CN112180647B - Devices containing colorful thin-film structures - Google Patents

Abstract

The invention discloses a device comprising a colorful film structure, which comprises a substrate, wherein the colorful film structure is connected with or integrally formed on the substrate and comprises at least one dielectric layer, each dielectric layer is matched with a first reflecting surface and a second reflecting surface to form an optical cavity, the first reflecting surface is the first surface of the dielectric layer, the second reflecting surface is the combined interface of the second surface of the dielectric layer and a second optical structure layer, and the first surface and the second surface are arranged oppositely. Further, the dielectric layer is formed of an electrochromic material. The improved colorful film structure is applied to consumer electronics, household appliances, buildings, vehicles, clothes and the like, and the colorful film structure has the characteristics of electrochromism and physical color fusion, so that colorful regulation and control of colors can be realized, the devices can present colorful changes, and the requirements of practical application, especially the personalized requirements of different crowds, can be fully met.

Description

Devices containing colorful thin-film structures

technical field

The present invention relates to a colorful optical structure, in particular to a device including a colorful thin film structure, such as consumer electronics products, household appliances, buildings, vehicles, clothing and the like.

Background technique

With the improvement of living standards, people have higher and higher requirements for the color changes of various devices in daily life and working environment, such as consumer electronics products, household appliances, buildings, vehicles, clothing, etc. For example, for consumer electronics such as mobile phones, in order to meet different individual needs, the industry has proposed a variety of mobile phone cases that can change colors. The existing color-changing mobile phone cases are generally realized by the following schemes, for example: spraying or printing a layer of color-changing material on the mobile phone case, but because the color-changing material is easy to wear or fall off, and the color-changing effect is relatively simple; or, using a multi-layer structure, For example, the photochromic layer, primer layer, heat dissipation layer, wear-resistant layer and transparent coating are formed into a multi-layer composite structure, but it is not easy to process, the discoloration efficiency is low, and there are also defects such as single discoloration effect.

In recent years, color-changing optical structures based on electrochromic materials have also been more and more widely used. For example, the industry has attempted to apply electrochromic optical structures to commercially available mobile phone casings, household appliance casings, windows of buildings or vehicles, and the like. However, the color modulation of the existing electrochromic structure is chemical color modulation, and its color depends on the intrinsic properties of the material, so it is relatively monotonous and difficult to meet actual needs.

Contents of the invention

The main purpose of the present invention is to provide a device including a colorful thin film structure to overcome the deficiencies in the prior art.

In order to realize the aforementioned object of the invention, the technical solutions adopted in the present invention include:

An embodiment of the present invention provides a device including a multicolored thin film structure, including a substrate, the substrate is connected or integrally formed with a multicolored thin film structure, and the multicolored thin film structure includes at least one dielectric layer, wherein each dielectric layer is connected to a The first reflective surface and a second reflective surface cooperate to form an optical cavity, the first reflective surface is the first surface of the medium layer, and the second reflective surface is the second surface of the medium layer and a second optical structure layer A bonding interface, the first surface is opposite to the second surface;

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第一反射面时的折射角。When the incident light enters the optical cavity, the phase shift between the reflected light formed on the first reflective surface and the reflected light formed on the second reflective surface

d is the thickness of the dielectric layer,

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

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

则所述第一反射面的反射系数

其中

为入射光的入射角；以及，若定义所述介质层第二表面上的媒介材料的折射率为

则所述第二反射面的反射系数

其中

为入射光在透过第二反射面时的折射角；主要由所述介质层和第二光学结构层组成的多彩薄膜结构的反射系数表示为：

反射率表示为：

Further, if the refractive index of the medium material on the first surface of the medium layer is defined as

Then the reflection coefficient of the first reflective surface

in

is the incident angle of the incident light; and, if the refractive index of the medium material on the second surface of the medium layer is defined

Then the reflection coefficient of the second reflective surface

in

Be the refraction angle of incident light when passing through the second reflective surface; The reflection coefficient of the colorful film structure mainly composed of the medium layer and the second optical structure layer is expressed as:

The reflectivity is expressed as:

Further, the material of the medium layer is selected from organic materials or inorganic materials, preferably electrochromic materials.

