KR101279610B1 - Thin film deposition method of the hard substrates and the transparent conductive substrate - Google Patents
Thin film deposition method of the hard substrates and the transparent conductive substrate Download PDFInfo
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- 238000007736 thin film deposition technique Methods 0.000 title claims 5
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- 239000002994 raw material Substances 0.000 claims abstract description 10
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- 239000010409 thin film Substances 0.000 claims description 27
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
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- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
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- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
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- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
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- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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Abstract
투명 하드기판 및 플렉시블 기판 코팅 방법에 있어서, 두 개의 롤이 수평으로 배치되고, 한 롤에서 필름이 공급되고 다른 롤에서 필름이 감기는 장치를 구비하고, 상기 롤과 롤이 이루는 평면과 동일한 평면의 90도 방향에 원료급기 및 배기노즐을 설치하고, 기판의 진행방향에 대하여 평면의 90도 방향에서 원료가 공급되고, 급기 노즐과 배기 노즐의 중심위치를 연결한 선이 기판이 위치한 면의 위치와 일치되고, 이에따라 상하면에 균일하게 원료가스가 공급되어 양면이 동일한 두께의 막을 코팅하는 단계로 구성되는 단계를 가짐에 따라, 투명 하드 기판 및 플렉시블 기판의 양면에 동시에 세라믹 코팅을 수행하는 것을 특징으로 한다.In the method of coating a transparent hard substrate and a flexible substrate, two rolls are arranged horizontally, and a device is provided in which a film is supplied on one roll and a film is wound on the other roll, and the same plane as the plane formed by the roll and the roll is provided. The raw material air supply and exhaust nozzle are installed in the 90 degree direction, the raw material is supplied in the 90 degree direction of the plane with respect to the traveling direction of the substrate, and the line connecting the center position of the air supply nozzle and the exhaust nozzle has In accordance with the above, the source gas is uniformly supplied to the upper and lower surfaces, and thus the both sides have a step of coating a film having the same thickness, and the ceramic coating is simultaneously performed on both sides of the transparent hard substrate and the flexible substrate. .
Description
본 발명에서는 플렉시블 기판 및 하드 기판의 양면에 동일한 저항과 서로 다른 저항을 갖는 FTO(Fluorine-doped Tin Oxide) 투명전도성막을 형성하는 방법에 관한 것으로, 상기 장치를 이용하여 양면에 코팅한 투명전도성막에 관한 것이다.The present invention relates to a method of forming a Fluorine-doped Tin Oxide (FTO) transparent conductive film having the same resistance and different resistances on both sides of a flexible substrate and a hard substrate. It is about.
투명전도막 (TCO: Transparent conducting oxide) 재료는 주로 금속 산화물로 구성되며, n-type semiconductor를 중심으로 연구되어 왔다. 통상적으로 물리, 화학적 증착 방법을 사용하여 SnO2, ZnO 및 In2O3 와 같은 산화물 투명전도막이 제조되고 있으며, 최근 스퍼터 방법을 이용한 대면적 롤투롤 코팅 기술이 산업적으로 활발하게 연구되고 있다. ITO 투명전도막은 디스플레이 및 터치패널 분야에서 가장 많이 활용되고 있는 반면에 차세대 박막형 실리콘 태양전지(Thin-Si)와 염료 감응형 태양전지(DSSC)는 ITO 대신에 FTO가 가장 많이 이용되고 있다. 그 이유로서 FTO 박막의 장점인 고온 내열성과 뛰어난 내화학성 및 내부식성을 갖추고 있기 때문이다.Transparent conducting oxide (TCO) materials are mainly composed of metal oxides and have been studied mainly on n-type semiconductors. Generally, oxide transparent conductive films such as SnO 2 , ZnO, and In 2 O 3 are manufactured by using physical and chemical vapor deposition methods, and a large area roll-to-roll coating technology using a sputtering method has been actively studied in the industry. ITO transparent conductive films are most commonly used in the display and touch panel fields, while FTO is the most widely used next-generation thin-film silicon solar cell (Thin-Si) and dye-sensitized solar cell (DSSC). This is because it has high temperature heat resistance, excellent chemical resistance and corrosion resistance which are advantages of FTO thin film.
