CN111430554A - Preparation method of perovskite thin film added with triiodide, preparation method of battery and battery - Google Patents
Preparation method of perovskite thin film added with triiodide, preparation method of battery and battery Download PDFInfo
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- CN111430554A CN111430554A CN202010219496.7A CN202010219496A CN111430554A CN 111430554 A CN111430554 A CN 111430554A CN 202010219496 A CN202010219496 A CN 202010219496A CN 111430554 A CN111430554 A CN 111430554A
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- 239000010409 thin film Substances 0.000 title claims abstract description 111
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 119
- -1 triiodide ions Chemical class 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims description 98
- 238000000576 coating method Methods 0.000 claims description 51
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 42
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 36
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 33
- 150000001768 cations Chemical class 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 23
- 239000010408 film Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 230000005540 biological transmission Effects 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052792 caesium Inorganic materials 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052701 rubidium Inorganic materials 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 15
- 229910001507 metal halide Inorganic materials 0.000 claims description 14
- 150000005309 metal halides Chemical class 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- 150000001408 amides Chemical class 0.000 claims description 12
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 150000008282 halocarbons Chemical class 0.000 claims description 12
- 230000005525 hole transport Effects 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 12
- 150000003457 sulfones Chemical class 0.000 claims description 12
- 150000003462 sulfoxides Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000005456 alcohol based solvent Substances 0.000 claims description 10
- 239000003759 ester based solvent Substances 0.000 claims description 10
- 239000004210 ether based solvent Substances 0.000 claims description 10
- 239000005453 ketone based solvent Substances 0.000 claims description 10
- 239000011133 lead Substances 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052789 astatine Inorganic materials 0.000 claims description 9
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000003599 detergent Substances 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 9
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052753 mercury Inorganic materials 0.000 claims description 9
- 229910052752 metalloid Inorganic materials 0.000 claims description 9
- 229910052755 nonmetal Inorganic materials 0.000 claims description 9
- 229910052762 osmium Inorganic materials 0.000 claims description 9
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052699 polonium Inorganic materials 0.000 claims description 9
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052711 selenium Inorganic materials 0.000 claims description 9
- 239000011669 selenium Substances 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 229910052716 thallium Inorganic materials 0.000 claims description 9
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229940006158 triiodide ion Drugs 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 6
- 239000012296 anti-solvent Substances 0.000 claims description 6
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 5
- 238000000151 deposition Methods 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 239000002800 charge carrier Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 125000000320 amidine group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910001417 caesium ion Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- NCCSSGKUIKYAJD-UHFFFAOYSA-N rubidium(1+) Chemical compound [Rb+] NCCSSGKUIKYAJD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 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
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- 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
- H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Photovoltaic Devices (AREA)
Abstract
The invention relates to a preparation method of three perovskite thin films added with triiodide, which is characterized in that triiodide ions are doped in the perovskite thin films, so that the triiodide ions with proper concentration are doped in a short preparation time, other impurities are not introduced, the triiodide ions participate in the intramolecular exchange process of perovskite, the internal defects of the perovskite material are passivated, and the charge-carrier life in the perovskite is prolonged, so that the performance and the stability of the perovskite material are improved, and the industrial production is promoted. The invention also discloses a preparation method of the perovskite battery containing the perovskite thin film and the prepared perovskite battery. The invention can rapidly fuse triiodide ions in the perovskite precursor solution and assist crystallization, passivates perovskite defects, thereby enhancing the life of charge carriers, optimizing space carrier dynamics, and realizing more excellent photovoltaic device performance.
Description
Technical Field
The invention belongs to the technical field of perovskite battery preparation, and particularly relates to a preparation method of a triiodide-added perovskite thin film and a battery thereof.
Background
In recent years, perovskite solar cells, which have perovskite materials as light absorbing layers, have attracted much attention. The perovskite is ABX3The thin film solar cell prepared by the material has simple and convenient process, low production cost, stability and high conversion rate. From 2009 to date, the laboratory conversion efficiency of perovskite photovoltaic cells ranges from 3.81% to 25.2%, showing a very rapid trend towards improvement. Although the perovskite cell is rotatedThe efficiency is constantly refreshed, but short plates with poor stability of their light absorbing layers add some uncertainty to their industrialization prospects.
Typical ABX3In the organic and inorganic perovskite materials, A generally refers to organic amine ions (e.g., MA)+、FA+) Occupying eight sites in the cube, B refers to a divalent metal ion (e.g., Pb)2+、Sn2+) In the body center of the cube, X generally refers to a halogen ion (e.g., I)-、Br-、Cl-) Or a plurality of halogen doping, occupying the face center of the hexahedron. Research shows that triiodide ions with a proper concentration are introduced to participate in the intramolecular exchange process of perovskite, thereby passivating the defects of perovskite materials and prolonging the charge-carrier life in the perovskite. The technical means used at present is to dissolve an iodine simple substance in IPA to form iodide ions, gradually generate triiodide ions after long-time stirring, add a solution containing triiodide ions into a perovskite precursor solution to assist crystallization, and the reaction equation is as follows:
(CH3)2CHOH+I2→(CH3)2C＝O+HI+I-，
however, the existing method for doping triiodide ions is only suitable for preparing a perovskite layer by a two-step solution method, the IPA solution of the iodine simple substance needs to be stirred for 7 days at 80 ℃ to fully form the triiodide ions, and the formed by-product acetone and the like can also cause the reduction of the crystal quality.
Disclosure of Invention
The invention aims to provide a preparation method of a perovskite thin film added with triiodide and a battery and the battery, which can realize the doping of triiodide ions without introducing byproducts, reduce the defect state concentration in a perovskite layer, prolong the service life of charge-carriers in the perovskite, form triiodide ions in a perovskite precursor solution in a short time, are easy for industrial production, reduce the yellow phase proportion in the perovskite, stabilize α phase and improve the efficiency and stability of the perovskite material.
