WO2021159773A1 - 一种电致变色器件及其制作方法 - Google Patents

一种电致变色器件及其制作方法 Download PDF

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WO2021159773A1
WO2021159773A1 PCT/CN2020/126379 CN2020126379W WO2021159773A1 WO 2021159773 A1 WO2021159773 A1 WO 2021159773A1 CN 2020126379 W CN2020126379 W CN 2020126379W WO 2021159773 A1 WO2021159773 A1 WO 2021159773A1
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layer
conductive
electrochromic device
photoresist
conductive gel
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PCT/CN2020/126379
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English (en)
French (fr)
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赵世晴
刘艳花
黄文彬
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苏州苏大维格科技集团股份有限公司
苏州大学
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Publication of WO2021159773A1 publication Critical patent/WO2021159773A1/zh

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    • 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 
    • G02F1/15—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  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • 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 
    • G02F1/15—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  based on an electrochromic effect
    • 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 
    • G02F1/15—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  based on an electrochromic effect
    • G02F1/153—Constructional details
    • 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 
    • G02F1/15—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  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes

Definitions

  • the invention relates to the technical field of electrochromic devices, in particular to an electrochromic device and a manufacturing method thereof.
  • Electrochromic device means that under the action of alternating positive and negative voltages, the transmittance, absorptivity, and reflectivity of the device also change regularly, and the appearance is expressed as the color change of the device.
  • Electrochromic devices are often used in transparent windows of airplanes, automobiles, high-speed rail and other transportation vehicles and buildings, anti-glare rearview mirrors, military camouflage, and flexible wearable devices.
  • smart color-changing windows used in buildings can control the light transmittance of the windows by applying voltage, which can adjust the heat of sunlight entering the room, thereby controlling the indoor temperature, and effectively saving electricity. This is a technology with great potential, which will greatly change the way of life of centuries in the future.
  • the current electrochromic device such as the existing patent CN200780032841.9, includes: first and second transparent substrates arranged to be opposite to each other; first and second transparent substrates formed on the first and second transparent substrates opposite to each other, respectively Sheet-shaped transparent electrode; an electrochromic layer pattern formed on at least one of the first and second transparent electrodes through an opening of a photoresist pattern formed by laser interference lithography; and a pattern for sealingly filling by The electrochromic layer pattern and the ion conductive layer defined by the gaps on the surfaces of the first and second transparent electrodes.
  • the number of layers is large, the thickness is relatively thick, and the ion conductive layer must be sealed and then filled first, which is complicated to produce and difficult to operate.
  • the purpose of the present invention is to provide a patterned and pixelated electrochromic device with a simple process and a manufacturing method thereof.
  • the present invention provides an electrochromic device, comprising a conductive substrate, a photoresist layer, a color changing layer and a conductive gel layer.
  • the photoresist layer is provided on the substrate, and the photoresist layer is provided with a first Pattern groove, the color changing layer is embedded in the first pattern groove, the conductive gel layer is provided with a plurality of second protrusions corresponding to the first pattern groove, the conductive gel
  • the glue layer covers the photoresist layer, and the end faces of the plurality of second protrusions are in contact with the surface of the color changing layer.
  • a tin-plated indium oxide (ITO) glass is provided on the surface of the conductive gel layer away from the color-changing layer, and the conductive gel layer and the tin-plated indium oxide (ITO) glass are provided ) There is a storage layer between the glass.
  • the photoresist layer is provided with a plurality of first protrusions forming the first pattern grooves, and the color changing layer also covers the plurality of first protrusions.
  • the thickness of the color changing layer is less than the height of the first pattern groove.
  • the bottom of the first pattern groove overlaps a part of the surface of the conductive substrate.
  • the conductive substrate includes a conductive layer and a transparent base, and the conductive layer is formed of a metal oxide plated on the transparent base.
  • the color-changing layer when the conductive substrate is connected to the negative electrode and the conductive gel layer is connected to the positive electrode, the color-changing layer is transparent to colored; when the conductive substrate is connected to the positive electrode, the conductive gel layer is connected to For the negative electrode, the color-changing layer is colored to transparent.
