KR101324558B1 - Transparent composite conductive oxide thin films and method for preparing the oxide thin films - Google Patents
Transparent composite conductive oxide thin films and method for preparing the oxide thin films Download PDFInfo
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- KR101324558B1 KR101324558B1 KR1020120035021A KR20120035021A KR101324558B1 KR 101324558 B1 KR101324558 B1 KR 101324558B1 KR 1020120035021 A KR1020120035021 A KR 1020120035021A KR 20120035021 A KR20120035021 A KR 20120035021A KR 101324558 B1 KR101324558 B1 KR 101324558B1
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- conductive oxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000010409 thin film Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 54
- 229910016553 CuOx Inorganic materials 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 11
- 238000004528 spin coating Methods 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- ZZCONUBOESKGOK-UHFFFAOYSA-N aluminum;trinitrate;hydrate Chemical compound O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZZCONUBOESKGOK-UHFFFAOYSA-N 0.000 claims description 5
- VWYGTDAUKWEPCZ-UHFFFAOYSA-L dichlorocopper;hydrate Chemical compound O.Cl[Cu]Cl VWYGTDAUKWEPCZ-UHFFFAOYSA-L 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 66
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 28
- 239000011787 zinc oxide Substances 0.000 abstract description 14
- 230000003287 optical effect Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 238000003980 solgel method Methods 0.000 abstract description 8
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 5
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 85
- 239000010949 copper Substances 0.000 description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- MOLNECDFJIUGDH-UHFFFAOYSA-L dichlorocopper hexahydrate Chemical compound O.O.O.O.O.O.Cl[Cu]Cl MOLNECDFJIUGDH-UHFFFAOYSA-L 0.000 description 6
- -1 for example Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 6
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- AQUVRCFASXFWHG-UHFFFAOYSA-N [Sn+2]=O.[Zn+2].[In+3].[Ag+].[O-2].[Zn+2].[In+3] Chemical compound [Sn+2]=O.[Zn+2].[In+3].[Ag+].[O-2].[Zn+2].[In+3] AQUVRCFASXFWHG-UHFFFAOYSA-N 0.000 description 1
- VQQONBUSTPHTDO-UHFFFAOYSA-N [Sn]=O.[In].[Ag].[Sn]=O.[In] Chemical compound [Sn]=O.[In].[Ag].[Sn]=O.[In] VQQONBUSTPHTDO-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UXIJQZSBOOKEKZ-UHFFFAOYSA-N oxocopper hydrate Chemical compound O.[Cu]=O UXIJQZSBOOKEKZ-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UEHUAEMPRCIIOZ-UHFFFAOYSA-N silver dizinc indium(3+) oxygen(2-) Chemical compound [O-2].[Zn+2].[In+3].[Ag+].[O-2].[Zn+2].[In+3] UEHUAEMPRCIIOZ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
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Abstract
졸-겔법의 화학적 방법에 의하여 제조되고, 산화구리(CuO)와, 알루미늄이 도핑된 산화아연(AZO)으로 구성되고, 상기 CuO의 몰비가 0.5 내지 2.0 몰%인 투명 복합체 전도성 산화막을 개시한다. 본 발명에 따른 복합 투명 전도성 산화막은 제조가 간편하면서도 비용이 적게 소요되는 졸-겔법을 이용하여 성막이 가능하다는 장점이 있고, 광학적 및 전기적 특성이 우수하여 각종 액정 디스플레이(Liquid Crystal Display; LCD), 플라즈마 디스플레이 패널(Plasma Display Panel), 유기발광소자(Organic Light Emitting Device; OLED), 태양전지 등의 디스플레이 장치 분야의 전극으로 유용하게 응용될 수 있다.Discloses a transparent composite conductive oxide film which is produced by a chemical method of a sol-gel method and is composed of copper oxide (CuO) and zinc oxide doped with aluminum (AZO), wherein the molar ratio of CuO is 0.5 to 2.0 mol%. The composite transparent conductive oxide film according to the present invention is advantageous in that it can be formed using a sol-gel process which is simple and inexpensive to manufacture, and has excellent optical and electrical properties, and can be applied to various liquid crystal displays (LCDs) The present invention can be effectively applied to an electrode of a display device such as a plasma display panel, an organic light emitting device (OLED), and a solar cell.
Description
본 발명은 투명 복합체 전도성 산화막 및 이의 제조방법에 관한 것으로서, 더욱 상세하게는 AZO에 산화구리 수화물을 혼합하여 CuO와 AZO가 화학적 방법에 의하여 복합체를 형성함으로써 투명하고 전기적 특성이 우수한 투명 복합체 전도성 산화막과 이러한 투명 복합체 전도성 산화막의 제조방법에 관한 것이다.
The present invention relates to a transparent composite conductive oxide film and a method for manufacturing the same, and more particularly, by mixing copper oxide hydrate with AZO to form a composite by CuO and AZO by a chemical method, a transparent composite conductive oxide film having excellent transparent and electrical properties. It relates to a method for producing such a transparent composite conductive oxide film.
투명 전도성 산화막(Transparent conductive oxide film; TCO)은 각종 디스플레이 장치, 예컨대 액정디스플레이(Liquid Crystal Display; LCD), 플라즈마 디스플레이 패널(Plasma Display Panel; PDP), 유기발광 디스플레이(Organic Electro Luminescence Display; OELD) 등과 그 외 태양전지, 전자파 차폐막 등에 사용되고 있다.Transparent conductive oxide film (TCO) can be applied to various display devices such as a liquid crystal display (LCD), a plasma display panel (PDP), an organic electroluminescence display (OELD) It is used in other solar cells, electromagnetic wave shielding films and the like.
이러한 투명 전도성 산화막으로서 예컨대 인듐주석산화물(Indium Tin Oxide; ITO)은 거의 모든 용도에서 사용되고 있는 박막 물질이다. ITO는 In2O3 : SnO2의 비율이 90:10 ~ 95:5의 비율로 Sn이 도핑된 In2O3로 표시되는 산화물이다. ITO 박막은 우수한 전기적 비저항 및 높은 투과도로 인해 이를 대체할 물질이 없을 정도로 독보적인 위치를 점유하여 왔다.As such a transparent conductive oxide film, for example, indium tin oxide (ITO) is a thin film material used in almost all applications. ITO is an oxide represented by In 2 O 3 doped with Sn at a ratio of In 2 O 3 : SnO 2 of 90:10 to 95: 5. ITO thin films have occupied a unique position because of their excellent electrical resistivity and high transmittance, so there is no substitute material.
그러나 이러한 ITO 투명 전도성 산화막은 원료 물질인 인듐이 매우 고가이어서 제조 단가가 높을 뿐만 아니라 그 매장량도 한정되어 있다는 점, 플라즈마에 노출되는 경우 열화로 인한 특성 변화가 오랫동안 문제점으로 지적되어 오고 있는 실정이다.However, such an ITO transparent conductive oxide film has been pointed out as a problem for a long time because the indium of the raw material is very expensive, so that the production cost is high and the storage amount thereof is also limited, and the characteristic change due to deterioration when exposed to plasma has been pointed out for a long time.
또한, ZnO계 박막은 적외선 및 가시광선 영역에서의 투과성 및 전기 전도성과 플라즈마에 대한 내구성이 우수하며, 낮은 온도에서 공정이 가능하고 원료 가격이 저렴하여 ITO 투명 전도성 박막을 대체할 수 있는 물질로 각광을 받아왔다.In addition, the ZnO-based thin film is excellent in transparency and electrical conductivity in the infrared and visible light range and durability against plasma, and can be processed at low temperature and low in cost of raw material, .
