WO2021133085A2 - Preparation method for organic halide for preparation of perovskite, perovskite prepared thereby, and solar cell - Google Patents
Preparation method for organic halide for preparation of perovskite, perovskite prepared thereby, and solar cell Download PDFInfo
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- WO2021133085A2 WO2021133085A2 PCT/KR2020/019067 KR2020019067W WO2021133085A2 WO 2021133085 A2 WO2021133085 A2 WO 2021133085A2 KR 2020019067 W KR2020019067 W KR 2020019067W WO 2021133085 A2 WO2021133085 A2 WO 2021133085A2
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- Prior art keywords
- perovskite
- prepared
- organic halide
- electrode
- alkali metal
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- 150000004820 halides Chemical class 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000005342 ion exchange Methods 0.000 claims abstract description 22
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims abstract description 10
- 229910001513 alkali metal bromide Inorganic materials 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 36
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 22
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 20
- NMVVJCLUYUWBSZ-UHFFFAOYSA-N aminomethylideneazanium;chloride Chemical compound Cl.NC=N NMVVJCLUYUWBSZ-UHFFFAOYSA-N 0.000 claims description 13
- 235000009518 sodium iodide Nutrition 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 6
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 29
- 239000010408 film Substances 0.000 description 23
- 229910010413 TiO 2 Inorganic materials 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- QWANGZFTSGZRPZ-UHFFFAOYSA-N aminomethylideneazanium;bromide Chemical compound Br.NC=N QWANGZFTSGZRPZ-UHFFFAOYSA-N 0.000 description 10
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 10
- -1 methylammonium halide Chemical class 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 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 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 4
- XPOLVIIHTDKJRY-UHFFFAOYSA-N acetic acid;methanimidamide Chemical compound NC=N.CC(O)=O XPOLVIIHTDKJRY-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
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- 231100000331 toxic Toxicity 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
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- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OLRBYEHWZZSYQQ-VVDZMTNVSA-N (e)-4-hydroxypent-3-en-2-one;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O OLRBYEHWZZSYQQ-VVDZMTNVSA-N 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000001704 evaporation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910001502 inorganic halide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
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- 229940116411 terpineol Drugs 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- GRLUHXSUZYFZCW-UHFFFAOYSA-N 3-(8,8-diethyl-2-aza-8-germaspiro[4.5]decan-2-yl)-n,n-dimethylpropan-1-amine;dihydrochloride Chemical compound Cl.Cl.C1C[Ge](CC)(CC)CCC11CN(CCCN(C)C)CC1 GRLUHXSUZYFZCW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QRCOYCIXYAXCOU-UHFFFAOYSA-K CN.I[Pb+](I)I Chemical compound CN.I[Pb+](I)I QRCOYCIXYAXCOU-UHFFFAOYSA-K 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
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- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- CLFSUXDTZJJJOK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide 4-tert-butyl-2-pyrazol-1-ylpyridine cobalt(3+) Chemical compound [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.[N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.[N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.[Co+3].N1(N=CC=C1)C1=NC=CC(=C1)C(C)(C)C.N1(N=CC=C1)C1=NC=CC(=C1)C(C)(C)C.N1(N=CC=C1)C1=NC=CC(=C1)C(C)(C)C CLFSUXDTZJJJOK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
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- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
-
- 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
- H10K30/50—Photovoltaic [PV] devices
-
- 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
-
- 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
Definitions
- the present invention relates to a method for preparing an organic halide for preparing perovskite, the perovskite produced thereby, and a solar cell. Specifically, the present invention relates to the above production method, characterized in that an alkali metal iodide or bromide is used, a perovskite produced thereby, and a solar cell.
- Perovskite solar cells have developed very rapidly over the past few years as a potential alternative to crystalline silicon solar cells, which currently account for 93% of the global solar cell market.
- Perovskite solar cells have excellent photo-electric properties in terms of high light absorption efficiency, long charge carrier lifetime, and long diffusion distance of charge carriers. % to 25.2%, a dazzling improvement.
- the perovskite photoactive layer is in solution. It is prepared by a simple spin coating method using an organic halide and a PbX 2 precursor. Due to the characteristics of the solution process, organometallic trihalide-based perovskite solar cells have higher economic efficiency and competitiveness than thin film solar cells that rely on vacuum technology.
- the synthetic procedures for MAX and FAX are mostly related to the use of toxic and expensive hydrogen halide precursors.
- MAI is synthesized by an acid-base reaction between aqueous methylamine and HI
- FAI is likewise prepared by the reaction between formamidinium acetate (FAAc) and HI.
- the perovskite solar cell has the advantage of low production cost, but excessive use of HI to increase the reaction yield in the reaction of MA or FA with HI increases the manufacturing cost, so the perovskite solar cell economic efficiency will be lowered.
- One object of the present invention is to provide a method for preparing an organic halide for preparing perovskite, which does not use toxic conventional HI or HBr.
- Another object of the present invention is to provide a perovskite prepared by using an organic halide that can be prepared by the above production method as a precursor.
- Another object of the present invention is to provide a solar cell including the perovskite.
- a method for preparing an organic halide for preparing perovskite comprising the step (a) of reacting methylammonium chloride or formamidinium chloride with an alkali metal iodide or alkali metal bromide is provided
- a perovskite prepared by using the organic halide prepared by the above production method as a precursor.
- a first electrode, a second electrode opposite the first electrode, and a photoactive layer disposed at least partially between the first electrode and the second electrode, comprising:
- a solar cell comprising a photoactive layer comprising a perovskite obtained by including and using an organic halide prepared by the present invention as a precursor.
- a perovskite precursor can be prepared in an easy and environmentally friendly way.
- strong acids such as HI or HBr are used, they are oxidized by reacting with oxygen when stored for a long time in air, so special storage conditions are required, so they are not suitable for mass production and can be used in drug manufacture. It is a List I compound from the Administration (DEA) and subject to monitoring.
- DEA Administration
- an additional cooling system is required due to the strong exothermic nature of the acid-base reaction.
- the manufacturing method according to the present invention since such a strong acid is not used, manufacturing equipment can be simplified, raw material cost is low, and waste disposal can be easily carried out, thereby enabling a safer and simpler mass production design.
- the manufacturing method according to the present invention has a high production yield. Therefore, the manufacturing method of the present invention has significantly higher economic efficiency than the prior art method.
- Figure 1a is a schematic diagram of a method for producing an organic halide for perovskite according to the prior art
- Figure 1b is a schematic diagram of a production method according to an embodiment of the present invention.
- FIG. 5 shows X-ray diffraction patterns of samples prepared according to an experimental example of the present invention.
- XRF X-ray fluorescence analysis
- FIG. 7a shows the UV-Vis absorption spectrum of a perovskite film prepared using an organic halide prepared according to an experimental example of the present invention or a commercially available organic halide
- FIG. 7b is prepared according to an experimental example of the present invention.
- the XRD pattern of the perovskite film prepared using the organic halide or commercially available organic halide is shown.
- 7c and 7d are top views of SEM images of perovskite films prepared using organic halides prepared according to an experimental example of the present invention or commercially available organic halides, respectively.
- FIG. 8A to 8C are enlarged views of the XRD pattern of FIG. 7B of an organic halide prepared according to an experimental example of the present invention or a perovskite film prepared using a commercially available organic halide.
- FIG. 9A shows the structure of a mesoporous perovskite solar cell (PSC) prepared in an experimental example of the present invention
- FIG. 9B shows a cross-sectional SEM image of the solar cell.
- 9c to 9g are current density-voltage curves (JV curves) of PSCs prepared using organic halides prepared according to an experimental example of the present invention and PSCs prepared using commercially available organic halides (Fig. 9c) ), short circuit current density (Jsc) (FIG. 9D), open circuit voltage (Voc) (FIG. 9E), charge factor (FF) (FIG. 9F), and power conversion efficiency (PCE) (FIG. 9G).
- JV curves current density-voltage curves
- FIG. 9D short circuit current density
- Voc open circuit voltage
- FF charge factor
- PCE power conversion efficiency
- perovskite refers to an organic-inorganic halide in which cations (R and M) and anions (X) are composed of the chemical formula of RMX 3 , and have the same crystal structure as CaTiO 3 , the first perovskite-type material. means material.
- perovskite solar cell refers to a solar cell comprising an organic-inorganic halide material having a perovskite crystal structure.
- methylammonium chloride or formamidinium chloride is used as an alkali metal iodide or alkali metal bromide. and reacting with (a).
- the alkali metal is not particularly limited as long as it reacts with the methylammonium chloride or formamidinium chloride, and specifically lithium, sodium, potassium, and the like.
- the alkali metal iodide or alkali metal bromide may be sodium iodide (NaI) or sodium bromide (NaBr).
- NaI and NaBr may be useful in that they have high solubility in solvents such as water and alcohol.
- the organic halide in the preparation method of the present invention may be methylammonium iodide (MAI), methylammonium bromide (MABr), formamidinium iodide (FAI), or formamidinium bromide (FABr).
- MAI methylammonium iodide
- MABr methylammonium bromide
- FAI formamidinium iodide
- FABr formamidinium bromide
- the reaction step (a) may be performed by an ion exchange reaction in a solvent.
- the solvent may be water or an alcohol, wherein the alcohol may be a monohydric or dihydric alcohol having 1 to 5 carbon atoms, specifically, a monohydric alcohol having 1 to 5 carbon atoms, more specifically ethanolyl can
- the reaction step (a) may be carried out in a solvent at room temperature or under reflux.
- a suitable temperature for the reflux may be appropriately determined depending on the solvent used, for example, 100° C. when water is used as a solvent, and 78° C. when ethanol is used as a solvent.
- the reaction time may be determined according to the reaction rate and desired yield, and for example, may be carried out from 1 minute to 24 hours under stirring. However, the present invention is not limited thereto and may be performed for 24 hours or more.
- the step (b) of filtering the product of the reaction step (a), and the step (c) of removing the solvent further comprising can do.
- NaCl a reaction by-product
- the solvent removal step (c) when the solvent is water, the water is first removed in step (c), then the product may be dissolved in alcohol and the filtration step (b) may be performed.
- the solvent when the solvent is an alcohol, the filtration step (b) may be performed first, and then the step (c) may be performed, and wherein the step (c) may be performed by evaporating the alcohol.
- the step (d) of removing the alkali metal chloride by recrystallization from the organic halide produced in the reaction step (a) may be further included.
- the organic halide produced in step (a) inevitably contains ionic salt impurities (eg, alkali metal chloride, alkali metal iodide, methylammonium chloride, or formamidinium chloride) according to the ion exchange method.
- ionic salt impurities eg, alkali metal chloride, alkali metal iodide, methylammonium chloride, or formamidinium chloride
- a perovskite prepared by using the organic halide prepared by the method for producing an organic halide as described above as a precursor.
- the perovskite has a RMX 3 structure, and according to the present invention, R may be a methylammonium cation or a formamidinium cation, X may be an iodide anion or a bromide anion, M is Pb 2 It may be a divalent metal cation selected from the group consisting of + , Sn 2+ , Ge 2+ , and combinations thereof.
- a photoactive layer disposed at least partially between a first electrode, a second electrode opposite the first electrode, and between the first electrode and the second electrode, comprising an organic as described above.
- a solar cell comprising a photoactive layer comprising a perovskite obtained by including and using an organic halide prepared by the method of halide as a precursor is provided.
- the perovskite may be obtained by reacting an organic halide as described above with a compound of Formula MX 2 .
- X may be an iodide anion or a bromide anion
- M may be a divalent metal cation selected from the group consisting of Pb 2+ , Sn 2+ , Ge 2+ and combinations thereof.
- the photoactive layer comprising the perovskite can be prepared simply by, for example, spin coating using the organic halide in solution and the compound of Formula MX 2 .
- the first electrode may be one of an anode and a cathode
- the second electrode may be the other one of an anode and a cathode.
- any one or both of the first electrode and the second electrode may be coated on the substrate.
- the solar cell may further include an electron transport layer and a hole transport layer between the first electrode and the second electrode.
- the photoactive layer may further include a photoactive material other than the perovskite material, for example, a semiconductor material.
- the photoactive layer may further include, in addition to the perovskite layer, a layer comprising another photoactive material, for example, a semiconductor layer.
- Formamidinium chloride was prepared in a conventional manner, namely by reaction of FAAc and HCl solution (see I. Levchuk, A. Osvet, X. Tang, M. Brandl, JD Perea, F. Hoegl, GJ Matt, R. Hock, M. Batentschuk and CJ Brabec, Nano Lett. 2017, 17 , 2765-2770])
- MAI was synthesized under the same conditions as those used for the MAI of 1-(1)-1.
