CN111261745A - 一种钙钛矿电池及其制备方法 - Google Patents
一种钙钛矿电池及其制备方法 Download PDFInfo
- Publication number
- CN111261745A CN111261745A CN201811450984.8A CN201811450984A CN111261745A CN 111261745 A CN111261745 A CN 111261745A CN 201811450984 A CN201811450984 A CN 201811450984A CN 111261745 A CN111261745 A CN 111261745A
- Authority
- CN
- China
- Prior art keywords
- layer
- perovskite
- inorganic
- inorganic perovskite
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- -1 lanthanide metal halide Chemical class 0.000 claims abstract description 10
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 7
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 18
- 230000005525 hole transport Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 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 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- ICKYUJFKBKOPJT-UHFFFAOYSA-K samarium(3+);tribromide Chemical compound Br[Sm](Br)Br ICKYUJFKBKOPJT-UHFFFAOYSA-K 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000003504 photosensitizing agent Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- 229910052701 rubidium Inorganic materials 0.000 claims 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 claims 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 1
- 239000005751 Copper oxide Substances 0.000 claims 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims 1
- 229920002873 Polyethylenimine Polymers 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims 1
- 239000003570 air Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 238000000231 atomic layer deposition Methods 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 claims 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910000431 copper oxide Inorganic materials 0.000 claims 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 229910003437 indium oxide Inorganic materials 0.000 claims 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims 1
- 238000001755 magnetron sputter deposition Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 229940071182 stannate Drugs 0.000 claims 1
