KR101117797B1 - Preparation method of transparent conductive complex comprising Yb doped ZnO, transparent conductive composition, coating film and optical device comprising the same - Google Patents
Preparation method of transparent conductive complex comprising Yb doped ZnO, transparent conductive composition, coating film and optical device comprising the same Download PDFInfo
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- KR101117797B1 KR101117797B1 KR1020090035996A KR20090035996A KR101117797B1 KR 101117797 B1 KR101117797 B1 KR 101117797B1 KR 1020090035996 A KR1020090035996 A KR 1020090035996A KR 20090035996 A KR20090035996 A KR 20090035996A KR 101117797 B1 KR101117797 B1 KR 101117797B1
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- South Korea
- Prior art keywords
- transparent conductive
- ytterbium
- conductive composition
- composite
- zinc
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 229910052769 Ytterbium Inorganic materials 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 title claims description 14
- 239000011248 coating agent Substances 0.000 title claims description 11
- 230000003287 optical effect Effects 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- -1 ytterbium metal oxide Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000010408 film Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000003752 zinc compounds Chemical class 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000010790 dilution Methods 0.000 abstract description 4
- 239000012895 dilution Substances 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000003574 free electron Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 description 4
- 239000011667 zinc carbonate Substances 0.000 description 4
- 235000004416 zinc carbonate Nutrition 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 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
- 238000009826 distribution Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- JCDQGOSXWGXOQQ-UHFFFAOYSA-H ytterbium(3+);tricarbonate Chemical compound [Yb+3].[Yb+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O JCDQGOSXWGXOQQ-UHFFFAOYSA-H 0.000 description 2
- SJHMKWQYVBZNLZ-UHFFFAOYSA-K ytterbium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Yb+3] SJHMKWQYVBZNLZ-UHFFFAOYSA-K 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- FLJKBWKLGAYSFH-UHFFFAOYSA-H oxalate;ytterbium(3+) Chemical compound [Yb+3].[Yb+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O FLJKBWKLGAYSFH-UHFFFAOYSA-H 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000728 polyester 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
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 description 1
- KVCOOBXEBNBTGL-UHFFFAOYSA-H ytterbium(3+);trisulfate Chemical compound [Yb+3].[Yb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KVCOOBXEBNBTGL-UHFFFAOYSA-H 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/30—Drying; Impregnating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
Abstract
본 발명은 a) 산화아연과 이터븀 금속산화물이 50 내지 99 : 1 내지 50의 몰비로 함유된 복합체 0.1 내지 60 중량%; 및 b) 잔량의 희석용 용제를 포함하는 것을 특징으로 하는 투명전도성 조성물을 제공한다.The present invention comprises a) 0.1 to 60% by weight of a composite containing zinc oxide and ytterbium metal oxide in a molar ratio of 50 to 99: 1 to 50; And b) provides a transparent conductive composition comprising a residual amount of the solvent for dilution.
이터븀, 산화아연, 투명전도성산화물 Ytterbium, Zinc Oxide, Transparent Conductive Oxide
Description
본 발명은 투명전도성 복합체의 제조방법에 관한 것으로, 보다 상세하게는 안정성이 우수하고, 가시광선의 투과율이 우수하면서도, 전기전도성이 우수한 투명전도성 복합체의 제조방법 및 동 방법에 의해 제조된 복합체의 응용에 관한 것이다.The present invention relates to a method for producing a transparent conductive composite, and more particularly, to a method for preparing a transparent conductive composite having excellent stability, excellent transmittance of visible light and excellent electrical conductivity, and to application of the composite prepared by the same method. It is about.
최근 광전자 분야의 지속적인 연구와 발전에 따라 높은 광 투과율과 전기 전도성을 함께 구형하는 투명 전도막(transparent conducting film)에 관한 연구가 많이 진행되고 있다. 디스플레이 산업을 대표하는 투명 전도막으로 가장 상용화되어 있는 것은 인듐주석산화물(ITO; Indium Tin Oxide)이다. ITO(Indium Tin Oxide, 또는 Tin-doped Indium Oxide)란 인듐 산화물(In2O3)에 주석 산화물(SnO2)이 첨가된 고용체(solid solution)를 일컫는다. 이러한 ITO 박막은 3eV 이상의 비교적 큰 밴 드갭(band gap)을 가짐으로 가시광 파장 영역에서 85% 이상의 높은 광 투과도와 10-4 Ω㎝ 정도의 전기 전도성을 구현하는 물성 때문에 광학재료로서 평판 디스플레이, 태양전지, 전기 변색 표시 소자 등에 널리 응용되고 있다.Recently, with the continuous research and development of the optoelectronic field, a lot of researches on the transparent conducting film (sphere) having a high light transmittance and electrical conductivity together. Indium Tin Oxide (ITO) is the most commercialized transparent film representing the display industry. ITO (Indium Tin Oxide, or Tin-doped Indium Oxide) refers to a solid solution in which tin oxide (SnO 2 ) is added to indium oxide (In 2 O 3 ). The ITO thin film has a relatively large band gap of 3 eV or more, and thus is a flat panel display and a solar cell as an optical material because of its physical property of high light transmittance of 85% or more in the visible wavelength range and electrical conductivity of about 10 -4 Ωcm. It is widely applied to electrochromic display elements.
