TWI719752B - 積層體之製造方法及鈣鈦礦型太陽電池之製造方法 - Google Patents
積層體之製造方法及鈣鈦礦型太陽電池之製造方法 Download PDFInfo
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- TWI719752B TWI719752B TW108145356A TW108145356A TWI719752B TW I719752 B TWI719752 B TW I719752B TW 108145356 A TW108145356 A TW 108145356A TW 108145356 A TW108145356 A TW 108145356A TW I719752 B TWI719752 B TW I719752B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 230000005525 hole transport Effects 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 17
- 230000010287 polarization Effects 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 5
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical group C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 claims description 5
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 claims description 4
- MRSOZKFBMQILFT-UHFFFAOYSA-L diazanium;oxalate;titanium(2+) Chemical compound [NH4+].[NH4+].[Ti+2].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O MRSOZKFBMQILFT-UHFFFAOYSA-L 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- 150000004683 dihydrates Chemical class 0.000 claims 2
- GKMXREIWPASRMP-UHFFFAOYSA-J dipotassium;oxalate;oxygen(2-);titanium(4+) Chemical compound [O-2].[K+].[K+].[Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GKMXREIWPASRMP-UHFFFAOYSA-J 0.000 claims 2
- 239000004793 Polystyrene Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 23
- 239000011521 glass Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- -1 ammonium metal halides Chemical class 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 239000010931 gold Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910001439 antimony ion Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GNRMKQMKBAJVLN-UHFFFAOYSA-J dipotassium;oxalate;oxygen(2-);titanium(4+);dihydrate Chemical compound O.O.[O-2].[K+].[K+].[Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GNRMKQMKBAJVLN-UHFFFAOYSA-J 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910001449 indium ion Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 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
