluminum oxide doped zinc oxide (AZO), indium oxide doped zinc oxide (IZO), fluorine-doped tin oxide (FTO), zirconium-doped indium oxide (IZO) and tungsten-doped indium oxide (IWO) doped zinc oxide (BZO), and the thickness of the back electrode layer is 20 nm-1000 nm.
The invention is realized by providing the preparation method of the perovskite solar cell containing the superposed composite transmission layer, which is as described above, and the structural form A of the superposed composite transmission layer0N =1 in + n (ba) type, i.e. the structural form of the superimposed composite transport layer is a0B1A1Preparing a zero-layer filmLayer A0And film layer A of layer 11Is 2,2',7,7' -tetra (N, N-p-methoxyanilino) -9,9' -spirobifluorene (Spiro-MeOTAD), and a film layer B of the 1 st layer is prepared1The material is 9, 10-bis [ N, N-di (p-tolyl) amino]Anthracene (TTPA), specifically including the steps of:
step 41, the transparent substrate adopts glass coated with an Indium Tin Oxide (ITO) conducting layer, the glass surface is an illumination incidence surface, and the surface coated with the ITO conducting layer is used as a first electrode layer;
step 42, preparing an electron transport layer on the first electrode layer, where the preparation method of the electron transport layer includes any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering, and the material for preparing the electron transport layer includes titanium dioxide (TiO)2) Tin dioxide (SnO)2) Zinc oxide (ZnO), Di-PDI, ITCPTC-Th, carbon 60(C60), carbon 70(C70), alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester (PC)61BM), alkyl fullerene phenyl-C72-butyric acid-methyl ester (PC)72BM), PCBM and novel indene and C60 double adduct (IC)60BA) or a variant of the fullerene-based organic substance and any one of the dopants as an electron transport layer material, wherein the thickness of the electron transport layer material is 5nm to 50 nm;
step 43, preparing a perovskite layer on the electron transport layer, wherein the method for preparing the perovskite layer comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness of the film is 300 nm-2 μm;
step 44, preparing a superposed composite transmission layer on the perovskite layer, wherein the method for preparing the superposed composite transmission layer comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer0A film layer B of the 1 st layer1And film layer A of layer 11(ii) a Wherein, the film layer A of the zero layer0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm;
and step 45, preparing a back electrode layer on the superposed composite transmission layer, wherein the method for preparing the back electrode layer comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes, the material for preparing the back electrode layer comprises any one of stainless steel, tin brass, tin bronze, nickel brass and silicon brass, and the thickness of the back electrode layer is 20 nm-1000 nm.
Compared with the prior art, the perovskite solar cell containing the superposed composite transmission layer and the preparation method thereof have the following characteristics:
1. the materials used by the superposed composite transmission layer are common organic materials in the perovskite solar cell, and can form a consistent energy band structure with the perovskite materials, so that the integrity and the energy level matching degree of the cell structure are not damaged, and the carrier extraction and transmission efficiency is not sacrificed.
2. The superposed composite transmission layer is formed by the transmission layer, so that sputtering damage only occurs on the surface of the outermost organic transmission composite structure, the damage can be absorbed and passivated through the integral structure and the energy band, and the efficiency of the integral transmission layer for transmitting carriers is not influenced.
3. The superimposed composite transmission layer has an A + n (BA) type structure, and n =1, 2, 3 and …, so that on the premise of ensuring that sputtering damage does not influence the overall structure and function of the battery, high kinetic energy particles in the sputtering process can be partially embedded into the superimposed composite transmission layer due to the use of organic materials, the coupling with a back electrode is enhanced, the mechanical strength of an interface is improved, and meanwhile, the reduction of series resistance is facilitated, and the transmission and collection efficiency of current carriers is improved.
4. The materials used for the superposed composite transmission layer are all organic materials, the cost is controllable, the equipment and the process are common to perovskite solar cells, and the composite transmission layer can be used for preparing large-area components.
5. The use of the superposed composite transmission layer in the perovskite solar cell enables the sputtering coating film to be used for preparing various metal back electrodes of the perovskite solar cell, including high-melting-point low-price metal and corrosion-resistant alloy, thereby reducing the preparation cost of the perovskite solar cell and improving the environmental stability of the perovskite solar cell.
6. The use of the superposed composite transmission layer in the perovskite solar cell enables the sputtering coating film to be used for preparing various transparent electrodes of the perovskite solar cell, and lays a solid foundation for the high-efficiency semitransparent perovskite solar cell and the development and application of the laminated perovskite solar cell.