그리고 FTO 제조 공정 기술은 대표적으로 스프레이 파이로졸(Sparay Pyrosol)과 상압 CVD 법을 통하여 제조된다. 전자인 경우 액상 FTO 프리커서 용액을 기상으로 미스트화(마이크로 액적 : Sn, F 프리커서, 용매, 첨가물 등 혼합액 상태)시켜 가열된 기판위에 보내서 코팅하는 기술이며, 후자인 경우 Sn과 F 함유 프리커서를 분자단위에서 증발시켜 가열된 기판위로 보내서 코팅하는 기술이다. In addition, the FTO manufacturing process technology is typically manufactured through spray pyrosol and atmospheric CVD. In the former case, the liquid FTO precursor solution is misted in a gaseous phase (microdroplets: Sn, F precursor, solvent, additives, etc.) and then coated onto a heated substrate. In the latter case, Sn and F-containing precursors are coated. Is a technique of coating by evaporating at a molecular level and sending it onto a heated substrate.
또한, 스프레이 파이로졸법은 상부에서 하부로 FTO 프리커서를 수직분사하여 증착시키는 증착 챔버를 사용함으로서 하드 기판상의 일면에 박막 표면 요철 및 헤이즈를 제어 하였으나, 최근 IT 산업의 급속한 발전으로 각 종 모바일 기기 , 광학기기, 노트북, 프린터, LCD등의 경량화 및 간소화에 따라 투명전도막 소재의 경박단소화가 이루어지는 추세이다. In addition, the spray pyrosol method controls the thin film surface unevenness and haze on one surface of a hard substrate by using a deposition chamber that vertically sprays an FTO precursor from top to bottom. However, due to the rapid development of the IT industry, various mobile devices have been developed. As the light weight and simplicity of optical devices, notebooks, printers, LCDs, etc. are reduced, the thin and short size of the transparent conductive film material is being made.
투명전도막의 경박단소화에는 유연성 및 내열성을 겸비한 기판소재가 쓰이며, 전자회로 기판의 미세화와 인접회로간의 고속전송을 위해서 양면상의 전도성이 우수한 투면전도막이 요구되어 진다. In the thin and short size of the transparent conductive film, a substrate material having flexibility and heat resistance is used, and a transparent conductive film having excellent conductivity on both sides is required for miniaturization of an electronic circuit board and high-speed transfer between adjacent circuits.
플렉시블 기판과 하드 기판의 양면에 박막을 형성해야 하는 경우, 일면을 코팅후 반대면에 재 코팅해야 하는 번거러운 공정을 필요로 하게 된다. If a thin film is to be formed on both sides of the flexible substrate and the hard substrate, it requires a cumbersome process of recoating one side after coating.
따라서 공정이 매우 복잡해지고, 시간이 많이 소요되므로, 본 발명에서는 하나의 공정 챔버에서 기판 양면에 박막을 형성할 수 있는 장치 및 그에 따른 양면 투명전도막을 포함한다.Therefore, since the process becomes very complicated and time-consuming, the present invention includes a device capable of forming a thin film on both sides of a substrate in one process chamber and a double-sided transparent conductive film accordingly.
본 발명에서는 FTO 투명전도막을 상압 CVD 및 스프레이 파이로졸법에 의하여 기판의 양면에 동시에 제조하는 방법을 제공한다.The present invention provides a method of simultaneously manufacturing the FTO transparent conductive film on both sides of the substrate by atmospheric pressure CVD and spray pyrosol method.
상기 투명전도막 코팅을 하기 위한 기판으로 내열성 폴리머 필름인 폴리이미드 (PI), 테플론수지 (PTFE), 폴리노르보닌 (PNB) 수지 및 소다라임 유리(Sodalime Glass), 저철분 유리(Low-Fe Glass)등을 포함한다. 또한 양면 투명전도막 코팅재료로서 FTO, ITO, AZO, ZnO, SnO2, IZO, GZO, TiO2 , SiO2 등과 같이 한정되지는 않는다.As a substrate for coating the transparent conductive film, polyimide (PI), Teflon resin (PTFE), polynorbornin (PNB) resin, soda lime glass, low iron glass, low iron glass, which are heat-resistant polymer films ), Etc. In addition, the double-sided transparent conductive film coating material is not limited to FTO, ITO, AZO, ZnO, SnO 2 , IZO, GZO, TiO 2 , SiO 2 and the like.
