KR20110113292A - Method for manufacturing low resistivity and high transparent f-doped tin oxide heater - Google Patents
Method for manufacturing low resistivity and high transparent f-doped tin oxide heater Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 title description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title description 5
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000007921 spray Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims 1
- 239000002346 layers by function Substances 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000005507 spraying Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Surface Heating Bodies (AREA)
Abstract
본 발명은 FTO 투명전도막과 글라스 유리기판 사이에 상기 FTO 투명전도막보다도 저전기저항성의 금속 메쉬를 그리드 형태로 형성시켜 대면적 투명 발열히터를 제작하는 방법으로, FTO 투명전도막층은 스프레이 파이로졸법에 의해 형성된다.The present invention is a method of forming a large area transparent heating heater by forming a metal mesh having a lower electrical resistance than the FTO transparent conductive film in a grid form between the FTO transparent conductive film and the glass glass substrate, wherein the FTO transparent conductive film layer is spray py It is formed by the sol method.
Description
본 발명은 저저항성 발열히터의 제조방법에 관한 것으로, 특히 FTO 투명전도막의 하단에 저저항 전도체 금속/합금 그리드를 형성시켜 대면적 투명발열 히터를 제조하는 공정에 관한 기술이다.BACKGROUND OF THE
최근 F-doped Tin Oxide (FTO) 박막 소재는 액정표시소자, 플라스마 발광표시소자, 일렉트로루미네센스 표시소자 등의 디스플레이용 투명전도막 , 친환경을 위한 에너지절약 유리인 로이(Low-e), 태양전지용 투명전도막, 자동차용 솔라(Solar)유리, 자동차, 항공기, 건축물 등의 창 유리의 결로방지 또는 빙결방지를 위한 발열저항체나 가시광에 대하여 고투과성을 갖는 중요한 전극소재로 부각되고 있다.Recently, the F-doped Tin Oxide (FTO) thin film material is a transparent conductive film for displays such as liquid crystal display devices, plasma light emitting display devices, electroluminescent display devices, low-e, energy-saving glass for the environment, solar It is emerging as an important electrode material having high permeability to heating resistor or visible light for preventing condensation or freezing of window glass of battery transparent conductive film, solar glass for automobiles, automobiles, aircrafts and buildings.
FTO 박막소재와 같은 용도로 쓰이는 전극재료로는 안티몬을 함유하는 산화주석(ATO), 주석을 함유하는 산화인듐(ITO), 아연을 함유하는 산화아연(ZnO)등이 알려져 있다. 그러나 일반적으로 쓰이는 ITO 투명전도막 유리는 150 이상의 온도에서 가열하여 성형할 경우 ITO의 전기적 물성이 바뀌고 열화되는 문제점이 있고, 내열성, 내화학성 및 내마모성이 약한 문제점을 가지고 있다. As electrode materials used for applications such as FTO thin film materials, tin oxide (ATO) containing antimony, indium oxide (ITO) containing tin, and zinc oxide (ZnO) containing zinc are known. However, commonly used ITO transparent conductive film glass has a problem that the electrical properties of the ITO is changed and deteriorated when formed by heating at a temperature of 150 or more, and has a weak problem of heat resistance, chemical resistance and abrasion resistance.
이러한 이유로 인해 기타 투명전도막들과 차별화 되는 고온 내열성 (약 500도), 내화학성/내부식성이 요구되어진다. FTO투명 전극은 고온, 고전압에 대한 안전성이 높고 투명하면서 전기를 통하는 우수한 투명전극소재로 많이 알려져 있다. For this reason, high temperature heat resistance (about 500 degrees) and chemical resistance / corrosion resistance which are different from other transparent conductive films are required. FTO transparent electrode is known as a good transparent electrode material having high safety against high temperature and high voltage, and is transparent.
일반적으로 자동차, 항공기, 건축물 등에 사용되는 대면적 발열히터 소재로서 가장 우수한 소재는 금속이다. 그러나 금속은 불투명하여 시각적 투명성을 요구하는 분야에는 사용할 수 없다. 비록 투명도가 우수하며 고온 내화학성이 우수한 FTO는 평판 및 다양한 형상의 투명 발열히터로서 크게 기대되고 있지만 세라믹계 투명전도막의 저항의 한계로 인하여 대면적에서는 큰 선저항이 발생하여 큰 전압과 늦은 응답속도를 갖게 되어 실제로 사용하는데 큰 장애가 된다.In general, a large area heating heater material used in automobiles, aircraft, buildings, etc., the most excellent material is metal. However, metals are opaque and cannot be used in applications that require visual transparency. Although the FTO has excellent transparency and high temperature chemical resistance, it is expected to be a transparent heating heater with a flat plate and various shapes. However, due to the limitation of the resistance of the ceramic transparent conductive film, a large wire resistance occurs in large areas, resulting in large voltage and slow response speed. It becomes a big obstacle to actually use.