ZnO는 상온에서 3.3 eV의 넓은 밴드 갭의 직접 천이형 에너지 밴드 갭을 가지고 있어 기존의 자외선/청색 발광 다이오드(LED) 및 레이저 다이오드(LD) 소자의 재료인 GaN과 유사한 광학적 특성을 가지고 있다. 특히, 상온에서 GaN의 3배나 되는 여기 구속 에너지(Exciton Binding Energy, 약 60 meV)를 갖는바, 고효율의 발광이 가능하고, 레이저 펌핑에 의한 자발적 발광(Stimulated Spontaneous Emission) 시 문턱에너지가 매우 낮다는 좋은 특성을 가지고 있는 것으로 보고되어 있다.ZnO has a direct band gap energy bandgap of 3.3 eV at room temperature and has optical characteristics similar to that of GaN, which is a material of conventional ultraviolet / blue light emitting diode (LED) and laser diode (LD) devices. Especially, it has exciton binding energy (about 60 meV) which is three times that of GaN at room temperature. As a result, it is possible to emit light at a high efficiency and have a very low threshold energy at the time of stimulated spontaneous emission by laser pumping It has been reported to have good properties.
그러나 투명 전도성 산화막으로서 ZnO계 박막은 불순물이 첨가되지 않은 ZnO계 박막의 경우 대기 중에 장시간 노출되는 경우 산소의 영향으로 Zn과 O의 정량비가 변함에 따라 전기적 성질의 변화가 발생하고, 고온 분위기에서 안정하지 못한 단점이 있다. 따라서, 이의 문제점을 보완하기 위해 많은 연구자들은 Al, In, Ga, B 등의 3족 원소가 n형 도펀트로서 도핑된 ZnO 박막을 투명 전도성 산화막으로 이용하려는 연구를 수행해 왔다.However, ZnO-based thin films, which are transparent conductive oxide films, show a change in electrical properties as a result of changes in the quantitative ratios of Zn and O due to the influence of oxygen when exposed to the atmosphere for a long time in the atmosphere, There is a disadvantage that it can not do. Therefore, in order to overcome this problem, many researchers have studied the use of a ZnO thin film doped with an n-type dopant as a transparent conductive oxide film by a group III element such as Al, In, Ga,
일본 공개특허번호 제2010-251476호에서는 금속 미립자 또는 금속의 2종류 이상을 포함하는 합금 미립자로 구성되어 지는 네트 모양의 구조물로서 도전성층을 내포하는 투명 수지층을 적층하고 제작한 투명 수지막을 개시하고 있다.Japanese Laid-Open Patent Application No. 2010-251476 discloses a transparent resin film produced by laminating a transparent resin layer containing a conductive layer as a net-like structure composed of metal fine particles or alloy fine particles containing two or more kinds of metals have.
상기 공개특허문헌은 전자파 차폐재로서 사용될 수 있는 투명 수지박막에 관한 것으로서 구리, 아연을 포함한 다양한 금속의 합금 미립자를 포함한 투명 수지층을 개시하고 있다. 그러나 상기 특허문헌에서도 GaN LED에서의 평면 AZO 박막의 전기적 능력이 만족스럽지 못하다는 문제점이 있었다. The above publication discloses a transparent resin thin film that can be used as an electromagnetic wave shielding material and includes a transparent resin layer containing alloy microparticles of various metals including copper and zinc. However, the above-mentioned patent documents also have a problem in that the electric capacity of the planar AZO thin film in the GaN LED is unsatisfactory.
상기 문제점을 해결하기 위하여, 본 발명은In order to solve the above problems,
제조공정이 간단하고 광학적 및 전기적 특성이 우수하여 평판 표시 장치에 있어서 투명전도성 막으로서 휘도 효율이 높은 투명 복합체 전도성 산화막을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a transparent composite conductive oxide film which is simple in manufacturing process and excellent in optical and electrical characteristics and has high luminance efficiency as a transparent conductive film in a flat panel display.
상기 문제점을 해결하기 위하여, 본 발명은In order to solve the above problems,
제조공정이 간단하고 광학적 및 전기적 특성이 우수한 투명 복합체 전도성 산화막의 제조방법을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a method for producing a transparent composite conductive oxide film having a simple manufacturing process and excellent optical and electrical properties.
상기 문제점을 해결하기 위하여, 본 발명은In order to solve the above problems,
AZO층에 CuO가 도핑되어 광학적 및 전기적 특성이 우수한 투명 복합체 전도성 산화막을 채용하여 제조된 평판 표시 장치를 제공하는 것을 목적으로 한다.
And an object of the present invention is to provide a flat panel display device manufactured by employing a transparent composite conductive oxide film doped with CuO in an AZO layer and having excellent optical and electrical characteristics.
상기 목적을 해결하기 위하여, 본 발명은In order to solve the above object,
졸-겔법의 화학적 방법에 의하여 제조되고, 산화구리(CuO)와, 알루미늄이 도핑된 산화아연(AZO)으로 구성되고, 상기 CuO의 몰비가 0.5 내지 2.0 몰%인 것을 특징으로 하는 CuOx:AZO 투명 복합체 전도성 산화막을 제공한다.Sol - are prepared by the chemical method of the gel method, the copper oxide (CuO), aluminum is composed of zinc oxide doped (AZO), CuO x of the mole ratio of said CuO characterized in that 0.5 to 2.0 mole%: AZO Thereby providing a transparent composite conductive oxide film.
상기 다른 목적을 해결하기 위하여, 본 발명은In order to solve the above another object, the present invention
(a) 아연 아세테이트 수화물을 유기 용매에 용해하고, 동일한 몰의 알코올아민을 혼합하여 AZO 전구체를 형성하는 단계;(a) dissolving zinc acetate hydrate in an organic solvent and mixing the same mole of alcohol amine to form an AZO precursor;
(b) 상기 AZO 전구체 용액에 질산알루미늄 수화물을 투입하여 실온에서 AZO 용액을 형성하는 단계;(b) adding an aluminum nitrate hydrate to the AZO precursor solution to form an AZO solution at room temperature;
(c) 상기 AZO 용액에 염화구리 수화물을 용해하여 CuOx:AZO 복합 용액을 형성하는 단계;(c) CuO x by dissolving copper chloride hydrate solution to the AZO: forming an AZO complex solution;
(d) 상기 복합 용액을 기판에 스핀코팅한 다음 건조하고, 기판 상의 용매를 증발시키고 유기 잔류물을 제거하는 과정을 반복하는 단계; 및(d) repeating the step of spin-coating the composite solution on the substrate, followed by drying, evaporating the solvent on the substrate, and removing organic residues; And
(e) 상기 박막을 400 내지 450℃의 Ar 분위기에서 소결하고, 소결된 시료를 400 내지 450℃의 N2/H2 가스 분위기에서 어닐링하여 CuO의 몰비가 0.5 내지 2.0몰%인 CuOx:AZO 박막을 형성하는 단계를 포함하는 투명 복합체 전도성 산화막의 제조방법을 제공한다.(e) The CuOx: AZO thin film having a molar ratio of 0.5 to 2.0 mol% by sintering the thin film in an Ar atmosphere of 400 to 450 ° C. and annealing the sintered sample in an N 2 / H 2 gas atmosphere of 400 to 450 ° C. It provides a method for producing a transparent composite conductive oxide film comprising forming a.
