WO2020173065A1

WO2020173065A1 - Optical film structure, and manufacturing method therefor and use thereof

Info

Publication number: WO2020173065A1
Application number: PCT/CN2019/103280
Authority: WO
Inventors: 赵志刚; 陈健; 王振; 丛杉
Original assignee: 中国科学院苏州纳米技术与纳米仿生研究所
Priority date: 2019-02-27
Filing date: 2019-08-29
Publication date: 2020-09-03

Abstract

Disclosed are an optical film structure, and a manufacturing method therefor and the use thereof. The optical film structure comprises a first optical structure layer (4) and a second optical structure layer (2) that are arranged in parallel; the first optical structure layer (4) and the second optical structure layer (2) are optically reflective and/or transmissive; a dielectric layer (3) is arranged between the first optical structure layer (4) and the second optical structure layer (2); the bonding interfaces between the dielectric layer (3) and the first optical structure layer (4) and between the dielectric layer (3) and the second optical structure layer (2) are a first surface and a second surface of the dielectric layer (3) respectively; and the first surface, the second surface and the dielectric layer (3) define an optical cavity. The optical film structure shows colorful reflection/transmission colors, and particularly when an electrochromic material is used to form the dielectric layer (3), adjusting the magnitude of the voltage applied to the dielectric layer (3) also can realize fusion of the structural color and electrochromism of the optical film structure, so that the optical film structure shows more colorful color changes, and therefore can be widely applied in multiple fields.

Description

Optical film structure and its preparation method and application

Technical field

This application relates to an optical film, in particular to an optical film structure with a reflection/transmission dual mode and a preparation method and application thereof, belonging to the field of optics or optoelectronic technology.

Background technique

In the optoelectronic information industry, the most promising three types of products in communication, display and storage are inseparable from the optical film structure, such as projectors, rear projection TVs, digital cameras, camcorders, DVDs, and DWDM and GFF in optical communications Filters, etc., the performance of the optical film structure to a large extent determines the final performance of these products. Optical film structure is breaking through the traditional category, and it has penetrated more and more widely into various disciplines such as optoelectronic devices, space detectors, integrated circuits, biochips, laser devices, liquid crystal displays, integrated optics, etc., contributing to the progress of science and technology and the global Economic development plays an important role. With the rapid development of modern science and technology, in addition to requiring optical film structure products to have practical versatility to meet the business needs of the optoelectronic information industry, energy industry and other fields, there are also urgent needs for their aesthetic versatility. It is expected to be used in the fields of construction, automobiles, art decoration, and anti-counterfeiting. This has prompted the development of a series of new optical thin film structures and their preparation technology. However, many optical films currently have single-function structures, complex structures, and cumbersome preparation techniques, which cannot meet the needs of multi-functionality, limiting the further development of industries such as optoelectronics, energy, art decoration, anti-counterfeiting, sensing, and communications.

Application content

The main purpose of this application is to provide an optical film structure and its preparation method and application to overcome the deficiencies in the prior art.

In order to achieve the purpose of the aforementioned application, the technical solutions adopted in this application include:

The embodiment of the application provides an optical film structure, including a first optical structure layer and a second optical structure layer arranged in parallel, the first optical structure layer and the second optical structure layer are optically reflective and/or optically transmissive Sexually, a medium layer is provided between the first optical structure layer and the second optical structure layer, and the bonding interface between the medium layer and the first optical structure layer and the second optical structure layer is the first optical structure layer of the medium layer. A surface and a second surface, the first surface, the second surface and the medium layer constitute an optical cavity; when incident light enters the optical cavity from the first optical structure layer or the second optical structure layer, the The phase shift between the reflected light formed on the surface and the reflected light formed on the second 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 passing through the first surface or the second surface.

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

The embodiments of the present application also provide applications of the optical film structure, for example, applications in the preparation of optical devices, optoelectronic devices, electronic devices and other equipment.

For example, an embodiment of the present application provides a device that includes a working electrode and a counter electrode that cooperate with each other. The working electrode includes any of the foregoing optical film structures, and the dielectric layer in the optical film structure is mainly composed of electrochromic Material composition. The device may be an optical device, an electronic device, or an optoelectronic device, etc., and is not limited thereto.

