CN100336136C - Transparent conductive film forming liquid and mfg. method of adheved substrate of transparent conductive film contg. such forming liquid - Google Patents
Transparent conductive film forming liquid and mfg. method of adheved substrate of transparent conductive film contg. such forming liquid Download PDFInfo
- Publication number
- CN100336136C CN100336136C CNB2003101202939A CN200310120293A CN100336136C CN 100336136 C CN100336136 C CN 100336136C CN B2003101202939 A CNB2003101202939 A CN B2003101202939A CN 200310120293 A CN200310120293 A CN 200310120293A CN 100336136 C CN100336136 C CN 100336136C
- Authority
- CN
- China
- Prior art keywords
- nesa coating
- transparent conductive
- conductive film
- matrix
- expression
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000000758 substrate Substances 0.000 title description 37
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 63
- 150000002472 indium compounds Chemical class 0.000 claims abstract description 61
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 125000002252 acyl group Chemical group 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 151
- 239000011248 coating agent Substances 0.000 claims description 149
- 239000011159 matrix material Substances 0.000 claims description 106
- 238000004519 manufacturing process Methods 0.000 claims description 34
- 229910052783 alkali metal Inorganic materials 0.000 claims description 25
- 150000001340 alkali metals Chemical class 0.000 claims description 25
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 abstract 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 29
- 229910052738 indium Inorganic materials 0.000 description 24
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 24
- 239000000835 fiber Substances 0.000 description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011521 glass Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LJNUVXBFIMZICY-UHFFFAOYSA-N dibutyl oxalate;tin Chemical compound [Sn].CCCCOC(=O)C(=O)OCCCC LJNUVXBFIMZICY-UHFFFAOYSA-N 0.000 description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 6
- 238000001802 infusion Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- VMZCHSVMQLKOOM-KVVVOXFISA-N (z)-2,3-dibutylbut-2-enedioic acid;tin Chemical compound [Sn].CCCC\C(C(O)=O)=C(C(O)=O)/CCCC VMZCHSVMQLKOOM-KVVVOXFISA-N 0.000 description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 3
- -1 Methyl Chemical group 0.000 description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- PUZCUNCKTTTWOS-UHFFFAOYSA-N [Sn].CC(=O)C Chemical compound [Sn].CC(=O)C PUZCUNCKTTTWOS-UHFFFAOYSA-N 0.000 description 3
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 description 3
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- VIFFNYAVJACGFW-UHFFFAOYSA-N 2-butylhexanoic acid;tin Chemical compound [Sn].CCCCC(C(O)=O)CCCC VIFFNYAVJACGFW-UHFFFAOYSA-N 0.000 description 2
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CXCNNFBZPHCLAO-UHFFFAOYSA-N C1=CC=C(C=C1)C(=O)C(C(=O)C2=CC=CC=C2)(C(=O)C3=CC=CC=C3)[In] Chemical compound C1=CC=C(C=C1)C(=O)C(C(=O)C2=CC=CC=C2)(C(=O)C3=CC=CC=C3)[In] CXCNNFBZPHCLAO-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 239000005307 potash-lime glass Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The present invention provides transparent conductive film forming liquid for forming film resistance values and transparent conductive film with extremely even transparency. The present invention also provides a making method of a base body attaching to the transparent conductive film which has film resistance and the transparent conductive film with extremely even transparency. Specially the present invention provides the transparent conductive film forming liquid and the method for making the body base attaching to the transparent conductive film with the transparent conductive film forming liquid, and has the following characteristics. The transparent conductive film forming liquid is characterized in that indium compounds expressed by a formula [1] and tin compounds expressed by a formula [2] are contained; according to the condition, beta-diketone compounds for dissolving the indium compounds expressed by the formula [1] and the tin compounds expressed by a formula [2] are also contained: In (R<1>COCHCOR<2>) 31, wherein R<1> and R<2> respectively and independently denote alkyl or phenyl with 1 to 10 of the number of carbon atoms; (R<3>) 2Sn (OR<4>) 22, wherein R<3> denotes alkyl with 1 to 10 of the number of carbon atoms, R<4>denotes alkyl with 1 to 10 of the number of carbon atoms, or acyl with 1 to 10 of the number of carbon atoms.
Description
Technical field
The present invention relates to nesa coating forms liquid and comprises the manufacture method that this nesa coating forms the transparent conductive film cling matrix of liquid.
Background technology
Nesa coating (ITO film) is to utilize its outstanding transparency and conductivity and be widely used in LCD, electroluminescent display, face heating element (Mian development Hot body), aspect such as contact ( Star チ パ ネ Le) electrode, solar cell.
Because nesa coating so is widely used in a lot of fields, require it to have various sheet resistance value and transparency according to application target.For example, it is the film of low resistance high permeability that the nesa coating that is used for flat-panel monitor requires, and it is the film of high resistance high permeability that the nesa coating that is used for touch panel then requires.Especially, the market demand of exploitation increases in recent years writes the nesa coating that the input touch panel uses and requires this film to have very high location recognition precision, therefore needs the high resistance membrane that sheet resistance value is 200～3000 Ω/ badly.This sheet resistance value is to use the numerical value of obtaining than the thickness of resistance/conducting film.
Form aforesaid method with nesa coating of required sheet resistance value, for example have, the spy open 2001-35273 communique and spy open on the 2002-133956 communique disclosed form nesa coating by sputtering method, electronic beam method, ion plating method or chemical vapour phase growth method after, nesa coating methods of heating treatment in the presence of the finite concentration organic solvent.In described communique, about forming the raw material of nesa coating, exemplified indium compound, as: praseodynium indium, tri-benzoyl methyl indium (イ Application ジ ウ system ト リ ス ベ Application ゾ イ Le メ ネ one ト), indium trichloride, indium nitrate, three isopropoxy indiums etc.; Tin compound, as: stannic chloride, dimethyltin chloride, dibutyl tin dichloride, tetrabutyltin, stannous octoate (ス ニ ア ス オ Network ト エ one ト), dibutyl maleic acid tin, di-n-butylacetic acid tin, dibutyl diacetyl group acetone tin etc.In addition, also exemplify following solvent, comprised ketones solvents such as acetylacetone,2,4-pentanedione, acetone, methyl iso-butyl ketone (MIBK), metacetone; Alcohols solvents such as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols; Esters solvent such as ethyl acetate, butyl acetate; Ether solvents such as methyl Cellosolve, oxolane; Arenes such as benzene,toluene,xylene; Fat hydrocarbons such as hexane, heptane, octane, cyclohexane etc.