  • the present invention also provides a manufacturing method of the electrochromic device, the method including:
  • the conductive gel is coated on the photoresist layer and cured to form a conductive gel layer, and the conductive gel layer is in contact with the color changing layer.
  • a photolithography mask is included, and in the step of forming a first pattern groove on the photoresist layer: the surface of the conductive substrate is cleaned with a dust remover, and a spin-coated method is used. Method After coating a layer of photoresist on the surface, place it in a 90° oven and heat it for one hour, and then use the mask to expose it, then develop and etch to obtain a photoresist with the first patterned groove Layer 2, the bottom of the first pattern groove overlaps a part of the surface of the conductive substrate.
  • the material with the color-changing layer is uniformly filled in the first pattern groove by spin coating or electrodeposition, and the color-changing material does not fill all the holes.
  • the first patterned groove is heated and cured to obtain the color-changing layer.
  • the step of forming the conductive gel layer spin coating or knife coating is used to coat the conductive gel on the photoresist layer, and the conductive gel is formed after curing Floor.
  • the photoresist layer is covered by the conductive gel layer, and the end faces of the plurality of second protrusions are in contact with the surface of the color changing layer, thereby reducing the electrochromic device thickness of.
  • Figure 1 is a structural diagram of an electrochromic device according to a first embodiment of the present invention
  • FIG. 2 is a flow chart of the steps of the manufacturing method of the electrochromic device according to the first embodiment of the present invention
  • Figure 3 is a structural diagram of an electrochromic device according to a second embodiment of the present invention.
  • FIG. 4 is a structural diagram of an electrochromic device according to a third embodiment of the present invention.
  • Fig. 5 is a structural diagram of an electrochromic device according to a fourth embodiment of the present invention.
  • the electrochromic device provided in the embodiment of the present invention includes a conductive substrate 1, a photoresist layer 2, a color changing layer 3, and a conductive gel layer 4.
  • the photoresist layer 2 is provided on the conductive substrate 1, the photoresist layer 2 is provided with a first patterned groove 21, the color changing layer 3 is embedded in the first patterned groove 21, and the conductive gel layer 4 is provided with the first patterned groove 21.
  • the conductive gel layer 4 covers the photoresist layer 2, and the end surfaces of the plurality of second protrusions 41 are in contact with the surface of the color changing layer 3.
  • the conductive substrate 1 includes a conductive layer 12 and a transparent substrate 11; the transparent substrate 11 is glass or a flexible substrate; the conductive layer 12 is formed of metal oxide plated on the transparent substrate 11.
  • the glass is tin-doped indium oxide (ITO) and fluorine-doped tin oxide (FTO) glass; the material of the flexible substrate is polydimethylsiloxane (PDMS), polyethylene terephthalate (PET) .
  • the photoresist layer 2 is made of positive photoresist or negative photoresist or reversed photoresist.
  • the positive photoresist is the exposed area that dissolves during development to leave grooves
  • the negative photoresist is the area where the exposed area is cross-linked and becomes a barrier to development
  • the reversal photoresist is through two exposures, using negative
  • the offset plate obtains the graphics of the positive offset plate, which solves the problem that the positive offset plate is difficult to match the plate.
  • the photoresist layer 2 is provided with a plurality of first protrusions 23 forming the first patterned groove 21, the top end surface of the first protrusion 23 is in contact with the conductive gel layer 4, and the first protrusion 23 is not conductive.
  • the bottom of the first pattern groove 21 overlaps a part of the surface of the conductive substrate 1.
  • the thickness of the color changing layer 3 is smaller than the height of the first pattern groove 21.
  • the material of the color changing layer 3 is an electrochromic material, including any one or more of organic electrochromic materials, inorganic electrochromic materials, and composite electrochromic materials.
  • inorganic electrochromic materials include metal oxides, preferably tungsten trioxide and nickel oxide; organic electrochromic materials are preferably viologens, isophthalates, metal phthalocyanines, and pyridines. Any one or more of metal complexes, polyanilines, polypyrroles, and polythiophenes.