Further, the device further includes an electrolyte, and the electrolyte is distributed between the working electrode and the counter electrode.

The embodiment of the present application provides a method for adjusting and controlling the device, which includes:

Connect the working electrode and the counter electrode to the power source to form a working circuit;

The potential difference between the working electrode and the counter electrode is adjusted to at least change the refractive index of the electrochromic material in the dielectric layer, thereby adjusting the color of the device.

An embodiment of the present application also provides a device, which includes the device described above.

Compared with the prior art, the advantages of this application are:

1) In the embodiments of the present application, by adjusting the material and/or thickness of each optical structure layer and medium layer in the optical film structure, a colorful reflection/transmission structure color can be obtained. The more interesting thing is that the The structure of the optical film, viewed from its opposite sides, has a completely different reflection structure color, and also a transmission structure color.

2) Preferably, the optical film structure of the embodiment of the present application adopts electrochromic material to form the dielectric layer. By applying a voltage to the dielectric layer, the refractive index of the electrochromic material changes, which in turn changes the optical parameters of the dielectric layer, and finally leads to optical The change of the color of the film structure, the fusion of the structure color and the electrochromic can realize the reflection/transmission dual-mode colorful electrochromic structure with rich color changes.

3) The optical film structure provided by the embodiments of the application has a simple preparation process and low cost. It only needs to adjust the material and/or thickness of each optical structure layer and dielectric layer to control its color, reflectance and transmittance, which is suitable for Large-scale production and multi-functional applications have broad application prospects in the fields of machinery, photovoltaics, energy, transportation, and construction.

Description of the drawings

Fig. 1 is a schematic diagram of a novel film structure in a typical embodiment of the present application;

Figure 2a is a schematic diagram of a novel reflective/transmissive dual-mode colorful electrochromic structure in a typical embodiment of the present application;

Figure 2b is a schematic diagram of the structure of the electrochromic working electrode in Figure 2a;

3 is a schematic diagram of a manufacturing process of a high-precision patterned colorful film in a typical embodiment of the present application;

4 is a schematic structural diagram of a novel optical film structure in Embodiment 1 of the present application;

5 is a photograph of the reflection color of the novel optical thin film structure with different tungsten oxide thicknesses as seen from the side of the first optical structure in Example 1 of the present application;

FIG. 6 is a photograph of the reflection color of the novel optical film structure with different tungsten oxide thicknesses as seen from the direction of the PET substrate in Example 1 of the application;

7 is a photograph of the transmission color of the novel optical thin film structure under different tungsten oxide thicknesses in Example 1 of the application;

8 is a schematic structural diagram of a novel optical film structure in Embodiment 3 of the application;

FIG. 9 is a photograph of the reflection color of the novel optical thin film structure with different tungsten oxide thicknesses as seen from the side of the first optical structure in Example 3 of the application;

10 is a photograph of the reflection color of the novel optical film structure with different thicknesses of tungsten oxide in Example 3 of the present application as seen from the direction of the PET substrate;

11 is a photograph of the transmission color of the novel optical thin film structure under different tungsten oxide thicknesses in Example 3 of the present application;

12 is a schematic diagram of the structure of the working electrode of a novel reflective/transmissive dual-mode multi-color electrochromic device in Example 7 of the present application;

13 is a photograph of the working electrode (taken from both sides of the first optical structure and the substrate) in the colorful electrochromic device with different tungsten oxide thickness in Example 7 of the present application under different voltages;

FIG. 14 is a schematic structural diagram of a mobile phone according to Embodiment 15 of the present application;

FIG. 15 is a schematic diagram of the structure of the colorful film forming the Logo in FIG. 14.

detailed description

In view of the shortcomings in the existing technology, the applicant in this case was able to propose the technical solution of the application after long-term research and extensive practice. The technical solution, its implementation process and principle will be further explained as follows.

In order to more clearly describe the technical solutions in the embodiments of the present application 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 drawings in the following description are only These are some embodiments described in this application, but not all examples. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of this application. The implementation conditions used in the following embodiments can be further adjusted according to actual needs, and the implementation conditions that are not specified are usually conditions in routine experiments.