所述第二光学结构层的折射率为

Further, the first reflective surface is the interface between the first surface of the medium layer and the first optical structure layer, and the refractive index of the first optical structure layer is

The refractive index of the second optical structure layer is

其中

为入射光于第一表面的入射角，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，主要由所述第一光学结构层、介质层和第二光学结构层组成的多彩薄膜结构的透射系数表示为：

透过率表示为：

Further, the transmission coefficient of the first optical structure layer

in

is the incident angle of incident light on the first surface, the transmission coefficient of the second optical structure layer

in

is the refraction angle of incident light when passing through the second surface, and the transmission coefficient of the colorful film structure mainly composed of the first optical structure layer, the medium layer and the second optical structure layer is expressed as:

The transmittance is expressed as:

Further, the colorful film structure mainly composed of the first optical structure layer, the medium layer and the second optical structure layer has an optical transmission working mode, an optical reflection working mode or an optical transmission and reflection working mode; wherein, in the optical In the reflective working mode, the colorful thin film structure has a double-sided asymmetric structural color, and in the optical transmission working mode, the colorful thin film structure has a transparent structural color.

Further, the colorful film structure includes a working electrode, a counter electrode, and an electrolyte distributed between the working electrode and the counter electrode, and the working electrode includes a dielectric layer formed of an electrochromic material.

Further, the device is a consumer electronic product or a household appliance, and the colorful film structure is connected and/or integrally formed on the housing and/or the display screen of the device.

Further, the device is a building, and any one of the inner wall, outer wall, and window of the building is connected to and/or integrally formed with the colorful film structure.

Further, the device is a vehicle, and the colorful film structure is connected to and/or integrally formed on any one of the shell, the inner wall, and the window of the vehicle.

Further, the device is shoes, hats or clothing, and the surface of the device is connected and/or integrally formed with the colorful film structure.

Further, the colorful film structure presents a set graphic structure.

Compared with the prior art, the present invention applies an improved colorful film structure to devices such as consumer electronics, household appliances, buildings, vehicles, clothing, etc., because the colorful film structure has electrochromic and physical color The characteristics of fusion, that is, the organic combination of the two advantages of electrochromic color adjustment and physical color wide color can realize colorful control of color, and the controllability is good, so that the aforementioned devices show rich color changes Colorful, can fully meet the needs of practical applications, especially the individual needs of different groups of people.

Description of drawings

Fig. 1 is a schematic structural diagram of a mobile phone according to Embodiment 1 of the present invention;

Fig. 2 is a structural schematic diagram of the colorful film forming the Logo in Fig. 1 .

Detailed ways

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments described in the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.

Also, it should be noted that in this specification, relative terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply these No such actual relationship or order exists between entities or operations. Furthermore, the term "comprises", "comprises" or any other variation thereof is intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus comprising a set of elements includes not only those elements, but also includes elements not expressly listed. other elements of or also include elements inherent in such a process, method, article, or device. Without further limitations, an element defined by the phrase "comprising at least one of ..." does not exclude the presence of additional identical elements in the process, method, article or device comprising said element.

One aspect of the embodiments of the present invention provides a device containing a multicolored thin film structure, including a substrate, the substrate is connected with or integrally formed with a multicolored thin film structure, and the multicolored thin film structure includes at least one dielectric layer, each of which The medium layer cooperates with a first reflective surface and a second reflective surface to form an optical cavity, the first reflective surface is the first surface of the medium layer, and the second reflective surface is the second surface of the medium layer and a first reflective surface. The bonding interface of the two optical structure layers, the first surface and the second surface are arranged opposite to each other;

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第一反射面时的折射角。When the incident light enters the optical cavity, the phase shift between the reflected light formed on the first reflective surface and the reflected light formed on the second reflective surface

d is the thickness of the dielectric layer,

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

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

则所述第一反射面的反射系数

其中

为入射光的入射角；以及，若定义所述介质层第二表面上的媒介材料的折射率为

则所述第二反射面的反射系数

其中

为入射光在透过第二反射面时的折射角；主要由所述介质层和第二光学结构层组成的多彩薄膜结构的反射系数表示为：

反射率表示为：

Further, if the refractive index of the medium material on the first surface of the medium layer is defined as

Then the reflection coefficient of the first reflective surface

in

is the incident angle of the incident light; and, if the refractive index of the medium material on the second surface of the medium layer is defined

Then the reflection coefficient of the second reflective surface

in

Be the refraction angle of incident light when passing through the second reflective surface; The reflection coefficient of the colorful film structure mainly composed of the medium layer and the second optical structure layer is expressed as:

The reflectivity is expressed as:

In some embodiments, the second optical structure layer is a metal material layer with a thickness of more than 20 nm. Preferably, the thickness of the metal reflective layer is 50-3000 nm. That is, the second optical structure layer can be regarded as a metal reflective layer. At this time, the reflected light formed by the incident light on the first surface of the medium layer (ie, the first reflective surface) and the reflection formed by the incident light passing through the medium layer on the surface of the metal layer (ie, the second reflective surface) Light interference superposition.