  • the conductive gel layer 4 is provided with a second patterned groove 43 formed by a plurality of second protrusions 41, the second patterned groove 43 accommodates the plurality of first protrusions 23, and the inner wall and bottom of the second patterned groove 43 They are in contact with the corresponding outer surfaces of the first protrusions 23, respectively.
  • the conductive gel layer 4 is an inorganic gel layer or an organic gel layer.
  • the material of the inorganic gel layer is acrylamide, sodium chloride, lithium chloride, sodium perchlorate, lithium perchlorate and other electrolytes, tetramethylethylenediamine, ammonium persulfate, methylenebisacrylamide, Deionized water.
  • the organic gel layer includes organic polymers such as acrylonitrile-styrene, curing agents such as 1-methylimidazole, 4-methylimidazole, and electrolytes such as sodium chloride, lithium chloride, sodium perchlorate, and lithium perchlorate.
  • Organic solvents such as acetonitrile, tetrahydrofuran and toluene.
  • the color-changing layer 3 when the conductive substrate 1 is connected to the negative electrode and the conductive gel layer 4 is connected to the positive electrode, the color-changing layer 3 is realized from transparent to colored; when the conductive substrate 1 is connected to the positive electrode, the conductive gel layer 4 is connected to the negative electrode, and the color-changing layer 3 is realized. From colored to transparent.
  • the conductive gel layer 4 and the color-changing layer 3 made of different materials and proportions have different voltages to achieve color change and different color-changing effects.
  • the present invention also provides a manufacturing method of an electrochromic device, which is used to manufacture the above-mentioned electrochromic device, and the method includes:
  • step S2 including a reticle for photolithography. First clean the surface of the conductive substrate 1 with a dust remover, apply a layer of photoresist (AZ4620 or AZ4562 model photoresist) on the surface by spin coating, and then put it in a 90° oven to heat it up. After hours, the photoresist layer 2 with the first patterned groove 21 is obtained after exposure using a mask, and the photoresist layer 2 with the first patterned groove 21 overlaps a part of the surface of the conductive substrate 1.
  • a reticle for photolithography First clean the surface of the conductive substrate 1 with a dust remover, apply a layer of photoresist (AZ4620 or AZ4562 model photoresist) on the surface by spin coating, and then put it in a 90° oven to heat it up. After hours, the photoresist layer 2 with the first patterned groove 21 is obtained after exposure using a mask, and the photoresist layer 2 with the first patterned groove 21 overlaps a part of the
  • step S3 the production of the material of the color changing layer 3 is also included. Specifically, 2.5g of tungsten powder was put into 10ml of hydrogen peroxide (concentration of 30%) solution, and then stirred until the powder was completely dissolved, then the excess hydrogen peroxide was removed, 10g of ethanol was added, and it was condensed and refluxed at 80°C for 6 hours to obtain trioxide Tungsten color layer 3 material.
  • hydrogen peroxide concentration of 30%
  • the material with the tungsten trioxide color changing layer 3 is uniformly filled in the first pattern groove 21 by electrodeposition, and the color changing material does not fill the first pattern groove 21, and the color changing layer 3 is obtained after heating and curing.
  • step S4 the production of conductive gel is also included. Specifically, 0.782g acrylamide, 1.12g sodium chloride, lithium chloride sodium hypochlorite, lithium hypochlorite, 0.47mg tetramethylethylenediamine, 1.33mg ammonium persulfate, 2.5mg methylenebisacrylamide, 5g Mix the deionized water together, then stir evenly, and heat on a hot plate at 60° for 1 hour.
  • the organic solvent acetonitrile and tetrahydrofuran are mixed in a volume ratio of 4:1, poured into a weighing bottle, and the weighing bottle is placed on a magnetic constant temperature stirrer and stirred for 1 minute.
  • the substance is completely dissolved, and finally 1% 1-methylimidazole is added and stirred for 1 minute to obtain a conductive gel.
  • the conductive gel is coated on the photoresist layer 2 by spin coating or knife coating, and the conductive gel layer 4 is formed after curing.
