WO2005114674A1 - 透明導電材料、透明導電ペースト、透明導電膜及び透明電極 - Google Patents
透明導電材料、透明導電ペースト、透明導電膜及び透明電極 Download PDFInfo
- Publication number
- WO2005114674A1 WO2005114674A1 PCT/JP2005/009260 JP2005009260W WO2005114674A1 WO 2005114674 A1 WO2005114674 A1 WO 2005114674A1 JP 2005009260 W JP2005009260 W JP 2005009260W WO 2005114674 A1 WO2005114674 A1 WO 2005114674A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- transparent conductive
- conductive material
- transparent
- indium
- oxide
- Prior art date
Links
- 239000004020 conductor Substances 0.000 title claims abstract description 142
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 31
- 150000002367 halogens Chemical class 0.000 claims description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000012780 transparent material Substances 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 18
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 10
- -1 indium cations Chemical class 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 229910001449 indium ion Inorganic materials 0.000 description 2
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical compound [Zn].[Sb] CZJCMXPZSYNVLP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/12—Organic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
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- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
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- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
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Definitions
- Transparent conductive material transparent conductive paste, transparent conductive film and transparent electrode
- the present invention relates to a transparent conductive material, a transparent conductive paste, a transparent conductive film, and a transparent electrode.
- Transparent electrodes are used in LCDs, PDPs, organic ELs, touch panels, and the like, and the large transparent electrodes are made of a transparent conductive material.
- a transparent conductive material metal oxides such as tin oxide, indium-tin composite oxide, indium oxide, zinc oxide, and zinc-antimony composite oxide have been known.
- These transparent conductive materials are formed as films on substrates by various methods such as sputtering, vapor deposition, ion plating, and CVD, and are used as transparent conductive films.
- a transparent conductive material obtained by a liquid phase synthesis method has an advantage of being inexpensive to manufacture, but generally uses a chloride containing a halogen in a molecule such as indium chloride tetrahydrate. It tends to contain a large amount of a halogen element as an impurity. Therefore, a transparent electrode using a transparent conductive material obtained by a liquid phase synthesis method has a problem that the resistance value is unstable or large due to the influence of impurities.
- Patent Document 1 JP 05-201731 A
- the present inventors have noticed that the ITO conductive powder described in Patent Document 1 mentioned above may have an increased resistance value particularly when used for a long period of time in a high humidity environment. I found it. [0007]
- the present invention has been made in view of the above circumstances, and a transparent conductive material, a transparent conductive paste, and a transparent material that can sufficiently prevent a change in resistance value with time even in a high humidity environment.
- An object is to provide a conductive film and a transparent electrode.
- the present inventors have conducted intensive studies to solve the above-mentioned problems. For example, the present inventors performed X-ray diffraction on tin-doped indium oxide (ITO) under a high-temperature and high-humidity environment, and found a peak corresponding to In (OH) in an X-ray diffraction spectrum. We have this peak
- the dissociable hydrogen atoms present in the particles combine with the halogen element contained as an impurity in the ITO particles to form halogenated hydrogen, and the hydrogen halide etches the ITO particles to form indium cations.
- the present inventors thought that this was caused by the indium ions binding to moisture.
- the present inventors have conducted further intensive studies based on a strong guess, and as a result, have found that the above-mentioned object can be solved by the following invention, and have completed the present invention.
- the present invention provides an indium composite in which indium oxide or indium oxide is doped with at least one element selected from the group consisting of tin, zinc, tellurium, silver, gallium, zirconium, hafnium and magnesium.
- a transparent conductive material containing an oxidized product, wherein the pH of the mixture containing lwt% of the transparent conductive material is 3 or more, preferably 4 to 9. is there.
- the present invention also provides an indium composite acid obtained by doping indium oxide or at least one element selected from the group consisting of tin, zinc, tellurium, silver, gallium, zirconium, hafnium, and magnesium.
- Transparent conductive material is obtained by doping indium oxide or at least one element selected from the group consisting of tin, zinc, tellurium, silver, gallium, zirconium, hafnium, and magnesium.
- the present invention provides a transparent conductive material containing a tin composite oxide obtained by doping tin oxide or tin oxide with at least one element selected from the group consisting of antimony, zinc and fluorine.