Further, the material of the metal reflective layer may be selected from inactive metals, such as chromium, gold, silver, copper, tungsten, titanium or alloys thereof, and is not limited thereto.

In some embodiments, if the dielectric layer in the colorful thin film structure is formed of an electrochromic material, so that the colorful thin film structure is an electrochromic structure, the metal reflective layer also serves as a current collector for the dielectric layer. Therefore, the metal reflective layer may preferably be formed of a metal material with high conductivity, for example, may be formed of a material with high conductivity such as silver (Ag) or copper (Cu).

In some embodiments, the second optical structure layer adopts a metal material layer with a thickness greater than 0 and less than 20 nm.

所述第二光学结构层的折射率为

In some implementations, the first reflective surface is the bonding surface between the first surface of the medium layer and the first optical structure layer, and the refractive index of the first optical structure layer is

The refractive index of the second optical structure layer is

Further, the reflectance and reflectance of the colorful film structure are also applicable to the case where the incident light enters the optical cavity from the second optical structure layer.

Further, the first optical structure layer and the second optical structure layer are arranged in parallel, and have optical reflectivity and/or optical transmittance.

Further, for the colorful film structure, the reflected light formed on the first surface by the incident light incident from the first optical structure layer and the reflected light formed on the second surface by the incident light transmitted through the medium layer Interference superposition of reflected light. And vice versa, that is, the reflected light formed on the second surface by the incident light from the second optical structure layer interferes and superimposes the reflected light formed on the first surface by the incident light transmitted through the medium layer.

其中

为入射光于第一表面的入射角，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，主要由所述第一光学结构层、介质层和第二光学结构层组成的多彩薄膜结构的透射系数表示为：

透过率表示为：

Specifically, the transmission coefficient of the first optical structure layer

in

is the incident angle of incident light on the first surface, the transmission coefficient of the second optical structure layer

in

is the refraction angle of incident light when passing through the second surface, and the transmission coefficient of the colorful film structure mainly composed of the first optical structure layer, the medium layer and the second optical structure layer is expressed as:

The transmittance is expressed as:

Further, the transmittance and transmittance of the colorful thin film structure are also applicable to the case where the incident light enters the optical cavity from the second optical structure layer.

In some embodiments, the colorful thin film structure includes one or more first optical structural layers, one or more dielectric layers, and one or more second optical structural layers.

In some embodiments, the colorful thin film structure includes multiple first optical structural layers and/or multiple second optical structural layers and multiple dielectric layers.

In some embodiments, the first optical structure layer is a metal material layer or consists of gas.

Further, the thickness of the first optical structure layer is preferably 0-20 nm, preferably greater than 0 and less than 20 nm.

In some embodiments, the first optical structural layer is a metal layer.

In some embodiments, the first optical structural layer is air-formed.

In some embodiments, the first optical structural layer or the second optical structural layer is absent.

Further, the material of the metal material layer includes any one or a combination of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, palladium, but not limited to this.

Further, an optimized medium layer can also be added between the first optical structure layer or the second optical structure layer and the medium layer, so as to optimize the color of the colorful film structure.

Further, an optimized medium layer may 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 may be arranged on the optimized medium layer, To optimize the color of the colorful film structure.

Further, the material of the optimized medium layer includes but 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.

For example, for some specific materials or thick colorful films in the embodiments of the present invention, adding a suitable thickness of semiconductor material can increase the intensity difference of the reflectivity curve, thereby increasing the color saturation.

Further, the thickness of the optimized medium layer is preferably 0-2000 nm, preferably 0-500 nm, preferably 0-300 nm, especially preferably 1-100 nm.

Further, the colorful thin film structure has an optical transmission working mode, an optical reflection working mode or an optical transmission and reflection working mode.

Wherein, in the optical reflection working mode, the colorful film structure has double-sided asymmetric structural colors. However, in the optical transmission working mode, the colorful film structure has a transparent structural color.

In some embodiments, the thickness of the dielectric layer is greater than 0 but less than or equal to 2000 nm, preferably 50-2000 nm, more preferably 100-500 nm, so that the color saturation of the colorful thin film structure is higher.

In some embodiments, the material of the medium layer is selected from organic materials or inorganic materials.

Further, the inorganic material includes any one or a combination of metal element or nonmetal element, inorganic salt, and oxide, but is not limited thereto.

Further, the non-metal elemental substance includes any one or a combination of single crystal silicon, polycrystalline silicon, and diamond, but is not limited thereto.