플렉시블 기판과 하드기판의 양면에 불소가 도핑된 산화주석의 전도성 박막을 코팅하기 위해서는 기판의 흐름의 방향과 수직한 방향에서 원료의 급기가 이루어져야 된다.In order to coat the conductive thin film of fluorine-doped tin oxide on both sides of the flexible substrate and the hard substrate, the raw material should be supplied in a direction perpendicular to the flow direction of the substrate.
이와 같이 기판의 진행방향에 대하여 평면의 90도 방향에서 원료가 공급되고 반대 방향에서 배기가스 노즐을 설치하여 코팅이 될 수 있도록 설계되었다.In this way, the raw material is supplied in the 90-degree direction of the plane with respect to the traveling direction of the substrate and designed to be coated by installing the exhaust gas nozzle in the opposite direction.
이 때 노즐과 배기부위의 높이와 기판의 상대적인 높이를 조절하게 되면 상하면의 박막의 코팅 두께를 임의로 조절이 가능해진다. At this time, by adjusting the height of the nozzle and the exhaust portion and the relative height of the substrate it is possible to arbitrarily adjust the coating thickness of the upper and lower surfaces.
급기 노즐과 배기 노즐은 항상 같은 높이에서 평행하여 위치하고 있고, 급기 노즐과 배기 노즐의 중심위치를 연결한 선이 기판이 위치한 면의 위치와 일치하게 되면 상하면에 균일하게 원료가스가 공급되어서 양면이 동일한 두께의 막이 코팅된다. 기판이 지나가는 면의 높이가 급기와 배기 노즐을 연결한 직선보다 위쪽에 존재하게 되면 윗면은 원료가스의 공급량이 적고 아랫면은 원료가스의 공급량이 많아서 윗면은 얇은 막이 아랫면은 두꺼운 막이 형성된다.The air supply nozzle and the exhaust nozzle are always parallel to each other at the same height, and if the line connecting the center position of the air supply nozzle and the exhaust nozzle coincides with the position of the surface on which the substrate is located, the source gas is uniformly supplied on the upper and lower sides so that both sides are the same. A thick film is coated. When the height of the surface where the substrate passes is above the straight line connecting the supply and exhaust nozzles, the upper surface has a small supply of raw material gas, and the lower surface has a large supply of raw material gas, so that the upper surface has a thin film and the lower surface has a thick film.
반대의 경우, 즉, 기판이 지나가는 면의 높이가 급기와 배기 노즐의 중심을 연결한 직선보다 낮은 곳에 위치하게 되면 상면은 두꺼운 코팅이 가능하고 하면은 얇은 코팅이 가능해진다. On the contrary, if the height of the surface through which the substrate passes is located below the straight line connecting the center of the supply and exhaust nozzles, the upper surface can be thick and the lower surface can be thin.
그러므로 필름이 이동하는 수평면의 높이와 급기/배기 노즐의 중심선의 상대적인 폭의 차이에 따라서 코팅되는 상하면의 코팅의 두께가 자유롭게 조절된다.Therefore, the thickness of the upper and lower coatings to be coated is freely adjusted according to the difference between the height of the horizontal plane through which the film moves and the relative width of the center line of the air supply / exhaust nozzle.
이 때 막의 상하면에 동일한 조성의 가스가 도포되면 상하면에는 동일한 박막이 형성되고 상하면에 다른 원료의 가스가 공급되면 다른 조성의 박막을 형성하는 것이 가능하고, 상면과 하면의 노즐을 각각 다르게 설치하는 것도 가능하다.At this time, when the gas of the same composition is applied to the upper and lower surfaces of the film, the same thin film is formed on the upper and lower surfaces, and when the gas of different raw materials is supplied to the upper and lower surfaces, it is possible to form thin films of different compositions, and the nozzles of the upper and lower surfaces may be provided differently. It is possible.