The invention is realized in such a way, and provides a preparation method of a perovskite thin film added with triiodide, which comprises the following steps:
step one, two precursors BX of perovskite2And AX and Triiodide MI3Respectively adding the three-iodide solution into an organic solvent for mixing to obtain a perovskite precursor solution containing triiodide;
coating the perovskite precursor solution prepared in the step one on the surface of the substrate with the prepared transmission layer by any one processing mode of spin coating, blade coating, slit type continuous coating and spraying to obtain a metal halide perovskite thin film layer containing triiodide ions;
step three, processing and annealing the metal halide perovskite thin film layer obtained in the step two by using an anti-solvent to obtain a perovskite thin film containing triiodide ions; wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X is at least one of a-1 ion or group comprising at least one anion of iodine, bromine, chlorine, astatine; a is at least one cation in + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, amine group, amidino group or alkali group;
m is at least one cation of + 1-valent alkali metals Cs and Rb, I3 -Is a triiodide anion;
the organic solvent comprises a main solvent and a solvent additive, wherein the main solvent is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents, and the solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents;
the anti-solvent comprises any one of chlorobenzene, diethyl ether, toluene and ethyl acetate.
The invention is realized in such a way, and also provides a preparation method of the perovskite thin film added with triiodide, which comprises the following steps:
step four, perovskite precursor BX2Or a perovskite precursor BX2And triiodide MI3Respectively adding the mixture into an organic solvent for mixing to obtain a perovskite precursor BX2Solution or triiodide ion-containing perovskite precursor BX2A solution;
step five, the perovskite precursor BX prepared in the step four is processed in any one of spin coating, blade coating, slit type continuous coating and spraying2Coating the solution on the surface of the substrate with the prepared transmission layer to obtain a perovskite precursor BX2Thin film layer or perovskite precursor BX containing triiodide ions2A thin film layer;
step six, the perovskite precursor BX in the step five is used2Immersing or coating the thin film layer in an alcohol solution containing a precursor AX or an alcohol solution containing the precursor AX and triiodide, and annealing to obtain a perovskite thin film containing triiodide ions; wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X is at least one of a-1 ion or group comprising at least one anion of iodine, bromine, chlorine, astatine; a is at least one cation in + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, amine group, amidino group or alkali group;
perovskite precursor BX in step five2At least one of the solution and the precursor AX solution in the sixth step is added with triiodide;
m is at least one cation of + 1-valent alkali metals Cs and Rb, I3 -Is a triiodide anion;
the organic solvent comprises a main solvent and a solvent additive, wherein the main solvent is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents, and the solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents;
the alcohol solution comprises any one of methanol, ethanol and isopropanol.
The invention is realized in such a way, and also provides a preparation method of the perovskite thin film added with triiodide, which comprises the following steps:
seventhly, performing perovskite precursor BX2And triiodide MI3Respectively adding the mixture into an organic solvent for mixing to obtain a perovskite precursor BX containing triiodide ions2A solution;
step eight, carrying out any one processing mode of spin coating, blade coating, slit type continuous coating and spray coating on the perovskite precursor BX prepared in the step seven2Coating the solution on the surface of the substrate with the prepared transmission layer to obtain a perovskite precursor BX containing triiodide ions2A thin film layer;
step nine, the perovskite precursor BX in the step eight2The film layer is arranged in a film forming cavity, the air pressure is controlled within a certain range by a vacuum pump, the heating temperature of the perovskite precursor AX powder is controlled, and the perovskite precursor AX gas molecules and the perovskite precursor BX containing triiodide ions2The thin film layer reacts to generate a perovskite thin film layer doped with triiodide ions;
step ten, washing the perovskite thin film layer by using isopropyl alcohol (IPA)2Drying and annealing to obtain a perovskite film containing triiodide ions; wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X is at least one of a-1 ion or group comprising at least one anion of iodine, bromine, chlorine, astatine; a is at least one cation in + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, amine group, amidino group or alkali group;
m is at least one cation of + 1-valent alkali metals Cs and Rb, I3 -Is triiodide anion.
The present invention has been achieved in such a manner that there is provided a method for producing a battery comprising the triiodide-added perovskite thin film as described above, comprising the steps of:
(11) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2Drying and then treating for 10min by UV O-zone;
(12) preparation of TiO on ITO2The electron transmission layer adopts a spraying method and has the thickness of 20 nm;
(13) 461mg of PbI2(1mmol), 172mg formamidine hydroiodide (1mmol), 5.14mg CsI3(0.01mmol) is dissolved in 1m L DMF solution, 96u L of anhydrous N-methyl pyrrolidone is added, the mixture is heated and stirred for 4h at 60 ℃, after complete mixing, a blade coating method is carried out to prepare a perovskite thin film layer doped with triiodide ions, chlorobenzene is quickly and uniformly coated on the perovskite thin film layer, and annealing is carried out for 5 min at 120 ℃ to obtain the perovskite thin film with the thickness of 500 nm;
(14) preparing a hole transport layer Spiro-OMeTAD on the perovskite thin film, and obtaining a Spiro-OMeTAD layer with the thickness of 100nm by adopting a slit coating method;
(15) preparing an electrode layer Au on the electron transmission layer, obtaining the electrode layer with the thickness of 150nm by adopting a magnetron sputtering method, and continuously finishing the preparation of the perovskite solar cell.
