WO2016068621A1 - Flexible thermochromic film - Google Patents

Flexible thermochromic film Download PDF

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Publication number
WO2016068621A1
WO2016068621A1 PCT/KR2015/011505 KR2015011505W WO2016068621A1 WO 2016068621 A1 WO2016068621 A1 WO 2016068621A1 KR 2015011505 W KR2015011505 W KR 2015011505W WO 2016068621 A1 WO2016068621 A1 WO 2016068621A1
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film
flexible
thermochromic
glass substrate
vanadium oxide
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PCT/KR2015/011505
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French (fr)
Korean (ko)
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이용욱
김봉준
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부경대학교 산학협력단
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Publication of WO2016068621A1 publication Critical patent/WO2016068621A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • 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
    • C03C4/00—Compositions for glass with special properties
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/66—Chemical treatment, e.g. leaching, acid or alkali treatment
    • C03C25/68—Chemical treatment, e.g. leaching, acid or alkali treatment by etching
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/26—Thermosensitive paints
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 

Definitions

  • the present invention relates to a flexible thermochromic film having a thermochromic function, and more particularly, because it can selectively block infrared rays above a specific temperature, it can be applied to the glass of a building or a vehicle to suppress an increase in room temperature. It relates to a flexible thermochromic film.
  • Smart window technology is a technology related to active and intelligent glass windows that can save energy by dramatically improving the heating and cooling load of buildings by automatically blocking the entrance and exit of infrared rays, the main culprit of heat energy transfer, while maintaining the transparency of the glass windows.
  • These include low-emissivity coating, thermochromic, electrochromic, polymer-dispersed liquid crystal (PDLC), and suspended-particle display (SPD).
  • PDLC polymer-dispersed liquid crystal
  • SPD suspended-particle display
  • thermochromic functions include vanadium dioxide (VO 2 ), titanium dioxide (TiO 2 ), iron oxide (Fe 2 O 3 ), and nickel oxide (NiO 2 ), but VO 2 is the most active thermochromic material. Is going on.
  • thermochromic properties are limited in application despite the excellent thermochromic properties because high quality crystals are formed only on inflexible and size-restricted substrates such as silicon (Si) and sapphire (Al 2 O 3 ) at high temperatures above 500 o C. Has been.
  • the present invention relates to a technology for manufacturing a high-quality VO 2 thin film-based film having flexibility and size without limitation in order to implement an energy-saving smart window applicable to a smart device equipped with a curved window or a flexible display.
  • Patent Document 1 Registration No. 1013998990000, Registration Date 2014.05.21, Thermochromic Window
  • Patent Document 2 Registration No. 1012756310000, registration date 2013.06.11, Graphene-based VO 2 laminate for smart windows and manufacturing method
  • Patent Document 3 Publication No. 1020140050249, Publication Date April 29, 2014, Method for producing tungsten-doped vanadium dioxide
  • Non-Patent Document 1 Y. Gao, S. Wang, H. Luo, L. Dai, C. Cao, Y. liu, Z. Chen and M. Kanehira, “Enhanced chemical stability of VO 2 nanoparticles by the formation of SiO 2 / VO 2 core / shell structures and the application to transparent and flexible VO 2 -based composite foils with excellent thermochromic properties for solar heat control ”, Energy & Environmental Science 5, 6104-6110 (2012).
  • Non-Patent Document 2 H. Kim, Y. Kim, KS Kim, HY Jeong, AR. Jang, SH han, DH Yoon, KS Suh, HS Shin, T. Kim, and W. S Yang, “Flexible thermochromic window based on hybridized VO 2 / Graphene”, ACS Nano 7, 5769-5776 (2013).
  • An object of the present invention is to provide a flexible thermochromic film having excellent flexibility of infrared ray blocking characteristics at a specific temperature using VO 2 .
  • an embodiment of the present invention is a flexible glass substrate; A vanadium oxide thin film formed on the flexible glass substrate; And it provides a swimming thermochromic film consisting of a protective film deposited on the vanadium oxide thin film.
  • the present invention provides a flexible thermochromic material by growing a material having a thermochromic property on a flexible substrate, and forming a protective, adhesive, reflective film, etc. on one surface of the manufactured thin film. It is characterized by the method of manufacturing a film. Use of tens or hundreds of microns thick glass to intense heat as the flexible substrate, and sputtering the VO 2 thin film on the glass substrate in the appropriate conditions of temperature (sputter), pulsed laser deposition (pulse laser deposition), soljel (sol-gel) Grow in such a way.
  • thermochromic films Since VO 2 is generally grown at a high temperature, sapphire or silicon substrates and the like have been commonly used until now, but examples of growth on a flexible substrate such as the glass substrate have not been reported. Only recently, the results of the production of VO 2 based thermochromic films by growing nanoparticles or nanowires by hydrothermal method, separating them, mixing them in a solution, and then spraying a flexible film with an appropriate thickness, have been recently reported. However, there is a disadvantage in that the thermochromic property is significantly reduced compared to VO 2 manufactured by the conventional method.
  • the flexible thermochromic film according to the present invention is applicable to an object having a curved surface because it is composed of a flexible substrate, and shows an excellent thermochromic property similar to that of the VO 2 fabricated on a non-flexible substrate, thus the application range. There is an effect that can greatly widen.
  • VO 2 grown on a flexible substrate can be utilized not only for electronic devices but also for various sensor devices such as temperature / light / pressure sensors. Research using VO 2 is continuously expanding, and switching phenomenon using bending as an electronic device has been reported, and this phenomenon can be applied to a pressure sensor.
