CN107275485B - 具有高耐热性的钙钛矿太阳电池 - Google Patents
具有高耐热性的钙钛矿太阳电池 Download PDFInfo
- Publication number
- CN107275485B CN107275485B CN201710218306.8A CN201710218306A CN107275485B CN 107275485 B CN107275485 B CN 107275485B CN 201710218306 A CN201710218306 A CN 201710218306A CN 107275485 B CN107275485 B CN 107275485B
- Authority
- CN
- China
- Prior art keywords
- solar cell
- chemical formula
- perovskite solar
- electrode
- hole transport
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000005525 hole transport Effects 0.000 claims abstract description 41
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims description 73
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 239000010410 layer Substances 0.000 description 52
- 239000000243 solution Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- -1 copper (copper) phthalocyanine derivatives Chemical class 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 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 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 6
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229940060037 fluorine Drugs 0.000 description 3
- 235000019000 fluorine Nutrition 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 2
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- VBVAVBCYMYWNOU-UHFFFAOYSA-N coumarin 6 Chemical compound C1=CC=C2SC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 VBVAVBCYMYWNOU-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- ZZTDEFHCSZAWMD-UHFFFAOYSA-L 2-(4-carboxylatopyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+) Chemical compound [Ru+2].[O-]C(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 ZZTDEFHCSZAWMD-UHFFFAOYSA-L 0.000 description 1
- XBGNOMBPRQVJSR-UHFFFAOYSA-N 2-(4-nitrophenyl)butanoic acid Chemical compound CCC(C(O)=O)C1=CC=C([N+]([O-])=O)C=C1 XBGNOMBPRQVJSR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910018572 CuAlO2 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- DTMUJVXXDFWQOA-UHFFFAOYSA-N [Sn].FOF Chemical compound [Sn].FOF DTMUJVXXDFWQOA-UHFFFAOYSA-N 0.000 description 1
- XPOLVIIHTDKJRY-UHFFFAOYSA-N acetic acid;methanimidamide Chemical compound NC=N.CC(O)=O XPOLVIIHTDKJRY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L2031/0344—Organic materials
-
- 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
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
-
- 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
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Photovoltaic Devices (AREA)
Abstract
本发明涉及钙钛矿太阳电池,本发明的钙钛矿太阳电池使用酞菁衍生物作为空穴传输物质,因而耐热性、耐久性及光电变换效率非常优异。
Description
技术领域
本发明涉及钙钛矿太阳电池,详细而言,涉及具有包含酞菁衍生物作为空穴传输物质的空穴传输层的钙钛矿太阳电池,所述空穴传输物质在宽的温度范围内也没有热转移而耐热性优异。
