TWI533461B - Transparent electrode substrate, method for producing the same, electronic device and solar cell having the transparent electrode substrate - Google Patents
Transparent electrode substrate, method for producing the same, electronic device and solar cell having the transparent electrode substrate Download PDFInfo
- Publication number
- TWI533461B TWI533461B TW100149395A TW100149395A TWI533461B TW I533461 B TWI533461 B TW I533461B TW 100149395 A TW100149395 A TW 100149395A TW 100149395 A TW100149395 A TW 100149395A TW I533461 B TWI533461 B TW I533461B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- transparent
- electrode substrate
- transparent electrode
- metal mesh
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims description 159
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 133
- 239000002184 metal Substances 0.000 claims description 133
- 238000000034 method Methods 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000059 patterning Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 236
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000463 material Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000010408 film Substances 0.000 description 22
- 239000004065 semiconductor Substances 0.000 description 18
- 239000010409 thin film Substances 0.000 description 15
- -1 polyethylene terephthalate Polymers 0.000 description 13
- 239000000956 alloy Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 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 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 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 7
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000005240 physical vapour deposition Methods 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910003472 fullerene Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000007733 ion plating Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002098 polyfluorene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052718 tin Inorganic materials 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
- 229910052719 titanium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001374 Invar Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 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
- 125000003118 aryl group Chemical group 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- OYQCBJZGELKKPM-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O-2].[Zn+2].[O-2].[In+3] OYQCBJZGELKKPM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- 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
Description
本發明係關於一種透明電極基板、其製造方法及具有該透明電極基板之太陽能電池。進一步詳言之，本發明係關於一種光線穿透率高的透明電極基板、其製造方法、具有該透明電極基板之電子裝置及太陽能電池。The present invention relates to a transparent electrode substrate, a method of manufacturing the same, and a solar cell having the transparent electrode substrate. More specifically, the present invention relates to a transparent electrode substrate having a high light transmittance, a method of manufacturing the same, an electronic device having the transparent electrode substrate, and a solar cell.
近年來，在有機電致發光(有機EL)、包含有機太陽能電池之各種太陽能電池、觸控面板或行動電話、電子紙等，正熱烈地探討具有透明導電層之透明電極基板。In recent years, transparent electrode substrates having a transparent conductive layer have been actively explored in organic electroluminescence (organic EL), various solar cells including organic solar cells, touch panels, mobile phones, and electronic paper.
一般而言，在玻璃基板等之基板上已形成透明導電層之透明電極基板係作為太陽能電池、有機EL等之電子裝置的電極所使用。然而，將通常之摻雜錫的氧化銦(以下，稱為ITO)等之金屬氧化物層作為透明導電層使用的透明電極基板，除了表面電阻係數不低以外，ITO本身之體積電阻係數也高。作為有機EL、各種太陽能電池、觸控面板、行動電話、電子紙等之透明導電基板係要求例如具有5Ω/□左右以下之表面電阻係數的透明導電基板。In general, a transparent electrode substrate in which a transparent conductive layer is formed on a substrate such as a glass substrate is used as an electrode of an electronic device such as a solar cell or an organic EL. However, a transparent electrode substrate using a metal oxide layer such as tin-doped indium oxide (hereinafter referred to as ITO) as a transparent conductive layer has a high volume resistivity of ITO itself except that the surface resistivity is not low. . A transparent conductive substrate such as an organic EL, various solar cells, a touch panel, a mobile phone, or an electronic paper is required to have a transparent conductive substrate having a surface resistivity of, for example, about 5 Ω/□.
對於如此之要求，已探討將體積電阻係數較透明導電層為極低的金屬材料層作為輔助電極使用的透明電極基板。For such a request, a transparent electrode substrate using a metal material layer having a volume resistivity lower than that of a transparent conductive layer as an auxiliary electrode has been considered.
例如，於專利文獻1中，揭示一種附透明導電膜的基體，其係在基板上，依序積層透明氧化物層、金屬層、透明氧化物層而成。然而，於如此之構造中，光線穿透率低，作為薄膜裝置之透明電極基板並不實用。另外，由於金屬層積層於透明氧化物層之整面，具有因金屬層之劣化而使得使用該附透明導電膜的基體之薄膜裝置的耐久性成為問題之情形。For example, Patent Document 1 discloses a substrate having a transparent conductive film formed by sequentially laminating a transparent oxide layer, a metal layer, and a transparent oxide layer on a substrate. However, in such a configuration, the light transmittance is low, and it is not practical as a transparent electrode substrate of a thin film device. Further, since the metal layer is laminated on the entire surface of the transparent oxide layer, there is a problem that the durability of the thin film device using the substrate with the transparent conductive film is a problem due to deterioration of the metal layer.
另外，於專利文獻2中，揭示一種電致發光面板，其係含有：在包含在基板上所形成的ITO之第1電極上形成包含金屬的長條狀或網目狀之輔助電極層，在其上劃定發光區域之發光層與在其上所形成的第2電極。Further, Patent Document 2 discloses an electroluminescence panel comprising: an elongated or mesh-shaped auxiliary electrode layer containing a metal formed on a first electrode of ITO formed on a substrate; The light-emitting layer of the light-emitting region and the second electrode formed thereon are defined.
還有，於專利文獻3中，揭示一種有機薄膜太陽能電池，其係具有：透明基板、包含在該透明基板上順序不同地積層的金屬膜的網目電極及透明電極、在該網目電極及透明電極之上所形成的光電轉換層、與在該光電轉換層上所形成的對向電極。Further, Patent Document 3 discloses an organic thin film solar cell including a transparent substrate, a mesh electrode including a metal film laminated on the transparent substrate in a different order, and a transparent electrode, and the mesh electrode and the transparent electrode. The photoelectric conversion layer formed on the upper surface and the counter electrode formed on the photoelectric conversion layer.
然而，於如此之構造中，具有引起因金屬腐蝕所造成的劣化等之問題的可能性。However, in such a configuration, there is a possibility of causing problems such as deterioration due to metal corrosion.
於專利文獻4中，揭示一種透明導電性薄膜，其係在透明基材片中至少之一側面具有卑金屬或包含卑金屬的合金製導電性金屬網目層、與包含導電性高分子層的透明導電性層；於專利文獻5中，揭示一種透明導電膜，其係在透明支撐體上具有藉至少一種金屬所形成的網目狀導電層之透明導電膜，且在該導電層之上設置含有遷移防止劑之透明導電層；於專利文獻6中，揭示一種色素增感型太陽能電池用電極，其係在基板上由形成透明導電膜所構成的色素增感型太陽能電池用電極中，在該基板與透明導電膜之間設置電阻值較該透明導電膜還低的導電體。Patent Document 4 discloses a transparent conductive film which has a base metal or a conductive metal mesh layer containing a base metal on at least one side surface of a transparent base material sheet, and a transparent conductive layer including a conductive polymer layer. Conductive layer; Patent Document 5 discloses a transparent conductive film having a transparent conductive film having a mesh-like conductive layer formed of at least one metal on a transparent support, and having a migration on the conductive layer A transparent conductive layer for a preventive agent, and an electrode for a dye-sensitized solar cell, which is an electrode for a dye-sensitized solar cell comprising a transparent conductive film formed on a substrate, is disclosed in Patent Document 6 An electric conductor having a lower resistance value than the transparent conductive film is disposed between the transparent conductive film and the transparent conductive film.
然而，作為太陽能電池、有機EL元件等之電子裝置的電極，於透明電極基板中，要求透明性或導電性及耐久性之進一步提高。However, as an electrode of an electronic device such as a solar cell or an organic EL device, transparency, conductivity, and durability are further improved in the transparent electrode substrate.
專利文獻1 日本特開平10-241464Patent Document 1 Japanese Special Kaiping 10-241464
專利文獻2 日本特開2008-103305Patent Document 2 Japanese Special Open 2008-103305
專利文獻3 日本特開2010-157681Patent Document 3 Japanese Special Open 2010-157681
專利文獻4 日本特開2009-081104Patent Document 4 Japanese Special Open 2009-081104
專利文獻5 日本特開2009-146678Patent Document 5 Japanese Special Open 2009-146678
專利文獻6 日本特開2004-296669Patent Document 6 Japanese Special Open 2004-296669
本發明係有鑒於如此之事實所完成者，本發明之目的係解決如上述之問題，提供一種光線穿透率高、具優越之導電性的透明電極基板、其製造方法及具有該透明電極基板之電子裝置。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a transparent electrode substrate having high light transmittance and excellent electrical conductivity, a method of manufacturing the same, and a transparent electrode substrate. Electronic device.
為了解決如上述之問題，本發明人等鑽研探討之結果發現藉由作成如下列之層構造而能夠解決上述問題，於是完成本發明。In order to solve the problems as described above, the inventors of the present invention have found that the above problems can be solved by creating a layer structure as follows, and thus the present invention has been completed.
亦即，本發明係提供如下所述：That is, the present invention provides the following:
(1)一種透明電極基板，其係由在透明基材之一側面，積層埋設有導電性金屬網目層的透明導電層所構成。(1) A transparent electrode substrate comprising a transparent conductive layer in which a conductive metal mesh layer is laminated on one side of a transparent substrate.
(2)記載於上述(1)之透明電極基板，其中該透明導電層係由金屬氧化物所構成的層。(2) The transparent electrode substrate according to (1) above, wherein the transparent conductive layer is a layer composed of a metal oxide.