The present invention has been achieved in such a manner that there is provided a method for producing a battery comprising the triiodide-added perovskite thin film as described above, comprising the steps of:
(21) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2Drying and then treating for 10min by UV O-zone;
(22) preparation of SnO on ITO2Electronic deviceThe transmission layer adopts a slit coating method and has the thickness of 30 nm;
(23) 414.9mg of PbI2(0.9mmol) and 36.7mg of PbBr2(0.1mmol), 4.66mg of RbI3(0.01mmol) is dissolved in 1m L DMF solution, 96u L of anhydrous N-methyl pyrrolidone is added, the mixture is heated and stirred for 4h at 55 ℃, and after complete mixing, a perovskite precursor thin film layer doped with triiodide ions is prepared by a slit coating method, wherein the thickness is 250 nm;
(24) 68mg of MABr (0.6mmol) was dissolved in 1m of L m IPA solution and stirred at 50 deg.C for 1 h;
(25) further spin-coating MABr solution on the perovskite precursor thin film layer obtained in the step (23), and annealing at 100 ℃ for 3 minutes to obtain a triiodide-doped perovskite thin film with the thickness of 450 nm;
(26) preparing a hole transport layer PTAA on the perovskite film, and obtaining a PTAA layer with the thickness of 20 nm-50 nm by adopting a blade coating method;
(27) preparing electrode layers Au and Ag on the electron transmission layer, and obtaining Au electrode layers with the thickness of 20nm and Ag electrode layers with the thickness of 110nm by adopting a magnetron sputtering method.
The present invention has been achieved in such a manner that there is provided a method for producing a battery comprising the triiodide-added perovskite thin film as described above, comprising the steps of:
(31) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2Drying and then treating for 10min by UV O-zone;
(32) NiO preparation on ITO by slit coating methodxThe film is used as a hole transport layer;
(33) 461mg of PbI2(1mmol), 25.68mg CsI3(0.05mmol) is dissolved in 1m L DMF solution, 70.9u L of anhydrous DMSO is added, the mixture is heated and stirred for 3h at 60 ℃, and perovskite precursor solution containing triiodide is obtained after complete mixing for standby;
(34) coating the perovskite precursor solution on the surface of a substrate with a prepared hole transport layer by a spraying method to obtain a metal halide perovskite thin film layer containing triiodide ions;
(35) the metal halide to be producedThe perovskite film layer is arranged in the film forming cavity, and the air pressure is controlled at 10 by a vacuum pump-5Pa～105Pa, controlling the heating temperature of formamidine hydroiodide (FAI) at 100-200 ℃, controlling the heating temperature of a substrate at 30-200 ℃, and reacting FAI gas molecules with a perovskite thin film layer to generate a triiodide ion doped perovskite thin film;
(36) depositing an electron transport layer PCBM on the perovskite thin film, wherein the thickness of the electron transport layer PCBM is 20 nm-50 nm;
(37) and evaporating a metal conducting layer Ag electrode on the electron transport layer to finish the preparation of the perovskite solar cell.
The present invention has been achieved in this way, and provides a perovskite battery including a perovskite thin film produced by the method for producing a triiodide-added perovskite thin film as described above, or a perovskite battery produced by the method for producing a battery using a triiodide-added perovskite thin film as described above.
Compared with the prior art, the preparation method of the triiodide-added perovskite thin film and the battery thereof can rapidly fuse triiodide ions in a perovskite precursor solution and assist crystallization, passivate perovskite defects, prolong the service life of charge carriers, optimize space carrier dynamics and realize more excellent photovoltaic device performance. The method realizes doping of triiodide ions with proper concentration in a short preparation time, does not introduce other impurities, participates in the intramolecular exchange process of the perovskite, passivates the internal defects of the perovskite material, and prolongs the charge-carrier life of the perovskite material, thereby improving the performance and stability of the perovskite material and promoting the industrial production.
The preparation method of the perovskite thin film added with triiodide and the battery thereof also have the following characteristics:
1. solves the problems of long time, easy introduction of byproducts and the like of the existing triiodide ion doping technology, and is derived from CsI3Or RbI3I of (A)3 -More stable, and provides a method for preparing a high-quality perovskite thin film by introducing triiodide.
2. The triiodide ion can be rapidly fused in the perovskite precursor solution and assists in crystallization, perovskite defects are passivated, so that the service life of charge carriers is prolonged, space carrier dynamics is optimized, open-circuit voltage and short-circuit current are improved, and the stability and the performance of a photovoltaic device are improved.
3. Particularly for FA and pure inorganic perovskite, the triiodide ions can reduce the generation of yellow phase, stabilize α phase and improve the performance and stability of the perovskite solar cell.
Drawings
FIG. 1 shows a doped CsI prepared by the method of the present invention3Perovskite solar cell and undoped CsI prepared by adopting conventional method3The perovskite solar cell is subjected to an aging comparison test to obtain a comparison curve schematic diagram.
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.
The molecular structural formula of the triiodide is MI3Wherein M is an alkali cation such as Cs+、Rb+，I3 -Is triiodide anion. In the preparation process of inorganic perovskite and organic-inorganic perovskite, the introduction of a small amount of alkali metal and triiodide ions is crucial to improving the performance and stability of the perovskite material.
According to the ionic compound size matching rule: the positive and negative ions are of the same size (i.e., large positive ions are matched with large negative ions, or small positive ions are matched with small negative ions), and the formed ionic compound has better stability. For example, CsI + I2→CsI3，RbI+I2→RbI3Relative to I-To say, I3 -Ions and Cs+Ions or Rb+The ion sizes are more matched.
Compared with the currently common method for dissolving iodine simple substance to obtain triiodide ions, the method has the advantages of long time and MI3In organic solventsMedium solubility is greater, shorter time, MI3In the precursor liquid can release I3 -Thus introducing MI3The triiodide ions can be added more easily, the preparation time is shortened, the triiodide ions are better fused in the perovskite precursor solution and assist in crystallization, and the iodine defects of the perovskite material are passivated, so that the service life of charge carriers is prolonged, the space carrier dynamics is optimized, the stability of the material is improved, and the more excellent performance of a photovoltaic device is realized.