- MAI (abbreviated as IE-MAI in the device characterization part) and commercially available MAI ( ⁇ 99.5%) prepared by the ion exchange method according to the above-mentioned 1-(1)-1 of the present invention , a product of Xi'an Polymer Light Technology Corp.) (abbreviated as CO-MAI in the device characterization part) was used to manufacture solar cells.
- IE-MAI and CO-MAI used for solar cell production were obtained by recrystallization from a mixed solvent of Et 2 O and EtOH.
- FTO Fluorine-doped tin oxide
- 2 X 2 cm 2 Silkington TEC8
- TEC8 Fluorine-doped tin oxide substrates of 2 X 2 cm 2
- the cleaned substrate was dried under a N 2 gas stream.
- a 1-butanol solution in which 0.15 M titanium diisopropoxide bis(acetylacetonate) was dissolved was spin-coated at 3000 rpm for 20 seconds to prepare a TiO 2 dense layer (c-TiO 2 ).
- the c-TiO 2 /FTO was baked at 125° C.
- a diluted TiO 2 paste (SC-HT040, manufactured by SCHARECHEM Co.) composed of TiO 2 nanoparticles ( ⁇ 50 nm average diameter) was spin-coated to form a mesoporous TiO 2 (mp-TiO 2 ) layer. was formed.
- the TiO 2 paste was diluted in a mixed solvent (1-propanol to terpineol in a 3.5:1 ratio) to a paste to solvent ratio of 1:3.5 ratio.
- the mp-TiO 2 layer was then baked at 125° C. for 5 minutes and annealed at 500° C. for 30 minutes.
- the MAPbI 3 membrane was prepared through a conventional solvent engineering method.
- a MAPbI 3 film was coated on the prepared mp-TiO 2 /c-TiO 2 /FTO/glass substrate by spin coating the precursor solution at 4000 rpm for 20 seconds.
- the precursor solution was prepared by dissolving 52 wt% of the precursor, ie, PbI 2 and the desired MAI (IE-MAI or CO-MAI), in a mixed solvent of anhydrous DMF and DMSO at a volume ratio of 7.33:1. Then, 0.5 mL of Et 2 O was injected into the substrate during spin coating. Next, the substrates were sequentially annealed at 65° C. (1 min) and 130° C. (10 min).
- a hole transport layer was spin coated on the perovskite layer at 3000 rpm for 30 seconds.
- the hole transport material precursor solution was prepared by sequentially adding 18 ⁇ L of Li-TFSI solution and 14.7 mg of Co-TFSI to 1 mL of spiro-MeOTAD solution.
- the Li-TFSI solution was prepared by dissolving 566 mg of Li-TSFI in 1 mL of acetonitrile.
- the spiro-MeOTAD solution was prepared by sequentially dissolving 80 mg of spiro-MeOTAD and 32 ⁇ L of 4-tert-butylpyridine in 1 mL of chlorobenzene.
- an Au electrode was deposited on the hole transport layer at a deposition rate of 1 ⁇ s ⁇ 1 according to a thermal evaporation method.
- the solar simulator was calibrated to irradiate AM 1.5G (100 mAcm -2 ) using a standard Si reference cell (Newport, 91150V). Current density-voltage (JV) curves were recorded from forward bias (0V to 1.2V) to reverse bias (1.2V to 0V) at scan rates of 30 mVs-1 or 100 mVs-1.
- the active area of each device was 0.107 cm 2 .
- the ion exchange method allows the design of safer and simpler mass production.
- an additional cooling system is required due to the strong exothermic nature of the acid-base reaction.
- only a very slight increase in temperature is observed in the ion exchange reaction.
- Replacing water with EtOH as solvent has the advantage that the water removal step can be omitted, which simplifies the synthesis method, and the final organic halide product can be isolated directly from the reaction mixture by filtration, thereby reducing energy consumption in mass production. .
- the reaction yield was substantially reduced compared to when water was used as the solvent (see FIG. 3 ).
- the reaction yield clearly depended on the characteristics of the anion rather than the cation of the product.
- Methylammonium lead triiodide (CH 3 NH 3 PbI 3 , MAPbI 3 ) perovskite thin film was prepared using IE-MAI synthesized according to 1-(1)-1 of the present invention, and its The optical, structural, and morphological properties were investigated. For comparison, a MAPbI 3 membrane using commercial MAI instead of IE-MAI of the present invention was also prepared using the same manufacturing method.
- Figure 7b shows the XRD pattern of the MAPbI 3 film.
- the diffraction pattern of tetragonal perovskite ( I4/mcm ) is clearly observed for both films, indicating that the matrix of both films is MAPbI 3 .
- the small peak at 12.7 o is from a small amount of PbI 2 , which is a common residue in solvent engineering methods. It is noteworthy that the peak intensities of PbI 2 for IE-MAPbI 3 and CO-MAPbI 3 are different (see Fig. 8a).
- MAPbI 3 (110) peak and 12.7 o PbI compared based on the intensity ratio between the two peaks, the relative amounts of PbI 2 in IE-MAPbI 3 (IE-MAPbI 3 and CO-MAPbI 3 0.04 and 0.13 for a) from It is smaller than 1/3 of the amount of PbI 2 in this CO-MAPbI 3 .
- This difference in the amount of PbI 2 appears to be due to the difference in the amount of chlorine in the MAI precursor.
- 0.12% chlorine was detected in IE-MAI, whereas no chlorine was detected in CO-MAI. It is reported that chlorine promotes the formation of MAPbI 3 resulting in less PbI 2 extraction from the perovskite layer.
- PCS Perovskite Solar Cells
- a perovskite solar cell (PCS) was prepared (IE-MAI synthesized according to 1-(1)-1 described above was used).
- PCS perovskite solar cell
- PSCs based on CO-MAI were prepared in the same manner.
- Figure 9a shows the structure of the prepared mesoporous PSC (FTO substrate as a conductive transparent electrode, dense TiO 2 (c-TiO 2 ) and mesoporous TiO 2 (mp-TiO 2 ) film as an electron transport layer, photoactive It consisted of a MAPbI 3 perovskite film as a layer, a spiro-MeOTAD film as a hole transport layer, and an Au electrode as a counter electrode).
- the thicknesses of the FTO, TiO 2 , MAPbI 3 , spiro-MeOTAD and Au films are as shown in Fig. 9b showing cross-sectional SEM images of PSCs, 600 nm, 220 nm, 430 nm, 200 nm, and 100 nm, respectively. it was
- IE-PSC vs CO-PSC twelve of each type of PSC (i.e., IE-PSC vs CO-PSC) were fabricated and their power conversion efficiency was measured by plotting current density-voltage (JV) curves under simulated sunlight (AM 1.5G, 100 mWcm ⁇ 2 ). Recorded and inspected. 9C compares the JV curves of IE-PSC and CO-PSC.
- Jsc short circuit current density
- Voc open circuit voltage
- FF charge factor
- PCE power conversion efficiency
- Jsc of IE-PSC was slightly higher than that of CO-PSC. It is known that the photocurrent of PSC is mainly affected by the light absorption capacity and charge transportability of the perovskite layer. As described above, the absorbance of the IE-MAPbI 3 film and the CO-MAPbI 3 film is the same. Therefore, the higher Jsc of the IE-PSC film may be due to the improvement of the charge transportability of the IE-MAPbI 3 film.
- the IE-MAPbI 3 film has a higher crystallinity and a larger particle size than the CO-MAPbI 3 film.
- PSCs were prepared using MAI prepared by the ion exchange method of the present invention in order to examine industrial applicability (IE-PSC).
- the IE-PSC exhibited similar or slightly higher PCE compared to commercial MAI-based solar cells (CO-PSC). Traces of Cl ⁇ ions were incorporated into the MAI after recrystallization, which promoted the formation of larger crystals during the coating of the perovskite layer, thereby improving the PCE.
- the ion exchange method of the present invention for PSC precursor is expected to contribute substantially to the field of PSC as an industrial-scale technology.
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Abstract
The present invention relates to a preparation method for an organic halide for preparation of perovskite, perovskite prepared thereby, and a solar cell. According to the present invention, an organic halide for perovskite can be prepared by an ion-exchange method using alkali metal iodide or alkali metal bromide.
Description
본 발명은 페로브스카이트 제조용 유기 할라이드의 제조 방법, 이에 의해 제조된 페로브스카이트, 및 태양 전지에 관한 것이다. 구체적으로, 본 발명은 알칼리 금속 아이오다이드 또는 브로마이드를 사용하는 것을 특징으로 하는 상기 제조 방법, 이에 의해 제조된 페로브스카이트, 및 태양 전지에 관한 것이다.The present invention relates to a method for preparing an organic halide for preparing perovskite, the perovskite produced thereby, and a solar cell. Specifically, the present invention relates to the above production method, characterized in that an alkali metal iodide or bromide is used, a perovskite produced thereby, and a solar cell.
페로브스카이트 태양 전지는, 현재 전세계 태양 전지 시장의 93%를 차지하고 있는 결정질 실리콘 태양 전지에 대한 잠재적 대안으로서, 지난 수년에 걸쳐 매우 빠른 속도로 발전하였다. 유기 할라이드, 예컨대 메틸암모늄 할라이드 (MAX, X=I 또는 Br) 및 포름아미디늄 할라이드 (FAX)는 페로브스카이트 태양 전지에서 유기금속 트리할라이드의 광활성 층에 사용되는 중요한 물질이다. 페로브스카이트 태양 전지는 광흡수 효율이 높고 전하 운반자(charge carrier) 수명이 길며 전하 운반자의 확산 거리가 길다는 점에서 광·전기적 성질이 탁월하고 이러한 성질로 인해 최근 수년간 전력 변환 효율에 있어서 3.8%에서 25.2%까지 눈부신 개선이 이루어졌다. 통상적인 박막 태양 전지 (예를 들어, Cu(In,Ga)(S,Se) 및 CdTe에 기반한 것들)는 진공 하에서 스퍼터링 또는 증착에 의해 제조되는 데 반해, 페로브스카이트 광활성 층은 용액 상태의 유기 할라이드와 PbX
2 전구체를 사용한 간단한 스핀 코팅 방법에 의해 제조된다. 이러한 용액 공정의 특성 때문에 유기금속 트리할라이드 기반 페로브스카이트 태양전지는, 진공 기술에 의존하는 박막형 태양전지보다 더 높은 경제성과 경쟁력을 갖추고 있다.Perovskite solar cells have developed very rapidly over the past few years as a potential alternative to crystalline silicon solar cells, which currently account for 93% of the global solar cell market. Organic halides such as methylammonium halide (MAX, X=I or Br) and formamidinium halide (FAX) are important materials used for the photoactive layer of organometallic trihalides in perovskite solar cells. Perovskite solar cells have excellent photo-electric properties in terms of high light absorption efficiency, long charge carrier lifetime, and long diffusion distance of charge carriers. % to 25.2%, a dazzling improvement. Whereas conventional thin-film solar cells (e.g., those based on Cu(In,Ga)(S,Se) and CdTe) are fabricated by sputtering or deposition under vacuum, the perovskite photoactive layer is in solution. It is prepared by a simple spin coating method using an organic halide and a PbX 2 precursor. Due to the characteristics of the solution process, organometallic trihalide-based perovskite solar cells have higher economic efficiency and competitiveness than thin film solar cells that rely on vacuum technology.