背景技术
就钙钛矿太阳电池而言,具体地,卤化铅钙钛矿太阳电池因具有优异的特性的钙钛矿材料的光活性层而通过几年的持续发展结果目前的效率已达到21%。
这种钙钛矿太阳电池在包括染料敏化及有机太阳电池在内的下一代太阳电池中最接近于商用化,因此需要对稳定性及大面积化进行正式研究。
尤其,正在对耐久性因素中的光、湿度、热的老化机制进行研究,但是对元件热稳定性的研究还处于初级阶段。就作为光活性层而主要进行研究的CH3NH3(=MA)PbI3和(NH2)2CH(=FA)PbI3的热稳定性而言,在85℃以上的高温下FAPbI3显示出更加提高的特性。
然而,元件稳定性在85℃以上的高温下显示出极具降低的效率,这与广泛使用的Spiro-OMeTAD单分子本身在高温下的热转移相关。
因此,作为解决该技术问题的技术方案需要导入在高温下也没有热转移的耐热性空穴传输物质,由此,正在对多种耐热性空穴传输物质进行研究。
作为一例,铜(copper)酞菁衍生物曾被应用为有机发光元件的空穴注入层,并且在有机单分子太阳电池中也被广泛应用为光活性层给体(d onor)。近年来,公开了作为钙钛矿太阳电池元件的空穴输送层的锌(zin c)酞菁衍生物。
然而,还没有得到能满足的光电变换效率。
[现有技术文献]
[非专利文献]
Dalton Trans,2015,44,10847
发明内容
要解决的技术问题
因此,为了改善这些问题,本发明提供钙钛矿太阳电池,其使用耐热性优异的酞菁衍生物作为空穴传输物质,从而与现有的钙钛矿太阳电池相比,具有显著优异的特性,尤其稳定性高的同时光电变换效率也优异。
技术方案
本发明涉及钙钛矿太阳电池,本发明的钙钛矿太阳电池包含用下述化学式1表示的酞菁衍生物:
[化学式1]
所述化学式1中,
R1至R4相互独立地为(C1-C10)烷基或(C1-C10)烷氧基,
o、p、q及r相互独立地为0或1至4的整数,当o、p、q及r为2以上时,R1至R4相互相同或不同。
优选地,本发明一实施例的所述化学式1中,R1至R4可以相互独立地为(C1-C8)烷基或(C1-C8)烷氧基。
优选地,本发明一实施例的所述化学式1可以用下述化学式2表示:
[化学式2]
在所述化学式2中,
R11至R14相互独立地为(C1-C5)烷基。
优选地,本发明一实施例的所述化学式2中,R11至R14可以相互独立地为叔丁基或辛氧基。
优选地,本发明一实施例的所述酞菁衍生物可以用作钙钛矿太阳电池的空穴传输物质,本发明一实施例的钙钛矿太阳电池可以包含:第一电极;电子传输层,其形成在所述第一电极上;光吸收层,其形成在所述电子传输层上且包含钙钛矿结构的化合物;空穴传输层,其形成在所述光吸收层上,并且包含用所述化学式1表示的酞菁衍生物;以及第二电极,其形成在所述空穴传输层上。
本发明一实施例的空穴传输层,可以是将包含用所述化学式1表示的酞菁衍生物的空穴传输物质通过溶液工序而形成。
发明效果
本发明的钙钛矿太阳电池使用在宽的温度范围内也不会产生相变而耐热性优异的酞菁衍生物作为空穴传输物质,从而耐久性、耐热性及保管稳定性非常高。
并且,本发明的钙钛矿太阳电池使用酞菁衍生物作为空穴传输物质,从而在高温即在85℃以上的温度下光电变换效率也高,进而在85℃以上的温度下也能够长时间维持高的光电变换效率。
并且,本发明的钙钛矿太阳电池无需通过高价的沉积工序来进行,而只需通过低价的溶液工序就能够形成空穴传输层,因此非常经济。
附图说明
图1是示出本发明的实施例1及比较例1~2的钙钛矿太阳电池根据温度的光电变换效率的图表。
图2是示出本发明的实施例1及比较例1~2的钙钛矿太阳电池的耐久性的图表。
图3是示出本发明的实施例1及比较例2的钙钛矿太阳电池的电流密度的图表。
具体实施方式
本发明提供具有优异的光电变换效率、耐久性及稳定性的钙钛矿太阳电池,本发明的钙钛矿太阳电池包含用下述化学式1表示的酞菁衍生物:
[化学式1]
所述化学式1中,
R1至R4相互独立地为(C1-C10)烷基或(C1-C10)烷氧基,
o、p、q及r相互独立地为0或1至4的整数,当o、p、q及r为2以上时,R1至R4相互相同或不同。
本发明的钙钛矿太阳电池使用在宽的温度范围内没有热转移而耐热性高,并且空穴输送能力突出,同时氧化稳定性也优异的用所述化学式1表示的酞菁衍生物作为空穴传输物质,从而在高的温度下稳定性及光电变换效率非常优异。
现有的使用Spiro-OMeTAD[2,2',7,7'-四(N,N-二-对甲氧基苯胺)-9,9'-螺螺二芴]([2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobi flu orine])单分子的钙钛矿太阳电池在85℃以上的高温下效率降低的耐热性会显著降低。其原因在于Spiro-OMeTAD具有低的热转移温度(125℃),导致在薄膜上产生针孔等损伤,从而耐久性及稳定性降低。使用本发明的用所述化学式1表示的酞菁衍生物的钙钛矿太阳电池克服了这种缺点,从而在高的温度下晶体结构也不会发生变化,从而确保了稳定性。
进而,与使用有机配体与金属配位结合的酞菁的钙钛矿太阳电池相比,使用本发明的用化学式1表示的酞菁衍生物的钙钛矿太阳电池竟然具有高的光电变换效率。
即,本发明的钙钛矿太阳电池没有使用有机配体与金属配位结合的酞菁,而是使用没有金属配位的酞菁衍生物作为钙钛矿太阳电池的空穴传输物质,从而与使用金属配位的酞菁的钙钛矿太阳电池相比,耐久性及耐热性高,从而具有优异的稳定性和显著提高的光电变换效率。
此外,就本发明的钙钛矿太阳电池而言,用所述化学式1表示的酞菁衍生物对溶剂的溶解度高,从而包含其的空穴传输层能够通过溶液工序实现薄膜形成,因此非常经济,并且商业上的适用也容易。
优选地,本发明一实施例的所述化学式1中,R1至R4可以相互独立地为(C1-C8)烷基或(C1-C8)烷氧基,更优选为(C1-C5)烷基或(C1-C5)烷氧基。
从为了提高钙钛矿太阳电池的高温稳定性及光电变换效率的方面考虑,本发明一实施例的所述化学式1优选可以用下述化学式2表示:
[化学式2]
在所述化学式2中,
R11至R14相互独立地为(C1-C5)烷基。