  • the difference between the electrochromic device provided in the second embodiment of the present invention and the above-mentioned first embodiment is that, in this embodiment, as shown in FIG. Starting from 23, since the photoresist layer is not conductive, and the thickness of the part of the color-changing layer 3 disposed in the first pattern groove 21 is lower than the height of the first pattern groove 21, that is, the thickness of the portion disposed in the first pattern groove 21 The part of the color changing layer 3 is not in contact with the part of the color changing layer 3 disposed on the top of the plurality of first protrusions 23, and therefore, the part of the color changing layer 3 disposed on the top of the plurality of first protrusions 23 does not change color.
  • PEDOT PSS solution (a high molecular polymer aqueous solution, PEDOT is a polymer of EDOT (3,4-ethylenedioxythiophene monomer), PSS is polystyrene sulfonate) by spin coating or The method of squeegee coating is evenly distributed on the ITO conductive substrate with the target pattern, and the PEDOT:PSS color-changing layer 3 is obtained by drying on a hot plate at 100°C for 20 minutes.
  • the material of the color changing layer 3 described above is not only the PEDOT:PSS solution, but also the material of the color changing layer 3 in the first embodiment.
  • the electrochromic device provided by the third embodiment of the present invention is: on the basis of the above-mentioned first embodiment or the second embodiment, a tin-plated indium oxide ( ITO) glass 5, a tin-plated indium oxide (ITO) glass 5 can also be provided on the surface of the transparent substrate 11 on the side away from the conductive layer 12, please refer to FIG. 4, which is the electrochromic provided in the second embodiment
  • a schematic diagram of tin-plated indium oxide (ITO) glass 5 is provided on the upper and lower surfaces.