유기 할라이드 중에서도 메틸암모늄 아이오다이드 (MAX, X=I)는 재현성도 높을 뿐만 아니라, 이를 이용하여 제조한 MAPbI
3 기반 페로브스카이트 태양전지는 광·전기적 성질이 탁월하고 ~21.2% 에 이르는 전력 변환 효율을 나타내므로, 메틸암모늄 아이오다이드는 중요한 전구체이다. 또한, MA 부분을 FA 로 대체하면 광흡수 파장이 더 긴 파장 영역까지 확장되어서 태양 스펙트럼의 흡수 범위가 더 넓어지므로 태양 전지의 전력 생산량이 향상된다. 그러나, MAX 및 FAX 의 합성 절차는 대부분, 유독하고 값비싼 할로겐화 수소 전구체의 사용과 관련되어 있다. 예를 들어, MAI 는 수성 메틸아민과 HI 사이의 산-염기 반응으로 합성되고, FAI도 마찬가지로, 포름아미디늄 아세테이트 (FAAc)과 HI 사이의 반응으로 제조된다. 유기 아이오다이드의 제조 방법은 수율과 재현성이 비교적 높기는 하지만, 합성시 HI를 사용하기 때문에 합성 동안에 반응 혼합물의 처리에 매우 주의해야 한다. HI는 할로겐화 수소 중에서도 가장 강한 산이고 (HI의 pKa = -9.3), 공기에 노출되었을 때 산소에 의해 쉽게 산화되어 I
2로 변하므로, 영국 전문가들이 설정한 2006년 대기 오염 기준에 따르면 HI 및 HBr의 경우 0.1 ppm 및 0.2 ppm 이하의 농도가 권장된다. 또한, 페로브스카이트 태양 전지는 생산 비용이 낮다는 장점을 가졌으나, MA 또는 FA와 HI의 반응에서 반응 수율을 높이기 위해 HI를 과도하게 사용하면 제조 비용이 높아지기 때문에, 페로브스카이트 태양 전지의 경제성은 저하되게 된다.Among organic halides, methylammonium iodide (MAX, X=I) not only has high reproducibility, but the MAPbI 3- based perovskite solar cell manufactured using it has excellent photo-electrical properties and an electric power of ~21.2%. Because of its conversion efficiency, methylammonium iodide is an important precursor. In addition, when the MA portion is replaced with FA, the light absorption wavelength is extended to a longer wavelength region, so that the absorption range of the solar spectrum is wider, so that the power production of the solar cell is improved. However, the synthetic procedures for MAX and FAX are mostly related to the use of toxic and expensive hydrogen halide precursors. For example, MAI is synthesized by an acid-base reaction between aqueous methylamine and HI, and FAI is likewise prepared by the reaction between formamidinium acetate (FAAc) and HI. Although the method for preparing organic iodide has relatively high yield and reproducibility, since HI is used in the synthesis, great care must be taken in the treatment of the reaction mixture during synthesis. HI is the strongest acid among hydrogen halides (pKa of HI = -9.3) and is easily oxidized to I 2 by oxygen when exposed to air, so according to the 2006 air pollution standards set by UK experts, HI and HBr Concentrations of 0.1 ppm and 0.2 ppm or less are recommended. In addition, the perovskite solar cell has the advantage of low production cost, but excessive use of HI to increase the reaction yield in the reaction of MA or FA with HI increases the manufacturing cost, so the perovskite solar cell economic efficiency will be lowered.
제조 공정의 관점에서는, 유독성 수성 혼합물로부터 생성물을 분리하기 위해 물 및 미반응 HI 또는 HBr을 감압 제거하는 공정에서 특별한 주의가 필요하다. 결론적으로, 유기 할라이드를 경제적이고 친환경적으로 합성하는 방법을 개발하는 것이 페로브스카이트 태양 전지의 산업적 생산에 중요하다. 페로브스카이트 태양 전지에 있어서 안정성과 전력 변환 효율을 향상시키기 위한 방안이 최근 수년간 광범위하게 연구되어 왔으나, 유기 할라이드 전구체 제조에 대한 이슈를 다루는 연구와 특허는 거의 보고된 바가 없다.From the point of view of the manufacturing process, special care is required in the process of depressurizing water and unreacted HI or HBr to separate the product from the toxic aqueous mixture. In conclusion, developing an economical and environmentally friendly method for synthesizing organic halides is important for the industrial production of perovskite solar cells. Methods for improving the stability and power conversion efficiency of perovskite solar cells have been extensively studied in recent years, but few studies and patents addressing the issues of organic halide precursor preparation have been reported.
본 발명의 일 목적은 유독성이 있는 종래의 HI 또는 HBr을 사용하지 않는, 페로브스카이트 제조용 유기 할라이드의 제조 방법을 제공하는 것이다.One object of the present invention is to provide a method for preparing an organic halide for preparing perovskite, which does not use toxic conventional HI or HBr.
본 발명의 다른 목적은 상기 제조 방법에 의해 제조될 수 있는 유기 할라이드를 전구체로서 포함하여 사용함으로써 제조되는 페로브스카이트를 제공하는 것이다.Another object of the present invention is to provide a perovskite prepared by using an organic halide that can be prepared by the above production method as a precursor.
본 발명의 또 다른 목적은 상기 페로브스카이트를 포함하는 태양 전지를 제공하는 것이다.Another object of the present invention is to provide a solar cell including the perovskite.
본 발명의 제1 양태에 따르면, 메틸암모늄 클로라이드 또는 포름아미디늄 클로라이드를 알칼리 금속 아이오다이드 또는 알칼리 금속 브로마이드와 반응시키는 단계 (a)를 포함하는, 페로브스카이트 제조용 유기 할라이드의 제조 방법이 제공된다.According to a first aspect of the present invention, there is provided a method for preparing an organic halide for preparing perovskite, comprising the step (a) of reacting methylammonium chloride or formamidinium chloride with an alkali metal iodide or alkali metal bromide is provided
본 발명의 제2 양태에 따르면, 상기 제조 방법에 의해 제조된 유기 할라이드를 전구체로서 포함하여 사용함으로써 제조되는 페로브스카이트가 제공된다.According to a second aspect of the present invention, there is provided a perovskite prepared by using the organic halide prepared by the above production method as a precursor.
본 발명의 제3 양태에 따르면, 제1 전극, 상기 제1 전극과 대향하는 제2 전극, 및 상기 제1 전극과 상기 제2 전극 사이에 적어도 부분적으로 배치되는 광활성 층으로서, 제1항의 방법에 의해 제조된 유기 할라이드를 전구체로서 포함하여 사용함으로써 수득된 페로브스카이트를 포함하는 광활성 층을 포함하는 태양 전지가 제공된다.According to a third aspect of the invention, there is provided a first electrode, a second electrode opposite the first electrode, and a photoactive layer disposed at least partially between the first electrode and the second electrode, comprising: There is provided a solar cell comprising a photoactive layer comprising a perovskite obtained by including and using an organic halide prepared by the present invention as a precursor.
본 발명에서는 할라이드 공급원으로 유독성이 있는 종래의 HI 또는 HBr을 사용하는 대신에 알칼리 금속 아이오다이드 또는 알칼리 금속 브로마이드를 사용함으로써, 손쉽고 친환경적인 방법으로 페로브스카이트 전구체를 제조할 수 있다. 종래 기술에 따라 HI 또는 HBr 과 같은 강산을 사용할 경우, 공기 중에 장시간 보관시 산소와 반응하여 산화되기 때문에 특수 보관 조건이 필요하여 대량 생산에 적합하지 않으며 마약 제조에도 이용될 수 있어 미국 United States Drug Enforcement Administration (DEA)의 List I 화합물로 감시 대상이 된다. 그 뿐만 아니라 산-염기 반응의 강한 발열 특성으로 인하여 추가의 냉각 시스템이 필요하다. 이에 비해, 본 발명에 따르면, 이러한 강산을 사용하지 않기 때문에 제조 설비를 단순화할 수 있으며, 원료 비용이 싸고 폐기물 처리도 쉽게 할 수 있어, 더 안전하고 더 간단한 대량 생산을 디자인할 수 있게 하여준다. 아울러, 본 발명에 따른 제조 방법은 생산 수율도 높다. 따라서, 본 발명의 제조 방법은 종래 기술의 방법에 비하여 월등히 높은 경제성을 가진다.In the present invention, by using alkali metal iodide or alkali metal bromide instead of using conventional toxic HI or HBr as a halide source, a perovskite precursor can be prepared in an easy and environmentally friendly way. According to the prior art, when strong acids such as HI or HBr are used, they are oxidized by reacting with oxygen when stored for a long time in air, so special storage conditions are required, so they are not suitable for mass production and can be used in drug manufacture. It is a List I compound from the Administration (DEA) and subject to monitoring. In addition, an additional cooling system is required due to the strong exothermic nature of the acid-base reaction. On the other hand, according to the present invention, since such a strong acid is not used, manufacturing equipment can be simplified, raw material cost is low, and waste disposal can be easily carried out, thereby enabling a safer and simpler mass production design. In addition, the manufacturing method according to the present invention has a high production yield. Therefore, the manufacturing method of the present invention has significantly higher economic efficiency than the prior art method.
도 1a 는 종래 기술에 따른 페로브스카이트용 유기 할라이드의 제조 방법을 도식화한 것이고, 도 1b 는 본 발명의 일 실시예에 따른 제조 방법을 도식화한 것이다.Figure 1a is a schematic diagram of a method for producing an organic halide for perovskite according to the prior art, Figure 1b is a schematic diagram of a production method according to an embodiment of the present invention.
도 2 는 본 발명의 일 실험예에 따라 에탄올(EtOH) 또는 물을 용매로 하여 환류 조건 하에 제조된 4가지 유기 할라이드의 수율을 나타낸 것이다.2 shows the yields of four organic halides prepared under reflux conditions using ethanol (EtOH) or water as a solvent according to an experimental example of the present invention.
도 3 은 본 발명의 일 실험예에 따라 에탄올(EtOH) 또는 물을 용매로 하여 실온에서 제조된 4가지 유기 할라이드의 수율을 나타낸 것이다.3 shows the yields of four organic halides prepared at room temperature using ethanol (EtOH) or water as a solvent according to an experimental example of the present invention.
도 4 는 본 발명의 일 실험예에 따라 제조된 시료들의 수소 핵자기공명 (
1H NMR) 스펙트럼을 나타낸 것이다. 4 shows hydrogen nuclear magnetic resonance (1 H NMR) spectra of samples prepared according to an experimental example of the present invention.
도 5 는 본 발명의 일 실험예에 따라 제조된 시료들의 X선 회절 패턴을 나타낸 것이다.5 shows X-ray diffraction patterns of samples prepared according to an experimental example of the present invention.
도 6 은 본 발명의 일 실험예에 따라 제조된 시료들의 X선 형광분석 (XRF) 원소분석결과를 보여주는 표이며, a 괄호 안의 숫자는 제조된 시료들의 재결정 후의 분석 결과이다.6 is a table showing X-ray fluorescence analysis (XRF) elemental analysis results of samples prepared according to an experimental example of the present invention, and a number in parentheses is an analysis result after recrystallization of the prepared samples.
도 7a 는 본 발명의 일 실험예에 따라 제조된 유기 할라이드 또는 시판되는 유기 할라이드를 사용하여 제조된 페로브스카이트 막의 UV-Vis 흡수 스펙트럼을 나타내고, 도 7b 는 본 발명의 일 실험예에 따라 제조된 유기 할라이드 또는 시판되는 유기 할라이드를 사용하여 제조된 페로브스카이트 막의 XRD 패턴을 나타낸다. 또한, 도 7c 및 7d 는 각각, 본 발명의 일 실험예에 따라 제조된 유기 할라이드 또는 시판되는 유기 할라이드를 사용하여 제조된 페로브스카이트 막의 SEM 이미지의 상면도이다.7a shows the UV-Vis absorption spectrum of a perovskite film prepared using an organic halide prepared according to an experimental example of the present invention or a commercially available organic halide, and FIG. 7b is prepared according to an experimental example of the present invention. The XRD pattern of the perovskite film prepared using the organic halide or commercially available organic halide is shown. 7c and 7d are top views of SEM images of perovskite films prepared using organic halides prepared according to an experimental example of the present invention or commercially available organic halides, respectively.
도 8a 내지 도 8c 는 본 발명의 일 실험예에 따라 제조된 유기 할라이드 또는 시판되는 유기 할라이드를 사용하여 제조된 페로브스카이트 막의 상기 도 7b의 XRD 패턴을 확대한 것이다.8A to 8C are enlarged views of the XRD pattern of FIG. 7B of an organic halide prepared according to an experimental example of the present invention or a perovskite film prepared using a commercially available organic halide.
도 9a 는 본 발명의 일 실험예에서 제조한 메조포러스형 페로브스카이트 태양 전지(PSC)의 구조를 도시하며, 도 9b 는 상기 태양 전지의 횡단면 SEM 이미지를 도시한다. 또한, 도 9c 내지 도 9g 는 본 발명의 일 실험예에 따라 제조한 유기 할라이드를 사용하여 제작한 PSC 및 시판되는 유기 할라이드를 사용하여 제작한 PSC의 전류 밀도-전압 곡선 (J-V 곡선)(도 9c), 단락 회로 전류 밀도 (Jsc) (도 9d), 개방 회로 전압 (Voc) (도 9e), 충전 인자 (FF) (도 9f), 및 전력 변환 효율 (PCE) (도 9g)을 나타낸다.9A shows the structure of a mesoporous perovskite solar cell (PSC) prepared in an experimental example of the present invention, and FIG. 9B shows a cross-sectional SEM image of the solar cell. 9c to 9g are current density-voltage curves (JV curves) of PSCs prepared using organic halides prepared according to an experimental example of the present invention and PSCs prepared using commercially available organic halides (Fig. 9c) ), short circuit current density (Jsc) (FIG. 9D), open circuit voltage (Voc) (FIG. 9E), charge factor (FF) (FIG. 9F), and power conversion efficiency (PCE) (FIG. 9G).