  • the use of a voltage sensor as a temperature sensor has been reported, and recently, many studies have been conducted on VO 2 thin films for metamaterials and optical devices.
  • thermochromic film composed of VO 2 , a protective film, and an antireflection film grown on a flexible glass substrate having a thickness of several tens or hundreds of micrometers.
  • thermochromic film made of a protective film and an antireflection film after removing the glass substrate after VO 2 is grown on a tens or hundreds of micrometer thick glass substrates.
  • 3 is a graph showing resistance characteristics according to temperature of VO 2 grown on a flexible glass substrate.
  • thermochromic characteristic curve of VO 2 is a graph showing a typical thermochromic characteristic curve of VO 2 .
  • FIG. 5 is a graph illustrating a comparison of transmittance characteristics according to temperature of VO 2 thin films when tungsten (W) is doped and not doped.
  • thermochromic film 6 is a device schematic for producing a large area flexible thermochromic film.
  • the flexible glass substrate 100 has a thickness of several tens of micrometers and can be easily bent, bent in a range that is not broken, and light. Unlike plastic, glass is a stable material that does not react to gas or moisture, blocks heat, and has the advantage of being transparent.
  • the flexible glass substrate may be variously applied to a display panel, an electronic paper, a secondary battery, a solar cell, etc., and belongs to an important material in the present invention. In addition, it does not deform even at a high temperature of 500 ° C., and thus has excellent thermal characteristics.
  • VO 2 (110) is depending on the oxygen content VO, VO 2 , V 2 O 5 , V 2 O 3 , V 3 O 7 , V 4 O 7 , V 5 O 9 , V 6 O 11 , V 6 O 13 , Various crystal phases such as V 7 O 13 are formed, V 2 O 3 has a metal resistance at room temperature, VO 2 is a few M ⁇ , V 2 O 5 is an insulating phase of several tens of G ⁇ .
  • VO 2 has a characteristic of changing from an insulator to a metal in the vicinity of 70 ° C, which has been of great interest in terms of application.
  • the resistance is sensitive to external variables such as temperature, light, and pressure, so that the temperature sensor and the light sensor For the application to strain sensors, research is being actively conducted.
  • sapphire is mainly manufactured by sputtering deposition method, pulse laser deposition method, sol-gel method etc. at high temperature above 500 °C, and resistance between room temperature (25 °C) and high temperature ( ⁇ 100 °C) The rate of change is about 10,000 times.
  • SiO 2 , Si 3 N 4, or the like having no substrate crystallinity is used, a difference in resistance change of about 1,000 times is shown.
  • a VO 2 was grown at 500 ° C. by a sputtering deposition method using a 50 ⁇ m thick glass substrate.
  • polymer organic materials such as PET, PMMA, and PI (Polyimide) were used as the VO 2 protective film, and an anti-reflection film was deposited on the flexible glass substrate as shown in FIG.
  • Figure 2 shows a cross-sectional view of the flexible thermochromic film after removing the flexible glass substrate.
  • the glass can be easily etched by hydrofluoric acid (HF).
  • HF hydrofluoric acid
  • a first coating on the PET such as VO 2 highly transparent polymer film for protection and support of the VO 2, and then eliminates the glass.
  • the protective PET film on the glass-removed surface (103 in FIG. 2), a flexible thermochromic film based on VO 2 having excellent thermochromic properties may be manufactured.
  • FIG. 3 is a result of measuring the resistance characteristics according to the temperature of the VO 2 thin film grown on the flexible glass substrate.
  • a phase transition from the insulator to the metal occurs around 70 ° C, and the resistance change rate is about 100 times.
  • the temperature is reduced, a phase transition from metal to insulator occurs around 60 ° C, and hysteresis characteristic of resistance change with temperature occurs. This result shows that the VO 2 phase was formed on the glass substrate.
  • Figure 4 shows the change in transmittance at room temperature (25 °C) and high temperature (90 °C) as a result of the preliminary report on the VO 2 thin film grown at a high temperature on a non-flexible substrate, the thermochromic efficiency before and after the phase transition in the infrared band
  • the total transmittance can be expressed as a value obtained by subtracting the transmittance after the phase transition (%).
  • the thermochromic efficiency is ⁇ 50%, and in the visible light band, the thermochromic efficiency is 0 to 10%.
  • Figure 5 is showing the result of measuring the transmittance at 4000nm changes in temperature of this thin film as a study reported in the group VO 2 and the tungsten (W) is doped 1- x W x V 2 O thin film, VO 2
  • the thin film has a heat dissipation efficiency of ⁇ 75% and the V 1- x W x O 2 thin film with thermochromic temperature controlled at ⁇ 45%.
  • FIG. 6 shows a schematic diagram of an apparatus for manufacturing a flexible thermochromic film to a size applicable to a glass window of an actual building, and a rectangular sputter gun was used as a roll-to-roll method.
  • the roll-to-roll manufacturing method is also a commonly used method for mass-producing flexible solar cells, and is a suitable equipment for large-area manufacturing of flexible thermochromic film of the present patent.
  • the in-line process is carried out in a vacuum state, the entire process may be divided into each step as necessary, may also proceed to each step in-line process.
  • VO 2 is deposited in the sputter system 210 capable of depositing a uniform thickness on the flexible glass substrate 200 wound in a roll shape.
  • a high temperature plate heater capable of maintaining a temperature of about 500 ° C.
  • an appropriate gas atmosphere such as argon (Ar) and oxygen (O 2 ) is required.
  • VO 2 may be deposited in a gas atmosphere.