从钙钛矿太阳电池的高温稳定性、光电变换效率及溶解度方面考虑,本发明一实施例的所述化学式2中,优选地,R11至R14可以相互独立地为叔丁基或辛氧基(octyloxy(-OCH2(CH2)6CH3)),进一步优选地,相互相同地为叔丁基或辛氧基(octyloxy(-OCH2(CH2)6CH3))。
本发明中记载的包含「烷基」、「烷氧基」及其之外「烷基」部分的取代基包括直链或支链形状,在酞菁衍生物的情况下具有1~10个碳原子,优选具有1~8个碳原子,在烷基的情况下更优选具有1~5个碳原子。
在酞菁衍生物以外的情况下具有1~30个碳原子,优选具有1~25个碳原子。
此外,本发明中记载的「芳基」为通过去除一个氢而从芳香族碳化氢诱导出的有机自由基,其包括在各环中适当地包含4~7个环原子,优选包含5个或6个环原子的单环系或稠环系,并且还包括多个芳基通过单键连接的形状。具体例包括如苯基、萘基、联苯、蒽基、茚基(indeny l)、芴基等,但并不限定于此。
本发明中记载的「环烷基」表示具有3~20个碳原子的非芳香族单环式(monocyclic)或多环式(multicyclic)环系,单环式环非限制性地包括环丙基、环丁基、环戊基及环己基。作为多环式环烷基的一例,包括全氢化萘基(perhydronaphthyl)、全氢化茚基(perhydroindenyl)等;桥连化(bridg ed)的多环式环烷基包括金刚烷基(adamantly)及降冰片基(norbornyl)等。
优选地,本发明一实施例的所述酞菁衍生物可以与空穴传输层及钙钛矿太阳电池的包含钙钛矿结构的化合物的光吸收层进行相互作用,从而能够用作缓冲层,优选用作钙钛矿太阳电池的空穴传输物质。
本发明一实施例的钙钛矿太阳电池可以包含:第一电极;电子传输层,其形成在所述第一电极上;光吸收层,其形成在所述电子传输层上且包含钙钛矿结构的化合物;空穴传输层,其形成在所述光吸收层上,并且包含用所述化学式1表示的酞菁衍生物;以及第二电极,其形成在所述空穴传输层上。
本发明一实施例的钙钛矿太阳电池的对应于各结构成分的部分中,除了必须包含用所述化学式1表示的酞菁衍生物的空穴传输层以外,包含国际专利PCT-KR2014-012727号中记载的内容。
具体而言,本发明一实施例的第一电极只要是能够与电子传输层欧姆接触(ohmic-bonded)的导电性电极均可以使用,第二电极只要是能够与电子传输层欧姆接触的导电性电极均可以使用。
此外,第一电极及第二电极只要是通常用作太阳电池的正面电极或背面电极的电极物质的物质就可以使用。作为非限定性一例,当第一电极及第二电极为背面电极的电极物质时,第一电极及第二电极可以是选自金、银、铂、钯、铜、铝、碳、硫化钴、硫化铜、氧化镍及它们的复合物中的一种以上。作为非限定性一例,当第一电极及第二电极为透明电极时,第一电极及第二电极可以为如含氟氧化锡(FTO;Fouorine dope d Tin Oxide)、含铟氧化锡(ITO;Indium doped Tin Oxide)、ZnO、CN T(碳纳米管)、石墨烯(Graphene)等无机类导电性电极,也可以是如聚乙撑二氧噻吩(PEDOT):聚苯乙烯磺酸钠(PSS)等有机类导电性电极。当欲提供透明太阳电池时,第一电极及第二电极优选为透明电极,当第一电极及第二电极为有机类导电性电极时,欲提供柔性太阳电池或透明电池时更为优选。
第一电极可以通过在坚硬(rigid)的基板或柔性(flexible)基板上沉积或涂布来形成。沉积可以通过物理沉积(物理气相沉积(physical vapor depo sition))或化学沉积(化学气相沉积(chemical vapor deposition))来形成,也可以通过热沉积(热蒸镀(thermal evaporation))来形成。涂布可以通过将电极物质的溶解液或电极物质的分散液涂布在基板后进行干燥,或者选择性地对干燥的膜进行热处理来实施。然而,第一电极及第二电极当然也可以通过在常规的太阳电池中形成正面电极或背面电极时所使用的方法来形成。
本发明的形成在第一电极的上部的电子传输层可以是电子导电性有机物层或无机物层。电子导电性有机物可以是常规的有机太阳电池中用作n型半导体的有机物。作为具体且非限制性的一例,电子导电性有机物可以包含富勒烯-衍生物(Fullerene-derivative)、PBI(聚苯并咪唑(polybe nzimidazole))、PTCBI(3,4,9,10-苝四羧酸二苯并咪唑(3,4,9,10-perylenetetr acarboxylic bisbenzimidazole))、F4-TCNQ(四氟四氰基醌二甲烷(tetra flu orotetracyanoquinodimethane))或它们的混合物,其中所述富勒烯-衍生物包含富勒烯(C60、C70、C74、C76、C78、C82、C95)、PCBM([6,6]-苯基-C61丁酸甲酯([6,6]-phenyl-C61butyric acid methyl ester))及C71-PCB M、C84-PCBM、PC70BM([6,6]-苯基C70-丁酸甲酯([6,6]-phenyl C70-butyri c acid methyl ester))。电子导电性无机物可以是常规的基于量子点的太阳电池或染料敏化太阳电池中为了电子传输而使用的电子导电性金属氧化物。作为具体一例,电子导电性金属氧化物可以是n-型金属氧化物半导体。作为n型金属氧化物半导体的非限定性一例,可以例举如选自Ti氧化物、Zn氧化物、In氧化物、Sn氧化物、W氧化物、Nb氧化物、Mo氧化物、Mg氧化物、Ba氧化物、Zr氧化物、Sr氧化物、Yr氧化物、L a氧化物、V氧化物、Al氧化物、Y氧化物、Sc氧化物、Sm氧化物、G a氧化物及SrTi氧化物中的一种或两种以上的物质,也可以例举如它们的混合物或它们的复合体(composite)。
本发明的钙钛矿太阳电池的一实施例的形成在电子传输层上的光吸收层包含钙钛矿结构的化合物,钙钛矿结构的化合物可以是本发明的技术领域的技术人员所认知的范围内所包含的所有化合物。
作为一例,表示含有一价的有机阳离子、二价金属阳离子及卤素阴离子且具有钙钛矿结构的化合物。
作为具体一例,本发明的具有钙钛矿结构的化合物可以是选自满足下述化学式11~12的钙钛矿化合物中的一种或两种以上的物质:
[化学式11]
AMX3
化学式11中,A为一价的有机铵离子或Cs+,M为二价的金属离子,X为卤素离子。
