WO2016093485A1 - 유무기 하이브리드 페로브스카이트 화합물, 이의 제조방법 및 이를 포함하는 태양전지 - Google Patents
유무기 하이브리드 페로브스카이트 화합물, 이의 제조방법 및 이를 포함하는 태양전지 Download PDFInfo
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- WO2016093485A1 WO2016093485A1 PCT/KR2015/011034 KR2015011034W WO2016093485A1 WO 2016093485 A1 WO2016093485 A1 WO 2016093485A1 KR 2015011034 W KR2015011034 W KR 2015011034W WO 2016093485 A1 WO2016093485 A1 WO 2016093485A1
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- Prior art keywords
- organic
- solar cell
- inorganic hybrid
- perovskite compound
- formula
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 230000031700 light absorption Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000003868 zero point energy Methods 0.000 abstract description 5
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 37
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 239000000975 dye Substances 0.000 description 12
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 11
- 229910052805 deuterium Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000011244 liquid electrolyte Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000010248 power generation Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 3
- FZHSXDYFFIMBIB-UHFFFAOYSA-L diiodolead;methanamine Chemical compound NC.I[Pb]I FZHSXDYFFIMBIB-UHFFFAOYSA-L 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- GMBYGKGAMHGYAJ-UHFFFAOYSA-N CN.[Pb+2] Chemical compound CN.[Pb+2] GMBYGKGAMHGYAJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MJFXORGVTOGORM-UHFFFAOYSA-L lead(2+) methanamine dibromide Chemical compound [Pb+2].[Br-].CN.[Br-] MJFXORGVTOGORM-UHFFFAOYSA-L 0.000 description 2
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- QTLXPKVSXWLULT-UHFFFAOYSA-L CN.Br[Pb]I Chemical compound CN.Br[Pb]I QTLXPKVSXWLULT-UHFFFAOYSA-L 0.000 description 1
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 1
- VEXZGXHMUGYJMC-DYCDLGHISA-N Deuterium chloride Chemical compound [2H]Cl VEXZGXHMUGYJMC-DYCDLGHISA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- FMSNOASLYQNGEK-UHFFFAOYSA-N N.[Pb+2] Chemical compound N.[Pb+2] FMSNOASLYQNGEK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- HXYXTCJDWHHCBW-UHFFFAOYSA-N acetonitrile;toluene Chemical compound CC#N.CC1=CC=CC=C1 HXYXTCJDWHHCBW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- CPELXLSAUQHCOX-DYCDLGHISA-N deuterium bromide Chemical compound [2H]Br CPELXLSAUQHCOX-DYCDLGHISA-N 0.000 description 1
- XMBWDFGMSWQBCA-DYCDLGHISA-N deuterium iodide Chemical compound [2H]I XMBWDFGMSWQBCA-DYCDLGHISA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- -1 halogen ion Chemical group 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- VRGUHZVPXCABAX-UHFFFAOYSA-N methyllead Chemical compound [Pb]C VRGUHZVPXCABAX-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-OMNVKBNWSA-N n,n,1,1,1-pentadeuteriomethanamine Chemical compound [2H]N([2H])C([2H])([2H])[2H] BAVYZALUXZFZLV-OMNVKBNWSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002382 photo conductive polymer Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052959 stibnite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- 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
Definitions
- Organic-inorganic hybrid perovskite compound, preparation method thereof and solar cell comprising same
- the present invention relates to an organic-inorganic hybrid perovskite compound having deuterium, a method for preparing the same, and a solar cell including the same.
- the solar cell refers to a battery that generates a current-voltage using a photovoltaic effect of absorbing light energy from sunlight to generate electrons and holes.
- Si np diode-type silicon
- Compound semiconductors such as gallium arsenide (GaAs), which have higher conversion efficiency, are used.
- GaAs gallium arsenide
- Dye-sensitized solar cells were developed by Michael Gratzel of the Swiss University of Lausanne (EPFL) in 1991 and successfully developed in Nature (Vol. 353, p. 737). Initially, the dye-sensitized solar cell structure is a simple structure in which a light-absorbing dye is adsorbed on a porous photoanode on a transparent electrode film that is electrically connected to light, and then another conductive glass substrate is placed on top and filled with a liquid electrolyte. It is.