이하, 본 출원에서 사용한 용어는 단지 특정한 구현예를 설명하기 위해 사용된 것으로서 본 발명을 한정하려는 의도가 아니다. 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.Hereinafter, the terms used in the present application are used only to describe specific embodiments and are not intended to limit the present invention. Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. Throughout this specification, when a part "includes" a component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.
본원 명세서 전체에서 "페로브스카이트"는 양이온(R 및 M)과 음이온(X)이 RMX
3 의 화학식으로 구성되며, 최초의 페로브스카이트형 물질인 CaTiO
3와 같은 결정 구조를 가지는 유기무기 할라이드 물질을 의미한다.Throughout this specification, "perovskite" refers to an organic-inorganic halide in which cations (R and M) and anions (X) are composed of the chemical formula of RMX 3 , and have the same crystal structure as CaTiO 3 , the first perovskite-type material. means material.
본원 명세서 전체에서, "페로브스카이트 태양 전지"는 페로브스카이트 결정 구조를 갖는 유기무기 할라이드 물질을 포함하는 태양 전지를 의미한다.Throughout this specification, "perovskite solar cell" refers to a solar cell comprising an organic-inorganic halide material having a perovskite crystal structure.
페로브스카이트 제조용 유기 할라이드의 제조 방법Method for the preparation of organic halides for the production of perovskite
본 발명의 제1 양태에 따르면, 본 발명의 페로브스카이트 제조용 유기 할라이드의 제조 방법은 메틸암모늄 클로라이드(methylammonium chloride) 또는 포름아미디늄 클로라이드(formamidinium chloride)를 알칼리 금속 아이오다이드 또는 알칼리 금속 브로마이드와 반응시키는 단계 (a)를 포함한다.According to a first aspect of the present invention, in the method for preparing an organic halide for preparing perovskite of the present invention, methylammonium chloride or formamidinium chloride is used as an alkali metal iodide or alkali metal bromide. and reacting with (a).
본 발명의 상기 알칼리 금속 아이오다이드 또는 알칼리 금속 브로마이드에서, 상기 알칼리 금속은 상기 메틸암모늄 클로라이드 또는 포름아미디늄 클로라이드와 반응한다면 특별히 제한되지 않으며, 구체적으로 리튬, 나트륨, 칼륨 등일 수 있다. 본 발명의 일 구현예에 따르면, 상기 알칼리 금속 아이오다이드 또는 알칼리 금속 브로마이드는 나트륨 아이오다이드 (NaI) 또는 나트륨 브로마이드 (NaBr)일 수 있다. 상기 NaI 및 NaBr 은 물 및 알콜과 같은 용매 중에서 용해도가 높다는 점에서 유용할 수 있다. In the alkali metal iodide or alkali metal bromide of the present invention, the alkali metal is not particularly limited as long as it reacts with the methylammonium chloride or formamidinium chloride, and specifically lithium, sodium, potassium, and the like. According to one embodiment of the present invention, the alkali metal iodide or alkali metal bromide may be sodium iodide (NaI) or sodium bromide (NaBr). The NaI and NaBr may be useful in that they have high solubility in solvents such as water and alcohol.
본 발명의 상기 제조 방법에서 유기 할라이드는 메틸암모늄 아이오다이드 (MAI), 메틸암모늄 브로마이드 (MABr), 포름아미디늄 아이오다이드 (FAI), 또는 포름아미디늄 브로마이드 (FABr)일 수 있다.The organic halide in the preparation method of the present invention may be methylammonium iodide (MAI), methylammonium bromide (MABr), formamidinium iodide (FAI), or formamidinium bromide (FABr).
본 발명의 일 구현예에 따르면, 상기 반응 단계 (a)는 용매 중에서 이온 교환 반응에 의해 수행되는 것일 수 있다. 상기 용매는 물 또는 알콜일 수 있으며, 여기서 상기 알콜은 탄소수 1 내지 5개의 1가 또는 2가 알콜일 수 있으며, 구체적으로는 탄소수 1 내지 5개의 1가 알콜일 수 있고, 더 구체적으로는 에탄올일 수 있다.According to one embodiment of the present invention, the reaction step (a) may be performed by an ion exchange reaction in a solvent. The solvent may be water or an alcohol, wherein the alcohol may be a monohydric or dihydric alcohol having 1 to 5 carbon atoms, specifically, a monohydric alcohol having 1 to 5 carbon atoms, more specifically ethanolyl can
또한, 본 발명의 일 구현예에 따르면, 상기 반응 단계 (a)는 용매 중에서 실온 또는 환류 하에 수행될 수 있다. 상기 환류에 적합한 온도는 사용 용매 등에 따라 적절히 결정될 수 있으며, 물을 용매로 사용할 경우 예를 들어 100℃, 에탄올을 용매로 사용할 경우 예를 들어 78℃ 일 수 있다. 상기 반응 시간은 반응 속도 및 목적하는 수득율 등에 따라 결정될 수 있으며, 예를 들어 교반 하에 1분에서 24시간까지 수행될 수 있다. 그러나, 이에 제한되는 것이 아니라 24시간 이상의 시간으로도 수행될 수 있다.In addition, according to one embodiment of the present invention, the reaction step (a) may be carried out in a solvent at room temperature or under reflux. A suitable temperature for the reflux may be appropriately determined depending on the solvent used, for example, 100° C. when water is used as a solvent, and 78° C. when ethanol is used as a solvent. The reaction time may be determined according to the reaction rate and desired yield, and for example, may be carried out from 1 minute to 24 hours under stirring. However, the present invention is not limited thereto and may be performed for 24 hours or more.
또한, 본 발명의 다른 일 구현예에 따르면, 상기 반응 단계 (a) 이후에, 상기 반응 단계 (a)의 생성물을 여과하는 단계 (b), 및 용매를 제거하는 단계 (c)를 추가로 포함할 수 있다. 상기 여과 단계 (b)에 의해 반응 부산물인 NaCl이 제거될 수 있다. 또한, 상기 용매 제거 단계 (c)에 있어서, 용매가 물일 경우, 물을 단계 (c)에서 먼저 제거한 후, 알콜에 생성물을 용해시키고 여과 단계 (b)를 수행할 수 있다. 한편, 용매가 알콜일 경우, 여과 단계 (b)를 먼저 수행한 후, 단계 (c)를 수행할 수 있고, 또한, 여기서 상기 단계 (c)는 알콜을 증발시킴으로써 수행될 수 있다.In addition, according to another embodiment of the present invention, after the reaction step (a), the step (b) of filtering the product of the reaction step (a), and the step (c) of removing the solvent further comprising can do. NaCl, a reaction by-product, may be removed by the filtration step (b). In addition, in the solvent removal step (c), when the solvent is water, the water is first removed in step (c), then the product may be dissolved in alcohol and the filtration step (b) may be performed. On the other hand, when the solvent is an alcohol, the filtration step (b) may be performed first, and then the step (c) may be performed, and wherein the step (c) may be performed by evaporating the alcohol.
본 발명의 또다른 일 구현예에 따르면, 상기 반응 단계 (a)에서 생성된 유기 할라이드로부터 알칼리 금속 클로라이드를 재결정하여 제거하는 단계 (d)를 추가로 더 포함할 수 있다. 상기 단계 (a)에서 생성된 유기 할라이드에는 이온교환법의 수행에 따라 필연적으로 이온성 염 불순물 (예를 들어, 알칼리 금속 클로라이드, 알칼리 금속 아이오다이드, 메틸암모늄 클로라이드, 또는 포름아미디늄 클로라이드)이 있을 수 있다. 따라서, 상기 단계 (a)를 수행하고, 필요에 따라 상기 단계 (b) 및/또는 (c)를 더 수행한 후, 재결정함으로써 이온성 염 불순물, 구체적으로 알칼리 금속 클로라이드 등을 추가로 더 제거할 수 있다.According to another embodiment of the present invention, the step (d) of removing the alkali metal chloride by recrystallization from the organic halide produced in the reaction step (a) may be further included. The organic halide produced in step (a) inevitably contains ionic salt impurities (eg, alkali metal chloride, alkali metal iodide, methylammonium chloride, or formamidinium chloride) according to the ion exchange method. there may be Therefore, after performing step (a), if necessary, further performing steps (b) and/or (c), and then recrystallizing to further remove ionic salt impurities, specifically alkali metal chloride, etc. can
본 발명의 유기 할라이드로부터 제조되는 페로브스카이트Perovskite prepared from organic halide of the present invention
본 발명의 제2 양태에 따르면, 전술한 바와 같은 유기 할라이드의 제조 방법에 의해 제조된 유기 할라이드를 전구체로서 포함하여 사용함으로써 제조되는 페로브스카이트가 제공된다.According to a second aspect of the present invention, there is provided a perovskite prepared by using the organic halide prepared by the method for producing an organic halide as described above as a precursor.
상기 페로브스카이트는 RMX
3 구조를 가지는 것으로서, 본 발명에 따르면, 상기 R은 메틸암모늄 양이온 또는 포름아미디늄 양이온일 수 있고, X는 아이오다이드 음이온 또는 브로마이드 음이온일 수 있고, M은 Pb
2+, Sn
2+, Ge
2+ 및 이들의 조합으로 이루어진 군에서 선택되는 2가의 금속 양이온일 수 있다.The perovskite has a RMX 3 structure, and according to the present invention, R may be a methylammonium cation or a formamidinium cation, X may be an iodide anion or a bromide anion, M is Pb 2 It may be a divalent metal cation selected from the group consisting of + , Sn 2+ , Ge 2+ , and combinations thereof.
태양 전지solar cell
본 발명의 제3 양태에 따르면, 제1 전극, 상기 제1 전극과 대향하는 제2 전극, 및 상기 제1 전극과 상기 제2 전극 사이에 적어도 부분적으로 배치되는 광활성 층으로서, 전술한 바와 같은 유기 할라이드의 방법에 의해 제조된 유기 할라이드를 전구체로서 포함하여 사용함으로써 수득된 페로브스카이트를 포함하는 광활성 층을 포함하는 태양 전지가 제공된다.According to a third aspect of the present invention, there is provided a photoactive layer disposed at least partially between a first electrode, a second electrode opposite the first electrode, and between the first electrode and the second electrode, comprising an organic as described above. A solar cell comprising a photoactive layer comprising a perovskite obtained by including and using an organic halide prepared by the method of halide as a precursor is provided.
본 발명의 일 구현예에 따르면, 상기 페로브스카이트는 전술한 바와 같은 유기 할라이드를 화학식 MX
2 의 화합물과 반응시켜 수득되는 것일 수 있다. 여기서, X는 아이오다이드 음이온 또는 브로마이드 음이온일 수 있고, M은 Pb
2+, Sn
2+, Ge
2+ 및 이들의 조합으로 이루어진 군에서 선택되는 2가의 금속 양이온일 수 있다. 상기 페로브스카이트를 포함하는 광활성 층은 용액 상태의 상기 유기 할라이드와 화학식 MX
2의 화합물을 사용하여 예를 들어, 스핀 코팅함으로써 간단히 제조될 수 있다.According to one embodiment of the present invention, the perovskite may be obtained by reacting an organic halide as described above with a compound of Formula MX 2 . Here, X may be an iodide anion or a bromide anion, and M may be a divalent metal cation selected from the group consisting of Pb 2+ , Sn 2+ , Ge 2+ and combinations thereof. The photoactive layer comprising the perovskite can be prepared simply by, for example, spin coating using the organic halide in solution and the compound of Formula MX 2 .
본 발명의 일 구현예에 따르면, 상기 제1 전극은 애노드 및 캐소드 중 하나일 수 있고, 상기 제2 전극은 애노드 및 캐소드 중의 다른 하나일 수 있다. 본 발명의 다른 일 구현예에 따르면, 상기 제1 전극 및 제2 전극 중 어느 하나 또는 둘 모두가 기판 상에 코팅될 수 있다. 본 발명의 또다른 일 구현예에 따르면, 상기 태양 전지는 상기 제1 전극과 제2 전극 사이에 전자 전달 층 및 정공 전달 층을 추가로 더 포함할 수 있다. 또한, 상기 태양 전지는 상기 광활성 층이 페로브스카이트 물질 이외의 다른 광활성 물질, 예를 들어 반도체 물질을 더 포함할 수 있다. 또한, 상기 광활성 층은 페로브스카이트 층 이외에, 추가의 다른 광활성 물질을 포함하는 층, 예를 들어, 반도체 층을 더 포함할 수 있다.According to one embodiment of the present invention, the first electrode may be one of an anode and a cathode, and the second electrode may be the other one of an anode and a cathode. According to another embodiment of the present invention, any one or both of the first electrode and the second electrode may be coated on the substrate. According to another embodiment of the present invention, the solar cell may further include an electron transport layer and a hole transport layer between the first electrode and the second electrode. In addition, in the solar cell, the photoactive layer may further include a photoactive material other than the perovskite material, for example, a semiconductor material. In addition, the photoactive layer may further include, in addition to the perovskite layer, a layer comprising another photoactive material, for example, a semiconductor layer.