Further, the inorganic salt includes any one or a combination of fluoride, sulfide, selenide, chloride, bromide, iodide, arsenide or telluride, but is not limited thereto.

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 more, but not limited to this.

Further, the sulfide includes any one or a combination of ZnS, GeS, MoS ₂ , Bi ₂ S ₃ , but is not limited thereto.

Further, the selenide includes ZnSe, any one or combination of GeSe, MoSe ₂ , PbSe, Ag ₂ Se, but not limited thereto.

Further, the chloride includes AgCl, etc., but not limited thereto.

Further, the bromide includes any one or a combination of AgBr and TlBr, but is not limited thereto.

Further, the iodide includes AgI, etc., but not limited thereto.

Further, the arsenide includes GaAs, etc., but is not limited thereto.

Further, the antimonide includes GdTe, etc., but not limited thereto.

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, Prussian green A combination of any one or more of them, but not limited thereto.

Further, the material of the medium layer includes liquid crystal material or MOF material, but is not limited thereto.

Further, the organic material includes small organic molecules and/or polymers, but is not limited thereto.

Further, the organic material includes viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthalate, dimethyl benzidine, tetrathiafulvene, alkyl bipyridine , phenothiazole, polyamide, epoxy resin, polydiyne any one or a combination of more, but not limited thereto.

In some embodiments, the dielectric layer can consist essentially of 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 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, terephthalamide, dimethyl benzidine, tetrathiafulvene, alkyl bipyridine, phen Thiazoles, polydiynes, etc., but not limited thereto.

In some embodiments, the thickness and/or material of the first optical structure layer, the second optical structure layer, and the medium layer can also be adjusted, thereby adjusting the color of the colorful film structure.

In some embodiments, the colorful thin film structure includes a working electrode, a counter electrode, and an electrolyte distributed between the working electrode and the counter electrode, and the working electrode includes a dielectric layer formed of an electrochromic material.

Further, the electrochromic material may be selected from organic electrochromic materials or inorganic electrochromic materials. Among them, the inorganic electrochromic material can be the oxides of Co, Rh, Ir, Ni, Cr, Mn, Fe, Ti, V, Nb, Ta, Mo, W, such as LiNiO ₂ (lithium nickelate), IrO ₂ , NiO, V ₂ O ₅ , LixCoO ₂ (lithium cobaltate), Rh ₂ O ₃ , CrO ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , or TiO _{2 ,} etc., but not limited thereto. Among them, the organic electrochromic material can be organic polymers, organic small molecules, metal supramolecular polymers, metal organic compounds, etc., such as methyl viologen, viologen, polyaniline, polythiophene, polypyrrole, Prussian blue , metal-organic chelates (such as cyanine compounds), polydiynes, etc., and are not limited thereto.

Further, 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.

In some embodiments, the electrolyte is in contact with the dielectric layer and provides a material for the mobility of ions, such as hydrogen ions or lithium ions, for discoloring or decolorizing the electrochromic material.

In some embodiments, the electrolyte may comprise one or more compounds, such as 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 intercalated or removed from the dielectric layer according to the polarity of the applied voltage.

In some embodiments, the electrolyte may be a mixed electrolyte, for example, a mixed electrolyte composed of two or more salts in aqueous LiCl, AlCl ₃ , HCl, MgCl ₂ , ZnCl ₂ and other salts. When an electrolyte solution containing two or more ions is used, compared to the case of using an electrolyte solution containing only a single ion, the color change of the colorful thin film structure of the foregoing embodiments of the present invention can be made more abundant and saturated. higher degree.

In some embodiments, the electrolyte may be a liquid electrolyte, such as an aqueous LiCl, AlCl ₃ , HCl, H ₂ SO ₄ aqueous solution, and the like.

In some embodiments, the electrolyte may also include a carbonate compound. Since the carbonate-based compound has a high dielectric constant, it is possible to increase the ionic conductivity provided by the lithium salt. 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 LiClO ₄ , Na(ClO ₄ ) ₃ propylene carbonate electrolytic solution, etc. can be used.

In some embodiments, the electrolyte may be a gel electrolyte, such as PMMA-PEG-LiClO ₄ , PVDF-PC-LiPF ₆ , LiCl/PVA, H ₂ SO ₄ /PVA, etc., but not limited thereto.