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 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
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- 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
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- 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
-
- 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
- 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
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- 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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- 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
-
- 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
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- 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
- 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
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
-
- H—ELECTRICITY
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Abstract
本發明係提供於依序設有:透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層的鈣鈦礦型太陽電池中成為透光性電極層與電子輸送層之積層體的新穎製造方法。上述方法係在含有Ti成分的處理液中,藉由將成為上述透光性電極層的構件施行陰極極化,而在上述構件上形成成為上述電子輸送層的氧化鈦層。
Description
本發明係關於積層體之製造方法及鈣鈦礦型太陽電池之製造方法。
習知已知有鈣鈦礦型太陽電池(參照專利文獻1)。
鈣鈦礦型太陽電池係例如依序具有:透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本專利特開2015-56430號公報
如上述,鈣鈦礦型太陽電池係例如依序具有:透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層。
本發明目的在於提供:製造此種鈣鈦礦型太陽電池中,成為透光性電極層與電子輸送層之積層體的新穎方法。
本發明者等經深入鑽研,結果發現藉由採用下述構成可達成上述目的,遂完成本發明。
即,本發明係提供以下的[1]~[5]。
[1]一種積層體之製造方法,係於依序具有:透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層的鈣鈦礦型太陽電池之成為上述透光性電極層與上述電子輸送層的積層體的製造方法;係在含有Ti成分的處理液中,藉由將成為上述透光性電極層的構件施行陰極極化,而在上述構件上形成成為上述電子輸送層的氧化鈦層。
[2]如上述[1]所記載的積層體之製造方法,其中,上述處理液中的Ti含有量係0.004mol/L以上且1.300mol/L以下。