The invention discloses a preparation method of a perovskite thin film added with triiodide, which is referred to as a one-step solution method for short, and comprises the following steps:
step one, two precursors BX of perovskite2And AX and Triiodide MI3Respectively adding the three-iodide solution into an organic solvent and mixing to obtain the perovskite precursor solution containing triiodide.
And step two, coating the perovskite precursor solution prepared in the step one on the surface of the substrate with the prepared transmission layer by any one processing mode of spin coating, blade coating, slit type continuous coating and spray coating to obtain the metal halide perovskite thin film layer containing triiodide ions.
And step three, processing and annealing the metal halide perovskite thin film layer obtained in the step two by using an anti-solvent to obtain a uniform and flat perovskite thin film containing triiodide ions. Wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium. X is at least one of-1 ion or group, including at least one anion of iodine, bromine, chlorine, astatine. A is at least one cation of + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, an amine group, an amidine group or a basic group.
M is at least one cation of + 1-valent alkali metals Cs and Rb, I3 -Is triiodide anion.
The organic solvent comprises a main solvent and a solvent additive, wherein the main solvent can dissolve metal halide and other additives, and any one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon solvent, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent and an aromatic hydrocarbon solvent. The solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents.
The anti-solvent comprises any one of chlorobenzene, diethyl ether, toluene and ethyl acetate.
The precursor BX2The concentration of (A) is 0.5 mol/L-2 mol/L, and the addition amount of the precursor AX is the precursor BX290-110% of molar weight, triiodide MI3The added amount is precursor BX20-10% of molar weight, wherein the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GB L), the solvent additive is at least one of DMSO, NMP, 1, 3-dimethyl-2-imidazolidinone (DMI), 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB) and toluene, and the adding amount of the solvent additive is equal to that of the precursor BX2The molar ratio of (A) to (B) is 0 to 300%.
The invention discloses a preparation method of a perovskite thin film added with triiodide, which is called a two-step solution method for short, and comprises the following steps:
step four, perovskite precursor BX2Or a perovskite precursor BX2And triiodide MI3Respectively adding the mixture into an organic solvent for mixing to obtain a perovskite precursor BX2Solution or triiodide ion-containing perovskite precursor BX2And (3) solution.
Step five, the perovskite precursor BX prepared in the step four is processed in any one of spin coating, blade coating, slit type continuous coating and spraying2Coating the solution on the surface of the substrate with the prepared transmission layer to obtain a perovskite precursor BX2Thin film layer or perovskite precursor BX containing triiodide ions2A thin film layer.
Step six, before the perovskite in the step fiveBody BX2And immersing or coating the thin film layer in an alcohol solution containing a precursor AX or an alcohol solution containing the precursor AX and triiodide, and annealing to obtain the uniform and flat perovskite thin film containing triiodide ions. Wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium. X is at least one of-1 ion or group, including at least one anion of iodine, bromine, chlorine, astatine. A is at least one cation of + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, an amine group, an amidine group or a basic group.
Perovskite precursor BX in step five2And adding triiodide into at least one of the solution and the precursor AX solution in the step six.
M is at least one cation of + 1-valent alkali metals Cs and Rb, I3 -Is triiodide anion.
The organic solvent comprises a main solvent and a solvent additive, wherein the main solvent can dissolve metal halide and other additives, and any one of an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon solvent, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent and an aromatic hydrocarbon solvent. The solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents.
The alcohol solution comprises any one of methanol, ethanol and isopropanol.
The precursor BX2The concentration of (A) is 0.5 mol/L-2 mol/L, and the addition amount of the precursor AX is the precursor BX290-110% of molar weight, triiodide MI3The added amount is precursor BX20-10% of molar weight, wherein the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GB L), and the solvent is addedThe agent is at least one of DMSO, NMP, 1, 3-dimethyl-2-imidazolidinone (DMI), 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB) and toluene. Solvent additive addition and precursor BX2The molar ratio of (A) to (B) is 0 to 300%.
The invention discloses a preparation method of a perovskite thin film added with triiodide, which is referred to as a gas-phase solution auxiliary method for short, and comprises the following steps:
seventhly, performing perovskite precursor BX2And triiodide MI3Respectively adding the mixture into an organic solvent for mixing to obtain a perovskite precursor BX containing triiodide ions2And (3) solution.
Step eight, carrying out any one processing mode of spin coating, blade coating, slit type continuous coating and spray coating on the perovskite precursor BX prepared in the step seven2Coating the solution on the surface of the substrate with the prepared transmission layer to obtain a perovskite precursor BX containing triiodide ions2A thin film layer.
Step nine, the perovskite precursor BX in the step eight2The film layer is arranged in a film forming cavity, the air pressure is controlled within a certain range by a vacuum pump, the heating temperature of the perovskite precursor AX powder is controlled, and the perovskite precursor AX gas molecules and the perovskite precursor BX containing triiodide ions2The thin film layer reacts to generate a perovskite thin film layer doped with triiodide ions.
Step ten, washing the perovskite thin film layer by using isopropyl alcohol (IPA)2And (4) annealing after blow-drying to obtain the uniform and flat perovskite film containing triiodide ions. Wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium. X is at least one of-1 ion or group, including at least one anion of iodine, bromine, chlorine, astatine. A is at least one cation of + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, an amine group, an amidine group or a basic group.
M is a +1 valent baseAt least one cation of the metals Cs and Rb, I3 -Is triiodide anion.