  • a high purity metal vanadium target, or V 2 O 5 oxide target, may be used to deposit VO 2 by the sputtering method.
  • a protective film 220 PET is coated on the VO 2 .
  • the protective film not only acts as a protective film of VO 2 but also serves as a supporting film that can support VO 2 when the flexible glass substrate is etched.
  • the structure of PET / VO 2 / Glass becomes the flexible glass substrate thermochromic film structure shown in FIG. 1 by coating the antireflection film on the flexible glass substrate.
  • the next step is to remove the flexible glass substrate 230 where the flexible glass substrate of the film having the PET / VO 2 / Glass structure is completely removed from the etching vessel.
  • the etching rate can be controlled by dilution with an appropriate ratio with water using hydrofluoric acid as an etching solution.
  • the residual hydrofluoric acid is washed with distilled water (DI water) and then dried.
  • DI water distilled water
  • the glass substrate is etched to the final step once again to protect the VO 2 coated with a PET film 240 to the VO 2 side.
  • thermochromic film shown in Figure 2 by coating an antireflection film on the PET in order to increase the thermochromic efficiency.
  • the coating of TiO 2 on PET may give an effect of varying the color of the film as well as self-cleaning.

Abstract

The present invention relates to a flexible thermochromic film capable of obtaining an excellent thermochromic effect by depositing vanadium oxide on a flexible glass substrate. The flexible thermochromic film can be manufactured by protecting vanadium oxide using a highly transparent polymer film, such as PET, through a technique in which the flexible glass substrate is removed to obtain a vanadium oxide thin film. In addition, the thermochromic efficiency can be increased by depositing an anti-reflective film on the protective film, and thermochromic performance is allowable at a particular temperature by using a doping material to change the thermochromic temperature.

Description

유연 열변색 필름Flexible Thermochromic Film
본 발명은 열변색 기능을 갖는 유연한 열변색 필름에 관한 것으로, 더욱 상세하게는, 특정 온도 이상에서 적외선만을 선택적으로 차단할 수 있기 때문에 건물이나 자동차의 유리에 적용되어 실내온도의 상승을 억제할 수 있는 유연 열변색 필름에 관한 것이다.The present invention relates to a flexible thermochromic film having a thermochromic function, and more particularly, because it can selectively block infrared rays above a specific temperature, it can be applied to the glass of a building or a vehicle to suppress an increase in room temperature. It relates to a flexible thermochromic film.
스마트 윈도우 기술은 유리창의 투명성은 유지하면서 열에너지 전달의 주범인 적외선의 출입을 자동으로 차단함으로써 건물의 냉난방 부하를 획기적으로 개선하여 에너지를 절감할 수 있는 능동적이고 지능적인 유리창에 관한 기술이며, 이러한 기술에는 저방사 코팅(low-emissivity coating), 열변색(thermochromic), 전기변색(electrochromic), PDLC(polymer-dispersed liquid crystal), SPD(suspended-particle display) 등이 있고, 특히 열변색 기반 스마트 윈도우는 특정온도 이상에서 적외선을 차단하는 기능이 있어 가장 큰 시장이 형성되어 있다. Smart window technology is a technology related to active and intelligent glass windows that can save energy by dramatically improving the heating and cooling load of buildings by automatically blocking the entrance and exit of infrared rays, the main culprit of heat energy transfer, while maintaining the transparency of the glass windows. These include low-emissivity coating, thermochromic, electrochromic, polymer-dispersed liquid crystal (PDLC), and suspended-particle display (SPD). The ability to block infrared rays above a certain temperature has created the largest market.
열변색 기능을 갖는 물질에는 이산화바나듐(VO2), 이산화티타늄(TiO2), 산화철(Fe2O3), 산화니켈(NiO2) 등이 있지만, VO2가 대표적인 열변색 소재로서 가장 활발한 연구가 진행되고 있다. Materials that have thermochromic functions include vanadium dioxide (VO 2 ), titanium dioxide (TiO 2 ), iron oxide (Fe 2 O 3 ), and nickel oxide (NiO 2 ), but VO 2 is the most active thermochromic material. Is going on.
그러나, VO2는 500oC 이상의 고온에서 실리콘(Si), 사파이어(Al2O3) 등 유연성이 없고 크기에 제한이 있는 기판에서만 양질의 결정이 형성되어 우수한 열변색 특성에도 불구하고 응용에 한계가 있어 왔다. However, VO 2 is limited in application despite the excellent thermochromic properties because high quality crystals are formed only on inflexible and size-restricted substrates such as silicon (Si) and sapphire (Al 2 O 3 ) at high temperatures above 500 o C. Has been.