Drawings
FIG. 1 is a schematic plan view of the structure of a perovskite solar cell of the present invention comprising a superimposed composite transport layer;
FIG. 2 is a schematic plan view of the structure of a perovskite solar cell comprising a superimposed composite transport layer according to example 1 of the present invention;
FIG. 3 is a schematic plan view of the structure of a perovskite solar cell containing a superimposed composite transport layer according to example 2 of the present invention;
FIG. 4 is a schematic plan view of the structure of a perovskite solar cell containing a superimposed composite transport layer according to example 3 of the present invention;
fig. 5 is a schematic structural plan view of a perovskite solar cell containing a superimposed composite transport layer according to example 4 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, in the preferred embodiment of the perovskite solar cell with a stacked composite transmission layer according to the present invention, the transparent substrate 1, the first electrode layer 2, the transmission layer 3, the perovskite layer 4, the stacked composite transmission layer 5 and the back electrode layer 6 are sequentially disposed from the light incident surface (the front surface of the cell) to the back surface of the cell.
The structure form of the superposed composite transmission layer 5 is A0+ n (ba) type, where n =1, 2, 3, …. Film layer A at zero layer0And a thin film layer A on the n-th layernRespectively, organic transport layers, which are capable of efficiently extracting free electrons or holes. A film layer B on the n-th layernA thin film layer A capable of modifying zero layer for organic insulating layer0And a thin film layer A on the n-th layernReducing recombination of electrons and holes. Zero-layer film layer A0The preparation material and the thin film layer A of the n-th layernThe preparation material of (2) can be the same material or different materials, but needs to be an organic hole transport material or an organic electron transport material at the same time, and is opposite to the material for preparing the transport layer. When the material for preparing the transmission layer is a hole transmission layer material, the film layer A of the zero layer0The preparation material and the thin film layer A of the n-th layernThe preparation material of (2) is an organic electron transport material. When the material for preparing the transmission layer is the material of the electron transmission layer, the film layer A of the zero layer0The preparation material and the thin film layer A of the n-th layernThe preparation material of (2) is a hole transport layer material. Film layer B of the n-th layernThe preparation material of (a) is an organic insulating/barrier material.
Preparing a zero-layer film layer A0The preparation material and the thin film layer A of the n-th layernThe material comprises an electron transport material and a hole transport material, wherein the electron transport material comprises Di-PDI, ITCPTC-Th, carbon 60(C60), carbon 70(C70), alkyl fullerene phenyl-carbon 61-methyl butyrate (PC)61BM), alkyl fullerene phenyl-C72-butyric acid-methyl ester (PC)72BM), PCBM and novel indene and C60 double adduct (IC)60BA) or a variant or dopant of the above fullerenyl organic; the hole transport material comprises poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl)) Amines as pesticides](PTAA), 2',7,7' -tetra (N, N-P-methoxyanilino) -9,9' -spirobifluorene (Spiro-MeOTAD), 3, 4-Ethylenedioxythiophene (EDOT), poly (3-hexylthiophene-2, 5-diyl) (P3 HT), poly [ bis (4-phenyl) (4-butylphenyl) amine](polyTPD). Zero-layer film layer A0The thickness of (A) is 1 nm-100 nm, and the main task of extracting electrons or holes is borne. Film layer A of the n-th layernThe thickness of the film is 1 nm-100 nm, and the film is in contact with the transparent conductive oxide layer to passivate sputtering defects and reduce the film layer B of the n-th layernThe carriers generated by tunneling have the effect of recombination at the interface of the back electrode layer and the organic layer.
Preparing the film layer B of the n-th layernThe material of (a) includes 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (BCP), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 9, 10-bis [ N, N-di (p-tolyl) amino]The thickness of any one of anthracene (TTPA), Polyethyleneimine (PEI) and 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi) is 1 nm-20 nm, and the forbidden band width is not less than 2eV and often exceeds 2.5 eV.
The material for preparing the first electrode layer 2 includes any one of Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), Indium Zinc Oxide (IZO), fluorine-doped tin oxide (FTO), zirconium-doped indium oxide (IZO), and tungsten-doped indium oxide (IWO), and the thickness of the material is 100nm to 300 nm.