통상적으로 금속 메쉬 위에 투명전도막 형성은 ITO와 같이 스퍼터 및 CVD 방법을 이용하여 수행되어 왔으나, 스프레이 파이로졸 방법으로 투명전도막을 형성하는 것은 형성과정 중에 막대한 양의 염산과 불산이 발생하여 실버 배선을 녹인다는 선입관 때문에 그동안 금속기판 위에 스프레이 파이로졸 방법을 이용하여 FTO막 형성하는 방법은 사용되고 있지 않았다.Typically, the formation of a transparent conductive film on a metal mesh has been performed using a sputtering and CVD method like ITO, but the formation of a transparent conductive film by spray pyrosol method generates a large amount of hydrochloric acid and hydrofluoric acid during formation. Because of the preconceived notion of dissolving, the method of forming FTO film on the metal substrate by spray pyrosol method has not been used.
그럼에도 불구하고 본 발명에서는 그 선입관을 깨고 실버 페이스트 배선 위에 FTO막을 형성시켜도 실버 메쉬 및 FTO 막에는 아무런 영향이 없음을 본 발명을 통하여 처음으로 밝혔다.Nevertheless, the present invention revealed for the first time that there is no effect on the silver mesh and the FTO film even if the FTO film is formed on the silver paste wiring by breaking the preconceived notion.
본 발명에서는 금속라인을 시각적(광학적)으로 크게 방해를 받지 않게 모재 위에 형성시키고 그 위에 FTO 막을 형성시켜 금속과 FTO가 융합된 구조체 투명히터를 제조하여 상기 문제를 해결하고자 한다.In the present invention, to solve the above problems by forming a structure transparent heater fused with metal and FTO by forming a metal line on the base material and a FTO film thereon so as not to be disturbed visually (optical) significantly.
상기 문제점들을 해결하기 위하여 대표적으로 공지된 실버 배선 기술들을 활용하여 평판 및 곡면 유리기판상에 금속 메쉬를 형성시키고,In order to solve the above problems, a metal mesh is formed on a flat plate and a curved glass substrate by using representatively known silver wiring techniques,
상기 실버 메쉬가 형성된 기판위에 스프레이 파이로졸 방법을 이용하여 FTO 막을 형성시켜 본 발명을 수행하였다. FTO 투명전도막 하부상의 형성되는 메쉬들은 금속 또는 합금으로 이루어질 수 있다.The present invention was performed by forming an FTO film on the substrate on which the silver mesh was formed by using a spray pyrosol method. The meshes formed on the bottom of the FTO transparent conductive film may be made of metal or alloy.
금속 또는 합금 메쉬를 형성시키는 방법으로서 스크린프린팅(Screen Printing), 그라비어 프린팅(Gravure Printing), 옵셋 프린팅(Off-Set Printing), 잉크젯 프린팅(Ink-Jet Printing), 스퍼터법, CVD, PVD, 도금, 리소그라피(Lithography), 엣칭 방법들이 이용될 수 있다. As a method of forming a metal or alloy mesh, screen printing, gravure printing, off-set printing, ink-jet printing, sputtering, CVD, PVD, plating, Lithography, etching methods can be used.
메쉬의 선폭은 시각적으로 크게 방해받지 않는 영역 즉, 두께가 35um이하 이며 선간 간격은 100~150um 이상의 그리드 형태로 이루어지는 것이 바람직하다. It is preferable that the line width of the mesh is a visually unobstructed area, that is, the thickness is less than 35 μm and the line spacing is formed in a grid form of 100 to 150 μm or more.
FTO 투명전극 형성은 초음파 분무, 액상 스프레이 분무방법들을 기초로 하여 스프레이 파이로졸(Spray Pyrosol)법으로 제작되었으며, 종래의 일반적인 CVD(Chemical vapor deposition)법 등과 같은 진공을 유지하거나 가스 및 전구체를 투입하기 위해 복잡한 형상의 고가 장치를 필요로 하지 않는다.FTO transparent electrode is formed by spray pyrosol method based on ultrasonic spraying and liquid spray spraying methods, and maintains vacuum or injects gas and precursors such as conventional chemical vapor deposition (CVD). It does not require expensive devices of complex shape to do so.