- 229910001930 tungsten oxide Inorganic materials 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 230000006750 UV protection Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 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 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KURZCZMGELAPSV-UHFFFAOYSA-N [Br].[I] Chemical compound [Br].[I] KURZCZMGELAPSV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HXEMSKJAVGFLCT-UHFFFAOYSA-N acetonitrile;cobalt Chemical compound [Co].CC#N HXEMSKJAVGFLCT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
本发明提供了一种无机钙钛矿电池及其制备方法。本发明采用无机钙钛矿材料制备钙钛矿电池,并采用镧系金属卤化物对钙钛矿层/电子传输层进行界面修饰以制备高质量无机钙钛矿电池。本发明中的无机钙钛矿电池优势在于无机钙钛矿材料热稳定性良好,具有优良的抗紫外能力,同时其吸光范围可控,有利于调控电池的光响应范围。本发明提出的界面修饰方法区别于常规的掺杂方法,可以更加明显提高器件光电性能。
Description
技术领域
本发明属于太阳能电池技术领域,涉及一种基于CsPbIBr2的无机钙钛矿电池及其制备方法
背景技术
太阳能是取之不尽、用之不竭的能源,既清洁环保,又无需运输,是21世纪最重要的新能源之一。太阳能电池是一种将光能转换为电能的半导体光电器件,在能源转化领域具有重要研究价值。同时,太阳能电池可以与发电窗、温室顶棚或玻璃幕墙等集成应用于光伏建筑一体化,具有广阔前景。钙钛矿电池是一种新型全固态薄膜太阳能电池,其光敏剂具有钙钛矿型晶体结构,具有消光系数高,激子结合能低,载流子扩散距离长等优势,因此钙钛矿电池展现出其他种类电池无法比拟的迅猛发展速度,其光电转换效率在短短几年内迅速增长到23%以上,展示出巨大的商业化前景。
钙钛矿电池主要由透明导电基板、电子传输层、有机-无机复合钙钛矿、空穴传输层和背电极组成。其工作过程如下:首先钙钛矿层吸收太阳光后产生电子(e-)与空穴(h+);e-扩散到电子传输层界面时被迅速注入其导带中,然后经导电基底导入外电路;h+被空穴传输层传输到背电极,最终于外电路中的e-复合,从而形成一个完整的电流循环。由此可见,钙钛矿层是钙钛矿电池的重要组成部分。目前钙钛矿层多采用有机-无机复合金属卤化钙钛矿材料ABX3,其中A=CH3NH3或NH2CH=NH2,B=Pb或Sn,X=I或Br。由于该材料具有良好的光电性能,致使钙钛矿电池的效率已达到20%以上。然而该类有机-无机复合金属卤化钙钛矿材料化学性质不稳定,热稳定性较差,在紫外光照射下易分解,极大地限制了钙钛矿电池的产业化发展。
通过Cs+完全取代有机组分(CH3NH3 +,NH=CHNH3 +)可制备无机钙钛矿电池。基于CsPbX3(X=I,Br)的无机钙钛矿电池具有优异的热稳定性,通过调整I/Br的比例,可以调控其禁带宽度,达到1.7eV~2.3eV,不仅适合与硅基太阳能电池结合制备叠层器件,还适合制备半透明电池。然而,目前基于无机钙钛矿的器件性能仍然较低,缺乏合适的性能优化技术。因此开发制备高效无机钙钛矿电池的方法具有重要意义。
发明内容
为了解决现有技术的不足之处,本发明旨在提供一种新型制备无机钙钛矿电池的方法,针对无机钙钛矿体系提出一种性能优化工艺,达到提升无机钙钛矿电池性能的目的。
本发明的技术方案:
一种无机钙钛矿电池,由导电基板、电子传输层、界面修饰层、钙钛矿、空穴传输层以及背电极组成。
(1)在导电基底a上制备电子传输层b。
(2)在保护气氛下,在电子传输层b上制备界面修饰层c,采用的材料是镧系金属卤化物。制备得到薄膜后将薄膜加热退火一段时间,加热完毕冷却至室温。
(3)在保护气氛下,以一定摩尔比例配置一定浓度的卤化铅和卤化铯混合溶液,搅拌溶解后过滤。采用该溶液在界面修饰层c上制备薄膜,然后将薄膜加热退火一段时间。加热完毕冷却至室温即得无机钙钛矿层d。
(4)在无机钙钛矿层d制备空穴传输层e。
(5)在空穴传输层e上制备背电极f。