투명전극으로 사용되는 ITO는 주로 박막형태로 이용되며 졸-겔, 딥코팅, 화학증착, 분무열분해, 스퍼터링 등의 다양한 방법들로 제조된다. 지금까지의 알려진 박막제조 방법들 중 타겟을 이용한 스퍼터링법이 기타 공정상의 변수에도 불구하고 막의 균일성과 재현성에서 우수한 특성을 획득할 수 있는 제조법으로 알려져 있으며 널리 사용되고 있다. 한편 스퍼터링법을 이용한 박막의 제조에 있어서 타겟 특성은 최종 생성물의 물성을 좌우하는 핵심적인 공정 변수 중의 하나로 알려져 있으며 일반적으로 타겟이 치밀할수록 증착속도가 증가하며 증착된 박막의 저항에 있어 안정한 장점이 있다고 한다. 따라서 투명전도막에 우수한 특성 발휘를 위해서는 고밀도에 ITO 스퍼터링 타겟이 필수조건이라 할 수 있다.ITO, which is used as a transparent electrode, is mainly used in the form of a thin film and manufactured by various methods such as sol-gel, dip coating, chemical vapor deposition, spray pyrolysis, and sputtering. Among the known thin film manufacturing methods, sputtering using a target is known as a manufacturing method that can obtain excellent properties in film uniformity and reproducibility despite other process variables and is widely used. On the other hand, in the production of thin film by sputtering method, the target property is known as one of the key process variables that influence the physical properties of the final product. In general, the denser the target, the faster the deposition rate and the more stable the resistance of the deposited thin film. do. Therefore, ITO sputtering targets are essential conditions in order to exhibit excellent characteristics in the transparent conductive film.
이러한 우수한 재료적인 측면에도 불구하고 ITO의 경우 In 재료의 고갈 문제 및 원재료 가격 상승으로 대체제가 절실히 필요한 실정이다. Despite these excellent material aspects, ITO is in desperate need of substitutes due to the depletion of In materials and rising raw material prices.
본 발명은 상기한 바와 같이 종래기술이 가지는 문제를 해결하기 위해 제안된 것으로, 그 목적은 안정성이 우수하고, 가시광선의 투과율은 우수하면서도 높은 전기전도성을 가지는 투명전도성 조성물을 제공함에 있다.The present invention has been proposed to solve the problems of the prior art as described above, the object is to provide a transparent conductive composition having excellent stability, excellent transmittance of visible light and high electrical conductivity.
본 발명의 다른 목적은 상기와 같은 투명전도성 조성물로 이루어진 코팅 필름을 제공함에 있다.Another object of the present invention is to provide a coating film made of the transparent conductive composition as described above.
본 발명의 또 다른 목적은 상기 투명전도성 조성물로 이루어진 박막을 포함하는 광학소자를 제공함에 있다.Still another object of the present invention is to provide an optical device including a thin film made of the transparent conductive composition.
상기한 바와 같은 본 발명의 기술적 과제는 다음과 같은 수단에 의해 달성되어진다.The technical problem of the present invention as described above is achieved by the following means.
(1) 아연화합물과 이터븀 금속화합물을 액상반응시켜 얻은 이터븀이 함유된 아연전구체를 100~150℃로 건조하는 단계;
상기 건조된 이터븀이 함유된 아연전구체를 200~800℃의 온도에서 소성하여 평균입경이 10~200nm이고, 산화아연과 Yb 금속산화물이 90 내지 98.5:1.5 내지 10의 몰비로 이루어진 복합체를 제조하는 단계;
를 포함하는 투명전도성 복합체의 제조방법.
(2) 제1항에 있어서, 소성은 5 내지 200분 동안 산소분위기에서 이루어지는 것을 특징으로 하는 투명전도성 복합체의 제조방법.
(3) a) 제1항에 의해 제조된 투명전도성 복합체 0.1 내지 60 중량%; 및
b) 잔량의 희석용 용제를 포함하는 것을 특징으로 하는 투명전도성 조성물.
(4) 제3항에 있어서, 바인더 또는 분산제를 더 포함하는 것을 특징으로 하는 투명전도성 조성물.
(5) 제3항의 투명전도성 조성물로 이루어진 코팅 필름.
(6) 제5항에 있어서, 두께가 50 내지 1000 nm인 것을 특징으로 하는 코팅 필름.
(7) 제3항에 의한 투명전도성 조성물로 이루어진 박막을 포함하는 광학소자.(1) drying the ytterbium-containing zinc precursor obtained by the liquid phase reaction of the zinc compound and the ytterbium metal compound at 100 to 150 ° C;
The dried ytterbium-containing zinc precursor is calcined at a temperature of 200 ~ 800 ℃ to produce a composite having an average particle diameter of 10 ~ 200nm, zinc oxide and Yb metal oxide 90 to 98.5: 1.5 to 10 molar ratio. step;
Method for producing a transparent conductive composite comprising a.
(2) The method for producing a transparent conductive composite according to claim 1, wherein the calcination is performed in an oxygen atmosphere for 5 to 200 minutes.