Furthermore, it should be noted that in this specification, relational 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 There is any such actual relationship or sequence between entities or operations. Moreover, the terms "include", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article, or device that includes a series of elements includes not only those elements, but also includes Other elements of, or also include elements inherent to this process, method, article or equipment. If there are no more restrictions, the element defined by the sentence "including a..." does not exclude the existence of other same elements in the process, method, article, or equipment including the element.

An aspect of the embodiments of the present application provides an optical film structure including a first optical structure layer and a second optical structure layer arranged in parallel, and the first optical structure layer and the second optical structure layer are optically reflective and/or Optically transmissive, a medium layer is provided between the first optical structure layer and the second optical structure layer, and the bonding interface between the medium layer and the first optical structure layer and the second optical structure layer is the medium layer The first surface, the second surface, the first surface, the second surface and the dielectric layer form an optical cavity.

Further, for the optical film structure, the reflected light formed on the first surface by incident light from the first optical structure layer and the reflected light formed on the second surface by the incident light passing through the dielectric layer Reflected light interference and superposition. The reverse is also true, that is, the reflected light formed on the second surface by the incident light incident from the second optical structure layer and the reflected light formed on the first surface by the incident light passing through the medium layer are interfered and superposed.

Further, when incident light enters the optical cavity from the first optical structure layer or the second optical structure layer, the phase shift between 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,

In some embodiments, if the refractive index of the first optical structure layer is defined as

The reflection coefficient of the first surface

among them

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

In some embodiments, if the refractive index of the second optical structure layer is defined as

The reflection coefficient of the second surface

among them

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

In some embodiments, the reflection coefficient of the optical film structure is expressed as:

The reflectivity is expressed as:

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

The transmission coefficient of the first optical structure layer

among them

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

The transmission coefficient of the second optical structure layer

among them

In some embodiments, the transmission coefficient of the optical film structure is expressed as:

The transmittance is expressed as:

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

Wherein, in the optical reflection working mode, the optical film structure has a double-sided asymmetric structure color.

Wherein, in the optical transmission working mode, the optical film structure has a transparent structural color.

In some embodiments, the optical film structure includes one or more first optical structure layers, one or more medium layers, and one or more second optical structure layers.

In some embodiments, the optical film structure includes multiple first optical structure layers and/or multiple second optical structure layers and multiple medium layers.

In some embodiments, the material of at least one of the first optical structure layer and the second optical structure layer includes a metal material.

In some embodiments, the first optical structure layer or the second optical structure layer is a metal layer.

In some embodiments, the first optical structure layer and the second optical structure layer are both metal layers.

In some embodiments, the first optical structure layer or the second optical structure layer is directly air.

In some embodiments, the first optical structure layer or the second optical structure layer is not present.

Further, the metal material includes tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, palladium, etc., but is not limited thereto.

Further, the thickness of the first optical structure layer or the second optical structure layer is preferably 0-20 nm, preferably greater than 0 and less than 20 nm, or at least one of the first optical structure layer and the second optical structure layer The thickness of one is above 20 nm; preferably, the thickness of at least one of the first optical structure layer and the second optical structure layer is 50-3000 nm.

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 non-metal element, inorganic salt, and oxide, but is not limited thereto.

Further, the non-metallic element 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 oxide 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 , 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 than one, but not Limited to this.

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 A combination of one or more, but not limited to this.

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

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

Further, the chloride includes any one or a combination of AgCl, NaCl, and KCl, but is not limited thereto.

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

Further, the iodide includes any one or a combination of AgI, NaI, KI, RbI, and CsI, but is not limited thereto.

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

Further, the antimony compound includes GdTe and the like, but is 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 Any one or more of the combination of, but not limited to this.

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 molecular compounds and/or polymers, but is not limited thereto.

Further, the organic material includes viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthalate, dimethylbenzidine, 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 may be mainly composed of electrochromic materials. The electrochromic material can be selected from inorganic, organic materials or liquid crystal materials and MOF materials. 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 to this. The organic material may include viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthalate, dimethylbenzidine, tetrathiafulvene, alkyl bipyridine, phene Thiazole, polydiyne, etc., but not limited thereto.

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

Further, an optimized medium layer may be added between the first optical structure layer or the second optical structure layer and the medium layer to optimize the color of the optical film structure.

Further, an optimized medium layer may be added to the first optical structure layer or the second optical structure layer, or the first optical structure layer or the second optical structure layer may also be arranged on the optimized medium layer, To optimize the color of the optical film structure.