  • the electrochromic device of this embodiment is connected to the positive electrode or the negative electrode by tin-plated indium oxide (ITO) glass 5 on both sides, and the electrodes connected to the two are not consistent, that is, one is connected to the positive electrode and the other is connected to the negative electrode.
  • the conductive gel layer 4 itself can conduct electricity, and the conductive layer of tin-plated indium oxide (ITO) glass 5 can be omitted. By adding tin-plated indium oxide (ITO) glass 5, the conductivity of the electrochromic device is better.
  • a storage layer 6 is provided between the conductive gel layer 4 and tin-plated indium oxide (ITO) glass 5, please refer to FIG. 5. .
  • the storage layer 6 can make the color-changing device last longer after being colored until the fading voltage is applied. Compared with the conductive gel layer 4, it has a good steady-state effect and avoids natural fading in a short time after coloring.
  • the terms “installed”, “connected”, and “connected” shall be interpreted broadly, for example, it may be a fixed connection, a detachable connection, or an integral connection; It is a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • installed shall be interpreted broadly, for example, it may be a fixed connection, a detachable connection, or an integral connection; It is a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

一种电致变色器件，包括导电基板（1）、光刻胶层（2）、变色层（3）和导电凝胶层（4），光刻胶层（2）设置在导电基板（1）上，光刻胶层（2）设有第一图形凹槽（21），变色层（3）嵌设在第一图形凹槽（21）内，导电凝胶层（4）设有与第一图形凹槽（21）相对应的多个第二凸起（41），导电凝胶层（4）覆盖光刻胶层（2），且多个第二凸起（41）的端面与变色层（3）的表面接触。一种电致变色器件的制作方法，用于制作电致变色器件。通过导电凝胶层（4）覆盖光刻胶层（2），且多个第二凸起（41）的端面与变色层（3）的表面接触，降低了电致变色器件的厚度。

Description

一种电致变色器件及其制作方法
本申请要求了申请日为2020年02月14日，申请号为202010093505.2的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及电致变色器件技术领域，特别是涉及一种电致变色器件及其制作方法。
背景技术
电致变色器件(ECD，electrochromic device)是指在正负交替变化的电压作用下，器件的透过率、吸收率、反射率也出现规律的交替变化，外观上表现为器件的颜色变化。电致变色器件常被用于飞机、汽车、高铁等运输工具和建筑物的透明窗，防眩光后视镜，军事伪装和柔性可穿戴设备等。例如用于建筑物的智能变色窗通过外加电压控制窗户对光线的透过率，可以实现对太阳光线进入室内热量的调节，进而控制室内温度，有效的节省电量。这是一项具有很大潜力的技术，在未来会很大程度改变人类的生活方式。