또한 단일 노즐로 코팅하는 것뿐만 아니라 여러 개의 노즐로 코팅하는 것이 가능하게 된다. 단일 노즐로 코팅하는 경우에는 기판의 상하면에 1종류의 세라믹 박막을 코팅하게 된다. 하지만, 단일노즐이 아닌 여러 개의 노즐을 사용하게 되면, 상하의 노즐이 쌍을 이루어 급기 배기가 구성되어져 상부노즐을 통하여 A 종의 가스가 공급되고 하부의 노즐을 통하여 B종의 가스가 공급된다. 이로 인해 상면에는 A종의 박막이 형성되고 하면에는 B종의 박막이 형성될 수 있다. In addition to coating with a single nozzle, it is also possible to coat with multiple nozzles. In the case of coating with a single nozzle, one type of ceramic thin film is coated on the upper and lower surfaces of the substrate. However, when a plurality of nozzles are used instead of a single nozzle, the upper and lower nozzles are paired to form an exhaust air, so that the gas of type A is supplied through the upper nozzle and the type B gas is supplied through the lower nozzle. As a result, a thin film of A type may be formed on the upper surface thereof, and a thin film of B type may be formed on the lower surface thereof.
상기 투명전도막을 코팅하기 위한 기판으로는 앞에서 언급한 플렉시블 필름 및 하드기판이 있으며, 플렉시블 필름에 무수히 작은 구멍(1~100)을 뚫어 이 구멍을 통하여 상하면의 전기전도성이 우수한 투명전도막을 만들 수도 있다. Substrates for coating the transparent conductive film include a flexible film and a hard substrate as mentioned above, and a transparent conductive film having excellent electrical conductivity on the upper and lower surfaces may be made through the hole by innumerable small holes (1 to 100). .
하나의 공정 챔버에서 플렉시블 기판과 하드 기판의 양면에 박막을 형성할 수 있는 효과도 있다.There is also an effect that a thin film can be formed on both sides of the flexible substrate and the hard substrate in one process chamber.
도 1은 종래기술의 기판의 일면에 코팅하는 노즐 및 배기시스템.
도 2는 본 발명에서 기판의 양면에 세라믹 박막을 코팅하는 장치의 개략도.
도 3은 본 발명에서 상부와 하부층에 코팅된 일종의 세라믹 박막 모식도.
도 4는 본 발명에서 상부와 하부층에 코팅된 이종의 세라믹 박막 모식도 및 기판 상하면의 전기전도성이 우수한 투명전도막.
도 5는 기판 상하면의 전기전도성이 우수한 투명전도막의 디지털 사진.
도 6은 본 발명에서 기판의 상하면에 이종의 세라믹 박막이 코팅된 전기 전도도 분포도 결과.
도 7은 본 발명에서 양면의 세라믹 박막이 코팅된 단면 SEM (Scanning Electron Micrograph) 사진.
도 8은 본 발명에서 양면의 세라믹 박막이 코팅된 상하부 각각의 단면 SEM (Scanning Electron Micrograph) 사진.
도 9는 양면의 투명전도막을 형성한 염료감응형 태양전지 개념도.
도 10은 양면의 투명전도막을 형성한 터치 패널 개념도1 is a nozzle and exhaust system for coating on one side of a substrate of the prior art.
Figure 2 is a schematic diagram of a device for coating a ceramic thin film on both sides of the substrate in the present invention.
Figure 3 is a schematic diagram of a kind of ceramic thin film coated on the upper and lower layers in the present invention.
Figure 4 is a schematic diagram of the heterogeneous ceramic thin film coated on the upper and lower layers in the present invention and the transparent conductive film excellent in the electrical conductivity of the upper and lower surfaces.
5 is a digital photograph of a transparent conductive film having excellent electrical conductivity on upper and lower surfaces of a substrate.
Figure 6 is a result of the electrical conductivity distribution coated with a heterogeneous ceramic thin film on the upper and lower surfaces of the substrate in the present invention.
Figure 7 is a cross-sectional SEM (Scanning Electron Micrograph) photograph coated with a ceramic thin film on both sides in the present invention.
FIG. 8 is a SEM (Scanning Electron Micrograph) photograph of each of the upper and lower surfaces of the ceramic thin film coated on both sides in the present invention. FIG.