(3) a) 0.1 to 60% by weight of the transparent conductive composite prepared according to claim 1; And
b) A transparent conductive composition comprising the remaining amount of the diluent solvent.
(4) The transparent conductive composition according to claim 3, further comprising a binder or a dispersant.
(5) A coating film made of the transparent conductive composition of claim 3.
(6) The coating film according to claim 5, wherein the coating film has a thickness of 50 to 1000 nm.
(7) An optical element comprising a thin film made of the transparent conductive composition according to (3).
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이상에서 설명한 바와 같이, 본 발명의 투명전도성 조성물은 안정성이 우수하고, 가시광선의 투과율은 우수하면서도 높은 전기전도성을 가진다. As described above, the transparent conductive composition of the present invention is excellent in stability and excellent in transmittance of visible light and has high electrical conductivity.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
이터븀(Yb)이 함유된 산화아연은 일반적으로 밴드갭 에너지(3.55eV)가 크기 때문에 가시광 영역의 파장에 대한 높은 광투과도(>85%)를 가지며 자유전자의 진동 주파수가 적외선영역의 파장 범위에 존재하기 때문에 이 영역의 전자기파에 대한 반사 특성을 나타낸다. 즉 적외선영역의 파장대에서는 자유전자의 진동으로 인하여 반사특성을 가지며, 자외선 영역의 파장대에서는 밴드 대 밴드 전이(band-to-band transition)로 인하여 흡수특성을, 그리고 이 두 영역 사이의 가시광선 영역에서는 투광특성을 가진다. 반사특성 영역에서 투광특성 영역으로의 전이가 일어나는 파장영역을 플라즈마 반사에지(plasma reflection edge)(P)라고 하며, P는 자유전자의 농도가 증가할수록 단파장 쪽으로 이동하게 된다. 즉 다시 말하면 이터븀이 함유된 산화아연 박막에 있어 Yb의 첨가량이 증가할수록 이온간의 치환으로 인하여 자유전자의 농도가 증가하며 P는 단파장 쪽으로 이동하게 된다.Zinc oxide containing ytterbium (Yb) generally has a high band gap energy (3.55 eV) and thus has a high light transmittance (> 85%) with respect to the wavelength of the visible region, and the oscillation frequency of the free electrons is in the wavelength range of the infrared region. Because it exists in, it shows the reflection characteristic of electromagnetic wave in this region. In other words, in the wavelength range of the infrared region, it has reflection characteristics due to vibration of free electrons, and in the wavelength range of the ultraviolet region, absorption characteristics are caused by band-to-band transition, and in the visible region between these two regions. It has a light transmitting property. The wavelength region where the transition from the reflective region to the transmissive region is called a plasma reflection edge P, and P moves toward the shorter wavelength as the concentration of free electrons increases. In other words, in the zinc oxide thin film containing ytterbium, as the amount of Yb added increases, the concentration of free electrons increases due to substitution between ions, and P moves to a shorter wavelength.
위와 같이 다양한 용도로 사용되는 이터븀이 함유된 산화아연은 전형적인 n-형 반도체로 넓은 밴드 갭 에너지(3.4eV)을 가지고 있으며 가시광 영역에서 높은 광투과도와 높은 전기전도성을 가지고 있어 투명전도성산화물(Transparent Conducting Oxide : TCOs)로서 광범위 하게 사용될 수 있다. 또한 제조원가가 ITO (Indium Tin Oxide) 및 ATO(Antimony Tin Oxide)에 비하여 월등히 저렴하며 내화학성과 내마모성이 우수하다는 점 등으로 인하여 ITO 및 ATO의 대체제로 사용 가능하며 이터븀이 함유된 아연 산화물 박막의 경우 비저항 값이 10-3 ~ 10-2Ω ㎝정도로 낮출 수 있는 소재이며, 전기 전도성을 향상시키기 위해 산화아연에 적절한 도펀트 를 첨가하여 조절하는 것도 가능하다.Ytterbium-containing zinc oxide, which is used for various purposes as described above, is a typical n-type semiconductor. It has a wide band gap energy (3.4 eV) and has a high light transmittance and high electrical conductivity in the visible region. Conducting Oxide (TCOs) can be widely used. In addition, due to its low cost and superior chemical resistance and abrasion resistance compared to indium tin oxide (ITO) and antimony tin oxide (ATO), it can be used as an alternative to ITO and ATO, In this case, the specific resistance value can be lowered to about 10 -3 ~ 10 -2 Ω cm, and it is also possible to adjust by adding a suitable dopant to zinc oxide to improve electrical conductivity.
이와 같은 특성을 이용하는 본 발명의 투명전도성 조성물은 산화아연과 이터븀 금속산화물을 포함하는 것을 특징으로 한다. The transparent conductive composition of the present invention utilizing such characteristics is characterized in that it comprises zinc oxide and ytterbium metal oxide.
바람직하게는 상기 본 발명 투명전도성 조성물은 a) 산화아연과 이터븀 금속산화물이 50 내지 99 : 1 내지 50의 몰비로 함유된 복합체 0.1 내지 60 중량%; 및 b) 잔량의 희석용 용제를 포함한다.Preferably the transparent conductive composition of the present invention comprises a) 0.1 to 60% by weight of a composite containing zinc oxide and ytterbium metal oxide in a molar ratio of 50 to 99: 1 to 50; And b) residual solvent for dilution.