이와 같은 구조는 투명발열히터의 저항을 크게 낮추어줌으로서 대면적 투명히터로서 기능을 발휘하여 자동차, 항공기, 선박, 가전제품등에 김 서림 방지, 성에 제거, 온수/난방기등에 크게 활용될 수 있으며, 또한 여러가지 전자 디바이스에도 적용할 수 있다. 일례로 하부층의 금속메쉬는 외부 전자기파에 감응하는 안테나로서도 기능을 발휘할 수 있으며, 또한 투명 도전성막을 활용하는 각종 디바이스 즉, 센서, 태양전지, 디스플레이 등의 메쉬형 금속 전극으로도 활용가능하다.This structure greatly reduces the resistance of the transparent heating heater, and thus functions as a large-area transparent heater, which can be widely used for preventing fog, eliminating frost, and hot water / heater for automobiles, aircraft, ships, and home appliances. It can be applied to various electronic devices. For example, the metal mesh of the lower layer may also function as an antenna sensitive to external electromagnetic waves, and may also be used as a mesh type metal electrode such as a sensor, a solar cell, and a display using a transparent conductive film.
도 1. 평판 FTO 투명발열 히터의 개략도.
도 2. 본 발명의 복잡한 형상(곡면)의 FTO 투명발열 히터 개략도.
도 3. 실시예 1,2,3에 있어서 저항 분포도 측정 방법 모식도.
도 4. 실시예 1,2,3에 있어서 일정 전압인가 후 시간 변화에 따른 발열온도 그래프.1. Schematic diagram of a flat plate FTO transparent heating heater.
2. Schematic diagram of the FTO transparent heating element of the complex shape (curved) of the present invention.
3. Schematic diagram of the method for measuring resistance distribution in Examples 1, 2 and 3;
4. Exothermic temperature graph according to the time change after applying a constant voltage in Examples 1,2,3.
도 1에 평판형 타입, 도 2, 도 3에 곡면형 타입의 예시를 나타내었다. FTO 투명전도막 하부에 구성되는 금속 그리드는 간략하게 기능성층이라 대표 명명하였다. 도 2가 가능해짐에 따라 복잡 형상의 투명발열히터가 가능해진다.1 shows an example of a flat type, and FIGS. 2 and 3 show a curved type. The metal grid formed under the FTO transparent conductive film was briefly named as a functional layer. As shown in FIG. 2, a transparent heat generating heater having a complicated shape is possible.
스프레이 파이로졸 방법으로서 비교적 저온공정에서 FTO 프리커서 액적을 기판과 평행하게 흘려 균질한 막을 형성시켰고, 분무 압력 및 석션 압력을 조절함으로서 FTO 결정성장을 제어하였다. 상기 코팅법으로 제조된 FTO 투명전도막은 결정표면을 부드럽게 하여 헤이즈(haze)가 작은 투명전도막을 형성할 수 있다는 장점이 있다. 이때 상기 산화주석의 전구체는 당 분야에서 일반적으로 사용되는 것으로 특별히 한정하지는 않으나 구체적으로 SnCl4·5H2O, SnCl2, SnCl4 및 SnCl2·2H2O로 이루어지는 군으로부터 선택된 원료를 사용할 수 있고, 불소의 전구체로는 NH4F를 이용하였다. 기타 HF 및 F 함유 유기금속화합물이 사용될 수 있다.As a spray pyrosol method, in a relatively low temperature process, the FTO precursor droplets were flowed in parallel with the substrate to form a homogeneous film, and the FTO crystal growth was controlled by adjusting the spray pressure and suction pressure. The FTO transparent conductive film prepared by the coating method has an advantage of forming a transparent conductive film having a small haze by softening the crystal surface. In this case, the precursor of tin oxide is generally used in the art, but is not particularly limited, and specifically, a raw material selected from the group consisting of
상기 스프레이 파이로졸법은 기존과 달리 일측면부에 구비되는 노즐로부터 FTO 프리커서가 분사되고 FTO 박막의 증착이 이루어지는 동시에 반대측면부에서 석션을 함으로써 FTO 프리커서 플로우가 기판과 평행하게 흐르게 함으로써 가열된 기판에 FTO가 균일하게 도포되게 하는 FTO 투명전도막 스프레이 파이로졸 증착장비에 의해 구현된다. 즉, 스프레이 파이로졸 방법으로 챔버의 측면부에 부착된 노즐부 및 배기부의 상호의존관계(분사-흡입(석션)관계)를 통하여 FTO 프리커서 액적이 기판과 평행하게 흐르며 증착이 이루어지고 결정성장을 제어하게 되는 것이다.Unlike the conventional spray pyrosol method, the FTO precursor is injected from a nozzle provided on one side and the FTO thin film is deposited, and the suction is performed on the opposite side, thereby allowing the FTO precursor flow to flow in parallel with the substrate. It is realized by the FTO transparent conductive film spray pyrosol deposition equipment that allows the FTO to be uniformly applied. That is, the spray pyrosol method causes the FTO precursor droplets to flow in parallel with the substrate through the interdependence (spray-suction) relationship between the nozzle part and the exhaust part attached to the side of the chamber. To control.