The material for preparing the transport layer 3 includes nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid (PEDOT: PSS), cuprous thiocyanate (CuSCN), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA), 2',7,7' -tetra (N, N-P-methoxyanilino) -9,9' -spirobifluorene (Spiro-MeOTAD), 3, 4-Ethylenedioxythiophene (EDOT), poly (3-hexylthiophene-2, 5-diyl) (P3 HT), poly [ bis (4-phenyl) (4-butylphenyl) amine]At least one hole transport layer material in (polyTPD), or comprises titanium dioxide (TiO)2) Tin dioxide (SnO)2) Zinc oxide (ZnO), Di-PDI, ITCPTC-Th, carbon 60(C60), carbon 70(C70), alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester (PC)61BM), alkyl fullerene phenyl-C72-butyric acid-methyl ester (PC)72BM), PCBM and novel indene and C60 double adduct (IC)60BA) or a variant of the above fullerene-based organic substance and a dopant, and has a thickness of 5nm to 50 nm.
The material for preparing the back electrode layer 6 comprises any one of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc or any one of stainless steel, tin brass, tin bronze, nickel brass and silicon brass, and the thickness of the material is 20 nm-1000 nm; or any one of Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), Indium Zinc Oxide (IZO), fluorine-doped tin oxide (FTO), zirconium-doped indium oxide (IZOz) and tungsten-doped indium oxide (IWO), and the thickness of the film is 10nm to 2000 nm.
The band gap of the prepared perovskite layer 4 is not more than 3.0eV, and the structural formula of a compound of the composition structure is GMX3Wherein G is a monovalent cation, G is an alkali metal cation or an organic cation, and G comprises a methylamine Cation (CH)3NH3+) Formamidine cation (NH)2CHNH2+) Cesium cation (Cs)+) And rubidium cation (Rb)+) M is a divalent cation, M is any one of a transition metal and a divalent cation of a group 13 to 15 element, and M includes Pb2+、Ge2+、Sn2+、Cu2+、Bi2+X is a monovalent anion, X is a halide anion or a thiocyanate ion (SCN)-) Any of which, moreover, the G, M and X positions are occupied by multiple types of ions; the thickness of the perovskite layer 4 is 300nm to 2 μm.
In particular, the material from which the perovskite layer 4 is made comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3。
The following will further illustrate the preparation method of the perovskite solar cell with the superimposed composite transmission layer according to the present invention with reference to specific examples.
Example 1
Referring to fig. 2, in a first method for manufacturing a perovskite solar cell including a stacked composite transmission layer according to the present invention, a structural form a of a stacked composite transmission layer 5 is shown0N =1 in + n (ba) type, i.e. the structural form of the superimposed composite transmission layer 5 is a0B1A1Alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester or alkyl fullerene phenyl-carbon 72-butyric acid-methyl ester (PCBM) to prepare the thin film layer B of the 1 st layer1The material is selected from 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (BCP), and a film layer A of a 1 st layer is prepared1The material is selected from carbon 60(C60) or carbon 70(C70), and the method specifically comprises the following steps:
and step 11, the transparent substrate 1 adopts glass coated with an Indium Tin Oxide (ITO) conducting layer, the glass surface is a light incidence surface, and the surface coated with the ITO conducting layer is used as a first electrode layer 2. The first electrode layer 2 is used as a battery anode connection wire when the preparation of the perovskite battery is completed, and the back electrode layer 6 is connected with a negative electrode.
And 12, preparing a hole transport layer on the first electrode layer 2, wherein the preparation method of the hole transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes. The material for preparing the hole transport layer comprises at least one hole transport layer material of nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), cuprous thiocyanate (CuSCN), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), 2',7,7' -tetra (N, N-P-methoxyanilino) -9,9' -spirobifluorene (Spiro-MeOTAD)), 3, 4-Ethylenedioxythiophene (EDOT), poly (3-hexylthiophene-2, 5-diyl) (P3 HT) and poly [ bis (4-phenyl) (4-butylphenyl) amine ] (polyTPD), and the thickness of the hole transport layer material is 5nm to 50 nm.
Step 13, preparing a perovskite layer 3 on the hole transport layer, wherein the method for preparing the perovskite layer 4 comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer 4 comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness is 300nm to 2 μm.
And 14, preparing the superposed composite transmission layer 5 on the perovskite layer 4, wherein the method for preparing the superposed composite transmission layer 5 comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes. Sequentially preparing zero-layer thin film layer A on the perovskite layer 40A film layer B of the 1 st layer1And film layer A of layer 11. Wherein, the film layer A of the zero layer0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm.
And step 15, preparing the back electrode layer 6 on the superposed composite transmission layer 5, wherein the method for preparing the back electrode layer 6 comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes, the material for preparing the back electrode layer 6 comprises any one of metals or any one of alloys of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and the thickness of the metal is 20 nm-1000 nm.
