CN108428797A - A kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology - Google Patents
A kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology Download PDFInfo
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- CN108428797A CN108428797A CN201810279295.9A CN201810279295A CN108428797A CN 108428797 A CN108428797 A CN 108428797A CN 201810279295 A CN201810279295 A CN 201810279295A CN 108428797 A CN108428797 A CN 108428797A
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- roller coating
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- solar cell
- flexible
- perovskite
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- 238000007761 roller coating Methods 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000005516 engineering process Methods 0.000 title claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 29
- 230000005540 biological transmission Effects 0.000 claims abstract description 22
- 239000010410 layer Substances 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- -1 carboxylic acid ion Chemical class 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 8
- 241000370738 Chlorion Species 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 229940006460 bromide ion Drugs 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229910003472 fullerene Inorganic materials 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 4
- 229940006461 iodide ion Drugs 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims description 4
- 238000009832 plasma treatment Methods 0.000 claims description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 4
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 4
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- LGDCSNDMFFFSHY-UHFFFAOYSA-N 4-butyl-n,n-diphenylaniline Chemical compound C1=CC(CCCC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LGDCSNDMFFFSHY-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000005301 willow glass Substances 0.000 claims description 2
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- IQBDNAFWMWZTMD-UHFFFAOYSA-N N#CO.[S] Chemical compound N#CO.[S] IQBDNAFWMWZTMD-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000004888 barrier function Effects 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 3
- 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 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 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 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 101001102158 Homo sapiens Phosphatidylserine synthase 1 Proteins 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 102100039298 Phosphatidylserine synthase 1 Human genes 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- BZWKPZBXAMTXNQ-UHFFFAOYSA-N sulfurocyanidic acid Chemical compound OS(=O)(=O)C#N BZWKPZBXAMTXNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The preparation method of the invention discloses a kind of flexible large area perovskite solar cell based on roller coating technology, includes the following steps：One, flexible conductive substrates are handled；Two, electron transfer layer, perovskite absorbed layer, hole transmission layer are sequentially prepared on flexible conductive substrates using roller coating technology, or hole transmission layer, perovskite absorbed layer, electron transfer layer are sequentially prepared on flexible conductive substrates using roller coating technology；Three, top electrode and hearth electrode are prepared, perovskite solar cell is made.The present invention can effectively solve that flexible substrate is yielding, perovskite crystalline is of poor quality and the technical barriers such as uneven thickness by adjusting roller coating technology parameter；Plated film homogeneity and planarization are improved, the preparation of flexible especially large area perovskite solar cell may be implemented, expanded the application scenarios of perovskite solar cell；This method is expected to really realize quick, inexpensive, roll-to-roll production large area perovskite battery on flexible substrates.
Description
Technical field
The present invention relates to perovskite technical field of solar cells, specifically a kind of flexible large area calcium based on roller coating technology
The preparation method of titanium ore solar cell.
Background technology
From 2009, perovskite solar cell achieved rapid development, the photoelectricity of the perovskite solar cell of rigid substrate
Transfer efficiency alreadys exceed 22%, and the photoelectric conversion efficiency of flexible substrate perovskite solar cell alreadys exceed 16%.
Currently, in the preparation of perovskite battery, still based on nonbreakable glass substrate, because of its surfacing, the calcium titanium of preparation
Mine battery repeatability is high, but glass substrate has the shortcomings that frangible, weight is heavy, can not be bent, and limits the scene of its application.It is soft
Property substrate perovskite solar cell have many advantages, such as impact resistance, light-weight, flexible, it is easy to carry, be suitble to development flexibility can
Wearable device.But most flexible substrate perovskite batteries still use produced in conventional processes, such as spin-coating method, conventional method only to fit
The method for closing the production of laboratory small area, it is difficult to be applied to the industrial production of broad area device, and the effective rate of utilization of material
It is low, serious waste of resources.In addition flexible substrate surface irregularity, there is a convex-concave, substrate discontinuity equalization in conventional method, when coating
It is yielding, the defects of leading to perovskite crystalline of poor quality, uneven thickness, it is difficult to realize roll-to-roll large area production.Therefore how
Prepare that thickness is uniform, the functional layer of smooth densification is to prepare one of the difficult point of high-efficiency soft solar cell.