9 is a conceptual diagram of a dye-sensitized solar cell having a double-sided transparent conductive film formed thereon.
10 is a conceptual view illustrating a touch panel on which double-sided transparent conductive films are formed.
실시예Example 1: One: FTOFTO 투명전도막 형성 공정 Transparent conductive film forming process
본 발명의 스프레이 파이로졸 코팅방법에 있어서 산화주석의 전구체는 SnCl45H2O, (C4H9)2Sn(CH3COO)2, (CH3)2SnCl2, (C4H9)3SnH, SnCl4 등 주석 함유 유기금속 화합물이 사용될 수 있다. 산화주석에 도핑되는 불소 공급원으로 작용하는 불소 화합물로는 NH4F, CF3Br, CF2Cl2, CH3CClF2, CF3COOH, CH3CHF2, HF 등 다양한 불소 공급원이 사용될 수 있으며, 특별히 한정되지 않는다. Sn/F 비율은 소정의 비율이 되도록 혼합하여 FTO 프리커서를 제조한다. 용매는 물과 알콜, 또는 이들의 혼합 시스템을 사용할 수 있으나 안정성 측면에서는 물과 에탄올 시스템을 사용할 수 없고 물과 에탄올을 혼합하여 사용할 수 있다. 통상적으로 5wt% 에탄올 (H2O비)이 용매로 사용될 수 있다.In the spray pyrosol coating method of the present invention, the precursor of tin oxide is SnCl 4 5H 2 O, (C 4 H 9 ) 2 Sn (CH 3 COO) 2 , (CH 3 ) 2 SnCl 2 , (C 4 H 9 3 ) tin-containing organometallic compounds such as SnH and SnCl 4 may be used. Various fluorine sources such as NH 4 F, CF 3 Br, CF 2 Cl 2 , CH 3 CClF 2 , CF 3 COOH, CH 3 CHF 2 , HF can be used as the fluorine source that acts as a fluorine source doped with tin oxide. It does not specifically limit. The Sn / F ratio is mixed so as to be a predetermined ratio to produce an FTO precursor. The solvent may be water and alcohol, or a mixing system thereof, but in terms of stability, water and ethanol system may not be used, and water and ethanol may be mixed. Typically 5 wt% ethanol (H 2 O ratio) may be used as the solvent.
FTO 전구체 용액은 노즐 (스프레이 노즐, 초음파 스프레이 노즐, 초음파 미스트 분무)을 통하여 캐리어 가스와 함께 기판의 양면에 분무되며, 분무된 마이크로 액적은 양면의 기판상에 증착된다. 이 때 증착챔버에는 적절한 배기 시스템을 주어 반응가스 및 미반응체를 뽑아내준다. 노즐을 통하여 전구체 마이크로 액적을 형성하는 방법은 일반적인 스프레이 노즐 및 슬릿 노즐을 사용할 수 있으나, 이와 같은 방법은 비교적 큰 액적이 형성되는 경향이 있다. 좀 더 미세한 액적을 형성시키기 위해서는 초음파 분무를 통하여 초미세 미스트 전구체를 1차적으로 형성시키고 이를 캐리어 가스 시스템 및 벤트 시스템을 통하여 적절하게 증착 챔버로 수송하는 것이 바람직하다.
The FTO precursor solution is sprayed on both sides of the substrate with the carrier gas through a nozzle (spray nozzle, ultrasonic spray nozzle, ultrasonic mist spray), and the sprayed micro droplets are deposited on the substrate on both sides. At this time, the deposition chamber is provided with an appropriate exhaust system to extract the reaction gas and the unreacted material. The method of forming the precursor microdroplets through the nozzle may use a general spray nozzle and a slit nozzle, but such a method tends to form relatively large droplets. In order to form finer droplets, it is desirable to first form the ultrafine mist precursor via ultrasonic spraying and transport it to the deposition chamber as appropriate through the carrier gas system and the vent system.