- a transparent conductive material wherein the pH of a mixed solution containing lwt% of the transparent conductive material is 1 or more and the halogen element concentration is 1.5% by mass or less.
- the present invention provides a zinc composite in which zinc oxide or zinc oxide is doped with at least one element selected from the group consisting of aluminum, gallium, indium, boron, fluorine and manganese.
- the present invention is a transparent conductive paste containing the above-mentioned transparent conductive material. Further, the present invention is a transparent conductive film containing the above-mentioned transparent conductive material. Furthermore, the present invention is a transparent electrode including a substrate and a transparent conductive layer provided on one surface side of the substrate, wherein the transparent conductive layer contains the transparent conductive material.
- a transparent conductive material capable of sufficiently preventing a change in resistance value with time even in a high humidity environment. be able to.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of the transparent electrode of the present invention.
- FIG. 2 is a cross-sectional view showing an apparatus for measuring a green compact resistance in an example.
- FIG. 1 is a schematic sectional view showing one embodiment of the transparent electrode of the present invention.
- the transparent electrode 1 according to the present embodiment includes a substrate 10 and a transparent conductive layer 20 formed on one surface of the substrate 10 and containing a transparent conductive material.
- the transparent conductive material contained in the transparent conductive layer 20 contains indium oxide.
- the transparent conductive material has a pH of 3 or more in a mixed solution containing lwt% of the transparent conductive material. According to this transparent conductive material, it is possible to sufficiently prevent the resistance value from changing with time, even in a high humidity environment, regardless of the concentration of the halogen element present in the indium oxide. Although the reason for this is not clear, if the pH of the mixture containing lwt% of the transparent conductive material is 3 or more, the number of dissociable hydrogen atoms can be reduced sufficiently, and it is assumed that halogenated hydrogen is generated. Does not dissolve the transparent conductive material, and as a result, the generation of the insulator In (OH) is sufficiently suppressed, and the resistance of the transparent conductive material is sufficiently increased.
- the pH of a mixed solution containing lwt% of the transparent conductive material is less than 3, and the transparent conductive material having a halogen element concentration of more than 0.2% by mass is used.
- the transmittance of the transparent electrode 1 can be sufficiently increased.
- the transparent conductive material preferably has a pH of 4 or more in a mixed solution containing 1 wt% of the transparent conductive material.
- the pH of the mixed solution containing lwt% of the transparent conductive material is less than 4, the transparent conductive material may generate insolubles such as indium ions and tin ions as compared with the case where the pH is 4 or more. Tend to be higher.
- the transparent conductive material shall have a pH of 9 or less in a mixture containing lwt% of the transparent conductive material. Is preferred.
- pH is set to a value greater than 9
- by-products such as sodium ions and ammonium ions generated will be adsorbed on the surface of the transparent conductive material, and the characteristic will be reduced. Is likely to decrease.
- the transparent conductive material has a pH of 3 or more in a mixed solution containing lwt% of the transparent conductive material, and the halogen element concentration is 0.2% by mass or less. In this case, an increase in the resistance value can be more sufficiently prevented as compared with the case where the concentrations of the element (a) and the element (b) exceed 0.2% by mass.
- the transparent conductive material may have a pH of less than 3 in a mixture containing lwt% of the transparent conductive material, and may have a halogen element concentration of 0.2% by mass or less. Even in this case, it is possible to sufficiently prevent the resistance value from changing with time even in a high humidity environment. This is because when the transparent conductive material has a pH of less than 3 in a liquid mixture containing lwt% of the transparent conductive material, halogenated hydrogen may be sufficiently generated. It is considered that the production of hydrogen halide is sufficiently reduced by setting the concentration to 0.2% by mass or less.
- the form of the transparent conductive material is usually a powder.
- the average particle size of the powder made of the transparent conductive material is preferably 10 to 80 nm! If the average particle size is less than lOnm, the conductivity of the transparent conductive material tends to be unstable. That is, the transparent conductive material according to the present invention generates conductivity due to oxygen deficiency.
- the transparent conductive material has such a small particle size, for example, when the external oxygen concentration is high, the oxygen deficiency occurs. And the conductivity may fluctuate.