Invention content
The preparation of the purpose of the present invention is to provide a kind of flexible large area perovskite solar cell based on roller coating technology
Method, the present invention can effectively solve that flexible substrate is yielding, perovskite crystalline is of poor quality and thickness by adjusting roller coating technology
Unequal technical barrier；Plated film homogeneity and planarization are improved, flexible especially large area perovskite solar cell may be implemented
Preparation, expanded the application scenarios of perovskite solar cell；This method be expected to really realize it is quick on flexible substrates, low at
Originally, roll-to-roll production large area perovskite battery.
To achieve the above object, the present invention provides the following technical solutions：
A kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, includes the following steps：
One, flexible conductive substrates are handled：By clean flexible conductive substrates UV ozone processing or oxygen plasma treatment；
Two, electron transfer layer, perovskite absorbed layer, hole transmission layer are prepared on flexible conductive substrates using roller coating technology；Roller
Painting speed is 1-100 mm/seconds；
Three, top electrode and hearth electrode are prepared, so obtained perovskite solar cell.
As a further solution of the present invention：The flexible substrate is the thin polymer film for being coated with ITO or FTO, metal liner
Bottom, the combined substrate of metal/oxide, willow glass/ITO substrates, metal-based fibers substrate or paper substrate.Be coated with ITO or
The thin polymer film of FTO：Such as polyethylene naphthalate（PET）, polyethylene naphthalate（PEN）, polyimides
Material, polyetheretherketonematerials materials etc.；Metal substrate：Such as titanium, stainless steel, nickel, copper etc..
As a further solution of the present invention：Electron transfer layer is：Titanium dioxide (TiO2), stannic oxide（SnO2）, oxidation
Zinc（ZnO）, fullerene derivate（Such as PCBM）, graphene, zinc-tin oxide, metal phthalocyanine molecular material, fullerene, in chromium oxide
One kind；
Hole transmission layer is：Nickel oxide（NiO）, it is poly-（3,4-rthylene dioxythiophene）Poly styrene sulfonate（Such as PEDOT:
PSS）, poly styrene sulfonate（Such as PSSA）, cuprous sulfocyanide, 4- butyl-N, N- diphenyl aniline homopolymer（Poly-TPD）、
Two fluorenes of 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells（ Spiro-OMeTAD ）, poly- [bis- (4- benzene
Base) (2,4,6- trimethylphenyls) amine]（PTAA）, tetra- cyanogen dimethyl-parabenzoquinone (F4- of 2,3,5,6- tetra- fluoro- 7,7', 8,8'-
TCNQ), polyvinylcarbazole（PVK）In one kind.
As a further solution of the present invention：Step 2）It is middle that perovskite absorbed layer is prepared using a step rolling method：It prepares
PbX2, AZ mixed solution to get to perovskite precursor solution, roller coating perovskite precursor solution, nitrogen stream is blown after roller coating
It is dry, it anneals 5-20 minutes under the conditions of 50-200 DEG C, obtains perovskite absorbed layer；
Wherein X is at least one of chlorion, bromide ion, iodide ion and carboxylic acid ion, Z be chlorion, bromide ion, iodine from
At least one of son, A are at least one in Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation
Kind；Solution uses solvent for water, dimethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, N-Methyl pyrrolidone, acetonitrile, different
It is one or more in propyl alcohol, ethyl alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes.It is furthermore preferred that before preparing perovskite
When driving liquid solution, in PbX2, addition ion solution additive MY in AZ mixed solutions；A and M is Organoalkyl cationic amine salt, has
At least one of machine acid amidine salt cation and alkali family cation；Y is carboxylic acid ion.
As a further solution of the present invention：Step 2）It is middle to prepare perovskite absorbed layer using two step rolling methods：First roller coating
One layer of PbX2Solution, roller coating AZ solution, nitrogen stream dry up again after drying, anneal 5-20 minutes, obtain under the conditions of 50-200 DEG C
Perovskite absorbed layer；
Wherein X is at least one of chlorion, bromide ion, iodide ion and carboxylic acid ion, Z be chlorion, bromide ion, iodine from
At least one of son, A are at least one in Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation
Kind；Solution uses solvent for water, dimethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, N-Methyl pyrrolidone, acetonitrile, different
It is one or more in propyl alcohol, ethyl alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes.It is furthermore preferred that in PbX2Solution
And/or ion solution additive MY is added in AZ solution；A and M be Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and
At least one of alkali family cation；Y is carboxylic acid ion.