本发明中制备的钙钛矿电池不仅具有高转换效率,而且其吸收范围易于调控,适合与多样化建筑材料集成,具有广阔利用前景。
本发明采用无机钙钛矿材料制备钙钛矿电池,并采用镧系金属卤化物对钙钛矿层/电子传输层进行界面修饰以制备高质量无机钙钛矿电池。无机钙钛矿材料吸光范围可控,有利于调控电池的光响应范围。本发明提出的界面修饰方法区别于常规的掺杂方法,可以更加明显提高器件光电性能。
由于上述技术方案的应用,本发明与现有的技术相比有以下优点:
(1)与传统有机-无机复合钙钛矿材料相比,无机钙钛矿材料光电性能优越,热稳定性好,具有良好的抗紫外能力。基于该材料制备的太阳能电池可以达到较长的理论寿命。通过调节钙钛矿前驱体溶液中的碘溴比例不仅可以制备电池,还可以实现对电池吸光范围的调控,有利于与温室大棚等建筑物结合。
(2)本发明采用镧系金属卤化物修饰电子传输层与无机钙钛矿界面,该类材料不仅可以大幅度提升器件性能,而且其成本也低于传统富勒烯基界面修饰材料,有利于控制电池成本。
附图说明
图1是无机钙钛矿电池的制备过程示意图。(a)化学浴沉积过程;(b)氧化钛薄膜;(c)旋涂制备溴化钐薄膜;(d)旋涂制备钙钛矿薄膜;(e)旋涂制备空穴传输层;(f)蒸镀制备金电极
图2是氧化钛薄膜的扫描电镜图片
图3是钙钛矿薄膜的扫描电镜图片
图4是钙钛矿薄膜的X射线衍射结果
图5是钙钛矿电池的I-V曲线(实施例1)
图6是无机钙钛矿电池结构,其中,a为导电基底,b为电子传输层,c为界面修饰层,d为无机钙钛矿层,e为空穴传输层,f为背电极。
具体实施方式
为了能够进一步了解本发明的方法和操作过程,现结合实施例并附以附图详细说明如下。但是,应当理解本发明并不限于这里所述的特殊实例和实施方案。这里所包含的特殊实例和实施方案旨在帮助本领域的技术人员实践本发明。
实施例1:
在空气中,将经过臭氧处理后的导电基板导电面朝上放入培养皿中,倒入40mM的四氯化钛水溶液,保持70℃恒温1h。沉积之后将导电基板取出,分别经去离子水和乙醇洗涤。氮气枪吹扫后200℃退火30min,然后臭氧处理20min。在氮气气氛下,在氧化钛表面旋涂0.04M的溴化钐的二甲基亚砜溶液,速率为3000rpm/s,时间为30s。旋涂之后室温放置10min。在其表面旋涂1M等比例的溴化铅/碘化铯混合溶液,以1500rpm/s的速度旋涂150s,旋涂之后将基板在225℃下加热10min。加热完毕冷却至室温即得无机钙钛矿层。配制浓度为72.3mg/mL的Spiro-OMeTAD的氯苯溶液,加入三种添加剂:分别为520mg/mL的LiTFSI乙腈溶液、4-叔丁基吡啶和300mg/mL的钴盐乙腈溶液,三者的体积比为11:18:12,室温下搅拌1h,即得到Spiro-OMeTAD溶液;在氮气保护下,将Spiro-OMeTAD溶液滴加到钙钛矿层上然后进行旋涂,以4000rpm/s的速度旋涂30s,即得空穴传输层。将制备好的电池放入真空蒸镀仪中,在气压小于10-4Pa时,将金丝加热沉积到空穴传输层上,金电极的厚度为50nm。如此即得到无机钙钛矿电池。
实施例2:
如实施例1所述制备方法,将溴化钐的二甲基亚砜溶液浓度改为0.01M也可以得到高效无机钙钛矿电池。
实施例3:
如实施例1所述制备方法,将溴化钐改为溴化铈也可以得到高效无机钙钛矿电池。
实施例4:
如实施例1所述制备方法,将1M等比例的溴化铅/碘化铯混合溶液浓度降为0.9M;或将铅与铯的摩尔比改为0.95均可以得到高效无机钙钛矿电池
实施例5:
如实施例1所述制备方法,将溴化铅改为碘化铅溶液也可以得到高效无机钙钛矿电池。
实施例6:
如实施例1所述制备方法,将Spiro-OMeTAD溶液改为PTAA溶液也可以得到高效无机钙钛矿电池。
实施例7:
如实施例1所述制备方法,将氧化钛改为氧化锡也可以得到无机钙钛矿电池。
实施例8:
如实施例1所述制备方法,将金电极改为溅射铟掺杂氧化锡可以得到半透明无机钙钛矿电池。
以上内容是结合具体的实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。在不脱离本发明构思的前提下做出的若干替代或变形,且性能相近或用途相同,都应当视为属于本发明的保护范围。
Claims (10)
1.一种钙钛矿电池的制备方法,其特征在于,其具体制备步骤如下:
(1)在导电基底(a)上制备电子传输层(b);
(2)在保护气氛下,在电子传输层(b)上制备界面修饰层(c),界面修饰层采用的材料是镧系金属卤化物;制备得到薄膜层后将薄膜加热退火,加热完毕冷却至室温;
(3)在保护气氛下,配置卤化铅和卤化铯混合溶液,搅拌溶解后过滤;采用该溶液在界面修饰层c上制备薄膜,然后将薄膜加热退火;加热完毕冷却至室温即得无机钙钛矿层(d);
(4)在无机钙钛矿层(d)上制备空穴传输层(e);在空穴传输层(e)上制备背电极(f);
或在无机钙钛矿层(d)上制备背电极(f)。