- the average particle size exceeds 80 nm for example, light scattering increases in the wavelength region of visible light, the transmittance of the transparent electrode 1 decreases in the wavelength region of visible light, and the haze value tends to increase.
- the specific surface area of the powder which also becomes the transparent conductive material is preferably 10 to 50 m 2 Zg.
- the specific surface area refers to a value measured after vacuum drying a sample at 300 ° C for 30 minutes using a specific surface area measuring device (model: NOVA2000, manufactured by Cantachrome).
- the substrate 10 is not particularly limited as long as it has transparency, but a material constituting the substrate 10 is preferably excellent in transparency. Specific examples of such a material include films of polyester, polyethylene, polypropylene and the like, in addition to glass.
- the indium oxide may be doped with at least one element selected from the group consisting of tin, zinc, tellurium, silver, gallium, zirconium, hafdium, and magnesium.
- the transparent conductive material may contain an indium composite oxide. Even in this case, it is possible to sufficiently prevent the resistance value from changing with time even in a high humidity environment.
- tin is preferable from the viewpoint of sufficiently suppressing the change over time in the resistance value.
- the transparent electrode 1 can be manufactured as follows.
- a co-precipitation is performed by neutralizing the chloride of the element to be doped using an aluminum alloy (precipitation step).
- indium is used as the metal.
- by-product salts are removed by decantation or centrifugation. Since the obtained coprecipitate is contained in the medium, the medium is dried, and the obtained coprecipitate is subjected to calcination and pulverization. Thus, a powdery transparent conductive material is manufactured.
- the baking treatment is preferably performed in a nitrogen atmosphere or a rare gas atmosphere such as helium, argon, or xenon, from the viewpoint of sufficiently suppressing generation of impurities.
- a powder of the transparent conductive material is dispersed in a liquid, and the dispersion is applied on one surface of the substrate 10.
- the liquid in which the transparent conductive material is dispersed include water, saturated hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol, and butanol, acetone, and methylethyl.
- Ketones such as ketone, isobutyl methyl ketone and diisobutyl ketone, esters such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran, dioxane and getyl ether, N, N-dimethylacetamide, N, N-dimethylformamide And amides such as N-methylpyrrolidone.
- the transparent conductive materials are adhered to each other to make the thickness of the transparent conductive layer 20 uniform. Therefore, it is preferable to add a binder.
- the binder for example, polymethyl methacrylate can be used.
- the method of applying the dispersion onto the substrate 10 is not particularly limited, and a known method can be used.
- a known method can be used.
- reverse roll method direct roll method, blade method, knife method, extrusion method, nozzle method, curtain method, gravure roll method, bar coat method, dip method, kiss coat method, spin coat method, squeeze method, spray method Is mentioned.
- the dispersion is dried.
- the transparent conductive layer 20 is formed on one surface side of the substrate 10, and the transparent electrode 1 is obtained.
- the solution during the neutralization treatment described above is adjusted.
- the pH of the solution may be adjusted. That is, for example, if the solution is made alkaline, the obtained powdery transparent conductive material can be made alkaline, and the pH of the mixed solution can be increased. Conversely, if the pH of the above solution is lowered by reducing the amount of alkali used in obtaining the coprecipitate, the resulting powdery transparent conductive material can be made acidic, and pH can be lowered. Even after the production of the transparent conductive material, the pH of the mixed solution can be adjusted to an acidic range or a neutral range by sufficiently washing the transparent conductive material.
- the concentration of a halogen element (for example, the concentration of chlorine) in the transparent conductive material can be controlled by a neutralization method in the precipitation step. That is, if a sufficient neutralization treatment is not performed in the precipitation step, the resulting powdery transparent conductive material contains unreacted chloride (such as indium chloride), and the transparent conductive material The concentration of halogen elements in them can be increased. On the other hand, if a sufficient neutralization treatment is performed in the precipitation step to make the solution into a neutral region or an alkaline region, the amount of chlorine in the resulting powdery transparent conductive material can be reduced, and the amount of chlorine in the transparent conductive material can be reduced. The halogen element concentration can be reduced.