본 발명은 곡면형태의 창이나 플렉서블 디스플레이를 탑재한 스마트 기기에 적용 가능한 에너지 절감형 스마트 윈도우를 구현하기 위해 유연성을 가지고 크기에 제한이 없는 양질의 VO2 박막 기반 필름을 제작하는 기술에 관한 것이다.The present invention relates to a technology for manufacturing a high-quality VO 2 thin film-based film having flexibility and size without limitation in order to implement an energy-saving smart window applicable to a smart device equipped with a curved window or a flexible display.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 등록번호 1013998990000, 등록일자 2014.05.21, 써모크로믹 윈도우(Patent Document 1) Registration No. 1013998990000, Registration Date 2014.05.21, Thermochromic Window
(특허문헌 2) 등록번호 1012756310000, 등록일자 2013.06.11, 스마트 윈도우용 그래핀 기반 VO2 적층체 및 제조방법(Patent Document 2) Registration No. 1012756310000, registration date 2013.06.11, Graphene-based VO 2 laminate for smart windows and manufacturing method
(특허문헌 3) 공개번호 1020140050249, 공개일자 2014.04.29, 텅스텐이 도핑된 이산화바나듐의 제조 방법(Patent Document 3) Publication No. 1020140050249, Publication Date April 29, 2014, Method for producing tungsten-doped vanadium dioxide
[비특허문헌][Non-Patent Documents]
(비특허문헌 1) Y. Gao, S. Wang, H. Luo, L. Dai, C. Cao, Y. liu, Z. Chen and M. Kanehira, “Enhanced chemical stability of VO2 nanoparticles by the formation of SiO2/VO2 core/shell structures and the application to transparent and flexible VO2-based composite foils with excellent thermochromic properties for solar heat control”, Energy & Environmental Science 5, 6104-6110 (2012).(Non-Patent Document 1) Y. Gao, S. Wang, H. Luo, L. Dai, C. Cao, Y. liu, Z. Chen and M. Kanehira, “Enhanced chemical stability of VO 2 nanoparticles by the formation of SiO 2 / VO 2 core / shell structures and the application to transparent and flexible VO 2 -based composite foils with excellent thermochromic properties for solar heat control ”, Energy & Environmental Science 5, 6104-6110 (2012).
(비특허문헌 2) H. Kim, Y. Kim, K. S. Kim, H. Y. Jeong, A-R. Jang, S. H. han, D. H. Yoon, K. S. Suh, H. S. Shin, T. Kim, and W. S Yang, “Flexible thermochromic window based on hybridized VO2/Graphene”, ACS Nano 7, 5769-5776 (2013).(Non-Patent Document 2) H. Kim, Y. Kim, KS Kim, HY Jeong, AR. Jang, SH han, DH Yoon, KS Suh, HS Shin, T. Kim, and W. S Yang, “Flexible thermochromic window based on hybridized VO 2 / Graphene”, ACS Nano 7, 5769-5776 (2013).
본 발명의 과제는 VO2를 이용하여 특정온도에서 적외선 차단 특성이 뛰어난 유연성이 있는 유연 열변색 필름을 제공하는 것이다.An object of the present invention is to provide a flexible thermochromic film having excellent flexibility of infrared ray blocking characteristics at a specific temperature using VO 2 .
상기 기술적 과제를 달성하기 위하여, 본 발명의 일실시예는 유연 유리 기판; 상기 유연 유리 기판 상에 형성된 바나듐산화물 박막; 및 상기 바나듐산화물 박막 위에 증착된 보호막으로 구성된 유영 열변색 필름을 제공한다.In order to achieve the above technical problem, an embodiment of the present invention is a flexible glass substrate; A vanadium oxide thin film formed on the flexible glass substrate; And it provides a swimming thermochromic film consisting of a protective film deposited on the vanadium oxide thin film.
상기 목적을 달성하기 위해 제안된 본 발명은 유연한 기판에 열변색 특성이 있는 물질을 박막으로 성장시키고, 보호용, 접착성, 반사용 필름 등을 상기 제작된 박막의 어느 한쪽 면에 형성함으로써 유연 열변색 필름을 제작하는 방법에 대한 것을 특징으로 하고 있다. 유연한 기판으로서 열에 강한 수십 또는 수백 마이크로미터 두께의 유리를 사용하며, 고온의 적합한 조건에서 상기 유리 기판 위에 VO2 박막을 스퍼터(sputter), 펄스 레이저 증착(pulse laser deposition), 솔젤(sol-gel) 등의 방법으로 성장한다. VO2는 일반적으로 고온에서 성장되기 때문에 현재까지는 사파이어 또는 실리콘 기판 등이 보편적으로 사용되어 왔으나, 상기 유리 기판과 같은 유연 기판 위에 성장한 예는 보고된 바가 없다. 단지, 나노 입자 또는 나노 와이어를 용액성장법(hydrothermal method)으로 성장하여 분리 후 용액에 섞은 후 유연한 필름에 적절한 두께로 분사하여 VO2 기반 열변색 필름을 제작한 결과는 최근에 보고되었다. 하지만, 기존 방식으로 제작된 VO2에 비해 열변색 특성이 크게 저하된다는 단점이 있다.In order to achieve the above object, the present invention provides a flexible thermochromic material by growing a material having a thermochromic property on a flexible substrate, and forming a protective, adhesive, reflective film, etc. on one surface of the manufactured thin film. It is characterized by the method of manufacturing a film. Use of tens or hundreds of microns thick glass to intense heat as the flexible substrate, and sputtering the VO 2 thin film on the glass substrate in the appropriate conditions of temperature (sputter), pulsed laser deposition (pulse laser deposition), soljel (sol-gel) Grow in such a way. Since VO 2 is generally grown at a high temperature, sapphire or silicon substrates and the like have been commonly used until now, but examples of growth on a flexible substrate such as the glass substrate have not been reported. Only recently, the results of the production of VO 2 based thermochromic films by growing nanoparticles or nanowires by hydrothermal method, separating them, mixing them in a solution, and then spraying a flexible film with an appropriate thickness, have been recently reported. However, there is a disadvantage in that the thermochromic property is significantly reduced compared to VO 2 manufactured by the conventional method.