실시예Example 2: 2: FTOFTO 프리커서Precursor 제조 방법 Manufacturing method
FTO 프리커서 용액은 SnCl45H20를 3차 증류수에 녹여 0.68 M이 되게 하고 F 도핑제로서 NH4F를 에탄올 용매에 녹여 1.2 M로 한 후 이 두 용액을 혼합 교반시키고, 필터링 하여 제조하였다. 또한 코팅용액은 SnCl45H2O를 순수한 D.I 물에 5%의 에탄올을 혼합한 용매에 0.68M이 되도록 혼합하고 교반하여 제조하였으며, F의 소스로는 NH4F를 F/Sn의 비가 1.76이 되도록 하여 합성하였다. 또한 전구체 용액은 다양한 형태의 FTO막을 제조하기 위하여 상기 용액 조성 이외에도 알콜류, 에틸렌 글리콜(Ethylene Glycol)를 부수적으로 첨가할 수 있다.FTO precursor solution was prepared by dissolving SnCl 4 5H 2 0 in tertiary distilled water to 0.68 M, and dissolving NH 4 F as an F dopant in ethanol to 1.2 M, then mixing and stirring the two solutions and filtering. . In addition, the coating solution was prepared by mixing and stirring SnCl 4 5H 2 O to 0.68 M in a solvent in which 5% ethanol was mixed with pure DI water, and the source of F was NH 4 F with a ratio of F / Sn of 1.76. It was synthesize | combined as much as possible. In addition, the precursor solution may additionally add alcohols, ethylene glycol (Ethylene Glycol) in addition to the solution composition in order to prepare a variety of FTO film.
F 도핑량을 조절하기 위하여 NH4F의 량을 0.1에서 3 M까지 변화시키거나 불산(HF)를 0-2M 첨가할 수도 있다. 따라서 본 FTO 막 제조용 프리커서 용액은 위에서 보여준 조성에 한정되는 것은 아니다.
In order to control the amount of F doping, the amount of NH 4 F may be changed from 0.1 to 3 M, or 0-2 M of hydrofluoric acid (HF) may be added. Therefore, the precursor solution for preparing the FTO membrane is not limited to the composition shown above.
실시예Example 3: 3: 프리커서Precursor 마이크로 Micro 액적Droplet ( ( 미스트화Mist 방법) Way)
FTO 프리커서를 기상으로 무화시켜 프리커서 플로우를 얻기 위하여 프리커서 소스부에는 스프레이 코팅법, 초음파 분무 코팅법, 초음파 스프레이 분무법 3가지 장치가 별도로 연결된다.The spray source method, the ultrasonic spray coating method, and the ultrasonic spray spray method are separately connected to the precursor source part to obtain the precursor flow by vaporizing the FTO precursor in the gas phase.
간단히 살펴보면, 스프레이 코팅법은 미세한 노즐부를 통하여 외부의 가스가 팽창되어 나갈 때 액체를 끌어당기는 힘이 생겨 액상 프리커서를 마이크로 액적으로 분무시키는 방법이다. 초음파 분무법은 일반 초음파 가습기처럼 액상 전구체를 초음파 진동자로 진동시켜 무화 시킨 후 단순히 캐리어 기체로 운반시켜서 코팅하는 방법이다. 마지막으로 초음파 스프레이 분무법은 초음파 진동자 부분을 스프레이 노즐처럼 변화시켜서 무화된 프리커서를 스프레이 원리에 의하여 분사시켜서 코팅하는 방법이다.In brief, the spray coating method is a method of spraying the liquid precursor into the micro droplets as the force to attract the liquid when the external gas is expanded through the fine nozzle unit. Ultrasonic spraying is a method in which a liquid precursor is vibrated by an ultrasonic vibrator and atomized by a carrier gas, just like a general ultrasonic humidifier. Finally, ultrasonic spray spraying is a method in which an ultrasonic vibrator portion is changed like a spray nozzle to spray the atomized precursor according to the spray principle.
