WO2022061953A1 - Multi-color electrochromic structure having high brightness, saturation and purity, multi-color electrochromic device, and method for preparing structure - Google Patents

Abstract

Disclosed in the present application are a multi-color electrochromic structure having a high brightness, saturation and purity, a multi-color electrochrmic device, and a method for preparing the structure. The multi-color electrochromic structure comprises an electrochromic layer, which comprises a plurality of layer number pair structures formed by sequentially and alternately superposing and arranging first optical structure layers or second optical structure layers and dielectric layers, wherein bonding interfaces of the dielectric layers and the first optical structure layers and of the dielectric layers and the second optical structure layers are respectively first surfaces and second surfaces of the dielectric layers, and the first surfaces and the second surfaces are fitted with the dielectric layers to form optical cavities. Further disclosed in the present application is the multi-color electrochromic device. In the present application, metal layers of different thicknesses or dielectric layers of different thicknesses are deposited on different substrates to serve as electrochromic structures, such that the multi-color electrochromic structures having different brightnesses, saturations and purities can be realized. The multi-color electrochromic structure of the present application belongs to structural colors, is stable in color, is brightly colored and has a high degree of manufacturability, and cannot age or lose color after being exposed to an outdoor environment for a long time.

Description

高亮度、饱和度、纯度的多彩电致变色结构、器件及制法Colorful electrochromic structure, device and manufacturing method with high brightness, saturation and purity

本申请基于并要求于2020年9月22日递交的申请号为202011004881.6、发明名称为“高亮度、饱和度、纯度的多彩电致变色结构、器件及制法”的中国专利申请的优先权。This application is based on and claims the priority of the Chinese patent application filed on September 22, 2020 with the application number 202011004881.6 and the invention titled "High Brightness, Saturation, Purity Colorful Electrochromic Structure, Device and Manufacturing Method".

技术领域technical field

本申请涉及一种多彩薄膜，具体涉及一种高亮度、饱和度、纯度的多彩电致变色结构、其制备方法及相应的多彩电致变色器件，属于光学或光电技术领域。The application relates to a colorful film, in particular to a colorful electrochromic structure with high brightness, saturation and purity, a preparation method thereof and a corresponding colorful electrochromic device, which belong to the technical field of optics or optoelectronics.

背景技术Background technique

电致变色是材料的光学属性在施加电压下发生循环可逆变化的现象，对于最常使用的智能窗，电致变色材料器件只需要满足光线透明度的调制，而在显示器件的应用领域，电致变色则是通过电压实现不同颜色的动态调控。多彩电致变色显示是在变色前后，材料表现出不一样的颜色，这在显示器件以及智能服装领域有着极强的吸引力。多彩电致变色技术以往主要是有机小分子或共轭聚合物电致变色材料在不同的氧化还原状态下能表现出不同本征颜色，这属于本征化学色的多彩电致变色。Electrochromism is a phenomenon in which the optical properties of materials undergo cyclic and reversible changes under an applied voltage. For the most commonly used smart windows, electrochromic material devices only need to meet the modulation of light transparency. In the application field of display devices, electrochromic materials Discoloration is the dynamic regulation of different colors through voltage. Colorful electrochromic display is that the material shows different colors before and after discoloration, which is extremely attractive in the field of display devices and smart clothing. In the past, multi-color electrochromic technology mainly used organic small molecule or conjugated polymer electrochromic materials to exhibit different intrinsic colors in different redox states, which belongs to the multi-color electrochromic of intrinsic chemical colors.

而在自然界中，关于颜色的分类主要分两大类，一种是化学色，另一种是物理色。物理色又称为结构色，结构色是物体特殊的组织结构使光发生色散、散射、干涉和衍射等现象而产生的视觉效果，它与色素着色无关，利用不褪色和虹彩效应等优点可以制作隐身材料、防伪纸币、仿生材料等。In nature, the classification of colors is mainly divided into two categories, one is chemical color, the other is physical color. Physical color is also known as structural color. Structural color is the visual effect caused by the phenomenon of dispersion, scattering, interference and diffraction of light caused by the special organizational structure of the object. It has nothing to do with pigment coloring. Stealth materials, anti-counterfeiting banknotes, bionic materials, etc.

近年来，研究学者发现：将电致变色材料和结构色通过某种方式相结合，可以使电致变色材料表现出和其本征颜色不一样的结构色。结构色融合的电致变色可以克服一些电致变色材料颜色单调的缺点而实现多彩的电致变色显示。但是目前为止，多彩薄膜的颜色饱和度不高，或亮度有待提高，又或是色域较小，这种结构色的应用很难满足大众的需求。因此，如何对多彩电致变色结构的工作电极进行优化，寻求一种制备具有高亮度、饱和度、纯度的多彩薄膜的新技术，已然成为业界研究人员长期以来一直努力的方向。In recent years, researchers have found that by combining electrochromic materials and structural colors in some way, electrochromic materials can exhibit structural colors that are different from their intrinsic colors. Structural color fusion electrochromic can overcome the shortcoming of monotonous color of some electrochromic materials and realize colorful electrochromic display. However, so far, the color saturation of the colorful film is not high, or the brightness needs to be improved, or the color gamut is small, and the application of such structural colors is difficult to meet the needs of the public. Therefore, how to optimize the working electrode of colorful electrochromic structure and seek a new technology to prepare colorful thin films with high brightness, saturation and purity has become the direction that researchers in the industry have been working on for a long time.

发明内容SUMMARY OF THE INVENTION

本申请的主要目的在于提供一种高亮度、饱和度、纯度的多彩电致变色结构及其制备方 法，以克服现有技术中的不足。The main purpose of this application is to provide a colorful electrochromic structure with high brightness, saturation, and purity and a preparation method thereof, to overcome the deficiencies in the prior art.

本申请的另一目的在于提供一种多彩电致变色器件。Another object of the present application is to provide a colorful electrochromic device.

为实现前述发明目的，本申请采用的技术方案包括：In order to achieve the aforementioned purpose of the invention, the technical solutions adopted in this application include:

本申请实施例提供了一种高亮度、饱和度、纯度的多彩电致变色结构，其包括电致变色层，所述电致变色层包括：复数个由第一光学结构层或第二光学结构层、介质层依次交替叠加排列形成的层数对结构；The embodiments of the present application provide a colorful electrochromic structure with high brightness, saturation, and purity, which includes an electrochromic layer, and the electrochromic layer includes: a plurality of layers composed of a first optical structure layer or a second optical structure Layers and dielectric layers are alternately stacked and arranged in turn to form a pair of layers structure;

其中，所述第一光学结构层、第二光学结构层是光学反射性和/或光学透射性的，所述介质层与第一光学结构层、第二光学结构层的结合界面分别为所述介质层的第一表面、第二表面，所述第一表面、第二表面与介质层配合形成一光学腔；在入射光从第一光学结构层或第二光学结构层入射所述光学腔时，于所述第一表面形成的反射光和于所述第二表面形成的反射光的相移

d为所述介质层的厚度，

为所述介质层的折射率，λ为所述入射光的波长，

为所述入射光在透过所述第一表面或第二表面时的折射角。 Wherein, the first optical structure layer and the second optical structure layer are optically reflective and/or optically transmissive, and the bonding interface between the dielectric layer and the first optical structure layer and the second optical structure layer is the The first surface and the second surface of the dielectric layer, the first surface and the second surface cooperate with the dielectric layer to form an optical cavity; when incident light enters the optical cavity from the first optical structure layer or the second optical structure layer , the phase shift of the reflected light formed on the first surface and the reflected light formed on the second surface

d is the thickness of the dielectric layer,

is the refractive index of the dielectric layer, λ is the wavelength of the incident light,

is the refraction angle of the incident light when it passes through the first surface or the second surface.

进一步地，所述电致变色层具有光学透射工作模式、光学反射工作模式或者光学透射及反射工作模式。Further, the electrochromic layer has an optical transmission working mode, an optical reflection working mode or an optical transmission and reflection working mode.

进一步地，所述第一光学结构层和第二光学结构层的厚度和/或材质不同。Further, the thickness and/or material of the first optical structure layer and the second optical structure layer are different.

进一步地，其中两个不同介质层的厚度和/或材质不同。Further, the thicknesses and/or materials of the two different dielectric layers are different.

进一步地，施加于所述多彩电致变色结构的电致变色电压为-0.8V～1.0V。Further, the electrochromic voltage applied to the colorful electrochromic structure is -0.8V-1.0V.

相应的，本申请实施例还提供了所述高亮度、饱和度、纯度的多彩电致变色结构的制备方法，其包括：Correspondingly, the embodiment of the present application also provides a method for preparing the colorful electrochromic structure with high brightness, saturation and purity, which includes:

提供基底；provide a base;

在所述基底上交替沉积形成第一光学结构层或第二光学结构层和介质层，并重复操作两次以上，获得所述高亮度、饱和度、纯度的多彩电致变色结构。Alternately depositing a first optical structure layer or a second optical structure layer and a dielectric layer on the substrate, and repeating the operation for more than two times, the multicolor electrochromic structure with high brightness, saturation and purity is obtained.

本申请实施例还提供了所述高亮度、饱和度、纯度的多彩电致变色结构的应用，例如在制备光学器件、光电器件、电子器件等设备内的应用。The embodiments of the present application also provide applications of the colorful electrochromic structures with high brightness, saturation, and purity, such as applications in the preparation of optical devices, optoelectronic devices, and electronic devices.

例如，本申请实施例提供了一种高亮度、饱和度、纯度的多彩电致变色器件，包括工作电极、电解质和对电极，所述电解质分布于工作电极和对电极之间，所述工作电极包括前述高亮度、饱和度、纯度的多彩电致变色结构。For example, the embodiments of the present application provide a colorful electrochromic device with high brightness, saturation and purity, including a working electrode, an electrolyte and a counter electrode, the electrolyte is distributed between the working electrode and the counter electrode, and the working electrode Including the above-mentioned colorful electrochromic structure with high brightness, saturation and purity.

本申请实施例还提供了所述高亮度、饱和度、纯度的多彩电致变色器件的制备方法包括：The embodiment of the present application also provides the preparation method of the colorful electrochromic device with high brightness, saturation and purity, including:

提供基底；provide a base;

在所述基底上交替沉积形成第一光学结构层或第二光学结构层和介质层，并重复操作两 次以上，获得电致变色层，进而获得工作电极；以及，将工作电极、电解质、对电极组装形成高亮度、饱和度、纯度的多彩电致变色器件。Alternately depositing a first optical structure layer or a second optical structure layer and a dielectric layer on the substrate, and repeating the operation for more than two times, to obtain an electrochromic layer, and then to obtain a working electrode; The electrodes are assembled to form colorful electrochromic devices with high brightness, saturation and purity.

本申请实施例提供了一种所述多彩电致变色器件的调控方法，其包括：The embodiment of the present application provides a method for regulating and controlling the colorful electrochromic device, which includes:

将工作电极、对电极与电源连接形成工作电路；Connect the working electrode, the counter electrode and the power source to form a working circuit;

调整工作电极与对电极之间的电势差，使介质层内电致变色材料的折射率发生变化，从而调控所述多彩电致变色器件的颜色。The potential difference between the working electrode and the counter electrode is adjusted to change the refractive index of the electrochromic material in the dielectric layer, thereby regulating the color of the colorful electrochromic device.

本申请实施例还提供了一种装置，其包括所述的多彩电致变色器件。The embodiment of the present application also provides a device, which includes the multi-colored electrochromic device.

与现有技术相比，本申请的优点在于：Compared with the prior art, the advantages of the present application are:

1)本申请的各光学结构层和介质层构成一种光学结构-介质结构，能产生光学多层薄膜干涉，从而显示出多彩色；各光学结构层厚度的不同可以使多彩薄膜显示出不同的亮度、饱和度、纯度；介质层厚度的不同可以使多彩薄膜显示出不同的亮度、饱和度、纯度；基底的不同可以使多彩薄膜显示出不同的亮度、饱和度、纯度；各光学结构层和介质层交替排列；光学结构层和介质层组成层数对，随着层数对的改变，颜色的高亮度、饱和度、纯度也有所改变；1) Each optical structure layer and dielectric layer of the present application constitute an optical structure-dielectric structure, which can produce optical multilayer film interference, thereby showing multicolor; the thickness of each optical structure layer can make the multicolor film show different Brightness, saturation and purity; the thickness of the dielectric layer can make the colorful film show different brightness, saturation and purity; the difference of the substrate can make the colorful film display different brightness, saturation and purity; The dielectric layers are alternately arranged; the optical structure layer and the dielectric layer form a pair of layers. With the change of the number of layers, the high brightness, saturation and purity of the color also change;

2)本申请通过在不同的基底上沉积不同厚度的金属层或不同厚度的介质层，可以实现不同亮度、不同饱和度、不同纯度的多彩电致变色结构。本申请的高亮度、饱和度、纯度的多彩电致变色结构的电致变色层属于一种结构色，相比市场上现有的各种颜色染料制备的多彩薄膜，其颜色稳定，色彩绚丽，可制造程度高，长时间暴露在室外环境下不会老化失色；2) In the present application, by depositing metal layers with different thicknesses or dielectric layers with different thicknesses on different substrates, colorful electrochromic structures with different brightness, different saturation and different purity can be realized. The electrochromic layer of the multi-color electrochromic structure with high brightness, saturation and purity of the present application belongs to a kind of structural color. High degree of manufacturability, long-term exposure to outdoor environment will not age;

3)本申请中的多彩电致变色结构在组装成电致变色器件后，器件颜色仍能保持较高的亮度、饱和度、纯度。3) After the colorful electrochromic structure in the present application is assembled into an electrochromic device, the color of the device can still maintain high brightness, saturation and purity.