Example 2
Referring to fig. 3, in a second method for manufacturing a perovskite solar cell including a stacked composite transmission layer according to the present invention, a structural form a of a stacked composite transmission layer 5 is shown0N =2 in + n (ba) type, i.e. the structural form of the superimposed composite transmission layer 5 is a0B1A1B2A2Preparing a zero-layer film layer A0Layer 1, thin film layer A1And film layer A of layer 22All the materials are poly [ bis (4-phenyl) (4-butylphenyl) amine](polytPD) preparation of layer 1 film layer B1And film layer B of layer 22The material is Polyethyleneimine (PEI), and specifically comprises the following steps:
step 21, the transparent substrate 1 is made of glass coated with an Indium Tin Oxide (ITO) conductive layer, the glass surface is a light incidence surface, and the surface coated with the ITO conductive layer is used as the first electrode layer 2. The first electrode layer 2 is used as a battery cathode wiring when the preparation of the perovskite battery is finished, and the back electrode layer 6 is connected with the anode;
and 22, preparing an electron transport layer on the first electrode layer 2, wherein the preparation method of the electron transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes. The material for preparing the electron transport layer comprises titanium dioxide (TiO)2) Tin dioxide (SnO)2) Zinc oxide (ZnO), Di-PDI, ITCPTC-Th, carbon 60(C60), carbon 70(C70), alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester (PC)61BM), alkyl fullerene phenyl-C72-butyric acid-methyl ester (PC)72BM), PCBM and novel indene and C60 double adduct (IC)60BA) or a variant of the above fullerene-based organic substance and a dopant, and has a thickness of 5nm to 50 nm.
Step 23, preparing the perovskite layer 4 on the electron transport layer, wherein the method for preparing the perovskite layer 4 comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer 4 comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness is 300nm to 2 μm.
Step 24, preparing the superposed composite transmission layer 5 on the perovskite layer 4, wherein the method for preparing the superposed composite transmission layer 5 comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and the zero-layer thin film layer A is sequentially prepared on the perovskite layer 40A film layer B of the 1 st layer1Layer 1, thin film layer A1A 2 nd thin film layer B2And film layer A of layer 22Wherein, the film layer A of the zero layer0Layer 1, thin film layer A1And film layer A of layer 22The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1And film layer B of layer 22The thickness of (a) is 1nm to 20 nm.
And 25, preparing the back electrode layer 6 on the superposed composite transmission layer 5, wherein the method for preparing the back electrode layer 6 comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes. The material for preparing the back electrode layer 6 comprises any one metal or any one alloy of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and the thickness of the material is 20 nm-1000 nm.
Example 3
Referring to fig. 4, in a third method for manufacturing a perovskite solar cell including a stacked composite transmission layer according to the present invention, a structural form a of a stacked composite transmission layer 5 is shown0N =1 in + n (ba) type, i.e. the structural form of the superimposed composite transmission layer 5 is a0B1A1Preparing a zero-layer film layer A0And film layer A of layer 11Is carbon 60(C60) or carbon 70(C70), respectively, to prepare the thin film layer B of layer 11The material is selected from 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the method specifically comprises the following steps:
step 31, the transparent substrate 1 is made of glass coated with an Indium Tin Oxide (ITO) conductive layer, the glass surface is a light incidence surface, and the surface coated with the ITO conductive layer is used as the first electrode layer 2. The first electrode layer 2 is used as a battery anode connection wire when the preparation of the perovskite battery is completed, and the back electrode layer 6 is connected with a negative electrode.
And step 32, preparing a hole transport layer on the first electrode layer 2, wherein the preparation method of the hole transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes. The material for preparing the hole transport layer comprises at least one of nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), cuprous thiocyanate (CuSCN) and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), and the thickness of the hole transport layer is 5 nm-50 nm.
Step 33, preparing the perovskite layer 4 on the hole transport layer, wherein the method for preparing the perovskite layer 4 comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer 4 comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness is 300nm to 2 μm.
Step 34, preparing the superposed composite transmission layer 5 on the perovskite layer 4, wherein the method for preparing the superposed composite transmission layer 5 comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer 40A film layer B of the 1 st layer1And film layer A of layer 11(ii) a Wherein,zero-layer film layer A0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm.