- the transparent conductive material having a high halogen element concentration (for example, about 0.5 wt%) and lowering the pH of a mixed liquid containing lwt% of the transparent conductive material (for example, setting the pH to 3.1) is as described above.
- a high halogen element concentration for example, about 0.5 wt%
- lowering the pH of a mixed liquid containing lwt% of the transparent conductive material for example, setting the pH to 3.1
- the transparent conductive material whose concentration of halogen element is so low as to be undetectable and lowers the pH of the mixed solution uses indium nitrate or the like as an indium source used in the above-mentioned precipitation step. In an acidic region.
- the method of adjusting the halogen element concentration is not limited to this, and the method of vaporizing halogen by increasing the heating temperature at the time of oxide generation, the method of ion exchange by using an ion exchange membrane, the method of A method of removing a halogen element contained in impurities by performing washing can be used.
- the concentration of the halogen element in the transparent conductive material can be reduced by performing a water washing step on the transparent conductive material.
- the efficiency of removing the halogen element decreases, and the halogen element concentration cannot be sufficiently reduced. Therefore, in order to further reduce the halogen element concentration, an alkali washing step of washing with an alkali solution is added to the above-mentioned water washing step. As a result, the efficiency of removing the halogen element from the transparent conductive material can be increased, and the concentration can be sufficiently reduced to such an extent that the halogen element concentration cannot be detected.
- the dispersion When a dispersion without a binder is used as the dispersion, the dispersion is applied on one surface of the substrate 10 and dried to form a transparent conductive layer 20 containing a transparent conductive material. After that, the transparent conductive layer 20 may be compressed into a compressed layer of a transparent conductive material. In this case, the transparent conductive layer 20 can be bonded to the substrate 10 without using any solder, which is useful. This compression can be performed by a sheet press, a roll press, or the like. Further, a transparent conductive material can be fixed by impregnating the binder into the compressed layer.
- the transparent electrode of this embodiment is one in which the transparent conductive material contains tin oxide instead of indium oxide, the pH of the mixed solution containing lwt% of the transparent conductive material is 1 or more, and the halogen element concentration is This is different from the transparent electrode of the first embodiment in that an electrode having a content of 1.5% by mass or less is used.
- the transparent electrode since the transparent conductive material is included, it is possible to sufficiently prevent the resistance value from changing with time even in a high humidity environment. Also, by using this transparent conductive material, the pH of the mixed solution containing lwt% of the transparent conductive material is reduced to less than 1, and the transparent conductive material having a halogen element concentration exceeding 1.5% by mass is used. Thus, the transmittance of the transparent electrode can be made sufficiently high.
- the halogen element concentration in the transparent conductive material is more preferably 1.0% by mass or less. In this case, there is an advantage that the moisture resistance is improved as compared with the case where the halogen element concentration exceeds 1.0% by mass.
- the tin oxide may be doped with at least one element selected from the group consisting of antimony, zinc, and fluorine.
- the transparent conductive material may contain a tin composite oxide. In this case, it is possible to sufficiently prevent the resistance value from changing with time even in a high humidity environment.
- antimony is preferable from the viewpoint of sufficiently suppressing the change with time in the resistance value.
- the transparent electrode of the present embodiment is different from the first embodiment in that a transparent conductive material containing zinc oxide instead of indium oxide and having a pH of 4 to 9 in a mixed solution containing lwt% of the transparent conductive material is used. It is different from the transparent electrode of the form.
- the transparent electrode since the transparent conductive material is included, a change in the resistance value with time can be sufficiently prevented even in a high humidity environment.
- the transmittance of the transparent electrode can be sufficiently increased compared to the case where the pH of the mixed solution containing lwt% of the transparent conductive material is made less than 4 or the case where the transparent conductive material is made more than 9 is used. Can be higher. If the pH of the mixture containing lwt% of the transparent conductive material is higher than 9, deterioration under high temperature and high humidity tends to be promoted.
- the transparent conductive material preferably has a pH of 5 or more in a mixed solution containing lwt% of the transparent conductive material.
- impurities can be reduced as compared with a transparent conductive material in which the pH of a mixture containing lwt% of the transparent conductive material is less than 5.