(3)記載於上述(1)之透明電極基板，其中該導電性金屬網目層的厚度為1至100 nm。(3) The transparent electrode substrate according to (1) above, wherein the conductive metal mesh layer has a thickness of from 1 to 100 nm.
(4)記載於上述(1)之透明電極基板，其中該導電性金屬網目層的開口部之開口率為75%以上。(4) The transparent electrode substrate according to (1) above, wherein an opening ratio of the opening of the conductive metal mesh layer is 75% or more.
(5)記載於上述(1)之透明電極基板，其中該透明導電層係以氧化銦作為主要成分之層。(5) The transparent electrode substrate according to (1) above, wherein the transparent conductive layer is a layer containing indium oxide as a main component.
(6)記載於上述(1)之透明電極基板，其中該導電性金屬網目層係由金、銀、銅、鉑、鋁、鎳與鉻所選出的至少一種所構成的層。(6) The transparent electrode substrate according to (1) above, wherein the conductive metal mesh layer is a layer composed of at least one selected from the group consisting of gold, silver, copper, platinum, aluminum, nickel, and chromium.
(7)一種透明電極基板之製造方法，其係藉由在透明基材之一側面形成第1透明導電層，在該透明導電層上形成導電性金屬層，光阻圖案化處理該導電性金屬層而形成導電性金屬網目層，在該金屬網目層的面形成第2透明導電層而經該透明導電層被覆該導電性金屬網目層。(7) A method of producing a transparent electrode substrate, wherein a first transparent conductive layer is formed on one side surface of a transparent substrate, a conductive metal layer is formed on the transparent conductive layer, and the conductive metal is patterned by photoresist A conductive metal mesh layer is formed in a layer, and a second transparent conductive layer is formed on the surface of the metal mesh layer, and the conductive metal mesh layer is coated through the transparent conductive layer.
(8)記載於上述(7)之透明電極基板之製造方法，其中在該透明基材之一側面所形成的第1透明導電層的厚度為10至1000 nm。(8) The method for producing a transparent electrode substrate according to (7) above, wherein the first transparent conductive layer formed on one side surface of the transparent substrate has a thickness of 10 to 1000 nm.
(9)記載於上述(7)或(8)之透明電極基板之製造方法，其中在該金屬網目層的面所形成的第2透明導電層的厚度為1至200 nm。(9) The method for producing a transparent electrode substrate according to (7) or (8) above, wherein the second transparent conductive layer formed on the surface of the metal mesh layer has a thickness of 1 to 200 nm.
(10)一種電子裝置，其係具有記載於上述(1)至(6)中任一項之透明電極基板。(10) An electronic device comprising the transparent electrode substrate according to any one of the above (1) to (6).
(11)一種太陽能電池，其係具有記載於上述(1)至(6)中任一項之透明電極基板。(11) A solar cell comprising the transparent electrode substrate according to any one of the above (1) to (6).
本發明之透明電極基板係高度維持光線穿透率，同時表面電阻係數也低，具優越之導電性。另外，於使用本發明之透明電極基板的太陽能電池中，可以獲得高的光電轉換效率。The transparent electrode substrate of the present invention maintains light transmittance at a high level, and has a low surface resistivity and excellent electrical conductivity. Further, in the solar cell using the transparent electrode substrate of the present invention, high photoelectric conversion efficiency can be obtained.
以下，針對本發明而詳加說明。Hereinafter, the present invention will be described in detail.
本發明之透明電極基板係由在透明基材之一側面，積層埋設有導電性金屬網目層的透明導電層所構成者。The transparent electrode substrate of the present invention comprises a transparent conductive layer in which a conductive metal mesh layer is laminated on one side of a transparent substrate.
以下，針對本發明之透明電極基板之構造材料而加以說明。Hereinafter, the material of the transparent electrode substrate of the present invention will be described.
以透明基材而言係從透明性之觀點，較佳為全光線透射率為85%以上者，作為如此之透明基板而言，一般係使用玻璃(板)或塑膠薄膜等。In the transparent substrate, from the viewpoint of transparency, the total light transmittance is preferably 85% or more. As such a transparent substrate, glass (plate), a plastic film, or the like is generally used.
例如，作為塑膠薄膜之種類而言，係可舉例包含聚對苯二甲酸乙二酯、聚對萘二甲酸乙二酯、三乙醯基纖維素、間規(syndiotactic)聚苯乙烯、聚苯硫醚、聚碳酸酯、聚芳香酯、聚碸、聚酯碸、聚醚醯亞胺、環狀聚烯烴等的塑膠薄膜。其中，作為具優越之機械強度、耐久性、透明性、泛用性等者，較佳為包含玻璃(板)或聚對苯二甲酸乙二酯、聚對萘二甲酸乙二酯、聚芳香酯等的塑膠薄膜。從均衡機械強度、耐久性、及透明性之觀點，基材之厚度較佳為3 μm至5 mm，更佳為5 μm至3 mm，特佳為10 μm至1 mm。For example, as a kind of plastic film, polyethylene terephthalate, polyethylene naphthalate, triethylene sulfonate, syndiotactic polystyrene, poly benzene may be exemplified. A plastic film such as thioether, polycarbonate, polyarylate, polyfluorene, polyester oxime, polyether quinone, or cyclic polyolefin. Among them, as a superior mechanical strength, durability, transparency, versatility, etc., it is preferable to contain glass (plate) or polyethylene terephthalate, polyethylene naphthalate, poly aromatic A plastic film such as an ester. The thickness of the substrate is preferably from 3 μm to 5 mm, more preferably from 5 μm to 3 mm, particularly preferably from 10 μm to 1 mm, from the viewpoint of equalizing mechanical strength, durability, and transparency.
雖然作為透明導電層之材料並非予以特別限定者，但可舉例導電性金屬氧化物，例如：銦、錫、鋅、鎵等之氧化物及此等之元素的複合氧化物等。The material of the transparent conductive layer is not particularly limited, and examples thereof include conductive metal oxides such as oxides such as indium, tin, zinc, and gallium, and composite oxides of these elements.
更具體而言，可舉例摻雜錫之氧化銦(ITO)、氧化銥(IrO2)、氧化銦(In2O3)、氧化錫(SnO2)、摻雜氟之氧化錫(FTO)、氧化銦-氧化鋅(IZO)、氧化鋅(ZnO)、摻雜鎵之氧化鋅(GZO)、摻雜鋁之氧化鋅(AZO)、氧化鉬(MoO3)、氧化鈦(TiO2)等。More specifically, tin-doped indium oxide (ITO), yttrium oxide (IrO 2 ), indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), fluorine-doped tin oxide (FTO), Indium oxide-zinc oxide (IZO), zinc oxide (ZnO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AZO), molybdenum oxide (MoO 3 ), titanium oxide (TiO 2 ), and the like.
透明導電層之厚度較佳為20至1200 nm，進一步較佳為30至1000 nm，特佳為35至700 nm。The thickness of the transparent conductive layer is preferably from 20 to 1200 nm, further preferably from 30 to 1000 nm, and particularly preferably from 35 to 700 nm.
在透明基材上形成透明導電層之方法並未予以特別限定，能夠利用習知之方法。例如，能夠利用真空蒸鍍、濺鍍、離子電鍍等之PVD(物理氣相蒸鍍)；或是熱CVD、原子層堆積(ALD)等CVD(化學氣相蒸鍍)等之乾式程序或濕式程序的噴射法或網版印刷法等之習知方法而形成此等之透明導電層材料，按照透明基材或透明導電層之材料而予以適當選擇。The method of forming the transparent conductive layer on the transparent substrate is not particularly limited, and a conventional method can be used. For example, PVD (physical vapor deposition) such as vacuum deposition, sputtering, ion plating, or dry process such as thermal CVD, atomic layer deposition (ALD), or the like can be used or wet. The transparent conductive layer material is formed by a conventional method such as a jet method or a screen printing method, and is appropriately selected depending on the material of the transparent substrate or the transparent conductive layer.
透明導電層係表面電阻係數較佳為50 Ω/□以下，進一步較佳為10 Ω/□以下。The surface resistivity of the transparent conductive layer is preferably 50 Ω/□ or less, and more preferably 10 Ω/□ or less.
若表面電阻係數超過50 Ω/□時，例如將透明電極基板應用於薄膜太陽能電池之情形，由於內部電阻大，因光電轉換效率降低而不佳。When the surface resistivity exceeds 50 Ω/□, for example, when a transparent electrode substrate is applied to a thin film solar cell, since the internal resistance is large, the photoelectric conversion efficiency is not preferable.
於本發明之透明電極基板中，透明導電層係利用在內部埋設有導電性金屬網目層的形狀而積層於透明基材之一側面。In the transparent electrode substrate of the present invention, the transparent conductive layer is laminated on one side surface of the transparent substrate by a shape in which a conductive metal mesh layer is buried.
埋設有導電性金屬網目層的透明導電層係形成於透明基材之一側面，導電性金屬網目層較佳為埋設於接近透明導電層之透明基材側與相反側的表面。The transparent conductive layer in which the conductive metal mesh layer is embedded is formed on one side of the transparent substrate, and the conductive metal mesh layer is preferably buried on the side opposite to the transparent substrate side and the opposite side of the transparent conductive layer.
亦即，導電性金屬網目層係將透明導電層整體之厚度設為100%之情形，較佳為埋設於距離透明導電層整體厚度之透明基材側50至99%之範圍的位置。That is, the conductive metal mesh layer has a thickness of 100% as a whole of the transparent conductive layer, and is preferably embedded in a range of 50 to 99% of the transparent substrate side from the entire thickness of the transparent conductive layer.