The precursor BX2The concentration of (A) is 0.5 mol/L-2 mol/L, and the addition amount of the precursor AX is the precursor BX290-110% of molar weight, triiodide MI3The added amount is precursor BX20-10% of molar weight, wherein the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GB L), the solvent additive is at least one of DMSO, NMP, 1, 3-dimethyl-2-imidazolidinone (DMI), 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB) and toluene, and the adding amount of the solvent additive is equal to that of the precursor BX2The molar ratio of (A) to (B) is 0-300%; air pressure range of 10-5Pa～105Pa, the heating temperature of the precursor AX is controlled to be 100-200 ℃, the heating temperature of the substrate is controlled to be 30-200 ℃, the reaction time is controlled to be 3-120 min, and the thickness of the prepared perovskite thin film is 200-500 nm.
The following will further illustrate the method of preparing a battery of a triiodide-added perovskite thin film according to the present invention with reference to specific examples.
Example 1
The first method for preparing a battery comprising the triiodide-added perovskite thin film, namely the one-step solution method, comprises the following steps:
(11) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2And after drying, carrying out UV O-zone treatment for 10 min.
(12) Preparation of TiO on ITO2The electron transmission layer is sprayed by a spraying method and has the thickness of 20 nm.
(13) Preparing the triiodide ion doped perovskite film by a one-step method: 461mg of PbI2(1mmol), 172mg formamidine hydroiodide (1mmol), 5.14mg CsI3(0.01mmol) is dissolved in DMF solution of 1m L, 96u L of anhydrous N-methyl pyrrolidone is added, the mixture is heated and stirred for 4h at the temperature of 60 ℃, after complete mixing, a blade coating method is carried out to prepare the perovskite thin film layer doped with triiodide ions,and (3) quickly and uniformly coating chlorobenzene on the perovskite thin film layer, and annealing at 120 ℃ for 5 minutes to obtain the perovskite thin film with the thickness of 500 nm.
(14) Preparing a hole transport layer Spiro-OMeTAD on the perovskite thin film, and obtaining a Spiro-OMeTAD layer with the thickness of 100nm by adopting a slit coating method.
(15) Preparing an electrode layer Au on the electron transmission layer, obtaining the electrode layer with the thickness of 150nm by adopting a magnetron sputtering method, and continuously finishing the preparation of the perovskite solar cell.
Example 2
The second method of the present invention for producing a battery comprising a triiodide-added perovskite thin film as described above, a two-step solution method, comprises the steps of:
(21) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2And after drying, carrying out UV O-zone treatment for 10 min.
(22) Preparation of SnO on ITO2The electron transmission layer is coated by slit coating method, and the thickness is 30 nm.
(23) Preparing the triiodide ion doped perovskite film by a two-step method: 414.9mg of PbI2(0.9mmol) and 36.7mg of PbBr2(0.1mmol), 4.66mg of RbI3(0.01mmol) is dissolved in 1m L DMF solution, 96u L of anhydrous N-methyl pyrrolidone is added, the mixture is heated and stirred for 4h at 55 ℃, and after complete mixing, the perovskite precursor thin film layer doped with triiodide ions is prepared by a slit coating method, and the thickness is 250 nm.
(24) 68mg of MABr (0.6mmol) were dissolved in 1m of L m IPA solution and stirred at 50 deg.C for 1 h.
(25) And (4) further spin-coating MABr solution on the perovskite precursor thin film layer obtained in the step (23), and annealing at 100 ℃ for 3 minutes to obtain the triiodide-doped perovskite thin film with the thickness of 450 nm.
(26) Preparing a hole transport layer PTAA on the perovskite film, and obtaining a PTAA layer with the thickness of 20 nm-50 nm by adopting a blade coating method.
(27) Preparing electrode layers Au and Ag on the electron transmission layer, and obtaining Au electrode layers with the thickness of 20nm and Ag electrode layers with the thickness of 110nm by adopting a magnetron sputtering method.
Example 3
The third method for preparing a battery comprising the triiodide-added perovskite thin film, namely the gas-phase solution-assisted method, comprises the following steps:
(31) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2And after drying, carrying out UV O-zone treatment for 10 min.
(32) NiO preparation on ITO by slit coating methodxThe film acts as a hole transport layer.
(33) Preparing the perovskite thin film by a gas-phase solution auxiliary method: 461mg of PbI2(1mmol), 25.68mg CsI3(0.05mmol) is dissolved in DMF solution of 1m L, 70.9u L of anhydrous DMSO is added, the mixture is heated and stirred for 3h at 60 ℃, and the perovskite precursor solution containing triiodide ions is obtained after complete mixing for standby.
(34) And coating the perovskite precursor solution on the surface of the substrate with the prepared hole transport layer by a spraying method to obtain the metal halide perovskite thin film layer containing triiodide ions.
(35) Placing the prepared metal halide perovskite film layer in a film forming cavity, and controlling the air pressure at 10 by using a vacuum pump-5Pa～105Pa, controlling the heating temperature of formamidine hydroiodide (FAI) at 100-200 ℃, controlling the heating temperature of the substrate at 30-200 ℃, and reacting FAI gas molecules with the perovskite thin film layer to generate the perovskite thin film doped with triiodide ions.
(36) Depositing an electron transport layer PCBM on the perovskite thin film, wherein the thickness is 20 nm-50 nm.
(37) And evaporating a metal conducting layer Ag electrode on the electron transport layer to finish the preparation of the perovskite solar cell.
The doped CsI prepared in this example3Perovskite solar cell and undoped CsI prepared by adopting conventional method3The perovskite solar cell is subjected to performance test, and a cell performance parameter comparison table as shown in the following table is obtained.
As is apparent from the comparison of the above table, the doped CsI prepared in this example3The performance of the perovskite solar cell is obviously superior to that of the undoped CsI prepared by the conventional method3The perovskite solar cell of (1).