[3]如上述[1]或[2]所記載的積層體之製造方法,其中,上述Ti成分係從六氟鈦酸、六氟鈦酸鉀、六氟鈦酸鈉、六氟鈦酸銨、草酸氧鈦銨、草酸氧鈦鉀二水合物、硫酸鈦、及乳酸鈦所構成群組中選擇之至少1種。
[4]如上述[1]~[3]中任一項所記載的積層體之製造方法,其中,將上述成為透光性電極層的構件設為陰極,依0.01A/dm2以上且未滿1.00A/dm2的電流密度通電。
[5]一種鈣鈦礦型太陽電池之製造方法,係使用利用上述[1]~[4]
中任一項所記載的積層體之製造方法所獲得之積層體,製造依序具有透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層的鈣鈦礦型太陽電池。
根據本發明可提供:製造鈣鈦礦型太陽電池中,成為透光性電極層與電子輸送層的積層體的新穎方法。
[鈣鈦礦型太陽電池]
首先,針對鈣鈦礦型太陽電池進行說明。
鈣鈦礦型太陽電池係例如依序具有:透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層。
各層的厚度等係可適當設定。
透光性電極層係可舉例如:ITO(Indium Tin Oxide)膜、FTO(Fluorine-doped Tin Oxide)膜等導電性金屬氧化物的膜。透光性電極層亦可配置於玻璃基板、樹脂薄膜等透明性基板上。
電子輸送層係可舉例如:含有n型半導體之氧化鈦(TiO2)的氧化鈦層。
鈣鈦礦結晶層係可舉例如:含有經摻雜金屬離子之1~4取代或無取代之銨金屬鹵化物的層。
構成1~4取代或無取代之銨金屬鹵化物的金屬,從構成鈣鈦礦構造、且可摻雜的觀點而言,可舉例如週期表第11~15族的金屬,較佳係鉛、銦、鋅、錫、銀、銻、銅,更佳係鉛、錫,特佳係鉛。
構成1~4取代或無取代之銨金屬鹵化物的鹵,較佳係碘、氯、溴,更佳係碘。
此種1~4取代或無取代之銨金屬鹵化物係可舉例如:(CH3NH3)PbI3、(C6H5C2H4NH3)2PbI4、(C10H7CH2NH3)2PbI4、(C6H13NH3)2PbI4等1取代銨鉛鹵化物,較佳係(CH3NH3)PbI3。
在1~4取代或無取代之銨金屬鹵化物中所摻雜的金屬離子,係可舉例如週期表第11~15族金屬的離子,較佳係銦離子、鋅離子、錫離子、銀離子、銻離子、銅離子等,更佳係銦離子、銻離子等。
金屬摻雜量,係相對於構成1~4取代或無取代之銨金屬鹵化物的金屬1莫耳,較佳0.01~0.5莫耳、更佳0.05~0.2莫耳。
電洞輸送層的材料係可舉例如:碘化銅(CuI)等碘化物;層狀鈷氧化物等鈷錯合物;CuSCN;氧化鉬;氧化鎳;4CuBr‧3S(C4H9);有機電洞輸送材等。
集電極層係可舉例如:Au電極層、Ag電極層、Al電極層、Ca電極層等,其中,較佳係Au電極層。
[積層體之製造方法]
本發明積層體的製造方法,概略而言係製造上述鈣鈦礦型太陽電池中成為透光性電極層與電子輸送層之積層體的方法。
更詳言之,在含有Ti成分的處理液中,將成為透光性電極層的構件施行陰極極化。即,將成為透光性電極層的構件作為陰極並通電。藉此,在成為透光性電極層的構件上形成成為電子輸送層的氧化鈦層。另外,反電極係使用白金電極等不溶性電極。
氧化鈦層係推測如下形成。首先,成為透光性電極層的構件的表面係隨氫生成而pH上升。結果,例如當處理液中的Ti成分係六氟鈦酸及/或其鹽的情況,處理液中的六氟鈦酸離子一邊脫F、一邊生成氫氧化鈦。該氫氧化鈦附著於成為透光性電極層的構件的表面,經由後續的洗淨、乾燥等脫水縮合,判斷將形成氧化鈦層。但,除此以外的機制亦屬於本發明範圍內。
成為透光性電極層的構件較佳係具有導電性的構件,例如:ITO膜、FTO膜等導電性金屬氧化物之膜。
成為透光性電極層的構件亦可配置於玻璃基板、樹脂薄膜等透明性基板上。此情況,將具有成為透光性電極層的構件的透明性基板(例如具有FTO膜之玻璃基板)施行陰極極化。此情況,所獲得積層體亦更進一步具有該透明性基板。
處理液係含有用於對所形成氧化鈦層供應Ti(鈦元素)的Ti成分(Ti化合物)。
Ti成分較佳係從六氟鈦酸(H2TiF6)、六氟鈦酸鉀(K2TiF6)、六氟
鈦酸鈉(Na2TiF6)、六氟鈦酸銨((NH4)2TiF6)、草酸氧鈦銨((NH4)2[TiO(C2O4)2])、草酸氧鈦鉀二水合物(K2[TiO(C2O4)2]‧2H2O)、硫酸鈦(Ti(SO4)2)、及乳酸鈦(Ti(OH)2[OCH(CH3)COOH]2)所構成群組中選擇至少1種。
該等之中,從處理液安定性、取得容易性等觀點而言,較佳係六氟鈦酸及/或其鹽(六氟鈦酸鉀、六氟鈦酸鈉、六氟鈦酸銨)。