目前的电致变色器件，如现有专利CN200780032841.9，包括：设置成彼此相对的第一和第二透明基板；在彼此相对的第一和第二透明基板上分别形成的第一和第二片状透明电极；经过由激光干涉光刻法形成的光刻胶图形的开口在第一和第二透明电极中的至少一层上形成的电致变色层图形；和用于密封地填充由所述电致变色层图形与第一和第二透明电极表面所限定的空隙的离子导电层。但其层数较多，厚度较厚，且先要除出要先密封再填充离子导电层，如此制作复杂，操作不易。
前面的叙述在于提供一般的背景信息，并不一定构成现有技术。
发明内容
本发明的目的在于提供一种工艺简单的图形化和像素化的电致变色器件 及其制作方法。
本发明提供一种电致变色器件，包括导电基板、光刻胶层、变色层和导电凝胶层，所述光刻胶层设置在所述基板上，所述光刻胶层设有第一图形凹槽，所述变色层嵌设在于所述第一图形凹槽内，所述导电凝胶层设有与所述第一图形凹槽相对应的多个第二凸起，所述导电凝胶层覆盖所述光刻胶层，且所述多个第二凸起的端面与所述变色层的表面接触。
在其中一实施例中，在所述导电凝胶层远离所述变色层的一侧表面设有一镀锡氧化铟(ITO)玻璃，在所述导电凝胶层和所述镀锡氧化铟(ITO)玻璃之间设有存储层。
在其中一实施例中，所述光刻胶层设有形成所述第一图形凹槽的多个第一凸起，所述变色层还覆盖所述多个第一凸起。
在其中一实施例中，所述变色层的厚度小于所述第一图形凹槽的高度。
在其中一实施例中，所述第一图形凹槽的底部与所述导电基板的部分表面重叠。
在其中一实施例中，所述导电基板包括导电层和透明基底，所述导电层由在所述透明基底上镀的金属氧化物形成。
在其中一实施例中，当所述导电基板接负极，所述导电凝胶层接正极时，所述变色层实现从透明到有色；当所述导电基板接正极，所述导电凝胶层接负极，所述变色层实现从有色到透明。
本发明还提供一种电致变色器件的制作方法，该方法包括：
提供一导电基板；
在所述导电基板上旋涂一层光刻胶形成光刻胶层，对所述光刻胶层进行光刻，在所述光刻胶层上形成第一图形凹槽；
将变色层材料填充在所述第一图形凹槽内，固化后形成变色层；
将导电凝胶涂布在所述光刻胶层上，固化后形成导电凝胶层，所述导电凝胶层与所述变色层接触。
在其中一实施例中，包括实现光刻的掩模版，在所述光刻胶层上形成第一图形凹槽的步骤中：用除尘剂将所述导电基板的表面清洗干净，采用旋涂的方式在所述表面涂一层光刻胶后，放入90°的烘箱加热一小时，然后利用所述掩模版曝光后，进行显影、蚀刻，得到具有所述第一图形凹槽的光刻胶层2，所述第一图形凹槽的底部与所述导电基板的部分表面重叠。
在其中一实施例中，在形成所述变色层的步骤中：将具有变色层材料采用旋涂或电沉积法均匀填充在所述第一图形凹槽内，且所述变色材料未填满所述第一图形凹槽，加热固化后得到所述变色层。
在其中一实施例中，在所述形成导电凝胶层的步骤中：采用旋涂或刮涂的方式将导电凝胶涂布在所述光刻胶层上，固化后形成所述导电凝胶层。
本发明提供的电致变色器件，通过所述导电凝胶层覆盖所述光刻胶层，且所述多个第二凸起的端面与所述变色层的表面接触，降低了电致变色器件的厚度。
附图说明
图1为本发明第一实施例电致变色器件的结构图；
图2为本发明第一实施例电致变色器件的制作方法的步骤流程图；
图3为本发明第二实施例电致变色器件的结构图；
图4为本发明第三实施例电致变色器件的结构图；
图5为本发明第四实施例电致变色器件的结构图。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
第一实施例
请参图1，本发明实施例中提供的电致变色器件，包括导电基板1、光刻 胶层2、变色层3和导电凝胶层4。光刻胶层2设置在导电基板1上，光刻胶层2设有第一图形凹槽21，变色层3嵌设在于第一图形凹槽21内，导电凝胶层4设有与第一图形凹槽21相对应的多个第二凸起41。导电凝胶层4覆盖光刻胶层2，且多个第二凸起41的端面与变色层3的表面接触。
导电基板1包括导电层12和透明基底11；透明基底11为玻璃或柔性基底；导电层12由在透明基底11上镀的金属氧化物形成。具体地，玻璃为掺锡氧化铟(ITO)和掺氟氧化锡(FTO)的玻璃；柔性基底的材质为聚二甲基硅氧烷(PDMS)、聚对苯二甲酸乙二酯(PET)。
光刻胶层2的材质为正性光刻胶或负性光刻胶或反转胶。其中，正性光刻胶为曝光的区域在显影中溶解从而留下凹槽；负性光刻胶为曝光区域发生交联变成阻隔显影的区域；反转胶为通过两次曝光，用负胶版得到正胶版的图形，解决正胶版难对版的问题。
光刻胶层2设有形成第一图形凹槽21的多个第一凸起23，第一凸起23的顶部端面与导电凝胶层4接触，且第一凸起23不导电。第一图形凹槽21的底部与导电基板1的部分表面重叠。
变色层3的厚度小于第一图形凹槽21的高度。变色层3的材质为电致变色材料，包括有机电致变色材料、无机电致变色材料、复合电致变色材料中的任一种或多种。具体地，无机电致变色材料包括金属氧化物，优选的为三氧化钨、氧化镍；有机电致变色材料优选的为紫萝精类、间苯二酸酯类、金属酞菁类、吡啶类金属配合物、聚苯胺类、聚吡咯类、聚噻吩类中的任一种或多种。