Yet, in above-mentioned communique, though disclose the method for the nesa coating that obtains having required resistance value, but as how preferred its combination or of raw-material indium compound and tin compound to this combination preferred its solvent how, and on the relation of its particular combinations about the also not research of uniformity of the sheet resistance value in the nesa coating and the transparency.The inventor considers nesa coating, the especially extensive use of ITO film etc. in the future, has studied the uniformity that how further to improve the sheet resistance value and the transparency.
Especially in fields such as LCD or OLED display, if contain alkali metal, then have influence on the reliability of light-emitting component, thus in light-emitting component (the デ バ イ ス sub-prime) organic compounds such as formation liquid crystal or organic EL, when making light-emitting component, wish to remove as far as possible alkali metal.
When making light-emitting component, for example, when using cheap soda lime substrate (being called for short the SLG substrate) as the matrix (glass substrate) of nesa coating, the alkali metal of matrix itself is diffused in the organic compound that constitutes light-emitting component, reduced the reliability of element significantly, in order to prevent these, silicon oxide film (SiO
2Film) suppresses alkali-metal diffusion as the undercoating film, but work as at SiO
2When the ELD of film forming itself contained alkali metal on the film, this alkali metal was diffused into light-emitting component, consequently, and SiO
2Film can't work.Therefore, needing the reliability that prevents the light-emitting component that causes because of alkali metal badly reduces.
The film build method of described nesa coating further comprises physical film deposition method such as sputtering method that utilizes physical phenomenon in a vacuum and chemical membrane method such as the infusion process of utilizing chemical reaction.
But, when film forming when having the matrix of curved surface or concaveconvex shape, if during physical film deposition methods such as the described sputtering method of use, this physical film deposition method begins to carry out evaporation and film forming from a direction of matrix, so just is difficult in curved face part or jog and forms the uniform nesa coating of thickness.Specifically, for example, when on quartz fibre, forming nesa coating, during with physical film deposition methods such as sputtering methods, must make the quartz fibre rotation make it uniform film thickness in the film forming, yet its rotary speed control is very difficult, and the nesa coating of formation uniform film thickness is also very difficult.
In the infusion process of one of chemical membrane method, can form liquid to nesa coating coats on the matrix with curved surface or concaveconvex shape equably, but in next step heating and decomposition, dry run, owing to be difficult to remove equably desolvate, just be difficult to form the nesa coating of uniform film thickness, therefore, be necessary to develop the method that can on matrix, form the nesa coating of uniform film thickness with curved surface or concaveconvex shape.
Summary of the invention
The present invention is exactly in view of a kind of like this present situation, and its purpose is, the manufacture method that provides a kind of nesa coating to form liquid and transparent conductive film cling matrix, and described nesa coating can form sheet resistance value and the extremely uniform nesa coating of the transparency; Described transparent conductive film cling matrix has sheet resistance value and the extremely uniform nesa coating of the transparency.
The present invention also aims to provide a kind of nesa coating to form the manufacture method of liquid and transparent conductive film cling matrix, described nesa coating forms liquid can form the nesa coating that the reliability that can make light-emitting component is improved, and described manufacture method can be made the transparent conductive film cling matrix that the reliability that can make light-emitting component is improved at an easy rate.
The present invention also aims to provide a kind of manufacture method of transparent conductive film cling matrix, this method forms thickness nesa coating extremely uniformly easily on the matrix with curved surface or concaveconvex shape.
The inventor has carried out concentrated research to forming membranous more uniform nesa coating, found that, form contained indium compound in the liquid with the indium compound shown in the aftermentioned formula [1] as the nesa coating that is used to form nesa coating, with the tin compound shown in the aftermentioned formula [2] as tin compound, and with the solvent of beta-diketone compounds as the dissolving above-claimed cpd, can form membranous more uniform nesa coating thus, thereby finish the present invention.
In addition, the inventor concentrates one's attention on to study to the reliability that how to improve light-emitting component in technical fields such as LCD or OLED display repeatedly, found that, can significantly improve the reliability of light-emitting component by alkali-metal content in the nesa coating formation liquid that is used to form nesa coating is set in specified quantitative (2 quality ppm) with next, thereby finish the present invention.
In addition, the inventor is to having carried out concentrated research having the method that is formed uniformly nesa coating on curved surface or the concavo-convex matrix, found that, by utilizing pyrosol facture (パ イ ロ ゾ Le プ ロ セ ス method) that evenly film forming can be had on curved surface or the concavo-convex matrix, thereby finish the present invention.Promptly, in the pyrosol facture, make nesa coating form liquid by ultrasonic wave and form droplet, put in the film forming stove that heated as carrier with air etc., the nesa coating that forms the uniform gas state forms liquid and slips into around the matrix, through contact and thermal decomposition, even also can form the nesa coating of homogeneous thickness at curved face part or jog
Promptly the present invention relates to nesa coating and form liquid, it is characterized in that, contain the indium compound of following formula [1] expression and the tin compound of following formula [2] expression:
In(R
1COCHCOR
2)
3 [1]
Wherein, R
1And R
2Represent independently that respectively carbon number is the alkyl or phenyl of 1-10;
(R
3)
2Sn(OR
4)
2 [2]
Wherein, R
3The expression carbon number is the alkyl of 1-10, R
4The expression carbon number is the alkyl of 1-10 or the acyl group (claim 1) that carbon number is 1-10; The invention still further relates to the described nesa coating of claim 1 and form liquid, it is characterized in that, the solvent of the tin compound of the indium compound of dissolution type [1] expression and formula [2] expression is a beta-diketone compounds (claim 2).The invention still further relates to the described nesa coating of claim 1 and form liquid, it is characterized in that contained alkali-metal amount is 2 quality ppm or following (claim 3).
In addition, the present invention relates to the manufacture method of transparent conductive film cling matrix, this method is directly or by intermediate coat to form the method that nesa coating is made transparent conductive film cling matrix on matrix, it is characterized in that, on described matrix or intermediate coat, use contains the indium compound of following formula [1] expression and the nesa coating of the tin compound that following formula [2] is represented forms liquid, forms nesa coating by chemical thermal decomposition:
In(R
1COCHCOR
2)
3 [1]
Wherein, R
1And R
2Represent independently that respectively carbon number is the alkyl or phenyl of 1-10;
(R
3)
2Sn(OR
4)
2 [2]
Wherein, R
3The expression carbon number is the alkyl of 1-10, R
4The expression carbon number is the alkyl of 1-10 or the acyl group (claim 4) that carbon number is 1-10; The invention still further relates to the manufacture method of the described transparent conductive film cling matrix of claim 4, it is characterized in that, the solvent of the tin compound of the indium compound of dissolution type [1] expression and formula [2] expression is a beta-diketone compounds (claim 5); The invention still further relates to the manufacture method of the described transparent conductive film cling matrix of claim 4, it is characterized in that, contained alkali-metal amount is 2 quality ppm or following (claim 6).