若導電性金屬網目層所埋設的位置為此範圍的話，導電性為良好。認為此係由於藉由將導電性優異的導電性金屬網目層埋設於接近與透明導電層之透明基材相反側之面，能夠使透明導電層之表面電阻係數降低，並使導電性提高。When the position where the conductive metal mesh layer is buried is in this range, the conductivity is good. This is considered to be because the conductive metal mesh layer having excellent conductivity is buried on the surface opposite to the transparent substrate of the transparent conductive layer, whereby the surface resistivity of the transparent conductive layer can be lowered and the conductivity can be improved.
於本發明之透明電極基板中，導電性金屬網目層係由金屬或合金所構成，埋設於透明基材之一側面所形成的透明導電層中。作為導電性金屬網目層而言，係可舉例因金屬柵極圖案所導致的微細網目構造之層。In the transparent electrode substrate of the present invention, the conductive metal mesh layer is made of a metal or an alloy and is embedded in a transparent conductive layer formed on one side of the transparent substrate. As the conductive metal mesh layer, a layer of a fine mesh structure due to a metal gate pattern can be exemplified.
導電性金屬網目層係具有貫穿於厚度方向之開口部。The conductive metal mesh layer has an opening penetrating through the thickness direction.
從透明性之觀點，開口部之開口率較佳為75%以上，更佳為80%以上，進一步較佳為90%以上。開口率係如下方式所求得：The aperture ratio of the opening portion is preferably 75% or more, more preferably 80% or more, and still more preferably 90% or more from the viewpoint of transparency. The aperture ratio is obtained as follows:
開口率(%)=[開口部之面積/(導電性金屬網目層之面積+開口部之面積)]×100%。The aperture ratio (%) = [area of the opening / (area of the conductive metal mesh layer + area of the opening)] × 100%.
導電性金屬網目層的形狀最好具有開口部，但並未予以特別限定。例如，可舉例如第2圖所示之正方形、長方形、六角形等之有周期性的網目形狀等。The shape of the conductive metal mesh layer preferably has an opening, but is not particularly limited. For example, a periodic mesh shape such as a square, a rectangle, or a hexagon as shown in FIG. 2 may be mentioned.
開口部之間距較佳為0.1至10 mm，更佳為0.5至5 mm。開口部之間距低於0.1 mm之情形，具有透明性降低之情形；若超過10 mm時，難以獲得導電性提高之效果。The distance between the openings is preferably from 0.1 to 10 mm, more preferably from 0.5 to 5 mm. When the distance between the openings is less than 0.1 mm, the transparency is lowered. When it exceeds 10 mm, it is difficult to obtain an effect of improving the conductivity.
導電性金屬網目層的線寬較佳為10 nm至1000 μm，更佳為20 nm至500 μm。若線寬超過1000 μm時，由於開口率變低，則有透明性降低之情形；若低於10 nm時，則難以獲得導電性提高之效果。The line width of the conductive metal mesh layer is preferably from 10 nm to 1000 μm, more preferably from 20 nm to 500 μm. When the line width exceeds 1000 μm, the transparency is lowered because the aperture ratio is lowered, and when it is less than 10 nm, it is difficult to obtain an effect of improving conductivity.
導電性金屬網目層的厚度較佳為1至100 nm，更佳為2至50 nm左右。藉由設為1 nm以上，能夠維持導電性；藉由設為100 nm以下，能夠薄化地保持整體的厚度，且能夠節省材料之浪費。The thickness of the conductive metal mesh layer is preferably from 1 to 100 nm, more preferably from about 2 to 50 nm. When the thickness is 1 nm or more, the conductivity can be maintained, and when the thickness is 100 nm or less, the overall thickness can be kept thin, and waste of materials can be saved.
作為為了形成導電性金屬網目層的材料而言，可舉例金屬或合金。例如：可舉例金、銀、銅、鋁、鈦、鉻、鐵、鈷、鎳、鋅、錫、銥、銦、鎢、鉬、鉑、銥、鉿、鈮、鉭、鎢、鎂等之單體的金屬，或是以包含此等群組的金屬中之至少一種作為主體之合金等。此等之中，從具有耐腐蝕性且導電性高的觀點，較佳為金、銀、銅、鉑、鋁、鈦、鎳及鉻之金屬，更佳為金、銀、銅、鉑、鋁、鎳及鉻。As a material for forming the conductive metal mesh layer, a metal or an alloy can be exemplified. For example: gold, silver, copper, aluminum, titanium, chromium, iron, cobalt, nickel, zinc, tin, antimony, indium, tungsten, molybdenum, platinum, rhodium, ruthenium, osmium, iridium, tungsten, magnesium, etc. The metal of the body is an alloy or the like mainly composed of at least one of metals including such groups. Among these, from the viewpoint of corrosion resistance and high conductivity, metals such as gold, silver, copper, platinum, aluminum, titanium, nickel, and chromium are preferable, and gold, silver, copper, platinum, and aluminum are more preferable. , nickel and chromium.
作為合金而言，能夠適當選擇不銹鋼、鎳-鉻、英高鎳(Inconel)(商品名)、青銅、磷青銅、黃銅、硬鋁、白銅、恆範鋼(invar)、莫內爾合金(Monel)、鎳磷合金等之金屬磷化合物；鎳硼等之金屬硼化合物；氮化鈦等之金屬氮化物等。尤其，因為以銅為主體之合金、以鎳為主體之合金、以鈷為主體之合金、以鉻為主體之合金、以鋁為主體之合金係具優越之導電性、加工性也良好而較佳被使用。As the alloy, stainless steel, nickel-chromium, Inconel (trade name), bronze, phosphor bronze, brass, hard aluminum, white copper, invar, and monel alloy can be appropriately selected ( Monel), a metal phosphorus compound such as a nickel phosphorus alloy; a metal boron compound such as nickel boron; a metal nitride such as titanium nitride. In particular, copper-based alloys, nickel-based alloys, cobalt-based alloys, chromium-based alloys, and aluminum-based alloys have superior electrical conductivity and processability. Good is used.
導電性金屬網目層可以為由金屬或合金所構成的單層，也可以為積層由至少二種以上之金屬或合金所構成的層之多層構造。The conductive metal mesh layer may be a single layer made of a metal or an alloy, or may have a multilayer structure in which a layer composed of at least two kinds of metals or alloys is laminated.
接著，針對將導電性金屬網目層埋設於透明基材上所設置的透明導電層之內部的方法而加以說明。Next, a method of embedding a conductive metal mesh layer inside the transparent conductive layer provided on the transparent substrate will be described.
埋設導電性金屬網目層的方法並未予以特別限定，按照導電性金屬網目層的材料、網目的形狀，能夠適當選擇利用習知之方法。例如，可舉例使用接著劑或導電性糊等而將所預先製作的導電性金屬網目層貼附於透明基材上所設置的透明導電層上，進一步在其上形成透明導電層之方法；或是利用噴墨法、網版印刷法等而在透明基材上所設置的透明導電層上形成導電性金屬網目層，進一步在其上形成透明導電層之方法；另外，將未進行網目加工的導電性金屬層(以下，有單純地稱為導電性金屬層之情形)形成於透明基材上所設置的透明導電層上，將此導電性金屬層加工成網目形狀，形成導電性金屬網目層，進一步在其上形成透明導電層之方法等。The method of embedding the conductive metal mesh layer is not particularly limited, and a conventional method can be appropriately selected and used according to the material of the conductive metal mesh layer and the mesh shape. For example, a method of attaching a preformed conductive metal mesh layer to a transparent conductive layer provided on a transparent substrate using an adhesive or a conductive paste or the like, and further forming a transparent conductive layer thereon may be exemplified; or A method of forming a conductive metal mesh layer on a transparent conductive layer provided on a transparent substrate by an inkjet method, a screen printing method, or the like, and further forming a transparent conductive layer thereon; and, otherwise, performing mesh processing A conductive metal layer (hereinafter, simply referred to as a conductive metal layer) is formed on a transparent conductive layer provided on a transparent substrate, and the conductive metal layer is processed into a mesh shape to form a conductive metal mesh layer. Further, a method of forming a transparent conductive layer thereon or the like.
以下，針對形成導電性金屬網目層之方法而加以說明。Hereinafter, a method of forming a conductive metal mesh layer will be described.
首先，藉由上述之方法而將導電性金屬層形成於透明基材上所設置的透明導電層上。上述方法係按照導電性金屬層的材料而予以適當選擇。First, a conductive metal layer is formed on the transparent conductive layer provided on the transparent substrate by the above method. The above method is appropriately selected in accordance with the material of the conductive metal layer.
接著，針對所形成的導電性金屬層，藉由實施利用光蝕刻法而蝕刻、形成網目圖案之方法等各種習知之機械性處理或化學性處理等，加工成網目之形狀，形成導電性金屬網目層。Then, the conductive metal layer to be formed is processed into a mesh shape by various conventional mechanical treatments or chemical treatments such as a method of etching by photolithography and forming a mesh pattern, thereby forming a conductive metal mesh. Floor.
如上所述，藉由在所形成的導電性金屬網目層之上，進一步利用上述之方法而形成透明導電層，可以獲得在透明導電層之內部埋設有導電性金屬網目層的形態之本發明的透明電極基板。As described above, by forming the transparent conductive layer on the formed conductive metal mesh layer by the above method, it is possible to obtain the form of the present invention in which the conductive metal mesh layer is embedded in the transparent conductive layer. Transparent electrode substrate.