2.根据权利要求1所述的制备方法,其特征在于,步骤(2)中界面修饰层的制备方法包含但不局限于磁控溅射、原子层沉积、真空蒸镀沉积、旋涂等方法中的一种或二种以上;界面修饰层的材料是镧系金属卤化物,例如碘化铈、氯化铕、溴化钐中的一种或二种以上。
3.根据权利要求1或2所述的制备方法,其特征在于:步骤(2)中界面修饰层(c)的退火温度为25℃~400℃,退火时间为2s~1000min;
界面修饰层的厚度为1nm~100nm,最好是10nm。
4.根据权利要求1所述的制备方法,其特征在于:步骤(3)无机钙钛矿层前驱体溶液中,卤化铅或卤化铯的浓度为0.4M~1.2M,铅与铯的摩尔比为0.8~1.2,钙钛矿退火温度是30℃~400℃,退火时间为2s~1000min,所获得钙钛矿层厚度范围是50nm~1500nm。
5.根据权利要求4所述的制备方法,其特征在于:步骤(3)中无机钙钛矿层前驱体溶液中不添加或还可添加有锂、钠、钾、铷、锡中一种或二种以上的卤化物;
形成的无机钙钛矿层基本组成是CsPbIxBry,主要是CsPbI3,CsPbI2Br,CsPbIBr2,CsPbBr3中一种或二种以上;或也包括相应的经过锂、钠、钾、铷、锡等元素中一种或二种以上掺杂的钙钛矿材料。
6.根据权利要求4或5所述的制备方法,其特征在于:步骤(3)中无机钙钛矿层前驱体溶液中不添加或还可添加有机物,使钙钛矿是二维或三维结构的有机-无机复合金属卤化钙钛矿材料,钙钛矿中有机部分组成可以是甲脒、甲胺、乙胺、丁胺、苯乙基胺、2-碘-乙胺、聚乙烯亚胺等材料中一种或二种以上。
7.根据权利要求1所述的制备方法,其特征在于:步骤(2)和(3)在保护气氛下进行;气氛包括相对在湿度为10%到50%间的空气,氮气,氩气,氦气,氖气,二氧化碳中的一种或两种以上。
8.根据权利要求1所述的制备方法,步骤(4)中的空穴传输层的材料可以是有机空穴传输材料和/或无机空穴传输材料,例如Spiro-OMeTAD,PTAA,氧化镍,氧化铜,氧化钴,氧化钒,氧化钼,碘化亚铜,硫氰化亚铜等中一种或二种以上,并且可以酌情省略空穴传输层;
步骤(4)中的背电极的材料是可以是金、银、铜、镍、铝以及碳电极等中一种或二种以上。
电子传输层(b)的材料是n型半导体,可以是氧化钛,氧化锡,氧化锌,氧化钨,氧化铟,氧化铁,硫化镉,硒化镉,锡酸锌,锡酸钡等中一种或二种以上。
9.一种权利要求1-8任一所述方法制备的钙钛矿电池。
10.根据权利要求1所述的钙钛矿电池,其特征在于:
电池器件采用全无机钙钛矿材料为光敏剂,同时采用镧系金属卤化物为界面修饰层,制备无机钙钛矿电池。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811450984.8A CN111261745B (zh) | 2018-11-30 | 2018-11-30 | 一种钙钛矿电池及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811450984.8A CN111261745B (zh) | 2018-11-30 | 2018-11-30 | 一种钙钛矿电池及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111261745A true CN111261745A (zh) | 2020-06-09 |
CN111261745B CN111261745B (zh) | 2021-11-16 |
Family
ID=70950140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811450984.8A Active CN111261745B (zh) | 2018-11-30 | 2018-11-30 | 一种钙钛矿电池及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111261745B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112736202A (zh) * | 2020-12-30 | 2021-04-30 | 无锡极电光能科技有限公司 | 提高钙钛矿墨水与电性传输层间浸润性的方法及其应用 |
CN113087633A (zh) * | 2021-03-26 | 2021-07-09 | 河南大学 | 一类兼备界面钝化与空穴传输的空穴传输材料、其制备方法及其应用 |
CN113880718A (zh) * | 2021-11-05 | 2022-01-04 | 中国科学院福建物质结构研究所 | 具有共生结构的卤化物钙钛矿材料、制备方法及其用途 |