본 발명에서 사용하는 산화주석 전구체 및 불소 전구체는 알콜류를 포함하지 않으며, 결정성장을 제어하기 위해 에틸렌글리콜(EG), 디메틸틴디크롤라이드(DMTC) 모노부틸틴트리클로라이드(MBTC), 테트라메틸틴(TMT) 등의 알킬기를 포함하여 사용할 수 있으나 특별히 한정하지는 않는다. 또한 본 발명의 스프레이 용액의 용매는 탈이온수를 사용할 수도 있는데, 이는 탈이온수가 FTO 투명전도막의 결정성장을 억제하는 역할을 함으로써, 표면의 미세구조가 과도하게 성장하지 않고 매끄럽게 형성되어 표면에서 일어나는 빛의 산란을 방지하는 것에 의하여 FTO 투명전도막을 포함하는 기능성층에서 비롯되는 헤이즈(haze)를 줄일 수 있는 효과를 보이기 때문이다. The tin oxide precursor and the fluorine precursor used in the present invention do not contain alcohols, and in order to control crystal growth, ethylene glycol (EG), dimethyl tin dichloride (DMTC) monobutyl tin trichloride (MBTC), tetramethyl tin ( TMT) may be used including an alkyl group, but is not particularly limited. In addition, the solvent of the spray solution of the present invention may use deionized water, which deionized water serves to suppress crystal growth of the FTO transparent conductive film, so that the microstructure of the surface is smoothly formed without excessive growth and light is generated on the surface. This is because by preventing the scattering of the haze (haze) resulting from the functional layer including the FTO transparent conductive film can be reduced.
실버그리드 두께(μm)
Silver Grid Thickness (μm)
<실시 예 1>≪ Example 1 >
FTO 투명전도막 코팅용액은 SnCl4·5H2O를 순수한 D.I 물에 5%의 에탄올을 혼합한 용매에 0.68M이 되도록 혼합하고 교반하여 제조하였으며, F의 소스로는 NH4F를 F/Sn의 비가 1.5이 되도록 하여 합성하였다.The FTO transparent conductive coating coating solution was prepared by mixing and stirring
제조된 코팅 용액은 스프레이 파이로졸 법에 의해 박막을 형성할 수 있다.The prepared coating solution can form a thin film by the spray pyrosol method.
이때,At this time,
제조된 FTO 투명전도막은 대면적에 저저항성 고투과율 투명 발열 히터를 제조하기 위해 기능성층(메탈 그리드)을 기판과 FTO 투면전도막 사이에 구비하였으며, 이때 기능성 층은 스크린프린팅(Screen Printing)으로 형성하였다. 상세하게는 위의 조건을 따른다.(참조: 표1,2 #1) The manufactured FTO transparent conductive film was provided with a functional layer (metal grid) between the substrate and the FTO transparent conductive film in order to manufacture a low resistance high transmittance transparent heating heater with a large area, wherein the functional layer was formed by screen printing. It was. In detail, the above conditions are met (see Tables 1 and 2 # 1).
저저항성 고투과율 투명발열 히터를 제작하기 위해서 약 150um 두께의 상기 기능성층을 형성하며, 그 후 약 7분의 코팅시간으로 FTO 투명전도막을 증착한다.In order to fabricate a low-resistance, high-transmittance transparent heating heater, the functional layer was formed to have a thickness of about 150 um, and then a FTO transparent conductive film was deposited with a coating time of about 7 minutes.