In some embodiments, the first optical structure layer or the second optical structure layer is combined with a substrate.

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 or a combination of materials such as glass, organic glass, PET, PES, PEN, PC, PMMA, PDMS, etc. Not limited to this.

Further, the aforementioned optimized medium layer may be disposed between the first optical structure layer or the second optical structure layer and the substrate.

Further, the material of the optimized dielectric 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), but not limited to this.

Further, the thickness of the optimized dielectric layer is preferably 0-2000 nm, preferably 100-500 nm.

In a more typical implementation, please refer to FIG. 1, an optical film structure includes a second optical structure layer 2, a medium layer 3 and a first optical structure layer 4 disposed on a substrate 1. The first optical structure layer 4 and the second optical structure layer 2 are reflection/transmission layers, which can be made of metal.

Wherein, the first optical structure layer 4 can also be directly air.

Among them, the second optical structure layer 2 may not exist.

In this exemplary embodiment, the material and thickness of the first optical structure layer, the second optical structure layer, and the medium layer may be as described above. Moreover, by adjusting the material and thickness of the first optical structure layer 4, the second optical structure layer 2, the dielectric layer 3, etc., the reflection/transmission structure color, reflectance, and transmittance of the optical film structure can be changed.

Another aspect of the embodiments of the present application also provides a method for preparing the optical film structure, which may include:

The formation of the said section by means of 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 technology, etc. An optical structure layer or a second optical structure layer, a medium layer, etc. are not limited thereto.

In some embodiments, the first optical or second optical structure layer and the medium layer may be sequentially formed on the substrate.

Further, electrochromic devices made of electrochromic materials have been widely used in smart windows, smart indicators, imaging equipment, and the like. The principle of electrochromism is the phenomenon that the electronic structure and optical properties (reflectance, transmittance, absorption, etc.) of inorganic or organic electrochromic materials undergo stable and reversible changes under the action of an external electric field or current. Its appearance is expressed as a reversible change in color and transparency. Traditional electrochromic devices 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 monotonous color modulation of electrochromic has become a bottleneck that limits its application range.

In some embodiments, the thickness and/or material of the first optical structure layer, the second optical structure layer, and the dielectric layer can be adjusted during the process of the preparation method, so as to adjust the structure of the optical film. Reflection/transmission structure color.

Another aspect of the embodiments of the present application also provides a device, including a working electrode and a counter electrode that cooperate with each other. The working electrode includes any of the foregoing optical film structures, and the dielectric layer in the optical film structure is mainly composed of Composed of electrochromic materials.

In some embodiments, the device further includes an electrolyte distributed between the working electrode and the counter electrode.

Further, in the foregoing embodiments of the present application, the type of the electrolyte is not particularly limited, and liquid electrolyte, gel polymer electrolyte or inorganic solid electrolyte can be used. In some embodiments, the electrolyte is in contact with the dielectric layer, and provides a material in a mobile environment for discoloring or decolorizing the electrochromic material, such as hydrogen ions or lithium ions.

In some embodiments, the electrolyte may contain one or more compounds, for example containing H ⁺ , Li ⁺ , Al ³⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Ca ²⁺ , Zn ²⁺ , Mg ^{2 +} Or Cs ⁺ compound. In one embodiment, the electrolyte layer may include 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 of the device or the change in light transmittance when being inserted into or removed from the dielectric layer according to the polarity of the applied voltage. In some embodiments, the electrolyte used contains a mixture of multiple ions, which can make the color change of the device richer and fuller than a single ion.

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

In some embodiments, the electrolyte may further 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). For example, organic LiClO ₄ , Na(ClO ₄ ) ₃ propylene carbonate electrolyte, 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 is not limited thereto.

In some preferred embodiments, when an inorganic solid electrolyte is used as the electrolyte, the electrolyte may include LiPON or Ta ₂ O ₅ . For example, the electrolyte may be, but is not limited to, a Li-containing metal oxide film, such as LiTaO or LiPO. 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, it may be LiBO ₂ +Li ₂ SO ₄ , LiAlF ₄ , LiNbO ₃ , Li ₂ OB ₂ O ₃ etc.

Preferably, the device further includes an ion storage layer.