이하, 실시예를 참조하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예][Example]
사용한 재료material used
하기의 재료를 추가 정제 없이 구입한 그대로 사용하였다: NaI (99.5%, Wako 제품), NaBr (99.5%, Junsei 제품), 메틸암모늄 클로라이드 (MACl, 98.0%, Junsei 제품), FAAc (98%, TCI 제품), 에탄올 (EtOH, 99.5%, 삼전화학 제품), 디에틸 에테르 (Et
2O, ≥99.7%, Sigma-Aldrich 제품), 메틸아민 용액 (수 중 40 wt%, TCI 제품), 요오드화 수소산 (HI, 수 중 57 wt%, Sigma-Aldrich 제품), 브롬화 수소산 (HBr, 수 중 48 wt%, Sigma-Aldrich 제품), 티타늄 디이소프로폭시드 비스(아세틸아세토네이트) (이소프로판올 중 75 wt%, Sigma-Aldrich 제품), 1-부탄올 (99%, Sigma-Aldrich 제품), 테르피네올 (무수, Sigma-Aldrich 제품), PbI
2 (99.9%, TCI 제품), N,N-디메틸포름아미드 (DMF, 99.8%, Sigma-Aldrich 제품), 디메틸 술폭시드 (DMSO, ≥99.9%, Sigma-Aldrich 제품), 아세토니트릴 (무수, 99.8%, Sigma-Aldrich 제품), 2,2',7,7'-테트라키스(N,N-디-p-메톡시페닐아민)-9,9'-스피로비플루오렌 (스피로-MeOTAD, >99.5%, Luminescence Technology Corp. 제품), 비스(트리플루오로메탄)술폰아미드 리튬 염 (Li-TFSI, 99%, Alfa Aesar 제품), 트리스(2-(1H-피라졸-1-일)-4-tert-부틸피리딘) 코발트(III) 트리[비스(트리플루오로메탄)술폰아미드] (Co-TFSI, FK209, Greatcell Solar 제품), 및 4-tert-부틸피리딘 (96%, Sigma-Aldrich 제품). 포름아미디늄 클로라이드 (FACl)은 통상의 방법, 즉, FAAc 및 HCl 용액의 반응으로 제조하였다 (하기 참조: [I. Levchuk, A. Osvet, X. Tang, M. Brandl, J.D. Perea, F. Hoegl, G.J.Matt, R. Hock, M. Batentschuk and C.J.Brabec,
Nano Lett. 2017,
17, 2765-2770])The following materials were used as received without further purification: NaI (99.5%, from Wako), NaBr (99.5%, from Junsei), methylammonium chloride (MACl, 98.0%, from Junsei), FAAc (98%, TCI) product), ethanol (EtOH, 99.5%, manufactured by Samchun Chemical), diethyl ether (Et 2 O, ≥99.7%, manufactured by Sigma-Aldrich), methylamine solution (40 wt% in water, manufactured by TCI), hydroiodic acid ( HI, 57 wt% in water, from Sigma-Aldrich), hydrobromic acid (HBr, 48 wt% in water, from Sigma-Aldrich), titanium diisopropoxide bis(acetylacetonate) (75 wt% in isopropanol, Sigma-Aldrich), 1-butanol (99%, from Sigma-Aldrich), terpineol (anhydrous, from Sigma-Aldrich), PbI 2 (99.9%, from TCI), N,N-dimethylformamide (DMF) , 99.8%, from Sigma-Aldrich), dimethyl sulfoxide (DMSO, ≥99.9%, from Sigma-Aldrich), acetonitrile (anhydrous, 99.8%, from Sigma-Aldrich), 2,2',7,7'- Tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-MeOTAD, >99.5%, from Luminescence Technology Corp.), bis(trifluoromethane)sulfone Amide lithium salt (Li-TFSI, 99%, from Alfa Aesar), tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine) cobalt(III) tri[bis(trifluoromethane) )sulfonamide] (Co-TFSI, FK209, from Greatcell Solar), and 4-tert-butylpyridine (96%, from Sigma-Aldrich). Formamidinium chloride (FACl) was prepared in a conventional manner, namely by reaction of FAAc and HCl solution (see I. Levchuk, A. Osvet, X. Tang, M. Brandl, JD Perea, F. Hoegl, GJ Matt, R. Hock, M. Batentschuk and CJ Brabec, Nano Lett. 2017, 17 , 2765-2770])
1. 실험예1. Experimental example
1-(1). MAX 및 FAX (X = Br 및 I) 유기 할라이드의 합성1-(1). Synthesis of MAX and FAX (X = Br and I) organic halides
1-(1)-①. MAI 의 합성1-(1)-①. Synthesis of MAI
NaX (X = Br 또는 I)를 물 (또는 EtOH) 중에서 MACl 또는 FACl과 함께 적합한 온도에서 반응시켜, MAX 및 FAX의 유기 할라이드를 합성하였다. 이온 교환 반응을 통한 MAI의 합성을 위해, 20 mmol (3.0 g)의 NaI 및 20 mmol (1.35 g)의 MACl을 100 mL의 탈이온수 중에 각각 따로 용해시킨 후, 실온에서 500 mL 둥근 바닥 플라스크에 함께 넣었다. 환류 하에 (또는 실온에서) 혼합수용액을 100℃ 이상의 환류 조건 (EtOH의 경우 약 78℃)에서 격렬히 교반하며 3 시간 동안 반응을 수행하였다. 반응 완료 후, 반응 혼합물로부터 물을 진공 하에 제거하였다. 황색빛의 흰색 분말이 생성되었고, 이를 EtOH (또는 이소프로판올)에 분산시킨 후, 여과하여 NaCl을 제거하였다 (이소프로판올을 사용할 경우, EtOH 보다 많이 필요하지만 불순물인 NaCl의 양은 많이 감소하였다). EtOH (또는 이소프로판올)은 진공 하에 증발시켰다. 얻어진 생성물은 Et
2O로 수차례 세척하고, 잔류 용매를 증발시켜 고순도의 MAI를 수득하였다. 용매로서 물 대신에 EtOH을 사용한 경우, MAI 여과 및 후속하는 EtOH 증발과 Et
2O로의 세척 이후에 MAI가 곧바로 수득되었다. EtOH을 용매로 사용하여 반응을 진행할 경우, 환류 조건에서 상온으로 냉각한 후, NaCl을 여과하고 용매를 제거하여 MAI를 수득하였다.Organic halides of MAX and FAX were synthesized by reacting NaX (X = Br or I) with MACl or FACl in water (or EtOH) at a suitable temperature. For the synthesis of MAI via ion exchange reaction, 20 mmol (3.0 g) of NaI and 20 mmol (1.35 g) of MACl were each separately dissolved in 100 mL of deionized water and then together in a 500 mL round bottom flask at room temperature. put The reaction was carried out for 3 hours under reflux (or at room temperature) while vigorously stirring the mixed aqueous solution under reflux conditions of 100° C. or higher (about 78° C. for EtOH). After completion of the reaction, water was removed from the reaction mixture under vacuum. A yellowish white powder was produced, which was dispersed in EtOH (or isopropanol) and filtered to remove NaCl (when isopropanol is used, more than EtOH is required, but the amount of NaCl as an impurity is greatly reduced). EtOH (or isopropanol) was evaporated under vacuum. The obtained product was washed several times with Et 2 O, and the residual solvent was evaporated to obtain MAI of high purity. When EtOH was used instead of water as solvent, MAI was obtained immediately after MAI filtration and subsequent EtOH evaporation and washing with Et 2 O. When the reaction was carried out using EtOH as a solvent, after cooling to room temperature under reflux conditions, NaCl was filtered and the solvent was removed to obtain MAI.
1-(1)-②. MABr, FABr, 및 FAI 의 합성1-(1)-②. Synthesis of MABr, FABr, and FAI
상기 MAI에 사용된 합성 조건과 동일한 조건을 유지하되, 상이한 전구체를 사용하여 다른 유기 할라이드를 제조하였다: MACl 및 NaBr을 사용하여 MABr을 제조하였고; FACl 및 NaBr을 사용하여 FABr을 제조하였고; FACl 및 NaI를 사용하여 FAI를 제조하였다.Other organic halides were prepared using different precursors, maintaining the same synthetic conditions used for MAI above: MACl and NaBr were used to prepare MABr; FACl and NaBr were used to prepare FABr; FAI was prepared using FACl and NaI.
1-(1)-③. MAI 의 합성1-(1)-③. Synthesis of MAI
MACl 7.36 g 및 NaI 16.34 g을 100 mL의 EtOH 에 용해시킨 것을 제외하고는, 상기 1-(1)-①의 MAI에 사용된 합성 조건과 동일한 조건을 유지하여 MAI를 합성하였다.Except that 7.36 g of MACl and 16.34 g of NaI were dissolved in 100 mL of EtOH, MAI was synthesized under the same conditions as those used for the MAI of 1-(1)-①.
1-(1)-④. FAI 의 합성1-(1)-④. Synthesis of FAI
FACl 14.92 g 및 NaI 27.79 g을 100 mL의 EtOH 에 용해시킨 것을 제외하고는, 상기 1-(1)-①의 MAI에 사용된 합성 조건과 동일한 조건을 유지하여 FAI를 합성하였다.Except that 14.92 g of FACl and 27.79 g of NaI were dissolved in 100 mL of EtOH, FAI was synthesized by maintaining the same conditions as those used for MAI in 1-(1)-①.
1-(2). 페로브스카이트 태양 전지 (PSC)의 제조1-(2). Fabrication of perovskite solar cells (PSCs)
장치 성능의 비교를 위해, 본 발명의 전술한 1-(1)-①에 따라 이온 교환 방법에 의해 제조된 MAI (장치의 특성 분석 부분에서는 IE-MAI로 약칭했음)와 MAI 시판품 (≥99.5%, Xi'an Polymer Light Technology Corp. 제품)(장치의 특성 분석 부분에서는 CO-MAI로 약칭했음)을 태양 전지 제조에 사용하였다. 태양 전지 제조에 사용된 IE-MAI 및 CO-MAI 모두, Et
2O 및 EtOH 의 혼합 용매로부터 재결정하여 얻었다.For comparison of device performance, MAI (abbreviated as IE-MAI in the device characterization part) and commercially available MAI (≥99.5%) prepared by the ion exchange method according to the above-mentioned 1-(1)-① of the present invention , a product of Xi'an Polymer Light Technology Corp.) (abbreviated as CO-MAI in the device characterization part) was used to manufacture solar cells. Both IE-MAI and CO-MAI used for solar cell production were obtained by recrystallization from a mixed solvent of Et 2 O and EtOH.
모든 장치는 통상의 방법에 따라 제조되었다. 2 X 2 cm
2 (Pilkington TEC8)의 불소-도핑된 산화주석 (FTO) 기판을, 아세톤, 탈이온수 및 이소프로필 알콜을 순차적으로 사용하여 15분 동안 초음파 욕조에서 세정하였다. 세정된 기판을 N
2 가스 스트림 하에 건조하였다. 먼저, 0.15 M 티타늄 디이소프로폭시드 비스(아세틸아세토네이트)가 녹아있는 1-부탄올 용액을 20초 동안 3000 rpm에서 스핀 코팅하여 TiO
2 치밀 층 (c-TiO
2)을 제조하였다. 상기 c-TiO
2/FTO를 5분 동안 125℃에서 구운 후, 30분 동안 70℃에서 0.05 M TiCl
4 용액 중에 침지시키고, 탈이온수 및 이소프로필 알콜로 헹구었다. 그 후, TiO
2 나노입자 (~50 nm 평균 직경)으로 구성된 희석된 TiO
2 페이스트 (SC-HT040, SCHARECHEM Co. 제품)를 스핀 코팅하여, 메조포러스(mesoporous) TiO
2 (mp-TiO
2) 층을 형성시켰다. 상기 TiO
2 페이스트는, 혼합 용매 (3.5:1 비의 1-프로판올 대 테르피네올) 중에, 1:3.5 비의 페이스트 대 용매 비로 희석하였다. 그 후, mp-TiO
2 층을 5분 동안 125℃에서 굽고, 30분 동안 500℃에서 어닐링하였다.All devices were prepared according to conventional methods. Fluorine-doped tin oxide (FTO) substrates of 2 X 2 cm 2 (Pilkington TEC8) were cleaned in an ultrasonic bath for 15 minutes using sequentially acetone, deionized water and isopropyl alcohol. The cleaned substrate was dried under a N 2 gas stream. First, a 1-butanol solution in which 0.15 M titanium diisopropoxide bis(acetylacetonate) was dissolved was spin-coated at 3000 rpm for 20 seconds to prepare a TiO 2 dense layer (c-TiO 2 ). The c-TiO 2 /FTO was baked at 125° C. for 5 minutes, then immersed in a 0.05 M TiCl 4 solution at 70° C. for 30 minutes, and rinsed with deionized water and isopropyl alcohol. Thereafter, a diluted TiO 2 paste (SC-HT040, manufactured by SCHARECHEM Co.) composed of TiO 2 nanoparticles (~50 nm average diameter) was spin-coated to form a mesoporous TiO 2 (mp-TiO 2 ) layer. was formed. The TiO 2 paste was diluted in a mixed solvent (1-propanol to terpineol in a 3.5:1 ratio) to a paste to solvent ratio of 1:3.5 ratio. The mp-TiO 2 layer was then baked at 125° C. for 5 minutes and annealed at 500° C. for 30 minutes.