- the halogen element concentration in the transparent conductive material is preferably 0.05% by mass or less. This In this case, even in a high-humidity environment, an increase in resistance can be prevented more sufficiently.
- the zinc oxide may be doped with at least one element selected from the group consisting of aluminum, gallium, indium, boron, fluorine and manganese.
- the transparent conductive material may contain a zinc composite oxide. In this case, it is possible to sufficiently prevent the resistance value from changing with time even in a high humidity environment.
- Al and Ga are preferable from the viewpoint of sufficiently suppressing the change over time in the resistance value.
- the present invention is not limited to the above embodiment.
- the above embodiment relates to a transparent electrode, but the present invention may be a transparent conductive paste containing the above-described transparent conductive material.
- the strong transparent conductive paste contains the transparent conductive material described above. For this reason, the strong transparent conductive paste can sufficiently prevent the resistance value from changing with time even in a high humidity environment. Since the transparent conductive paste has a certain viscosity, it can be uniformly applied to the substrate 10 and can be easily applied to a narrow portion or a concave / convex portion.
- This transparent conductive paste can be obtained by adding a viscosity-increasing agent such as an acrylic resin to the above-described dispersion and drying the dispersion.
- a viscosity-increasing agent such as an acrylic resin
- the present invention may be a transparent conductive film containing the above-mentioned transparent conductive material.
- an acrylic monomer, an epoxy monomer, or the like may be added to the above-described dispersion, and the dispersion may be cured by UV irradiation, EB irradiation, or heating.
- the transparent conductive layer 20 and the substrate 10 are in direct contact, but the transparent electrode of the present invention is provided between the transparent conductive layer and the substrate. It is preferable to provide an anchor coat layer for increasing the adhesive strength to the substrate.
- an anchor coat layer for example, a resin such as urethane is used.
- the diluted product is mixed while adjusting so that the pH is around 5 to 7, and in the case of Example 8, it is adjusted so that the pH is around 7 and mixed.
- mixing was carried out while adjusting the pH to be around 9, thereby producing a white precipitate (coprecipitate).
- the liquid containing the generated precipitate was subjected to solid-liquid separation with a centrifuge to obtain a solid. This was further poured into 100 g of water, dispersed with a homogenizer, and subjected to solid-liquid separation with a centrifuge. This operation of dispersion and solid-liquid separation was repeated so that the chlorine content and pH became the values shown in Table 2, thereby obtaining an indium-tin composite hydroxide.
- the chlorine content in Table 2 was measured using a fluorescent X-ray analyzer (model: ZSX100e, manufactured by Rigaku Corporation). In Table 2, “not detectable” means that the chlorine content is less than 10 ppm.
- Example 2 the pH in Table 2 was measured using a pH meter (model: HM-40S, manufactured by Toa Denpa Kogyo) after mixing the transparent conductive material lg with 99 g of water and leaving it to stand for 10 minutes.
- a pH meter model: HM-40S, manufactured by Toa Denpa Kogyo
- Example 1 an indium tin composite oxide having a chlorine content equal to or lower than the detection limit value and a 1N acetic acid aqueous solution were mixed and dried at 100 ° C. for 1 hour.
- the indium-tin composite hydroxide was dried with a spray drier and heated in a nitrogen atmosphere at 600 ° C for 1 hour to obtain an indium-tin composite oxide as a transparent conductive material. .
- the obtained transparent conductive material an acrylic monomer (lwt% of a UV curing agent was added to a mixture of equal amounts of methyl methacrylate and polyethylene glycol dimethacrylate) and methyl ethyl ketone were added to methyl ethyl ketone.
- the transparent conductive material after volatilization was adjusted to 20% by volume and mixed to prepare a paste.
- This paste is applied to a glass substrate of 5 cm square by a spin coating method, and after methylethylketone is volatilized, the number of rotations is adjusted so that the film thickness becomes 5 m, and the transparent conductive film is irradiated with UV. Got.
- a transparent conductive film was obtained in the same manner as in Example 1, except that the chlorine content was controlled as described below using a Shii-Dani Ammodium. That is, the chlorine content control is performed by mixing an indium tin composite oxidized product having a chlorine content of not more than the detection limit value with a 1N aqueous solution of a salted amide. went. In addition, in the case of Example 7, mixing was performed while adjusting the pH to be around 7, to produce a white precipitate (coprecipitate).