In some preferred embodiments, when an inorganic solid electrolyte is used as the electrolyte, the electrolyte may contain LiPON or Ta ₂ O ₅ . For example, the electrolyte may be, but not limited to, a Li-containing metal oxide film, such as LiTaO or LiPO films. In addition, the inorganic solid electrolyte can be an electrolyte in which LiPON or Ta ₂ O ₅ is added with components such as B, S, and W, for example, it can be LiBO ₂ +Li ₂ SO ₄ , LiAlF ₄ , LiNbO ₃ , Li ₂ OB ₂ O ₃ et al.

Preferably, the device further includes an ion storage layer.

Further, the ion storage layer is in contact with the electrolyte.

Further, the counter electrode may include a substrate, a transparent conductive layer and an ion storage layer.

Further, the material of the ion storage layer may be selected from but not limited to NiO, Fe ₂ O ₃ , TiO ₂ , Prussian blue, IrO ₂ and the like.

In some embodiments, the counter electrode is transparent or translucent.

In some embodiments, the working electrode may also include a transparent conductive electrode and the like. The transparent conductive electrode can be formed by including materials with characteristics such as high light transmittance and low sheet resistance, for example, it can be formed by including any of the following: selected from ITO (indium tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), ATO (antimony-doped tin oxide), IZO (indium-doped zinc oxide), Transparent conducting oxides of NTO (niobium-doped titanium oxide), ZnO, OMO (oxide/metal/oxide), and CTO; silver (Ag) nanowires; metal meshes; or OMO (oxide metal oxide) .

A method of forming the transparent conductive electrode or transparent conductive layer is not particularly limited, and any known method may be used without limitation. For example, a thin film electrode layer containing transparent conductive oxide particles can be formed on the glass base layer by a method such as sputtering or printing (screen printing, gravure printing, inkjet printing, etc.). In the case of the vacuum method, the thickness of the electrode layer thus prepared may range from 10 nm to 500 nm, and in the case of the printing method, the thickness may range from 0.1 μm to 20 μm. In one example, the visible light transmittance of the transparent conductive electrode layer may be 70% to 95%.

In some preferred embodiments, the electrolyte is an all-solid electrolyte, which can be combined to form a solid-state dielectric layer, a first optical structure layer, a second optical structure layer, and a counter electrode to form an all-solid colorful film structure. For example, the all-solid-state electrolyte in the all-solid-state colorful film structure can be in the form of a solid-state ion-conducting layer. The discoloration principle of this kind of all-solid-state colorful film structure is: the metal reflective layer and other layer materials form a metal-medium structure, and can also include other layers, such as ion conducting layers, ion storage layers and transparent conducting layers, etc., by adjusting the When the thickness of each layer of material reaches an appropriate range, an electrochromic structure with structural color can be prepared. Further, by applying a voltage, the refractive index of the electrochromic material can be adjusted, and the color of the all-solid-state colorful film structure can be further adjusted. .

In some embodiments, in addition to adjusting the color (structural color) of the colorful thin film structure by adjusting the thickness and/or material of the first optical structure layer, the second optical structure layer, and the medium layer, it can also be adjusted by The potential difference applied between the aforementioned working electrode and the counter electrode is adjusted to at least change the refractive index of the electrochromic material in the dielectric layer, thereby regulating the color of the colorful thin film structure. This regulation process can be dynamic, which realizes the fusion of colorful structural color and electrochromic, which greatly enriches the color modulation of colorful thin film structures.

Of course, the device may also include components such as a control module and a power supply module that match the colorful film structure, and these accessory components may be included in the device or additionally added.

In some embodiments of the present invention, at least any one of magnetron sputtering, ion plating, electron beam evaporation, thermal evaporation, chemical vapor deposition, and electrochemical deposition can be used to form the aforementioned first optical structure layer, Second optical structure layer, dielectric layer, etc.

More specifically, the dielectric layer can be prepared by magnetron sputtering, ion plating, electron beam evaporation, thermal evaporation, chemical vapor deposition, electrochemical deposition, etc., but not limited thereto. For example, the dielectric layer may be formed by processing metal materials or the like by means of laser direct writing, chemical etching, or the like.

More specifically, the first optical structure layer and the second optical structure layer can be prepared by magnetron sputtering, ion plating, electron beam evaporation, thermal evaporation, chemical vapor deposition, and the like.

In addition, the first optical structure layer or the second optical structure layer, the medium layer, etc. may also be formed by coating, printing, film casting, atomic force deposition, sol-gel technology, etc., and are not limited thereto.

Further, the device is a consumer electronic product or a household appliance, and the colorful film structure is connected and/or integrally formed on the housing and/or the display screen of the device.

Wherein, the consumer electronic product includes a mobile phone, a bracelet, a tablet computer or a notebook computer, etc., and is not limited thereto.