[化学式12]
A2MX4
化学式12中,A为一价的有机铵离子或Cs+,M为二价的金属离子,X为卤素离子。
这时,M在钙钛矿结构中位于晶胞(unit cell)的中心,X位于晶胞的各面的中心,以M为中心形成八面体(octahedron)结构,A可以位于晶胞的各个角落(corner)。
详细而言,光吸收层可以相互独立地选自满足下述化学式13~16的化合物中的一种或两种以上:
[化学式13]
(R1-NH3 +)MX3
化学式13中,R1为(C1-C24)烷基、(C3-C20)环烷基或(C6-C20)芳基,M为选自Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cr2+、Pd2+、Cd2+、Ge2+、Sn2+、Pb2+及Yb2+中的一种或两种以上的金属离子,X为选自Cl-、Br-及I-中的一种或两种以上的卤素离子。
[化学式14]
(R1-NH3 +)2MX4
化学式14中,R1为(C1-C24)烷基、(C3-C20)环烷基或(C6-C20)芳基,M为选自Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cr2+、Pd2+、Cd2+、Ge2+、Sn2+、Pb2+及Yb2+中的一种或两种以上的金属离子,X为选自Cl-、Br-及I-中的一种或两种以上的卤素离子。
[化学式15]
(R2-C3H3N2 +-R3)MX3
化学式15中,R2为(C1-C24)烷基、(C3-C20)环烷基或(C6-C20)芳基,R3为氢或(C1-C24)烷基,M为选自Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cr2+、Pd2+、Cd2+、Ge2+、Sn2+、Pb2+及Yb2+中的一种或两种以上的金属离子,X为选自Cl-、Br-及I-中的一种或两种以上的卤素离子。
[化学式16]
(R2-C3H3N2 +-R3)2MX4
化学式16中,R2为(C1-C24)烷基、(C3-C20)环烷基或(C6-C20)芳基,R3为氢或(C1-C24)烷基,M为选自Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cr2+、Pd2+、Cd2+、Ge2+、Sn2+、Pb2+及Yb2+中的一种或两种以上的金属离子,X为选自Cl-、Br-及I-中的一种或两种以上的卤素离子。
作为一例,钙钛矿结构的化合物可以为AMXa xXb y或A2MXa xXb y(0<x<3的实数,0<y<3的实数,x+y=3,Xa和Xb为相互不同的卤素离子)。
作为一例,化学式13或化学式14中,R1可以为(C1-C24)的烷基,优选为(C1-C7)烷基,更优选为甲基。作为具体一例,钙钛矿结构的化合物可以为选自CH3NH3PbIxCly(0≤x≤的实数,0≤y≤3的实数及x+y=3)、CH3NH3PbIxBry(0≤x≤3的实数,0≤y≤3的实数及x+y=3)、CH3NH3PbClxBr y(0≤x≤3的实数,0≤y≤3的实数及x+y=3)及CH3NH3PbIxFy(0≤x≤3的实数,0≤y≤3的实数及x+y=3)中的一种或两种以上,此外,可以为选自(C H3NH3)2PbIxCly(0≤x≤4的实数,0≤y≤4的实数及x+y=4)、CH3NH3PbIxBry(0≤x≤4的实数,0≤y≤4的实数及x+y=4)、CH3NH3PbClxBry(0≤x≤4的实数,0≤y≤4的实数及x+y=4)及CH3NH3PbIxFy(0≤x≤4的实数,0≤y≤4的实数及x+y=4)中的一种或两种以上。
作为一例,化学式15或化学式16中,R2可以为(C1-C24)烷基,R3可以为氢或(C1-C24)烷基,优选地,R2为(C1-C7)烷基,R3为氢或(C1-C7)烷基,更优选地,R2为甲基,R3为氢。
优选地,本发明一实施例的钙钛矿结构的化合物可以用下述化学式17表示:
[化学式17]
化学式17中,R21为(C1-C24)烷基、(C3-C20)环烷基或(C6-C20)芳基,R22至R26相互独立地为氢、(C1-C24)烷基、(C3-C20)环烷基或(C6-C20)芳基,M为二价金属离子,Xa为碘离子,Xb为溴离子,x为0.1≤x≤0.3的实数。
优选地,本发明一实施例的光吸收层可以为包含铅的钙钛矿结构的化合物。
本发明一实施例的钙钛矿太阳电池的空穴传输层必须包含本发明的用所述化学式1表示的酞菁衍生物。
具体而言,本发明的空穴传输层必须包含本发明的用所述化学式1表示的酞菁衍生物作为空穴传输物质,其可以单独包含,并且可以进一步包含除了用所述化学式1表示的酞菁衍生物以外的有机空穴传输物质、无机空穴传输物质或它们的混合物。当空穴传输物质为无机空穴传输物质时,无机空穴传输物质可以为具有空穴导电性的,即作为p型半导体的氧化物半导体、硫化物半导体、卤化物半导体或它们的混合物。作为氧化物半导体的例,可以例举如NiO、CuO、CuAlO2、CuGaO2等,作为硫化物半导体的例,可以例举如PbS,作为卤化物半导体的例,可以例举如PbI2等,但并不限定于此。
当空穴传输物质为有机空穴传输物质时,可以包含单分子乃至高分子有机空穴传输物质(空穴导电性有机物)。就有机空穴传输物质而言,只要是在将无机半导体量子点用作染料的常规的基于无机半导体的太阳电池中使用的有机空穴传输物质就可以使用。作为单分子乃至高分子有机空穴传输物质的非限定性一例,可以例举如选自并五苯(pentacene)、香豆素6(coumarin 6,3-(2-苯并噻唑基)-7-(二乙氨基)香豆素(3-(2-benzot hiazolyl)-7-(diethylamino)coumarin))、ZnPC(锌酞菁(zinc phthalocyanine))、CuPC(铜酞菁(copper phthalocyanine))、TiOPC(氧钛酞菁(titanium o xidephthalocyanine))、Spiro-OMeTAD(2,2',7,7'-四(N,N-对-二甲氧基苯胺)-9,9'-螺二芴(2,2',7,7'-tetrkis(N,N-di-p-methoxyphenylamine)-9,9'-spirobi fl uorine))、F16CuPC(铜(II)1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-十六氟-29H,31H-酞菁(copper(II)1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexade cafluoro-29H,31H-phthalocyanine))、SubPc(氯化硼亚酞菁(boron subpht halocyanine chloride))及N3(顺-二(氰硫基)-双(2,2'-联吡啶-4,4'-二羧酸)-钌(II)(cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(I I)))中的一种或两种以上的物质,但并不限定于此。