nmThickness
nm
비교예Comparative example 1: One:
실시예 2에서 제조된 프리커서 조건으로 실시예 1의 방법으로 여러 종류의 세라믹 박막을 형성하였다. 이때 제조된 양면상의 FTO 투명전도막은 박막의 종류에 따라서(sample 1~5) 박막의 두께 및 표면저항의 변화가 나타나고 전자 홀 특성 분석시 전자이동도 및 전자갯수 그리고 비저항의 변화값을 나타내었다. 상세하게는 위의 조건을 따른다. (참조: 표 1)Various kinds of ceramic thin films were formed by the method of Example 1 under the precursor condition prepared in Example 2. At this time, the prepared double-sided FTO transparent conductive film showed the change of thickness and surface resistance of the thin film according to the type of thin film (samples 1 ~ 5) and the change of electron mobility, number of electrons and specific resistance when analyzing electron hole characteristics. In detail, the above conditions are followed. (See Table 1)
도 7 도 8은 실시예1에서 형성된 양면의 FTO투명전도막의 미세구조 및 박막두께를 나타내는 FE-SEM 사진이다. 기판의 상하면의 FTO 투명전도막이 형성되어 있으며, 기판의 두께는 약 60㎛ 이고, FTO 박막의 두께는 약 1㎛이하를 나타내고 있다.
7 is a FE-SEM photograph showing the microstructure and thin film thickness of the double-sided FTO transparent conductive film formed in Example 1. An FTO transparent conductive film on the upper and lower surfaces of the substrate was formed, and the thickness of the substrate was about 60 µm, and the thickness of the FTO thin film was about 1 µm or less.
Claims (7)
두 개의 롤이 수평으로 배치되고,
한 롤에서 필름이 공급되고 다른 롤에서 필름이 감기는 장치를 구비하고,
상기 롤과 롤이 이루는 평면과 동일한 평면의 90도 방향에 원료급기 및 배기노즐을 설치하고,
기판의 진행방향에 대하여 평면의 90도 방향에서 원료가 공급되고,
급기 노즐과 배기 노즐의 중심위치를 연결한 선이 기판이 위치한 면의 위치와 일치되고, 이에따라 상하면에 원료가스가 공급되어 양면이 동일한 두께의 막을 코팅하는 단계로 구성되는 단계를 가짐에 따라, 투명 하드 기판 및 플렉시블 기판의 양면에 동시에 세라믹 코팅을 수행하는 것을 특징으로 하는 하드기판 및 플렉시블 기판의 투명전도성 박막 증착 방법.In the transparent conductive thin film deposition method of a hard substrate and a flexible substrate,
Two rolls are placed horizontally,
With a device in which the film is fed in one roll and the film is wound in another roll,
The raw material supply and exhaust nozzles are installed in the 90 degree direction of the same plane as the plane formed by the rolls,
The raw material is supplied in a 90 degree direction of the plane with respect to the traveling direction of the substrate,
As the line connecting the center position of the air supply nozzle and the exhaust nozzle coincides with the position of the surface on which the substrate is located, the raw material gas is supplied on the upper and lower surfaces so that both sides have a step of coating a film having the same thickness. A method for depositing a transparent conductive thin film on a hard substrate and a flexible substrate, wherein the ceramic coating is simultaneously performed on both surfaces of the hard substrate and the flexible substrate.
The method of claim 6, wherein the transparent hard substrate and the flexible substrate on which the transparent conductive film is formed are used in a touch panel, a dye-sensitized solar cell, and a thin film solar cell.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100624764B1 (en) | 2004-06-25 | 2006-09-20 | 한국전기연구원 | Light-sensitized solar cell having plural light-sensitizing layers and mafacturing method thereof |
| KR20100096642A (en) * | 2009-02-25 | 2010-09-02 | 부산대학교 산학협력단 | Manufacturing method of compound sollar cell using window layer by atmospheric plasma treatment and the compound sollar cell |
| KR20100096645A (en) * | 2009-02-25 | 2010-09-02 | 부산대학교 산학협력단 | Flexible transparent conducting plate using plasma controlled flexible substrate and the manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100624764B1 (en) | 2004-06-25 | 2006-09-20 | 한국전기연구원 | Light-sensitized solar cell having plural light-sensitizing layers and mafacturing method thereof |
| KR20100096642A (en) * | 2009-02-25 | 2010-09-02 | 부산대학교 산학협력단 | Manufacturing method of compound sollar cell using window layer by atmospheric plasma treatment and the compound sollar cell |
| KR20100096645A (en) * | 2009-02-25 | 2010-09-02 | 부산대학교 산학협력단 | Flexible transparent conducting plate using plasma controlled flexible substrate and the manufacturing method |
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