Further, the invention still further relates to the manufacture method of transparent conductive film cling matrix, it is characterized in that, on matrix, directly or by intermediate coat, form nesa coating (claim 7) by the pyrosol facture with curved surface or concaveconvex shape.The invention still further relates to the manufacture method of transparent conductive film cling matrix, it is characterized in that, on matrix,, form nesa coating (claim 8) with the pyrosol facture by the intermediate coat that forms by the pyrosol facture with curved surface or concaveconvex shape.The invention still further relates to the manufacture method of transparent conductive film cling matrix, it is characterized in that, on matrix with curved surface or concaveconvex shape, directly or pass through intermediate coat, use the described nesa coating of claim 1 to form liquid, form nesa coating (claim 9) by the pyrosol facture.
Description of drawings
Fig. 1 represents to measure by ESCA the result of transparent conductive film cling matrix of the present invention (the ITO film glassivation substrate of embodiment 1-3).
Fig. 2 represents to measure by ESCA the indium content results of the transparent conductive film cling matrix (the ITO film bosh fiber of embodiment 5) that the transparent conductive film cling matrix manufacture method is made according to the present invention.
Fig. 3 represents to measure indium and the tin content results of transparent conductive film cling matrix (the ITO film bosh fiber of embodiment 5) on ITO film depth direction that the transparent conductive film cling matrix manufacture method is made according to the present invention by ESCA.
Fig. 4 represents to measure by ESCA the indium content results of the ITO film bosh fiber of making according to the transparent conductive film cling matrix manufacture method of comparative example 2 (transparent conductive film cling matrix).
Fig. 5 represents to measure indium and the tin content results of ITO film bosh fiber (transparent conductive film cling matrix) on ITO film depth direction of making according to the transparent conductive film cling matrix manufacture method of comparative example 2 by ESCA.
Embodiment
Below, in explanation of the present invention, except the explanation specific implementations, all be identical about the explanation of all execution modes of the present invention.
First execution mode that nesa coating of the present invention forms liquid is characterized as the indium compound that contains following formula [1] expression:
In(R
1COCHCOR
2)
3 [1]
Tin compound with usefulness following formula [2] expression:
(R
3)2Sn(OR
4)
2 [2]
In the formula [1], R
1And R
2Represent independently that respectively carbon number is the alkyl or phenyl (down together) of 1-10.Concrete example is as methyl, ethyl, n-pro-pyl, normal-butyl, the tert-butyl group etc.Wherein, as the preferred especially praseodynium indium (In (CH of the indium compound of formula [1] expression
3COCHCOCH
3)
3).
In the formula [2], R
3The expression carbon number is the alkyl of 1-10, R
4The expression carbon number is the alkyl of 1-10 or the acyl group that carbon number is 1-10 (down together).Specifically, R
3Methyl, ethyl, n-pro-pyl, normal-butyl, the tert-butyl group etc. are for example arranged; R
4Alkyl such as methyl, ethyl, n-pro-pyl, normal-butyl, the tert-butyl group are for example arranged, acyl groups such as acetyl group, propiono.Wherein, as the preferred especially di-n-butyl oxalic acid tin ((n-Bu) of the tin compound of formula [2] expression
2Sn (OCOCH
3)
2).
When using nesa coating to form liquid formation nesa coating, it has been generally acknowledged that the heat decomposition temperature of indium compound contained in nesa coating formation liquid and tin compound is approaching more, both diffusions are even more, can form membranous uniformly.Form in the liquid at nesa coating of the present invention, the heat decomposition temperature of the tin compound of the indium compound of formula [1] expression and formula [2] expression is approaching, specifically, the heat decomposition temperature of praseodynium indium is about 320 ℃, and di-n-butyl oxalic acid tin is about 360 ℃.
Therefore, when using nesa coating of the present invention to form liquid formation nesa coating, decompose indium compound and tin compound by heat, and then when on matrix or intermediate coat, piling up, it has been generally acknowledged that indium compound and tin compound almost carry out thermal decomposition simultaneously under institute's fixed temperature, both evenly spread and pile up (evaporation), form membranous film extremely uniformly, thereby can form conductivity and the extremely uniform nesa coating of the transparency.In addition, the coating nesa coating forms after the liquid, indium compound and tin compound decompose by heat, and then on matrix or intermediate coat fixedly the time, in the drying and/or calcination after coating, it has been generally acknowledged that indium compound and tin compound almost carry out thermal decomposition simultaneously under institute's fixed temperature, both evenly spread and are fixed on matrix or the intermediate coat, membranous film extremely uniformly be can form, thereby conductivity and the extremely uniform nesa coating of the transparency formed.So, the film that forms liquid formation with nesa coating of the present invention has the good conductivity and the transparency, therefore can be widely used in fields such as LCD, electroluminescent display, face heating element, contact electrode, solar cell.
As long as forming liquid, nesa coating of the present invention comprises indium compound and tin compound, contained ratio does not have special restriction, but the In in the preferred indium compound is qualitatively than the Sn in the tin compound many (formed nesa coating is the ITO film), more preferably according to mass ratio, In in relative 1 part of indium compound, the content of Sn is 0.001～0.5 in the tin compound, more preferably 0.05～0.35.
Contain indium compound and tin compound according to above-mentioned quality than scope, can form transparency and the good nesa coating of resistance value homogeneity thus, the nesa coating with described resistance value is particularly suitable for for example being used as the transparency electrode that touch panel is used.
The nesa coating of first embodiment of the invention forms the indium compound that liquid contains formula [1] expression, but it also can unite use with other indium compound.Form the material of indium oxide after the preferred thermal decomposition of the indium compound of associating use, for example, indium trichloride (InCl
3), indium nitrate (In (NO
3)
3), three isopropoxy indiums (In (OiPr)
3) etc.
When uniting when using with other indium compound, the content of indium compound in all indium compounds of formula [1] expression be preferably 80 quality % or more than, more preferably 90 quality % or more than, further preferred 95 quality % or more than.The indium compound that preferably contains more formulas [1] expression.
The nesa coating of first embodiment of the invention forms the tin compound that liquid contains formula [2] expression, but it also can unite use with other tin compound.Form the material of tin oxide after the preferred thermal decomposition of the tin compound of associating use, for example, stannic chloride, dimethyltin chloride, dibutyl tin dichloride, tetrabutyltin, stannous octoate (Sn (OCOC
7H
15)
2), dibutyl maleic acid tin, dibutyl diacetyl group acetone tin etc.
When uniting when using with other tin compound, in all tin compounds, the preferred 80 quality % of content of the tin compound of formula [2] expression or more than, more preferably 90 quality % or more than, further preferred 95 quality % or more than.The tin compound that preferably contains more formula [2] expression.