导电凝胶层4设有由多个第二凸起41形成的第二图形凹槽43，第二图形凹槽43收容多个第一凸起23，且第二图形凹槽43的内壁和底部分别与第一凸起23相应的外表面接触。导电凝胶层4为无机凝胶层或有机凝胶层。其中，无机凝胶层的材质为丙烯酰胺，氯化钠、氯化锂、高氯酸钠、高氯酸锂等电解质，四甲基乙二胺，过硫酸铵，亚甲基双丙烯酰胺，去离子水。有机 凝胶层包括丙烯腈-苯乙烯等有机聚合物，1-甲基咪唑，4-甲基咪唑等固化剂，氯化钠、氯化锂、高氯酸钠、高氯酸锂等电解质，乙腈、四氢呋喃、甲苯等有机溶剂。
在本实施例中，当导电基板1接负极，导电凝胶层4接正极时，变色层3实现从透明到有色；当导电基板1接正极，导电凝胶层4接负极，变色层3实现从有色到透明。不同材质、比例制成的导电凝胶层4和变色层3，实现变色的电压也不同，变色的效果也不同。
请参考图2，本发明还提供一种电致变色器件的制作方法，用于制作上述电致变色器件，该方法包括：
S1：提供一导电基板1；
S2：在导电基板1上旋涂一层光刻胶形成光刻胶层2，对光刻胶层2进行光刻，在光刻胶层2上形成第一图形凹槽21；
S3：将变色层3材料填充在第一图形凹槽21内，固化后形成变色层3；
S4：将导电凝胶涂布在光刻胶层2上，固化后形成导电凝胶层4，导电凝胶层4与所述变色层3接触。
在步骤S2中：包括实现光刻的掩模版。先用除尘剂将所述导电基板1的表面清洗干净，采用旋涂的方式在所述表面涂一层光刻胶(AZ4620或AZ4562型号的光刻胶)后，放入90°的烘箱加热一小时，然后利用掩模版曝光后，进行显影、蚀刻，得到具有所述第一图形凹槽21的光刻胶层2，第一图形凹槽21的底部与导电基板1的部分表面重叠。
在步骤S3中：还包括变色层3材料的制作。具体地，将2.5g钨粉放入10ml过氧化氢(浓度为30％)溶液，然后搅拌至粉末完全溶解，然后去除多余过氧化氢，加入10g的乙醇，80℃冷凝回流6小时得到三氧化钨变色层3材料。
将具有三氧化钨变色层3材料采用电沉积法均匀填充在第一图形凹槽21内，且变色材料未填满所述第一图形凹槽21，加热固化后得到变色层3。
在步骤S4中：还包括导电凝胶的制作。具体地，将0.782g丙烯酰胺，1.12g 氯化钠、氯化锂次氯酸钠、次氯酸锂、0.47mg四甲基乙二胺、1.33mg过硫酸铵、2.5mg亚甲基双丙烯酰胺、5g去离子水混合在一起，然后搅拌均匀，热板60°加热1小时。
在其它实施例中，将有机溶剂乙腈和四氢呋喃按体积比4∶1混合，倒入称量瓶中，称量瓶放置于磁力恒温搅拌器上搅拌1分钟。称取10wt％的氯化锂，20wt％的丙烯腈-苯乙烯有机聚合物，分别缓慢地加入到有机溶剂中，密封恒温75～85摄氏度搅拌10～15分钟至丙烯腈-苯乙烯等有机聚合物完全溶解，最后加入1％的1-甲基咪唑搅拌1分钟得到导电凝胶。
采用旋涂或刮涂的方式将导电凝胶涂布在所述光刻胶层2上，固化后形成所述导电凝胶层4。
上述按不同物质、比例、方法制成的变色层3和导电凝胶层4可以任一组合形成新电致变色器件。
第二实施例
本发明第二实施例提供的电致变色器件与上述第一实施例的区别在于，在本实施例中，如图3所示，变色层3还覆盖设置于光胶层的多个第一凸起23，由于光胶层不导电，且设置于第一图形凹槽21内的变色层3部分的厚度低于第一图形凹槽21的高度，即，设置于第一图形凹槽21内的变色层3部分与设置于多个第一凸起23顶部的变色层3部分不接触，因此，设置于多个第一凸起23顶部的变色层3部分不变色。
有鉴于此，在制作变色层3时，先将变色层3材料滴在多个第一凸起23的顶部，部分变色层3材料会流入第一图形凹槽21内，再进行匀速旋转后固化。
如：将PEDOT：PSS溶液(是一种高分子聚合物的水溶液，PEDOT是EDOT(3，4-乙烯二氧噻吩单体)的聚合物，PSS是聚苯乙烯磺酸盐)通过旋涂或刮涂的方式均匀分布在具有目标图案的ITO导电基底上，热板100℃烘干20分钟得到PEDOT：PSS变色层3。
上述变色层3材料不仅仅是PEDOT：PSS溶液，还包括第一实施例中的变色层3材料。
第三实施例
本发明第三实施例提供的电致变色器件为：在上述第一实施例或第二实施例的基础上，在导电凝胶层4远离变色层3的一侧表面设一镀锡氧化铟(ITO)玻璃5，还可在透明基底11远离导电层12一侧的表面也设一镀锡氧化铟(ITO)玻璃5，请参考图4，图4为在第二实施例提供的电致变色器件的基础上，上下表面均设镀锡氧化铟(ITO)玻璃5的示意图。
本实施例电致变色器件是由两侧的镀锡氧化铟(ITO)玻璃5连接正极或负极，且二者连接的电极不一致，即，一个连接正极，另一个连接负极。导电凝胶层4本身可以导电可以省去上面的镀锡氧化铟(ITO)玻璃5导电层。通过加了镀锡氧化铟(ITO)玻璃5，使电致变色器件的导电性更好。