- the working principle of dye-sensitized solar cells is that when dye molecules chemically adsorbed on the surface of a porous photocathode absorb solar light, the dye molecules generate electron-hole pairs, and the electrons are conductive bands of the semiconductor oxide used as the porous photocathode. It is injected and transferred to the transparent conductive film to generate a current. Holes remaining in the dye molecules are transferred to the photocathode by the hole conduction by the oxidation-reduction reaction of the liquid or solid electrolyte or by the photoconductive polymer to form a complete solar cell circuit.
- FTCKFluorine doped Tin Oxide or ITCX Indium doped Tin Oxide
- nanoparticles having a wide band3 ⁇ 4 are used as the porous photocathode.
- the dye is particularly well absorbed and has a higher level of energy than the condensation ion ' band energy level of the photocathode material, making it easier to isolate the acetone produced by the light due to higher energy levels of LUM0 (lower unoccupied mol ecul ar orbital).
- LUM0 lower unoccupied mol ecul ar orbital
- organic solar cells which have been studied in full swing since mid 1990, have characteristics of electron donor (D, or sometimes called hole acceptor) and electron acceptor (A). It consists of organic matter having.
- D or sometimes called hole acceptor
- A electron acceptor
- It consists of organic matter having.
- exciton Axtone moves to the DA interface to separate charges, electrons move to the acceptor, and holes move to the donor to generate photocurrent.
- the excitons generated by the electron donor are usually within 10 nm, so they can not be stacked thickly, so the light absorption is low and the efficiency is low.
- the present inventors have an organic-inorganic to increase the stability of solar cells During the research to change the structure of the hybrid perovskite, when deuterium is substituted in the organic-inorganic hybrid perovskite structure, the zero point energy is lowered and chemically stabilized, so that the stability of the solar cell can be confirmed. And completed the present invention.
- the present invention is to provide an organic-inorganic hybrid perovskite compound of a novel structure substituted with deuterium in order to increase the stability of the solar cell.
- the present invention is to provide a method for producing the organic-inorganic hybrid perovskite compound.
- the present invention is to provide a solar cell comprising the organic-inorganic hybrid perovskite art compound.
- A is CD 3 - a H a N + D 3 ⁇ b H b , where a is a real number from 0 to 3, b is a real number from 0 to 3, provided that a is 3 and b is 3 or a is Except when 3 is b and 0 or a is 0 and b is 3.
- M is a divalent metal silver
- X is a halogen ion.
- perovski te used in the present invention is named after the Russian mineralogist Lev Perovski, in which the silver (A and M) and the anion (X) are AMX, as shown in Chemical Formulas 1 and 2 above. 3 or A 2 MX 4 It means a material having the same structure as CaTi0 3 found in Ural acid, the first perovskite material.
- a monovalent ammonium salt is usually used as a cation corresponding to A. Accordingly, the term "organic-inorganic hybrid" is used.
- Perovskite used in the conventional solar cell is typical of CH 3 N3 ⁇ 4PbI 3 using a methylammonium salt.
- the above materials have a high band gap and are limited in increasing the efficiency of solar cells, and there is a problem of chemical instability.
- the present invention in order to increase the chemical stability of the perovskite compound, it has a structure in which deuterium is substituted for hydrogen.
- Salts corresponding to A in Formulas 1 and 2 are CD 3 - a H a N + D 3 _ b H b , where a is a real number of 0 to 3, b is a real number of 0 to 3, a and b Since A is all 3, A has at least one deuterium.
- At least one of hydrogen directly substituted with nitrogen is characterized as deuterium.
- the zero point energy is lower than that of the perovskite, which has only hydrogen, so that it can be more chemically stabilized.
- a and b are 0.
- all of the hydrogens of the salt corresponding to A have a structure (CD 3 N + D 3 ) substituted with deuterium.
- M is Pb 2+ , Sn 2+ , Ti 2+ , Nb 2+ , Zr 2+ or Ce 2+ , and more preferably Pb 2+ .
- X is CI—, Br " or ⁇ .
- the organic-inorganic hybrid ring of Formulas 1 and 2 substituted with deuterium according to the present invention The lobeskade compound is conventionally It was confirmed that the stability of the solar cell is improved compared to the CH 3 N3 ⁇ 4PbI 3 used, which is due to the substitution of hydrogen with deuterium.
- the present invention provides a method for preparing an organic-inorganic hybrid perovskite compound represented by Formulas 1 and 2 as follows:
- the definitions of A, M and X are as defined above.