And step 35, preparing the back electrode layer 6 on the superposed composite transmission layer 5, wherein the method for preparing the back electrode layer 6 comprises any one of magnetron sputtering, plasma enhanced chemical vapor deposition and monoatomic layer deposition processing modes. The material for preparing the back electrode layer 6 comprises any one of Indium Tin Oxide (ITO), aluminum oxide doped zinc oxide (AZO), indium oxide doped zinc oxide (IZO), fluorine-doped tin oxide (FTO), zirconium-doped indium oxide (IZO), tungsten-doped indium oxide (IWO) and boron-doped zinc oxide (BZO), and the thickness of the material is 20 nm-1000 nm. Taking BZO as an example, when the BZO process layer is prepared by magnetron sputtering, a radio frequency or direct current power supply is adopted as a sputtering power supply, and the background vacuum is less than 5 multiplied by 10-4Pa, the working vacuum is 0.1-2 Pa, and the working power is 30-200W. When a transparent conductive oxide such as boron-doped zinc oxide is used as the back electrode layer 6 of the perovskite solar cell, the prepared perovskite solar cell is a semitransparent perovskite solar cell. The semi-transparent perovskite solar cell can effectively enable light with the wavelength larger than the absorption limit of the perovskite material to be transmitted, and can be used as a sub-cell to form a laminated solar cell together with any solar cell conforming to the laminating principle. Therefore, the semitransparent perovskite solar cell prepared by superposing the composite transmission layer in the invention is used as a laminated cell of the sub-cell and is also considered to be protected by the invention.
Example 4
Referring to fig. 5, in a fourth method for manufacturing a perovskite solar cell including a stacked composite transmission layer according to the present invention, a structural form a of the stacked composite transmission layer 5 is shown0N =1 in + n (ba) type, i.e. the structural form of the superimposed composite transmission layer 5 is a0B1A1Preparing a zero-layer film layer A0And film layer A of layer 11Is 2,2',7,7' -tetra (N, N-p-methoxyanilino) -9,9' -spirobifluorene (Spiro-MeOTAD), and a film layer B of the 1 st layer is prepared1The material is 9, 10-bis [ N, N-di (p-tolyl) amino]Anthracene (TTPA), including in particularThe following steps:
step 41, the transparent substrate 1 is made of glass coated with an Indium Tin Oxide (ITO) conductive layer, the glass surface is a light incidence surface, and the surface coated with the ITO conductive layer is used as the first electrode layer 2. The first electrode layer 2 is used as a battery negative electrode wiring when the preparation of the perovskite battery is completed, and the back electrode layer 6 is connected with a positive electrode.
And 42, preparing an electron transport layer on the first electrode layer 2, wherein the preparation method of the electron transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes. The material for preparing the electron transport layer comprises titanium dioxide (TiO)2) Tin dioxide (SnO)2) Zinc oxide (ZnO), Di-PDI, ITCPTC-Th, carbon 60(C60), carbon 70(C70), alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester (PC)61BM), alkyl fullerene phenyl-C72-butyric acid-methyl ester (PC)72BM), PCBM and novel indene and C60 double adduct (IC)60BA) or a variant of the above fullerene-based organic substance and a dopant, and has a thickness of 5nm to 50 nm.
And 43, preparing the perovskite layer 4 on the electron transport layer, wherein the method for preparing the perovskite layer 4 comprises any one of coating, spraying and thermal evaporation processing modes. The material from which the perovskite layer 4 is made comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness is 300nm to 2 μm.
Step 44 of preparing a superimposed composite transport layer on the perovskite layer 4And 5, the method for preparing the superposed composite transmission layer 5 comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes. Sequentially preparing zero-layer thin film layer A on the perovskite layer 40A film layer B of the 1 st layer1And film layer A of layer 11Wherein, the film layer A of the zero layer0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm.
And step 45, preparing the back electrode layer 6 on the superposed composite transmission layer 5, wherein the method for preparing the back electrode layer 6 comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes, the material for preparing the back electrode layer 6 comprises any one of stainless steel, tin brass, tin bronze, nickel brass and silicon brass, and the thickness of the material is 20 nm-1000 nm.
Taking magnetron sputtering preparation of 1Cr18Ni9 stainless steel electrode as an example, when the stainless steel electrode is prepared by magnetron sputtering, a target material prepared by 1Cr18Ni9 stainless steel is used, a radio frequency or direct current power supply is adopted as a sputtering power supply, and the background vacuum is less than 5 multiplied by 10-4Pa, the working vacuum is 0.1-2 Pa, and the working power is 30-300W. When a corrosion-resistant electrode such as stainless steel is used as the back electrode layer 6 of the perovskite solar cell, the perovskite solar cell has better capability of resisting water and oxygen in the environment, so that the stability of the perovskite solar cell is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The perovskite solar cell is characterized in that a transparent substrate, a first electrode layer, a transmission layer, a perovskite layer, a superposed composite transmission layer and a back electrode layer are sequentially arranged in the internal structure from a light incident surface (the front surface of the cell) to the back surface of the cell, and the structural form of the superposed composite transmission layer is A0+ n (ba) type, where n =1, 2, 3, …, thin film layer at zero levelA0And a thin film layer A on the n-th layernRespectively an organic transmission layer and a thin film layer B arranged on the n-th layernA thin film layer A of an organic insulating layer, zero layer0The preparation material and the thin film layer A of the n-th layernThe preparation material is organic hole transport material or organic electron transport material, and the thin film layer B of the n-th layernThe preparation material of (a) is an organic insulating/barrier material.