Wherein, the household appliance includes a TV, a refrigerator, an electric fan or an air conditioner, etc., and is not limited thereto.

Further, the device is a building, and any one of the inner wall, outer wall, ceiling, and window of the building is connected to and/or integrally formed with the colorful film structure.

Further, the device is a vehicle, and the colorful film structure is connected to and/or integrally formed on any one of the shell, the inner wall, and the window of the vehicle.

The means of transportation may be various types of motor vehicles such as automobiles, motorcycles, and electric vehicles, and may also be yachts, airplanes, etc., and is not limited thereto.

Further, the device is shoes, hats or clothing (including but not limited to clothing, belts, scarves, wristbands, hair bands, etc.), the surface of the device is connected and/or integrally formed with the colorful film structure.

Further, the colorful thin film structure may present a set graphic structure, such as patterns, characters, etc., and is not limited thereto.

The technical solutions of the present invention will be further described in detail below through several embodiments and in conjunction with the accompanying drawings. However, the selected examples are only for illustrating the present invention and do not limit the scope of the present invention.

Embodiment 1 Refer to Fig. 1-shown in Fig. 2, this embodiment discloses a kind of mobile phone, comprises mobile phone body 1 and mobile phone shell 2, and it comprises shell 10, and described shell is integrally provided with and is formed by colorful film structure. Logo3. The colorful film structure is an all-solid-state electrochromic structure, which includes a working electrode, an electrolyte layer and a counter electrode, and the electrolyte layer is arranged between the working electrode and the counter electrode. The working electrode includes a metal tungsten layer 11 with a thickness of about 100 nm and a tungsten oxide dielectric layer 12 with a thickness of about 150 nm to 400 nm, which are sequentially deposited on the shell of the mobile phone by magnetron sputtering. The electrolyte 13 uses LiNbO ₃ with a thickness of about 600 nm. The counter electrode 15 uses ITO with a thickness of about 200 nm. An ion storage layer NiO14 with a thickness of about 200 nm is set between the counter electrode and the electrolyte. Of course, the aforementioned tungsten film and tungsten oxide layer can also be prepared by methods known in the industry such as electron beam evaporation, thermal evaporation, and ion plating.

When the logo is not powered on, it appears as a single color, and after the power supply (mobile phone power supply), by adjusting the voltage (which can be realized through the voltage regulation function of the mobile phone or by adding a voltage regulation component), the Logo's The color can be converted among various colors with the change of voltage, for example, it can be changed from red to yellow, and then from yellow to green, and it can also be blue, purple, etc., and the hue, saturation, brightness, etc. are all can be adjusted in real time.

Embodiment 2: This embodiment discloses a refrigerator panel, which includes a transparent cover plate covered on the front side of the refrigerator, and the inner wall of the transparent cover plate is covered with a colorful film structure. The colorful film structure is an all-solid-state electrochromic structure, which includes a working electrode, an electrolyte layer and a counter electrode, and the electrolyte layer is arranged between the working electrode and the counter electrode. The working electrode includes a metal Cr layer with a thickness of about 50 nm deposited sequentially on the shell of the mobile phone by magnetron sputtering, and a Prussian blue layer with a thickness of about 100 nm deposited on the metal Cr layer by electrochemical deposition. A ZnS layer with a thickness of about 1nm-15nm is deposited on the Prussian blue layer by magnetron sputtering. A LiAlF ₄ electrolyte layer with a thickness of about 300 nm is formed on the ZnS layer. An Fe ₂ O ₃ layer with a thickness of about 100 nm was formed on the electrolyte layer. AZO with a thickness of about 80 nm is set on the Fe ₂ O ₃ layer as a counter electrode.

When the multi-color thin film structure is not powered on, it appears as a single color, and after the power supply (the power module of the refrigerator) is turned on, the color of the multi-color thin film structure can be adjusted by adjusting the voltage (through the additional voltage control element). Switch freely between red, yellow and blue.

Embodiment 3: This embodiment discloses a building with more than one window, some of which include a window frame and glass fixed on the window frame, the glass is covered with a multi-color film structure, and the multi-color The film structure includes a first medium layer, a second optical structure layer, a second medium layer, and a first optical structure layer formed on the glass in sequence. Wherein, the first optical structure layer is air, the second optical structure layer is metal tungsten film, and the first and second dielectric layers are formed of tungsten oxide layer.