The two battery samples were subjected to aging comparative tests to obtain comparative curves as shown in fig. 1. Doped CsI3The efficiency of the perovskite cell sample is reduced to 97.4 percent after 1000 hours of photo-thermal aging, and the undoped CsI3The efficiency of the perovskite cell sample is reduced to 60.1% after 1000 hours of photo-thermal aging, and the comparison curve shows that: after 200 hours, the stability of the two appears obviously different, and the CsI is doped3The perovskite battery of (a) has better long-term stability.
The invention also discloses a perovskite battery, which contains the perovskite thin film prepared by the preparation method of the perovskite thin film added with triiodide, or is prepared by the preparation method of the perovskite thin film added with triiodide.
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. A preparation method of a perovskite thin film added with triiodide is characterized by comprising the following steps:
step one, two precursors BX of perovskite2And AX and Triiodide MI3Respectively adding the three-iodide solution into an organic solvent for mixing to obtain a perovskite precursor solution containing triiodide;
coating the perovskite precursor solution prepared in the step one on the surface of the substrate with the prepared transmission layer by any one processing mode of spin coating, blade coating, slit type continuous coating and spraying to obtain a metal halide perovskite thin film layer containing triiodide ions;
step three, processing and annealing the metal halide perovskite thin film layer obtained in the step two by using an anti-solvent to obtain a perovskite thin film containing triiodide ions; wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X is at least one of a-1 ion or group comprising at least one anion of iodine, bromine, chlorine, astatine; a is at least one cation in + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, amine group, amidino group or alkali group;
m is at least one cation of + 1-valent alkali metals Cs and Rb, I3 -Is a triiodide anion;
the organic solvent comprises a main solvent and a solvent additive, wherein the main solvent is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents, and the solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents;
the anti-solvent comprises any one of chlorobenzene, diethyl ether, toluene and ethyl acetate.
2. The method of preparing the triiodide-added perovskite thin film according to claim 1, wherein the precursor BX is2The concentration of (A) is 0.5 mol/L-2 mol/L, and the addition amount of the precursor AX is the precursor BX290-110% of molar weight, triiodide MI3The added amount is precursor BX20-10% of molar weight, the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GB L), and the solvent additive is DMSO, NMP, 1, 3-dimethyl-2-imidazolidinone (DMI) or 1, 8-dimethyl-2-imidazolidinone (DMI)-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB), toluene, solvent additive in an amount to react with the precursor BX2The molar ratio of (A) to (B) is 0 to 300%.
3. A preparation method of a perovskite thin film added with triiodide is characterized by comprising the following steps:
step four, perovskite precursor BX2Or a perovskite precursor BX2And triiodide MI3Respectively adding the mixture into an organic solvent for mixing to obtain a perovskite precursor BX2Solution or triiodide ion-containing perovskite precursor BX2A solution;
step five, the perovskite precursor BX prepared in the step four is processed in any one of spin coating, blade coating, slit type continuous coating and spraying2Coating the solution on the surface of the substrate with the prepared transmission layer to obtain a perovskite precursor BX2Thin film layer or perovskite precursor BX containing triiodide ions2A thin film layer;
step six, the perovskite precursor BX in the step five is used2Immersing or coating the thin film layer in an alcohol solution containing a precursor AX or an alcohol solution containing the precursor AX and triiodide, and annealing to obtain a perovskite thin film containing triiodide ions; wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X is at least one of a-1 ion or group comprising at least one anion of iodine, bromine, chlorine, astatine; a is at least one cation in + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, amine group, amidino group or alkali group;
perovskite precursor BX in step five2At least one of the solution and the precursor AX solution in the sixth step is added with triiodide;
m is at least one cation of + 1-valent alkali metals Cs and Rb, I3 -Is a triiodide anion;
the organic solvent comprises a main solvent and a solvent additive, wherein the main solvent is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents, and the solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbon solvents;
the alcohol solution comprises any one of methanol, ethanol and isopropanol.
4. The method of preparing the triiodide-added perovskite thin film as claimed in claim 3, wherein the precursor BX is2The concentration of (A) is 0.5 mol/L-2 mol/L, and the addition amount of the precursor AX is the precursor BX290-110% of molar weight, triiodide MI3The added amount is precursor BX20-10% of molar weight, the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GB L), the solvent additive is at least one of DMSO, NMP, 1, 3-dimethyl-2-imidazolidinone (DMI), 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB) and toluene, and the addition amount of the solvent additive is equal to that of the precursor BX2The molar ratio of (A) to (B) is 0 to 300%.
5. A preparation method of a perovskite thin film added with triiodide is characterized by comprising the following steps:
seventhly, performing perovskite precursor BX2And triiodide MI3Respectively adding the mixture into an organic solvent for mixing to obtain a perovskite precursor BX containing triiodide ions2A solution;
step eight, carrying out any one processing mode of spin coating, blade coating, slit type continuous coating and spray coating on the perovskite precursor BX prepared in the step seven2The solution is coated on the surface of the substrate with the prepared transmission layer to obtain the product containing triiodide ionsPerovskite precursor BX2A thin film layer;
step nine, the perovskite precursor BX in the step eight2The film layer is arranged in a film forming cavity, the air pressure is controlled within a certain range by a vacuum pump, the heating temperature of the perovskite precursor AX powder is controlled, and the perovskite precursor AX gas molecules and the perovskite precursor BX containing triiodide ions2The thin film layer reacts to generate a perovskite thin film layer doped with triiodide ions;
step ten, washing the perovskite thin film layer by using isopropyl alcohol (IPA)2Drying and annealing to obtain a perovskite film containing triiodide ions; wherein,
b is at least one of a +2 valent metal or metalloid ion or group comprising at least one cation of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X is at least one of a-1 ion or group comprising at least one anion of iodine, bromine, chlorine, astatine; a is at least one cation in + 1-valent metal or non-metal ions or groups, and comprises at least one of cesium, rubidium, amine group, amidino group or alkali group;
m is at least one cation of + 1-valent alkali metals Cs and Rb, I3 -Is triiodide anion.