於本發明中，因為在透明導電層中埋設有導電性金屬網目層，與如習知在透明導電層之間設置未予以網目加工之導電性金屬層的構造者作比較，透明電極基板之透明性將提高。另外，進一步與在如習知之透明基材上僅直接設置透明導電層之構造的透明電極基板、或在透明基材上直接設置導電性金屬網目層且在其上設置透明導電層之透明電極基板(亦即，設置未埋設導電性金屬網目層的透明導電層之透明電極基板)作比較，表面電阻係數更低，更具優越之導電性。In the present invention, since the conductive metal mesh layer is embedded in the transparent conductive layer, the transparency of the transparent electrode substrate is compared with a structure in which a conductive metal layer which is not subjected to mesh processing is provided between the transparent conductive layers. Sex will increase. Further, a transparent electrode substrate further having a structure in which a transparent conductive layer is directly provided on a transparent substrate as in a conventional one, or a transparent electrode substrate on which a conductive metal mesh layer is directly provided on a transparent substrate and a transparent conductive layer is provided thereon (In other words, the transparent electrode substrate in which the transparent conductive layer of the conductive metal mesh layer is not embedded is provided), the surface resistivity is lower, and the conductivity is superior.
接著，針對製造本發明之透明電極基板之方法而加以說明。Next, a method of manufacturing the transparent electrode substrate of the present invention will be described.
本發明之透明電極基板之製造方法係如下所述。The method for producing the transparent electrode substrate of the present invention is as follows.
其具有如下之特徵者：首先在透明基材之一側面形成第1透明導電層，在該第1透明導電層上形成導電性金屬層，藉由光阻圖案處理該導電性金屬層等而形成導電性金屬網目層，在該金屬網目層的面上形成第2透明導電層，藉由該第2透明導電層而被覆該導電性金屬網目層後，於透明導電層中埋設導電性金屬網目層。It has the following characteristics: first, a first transparent conductive layer is formed on one side of a transparent substrate, a conductive metal layer is formed on the first transparent conductive layer, and the conductive metal layer or the like is formed by a photoresist pattern. In the conductive metal mesh layer, a second transparent conductive layer is formed on a surface of the metal mesh layer, and the conductive metal mesh layer is covered by the second transparent conductive layer, and then a conductive metal mesh layer is buried in the transparent conductive layer. .
於此，所謂光阻圖案處理係利用光蝕刻法而蝕刻導電性金屬層，在導電性金屬層中形成網目圖案。Here, in the photoresist pattern processing, the conductive metal layer is etched by photolithography, and a mesh pattern is formed in the conductive metal layer.
若根據此方法，能夠有效率地製造由在透明基材之一側面積層埋設有導電性金屬網目層的透明導電層所構成的本發明之透明電極基板。According to this method, the transparent electrode substrate of the present invention comprising the transparent conductive layer in which the conductive metal mesh layer is embedded in one side of the transparent substrate can be efficiently produced.
作為用以形成導電性金屬層之材料而言，係可舉例與形成上述之導電性金屬網目層之材料相同者，作為形成導電性金屬層之方法而言，係可舉例與形成上述之透明導電層之方法相同者，按照導電性金屬層之材料而予以適當選擇。具體而言，例如使用如銀或銅之材料，利用真空蒸鍍、濺鍍、離子電鍍等之PVD(物理氣相蒸鍍)；或是熱CVD、原子層堆積(ALD)等之CVD(化學氣相蒸鍍)等之乾式程序；或是濕式程序之噴墨法或網版印刷法等之習知方法而能夠形成導電性金屬層。The material for forming the conductive metal layer may be the same as the material for forming the conductive metal mesh layer described above. As a method of forming the conductive metal layer, the transparent conductive material may be exemplified and formed. The method of the layer is the same, and it is suitably selected according to the material of a conductive metal layer. Specifically, for example, a material such as silver or copper, PVD (physical vapor deposition) such as vacuum evaporation, sputtering, ion plating, or CVD (chemical CVD, atomic layer deposition (ALD), etc.) is used. A conductive process such as a vapor phase vapor deposition method or a conventional method such as a wet process inkjet method or a screen printing method can form a conductive metal layer.
作為用以形成第1透明導電層及第2透明導電層之材料而言，係可舉例與形成上述之透明導電層的材料相同者。The material for forming the first transparent conductive layer and the second transparent conductive layer may be the same as the material for forming the transparent conductive layer described above.
在透明基材之一側面所形成的第1透明導電層及在導電性金屬網目上所形成的第2透明導電層之材料可以為相同者，也可以為不同者，但通常較佳為相同材料者。The material of the first transparent conductive layer formed on one side of the transparent substrate and the second transparent conductive layer formed on the conductive metal mesh may be the same or different, but generally the same material is preferable. By.
作為形成第1透明導電層及第2透明導電層之方法而言，係可舉例與形成上述之透明導電層之方法相同者，按照透明導電層之材料而予以適當選擇。The method of forming the first transparent conductive layer and the second transparent conductive layer can be appropriately selected in accordance with the material of the transparent conductive layer, for example, in the same manner as the method of forming the transparent conductive layer described above.
另外，通常在導電性金屬網目層上所形成的第2透明導電層之厚度係較佳為更薄地形成在透明基材之一側面上所形成的第1透明導電層之厚度。Further, the thickness of the second transparent conductive layer which is usually formed on the conductive metal mesh layer is preferably a thickness of the first transparent conductive layer formed on one side of the transparent substrate.
從透明性與導電性之觀點，在透明基材之一側面所形成的第1透明導電層之厚度通常為10至1000 nm，較佳為10至500 nm，特佳為30至300 nm。The thickness of the first transparent conductive layer formed on one side of the transparent substrate is usually from 10 to 1000 nm, preferably from 10 to 500 nm, particularly preferably from 30 to 300 nm, from the viewpoints of transparency and conductivity.
在導電性金屬網目上所形成的第2透明導電層之厚度通常為1至200 nm，較佳為10至200 nm，進一步較佳為20至100 nm，特佳為25至50 nm。由於上述本發明之透明電極基板係具優越之透明性及導電性，能夠作為電極而適用於各種之電子裝置。The thickness of the second transparent conductive layer formed on the conductive metal mesh is usually from 1 to 200 nm, preferably from 10 to 200 nm, further preferably from 20 to 100 nm, and particularly preferably from 25 to 50 nm. Since the transparent electrode substrate of the present invention has excellent transparency and conductivity, it can be used as an electrode for various electronic devices.
本發明之電子裝置係以具有上述本發明之透明電極基板為特徵者。The electronic device of the present invention is characterized by having the above-described transparent electrode substrate of the present invention.
作為能夠適用本發明之透明電極基板之電子裝置而言，可舉例電晶體、記憶體、有機EL、有機薄膜太陽能電池等之有機裝置；液晶顯示器；電子紙；薄膜電晶體；電色顯示器；電化學發光裝置；觸控面板；顯示器；光電轉換裝置；熱電轉換裝置；壓電轉換裝置；蓄電裝置等。As an electronic device to which the transparent electrode substrate of the present invention can be applied, an organic device such as a transistor, a memory, an organic EL, an organic thin film solar cell, or the like; a liquid crystal display; an electronic paper; a thin film transistor; an electrochromic display; Learning light-emitting device; touch panel; display; photoelectric conversion device; thermoelectric conversion device; piezoelectric conversion device;
本發明之太陽能電池係以具有上述本發明之透明電極基板為特徵者。The solar cell of the present invention is characterized by having the above-described transparent electrode substrate of the present invention.
作為能夠適用本發明之透明電極基板的太陽能電池而言，可舉例有機薄膜太陽能電池、薄膜矽型太陽能電池、混合型太陽能電池、多接合型太陽能電池、球狀矽型太陽能電池、電場效果型太陽能電池、色素增感太陽能電池等各種之太陽能電池。其中，本發明之太陽能電池較佳為具有上述本發明之透明電極基板的有機薄膜太陽能電池。Examples of the solar cell to which the transparent electrode substrate of the present invention can be applied include an organic thin film solar cell, a thin film germanium solar cell, a hybrid solar cell, a multi-junction solar cell, a spherical germanium solar cell, and an electric field effect solar cell. Various solar cells such as batteries and dye-sensitized solar cells. Among them, the solar cell of the present invention is preferably an organic thin film solar cell having the above-described transparent electrode substrate of the present invention.
於此，舉出有機薄膜太陽能電池為例而加以說明。Here, an organic thin film solar cell will be described as an example.
第1圖係顯示構成本發明之太陽能電池之一例的有機薄膜太陽能電池之層之一例的剖面圖。於第1圖中，1係透明基材、2係第1透明導電層、3係導電性金屬網目層、4係第2透明導電層、5係光電轉換層、6係電極、7係基材層、8係埋設有導電性金屬網目層的透明導電層、9係本發明之透明電極基板、10係有機薄膜太陽能電池。Fig. 1 is a cross-sectional view showing an example of a layer of an organic thin film solar cell constituting an example of a solar cell of the present invention. In the first embodiment, a 1st transparent substrate, a 2nd first transparent conductive layer, a 3rd conductive metal mesh layer, a 4th second transparent conductive layer, a 5th photoelectric conversion layer, a 6th electrode, and a 7th substrate are used. Layers, 8 series of transparent conductive layers in which a conductive metal mesh layer is embedded, 9 series of transparent electrode substrates of the present invention, and 10 series organic thin film solar cells.