The tungsten oxide layer as the first dielectric layer can be formed by means of magnetron sputtering or the like, with a thickness of about 1 nm to 400 nm. The metal tungsten film has a thickness of about 10 nm. The thickness of the tungsten oxide layer as the second dielectric layer is about 100nm-400nm, which can be formed on the metal tungsten film by magnetron sputtering.

Viewed from one side of the first optical structure layer, a colorful film structure reflecting rich and brilliant colors can be obtained. Viewed from the side of the glass, the corresponding reflected color is also rich and brilliant, and this color is completely different from the color seen from the direction of the film. And, through the colorful thin film structure, transmission structural color can be obtained, and the transmission structural color also presents rich and gorgeous colors, and the transmittance of the reflection color and transmission color of the colorful thin film structure is determined by the metal tungsten layer and the The thickness of the tungsten oxide layer is determined.

Embodiment 4: This embodiment discloses a kind of automobile, and the window glass of this automobile is conformally covered with a kind of reflective/transmissive dual-mode multi-color film structure, which includes a working electrode, an electrolyte layer and a counter electrode, and the electrolyte layer is located on the working electrode. between the electrode and the counter electrode.

The working electrode includes first and second optical structure layers and a dielectric layer, wherein the first optical structure layer is a tungsten film with a thickness of about 5 nm, the second optical structure layer is a silver film with a thickness of about 10 nm, and the dielectric layer is a tungsten film with a thickness of about 100 nm to 400 nm. Titanium oxide layer. A transparent conductive layer formed by silver nano wires is also formed on the window glass of the automobile, and the first or second optical structure layer is formed on the transparent conductive layer.

The vehicle window glass of this embodiment will show different colors when viewed from both sides, and also has a transmission structural color.

Then the aforementioned working electrode is matched with a pair of electrodes (such as NiO counter electrode), and LiCl/PVA gel electrolyte is set between the two, and then the lead wire is connected to the automobile power supply, and the voltage is applied to the colorful film structure. By adjusting the voltage range, the color of the colorful film structure can be further modulated to change between more colors, especially the color changes on both sides of the window glass are not completely the same.

Embodiment 5: This embodiment discloses a sun visor hat, the partial area of the sun visor hat body is made of PET film, and the PET film is formed with a colorful pattern with a colorful film structure, and the colorful film structure includes a working electrode , an electrolyte layer and a counter electrode, the electrolyte layer is arranged between the working electrode and the counter electrode. The working electrode and the counter electrode are also electrically connected with the organic photovoltaic cell arranged on the sun visor through the voltage control module.

The working electrode includes a tungsten film with a thickness of about 500nm sputtered on the PET film by magnetron sputtering. Each pixel point of the tungsten film (corresponding to the colorful pattern) is oxidized by laser direct writing to form tungsten oxide layers of different thicknesses as the dielectric layer. . The thickness of the dielectric layer is about 0-300nm. The process conditions of the laser direct writing include: the tungsten film can be placed on the table controlled by XY computer, the moving speed is 15mm/s, the continuous laser power is 100W, the laser rectangular spot size is 1.4mm×1.4mm, the defocus The measurement is 5mm, the spot overlap rate is 40%, and the laser action time is 0-5s. The aforementioned counter electrode may be a NiO counter electrode layer. A LiBO ₂ +Li ₂ SO ₄ solid electrolyte is packaged between the working electrode and the counter electrode, and then leads are drawn out. The color of the colorful film structure can be further modulated by applying a voltage through the organic photovoltaic cell. When the voltage is -2.5V～+2.5V, the red area of the working electrode will change in real time between red, orange and yellow; the blue area will change in real time between blue, purple and red.

It should be understood that the above-mentioned embodiments are only to illustrate the technical concept and features of the present invention, the purpose of which is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (28)

1. A device comprising a multicolored film structure, said device being selected from the group consisting of consumer electronics, household appliances, buildings, vehicles, shoes, hats, and apparel, and said device comprising a substrate having a multicolored film structure attached to or integrally formed thereon, wherein: the colorful thin film structure comprises at least one dielectric layer, wherein the material of the dielectric layer is selected from inorganic electrochromic materials and/or organic electrochromic materials, each dielectric layer is matched with a first reflecting surface and a second reflecting surface to form an optical cavity, the first reflecting surface is the first surface of the dielectric layer, the second reflecting surface is the combined interface of the second surface of the dielectric layer and a second optical structure layer, and the first surface and the second surface are arranged oppositely;

when the incident light enters the optical cavity, the phase shift of the reflected light formed on the first reflecting surface and the reflected light formed on the second reflecting surface

d is the thickness of the dielectric layer,

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

the refraction angle of the incident light when the incident light passes through the first reflecting surface is shown;

a reflection coefficient of the first reflection surface

Wherein

Is the angle of incidence of the incident light,

is the refractive index of the medium material on the first surface of the medium layer;

a reflection coefficient of the second reflecting surface

Wherein

Is the refraction angle of the incident light when passing through the second reflective surface,

is the refractive index of the medium material on the second surface of the medium layer;

the reflectance of the multicolor film structure is expressed as:

the reflectance is expressed as:

the second optical structure layer adopts a metal reflecting layer.