第四实施例
本发明第四实施例提供的电致变色器件与上述第三实施例的区别在于：在导电凝胶层4和镀锡氧化铟(ITO)玻璃5之间设有存储层6，请参考图5。
存储层6可以使变色器件着色后能够维持更长时间，直到加上褪色电压，相对于只有导电凝胶层4的话，其稳态效果好，避免着色后短时间内自然褪色。
在附图中，为了清晰起见，会夸大层和区域的尺寸和相对尺寸。应当理解的是，当元件例如层、区域或基板被称作“形成在”、“设置在”或“位于”另一元件上时，该元件可以直接设置在所述另一元件上，或者也可以存在中间元件。相反，当元件被称作“直接形成在”或“直接设置在”另一元件上时，不存在中间元件。
在本文中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过 中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语的具体含义。
在本文中，术语“上”、“下”、“前”、“后”、“左”、“右”、“顶”、“底”、“内”、“外”、“竖直”、“水平”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了表达技术方案的清楚及描述方便，因此不能理解为对本发明的限制。
在本文中，用于描述元件的序列形容词“第一”、“第二”等仅仅是为了区别属性类似的元件，并不意味着这样描述的元件必须依照给定的顺序，或者时间、空间、等级或其它的限制。
在本文中，除非另有说明，“多个”、“若干”的含义是两个或两个以上。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，除了包含所列的那些要素，而且还可包含没有明确列出的其他要素。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (11)

  1. 一种电致变色器件，其特征在于，包括导电基板、光刻胶层、变色层和导电凝胶层，所述光刻胶层设置在所述导电基板上，所述光刻胶层设有第一图形凹槽，所述变色层嵌设在于所述第一图形凹槽内，所述导电凝胶层设有与所述第一图形凹槽相对应的多个第二凸起，所述导电凝胶层覆盖所述光刻胶层，且所述多个第二凸起的端面与所述变色层的表面接触。
  2. 如权利要求1所述的电致变色器件，其特征在于，在所述导电凝胶层远离所述变色层的一侧表面设有一镀锡氧化铟(ITO)玻璃，在所述导电凝胶层和所述镀锡氧化铟(ITO)玻璃之间设有存储层。
  3. 如权利要求1所述的电致变色器件，其特征在于，所述光刻胶层设有形成所述第一图形凹槽的多个第一凸起，所述变色层还覆盖所述多个第一凸起。
  4. 如权利要求1所述的电致变色器件，其特征在于，所述变色层的厚度小于所述第一图形凹槽的高度。
  5. 如权利要求1所述的电致变色器件，其特征在于，所述第一图形凹槽的底部与所述导电基板的部分表面重叠。
  6. 如权利要求1所述的电致变色器件，其特征在于，所述导电基板包括导电层和透明基底，所述导电层由在所述透明基底上镀的金属氧化物形成。
  7. 如权利要求1至6任一项所述的电致变色器件，其特征在于，当所述导电基板接负极，所述导电凝胶层接正极时，所述变色层实现从透明到有色；当所述导电基板接正极，所述导电凝胶层接负极，所述变色层实现从有色到透明。
  8. 一种电致变色器件的制作方法，其特征在于，该方法包括：
    提供一导电基板；
    在所述导电基板上旋涂一层光刻胶形成光刻胶层，对所述光刻胶层进行光刻，在所述光刻胶层上形成第一图形凹槽；
    将变色层材料填充在所述第一图形凹槽内，固化后形成变色层；
    将导电凝胶涂布在所述光刻胶层上，固化后形成导电凝胶层，所述导电凝胶层与所述变色层接触。
  9. 如权利要求7所述的电致变色器件的制作方法，其特征在于，包括实现光刻的掩模版，在所述光刻胶层上形成第一图形凹槽的步骤中：用除尘剂将所述导电基板的表面清洗干净，采用旋涂的方式在所述表面涂一层光刻胶后，放入90°的烘箱加热一小时，然后利用所述掩模版曝光后，进行显影、蚀刻，得到具有所述第一图形凹槽的光刻胶层，所述第一图形凹槽的底部与所述导电基板的部分表面重叠。
  10. 如权利要求7所述的电致变色器件的制作方法，其特征在于，在形成所述变色层的步骤中：将具有变色层材料采用旋涂或电沉积法均匀填充在所述第一图形凹槽内，且所述变色材料未填满所述第一图形凹槽，加热固化后得到所述变色层。
  11. 如权利要求7所述的电致变色器件的制作方法，其特征在于，在所述形成导电凝胶层的步骤中：采用旋涂或刮涂的方式将导电凝胶涂布在所述光刻胶层上，固化后形成所述导电凝胶层。
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