- Example 2 The procedure of dispersing with a homogenizer and performing solid-liquid separation with a centrifugal separator was repeated, and the chlorine content and the pH were adjusted to the values shown in Table 2 to obtain indium tin composite hydroxide. In the same manner as in Example 1, a transparent conductive film was obtained. In the case of Comparative Examples 1 and 2, the pH was adjusted to be around 5 to 7 and mixed, and in the case of Comparative Example 3, the pH was adjusted to be around 9 and mixed. (Coprecipitate) was formed.
- Example 11 The liquid containing the generated precipitate was subjected to solid-liquid separation with a centrifuge to obtain a solid. This was further poured into 100 g of water, dispersed with a homogenizer, and subjected to solid-liquid separation with a centrifuge. This operation of dispersion and solid-liquid separation was repeated so that the chlorine content and the pH became the values shown in Table 3, to obtain a tin hydroxide.
- Example 11 a mixture of a stannic oxide having a chlorine content equal to or lower than the detection limit and a 1N aqueous nitric acid solution and dried at 100 ° C. for 1 hour was used.
- the tin hydroxide was dried with a spray dryer and heat-treated at 600 ° C for 1 hour in a nitrogen atmosphere to obtain a tin oxide.
- the obtained transparent conductive material an acrylic monomer (lwt% of a UV curing agent was added to a mixture of equal amounts of methyl methacrylate and polyethylene glycol dimethacrylate) and methyl ethyl ketone were converted to methyl ethyl ketone.
- the paste was prepared by mixing the components prepared so that the transparent conductive material after volatilization was 20% by volume.
- This paste was applied to a 5 cm square glass substrate by spin coating, and after methylethylketone was evaporated, the number of revolutions was adjusted so that the film thickness was 5 / zm. This was irradiated with UV to obtain a transparent conductive film.
- Examples 15-18 and Comparative Examples were prepared by dissolving an aqueous solution obtained by dissolving 10 g of Shii-dani zinc (manufactured by Kanto Idani Gakusha) in 990 g of water and diluting ammonia water (manufactured by Kanto Kagaku) 10-fold with water.
- aqueous solution obtained by dissolving 10 g of Shii-dani zinc (manufactured by Kanto Idani Gakusha) in 990 g of water and diluting ammonia water (manufactured by Kanto Kagaku) 10-fold with water.
- mixing was performed while adjusting the pH to around 5 to 7
- Example 19 and Comparative Example 6 the mixing was performed while adjusting the pH to around 9 to obtain a white precipitate. (Coprecipitate).
- the zinc hydroxide was dried with a spray drier and heat-treated at 600 ° C for 1 hour in a nitrogen atmosphere to obtain a zinc oxide.
- the obtained transparent conductive material an acrylic monomer (lwt% of a UV curing agent added to a mixture of equal amounts of methyl methacrylate and polyethylene glycol dimethacrylate) and methyl ethyl ketone were added to methyl ethyl ketone.
- the paste was prepared by mixing the components prepared so that the transparent conductive material after volatilization was 20% by volume.
- This paste was applied to a 5 cm square glass substrate by spin coating, and after methylethylketone was evaporated, the number of revolutions was adjusted so that the film thickness became 5 / zm. This was irradiated with UV to obtain a transparent conductive film.
- the change in resistance of the transparent conductive film obtained as described above was measured as follows. That is, the measurement point of the surface resistance of the transparent conductive film is determined in advance, and the measurement point is measured using a four-probe surface resistance measurement device (MCP-T600, manufactured by Mitsubishi Electric Corporation). Next, the transparent conductive film was left at 60 ° C. and 95% RH for 1000 hours, taken out, and left in the air for 1 hour. The measurement point of the transparent conductive film was measured again. Tables 2 to 4 show the results of resistance change before and after humidification.
- the green compact resistance was measured using the apparatus shown in FIG.
- the device 30 has a diameter of 15 mm at the bottom, A stainless steel jig 31 having a convex portion 31a with a height of 6 mm at the center is provided.
- a cylindrical body 32 is provided.