本发明一实施例的空穴传输层可以将包含用所述化学式1表示的酞菁衍生物的空穴传输物质通过溶液工序来形成。作为根据本发明一实施例进行的溶液工序的一例,可以例举如丝网印刷(screen printing)、旋转涂布(Spin coating)、棒涂布(Bar coating)、凹面涂布(Gravure coating)、刮涂(Blade coating)及辊式涂布(Roll coating)等,但并不限定于此。
下面,将通过本发明的具体实施例作为例示,对本发明进行具体说明,但这并不是为了限定本发明的权利要求书而提出的。
[实施例1]
多孔性TiO2薄膜基板的制备
将涂布有含氟氧化锡的玻璃基板(FTO;F-掺杂(doped)SnO2,8欧姆(ohms)/cm2,皮尔金顿(Pilkington),以下为FTO基板(第一电极))切成25x25mm的大小,并对末端部分进行蚀刻(etched)而部分去除FTO。
通过喷雾热分解法在切断及部分蚀刻的FTO基板上制备50nm厚度的TiO2致密膜作为金属氧化物薄膜。喷雾热分解是利用TAA(乙酰丙酮钛(Titanium acetylacetonate)):EtOH(1:9v/v%)溶液来实施,通过重复对放在维持450℃的热板上的FTO基板上喷洒3秒并停止10秒的方法的方法调节了厚度。
通过以下方法来制备TiO2浆体:平均粒子大小(直径)为50nm的Ti O2粉末(将以TiO2为基准,溶解有1重量%的过氧化钛复合物(titanium p eroxocomplex)水溶液在250℃下进行水热处理12小时来制备)中添加以10重量%的乙基纤维素(ethyl cellulose)的量溶解于乙醇的乙基纤维素溶液,其中每1g的TiO2粉末中添加5ml的所述乙基纤维素溶液,然后每1g的TiO2粉末中添加5g的松油醇(terpinol)并进行混合,然后通过减压蒸馏法去除乙醇,从而制备TiO2浆体。
在制备的TiO2粉末浆体中添加乙醇来制备了用于旋转涂布的TiO2浆料。利用用于旋转涂布的TiO2浆料,并通过旋转涂布方法在FTO基板的TiO2薄膜上进行涂布,并在500℃下进行热处理60分钟,然后在60℃的30mM的TiCl4水溶液中浸泡经过热处理的基板,放置30分钟,然后用去离子水和乙醇进行洗涤及干燥,并在500℃下再次进行热处理30分钟,从而制备多孔性TiO2薄膜(多孔性电子传输层)。
光吸收层溶液的制备
在0℃下,在250ml的二口圆烧瓶中使30ml的氢碘酸(Hydriodic aci d,HI)(在水中为57%,奥德里奇(Aldrich))和27.86ml的乙酸甲脒(forma midine acetate,FAAc,奥德里奇)反应2小时。将在50℃下对反应混合物进行减压蒸馏1小时而得到沉淀物溶解于乙醇中,并使用乙醚进行再结晶,然后在60℃下干燥24小时,从而制备了NH2CH=NH2I(FAI)。
将如上述获得的NH2CH=NH2I(FAI)、甲基碘化铵(CH3NH3I,MAI)及PbI2混合溶解于γ-丁内酯(γ-butyrolactone)和二甲亚砜(dimethylsulfoxid e)的混合溶液(以体积比为8:2)中,从而制备光吸收层溶液,使得满足(F A0.85MA0.15)Pb(I0.85Br0.15)3。以(FA0.85MA0.15)Pb(I0.85Br0.15)3为基准,光吸收层溶液具有0.96M的浓度。
钙钛矿光吸收层的制备
在如上述制备的多孔性TiO2薄膜基板(mp-TiO2/bl-TiO2/FTO)上以1000rpm涂布上述制备的光吸收层溶液((FA0.85MA0.15)Pb(I0.85Br0.15)3溶液)90秒,再以5000rpm涂布30秒,并在100℃下干燥10分钟,从而制备了光吸收层。其中,在第二次旋转涂布步骤中,在基材上逐滴滴入(dropwi se)1ml的甲苯。
用于形成空穴传输层的空穴传输层溶液的制备
为了形成空穴传输层,将0.01g的下述化合物1的酞菁衍生物(西格玛-奥德里奇(sigma-aldrich))作为空穴传输物质溶解于甲苯中,从而制备浓度为10mM的空穴传输层溶液,在其中添加10μl的锂-双(三氟甲磺酰基)酰亚胺(Li-bis(trifluoromethanesulfonyl)imide,Li-TFSI)/乙腈(acetonitr ile)(170mg/1ml)和5μl的TBP(4-叔丁基吡啶(4-tert-Butylpyridine))作为添加剂,从而制备了空穴传输层溶液:
[化合物1]
钙钛矿太阳电池的制备
在上述制备的多孔性电极中,将如上述制备的空穴传输层溶液以3000rpm旋转涂布于如上述制备的光吸收结构体所形成的复合层上,共进行30秒,从而形成了空穴传输层。
之后,用高真空(5x10-6托以下)的热蒸镀机(thermal evaporator)在空穴传输层的上部真空沉积Au,从而形成厚度为70nm的Au电极(第二电极),由此制备了Au/酞菁/(FA0.85MA0.15)Pb(I0.85Br0.15)3(或表示为(FAPbI3)0.85(MAPbBr3)0.15)/mp-TiO2/bl-TiO2/FTO形状的太阳电池。
这种电极的活性面积为0.16cm2。
制备的太阳电池的特性表示在图1~3中。
[比较例1]