표 1,2에 도시한 바와 같이 #1의 메탈 그리드 두께는 150um 이고, FTO 투명전도막을 증착시킨 후 투과도를 측정한 결과 80.8%를 나타내었다. 헤이즈(Haze)는 5.4%, 면저항 5옴을 보인다. 또한 막 균일도와 견주어 말할 수 있는 저항 분포도를 도 3과 같이 나열하여 측정해 보면, 5~5.5옴의 막 균일성을 나타낸다. As shown in Tables 1 and 2, the metal grid thickness of # 1 was 150 μm, and as a result of measuring the transmittance after depositing the FTO transparent conductive film, it showed 80.8%. Haze shows 5.4% and sheet resistance of 5 ohms. In addition, when the resistance distribution chart comparable to the film uniformity is measured as shown in Fig. 3, the film uniformity is 5 to 5.5 ohms.
도 4에서 5~5.5옴의 저항분포도를 갖는 투명발열 히터에 일정 전압을 인가한 후 시간 변화에 따른 발열 특성을 그래프로 나타낸 것이다. In Figure 4 it is shown a graph of the heat generation characteristics according to the time change after applying a constant voltage to a transparent heating heater having a resistance distribution of 5 ~ 5.5 ohms.
초기 약 27도에서 55도까지 600초 내에 발열하는 것을 확인할 수 있다.
It can be seen that heat is generated within 600 seconds from the initial about 27 to 55 degrees.
<실시 예 2><Example 2>
실시 예1에서 제조된 프리커서 조건으로 스프레이 파이로졸법에 의해 박막을 형성할 수 있다. A thin film can be formed by the spray pyrosol method under the precursor condition prepared in Example 1.
이때, 제조된 FTO 투명전도막은 대면적에 저저항항의 고투과율 투명 발열 히터를 제조하기 위해 기능성층(메탈 그리드)을 기판과 FTO 투면전도막 사이에 구비하였으며, 이때 기능성 층은 스크린프린팅(Screen Printing)으로 형성한다. 상세하게는 위의 조건을 따른다.(참조: 표1,2 #2) In this case, the manufactured FTO transparent conductive film was provided with a functional layer (metal grid) between the substrate and the FTO transparent conductive film in order to manufacture a high transmittance transparent heating heater having a low resistance term in a large area, wherein the functional layer was screen printed. To form). In detail, the above conditions are met (see Tables 1 and 2 # 2).
저저항의 고투과율 투명발열 히터를 제작하기 위해서 약 180um 두께의 상기 기능성층을 형성하며, 그 후 약 8분의 코팅시간으로 FTO 투명전도막을 증착한다.In order to fabricate a low-resistance, high-transmittance transparent heating heater, the functional layer was formed to have a thickness of about 180 μm, and then a FTO transparent conductive film was deposited with a coating time of about 8 minutes.
표 1,2에 도시한 바와 같이 #2의 메탈 그리드 두께는 180um 이고, FTO 투명전도막을 증착시킨 후 투과도를 측정한 결과 76.3%를 나타내었다. 헤이즈는 7.7%, 면저항 4옴을 보인다. 또한 막 균일도와 견주어 말할 수 있는 저항 분포도를 도 3과 같이 나열하여 측정해 보면, 3.8~4.4옴의 막 균일성을 나타낸다. As shown in Tables 1 and 2, the metal grid thickness of # 2 was 180 μm, and the transmittance was measured after depositing the FTO transparent conductive film, which showed 76.3%. Haze showed 7.7% and sheet resistance of 4 ohms. In addition, when the resistance distribution chart comparable to the film uniformity is measured as shown in Fig. 3, the film uniformity is 3.8 to 4.4 ohms.
도 4에서 3.8~4.4옴의 저항분포도를 갖는 투명발열 히터에 일정 전압을 인가한 후 시간 변화에 따른 발열 특성을 그래프로 나타낸 것이다. In FIG. 4, a graph shows heat generation characteristics according to time change after applying a constant voltage to a transparent heating heater having a resistance distribution of 3.8 to 4.4 ohms.
초기 약 26도에서 47도까지 600초 내에 발열하는 것을 확인할 수 있었다.
It was confirmed that the fever within 600 seconds from the initial about 26 to 47 degrees.
<실시 예 3>≪ Example 3 >
실시 예1에서 제조된 프리커서 조건으로 스프레이 파이로졸법에 의해 박막을 형성할 수 있다. A thin film can be formed by the spray pyrosol method under the precursor condition prepared in Example 1.