As a further solution of the present invention：The hearth electrode and top electrode are ito transparent electrode, FTO transparent electrodes, gold
Belong to nano wire oxide mixed transparent electrode, metal and oxide multilevel hierarchy transparent electrode, alloy, metal electrode, carbon material
One kind in electrode；The preparation method of hearth electrode and top electrode is using roller coating, spin coating, thermal evaporation, magnetron sputtering method, blade coating, narrow
Stitch one kind in coating, silk-screen printing, printing, electron beam evaporation, chemical vapor deposition method.
As a further solution of the present invention：The regular groove of roller coating technology roller surfaces, gash depth 0-
500 microns, the density of groove is 1-10/millimeter, and roller uses corrosion-resistant, inertia material.The present invention is by adjusting molten
Liquid concentration, roll coating speeds, the gash depth of roller surfaces and density adjust wet-film thickness.
As a further solution of the present invention：Step 2）In electron transfer layer, calcium are sequentially prepared on flexible conductive substrates
Titanium ore absorbed layer, hole transmission layer, the electron transfer layer preparation method are：The direct roller coating layer material solution, dries or blows
100-200 after dryoIt anneals 10-30 minutes under C；The hole transmission layer preparation method is：The direct roller coating layer material solution, does
Dry or drying.
As a further solution of the present invention：Step 2）In hole transmission layer, calcium are sequentially prepared on flexible conductive substrates
Titanium ore absorbed layer, electron transfer layer；The hole transmission layer preparation method is：The direct roller coating layer material solution, dries or blows
100-200 after dryoIt anneals 10-30 minutes under C；The electron transfer layer preparation method is：The direct roller coating layer material solution, does
Dry or drying.Compared with prior art, the beneficial effects of the invention are as follows：
1. the present invention prepares perovskite battery on flexible substrates using roller coating technology, this method is easy to operate, production efficiency is high,
So that perovskite battery preparation technique is more compatible, really it is suitble to roll-to-roll production large area flexible perovskite battery.
2. making rough flexible substrate become smooth since the contact squeeze of roller acts in roller coating process, preventing from serving as a contrast
Bottom deforms.
3. the present invention during preparing perovskite absorbed layer, is handled without toxic anti-solvent, is reduced in preparation process
Toxic hazard and process complexity, more commercial application potentiality.
4. the gash depth and density on middle roller surface of the present invention can effectively control film thickness, traditional system is overcome
The shortcomings that perovskite crystalline is of poor quality caused by flexible substrate is easily deformed during standby, uneven thickness.
5. rolling method uses in the present invention electron transfer layer or hole transmission layer solution and perovskite precursor solution etc.
The effective rate of utilization of material is about 95%, far above 10% or so utilization rate of the conventional methods such as spin-coating method, overcomes traditional work
In skill the shortcomings that waste of material, battery production cost is greatlyd save.
Description of the drawings
Fig. 1 is one of the structural schematic diagram of n-i-p type flexibility perovskite batteries.
Fig. 2 is the second structural representation of p-i-n type flexibility perovskite batteries.
Fig. 3 is that rolling method prepares film schematic diagram.
Fig. 4 is the structural schematic diagram of roller used in rolling method.
Wherein 1- top electrodes；2- hole transmission layers；3- perovskite absorbed layers；4- electron transfer layers；5- flexible conductive substrates；
6- hearth electrodes.
Specific implementation mode
The technical solution of this patent is described in more detail With reference to embodiment.