附图说明Description of drawings

为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only These are some embodiments described in this application. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

图1是本申请一典型实施方案中一种电致变色层的结构示意图；1 is a schematic structural diagram of an electrochromic layer in a typical embodiment of the present application;

图2是本申请一典型实施方案中一种电致变色层的实物图片；2 is a physical picture of an electrochromic layer in a typical embodiment of the present application;

图3是本申请一典型实施方案中一种电致变色层可见光区的反射率曲线图；Fig. 3 is the reflectivity curve diagram of an electrochromic layer in the visible light region in a typical embodiment of the present application;

图4是本申请一典型实施方案中一种电致变色层的色坐标图；4 is a color coordinate diagram of an electrochromic layer in an exemplary embodiment of the present application;

图5是本申请一典型实施方案中一种高亮度、饱和度、纯度的不同层数对(N≥2，注： 其中N＝1为对照组)的多彩电致变色结构在电致变色过程中的实物图片；Fig. 5 is a multi-color electrochromic structure with high brightness, saturation, and purity of different layers (N≥2, note: where N=1 is the control group) in an electrochromic process in a typical embodiment of the present application. real pictures in;

图6是本申请一典型实施方案中一种高亮度、饱和度、纯度的不同金属层厚度的多彩电致变色结构在电致变色过程中实物图片。6 is a real picture of a multi-colored electrochromic structure with different metal layer thicknesses with high brightness, saturation and purity in an electrochromic process according to a typical embodiment of the present application.

具体实施方式detailed description

针对现有技术的诸多缺陷，本案发明人经长期研究和大量实践，得以提出本申请的技术方案。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。但是，应当理解，在本申请范围内，本申请的上述各技术特征和在下文(实施例)中具体描述的各技术特征之间都可以相互结合，从而构成新的或者优选的技术方方案。限于篇幅，在此不再一一赘述。In view of the many defects of the prior art, the inventor of the present application has been able to propose the technical solution of the present application after long-term research and extensive practice. The technical solution, its implementation process and principle will be further explained as follows. However, it should be understood that within the scope of the present application, the above-mentioned technical features of the present application and the technical features specifically described in the following (embodiments) can be combined with each other to constitute new or preferred technical solutions. Due to space limitations, they will not be repeated here.

为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请中记载的一些实施方案，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本申请保护的范围。以下实施例中采用的实施条件可以根据实际需要而做进一步调整，未注明的实施条件通常为常规实验中的条件。In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only Some, but not all, examples are described in this application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present application. The implementation conditions adopted in the following examples can be further adjusted according to actual needs, and the unremarked implementation conditions are usually the conditions in routine experiments.

又及，需要说明的是，在本说明书中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，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，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个......”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。Also, it should be noted that in this specification, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply these There is no such actual relationship or sequence between entities or operations. Moreover, the terms "comprising", "comprising" or any other variation thereof are intended to encompass a non-exclusive inclusion such that a process, method, article or device that includes a list of elements includes not only those elements, but also includes not explicitly listed or other elements inherent to such a process, method, article or apparatus. Without further limitation, an element defined by the phrase "comprising a..." does not preclude the presence of additional identical elements in a process, method, article or apparatus that includes the element.

本申请实施例的一个方面提供的一种高亮度、饱和度、纯度的多彩电致变色结构，包括电致变色层，所述电致变色层包括：复数个由第一光学结构层或第二光学结构层、介质层依次交替叠加排列形成的层数对结构；An aspect of the embodiments of the present application provides a colorful electrochromic structure with high brightness, saturation, and purity, including an electrochromic layer, and the electrochromic layer includes: a plurality of layers composed of a first optical structure layer or a second optical structure layer. The optical structure layer and the dielectric layer are alternately stacked and arranged in turn to form a pair of layers structure;

其中，所述第一光学结构层、第二光学结构层是光学反射性和/或光学透射性的，所述介质层与第一光学结构层、第二光学结构层的结合界面分别为所述介质层的第一表面、第二表面，所述第一表面、第二表面与介质层配合形成光学腔。Wherein, the first optical structure layer and the second optical structure layer are optically reflective and/or optically transmissive, and the bonding interface between the dielectric layer and the first optical structure layer and the second optical structure layer is the The first surface and the second surface of the dielectric layer, the first surface and the second surface cooperate with the dielectric layer to form an optical cavity.

进一步地，对于所述电致变色层而言，由从第一光学结构层入射的入射光在所述第一表面形成的反射光与由透过所述介质层的入射光在第二表面形成的反射光干涉叠加。反之亦然，即，由从第二光学结构层入射的入射光在所述第二表面形成的反射光与由透过所述介质层的 入射光在第一表面形成的反射光干涉叠加。Further, for the electrochromic layer, the reflected light formed on the first surface by the incident light incident from the first optical structure layer and the incident light formed on the second surface by the incident light transmitted through the dielectric layer are formed on the second surface. The reflected light interference superposition. Vice versa, that is, the reflected light formed on the second surface by the incident light incident from the second optical structure layer interferes with the reflected light formed on the first surface by the incident light transmitted through the dielectric layer.

进一步地，在入射光从第一光学结构层或第二光学结构层入射所述光学腔时，于所述第一表面形成的反射光和于所述第二表面形成的反射光的相移

d为所述介质层的厚度，

为所述介质层的折射率，λ为所述入射光的波长，

为所述入射光在透过所述第一表面或第二表面时的折射角。 Further, when incident light enters the optical cavity from the first optical structure layer or the second optical structure layer, the phase shift of the reflected light formed on the first surface and the reflected light formed on the second surface

d is the thickness of the dielectric layer,

is the refractive index of the dielectric layer, λ is the wavelength of the incident light,

is the refraction angle of the incident light when it passes through the first surface or the second surface.

在一些实施方案中，若定义所述第一光学结构层的折射率为

则所述第一表面的反射系数

其中

为入射光于第一表面的入射角。 In some embodiments, if the refractive index of the first optical structure layer is defined as

Then the reflection coefficient of the first surface

in

is the incident angle of the incident light on the first surface.

在一些实施方案中，若定义所述第二光学结构层的折射率为

则所述第二表面的反射系数

其中

为入射光在透过第二表面时的折射角。 In some implementations, if the refractive index of the second optical structure layer is defined as

Then the reflection coefficient of the second surface

in

is the refraction angle of the incident light when it passes through the second surface.

在一些实施方案中，所述电致变色层的反射系数表示为：

反射率表示为：

In some embodiments, the reflection coefficient of the electrochromic layer is expressed as:

The reflectance is expressed as:

进一步地，所述电致变色层的反射系数、反射率同样适用于入射光从第二光学结构层入射所述光学腔的情况。Further, the reflection coefficient and reflectivity of the electrochromic layer are also applicable to the case where the incident light enters the optical cavity from the second optical structure layer.

在一些实施方案中，若定义所述第一光学结构层的折射率为

则所述第一光学结构层的透射系数

其中

为入射光于第一表面的入射角。 In some embodiments, if the refractive index of the first optical structure layer is defined as

Then the transmission coefficient of the first optical structure layer

in

is the incident angle of the incident light on the first surface.

在一些实施方案中，若定义所述第二光学结构层的折射率为

则所述第二光学结构层的透射系数

其中

为入射光在透过第二表面时的折射角。 In some implementations, if the refractive index of the second optical structure layer is defined as

Then the transmission coefficient of the second optical structure layer

in

is the refraction angle of the incident light when it passes through the second surface.

在一些实施方案中，所述电致变色层的透射系数表示为：

透过率表示为：

In some embodiments, the transmission coefficient of the electrochromic layer is expressed as:

The transmittance is expressed as:

进一步地，所述电致变色层的透射系数、透过率同样适用于入射光从第二光学结构层入射所述光学腔的情况。Further, the transmittance and transmittance of the electrochromic layer are also applicable to the case where the incident light enters the optical cavity from the second optical structure layer.

进一步地，所述电致变色层具有光学透射工作模式、光学反射工作模式或者光学透射及反射工作模式。Further, the electrochromic layer has an optical transmission working mode, an optical reflection working mode or an optical transmission and reflection working mode.

其中，在所述光学反射工作模式下，所述电致变色层具有双面不对称结构色。Wherein, in the optical reflection working mode, the electrochromic layer has a double-sided asymmetric structural color.

其中，在所述光学透射工作模式下，所述电致变色层具有透明结构色。Wherein, in the optical transmission working mode, the electrochromic layer has a transparent structural color.

在一些实施方案中，所述第一光学结构层和第二光学结构层中至少一者的材质包括金属材料。In some implementations, the material of at least one of the first optical structure layer and the second optical structure layer includes a metal material.

进一步地，各光学结构层和介质层构成一种光学结构-介质结构，能产生光学多层薄膜干涉，从而显示出多彩色。Further, each optical structure layer and the dielectric layer constitute an optical structure-dielectric structure, which can produce optical multilayer thin film interference, thereby displaying multicolor.

进一步地，各光学结构层和介质层交替排列组成层数对，随着层数对的改变，颜色的高亮度、饱和度、纯度也有所改变，所述层数对结构的数量N≥2，优选为N＝2～6。Further, each optical structure layer and the medium layer are alternately arranged to form a layer pair, and with the change of the layer pair, the high brightness, saturation, and purity of the color also change, and the number of the layer pair structure N≥2, Preferably N=2-6.

在一些实施方案中，所述第一光学结构层或第二光学结构层为金属层。In some embodiments, the first optical structure layer or the second optical structure layer is a metal layer.

在一些实施方案中，所述第一光学结构层和第二光学结构层均为金属层。In some embodiments, the first optical structure layer and the second optical structure layer are both metal layers.

进一步地，本申请的电致变色层中不需要限定最顶层为介质层或金属层，可以根据需要在顶层添加金属层来达到材料的其他目的。Further, in the electrochromic layer of the present application, it is not necessary to define the topmost layer as a dielectric layer or a metal layer, and a metal layer can be added on the top layer as required to achieve other purposes of the material.

进一步地，所述电致变色层包括多层薄层金属层和多层介质层交替排列；单层的所述金属层和所述介质层由于发生光的干涉而实现光线的选择性吸收和反射；多层的所述金属层和所述介质层由于发生光的多层干涉而提高颜色的亮度、饱和度和纯度。Further, the electrochromic layer includes multiple thin metal layers and multiple dielectric layers alternately arranged; the single layer of the metal layer and the dielectric layer achieves selective absorption and reflection of light due to light interference. ; The multi-layered metal layer and the dielectric layer improve the brightness, saturation and purity of the color due to the multi-layer interference of light.

在一些实施方案中，所述第一光学结构层或第二光学结构层直接为空气。In some embodiments, the first optical structure layer or the second optical structure layer is directly air.

在一些实施方案中，所述第一光学结构层或第二光学结构层不存在。In some embodiments, the first optical structure layer or the second optical structure layer is absent.

进一步地，所述金属材料包括钨、金、银、铜、钛、铝、铬、铁、钴、镍、铂、锗、钯等，但不限于此。Further, the metal material includes tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, palladium, etc., but is not limited thereto.

在一些实施方案中，所述第一光学结构层和第二光学结构层的厚度和/或材质不同。其中，光学结构层厚度的不同可以使电致变色层显示出不同的亮度、饱和度、纯度。In some embodiments, the thickness and/or material of the first optical structure layer and the second optical structure layer are different. Among them, the different thickness of the optical structure layer can make the electrochromic layer show different brightness, saturation and purity.

进一步地，所述第一光学结构层或第二光学结构层的厚度为0～30nm，优选为10～30nm。Further, the thickness of the first optical structure layer or the second optical structure layer is 0-30 nm, preferably 10-30 nm.

进一步地，所述第一光学结构层或第二光学结构层还与基底结合。Further, the first optical structure layer or the second optical structure layer is also combined with the substrate.

进一步地，与基底结合的第一光学结构层或第二光学结构层的厚度在100nm以上，优选为100～3000nm，其余第一光学结构层或第二光学结构层的厚度为10～30nm。Further, the thickness of the first optical structure layer or the second optical structure layer combined with the substrate is more than 100 nm, preferably 100-3000 nm, and the thickness of the remaining first or second optical structure layers is 10-30 nm.

在一些实施方案中，其中两个不同介质层的厚度和/或材质不同。其中，介质层厚度的不同可以使电致变色层显示出不同的亮度、饱和度、纯度。In some embodiments, the thicknesses and/or materials of the two different dielectric layers are different. Among them, the different thickness of the dielectric layer can make the electrochromic layer show different brightness, saturation and purity.

进一步地，基于其中两个不同介质层的两个不同光学腔呈现的颜色不同。Further, two different optical cavities based on two different dielectric layers exhibit different colors.