2. The perovskite solar cell with an overlying composite transport layer as claimed in claim 1, wherein the zero layer thin film layer a is prepared0The preparation material and the thin film layer A of the n-th layernThe material comprises an electron transport material and a hole transport material, wherein the electron transport material comprises at least one of Di-PDI, ITCPTC-Th, carbon 60, carbon 70, alkyl fullerene phenyl-carbon 61-methyl butyrate, alkyl fullerene phenyl-carbon 72-methyl butyrate, PCBM, novel indene and C60 double adduct or a variant and a dopant of the fullerene organic compound, and the hole transport material comprises poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]2,2',7,7' -tetrakis (N, N-p-methoxyanilino) -9,9' -spirobifluorene, 3, 4-Ethylenedioxythiophene (EDOT), poly (3-hexylthiophene-2, 5-diyl), poly [ bis (4-phenyl) (4-butylphenyl) amine]At least one of (1); zero-layer film layer A0The thickness of (1 nm) - (100 nm) and the thin film layer A of the n-th layernThe thickness of (a) is 1nm to 100 nm.
3. The perovskite solar cell with a superimposed composite transport layer according to claim 2, wherein the thin film layer B of the n-th layer is preparednThe material of (1) includes 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline, 9, 10-bis [ N, N-di (p-tolyl) amino group]Any one of anthracene, polyethyleneimine and 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, wherein the thickness of the benzene is 1 nm-20 nm.
4. The perovskite solar cell with the superposed composite transmission layer as claimed in claim 1, wherein the first electrode layer is made of a material comprising any one of indium tin oxide, zinc aluminum oxide, indium zinc oxide, fluorine-doped tin oxide, zirconium-doped indium oxide and tungsten-doped indium oxide, and the thickness of the material is 100nm to 300 nm; the material for preparing the transmission layer comprises at least one hole transmission layer material selected from nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid, cuprous thiocyanate, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], 2',7,7' -tetrakis (N, N-p-methoxyanilino) -9,9' -spirobifluorene, 3, 4-ethylenedioxythiophene, poly (3-hexylthiophene-2, 5-diyl), poly [ bis (4-phenyl) (4-butylphenyl) amine ], or titanium dioxide, tin dioxide, zinc oxide, Di-PDI, ITCPTC-Th, carbon 60, carbon 70, alkylfullerene-phenyl-carbon 61-butyric acid-methyl ester, The thickness of the electron transport layer material is 5 nm-50 nm, wherein the electron transport layer material is any one of alkyl fullerene phenyl-carbon 72-butyric acid-methyl ester, PCBM, novel indene and C60 double adducts or variants and dopants of the fullerene-based organic substance; the material for preparing the back electrode layer comprises any one of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc or any one of stainless steel, tin brass, tin bronze, nickel brass and silicon brass, and the thickness of the material is 20 nm-1000 nm, or any one of indium tin oxide, zinc aluminum oxide, indium zinc oxide, fluorine-doped tin oxide, zirconium-doped indium oxide and tungsten-doped indium oxide, and the thickness of the material is 10 nm-2000 nm.
5. The perovskite solar cell with the superimposed composite transport layer as claimed in claim 1, wherein the perovskite layer is prepared with a band gap of not more than 3.0eV and the compound of the composition structure is GMX3Wherein G is a monovalent cation, G is an alkali metal cation or an organic cation, G includes any one of a methylamine cation, a formamidine cation, a cesium cation and a rubidium cation, M is a divalent cation, M is any one of a transition metal and a divalent cation of a group 13 to 15 element, and M includes Pb2+、Ge2+、Sn2+、Cu2+、Bi2+X is a monovalent anion, X is any one of a halogen anion or a thiocyanate ion, and the positions G, M and X are occupied by various types of ions;the thickness of the perovskite layer is 300 nm-2 mu m.