본 발명에 있어서 상기 복합체는 산화아연, 탄산아연, 또는 수산화아연 등의 아연화합물과 산화이터븀, 탄산이터븀, 또는 수산화이터븀 등의 이터븀 금속화합물을 첨가하여 혼합된 복합체로부터 제조될 수 있다. 구체적인 일예로 산화아연은 질산아연, 염화아연, 황산아연, 초산아연 등의 가용성 아연 염; 유기 용매에 가용성이 있는 알콕사이드류; 또는 탄산아연, 수산화아연, 옥살산아연 등 물에 불용성인 아연 화합물 등을 출발물질로 하여 공지의 화학반응을 통하여 수득할 수 있으며, 시판되는 것을 사용할 수도 있다. 또 이터븀 금속 산화물은 질산 이터븀, 염화 이터븀, 황산 이터븀, 초산 이터븀 등의 가용성 Yb 금속염; 유기 용매에 가용성이 있는 알콕사이드류; 또는 탄산 이터븀, 수산화 이터븀, 옥살산 이터븀 등 물에 불용성인 Yb 금속 화합물 등을 출발물질로 하여 공지의 화학반응을 통하거나 시판되는 것을 사용할 수도 있다.In the present invention, the composite may be prepared from a composite mixed by adding a zinc compound such as zinc oxide, zinc carbonate, or zinc hydroxide and an ytterbium metal compound such as ytterbium oxide, ytterbium carbonate, or ytterbium hydroxide. . Specific examples of zinc oxide include soluble zinc salts such as zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate; Alkoxides soluble in organic solvents; Alternatively, zinc compounds insoluble in water such as zinc carbonate, zinc hydroxide and zinc oxalate may be obtained through known chemical reactions as starting materials, and commercially available ones may be used. Ytterbium metal oxides include soluble Yb metal salts such as ytterbium nitrate, ytterbium chloride, ytterbium sulfate, and ytterbium acetate; Alkoxides soluble in organic solvents; Alternatively, a commercially available or commercially available chemical reaction may be used using, as a starting material, a Yb metal compound insoluble in water such as ytterbium carbonate, ytterbium hydroxide and ytterbium oxalate as a starting material.
이때, 상기 복합체의 제조를 위해 소성은 입자의 응집을 최소화하고 나노크기의 미립자를 얻기 위하여 저온 소성하는 것이 바람직하며, 특히 200 내지 800 ℃ 의 온도에서 소성되는 것이 바람직하다. 또한, 원활한 산화와 공정시간의 단축을 위하여 200 내지 800 ℃의 온도에서 5 내지 200분 동안, 산소가스 등의 산화 분위기에서 소성하는 것이 더욱 바람직하다.At this time, the firing for the production of the composite is preferably low-temperature firing in order to minimize the aggregation of the particles and to obtain nano-sized microparticles, particularly preferably at a temperature of 200 to 800 ℃. In addition, it is more preferable to bake in an oxidizing atmosphere such as oxygen gas for 5 to 200 minutes at a temperature of 200 to 800 ℃ for smooth oxidation and shortening of the process time.
또한 상기 산화아연과 Yb금속산화물은 50 내지 99 : 1 내지 50의 몰비로 함유된다. 상기 범위를 벗어나는 경우 복합체의 안정성이 떨어지며, 전기전도성이 떨어지기 된다. 바람직하게는 산화아연과 Yb금속산화물 90 내지 98.5 : 1.5 내지 10의 몰비로 함유되는 것이 좋다.In addition, the zinc oxide and the Yb metal oxide is contained in a molar ratio of 50 to 99: 1 to 50. Outside the above range, the stability of the composite is lowered, and the electrical conductivity is lowered. Preferably it is contained in a molar ratio of zinc oxide and Yb metal oxide 90 to 98.5: 1.5 to 10.
상기와 같이 소성된 상기 복합체는 나노크기의 미립자로 제조하기 위하여 분쇄하는 단계를 실시할 수 있으며, 이때 상기 분쇄는 제트밀(Jet mill) 등의 건식 분쇄, 비즈밀(Beeds mill) 등의 습식 분쇄 등 통상의 방법으로 실시될 수 있음은 물론이다.The composite fired as described above may be pulverized to produce nano-sized fine particles, wherein the pulverization may be performed by dry grinding such as a jet mill or wet grinding such as a beads mill. Of course, it can be carried out in a conventional manner.
상기와 같이 제조되어 본 발명의 코팅용 조성물에 함유되는 상기 복합체는 평균입경이 미세할수록 더욱 좋으며, 특히 최대입경이 1000 nm 미만, 평균입경이 10 내지 200 ㎚인 것이 더욱 좋다. 입경이 1000 nm를 초과하는 경우 가시광선의 투과율을 감소시킬 수 있다.The composite prepared as described above and contained in the coating composition of the present invention is better as the average particle diameter is fine, in particular, the maximum particle size is less than 1000 nm, the average particle diameter is more preferably 10 to 200 nm. When the particle diameter exceeds 1000 nm, the transmittance of visible light can be reduced.