본 발명에 따른 상기 유연 열변색 필름은 유연 기판으로 구성되어 있으므로 곡면이 있는 물체에도 적용 가능하며, 비유연 기판에 제작되는 VO2의 열변색 특성과 유사한 수준의 우수한 열변색 특성을 보이므로 응용 범위를 크게 넓힐 수 있다는 효과가 있다. 또한, 유연 기판에 성장된 VO2는 전자소자 뿐만 아니라 온도/광/압력 센서 등 다양한 센서 소자로도 활용이 가능하다. VO2를 이용한 연구는 지속적으로 확장되고 있는 추세이며, 전자소자로서 굽힘(bending)을 이용한 스위칭 현상이 보고되었고, 이러한 현상은 압력 센서에 응용될 수 있다. 또한, 전압 펄스를 이용한 온도 센서로의 사용도 보고되었으며, 최근에는 메타물질 (metamaterial)과 광소자 관련 연구에도 VO2 박막이 다수 사용되어 활발한 연구가 진행되고 있다.The flexible thermochromic film according to the present invention is applicable to an object having a curved surface because it is composed of a flexible substrate, and shows an excellent thermochromic property similar to that of the VO 2 fabricated on a non-flexible substrate, thus the application range. There is an effect that can greatly widen. In addition, VO 2 grown on a flexible substrate can be utilized not only for electronic devices but also for various sensor devices such as temperature / light / pressure sensors. Research using VO 2 is continuously expanding, and switching phenomenon using bending as an electronic device has been reported, and this phenomenon can be applied to a pressure sensor. In addition, the use of a voltage sensor as a temperature sensor has been reported, and recently, many studies have been conducted on VO 2 thin films for metamaterials and optical devices.
도 1은 수십 또는 수백 마이크로미터 두께의 유연 유리 기판에 성장된 VO2와 보호용 필름, 반사방지막으로 이루어진 유연 유리 기판 열변색 필름의 단면도이다.1 is a cross-sectional view of a flexible glass substrate thermochromic film composed of VO 2 , a protective film, and an antireflection film grown on a flexible glass substrate having a thickness of several tens or hundreds of micrometers.
도 2는 VO2가 수십 또는 수백 마이크로미터 두께 유리 기판에 성장된 후 유리 기판을 제거한 후 보호용 필름, 반사방지막으로 이루어진 유연 열변색 필름의 단면도이다.2 is a cross-sectional view of a flexible thermochromic film made of a protective film and an antireflection film after removing the glass substrate after VO 2 is grown on a tens or hundreds of micrometer thick glass substrates.
도 3은 유연 유리 기판에 성장된 VO2의 온도에 따른 저항 특성을 나타낸 그래프이다.3 is a graph showing resistance characteristics according to temperature of VO 2 grown on a flexible glass substrate.
도 4는 VO2의 대표적인 열변색 특성 곡선을 나타낸 그래프이다.4 is a graph showing a typical thermochromic characteristic curve of VO 2 .
도 5는 텅스텐(W)이 도핑되었을 때와 도핑되지 않았을 때 VO2 박막의 온도에 따른 투과율 특성 비교를 나타낸 그래프이다.FIG. 5 is a graph illustrating a comparison of transmittance characteristics according to temperature of VO 2 thin films when tungsten (W) is doped and not doped.
도 6은 대면적 유연 열변색 필름을 제조하기 위한 장치 개략도이다.6 is a device schematic for producing a large area flexible thermochromic film.
이하 첨부된 도면을 참조하면서 본 발명의 바람직한 실시예를 상세히 설명한다. 다음에서 설명되는 실시예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술되는 실시예에 한정되는 것은 아니다. 본 발명의 실시예들은 당해 분야에서 통상의 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위하여 제공되는 것이다. 도면에 있어서, 층 영역들의 두께는 명확성을 기하기 위하여 실제 두께에 비해 과장되어 도시될 수 있다. Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art. In the drawings, the thicknesses of layer regions may be exaggerated relative to actual thickness for clarity.
도 1은 본 발명의 제 1 실시예에 따른 수십 ㎛ 두께의 유연 유리 기판(100)에 성장된 VO2(110)와 보호용 필름(120), 반사방지막(anti-reflection coating)(130)으로 이루어진 유연 유리 기판 열변색 필름의 단면도이다. 유연 유리 기판(100)은 수십 ㎛ 두께를 가지며 쉽게 휠 수 있고, 파손되지 않는 범위에서 구부릴 수 있으며 가볍다. 플라스틱과는 달리 유리재질이기 때문에 가스 또는 수분에 반응하지 않는 안정된 재료이며, 열을 차단하며, 투명하다는 장점이 있다. 이러한 유연 유리 기판은 디스플레이 패널, 전자종이, 이차전지, 태양전지 등에 다양하게 응용될 수 있으며, 본 발명에서도 중요한 소재에 속한다. 또한, 500℃의 고온에서도 변형이 되지 않아 열적 특성도 우수하다. 1 is a VO 2 (110), a protective film 120, an anti-reflection coating (130) grown on a flexible glass substrate 100 of several tens of micrometers thick according to the first embodiment of the present invention It is sectional drawing of a flexible glass substrate thermochromic film. The flexible glass substrate 100 has a thickness of several tens of micrometers and can be easily bent, bent in a range that is not broken, and light. Unlike plastic, glass is a stable material that does not react to gas or moisture, blocks heat, and has the advantage of being transparent. The flexible glass substrate may be variously applied to a display panel, an electronic paper, a secondary battery, a solar cell, etc., and belongs to an important material in the present invention. In addition, it does not deform even at a high temperature of 500 ° C., and thus has excellent thermal characteristics.