6. The superimposed composite transport layer-containing perovskite solar cell of claim 5, wherein the material from which the perovskite layer is fabricated comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3。
7. A process for the preparation of a perovskite solar cell comprising an overlying composite transport layer according to claims 1 to 6, characterized in that the structural form A of the overlying composite transport layer is0N =1 in + n (ba) type, i.e. the structural form of the superimposed composite transport layer is a0B1A1Preparing a zero-layer film layer A0The material is selected from alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester or alkyl fullerene phenyl-carbon 72-butyric acid-methyl ester to prepare the film layer B of the 1 st layer1The material is selected from 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, and a film layer A of the 1 st layer is prepared1The material is selected from carbon 60 or carbon 70, and the method specifically comprises the following steps:
step 11, the transparent substrate adopts glass coated with an indium tin oxide conducting layer, the glass surface is an illumination incidence surface, and the surface coated with the indium tin oxide conducting layer is used as a first electrode layer;
step 12, preparing a hole transport layer on the first electrode layer, wherein the preparation method of the hole transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering, and the material for preparing the hole transport layer comprises at least one hole transport layer material selected from nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, cuprous thiocyanate, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], 2',7,7' -tetrakis (N, N-p-methoxyanilino) -9,9' -spirobifluorene, 3, 4-ethylenedioxythiophene, poly (3-hexylthiophene-2, 5-diyl) and poly [ bis (4-phenyl) (4-butylphenyl) amine ], the thickness of the material is 5 nm-50 nm;
step 13, preparing a perovskite layer on the hole transport layer, wherein the method for preparing the perovskite layer comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness of the film is 300 nm-2 μm;
step 14, preparing a superposed composite transmission layer on the perovskite layer, wherein the method for preparing the superposed composite transmission layer comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer0A film layer B of the 1 st layer1And film layer A of layer 11(ii) a Wherein, the film layer A of the zero layer0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm;
and step 15, preparing a back electrode layer on the superposed composite transmission layer, wherein the method for preparing the back electrode layer comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes, the material for preparing the back electrode layer comprises any one of metals or any one of alloys of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and the thickness of the back electrode layer is 20 nm-1000 nm.
8. A process for the preparation of a perovskite solar cell comprising an overlying composite transport layer according to claims 1 to 6, characterized in that the structural form A of the overlying composite transport layer is0N =2 in + n (ba) type, i.e. the structural form of the superimposed composite transport layer is a0B1A1B2A2Preparing a zero-layer film layer A0Layer 1, thin film layer A1And film layer A of layer 22All the materials are poly [ bis (4-phenyl) (4-butylphenyl) amine]Preparing a film layer B of the 1 st layer1And film layer B of layer 22The material is polyethyleneimine, and the method specifically comprises the following steps:
step 21, the transparent substrate adopts glass coated with an indium tin oxide conducting layer, the glass surface is an illumination incidence surface, and the surface coated with the indium tin oxide conducting layer is used as a first electrode layer;
step 22, preparing an electron transport layer on the first electrode layer, wherein the preparation method of the electron transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes, and the materials for preparing the electron transport layer comprise any one of titanium dioxide, tin dioxide, zinc oxide, Di-PDI, ITCPTC-Th, carbon 60, carbon 70, alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester, alkyl fullerene phenyl-carbon 72-butyric acid-methyl ester, PCBM, a novel indene and C60 double adduct or a variant of the fullerene organic matter and a dopant, and the thickness of the electron transport layer is 5 nm-50 nm;
step 23, preparing a perovskite layer on the electron transport layer, wherein the method for preparing the perovskite layer comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness of the film is 300 nm-2 μm;
step 24, preparing a superposed composite transmission layer on the perovskite layer, wherein the method for preparing the superposed composite transmission layer comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer0A film layer B of the 1 st layer1Layer 1, thin film layer A1A 2 nd thin film layer B2And film layer A of layer 22Wherein, the film layer A of the zero layer0Layer 1, thin film layer A1And film layer A of layer 22The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1And film layer B of layer 22The thickness of (a) is 1 nm-20 nm;
and 25, preparing a back electrode layer on the superposed composite transmission layer, wherein the method for preparing the back electrode layer comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes, the material for preparing the back electrode layer comprises any one of metals or any one of alloys of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and the thickness of the back electrode layer is 20 nm-1000 nm.