- the molar ratio of the compound represented by Chemical Formula 3 and the compound represented by Chemical Formula 4 in the acid group step 1 is preferably about 1: 1.
- the present invention provides a solar cell comprising an organic-inorganic hybrid perovskite compound represented by the formula (1) and (2). Since the organic-inorganic hybrid perovskite compound represented by Formulas 1 and 2 according to the present invention serves to absorb sunlight, it is possible to configure a light absorbing layer in the solar cell. Therefore, the solar cell using the organic-inorganic hybrid perovskite compound of the present invention can be configured as follows. A first electrode containing a conductive transparent substrate;
- the solar cell can be manufactured as follows.
- step 3 forming an electrolyte layer by injecting an electrolyte solution located between the first electrode and the second electrode.
- Adsorption of the organic-inorganic hybrid perovskite compound of step 1 may be performed for 10 seconds to 5 minutes by spin-coating, dip coating, screen coating, spray coating, electrospinning, and the like.
- the solvent for dispersing the organic-inorganic hybrid perovskite compound is not particularly limited as long as the perovskite is easily dissolved, and gamma-butyrolactone, DMF, and the like are preferable.
- the heat treatment temperature after adsorption is preferably 40 to 300 ° C.
- the conductive transparent substrate may be doped with a material selected from the group consisting of Ti, In, Ga, and A1.
- a conductive insect including at least one material selected from the group consisting of Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C, and a conductive polymer may be formed.
- electrolyte iodine and additives dissolved in a solvent are used, for example, a group consisting of urea, thiourea, tert-butylpyridine, guanidiura thiotianate, and the like.
- At least one additive selected from One or more solvents selected from the group consisting of ethyl acetate, acetonitrile toluene, methoxy propionityl, and the like may be used, but is not limited thereto.
- the organic-inorganic hybrid perovskite compound according to the present invention lowers the zero point energy by replacing deuterium, thereby increasing the chemical stability of the perovskite compound to increase the stability of the solar cell. Therefore, the organic-inorganic hybrid perovskite compound according to the present invention can be usefully used as a light absorber of a solar cell.
- Figure 1 shows the power generation efficiency measured over time for the solar cell manufactured in one embodiment and comparative example of the present invention.
- Methyl amine-d 5 gas was injected into a 2L flask under vacuum. The flask was held for about 15 minutes at ⁇ 78 ° C. (Dry i ce and acetone bath) until the gas was condensed and liquid. Inject 5 g of Methanol-d 4 into the flask with a syringe, stir for 30 minutes and raise the temperature to 0 ° C. Hydr iodi c acid (HI 57 wt) (22.66 mL, 0.17 mol) was injected and stirred for 1.5 hours.
- Hydr iodi c acid HI 57 wt
- Methyl ammonium chloride-ds-i was prepared in the same manner except that hydrochloric acid (HCl 37 wt3 ⁇ 4>) was used instead of hydriodic acid (HI 57 wt) in Preparation Example 1.
- Methyl aonium iodide-d 6 was prepared by the same method except that 57 ⁇ %) was used.
- Methyl ammonium bromide-d ⁇ was prepared in the same manner, except that Deuterium bromide (DBr 47 wt%) was used instead of Hydrobromic acid (HBr 48 wt%) in Preparation Example 2.
- Methyl ammonium chloride—d ⁇ was prepared in the same manner, except that Deuterium chloride (DCl 35 ⁇ %) was used instead of Hydrochloric acid (HCl 37 wt%) in Preparation Example 3.
- Methyl ammonium iodide-d 5 and lead iodide (II) prepared in Preparation Example 1 were dissolved in l-methyl-2-pyrrol idone in a molar ratio of 1: 1, and stirred at 70 ° C. for 2 hours to 40% Methyl. An ammonium lead iodide—d 5 solution was prepared.
- Example 2 Preparation of Methyl ammonium lead bromide 'ds
- Methyl ammonium bromide-d 5 and lead bromide (II) prepared in Preparation Example 2 were dissolved in l-methyl-2-pyrrolidone in a molar ratio of 1: 1, and then stirred at 70 ° C. for 2 hours to 40 wt% Methyl. An aium onium lead bromide—d 5 solution was prepared.