Embodiment 1
It please refers to Fig.1 and Fig. 3-4, a kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, packet
Include following steps：
Handle ITO flexible substrates（PET）：Clean flexible conductive substrates are handled with UV ozone；
Electron transfer layer is prepared on flexible conductive substrates using roller coating technology：Add SnO2Nano particle aqueous solution, it is even immediately
Fast roller coating（As shown in Figure 3）, it is used in combination nitrogen stream to dry up, anneals 30 minutes at 100 DEG C, electron transfer layer 4 is made；
Prepare CH3NH3I and PbI2Mixed solution, PbI2A concentration of 0.5 mol/L, solvent use dimethylformamide,
PbI2And CH3NH3I molar ratios are 1:1, perovskite precursor solution is made, above-mentioned mixed solution is added dropwise on the electron transport layer,
It is at the uniform velocity coated with and is dried up with nitrogen stream immediately, annealed 10 minutes at 100 DEG C, perovskite absorbed layer is made；In the present embodiment, roller
Painting speed is 10-20 mm/seconds, and the gash depth of roller coating roller is 300 microns, density is 6 groove/millimeters；
Then roller coating Spiro-OMeTAD solution is at the uniform velocity coated with and is dried up with nitrogen stream, and hole transmission layer is made；
Last gold evaporation obtains n-i-p type flexibility perovskite solar cells to electrode（Fig. 1）；The flexible liner in roller coating process
Bottom is fixed on objective table, and roller coating process remains a constant speed coating.
Embodiment 2
It please refers to Fig.1 and Fig. 3-4, a kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, packet
Include following steps：
Handle stainless steel lining bottom：Clean flexible conductive substrates are handled with UV ozone；
Electron transfer layer is prepared on flexible conductive substrates using roller coating technology：Add nano-titanium dioxide (TiO2) solution, it stands
That is at the uniform velocity roller coating（As shown in Figure 3）, it is used in combination nitrogen stream to dry up, anneals 10 minutes at 200 DEG C, electron transfer layer 4 is made；
Prepare CH3NH3I and PbCl2Mixed solution, PbCl2A concentration of 1 mol/L, then add precursor solution 10wt%
Ion solution additive MY（Wherein A is ethyl dimethylamine salt cation, and Y is formate ion；CH3NH3I and PbCl2Molar ratio
It is 3:1, solvent is dimethylformamide and water, volume ratio 20:1）, CH is added dropwise on the electron transport layer3NH3I、PbCl2And ion
The mixed solution of solution additive MY is at the uniform velocity coated with and is dried up with nitrogen stream, annealed 5 minutes at 200 DEG C immediately, and perovskite is made
Absorbed layer；In the present embodiment, roll coating speeds are 30-40 mm/seconds, and the gash depth of roller coating roller is 50 microns, density
For 10 groove/millimeters；
Then roller coating is poly- [bis- (4- phenyl) (2,4,6- trimethylphenyls) amine]（PTAA）Solution, at the uniform velocity coating and low temperature drying,
Hole transmission layer is made；
Hearth electrode and top electrode are finally prepared, hearth electrode and top electrode are metallic silver to electrode；The preparation of hearth electrode and top electrode
Evaporation may be used in method, obtains flexible perovskite solar cell；Flexible substrate is fixed on objective table in roller coating process
On, roller coating process remains a constant speed coating.
Embodiment 3
It please refers to Fig.1 and Fig. 3-4, a kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, packet
Include following steps：
Handle polyethylene naphthalate（PEN）Flexible substrate：By clean flexible conductive substrates oxygen plasma treatment；
Electron transfer layer is prepared on flexible conductive substrates using roller coating technology：Nano-ZnO solution is added, immediately at the uniform velocity roller coating
（As shown in Figure 3）, it is used in combination nitrogen stream to dry up, anneals 20 minutes at 110 DEG C, electron transfer layer 4 is made；
Compound concentration is the PbBr of 1 mol/L2Solution adds the ion solution additive MY of 0.1wt%（Wherein, M is methyl amidine salt
Cation, Y are propionate ion, and solvent is N-Methyl pyrrolidone）.One layer of PbBr of first roller coating2With the mixed solution of MY, wait for certainly
So after drying, then a concentration of 0.5 mol/L carbonamidine bromine solutions of roller coating（Solvent is N-Methyl pyrrolidone）, nitrogen stream drying, 50
It anneals 20 minutes under the conditions of DEG C, you can perovskite absorbed layer is made；In the present embodiment, roll coating speeds are 20-30 mm/seconds, roller
The gash depth of painting roller is 300 microns, density is 5 groove/millimeters；
Then roller coating 4- butyl-N, N- diphenyl aniline homopolymer（Poly-TPD）Solution is at the uniform velocity coated with and is dried up with nitrogen stream,
Hole transmission layer is made；
Hearth electrode and top electrode are finally prepared, hearth electrode and top electrode are carbon material electrode；The preparation side of hearth electrode and top electrode
Silk-screen printing may be used in method, obtains flexible perovskite solar cell；Flexible substrate is fixed on objective table in roller coating process
On, roller coating process remains a constant speed coating.