光電轉換層(第1圖中之5)係進行光電轉換之層，從原料之低成本化、柔軟性、形成之容易性、吸光係數之高低、輕量化、耐撞擊性等之觀點，較佳為有機半導體。The photoelectric conversion layer (5 in the first drawing) is a layer for photoelectric conversion, and is preferably from the viewpoints of cost reduction, flexibility, ease of formation, high light absorption coefficient, light weight, impact resistance, and the like of the raw material. For organic semiconductors.
光電轉換層可以由單層而成，也可以由複數層而成。單層之情形下，光電轉換層通常係由本性半導體(i型半導體)所形成。The photoelectric conversion layer may be formed of a single layer or a plurality of layers. In the case of a single layer, the photoelectric conversion layer is usually formed of a natural semiconductor (i-type semiconductor).
另外，複數層之情形，為(p型半導體層/n型半導體層)之積層或(p型半導體層/本性半導體層/n型半導體層)等。Further, in the case of a plurality of layers, it is a laminate of (p-type semiconductor layer/n-type semiconductor layer) or (p-type semiconductor layer/negative semiconductor layer/n-type semiconductor layer).
從單層或複數層之情形且不同者為導電性、激勵子擴散距離之觀點，光電轉換層之厚度一般較佳為30 nm至2 μm，特佳為40 nm至300 nm。The thickness of the photoelectric conversion layer is generally preferably from 30 nm to 2 μm, particularly preferably from 40 nm to 300 nm, from the viewpoint of the case of a single layer or a plurality of layers, and the difference between the conductivity and the diffusion distance of the excitons.
以下，針對光電轉換層所用之有機半導體而加以說明。Hereinafter, the organic semiconductor used in the photoelectric conversion layer will be described.
作為本性半導體之材料而言，能夠使用所獲得之半導體成為本性半導體的方式來混合包含例如富勒烯、富勒烯衍生物、具有半導體性之碳奈米管(CNT)及CNT化合物中至少一種的第1材料、與包含聚苯伸乙烯(PPV)之衍生物或聚噻吩系高分子材料的第2材料之混合物。As a material of the intrinsic semiconductor, at least one of a fullerene, a fullerene derivative, a semiconducting carbon nanotube (CNT), and a CNT compound can be mixed so that the obtained semiconductor becomes an intrinsic semiconductor. A first material and a mixture of a second material comprising a polyphenylene vinylene (PPV) derivative or a polythiophene polymer material.
作為富勒烯衍生物而言，例如能夠使用[6,6]-苯基-C61-丁酸甲酯(PCBM)等，另外，也能夠使用富勒烯之二量體、或是導入鹼金屬或鹼土金屬等之富勒烯化合物等。另外，作為CNT而言，係能夠使用內藏富勒烯或是金屬內藏富勒烯之碳奈米管等。還有，也能夠使用將各種分子附加於CNT之側壁或尖端的CNT化合物等。As the fullerene derivative, for example, [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) or the like can be used, and in addition, a fullerene or a base can be used. A fullerene compound such as a metal or an alkaline earth metal. Further, as the CNT, a carbon nanotube or the like in which fullerenes or metal-filled fullerenes are contained can be used. Further, a CNT compound or the like in which various molecules are added to the side wall or the tip end of the CNT can also be used.
作為聚苯伸乙烯之衍生物而言，係能夠使用聚[2-甲氧基-5-(2’-乙基環己氧基)對苯伸乙烯](MEH-PPV)等；作為聚噻吩系高分子材料而言，係能夠使用聚-3-己基噻吩(P3HT)等之聚(3-烷基噻吩)、二辛基茀-聯噻吩共聚物(F8T2)等。As a derivative of polystyrene, it is possible to use poly[2-methoxy-5-(2'-ethylcyclohexyloxy)-p-vinylene] (MEH-PPV) or the like; as a polythiophene For the polymer material, poly(3-alkylthiophene) such as poly-3-hexylthiophene (P3HT), dioctylfluorene-bithiophene copolymer (F8T2), or the like can be used.
作為特佳的本性半導體而言，係可舉例以質量比1：0.3至1：4混合PCBM與P3HT的混合物。As a particularly preferred semiconductor, a mixture of PCBM and P3HT can be exemplified by mixing a mass ratio of 1:0.3 to 1:4.
作為p型半導體之材料而言，例如：可舉例聚烷基噻吩及其衍生物、聚苯及其衍生物、聚苯伸乙烯及其衍生物、聚矽烷及其衍生物、卟啉衍生物、酞青素衍生物、有機金屬聚合物等。其中，較佳為聚烷基噻吩及其衍生物。另外，也可以為此等有機材料之混合物。作為導電性高分子化合物而言，係較佳能夠使用聚(3,4)-伸乙二氧基噻吩/聚苯乙烯磺酸鹽(PEDOT：PSS)。Examples of the material of the p-type semiconductor include polyalkylthiophene and derivatives thereof, polyphenylene and derivatives thereof, polyphenylene ethylene and derivatives thereof, polydecane and derivatives thereof, and porphyrin derivatives. Anthraquinone derivatives, organometallic polymers, and the like. Among them, polyalkylthiophene and derivatives thereof are preferred. In addition, a mixture of organic materials such as this may also be used. As the conductive polymer compound, poly(3,4)-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS) can be preferably used.
作為n型半導體之材料而言，特佳為富勒烯衍生物。例如，作為富勒烯衍生物而言，係能夠使用[6,6]-苯基-C61-丁酸甲酯(PCBM)等。As a material of the n-type semiconductor, a fullerene derivative is particularly preferred. For example, as the fullerene derivative, [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) or the like can be used.
作為形成光電轉換層5之方法而言，係適當選擇真空蒸鍍法、濺鍍法等之乾式程序；浸塗、旋轉塗布、噴霧塗布、棒塗布等之各種塗布程序等。As a method of forming the photoelectric conversion layer 5, a dry procedure such as a vacuum deposition method or a sputtering method, or various coating procedures such as dip coating, spin coating, spray coating, and bar coating are appropriately selected.
與成為對向電極之透明導電層的材質(例如ITO電極)作比較，電極(在第1圖之6)之材料較佳為功函數之差大者。例如，可舉例除了銀、鋁、鉑、金、銥、鉻、氧化鋅等之金屬、金屬氧化物或是合金之外，還有與上述金屬、金屬氧化物或合金之複合物。In comparison with the material (for example, the ITO electrode) which becomes the transparent conductive layer of the counter electrode, the material of the electrode (in FIG. 1 and 6) preferably has a large difference in work function. For example, in addition to metals, metal oxides or alloys of silver, aluminum, platinum, gold, rhodium, chromium, zinc oxide, etc., there may be a composite with the above metals, metal oxides or alloys.
電極之厚度較佳為20 nm至1 μm，特佳為30 nm至100 nm。The thickness of the electrode is preferably from 20 nm to 1 μm, particularly preferably from 30 nm to 100 nm.
作為在光電轉換層5上形成電極6之方法而言，可舉例真空蒸鍍、濺鍍、離子電鍍等之PVD(物理氣相蒸鍍)，按照對向電極之材料(功函數等)而予以適當選擇。As a method of forming the electrode 6 on the photoelectric conversion layer 5, PVD (physical vapor deposition) such as vacuum vapor deposition, sputtering, ion plating, or the like can be exemplified, and the material (work function, etc.) of the counter electrode is used. Appropriate choice.
作為基材層(在第1圖之7)而言，一般可舉例玻璃(板)或塑膠薄膜，按照電子裝置之用途而予以適當選擇。例如，作為塑膠薄膜而言，係可舉例聚對苯二甲酸乙二酯、聚對萘二甲酸乙二酯、四乙醯基纖維素、間規聚苯乙烯、聚苯硫醚、聚碳酸酯、聚芳香酯、聚碸、聚酯碸、聚醚醯亞胺、環狀聚烯烴等之薄膜，較佳為具優越之機械強度、耐久性等者。As a base material layer (7 of FIG. 1), a glass (plate) or a plastic film is generally exemplified, and it is suitably selected according to the use of an electronic device. For example, as the plastic film, polyethylene terephthalate, polyethylene naphthalate, tetraethyl cellulose, syndiotactic polystyrene, polyphenylene sulfide, polycarbonate can be exemplified. The film of polyarylate, polyfluorene, polyester oxime, polyether quinone, cyclic polyolefin or the like is preferably one having superior mechanical strength and durability.
以下，藉由參考例、實施例及比較例而更詳細地說明本發明，但本發明並不受此等所限定。Hereinafter, the present invention will be described in more detail by way of Reference Examples, Examples and Comparative Examples, but the invention is not limited thereto.
作為在透明基材之一側面已積層第1透明導電層之基板而言，係準備Geomatec(股份公司)製、產品名「Flat ITO」(作為基材而言，係在厚度0.7 mm玻璃之一側面具有250 nm之ITO膜的基板)。The substrate having the first transparent conductive layer laminated on one side of the transparent substrate is prepared by Geomatec Co., Ltd. under the product name "Flat ITO" (as a substrate, it is one of the thickness of 0.7 mm glass). A substrate having an ITO film of 250 nm on the side).