- Example 3 Preparation of Methyl ammonium lead chloride—ds
- Methyl ammonium chloride-d 5 and lead chloride (II) prepared in Preparation Example 3 were dissolved in l-methyI-2-pyrrol idone in a molar ratio of 1: 1, and then stirred at 70 ° C. for 2 hours to 40% of methyl. a ⁇ onium lead chloride-d 5 The solution was prepared.
- Example 4 Preparation of Methyl ammonium lead fluoride-ds
- Methyl adium onium fluoride_d 5 and lead fluoride (II) prepared in Preparation Example 4 were dissolved in 1-methy ⁇ 2-pyrrol idone in a molar ratio of 1: 1, and stirred at 70 ° C. for 2 hours to obtain 40 wt% of Methyl adium onium lead fluoride-d 5 solution was prepared.
- Example 5 Preparation of Methyl ammonium lead iodide de
- Methyl ammonium iodide-d 6 and lead iodide (II) prepared in Preparation Example 5 were dissolved in 1-methyl- 2-pyrrolidone in a molar ratio of 1: 1, and then stirred at 70 ° C. for 2 hours to obtain 40) Methyl ammonium. A lead iodide-d 6 solution was prepared.
- Example 6 Preparation of Methyl ammonium lead bromide
- Methyl ammonium bromide-d 6 and lead bromide (II) prepared in Preparation Example 6 were dissolved in 1-methy ⁇ 2-pyrro done in a molar ratio of 1: 1, and then stirred at 70 ° C. for 2 hours to obtain 40 wt% of Methyl adium onium lead bromide-d 6 solution was prepared.
- Example 7 Preparation of Methyl ammonium lead iodide bromide
- Methylamine solution (40 wt in methanol) (30 mL) was added to a 250 mL flask and cooled to 0 ° C in an ice bath. Hydr iodic acid (HI 57 wt%) (32.3 mL) was injected and stirred for 1.5 h. The solvent was removed with a rotatory evaporator, washed with diethyl ether, filtered and dried in vacuo to afford Methyl aonium iodide (yield: 80.4%).
- Methyl ammonium iodide and lead iodide (II) prepared above were dissolved in l-methyl-2-pyrrolidone in a 1: 1 molar ratio, and then stirred at 70 ° C. for 2 hours to remove 40% Methyl amonium iodide solution. Prepared.
- Experimental Example 1 Methyl ammonium iodide and lead iodide (II) prepared above were dissolved in l-methyl-2-pyrrolidone in a 1: 1 molar ratio, and then stirred at 70 ° C. for 2 hours to remove 40% Methyl amonium iodide solution. Prepared.
- FT0 glass (Pikington, TEC-7, 7 ⁇ / sq) was washed with ethane for 40 minutes using ultrasound.
- the FT0 substrate was coated by spin coating with 0.1 M Titanium (IV) bis (ethyl acetoacetato) di isopropoxide / 1-butane solution (prepared first electrode). After 3 ⁇ 4 treatment at 500 ° C. for 15 minutes, a solution in which 1 g Ti0 2 paste was diluted in 10 mL ethanol was spin coated to Ti0 2 paste. The thickness can be controlled by Ti0 2 paste concentration and spin rate. Subsequently, heat treatment was performed at 5 (xrc for 1 hour.
- a hole transport layer was prepared by coating 60 mM Spiro-OMeTAD / Li-TFSI / tert-butylpyridine / chlorobenzene (Aldrich) by spin coating.
- An anode (second electrode) was prepared by scraping the anode to a width of 2.5 cm and a length of 0.5 cm, placing a mask, and depositing Au.
- the solar cell efficiency was measured using the manufactured solar cell, and the results are shown in Table 1 and FIG. 1. Humidity was kept at 20% during the measurement.
- Table 1 is a measurement result at the time of initial measurement, Figure 1 shows the power generation efficiency measured over time. [Table 1] As shown in Table 1 and FIG.
- the organic-inorganic hybrid perovskite compound according to the present invention has a low zero point energy by replacing deuterium, thereby increasing chemical stability, thereby increasing the stability of the solar cell.
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EP15867780.7A EP3156408B1 (en) | 2014-12-08 | 2015-10-19 | Organic-inorganic hybrid perovskite compound, method for preparing same, and solar cell comprising same |
US15/323,664 US20170154735A1 (en) | 2014-12-08 | 2015-10-19 | Organic-inorganic hybrid perovskite compound, its preparation method and solar cell comprising the same |
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