處理液中的Ti含有量較佳係0.004mol/L以上、更佳係0.010mol/L以上、特佳係0.020mol/L以上。
另一方面,處理液中的Ti含有量較佳係1.300mol/L以下、更佳係1.000mol/L以下、又更佳係0.700mol/L以下、特佳係0.300mol/L以下、最佳係0.150mol/L以下。
處理液的溶劑係使用水。
處理液的pH並無特別的限定,例如:pH2.0~5.0。pH調整時可使用公知的酸成分(例如:磷酸、硫酸等)、或鹼成分(例如:氫氧化鈉、氨水等)。
處理液中,視需要亦可含有:月桂基硫酸鈉、乙炔二醇等界面活性劑。從附著行為的經時安定性觀點而言,在處理液中亦可含有焦磷酸鹽等縮合磷酸鹽。
處理液的液溫較佳係20~80℃、更佳係40~60℃。
處理液亦可更進一步含有傳導助劑。
傳導助劑係可舉例如:硫酸鉀、硫酸鈉、硫酸鎂、硫酸鈣等硫酸鹽;硝酸鉀、硝酸鈉、硝酸鎂、硝酸鈣等硝酸鹽;氯化鉀、氯化
鈉、氯化鎂、氯化鈣等氯化物鹽等等。
處理液中的傳導助劑含有量,較佳係0.010~1.000mol/L、較佳係0.020~0.500mol/L。
施行陰極極化時的電流密度較佳係0.01A/dm2以上、更佳係0.10A/dm2以上、特佳係0.20A/dm2以上。
另一方面,施行陰極極化時的電流密度較佳係未滿1.00A/dm2、更佳係0.80A/dm2以下、特佳係0.60A/dm2以下。
通電時間係可適當設定,例如5~60秒、較佳係10~40秒。
經陰極極化後,亦可施行水洗。
水洗的方法並無特別的限定,可舉例如:在陰極極化後浸漬於水中的方法等。水洗時所使用之水的溫度(水溫)較佳係40~90℃。
水洗時間較佳係超過0.5秒、更佳係1.0~5.0秒。
再者,亦可取代水洗、或經水洗後,施行乾燥。乾燥時的溫度與方式並無特別的限定,可應用例如使用普通乾燥機或電爐的乾燥方式。乾燥溫度較佳係100℃以下。
[鈣鈦礦型太陽電池之製造方法]
本發明鈣鈦礦型太陽電池的製造方法,係使用依照上述本發明積層體的製造方法所獲得之積層體,製造依序具有:透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層的鈣鈦礦型太陽電池之方法。
例如在依本發明積層體之製造方法所獲得之積層體中,於成為
電子輸送層的氧化鈦層上,依序形成成為鈣鈦礦結晶層、電洞輸送層及集電極層之層。
鈣鈦礦結晶層係例如在含有經摻雜In離子的(CH3NH3)PbI3之層時,首先,將由PbI2及InCl3依Pb與In莫耳比成為所需摻雜量之方式混合的混合溶液,利用旋塗法等在成為電子輸送層的氧化鈦層上成膜,並乾燥。接著,浸漬於CH3NH3I溶液中,經乾燥。混合溶液與溶液的溶劑係可舉例如:γ-丁內酯、N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、異丙醇等極性溶劑。乾燥與浸漬的溫度及時間等係可適當設定。
電洞輸送層係例如藉由重複施行在鈣鈦礦結晶層上滴下電洞輸送層材料的溶液、形成均勻表面的操作而形成。溶液的溶劑係可舉例如:正丙基硫醚等有機溶劑。
集電極層係例如在電洞輸送層上,藉由蒸鍍Au等金屬而形成。
形成各層的方法並不侷限於該等方法,可適當使用習知公知方法。
[實施例]
以下,列舉實施例針對本發明進行具體說明。惟,本發明並不侷限於以下實施例。
<成為透光性電極層的構件之準備>
準備在玻璃基板(30mm×35mm、厚度0.7mm)其中一面上,利用濺鍍積層了FTO(Fluorine-doped Tin Oxide)膜的具有FTO膜之玻璃基板(Ideal Star公司製)。將該具有FTO膜之玻璃基板使用為具有
成為透光性電極層之構件的透明性基板。
<成為透光性電極層與電子輸送層的積層體之製作>
使用所準備的具有FTO膜之玻璃基板(具有成為透光性電極層之構件的透明性基板),如下述製作成為透光性電極層與電子輸送層的積層體。
首先,調製含有0.040mol/L六氟鈦酸鉀(K2TiF6)與0.10mol/L硫酸鉀(K2SO4),且經利用氫氧化鉀調整pH為4.0的處理液(以下簡稱「處理液」)。
其次,將所準備的具有FTO膜之玻璃基板,浸漬於將Semi Clean M4(橫濱油脂工業公司製)經離子交換水稀釋20倍的洗淨液中,施行10分鐘超音波洗淨。然後,從洗淨液中取出具有FTO膜之玻璃基板,浸漬於離子交換水中,施行10分鐘超音波洗淨。