상기 또 다른 목적을 해결하기 위하여, 본 발명은According to another aspect of the present invention,
상기 투명 복합체 전도성 산화막을 이용하여 제조된 평면 디스플레이 장치를 제공한다.
And a flat display device manufactured using the transparent composite conductive oxide film.
본 발명에 따른 복합 투명 전도성 산화막은 제조가 간편하면서도 비용이 적게 소요되는 졸-겔법을 이용하여 성막이 가능하다는 장점이 있고, 광학적 및 전기적 특성이 우수하여 각종 액정 디스플레이(Liquid Crystal Display; LCD), 플라즈마 디스플레이 패널(Plasma Display Panel), 유기발광소자(Organic Light Emitting Device; OLED), 태양전지 등의 디스플레이 장치 분야의 전극으로 유용하게 응용될 수 있다.
The composite transparent conductive oxide film according to the present invention has advantages in that it can be formed using a sol-gel method which is simple and easy to manufacture, and has excellent optical and electrical properties, and can be applied to various liquid crystal displays (LCDs) The present invention can be effectively applied to an electrode of a display device such as a plasma display panel, an organic light emitting device (OLED), and a solar cell.
도 1은 본 발명의 일 실시예에 따른 공정도를 도시한 것이다.
도 2는 본 발명의 일실시예에 의한 CuO의 다양한 몰비에 따른 CuO:AZO 박막의 전기적 특성을 도시한 것이다.
도 3은 본 발명의 일실시예에 따른 CuO의 다양한 몰비에 따른 CuO:AZO 박막의 XRD 패턴을 도시한 것이다.
도 4는 본 발명의 일실시예에 따른 CuO의 다양한 몰비에 따른 CuO:AZO 박막의 광학적인 투명도를 도시한 것이다.1 shows a process diagram according to an embodiment of the present invention.
FIG. 2 illustrates electrical characteristics of a CuO: AZO thin film according to various molar ratios of CuO according to an embodiment of the present invention.
FIG. 3 shows XRD patterns of CuO: AZO thin films according to various molar ratios of CuO according to an embodiment of the present invention.
FIG. 4 illustrates optical transparency of a CuO: AZO thin film according to various molar ratios of CuO according to an embodiment of the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 졸-겔법의 화학적 방법에 의하여 제조되고, 산화구리(CuO)와, 알루미늄이 도핑된 산화아연(AZO)으로 구성되는 CuOx:AZO 투명 복합체 전도성 산화막에 있어서, 상기 CuO의 몰비가 0.5 내지 2.0 몰%인 것을 특징으로 하는 투명 복합체 전도성 산화막을 제공한다.The present invention relates to a CuO x : AZO transparent composite conductive oxide film produced by a chemical method of a sol-gel process and composed of copper oxide (CuO) and aluminum-doped zinc oxide (AZO) To 2.0 mol% based on the total weight of the transparent composite conductive oxide film.
일반적으로 전도성 산화막은 인듐주석산화물(ITO), 인듐아연산화물(IZO), 인듐아연주석산화물(IZTO), 알루미늄아연산화물(AZO), 인듐주석산화물-은-인듐주석산화물(ITO-Ag-ITO), 인듐아연산화물-은-인듐아연산화물(IZO-Ag-IZO), 인듐아연산화물-은-인듐아연주석산화물(IZTO-Ag-IZTO) 및 알루미늄아연산화물-은-알루미늄아연산화물(AZO-Ag-AZO) 등을 사용할 수 있고, 상기 물질이 둘 이상 포함된 혼합물로 형성될 수 있다. In general, the conductive oxide film is made of indium tin oxide (ITO), indium zinc oxide (IZO), indium zinc tin oxide (IZTO), aluminum zinc oxide (AZO), indium tin oxide-silver-indium tin oxide (ITO- , Indium zinc oxide-silver-indium zinc oxide (IZO-Ag-IZO), indium zinc oxide-silver-indium zinc tin oxide (IZTO-Ag-IZTO) and aluminum zinc oxide- AZO), and the like, and may be formed of a mixture containing two or more of the above materials.
본 발명에서는 알루미늄이 도핑된 아연산화물(AZO)이 사용되고, 일반적으로 잘 알려진 금속 원소를 도핑하는 방법으로는 화학적 도핑법(Chemical Doping), 전기화학적 도핑법(Electrochemical Doping) 또는 이온주입법(Ion Implantation) 등과 같은 도핑방법을 사용하여 금속 원소를 도핑할 수 있으나, 본 발명에서는 화학적 도핑법에 의한 도핑법을 이용하는 것을 특징으로 한다. 이러한 화학적 도핑법에 의하면, 다른 도핑법과 비교하여 제조공정이 간단하고 제조비용이 저렴하다는 장점이 있다. In the present invention, aluminum-doped zinc oxide (AZO) is used. In general, well known metal element doping methods include chemical doping, electrochemical doping, ion implantation, Or the like can be used to dope a metal element. However, the present invention is characterized in that a doping method using a chemical doping method is used. According to this chemical doping method, there is an advantage that the manufacturing process is simple and the manufacturing cost is low as compared with other doping methods.
아연산화물에 알루미늄을 도핑하는 단계뿐만 아니라 AZO에 산화구리를 사용하여 복합체를 형성하는 과정에서도 졸-겔법에 의한 화학적 방법을 이용한다. 구체적인 화학적 방법에 대해서는 이하에서 별도로 설명한다. In addition to the step of doping aluminum oxide with zinc oxide, the chemical method by sol-gel method is also used in the process of forming complex by using copper oxide in AZO. Specific chemical methods are described separately below.
본 발명의 산화막은 산화아연, 산화알루미늄, 및 산화구리로 이루어진 군으로부터 선택된 물질들이 투명 전도성 복합체를 형성하는 것이다. 본 발명의 명세서에서 "CuOx"는 구리 산화물 또는 산화구리 화합물을 나타낸다. 여기서 "CuOx"로 표시하는 것은 비화학양론적(nonstoichiometric)이 될 수 있기 때문이다. Cu와 O는 1:1을 나타내지만, x는 구리 성분이 Cu+ 및 Cu2 + 각각 두 개의 산화 상태에서 산화물로 동시에 존재할 수 있음을 의미하는 것이다. The oxide film of the present invention is such that materials selected from the group consisting of zinc oxide, aluminum oxide, and copper oxide form a transparent conductive composite. In the present specification, "CuO x " represents a copper oxide or a copper oxide compound. Here, the expression "CuO x " can be nonstoichiometric. Cu and O represent 1: 1, but x means that the copper component can simultaneously exist as an oxide in the two oxidation states of Cu + and Cu 2 +, respectively.
본 발명에서 투명 복합체 전도성 산화막은 AZO에 CuO이 도핑되어 복합체를 형성하고 있으며, AZO에 투입되는 CuO의 몰비는 0.5 내지 2.0 몰%인 것이 바람직하다. 여기서 CuO의 몰비가 0.5 몰% 미만인 경우에는 소량의 CuO로 인하여 큰 비저항성을 가지므로 바람직하지 못하고, 2.0 몰%를 초과하는 경우에는 p-type이나 CuO의 몰%에 의해 큰 비저항성을 가지므로 바람직하지 못하다.In the present invention, AZO is doped with CuO to form a complex, and the molar ratio of CuO to AZO is preferably 0.5 to 2.0 mol%. If the molar ratio of CuO is less than 0.5 mol%, it is undesirable because it has a small resistivity due to a small amount of CuO. When the molar ratio exceeds 2.0 mol%, CuO has a large resistivity due to the molar percentage of p-type or CuO It is not desirable.