Nesa coating of the present invention forms liquid except containing indium compound and tin compound, also preferably comprises the compound of following monomer or these monomers as the 3rd component: the periodic table of elements the 2nd major element such as Mg, Ca, Sr, Ba etc.; The 3rd subgroup element such as Sc, Y etc.; Lanthanide series such as La, Ce, Nd, Sm, Gd etc.; The 4th subgroup element such as Ti, Zr, Hf etc.; The 5th subgroup element such as V, Nb, Ta etc.; The 6th subgroup element such as Cr, Mo, W etc.; The 7th subgroup element such as Mn etc.; The 9th subgroup element such as Co etc.; The 10th subgroup element such as Ni, Pd, Pt etc.; The 11st subgroup element such as Cu, Ag etc.; The 12nd subgroup element such as Zn, Cd etc.; The 13rd major element such as B, Al, Ga etc.; The 14th major element such as Si, Ge, Pb etc.; The 15th major element such as P, As, Sb etc.; The 16th major element Se, Te etc.
With respect to indium, about preferred 0.05～20 atom % of the adding proportion of described element, element is different to be changed adding proportion with adding, and can suitably select to meet the element and the addition of required resistance value.
Described nesa coating of the present invention forms the used organic solvent of liquid and can enumerate: ketones solvents such as acetone, methyl iso-butyl ketone (MIBK), metacetone; Alcohols solvents such as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols; Esters solvent such as ethyl acetate, butyl acetate; Ether solvents such as methyl Cellosolve, oxolane; Aromatic hydrocarbons such as benzene,toluene,xylene; Fat hydrocarbons such as hexane, heptane, octane, cyclohexane etc.
The kind of above-mentioned organic solvent and addition depend on fixed nesa coating sheet resistance value etc., according to can suitably determining the kind of the kind of nesa coating, the thickness of nesa coating, used organic solvent, heating-up temperature, heating time etc.Such as, under the identical situation of other condition,, can reduce sheet resistance value by the organic solvent of the easier thermal decomposition of a large amount of interpolations.As mentioned above, the nesa coating that can obtain to have required sheet resistance value by suitable selection, the kind of determining used organic solvent, addition and heating-up temperature.
Being characterized as of second execution mode of nesa coating of the present invention comprises the indium compound that following formula [1] is represented:
In(R
1COCHCOR
2)
3 [1]
And the tin compound of following formula [2] expression:
(R
3)
2Sn(OR
4)
2 [2]
Also comprise the indium compound of dissolution type [1] expression and the beta-diketone compounds of the tin compound that formula [2] is represented.
At this moment, described beta-diketone compounds comprises, beta-diketone compounds such as acetylacetone,2,4-pentanedione etc.; Beta-ketoester such as methyl acetoacetate, ethyl acetoacetate etc.; β-dicarboxylic ester such as dimethyl malenate, diethyl malonate etc., wherein preferred acetylacetone,2,4-pentanedione.Can more effectively bring into play effect of the present invention by using acetylacetone,2,4-pentanedione.
Nesa coating in second embodiment of the invention forms in the liquid, fully dissolved with the indium compound of formula [1] expression and the tin compound of representing with formula [2], the ratio of components that nesa coating forms in the liquid can not change, so think by using this nesa coating formation liquid formation nesa coating can form membranous uniform nesa coating.
As long as the nesa coating in the second embodiment of the invention forms the indium compound that beta-diketone compounds in the liquid can dissolution type [1] expression and the tin compound of formula [2] expression, there is no particular limitation to its amount, but the addition of preferred beta-diketone compounds is as follows: according to mass ratio, relative 1 part of beta-diketone compounds, the content of total metal ingredient (In+Sn) of the tin compound of the indium compound of formula [1] expression and formula [2] expression be 0.07 or below, more preferably 0.00001～0.07 scope, further preferred 0.001～0.04 scope.By using beta-diketone compounds according to above-mentioned scope, can be at the indium compound of dissolution type under the debita spissitudo [1] expression and the tin compound of formula [2] expression, thus can form membranous more uniform nesa coating.
In addition, the nesa coating in the second embodiment of the invention forms other solvents that liquid can illustrate and unites use in above-mentioned beta-diketone compounds and above-mentioned first execution mode.
The solvent species of associating use and addition depend on the set point of sheet resistance value of nesa coating or film formation method etc., for more effectively bringing into play effect of the present invention, beta-diketone compounds in whole solvents the preferred 80 quality % of content or more than, more preferably 90 quality % or more than, further preferred 95 quality % or more than, preferably contain more beta-diketone compounds.
Nesa coating in the second embodiment of the invention forms liquid can unite other indium compounds that illustrate in above-mentioned first execution mode of use, equally also can unite and use other tin compounds that illustrate in above-mentioned first execution mode.
Nesa coating in the third embodiment of the invention forms being characterized as of liquid and contains indium compound and tin compound, and the alkali metal content that nesa coating forms in the liquid is 2 quality ppm or following.
With alkali metal content is that the nesa coating that 2 quality ppm or following nesa coating formation liquid form can not produce harmful effect to light-emitting component in fields such as LCD especially, and it can significantly improve the reliability of light-emitting component.
Nesa coating in third embodiment of the invention forms in the liquid, and as mentioned above, alkali-metal content is necessary for 2 quality ppm or following, preferred 1.5 quality ppm or following, more preferably 1 quality ppm or following, further preferred 0.1 quality ppm or following.
At this moment, described alkali metal has lithium, sodium, potassium, rubidium, caesium, francium etc., considers that in fact might sneak into nesa coating forms in the liquid, in fact, thinks that the total amount that regulates sodium and potassium gets final product.
Become the material of indium oxide compound after the preferred thermal decomposition of indium compound in the nesa coating formation liquid of third embodiment of the invention, for example, praseodynium indium (In (CH
3COCHCOCH
3)
3), tri-benzoyl methyl indium (In (C
6H
5COCHCOC
6H
5)
3), indium trichloride (InCl
3), indium nitrate (In (NO
3)
3), three isopropoxy indiums (In (O-i-Pr)
3) etc.
Become the material of oxidation distannic compound after the preferred thermal decomposition of tin compound in the third embodiment of the invention nesa coating formation liquid, for example, stannic chloride, dimethyltin chloride, dibutyl tin dichloride, tetrabutyltin, stannous octoate (Sn (OCOC
7H
15)
2), dibutyl maleic acid tin, dibutyl diacetyl group acetone tin, di-n-butylacetic acid tin etc.
In addition, contain indium compound and tin compound as long as the third embodiment of the invention nesa coating forms liquid, its kind is not particularly limited, but the indium compound that preferred indium compound is above-mentioned formula [1] expression:
In(R
1COCHCOR
2)
3 [1]
Tin compound is the tin compound of above-mentioned formula [2] expression:
(R
3)
2Sn(OR
4)
2 [2]
Wherein, the preferred especially praseodynium indium (In (CH of the indium compound of formula [1] expression
3COCHCOCH
3)
3), the preferred especially di-n-butyl oxalic acid tin ((n-Bu) of the tin compound of formula [2] expression
2Sn (OCOCH
3)
2).