接著，在此基板之ITO膜上，於1×10-4 Pa以下之減壓下，利用真空蒸鍍法而使厚度成為5 nm的方式將銀(Ag)製膜而形成導電性金屬層。Next, on the ITO film of the substrate, silver (Ag) was formed into a film having a thickness of 5 nm by a vacuum deposition method under a reduced pressure of 1 × 10 -4 Pa or less to form a conductive metal layer.
接著，對導電性金屬層進行光阻圖案處理，之後，進行蝕刻處理(光阻圖案處理)而作成導電性金屬網目層，形成有正方形周期性之網目形狀(開口部之間距1 mm、導電性金屬網目層的線寬30 μm、開口率94.1%、厚度5 nm)。Next, the conductive metal layer is subjected to a photoresist pattern treatment, and then an etching treatment (resist pattern processing) is performed to form a conductive metal mesh layer, and a square periodic mesh shape is formed (distance between openings is 1 mm, conductivity) The metal mesh layer has a line width of 30 μm, an aperture ratio of 94.1%, and a thickness of 5 nm.
接著，在導電性金屬網目層上，於1×10-4 Pa以下之減壓下，利用濺鍍法(ULVAC製之濺鍍裝置，裝置名稱「i-sputter」)，將厚度30 nm之ITO膜作為第2透明導電層而形成，製得在透明導電層內埋設有導電性金屬網目層的本發明之透明電極基板。Next, on the conductive metal mesh layer, ITO having a thickness of 30 nm was deposited by a sputtering method (spraying device manufactured by ULVAC, device name "i-sputter") under a reduced pressure of 1 × 10 -4 Pa or less. The film is formed as a second transparent conductive layer, and a transparent electrode substrate of the present invention in which a conductive metal mesh layer is embedded in a transparent conductive layer is obtained.
除了將導電性金屬網目層(Ag)的厚度變更為表1中記載的厚度以外，與實施例1同樣地製得本發明之透明電極基板。The transparent electrode substrate of the present invention was obtained in the same manner as in Example 1 except that the thickness of the conductive metal mesh layer (Ag) was changed to the thickness described in Table 1.
除了將導電性金屬層(Ag)的厚度變更為表1中記載的厚度，且對導電性金屬不進行光阻圖案處理以外，與實施例1同樣地製得比較用之透明電極基板。亦即，製得在透明導電層內埋設有未予以網目加工之導電性金屬層的比較用之透明電極基板。A transparent electrode substrate for comparison was produced in the same manner as in Example 1 except that the thickness of the conductive metal layer (Ag) was changed to the thickness described in Table 1, and the conductive metal was not subjected to the photoresist pattern treatment. That is, a comparative transparent electrode substrate in which a conductive metal layer not subjected to mesh processing is embedded in a transparent conductive layer is obtained.
除了未形成導電性金屬層(Ag)之外，進行與實施例1同樣的方式，在作為第1透明導電層之厚度250 nm的ITO膜上，直接形成作為第2透明導電層之厚度30 nm的ITO膜，製得比較用之透明電極基板。亦即，製得僅設置透明導電層之構造的比較用之透明電極基板。In the same manner as in Example 1, except that the conductive metal layer (Ag) was not formed, the thickness of the second transparent conductive layer was directly formed on the ITO film having a thickness of 250 nm as the first transparent conductive layer. The ITO film was used to prepare a transparent electrode substrate for comparison. That is, a comparative transparent electrode substrate having a structure in which only a transparent conductive layer is provided is obtained.
在作為透明基材之玻璃板(河村久三商店公司製、厚度3 mm)之一側面，在與於實施例2相同之條件下形成厚度10 nm之導電性金屬層，進行導電性金屬層之光阻圖案處理，形成開口率94.1%之導電性金屬網目層。接著，在與實施例2相同之方法下，在導電性金屬網目層的面上形成ITO膜作為厚度150 nm之透明導電層而製得比較用之透明電極基板。亦即，製得設置未埋設導電性金屬網目層的透明導電層之比較用的透明電極基板。A conductive metal layer having a thickness of 10 nm was formed on one side of a glass plate (manufactured by Kawamura K.K., Ltd., thickness: 3 mm) as a transparent substrate under the same conditions as in Example 2, and a conductive metal layer was formed. The photoresist pattern was processed to form a conductive metal mesh layer having an aperture ratio of 94.1%. Next, in the same manner as in Example 2, an ITO film was formed on the surface of the conductive metal mesh layer as a transparent conductive layer having a thickness of 150 nm to prepare a transparent electrode substrate for comparison. That is, a comparative transparent electrode substrate in which a transparent conductive layer in which a conductive metal mesh layer is not embedded is provided is prepared.
於比較例6中，除了將導電性金屬層(Ag)的厚度變更為20 nm以外，同樣地製得比較用之透明電極基板。亦即，製得設置未埋設導電性金屬網目層的透明導電層之比較用的透明電極基板。In Comparative Example 6, a transparent electrode substrate for comparison was obtained in the same manner except that the thickness of the conductive metal layer (Ag) was changed to 20 nm. That is, a comparative transparent electrode substrate in which a transparent conductive layer in which a conductive metal mesh layer is not embedded is provided is prepared.
於比較例6中，除了將導電性金屬層(Ag)的厚度變更為30 nm以外，同樣地製得比較用之透明電極基板。亦即，製得設置未埋設導電性金屬網目層的透明導電層之比較用的透明電極基板。In Comparative Example 6, a transparent electrode substrate for comparison was obtained in the same manner except that the thickness of the conductive metal layer (Ag) was changed to 30 nm. That is, a comparative transparent electrode substrate in which a transparent conductive layer in which a conductive metal mesh layer is not embedded is provided is prepared.
於比較例6中，除了將導電性金屬層(Ag)的厚度變更為50 nm以外，同樣地製得比較用之透明電極基板。亦即，製得設置未埋設導電性金屬網目層的透明導電層之比較用的透明電極基板。In Comparative Example 6, a transparent electrode substrate for comparison was obtained in the same manner except that the thickness of the conductive metal layer (Ag) was changed to 50 nm. That is, a comparative transparent electrode substrate in which a transparent conductive layer in which a conductive metal mesh layer is not embedded is provided is prepared.
於比較例6中，未形成導電性金屬網目層(Ag)，在透明基材上直接形成厚度150 nm之作為透明導電層的ITO膜，製得比較用之透明電極基板。亦即，製得僅在透明基材上設置透明導電層之構造的比較用之透明電極基板。In Comparative Example 6, a conductive metal mesh layer (Ag) was not formed, and an ITO film as a transparent conductive layer having a thickness of 150 nm was directly formed on the transparent substrate to obtain a transparent electrode substrate for comparison. That is, a comparative transparent electrode substrate having a structure in which a transparent conductive layer is provided only on a transparent substrate is obtained.
除了作成透明導電層之厚度250 nm以外，進行相同於比較例10的方式而製得比較用之透明電極基板。亦即，製得僅設置透明導電層之構造的比較用之透明電極基板。A transparent electrode substrate for comparison was produced in the same manner as in Comparative Example 10 except that the thickness of the transparent conductive layer was 250 nm. That is, a comparative transparent electrode substrate having a structure in which only a transparent conductive layer is provided is obtained.
將在實施例1至4所獲得之本發明的透明電極基板及比較例1至11所獲得之比較用透明電極基板之各特性彙整而記載於表1。The respective characteristics of the transparent electrode substrate of the present invention obtained in Examples 1 to 4 and the comparative transparent electrode substrate obtained in Comparative Examples 1 to 11 are summarized in Table 1.
在表1記載之材料的物性及透明電極基板之特性係進行如下的方式來測定。The physical properties of the materials described in Table 1 and the characteristics of the transparent electrode substrate were measured as follows.
透明導電層、導電性金屬網目層及導電性金屬層的厚度係藉由探針式表面形狀測定裝置(ULVAC公司製、產品名「Dektak 150」)而測得。The thickness of the transparent conductive layer, the conductive metal mesh layer, and the conductive metal layer was measured by a probe type surface shape measuring device (manufactured by ULVAC, product name "Dektak 150").
藉由表面電阻測定裝置(三菱化學公司製、產品名「LORESTA GP MCP-T600」)，利用四端子法而測定所獲得之透明電極基板的透明導電層表面之表面電阻係數。The surface resistivity of the surface of the transparent conductive layer of the obtained transparent electrode substrate was measured by a four-terminal method by a surface resistance measuring device (manufactured by Mitsubishi Chemical Corporation, product name "LORESTA GP MCP-T600").
使用光線穿透率測定裝置[日本電色工業公司製、產品名「NDH-5000」]而依照JIS K7361-1，測得透明電極基板之全光線透射率。The total light transmittance of the transparent electrode substrate was measured in accordance with JIS K7361-1 using a light transmittance measuring device [manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH-5000").
使用在實施例3所製得的本發明之透明電極基板而製得太陽能電池。A solar cell was produced using the transparent electrode substrate of the present invention obtained in Example 3.