VO2(110)는 산소의 함량에 따라 VO, VO2, V2O5, V2O3, V3O7, V4O7, V5O9, V6O11, V6O13, V7O13 등의 다양한 결정상이 만들어지며, V2O3는 상온에서 금속 저항을 가지고, VO2는 수 MΩ, V2O5는 수십 GΩ의 절연상으로 변한다. 특히, VO2는 70℃ 근방에서 절연체에서 금속으로 변하는 특성을 가지고 있어 응용적인 측면에서 큰 관심이 있어왔으며, 온도, 광, 압력 등 외부 변수에 대해 저항이 민감하게 변화하여 각각 온도 센서, 광 센서, 스트레인 센서 등으로의 응용을 위해 활발히 연구가 진행되고 있다. VO 2 (110) is depending on the oxygen content VO, VO 2 , V 2 O 5 , V 2 O 3 , V 3 O 7 , V 4 O 7 , V 5 O 9 , V 6 O 11 , V 6 O 13 , Various crystal phases such as V 7 O 13 are formed, V 2 O 3 has a metal resistance at room temperature, VO 2 is a few MΩ, V 2 O 5 is an insulating phase of several tens of GΩ. In particular, VO 2 has a characteristic of changing from an insulator to a metal in the vicinity of 70 ° C, which has been of great interest in terms of application.The resistance is sensitive to external variables such as temperature, light, and pressure, so that the temperature sensor and the light sensor For the application to strain sensors, research is being actively conducted.
고품질의 VO2 박막을 얻기 위해서는 주로 사파이어를 사용하여 500℃ 이상의 고온에서 스퍼터링 증착법이나 펄스레이저 증착법, 솔젤법 등으로 제작이 이루어지고 있으며, 상온(25℃)과 고온(~100℃) 사이의 저항변화율은 10,000배 정도의 차이를 보이고 있다. 그리고, 기판의 결정성이 없는 SiO2, Si3N4 등을 사용했을 경우에는 ~1,000배 정도의 저항변화율 차이를 보이고 있다. 본 발명에서는 50㎛ 두께의 유리 기판을 사용하여 스퍼터링 증착법에 의해 500℃에서 VO2를 성장하였다. In order to obtain high quality VO 2 thin film, sapphire is mainly manufactured by sputtering deposition method, pulse laser deposition method, sol-gel method etc. at high temperature above 500 ℃, and resistance between room temperature (25 ℃) and high temperature (~ 100 ℃) The rate of change is about 10,000 times. In addition, when SiO 2 , Si 3 N 4, or the like having no substrate crystallinity is used, a difference in resistance change of about 1,000 times is shown. In the present invention, a VO 2 was grown at 500 ° C. by a sputtering deposition method using a 50 μm thick glass substrate.
도 1의 120에서와 같이 박막 증착 후 PET, PMMA, PI(Polyimide) 등 고분자 유기물을 VO2 보호용 필름으로 사용하였으며, 가시광 투과도를 높이기 위해서 유연 유리 기판에 도 1의 130에서와 같이 반사방지막을 증착함으로써 적외선의 투과효율도 함께 높일 수 있는 이점이 있다. 이러한 반사방지막은 열변색시 가시광 반사율은 그대로 유지하는 반면, 적외선 반사율을 크게 높여 열변색 효율을 개선할 수 있다.After deposition of a thin film as shown in 120 of FIG. 1, polymer organic materials such as PET, PMMA, and PI (Polyimide) were used as the VO 2 protective film, and an anti-reflection film was deposited on the flexible glass substrate as shown in FIG. By doing so, there is an advantage that the transmission efficiency of infrared rays can also be increased. The anti-reflection film can maintain the visible light reflectance as it is, while increasing the infrared reflectance, thereby improving thermochromic efficiency.
도 2는 유연 유리 기판을 제거한 후의 유연 열변색 필름의 단면도를 보여주고 있다. 유연 유리 기판에 고품질의 VO2가 성장된 후 불산(HF)에 의해 유리는 쉽게 식각이 가능하다. 유리를 식각하기 전에, VO2의 보호 및 지지를 위해 PET 등 고투명 고분자 필름을 먼저 VO2 위에 코팅한 다음 유리를 제거해준다. 마지막으로 유리가 제거된 면에 다시 보호용 PET 필름을 코팅함으로써(도 2의 103) 우수한 열변색 특성을 갖는 VO2 기반의 유연 열변색 필름을 제작할 수 있다.Figure 2 shows a cross-sectional view of the flexible thermochromic film after removing the flexible glass substrate. After high quality VO 2 is grown on the flexible glass substrate, the glass can be easily etched by hydrofluoric acid (HF). Before etching the glass, a first coating on the PET such as VO 2 highly transparent polymer film for protection and support of the VO 2, and then eliminates the glass. Finally, by coating the protective PET film on the glass-removed surface (103 in FIG. 2), a flexible thermochromic film based on VO 2 having excellent thermochromic properties may be manufactured.
상기 50㎛ 두께의 유연 유리 기판에 증착된 VO2 박막의 두께는 ~100nm이며, 도 3은 유연 유리 기판에 성장된 VO2 박막의 온도에 따른 저항 특성을 측정한 결과이다. 온도를 증가시킬 때 70℃ 근방에서 절연체에서 금속으로의 상전이(phase transition)가 일어나며 ~100배 정도의 저항변화율을 보이고 있다. 온도를 감소시킬 경우에는 60℃ 부근에서 금속에서 절연체로 상전이가 일어나며, 온도에 따른 저항 변화의 이력(hysteresis) 특성이 생긴다. 이 결과로부터 유리 기판 위에 VO2 상이 형성되었다는 것을 알 수 있다. The thickness of the VO 2 thin film deposited on the 50 μm thick flexible glass substrate is ˜100 nm, and FIG. 3 is a result of measuring the resistance characteristics according to the temperature of the VO 2 thin film grown on the flexible glass substrate. When the temperature is increased, a phase transition from the insulator to the metal occurs around 70 ° C, and the resistance change rate is about 100 times. When the temperature is reduced, a phase transition from metal to insulator occurs around 60 ° C, and hysteresis characteristic of resistance change with temperature occurs. This result shows that the VO 2 phase was formed on the glass substrate.