Below, the manufacture method of transparent conductive film cling matrix of the present invention is described.
The manufacture method of transparent conductive film cling matrix of the present invention is directly or by intermediate coat to form the method that nesa coating is made transparent conductive film cling matrix on matrix, it is characterized in that, on described matrix or intermediate coat, each nesa coating forms liquid in use first to the 3rd execution mode, forms nesa coating by chemical thermal decomposition.That is, it is characterized by, use above-mentioned nesa coating to form liquid, form nesa coating by chemical thermal decomposition.
Here, chemical thermal decomposition is meant following method, i.e. indium compound that nesa coating is formed contained in the liquid by thermal decomposition and the tin compound method of on matrix or intermediate coat, piling up, and after the coating nesa coating forms liquid, indium compound that nesa coating is formed contained in the liquid by thermal decomposition and tin compound fixing method on matrix or intermediate coat.For example, spray-on process, immersion plating, spin coating (ス ピ Application コ one ト method), LB method, sol-gel process, liquid phase epitaxial method, CVD method (chemical vapor deposition) are as hot CVD method, plasma CVD method, mocvd method, pyrosol facture (by the atmospheric pressure cvd method of ultrasonic atomization), SPD method, Cat-CVD method etc., wherein, preferred especially pyrosol facture.The pyrosol facture can produce membranous more uniform nesa coating.In the pyrosol facture, nesa coating forms liquid and is admitted to the chance that furnace conveyor (film formation device) back contacts with alkali metal before fully to nesa coating formation, so can extremely easily form the few nesa coating of alkali metal content.
The manufacture method of transparent conductive film cling matrix according to the present invention forms liquid by using above-mentioned nesa coating, and indium compound that heat decomposition temperature is very approaching and tin compound can evenly spread at a certain temperature and form membranous uniform nesa coating.In addition, form liquid by the nesa coating that uses the invention described above second execution mode, the tin compound of the indium compound of wushu [1] expression and formula [2] expression dissolves fully, then the ratio of component in the nesa coating formation liquid can not change, and can form membranous uniform nesa coating thus.In addition, form liquid by the nesa coating that uses the invention described above the 3rd execution mode, in fields such as LCD, can not cause harmful effect, can easily make the transparent conductive film cling matrix that can significantly improve the light-emitting component reliability light-emitting component.
Specifically, when forming indium compound and tin compound contained in the liquid by the thermal decomposition nesa coating and making it on matrix or intermediate coat, to pile up, think that indium compound and tin compound almost carry out thermal decomposition at a certain temperature simultaneously and then evenly spread and pile up (evaporation), membranous film extremely uniformly be can form, thereby conductivity and the extremely uniform nesa coating of the transparency formed.Also have, after the coating nesa coating forms liquid, by thermal decomposition indium compound and tin compound and on matrix or intermediate coat fixedly the time, think that using the uniform nesa coating of composition to form liquid is coated with, again in the drying and/or calcination after coating, indium compound that heat decomposition temperature is approaching and tin compound almost carry out thermal decomposition at a certain temperature simultaneously, both evenly spread and are fixed on matrix or the intermediate coat, form membranous film extremely uniformly, thereby form conductivity and the extremely uniform nesa coating of the transparency.
In addition, the nesa coating that the manufacture method of transparent conductive film cling matrix produces according to the present invention has the good conductivity and the transparency, so can be widely used in aspects such as LCD, electroluminescent display, face heating element, contact electrode, solar cell.Further, in the manufacture method of transparent conductive film cling matrix of the present invention, be that chemical thermal decomposition can form homogeneous membrane easily by the general approach that uses film forming.
Described intermediate coat can be that monofilm also can be two-layer or two-layer above film.Described intermediate coat for example has, silicon oxide film, the polysilane film, the MgF that are formed by the organopolysilane compound
2Film, CaF
2Film, SiO
2And TiO
2Complex oxide film etc.The formation of these intermediate coats is the Na ions diffusion that is used to prevent when using soda-lime glass as substrate for example.In addition, also can prevent reflection or improve transparent by the counterdie of formation with nesa coating different refractivity, preferred low-refraction.Described film can adopt known film build method as, formation such as sputtering method, CVD method, spray-on process, infusion process, the not special restriction of the thickness of described film, but be generally about 20～200nm.
Described matrix can be sheet (substrate), cellular, fibrous, spherical, foam-like or their compound etc., as long as the component of nesa coating formation liquid has thermal endurance and then is not subjected to any restriction, for example glass substrate, ceramic substrate, metal substrate etc. under the temperature of thermal decomposition.Wherein, the preferred glass substrate that uses in the manufacture method of transparent conductive film cling matrix of the present invention.Described glass substrate for example has silicate glasses (quartz glass), silicate base glass, soda-lime glass, potash-lime glass, lead glass, barium glass, pyrex etc.
The thickness of the nesa coating that forms in transparent conductive film cling matrix manufacture method of the present invention is not particularly limited, can suitably select according to its purposes etc., but when forming sheet resistance value and be the ITO film of 30 Ω/below the, be generally 50nm or more than, when the formation sheet resistance value is the ITO film of 60-200 Ω/, be generally 30nm or more than, when forming sheet resistance value and be the ITO film of 200-3000 Ω/, be generally 10-25nm.
In the manufacture method of transparent conductive film cling matrix of the present invention, when adopting described pyrosol facture, with ultrasonic wave indium compound and tin compound being dissolved in nesa coating in the organic solvent forms liquid and makes the aerosol that is formed by granular more regular droplet by spray-on process, indium compound and tin compound are delivered on the matrix in the heating furnace, the temperature of this heating furnace is controlled at the uniform temperature of indium compound and tin compound generation thermal decomposition formation indium oxide and tin oxide, for example 300-800 ℃, make indium compound and tin compound gasification becoming gaseous state in heating furnace, reaction forms nesa coating on matrix then.
When use has the matrix of curved surface or concaveconvex shape, preferably directly or by intermediate coat utilize the pyrosol facture to form nesa coating.By adopting the pyrosol facture can on matrix, easily form thickness nesa coating extremely uniformly with curved surface or concaveconvex shape.Promptly, on matrix, in general be very difficult with the homogeneous film thickness film forming with curved surface or concaveconvex shape, but if adopt the pyrosol facture, the metallic compound that becomes gaseous state by heating sublimation is at curved face part or jog also even contact and carry out thermal decomposition, can produce to have the whole thickness transparent conductive film cling matrix of nesa coating extremely uniformly.