- the inner wall of the body 32 is provided with an insulating plastic inner 33 having a thickness of lmm.
- the side surface of the protrusion 31a and the inner wall of the body 32 form the inner 33. It is pinched.
- the upper surface of the convex portion 31a is flat so that the sample 35 can be placed thereon.
- ITO in Table 1 is an evaluation when the conductive material is ITO (Examples 1 to 10 and Comparative Examples 1 to 3), and SnO is a case where the conductive material is SnO ( Evaluation of Examples 11 to 14 and Comparative Example 4)
- ZnO is an evaluation when the conductive material is ZnO (Examples 15 to 19 and Comparative Examples 5 and 6).
- Example 1 IT 0 Undetectable 3.0 1 .1 8 0 .05 A
- Example 2 IT 0 0 .0 8 3.91 .1 6 0 .06 A
- Example 3 IT 0 0 .1 0 3 7 1 .3 3 0.06 A
- Example 4 IT 0 0 .1 1 3.5 .2 3 0 .0 6 B
- Example 5 IT 0 .2 0 2.9 5.83.
- Example 6 IT 0 0.3 0 3 .1 4.0 2 0 .0 5 B
- Example 7 IT 0 0 .5 0 7.5 5 .4 5 0 .0 7
- Example 8 IT 0 0.06 5.0 0 .1 3 0 .0 7
- Example 9 IT 0 0 .0 7 8.8 1 .2 7 0 .1 3 B
- Example 10 IT 0 0 .0 8 9.0 1. 3 5 0. 1 2 B Comparative example 1 IT 0 0. 7 2 2. 5 6. 7 5 X 1 0 8 0. 0 5 C Comparative example 2 IT 0 0. 5 9 2. 7 9. 7 6 X 1 0 0. 0 5 C Comparative Example 3 IT 0 0 .0 9 9.3 1.4 .2 0 .3 0 c
- ITO Examples 1 to: L0 can sufficiently prevent the resistance value from increasing over time because the resistance value change is significantly smaller than Comparative Examples 1 and 2 related to ITO. Helped.
- Examples 1 to 5 relating to ITO: LO is the same as Comparative Example 3 relating to ITO. It was a component that the resistance value of the green compact could be considerably reduced.
- Examples 11 to 14 relating to SnO had a higher resistance than Comparative Example 4 relating to SnO.
- the transparent conductive material of the present invention can sufficiently prevent the resistance value from changing with time even in a high humidity environment.
- a transparent conductive material a transparent conductive paste, a transparent conductive film, and a transparent electrode capable of sufficiently preventing a change in resistance value with time even in a high humidity environment.
- These can be suitably used for LCDs, PDPs, organic ELs, touch panels, and the like.
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- Crystallography & Structural Chemistry (AREA)
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Abstract
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US11/597,133 US20080014452A1 (en) | 2004-05-21 | 2005-05-20 | Transparent Conductive Material, Transparent Conductive Paste, Transparent Conductive Film and Transparent Electrode |
Applications Claiming Priority (4)
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JP2004152444 | 2004-05-21 | ||
JP2004-152444 | 2004-05-21 | ||
JP2005-133156 | 2005-04-28 | ||
JP2005133156A JP2006012783A (ja) | 2004-05-21 | 2005-04-28 | 透明導電材料、透明導電ペースト、透明導電膜及び透明電極 |
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WO2005114674A1 true WO2005114674A1 (ja) | 2005-12-01 |
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PCT/JP2005/009260 WO2005114674A1 (ja) | 2004-05-21 | 2005-05-20 | 透明導電材料、透明導電ペースト、透明導電膜及び透明電極 |
Country Status (4)