6. The method of preparing the triiodide-added perovskite thin film according to claim 1, wherein the precursor BX is2The concentration of (A) is 0.5 mol/L-2 mol/L, and the addition amount of the precursor AX is the precursor BX290-110% of molar weight, triiodide MI3The added amount is precursor BX20-10% of molar weight, the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GB L), the solvent additive is at least one of DMSO, NMP, 1, 3-dimethyl-2-imidazolidinone (DMI), 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB) and toluene, and the addition amount of the solvent additive is equal to that of the precursor BX2The molar ratio of (A) to (B) is 0-300%; air pressure rangeEnclose as 10-5Pa～105Pa, the heating temperature of the precursor AX is controlled to be 100-200 ℃, the heating temperature of the substrate is controlled to be 30-200 ℃, the reaction time is controlled to be 3-120 min, and the thickness of the prepared perovskite thin film is 200-500 nm.
7. A method for producing a battery comprising the triiodide-added perovskite thin film as set forth in claim 1 or 2, characterized by comprising the steps of:
(11) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2Drying and then treating for 10min by UV O-zone;
(12) preparation of TiO on ITO2The electron transmission layer adopts a spraying method and has the thickness of 20 nm;
(13) 461mg of PbI2(1mmol), 172mg formamidine hydroiodide (1mmol), 5.14mg CsI3(0.01mmol) is dissolved in 1m L DMF solution, 96u L of anhydrous N-methyl pyrrolidone is added, the mixture is heated and stirred for 4h at 60 ℃, after complete mixing, a blade coating method is carried out to prepare a perovskite thin film layer doped with triiodide ions, chlorobenzene is quickly and uniformly coated on the perovskite thin film layer, and annealing is carried out for 5 min at 120 ℃ to obtain the perovskite thin film with the thickness of 500 nm;
(14) preparing a hole transport layer Spiro-OMeTAD on the perovskite thin film, and obtaining a Spiro-OMeTAD layer with the thickness of 100nm by adopting a slit coating method;
(15) preparing an electrode layer Au on the electron transmission layer, obtaining the electrode layer with the thickness of 150nm by adopting a magnetron sputtering method, and continuously finishing the preparation of the perovskite solar cell.
8. A method for producing a battery comprising the triiodide-added perovskite thin film as set forth in claim 3 or 4, characterized by comprising the steps of:
(21) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2Drying and then treating for 10min by UV O-zone;
(22) preparation of SnO on ITO2The electron transmission layer adopts a slit coating method and has the thickness of 30 nm;
(23) 414.9mg of PbI2(0.9mmol) and 36.7mg of PbBr2(0.1mmol), 4.66mg of RbI3(0.01mmol) is dissolved in 1m L DMF solution, 96u L of anhydrous N-methyl pyrrolidone is added, the mixture is heated and stirred for 4h at 55 ℃, and after complete mixing, a perovskite precursor thin film layer doped with triiodide ions is prepared by a slit coating method, wherein the thickness is 250 nm;
(24) 68mg of MABr (0.6mmol) was dissolved in 1m of L m IPA solution and stirred at 50 deg.C for 1 h;
(25) further spin-coating MABr solution on the perovskite precursor thin film layer obtained in the step (23), and annealing at 100 ℃ for 3 minutes to obtain a triiodide-doped perovskite thin film with the thickness of 450 nm;
(26) preparing a hole transport layer PTAA on the perovskite film, and obtaining a PTAA layer with the thickness of 20 nm-50 nm by adopting a blade coating method;
(27) preparing electrode layers Au and Ag on the electron transmission layer, and obtaining Au electrode layers with the thickness of 20nm and Ag electrode layers with the thickness of 110nm by adopting a magnetron sputtering method.
9. A method for producing a battery comprising the triiodide-added perovskite thin film as set forth in claim 5 or 6, characterized by comprising the steps of:
(31) sequentially and ultrasonically cleaning ITO transparent conductive glass for 30min by using detergent, deionized water, acetone and isopropanol, and then using N2Drying and then treating for 10min by UV O-zone;
(32) NiO preparation on ITO by slit coating methodxThe film is used as a hole transport layer;
(33) 461mg of PbI2(1mmol), 25.68mg CsI3(0.05mmol) is dissolved in 1m L DMF solution, 70.9u L of anhydrous DMSO is added, the mixture is heated and stirred for 3h at 60 ℃, and perovskite precursor solution containing triiodide is obtained after complete mixing for standby;
(34) coating the perovskite precursor solution on the surface of a substrate with a prepared hole transport layer by a spraying method to obtain a metal halide perovskite thin film layer containing triiodide ions;
(35) placing the prepared metal halide perovskite film layer in a film forming cavity, and controlling the air pressure at 10 by using a vacuum pump-5Pa～105Pa, controlling the heating temperature of formamidine hydroiodide (FAI) at 100-200 ℃, controlling the heating temperature of a substrate at 30-200 ℃, and reacting FAI gas molecules with a perovskite thin film layer to generate a triiodide ion doped perovskite thin film;
(36) depositing an electron transport layer PCBM on the perovskite thin film, wherein the thickness of the electron transport layer PCBM is 20 nm-50 nm;
(37) and evaporating a metal conducting layer Ag electrode on the electron transport layer to finish the preparation of the perovskite solar cell.