In addition, when adopting pyrosol facture film forming on flat board, the metallic compound of heating sublimation slips into the inboard (outer peripheral portion of inner face) of flat board sometimes, becomes the bad reasons of conduction such as touch panel therefrom.For this reason, be necessary to control to prevent to slip into the inboard of flat board, but matrix (as fibrous matrix or spherical matrix) with regard to curved surface or concaveconvex shape, there's no one who doesn't or isn't as utilize its inboard of slipping into flat board and, also can form the nesa coating of uniform film thickness at inner face because of situation difference (as the situation of hemisphere matrixes such as bowl type etc.) in curved surface or concavo-convex outside.
Can form the matrix of nesa coating by the pyrosol facture, do not make particular restriction if having the matrix of curved surface or concaveconvex shape, even a part be the flaky matrix (substrate) of curved surface or concaveconvex shape, cellular matrix, fibrous matrix, spherical matrix, foam-like matrix etc. also can, but optimum fiber shape or spherical matrix.In addition, the matrix preferred curvature radius with described curved surface is the curved surface matrix about 1-1000mm.
Here, described fibrous matrix is meant that diameter is the fibrous matrix about 0.01-15mm, described spherical matrix be meant the spherical matrix (as hemispherical) of oval ball matrix, excalation and lamp bulb-shaped matrix etc. interior sphere be included as whole substrate surface (one-tenth membrane portions) 30% or more than, preferred 50% or more than, more preferably 80% or above matrix.
Described fibrous transparent conductive film cling matrix is specially adapted to optical telecommunication cables, preferred especially quartz fibre.And the spherical transparent conductive film cling matrix is specially adapted to the electric consumption on lighting utmost point.
In addition, according to the present invention, the nesa coating that can adopt the pyrosol facture to form on the matrix with curved surface or concaveconvex shape is not limited to mix the indium oxide film (ITO film) of tin, mix in addition fluorine tin oxide film (FTO film), mix antimony tin oxide film (ATO film), mix indium Zinc oxide film, mix the Zinc oxide film of aluminium etc.
Embodiment
Below, further specify the present invention by embodiment, but this explanation do not limit technical scope of the present invention for example.
Embodiment 1
Praseodynium indium (In (AcAc)
3) being dissolved in acetylacetone,2,4-pentanedione, to make it molar concentration be 0.2mol/L, obtains yellow transparent solution.In this solution, add di-n-butyl oxalic acid tin as tin compound, make it to reach Sn/In=5 quality %, prepare the ITO film thus and form liquid (nesa coating formation liquid).At this moment, alkali-metal content is as follows: the praseodynium indium is 0.03 quality ppm, and acetylacetone,2,4-pentanedione is 0.05 quality ppm, and di-n-butyl oxalic acid tin is 0.03 quality ppm.
Form liquid by the pyrosol facture with this ITO film, regulate the ITO film and form the chemical heat decomposition amount that the liquid atomizing produces, simultaneously, by infusion process SiO
2(SLG substrate) formation thickness is the ITO film of 20nm on the glass substrate of film linging, obtains having the ITO film glassivation substrate (transparent conductive film cling matrix) of water white transparency ITO film.
Embodiment 2
On glass substrate, form the ITO film that thickness is 40nm with the foregoing description 1 with method, obtain having the ITO film glassivation substrate of transparent ITO film.
Embodiment 3
On glass substrate, form the ITO film that thickness is 200nm with the foregoing description 1 with method, obtain having the ITO film glassivation substrate of transparent ITO film.
Comparative example 1
The praseodynium indium is dissolved in acetylacetone,2,4-pentanedione, and making it molar concentration is 0.2mol/L, obtains yellow transparent solution.In this solution, add three-n-octyl tin oxide (ト リ-n-オ Network チ Le ス ズ オ キ サ イ De) and, make it to reach Sn/In=5 quality %, prepare the ITO film thus and form liquid as tin compound.
Adopt this ITO film to form liquid, regulate the ITO film and form the chemical heat decomposition amount that the liquid atomizing produces by the pyrosol facture, simultaneously, by infusion process SiO
2(SLG substrate) formation thickness is the ITO film of 30nm on the glass substrate of film linging, makes the ITO film glassivation substrate with flavescent transparent ITO film.
The praseodynium indium is dissolved in acetylacetone,2,4-pentanedione, and making it molar concentration is 0.2mol/L, obtains yellow transparent solution.Adding alkali metal content in this solution is the di-n-butyl oxalic acid tin of 0.03 quality ppm, makes it to reach Sn/In=5 quality %, adds odium stearate then, makes it to reach Na/In=10 quality ppm, prepares the ITO film thus and forms liquid.
Adopt this ITO film to form liquid, regulate the ITO film and form the chemical heat decomposition amount that the liquid atomizing produces by the pyrosol facture, simultaneously, by infusion process SiO
2(SLG substrate) formation thickness is the ITO film of 40nm on the glass substrate of film linging, produces ITO film glassivation substrate.
Estimate
Measure the ratio resistance value of the ITO film glassivation substrate in the foregoing description 1-4 and the comparative example 1 with ロ レ ス (Mitsubishi Chemical Ind), and obtain sheet resistance value.Sheet resistance value is obtained than the thickness of resistance value/conducting film in addition.Optional part a-c (3 place) measures the light transmittance of 550nm wavelength with magnetic spectrophotometer (Hitachi) in the ITO film glassivation substrate of embodiment 1-4 and comparative example 1.In addition, measure in the ITO film glassivation substrate of embodiment 1-3 and comparative example 1 indium content and tin content by ESCA at ITO film depth direction.With the ITO film in the ITO film glassivation substrate of acid corrosion dissolving embodiment 1-4, measure alkali-metal content with ICP emission spectro-chemical analysis device.
The measurement result of sheet resistance value is as shown in table 1, and the measurement result of light transmittance is as shown in table 2, and the measurement result of alkali metal amount is as shown in table 3.In addition, Fig. 1 represents the result of the ITO film glassivation substrate of the embodiment 1-3 that measures with ESCA.
Table 1
| The thickness of ITO film (nm) | The sheet resistance value of ITO film (Ω/) | |
| Embodiment 1 | 20 | 500 |
| Embodiment 2 | 40 | 100 |
| Embodiment 3 | 200 | 10 |
| | 40 | 100 |
| Comparative example 1 | 30 | 10000 |
Table 2
| The light transmittance a (%) of ITO film | The light transmittance b (%) of ITO film | The light transmittance c (%) of ITO film | |
| Embodiment 1 | 90 | 90 | 91 |
| Embodiment 2 | 88 | 89 | 89 |
| Embodiment 3 | 80 | 81 | 80 |
| | 88 | 88 | 89 |
| Comparative example 1 | 88 | 86 | 90 |
Table 3
| Alkali-metal content (quality ppm) | |
| Embodiment 1 | 0.1 |
| Embodiment 2 | 0.1 |
| Embodiment 3 | 0.1 |
| | 12 |
(result)
As known from Table 1, manufacture method according to transparent conductive film cling matrix of the present invention, variation by thickness can produce the ITO film cling matrix that sheet resistance value is 10-500 Ω/, obtains being applicable to the ITO film cling matrix of having of various uses of required sheet resistance value ITO film.