CN114975785A (zh) * | 2022-04-25 | 2022-08-30 | 厦门大学 | 太阳能电池电子传输层及其制备方法 |
WO2024023437A1 (fr) | 2022-07-29 | 2024-02-01 | Universite de Bordeaux | Procédé de formation d'une couche de matériau semi-conducteur dopé sur un substrat |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106159087A (zh) * | 2016-07-08 | 2016-11-23 | 合肥工业大学 | 一种CsPbI3薄膜的溶液制备方法及其光伏器件的应用 |
CN107312528A (zh) * | 2017-06-19 | 2017-11-03 | 湖北大学 | 一种室温富卤素CsPbX3无机钙钛矿纳米晶体的制备方法 |
CN108258128A (zh) * | 2018-01-17 | 2018-07-06 | 杭州纤纳光电科技有限公司 | 一种具有界面修饰层的钙钛矿太阳能电池及其制备方法 |
CN108400249A (zh) * | 2018-03-07 | 2018-08-14 | 华中科技大学鄂州工业技术研究院 | 一种基于高透明导电镍酸镧空穴传输层的钙钛矿太阳能电池及其制备方法 |
-
2018
- 2018-11-30 CN CN201811450984.8A patent/CN111261745B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106159087A (zh) * | 2016-07-08 | 2016-11-23 | 合肥工业大学 | 一种CsPbI3薄膜的溶液制备方法及其光伏器件的应用 |
CN107312528A (zh) * | 2017-06-19 | 2017-11-03 | 湖北大学 | 一种室温富卤素CsPbX3无机钙钛矿纳米晶体的制备方法 |
CN108258128A (zh) * | 2018-01-17 | 2018-07-06 | 杭州纤纳光电科技有限公司 | 一种具有界面修饰层的钙钛矿太阳能电池及其制备方法 |
CN108400249A (zh) * | 2018-03-07 | 2018-08-14 | 华中科技大学鄂州工业技术研究院 | 一种基于高透明导电镍酸镧空穴传输层的钙钛矿太阳能电池及其制备方法 |
Non-Patent Citations (1)
Title |
---|
SHOY EBMOHA MAD F. SHAI KH等: ""La2O3 interface modification of mesoporous TiO2 nanostructures enabling highly efficient perovskite solar cells"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112736202A (zh) * | 2020-12-30 | 2021-04-30 | 无锡极电光能科技有限公司 | 提高钙钛矿墨水与电性传输层间浸润性的方法及其应用 |
CN112736202B (zh) * | 2020-12-30 | 2024-02-13 | 无锡极电光能科技有限公司 | 提高钙钛矿墨水与电性传输层间浸润性的方法及其应用 |
CN113087633A (zh) * | 2021-03-26 | 2021-07-09 | 河南大学 | 一类兼备界面钝化与空穴传输的空穴传输材料、其制备方法及其应用 |
CN113087633B (zh) * | 2021-03-26 | 2022-03-08 | 河南大学 | 一类兼备界面钝化与空穴传输的空穴传输材料、其制备方法及其应用 |
CN113880718A (zh) * | 2021-11-05 | 2022-01-04 | 中国科学院福建物质结构研究所 | 具有共生结构的卤化物钙钛矿材料、制备方法及其用途 |
CN113880718B (zh) * | 2021-11-05 | 2023-10-10 | 中国科学院福建物质结构研究所 | 具有共生结构的卤化物钙钛矿材料、制备方法及其用途 |
CN114975785A (zh) * | 2022-04-25 | 2022-08-30 | 厦门大学 | 太阳能电池电子传输层及其制备方法 |
WO2024023437A1 (fr) | 2022-07-29 | 2024-02-01 | Universite de Bordeaux | Procédé de formation d'une couche de matériau semi-conducteur dopé sur un substrat |