2. The apparatus of claim 1, wherein: the thickness of the metal reflecting layer is more than 20nm.

3. The apparatus of claim 2, wherein: the thickness of the metal reflecting layer is 50-3000 nm.

4. The apparatus of claim 1, wherein: the thickness of the dielectric layer is greater than 0 and less than or equal to 2000nm.

5. The apparatus of claim 4, wherein: the thickness of the dielectric layer is 100-500 nm.

6. The apparatus of claim 1, wherein: the inorganic electrochromic material comprises oxides of Co, rh, ir, ni, cr, mn, fe, ti, V, nb, ta, mo or W.

7. The apparatus of claim 1, wherein: the organic electrochromic material comprises an organic polymer, an organic small molecule, a metal supramolecular polymer or a metal organic compound.

8. The apparatus of claim 7, wherein: the organic electrochromic material is selected from methyl viologen, polyaniline, polythiophene, polypyrrole, prussian blue, metal organic chelate or polydiacetylene.

9. The apparatus of claim 1, wherein: the first reflecting surface is a joint surface of the first surface of the dielectric layer and the first optical structure layer.

10. The apparatus of claim 9, wherein: transmission coefficient of the first optical structure layer

Transmission coefficient of the second optical structure layer

The transmission coefficient of the multicolor film structure is expressed as:

the transmittance is expressed as:

11. the apparatus of claim 9 or 10, wherein: the first optical structure layer is a metal material layer or is composed of gas.

12. The apparatus of claim 11, wherein: the first optical structure layer adopts a metal material layer with the thickness of more than 0 and less than or equal to 20nm.

13. The apparatus of claim 1, wherein: the material of the metal reflecting layer is selected from any one or combination of more of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium and palladium.

14. The apparatus of claim 1, wherein: and an optimized dielectric layer is distributed between the dielectric layer and the first optical structure layer or the second optical structure layer.

15. The apparatus of claim 14, wherein: the material of the optimized dielectric layer is selected from 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 And silicon nitride.

16. The apparatus of claim 14, wherein: the thickness of the optimized dielectric layer is greater than 0 and less than or equal to 2000nm.

17. The apparatus of claim 16, wherein: the thickness of the optimized dielectric layer is more than 0 and less than or equal to 300nm.

18. The apparatus of claim 17, wherein: the thickness of the optimized dielectric layer is 1-100 nm.

19. The apparatus of claim 1, wherein: the colorful film structure comprises a working electrode, a counter electrode and electrolyte, wherein the working electrode comprises the dielectric layer, the counter electrode comprises a transparent conductive electrode and an ion storage layer, the electrolyte is distributed between the working electrode and the counter electrode, and the ion storage layer is distributed between the transparent conductive electrode and the dielectric layer.

20. The apparatus of claim 19, wherein: the electrolyte is selected from a liquid electrolyte, a gel electrolyte or a solid electrolyte.

21. The apparatus of claim 20, wherein: the electrolyte adopts a solid electrolyte, and the colorful thin film structure is of an all-solid-state structure.

22. The apparatus of claim 1, wherein: the device is a consumer electronic product or a household appliance, and the multicolor film structure is connected and/or integrally formed on a shell and/or a display screen of the device.

23. The apparatus of claim 22, wherein: the consumer electronic product comprises a mobile phone, a bracelet, a tablet computer or a notebook computer.

24. The apparatus of claim 22, wherein: the household appliances comprise a television, a refrigerator, an electric fan or an air conditioner.

25. The apparatus of claim 1, wherein: the device is a building, and the colorful film structure is connected and/or integrally formed on any one of an inner wall, an outer wall and a window of the building.

26. The apparatus of claim 1, wherein: the device is a vehicle having the multicolored film structure attached to and/or integrally formed on any of an exterior housing, interior wall, window of the vehicle.

27. The apparatus of claim 1, wherein: the device is a shoe, a hat or a piece of apparel, and the colorful film structure is connected and/or integrally formed on the surface of the device.

28. The apparatus of claim 1, wherein: the colorful film structure is a set image-text structure.

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