进一步地，所述介质层的厚度为0～3000nm，优选可以为10～3000nm，尤其优选为100～500nm，尤其优选为150～250nm。Further, the thickness of the dielectric layer is 0-3000 nm, preferably 10-3000 nm, particularly preferably 100-500 nm, particularly preferably 150-250 nm.

在一些实施方案中，所述介质层的材质选自有机材料或无机材料。In some embodiments, the material of the dielectric layer is selected from organic materials or inorganic materials.

进一步地，所述无机材料包括金属单质或非金属单质、无机盐、氧化物中任意一种或多 种的组合，但不限于此。Further, the inorganic material includes any one or a combination of metal element or non-metal element, inorganic salt, oxide, but is not limited thereto.

进一步地，所述非金属单质包括单晶硅、多晶硅、金刚石中任意一种或多种的组合，但不限于此。Further, the non-metal element includes any one or a combination of single crystal silicon, polycrystalline silicon, and diamond, but is not limited thereto.

进一步地，所述无机盐包括氟化物、硫化物、硒化物、氯化物、溴化物、碘化物、砷化物或碲化物中任意一种或多种的组合，但不限于此。Further, the inorganic salt includes, but is not limited to, a combination of any one or more of fluoride, sulfide, selenide, chloride, bromide, iodide, arsenide or telluride.

进一步地，所述氧化物包括WO ₃、NiO、TiO ₂、Nb ₂O ₅、Fe ₂O ₃、V ₂O ₅、Co ₂O ₃、Y ₂O ₃、Cr ₂O ₃、MoO ₃、Al ₂O ₃、SiO ₂、MgO、ZnO、MnO ₂、CaO、ZrO ₂、Ta ₂O ₅、Y ₃Al ₅O ₁₂、Er ₂O ₃、IrO ₂中任意一种或多种的组合，但不限于此。 Further, the oxides include WO ₃ , NiO, TiO ₂ , Nb ₂ O ₅ , Fe ₂ O ₃ , V ₂ O ₅ , Co ₂ O ₃ , Y ₂ O ₃ , Cr ₂ O ₃ , MoO ₃ , Al ₂ O ₃ , SiO ₂ , MgO, ZnO, MnO ₂ , CaO, ZrO ₂ , Ta ₂ O ₅ , Y ₃ Al ₅ O ₁₂ , Er ₂ O ₃ , IrO ₂ , any one or a combination of them, but not limited to this.

更进一步地，所述氟化物包括MgF ₂、CaF ₂、GeF ₂、YbF ₃、YF ₃、Na ₃AlF ₆、AlF ₃、NdF ₃、LaF ₃、LiF、NaF、BaF ₂、SrF ₂中任意一种或多种的组合，但不限于此。 Further, the fluoride includes any one of MgF ₂ , CaF ₂ , GeF ₂ , YbF ₃ , YF ₃ , Na ₃ AlF ₆ , AlF ₃ , NdF ₃ , LaF ₃ , LiF , NaF , BaF ₂ , SrF ₂ One or more combinations, but not limited to this.

进一步地，所述硫化物包括ZnS、GeS、MoS ₂、Bi ₂S ₃中任意一种或多种的组合，但不限于此。 Further, the sulfide includes, but is not limited to, a combination of any one or more of ZnS, GeS, MoS ₂ , and Bi ₂ S ₃ .

进一步地，所述硒化物包括ZnSe，GeSe、MoSe ₂、PbSe、Ag ₂Se中任意一种或多种的组合，但不限于此。 Further, the selenide includes, but is not limited to, any one or a combination of ZnSe, GeSe, MoSe ₂ , PbSe, and Ag ₂ Se.

进一步地，所述氯化物包括AgCl、NaCl、KCl中任意一种或多种的组合，但不限于此。Further, the chloride includes any one or a combination of AgCl, NaCl, and KCl, but is not limited thereto.

进一步地，所述溴化物包括AgBr、NaBr、KBr、TlBr、CsBr中任意一种或多种的组合，但不限于此。Further, the bromide includes any one or a combination of AgBr, NaBr, KBr, TlBr, and CsBr, but is not limited thereto.

进一步地，所述碘化物包括AgI、NaI、KI、RbI、CsI中任意一种或多种的组合，但不限于此。Further, the iodide includes any one or a combination of AgI, NaI, KI, RbI, and CsI, but is not limited thereto.

进一步地，所述砷化物包括GaAs等，但不限于此。Further, the arsenide includes GaAs and the like, but is not limited thereto.

进一步地，所述锑化物包括GdTe等，但不限于此。Further, the antimonide compound includes GdTe and the like, but is not limited thereto.

进一步地，所述介质层的材质包括SrTiO ₃、Ba ₃Ta ₄O ₁₅、Bi ₄Ti ₃O ₂、CaCO ₃、CaWO ₄、CaMnO ₄、LiNbO ₄、普鲁士蓝、普鲁士黑、普鲁士白、普鲁士绿中任意一种或多种的组合，但不限于此。 Further, the material of the dielectric layer includes SrTiO ₃ , Ba ₃ Ta ₄ O ₁₅ , Bi ₄ Ti ₃ O ₂ , CaCO ₃ , CaWO ₄ , CaMnO ₄ , LiNbO ₄ , Prussian blue, Prussian black, Prussian white, and Prussian green A combination of any one or more of, but not limited to.

进一步地，所述介质层的材质包括液晶材料或MOF材料，但不限于此。Further, the material of the dielectric layer includes liquid crystal material or MOF material, but is not limited thereto.

进一步地，所述有机材料包括有机小分子化合物和/或聚合物，但不限于此。Further, the organic material includes, but is not limited to, organic small molecule compounds and/or polymers.

进一步地，所述有机材料包括紫罗精、聚吡咯、聚苯胺、聚噻吩、聚咔唑、酞菁、对苯二甲脂、二甲基联二苯胺、四噻富烯、烷基联吡啶、吩噻唑、聚酰胺、环氧树脂、聚二炔中任意一种或多种的组合，但不限于此。Further, the organic material includes viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthalene, dimethylbenzidine, tetrathifulene, alkyl bipyridine , phenothiazole, polyamide, epoxy resin, polydiyne, any one or a combination, but not limited thereto.

在一些实施方案中，所述介质层可以主要由电致变色材料组成。所述的电致变色材料可以选自无机、有机材料或者液晶材料和MOF材料等。例如，所述无机材料可以包括过渡金属氧化物WO ₃、NiO、TiO ₂、Nb ₂O ₅、Fe ₂O ₃、V ₂O ₅、Co ₂O ₃、Y ₂O ₃、MoO ₃、IrO ₂、普鲁士蓝、 普鲁士黑、普鲁士白、普鲁士绿等，且不限于此。所述有机材料可以包括紫罗精、聚吡咯、聚苯胺、聚噻吩、聚咔唑、酞菁、对苯二甲脂、二甲基联二苯胺、四噻富烯、烷基联吡啶、吩噻唑、聚二炔等，但不限于此。 In some embodiments, the dielectric layer may consist essentially of an electrochromic material. The electrochromic material can be selected from inorganic, organic materials, or liquid crystal materials, MOF materials, and the like. For example, the inorganic material may include transition metal oxides WO ₃ , NiO, TiO ₂ , Nb ₂ O ₅ , Fe ₂ O ₃ , V ₂ O ₅ , Co ₂ O ₃ , Y ₂ O ₃ , MoO ₃ , IrO ₂ , Prussian blue, Prussian black, Prussian white, Prussian green, etc., but not limited thereto. The organic material may include viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthalate, dimethylbenzidine, tetrathiefene, alkyl bipyridine, Thiazole, polydiyne, etc., but not limited thereto.

进一步地，还可以在所述第一光学结构层或第二光学结构层与介质层之间增加优化介质层，以优化所述电致变色层的颜色。Further, an optimized dielectric layer can also be added between the first optical structure layer or the second optical structure layer and the dielectric layer to optimize the color of the electrochromic layer.

进一步地，还可以在所述第一光学结构层或第二光学结构层上增加优化介质层，或者，也可以将所述第一光学结构层或第二光学结构层设置在优化介质层上，以优化所述电致变色层的颜色。Further, an optimized medium layer can also be added on the first optical structure layer or the second optical structure layer, or, the first optical structure layer or the second optical structure layer can also be arranged on the optimized medium layer, to optimize the color of the electrochromic layer.

在一些实施方案中，所述第一光学结构层或第二光学结构层与基底结合。In some embodiments, the first optical structure layer or the second optical structure layer is bonded to the substrate.

进一步地，所述基底为透明或半透明的。相应的，所述基底的材质可以是透明或半透明的，例如可以选自塑料制品、织物、金属合金、陶瓷、有机玻璃、PET、PES、PEN、PC、PMMA、PDMS等材料中的任意一种或多种的组合，或者可以是其他柔性或刚性衬底，但不限于此。本申请中基底的不同可以使电致变色层显示出不同的亮度、饱和度、纯度。Further, the substrate is transparent or translucent. Correspondingly, the material of the substrate can be transparent or translucent, for example, can be selected from any one of plastic products, fabrics, metal alloys, ceramics, plexiglass, PET, PES, PEN, PC, PMMA, PDMS and other materials A combination of one or more, or may be other flexible or rigid substrates, but not limited thereto. Different substrates in this application can make the electrochromic layer show different brightness, saturation, and purity.

进一步地，前述优化介质层可以设置在所述第一光学结构层或第二光学结构层与基底之间。Further, the aforementioned optimized medium layer may be disposed between the first optical structure layer or the second optical structure layer and the substrate.

进一步地，所述优化介质层的材质包括但不仅限于WO ₃、NiO、TiO ₂、Nb ₂O ₅、Fe ₂O ₃、V ₂O ₅、Co ₂O ₃、Y ₂O ₃、Cr ₂O ₃、MoO ₃、Al ₂O ₃、SiO ₂、MgO、ZnO、MnO ₂、CaO、ZrO ₂、Ta ₂O ₅、Y ₃Al ₅O ₁₂、Er ₂O ₃、ZnS、MgF ₂、SiN _x(氮化硅)等，但不限于此。 Further, the material of the optimized dielectric layer includes but is not limited to WO ₃ , NiO, TiO ₂ , Nb ₂ O ₅ , Fe ₂ O ₃ , V ₂ O ₅ , Co ₂ O ₃ , Y ₂ O ₃ , Cr ₂ O ₃ , MoO ₃ , Al ₂ O ₃ , SiO ₂ , MgO, ZnO, MnO ₂ , CaO, ZrO ₂ , Ta ₂ O ₅ , Y ₃ Al ₅ O ₁₂ , Er ₂ O ₃ , ZnS, MgF ₂ , SiN _x ( silicon nitride), etc., but not limited thereto.

进一步地，所述优化介质层的厚度优选为0～2000nm，优选为100～500nm。Further, the thickness of the optimized dielectric layer is preferably 0-2000 nm, preferably 100-500 nm.

在一个较为典型的实施方案中，请参阅图1所示，一种电致变色层的结构示意图，包括基底、金属层、介质层。金属层和介质层构成一种金属-介质结构，能产生光学多层薄膜干涉，从而显示出多彩色。In a more typical embodiment, please refer to FIG. 1 , which is a schematic structural diagram of an electrochromic layer, including a substrate, a metal layer, and a dielectric layer. The metal layer and the dielectric layer constitute a metal-dielectric structure, which can produce optical multilayer thin film interference, thereby showing multicolor.

进一步地，施加于所述多彩电致变色结构的电致变色电压为-0.8V～1.0V。Further, the electrochromic voltage applied to the colorful electrochromic structure is -0.8V-1.0V.

本申请实施例的另一个方面还提供了一种制备所述高亮度、饱和度、纯度的多彩电致变色结构的方法，其可以包括：Another aspect of the embodiments of the present application also provides a method for preparing the colorful electrochromic structure with high brightness, saturation and purity, which may include:

提供基底；provide a base;

在所述基底上交替沉积形成第一光学结构层或第二光学结构层和介质层，并重复操作两次以上，获得所述高亮度、饱和度、纯度的多彩电致变色结构。Alternately depositing a first optical structure layer or a second optical structure layer and a dielectric layer on the substrate, and repeating the operation for more than two times, the multicolor electrochromic structure with high brightness, saturation and purity is obtained.

在一些实施方案中，所述多彩电致变色结构的制备方法包括：通过物理或化学沉积方式，例如涂布、印刷、铸膜等方式或者磁控溅射、电子束蒸发、热蒸发、电化学沉积、化学气相沉积、原子力沉积、溶胶凝胶技术等形成所述第一光学结构层或第二光学结构层、介质层等， 且不限于此。In some embodiments, the preparation method of the colorful electrochromic structure includes: by physical or chemical deposition, such as coating, printing, film casting, etc. or magnetron sputtering, electron beam evaporation, thermal evaporation, electrochemical Deposition, chemical vapor deposition, atomic force deposition, sol-gel technique, etc., form the first optical structure layer or the second optical structure layer, the dielectric layer, etc., and are not limited thereto.

进一步地，所述多彩电致变色结构的制备方法具体包括：Further, the preparation method of the colorful electrochromic structure specifically includes:

提供一种基底；采用PVD沉积的方式，先在所述基底上沉积第一光学结构层或第二光学结构层，再在所述第一光学结构层或第二光学结构层上沉积介质层；根据需求沉积不同层数对。A substrate is provided; by PVD deposition, a first optical structure layer or a second optical structure layer is first deposited on the substrate, and then a dielectric layer is deposited on the first optical structure layer or the second optical structure layer; Pairs of different layers are deposited as required.