상기 CuO를 도핑하여 복합체를 형성하기 이전 산화아연(ZnO)에 알루미늄(Al)을 도핑하여 AZO를 형성한다. 알루미늄(Al)의 도핑 농도는 0.05 내지 5.0 원자%인 것이 바람직하다. 산화아연에 알루미늄의 도핑 농도가 0.05 원자% 미만이거나 5.0 원자%를 초과하는 경우에는 높은 비저항성을 가지므로 바람직하지 못하다.Before the complex is formed by doping CuO, aluminum (ZnO) is doped with aluminum (Al) to form AZO. The doping concentration of aluminum (Al) is preferably 0.05 to 5.0 atomic%. When the doping concentration of aluminum to zinc oxide is less than 0.05 atomic% or more than 5.0 atomic%, it is not preferable because it has high non-resistivity.
본 발명에 따른 산화막은 광학적 특성과 전기적 특성이 우수하다. 제조된 산화막의 광 투과도는 가시광선의 일반적인 파장인 380 nm ~ 800 nm에서 80% 이상을 나타내고 있으며, 바람직하게는 80% 내지 90%를 나타낸다. 이러한 우수한 투명도는 전극 재료로 이용되고 이를 평판 표시 장치 또는 조명 장치에 적용하였을 경우 높은 휘도 성능을 나타낼 수 있고, 각종 액정 디스플레이(Liquid Crystal Display; LCD), 플라즈마 디스플레이 패널(Plasma Display Panel), 유기발광소자(Organic Light Emitting Device; OLED), 태양전지 등에 이용될 수 있다.The oxide film according to the present invention is excellent in optical characteristics and electrical characteristics. The light transmittance of the prepared oxide film shows 80% or more, preferably 80% to 90% at 380 nm to 800 nm which is a general wavelength of visible light. Such an excellent transparency is used as an electrode material and when applied to a flat panel display or a lighting device, it can exhibit a high luminance performance and can be applied to various liquid crystal displays (LCDs), plasma display panels (Plasma Display Panel) An organic light emitting device (OLED), a solar cell, and the like.
또한 본 발명에 따른 산화막은 전기적 특성이 우수하며, 이러한 우수한 전기적 성질은 산소 디펙트(defect)의 발생, AZO 격자 내부에 도전성 금속인 Cu 나노입자의 형성 등에 기인한 것이다. 결국 전기적 특성을 개선하기 위해서는 AZO에 투입되는 CuO의 몰비를 일정하게 한정하는 필요하고, 이미 설명한 바와 같은 함량으로 조절될 때에 바람직한 특성을 나타낸다. 여기서 형성된 산화막의 전기 저항은 2.07×10-3 내지 2.39×10-1 Ωcm인 것이 바람직하다. 전기 저항이 2.07×10-3 Ωcm 미만인 경우에는 전기적 특성의 변화가 나타나지 못하므로 바람직하지 못하고, 2.39×10-1 Ωcm를 초과하는 경우에는 비저항성이 높으므로 바람직하지 못하다.Further, the oxide film according to the present invention has excellent electrical characteristics, and such excellent electrical properties are attributable to the generation of oxygen defects and the formation of Cu nanoparticles which are conductive metals in the AZO lattice. As a result, in order to improve the electrical characteristics, the molar ratio of CuO to be added to AZO needs to be limited to a certain level, and exhibits desirable characteristics when the content is adjusted to the content as described above. Electric resistance of the oxide film is 2.07 × 10 -3 to 2.39 × 10 -1 Ωcm formed where the . When if the electrical resistance is less than 2.07 × 10 -3 Ωcm is not preferable because it did not show a change in electrical properties, exceeds 2.39 × 10 -1 Ωcm is not preferred because the higher the specific resistance.
본 발명의 복합 전도성 산화막의 두께는 100 내지 400 ㎚ 범위로 제조할 수 있다. 상기 전도성 산화막의 두께가 100 ㎚ 미만인 경우에는 비저항이 증가하여 바람직하지 못하고, 400 ㎚를 초과하는 경우에는 투과도가 저하되기 때문에 바람직하지 못하다.The thickness of the composite conductive oxide film of the present invention may be in the range of 100 to 400 nm. When the thickness of the conductive oxide film is less than 100 nm, the resistivity increases, which is undesirable. When the thickness exceeds 400 nm, the transmittance is lowered.
본 발명의 다른 일 형태에 따르면, (a) 아연 아세테이트 수화물을 유기 용매에 용해하고, 동일한 몰의 알코올아민을 혼합하여 AZO 전구체를 형성하는 단계; (b) 상기 AZO 전구체 용액에 질산알루미늄 수화물을 투입하여 실온에서 AZO 용액을 형성하는 단계; (c) 상기 AZO 용액에 염화구리 수화물을 용해하여 CuOx:AZO 복합 용액을 형성하는 단계; (d) 상기 복합 용액을 기판에 스핀코팅한 다음 건조하고, 기판 상의 용매를 증발시키고 유기 잔류물을 제거하는 과정을 반복하는 단계; 및 (e) 상기 박막을 400 내지 450℃의 Ar 분위기에서 소결하고, 소결된 시료를 400 내지 450℃의 N2/H2 가스 분위기에서 어닐링하여 CuO의 몰비가 0.5 내지 2.0몰%인 CuOx:AZO 박막을 형성하는 단계를 포함하는 투명 복합체 전도성 산화막의 제조방법을 제공한다. (A) dissolving zinc acetate hydrate in an organic solvent and mixing the same mole of alcohol amine to form an AZO precursor; (b) adding an aluminum nitrate hydrate to the AZO precursor solution to form an AZO solution at room temperature; (c) dissolving the copper chloride hydrate in the AZO solution to form a CuOx: AZO complex solution; (d) repeating the step of spin-coating the composite solution on the substrate, followed by drying, evaporating the solvent on the substrate, and removing organic residues; And (e) sintering the thin film in an Ar atmosphere at 400 to 450 ° C. and annealing the sintered sample in an N 2 / H 2 gas atmosphere at 400 to 450 ° C. to obtain CuO x: AZO And forming a thin film on the transparent conductive oxide film.
상세하게는 먼저 (a) 아연 아세테이트 수화물을 유기 용매에 용해하고, 동일한 몰의 알코올아민을 혼합하여 AZO 전구체를 형성한다. 유기 용매는 불활성 용매를 사용하고 반응에 사용되는 불활성 용매로는, 특별히 한정되지 않으며, 예를 들어 헥산, 헵탄, 리그로인, 석유 에테르와 같은 지방족 탄화수소류; 톨루엔, 벤젠, 자일렌과 같은 방향족 탄화수소류; 디클로로메탄, 클로로포름, 사염화탄소, 디클로로에탄, 클로로벤젠, 디클로로벤젠과 같은 할로겐화 탄화수소류；모노에틸에테르, 디에틸 에테르, 디이소프로필 에테르, 테트라히드로푸란, 디옥산, 디메톡시에탄, 디에틸렌글리콜 디메틸 에테르와 같은 에테르류;가 이용될 수 있고, 바람직하게는 프로필렌글리골 모노에틸에테르(PGME)를 사용한다. 알코올아민은 알코올과 아민이 결합된 형태를 나타내고, 알코올의 형태에 제한은 없고 예를 들면, 메탄올, 에탄올, n-프로판올, 이소프로판올, n-부탄올, 이소부탄올, t-부탄올, 이소아밀알코올, 디에틸렌글리콜, 글리세린, 옥탄올, 시클로헥산올, 메틸 셀로솔브 등과 아민과의 화합물이 사용될 수 있고, 바람직하게는 디에탄올아민이 될 수 있다.Specifically, (a) zinc acetate hydrate is first dissolved in an organic solvent and an alcohol amine of the same mole is mixed to form an AZO precursor. The inert solvent used for the reaction is not particularly limited and includes, for example, aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether; Aromatic hydrocarbons such as toluene, benzene and xylene; Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene; monoethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether May be used, and propylene glycol monoethyl ether (PGME) is preferably used. The alcohol amine is a form in which an alcohol and an amine are bonded. There is no limitation on the form of the alcohol, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, isoamyl alcohol, A compound with an amine such as ethylene glycol, glycerin, octanol, cyclohexanol, methyl cellosolve and the like may be used, preferably diethanolamine.
(b) 상기 AZO 전구체 용액에 질산알루미늄 수화물을 투입하여 실온에서 AZO 용액을 형성한다. 질산알루미늄 수화물은 질산알루미늄 9수화물(Aluminum nitrate nonahydrate)이 바람직하고, 형성된 AZO 용액에서 Al/Zn 중 Al의 도핑 농도는 0.05 내지 5.0 원자%인 것이 바람직하다. 알루미늄의 도핑 농도가 0.05 원자% 미만이거나 5.0 원자%를 초과하는 경우에는 비저항성이 높기 때문에 바람직하지 못하다.(b) An aluminum nitrate hydrate is added to the AZO precursor solution to form an AZO solution at room temperature. The nitrate aluminum hydrate is preferably aluminum nitrate nonahydrate, and it is preferable that the doping concentration of Al in Al / Zn in the formed AZO solution is 0.05 to 5.0 atomic%. When the doping concentration of aluminum is less than 0.05 atomic% or exceeds 5.0 atomic%, the resistivity is high, which is not preferable.
(c) 상기 AZO 용액에 염화구리 수화물을 용해하여 CuOx:AZO 복합 용액을 형성한다. 염화구리 수화물은 염화구리 6수화물(Cu(II) chloride hexahydate)이 바람직하고, 형성된 CuOx:AZO 복합 용액에서 CuO의 몰비는 0.5 내지 2.0 몰%인 것이 바람직하다. 여기서 CuO의 몰비가 0.5 몰% 미만인 경우에는 소량의 CuO로 인하여 큰 비저항성을 가지므로 바람직하지 못하고, 2.0 몰%를 초과하는 경우에는 p-type이나 CuO의 몰%에 의하여 큰 비저항성을 가지므로 바람직하지 못하다.(c) dissolving the copper chloride hydrate in the AZO solution to form a CuOx: AZO complex solution. The copper chloride hydrate is preferably copper (II) chloride hexahydrate, and the molar ratio of CuO in the formed CuOx: AZO complex solution is preferably 0.5 to 2.0 mol%. If the molar ratio of CuO is less than 0.5 mol%, it is undesirable because it has a small non-resistivity due to a small amount of CuO. When the molar ratio exceeds 2.0 mol%, CuO has a large resistivity due to the molar percentage of p-type or CuO It is not desirable.
(d) 상기 복합 용액을 기판에 스핀코팅한 다음 건조하고, 기판상의 용매를 증발시키고 유기 잔류물을 제거하는 과정을 반복한다. 스핀코팅의 속도는 1500 내지 3000rpm이 바람직하고, 10 내지 40 초 동안 수행하는 것이 바람직하다. 이후에 160 내지 190℃의 온도에서 5 내지 15분간 건조하고, 로 내부에서 350 내지 450℃의 온도에서 5분 내지 15분 동안 탈산소화한다. 스핀코팅, 건조, 탈산소화 공정을 순차적으로 여러 번 반복하는 것이 바람직하고, 10회 이상 반복하는 것이 바람직하다. (d) spin coating the composite solution on the substrate, drying the solution, evaporating the solvent on the substrate, and removing the organic residue. The spin coating speed is preferably 1500 to 3000 rpm, and preferably 10 to 40 seconds. Thereafter, it is dried at a temperature of 160 to 190 DEG C for 5 to 15 minutes, and deoxidized in the furnace at a temperature of 350 to 450 DEG C for 5 to 15 minutes. It is preferable to repeat the spin coating, drying, and deoxygenation processes in succession several times, and it is preferable to repeat the spin coating, drying, and deoxygenation at least 10 times.
(e) 상기 박막을 400 내지 450℃의 Ar 분위기에서 소결하고, 소결된 시료를 400 내지 450℃의 N2/H2 가스 분위기에서 어닐링하여 CuO의 몰비가 0.5 내지 2.0몰%인 CuOx:AZO 박막을 형성하여 본 발명의 투명 복합체 전도성 산화막을 완성한다. 특히 본 발명에서는 400 내지 450℃의 N2/H2 가스 분위기에서 1 내지 2시간 정도 어닐링하는 것이 중요하다. 이러한 어닐링을 통하여 p-type으로 전환이 가능하다.(e) sintering the thin film in an Ar atmosphere at 400 to 450 ° C and annealing the sintered sample in an N 2 / H 2 gas atmosphere at 400 to 450 ° C to obtain a CuOx: AZO thin film having a CuO molar ratio of 0.5 to 2.0 mol% Thereby completing the transparent composite conductive oxide film of the present invention. In particular, in the present invention, it is important to anneal in an N 2 / H 2 gas atmosphere at 400 to 450 ° C. for about 1 to 2 hours. It is possible to switch to p-type through such annealing.
본 발명의 다른 일 형태에 따르면, 졸-겔법의 화학적 방법에 의하여 제조되고, 산화구리(CuO)와, 알루미늄이 도핑된 산화아연(AZO)으로 구성되는 CuOx:AZO 투명 복합체 전도성 산화막에 있어서, 상기 CuO의 몰비가 0.5 내지 2.0 몰%인 투명 복합체 전도성 산화막을 이용하여 제조된 평면 디스플레이 장치를 제공한다. 본 발명에 따른 복합 투명 전도성 산화막은 제조가 간편하면서도 비용이 적게 소요되는 졸-겔법을 이용하여 성막이 가능하다는 장점이 있고, 광학적 및 전기적 특성이 우수하여 각종 액정 디스플레이(Liquid Crystal Display; LCD), 플라즈마 디스플레이 패널(Plasma Display Panel), 유기발광소자(Organic Light Emitting Device; OLED), 태양전지 등의 디스플레이 장치 분야의 전극으로 유용하게 응용될 수 있다.
According to another aspect of the present invention, there is provided a CuO x : AZO transparent composite conductive oxide film produced by a chemical method of a sol-gel method and composed of copper oxide (CuO) and aluminum-doped zinc oxide (AZO) And a CuO molar ratio of 0.5 to 2.0 mol%. The present invention also provides a flat display device using the transparent conductive oxide film. The composite transparent conductive oxide film according to the present invention has advantages in that it can be formed using a sol-gel method which is simple and easy to manufacture, and has excellent optical and electrical properties, and can be applied to various liquid crystal displays (LCDs) The present invention can be effectively applied to an electrode of a display device such as a plasma display panel, an organic light emitting device (OLED), and a solar cell.
이하 본 발명의 내용을 실시예에 의해 보다 상세하게 설명하기로 한다. 다만 이들 실시예는 본 발명의 내용을 이해하기 위해 제시되는 것일 뿐 본 발명의 권리범위가 이들 실시예에 한정되어지는 것으로 해석되어져서는 아니된다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood, however, that these examples are provided so that the scope of the present invention is not limited thereto.
실시예
Example
실시예 1Example 1
먼저 아연 아세테이트 디하이드레이트 0.5M을 프로필렌글리콜 모노에틸 에테르(PEMG: 시그마 알드리치로부터 구입)에 용해하였다. First, 0.5M zinc acetate dihydrate was dissolved in propylene glycol monoethyl ether (PEMG: purchased from Sigma Aldrich).
AZO 전구체 용액은 적량의 질산알루미늄 9수화물을 상기 용액에 투입하여 Al/Zn의 원자비가 1.5 몰%가 되도록 하였다. 이어서 혼합물을 실온에서 1시간 동안 교반하고 깨끗하고 투명한 AZO 용액을 형성하였다. 염화구리(II) 6수화물을 상기 AZO 용액에 용해하여 CuO의 몰비가 0.5%인 CuOx:AZO를 얻었다. 이어서 형성된 용액은 밤새 교반하였다. 충분한 양의 아연 아세테이트 디하이드레이트를 추출하기 위하여 아연과 비교하여 2배 몰의 디에탄올아민(DEA: 시그마 알드리치로부터 구입)을 투입하고 PEMG와 함께 혼합하였다. The AZO precursor solution was loaded with an appropriate amount of aluminum nitrate nonahydrate into the solution so that the atomic ratio of Al / Zn was 1.5 mol%. The mixture was then stirred at room temperature for 1 hour to form a clear and clear AZO solution. Copper (II) chloride hexahydrate was dissolved in the AZO solution to obtain CuOx: AZO having a CuO molar ratio of 0.5%. The resulting solution was then stirred overnight. To extract a sufficient amount of zinc acetate dihydrate, 2-fold molar equivalents of diethanolamine (DEA: purchased from Sigma Aldrich) as compared to zinc was added and mixed with PEMG.
박막을 형성하기 위하여, 제조된 용액을 세정된 유리 기판(Corning glass E2000)에 적하하였다. 기판은 2000 rpm에서 30초간 스핀코팅한 다음 180℃의 핫플레이트에서 10분 동안 두어 박막을 건조하였다. 이러한 단계를 거쳐 상기 기판을 400℃의 로에서 10분 동안 두어 용매를 증발시키고 유기 잔류물을 제거하였다. 스핀 코팅과 건조 공정을 10회 반복하였다. 마지막으로 상기 박막을 400℃의 Ar 분위기에서 2시간 동안 소결하였다. 소결된 시료를 400℃로의 N2/H2(95/5) 가스 분위기에서 1시간 동안 어닐링하여 CuO에서 Cu 나노파티클로의 변화를 감소시키고 CuOx:AZO 도전성 필름을 얻었다.
To form a thin film, the prepared solution was dripped onto a cleaned glass substrate (Corning glass E2000). The substrate was spin-coated at 2000 rpm for 30 seconds and then placed on a hot plate at 180 ° C for 10 minutes to dry the film. After this step, the substrate was placed in a furnace at 400 DEG C for 10 minutes to evaporate the solvent and remove organic residues. The spin coating and drying processes were repeated 10 times. Finally, the thin film was sintered in an Ar atmosphere at 400 ° C for 2 hours. The sintered samples were annealed in a N 2 / H 2 (95/5) gas atmosphere at 400 ° C. for 1 hour to reduce the change from CuO to Cu nanoparticles and to obtain a CuO x: AZO conductive film.
실시예 2Example 2
염화구리(II) 6수화물을 상기 AZO 용액에 용해하여 CuO의 몰비가 1.0%인 CuOx:AZO를 얻는 점을 제외하고는 실시예 1과 동일하게 실시하여 CuOx:AZO 도전성 필름을 얻었다.
A CuOx: AZO conductive film was obtained in the same manner as in Example 1, except that cupric chloride (II) hexahydrate was dissolved in the AZO solution to obtain CuOx: AZO having a CuO molar ratio of 1.0%.
실시예 3Example 3
염화구리(II) 6수화물을 상기 AZO 용액에 용해하여 CuO의 몰비가 1.5%인 CuOx:AZO를 얻는 점을 제외하고는 실시예 1과 동일하게 실시하여 CuOx:AZO 도전성 필름을 얻었다.
A CuOx: AZO conductive film was obtained in the same manner as in Example 1, except that cupric chloride (II) hexahydrate was dissolved in the AZO solution to obtain CuOx: AZO having a CuO molar ratio of 1.5%.
실시예 4Example 4
염화구리(II) 6수화물을 상기 AZO 용액에 용해하여 CuO의 몰비가 2.0%인 CuOx:AZO를 얻는 점을 제외하고는 실시예 1과 동일하게 실시하여 CuOx:AZO 도전성 필름을 얻었다.
A CuOx: AZO conductive film was obtained in the same manner as in Example 1, except that cupric chloride (II) hexahydrate was dissolved in the AZO solution to obtain CuOx: AZO having a CuO molar ratio of 2.0%.
비교예 1Comparative Example 1
먼저 아연 아세테이트 디하이드레이트 0.5M을 프로필렌글리콜 모노에틸 에테르(PEMG: 시그마 알드리치로부터 구입)에 용해하였다.First, 0.5M zinc acetate dihydrate was dissolved in propylene glycol monoethyl ether (PEMG: purchased from Sigma Aldrich).
AZO 전구체 용액은 적량의 질산알루미늄 9수화물을 상기 용액에 투입하여 Al/Zn의 원자비가 1.5원자%가 되도록 하였다. 이어서 혼합물을 실온에서 1시간 동안 교반하고 깨끗하고 투명한 AZO 용액을 형성하였다. 염화구리(II) 6수화물을 상기 AZO 용액에 용해하여 CuO의 몰비가 3.0%인 CuOx:AZO를 얻었다. 이어서 형성된 용액은 밤새 교반하였다. 충분한 양의 징크 아세테이트 디하이드레이트를 추출하기 위하여 아연과 비교하여 2배 몰의 디에탄올아민(DEA: 시그마 알드리치로부터 구입)을 투입하고 PEMG와 함께 혼합하였다. The AZO precursor solution was loaded with an appropriate amount of aluminum nitrate nonahydrate into the solution so that the atomic ratio of Al / Zn was 1.5 atomic%. The mixture was then stirred at room temperature for 1 hour to form a clear and clear AZO solution. Copper (II) chloride hexahydrate was dissolved in the AZO solution to obtain CuOx: AZO having a CuO molar ratio of 3.0%. The resulting solution was then stirred overnight. To extract a sufficient amount of zinc acetate dihydrate, 2-fold molar equivalents of diethanolamine (DEA: purchased from Sigma-Aldrich) as compared to zinc was added and mixed with PEMG.
박막을 형성하기 위하여, 제조된 용액을 세정된 유리 기판(Corning glass E2000)에 적하하였다. 기판은 2000rpm에서 30초간 스핀코팅한 다음 180℃의 핫플레이트에서 10분 동안 두어 박막을 건조하였다. 이러한 단계를 거쳐 상기 기판을 400℃의 로에서 10분 동안 두어 용매를 증발시키고 유기 잔류물을 제거하였다. 스핀 코팅과 건조 공정을 10회 반복하였다. 마지막으로 상기 박막을 400℃의 Ar 분위기에서 2시간 동안 소결하였다. 소결된 시료를 400℃의 N2/H2(95/5) 가스 분위기에서 1시간 동안 어닐링하여 CuO에서 Cu 나노파티클로의 변화를 감소시키고 CuOx:AZO 도전성 필름을 얻었다.
To form a thin film, the prepared solution was dripped onto a cleaned glass substrate (Corning glass E2000). The substrate was spin-coated at 2000 rpm for 30 seconds and then placed on a hot plate at 180 DEG C for 10 minutes to dry the thin film. After this step, the substrate was placed in a furnace at 400 DEG C for 10 minutes to evaporate the solvent and remove organic residues. The spin coating and drying processes were repeated 10 times. Finally, the thin film was sintered in an Ar atmosphere at 400 ° C for 2 hours. The sintered samples were annealed in a N 2 / H 2 (95/5) gas atmosphere at 400 ° C for 1 hour to reduce the change from CuO to Cu nanoparticles and to obtain a CuO x: AZO conductive film.
비교예 2Comparative Example 2
염화구리(II) 6수화물을 상기 AZO 용액에 용해하여 CuO의 몰비가 5.0%인 CuOx:AZO를 얻는 점을 제외하고는 비교예 1과 동일하게 실시하여 CuOx:AZO 도전성 필름을 얻었다.
A CuOx: AZO conductive film was obtained in the same manner as in Comparative Example 1, except that copper (II) chloride hexahydrate was dissolved in the AZO solution to obtain CuOx: AZO having a CuO mole ratio of 5.0%.
비교예 3Comparative Example 3
염화구리(II) 6수화물을 상기 AZO 용액에 용해하여 CuO의 몰비가 7.0%인 CuOx:AZO를 얻는 점을 제외하고는 비교예 1과 동일하게 실시하여 CuOx:AZO 도전성 필름을 얻었다.
A CuOx: AZO conductive film was obtained in the same manner as in Comparative Example 1, except that copper (II) chloride hexahydrate was dissolved in the AZO solution to obtain CuOx: AZO having a CuO molar ratio of 7.0%.
비교예 4Comparative Example 4
염화구리(II) 6수화물을 상기 AZO 용액에 용해하여 CuO의 몰비가 9.0%인 CuOx:AZO를 얻는 점을 제외하고는 비교예 1과 동일하게 실시하여 CuOx:AZO 도전성 필름을 얻었다.
A CuOx: AZO conductive film was obtained in the same manner as in Comparative Example 1 except that CuOx: AZO having a CuO molar ratio of 9.0% was obtained by dissolving copper (II) chloride hexahydrate in the AZO solution.
비교예 5Comparative Example 5
징크 아세테이트 디하이드레이트 0.5M을 프로필렌글리콜 모노에틸 에테르(PEMG: 시그마 알드리치로부터 구입)에 용해하였다. 0.5 M of zinc acetate dihydrate was dissolved in propylene glycol monoethyl ether (PEMG: purchased from Sigma Aldrich).
AZO 전구체 용액은 적량의 알루미늄 나이트레이트 노나하이드레이트를 상기 용액에 투입하여 Al/Zn의 원자비가 1.5원자%가 되도록 하였다. 이어서 혼합물을 실온에서 1시간 동안 교반하고 깨끗하고 투명한 AZO 용액을 형성하였다. 형성된 용액은 밤새 교반하였다. 충분한 양의 징크 아세테이트 디하이드레이트를 추출하기 위하여 아연과 비교하여 2배 몰의 디에탄올아민(DEA: 시그마 알드리치로부터 구입)을 투입하고 PEMG와 함께 혼합하였다. In the AZO precursor solution, an appropriate amount of aluminum nitrate nonahydrate was added to the solution so that the atomic ratio of Al / Zn was 1.5 atomic%. The mixture was then stirred at room temperature for 1 hour to form a clear and clear AZO solution. The formed solution was stirred overnight. To extract a sufficient amount of zinc acetate dihydrate, 2-fold molar equivalents of diethanolamine (DEA: purchased from Sigma-Aldrich) as compared to zinc was added and mixed with PEMG.
박막을 형성하기 위하여, 제조된 용액을 세정된 유리 기판(Corning glass E2000)에 적하하였다. 기판은 2000rpm에서 30초간 스핀코팅한 다음 180℃의 핫플레이트에서 10분 동안 두어 박막을 건조하였다. 이러한 단계를 거쳐 상기 기판을 400℃의 로에서 10분 동안 두어 용매를 증발시키고 유기 잔류물을 제거하였다. 스핀 코팅과 건조 공정을 10회 반복하였다. 마지막으로 상기 박막을 400℃의 Ar 분위기에서 2시간 동안 소결하였다. 소결된 시료를 400℃의 N2/H2(95/5) 가스 분위기에서 1시간 동안 어닐링하여 AZO 도전성 필름을 얻었다.
To form a thin film, the prepared solution was dripped onto a cleaned glass substrate (Corning glass E2000). The substrate was spin-coated at 2000 rpm for 30 seconds and then placed on a hot plate at 180 DEG C for 10 minutes to dry the thin film. After this step, the substrate was placed in a furnace at 400 DEG C for 10 minutes to evaporate the solvent and remove organic residues. The spin coating and drying processes were repeated 10 times. Finally, the thin film was sintered in an Ar atmosphere at 400 ° C for 2 hours. The sintered sample was annealed in an N 2 / H 2 (95/5) gas atmosphere at 400 ° C for 1 hour to obtain an AZO conductive film.
실험결과 및 평가
Experiment result and evaluation
X-X- 레이Lay 회절diffraction
도 2는 본 발명의 따라 CuO의 몰비를 다르게 하여 실험한 실시예의 AZO와 CuO:AZO 박막의 XRD 패턴을 도시한 것이다. 모든 박막의 두께는 평균 400 nm로 하였다. AZO 필름은 JCPDS 파일 no. 36-1451로 매칭된 폴리크리스탈린 섬유아연석(wurtzite) 헥사고날 구조를 나타내었다. 400℃로 N2/H2 어닐링 막에서 헥사고날 ZnO에 대응되는 브래크 피크(Bragg Peak)는 (100), (002), (101), (102), (110), (103) 및 (112) 반사에서 각각 2θ = 32°, 34.4°, 35.9°, 47.2°, 57.5°, 62°, 66.7°를 나타내었다. CuO를 포함한 모든 필름은 30.1°에서 다결정 Cu2O를 나타내었다. 여기서 (002) 피크는 (100) 및 (101)피크보다는 약하게 되었다. 이는 N2/H2 분위기에서 400℃로 어닐링 처리하는 것은 AZO 막에서 O원자와 결합된 H2를 만들었기 때문이다. 결과적으로 산소의 디펙트를 증가시키고 필름의 결정성을 낮추게 한다.
FIG. 2 shows the XRD patterns of the AZO and CuO: AZO thin films of the examples experimented with different molar ratios of CuO according to the present invention. The thickness of all thin films was 400 nm on average. AZO film is a JCPDS file no. 36-1451. ≪ / RTI >< RTI ID = 0.0 > Wurtzite < / RTI > Brake peaks corresponding to hexagonal ZnO in the N 2 / H 2 annealing film at 400 ° C. are (100), (002), (101), (102), (110) 32, 34.4, 35.9, 47.2, 57.5, 62 and 66.7 degrees, respectively. All films including CuO showed polycrystalline Cu 2 O at 30.1 °. Where the (002) peak was weaker than the (100) and (101) peaks. This is because annealing at 400 ° C in an N 2 / H 2 atmosphere produced H 2 bound to the O atom in the AZO film. As a result, the oxygen defects are increased and the crystallinity of the film is lowered.
전기적 특성Electrical characteristic
다양한 CuO 몰비를 갖는 AZO 필름의 전기적 저항, 전하 이동도, 및 전하 캐리어 농도를 측정하였고 이를 표 1에 나타내었다. 표 1을 참조하면, 본 발명에 따라 졸-겔법을 이용하여 합성한 다양한 몰비의 CuO:AZO 박막(실시예 1 내지 4)의 전기적 저항은 각각 6.94×10-3, 9.33×10-3, 1.22×10-3, 1.39×10-3, 1.66×10-2Ωcm인 것으로 나타났고, 홀 이동도는 각각 21.6, 17.6, 15.2, 12.6. 8.36cm2/Vs으로 나타났고, 캐리어 농도는 각각 1.99×1020, 3.56×1019, 1.49×1019, 6.78×1018, 5.41×1018/cm-3인 것으로 측정되었다.The electrical resistance, charge mobility, and charge carrier concentration of AZO films with various CuO molar ratios were measured and shown in Table 1. Referring to Table 1, the electrical resistivities of CuO: AZO thin films (Examples 1 to 4) of various molar ratios synthesized by the sol-gel method according to the present invention were 6.94 × 10 -3 , 9.33 × 10 -3 , 1.22 X 10 -3 , 1.39 x 10 -3 , and 1.66 x 10 -2 ? Cm, and the hole mobility was 21.6, 17.6, 15.2, and 12.6, respectively. 8.36 cm 2 / Vs, and the carrier concentrations were 1.99 × 10 20 , 3.56 × 10 19 , 1.49 × 10 19 , 6.78 × 10 18 , and 5.41 × 10 18 / cm -3 , respectively.
표 1을 참조하면, 실시예 1 내지 4의 범위에 해당되는 CuO의 몰비가 0.5 내지 2.0인 경우 전기 저항이 매우 낮은 것으로 나타났다. 일반적으로 CuO:AZO 박막에서 CuO 몰%의 증가로 인한 전기 저항의 증가는 전하 이동도 및 전하 농도 모두의 감소에 기인한다. 따라서 N2/H2 형성가스의 어닐링 공정 동안 산소 디펙트의 발생 및 AZO 격자 내에서 도전성 Cu 나노파티클의 형성은 우수한 전기적 특성을 얻을 수 있다.
Referring to Table 1, when the molar ratio of CuO corresponding to the ranges of Examples 1 to 4 was 0.5 to 2.0, electrical resistance was extremely low. Generally, the increase in electrical resistance due to the increase of CuO mole% in CuO: AZO thin films is due to the decrease of both charge mobility and charge concentration. Thus, the generation of oxygen defects during the annealing process of N 2 / H 2 forming gas and the formation of conductive Cu nanoparticles in the AZO lattice can provide good electrical properties.
광학적 특성Optical properties
도 4는 본 발명의 실시예에 따른 AZO 및 CuO:AZO 막의 투명도 스펙트럼을 도시한다. 도 4를 참조하면, 박막의 광학적 투명도는 CuO의 몰비에 의하여 영향을 받음을 확인할 수 있다. 본 발명에 따라 CuO의 몰비가 0.5 내지 2.0몰%인 경우에는 투명도가 70% 이상을 나타내었다. CuO:AZO 박막에서 CuO의 몰비를 증가시키는 것에 의하여 투명도가 감소되는 것을 확인할 수 있다. CuO:AZO 박막에서 흑색 컬러의 표시는 CuO상 및 Cu 나노입자를 나타낸다. Figure 4 shows the transparency spectra of AZO and CuO: AZO films according to embodiments of the present invention. Referring to FIG. 4, it can be confirmed that the optical transparency of the thin film is affected by the molar ratio of CuO. According to the present invention, when the molar ratio of CuO is 0.5 to 2.0 mol%, transparency is 70% or more. It can be confirmed that the transparency is decreased by increasing the molar ratio of CuO in the CuO: AZO thin film. In the CuO: AZO thin film, the black color indicates CuO phase and Cu nanoparticles.
이상의 결과로부터 본 발명에 따른 투명 복합체 전도성 산화막은 전기적 특성과 광학적 특성이 우수한 것을 확인할 수 있다. From the above results, it can be confirmed that the transparent conductive oxide film according to the present invention has excellent electrical characteristics and optical characteristics.
Claims (8)
(b) 상기 AZO 전구체 용액에 질산알루미늄 수화물을 투입한 다음 실온에서 AZO 용액을 형성하는 단계;
(c) 상기 AZO 용액에 염화구리 수화물을 용해하여 CuOx:AZO 복합 용액을 형성하는 단계;
(d) 상기 복합 용액을 기판에 스핀코팅한 다음 건조하고, 기판 상의 용매를 증발시키고 유기 잔류물을 제거하는 과정을 반복하여 박막을 형성하는 단계; 및
(e) 상기 (d)단계에서 형성된 박막을 400 내지 450℃의 Ar 분위기에서 소결하고, 소결된 박막을 400 내지 450℃의 N2/H2 가스 분위기에서 어닐링하여 CuO의 몰비가 0.5 내지 2.0몰%인 CuOx:AZO 박막을 형성하는 단계를 포함하는 투명 복합체 전도성 산화막의 제조방법.
(a) dissolving zinc acetate hydrate in an organic solvent and mixing the same moles of alcoholamine to form an AZO precursor;
(b) adding aluminum nitrate hydrate to the AZO precursor solution and then forming an AZO solution at room temperature;
(c) dissolving the copper chloride hydrate in the AZO solution to form a CuOx: AZO complex solution;
(d) spin-coating the complex solution onto a substrate and then drying, repeating the process of evaporating the solvent on the substrate and removing the organic residue to form a thin film; And
(e) The thin film formed in the step (d) is sintered in an Ar atmosphere of 400 to 450 ℃, the sintered thin film is annealed in an N 2 / H 2 gas atmosphere of 400 to 450 ℃ to a molar ratio of CuO of 0.5 to 2.0 mol A method for manufacturing a transparent composite conductive oxide film comprising forming a CuOx: AZO thin film which is%.
상기 (b) 단계에서 Al/Zn의 원자비가 0.05 내지 5.0 원자%가 되도록 산화아연(ZnO)에 알루미늄(Al)을 도핑하는 것을 특징으로 하는 투명 복합체 전도성 산화막의 제조방법.
The method of claim 5,
In the step (b), the aluminum oxide (ZnO) doped with aluminum (Al) so that the atomic ratio of Al / Zn is 0.05 to 5.0 atomic%, the method of manufacturing a transparent composite conductive oxide film.
A flat panel display device manufactured using a transparent composite conductive oxide film prepared by the method according to claim 5 or 6.
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