또한 본 발명은 희석용 용제를 포함하는 바, 상기 용제는 물 또는 유기 용매가 사용될 수 있으며, 구체적으로 물, 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, 또는 이소부탄올, 에틸셀루솔브, 부틸 셀루솔브, 에틸아세테이트, 부틸아세테이트 등을 사용할 수 있다.In addition, the present invention includes a dilution solvent, the solvent may be used water or an organic solvent, specifically, water, methanol, ethanol, propanol, isopropanol, butanol, or isobutanol, ethyl cellussolve, butyl cellussolve, Ethyl acetate, butyl acetate, etc. can be used.
본 발명의 투명전도성 조성물에 있어서 상기 a) 복합체는 0.1 내지 60 중량% 으로 포함된다. 상기 범위를 벗어나는 경우 제품의 안정성 및 전기전도성이 떨어지거나 균일한 코팅을 하기가 어려울 수 있다. 바람직하기로는 분산 및 코팅공정의 작업성을 위하여 5 내지 30 중량%로 포함되는 것이 더욱 바람직하다.In the transparent conductive composition of the present invention, the a) composite is included in an amount of 0.1 to 60 wt%. If it is out of the above range it may be difficult to have a uniform coating or the stability and electrical conductivity of the product. Preferably it is more preferably contained in 5 to 30% by weight for the workability of the dispersion and coating process.
상기와 같이 본 발명의 투명전도성 조성물에 함유되는 복합체와 용제는 교반기에 의한 분산, 호모나이저, 초음파 분산기, 볼밀, 비즈 밀 등의 통상의 방법으로 교반하여 혼합할 수 있으며, 특히 아연화합물의 최대입자가 1000 ㎚ 이하의 미립자로 분산시키기 위해서는 볼밀, 비즈 밀 등의 습식 분산기를 사용하는 것이 좋다.As described above, the composite and the solvent contained in the transparent conductive composition of the present invention may be mixed by stirring by a conventional method such as dispersion by a stirrer, homogenizer, ultrasonic disperser, ball mill, bead mill, and the like. In order to disperse | distribute to microparticles | fine-particles of 1000 nm or less, it is preferable to use wet dispersers, such as a ball mill and a bead mill.
상기와 같이 복합체 및 희석용 용제를 포함하는 본 발명의 투명전도성 조성물은 필요에 따라 바인더, 분산제 등을 추가로 포함할 수 있다.As described above, the transparent conductive composition of the present invention including the composite and the dilution solvent may further include a binder, a dispersant, and the like as necessary.
상기 바인더는 복합체를 코팅표면에 고착시키는 작용을 한다. 이러한 바인더는 통상의 유기계 바인더 또는 무기계 바인더가 사용될 수 있음은 물론이며, 구체적으로 니트로셀룰로오스, 에틸셀룰로오스 등의 셀룰로오스계, 에폭시계, 아크릴레이트계, 폴리에스테르계, 파라핀, 실리콘계 등의 유기계 바인더를 사용할 경우에는 코팅공정시 접착력 향상에 있어 좋으며, TEOS(tetraethly orthosilicate), MTMS(methyltrimethoxysilane), MTES(methyl triethoxy silane), HMDS(hexamethyldisilazane) 등의 실란 커플링 에이젼트계와 실리콘 바니쉬 등의 실리카계 무기계 바인더를 사용할 경우에는 코팅완료 후의 접착력 향상에 있어 좋다. 특히 상기 유기계 바인더와 무기계 바인더를 혼합하여 사용하는 것이 코팅공정시와 코팅완료후의 접착력 향상에 있어 더욱 좋다. 이때, 상기 유기계 바인더와 무기계 바인더는 100 : 1 내지 1 : 50의 중량비율로 혼합되는 것이 바람직하다.The binder serves to fix the composite to the coating surface. As such a binder, a conventional organic binder or an inorganic binder may be used, and specifically, organic binders such as cellulose, epoxy, acrylate, polyester, paraffin, and silicone may be used. In this case, it is good to improve adhesion during the coating process. Silane coupling agents such as TEOS (tetraethly orthosilicate), MTMS (methyltrimethoxysilane), MTES (methyl triethoxy silane), HMDS (hexamethyldisilazane), and silica-based inorganic binders such as silicone varnish can be used to improve adhesion after coating. . In particular, the use of the organic binder and the inorganic binder in combination is more preferable in improving the adhesion during the coating process and after the coating is completed. In this case, the organic binder and the inorganic binder are preferably mixed at a weight ratio of 100: 1 to 1:50.
상기와 같은 바인더는 조성물에 0.01 내지 10 중량%로 포함되는 것이 바람직하며, 그 함량이 상기 범위내일 경우에는 접착력 및 투과율저하 방지에 있어 더욱 좋다.It is preferable that such a binder is included in the composition in an amount of 0.01 to 10% by weight, and when the content is in the above range, it is more preferable in preventing adhesion and lowering of transmittance.
또한 상기 분산제는 조성물 내에서 복합체의 분산을 용이하게 하고, 조성물의 응집을 방지하는 작용을 한다.The dispersant also serves to facilitate dispersion of the composite in the composition and to prevent aggregation of the composition.
상기 분산제는 공지의 다양한 슬러리에 사용되는 분산제를 사용할 수 있음은 물론이며, 특히 수용성인 산성 그룹을 갖는 블록 공중합체의 알킬올 암모늄염을 사용하는 것이 좋다.Of course, the dispersant may be a dispersant used in a variety of known slurries, and it is particularly preferable to use alkylol ammonium salts of block copolymers having acidic groups which are water-soluble.
상기 분산제는 조성물에 0.1 내지 10 중량%로 포함되는 것이 바람직하며, 그 함량이 상기 범위 내일 경우에는 아연화합물의 분산성 향상에 있어 더욱 좋다.The dispersant is preferably included in 0.1 to 10% by weight in the composition, when the content is in the above range is better in improving the dispersibility of the zinc compound.
상기와 같은 성분으로 이루어지는 본 발명의 투명전도성 조성물은 분산의 적정성 유지를 위하여 염기도가 pH 5 내지 10인 것이 바람직하다.In the transparent conductive composition of the present invention comprising the above components, it is preferable that the basicity is pH 5 to 10 to maintain proper dispersion.
이와 같이 제조된 본 발명의 투명전도성 조성물은 안정성이 뛰어나며, 가시광선의 투과율이 우수하면서도 전기전도성을 높일 수가 있다. 특히 본 발명의 투명전도성 조성물을 50 내지 1000 nm의 두께로 코팅할 경우 가시광선은 85%, 바람직하게는 90%, 더욱 바람직하게는 95% 이상의 투과율을 나타내며, 전기전도성은 10-2Ω ㎝이하, 바람직하게는 10-3Ω ㎝ 이하까지 나타낼 수 있다.The transparent conductive composition of the present invention prepared as described above is excellent in stability and can improve electrical conductivity while having excellent transmittance of visible light. In particular, when the transparent conductive composition of the present invention is coated with a thickness of 50 to 1000 nm, visible light shows a transmittance of 85%, preferably 90%, more preferably 95% or more, and the electrical conductivity is 10 -2 Ω cm or less. Preferably, it can represent up to 10 <-3> ohm-cm.
또한 본 발명의 투명전도성 조성물은 자외선 차단을 요하는 다양한 장치에 사용되어지는 코팅층의 형성에 사용될 수 있으며, 바람직하기로는 상기 투명전도성 조성물을 함유한 코팅층의 두께는 50 내지 1000 nm인 것이 좋다. 상기 범위를 벗어나는 경우 전기전도성이 떨어지거나 가시광선 투과율이 떨어질 수 있다. 본 발명에 따른 코팅층은 가시광선의 투과율이 적어도 85% 이상이면서도, 전기전도성이 10-2Ω ㎝이하, 바람직하게는 10-3Ω ㎝ 이하까지 나타낼 수 있다. In addition, the transparent conductive composition of the present invention can be used for the formation of a coating layer to be used in various devices that require UV protection, preferably the thickness of the coating layer containing the transparent conductive composition is 50 to 1000 nm. If it is out of the above range, the electrical conductivity may be lowered or the visible light transmittance may be lowered. The coating layer according to the present invention may exhibit an electrical conductivity of 10 −2 Ω cm or less, preferably 10 −3 Ω cm or less, while having a visible light transmittance of at least 85% or more.
또한 본 발명은 상기 투명전도성 조성물의 코팅층을 필름 기재의 일측 부분에 포함하는 투명전도성 필름을 제공한다. 기재는 통상적으로 사용되는 필름 또는 유리일 수 있으며, 상기 필름 기재는 PET, PE 등 통상적으로 TCO(Transparent Conductive Oxide) 필름에 적용될 수 있는 필름일 수 있다. 상기 본 발명 코팅층의 두께는 제품 및 용도에 따라 임의로 선택하여 조절할 수 있으며, 바람직하기로는 50 내지 1000 nm인 것이 좋다.In another aspect, the present invention provides a transparent conductive film comprising a coating layer of the transparent conductive composition in one side of the film substrate. The substrate may be a film or glass that is commonly used, the film substrate may be a film that can be applied to a transparent conductive oxide (TCO) film, such as PET, PE. The thickness of the coating layer of the present invention can be arbitrarily selected and adjusted according to the product and the use, preferably 50 to 1000 nm.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.
[실시예][Example]
실시예 1. 2.5molYb-ZnO 복합체 제조Example 1.Preparation of 2.5molYb-ZnO Composite
산화아연의 출발원료로 황산아연을 이용하고, Yb의 출발원료로는 질산 이터븀을 이용하였으며, 탄산염의 출발원료로 암모늄카보네이트를 이용하여 액상반응으 로 인듐이 함유된 탄산아연을 제조하였다.Zinc carbonate was used as a starting material of zinc oxide, ytterbium nitrate was used as a starting material of Yb, and zinc carbonate containing indium was prepared by liquid phase reaction using ammonium carbonate as a starting material of carbonate.
구체적으로, 황산아연 1 mole/L의 수용액에 질산 이터븀 (황산아연과 질산 이터븀 몰비 97.5:2.5)을 혼합 후 암모늄카보네이트 1.5 mole/L 수용액을 가하여 제조한 이터븀이 함유된 아연 전구체를 초순수로 SO4 2- 및 NO3- 이온이 검출되지 않을 때까지 세정하여 전구체를 수득하였다. 그 다음 상기 수득한 전구체를 100～150 ℃의 온도에서 12 시간 동안 건조하였다.Specifically, an ytterbium-containing zinc precursor prepared by adding ytterbium nitrate (molar ratio of zinc sulfate and ytterbium nitrate 97.5: 2.5) to 1 mole / L of zinc sulfate and then adding 1.5 mole / L aqueous solution of ammonium carbonate to ultrapure water Furnace was washed until no SO 4 2- and NO 3- ions were detected, thereby obtaining a precursor. Then, the obtained precursor was dried at a temperature of 100 ~ 150 ℃ for 12 hours.
상기 건조된 건조물을 알루미나 도가니에 넣은 후, 700 ℃의 온도에서 120분 동안, 질소 분위기 하에서 소성한 후, 분쇄 분급하여 최종 나노크기의 분말을 제조하였다.The dried product was placed in an alumina crucible, calcined in a nitrogen atmosphere for 120 minutes at a temperature of 700 ° C., and then ground and classified to prepare a final nano-sized powder.
상기와 같이 제조한 분말을 EDX로 분석한 결과 이터븀과 아연으로 이루어진 화합물인 것을 확인할 수 있었다.As a result of analyzing the powder prepared as described above with EDX, it was confirmed that the compound was composed of ytterbium and zinc.
또한, 상기 분말의 입자표면을 주사형 전자 현미경으로 관찰한 결과 산화아연 입계가 관찰되었으며, 입계에 둘러싸인 산화아연의 1차 입경을 측정한 결과 분포의 중앙값이 20 ㎚이고, 최대값이 50 ㎚이었다. 또한 BET법에 의하여 비표면적의 측정한 결과 40 ㎡/g이었다.In addition, when the particle surface of the powder was observed with a scanning electron microscope, the zinc oxide grain boundary was observed. The primary particle diameter of the zinc oxide surrounded by the grain boundary was measured, and the median value of the distribution was 20 nm and the maximum value was 50 nm. . Moreover, it was 40 m <2> / g when the specific surface area was measured by BET method.
실시예 2. 5molYb-ZnO 복합체 제조Example 2. Preparation of 5molYb-ZnO Composite
상기 실시예 1에서 황산아연과 질산 이터븀의 몰비 95:5로 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 나노크기의 분말을 제조하였다.A nano-sized powder was prepared in the same manner as in Example 1, except that Example 1 was prepared in a molar ratio of 95: 5 of zinc sulfate and ytterbium nitrate.
상기와 같이 제조한 분말을 EDX로 분석한 결과 이터븀와 아연으로 이루어진 화합물인 것을 확인할 수 있었다.As a result of analyzing the powder prepared as described above with EDX, it was confirmed that the compound was composed of ytterbium and zinc.
또한, 상기 분말의 입자표면을 주사형 전자 현미경으로 관찰한 결과 산화아연 입계가 관찰되었으며, 입계에 둘러싸인 산화아연의 1차 입경을 측정한 결과 분포의 중앙값이 25 ㎚이고, 최대값이 100 ㎚이었다.In addition, when the particle surface of the powder was observed with a scanning electron microscope, the zinc oxide grain boundary was observed, and when the primary particle diameter of the zinc oxide surrounded by the grain boundary was measured, the median value of the distribution was 25 nm and the maximum value was 100 nm. .
또한 BET법에 의하여 비표면적의 측정한 결과 35 ㎡/g이었다.Moreover, it was 35 m <2> / g when the specific surface area was measured by BET method.
실시예 3. TCO(Transparent Conductive Oxide)조성물 제조Example 3 Preparation of Transparent Conductive Oxide (TCO) Composition
상기 실시예 1 내지 2에서 제조한 금속 산화물 복합체 분말 1,000 g, 분산제로 BYK-180(BYK-Chemie) 50g을 에틸알코올 750 g, 이소 프로필 알콜 750 g을 볼밀을 이용하여 6시간 이상 충분히 혼합한 후, 습식 비즈 밀로 분산시켜 균일하게 혼합하였다. 그 다음, 상기 혼합물에 에틸알코올과 이소프로필 알콜 1:1의 중량비율의 혼합액을 첨가하여 금속 산화물 복합체 분말이 20 중량%가 되도록 하여 자외선 차단 조성물을 제조하였다. 이 때 pH는 모두 8 내지 10이었으며, 점도는 모두 20 cP 이하였다.1,000 g of the metal oxide composite powder prepared in Examples 1 to 2 and 50 g of BYK-180 (BYK-Chemie) as a dispersant were sufficiently mixed with 750 g of ethyl alcohol and 750 g of isopropyl alcohol using a ball mill for 6 hours or more. The mixture was dispersed in a wet beads mill and uniformly mixed. Thereafter, a mixture of ethyl alcohol and isopropyl alcohol in a weight ratio of 1: 1 was added to the mixture so that the metal oxide composite powder was 20% by weight to prepare a sunscreen composition. At this time, the pH was all 8 to 10, the viscosity was all 20 cP or less.
또한 상기 조성물의 입도 분포를 레이저 회절법을 사용하여 측정한 결과, 중앙값은 130±20 ㎚이었고, 최대 입경이 1000 ㎚ 이상인 입자는 전혀 발견되지 않았다.In addition, the particle size distribution of the composition was measured using a laser diffraction method. As a result, the median value was 130 ± 20 nm, and no particles having a maximum particle size of 1000 nm or more were found.
실시예 4. 실리카계 무기계 바인더 제조Example 4 Preparation of Silica-Based Inorganic Binder
일본 신에츠사 실리콘 KBM403(3-Glycidoxypropyltrimethoxy) 0.5 mole, MTES (methyltrimethoxysilane) 0.6 mole, HMDS(hexamethyldisilazane) 0.024 mole, 에탄올 1 mole 혼합 후 교반기를 사용 30분간 교반을 행하였다. 그 후 순수 4 mole과 질산 0.02 mole 혼합액을 위 용액에 한번에 투입 후 2시간 동안 교반을 행하였다. 그 다음 이소부틸알콜 1.5 mole과 PM(propylene glycol monomethyl ether) 5 mole을 첨가한 후 1시간 동안 더 교반을 행하여 바인더 용액을 제조하였다.Nihon Shin-Etsu Co., Ltd. Silicone KBM403 (3-Glycidoxypropyltrimethoxy) 0.5 mole, MTES (methyltrimethoxysilane) 0.6 mole, HMDS (hexamethyldisilazane) 0.024 mole, and 1 mole of ethanol were mixed, followed by stirring for 30 minutes using a stirrer. Thereafter, 4 mole of pure water and 0.02 mole of nitric acid were added to the solution at once, followed by stirring for 2 hours. Thereafter, 1.5 mole of isobutyl alcohol and 5 mole of propylene glycol monomethyl ether (PM) were added thereto, followed by further stirring for 1 hour to prepare a binder solution.
실시예 5Example 5
상기 실시예 1의 TCO 조성물들 각각 97g과 상기 실시예 4의 바인더 3g을 1시간 동안 교반을 행한 후 투명 글라스에 스핀코팅하여 100 ~ 200nm의 두께로 코팅한 후 150℃에서 30분간 건조하였다.97 g of each of the TCO compositions of Example 1 and 3 g of the binder of Example 4 were stirred for 1 hour, then spin-coated to transparent glass, coated with a thickness of 100 to 200 nm, and dried at 150 ° C. for 30 minutes.
상기 TCO 조성물의 코팅층이 형성된 글라스를 4-Point prove(Jendel社제)로 전기전도도를 측정 시 면저항이 450Ω/sq이 나왔으며, 두께 확인시 130nm인 것을 확인하여 비저항 계산시 5.85×10-3Ω.cm가 나왔으며 UV 스펙트로포토미터 (SHIMADZU, 자외선/가시광선 분광광도계 및 근적외선 광도계)로 측정시 가시광선 영역에서의 투과율은 모두 93% 이상이었다The glass composition of the TCO coating layer formed 4-Point prove (Jendel社agent) the electrical conductivity of the sheet resistance is 450Ω / sq or been measured in, 5.85 × 10 -3 Ω when the specific resistance calculated and confirmed to be confirmed when the thickness 130nm .cm and the transmittance in the visible range were all over 93% as measured by UV spectrophotometer (SHIMADZU, UV / Visible Spectrophotometer and Near Infrared Photometer)
실시예 6Example 6
상기 실시예 2의 TCO 조성물들 각각 97g과 상기 실시예 4의 바인더 3g을 1시 간 동안 교반을 행한 후 투명 글라스에 스핀코팅하여 100 ~ 200nm의 두께로 코팅한 후 150℃에서 30분간 건조하였다.97 g of each of the TCO compositions of Example 2 and 3 g of the binder of Example 4 were stirred for 1 hour, then spin-coated to transparent glass, coated with a thickness of 100 to 200 nm, and dried at 150 ° C. for 30 minutes.
상기 TCO 조성물의 코팅층이 형성된 글라스를 4-Point prove(Jendel社제)로 전기전도도를 측정 시 면저항이 550Ω/sq이 나왔으며, 두께 확인시 150nm인 것을 확인하여 비저항 계산시 8.25×10-3Ω.cm가 나왔으며 UV 스펙트로포토미터 (SHIMADZU, 자외선/가시광선 분광광도계 및 근적외선 광도계)로 측정시 가시광선 영역에서의 투과율은 모두 91% 이상이었다.The glass composition of the TCO coating layer formed 4-Point prove the sheet resistance as measured by the electric conductivity (Jendel claim社) 550Ω / sq or has, 8.25 × 10 -3 Ω when calculating the specific resistance and confirmed to be confirmed when the thickness 150nm .cm and the transmittance in the visible range were all 91% or more when measured by UV spectrophotometer (SHIMADZU, ultraviolet / visible spectrophotometer and near infrared photometer).
상기와 같이, 본 발명의 바람직한 실시 예를 참조하여 설명하였지만 해당 기술 분야의 숙련된 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As described above, it has been described with reference to a preferred embodiment of the present invention, but those skilled in the art various modifications and changes of the present invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.
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