进一步地，所述PVD沉积的方式包括热蒸镀、电子束蒸发、磁控溅射等，但不限于此。Further, the PVD deposition method includes thermal evaporation, electron beam evaporation, magnetron sputtering, etc., but is not limited thereto.

进一步地，所述金属层(如W层)的制备方法有电子束蒸发、热蒸镀、磁控溅射等，而介质层(如WO ₃层)的制备方法有电子束蒸发、热蒸镀、磁控溅射、电化学沉积等。下面详细介绍电子束蒸发法、热蒸镀法、磁控溅射法和电化学沉积法四种制备方法。 Further, the preparation method of the metal layer (such as the W layer) includes electron beam evaporation, thermal evaporation, magnetron sputtering, etc., and the preparation method of the dielectric layer (such as the WO ₃ layer) includes electron beam evaporation, thermal evaporation. , magnetron sputtering, electrochemical deposition, etc. The four preparation methods of electron beam evaporation method, thermal evaporation method, magnetron sputtering method and electrochemical deposition method are introduced in detail below.

1.电子束蒸发法1. Electron beam evaporation method

电子束蒸发法是真空蒸发镀膜的一种技术，它的特点是很少或不会在目标三维结构的两侧覆盖，通常只会沉积在目标的表面，且制备出的薄膜纯度高、质量好，还可以准确的控制厚度。这种方法主要是指在真空条件下利用电子束进行直接加热蒸发材料，使蒸发材料气化并向基板输运，在基底上凝结形成薄膜，最后形成腕带所需要的金属反射层。Electron beam evaporation is a technology of vacuum evaporation coating, which is characterized by little or no coverage on both sides of the target three-dimensional structure, usually only deposited on the surface of the target, and the prepared film is of high purity and good quality , but also can accurately control the thickness. This method mainly refers to the use of electron beams to directly heat the evaporation material under vacuum conditions, so that the evaporation material is vaporized and transported to the substrate, condensed on the substrate to form a thin film, and finally forms the metal reflective layer required for the wristband.

2.热蒸镀法2. Thermal evaporation method

热蒸镀是在真空或者特定气氛的低压环境中通过将原材料加热成蒸汽在基底上沉积的技术。在沉积时，源材料一般为粉末或块状材料，由于沉积在低气压的环境中进行，蒸发温度一般略低于材料的熔点。蒸发后的材料从材料源逸出，到基底上冷凝之前与腔内的气体环境相互作用。因此工艺参数如蒸发温度、衬底温度、气体环境和压强等对达到理想的效果有着重要的作用。Thermal evaporation is a technique of depositing a substrate on a substrate by heating a raw material to vapor in a vacuum or low pressure environment of a specific atmosphere. During deposition, the source material is generally powder or bulk material. Since the deposition is carried out in a low-pressure environment, the evaporation temperature is generally slightly lower than the melting point of the material. The evaporated material escapes from the material source and interacts with the gaseous environment in the cavity before condensing on the substrate. Therefore, process parameters such as evaporation temperature, substrate temperature, gas environment and pressure play an important role in achieving the desired effect.

3.磁控溅射法3. Magnetron sputtering

磁控溅射是一种利用高能粒子轰击固体靶材料使其发射出原子的过程。因为它具有极高的能量和可控的参数，可以精确控制薄膜生长过程中的结晶度，因此能够很容易地实现大规模生产中的滚对滚工艺，是工业上最常用的沉积方法之一。沉积过程中可调整的工艺参数包括溅射的功率、基底的材质和温度、气体的成分含量和压强，这种方法制备得到的薄膜一般相对致密，制备的微结构薄膜往往无法实现较高的孔隙率，但是薄膜与衬底的结合力强，具有更好的稳定性。Magnetron sputtering is a process in which high-energy particles bombard a solid target material to emit atoms. Because of its extremely high energy and controllable parameters, it can precisely control the crystallinity during film growth, so it can easily realize the roll-to-roll process in large-scale production, and it is one of the most commonly used deposition methods in the industry. . The process parameters that can be adjusted during the deposition process include the power of sputtering, the material and temperature of the substrate, the component content and pressure of the gas. The films prepared by this method are generally relatively dense, and the prepared microstructured films often cannot achieve high porosity. rate, but the film has a strong bond with the substrate and has better stability.

4.电化学沉积法4. Electrochemical deposition method

电化学沉积是指在外电场作用下，在一定的电解质溶液中由阴极和阳极构成回路，通过发生氧化还原反应，使溶液中的粒子沉淀到阴极或者阳极的表面而形成腕带所需要的电致变色材料镀层。这种方法能够在各种结构复杂的基底上均匀沉积，且通常在室温或稍高于室温 的条件下进行，故这种方法也常用于纳米结构材料的制备。Electrochemical deposition means that under the action of an external electric field, a cathode and an anode form a circuit in a certain electrolyte solution, and through a redox reaction, the particles in the solution are precipitated on the surface of the cathode or anode to form a wristband. Color-changing material coating. This method can be uniformly deposited on various substrates with complex structures, and is usually carried out at room temperature or slightly higher than room temperature, so this method is also commonly used in the preparation of nanostructured materials.

进一步地，由电致变色材料做成的电致变色器件已经广泛应用于智能窗、智能指示器、成像设备等。电致变色的原理是在外加电场或者电流的作用下无机或有机的电致变色材料的电子结构和光学属性(反射率、透过率、吸收率等)发生稳定、可逆的变化的现象，在其外观上表现为颜色和透明度的可逆变化。传统的电致变色可分为两种模型，透过型电致变色器件和反射型电致变色器件，并且，电致变色器件的颜色仅仅只由电致变色本身的电子结构和光学属性决定。因此，电致变色的单一模式和单调颜色调制也成为了限制其应用范围的瓶颈。Further, electrochromic devices made of electrochromic materials have been widely used in smart windows, smart indicators, imaging devices, and the like. The principle of electrochromism is a phenomenon in which the electronic structure and optical properties (reflectivity, transmittance, absorptivity, etc.) of inorganic or organic electrochromic materials undergo stable and reversible changes under the action of an external electric field or current. It appears to be a reversible change in color and transparency. Traditional electrochromism can be divided into two models, transmissive electrochromic devices and reflective electrochromic devices, and the color of electrochromic devices is only determined by the electronic structure and optical properties of the electrochromic itself. Therefore, the single mode and monotonic color modulation of electrochromism also become a bottleneck limiting its application range.

在一些实施方案中，可以在所述制备方法进行的过程中，通过在不同的基底上沉积不同厚度的光学结构层或不同厚度的介质层，调整所述第一光学结构层或第二光学结构层、介质层的厚度和/或材质等，可以实现制备不同亮度、不同饱和度、不同纯度的多彩电致变色结构。In some embodiments, the first optical structure layer or the second optical structure can be adjusted by depositing optical structure layers of different thicknesses or dielectric layers of different thicknesses on different substrates during the process of the preparation method. Layer, the thickness and/or material of the dielectric layer, etc., can realize the preparation of colorful electrochromic structures with different brightness, different saturation, and different purity.

综上所述，本申请实施例通过各光学结构层和介质层的多层光学薄膜干涉作用而得到的多彩薄膜为物理结构色，相比市场上现有的各种颜色染料制备的电致变色结构，其颜色稳定，色彩绚丽，可制造程度高，长时间暴露在室外环境下不会老化失色。To sum up, the multi-color films obtained by the interference of the multilayer optical films of the optical structure layers and the dielectric layers in the examples of the present application are physical structural colors, which are compared with the electrochromic films prepared by various color dyes on the market. The structure is stable in color, brilliant in color, high in manufacturability, and will not age and fade when exposed to outdoor environments for a long time.

本申请实施例的一个方面还提供了一种高亮度、饱和度、纯度的多彩电致变色器件，包括工作电极、电解质和对电极，所述电解质分布于工作电极和对电极之间，所述工作电极包括前述的高亮度、饱和度、纯度的多彩电致变色结构。An aspect of the embodiments of the present application further provides a colorful electrochromic device with high brightness, saturation and purity, comprising a working electrode, an electrolyte and a counter electrode, the electrolyte is distributed between the working electrode and the counter electrode, and the The working electrode includes the aforementioned colorful electrochromic structure with high brightness, saturation, and purity.

在一些实施方案中，在本申请的前述实施例中，所述电解质的类型没有特别限制，可以使用液体电解质、凝胶聚合物电解质或无机固体电解质。In some embodiments, in the foregoing examples of the present application, the type of the electrolyte is not particularly limited, and a liquid electrolyte, a gel polymer electrolyte, or an inorganic solid electrolyte may be used.

在一些实施方案中，所述电解质与介质层接触，并提供用于使电致变色材料变色或脱色的离子，例如氢离子或锂离子的移动环境的材料。In some embodiments, the electrolyte is in contact with the dielectric layer and provides a material for a mobile environment for ions, such as hydrogen ions or lithium ions, to discolor or decolorize the electrochromic material.

在一些实施方案中，所述电解质可以包含一种或更多种化合物，例如含有H ⁺、Li ⁺、Al ³⁺、Na ⁺、K ⁺、Rb ⁺、Ca ²⁺，Zn ²⁺、Mg ²⁺或Cs ⁺的化合物。在一个实施案例中，电解质层可以包含锂盐化合物，例如LiClO ₄、LiBF ₄、LiAsF ₆或LiPF ₆。包含在电解质中的离子可以在根据施加的电压的极性被嵌入或移出介质层时对器件的变色或光透射率变化发挥作用。在一些实施方案中，所采用的电解质包含混合的多种离子，其较之单一离子，可以使器件的颜色变化更为丰富饱满。 In some embodiments, the electrolyte may comprise one or more compounds, for example containing H ⁺ , Li ⁺ , Al ³⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Ca ²⁺ , Zn ²⁺ , Mg ^{2 +} or Cs ⁺ compounds. In one embodiment, the electrolyte layer may contain a lithium salt compound such as LiClO ₄ , LiBF ₄ , LiAsF ₆ or LiPF ₆ . The ions contained in the electrolyte can contribute to the discoloration or light transmittance change of the device when inserted into or removed from the dielectric layer depending on the polarity of the applied voltage. In some embodiments, the electrolyte employed contains a mixture of ions that can result in a richer color change in the device than a single ion.

在一些实施方案中，所述电解质可以是液态电解质，例如水系的LiCl、AlCl ₃、HCl、H ₂SO ₄水溶液等。 In some embodiments, the electrolyte may be a liquid electrolyte, such as aqueous LiCl, AlCl ₃ , HCl, H ₂ SO ₄ aqueous solution, and the like.

在一些实施例中，所述电解质可以是混合电解质，例如水系的LiCl、AlCl ₃、HCl、MgCl ₂、ZnCl ₂等盐中两种或两种以上盐组成的混合电解质。在采用包含两种或更多种离子的电解液时，相比于采用仅含单种离子的电解液的情形，可以使得本申请前述实施例的电致变色结构的颜 色变化更为丰富，颜色饱和度更高。 In some embodiments, the electrolyte may be a mixed electrolyte, for example, a mixed electrolyte composed of two or more salts among salts such as LiCl, AlCl ₃ , HCl, MgCl ₂ , and ZnCl ₂ in an aqueous system. When an electrolyte containing two or more ions is used, compared with the case of using an electrolyte containing only a single ion, the color changes of the electrochromic structures of the foregoing embodiments of the present application can be more abundant, and the color Saturation is higher.

在一些实施方案中，所述电解质还可以包含碳酸酯化合物。由于基于碳酸酯的化合物具有高的介电常数，可以增加由锂盐提供的离子导电率。作为基于碳酸酯的化合物，可以使用以下的至少一种：PC(碳酸亚丙酯)、EC(碳酸亚乙酯)、DMC(碳酸二甲酯)、DEC(碳酸二乙酯)和EMC(碳酸乙基甲酯)。例如可以采用有机系的LiClO ₄、Na(ClO ₄) ₃的碳酸丙烯酯电解液等。 In some embodiments, the electrolyte may also include a carbonate compound. Since the carbonate-based compound has a high dielectric constant, the ionic conductivity provided by the lithium salt can be increased. As the carbonate-based compound, at least one of the following can be used: PC (propylene carbonate), EC (ethylene carbonate), DMC (dimethyl carbonate), DEC (diethyl carbonate), and EMC (carbonic acid) ethyl methyl ester). For example, an organic-based LiClO ₄ or Na(ClO ₄ ) ₃ propylene carbonate electrolyte solution or the like can be used.

在一些实施方案中，所述电解质可以是凝胶电解质，例如PMMA-PEG-LiClO ₄、PVDF-PC-LiPF ₆、LiCl/PVA，H ₂SO ₄/PVA等，但不限于此。 In some embodiments, the electrolyte may be a gel electrolyte, such as, but not limited to, PMMA-PEG-LiClO ₄ , PVDF-PC-LiPF ₆ , LiCl/PVA, H ₂ SO ₄ /PVA, and the like.