As known from Table 2, the light transmittance in arbitrary portion is almost equal respectively for the ITO film glassivation substrate of embodiment of the invention 1-4, shows that the transparency of film is even.
As known from Table 3, in the ITO film in the ITO film glass substrate of embodiment of the invention 1-3, alkali metal content is 0.1 quality ppm, by producing the higher light-emitting component of reliability with light-emitting components such as this ITO film production LCD.On the other hand, in the ITO film in the ITO film glass substrate of embodiment 4, alkali metal content is 12 quality ppm, and when with light-emitting components such as this ITO film production LCD, then the light-emitting component reliability is very low, and its application is restricted.
As shown in Figure 1, in the ITO film glassivation substrate of embodiment of the invention 1-3, the content of tin almost is certain, and is formed on film surface and inner indium of film and the homodisperse film of tin.On the other hand, in the ITO film glassivation substrate of comparative example 1, do not measure tin with ESCA, tin just is thermal decomposited, and does not form film with indium.
Embodiment 5
Use the ITO film of embodiment 1 to form liquid, by the pyrosol facture, regulate because of the ITO film forms the chemical heat decomposition amount that the atomizing of liquid produces, simultaneously, be to form the ITO film on the quartz fibre of 500 μ m at diameter, obtain ITO film bosh fiber (transparent conductive film cling matrix).
Comparative example 2
Use ITO object ( one ゲ Star the ト) (In of Sn/In=10 quality %
2O
3And SnO
2Sinter), be under the condition of 0.7Pa in partial pressure of oxygen, by sputtering method, be diameter that the quartz fibre 1 minute rotation of 500 μ m forms ITO 20 times, obtain ITO film bosh fiber.
(evaluation)
The ITO film bosh fiber of the foregoing description 5 and comparative example 2 is gone up length about cutting 1cm at an arbitrary position, measure indium content at 4 different surperficial positions with ESCA and detect the thickness of ITO film.On ITO film depth direction, measured the content (content ratio) of indium and tin with method.
Fig. 2 represents indium Determination on content result in the ITO film bosh fiber of embodiment 5, and Fig. 3 is illustrated in indium and tin Determination on content result on the ITO film depth direction.Fig. 4 represents indium Determination on content result in the ITO film bosh fiber of comparative example 2, and Fig. 5 is illustrated in indium and tin Determination on content result on the ITO film depth direction.
(result)
As can be seen from Figure 2, in the ITO film bosh fiber of embodiment 5, the thickness of ITO film is the 95-105nm scope, can form thickness ITO film extremely uniformly.In addition, as can be seen from Figure 3, in the ITO film bosh fiber of embodiment 5, the content of tin almost is certain, is formed on inner indium of film surface and film and the homodisperse film of tin.
On the contrary, in the ITO of comparative example 2 film bosh fiber, as shown in Figure 4, the thickness of ITO film is about the 70-100nm scope, and deviation is very big, and the ITO film of formation is the ITO film of membrane thickness unevenness.In addition, as shown in Figure 5, in the ITO of comparative example 2 film bosh fiber, it is at film surface tin content height that the tin in the film distributes, inhomogeneous.
The invention effect
Form liquid by nesa coating of the present invention, can form the indium compound of sheet resistance value, the transparency and nesa coating depth direction and the extremely uniform nesa coating in distribution aspect of tin compound. Form liquid by nesa coating of the present invention, can also form the nesa coating that can improve the light-emitting component reliability.
The manufacture method of transparent conductive film cling matrix according to the present invention can be made extremely uniformly transparent conductive film cling matrix of the indium compound of sheet resistance value, the transparency and nesa coating depth direction and tin compound distribution aspect. According to the manufacture method of transparent conductive film cling matrix of the present invention, produce easily the nesa coating that can improve the light-emitting component reliability.
The manufacture method of transparent conductive film cling matrix according to the present invention can have curved surface or the concavo-convex extremely uniform nesa coating of matrix formation thickness, and make easily extremely uniformly transparent conductive film cling matrix of thickness.
Claims (7)
1. nesa coating forms liquid, it is characterized in that: comprise the indium compound of following formula [1] expression and the tin compound of following formula [2] expression:
In(R
1COCHCOR
2)
3 [1]
Wherein, R
1And R
2Represent independently that respectively carbon number is the alkyl or phenyl of 1-10;
(R
3)
2Sn(OR
4)
2 [2]
Wherein, R
3The expression carbon number is the alkyl of 1-10, R
4The expression carbon number is that alkyl or the carbon number of 1-10 is the acyl group of 1-10.
2. the described nesa coating of claim 1 forms liquid, it is characterized in that: the solvent of the tin compound of the indium compound of dissolution type [1] expression and formula [2] expression is a beta-diketone compounds.
3. claim 1 or 2 described nesa coatings form liquid, and it is characterized in that: contained alkali-metal amount is 2 quality ppm or following.
4. the manufacture method of transparent conductive film cling matrix, this method is directly or by intermediate coat to form the method that nesa coating is made transparent conductive film cling matrix on matrix, it is characterized in that: on described matrix or intermediate coat, nesa coating with the tin compound of indium compound that comprises following formula [1] expression and following formula [2] expression forms liquid, forms nesa coating by chemical thermal decomposition:
In(R
1COCHCOR
2)
3 [1]
Wherein, R
1And R
2Represent independently that respectively carbon number is the alkyl or phenyl of 1-10;
(R
3)
2Sn(OR
4)
2 [2]
Wherein, R
3The expression carbon number is the alkyl of 1-10, R
4The expression carbon number is that alkyl or the carbon number of 1-10 is the acyl group of 1-10.
5. the manufacture method of the described transparent conductive film cling matrix of claim 4 is characterized in that: the solvent of the tin compound of the indium compound of dissolution type [1] expression and formula [2] expression is a beta-diketone compounds.
6. the manufacture method of claim 4 or 5 described transparent conductive film cling matrixes, it is characterized in that: contained alkali-metal amount is 2 quality ppm or following.