在透明電極基板之透明導電層表面，首先將聚噻吩系導電性聚合物之聚(3,4-環氧乙烷噻吩)(PEDOT)與聚苯乙烯磺酸(PSS)之混合物(PEDOT：PSS、H. C. Stark公司製、產品名「AI4083」)，利用旋轉塗布法而形成厚度50 nm之膜。接著，使用聚-3-己基噻吩(P3HT)與[6,6]-苯基-C61-丁酸甲酯(PCBM)之二種有機材料的混合溶液(莫耳比1：1)，利用旋轉塗布法而使厚度成為80 nm的方式來成膜。陰極係以真空蒸鍍而使厚度成為100 nm的方式將金屬鋁成膜。最後，藉由玻璃遮罩而密封，製作本發明之太陽能電池。On the surface of the transparent conductive layer of the transparent electrode substrate, a polythiophene-based conductive polymer is first mixed with poly(3,4-epoxyethane thiophene) (PEDOT) and polystyrenesulfonic acid (PSS) (PEDOT:PSS). The product name "AI4083" manufactured by HC Stark Co., Ltd. was formed into a film having a thickness of 50 nm by a spin coating method. Next, a mixed solution of two organic materials of poly-3-hexylthiophene (P3HT) and [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) (Mohr ratio 1:1) was used. Film formation was carried out by a spin coating method to a thickness of 80 nm. The cathode was formed into a film by vacuum deposition to a thickness of 100 nm. Finally, the solar cell of the present invention was fabricated by sealing with a glass mask.
使用比較例5之透明電極基板，進行相同於實施例5之方式而製得比較用之太陽能電池。Using the transparent electrode substrate of Comparative Example 5, a solar cell for comparison was obtained in the same manner as in Example 5.
在實施例5及比較例12所製得的太陽能電池之元件有效面積12 cm2，藉由太陽能模擬器(Wakom電創(股份公司)製、WXS-50S-1.5)而照射模擬太陽光光譜(AM1.5(100mW/cm2))，測得光電轉換效率。將太陽能電池之評估結果顯示於表2。The solar cells of Example 5 and Comparative Example 12 had an effective area of 12 cm 2 , and were irradiated with a simulated solar spectrum by a solar simulator (Wakom Electric Co., Ltd., WXS-50S-1.5). AM 1.5 (100 mW/cm 2 )), photoelectric conversion efficiency was measured. The evaluation results of the solar cells are shown in Table 2.
由表1及2，確認以下之事項：From Tables 1 and 2, confirm the following:
(1)如在表1之實施例1至4所示，確認本發明之透明電極基板係全光線透射率高、具優越之透明性，還有，表面電阻係數之值也低，具有優異的導電性。(1) As shown in Examples 1 to 4 of Table 1, it was confirmed that the transparent electrode substrate of the present invention has high total light transmittance, excellent transparency, and also has a low surface resistivity value and is excellent. Electrical conductivity.
(2)另一方面，在透明導電層內埋設有未被網目加工的導電性金屬層之比較例1至4的透明電極基板係全光線透射率低且透明性較實施例1至4為差。(2) On the other hand, the transparent electrode substrates of Comparative Examples 1 to 4 in which the conductive metal layer not subjected to the mesh processing is embedded in the transparent conductive layer have low total light transmittance and transparency is inferior to those of Examples 1 to 4. .
另外，與實施例1至4作比較，在透明基材僅設置透明導電層之構造的比較例5、10及11之透明電極基板係表面電阻係數高且導電性較差。Further, in comparison with Examples 1 to 4, the transparent electrode substrates of Comparative Examples 5, 10, and 11 in which only the transparent conductive layer was provided on the transparent substrate had a high surface resistivity and poor conductivity.
另外，如在比較例6至9所示，得知直接在透明基材上設置直接導電性金屬網目，未埋設導電性金屬網目層之情形，全光線透射率較實施例1至3為低，另外表面電阻係數之值也高，透明性及導電性較差。Further, as shown in Comparative Examples 6 to 9, it was found that the direct conductive metal mesh was directly provided on the transparent substrate, and the conductive metal mesh layer was not embedded, and the total light transmittance was lower than that of Examples 1 to 3. In addition, the value of the surface resistivity is also high, and the transparency and conductivity are poor.
如在表2之結果所示，與比較例12之太陽能電池作比較，使用本發明之透明電極基板之實施例5的太陽能電池可以獲得轉換效率高、提高17%左右之效率。此係藉由使用本發明之透明性高、表面電阻係數低的透明電極基板，因有機太陽能電池之內部電阻的降低而有光電轉換效率提高之結果。As shown by the results of Table 2, in comparison with the solar cell of Comparative Example 12, the solar cell of Example 5 using the transparent electrode substrate of the present invention can achieve high conversion efficiency and an efficiency of about 17%. By using the transparent electrode substrate having high transparency and low surface resistivity of the present invention, the photoelectric conversion efficiency is improved by the decrease in the internal resistance of the organic solar cell.
由於本發明之透明電極基板係透明性高、表面電阻係數低，具優越均衡之透明性與導電性。本發明之透明電極基板能夠使用於有機薄膜太陽能電池等之太陽能電池；電晶體、記憶體、有機EL等之有機裝置；液晶顯示器；電子紙；薄膜電晶體；電色顯示器；電化學發光裝置；觸控面板；顯示器；熱電轉換裝置；壓電轉換裝置；蓄電裝置等之電子裝置。Since the transparent electrode substrate of the present invention has high transparency and low surface resistivity, it has excellent balance of transparency and conductivity. The transparent electrode substrate of the present invention can be used for solar cells such as organic thin film solar cells; organic devices such as transistors, memories, and organic EL; liquid crystal displays; electronic paper; thin film transistors; electrochromic displays; Touch panel; display; thermoelectric conversion device; piezoelectric conversion device; electronic device such as power storage device.
1．．．透明基材1. . . Transparent substrate
2．．．第1透明導電層2. . . First transparent conductive layer
3．．．導電性金屬網目層3. . . Conductive metal mesh layer
4．．．第2透明導電層4. . . Second transparent conductive layer
5．．．光電轉換層5. . . Photoelectric conversion layer
6．．．電極6. . . electrode
7．．．基材7. . . Substrate
8．．．透明導電層8. . . Transparent conductive layer
9．．．透明電極基板9. . . Transparent electrode substrate
10．．．太陽能電池10. . . Solar battery
第1圖係顯示使用本發明之透明電極基板之太陽能電池之一例的有機薄膜太陽能電池剖面的示意圖。Fig. 1 is a schematic view showing a cross section of an organic thin film solar cell which is an example of a solar cell using the transparent electrode substrate of the present invention.
第2圖係顯示導電性金屬網目層形狀之一例的示意圖。Fig. 2 is a schematic view showing an example of the shape of a conductive metal mesh layer.
1．．．透明基材1. . . Transparent substrate
2．．．第1透明導電層2. . . First transparent conductive layer
3．．．導電性金屬網目層3. . . Conductive metal mesh layer
4．．．第2透明導電層4. . . Second transparent conductive layer
5．．．光電轉換層5. . . Photoelectric conversion layer
6．．．電極6. . . electrode
7．．．基材7. . . Substrate
8．．．透明導電層8. . . Transparent conductive layer
9．．．透明電極基板9. . . Transparent electrode substrate
10．．．太陽能電池10. . . Solar battery
Claims (12)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011000779A JP5913809B2 (en) | 2011-01-05 | 2011-01-05 | Transparent electrode substrate, method for producing the same, electronic device having the transparent electrode substrate, and solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201246578A TW201246578A (en) | 2012-11-16 |
| TWI533461B true TWI533461B (en) | 2016-05-11 |
Family
ID=46481609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100149395A TWI533461B (en) | 2011-01-05 | 2011-12-29 | Transparent electrode substrate, method for producing the same, electronic device and solar cell having the transparent electrode substrate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5913809B2 (en) |
| KR (1) | KR101897278B1 (en) |
| CN (1) | CN102593194A (en) |
| TW (1) | TWI533461B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11382245B2 (en) * | 2019-03-01 | 2022-07-05 | The Regents Of The University Of Michigan | Ultra-thin conductor based semi-transparent electromagnetic interference shielding |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101328483B1 (en) * | 2012-05-10 | 2013-11-13 | 전자부품연구원 | Transparent electrode thin-film with metal mesh structure and method thereof |
| JP2014052435A (en) * | 2012-09-05 | 2014-03-20 | Nitto Denko Corp | Transparent electrode substrate, method of producing the same, and image display device |
| KR101366740B1 (en) * | 2012-10-25 | 2014-02-26 | 한국생산기술연구원 | Method for fabricating nano/micro composite solar cell formed by pocl_3 doping and solar cell thereof |
| KR101375738B1 (en) * | 2012-10-25 | 2014-03-26 | 한국생산기술연구원 | Method for fabricating polycrystalline silicon thin film nano structure using ag nano particle, polycrystalline silicon nano structure fabibricated by the same and polycrystalline silicon thin film solar cell including polycrystalline silicon nano structure |
| KR101375781B1 (en) * | 2012-10-25 | 2014-03-19 | 한국생산기술연구원 | Method for fabricating solar cell with increase carrier life through sod doping and passivation lf nano and micro silicon complex structure and solar cell thereof |
| KR101366737B1 (en) * | 2012-10-25 | 2014-02-26 | 한국생산기술연구원 | Method for fabricating solar cell with increased reflection characteristic of silicon nano and micro structure through removing bundle and solar cell thereof |
| KR101504839B1 (en) * | 2012-11-30 | 2015-03-23 | 주식회사 엘지화학 | Conducting substrate and method for preparing the same |
| CN103971787B (en) * | 2013-02-04 | 2016-06-22 | 深圳欧菲光科技股份有限公司 | Transparent conductive body and preparation method thereof |
| TWI483411B (en) * | 2013-02-20 | 2015-05-01 | Motech Ind Inc | Solar cell and module comprising the same |