Embodiment 4
It please refers to Fig.1 and Fig. 3-4, a kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, packet
Include following steps：
Handle polyimide material flexible substrate：By clean flexible conductive substrates oxygen plasma treatment；
Electron transfer layer is prepared on flexible conductive substrates using roller coating technology：Graphene solution is added, immediately at the uniform velocity roller coating（Such as
Shown in Fig. 3）, low temperature drying is used in combination, then anneals 15 minutes at 130 DEG C, electron transfer layer 4 is made；
Prepare CH3NH3I, carbonamidine iodine, PbI2Mixed solution, PbI2A concentration of 1 mol/L, obtain precursor solution, add
The ion solution additive MY of precursor solution 50wt%（M is propyl methylamine salt cation, and Y is acetate ion；CH3NH3I, carbonamidine
Iodine, PbI2Molar ratio be 9:1:10, solvent is the mixture of dimethylformamide and dimethyl sulfoxide (DMSO), volume ratio 20:1）；
Above-mentioned mixed solution is added dropwise on electron transfer layer, at the uniform velocity roller coating and is dried up with nitrogen stream, is annealed 5 minutes at 130 DEG C immediately, makes
Obtain perovskite absorbed layer；In the present embodiment, roll coating speeds are 70-100 mm/seconds, and roller coating is smooth surface with roller；
Then roller coating PSSA solution is at the uniform velocity coated with and is dried up with nitrogen stream, and hole transmission layer is made；
Hearth electrode and top electrode are finally prepared, hearth electrode and top electrode are metal nanometer line oxide mixed transparent electrode；Bottom electricity
Magnetron sputtering may be used in the preparation method of pole and top electrode, obtains flexible perovskite solar cell；It is soft in roller coating process
Property substrate is fixed on objective table, and roller coating process remains a constant speed coating.
Embodiment 5
Please refer to Fig. 2 and Fig. 3-4, a kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, packet
Include following steps：
Handle ITO flexible substrates（PET）：Clean flexible conductive substrates are handled with UV ozone；
PTAA solution is added dropwise on flexible conductive substrates, immediately at the uniform velocity roller coating（As shown in Figure 3）, it is used in combination nitrogen stream to dry up, 100
It anneals 10 minutes at DEG C, hole transmission layer 2 is made；
Prepare CH3NH3I, lead acetate, PbI2Mixed solution, CH3NH3A concentration of 0.8 mol/L of I, addition solution 0.1wt%
Ion solution additive MY（Wherein M is methyl methylamine salt cation, and Y is formate ion；CH3NH3I, lead acetate, PbI2Rub
You are than being 10:2:7, solvent is dimethyl sulfoxide (DMSO), gamma-butyrolacton mixture, volume ratio 3:2）, it is added dropwise on the hole transport layer
Mixed solution is stated, at the uniform velocity roller coating and is dried up immediately with nitrogen stream, anneals 8 minutes at 120 DEG C later, perovskite absorbed layer is made；
In the present embodiment, roll coating speeds are 1-20 mm/seconds, and the gash depth of roller coating roller is 100 microns, density is 10 ditches
Slot/millimeter；
Then PCBM solution is added dropwise in roller coating electron transfer layer, as shown in figure 3, being at the uniform velocity coated with and being dried up with nitrogen stream, at 120 DEG C
Lower annealing 15 minutes, is made electron transfer layer；
For last gold evaporation to electrode, magnetron sputtering method may be used in the preparation method of hearth electrode and top electrode, obtains p-i-n types
Flexible perovskite solar cell（Such as Fig. 2）；Flexible substrate is fixed on objective table in roller coating process, and roller coating process remains a constant speed
Coating.