9. A process for the preparation of a perovskite solar cell comprising an overlying composite transport layer according to claims 1 to 6, characterized in that the structural form A of the overlying composite transport layer is0N =1 in + n (ba) type, i.e. the structural form of the superimposed composite transport layer is a0B1A1Preparing a zero-layer film layer A0And film layer A of layer 11Is carbon 60 or carbon 70, respectivelyFilm layer B with layer 11The material is selected from 4, 7-diphenyl-1, 10-phenanthroline, and the method specifically comprises the following steps:
step 31, the transparent substrate adopts glass coated with an indium tin oxide conducting layer, the glass surface is an illumination incidence surface, and the surface coated with the indium tin oxide conducting layer is used as a first electrode layer;
step 32, preparing a hole transport layer on the first electrode layer, wherein the preparation method of the hole transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes, the material for preparing the hole transport layer comprises at least one of nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide, poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, cuprous thiocyanate and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], and the thickness of the hole transport layer is 5 nm-50 nm;
step 33, preparing a perovskite layer on the hole transport layer, wherein the method for preparing the perovskite layer comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness of the film is 300 nm-2 μm;
step 34, preparing a superposed composite transmission layer on the perovskite layer, wherein the method for preparing the superposed composite transmission layer comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer0A film layer B of the 1 st layer1And film layer of layer 1A1(ii) a Wherein, the film layer A of the zero layer0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm;
and step 35, preparing a back electrode layer on the superposed composite transmission layer, wherein the method for preparing the back electrode layer comprises any one of magnetron sputtering, plasma enhanced chemical vapor deposition and monoatomic layer deposition processing modes, the material for preparing the back electrode layer comprises any one of indium tin oxide, aluminum oxide doped zinc oxide, indium oxide doped zinc oxide, fluorine-doped tin oxide, zirconium-doped indium oxide and tungsten-doped indium oxide doped boron-doped zinc oxide, and the thickness of the material is 20 nm-1000 nm.
10. A process for the preparation of a perovskite solar cell comprising an overlying composite transport layer according to claims 1 to 6, characterized in that the structural form A of the overlying composite transport layer is0N =1 in + n (ba) type, i.e. the structural form of the superimposed composite transport layer is a0B1A1Preparing a zero-layer film layer A0And film layer A of layer 11Is 2,2',7,7' -tetra (N, N-p-methoxyanilino) -9,9' -spirobifluorene respectively, and a film layer B of the 1 st layer is prepared1The material is 9, 10-bis [ N, N-di (p-tolyl) amino]The anthracene specifically comprises the following steps:
step 41, adopting glass plated with an indium tin oxide conducting layer as a transparent substrate, wherein the glass surface is an illumination incidence surface, and the surface plated with the indium tin oxide conducting layer is used as a first electrode layer;
step 42, preparing an electron transport layer on the first electrode layer, wherein the preparation method of the electron transport layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes, and the materials for preparing the electron transport layer comprise any one of titanium dioxide, tin dioxide, zinc oxide, Di-PDI, ITCPTC-Th, carbon 60, carbon 70, alkyl fullerene phenyl-carbon 61-butyric acid-methyl ester, alkyl fullerene phenyl-carbon 72-butyric acid-methyl ester, PCBM, a novel indene and C60 double adduct or a variant of the fullerene organic matter and a dopant, and the thickness of the electron transport layer is 5 nm-50 nm;
step 43, preparing a perovskite layer on the electron transport layer, wherein the method for preparing the perovskite layer comprises any one of coating, spraying and thermal evaporation processing modes, and the material for preparing the perovskite layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnIxBR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one of them, wherein 0<x<3; the thickness of the film is 300 nm-2 μm;
step 44, preparing a superposed composite transmission layer on the perovskite layer, wherein the method for preparing the superposed composite transmission layer comprises any one of coating, thermal evaporation, electron beam evaporation and pulse laser deposition processing modes, and sequentially preparing a zero-layer thin film layer A on the perovskite layer0A film layer B of the 1 st layer1And film layer A of layer 11(ii) a Wherein, the film layer A of the zero layer0The thickness of the film layer B is 1 nm-100 nm, and the film layer B of the 1 st layer1The thickness of (1) is 1 nm-20 nm, and the thin film layer A of the 1 st layer1The thickness of (a) is 3nm to 100 nm;
and step 45, preparing a back electrode layer on the superposed composite transmission layer, wherein the method for preparing the back electrode layer comprises any one of thermal evaporation, electron beam evaporation and magnetron sputtering processing modes, the material for preparing the back electrode layer comprises any one of stainless steel, tin brass, tin bronze, nickel brass and silicon brass, and the thickness of the back electrode layer is 20 nm-1000 nm.
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| CN115955848A (en) * | 2022-09-29 | 2023-04-11 | 宁德时代新能源科技股份有限公司 | Perovskite battery, photovoltaic module, photovoltaic power generation system and consumer |
| CN116209289B (en) * | 2023-05-06 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | Laminated solar cell, preparation method thereof and power utilization device |
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