除了使用Spiro-OMeTAD[2,2',7,7'-四(N,N-二-对-二甲氧基苯胺)-9,9'-螺二芴](2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobi fluor ine)来代替所述实施例1中的酞菁衍生物以外,与实施例1相同的方法来实施,从而制备了钙钛矿太阳电池,制备的太阳电池的特性表示在图1~3中。
[比较例2]
在所述实施例1中除了使用下述化合物2(西格玛-奥德里奇)来代替所述实施例1的酞菁衍生物以外,与实施例1相同的方法来实施,从而制备了钙钛矿太阳电池,制备的太阳电池的特性表示在图1~3中:
[化合物2]
图1中显示了实施例1(用PC表示)及比较例1(用Spiro-OMeTAD表示)~比较例2(用CuPC表示)的钙钛矿太阳电池根据温度的光电变换效率。如图1所示,可以看出本发明的实施例1及比较例2的钙钛矿太阳电池的光电变换效率在高的温度下也能够维持,但是比较例1的使用Spi ro-OMeTAD[2,2',7,7'-四(N,N-二-对-二甲氧基苯胺)-9,9'-螺二芴](2,2',7,7'-t etrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobi fluorine)单分子的钙钛矿太阳电池的光电变换效率在110℃下极具下降。
因此,可以知道本发明的钙钛矿太阳电池具有高的耐热性。
此外,为了测定本发明的实施例1及比较例1~2的钙钛矿太阳电池的耐久性,在85℃的温度、25~30%的平均相对湿度下放置200小时后,测定了光电变换效率,共实施了2次。即,本发明的实施例1(用PC表示)及比较例1(用Spiro-OMeTAD表示)~比较例2(用CuPC表示)的钙钛矿太阳电池的耐久性是将经过特定时间后的光电变换效率与初期值进行比较并表示在图2中。如图2所示,可以知道本发明的实施例1及比较例2的钙钛矿太阳电池的光电变换效率随着时间的流逝并没有大的变化,维持了与初期值相比为96%以上的光电变换效率,但是比较例1的光电变换效率显著减少。
此外,在图3及下述表1中显示了本发明的实施例1(用PC表示)及比较例2(用CuPC表示)的钙钛矿太阳电池的光电变换效率。
表1
如所述表1及图3所示,可以知道与使用金属配位的酞菁衍生物的比较例2的钙钛矿太阳电池相比,本发明的使用没有金属配位的酞菁衍生物的实施例1的钙钛矿太阳电池的光电变换效率显著得到提高。即,可以知道与比较例2的钙钛矿太阳电池相比,本发明的实施例1的钙钛矿太阳电池具有本领域技术人员不易推导出的水平的约5.4%以上的高光电变换效率。
Claims (6)
2.根据权利要求1所述的钙钛矿太阳电池,其特征在于,所述R1至R4相互独立地为C1-C8烷基。
4.根据权利要求1所述的钙钛矿太阳电池,其特征在于,所述R1至R4相互独立地为叔丁基。
5.根据权利要求1所述的钙钛矿太阳电池,其特征在于,所述钙钛矿太阳电池包含:第一电极;电子传输层,所述电子传输层形成在所述第一电极上;光吸收层,所述光吸收层形成在所述电子传输层上且包含钙钛矿结构的化合物;空穴传输层,所述空穴传输层形成在所述光吸收层上,并且包含用所述化学式1表示的酞菁衍生物;以及第二电极,所述第二电极形成在所述空穴传输层上。
6.根据权利要求5所述的钙钛矿太阳电池,其特征在于,所述空穴传输层是通过将包含用所述化学式1表示的酞菁衍生物的空穴传输物质进行溶液工程而形成。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2016-0041448 | 2016-04-05 | ||
KR1020160041448A KR102012711B1 (ko) | 2016-04-05 | 2016-04-05 | 높은 내열성을 가지는 페로브스카이트 태양전지 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107275485A CN107275485A (zh) | 2017-10-20 |
CN107275485B true CN107275485B (zh) | 2021-01-15 |
Family
ID=59961201
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710218306.8A Active CN107275485B (zh) | 2016-04-05 | 2017-04-05 | 具有高耐热性的钙钛矿太阳电池 |
Country Status (3)
Country | Link |
---|---|
US (1) | US20170287649A1 (zh) |
KR (1) | KR102012711B1 (zh) |
CN (1) | CN107275485B (zh) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108232014B (zh) * | 2017-12-30 | 2020-11-10 | 杭州纤纳光电科技有限公司 | 一种掺杂离子稳定剂的钙钛矿薄膜及其制备方法和应用 |
JP7431722B2 (ja) * | 2018-03-15 | 2024-02-15 | 積水化学工業株式会社 | 太陽電池 |
CN108831955B (zh) * | 2018-06-08 | 2020-08-11 | 海门名驰工业设计有限公司 | 一种硅太阳能电池及其制备方法 |
CN109897047A (zh) * | 2019-02-28 | 2019-06-18 | 兰州大学 | 一种可溶性铜酞菁及其制备方法和应用 |
KR102197017B1 (ko) * | 2019-05-30 | 2020-12-30 | 국민대학교산학협력단 | 장기안정성이 향상된 페로브스카이트 태양전지용 정공 수송 물질의 제조방법, 이에 의하여 제조된 페로브스카이트 태양전지용 정공 수송 물질 및 이를 포함하는 페로브스카이트 태양전지 |
CN114478554B (zh) * | 2020-10-26 | 2023-08-01 | 兰州大学 | 酞菁化合物及其在太阳能电池中的应用 |