在一些优选的实施方式中，当使用无机固体电解质作为所述电解质时，电解质可以包含LiPON或Ta ₂O ₅。例如，所述电解质可以但不限于为含Li的金属氧化物薄膜，比如LiTaO或LiPO等薄膜。此外，无机固体电解质可以为其中LiPON或Ta ₂O ₅被添加有诸如B、S和W等组分的电解质，例如可以是LiBO ₂+Li ₂SO ₄、LiAlF ₄、LiNbO ₃、Li ₂O-B ₂O ₃等。 In some preferred embodiments, when an inorganic solid electrolyte is used as the electrolyte, the electrolyte may comprise LiPON or Ta ₂ O ₅ . For example, the electrolyte may be, but is not limited to, a Li-containing metal oxide thin film, such as LiTaO or LiPO or the like. In addition, the inorganic solid electrolyte may be an electrolyte in which LiPON or Ta ₂ O ₅ is added with components such as B, S, and W, for example, may be LiBO ₂ +Li ₂ SO ₄ , LiAlF ₄ , LiNbO ₃ , Li ₂ OB ₂ O ₃ etc.

在一些实施方式中，所述多彩电致变色器件还包括离子存储层，所述离子存储层与所述电解质接触。In some embodiments, the multicolor electrochromic device further includes an ion storage layer in contact with the electrolyte.

在一些实施方案中，所述第一光学结构层或第二光学结构层还与基底结合。In some embodiments, the first optical structure layer or the second optical structure layer is also bonded to the substrate.

例如，所述工作电极可以包括基底。For example, the working electrode may comprise a substrate.

例如，所述对电极可以包括基底、透明导电层和离子存储层。For example, the counter electrode may include a substrate, a transparent conductive layer, and an ion storage layer.

所述基底的材质可如前文所述，此处不再赘述。The material of the substrate can be as described above, which will not be repeated here.

进一步地，所述离子存储层的材质可以选自但不限于NiO、Fe ₂O ₃、TiO ₂、普鲁士蓝、IrO ₂等。 Further, the material of the ion storage layer can be selected from, but not limited to, NiO, Fe ₂ O ₃ , TiO ₂ , Prussian blue, IrO ₂ and the like.

在一些实施方案中，所述基底上还设置有导电层。其中，所述导电层包括FTO、ITO、Ag纳米线、Ag纳米网栅、碳纳米管、石墨烯中的任意一种或多种的组合，且不限于此。In some embodiments, the substrate is further provided with a conductive layer. Wherein, the conductive layer includes any one or a combination of FTO, ITO, Ag nanowires, Ag nanogrids, carbon nanotubes, and graphene, and is not limited thereto.

在一些实施方案中，所述对电极为透明或半透明的。In some embodiments, the counter electrode is transparent or translucent.

本申请实施例的一个方面还提供了所述高亮度、饱和度、纯度的多彩电致变色器件的制备方法，其包括：An aspect of the embodiments of the present application also provides a method for preparing the colorful electrochromic device with high brightness, saturation, and purity, including:

采用前文所述的方法，在所述基底上交替沉积形成第一光学结构层或第二光学结构层和介质层，并重复操作两次以上，获得电致变色层，进而获得工作电极；以及，将工作电极、电解质、对电极组装形成高亮度、饱和度、纯度的多彩电致变色器件。Using the method described above, alternately depositing the first optical structure layer or the second optical structure layer and the dielectric layer on the substrate, and repeating the operation more than twice to obtain the electrochromic layer, and then obtain the working electrode; and, The working electrode, electrolyte and counter electrode are assembled to form colorful electrochromic devices with high brightness, saturation and purity.

其中，参阅前文内容，通过调整基底、各光学结构层、介质层的的材质和厚度等，可以实现不同亮度、不同饱和度、不同纯度的多彩电致变色结构。本申请的多彩电致变色结构属于一种结构色，相比市场上现有的各种颜色染料制备的多彩薄膜，其颜色稳定，色彩绚丽，可制造程度高，长时间暴露在室外环境下不会老化失色。而且，通过调整施加在电致变色材 料上的电压、电流等，还可以使介质层的颜色发生变化。如此，可以实现器件(特别是光学器件)固有的光学结构色和电致变色的融合，更为简单、可控的实现丰富的颜色变化。Among them, referring to the previous content, by adjusting the material and thickness of the substrate, each optical structure layer, and the dielectric layer, etc., a colorful electrochromic structure with different brightness, different saturation, and different purity can be realized. The colorful electrochromic structure of the present application belongs to a kind of structural color. Compared with the colorful films prepared by various color dyes on the market, the color is stable, the color is brilliant, the manufacturability is high, and it is not easy to be exposed to the outdoor environment for a long time. will age. Moreover, by adjusting the voltage, current, etc. applied to the electrochromic material, the color of the dielectric layer can also be changed. In this way, the fusion of the inherent optical structural color and electrochromism of the device (especially the optical device) can be realized, and rich color changes can be realized in a simpler and controllable manner.

本申请实施例的另一个方面还提供了所述多彩电致变色器件的调控方法，其包括：Another aspect of the embodiments of the present application also provides a control method for the colorful electrochromic device, which includes:

将工作电极、对电极与电源连接形成工作电路；Connect the working electrode, the counter electrode and the power source to form a working circuit;

调整工作电极与对电极之间的电势差，使介质层内电致变色材料的折射率发生变化，从而调控所述多彩电致变色器件的颜色。The potential difference between the working electrode and the counter electrode is adjusted to change the refractive index of the electrochromic material in the dielectric layer, thereby regulating the color of the colorful electrochromic device.

进一步地，施加外加偏压可以改变原本的物理色，电致变色电压为-0.8V～1.0V。Further, the original physical color can be changed by applying an external bias voltage, and the electrochromic voltage is -0.8V to 1.0V.

其中，所述多彩电致变色器件的工作电压可以依据实际情况而调整，例如可以是-0.8V～1.0V，但不限于此。Wherein, the working voltage of the multi-color electrochromic device can be adjusted according to the actual situation, for example, it can be -0.8V to 1.0V, but not limited thereto.

在本申请的前述实施方式中，所述器件将多彩的反射/透射结构色与电致变色融合，丰富电致变色器件的颜色调制，实现多彩色的动态调控。具体而言，可以通过调整光学薄膜结构中第一光学结构层、第二光学结构层及介质层等的厚度、材质等得到丰富多彩的结构色。同时，将所述电致变色层用作工作电极，通过施加电压，使介质层中的电致变色材料折射率的变化(可以是因电解质层中的离子***或脱出电致变色材料而引起)，导致介质层的光学参数改变，带来颜色的改变，最终能实现电致变色的反射/透射双模式和绚丽丰富的颜色调制，将极大促进电致变色技术发展以及其在多个领域的应用。In the aforementioned embodiments of the present application, the device integrates colorful reflective/transmissive structural colors with electrochromic, which enriches the color modulation of the electrochromic device and realizes dynamic regulation of multiple colors. Specifically, various structural colors can be obtained by adjusting the thicknesses, materials, etc. of the first optical structure layer, the second optical structure layer, and the dielectric layer in the optical film structure. At the same time, using the electrochromic layer as a working electrode, by applying a voltage, the refractive index of the electrochromic material in the dielectric layer changes (which may be caused by the insertion or extraction of ions in the electrolyte layer from the electrochromic material) , resulting in the change of the optical parameters of the dielectric layer, resulting in the change of the color, and finally realizes the reflection/transmission dual mode of electrochromic and brilliant and rich color modulation, which will greatly promote the development of electrochromic technology and its application in many fields. application.

本申请的电致变色层属于一种结构色，相比市场上现有的各种颜色染料制备的多彩薄膜，其颜色稳定，色彩绚丽，可制造程度高，长时间暴露在室外环境下不会老化失色。The electrochromic layer of the present application belongs to a structural color. Compared with the colorful films prepared by various color dyes on the market, the color is stable, the color is brilliant, the degree of manufacturability is high, and it will not be exposed to the outdoor environment for a long time. Aging fades.

本申请实施例还提供了所述多彩电致变色器件的用途，例如在电致变色、光致变色、建筑、汽车、艺术装饰、滤光片、防伪、太阳能电池、显示器、LED屏、通信、传感、照明等领域的应用。The embodiments of the present application also provide the use of the colorful electrochromic device, for example, in electrochromic, photochromic, architecture, automobile, art decoration, optical filter, anti-counterfeiting, solar cell, display, LED screen, communication, Applications in sensing, lighting and other fields.

本申请实施例的另一个方面还提供了一种装置，其包括所述的多彩电致变色器件。Another aspect of the embodiments of the present application further provides an apparatus, which includes the multi-colored electrochromic device.

进一步地，所述装置还包括电源，所述电源能与所述器件电连接形成工作回路。Further, the device further includes a power source, which can be electrically connected with the device to form a working loop.

在一些实施方案中，所述的装置还可包括附加的封装结构、控制模块、电源模块等组件，这些附件组件可以常规方式与所述多彩电致变色器件结合。In some embodiments, the device may further include additional packaging structures, control modules, power modules, etc., which may be combined with the multi-colored electrochromic device in a conventional manner.

进一步地，所述装置包括但不限于机械设备、光电设备、电子设备、建筑物、交通工具以及户外广告牌等，且不限于此。Further, the devices include, but are not limited to, mechanical equipment, optoelectronic equipment, electronic equipment, buildings, vehicles, and outdoor billboards, and are not limited thereto.

以下通过若干实施例并结合附图进一步详细说明本申请的技术方案。然而，所选的实施例仅用于说明本申请，而不限制本申请的范围。The technical solutions of the present application are further described in detail below through several embodiments and in conjunction with the accompanying drawings. However, the selected examples are only used to illustrate the present application and do not limit the scope of the present application.

对照例1Comparative Example 1

本对照例1提供的一种多彩薄膜制备方法。该多彩薄膜的制备过程如下：在干净的PET 基底上，用磁控溅射的方法沉积一层金属W层，厚度约10～30nm；再在金属W层上磁控溅射一层WO ₃层，厚度约150～250nm。参见图2或图5中N＝1所示。 This Comparative Example 1 provides a method for preparing a colorful film. The preparation process of the colorful film is as follows: on a clean PET substrate, a metal W layer with a thickness of about 10-30 nm is deposited by magnetron sputtering; and then a WO ₃ layer is magnetron sputtered on the metal W layer. , the thickness is about 150 ~ 250nm. See Fig. 2 or Fig. 5 where N=1.

控制WO ₃厚度的不同可以得到本对照例光学薄膜结构，从该光学薄膜正面方向看，该光学结构为反射率不高的结构色，且亮度、饱和度、纯度均有一定的差距。 The optical film structure of this comparative example can be obtained by controlling the difference in the thickness of WO _3. Viewed from the front direction of the optical film, the optical structure is a structural color with low reflectivity, and there are certain gaps in brightness, saturation and purity.

实施例1Example 1

本实施例公开的一种高亮度、饱和度、纯度的多彩电致变色薄膜结构(亦可称为多彩薄膜)的制备过程如下：在干净的PET基底上，用磁控溅射的方法沉积一层金属W层，厚度约10～30nm；再在金属W层上磁控溅射一层WO ₃层，厚度约150～250nm；根据不同需求，改变循环次数，可以得到不同层数对N＝2～6(原则上N≥2)的多彩薄膜。参见图1所示，本实施例的多彩电致变色薄膜包括基底、金属层、介质层，所述金属层和介质层交替排列，构成一种金属-介质结构，能产生光学多层薄膜干涉，从而显示出多彩色。图2示出了该多彩薄膜的实物图。 The preparation process of a multi-color electrochromic film structure (also called multi-color film) with high brightness, saturation and purity disclosed in this embodiment is as follows: on a clean PET substrate, a magnetron sputtering method is used to deposit a A metal W layer with a thickness of about 10-30nm; and then magnetron sputtering a WO ₃ layer on the metal W layer with a thickness of about 150-250nm; according to different needs, changing the number of cycles can obtain different layers for N=2 ~6 (in principle N≥2) colorful films. Referring to FIG. 1 , the colorful electrochromic film of this embodiment includes a substrate, a metal layer, and a dielectric layer. The metal layers and the dielectric layers are alternately arranged to form a metal-dielectric structure, which can generate optical multilayer thin film interference. Thus, multi-color is displayed. Figure 2 shows a real picture of the colorful film.

当然，前述的金属W层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的WO ₃层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned metal W layer can also be prepared by electron beam evaporation, thermal evaporation and other methods known in the industry. The aforementioned WO ₃ layer can be prepared by electron beam evaporation, thermal evaporation, electrochemical deposition and other methods known in the industry.

请参阅图3所示，为本实施例中高亮度、饱和度、纯度的多彩薄膜可见光区的反射率曲线图。Please refer to FIG. 3 , which is a graph of the reflectance in the visible light region of the colorful thin film with high brightness, saturation and purity in this embodiment.

请参阅图4所示，为本实施例中高亮度、饱和度、纯度的多彩薄膜的色坐标图。Please refer to FIG. 4 , which is a color coordinate diagram of a multi-color thin film with high brightness, saturation, and purity in this embodiment.