Embodiment 6
Please refer to Fig. 2 and Fig. 3-4, a kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, packet
Include following steps：
Handle polyetheretherketonematerials materials flexible substrate：Clean flexible conductive substrates are handled with UV ozone；
PEDOT is added dropwise on flexible conductive substrates:PSS solution, immediately at the uniform velocity roller coating（As shown in Figure 3）, anneal 10 points at 110 DEG C
Hole transmission layer 2 is made in clock；
Prepare CH3NH3I、CH3NH3Br and PbI2Mixed solution, PbI2A concentration of 0.4 mol/L（Wherein, CH3NH3I、
CH3NH3Br and PbI2Molar ratio be 8:2:10, solvent is the mixture of gamma-butyrolacton, N-Methyl pyrrolidone, volume ratio 4:
1）, above-mentioned mixed solution is added dropwise on the hole transport layer, immediately at the uniform velocity coating and low temperature drying, anneals 15 points at 90 DEG C later
Perovskite absorbed layer is made in clock；In the present embodiment, roll coating speeds are 50-70 mm/seconds, and the gash depth of roller coating roller is
400 microns, density be 2 groove/millimeters；
Then be added dropwise PCBM solution, dosage be 1-10 microlitres/square centimeter, as shown in figure 3, immediately at the uniform velocity roller coating and with stand do
It is dry, electron transfer layer is made；
Hearth electrode and top electrode are finally prepared, hearth electrode and top electrode are metal and oxide multilevel hierarchy transparent electrode；Bottom electricity
Sputtering method may be used in the preparation method of pole and top electrode（It also can be replaced printing, electron beam evaporation or chemical vapor deposition etc.
Method）, obtain flexible perovskite solar cell；Flexible substrate is fixed on objective table in roller coating process, and roller coating process is protected
It holds and is at the uniform velocity coated with.
In embodiment, the thickness of perovskite absorbed layer can pass through perovskite precursor solution concentration, roll coating speeds（1-
100 mm/seconds）With the gash depth of roller coating roller（0-500 microns）And density（1-10 groove/millimeter）To control
（Such as Fig. 4）；
In above-described embodiment, electron transfer layer can be：Zinc-tin oxide, metal phthalocyanine molecular material, fullerene, chromium oxide；It is empty
Cave transport layer is：Nickel oxide（NiO）, tetra- cyanogen dimethyl-parabenzoquinone (F4-TCNQ) of 2,3,5,6- tetra- fluoro- 7,7', 8,8'-, poly- second
Alkene carbazole（PVK）；
Hearth electrode and top electrode may be replaced by ito transparent electrode, FTO transparent electrodes, alloy electrode, can according to electrode property
With selection using roller coating, spin coating, thermal evaporation, magnetron sputtering method, blade coating, slot coated, silk-screen printing, printing, electron beam evaporation,
It is prepared by the methods of chemical vapor deposition method.
In above-described embodiment, following solvents are also can be replaced when preparing perovskite precursor solution：Acetonitrile, isopropanol, second
Alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes.
The better embodiment of this patent is explained in detail above, but this patent is not limited to above-mentioned embodiment party
Formula, one skilled in the relevant art within the scope of knowledge, can also be under the premise of not departing from this patent objective
Various changes can be made.
Claims (10)
1. a kind of preparation method of the flexible large area perovskite solar cell based on roller coating technology, which is characterized in that including with
Lower step：
One, flexible conductive substrates are handled：By clean flexible conductive substrates UV ozone processing or oxygen plasma treatment；
Two, electron transfer layer, perovskite absorbed layer, hole transmission layer are prepared on flexible conductive substrates using roller coating technology；Roller
Painting speed is 1-100 mm/seconds；
Three, top electrode and hearth electrode are prepared, so obtained perovskite solar cell.
2. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, the regular groove of roller coating technology roller surfaces, gash depth is 0-500 microns；The density of groove is
1-10/millimeter.
3. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, step 2）It is middle that perovskite absorbed layer is prepared using a step rolling method：Prepare PbX2, AZ mixed solution to get to
Perovskite precursor solution, roller coating perovskite precursor solution, nitrogen stream dries up after roller coating, and anneal 5-20 under the conditions of 50-200 DEG C
Minute, obtain perovskite absorbed layer；
Wherein X is at least one of chlorion, bromide ion, iodide ion and carboxylic acid ion, Z be chlorion, bromide ion, iodine from
At least one of son, A are at least one in Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation
Kind；Solution uses solvent for water, dimethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, N-Methyl pyrrolidone, acetonitrile, different
It is one or more in propyl alcohol, ethyl alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes.