MAPbI
3 막은 통상의 용매 엔지니어링(solvent engineering) 방법을 통해 제조하였다. 전구체 용액을 20초 동안 4000 rpm에서 스핀 코팅함으로써, 상기 제조한 mp-TiO
2/c-TiO
2/FTO/유리 기판에 MAPbI
3 막을 코팅하였다. 상기 전구체 용액은 52 wt%의 전구체, 즉, PbI
2 및 목적하는 MAI (IE-MAI 또는 CO-MAI)를, 부피비 7.33:1 로 하여 무수 DMF 및 DMSO의 혼합 용매 중에 용해시킴으로써 제조한 것이었다. 그 후, 0.5 mL의 Et
2O를 스핀 코팅 동안에 상기 기판에 주입하였다. 다음으로, 상기 기판을 순차적으로 65℃ (1 분) 및 130℃ (10 분)에서 어닐링하였다. 상기 페로브스카이트 층 위에 정공 전달 층을 30초 동안 3000 rpm에서 스핀 코팅하였다. 상기 정공 전달 재료 전구체 용액은, 18 μL의 Li-TFSI 용액 및 14.7 mg의 Co-TFSI를 1 mL의 스피로-MeOTAD 용액에 순차적으로 첨가함으로써 제조된 것이었다. 상기 Li-TFSI 용액은, 1 mL의 아세토니트릴 중에 566 mg의 Li-TSFI를 용해시킴으로써 제조한 것이었다. 상기 스피로-MeOTAD 용액은, 80 mg의 스피로-MeOTAD 및 32 μL의 4-tert-부틸피리딘을 1 mL 의 클로로벤젠에 순차적으로 용해시킴으로써 제조된 것이었다. 마지막으로, 상기 정공 전달 층 위에 열 증착법에 따라 1 Ås
-1 의 증착 속도로 Au 전극을 증착하였다.The MAPbI 3 membrane was prepared through a conventional solvent engineering method. A MAPbI 3 film was coated on the prepared mp-TiO 2 /c-TiO 2 /FTO/glass substrate by spin coating the precursor solution at 4000 rpm for 20 seconds. The precursor solution was prepared by dissolving 52 wt% of the precursor, ie, PbI 2 and the desired MAI (IE-MAI or CO-MAI), in a mixed solvent of anhydrous DMF and DMSO at a volume ratio of 7.33:1. Then, 0.5 mL of Et 2 O was injected into the substrate during spin coating. Next, the substrates were sequentially annealed at 65° C. (1 min) and 130° C. (10 min). A hole transport layer was spin coated on the perovskite layer at 3000 rpm for 30 seconds. The hole transport material precursor solution was prepared by sequentially adding 18 μL of Li-TFSI solution and 14.7 mg of Co-TFSI to 1 mL of spiro-MeOTAD solution. The Li-TFSI solution was prepared by dissolving 566 mg of Li-TSFI in 1 mL of acetonitrile. The spiro-MeOTAD solution was prepared by sequentially dissolving 80 mg of spiro-MeOTAD and 32 μL of 4-tert-butylpyridine in 1 mL of chlorobenzene. Finally, an Au electrode was deposited on the hole transport layer at a deposition rate of 1 Ås −1 according to a thermal evaporation method.
2. 특성 분석2. Characterization
1H 핵 자기 공명(NMR) 스펙트럼은 Bruker AVANCE III 500 분광계를 사용하여 얻었다. X선 회절 (XRD) 패턴은, Cu Kα 방사선원 (λ=1.5405 Å)이 장착된 PANalytical X'Pert PRO MPD에서 기록된 것이고, 스텝 사이즈는 0.016
o 이었다. 파장 분산 X선 형광 (WD-XRF) 분광계 (Bruker S8 Tiger)를 사용하여 원소 분석을 수행하였다. 페로브스카이트 태양 전지의 성능을 알아보기 위하여, 소스 미터 (Keithley 2450)가 있는 태양광 시뮬레이터 (Newport Oriel Solar 3A Class, 94023A)를 사용하였다. 상기 태양광 시뮬레이터는 표준 Si 참조 전지 (Newport, 91150V)를 사용하여 AM 1.5G (100 mAcm
-2)를 조사하도록 보정되었다. 전류 밀도-전압 (J-V) 곡선은 30 mVs-1 또는 100 mVs-1 의 주사 속도에서 순방향 바이어스 (0V 내지 1.2V)에서 역방향 바이어스 (1.2V 내지 0V)까지 기록하였다. 각 장치의 활성 영역은 0.107 cm
2 이었다. 1 H nuclear magnetic resonance (NMR) spectra were obtained using a Bruker AVANCE III 500 spectrometer. X-ray diffraction (XRD) patterns were recorded on a PANalytical X'Pert PRO MPD equipped with a Cu Kα radiation source (λ=1.5405 Å), with a step size of 0.016 o . Elemental analysis was performed using a wavelength dispersive X-ray fluorescence (WD-XRF) spectrometer (Bruker S8 Tiger). To investigate the performance of the perovskite solar cell, a solar simulator (Newport Oriel Solar 3A Class, 94023A) with a source meter (Keithley 2450) was used. The solar simulator was calibrated to irradiate AM 1.5G (100 mAcm -2 ) using a standard Si reference cell (Newport, 91150V). Current density-voltage (JV) curves were recorded from forward bias (0V to 1.2V) to reverse bias (1.2V to 0V) at scan rates of 30 mVs-1 or 100 mVs-1. The active area of each device was 0.107 cm 2 .
실험 결과Experiment result
2-(1). 이온 교환법에 의한 유기 할라이드의 합성2-(1). Synthesis of organic halides by ion exchange method
다양한 알칼리 금속 할라이드 중에서도 NaI 및 NaBr이, 본 실험에서 용매로 사용된 물과 EtOH 모두에서 용해도가 높기 때문에 (100 g의 EtOH 당 NaI는 ~46 g, NaBr은 2.32 g), MACl 또는 FACl을 사용한 이온 교환 반응물로 가장 적합하였다. 반면, 반응 부산물 NaCl의 낮은 용해도 특성 (~0.065 g/100 g EtOH)은, 간단한 여과에 의해 반응 혼합물로부터 MAI가 분리되게 하여 준다. 도 2는 전술한 1-(1)-① 및 1-(1)-②에 따라 환류 조건 하에 제조된 4가지 유기 할라이드 (MAI, MABr, FAI, 및 FABr)의 수율을 보여준다. 또한, 비록 도 2에는 나타내지 않았으나, 전술한 1-(1)-③에 따라 제조된 MAI 및 1-(1)-④에 따라 제조된 FAI의 경우 수율이 각각 98% 및 94.2% 였다. 본 실험의 모든 경우에서 간단한 이온 교환 반응에 의해서도 탁월한 수율이 달성되었다는 것을 알 수 있다 (할로겐화수소를 사용한 통상의 절차를 통해 달성된 수율과 유사한 수율).Among the various alkali metal halides, NaI and NaBr, because of their high solubility in both water and EtOH used as solvents in this experiment (~46 g NaI and 2.32 g NaBr per 100 g EtOH), ions using MACl or FACl It was most suitable as an exchange reactant. On the other hand, the low solubility properties of the reaction by-product NaCl (~0.065 g/100 g EtOH) allow MAI to be separated from the reaction mixture by simple filtration. 2 shows the yields of four organic halides (MAI, MABr, FAI, and FABr) prepared under reflux conditions according to 1-(1)-① and 1-(1)-② described above. In addition, although not shown in FIG. 2, in the case of MAI prepared according to 1-(1)-③ and FAI prepared according to 1-(1)-④, the yields were 98% and 94.2%, respectively. It can be seen that, in all cases of this experiment, excellent yields were achieved even by a simple ion exchange reaction (a yield similar to that achieved through a conventional procedure using hydrogen halide).
반응열과 관련해서, 이온 교환 방법은 더 안전하고 더 간단한 대량 생산을 디자인할 수 있게 하여준다. 종래 기술에 따른 유기 할라이드 합성의 HX 경로의 경우, 산-염기 반응의 강한 발열 특성으로 인하여 추가의 냉각 시스템이 필요하다. 이에 반해, 이온 교환 반응에서는 온도의 매우 경미한 상승만 관찰된다. 이러한 결과는 이온 교환 방법이 유기 할라이드 전구체의 대량 생산에 매우 적용가능하다는 점을 반영한다. 또한, 본 발명에 따르면, 고체 상태 MACl 및 NaX의 부식성이 무시할만한 수준이라는 점도, 이러한 반응물을 위한 특수 보관 조건을 필요로 하지 않기 때문에, 종래 기술의 HI 경로와 비교하여 대량 생산시의 뚜렷한 이점이 된다.With respect to the heat of reaction, the ion exchange method allows the design of safer and simpler mass production. In the case of the HX route of organic halide synthesis according to the prior art, an additional cooling system is required due to the strong exothermic nature of the acid-base reaction. In contrast, only a very slight increase in temperature is observed in the ion exchange reaction. These results reflect that the ion exchange method is highly applicable to the mass production of organic halide precursors. In addition, according to the present invention, the negligible level of corrosiveness of solid state MACl and NaX and the absence of special storage conditions for these reactants, a distinct advantage in mass production compared to the HI route of the prior art do.
용매로서 물을 EtOH 로 대체하면, 물 제거 단계를 생략할 수 있어서 합성 방법이 더 간단해지고 최종 유기 할라이드 생성물을 반응 혼합물에서 여과에 의해 곧바로 분리시킬 수 있어서 대량 생산시 에너지 소비가 감소한다는 이점이 있다. 그러나, 이온 교환을 EtOH 용매에서 실온으로 수행할 경우, 물을 용매로 했을 때에 비하여 반응 수율이 실질적으로 감소하였다 (도 3 참조). 한편, 도 3을 참조하면, 반응 수율은 생성물의 양이온이 아니라 음이온의 특성에 명확히 의존하였다. 즉, MAI 및 FAI가 MABr 및 FABr에 비하여 반응율이 훨씬 더 높았고, 실온에서 MAI 및 FAI의 최종 수율은 ~70%인 반면 MABr 및 FABr의 최종 수율은 ~50% 였다. 한편, 합성 온도는 EtOH가 용매로 사용되었을 때 반응 동역학에 강하게 영향을 미치는데, 용매로서 EtOH를 물로 대체하면 할라이드 음이온의 특성과 관계없이 실온에서 거의 100% 반응 수율을 달성하였다 (도 3 참조).Replacing water with EtOH as solvent has the advantage that the water removal step can be omitted, which simplifies the synthesis method, and the final organic halide product can be isolated directly from the reaction mixture by filtration, thereby reducing energy consumption in mass production. . However, when the ion exchange was performed in an EtOH solvent at room temperature, the reaction yield was substantially reduced compared to when water was used as the solvent (see FIG. 3 ). On the other hand, referring to FIG. 3 , the reaction yield clearly depended on the characteristics of the anion rather than the cation of the product. That is, MAI and FAI had much higher reaction rates compared to MABr and FABr, and the final yield of MAI and FAI at room temperature was ~70%, whereas the final yield of MABr and FABr was ~50%. On the other hand, the synthesis temperature strongly affects the reaction kinetics when EtOH is used as a solvent. When EtOH as a solvent is replaced with water, almost 100% reaction yield was achieved at room temperature regardless of the characteristics of the halide anion (see Fig. 3). .