FR3138452A1 (fr) | 2022-07-29 | 2024-02-02 | Universite de Bordeaux | Procédé de formation d’une couche de matériau semi-conducteur dopé sur un substrat |
Also Published As
Publication number | Publication date |
---|---|
CN111261745B (zh) | 2021-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111261745B (zh) | 一种钙钛矿电池及其制备方法 | |
CN107369766B (zh) | 一种高质量金属氧化物电子传输层的钙钛矿太阳电池及其制备方法 | |
CN107482122B (zh) | 一种钙钛矿太阳能电池及制备方法 | |
CN105870341B (zh) | 一种提高钙钛矿晶体生长质量的方法及太阳能电池器件 | |
CN104218109B (zh) | 一种高效率钙钛矿薄膜太阳电池及其制备方法 | |
CN107331775B (zh) | 一种高质量电子传输层的钙钛矿太阳电池及其制备方法 | |
CN108389969B (zh) | 一种用于制备钙钛矿太阳能电池钙钛矿层的绿色溶剂体系及混合溶液 | |
CN109950404A (zh) | 一种提高钙钛矿太阳能电池效率和湿热稳定性的方法 | |
CN109728169B (zh) | 一种掺杂有功能添加剂的钙钛矿太阳电池及其制备方法 | |
CN106299139B (zh) | 一种离子掺杂的钙钛矿太阳能电池及其制造方法 | |
CN110335945B (zh) | 一种双电子传输层无机钙钛矿太阳能电池及其制法和应用 | |
CN109659394A (zh) | 一种高质量全无机钙钛矿薄膜材料的制备方法及应用 | |
CN107887510A (zh) | 一种二维层状钙钛矿薄膜、太阳能电池及其制备方法 | |
CN110429179B (zh) | 一种azo/二氧化钛/二氧化锡-氧化石墨烯薄膜及利用其制得的钙钛矿太阳能电池 | |
CN108922971B (zh) | 一种快速提升基于有机空穴传输层钙钛矿太阳能电池性能的工艺 | |
CN110112062A (zh) | IIIA族元素掺杂CdS的CZTS太阳电池制备方法 | |
CN112490363A (zh) | 一种基于磁控溅射氧化锌/二氧化锡双电子传输层的钙钛矿太阳能电池制备方法 | |
CN114678472A (zh) | 一种FAPbI3钙钛矿薄膜及其高效的钙钛矿太阳能电池的方法 | |
CN111029470A (zh) | 基于纳米草状介孔层的钙钛矿太阳能电池及其制备方法 | |
CN107394044A (zh) | 一种高性能透明导电电极和电子传输层的钙钛矿太阳电池及其制备方法 | |
CN106252516A (zh) | 一种平面倒置半透明有机/无机杂化钙钛矿太阳电池器件及制备方法 | |
CN220023501U (zh) | 一种晶硅/钙钛矿叠层太阳能电池 | |
CN107910444A (zh) | 钙钛矿太阳电池 | |
CN108198939B (zh) | 一种基于多层掺杂镁铝的氧化锌复合薄膜作为电子传输层的有机太阳能电池 | |
CN108281551B (zh) | 基于光子晶体异质结的反式三维钙钛矿太阳能电池的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
EE01 | Entry into force of recordation of patent licensing contract | ||
EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20200609 Assignee: CHINA NATIONAL NUCLEAR POWER Co.,Ltd. Assignor: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023210000071 Denomination of invention: A perovskite battery and its preparation method Granted publication date: 20211116 License type: Exclusive License Record date: 20230808 |