EP4333088A1 (en) * | 2021-04-26 | 2024-03-06 | Canon Kabushiki Kaisha | Photoelectric conversion element, photoelectric conversion module having same, photoelectric conversion device, moving body, and building material |
WO2024085073A1 (ja) * | 2022-10-19 | 2024-04-25 | キヤノン株式会社 | 光電変換素子 |
CN115872902A (zh) * | 2022-12-09 | 2023-03-31 | 湖南铱太科技有限公司 | 一种甲脒氢碘酸盐的绿色提纯方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1592529A (zh) * | 2003-08-29 | 2005-03-09 | 株式会社丰田自动织机 | 有机电致发光元件 |
KR20080028783A (ko) * | 2006-09-27 | 2008-04-01 | 한국솔베이정밀화학 주식회사 | 태양전지용 프탈로시아닌 화합물 |
KR20150124397A (ko) * | 2014-04-28 | 2015-11-05 | 한국화학연구원 | 무/유기 하이브리드 페로브스카이트 태양전지용 정공전달 화합물 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5645666B2 (ja) * | 2007-10-31 | 2014-12-24 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | ハロゲン化フタロシアニン類の使用 |
WO2012095524A1 (en) * | 2011-01-14 | 2012-07-19 | Solvay Sa | Phthalocyanine dyes, method of making them, and their use in dye sensitized solar cells |
US9437825B2 (en) * | 2014-04-28 | 2016-09-06 | Korea Research Institute Of Chemical Technology | Hole-transporting material for inorganic/organic hybrid perovskite solar cells |
-
2016
- 2016-04-05 KR KR1020160041448A patent/KR102012711B1/ko active IP Right Grant
-
2017
- 2017-04-04 US US15/478,618 patent/US20170287649A1/en not_active Abandoned
- 2017-04-05 CN CN201710218306.8A patent/CN107275485B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1592529A (zh) * | 2003-08-29 | 2005-03-09 | 株式会社丰田自动织机 | 有机电致发光元件 |
KR20080028783A (ko) * | 2006-09-27 | 2008-04-01 | 한국솔베이정밀화학 주식회사 | 태양전지용 프탈로시아닌 화합물 |
KR20150124397A (ko) * | 2014-04-28 | 2015-11-05 | 한국화학연구원 | 무/유기 하이브리드 페로브스카이트 태양전지용 정공전달 화합물 |
Non-Patent Citations (1)
Title |
---|
《Perovskite solar cell with low cost Cu-phthalocyanine as hole transporting material》;Challuri Vijay Kumar, et al.;《RSC Advances》;20141205;第5卷;3786-3791 * |
Also Published As
Publication number | Publication date |
---|---|
US20170287649A1 (en) | 2017-10-05 |
KR20170114149A (ko) | 2017-10-13 |
KR102012711B1 (ko) | 2019-08-21 |
CN107275485A (zh) | 2017-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107275485B (zh) | 具有高耐热性的钙钛矿太阳电池 | |
Isikgor et al. | Molecular engineering of contact interfaces for high-performance perovskite solar cells | |
Pitchaiya et al. | A review on the classification of organic/inorganic/carbonaceous hole transporting materials for perovskite solar cell application | |
Ahmad et al. | Recent progress in cathode interlayer materials for non‐fullerene organic solar cells | |
Sidhik et al. | Improving the optoelectronic properties of mesoporous TiO2 by cobalt doping for high-performance hysteresis-free perovskite solar cells | |