2-(2). 이온 교환 방법에 의해 합성한 유기 할라이드의 특성 분석2-(2). Characterization of organic halide synthesized by ion exchange method
전술한 1-(1)-① 및 1-(1)-②에 따라 이온 교환에 의해 합성한 유기 할라이드 시료의 순도를
1H NMR 분광계로 확인하였다 (도 4). 모든 스펙트럼에서 유기 오염원(예를 들어 2.0 ppm 에서 메틸아민의 -NH
2)가 없는 순수한 MAX 및 FAX를 보여주었다.The purity of the organic halide samples synthesized by ion exchange according to 1-(1)-① and 1-(1)-② described above was confirmed with 1 H NMR spectrometer (FIG. 4). All spectra showed pure MAX and FAX without organic contaminants (eg -NH 2 of methylamine at 2.0 ppm).
생성물 순도를 추가로 확인하기 위하여, 전술한 1-(1)-① 및 1-(1)-②에 따라 합성한 MAI, MABr, FAI, 및 FABr의 X선 회절 패턴을 얻었다 (도 5). 도 5 에서 알 수 있듯이, 본 발명에 따라 제조한 시료의 회절 피크 모두가 참조용 MAX 및 FAX의 회절 피크와 잘 일치하였다. 다만, 이온 교환 방법에서는 NaCl 및 NaI와 같은 이온성 염 불순물을 피할 수가 없다. 따라서, 이온 교환 반응으로 제조한 시료의 원소 분석을,
1H NMR 분석에서 검출되지 않는 불순물 이온에 대해 XRF 로 수행하였고, 그 결과를 도 6 에 나타낸다. 예를 들어, 제조한 그대로의 시료들에서는 소량의 Na 와 Cl 이 검출되었고, 메탄올을 이용하여 재결정한 이후에는 MAI, MABr, FAI 및 FABr 모두 Na 와 Cl 이 검출되지 않았다.In order to further confirm the product purity, X-ray diffraction patterns of MAI, MABr, FAI, and FABr synthesized according to 1-(1)-① and 1-(1)-② described above were obtained (FIG. 5). As can be seen from FIG. 5 , all of the diffraction peaks of the sample prepared according to the present invention were in good agreement with the diffraction peaks of MAX and FAX for reference. However, ionic salt impurities such as NaCl and NaI cannot be avoided in the ion exchange method. Therefore, elemental analysis of the sample prepared by the ion exchange reaction was performed by XRF on impurity ions not detected in 1 H NMR analysis, and the results are shown in FIG. 6 . For example, a small amount of Na and Cl were detected in the as-prepared samples, and Na and Cl were not detected in all of MAI, MABr, FAI, and FABr after recrystallization using methanol.
2-(3). 페로브스카이트 막의 특성 분석2-(3). Characterization of Perovskite Membrane
본 발명의 전술한 1-(1)-① 에 따라 합성한 IE-MAI를 사용하여 메틸암모늄 납 트리아이오다이드(CH
3NH
3PbI
3, MAPbI
3) 페로브스카이트 박막을 제조하고, 이의 광학적, 구조적, 및 형태학적 성질을 조사하였다. 비교를 위해, 본 발명의 IE-MAI를 대신하여 상업용 MAI를 사용한 MAPbI
3 막도 동일한 제조 방법을 사용하여 제조하였다. Methylammonium lead triiodide (CH 3 NH 3 PbI 3 , MAPbI 3 ) perovskite thin film was prepared using IE-MAI synthesized according to 1-(1)-① of the present invention, and its The optical, structural, and morphological properties were investigated. For comparison, a MAPbI 3 membrane using commercial MAI instead of IE-MAI of the present invention was also prepared using the same manufacturing method.
도 7a 는 페로브스카이트 막의 UV-Vis 흡수 스펙트럼을 도시한다. MAI의 유형에 따른 광학 흡수 성질의 차이는 없었다. 두 막 모두가 전체 파장 범위에서의 흡광도 및 흡수 엣지가 정확히 동일하였다. 두 MaPbI
3 막의 두께가 동일하므로, MAI 공급원이 다르더라도 MaPbI
3 재료의 흡광 계수 α 값 (α= 2.303 A/t, 여기서, A가 흡광도, t는 두께)은 동일하게 된다. Figure 7a shows the UV-Vis absorption spectrum of the perovskite film. There was no difference in optical absorption properties according to the type of MAI. Both films had exactly the same absorbance and absorption edge over the entire wavelength range. Since the two MaPbI 3 films have the same thickness, the extinction coefficient α value of the MaPbI 3 material (α = 2.303 A/t, where A is the absorbance and t is the thickness) is the same even if the MAI source is different.
도 7b 는 MAPbI
3 막의 XRD 패턴을 보여준다. 정방 정계 페로브스카이트 (
I4/mcm)의 회절 패턴이 두 막 모두에 대해 선명하게 관찰되는데, 이는 두 막의 매트릭스가 MAPbI
3 라는 것을 나타낸다. 12.7
o 에서의 작은 피크는 소량의 PbI
2 에서 유래된 것인데, 이것은 용매 엔지니어링 방법에서의 통상적인 잔류물이다. IE-MAPbI
3 및 CO-MAPbI
3에 대한 PbI
2의 피크 강도가 상이하다는 점이 주목할 만하다 (도 8a 참조).Figure 7b shows the XRD pattern of the MAPbI 3 film. The diffraction pattern of tetragonal perovskite ( I4/mcm ) is clearly observed for both films, indicating that the matrix of both films is MAPbI 3 . The small peak at 12.7 o is from a small amount of PbI 2 , which is a common residue in solvent engineering methods. It is noteworthy that the peak intensities of PbI 2 for IE-MAPbI 3 and CO-MAPbI 3 are different (see Fig. 8a).
MAPbI
3 (110) 피크 및 12.7
o에서 PbI
2 피크 사이의 강도 비를 기준으로 비교했을 때(IE-MAPbI
3 및 CO-MAPbI
3 에 대해 0.04 및 0.13), IE-MAPbI
3에서 PbI
2의 상대적인 양이 CO-MAPbI
3 에서의 PbI
2의 양의 1/3 보다 작다. 이러한 PbI
2 양의 차이는 MAI 전구체 중의 염소의 양이 상이하기 때문인 것으로 보인다. XRF 분석에 의하면, IE-MAI의 경우 0.12% 염소가 검출된 반면에, CO-MAI에서는 염소가 검출되지 않았다. 염소는 MAPbI
3 형성을 촉진시킴으로써 페로브스카이트 층으로부터 PbI
2 가 더 적게 추출되게 하는 것으로 보고되어 있다. PbI
2가 존재할 경우, 태양 전지의 효율에 악영향을 끼치므로, PbI
2의 양이 적은 것이 태양 전지 장치의 상태에 바람직하다. 따라서, 상기와 같은 XRD 피크 강도 데이터에서 IE-MAPbI
3의 PbI
2의 강도가 상대적으로 약하므로 페로브스카이트 층에 존재하는 PbI
2의 양이 적은 것으로 보이며, 이에, IE-MAPbI
3를 사용한 페로브스카이트 층이 CO-MAPbI
3 를 사용한 페로브스카이트 층보다 상대적으로 더 우수한 성능을 제공할 것이라고 볼 수 있다.MAPbI 3 (110) peak and 12.7 o PbI compared based on the intensity ratio between the two peaks, the relative amounts of PbI 2 in IE-MAPbI 3 (IE-MAPbI 3 and CO-MAPbI 3 0.04 and 0.13 for a) from It is smaller than 1/3 of the amount of PbI 2 in this CO-MAPbI 3 . This difference in the amount of PbI 2 appears to be due to the difference in the amount of chlorine in the MAI precursor. According to XRF analysis, 0.12% chlorine was detected in IE-MAI, whereas no chlorine was detected in CO-MAI. It is reported that chlorine promotes the formation of MAPbI 3 resulting in less PbI 2 extraction from the perovskite layer. When PbI 2 is present, the efficiency of the solar cell is adversely affected, so that the amount of PbI 2 is small is preferable for the state of the solar cell device. Therefore, since in the XRD peak intensity data as described above, the strength of PbI 2 of the IE-MAPbI 3 relatively weak seems small, the amount of PbI 2 present in the perovskite layer, whereby, page with IE-MAPbI 3 It can be seen that the rovskite layer will provide relatively better performance than the perovskite layer using CO-MAPbI 3 .
IE-MAPbI
3 및 CO-MAPbI
3 의 XRD 패턴 사이의 다른 큰 차이점은 MAPbI
3 (110) 피크의 피크 면적 및 반치 전폭(FWHM) 이다. XRD 피크로부터 측정한, 가우스 피팅 결과를 아래의 [표 1]에 요약하였다. 가우스 피팅으로 얻은 (110) 피크 면적은 IE-MAPbI
3 및 CO-MAPbI
3 에 대해 각각 0.67 및 0.45 이고 (도 8 및 표 1 참조), 이는 IE-MAPbI
3 의 결정도가 더 높다는 것을 가리킨다. 또한, MAPbI
3 (110) 피크의 FWHM 은 IE-MAPbI
3 및 CO-MAPbI
3 의 패턴에서 각각, 13.33 및 12.14 인 것으로 나타났고, 이는 셰러(Scherrer) 방정식 [B = Kλ/Lcosθ, 여기서 B는 FWHM 이고, K는 형상 인자 (여기서는 1에 가까움)이고, λ는 X선 파장이고, θ는 브랙 각이고, L은 평균 입도 크기이다]에 따라 추정했을 때 IE-MAPbI
3 가 CO-MAPbI
3 보다 결정자 크기가 10% 더 크다는 것을 가리킨다.Another major difference between the XRD patterns of IE-MAPbI 3 and CO-MAPbI 3 is the peak area and full width at half maximum (FWHM) of the MAPbI 3 (110) peak. Gaussian fitting results measured from the XRD peaks are summarized in Table 1 below. The (110) peak areas obtained by Gaussian fitting are 0.67 and 0.45 for IE-MAPbI 3 and CO-MAPbI 3 , respectively (see FIG. 8 and Table 1), indicating higher crystallinity of IE-MAPbI 3 . In addition, the FWHM of the MAPbI 3 (110) peak was found to be 13.33 and 12.14 in the patterns of IE-MAPbI 3 and CO-MAPbI 3 , respectively, according to the Scherrer equation [B = Kλ/Lcosθ, where B is the FWHM. , where K is the shape factor (close to 1 here), λ is the X-ray wavelength, θ is the Brack angle, and L is the average grain size], IE-MAPbI 3 is more determinant than CO-MAPbI 3 . It indicates that the size is 10% larger.
[표 1][Table 1]
또한, IE-MAPbI
3 막의 입자 크기가 약간 더 크다는 것이 SEM 이미지에서 확인되었다. 도 7c 및 7d 는 각각 IE-MAPbI
3 막 및 CO-MAPbI
3 의 SEM 이미지 상면도를 나타낸다. IE-MAPbI
3 및 CO-MAPbI
3 의 입자 크기는 평균 입자 인터셉트 방법으로 측정했을 때 각각 343 nm 및 304 nm 이고, 이는 XRD 분석 결과와 일치하였다. 높은 결정도 및 큰 입자 크기는 IE-MAI 전구체 중의 염소 존재에서 기인한 것일 수 있다. 염소 이온의 혼입은 페로브스카이트의 결정화를 촉진하고 입자 성장을 가속화시킨다고 보고되어 있다.In addition, it was confirmed in the SEM image that the particle size of the IE-MAPbI 3 film was slightly larger. 7c and 7d show top views of SEM images of IE-MAPbI 3 membrane and CO-MAPbI 3 , respectively. The particle sizes of IE-MAPbI 3 and CO-MAPbI 3 were 343 nm and 304 nm, respectively, as measured by the average particle intercept method, which was consistent with the results of XRD analysis. The high crystallinity and large particle size may be due to the presence of chlorine in the IE-MAI precursor. It is reported that incorporation of chlorine ions promotes crystallization of perovskite and accelerates grain growth.