| JP6200004B2 (en) * | 2013-08-01 | 2017-09-20 | エルジー・ケム・リミテッド | TRANSPARENT CONDUCTIVE LAMINATE, TRANSPARENT ELECTRODE CONTAINING TRANSPARENT CONDUCTIVE LAMINATE, AND METHOD FOR PRODUCING TRANSPARENT CONDUCTIVE LAMINATE |
| RU2670303C2 (en) * | 2013-08-30 | 2018-10-22 | Июкф-Хю (Индастри-Юниверсити-Кооперейшн Фаундейшн Ханян Юниверсити) | Functional thin film and method of its manufacture |
| CN103885191B (en) * | 2014-03-12 | 2016-02-24 | 京东方科技集团股份有限公司 | 3D raster box and preparation method thereof, color membrane substrates and display device |
| JP2015195341A (en) * | 2014-03-24 | 2015-11-05 | 三菱電機株式会社 | Photoelectric conversion element and method of manufacturing photoelectric conversion element |
| KR101541517B1 (en) * | 2014-03-26 | 2015-08-03 | 부산대학교 산학협력단 | Transparent electrode using single crystal copper with nano-netted multi-layer and fabricating method thereof |
| EP3144970B1 (en) * | 2014-05-15 | 2021-02-17 | LG Display Co., Ltd. | Organic light emitting device |
| CN105702875B (en) | 2014-12-11 | 2018-04-27 | 财团法人工业技术研究院 | Light-emitting element, electrode structure and manufacturing method thereof |
| JP2016178117A (en) * | 2015-03-18 | 2016-10-06 | 積水化学工業株式会社 | Transparent electrode for solar cell and electrode laminate for solar cell |
| WO2016163323A1 (en) * | 2015-04-06 | 2016-10-13 | 株式会社カネカ | Transparent conductive film and display device |
| CN104834134B (en) * | 2015-05-21 | 2017-08-04 | 哈尔滨工业大学 | A kind of electrochomeric glass |
| KR102456121B1 (en) * | 2015-12-15 | 2022-10-17 | 엘지디스플레이 주식회사 | Light controlling device, transparent display device including the same and method for manufacturing the same |
| CN105449106B (en) * | 2015-12-28 | 2018-10-23 | 中国科学院重庆绿色智能技术研究院 | A kind of transparent electrode and preparation method thereof based on super thin metal |
| ITUA20162095A1 (en) * | 2016-03-30 | 2016-06-30 | Fabrizio Chiara | COATING PROCEDURE OF A PHOTOVOLTAIC SURFACE AND PHOTOVOLTAIC SURFACE REALIZED BY SUCH A PROCEDURE. |
| WO2018004280A1 (en) * | 2016-06-30 | 2018-01-04 | 부산대학교 산학협력단 | Copper oxide thin film structure using flawless single crystal copper thin film, and manufacturing method therefor |
| WO2018062283A1 (en) * | 2016-09-30 | 2018-04-05 | 日東電工株式会社 | Adhesive composition, adhesive layer, polarizing film coated with adhesive layer, liquid crystal panel, and image display device |
| KR102035689B1 (en) * | 2017-02-23 | 2019-10-23 | 동우 화인켐 주식회사 | Film type antenna and display device comprising the same |
| CN108630818A (en) * | 2017-03-15 | 2018-10-09 | Tcl集团股份有限公司 | Light emitting diode with quantum dots device and preparation method thereof with Novel anode structure |
| JP2021026902A (en) * | 2019-08-06 | 2021-02-22 | 日東電工株式会社 | Transparent conductive film |
| JP7336305B2 (en) * | 2019-08-06 | 2023-08-31 | 日東電工株式会社 | transparent conductive film |
| CN112908519B (en) * | 2021-01-19 | 2022-04-12 | 大正(江苏)微纳科技有限公司 | Chemical corrosion resistant transparent conductive film and preparation method thereof |
| CN113284957B (en) | 2021-04-21 | 2022-09-23 | 华为技术有限公司 | Solar cell and electronic device |
| KR102634852B1 (en) * | 2021-10-27 | 2024-02-06 | 인천대학교 산학협력단 | Bifacial Color-Tunable Transparent Photovoltaics and their manufacturing methods |
| CN114283994B (en) * | 2021-11-23 | 2023-05-09 | 华中科技大学 | Embedded metal grid flexible electrode film and preparation method and application thereof |
| WO2023210660A1 (en) * | 2022-04-25 | 2023-11-02 | 旭化成株式会社 | Photodetector element using metal grid transparent electrode and touchless user interface device using same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10241464A (en) | 1996-12-26 | 1998-09-11 | Asahi Glass Co Ltd | Substrate with transparent conductive film and manufacture thereof |
| JP2004296669A (en) | 2003-03-26 | 2004-10-21 | Bridgestone Corp | Dye-sensitized solar cell and electrode therefor |
| JP5009116B2 (en) * | 2006-09-28 | 2012-08-22 | 富士フイルム株式会社 | Self-luminous display device, transparent conductive film, electroluminescence element, transparent electrode for solar cell, and transparent electrode for electronic paper |
| KR100811473B1 (en) | 2006-10-17 | 2008-03-07 | 엘지전자 주식회사 | Light emitting panel and light source comprising the same |
| KR101352779B1 (en) * | 2007-02-28 | 2014-01-16 | 주식회사 동진쎄미켐 | Transparent electrode for solar cell and method for preparing the same |
| JP2009081104A (en) | 2007-09-27 | 2009-04-16 | Konica Minolta Holdings Inc | Transparent conductive film |
| JP5651910B2 (en) | 2007-12-13 | 2015-01-14 | コニカミノルタ株式会社 | Transparent conductive film and method for producing transparent conductive film |
| JP4985717B2 (en) * | 2008-12-04 | 2012-07-25 | 大日本印刷株式会社 | Organic thin film solar cell and method for producing the same |
-
2011
- 2011-01-05 JP JP2011000779A patent/JP5913809B2/en active Active
- 2011-12-01 KR KR1020110127777A patent/KR101897278B1/en active IP Right Grant
- 2011-12-01 CN CN201110394002XA patent/CN102593194A/en active Pending
- 2011-12-29 TW TW100149395A patent/TWI533461B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11382245B2 (en) * | 2019-03-01 | 2022-07-05 | The Regents Of The University Of Michigan | Ultra-thin conductor based semi-transparent electromagnetic interference shielding |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201246578A (en) | 2012-11-16 |
| CN102593194A (en) | 2012-07-18 |
| KR20120079803A (en) | 2012-07-13 |
| JP5913809B2 (en) | 2016-04-27 |
| JP2012142500A (en) | 2012-07-26 |
| KR101897278B1 (en) | 2018-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI533461B (en) | Transparent electrode substrate, method for producing the same, electronic device and solar cell having the transparent electrode substrate | |
| WO2012093530A1 (en) | Transparent conductive laminate body and organic thin film device | |
| Li et al. | ITO-free photovoltaic cell utilizing a high-resolution silver grid current collecting layer | |
| Lim et al. | Flexible PEDOT: PSS/ITO hybrid transparent conducting electrode for organic photovoltaics | |
| US20100018581A1 (en) | Large area solar cell | |
| Galagan et al. | Large area ITO-free organic solar cells on steel substrate | |
| Muhsin et al. | Flexible ITO-free polymer solar cells based on highly conductive PEDOT: PSS and a printed silver grid | |
| US20160111223A1 (en) | A laminated opto-electronic device and method for manufacturing the same | |
| US10468546B2 (en) | Solar cell module and method for manufacturing the same | |
| Kohlstädt et al. | Inverted ITO-and PEDOT: PSS-free polymer solar cells with high power conversion efficiency | |
| Zhang et al. | Efficient flexible polymer solar cells based on solution-processed reduced graphene oxide–Assisted silver nanowire transparent electrode | |
| Zhang et al. | Low-temperature all-solution-processed transparent silver nanowire-polymer/AZO nanoparticles composite electrodes for efficient ITO-free polymer solar cells | |
| Lee et al. | Nano-sized indium-free MTO/Ag/MTO transparent conducting electrode prepared by RF sputtering at room temperature for organic photovoltaic cells | |
| Ji et al. | Ultraflexible and high-performance multilayer transparent electrode based on ZnO/Ag/CuSCN | |
| Cho et al. | Efficient ITO-free semitransparent perovskite solar cells with metal transparent electrodes | |
| Lee et al. | Transparent and flexible PEDOT: PSS electrodes passivated by thin IZTO film using plasma-damage free linear facing target sputtering for flexible organic solar cells | |
| Wang et al. | Performance improvement in flexible polymer solar cells based on modified silver nanowire electrode | |
| CN109148693A (en) | Organic photovoltaic device and forming method thereof | |
| Park et al. | Bifunctional graphene oxide hole-transporting and barrier layers for transparent bifacial flexible perovskite solar cells | |
| Chang et al. | Top-illuminated organic solar cells fabricated by vacuum-free and all-solution processes | |
| Lu et al. | Utilizing insulating nanoparticles as the spacer in laminated flexible polymer solar cells for improved mechanical stability | |
| CN103180992B (en) | Trt | |
| Zhao et al. | The effect of hole transfer layers and anodes on indium-free TiO2/Ag/TiO2 electrode and ITO electrode based P3HT: PCBM organic solar cells | |
| KR101364461B1 (en) | Organic solar cell module and Method for preparing the same | |
| Cho et al. | Hierarchical silver network transparent conducting electrodes for thin-film solar cells |