实施例2Example 2

本实施例公开的一种高亮度、饱和度、纯度的多彩电致变色薄膜的制备过程如下：在干净的玻璃基底上，使用掩版得到所需图案，用磁控溅射的方法沉积一层金属W层，厚度约10～30nm；再在金属W层上磁控溅射一层WO ₃层，厚度约150～250nm；根据不同需求，改变循环次数，可以得到不同层数对N＝2～6(原则上N≥2)的多彩薄膜。 The preparation process of a colorful electrochromic film with high brightness, saturation and purity disclosed in this embodiment is as follows: on a clean glass substrate, use a mask to obtain the desired pattern, and deposit a layer of magnetron sputtering Metal W layer, with a thickness of about 10-30 nm; magnetron sputtering a layer of WO ₃ layer on the metal W layer, with a thickness of about 150-250 nm; according to different needs, changing the number of cycles can obtain different layers for N=2～ 6 (in principle N≥2) colorful films.

当然，前述的金属W层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的WO ₃层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned metal W layer can also be prepared by electron beam evaporation, thermal evaporation and other methods known in the industry. The aforementioned WO ₃ layer can be prepared by electron beam evaporation, thermal evaporation, electrochemical deposition and other methods known in the industry.

实施例3Example 3

将实施例1中的不同层数对(N≥2，注：其中N＝1为对照组)的多彩电致变色薄膜置于1M LiClO ₄/PC电解液中，施加一定的电压(原则上-0.8V～1.0V)，控制离子***/脱出的量，从而达到改变原光学结构多彩薄膜物理色的目的。请参见图5所示为不同层数对的电致变色层的多彩电致变色结构在电致变色过程中实际图片。 The multi-color electrochromic thin films with different layers in Example 1 (N≥2, note: N=1 is the control group) were placed in 1M LiClO ₄ /PC electrolyte, and a certain voltage was applied (in principle- 0.8V ~ 1.0V), control the amount of ion insertion/extraction, so as to achieve the purpose of changing the physical color of the original optical structure of the colorful film. Please refer to FIG. 5 for the actual pictures of the multi-colored electrochromic structures of electrochromic layers with different number pairs of electrochromic layers during the electrochromic process.

当然，前述电致变色处理的电解质包括但不限于液体电解质、凝胶电解质或固态电解质。Of course, the electrolyte for the aforementioned electrochromic treatment includes, but is not limited to, a liquid electrolyte, a gel electrolyte or a solid electrolyte.

实施例4Example 4

将实施例1中的不同金属层厚度的多彩电致变色薄膜置于1M LiClO ₄/PC电解液中，施加一定的电压(原则上-0.8V～0.8V)，控制离子***/脱出的量，从而达到改变原光学结构多彩薄膜物理色的目的。请参见图6所示为不同金属层厚度的电致变色层的多彩电致变色结构在电致变色过程中实际图片。 The colorful electrochromic films with different metal layer thicknesses in Example 1 were placed in 1M LiClO ₄ /PC electrolyte, and a certain voltage (-0.8V～0.8V in principle) was applied to control the amount of ion insertion/extraction, So as to achieve the purpose of changing the physical color of the original optical structure of the colorful film. Please refer to FIG. 6 for the actual pictures of the multi-colored electrochromic structures of electrochromic layers with different metal layer thicknesses during the electrochromic process.

当然，前述电致变色处理的电解质包括但不限于液体电解质、凝胶电解质或固态电解质。Of course, the electrolyte for the aforementioned electrochromic treatment includes, but is not limited to, a liquid electrolyte, a gel electrolyte or a solid electrolyte.

对照例2Comparative Example 2

本对照例2提供的一种多彩薄膜结构。该多彩薄膜的制备过程如下：在干净的PET基底上，用磁控溅射的方法沉积一层金属W层，厚度约100～3000nm；再在金属W层上磁控溅射一层WO ₃层，厚度约100～500nm。 This comparative example 2 provides a colorful film structure. The preparation process of the colorful film is as follows: on a clean PET substrate, a metal W layer with a thickness of about 100-3000 nm is deposited by magnetron sputtering; then a WO ₃ layer is magnetron sputtered on the metal W layer. , the thickness of about 100 ~ 500nm.

控制WO ₃厚度的不同可以得到本对照例光学薄膜结构，从该光学薄膜正面方向看，该光学结构为反射率一般的结构色，且亮度、饱和度、纯度均有一定的差距；从该光学薄膜反面看，为金属光泽色(银白色)，颜色具有局限性。 The optical film structure of this comparative example can be obtained by controlling the difference in the thickness of WO _3. Viewed from the front direction of the optical film, the optical structure is a structural color with a general reflectivity, and there are certain gaps in brightness, saturation and purity; On the reverse side of the film, it is metallic luster color (silver white), and the color is limited.

实施例5Example 5

本实施例提供的一种多彩电致变色薄膜结构，包括依次在基底上形成的第二光学结构层、介质层、第一光学结构层、介质层。该多彩电致变色薄膜结构的制备过程如下：在干净的PET-ITO基底上，用磁控溅射的方法沉积一层金属Au层，厚度约100～3000nm；再在金属Au层上磁控溅射一层WO ₃层，厚度约100～500nm；再在WO ₃层上磁控溅射一层金属层Au层，厚度为0～30nm；再在该金属Au层上磁控溅射一层WO ₃层，厚度约100～500nm。本实施例的多彩薄膜两层金属层厚度不同，底层金属层作为反射层，提高了整体多彩薄膜的反射率。 A multi-color electrochromic thin film structure provided in this embodiment includes a second optical structure layer, a dielectric layer, a first optical structure layer, and a dielectric layer formed on a substrate in sequence. The preparation process of the colorful electrochromic thin film structure is as follows: on a clean PET-ITO substrate, a metal Au layer with a thickness of about 100-3000 nm is deposited by magnetron sputtering; and then magnetron sputtering is performed on the metal Au layer. A WO ₃ layer with a thickness of about 100-500 nm is sprayed; then a metal Au layer is magnetron sputtered on the WO ₃ layer, with a thickness of 0-30 nm; a layer of WO is then magnetron sputtered on the metal Au layer ₃ layers, the thickness is about 100-500nm. The thicknesses of the two metal layers of the multi-colored film in this embodiment are different, and the bottom metal layer acts as a reflective layer, which improves the reflectivity of the overall multi-colored film.

当然，前述的金属Au层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的WO ₃层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned metal Au layer can also be prepared by electron beam evaporation, thermal evaporation and other methods known in the industry. The aforementioned WO ₃ layer can be prepared by electron beam evaporation, thermal evaporation, electrochemical deposition and other methods known in the industry.

实施例6Example 6

本实施例提供的一种多彩电致变色薄膜结构。该多彩电致变色薄膜结构的制备过程如下：在干净的ITO玻璃基底上，用磁控溅射的方法沉积一层金属Ag层，设置其厚度为15nm；再在金属Ag层上磁控溅射一层TiO ₂层，厚度约100～400nm；设置循环次数N＝3。本实施例的光学薄膜结构展示出与实施例1光学薄膜结构类似的性质。 This embodiment provides a colorful electrochromic thin film structure. The preparation process of the colorful electrochromic thin film structure is as follows: on a clean ITO glass substrate, a metal Ag layer is deposited by the method of magnetron sputtering, and its thickness is set to 15 nm; A layer of TiO ₂ with a thickness of about 100-400 nm; set the number of cycles to N=3. The optical film structure of this example exhibits similar properties to the optical film structure of Example 1.

当然，前述的金属Ag层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的TiO ₂层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned metal Ag layer can also be prepared by means known in the industry, such as electron beam evaporation and thermal evaporation. The aforementioned TiO ₂ layer can be prepared by electron beam evaporation, thermal evaporation, electrochemical deposition and other methods known in the industry.

实施例7Example 7

本实施例提供的一种多彩电致变色薄膜结构。该多彩电致变色薄膜结构的制备过程如下： 在干净的铁片基底上，用磁控溅射的方法沉积一层WO ₃层，厚度约100～500nm；再在WO ₃层上磁控溅射一层金属Cu层，设置其厚度为25nm；再在金属Cu层上磁控溅射一层WO ₃层，厚度约100～500nm。由此可以得到用铁片基底充当第二光学结构层的多彩薄膜结构。本实施例的光学薄膜结构展示出与实施例1光学薄膜结构类似的性质。 This embodiment provides a colorful electrochromic thin film structure. The preparation process of the colorful electrochromic thin film structure is as follows: On a clean iron substrate, a WO ₃ layer is deposited by magnetron sputtering with a thickness of about 100-500 nm; then magnetron sputtering is applied on the WO ₃ layer. A layer of metal Cu layer is set to have a thickness of 25 nm; and then a layer of WO ₃ is magnetron sputtered on the metal Cu layer, with a thickness of about 100-500 nm. Thereby, a multi-colored thin film structure with an iron plate substrate serving as the second optical structure layer can be obtained. The optical film structure of this example exhibits similar properties to the optical film structure of Example 1.

当然，前述的铁片基底可以用溅射Fe层的PET或ITO玻璃或其他基底替代。前述的金属Cu层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的WO ₃层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned iron sheet substrate can be replaced by PET or ITO glass or other substrates with sputtered Fe layer. The aforementioned metal Cu layer can also be prepared by means known in the industry, such as electron beam evaporation and thermal evaporation. The aforementioned WO ₃ layer can be prepared by electron beam evaporation, thermal evaporation, electrochemical deposition and other methods known in the industry.

实施例8Example 8

本实施例提供的一种多彩电致变色薄膜结构。该多彩电致变色薄膜结构的制备过程如下：在干净的PET/AgNWs薄膜基底上，用磁控溅射的方法沉积一层WO ₃层，厚度约100～500nm；再在WO ₃层上磁控溅射一层金属Co层，设置其厚度为15nm；再在金属Co层上磁控溅射一层WO ₃层，厚度约100～500nm。由此可以得到用PET/AgNWs薄膜基底充当第二光学结构层的多彩薄膜结构。本实施例的光学薄膜结构展示出与实施例1光学薄膜结构类似的性质。 This embodiment provides a colorful electrochromic thin film structure. The preparation process of the colorful electrochromic thin film structure is as follows: on a clean PET/AgNWs thin film substrate, a WO ₃ layer is deposited by magnetron sputtering with a thickness of about 100-500 nm _; A layer of metal Co is sputtered, and the thickness is set to 15 nm; and then a layer of WO ₃ is magnetron sputtered on the metal Co layer, with a thickness of about 100-500 nm. Thus, a colorful film structure with PET/AgNWs film substrate as the second optical structure layer can be obtained. The optical film structure of this example exhibits similar properties to the optical film structure of Example 1.

当然，前述的PET/AgNWs薄膜基底可以用溅射Co层的PET或ITO玻璃或其他基底替代。前述的金属Co层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的WO ₃层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned PET/AgNWs thin film substrate can be replaced by a Co layer sputtered PET or ITO glass or other substrates. The aforementioned metallic Co layer can also be prepared by electron beam evaporation, thermal evaporation and other methods known in the industry. The aforementioned WO ₃ layer can be prepared by electron beam evaporation, thermal evaporation, electrochemical deposition and other methods known in the industry.

实施例9Example 9

本实施例提供的一种多彩电致变色薄膜结构。该多彩电致变色薄膜结构的制备过程如下：在干净的PET-ITO基底上，用磁控溅射的方法沉积一层WO ₃层，厚度约为100～500nm；再设置循环次数N＝4，即金属Ni层和氧化物WO ₃层交替叠加排列。本实施例的光学薄膜结构，从正面看展示出与实施例1光学薄膜结构类似的性质，从背面看为更鲜艳的其他颜色。 This embodiment provides a colorful electrochromic thin film structure. The preparation process of the colorful electrochromic thin film structure is as follows: on a clean PET-ITO substrate, a WO ₃ layer is deposited by magnetron sputtering with a thickness of about 100-500 nm; That is, metal Ni layers and oxide WO ₃ layers are alternately stacked and arranged. The optical film structure of the present embodiment exhibits properties similar to those of the optical film structure of Example 1 from the front, and other more vivid colors from the back.

当然，前述的金属Ni层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的WO ₃层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned metal Ni layer can also be prepared by electron beam evaporation, thermal evaporation and other methods known in the industry. The aforementioned WO ₃ layer can be prepared by electron beam evaporation, thermal evaporation, electrochemical deposition and other methods known in the industry.

实施例10Example 10

本实施例提供的一种多彩电致变色薄膜结构。该多彩电致变色薄膜结构的制备过程如下：在干净的PET-ITO基底上，用磁控溅射的方法沉积一层金属层Pt，再在Pt层上沉积一层TiO ₂层，厚度约为100～400nm；设置循环次数N＝3，即金属Pt层和氧化物TiO ₂层交替叠加排列。本实施例的光学薄膜结构展示出与实施例1光学薄膜结构类似的性质。 This embodiment provides a colorful electrochromic thin film structure. The preparation process of the colorful electrochromic thin film structure is as follows: on a clean PET-ITO substrate, a metal layer Pt is deposited by magnetron sputtering, and then a _TiO2 layer is deposited on the Pt layer with a thickness of about 100-400 nm; set the number of cycles N=3, that is, the metal Pt layer and the oxide TiO ₂ layer are alternately stacked and arranged. The optical film structure of this example exhibits similar properties to the optical film structure of Example 1.

当然，前述的金属Pt层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的TiO ₂层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned metal Pt layer can also be prepared by methods known in the industry, such as electron beam evaporation and thermal evaporation. The aforementioned TiO ₂ layer can be prepared by electron beam evaporation, thermal evaporation, electrochemical deposition and other methods known in the industry.