2-(4). 페로브스카이트 태양 전지 (PCS)의 특성 분석2-(4). Characterization of Perovskite Solar Cells (PCS)
IE-MAI를 기재로 한 MAPbI
3 막을 평가하기 위해, 페로브스카이트 태양 전지 (PCS)를 제조하였다 (전술한 1-(1)-① 에 따라 합성한 IE-MAI를 사용하였다). 비교를 위해 CO-MAI를 기재로 한 PSC도 동일한 방법으로 제조하였다. 도 9a 는 상기 제조한 메조포러스형 PSC 의 구조를 도시한다 (전도성 투명 전극으로서 FTO 기판, 전자 전달 층으로서 치밀 TiO
2 (c-TiO
2) 및 메조포러스 TiO
2 (mp-TiO
2) 막, 광활성 층으로서 MAPbI
3 페로브스카이트 막, 정공 전달 층으로서 스피로-MeOTAD 막, 및 대향 전극으로서 Au 전극으로 구성되었음). FTO, TiO
2, MAPbI
3, 스피로-MeOTAD 및 Au 막의 두께는, PSC의 횡단면 SEM 이미지를 보여주는 도 9b 에 도시된 바와 같으며, 각각, 600 nm, 220 nm, 430 nm, 200 nm, 및 100 nm 였다. In order to evaluate the MAPbI 3 film based on IE-MAI, a perovskite solar cell (PCS) was prepared (IE-MAI synthesized according to 1-(1)-① described above was used). For comparison, PSCs based on CO-MAI were prepared in the same manner. Figure 9a shows the structure of the prepared mesoporous PSC (FTO substrate as a conductive transparent electrode, dense TiO 2 (c-TiO 2 ) and mesoporous TiO 2 (mp-TiO 2 ) film as an electron transport layer, photoactive It consisted of a MAPbI 3 perovskite film as a layer, a spiro-MeOTAD film as a hole transport layer, and an Au electrode as a counter electrode). The thicknesses of the FTO, TiO 2 , MAPbI 3 , spiro-MeOTAD and Au films are as shown in Fig. 9b showing cross-sectional SEM images of PSCs, 600 nm, 220 nm, 430 nm, 200 nm, and 100 nm, respectively. it was
PSC의 각 유형 (즉, IE-PSC vs CO-PSC)마다 12개를 제조하였고 이의 전력 변환 효율을, 모의 태양광 (AM 1.5G, 100 mWcm
-2 ) 하에서 전류 밀도-전압 (J-V) 곡선을 기록하여 검사하였다. 도 9c 는 IE-PSC 및 CO-PSC의 J-V 곡선을 비교한다. 단락 회로 전류 밀도 (Jsc), 개방 회로 전압 (Voc), 충전 인자 (FF), 및 전력 변환 효율 (PCE) 등의 파라미터에 대한 통계적 분석결과 각각에 대해 도 9d 내지 도 9g 에 나타내었으며, 그 결과를 하기 [표 2] 에 요약하였다. Twelve of each type of PSC (i.e., IE-PSC vs CO-PSC) were fabricated and their power conversion efficiency was measured by plotting current density-voltage (JV) curves under simulated sunlight (AM 1.5G, 100 mWcm −2 ). Recorded and inspected. 9C compares the JV curves of IE-PSC and CO-PSC. The statistical analysis results for parameters such as short circuit current density (Jsc), open circuit voltage (Voc), charge factor (FF), and power conversion efficiency (PCE) are shown in FIGS. 9D to 9G , respectively, and the results are shown in FIGS. are summarized in [Table 2] below.
[표 2][Table 2]
IE-PSC 모두, 히스테리시스(hysteresis)가 비교적 작은 우수한 다이오드형 J-V 곡선을 나타내었다. IE-PSC의 Jsc 가 CO-PSC 보다 약간 더 높았다. PSC의 광전류는 페로스브스카이트 층의 광 흡수 능력 및 전하 이송성에 의해 주로 영향을 받는다고 알려져 있다. 앞서 설명한 바와 같이, IE-MAPbI
3 막 및 CO-MAPbI
3 막의 흡광도는 동일하다. 따라서, IE-PSC 막의 Jsc 가 더 높다는 것은 IE-MAPbI
3 막의 전하 이송성의 향상으로 인한 것일 수 있다. IE-MAPbI
3 막은 CO-MAPbI
3 막에 비하여 결정도가 더 높고 입자 크기가 더 크다. 높은 결정도 및 큰 입자는 전하 환산 계수가 더 커지게 할 것이다. 또한, 결정 크기가 더 크면, 입자 경계의 밀도가 더 낮아져서 전하 트랩핑이 더 적어질 것이다. 더 높은 확산 계수 및 더 긴 수명은 확산 길이를 증가시킨다 (L =
, 여기서 L은 확산 길이이고, D는 확산 계수이고, τ는 수명이다). 최고의 장치는 18% 초과의 상당히 높은 PCE를 나타낸다. IE-PSC의 평균 PCE (17.5%)는 역방향 스캔에서 CO-PSC의 것 (17.5%)과 동일하였고, 정방향 스캔에서는 오직 0.3% 차이만 나타날 뿐 유사했다. 따라서, IE-PSC의 전력 변환 효율은 CO-PSC의 전력 변환 효율과 유사하다는 결론을 내릴 수 있으므로, 상기 유기 할라이드 전구체의 제조를 위한 이온 교환 방법의 생산 규모를 확대할 경우, 페로브스카이트 태양 전지 산업에 적용가능하다는 것을 입증한다.Both IE-PSCs exhibited excellent diode-type JV curves with relatively small hysteresis. Jsc of IE-PSC was slightly higher than that of CO-PSC. It is known that the photocurrent of PSC is mainly affected by the light absorption capacity and charge transportability of the perovskite layer. As described above, the absorbance of the IE-MAPbI 3 film and the CO-MAPbI 3 film is the same. Therefore, the higher Jsc of the IE-PSC film may be due to the improvement of the charge transportability of the IE-MAPbI 3 film. The IE-MAPbI 3 film has a higher crystallinity and a larger particle size than the CO-MAPbI 3 film. High crystallinity and large particles will result in a larger charge conversion factor. Also, the larger the crystal size, the lower the density of grain boundaries will result in less charge trapping. Higher diffusion coefficient and longer lifetime increase diffusion length (L = , where L is the diffusion length, D is the diffusion coefficient, and τ is the lifetime). The best devices show a fairly high PCE of >18%. The mean PCE (17.5%) of IE-PSC was the same as that of CO-PSC in the reverse scan (17.5%), and was similar with only a 0.3% difference in the forward scan. Therefore, it can be concluded that the power conversion efficiency of IE-PSC is similar to that of CO-PSC, so when the production scale of the ion exchange method for the preparation of the organic halide precursor is expanded, the perovskite solar It proves applicability to the battery industry.
결론conclusion
본 발명에서는, MAI, MABr, FAI, 및 FABr의 대량 생산을 위한, HI 및 HBr을 사용하는 통상의 방법에 대한 대안으로서, 간단하고 친환경적인 이온 교환 방법을 이용하였다. 본 방법은 NaI (또는 NaBr)과 MACl (또는 FACl) 사이의 이온 교환으로 진행되었고, 부산물로 NaCl이 생성되었다. 4가지 유기 할라이드에 대한 분리후 수율은 96 내지 100% 였다. 상기 생산 수율을 열역학적인 측면에서 고려하면, MAI의 경우, 이온 교환 방법에서 반응물의 거의 100%가 전환된 것이다. 제조된 MAI를 재결정함으로써 순도를 최고로 할 수 있었고, 이는 시판되는 물질과 유사한 순도였다.In the present invention, as an alternative to the conventional method using HI and HBr for mass production of MAI, MABr, FAI, and FABr, a simple and environmentally friendly ion exchange method was used. The process proceeded with ion exchange between NaI (or NaBr) and MACl (or FACl), and NaCl was produced as a by-product. The yield after separation for the four organic halides was 96-100%. Considering the production yield from a thermodynamic point of view, in the case of MAI, almost 100% of the reactants are converted in the ion exchange method. By recrystallizing the prepared MAI, the highest purity was possible, which was similar to that of a commercially available material.
산업적 적용가능성을 알아보기 위해 본 발명의 이온 교환 방법으로 제조한 MAI를 사용하여 PSC를 제조하였다 (IE-PSC). 상기 IE-PSC 는, 상업용 MAI를 기재로 한 태양 전지 (CO-PSC)에 비하여 유사하거나 또는 약간 더 큰 PCE 를 나타내었다. 재결정 이후 MAI 로 미량의 Cl
- 이온이 혼입되어, 페로브스카이트 층의 코팅 동안에 더 큰 결정 형성을 촉진시켰고, 이로써 PCE가 향상되었다.PSCs were prepared using MAI prepared by the ion exchange method of the present invention in order to examine industrial applicability (IE-PSC). The IE-PSC exhibited similar or slightly higher PCE compared to commercial MAI-based solar cells (CO-PSC). Traces of Cl − ions were incorporated into the MAI after recrystallization, which promoted the formation of larger crystals during the coating of the perovskite layer, thereby improving the PCE.
PSC 전구체를 위한 본 발명의 이온 교환 방법은 공업적 규모의 기술로서 PSC 분야에 실질적으로 기여할 것으로 기대된다.The ion exchange method of the present invention for PSC precursor is expected to contribute substantially to the field of PSC as an industrial-scale technology.
상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although the above has been described with reference to the preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. You will understand that you can.
Claims (10)
- 메틸암모늄 클로라이드 또는 포름아미디늄 클로라이드를 알칼리 금속 아이오다이드 또는 알칼리 금속 브로마이드와 반응시키는 단계 (a)를 포함하는, 페로브스카이트 제조용 유기 할라이드의 제조 방법.A method for preparing an organic halide for preparing perovskite, comprising the step (a) of reacting methylammonium chloride or formamidinium chloride with an alkali metal iodide or alkali metal bromide.
- 제1항에 있어서, 상기 알칼리 금속 아이오다이드 또는 알칼리 금속 브로마이드가 나트륨 아이오다이드 또는 나트륨 브로마이드인 것을 특징으로 하는 방법.The method according to claim 1, wherein the alkali metal iodide or alkali metal bromide is sodium iodide or sodium bromide.
- 제1항에 있어서, 상기 반응 단계 (a)가 용매 중에서 이온 교환 반응에 의해 수행되는 것을 특징으로 하는 방법.The method according to claim 1, wherein the reaction step (a) is carried out by an ion exchange reaction in a solvent.
- 제1항에 있어서, 상기 반응 단계 (a)가 용매로서 물 또는 알콜 중에 실온 또는 환류 하에서 수행되는 것을 특징으로 하는 방법.The process according to claim 1, characterized in that the reaction step (a) is carried out at room temperature or under reflux in water or alcohol as a solvent.
- 제1항에 있어서, 상기 반응 단계 (a)의 생성물을 여과하는 단계 (b), 및 용매를 제거하는 단계 (c)를 추가로 포함하는 것을 특징으로 하는 방법.The method of claim 1, further comprising the steps of (b) filtering the product of reaction step (a), and (c) removing the solvent.
- 제1항에 있어서, 생성된 유기 할라이드로부터 알칼리 금속 클로라이드를 재결정하여 제거하는 단계 (d)를 추가로 포함하는 것을 특징으로 하는 방법.The method according to claim 1, further comprising the step (d) of recrystallizing and removing alkali metal chloride from the resulting organic halide.
- 제1항의 방법에 의해 제조된 유기 할라이드를 전구체로서 포함하여 사용함으로써 제조되는 페로브스카이트.A perovskite prepared by using the organic halide prepared by the method of claim 1 as a precursor.
- 제1 전극, a first electrode;상기 제1 전극과 대향하는 제2 전극, 및 a second electrode opposite the first electrode; and상기 제1 전극과 상기 제2 전극 사이에 적어도 부분적으로 배치되는 광활성 층으로서, 제1항의 방법에 의해 제조된 유기 할라이드를 전구체로서 포함하여 사용함으로써 수득된 페로브스카이트를 포함하는 광활성 층을 포함하는 태양 전지.A photoactive layer disposed at least partially between the first electrode and the second electrode, comprising a photoactive layer comprising a perovskite obtained by using as a precursor the organic halide prepared by the method of claim 1 . solar cells.
- 제8항에 있어서, 상기 페로브스카이트는 제1항의 방법에 의해 제조된 유기 할라이드와 화학식 MX2 의 화합물 (X는 아이오다이드 음이온 또는 브로마이드 음이온일 수 있고, M은 Pb 2+, Sn 2+, Ge 2+ 및 이들의 조합으로 이루어진 군에서 선택되는 2가의 금속 양이온일 수 있다)을 반응시켜 수득되는 것을 특징으로 하는 태양 전지.The method according to claim 8, wherein the perovskite is an organic halide prepared by the method of claim 1 and a compound of formula MX2 (X may be an iodide anion or a bromide anion, M is Pb 2+ , Sn 2+ , A solar cell obtained by reacting Ge 2+ and a divalent metal cation selected from the group consisting of combinations thereof.
- 제8항에 있어서, 상기 제1 전극과 상기 제2 전극 사이에 전자 전달 층 및 정공 전달 층을 추가로 더 포함하는 것을 특징으로 하는 태양 전지.The solar cell of claim 8 , further comprising an electron transport layer and a hole transport layer between the first electrode and the second electrode.
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