10. A perovskite battery comprising a perovskite thin film produced by the method for producing a triiodide-added perovskite thin film according to any one of claims 1 to 6 in the perovskite battery, or produced by the method for producing a triiodide-added perovskite thin film according to any one of claims 7 to 9.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002815A (en) * | 2020-07-30 | 2020-11-27 | 隆基绿能科技股份有限公司 | Production method of perovskite thin film and preparation method of perovskite solar cell |
| CN112635679A (en) * | 2020-12-29 | 2021-04-09 | 中国科学院青岛生物能源与过程研究所 | Method for improving open-circuit voltage of organic-inorganic hybrid perovskite solar cell |
| CN112993165A (en) * | 2021-02-04 | 2021-06-18 | 昆山协鑫光电材料有限公司 | Biocompatible perovskite battery component, precursor liquid and preparation method thereof |
| CN113346023A (en) * | 2021-04-12 | 2021-09-03 | 北京理工大学 | Preparation method and application of perovskite material with gradient change structure |
| CN114944457A (en) * | 2022-05-12 | 2022-08-26 | 深圳职业技术学院 | Perovskite solar cell and preparation method thereof |
| CN114944456A (en) * | 2022-05-07 | 2022-08-26 | 深圳职业技术学院 | Perovskite solar cell and preparation method thereof |
| CN115536058A (en) * | 2022-09-19 | 2022-12-30 | 上海钙晶科技有限公司 | Method for reducing band gap of perovskite thin film by introducing iodine three anions through secondary annealing |
| WO2023164873A1 (en) * | 2022-03-03 | 2023-09-07 | 宁德时代新能源科技股份有限公司 | Radioactive perovskite, photovoltaic cell containing radioactive perovskite, and preparation method |
| CN117320463A (en) * | 2023-11-27 | 2023-12-29 | 华电电力科学研究院有限公司 | Mesoporous perovskite solar cell and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101013729A (en) * | 2006-01-30 | 2007-08-08 | 索尼株式会社 | Photoelectric conversion apparatus and gelling agent |
| CN105164775A (en) * | 2013-03-21 | 2015-12-16 | 日本瑞翁株式会社 | Dye-sensitized solar-cell element |
| US20160380125A1 (en) * | 2013-12-17 | 2016-12-29 | Isis Innovation Limited | Photovoltaic device comprising a metal halide perovskite and a passivating agent |
| US20170244057A1 (en) * | 2016-02-22 | 2017-08-24 | Alliance For Sustainable Energy, Llc | Methods for producing perovskite halide films |
| WO2018021794A1 (en) * | 2016-07-29 | 2018-02-01 | 한국화학연구원 | Method for preparing highly efficient perovskite compound film and solar cell comprising same |
| CN108232014A (en) * | 2017-12-30 | 2018-06-29 | 杭州纤纳光电科技有限公司 | A kind of perovskite thin film of Doped ions stabilizer and its preparation method and application |
-
2020
- 2020-03-25 CN CN202010219496.7A patent/CN111430554A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101013729A (en) * | 2006-01-30 | 2007-08-08 | 索尼株式会社 | Photoelectric conversion apparatus and gelling agent |
| CN105164775A (en) * | 2013-03-21 | 2015-12-16 | 日本瑞翁株式会社 | Dye-sensitized solar-cell element |
| US20160380125A1 (en) * | 2013-12-17 | 2016-12-29 | Isis Innovation Limited | Photovoltaic device comprising a metal halide perovskite and a passivating agent |
| US20170244057A1 (en) * | 2016-02-22 | 2017-08-24 | Alliance For Sustainable Energy, Llc | Methods for producing perovskite halide films |
| WO2018021794A1 (en) * | 2016-07-29 | 2018-02-01 | 한국화학연구원 | Method for preparing highly efficient perovskite compound film and solar cell comprising same |
| CN108232014A (en) * | 2017-12-30 | 2018-06-29 | 杭州纤纳光电科技有限公司 | A kind of perovskite thin film of Doped ions stabilizer and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| SUN, QIANG, GONG, ET AL.: "Direct formation of I3- ions in organic cation solution for efficient perovskite solar cells", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
| ZHANG M , BING J , CHO Y , ET AL.: "Synergistic effect of potassium and iodine from potassium triiodide complex additive on gas-quenched perovskite solar cells", 《NANO ENERGY》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002815A (en) * | 2020-07-30 | 2020-11-27 | 隆基绿能科技股份有限公司 | Production method of perovskite thin film and preparation method of perovskite solar cell |
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| CN112993165A (en) * | 2021-02-04 | 2021-06-18 | 昆山协鑫光电材料有限公司 | Biocompatible perovskite battery component, precursor liquid and preparation method thereof |
| CN113346023A (en) * | 2021-04-12 | 2021-09-03 | 北京理工大学 | Preparation method and application of perovskite material with gradient change structure |
| WO2023164873A1 (en) * | 2022-03-03 | 2023-09-07 | 宁德时代新能源科技股份有限公司 | Radioactive perovskite, photovoltaic cell containing radioactive perovskite, and preparation method |
| CN114944456A (en) * | 2022-05-07 | 2022-08-26 | 深圳职业技术学院 | Perovskite solar cell and preparation method thereof |
| CN114944456B (en) * | 2022-05-07 | 2023-02-21 | 深圳职业技术学院 | Perovskite solar cell and preparation method thereof |
| CN114944457A (en) * | 2022-05-12 | 2022-08-26 | 深圳职业技术学院 | Perovskite solar cell and preparation method thereof |
| CN115536058A (en) * | 2022-09-19 | 2022-12-30 | 上海钙晶科技有限公司 | Method for reducing band gap of perovskite thin film by introducing iodine three anions through secondary annealing |
| CN115536058B (en) * | 2022-09-19 | 2023-12-05 | 上海钙晶科技有限公司 | Method for reducing perovskite film band gap by introducing iodine triple anions through secondary annealing |
| CN117320463A (en) * | 2023-11-27 | 2023-12-29 | 华电电力科学研究院有限公司 | Mesoporous perovskite solar cell and preparation method thereof |
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