4. the preparation method of the flexible large area perovskite solar cell according to claim 3 based on roller coating technology,
It is characterized in that, when preparing perovskite precursor solution, in PbX2, in AZ mixed solutions addition 0.1-50wt% ionic liquid addition
Agent MY；M is at least one of Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation；Y is carboxylic acid
Radical ion.
5. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, step 2）It is middle to prepare perovskite absorbed layer using two step rolling methods：One layer of PbX of first roller coating2Solution, it is dry after roller again
AZ solution is applied, nitrogen stream dries up, and anneals 5-20 minutes under the conditions of 50-200 DEG C, obtains perovskite absorbed layer；
Wherein X is at least one of chlorion, bromide ion, iodide ion and carboxylic acid ion, Z be chlorion, bromide ion, iodine from
At least one of son, A are at least one in Organoalkyl cationic amine salt, Organoalkyl amidine salt cation and alkali family cation
Kind；Solution uses solvent for water, dimethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, N-Methyl pyrrolidone, acetonitrile, different
It is one or more in propyl alcohol, ethyl alcohol, methanol, toluene, ethyl acetate, chlorobenzene and dichloro-benzenes.
6. the preparation method of the flexible large area perovskite solar cell according to claim 5 based on roller coating technology,
It is characterized in that, in PbX2The ion solution additive MY of 0.1-50wt% is added in solution and/or AZ solution；M is Organoalkyl amine salt
At least one of cation, Organoalkyl amidine salt cation and alkali family cation；Y is carboxylic acid ion.
7. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, the hearth electrode and top electrode are ito transparent electrode, FTO transparent electrodes, metal nanometer line oxide mixed transparent
One kind in electrode, metal and oxide multilevel hierarchy transparent electrode, alloy, metal electrode, carbon material electrode；
The preparation method of hearth electrode and top electrode is using roller coating, spin coating, thermal evaporation, magnetron sputtering method, blade coating, slot coated, silk
One kind in wire mark brush, printing, electron beam evaporation, chemical vapor deposition method.
8. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, the flexible conductive substrates are the thin polymer film for being coated with ITO or FTO, metal substrate, the group of metal/oxide
Close one kind in substrate, willow glass/ITO substrates, metal-based fibers substrate or paper substrate；
The electron transfer layer is：Titanium dioxide, stannic oxide, zinc oxide, fullerene derivate, graphene, zinc-tin oxide, gold
Belong to one kind in Phthalocyanine material, fullerene, chromium oxide；
Hole transmission layer is：Nickel oxide gathers（3,4-rthylene dioxythiophene）Poly styrene sulfonate, poly styrene sulfonate, sulphur
Cyanic acid is cuprous, 4- butyl-N, N- diphenyl aniline homopolymer, 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino]-
Two fluorenes of 9,9'- spiral shells, poly- [bis- (4- phenyl) (2,4,6- trimethylphenyls) amine], 2,3,5,6- tetra- cyanogen two of tetra- fluoro- 7,7', 8,8'-
One kind in methyl-p-benzoquinone, polyvinylcarbazole.
9. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, step 2）In electron transfer layer, perovskite absorbed layer, hole transmission layer are sequentially prepared on flexible conductive substrates,
The electron transfer layer preparation method is：The direct roller coating layer material solution, 100-200 after dry or dryingoAnneal 10- under C
30 minutes；The hole transmission layer preparation method is：The direct roller coating layer material solution, dry or drying.
10. the preparation method of the flexible large area perovskite solar cell according to claim 1 based on roller coating technology,
It is characterized in that, step 2）In hole transmission layer, perovskite absorbed layer, electron transfer layer are sequentially prepared on flexible conductive substrates；
The hole transmission layer preparation method is：The direct roller coating layer material solution, 100-200 after dry or dryingoAnneal 10- under C
30 minutes；The electron transfer layer preparation method is：The direct roller coating layer material solution, dry or drying.
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| CN115573034A (en) * | 2022-11-04 | 2023-01-06 | 山东大学 | Hydrogen chloride-assisted growth perovskite single crystal film and preparation method and application thereof |
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