將經洗淨的具有FTO膜之玻璃基板浸漬於所調製的處理液(液溫:50℃)中。在處理液中,將具有FTO膜之玻璃基板,依電流密度0.40A/dm2、通電時間20秒的條件施行陰極極化。然後,在25℃水槽中浸漬2.0秒鐘而施行水洗後,使用鼓風機於室溫中施行乾燥。藉此,在具有FTO膜之玻璃基板之FTO膜上,依厚度約50nm形成成為電子輸送層的氧化鈦層。依此,製得形成了氧化鈦層的具有FTO膜之玻璃基板(成為透光性電極層與電子輸送層的積層體)。
<鈣鈦礦型太陽電池之製作>
使用所製作的積層體,依如下述製作鈣鈦礦型太陽電池。
《鈣鈦礦結晶層之形成》
首先,調製經調整為Pb濃度0.9mol/L、In濃度0.1mol/L的PbI2-InCl3混合溶液。又,調製10mg/mg的CH3NH3I之異丙醇溶液。
在室溫下,於形成了氧化鈦層之具有FTO膜之玻璃基板上,利用旋塗將上述所調製PbI2-InCl3混合溶液施行成膜,再於70℃下施行加熱乾燥30分鐘,經放冷,形成In摻雜PbI3層。將其在室溫下,浸漬於上述所調製CH3NH3I的異丙醇溶液中20秒鐘,然後為了馬上施行清洗而在異丙醇中浸漬1分鐘,再利用旋塗機除去多餘溶液。接著,依70℃施行30分鐘加熱乾燥,經放冷,然後,利用氣動噴槍除去多餘溶液。藉此,在氧化鈦層上形成In摻雜(CH3NH3)PbI3層(鈣鈦礦結晶層)。
《電洞輸送層之形成》
將In摻雜(CH3NH3)PbI3層、與形成了氧化鈦層之具有FTO膜之玻璃基板,放置於65℃加熱板上。在此狀態下,於In摻雜(CH3NH3)PbI3層上,一滴滴下CuSCN濃度0.05mol/L的正丙基硫醚溶液,並利用玻璃棒形成均勻表面,重複此項操作計30次,依厚度0.5~2μm形成CuSCN層(電洞輸送層)。
《集電極層之形成》
在CuSCN層(電洞輸送層)上,利用蒸鍍法形成Au電極層(集電極層)。更詳言之,將對應於電極形狀的遮罩、與已形成至電洞輸送層的玻璃基板,設置於處理室內。在經減壓過的處理室內將金線施行電阻加熱,而隔著遮罩,使金在電洞輸送層上成膜。
依此製作在玻璃基板其中一面上,依序積層了:FTO膜(透光性電極層)、氧化鈦層(電子輸送層)、In摻雜(CH3NH3)PbI3層(鈣鈦礦結晶層)、CuSCN層(電洞輸送層)、及Au電極層(集電極層)的鈣鈦礦型太陽電池。
<鈣鈦礦型太陽電池之評價>
針對所製作的鈣鈦礦型太陽電池,施行下述評價。
使用模擬太陽光光源裝置(SAN-EI Electric公司製、XES-502S),將具AM1.5G光譜分佈、且具100mW/cm2光強度的模擬太陽光,針對鈣鈦礦型太陽電池從FTO膜側施行照射。在此狀態下,使用線性掃描伏安(LSV)測定裝置(Hokuto Denko公司製、HZ-5000),測定鈣鈦礦型太陽電池的光電流-電壓分佈。
由該分佈計算出短路電流(絕對值、Jsc):8.39mA/cm2、開路電壓(Voc):0.540V、曲線因子(FF):0.57、及能量轉換效率(PCE):2.59%。
Claims (6)
- 一種積層體之製造方法,係依序具有透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層的鈣鈦礦型太陽電池之成為上述透光性電極層與上述電子輸送層的積層體的製造方法;係在含有Ti成分的處理液中,藉由將成為上述透光性電極層的構件施行陰極極化,而在成為上述透光性電極層的構件上形成成為上述電子輸送層的氧化鈦層;在將成為上述透光性電極層的構件施行陰極極化前,未使聚苯乙烯粒子吸黏於成為上述透光性電極層的構件上。
- 如請求項1之積層體之製造方法,其中,上述處理液中的Ti含有量係0.004mol/L以上且1.300mol/L以下。
- 如請求項1之積層體之製造方法,其中,上述Ti成分係從六氟鈦酸、六氟鈦酸鉀、六氟鈦酸鈉、六氟鈦酸銨、草酸氧鈦銨、草酸氧鈦鉀二水合物、硫酸鈦、及乳酸鈦所構成群組中選擇之至少1種。
- 如請求項2之積層體之製造方法,其中,上述Ti成分係從六氟鈦酸、六氟鈦酸鉀、六氟鈦酸鈉、六氟鈦酸銨、草酸氧鈦銨、草酸氧鈦鉀二水合物、硫酸鈦、及乳酸鈦所構成群組中選擇之至少1種。
- 如請求項1至4中任一項之積層體之製造方法,其中,將上述成為透光性電極層的構件作為陰極,依0.01A/dm2以上且未滿1.00A/dm2的電流密度通電。
- 一種鈣鈦礦型太陽電池之製造方法,係使用利用 請求項1至5中任一項之積層體之製造方法所獲得之積層體,製造依序具有透光性電極層、電子輸送層、鈣鈦礦結晶層、電洞輸送層及集電極層的鈣鈦礦型太陽電池。
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