도 4는 비유연 기판에 고온으로 성장된 VO2 박막에서 기 보고된 결과로서 상온(25℃) 및 고온(90℃)에서의 투과도 변화를 보여주고 있으며, 적외선 대역에서 상전이 전후 열변색 효율은 상전이 전 투과도에서 상전이 후 투과도를 뺀 값(%)으로 표현할 수 있고, 2000nm에서 열변색 효율은 ~50%이며, 가시광 대역에서는 0 ~ 10%의 열변색 효율을 보인다. 도 5는 VO2 및 텅스텐(W)이 도핑된 V1- xWxO2 박막에서 기 보고된 연구 결과로서 이러한 박막들의 온도에 따른 투과도 변화를 4000nm에서 측정한 결과를 보여주고 있으며, VO2 박막은 ~75%, 열변색 온도를 조절한 V1- xWxO2 박막은 ~45%의 열변색 효율을 보이고 있다.Figure 4 shows the change in transmittance at room temperature (25 ℃) and high temperature (90 ℃) as a result of the preliminary report on the VO 2 thin film grown at a high temperature on a non-flexible substrate, the thermochromic efficiency before and after the phase transition in the infrared band The total transmittance can be expressed as a value obtained by subtracting the transmittance after the phase transition (%). At 2000 nm, the thermochromic efficiency is ~ 50%, and in the visible light band, the thermochromic efficiency is 0 to 10%. Figure 5 is showing the result of measuring the transmittance at 4000nm changes in temperature of this thin film as a study reported in the group VO 2 and the tungsten (W) is doped 1- x W x V 2 O thin film, VO 2 The thin film has a heat dissipation efficiency of ~ 75% and the V 1- x W x O 2 thin film with thermochromic temperature controlled at ~ 45%.
도 6은 유연 열변색 필름을 실제 건물의 유리창에 적용 가능한 크기로 제작하기 위한 장치의 개략도를 보여주며, roll-to-roll 방법으로 사각구조의 스퍼터 건(sputter gun)이 사용되었다. 상기 roll-to-roll 제작법은 유연 태양전지를 대량 생산하기 위해 보편적으로 사용되는 방법이기도 하며, 본 특허의 유연 열변색 필름을 대면적으로 제조하기 위해 적합한 장비이다. 상기 in-line 공정은 진공 상태에서 이루어지며, 필요에 의해 전체 공정은 각각의 단계별로 나누어져 각 단계별 in-line 공정으로도 진행될 수도 있다. Roll 형태로 감겨있는 유연 유리 기판(200)에는 균일한 두께로 증착이 가능한 스퍼터 시스템(210)에서 VO2가 증착된다. VO2가 증착되기 위해서는 ~500℃를 유지할 수 있는 고온용 판상형 히터(plate heater)가 필요하며, 유연 유리 기판이 히터 위를 지날때, 아르곤(Ar), 산소(O2) 등 적절한 가스 분위기(gas atmosphere) 속에서 VO2가 증착될 수 있다. 스퍼터링 방법으로 VO2를 증착하기 위해 고순도의 금속 바나듐 타겟(V target), 또는 V2O5 산화물 타겟이 사용될 수 있다. 유연 유리 기판에 VO2가 증착된 다음에는 VO2 위에 보호용 필름(220, PET)을 입힌다. 상기 보호용 필름은 VO2의 보호막으로 작용할 뿐만 아니라 유연 유리 기판이 식각될 때 VO2를 지지시켜줄 수 있는 지지막(supporting film) 역할도 한다. PET/VO2/Glass의 구조는 유연 유리 기판에 반사방지막을 코팅함으로써 도 1에 나타낸 유연 유리 기판 열변색 필름 구조가 된다. FIG. 6 shows a schematic diagram of an apparatus for manufacturing a flexible thermochromic film to a size applicable to a glass window of an actual building, and a rectangular sputter gun was used as a roll-to-roll method. The roll-to-roll manufacturing method is also a commonly used method for mass-producing flexible solar cells, and is a suitable equipment for large-area manufacturing of flexible thermochromic film of the present patent. The in-line process is carried out in a vacuum state, the entire process may be divided into each step as necessary, may also proceed to each step in-line process. VO 2 is deposited in the sputter system 210 capable of depositing a uniform thickness on the flexible glass substrate 200 wound in a roll shape. In order to deposit VO 2 , a high temperature plate heater capable of maintaining a temperature of about 500 ° C. is required, and when a flexible glass substrate passes over the heater, an appropriate gas atmosphere such as argon (Ar) and oxygen (O 2 ) is required. VO 2 may be deposited in a gas atmosphere. A high purity metal vanadium target, or V 2 O 5 oxide target, may be used to deposit VO 2 by the sputtering method. After VO 2 is deposited on the flexible glass substrate, a protective film 220 (PET) is coated on the VO 2 . The protective film not only acts as a protective film of VO 2 but also serves as a supporting film that can support VO 2 when the flexible glass substrate is etched. The structure of PET / VO 2 / Glass becomes the flexible glass substrate thermochromic film structure shown in FIG. 1 by coating the antireflection film on the flexible glass substrate.