EP3044817B1 (en) | Inverted solar cell and process for producing the same | |
Armstrong et al. | Oxide contacts in organic photovoltaics: Characterization and control of near-surface composition in indium− tin oxide (ITO) electrodes | |
Li et al. | Graphene oxide modified hole transport layer for CH3NH3PbI3 planar heterojunction solar cells | |
Pae et al. | Improving uniformity and reproducibility of hybrid perovskite solar cells via a low-temperature vacuum deposition process for NiO x hole transport layers | |
Li et al. | Polyethyleneimine high-energy hydrophilic surface interfacial treatment toward efficient and stable perovskite solar cells | |
US20130061930A1 (en) | Surface-modified electrode layers in organic photovoltaic cells | |
Wang et al. | New insight into the Lewis basic sites in metal–organic framework-doped hole transport materials for efficient and stable Perovskite solar cells | |
KR102079941B1 (ko) | 스피로비플루오렌 화합물 및 이를 포함하는 페로브스카이트 태양전지 | |
Zhou et al. | Enhancing performance and uniformity of perovskite solar cells via a solution-processed C70 interlayer for interface engineering | |
KR102028331B1 (ko) | 페로브스카이트 태양전지 | |
Gkini et al. | Enhanced organic and perovskite solar cell performance through modification of the electron-selective contact with a bodipy–porphyrin dyad | |
Sun et al. | Improving efficiency by hybrid TiO2 nanorods with 1, 10-phenanthroline as a cathode buffer layer for inverted organic solar cells | |
Tian et al. | Post-treatment of perovskite films toward efficient solar cells via mixed solvent annealing | |
KR20220078544A (ko) | 페로브스카이트 용액, 이를 이용한 페로브스카이트 막의 제조방법 및 이를 이용한 페로브스카이트 태양전지의 제조방법 | |
Chatterjee et al. | Sequentially deposited antimony-doped CH3NH3PbI3 films in inverted planar heterojunction solar cells with a high open-circuit voltage | |
Yi et al. | Multifunctional polymer capping frameworks enable high-efficiency and stable all-inorganic perovskite solar cells | |
Alagumalai et al. | Interface Modification with Holistically Designed Push–Pull D–π–A Organic Small Molecule Facilitates Band Alignment Engineering, Efficient Defect Passivation, and Enhanced Hydrophobicity in Mixed Cation Planar Perovskite Solar Cells | |
Dehingia et al. | Compositional engineering in α-CsPbI3 toward the efficiency and stability enhancement of all inorganic perovskite solar cells | |
Zhang et al. | Functionalized rare-earth metal cluster-based materials as additives for enhancing the efficiency of perovskite solar cells | |
Liao et al. | Performance enhancement of evaporated CsPbI2Br perovskite solar cells with a CuSCN hole transport layer via a cesium bromide buffer layer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |