KR20030066167A - A method of producing ITO transparent conductive thin film by MOD processing - Google Patents

A method of producing ITO transparent conductive thin film by MOD processing Download PDF

Info

Publication number
KR20030066167A
KR20030066167A KR1020020006456A KR20020006456A KR20030066167A KR 20030066167 A KR20030066167 A KR 20030066167A KR 1020020006456 A KR1020020006456 A KR 1020020006456A KR 20020006456 A KR20020006456 A KR 20020006456A KR 20030066167 A KR20030066167 A KR 20030066167A
Authority
KR
South Korea
Prior art keywords
thin film
sol
transparent conductive
ito
substrate
Prior art date
Application number
KR1020020006456A
Other languages
Korean (ko)
Inventor
창 환 원
Original Assignee
창 환 원
최영기
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 창 환 원, 최영기 filed Critical 창 환 원
Priority to KR1020020006456A priority Critical patent/KR20030066167A/en
Publication of KR20030066167A publication Critical patent/KR20030066167A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606—Drying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9653—Translucent or transparent ceramics other than alumina

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

PURPOSE: A method for manufacturing ITO (indium tin oxide) transparent conductive thin film using MOD (metal-organic decomposition) process is provided to improve moisture stability by using hydrophobic solvent and obtain thin film without cracks by generating polymerization reaction after all solvent is evaporated even in drying process. CONSTITUTION: The method for manufacturing ITO transparent conductive thin film comprises the steps of mixing raw materials with common solvent in a mixing certain ratio; heating and stirring the mixture; synthesizing the reactant into sol in reactor; coating a product on substrate; and drying and heat treating the obtained product, wherein the sol is coated on the substrate with viscosity of the synthesized sol being controlled to 10 to 20 mPa·s, wherein the ITO sol is manufactured in such a way that a mole ratio of indium and tin is 1.86:0.14, and wherein the product is heat treated by drying the product coated on the substrate at 300 deg.C after coating the product on the substrate.

Description

ＭＯＤ법에 의한 ＩＴＯ 투명전도성 박막의 제조{A method of producing ITO transparent conductive thin film by MOD processing}A method of producing ITO transparent conductive thin film by MOD processing

본 발명은 MOD(Metal-Organic Decomposition)법을 이용하여 ITO(Indium TinOxide) 투명전도성 박막을 제조하는 방법에 관한 것이다.The present invention relates to a method of manufacturing an indium tin oxide (ITO) transparent conductive thin film using a metal-organic decomposition (MOD) method.

ITO(Indium Tin Oxide)는 박막으로 제조할 경우 광투과성 도전박막으로 가시광선에서의 투광성이 높으며 전기전도도 또한 높아서 액정표시소자(LCD), 태양전지, 광메모리, ECD(Electro-chromic Device) 등 전기광학재료의 전극 및 열반사 거울(heat reflector), 정전기 방지용 박막으로도 사용되고 있으며, 그 응용은 디스플레이 업계의 대형화 고급화 추세에 따라 수요도 계속 증가할 전망이다. 공침법의 경우 복잡한 조성의 성분을 제조할 경우 미반응물이 많이 잔류하며 수세과정에서 원료의 유실 및 불순물의 혼입 가능성이 있고, sol-gel법의 경우 출발물질인 alkoxide의 원재료비가 지나치게 높아 최종 생성물의 가격경쟁력 면에서 다소 불리한 점이 있다.Indium Tin Oxide (ITO) is a light-transmitting conductive thin film that has high light transmittance and high electric conductivity, so that it can be used for thin film manufacturing of ITO (Indium Tin Oxide). It is also used as an electrode for optical materials, heat reflector, and anti-static thin film, and its application is expected to continue to increase as the display industry becomes larger and more advanced. In the case of coprecipitation, a large amount of unreacted material remains when manufacturing a complex composition, and there is a possibility of loss of raw materials and incorporation of impurities during the washing process. There are some disadvantages in terms of price competitiveness.

본 발명은 이러한 단점을 극복하기 위하여 다음과 같이 MOD(Metal-Organic Decomposition)법을 적용하여 투명전도성 ITO 박막을 제조하였다. MOD법은 일반적인 습식법의 장점인 원료준비 단계에서부터 분자단위에 이르는 균일한 혼합이 가능할 뿐만 아니라 복잡한 조성의 성분을 제조할수 있으면서 비교적 장치와 설비가 간단하여 제조비가 저렴하다는 장점이 있다. 이 때문에 최종생성물을 안정하게 획득할 수 있어 재연성 확립이 용이하며, sol-gel법에 비해 sol의 수분에 대한 안정성도 뛰어나 산업화 및 응용에도 장점이 있다. 또한 출발물질의 원가도 sol-gel법에 비해서 저렴하다는 이점이 있다. sol의 합성을 완료하고 기판에 코팅하여 건조와 열처리를 거친 후 제조된 ITO 박막의 XRD pattern을 살펴보면 ITO(Indium TinOxide)막이 생성되었음을 확인할 수 있고, 그 두께는 1회 코팅에 약 0.1㎛였으며 가시광선영역에서의 투광성 측정결과 약 85% 이상의 투광도를 보였다. 또한 전기비저항은 진공분위기에서 600℃로 열처리할 경우 최대 7.0×10-4Ω㎝ 이었다.In order to overcome this disadvantage, the present invention applies a metal-organic decomposition (MOD) method to prepare a transparent conductive ITO thin film. The MOD method not only enables uniform mixing from the raw material preparation stage to the molecular unit, which is an advantage of the general wet method, but also has the advantage that the manufacturing cost is low because the device and the equipment are relatively simple while the components of the complex composition can be prepared. Because of this, it is possible to stably obtain the final product, so it is easy to establish reproducibility, and it is also excellent in industrialization and application because it has excellent stability against moisture of sol compared to sol-gel method. In addition, the cost of the starting material is also lower than the sol-gel method. The XRD pattern of the prepared ITO thin film after completion of the synthesis of the sol, the coating on the substrate, and the drying and heat treatment were confirmed that an ITO (Indium TinOxide) film was formed. The light transmittance in the region showed over 85% light transmittance. In addition, the electrical resistivity is up to 7.0 × 10 when heat treated at 600 ℃ in vacuum atmosphere.-4Ω cm It was.

도 1은 본 발명에 따른 ITO 투명전도성 박막의 제조 공정도이다.1 is a manufacturing process chart of the ITO transparent conductive thin film according to the present invention.

도 2는 본 발명에 사용된 ITO sol 합성장치의 개략도이다.Figure 2 is a schematic diagram of the ITO sol synthesis apparatus used in the present invention.

도 3은 본 발명에 사용된 ITO 투명전도성 박막 코팅 제조장치의 개략도이다.Figure 3 is a schematic diagram of the ITO transparent conductive thin film coating apparatus used in the present invention.

도 4는 본 발명의 바람직한 실시 예에 따라서 제조된 투명전도성 ITO 박막의 500∼700℃ 범위에서 열처리한 X-ray 회절패턴 결과이다.4 is an X-ray diffraction pattern of the heat-treated in the range of 500 ~ 700 ℃ of the transparent conductive ITO thin film prepared according to a preferred embodiment of the present invention.

도 5는 본 발명의 바람직한 실시 예에 따라서 기판에 15회 반복 코팅하여 제조된 투명전도성 ITO 박막의 가시광선 영역에서의 투광성 측정결과이다.5 is a light transmittance measurement result in a visible light region of a transparent conductive ITO thin film prepared by repeatedly coating the substrate 15 times in accordance with a preferred embodiment of the present invention.

도 6은 본 발명의 바람직한 실시 예에 따라서 1회 코팅하여 제조된 투명전도성 ITO 박막의 단면 SEM 사진이다.6 is a cross-sectional SEM photograph of a transparent conductive ITO thin film prepared by coating once according to a preferred embodiment of the present invention.

도 7은 본 발명의 바람직한 실시 예에 따라서 제조된 투명전도성 ITO 박막의 전기비저항 측정결과이다.7 is an electrical resistivity measurement result of a transparent conductive ITO thin film prepared according to a preferred embodiment of the present invention.

상기와 같은 목적을 달성하기 위해서 본 발명은,In order to achieve the above object, the present invention,

원료를 일정 비율로 공통용매에 혼합하는 단계(S1);Mixing the raw materials in a common solvent at a predetermined ratio (S1);

상기 단계(S1)에서 혼합된 혼합물을 가열·교반시키는 단계(S2);Heating and stirring the mixture mixed in the step (S1) (S2);

상기 반응물을 반응기에서 sol로 합성시키는 단계(S3);Synthesizing the reactants with sol in a reactor (S3);

상기 단계(S3)에서 만들어진 생성물을 코팅하는 단계(S4); 및Coating (S4) the product made in step S3; And

상기 단계(S4)에서 얻어진 생성물을 건조 및 열처리하는 단계(S5)를 포함하는 투명전도성 ITO(Indium Tin Oxide) 박막의 제조방법을 제공한다.It provides a method for producing a transparent conductive indium tin oxide (ITO) thin film comprising the step (S5) of drying and heat-treating the product obtained in the step (S4).

이상에서 언급한 바와 같이, 본 발명에 따른 ITO(Indium Tin Oxide) 박막의 제조 방법에서는 MOD법을 이용하여 투명전도성 박막을 제조한다. 이하 첨부된 도면들을 참조로 하여 본 발명에 따른 투명전도성 ITO(Indium Tin Oxide) 박막제조 공정을 보다 상세하게 설명하면 다음과 같다.As mentioned above, in the method of manufacturing an indium tin oxide (ITO) thin film according to the present invention, a transparent conductive thin film is manufactured using the MOD method. Hereinafter, a process for manufacturing a transparent conductive indium tin oxide (ITO) thin film according to the present invention will be described in detail with reference to the accompanying drawings.

먼저, 도 2는 본 발명을 수행하는데 사용되는 sol의 합성반응기 도면이다. 도 2를 참조하면, sol 합성반응기는 항온유지가 가능한 Heating Mantle과 Stirer 그리고 Thermocouple이 장착되고 기밀이 유지되는 Vessel로 이루어져 있다.First, FIG. 2 is a diagram of a synthesis reactor for sol used to carry out the present invention. Referring to FIG. 2, the sol synthesis reactor is composed of a heating mantle capable of maintaining a constant temperature, a stirer, and a vessel equipped with a thermocouple and kept hermetic.

한편, 도 1은 본 발명에 따른 투명전도성 ITO 박막제조 공정의 일 예를 나타낸 공정도이다. 도 1 및 도 2를 참조하여 MOD법에 의해 투명전도성 ITO박막의 제조공정을 설명한다.On the other hand, Figure 1 is a process chart showing an example of a transparent conductive ITO thin film manufacturing process according to the present invention. The manufacturing process of a transparent conductive ITO thin film by MOD method is demonstrated with reference to FIG. 1 and FIG.

본 발명은 원료를 Indium과 Tin의 고용한계(20%)와 재료비 및 박막특성을 고려하여 가장 좋은 몰비인 In:Sn=1.86:0.14의 몰비로 용매에 용해한 후 sol을 제조하고 제조된 sol을 기판에 코팅한 후 건조와 열처리를 거쳐 투명전도성 ITO 박막을 제조하는 방법이다. 본 발명을 통하여 제조된 ITO 박막은 바람직하게는 가시광선 영역에서의 투광성이 평균 85% 이상이고, 전기비저항은 약 10-3∼10-4Ω㎝이 된다.According to the present invention, after dissolving a raw material in a solvent at a molar ratio of In: Sn = 1.86: 0.14, which is the best molar ratio in consideration of the solid solution limit of indium and tin (20%), material cost, and thin film properties, a sol is prepared and a substrate is prepared. It is a method of manufacturing a transparent conductive ITO thin film by coating on the drying and heat treatment. The ITO thin film produced through the present invention is preferably at least 85% of the light transmittance in the visible light region, the electrical resistivity of about 10 -3 ~ 10 -4 Ωcm.

이하, 본 발명의 바람직한 실시 예를 간략하게 설명한다.Hereinafter, a preferred embodiment of the present invention will be briefly described.

실시 예Example

일정량의 Indium acetate를 공통용매인 2-Ethylhexanoic acid에 용해시키고, Indium과 Tin의 몰비를 1.86:0.14가 되도록 C16H36Sn를 2-Ethylhexanoic acid에 용해시켜 수용액 상태로 준비한다. 그 후 이 수용액들을 주 반응생성물인 Acetic acid를 제거하기 위해 Acetic acid의 휘발온도인 118℃보다 놓은 온도인 200℃로 유지되는 vessel에 장입하여 일정시간 교반시키면 용액은 불투명한 혼합수용액 상태에서 노란색의 투명한 ITO sol이 합성된다. 이 sol을 계속 같은 조건에서 숙성시키면 노란색에서 점차 적갈색을 띠는 농도가 짙은 sol이 형성된다. 이 sol을 2-Ethyl-1-hexanol을 첨가하고 교반하여 코팅하기에 적당한 점도인 10∼20mPa??s로 조절하고 초음파 세척기로 충분히 세척한 기판에 코팅한 후 300℃에서 건조하고 400∼600℃의 온도범위에서 열처리 하면 투명전도성 ITO 박막을 얻을 수 있다.A certain amount of indium acetate is dissolved in a common solvent, 2-Ethylhexanoic acid, and C 16 H 36 Sn is dissolved in 2-Ethylhexanoic acid to prepare an aqueous solution so that the molar ratio of Indium and Tin is 1.86: 0.14. Subsequently, the aqueous solution is charged into a vessel maintained at 200 ° C., which is a temperature higher than the volatilization temperature of Acetic acid 118 ° C. to remove Acetic acid, the main reaction product, and the solution is stirred for a certain period of time. Transparent ITO sol is synthesized. If this sol continues to mature under the same conditions, a darker reddish-brown sol is formed. This sol was added to 2-Ethyl-1-hexanol and stirred at 10-20 mPa ?? s, which is a suitable viscosity for coating, and then coated on a substrate sufficiently washed with an ultrasonic cleaner, dried at 300 ° C., and dried at 400 ° C. to 600 ° C. Heat treatment in the temperature range of to obtain a transparent conductive ITO thin film.

도 3은 도 2에 도시된 반응기를 통하여 ITO sol을 제조한 후 ITO 투명전도성 박막을 제조하는 Dip Coater의 개략도이다.FIG. 3 is a schematic diagram of a Dip Coater for preparing an ITO transparent conductive thin film after preparing the ITO sol through the reactor shown in FIG. 2.

도 4는 도 3에서 보인 Dip Coater를 사용하여 기판에 코팅 후 300℃에서 건조를 10회 반복하고 500℃, 600℃, 700℃로 각각 열처리한 기판의 XRD pattern을 보인 것이다. 그림으로 보아 ITO가 열처리를 통하여 합성되어 기판에 ITO 박막을 형성하고 있음을 알 수 있으며, 500℃이상에서 열처리 온도가 올라갈수록 peak intensity가 증가함을 알 수 있다.Figure 4 shows the XRD pattern of the substrate heat-treated at 500 ℃, 600 ℃, 700 ℃ 10 after repeated coating 10 times at 300 ℃ after coating the substrate using the Dip Coater shown in FIG. From the figure, it can be seen that ITO is synthesized through heat treatment to form an ITO thin film on the substrate, and the peak intensity increases as the heat treatment temperature increases above 500 ° C.

도 5는 기판에 sol을 10회 코팅한 후 가시광선 영역에서 기판의 투광성을 측정한 결과이다. 그림에서 알 수 있듯이 투광도는 전체적으로 85% 이상으로 높은 투광도를 보이고 있음을 알 수 있다.5 is a result of measuring the light transmittance of the substrate in the visible light region after coating the sol 10 times on the substrate. As can be seen from the figure, the transmittance shows a high transmittance of more than 85% as a whole.

도 6은 기판에 sol을 1회 코팅하여 ITO 박막을 합성한 후 그 단면을 SEM으로 관찰한 사진이다. 그림에서 알 수 있듯이 1회 코팅으로 약 0.1㎛의 코팅막을 얻을 수 있었으며, dip coating의 특성상 표면의 평활도는 다른 코팅법에 비해 거친 편이었다.6 is a photograph observing the cross-section SEM after the synthesis of the ITO thin film by coating the sol once on the substrate. As can be seen from the figure, the coating film of about 0.1㎛ was obtained by one coating, and the surface smoothness was rougher than other coating methods due to the characteristics of dip coating.

도 7은 합성된 ITO sol을 사용하여 코팅하고 300℃에서 건조한 후 400℃, 500℃, 600℃로 열처리하고 측정한 전기비저항값의 그래프이다. 이 결과에서 열처리 온도가 증가할수록 비저항값은 감소하여 600℃에서 7×10-4Ω㎝ 이었다. 특히 전기비저항은 대기 중에서 열처리할 때보다 진공이나 N2/H2혼합기체 분위기에서 열처리할 경우 산소결손으로 인한 이동도의 증가에 기인하여 훨씬 낮은 전기비저항값을 얻을 수 있음을 알 수 있었다.FIG. 7 is a graph of electrical resistivity values measured by coating with synthetic ITO sol, drying at 300 ° C., and then heat treating at 400 ° C., 500 ° C. and 600 ° C. FIG. In this result, as the heat treatment temperature was increased, the resistivity decreased and was 7 × 10 −4 Ωcm at 600 ° C. In particular, the electrical resistivity was found to be much lower due to the increased mobility due to oxygen deficiency when heat treated in a vacuum or N 2 / H 2 mixed gas atmosphere than in the air.

이상에서 언급한 바와 같이, 본 발명에 따른 MOD법에 의한 투명전도성 ITO 박막의 제조방법은 제조된 sol의 안정성이 높으며, 다른 제조방법에 비해 공정이 간단하고, 장비도 간단해서 상대적으로 제조비용이 저렴하다. 또한 코팅 후 건조과정에서도 용매가 모두 증발한 후 중합반응이 발생하기 때문에 박막의 수축이 기판과 평행하게 일어남으로서 균열이 없는 박막을 얻을 수 있다.As mentioned above, the manufacturing method of the transparent conductive ITO thin film by the MOD method according to the present invention has a high stability of the prepared sol, the process is simpler than other manufacturing methods, and the equipment is simple, so the manufacturing cost is relatively high. It is cheaper. In addition, since the polymerization reaction occurs after all the solvent evaporates in the drying process after coating, shrinkage of the thin film occurs in parallel with the substrate, thereby obtaining a thin film without cracking.

ITO 투명전도성 박막은 주로 PDP LCD, EL 등 전기광학재료의 전극으로 사용되며, 그 응용과 수요는 계속 늘어날 것으로 예상된다. 따라서 본 MOD법을 이용하여 ITO 박막을 제조함으로서 디스플레이 부문에서의 국제 경쟁력강화는 물론 국가경제발전에 크게 이바지할 수 있다.ITO transparent conductive thin films are mainly used as electrodes of electro-optic materials such as PDP LCD and EL, and their application and demand are expected to continue to increase. Therefore, by manufacturing ITO thin film using this MOD method, it can contribute to the national economic development as well as to strengthen international competitiveness in the display sector.

상기에서는 본 발명의 바람직한 실시 예를 참조하여 설명하였지만, 해당기술분야의 숙련된 당업자는 하기의 특허 청구의 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art various modifications and variations of the present invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

Claims (4)

원료를 일정 비율로 공통용매에 혼합하는 단계(S1);Mixing the raw materials in a common solvent at a predetermined ratio (S1); 상기 단계(S1)에서 혼합된 혼합물을 가열·교반시키는 단계(S2);Heating and stirring the mixture mixed in the step (S1) (S2); 상기 반응물을 반응기에서 sol로 합성시키는 단계(S3);Synthesizing the reactants with sol in a reactor (S3); 상기 단계(S3)에서 만들어진 생성물을 기판에 코팅하는 단계(S4); 및Coating the product made in the step (S3) on the substrate (S4); And 상기 단계(S4)에서 얻어진 생성물을 건조 및 열처리하는 단계(S5)를 포함하는 투명전도성 ITO 박막의 제조방법Method for producing a transparent conductive ITO thin film comprising the step (S5) of drying and heat-treating the product obtained in the step (S4) 제 1항에 있어서, 합성된 sol의 점도를 10∼20mPa??s로 조절하여 기판에 코팅하는 ITO sol로부터 ITO 박막의 제조방법The method of claim 1, wherein the viscosity of the synthesized sol is adjusted to 10-20 mPa ?? s to form a thin film of the ITO thin film from the ITO sol. 제 1항에 있어서, ITO sol을 Indium과 Tin의 몰비가 1.86:0.14가 되도록 제조하는 방법.The method of claim 1, wherein the ITO sol is prepared such that the molar ratio of Indium and Tin is 1.86: 0.14. 제 1항에 있어서, 코팅 후 300℃에서 건조하여 열처리를 하는 투명전도성 ITO 박막의 제조방법The method for preparing a transparent conductive ITO thin film according to claim 1, wherein the transparent conductive ITO thin film is dried and heat-treated at 300 ° C. after coating.
KR1020020006456A 2002-02-05 2002-02-05 A method of producing ITO transparent conductive thin film by MOD processing KR20030066167A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020020006456A KR20030066167A (en) 2002-02-05 2002-02-05 A method of producing ITO transparent conductive thin film by MOD processing

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020020006456A KR20030066167A (en) 2002-02-05 2002-02-05 A method of producing ITO transparent conductive thin film by MOD processing

Publications (1)

Publication Number Publication Date
KR20030066167A true KR20030066167A (en) 2003-08-09

Family

ID=32220518

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020020006456A KR20030066167A (en) 2002-02-05 2002-02-05 A method of producing ITO transparent conductive thin film by MOD processing

Country Status (1)

Country Link
KR (1) KR20030066167A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100819062B1 (en) * 2007-03-19 2008-04-03 한국전자통신연구원 Synthesis method of indium tin oxide(ito) electron-beam resist and pattern formation method of ito using the same
CN103345977A (en) * 2013-06-07 2013-10-09 深圳市亚太兴实业有限公司 Method for manufacturing ITO thin film mixed with silver
KR20210100810A (en) * 2020-02-07 2021-08-18 한남대학교 산학협력단 A method for coating Indium Tin Oxide(ITO) on flexible substrate using solution process
KR20220058248A (en) * 2020-10-30 2022-05-09 한남대학교 산학협력단 A method for coating Indium Tin Oxide(ITO) on flexible substrate using indium precursor and tin precursor
KR20220121377A (en) * 2021-02-25 2022-09-01 한남대학교 산학협력단 A method of hydrophilic surface treatment for improving metal oxide coating property of polyimide film

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100819062B1 (en) * 2007-03-19 2008-04-03 한국전자통신연구원 Synthesis method of indium tin oxide(ito) electron-beam resist and pattern formation method of ito using the same
US8101337B2 (en) 2007-03-19 2012-01-24 Electronics And Telecommunications Research Institute Method of synthesizing ITO electron-beam resist and method of forming ITO pattern using the same
CN103345977A (en) * 2013-06-07 2013-10-09 深圳市亚太兴实业有限公司 Method for manufacturing ITO thin film mixed with silver
KR20210100810A (en) * 2020-02-07 2021-08-18 한남대학교 산학협력단 A method for coating Indium Tin Oxide(ITO) on flexible substrate using solution process
KR20220058248A (en) * 2020-10-30 2022-05-09 한남대학교 산학협력단 A method for coating Indium Tin Oxide(ITO) on flexible substrate using indium precursor and tin precursor
KR20220121377A (en) * 2021-02-25 2022-09-01 한남대학교 산학협력단 A method of hydrophilic surface treatment for improving metal oxide coating property of polyimide film

Similar Documents

Publication Publication Date Title
CN101631746B (en) Method of synthesizing ITO electron-beam resist and method of forming ITO pattern using the same
JPS63258959A (en) Coating liquid for forming metallic oxide film
KR20030066167A (en) A method of producing ITO transparent conductive thin film by MOD processing
CN108165956A (en) A kind of preparation method for the AZO laminated films for adding graphene
JP2605855B2 (en) Method for producing conductive tin oxide powder
DE112008002142T5 (en) Porous silica precursor composition and method for preparing the precursor composition, porous silica film, and methods for producing the porous silica film, semiconductor element, image display apparatus, and liquid crystal display
KR100929433B1 (en) Method of manufacturing carbon nanotube conductive film
JP2008162863A (en) White electroconductive powder
Zhou et al. Synthesis and electrochromic properties of a graphene oxide/silicon dioxide/oligoaniline interpenetrating network composite
JP5224160B2 (en) White conductive powder and production method and use thereof
CN113337194B (en) Preparation method of coated conductive whisker/composite antistatic coating
JP6679023B2 (en) Organic conductive film and method for manufacturing the same
KR101102782B1 (en) Low melting point tin salt of carboxylic acid and method for producing the same
JPH05214545A (en) Process for producing film
KR20030066169A (en) A method of producing ITO sol by Metal-Organic Decomposition processing
JP2011134483A (en) Method of manufacturing conductive coating, and transparent conductive film
KR100475550B1 (en) Conductive black-colored coating composition for shielding electromagnetic waves, method for forming coating film using the same and the coating film
JPH09198926A (en) Conductive polymer composition and its manufacture
KR20030066170A (en) A method of producing nano-ITO powders by MOD processing
KR100200322B1 (en) Method of zinc-oxide thin film with coating sol
JP3976210B2 (en) Coating liquid for protective film formation
JPS5911532B2 (en) Method for producing conductive tin dioxide powder
CN109279614B (en) Bi2SiO5Bismuth silicate film material and preparation method and application thereof
KR100432647B1 (en) A composition for a protective layer of a transparent conductive layer and a method for preparing protective layer from the composition
JP2011150918A (en) Method for manufacturing transparent conductive substrate

Legal Events

Date Code Title Description
WITN Withdrawal due to no request for examination