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US (1) | US20080014452A1 (ja) |
JP (1) | JP2006012783A (ja) |
KR (1) | KR100846081B1 (ja) |
WO (1) | WO2005114674A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2009302020A (ja) * | 2008-06-17 | 2009-12-24 | Idemitsu Kosan Co Ltd | 導電性微粒子及びその製造方法 |
Families Citing this family (5)
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JP4590978B2 (ja) * | 2004-08-20 | 2010-12-01 | Tdk株式会社 | 透明導電材料及び透明導電体 |
JP5114846B2 (ja) * | 2006-02-02 | 2013-01-09 | 東レ・ファインケミカル株式会社 | 酸化亜鉛分散ペーストの製造方法 |
KR100862593B1 (ko) * | 2007-02-01 | 2008-10-09 | 한양대학교 산학협력단 | 투명 전도성 박막 및 이의 제조방법 |
WO2010035715A1 (ja) * | 2008-09-25 | 2010-04-01 | 日鉱金属株式会社 | 透明導電膜製造用の酸化物焼結体 |
KR101300560B1 (ko) * | 2009-07-01 | 2013-09-03 | 삼성코닝정밀소재 주식회사 | 산화아연계 전도체 |
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JPH05201731A (ja) * | 1991-10-15 | 1993-08-10 | Mitsubishi Materials Corp | 超微粒低抵抗スズドープ酸化インジウム粉末とその製法 |
JPH0822722A (ja) * | 1994-07-08 | 1996-01-23 | Mitsubishi Materials Corp | 透明導電膜形成用組成物 |
JPH08102227A (ja) * | 1994-09-30 | 1996-04-16 | Mitsubishi Materials Corp | 透明導電膜およびその形成方法 |
JPH08302246A (ja) * | 1995-05-09 | 1996-11-19 | Sumitomo Osaka Cement Co Ltd | 高導電性と高膜強度とを有する透明な被膜形成用の塗料及び高導電性と高膜強度とを有する透明な被膜の形成方法と、陰極線管 |
JPH1059720A (ja) * | 1996-08-12 | 1998-03-03 | Konica Corp | 非晶質酸化スズゾル及びその製造方法 |
Family Cites Families (5)
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JP3355733B2 (ja) * | 1992-12-28 | 2002-12-09 | 三菱マテリアル株式会社 | 低抵抗導電性顔料及びその製造方法 |
NL1004635C2 (nl) * | 1995-12-06 | 1999-01-12 | Sumitomo Chemical Co | Indiumoxyde-tinoxydepoeders en werkwijze voor het voortbrengen daarvan. |
JP2001332130A (ja) * | 2000-05-19 | 2001-11-30 | Tdk Corp | 機能性膜 |
US6605341B2 (en) * | 2000-05-19 | 2003-08-12 | Tdk Corporation | Functional film having specific surface dispersion ratio |
US6819044B2 (en) * | 2002-04-10 | 2004-11-16 | Tdk Corporation | Thin-film EL device and composite substrate |
-
2005
- 2005-04-28 JP JP2005133156A patent/JP2006012783A/ja active Pending
- 2005-05-20 WO PCT/JP2005/009260 patent/WO2005114674A1/ja active Application Filing
- 2005-05-20 KR KR1020067026995A patent/KR100846081B1/ko not_active IP Right Cessation
- 2005-05-20 US US11/597,133 patent/US20080014452A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH05201731A (ja) * | 1991-10-15 | 1993-08-10 | Mitsubishi Materials Corp | 超微粒低抵抗スズドープ酸化インジウム粉末とその製法 |
JPH0822722A (ja) * | 1994-07-08 | 1996-01-23 | Mitsubishi Materials Corp | 透明導電膜形成用組成物 |
JPH08102227A (ja) * | 1994-09-30 | 1996-04-16 | Mitsubishi Materials Corp | 透明導電膜およびその形成方法 |
JPH08302246A (ja) * | 1995-05-09 | 1996-11-19 | Sumitomo Osaka Cement Co Ltd | 高導電性と高膜強度とを有する透明な被膜形成用の塗料及び高導電性と高膜強度とを有する透明な被膜の形成方法と、陰極線管 |
JPH1059720A (ja) * | 1996-08-12 | 1998-03-03 | Konica Corp | 非晶質酸化スズゾル及びその製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2009302020A (ja) * | 2008-06-17 | 2009-12-24 | Idemitsu Kosan Co Ltd | 導電性微粒子及びその製造方法 |
Also Published As
Publication number | Publication date |
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JP2006012783A (ja) | 2006-01-12 |
KR100846081B1 (ko) | 2008-07-14 |
KR20070014205A (ko) | 2007-01-31 |
US20080014452A1 (en) | 2008-01-17 |
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