다음 단계는 유연 유리 기판을 제거하는 공정(230)으로 상기 PET/VO2/Glass 구조를 갖는 필름의 유연 유리 기판이 식각 용기에서 완전히 제거된다. 식각 용액으로는 불산을 사용하여 물과 적절한 비율로 희석함으로써 식각 속도를 제어할 수 있다. 식각이 끝난 후에는 증류수(DI water)를 이용하여 잔류 불산을 세척한 후 건조 과정을 거치게 된다. 마지막 단계로 유리 기판이 식각된 PET/VO2 구조에서 VO2의 보호를 위해 다시 한번 PET 필름(240)을 VO2 면에 입힌다. 최종적으로 PET/VO2/PET 구조를 가지게 되며, 열변색 효율을 높이기 위해 PET 위에 반사방지막을 코팅함으로써 도 2에 나타낸 유연 열변색 필름을 제작할 수 있다. 또한, TiO2를 PET 위에 코팅함으로써 자정작용(self-cleaning) 뿐만 아니라 필름의 색깔을 다양하게 바꿀 수 있는 효과를 줄 수도 있다.The next step is to remove the flexible glass substrate 230 where the flexible glass substrate of the film having the PET / VO 2 / Glass structure is completely removed from the etching vessel. The etching rate can be controlled by dilution with an appropriate ratio with water using hydrofluoric acid as an etching solution. After etching, the residual hydrofluoric acid is washed with distilled water (DI water) and then dried. In the PET / VO 2 structure, the glass substrate is etched to the final step once again to protect the VO 2 coated with a PET film 240 to the VO 2 side. Finally, it will have a PET / VO 2 / PET structure, it can be produced a flexible thermochromic film shown in Figure 2 by coating an antireflection film on the PET in order to increase the thermochromic efficiency. In addition, the coating of TiO 2 on PET may give an effect of varying the color of the film as well as self-cleaning.

Claims (10)

  1. 유연 유리 기판;Flexible glass substrates;
    상기 유연 유리 기판 상에 형성된 바나듐산화물 박막; 및A vanadium oxide thin film formed on the flexible glass substrate; And
    상기 바나듐산화물 박막 위에 증착된 보호막으로 구성된 유연 열변색 필름.Flexible thermochromic film consisting of a protective film deposited on the vanadium oxide thin film.
  2. 제1항에 있어서,The method of claim 1,
    상기 유연 유리 기판은 200㎛ 이하의 두께를 가지며 유연성을 가지는 유연 열변색 필름.The flexible glass substrate is a flexible thermochromic film having a thickness of less than 200㎛ having flexibility.
  3. 제1항에 있어서,The method of claim 1,
    상기 바나듐산화물은 VO, VO2, V2O5, V2O3, V3O7, V4O7, V5O9, V6O11, V6O13, V7O13 등을 포함하는 유연 열변색 필름.The vanadium oxide includes VO, VO 2 , V 2 O 5 , V 2 O 3 , V 3 O 7 , V 4 O 7 , V 5 O 9 , V 6 O 11 , V 6 O 13 , V 7 O 13 , and the like. Containing flexible thermochromic film.
  4. 제1항에 있어서,The method of claim 1,
    상기 바나듐산화물은 V1- xAxO2의 화학식을 가지는 산화물이며, 식에서 A는 도핑 물질이며, W, Cr, Ni, Zn, Al, Mo, Cu, Sn, Ce, Ru, Y, Ti, Ce, Mn, Sm, Nb 등이 사용되어 제작된 유연 열변색 필름.The vanadium oxide is an oxide having a general formula of V 1- x A x O 2, wherein A is a doping material, W, Cr, Ni, Zn , Al, Mo, Cu, Sn, Ce, Ru, Y, Ti, Flexible thermochromic film produced using Ce, Mn, Sm, Nb and the like.
  5. 제1항에 있어서,The method of claim 1,
    상기 보호막은 고분자 유기물 필름으로 PET, PMMA, Polyimide, PR 등이 사용되어 제작된 유연 열변색 필름.The protective film is a flexible thermochromic film produced using PET, PMMA, Polyimide, PR, etc. as a polymer organic film.
  6. 제1항에 있어서,The method of claim 1,
    상기 보호막 위에 반사방지막이 증착된 유연 열변색 필름.A flexible thermochromic film having an antireflection film deposited on the protective film.
  7. 제1항에 있어서,The method of claim 1,
    상기 유연 유리 기판이 식각된 후 바나듐산화물 박막과 보호막으로 이루어진 유연 열변색 필름.A flexible thermochromic film comprising a vanadium oxide thin film and a protective film after the flexible glass substrate is etched.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 유연 유리 기판의 식각을 위해 불산을 용액으로 사용하여 유리를 제거한 유연 열변색 필름.A flexible thermochromic film in which glass is removed using hydrofluoric acid as a solution for etching the flexible glass substrate.
  9. 제7항에 있어서,The method of claim 7, wherein
    상기 바나듐산화물 위에 보호막을 증착하여 보호막/바나듐산화물 박막/보호막으로 이루어진 유연 열변색 필름.Flexible thermochromic film consisting of a protective film / vanadium oxide thin film / protective film by depositing a protective film on the vanadium oxide.
  10. 제9항에 있어서,The method of claim 9,
    상기 보호막 위에 반사방지막을 증착한 유연 열변색 필름.Flexible thermochromic film deposited with an anti-reflection film on the protective film.
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