实施例11Example 11

本实施例提供的一种多彩电致变色薄膜结构。该多彩电致变色薄膜结构的制备过程如下：在干净的AgNWs导电布上，用磁控溅射的方法沉积一层金属层Ge，再在Ge层上沉积一层MoO ₃层，厚度约为100～500nm；再在MoO ₃层上沉积一层金属层Pd，最后最上面层再沉积一层TiO ₂，即形成金属层和氧化物层交替叠加排列的光学薄膜结构。本实施例的光学薄膜结构展示出与实施例1光学薄膜结构类似的性质。 This embodiment provides a colorful electrochromic thin film structure. The preparation process of the colorful electrochromic thin film structure is as follows: on a clean AgNWs conductive cloth, a metal layer Ge is deposited by magnetron sputtering, and then a MoO3 layer with a thickness _of about 100 is deposited on the Ge layer. ~500nm; deposit a layer of metal Pd on the MoO ₃ layer, and finally deposit a layer of TiO ₂ on the topmost layer, that is, to form an optical thin film structure in which metal layers and oxide layers are alternately stacked. The optical film structure of this example exhibits similar properties to the optical film structure of Example 1.

当然，前述的金属Ge、Pd层也可以采用电子束蒸发、热蒸镀等业界已知的方式制备。前述的MoO ₃、TiO ₂层可以采用电子束蒸发、热蒸镀、电化学沉积等业界已知的方式制备。 Of course, the aforementioned metal Ge and Pd layers can also be prepared by methods known in the industry, such as electron beam evaporation and thermal evaporation. The aforementioned MoO ₃ and TiO ₂ layers can be prepared by methods known in the industry, such as electron beam evaporation, thermal evaporation, and electrochemical deposition.

本申请以上实施例通过金属层和介质层的多层光学薄膜干涉作用而得到的多彩薄膜为物理结构色，相比市场上现有的各种颜色染料制备的多彩薄膜，其颜色稳定，色彩绚丽，可制造程度高，长时间暴露在室外环境下不会老化失色。The colorful films obtained by the interference effect of the multi-layer optical films of the metal layer and the dielectric layer in the above embodiments of the present application are physical structural colors. Compared with the colorful films prepared by various color dyes on the market, the color is stable and the color is brilliant. , High degree of manufacturability, long-term exposure to outdoor environment will not age and lose color.

此外，本申请的发明人还以本说明书列出的其他介质材料、金属材料、基底材料等替代前述实施例中的相应材料进行了试验，发现所获的多彩薄膜结构均具有相似的优点。In addition, the inventors of the present application also conducted experiments with other dielectric materials, metal materials, substrate materials, etc. listed in this specification instead of the corresponding materials in the foregoing embodiments, and found that the obtained colorful thin film structures all have similar advantages.

本申请前述实施例提供的多彩薄膜通过在不同的基底上沉积不同厚度的金属层或不同厚度的介质层，可以实现不同亮度、不同饱和度、不同纯度的多彩薄膜。本申请的高亮度、饱和度、纯度的多彩薄膜属于一种结构色，相比市场上现有的各种颜色染料制备的多彩薄膜，其颜色稳定，色彩绚丽，可制造程度高，长时间暴露在室外环境下不会老化失色。。The colorful thin films provided by the foregoing embodiments of the present application can realize colorful thin films with different brightness, different saturation, and different purities by depositing metal layers with different thicknesses or dielectric layers with different thicknesses on different substrates. The multi-color film with high brightness, saturation and purity of the present application belongs to a structural color. Compared with the multi-color films prepared by various color dyes on the market, the color is stable, the color is brilliant, the degree of manufacturability is high, and the long-term exposure It will not age and lose its color in outdoor environment. .

本申请的各方面、实施例、特征及实例应视为在所有方面为说明性的且不打算限制本申请，本申请的范围仅由权利要求书界定。在不背离所主张的本申请的精神及范围的情况下，所属领域的技术人员将明了其它实施例、修改及使用。The aspects, embodiments, features, and examples of this application are to be considered illustrative in all respects and are not intended to limit the application, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed application.

在本申请案中标题及章节的使用不意味着限制本申请；每一章节可应用于本申请的任何方面、实施例或特征。The use of headings and sections in this application is not meant to limit the application; each section applies to any aspect, embodiment or feature of the application.

在本申请案通篇中，在将组合物描述为具有、包含或包括特定组份之处或者在将过程描述为具有、包含或包括特定过程步骤之处，预期本申请教示的组合物也基本上由所叙述组份组成或由所叙述组份组成，且本申请教示的过程也基本上由所叙述过程步骤组成或由所叙述过程步骤组组成。Throughout this application, where a composition is described as having, comprising or including particular components, or where a process is described as having, comprising or including particular process steps, it is contemplated that the compositions taught herein are also substantially The above consists of or consists of the recited components, and the processes taught herein also consist essentially of, or consist of, the recited process steps.

除非另外具体陈述，否则术语“包含(include、includes、including)”、“具有(have、has或having)”的使用通常应理解为开放式的且不具限制性。The use of the terms "include, includes, including," "have, has, or having" should generally be understood to be open-ended and not limiting unless specifically stated otherwise.

应理解，各步骤的次序或执行特定动作的次序并非十分重要，只要本申请教示保持可操作即可。此外，可同时进行两个或两个以上步骤或动作。It should be understood that the order of steps or order in which particular actions are performed is not critical so long as the teachings of the present application remain operable. Furthermore, two or more steps or actions may be performed simultaneously.

尽管已参考说明性实施例描述了本申请，但所属领域的技术人员将理解，在不背离本申请的精神及范围的情况下可做出各种其它改变、省略及/或添加且可用实质等效物替代所述 实施例的元件。另外，可在不背离本申请的范围的情况下做出许多修改以使特定情形或材料适应本申请的教示。因此，本文并不打算将本申请限制于用于执行本申请的所揭示特定实施例，而是打算使本申请将包含归属于所附权利要求书的范围内的所有实施例。此外，除非具体陈述，否则术语第一、第二等的任何使用不表示任何次序或重要性，而是使用术语第一、第二等来区分一个元素与另一元素。Although the application has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions and/or additions may be made and substance, etc. may be made without departing from the spirit and scope of the application Effects replace elements of the described embodiments. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the application without departing from the scope of the application. Therefore, it is not intended herein to limit this application to the particular embodiments disclosed for carrying out the application, but it is intended that this application include all embodiments that fall within the scope of the appended claims. Furthermore, unless specifically stated, any use of the terms first, second, etc. does not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (24)

1. 一种高亮度、饱和度、纯度的多彩电致变色结构，包括电致变色层，其特征在于，所述电致变色层包括：复数个由第一光学结构层或第二光学结构层、介质层依次交替叠加排列形成的层数对结构；A colorful electrochromic structure with high brightness, saturation and purity, comprising an electrochromic layer, characterized in that, the electrochromic layer comprises: a plurality of layers composed of a first optical structure layer or a second optical structure layer, a medium A layer pair structure formed by alternately stacking layers in sequence;

   其中，所述第一光学结构层、第二光学结构层是光学反射性和/或光学透射性的，所述介质层与第一光学结构层、第二光学结构层的结合界面分别为所述介质层的第一表面、第二表面，所述第一表面、第二表面与介质层配合形成一光学腔；在入射光从第一光学结构层或第二光学结构层入射所述光学腔时，于所述第一表面形成的反射光和于所述第二表面形成的反射光的相移

   

   d为所述介质层的厚度，

   

   为所述介质层的折射率，λ为所述入射光的波长，

   

   为所述入射光在透过所述第一表面或第二表面时的折射角。 Wherein, the first optical structure layer and the second optical structure layer are optically reflective and/or optically transmissive, and the bonding interface between the dielectric layer and the first optical structure layer and the second optical structure layer is the The first surface and the second surface of the dielectric layer, the first surface and the second surface cooperate with the dielectric layer to form an optical cavity; when incident light enters the optical cavity from the first optical structure layer or the second optical structure layer , the phase shift of the reflected light formed on the first surface and the reflected light formed on the second surface

   

   d is the thickness of the dielectric layer,

   

   is the refractive index of the dielectric layer, λ is the wavelength of the incident light,

   

   is the refraction angle of the incident light when it passes through the first surface or the second surface.
2. 根据权利要求1所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：若定义所述第一光学结构层的折射率为

   

   则所述第一表面的反射系数

   

   

   其中

   

   为入射光于第一表面的入射角； The colorful electrochromic structure with high brightness, saturation and purity according to claim 1, wherein if the refractive index of the first optical structure layer is defined as

   

   Then the reflection coefficient of the first surface

   

   

   in

   

   is the incident angle of the incident light on the first surface;

   和/或，若定义所述第二光学结构层的折射率为

   

   则所述第二表面的反射系数

   

   

   其中

   

   为入射光在透过第二表面时的折射角。 And/or, if the refractive index of the second optical structure layer is defined as

   

   Then the reflection coefficient of the second surface

   

   

   in

   

   is the refraction angle of the incident light when it passes through the second surface.
3. 根据权利要求2所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述电致变色层的反射系数表示为：

   

   反射率表示为：

   

   

   The colorful electrochromic structure with high brightness, saturation and purity according to claim 2, wherein the reflection coefficient of the electrochromic layer is expressed as:

   

   The reflectance is expressed as:

   

   
4. 根据权利要求1-3中任一项所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：若定义所述第一光学结构层的折射率为

   

   则所述第一光学结构层的透射系数

   

   

   其中

   

   为入射光于第一表面的入射角； The colorful electrochromic structure with high brightness, saturation and purity according to any one of claims 1-3, wherein if the refractive index of the first optical structure layer is defined as

   

   Then the transmission coefficient of the first optical structure layer

   

   

   in

   

   is the incident angle of the incident light on the first surface;

   和/或，若定义所述第二光学结构层的折射率为

   

   则所述第二光学结构层的透射系数

   

   其中

   

   为入射光在透过第二表面时的折射角。 And/or, if the refractive index of the second optical structure layer is defined as

   

   Then the transmission coefficient of the second optical structure layer

   

   in

   

   is the refraction angle of the incident light when it passes through the second surface.
5. 根据权利要求4所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述电致变色层的透射系数表示为：

   

   透过率表示为：

   

   

   The multi-color electrochromic structure with high brightness, saturation and purity according to claim 4, wherein the transmission coefficient of the electrochromic layer is expressed as:

   

   The transmittance is expressed as:

   

   
6. 根据权利要求1所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述电致变色层具有光学透射工作模式、光学反射工作模式或者光学透射及反射工作模式；优选的，在所述光学反射工作模式下，所述电致变色层具有双面不对称结构色，而在所述光学透射工作模式下，所述电致变色层具有透明结构色。The colorful electrochromic structure with high brightness, saturation and purity according to claim 1, wherein the electrochromic layer has an optical transmission working mode, an optical reflection working mode or an optical transmission and reflection working mode; preferably In the optical reflection working mode, the electrochromic layer has a double-sided asymmetric structural color, and in the optical transmission working mode, the electrochromic layer has a transparent structural color.
7. 根据权利要求1所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述层数对结构的数量N≥2，优选为N＝2～6。The multi-color electrochromic structure with high brightness, saturation and purity according to claim 1, characterized in that: the number of layers to the structure is N≥2, preferably N=2-6.
8. 根据权利要求1所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：第一光学结构层、第二光学结构层中的任一者为金属层，另一者由气体组成，所述气体包括空气；或者，第一光学结构层、第二光学结构层均为金属层。The multi-color electrochromic structure with high brightness, saturation and purity according to claim 1, wherein either one of the first optical structure layer and the second optical structure layer is a metal layer, and the other is made of gas composition, the gas includes air; or, the first optical structure layer and the second optical structure layer are both metal layers.
9. 根据权利要求8所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述第一光学结构层和第二光学结构层中至少一者的材质包括金属材料；优选的，所述金属材料包括包括钨、金、银、铜、钛、铝、铬、铁、钴、镍、铂、锗、钯中的任意一种或多种的组合。The multi-color electrochromic structure with high brightness, saturation and purity according to claim 8, wherein the material of at least one of the first optical structure layer and the second optical structure layer comprises a metal material; preferably , the metal material includes any one or a combination of any one or more of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, and palladium.
10. 根据权利要求9所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述第一光学结构层和第二光学结构层的厚度和/或材质不同。The multi-color electrochromic structure with high brightness, saturation and purity according to claim 9, wherein the thickness and/or material of the first optical structure layer and the second optical structure layer are different.
11. 根据权利要求10所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述第一光学结构层或第二光学结构层的厚度为0～30nm，优选为10～30nm。The colorful electrochromic structure with high brightness, saturation and purity according to claim 10, wherein the thickness of the first optical structure layer or the second optical structure layer is 0-30 nm, preferably 10-30 nm .
12. 根据权利要求10所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述第一光学结构层或第二光学结构层还与基底结合；优选的，与基底结合的第一光学结构层或第二光学结构层的厚度在100nm以上，优选为100～3000nm，其余第一光学结构层或第二光学结构层的厚度为10～30nm。The colorful electrochromic structure with high brightness, saturation and purity according to claim 10, wherein the first optical structure layer or the second optical structure layer is further combined with the substrate; The thickness of the first optical structure layer or the second optical structure layer is more than 100 nm, preferably 100-3000 nm, and the thickness of the remaining first or second optical structure layers is 10-30 nm.
13. 根据权利要求1所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：其中两个不同介质层的厚度和/或材质不同；和/或，基于其中两个不同介质层的两个不同光学腔呈现的颜色不同。The colorful electrochromic structure with high brightness, saturation, and purity according to claim 1, characterized in that: the thicknesses and/or materials of the two different dielectric layers are different; and/or, based on the two different dielectric layers The two different optical cavities present in different colors.
14. 根据权利要求13所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述介质层的厚度为0～3000nm，优选为100～500nm，尤其优选为150～250nm。The multi-color electrochromic structure with high brightness, saturation and purity according to claim 13, wherein the thickness of the dielectric layer is 0-3000 nm, preferably 100-500 nm, particularly preferably 150-250 nm.
15. 根据权利要求13所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：The colorful electrochromic structure with high brightness, saturation and purity according to claim 13, characterized in that:

    所述介质层的材质选自有机材料或无机材料；The material of the dielectric layer is selected from organic materials or inorganic materials;

    优选的，所述无机材料包括金属单质或非金属单质、无机盐、氧化物中任意一种或多种 的组合；Preferably, the inorganic material includes any one or a combination of metal element or non-metal element, inorganic salt, oxide;

    更有选的，所述非金属单质包括单晶硅、多晶硅、金刚石中任意一种或多种的组合；More preferably, the non-metal element includes any one or a combination of single crystal silicon, polycrystalline silicon and diamond;

    更优选的，所述无机盐包括氟化物、硫化物、硒化物、氯化物、溴化物、碘化物、砷化物或碲化物中任意一种或多种的组合；More preferably, the inorganic salt includes any one or a combination of fluoride, sulfide, selenide, chloride, bromide, iodide, arsenide or telluride;

    更优选的，所述氧化物包括WO ₃、NiO、TiO ₂、Nb ₂O ₅、Fe ₂O ₃、V ₂O ₅、Co ₂O ₃、Y ₂O ₃、Cr ₂O ₃、MoO ₃、Al ₂O ₃、SiO ₂、MgO、ZnO、MnO ₂、CaO、ZrO ₂、Ta ₂O ₅、Y ₃Al ₅O ₁₂、Er ₂O ₃、IrO ₂中任意一种或多种的组合； More preferably, the oxides include WO ₃ , NiO, TiO ₂ , Nb ₂ O ₅ , Fe ₂ O ₃ , V ₂ O ₅ , Co ₂ O ₃ , Y ₂ O ₃ , Cr ₂ O ₃ , MoO ₃ , Any one or a combination of Al ₂ O ₃ , SiO ₂ , MgO, ZnO, MnO ₂ , CaO, ZrO ₂ , Ta ₂ O ₅ , Y ₃ Al ₅ O ₁₂ , Er ₂ O ₃ , and IrO ₂ ;

    更优选的，所述氟化物包括MgF ₂、CaF ₂、GeF ₂、YbF ₃、YF ₃、Na ₃AlF ₆、AlF ₃、NdF ₃、LaF ₃、LiF、NaF、BaF ₂、SrF ₂中任意一种或多种的组合； More preferably, the fluoride includes any one of MgF ₂ , CaF ₂ , GeF ₂ , YbF ₃ , YF ₃ , Na ₃ AlF ₆ , AlF ₃ , NdF ₃ , LaF ₃ , LiF , NaF , BaF ₂ , SrF ₂ one or more combinations;

    更优选的，所述硫化物包括ZnS、GeS、MoS ₂、Bi ₂S ₃中任意一种或多种的组合； More preferably, the sulfide includes any one or a combination of ZnS, GeS, MoS ₂ , Bi ₂ S ₃ ;

    更优选的，所述硒化物包括ZnSe，GeSe、MoSe ₂、PbSe、Ag ₂Se中任意一种或多种的组合； More preferably, the selenide comprises any one or a combination of ZnSe, GeSe, MoSe ₂ , PbSe, and Ag ₂ Se;

    更优选的，所述氯化物包括AgCl、NaCl、KCl中任意一种或多种的组合；More preferably, the chloride comprises any one or a combination of AgCl, NaCl, KCl;

    更优选的，所述溴化物包括AgBr、NaBr、KBr、TlBr、CsBr中任意一种或多种的组合；More preferably, the bromide includes any one or a combination of AgBr, NaBr, KBr, TlBr and CsBr;

    更优选的，所述碘化物包括AgI、NaI、KI、RbI、CsI中任意一种或多种的组合；More preferably, the iodide comprises any one or a combination of AgI, NaI, KI, RbI, and CsI;

    更优选的，所述砷化物包括GaAs；More preferably, the arsenide includes GaAs;

    更优选的，所述锑化物包括GdT _e； More preferably, the antimonide compound includes _GdTe ;

    优选的，所述介质层的材质包括SrTiO ₃、Ba ₃Ta ₄O ₁₅、Bi ₄Ti ₃O ₂、CaCO ₃、CaWO ₄、CaMnO ₄、LiNbO ₄、普鲁士蓝、普鲁士黑、普鲁士白、普鲁士绿中任意一种或多种的组合； Preferably, the material of the dielectric layer includes SrTiO ₃ , Ba ₃ Ta ₄ O ₁₅ , Bi ₄ Ti ₃ O ₂ , CaCO ₃ , CaWO ₄ , CaMnO ₄ , LiNbO ₄ , Prussian blue, Prussian black, Prussian white, and Prussian green any one or a combination of any of them;

    优选的，所述介质层的材质包括液晶材料或MOF材料；Preferably, the material of the dielectric layer includes liquid crystal material or MOF material;

    优选的，所述有机材料包括有机小分子化合物和/或聚合物；Preferably, the organic material includes small organic molecular compounds and/or polymers;

    更优选的，所述有机材料包括紫罗精、聚吡咯、聚苯胺、聚噻吩、聚咔唑、酞菁、对苯二甲脂、二甲基联二苯胺、四噻富烯、烷基联吡啶、吩噻唑、聚酰胺、环氧树脂、聚二炔中任意一种或多种的组合；More preferably, the organic material includes viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthalate, dimethylbenzidine, tetrathifulene, alkylated Any one or a combination of pyridine, phenothiazole, polyamide, epoxy resin and polydiyne;

    更优选的，所述介质层的材质选自无机电致变色材料和/或有机电致变色材料。More preferably, the material of the dielectric layer is selected from inorganic electrochromic materials and/or organic electrochromic materials.
16. 根据权利要求1所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：The colorful electrochromic structure with high brightness, saturation and purity according to claim 1, characterized in that:

    所述介质层与第一光学结构层或第二光学结构层之间还分布有优化介质层；An optimized medium layer is also distributed between the medium layer and the first optical structure layer or the second optical structure layer;

    或者，所述第一光学结构层或第二光学结构层上设有优化介质层；Alternatively, an optimized medium layer is provided on the first optical structure layer or the second optical structure layer;

    优选的，所述优化介质层的材质包括WO ₃、NiO、TiO ₂、Nb ₂O ₅、Fe ₂O ₃、V ₂O ₅、Co ₂O ₃、Y ₂O ₃、Cr ₂O ₃、MoO ₃、Al ₂O ₃、SiO ₂、MgO、ZnO、MnO ₂、CaO、ZrO ₂、Ta ₂O ₅、Y ₃Al ₅O ₁₂、Er ₂O ₃、 ZnS、MgF ₂、氮化硅中的任意一种或多种的组合； Preferably, the material of the optimized dielectric layer includes WO ₃ , NiO, TiO ₂ , Nb ₂ O ₅ , Fe ₂ O ₃ , V ₂ O ₅ , Co ₂ O ₃ , Y ₂ O ₃ , Cr ₂ O ₃ , MoO _3. Any of Al ₂ O ₃ , SiO ₂ , MgO, ZnO, MnO ₂ , CaO, ZrO ₂ , Ta ₂ O ₅ , Y ₃ Al ₅ O ₁₂ , Er ₂ O ₃ , ZnS, MgF ₂ , and silicon nitride a combination of one or more;

    优选的，所述优化介质层的厚度为0～2000nm。Preferably, the thickness of the optimized dielectric layer is 0-2000 nm.
17. 根据权利要求12所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：所述基底为透明或半透明的；优选的，所述基底的材质包括塑料制品、织物、有机玻璃、金属合金、陶瓷、PET、PES、PEN、PC、PMMA、PDMS中的任意一种或多种的组合。The colorful electrochromic structure with high brightness, saturation and purity according to claim 12, wherein the substrate is transparent or translucent; preferably, the material of the substrate includes plastic products, fabrics, organic Any one or a combination of glass, metal alloys, ceramics, PET, PES, PEN, PC, PMMA, PDMS.
18. 根据权利要求12所述的高亮度、饱和度、纯度的多彩电致变色结构，其特征在于：施加于所述多彩电致变色结构的电致变色电压为-0.8V～1.0V。The multi-color electrochromic structure with high brightness, saturation and purity according to claim 12, wherein the electrochromic voltage applied to the multi-color electrochromic structure is -0.8V to 1.0V.
19. 如权利要求1-18中任一项所述高亮度、饱和度、纯度的多彩电致变色结构的制备方法，其特征在于包括：The preparation method of the colorful electrochromic structure with high brightness, saturation and purity according to any one of claims 1-18, characterized in that it comprises:

    提供基底；provide a base;

    在所述基底上交替沉积形成第一光学结构层或第二光学结构层和介质层，并重复操作两次以上，获得所述高亮度、饱和度、纯度的多彩电致变色结构。Alternately depositing a first optical structure layer or a second optical structure layer and a dielectric layer on the substrate, and repeating the operation for more than two times, the multicolor electrochromic structure with high brightness, saturation and purity is obtained.
20. 一种高亮度、饱和度、纯度的多彩电致变色器件，包括工作电极、电解质和对电极，所述电解质分布于工作电极和对电极之间，其特征在于，所述工作电极包括权利要求1-18中任一项所述高亮度、饱和度、纯度的多彩电致变色结构。A colorful electrochromic device with high brightness, saturation and purity, comprising a working electrode, an electrolyte and a counter electrode, wherein the electrolyte is distributed between the working electrode and the counter electrode, characterized in that the working electrode comprises claim 1 The colorful electrochromic structure of any one of -18 with high brightness, saturation and purity.
21. 根据权利要求20所述的多彩电致变色器件，其特征在于：所述电解质包括液态电解质、凝胶电解质或固态电解质；The colorful electrochromic device according to claim 20, wherein the electrolyte comprises a liquid electrolyte, a gel electrolyte or a solid electrolyte;

    和/或，所述多彩电致变色器件还包括离子存储层，所述离子存储层与所述电解质接触；And/or, the colorful electrochromic device further comprises an ion storage layer, the ion storage layer is in contact with the electrolyte;

    优选的，所述基底上还设置有导电层；优选的，所述导电层包括FTO、ITO、Ag纳米线、Ag纳米网栅、碳纳米管、石墨烯中的任意一种或多种的组合；和/或，所述对电极为透明或半透明的。Preferably, a conductive layer is further provided on the substrate; preferably, the conductive layer includes any one or a combination of FTO, ITO, Ag nanowires, Ag nanogrids, carbon nanotubes, and graphene. ; and/or, the counter electrode is transparent or translucent.
22. 如权利要求20-21中任一项所述的高亮度、饱和度、纯度的多彩电致变色器件的制备方法，其特征在于包括：The method for preparing a multi-colored electrochromic device with high brightness, saturation and purity as claimed in any one of claims 20-21, characterized in that it comprises:

    提供基底；provide a base;

    在所述基底上交替沉积形成第一光学结构层或第二光学结构层和介质层，并重复操作两次以上，获得电致变色层，进而获得工作电极；Alternately depositing a first optical structure layer or a second optical structure layer and a dielectric layer on the substrate, and repeating the operation more than twice to obtain an electrochromic layer, and then a working electrode;

    以及，将工作电极、电解质、对电极组装形成高亮度、饱和度、纯度的多彩电致变色器件。And, the working electrode, the electrolyte and the counter electrode are assembled to form a colorful electrochromic device with high brightness, saturation and purity.
23. 如权利要求20-21中任一项所述多彩电致变色器件的调控方法，其特征在于包括：The control method of the colorful electrochromic device according to any one of claims 20-21, characterized in that it comprises:

    将工作电极、对电极与电源连接形成工作电路；Connect the working electrode, the counter electrode and the power source to form a working circuit;

    调整工作电极与对电极之间的电势差，使介质层内电致变色材料的折射率发生变化，从而调控所述多彩电致变色器件的颜色。The potential difference between the working electrode and the counter electrode is adjusted to change the refractive index of the electrochromic material in the dielectric layer, thereby regulating the color of the colorful electrochromic device.
24. 一种装置，其特征在于包括权利要求20-21中任一项所述多彩电致变色器件；优选的，所述装置还包括电源，所述电源能与所述多彩电致变色器件电连接形成工作回路。A device, characterized by comprising the multi-color electrochromic device according to any one of claims 20-21; preferably, the device further comprises a power source, which can be electrically connected to the multi-color electrochromic device to form a working circuit.

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