7. the manufacture method of transparent conductive film cling matrix is characterized in that: on the matrix with curved surface or concaveconvex shape, directly or by intermediate coat, form liquid with the described nesa coating of claim 1 and form nesa coating by the pyrosol facture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101202939A CN100336136C (en) | 2003-12-12 | 2003-12-12 | Transparent conductive film forming liquid and mfg. method of adheved substrate of transparent conductive film contg. such forming liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101202939A CN100336136C (en) | 2003-12-12 | 2003-12-12 | Transparent conductive film forming liquid and mfg. method of adheved substrate of transparent conductive film contg. such forming liquid |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100877920A Division CN101042950B (en) | 2003-12-12 | 2003-12-12 | Method for manufacturing transparent conductive film attachment substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1627449A CN1627449A (en) | 2005-06-15 |
| CN100336136C true CN100336136C (en) | 2007-09-05 |
Family
ID=34761512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101202939A Expired - Fee Related CN100336136C (en) | 2003-12-12 | 2003-12-12 | Transparent conductive film forming liquid and mfg. method of adheved substrate of transparent conductive film contg. such forming liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100336136C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111769166B (en) * | 2020-07-10 | 2022-02-08 | 浩物电子科技(苏州)有限公司 | Electrode and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60243280A (en) * | 1984-05-14 | 1985-12-03 | Alps Electric Co Ltd | Formation of transparent electrode |
| JPH05182765A (en) * | 1992-01-06 | 1993-07-23 | Kohjin Co Ltd | Binder for dispersion type el element and dispersion type el element |
| JPH06175144A (en) * | 1992-12-07 | 1994-06-24 | Tanaka Kikinzoku Kogyo Kk | Ink precursor for forming transparent conductive film and method for forming ITO transparent conductive film |
| CN1220291A (en) * | 1997-09-05 | 1999-06-23 | 三菱综合材料株式会社 | Transparent conductive film and composition for forming same |
| US5998011A (en) * | 1991-07-24 | 1999-12-07 | Matsushita Electric Industrial Co., Ltd. | Composition for use in a transparent and electrically conductive film and a method for making the film |
| CN1280960A (en) * | 2000-07-15 | 2001-01-24 | 昆明理工大学 | Process for preparing sol-gel of indium tin oxide film |
| JP2001035273A (en) * | 1999-07-23 | 2001-02-09 | Nippon Soda Co Ltd | Adjusting method for sheet resistance value of transparent conductive film and forming method for the transparent conductive film |
| JP2002133956A (en) * | 2000-10-19 | 2002-05-10 | Nippon Soda Co Ltd | Adjusting method for sheet resistance value of transparent conductive film and forming method for transparent conductive film |
-
2003
- 2003-12-12 CN CNB2003101202939A patent/CN100336136C/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60243280A (en) * | 1984-05-14 | 1985-12-03 | Alps Electric Co Ltd | Formation of transparent electrode |
| US5998011A (en) * | 1991-07-24 | 1999-12-07 | Matsushita Electric Industrial Co., Ltd. | Composition for use in a transparent and electrically conductive film and a method for making the film |
| JPH05182765A (en) * | 1992-01-06 | 1993-07-23 | Kohjin Co Ltd | Binder for dispersion type el element and dispersion type el element |
| JPH06175144A (en) * | 1992-12-07 | 1994-06-24 | Tanaka Kikinzoku Kogyo Kk | Ink precursor for forming transparent conductive film and method for forming ITO transparent conductive film |
| CN1220291A (en) * | 1997-09-05 | 1999-06-23 | 三菱综合材料株式会社 | Transparent conductive film and composition for forming same |
| JP2001035273A (en) * | 1999-07-23 | 2001-02-09 | Nippon Soda Co Ltd | Adjusting method for sheet resistance value of transparent conductive film and forming method for the transparent conductive film |
| CN1280960A (en) * | 2000-07-15 | 2001-01-24 | 昆明理工大学 | Process for preparing sol-gel of indium tin oxide film |
| JP2002133956A (en) * | 2000-10-19 | 2002-05-10 | Nippon Soda Co Ltd | Adjusting method for sheet resistance value of transparent conductive film and forming method for transparent conductive film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1627449A (en) | 2005-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1094113C (en) | Method of depositing tin oxide and titanium oxide coating on flat glass and resulting coated glass | |
| CN1074889A (en) | Coated products | |
| CN1476021A (en) | Composition for forming transparent conductive film, solution for forming transparent conductive film, and method for forming transparent conductive film | |
| CN1820091A (en) | Method for forming metal oxide coating film and vapor deposition apparatus | |
| JP5418502B2 (en) | Manufacturing method of transparent conductive film, transparent conductive film, transparent conductive substrate and device using the same | |
| CN1103327C (en) | Method for mfg. thermo-degradation layer on glass, glass-ceramic or enamel surface | |
| CN1864235A (en) | Transparent base with transparent conductive film, method for producing same, and photoelectric converter comprising such base | |
| JP5376822B2 (en) | Method for producing transparent conductive film | |
| JP2009536144A (en) | Method for depositing a zinc oxide coating on a substrate | |
| CN100336136C (en) | Transparent conductive film forming liquid and mfg. method of adheved substrate of transparent conductive film contg. such forming liquid | |
| CN101042950A (en) | Method for manufacturing transparent conductive film cling matrix | |
| CN1694769A (en) | Methods of Depositing Films on Substrates | |
| JP4377003B2 (en) | Method for adjusting sheet resistance value of transparent conductive film and method for forming transparent conductive film | |
| JP2011108637A (en) | Method for forming low-refractive-index transparent conductive film, low-refractive-index transparent conductive film, low-refractive-index transparent conductive substrate, and device using the low-refractive-index transparent conductive substrate | |
| JP5418933B1 (en) | Manufacturing method of coating liquid for forming transparent conductive film | |
| JP2004026554A (en) | Transparent conductive film-forming liquid and method for manufacturing substrate having transparent conductive film using the same | |
| JP2002133956A (en) | Adjusting method for sheet resistance value of transparent conductive film and forming method for transparent conductive film | |
| JP2708120B2 (en) | Method for producing coating liquid for transparent oxide thin film and substrate with transparent oxide thin film | |
| JP2004018913A (en) | Liquid for forming transparent conductive film and method for manufacturing substrate coated with transparent conductive film using the same | |
| JP2561680B2 (en) | Method for producing transparent oxide thin film-coated glass | |
| JP5413708B2 (en) | Transparent conductive film, transparent conductive substrate, device using the same, and method for producing transparent conductive film | |
| JP2009048986A (en) | Coating liquid for transparent conductive film formation, manufacturing method of transparent conductive film, and transparent conductive film | |
| CN1111216A (en) | Heat ray-reflecting glass | |
| KR100662320B1 (en) | Transparent conductive film forming liquid and manufacturing method of gas with transparent conductive film using the same | |
| JP2004022388A (en) | Manufacturing method of transparent conductive film forming liquid and substrate with transparent conductive film using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070905 Termination date: 20171212 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |