KR20020096536A - Method of producing electromagnetic shielding screen using indium tin oxide and screen display device comprising the screen - Google Patents
Method of producing electromagnetic shielding screen using indium tin oxide and screen display device comprising the screen Download PDFInfo
- Publication number
- KR20020096536A KR20020096536A KR1020010035096A KR20010035096A KR20020096536A KR 20020096536 A KR20020096536 A KR 20020096536A KR 1020010035096 A KR1020010035096 A KR 1020010035096A KR 20010035096 A KR20010035096 A KR 20010035096A KR 20020096536 A KR20020096536 A KR 20020096536A
- Authority
- KR
- South Korea
- Prior art keywords
- metal
- indium tin
- tin oxide
- composition
- solvent
- Prior art date
Links
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000010409 thin film Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 239000010419 fine particle Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- KVXKIRARVMGHKF-UHFFFAOYSA-G indium(3+);tin(4+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[In+3].[Sn+4] KVXKIRARVMGHKF-UHFFFAOYSA-G 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002471 indium Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 29
- 229910052709 silver Inorganic materials 0.000 abstract description 9
- 239000004332 silver Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 101710134784 Agnoprotein Proteins 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000007769 metal material Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 229940071575 silver citrate Drugs 0.000 description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 5
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 5
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 2
- RRXWRHLYVPTSIF-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;silver Chemical compound [Ag].OC(=O)CC(O)(C(O)=O)CC(O)=O RRXWRHLYVPTSIF-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 229910000337 indium(III) sulfate 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
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- INMGJBLKVVUBSX-UHFFFAOYSA-N indium;oxotin;silver Chemical compound [Ag].[In].[Sn]=O INMGJBLKVVUBSX-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 that is Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- H01L31/02—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]
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0033—Means for improving the coupling-out of light from the light guide
- G02B6/0058—Means for improving the coupling-out of light from the light guide varying in density, size, shape or depth along the light guide
- G02B6/0061—Means for improving the coupling-out of light from the light guide varying in density, size, shape or depth along the light guide to provide homogeneous light output intensity
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Optics & Photonics (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
[산업상 이용 분야][Industrial use]
본 발명은 인듐 주석 산화물을 사용한 투명 도전성 박막의 제조 방법 및 이 투명 도전성 박막을 포함하는 화면 표시 장치에 관한 것으로서, 더욱 상세하게는 도전성 및 투명성이 우수한 인듐 주석 산화물을 사용한 투명 도전성 박막의 제조 방법에 관한 것이다.The present invention relates to a method for producing a transparent conductive thin film using indium tin oxide and to a screen display device including the transparent conductive thin film, and more particularly, to a method for producing a transparent conductive thin film using indium tin oxide having excellent conductivity and transparency. It is about.
[종래 기술][Prior art]
화면 표시 장치의 투명 도전성 박막으로는 휘도를 떨어뜨리지 않기 위해 투광성과 도전성이 우수한 주석이 도핑된 인듐 산화물(tin doped indium oxide)(이하"인듐 주석 산화물(indium tin oixde: ITO)"이라 함)이 주로 사용되어 왔다. 그러나 최근에 화면 표시 장치가 점차 고정세화, 대형화해감에 따라 도전성이 더 우수한 물질이 요구되어 그에 관한 연구가 많이 이루어지고 있다. 그 예로 대한 민국 특허 공개 제 99-36350 호에 팔라듐과 은이 혼합된 투명 도전막 형성용 조성물이 기재되어 있고, 미국 특허 제 6,157,125 호에는 도전성 입자로 은을 사용한 은 슬러리액으로 형성된 도전성 반사 방지막이 기술되어 있으며, 대한 민국 특허 공개 제 99-64113 호에는 탄소 미세 섬유와 도전성 금속 산화물이 혼합된 투명 도전막이 기술되어 있다. 그러나 상술한 방법들은 모두 도전성이 높은 금속의 콜로이드를 사용하므로 일정 두께 이상으로 막을 형성하면 반사율이 급격하게 증가하여 광투과율이 낮아지므로 막의 두께가 얇아야한다. 이러한 제한 때문에 막의 균일도가 정확히 제어되지 않으면 약간의 불균일에도 불량이 생기는 경우가 많다.The transparent conductive thin film of the display device is made of tin doped indium oxide (hereinafter referred to as "indium tin oixde (ITO)") which has high light transmittance and high conductivity in order not to reduce brightness. Mainly used. Recently, however, as the screen display device has been increasingly high resolution and large in size, more conductive materials are required and many studies have been conducted. For example, Korean Patent Publication No. 99-36350 describes a composition for forming a transparent conductive film in which palladium and silver are mixed. US Pat. No. 6,157,125 describes a conductive antireflection film formed of a silver slurry using silver as conductive particles. Korean Patent Laid-Open Publication No. 99-64113 describes a transparent conductive film in which carbon fine fibers and a conductive metal oxide are mixed. However, all of the above methods use a colloid of a metal having high conductivity, so that when the film is formed to a predetermined thickness or more, the reflectance rapidly increases and the light transmittance is lowered. Because of these limitations, defects are often caused by slight unevenness if the film uniformity is not controlled accurately.
또한, 일본 특허 공개 평 7-258862 호에는 인듐 주석 산화물보다 도전성이 더 우수한 Au, Ag, Pt, Cu, Ni, Pb, Co, Cd, Pd, Rh, Ru 또는 Sn의 금속염 사용이 기재되어 있다. 일본 특허 공개 평 7-258862 호는 상기 금속염 용액에 도전성 미립자를 첨가하여, 도전성 미립자 표면을 금속염으로 코팅하는 방법으로서, 이 방법은 상기 금속염들이 표면에 있어서, 금속염 양이 증가할 경우 분산도가 급격히 저하되어 입자들이 뭉쳐 덩어리가 형성될 수 있다. 따라서, 금속염을 소량 사용하여야 하므로 도전성 향상 효과가 미미하다.In addition, Japanese Patent Laid-Open No. 7-258862 describes the use of metal salts of Au, Ag, Pt, Cu, Ni, Pb, Co, Cd, Pd, Rh, Ru or Sn, which are more conductive than indium tin oxide. Japanese Patent Laid-Open No. 7-258862 is a method of adding conductive fine particles to the metal salt solution to coat the surface of the conductive fine particles with a metal salt, which is a method of dispersing rapidly when the amount of the metal salt increases on the surfaces of the metal salts. Deterioration can cause the particles to clump together to form agglomerates. Therefore, since a small amount of metal salt should be used, the effect of improving conductivity is insignificant.
금속 콜로이드와 주석 첨가 산화 인듐을 단순히 혼합하여 코팅할 수도 있다. 그러나 금속 콜로이드는 도료로 사용할 만큼의 농도로 분산하기 위해서는 정전기적반발력을 부가해주는 분산제(예를 들어 구연산 나트륨 2수화물)를 사용해야하는데 주석 첨가 산화 인듐을 금속 콜로이드와 혼합하여 사용하면 주석 첨가 산화 인듐만으로 이루어진 막보다 도전성이 오히려 감소하여 바람직하지 않다.Metal colloids and tinned indium oxide may be simply mixed and coated. However, in order to disperse the metal colloid in a concentration sufficient to be used as a paint, a dispersant that adds electrostatic repulsion (for example, sodium citrate dihydrate) must be used. When indium tin oxide is mixed with a metal colloid, only tin indium oxide can be used. The conductivity is reduced rather than the film thus formed, which is not preferable.
본 발명은 상술한 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 도전성 및 투과성이 우수한 인듐 주석 산화물을 사용한 투명 도전성 박막의 제조 방법을 제공하는 것이다.The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing a transparent conductive thin film using indium tin oxide excellent in conductivity and permeability.
본 발명의 다른 목적은 상기 투명 도전성 박막을 포함하는 화면 표시 장치의 제조 방법을 제공하는 것이다.Another object of the present invention is to provide a method of manufacturing a screen display device including the transparent conductive thin film.
도 1은 본 발명의 실시예에 따라 제조된 투명 도전성 박막의 투과율을 나타낸 그래프.1 is a graph showing the transmittance of a transparent conductive thin film prepared according to an embodiment of the present invention.
상기 목적을 달성하기 위하여, 본 발명은 기판 상에 금속·인듐 주석 산화물 복합체 미립자 및 용매를 포함하는 제 1 조성물을 도포하고; 제 1 조성물이 도포된 기판에, 금속 알콕사이드 및 용매를 포함하는 제 2 조성물을 도포하고; 얻어진 생성물을 열처리하는 공정을 포함하는 투명 도전성 박막의 제조 방법을 제공한다.In order to achieve the above object, the present invention is coated with a first composition comprising a metal indium tin oxide composite fine particles and a solvent on a substrate; Applying to the substrate to which the first composition is applied a second composition comprising a metal alkoxide and a solvent; Provided are a method for producing a transparent conductive thin film, including a step of heat treating the obtained product.
본 발명은 또한 상기 제조 방법으로 제조된 투명 도전성 박막을 포함하는 화면 표시 장치를 제공한다.The present invention also provides a screen display device comprising a transparent conductive thin film manufactured by the above manufacturing method.
이하 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 금속·인듐 주석 산화물 복합체 미립자를 포함하는 투명 도전성 박막 조성물을 이용하여 투명 도전성 박막을 형성하는 방법에 관한 것이다.The present invention relates to a method for forming a transparent conductive thin film using a transparent conductive thin film composition containing metal indium tin oxide composite fine particles.
이 제조 방법은 먼저, 기판 상에 금속·인듐 주석 산화물 복합체 미립자 및용매를 포함하는 제 1 조성물을 도포한다.This manufacturing method first apply | coats the 1st composition containing a metal indium tin oxide composite microparticle and a solvent on a board | substrate.
상기 금속·인듐 주석 산화물 복합체 미립자는 인듐 주석 수산화물을 미리 형성하고, 낮은 온도, 즉 400℃ 이상, 하소 공정의 열처리 온도 이하의 낮은 온도에서 열분해되어 금속으로 석출될 수 있는 물질을 제조하여, 이 둘을 혼합하는 방법을 사용하는 방법으로 제조된 것을 사용한다.The metal-indium tin oxide composite fine particles are formed in advance to form an indium tin hydroxide, and to produce a material that can be thermally decomposed and precipitated as a metal at a low temperature, that is, at a temperature above 400 ° C. or below the heat treatment temperature of the calcination process. It is prepared by the method using the method of mixing.
이 제조 방법을 더욱 상세히 살펴보면, 인듐 주석 수산화물과 낮은 온도에서 열분해되어 금속으로 환원될 수 있는 물질을 혼합한다. 상기 인듐 주석 수산화물은 인듐염과 주석염을 사용하여 공침 방법으로 제조한다. 즉, 인듐염과 주석염을 물에 용해하고, 이어서 이 혼합물의 pH를 조절하면 인듐 주석 수산화물이 형성된다. pH 조절은 상기 혼합물에 pH 조절제를 첨가하여 실시하며, 상기 pH 조절제로는 pH를 증가시킬 수 있는 알칼리 물질로는 어떠한 것도 사용할 수 있으며, 그 예로는 암모니아 수 또는 암모니움 하이드로젠 카보네이트(ammonium hydrogen carbonate)를 사용할 수 있다. 상기 인듐염으로는 인듐을 포함하는 화합물은 어떠한 것도 사용할 수 있으며, 그 대표적인 예로 염화 인듐, 질산 인듐 또는 황산 인듐을 사용할 수 있으며, 상기 주석염으로는 주석을 포함하는 화합물은 어떠한 것도 사용할 수 있으며, 그 대표적인 예로 염화 주석을 사용할 수 있다.Looking more closely at this preparation method, indium tin hydroxide is mixed with a material that can be pyrolyzed and reduced to metal at low temperatures. The indium tin hydroxide is prepared by the coprecipitation method using an indium salt and tin salt. That is, indium salt and tin salt are dissolved in water, and then the pH of this mixture is adjusted to form indium tin hydroxide. pH control is performed by adding a pH adjuster to the mixture, and any pH can be used as an alkaline substance capable of increasing the pH, for example, ammonia water or ammonium hydrogen carbonate. ) Can be used. As the indium salt, any compound containing indium may be used, and representative examples thereof may include indium chloride, indium nitrate, or indium sulfate, and as the tin salt, any compound containing tin may be used. As a representative example, tin chloride can be used.
상기 낮은 온도에서 열분해되어 금속으로 환원될 수 있는 물질(이하 "저온 열분해성 금속 물질"이라 함)은 제 1 용매에 용해된 금속염 용액과 제 2 용매에 용해된 분산제 용액을 혼합하여 제조한다. 두 용액을 혼합하면, 금속염과 침전제가 반응하여 저온 열분해성 금속 물질이 석출된다. 상기 금속염에서 금속으로는 추후공정인 하소 공정의 열처리 온도 이하 내지 400℃ 이상에서 열분해되어 금속으로 석출될 수 있는 금속은 어떠한 것도 사용할 수 있으며, 그 대표적인 예로 Ag를 사용할 수 있다. 이러한 금속을 포함하는 금속염의 종류에는 특별히 제한되지 않으나, AgNO3와 같은 질산염이 대표적으로 사용될 수 있다.The material that can be pyrolyzed at a low temperature to be reduced to metal (hereinafter referred to as "low temperature pyrolytic metal material") is prepared by mixing a metal salt solution dissolved in a first solvent and a dispersant solution dissolved in a second solvent. When the two solutions are mixed, the metal salt and the precipitant react to precipitate a low temperature pyrolytic metal material. As the metal in the metal salt, any metal that can be thermally decomposed and precipitated as a metal at a heat treatment temperature below 400 ° C. or higher in a subsequent calcination process may be used, and Ag may be used as a representative example. The type of metal salt containing such a metal is not particularly limited, but nitrates such as AgNO 3 may be representatively used.
상기 침전제로는 탄산, 구연산(citric acid), 말레인산(maleic acid), 타르타르산(tartaric acid), 젖산(lactic acid) 또는 옥살린산(oxalic acid)을 사용할 수 있으며, 또한 이들의 나트륨, 칼륨 또는 암모늄염을 사용할 수 도 있다.The precipitant may be carbonic acid, citric acid, maleic acid, tartaric acid, lactic acid or oxalic acid, and also sodium, potassium or ammonium salts thereof. You can also use
얻어진 인듐 주석 수산화물과 저온 열분해성 금속 물질을 혼합하고 이를 하소한다. 하소 공정에서 인듐 주석 수산화물은 인듐 주석 산화물로 전환되고, 저온 열분해성 금속 물질이 분해되어 금속으로 석출되면서, 생성된 인듐 주석 산화물에 박혀, 금속이 박힌 인듐 주석 산화물 복합체 미립자가 제조된다. 상기 하소 공정은 400℃ 이상에서 실시하는 것이 적당하며, 400℃ 미만일 경우에는 결정질이 형성되지 않아 목적하는 산화물이 제조되지 않는다. 상기 인듐 주석 수산화물과 저온 열분해성 금속 물질의 혼합 비율은 투과율과 도전성 조절 목적에 따라 적절하게 조절할 수 있다. 즉, 저온 열분해성 금속 물질의 사용량이 증가하면(즉, 금속의 양이 증가하면), 투과율은 감소하고 도전성은 향상되거나 비슷한 수준을 유지한다.The obtained indium tin hydroxide and the low temperature pyrolytic metal material are mixed and calcined. In the calcination process, the indium tin hydroxide is converted to indium tin oxide, and the low-temperature pyrolytic metal material is decomposed and precipitated as a metal, and then embedded in the produced indium tin oxide, whereby the metal-embedded indium tin oxide composite fine particles are produced. The calcining step is preferably carried out at 400 ℃ or more, when less than 400 ℃ crystalline is not formed, the desired oxide is not produced. The mixing ratio of the indium tin hydroxide and the low temperature pyrolytic metal material may be appropriately adjusted according to the transmittance and conductivity control purpose. That is, as the amount of low temperature pyrolytic metal material used increases (ie, the amount of metal increases), the transmittance decreases and the conductivity improves or maintains a similar level.
하소된 인듐 주석 산화물을 투명 도전성 조성물에 그대로 사용할 수도 있고, 도전성을 더 향상시키기 위하여 환원 분위기 또는 비활성 분위기에서 소둔 (annealing)시켜 사용할 수 도 있다. 상기 소둔 공정은 환원 분위기에서 실시할경우 250 내지 500℃에서 실시하는 것이 바람직하다. 250℃ 미만에서 실시할 경우에는 환원 반응이 일어나지 않고, 500℃보다 높은 온도에서 실시할 경우에는 환원 반응이 너무 심하게 발생되어 인듐 주석 산화물의 매트릭스(matrix)가 붕괴될 수 있어 바람직하지 않다. 비활성 분위기에서 소둔시킬 경우 300℃ 이상에서 실시하는 것이 바람직하다.The calcined indium tin oxide may be used as it is in the transparent conductive composition, or may be annealed in a reducing atmosphere or an inert atmosphere in order to further improve conductivity. The annealing step is preferably carried out at 250 to 500 ℃ when carried out in a reducing atmosphere. When the temperature is lower than 250 ° C., the reduction reaction does not occur, and when the temperature is higher than 500 ° C., the reduction reaction occurs too badly, which may disintegrate the matrix of indium tin oxide. When annealing in an inert atmosphere, it is preferable to carry out at 300 degreeC or more.
형성된 금속·인듐 주석 산화물 복합체는 일차 입자 크기가 5 내지 50㎚의 평균 입경을 갖는 미립자이다.The formed metal-indium tin oxide composite is microparticles | fine-particles whose primary particle size is 5-50 nm.
상기 금속·인듐 주석 산화물 복합체 미립자는 인듐 주석 산화물 매트릭스에 금속이 박힌 형태로서 입자 표면이 주로 도전성 산화물로 이루어져서 분산제를 사용하지 않고 pH 조절만으로도 고농도로 분산시킬 수 있다. 따라서 고농도 콜로이드를 형성할 수 있으므로, 본 발명의 금속·인듐 주석 산화물 복합체 미립자는 투명 전극용 도료 및 페이스트 및 투명 도전성 박막을 제조하는데 사용되는 투명 도전성 조성물에 유용하게 사용될 수 있으며 이외에도 스퍼터 타겟 제조에도 사용될 수 있다. 본 발명의 금속·인듐 주석 산화물 복합체 미립자를 포함하는 투명 도전성 조성물에서 고형분인 금속·인듐 주석 산화물 복합체 미립자의 함량은 0.01 내지 80 중량%가 바람직하다. 총 고형분의 함량이 0.01 중량% 미만일 경우에는 도전성을 갖는 박막이 형성되지 않고, 80 중량%를 초과하는 경우에는 거의 분말 상태로 되어 투명 도전막 형성용 슬러리로 사용하기가 어려운 문제점이 있다. The metal-indium tin oxide composite fine particles are in the form of a metal embedded in an indium tin oxide matrix, and the surface of the particles is mainly composed of a conductive oxide, so that the metal-indium tin oxide composite fine particles can be dispersed at a high concentration without using a dispersant. Therefore, since a high concentration of colloids can be formed, the metal-indium tin oxide composite fine particles of the present invention can be usefully used in transparent conductive compositions used to prepare transparent electrode paints and pastes and transparent conductive thin films. Can be. In the transparent conductive composition containing the metal indium tin oxide composite fine particles of the present invention, the content of the metal indium tin oxide composite fine particles, which is a solid content, is preferably 0.01 to 80% by weight. When the total solid content is less than 0.01% by weight, a conductive thin film is not formed. When the total solid content is more than 80% by weight, the powder becomes almost powdery, making it difficult to use as a slurry for forming a transparent conductive film .
상기 투명 도전성 조성물은 용매를 20 내지 99.99 중량% 포함하며, 용매로는 메탄올, 에탄올 또는 n-부탄올의 알콜류를 주로 사용하나 사용 용도에 따라 알콜류외의 유기용매와 물도 사용할 수 있다.The transparent conductive composition includes 20 to 99.99 wt% of a solvent, and alcohols such as methanol, ethanol or n-butanol are mainly used as solvents, but organic solvents and water other than alcohols may be used depending on the intended use.
상기 투명 도전성 조성물은 이외에도 용도에 따라 당해 분야에서 널리 알려진 부가적인 첨가물을 더욱 포함할 수 도 있다. 예를 들어, 투명성을 더욱 향상시키기 위해 규소, 알루미늄, 지르코늄 또는 세륨 등의 무기 미립자, 또는 막 강도를 향상시키기 위해 폴리에스테르 수지, 아크릴 수지, 에폭시 수지, 실란(silane) 등의 바인더를 더욱 포함할 수 도 있으며, 이들을 포함할 경우 그 사용량은 목적에 따라 적절하게 조절할 수 있다.The transparent conductive composition may further include additional additives well known in the art, depending on the use. For example, inorganic fine particles such as silicon, aluminum, zirconium or cerium, or binders such as polyester resins, acrylic resins, epoxy resins, and silanes may be further included to improve film strength. In case of including these, the amount of use may be properly adjusted according to the purpose.
상기 제 1 조성물을 기판에 도포하는 방법은 조성물을 기판에 균일하게 도포할 수 있는 방법이면 되며, 특별히 제한되지는 않는다. 그러나 대표적인 방법은 스핀 코팅, 스프레이 코팅, 침적 코팅을 들 수 있다. 또한, 상기 기판으로는 특별히 종류를 제한하지는 않으며, 유리, 플라스틱 등을 사용할 수 있다.The method of apply | coating the said 1st composition to a board | substrate should just be a method which can apply | coat a composition uniformly to a board | substrate, and is not specifically limited. However, representative methods include spin coating, spray coating, and dip coating. In addition, the substrate is not particularly limited in kind, and glass, plastic, or the like can be used.
이어서, 제 1 조성물이 도포된 기판을 건조하여 제 1 코팅막을 형성한다. 이어서, 제 1 코팅막이 기판에 견고하게 부착시키고, 제 1 코팅막을 보호하기 위하여, 제 1 코팅막이 형성된 기판에 제 2 조성물을 도포한다. 이 제 2 조성물은 금속 알콕사이드 및 용매를 포함한다.Subsequently, the substrate coated with the first composition is dried to form a first coating film. Subsequently, in order to firmly adhere the first coating film to the substrate and protect the first coating film, the second composition is applied to the substrate on which the first coating film is formed. This second composition comprises a metal alkoxide and a solvent.
상기 금속 알콕사이드로는 하기 화학식 1의 금속 알콕사이드를 사용하는 것이 바람직하다.As the metal alkoxide, it is preferable to use a metal alkoxide of the following formula (1).
[화학식 1][Formula 1]
M1(OR)x M 1 (OR) x
(상기 화학식 1에서, M1은 Si, Ti, Sn, Zr, Al 및 In으로 이루어진 군에서 선택되는 것이고, 상기 R은 탄소수 1 내지 4의 알킬기이고, x는 3 내지 4의 정수임)(In Formula 1, M 1 is selected from the group consisting of Si, Ti, Sn, Zr, Al and In, wherein R is an alkyl group having 1 to 4 carbon atoms, x is an integer of 3 to 4)
상기 용매로는 메탄올, 에탄올, n-부탄올과 같은 알콜 용매, 물 또는 이들의 혼합 용매를 사용할 수 있다.The solvent may be an alcohol solvent such as methanol, ethanol, n-butanol, water or a mixed solvent thereof.
아울러, 도전성을 더욱 향상시키기 위하여, 상기 제 2 조성물은 도전성 금속염을 더욱 포함할 수 도 있다. 상기 도전성 금속염은 제 1 조성물에서 사용한 도전성 금속염은 어떠한 것도 사용할 수 있다.In addition, in order to further improve conductivity, the second composition may further include a conductive metal salt. Any of the conductive metal salts used in the first composition may be used as the conductive metal salts.
상기 제 2 조성물은 금속 알콕사이드의 가수 분해를 촉진하기 위하여 질산, 염산과 같은 산을 더욱 포함할 수 도 있다.The second composition may further include an acid such as nitric acid and hydrochloric acid to promote hydrolysis of the metal alkoxide.
이어서, 제 2 조성물이 도포된 기판을 건조하여 제 1 코팅막 위에 제 2 코팅막을 형성한다. 도전성 금속염을 더욱 포함하는 제 2 조성물을 사용할 경우, 이 건조 공정에 따라 제 2 조성물에 포함되어 있는 금속 알콕사이드의 졸-겔 반응에 의하여 매트릭스 구조가 형성되고 이 매트릭스 구조 내로 금속 이온이 도핑되거나, 금속 이온이 금속 알콕사이드와 결합하면서 제 2 코팅막에도 금속 이온이 존재하게 된다. 결과적으로, 제조된 투명 도전성 박막은 제 1 코팅막과, 이 제 1 코팅막 상부에 형성된 제 2 코팅막 모두에 금속 미립자가 존재하게 되므로 도전성이 매우 증가될 수 있게 된다.Subsequently, the substrate coated with the second composition is dried to form a second coating film on the first coating film. When using the second composition further comprising a conductive metal salt, a matrix structure is formed by the sol-gel reaction of the metal alkoxide included in the second composition according to this drying process and the metal ions are doped into the matrix structure, or the metal As the ions combine with the metal alkoxide, metal ions are also present in the second coating film. As a result, in the prepared transparent conductive thin film, since the fine metal particles are present in both the first coating film and the second coating film formed on the first coating film, the conductivity can be greatly increased.
상기 제 1 및 제 2 코팅막이 형성된 기판을 그대로 사용할 수 도 있고, 제 2코팅막 위에 제 2 조성물을 이용하여 요철이 형성되도록 코팅하여, 표면에서 난반사가 일어나는 난반사층을 더욱 형성할 수도 있다.The substrate on which the first and second coating layers are formed may be used as it is, or the second coating layer may be coated using a second composition to form irregularities, thereby further forming a diffuse reflection layer in which diffuse reflection occurs on the surface.
이와 같은 투명 도전성 박막은 칼라 음극선관 또는 플라즈마 디스플레이 패널 등과 같은 화면 표시 장치에 전자파 차폐막으로 유용하게 사용될 수 있다.Such a transparent conductive thin film may be usefully used as an electromagnetic shielding film in a screen display device such as a color cathode ray tube or a plasma display panel.
이하 본 발명의 바람직한 실시예 및 비교예를 기재한다. 그러나 하기한 실시예 및 비교예는 본 발명의 바람직한 일 실시예일 뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples and comparative examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.
(실시예 1)(Example 1)
염화인듐 4수화물(InCl3·4H2O) 40g과 염화 주석 5수화물(SnCl2·5H2O) 1.31g을 500㎖의 순수에 용해하고, 여기에 4M 암모니아 수 200㎖를 첨가하였다. 그 결과 인듐 주석 수산화물이 공침되어 형성되었으며, 얻어진 인듐 주석 수산화물을 세척하였다.40 g of indium chloride tetrahydrate (InCl 3 · 4H 2 O) and 1.31 g of tin chloride pentahydrate (SnCl 2 · 5H 2 O) were dissolved in 500 ml of pure water, and 200 ml of 4M ammonia water was added thereto. As a result, indium tin hydroxide was formed by coprecipitation, and the obtained indium tin hydroxide was washed.
AgNO30.53g을 순수 25㎖에 녹인 은염 용액과 구연산 나트륨 2수화물(Na3C6H5O7·2H2O) 0.91g을 25㎖에 녹인 첨가제 용액을 혼합하여 구연산 은을 제조하고, 제조된 구연산 은을 세척하였다.Silver citrate was prepared by mixing a silver salt solution in which 0.53 g of AgNO 3 was dissolved in 25 ml of pure water and an additive solution in which 0.91 g of sodium citrate dihydrate (Na 3 C 6 H 5 O 7 2H 2 O) was dissolved in 25 ml. Citric acid silver was washed.
상기 인듐 주석 수산화물과 구연산 은을 균일하게 혼합하여 건조한 후 700℃에서 2시간 하소하여 은 입자가 박힌 인듐 주석 산화물 복합체 미립자, 즉 은·인듐 주석 산화물 복합체 미립자를 얻었다.The indium tin hydroxide and silver citrate were uniformly mixed, dried and calcined at 700 ° C. for 2 hours to obtain indium tin oxide composite fine particles containing silver particles, that is, silver and indium tin oxide composite fine particles.
제조된 은·인듐 주석 산화물 복합체 미립자 2.1g을 메탄올 20g, 에탄올67.9g 및 n-부탄올 10g의 혼합 용매에 분산시켜 제 1 조성물(도포액 A라 칭함)을 제조하였다. 테트라에틸 오르토실리케이트 4.5g을 메탄올 30g, 에탄올 50g, n-부탄올 12g 및 순수 4g의 혼합 용매와 혼합하고, 여기에 질산 0.6g 및 질산은(AgNO3) 0.047g을 첨가하고 실온에서 약 24시간 동안 교반하여 제 2 조성물(도포액 B라 칭함)을 준비하였다.2.1 g of the prepared silver-indium tin oxide composite fine particles were dispersed in a mixed solvent of 20 g of methanol, 67.9 g of ethanol, and 10 g of n-butanol to prepare a first composition (called a coating solution A). 4.5 g of tetraethyl orthosilicate is mixed with a mixed solvent of 30 g of methanol, 50 g of ethanol, 12 g of n-butanol and 4 g of pure water, to which 0.6 g of nitric acid and 0.047 g of silver nitrate (AgNO 3 ) are added and stirred at room temperature for about 24 hours. To prepare a second composition (called a coating solution B).
깨끗하게 세정된 유리 패널을 약 90rpm으로 회전하면서 상기 도포액 A를 50cc 붓고 유리 패널의 회전 속도를 약 150rpm으로 상승시켰다. 그리고나서 도포액 B를 60cc 붓고 도포액 A와 동일한 방법으로 도포하였다. 그후 건조하여 패널 표면 온도를 200℃로 유지시키고 30분간 소성하여 투명 도전성 박막을 형성하였다.50 cc of the coating solution A was poured while rotating the clean glass panel at about 90 rpm, and the rotational speed of the glass panel was raised to about 150 rpm. Then, 60 cc of coating solution B was poured and applied in the same manner as coating solution A. After drying, the panel surface temperature was maintained at 200 ° C. and fired for 30 minutes to form a transparent conductive thin film.
(실시예 2)(Example 2)
코팅한 패널을 240℃에서 소성한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 투명 도전성 박막을 형성하였다.A transparent conductive thin film was formed in the same manner as in Example 1 except that the coated panel was baked at 240 ° C.
(실시예 3)(Example 3)
AgNO31.33g을 순수 25㎖에 녹인 은염 용액과 구연산 나트륨 2수화물(Na3C6H5O7·2H2O) 2.3g을 25㎖에 녹인 첨가제 용액과 혼합하여 구연산 은을 만든 것을 제외하고는 상기 실시예 2와 동일하게 실시하여 투명 도전성 박막을 형성하였다.Except that silver citrate was mixed with 1.33 g of AgNO 3 in 25 ml of pure water and 2.3 g of sodium citrate dihydrate (Na 3 C 6 H 5 O 7 · 2H 2 O) in an additive solution dissolved in 25 ml. Was carried out in the same manner as in Example 2 to form a transparent conductive thin film.
(실시예 4)(Example 4)
AgNO32.86g을 순수 25㎖에 녹인 은염 용액과 구연산 나트륨2수화물(Na3C6H5O7·2H2O) 4.81g을 25㎖에 녹인 첨가제 용액과 혼합하여 구연산 은을 만든 것을 제외하고는 상기 실시예 2와 동일하게 실시하여 투명 도전성 박막을 형성하였다.Except for producing silver citrate by mixing 2.86 g of AgNO 3 in 25 ml of pure water and 4.81 g of sodium citrate dihydrate (Na 3 C 6 H 5 O 7 · 2H 2 O) in an additive solution dissolved in 25 ml. Was carried out in the same manner as in Example 2 to form a transparent conductive thin film.
(실시예 5)(Example 5)
AgNO36.44g을 순수 25㎖에 녹인 은염 용액과 구연산 나트륨 2수화물(Na3C6H5O7·2H2O) 11.14g을 25㎖에 녹인 첨가제 용액과 혼합하여 구연산 은을 만든 것을 제외하고는 상기 실시예 2와 동일하게 실시하여 투명 도전성 박막을 형성하였다.Except for producing silver citrate by mixing 6.44 g of AgNO 3 in 25 ml of pure water and 11.14 g of sodium citrate dihydrate (Na 3 C 6 H 5 O 7 · 2H 2 O) in an additive solution dissolved in 25 ml. Was carried out in the same manner as in Example 2 to form a transparent conductive thin film.
(비교예 1)(Comparative Example 1)
염화인듐 4수화물(InCl3·4H2O) 40g과 염화주석 5수화물(SnCl4·5H2O) 1.31g을 500㎖의 순수에 용해하고, 여기에 4M 암모니아 수 200㎖를 첨가하였다. 그 결과 인듐 주석 수산화물이 공침되어 형성되었으며, 형성된 인듐 주석 수산화물을 세척하였다. 세척한 인듐 주석 수산화물을 건조한 후, 700℃에서 2시간 하소하여 주석 첨가 산화 인듐 미립자를 얻었다.40 g of indium chloride tetrahydrate (InCl 3 · 4H 2 O) and 1.31 g of tin chloride pentahydrate (SnCl 4 · 5H 2 O) were dissolved in 500 ml of pure water, and 200 ml of 4M ammonia water was added thereto. As a result, indium tin hydroxide was formed by coprecipitation, and the formed indium tin hydroxide was washed. The washed indium tin hydroxide was dried and then calcined at 700 ° C. for 2 hours to obtain tin-added indium oxide fine particles.
주석 첨가 산화 인듐 미립자 2.1g을 메탄올 20g, 에탄올 67.9g 및 n-부탄올 10g의 혼합 용매에 분산시켜 제 1 조성물(도포액 A라 칭함)을 제조하였다. 테트라에틸 오르토실리케이트(tetraethyl orthosilicate) 4.5g을 메탄올 30g, 에탄올 50g, n-부탄올 12g 및 순수 4g의 혼합 용매와 혼합하고, 여기에 질산 0.6g 및 질산은(AgNO3) 0.047g을 첨가하고 실온에서 약 24시간 동안 교반하여 제 2 조성물(도포액 B라 칭함)을 준비하였다.2.1 g of tin-added indium oxide fine particles were dispersed in a mixed solvent of 20 g of methanol, 67.9 g of ethanol, and 10 g of n-butanol to prepare a first composition (coating solution A). 4.5 g of tetraethyl orthosilicate is mixed with a mixed solvent of 30 g of methanol, 50 g of ethanol, 12 g of n-butanol and 4 g of pure water, to which 0.6 g of nitric acid and 0.047 g of silver nitrate (AgNO 3 ) are added and at room temperature Stirring for 24 hours to prepare a second composition (called the coating solution B).
깨끗하게 세정된 유리 패널을 약 90rpm으로 회전하면서 상기 도포액 A를 50cc 붓고 유리 패널의 회전 속도를 약 150rpm으로 상승시켰다. 그리고나서 도포액 B를 60cc 붓고 도포액 A와 동일한 방법으로 도포하였다. 그후 건조하여 패널 표면 온도를 200℃로 유지시키고 30분간 소성하여 투명 도전성 박막을 형성하였다.50 cc of the coating solution A was poured while rotating the clean glass panel at about 90 rpm, and the rotational speed of the glass panel was raised to about 150 rpm. Then, 60 cc of coating solution B was poured and applied in the same manner as coating solution A. After drying, the panel surface temperature was maintained at 200 ° C. and fired for 30 minutes to form a transparent conductive thin film.
(비교예 2)(Comparative Example 2)
코팅한 패널의 소성 공정을 240℃에서 실시한 것을 제외하고는 상기 비교예 1과 동일하게 실시하여 투명 도전성 박막을 형성하였다.A transparent conductive thin film was formed in the same manner as in Comparative Example 1 except that the firing process of the coated panel was performed at 240 ° C.
상기 실시예 1 내지 5 및 비교예 1 내지 2에 따라 형성된 투명 도전성 박막의 표면 저항을 측정하여 하기 표 1에 나타내었다. 또한, 수분에 의한 변화를 관찰하기 위해, 상기 실시예 1 및 비교예 1의 투명 도전성 박막을 60℃ 물에 24시간 동안 침적한 후, 표면 저항을 측정하여 그 결과도 하기 표 1에 나타내었다.The surface resistance of the transparent conductive thin films formed according to Examples 1 to 5 and Comparative Examples 1 to 2 was measured and shown in Table 1 below. In addition, in order to observe the change by moisture, the transparent conductive thin films of Example 1 and Comparative Example 1 were immersed in 60 ° C water for 24 hours, the surface resistance was measured and the results are also shown in Table 1 below.
상기 표 1에서, 비교예 1과 비교예 2의 표면 저항이 소성 온도가 증가함에 따라 증가하는 것은 소성 온도가 높아지면 치밀화가 더 일어나기는 하지만 인듐 주석 산화물 입자에 산소가 더 흡착하여 전자의 농도가 감소하여 저항이 증가하게 되는 것으로 생각된다. 그러나 실시예 1과 실시예 2를 비교하면 소성 온도가 증가함에 따라 저항이 감소하는 결과가 나타났다. 이는 인듐 주석 산화물 입자의 산화에 의한 저항 증가보다는 치밀화에 의한 저항 감소가 더 큰 영향을 미침을 알 수 있다.In Table 1, the surface resistance of Comparative Example 1 and Comparative Example 2 increases as the firing temperature is increased, but densification occurs when the firing temperature is increased, but oxygen is further adsorbed to the indium tin oxide particles to increase the concentration of electrons. It is thought that the resistance decreases to increase. However, comparing Example 1 and Example 2, the resistance was reduced as the firing temperature increases. It can be seen that the decrease in resistance due to densification has a greater effect than the increase in resistance due to oxidation of indium tin oxide particles.
이 결과로 실시예 1 내지 5에서는 높은 온도에서 소성을 실시할 수 있으므로 화학적 내구성이나 막경도가 우수한 투명 도전성 박막을 형성할 수 있으나, 비교예 1 내지 2에서는 소성 온도 증가에 따라 저항이 함께 증가하여 높은 온도에서 소성을 실시할 수 없으므로 화학적 내구성이나 막경도가 우수한 투명 도전성 박막을 제조하기 힘들다는 것을 알 수 있다. 실시예 2 내지 5를 비교하면 은이 약 5 원자%(실시예 3)까지는 저항에 큰 변화가 없으나 그 이상에서는 저항이 차츰 증가하는 것을 알 수 있다.As a result, in Examples 1 to 5, baking may be performed at a high temperature, thereby forming a transparent conductive thin film having excellent chemical durability or film hardness. In Comparative Examples 1 to 2, resistance increases with increasing firing temperature. It can be seen that it is difficult to produce a transparent conductive thin film having excellent chemical durability and film hardness because the baking cannot be performed at a high temperature. Comparing Examples 2 to 5, silver has no significant change in resistance up to about 5 atomic% (Example 3), but it can be seen that the resistance gradually increases beyond that.
침적 후 표면 저항의 결과를 보면, 실시예 1이 비교예 1에 비하여 표면 저항이 낮으므로 수분에 의한 영향이 훨씬 적을 것을 알 수 있으므로 내후성이 우수할 것을 예측할 수 있다.As a result of the surface resistance after the deposition, it can be seen that Example 1 has a lower surface resistance than Comparative Example 1, so that the effect by moisture is much less, and thus the weather resistance is excellent.
도 1에 실시예 3의 방법으로 만든 막의 투과율을 맨 유리판을 기준으로 하여 나타냈다. 도 1에서 투과율이 100%가 넘는 것은 맨 유리에서 광원쪽으로 반사가 더 많이 일어나기 때문인 것으로 추정된다. 이러한 예는 실시예 2의 방법으로 만든 17인치 브라운관의 휘도를 측정한 결과와 일치하며 이를 표 2에 나타냈다.The transmittance | permeability of the film | membrane made by the method of Example 3 was shown in FIG. 1 based on the bare glass plate. It is assumed that the transmittance of more than 100% in FIG. 1 is due to more reflection from the bare glass toward the light source. This example is consistent with the results of measuring the luminance of the 17-inch CRT made by the method of Example 2 and are shown in Table 2.
표 2의 결과에서 코팅막이 있는 조건(1)에서의 휘도가 모든 조건은 동일하게 하고 막만 벗겨낸 조건(2)보다 휘도가 높고 막이 없는 상태에서 같은 색좌표를 맞춘 조건(3)이 조건 1과 동일한 휘도를 갖게 하는 전류가 조건 1보다 높은 것으로 보아 휘도 향상 효과가 있는 것으로 볼 수 있다. 이것은 브라운관 패널과 코팅막 등의 계면에서의 반사가 코팅하지 않은 브라운관의 유리에서 반사보다 더 낮은데서 기인하는 것으로 추정된다. 그리고 도 1에서 코팅막이 가시광의 단파장 영역에서 흡수가 크게 일어나는 것을 알 수 있으며 막의 색을 갈색을 띤다. 이는 표 3에서 알 수 있는데, 같은 색좌표를 맞추기 위해 청색의 전자총 전류가 증가시켜야하는 것으로부터 단파장 영역에서 빛을 더 흡수함을 알 수 있다.In the results of Table 2, the luminance in the condition (1) with the coating film was the same in all conditions, and the luminance (3) with the same color coordinate in the state without the film was higher than the condition (2) with only the film peeled off. It can be seen that the luminance-improving effect is seen because the current which gives luminance is higher than condition 1. This is presumably due to the reflection at the interface between the CRT panel and the coating film being lower than the reflection in the glass of the uncoated CRT. In FIG. 1, it can be seen that the coating film has a large absorption in the short wavelength region of visible light and has a brown color. This can be seen in Table 3, which indicates that the electron gun current of blue has to be increased to match the same color coordinates, and thus it absorbs more light in the short wavelength region.
상술한 바와 같이, 본 발명은 도전성이 높아 전자파 차폐 효율이 증가하고 은의 함량에 따라 투과율을 조절할 수 있는 투명 도전성 박막을 제조할 수 있고, 이 투명 도전성 박막은 수분 등 외부 환경에 의한 경시 변화가 거의 없고, 내부 반사 감소에 의한 휘도 향상 효과가 있다.As described above, the present invention can produce a transparent conductive thin film that can increase the electromagnetic shielding efficiency and control the transmittance according to the content of silver due to its high conductivity, and the transparent conductive thin film has almost no change over time due to external environment such as moisture. There is no brightness improvement effect by the internal reflection reduction.
Claims (7)
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Cited By (5)
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| KR20020096534A (en) * | 2001-06-20 | 2002-12-31 | 삼성에스디아이 주식회사 | Method of preparing composite of metal and indium tin oxide and transparent conductive composition comprising composite of metal and indium tin oxide prepared by same |
| KR100748956B1 (en) * | 2004-12-01 | 2007-08-13 | 엘지전자 주식회사 | Plasma Display Panel and method of forming filter thereof |
| US7326460B2 (en) | 2003-03-26 | 2008-02-05 | Seiko Epson Corporation | Device, method of manufacturing the same, electro-optic device, and electronic equipment |
| KR20160045132A (en) * | 2013-09-27 | 2016-04-26 | 후지필름 가부시키가이샤 | Method for producing metal oxide film, metal oxide film, thin-film transistor, display device, image sensor, and x-ray sensor |
| US9704610B2 (en) | 2015-02-04 | 2017-07-11 | Korea Institute Of Science And Technology | Manganese tin oxide based transparent conducting oxide and transparent conductive film and method for fabricating transparent conductive film using the same |
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| US9704610B2 (en) | 2015-02-04 | 2017-07-11 | Korea Institute Of Science And Technology | Manganese tin oxide based transparent conducting oxide and transparent conductive film and method for fabricating transparent conductive film using the same |
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