이때, 제조된 FTO 투명전도막은 대면적에 저저항의 투명 발열 히터를 제조하기 위해 기능성층(메탈 그리드)을 기판과 FTO 투면전도막 사이에 구비하였으며, 이때 기능성 층은 스크린프린팅(Screen Printing)으로 형성한다. 상세하게는 위의 조건을 따른다.(참조: 표1,2 #3) In this case, the manufactured FTO transparent conductive film was provided with a functional layer (metal grid) between the substrate and the FTO transmissive conductive film in order to manufacture a transparent heating heater having a low resistance in a large area, wherein the functional layer was formed by screen printing. Form. In detail, the above conditions are met (see Tables 1 and 2 # 3).
저저항의 고투과율 투명발열 히터를 제작하기 위해서 약 200um 두께의 상기 기능성층 형성하며, 그 후 약 10분의 코팅시간으로 FTO 투명전도막을 증착한다.In order to fabricate a low-resistance, high-transmittance transparent heating heater, the functional layer was formed to a thickness of about 200 μm, and then a FTO transparent conductive film was deposited with a coating time of about 10 minutes.
표 1,2에 도시한 바와 같이 #3의 메탈 그리드 두께는 200um 이고, FTO 투명전도막을 증착시킨 후 투과도를 측정한 결과 68.5%를 나타내었다. 헤이즈는 14.2%, 면저항 3옴을 보인다. 또한 막 균일도와 견주어 말할 수 있는 저항 분포도를 도 3과 같이 나열하여 측정해 보면, 3~3.4옴의 막 균일성을 나타낸다. As shown in Tables 1 and 2, the metal grid thickness of # 3 was 200 μm, and the transmittance was measured after depositing the FTO transparent conductive film, which showed 68.5%. Haze shows 14.2% and
도 4에서 3~3.4옴의 저항분포도를 갖는 투명발열 히터에 일정 전압을 인가한 후 시간 변화에 따른 발열 특성을 그래프로 나타낸 것이다. In Figure 4 it is shown a graph of the heat generation characteristics according to the time change after applying a constant voltage to a transparent heating heater having a resistance distribution of 3 ~ 3.4 ohms.
초기 약 30도에서 69도까지 600초 내에 발열하는 것을 확인할 수 있다.It can be seen that the heat is generated within 600 seconds from about 30 degrees to 69 degrees.
Claims (6)
곡면 기판으로 모재를 형성하는 단계;
상기 모재에 금속 그리드를 형성시키는 단계;
스프레이 파이로졸 방법으로 챔버의 측면부에 부착된 노즐부 및 배기부의 상호의존관계(분사-흡입(석션)관계)를 통하여 FTO 프리커서 액적이 상기 금속 그리드가 형성된 기판과 평행하게 흐르게 함으로써 가열된 기판에 FTO가 균질한 박막을 형성하는 단계,
분무 압력 및 석션 압력을 조절함으로서 FTO 결정성장을 제어하는 단계로 구성되는 것을 특징으로 하는 저저항성 발열히터 제조방법.In the low resistance heating heater manufacturing method,
Forming a base material with a curved substrate;
Forming a metal grid on the base material;
Heated substrate by allowing the FTO precursor droplets to flow in parallel with the substrate on which the metal grid is formed through the interdependence (spray-suction) relationship between the nozzle portion and the exhaust portion attached to the side of the chamber by the spray pyrosol method Forming a homogeneous thin film on the FTO,
A method for producing a low resistance heating heater, characterized in that consisting of controlling the FTO crystal growth by adjusting the spray pressure and suction pressure.
상기 모재가 유리기판으로 형성되고, 상기 유리기판에 실버나노입자가 함유된 페이스트를 이용하여 유리기판상에 실버 그리드를 형성시키는 단계;
상기 유리 기판을 400-550도로 가열하며 스프레이 파이로졸 방식을 통하여 FTO 전도막을 형성시키는 단계를 더 포함하여 구성되는 것을 특징으로 하는 저저항성 실버 메쉬/FTO 기능성 투명전도막.The method according to claim 1 or 2,
Forming a silver grid on a glass substrate using the paste including the base material formed of a glass substrate and containing silver nanoparticles in the glass substrate;
And heating the glass substrate to 400-550 degrees to form an FTO conductive film through a spray pyrosol method.
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