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

In some embodiments, the first optical structure layer or the second optical structure layer is also combined with a substrate.

For example, the working electrode may include a substrate.

For example, the counter electrode may include a substrate, a transparent conductive layer, and an ion storage layer; the material of the substrate may be as described above, and will not be repeated here.

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.

In some embodiments, a conductive layer is also provided on the substrate. Wherein, the conductive layer includes any one or a combination of FTO, ITO, Ag nanowire, Ag nano grid, carbon nanotube, and graphene, and is not limited thereto.

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

The embodiment of the present application also provides a method for preparing the device, which includes:

The first optical structure layer, the second optical structure layer, the dielectric layer, etc. are fabricated using the method described above to form the working electrode;

And, the working electrode, the electrolyte and the counter electrode are assembled to form a device.

2a shows a device in a typical embodiment of the present application, which includes a working electrode 5, a counter electrode 7 and an electrolyte layer 6, and the electrolyte layer 6 is disposed between the working electrode 5 and the counter electrode 7.

Wherein, the electrolyte layer 6 can be selected from a suitable water phase electrolyte, an organic phase electrolyte, a gel electrolyte or a solid electrolyte, preferably LiCl, AlCl ₃ , HCl, H ₂ SO ₄ aqueous solution, LiClO ₄ propylene carbonate Electrolyte, LiCl/PVA, H ₂ SO ₄ /PVA gel electrolyte, etc., but not limited thereto.

Referring again to FIG. 2b, the working electrode 5 may include an optical film structure, which may include a conductive substrate 10, a metal reflection/transmission layer 11 as a second optical structure layer, and a dielectric layer 12, and the dielectric The air layer above the layer 12 can be used as the first optical structure layer, and the medium layer 12 is composed of an electrochromic material. Preferably, the thickness of the aforementioned second optical structure layer is greater than 0 and less than 20 nm.

Among them, referring to the previous content, by adjusting the material and thickness of the metal reflection/transmission layer and the dielectric layer, the reflection/transmission structure color of the optical film structure can be changed. 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, it is possible to realize the fusion of the inherent optical structural color and electrochromic of the device (especially the optical device), and realize rich color changes in a simpler and controllable manner.

Another aspect of the embodiments of the present application also provides a control method of the device, which includes:

Wherein, the operating voltage of the device can be adjusted according to actual conditions, for example, it can be -4V to 4V, but is not limited to this.

In the aforementioned embodiments of the present application, the device combines colorful reflection/transmission structural colors with electrochromic, enriches the color modulation of the electrochromic device, and realizes dynamic control of multiple colors. Specifically, by adjusting the thickness and material of the first optical structure layer, the second optical structure layer, and the dielectric layer in the optical film structure, a colorful structural color can be obtained. At the same time, using the optical film structure as a working electrode, by applying a voltage, the refractive index of the electrochromic material in the dielectric layer is changed (which may be caused by the insertion or extraction of ions in the electrolyte layer of the electrochromic material), The optical parameters of the dielectric layer are changed, and the color is changed. Finally, it can realize electrochromic reflection/transmission dual mode and brilliant and rich color modulation, which will greatly promote the development of electrochromic technology and its application in many fields. .

The embodiments of the present application also provide the use of the optical film structure or the device, such as electrochromic, photochromic, construction, automobile, art decoration, filter, anti-counterfeiting, solar cell, display, LED screen, Applications in communication, sensing, lighting and other fields.

Another aspect of the embodiments of the present application also provides a device, which includes the device described above.

Preferably, the device further includes a power supply, which can be electrically connected with the device to form a working circuit.

In some embodiments, the device may further include additional packaging structures, control modules, power modules and other components, and these accessory components can be combined with the optical film structure in a conventional manner.

The device includes, but is not limited to, mechanical equipment, optoelectronic equipment, electronic equipment, buildings, vehicles, outdoor billboards, etc., and is not limited thereto.

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

In some embodiments, the consumer electronic product includes a mobile phone, a bracelet, a tablet computer or a notebook computer, etc.; or, the household appliance includes a TV, a refrigerator, an electric fan, or an air conditioner, etc.

In some embodiments, the device is a building, and the optical film structure is connected and/or integrally formed with any one of the inner wall, the outer wall, and the window of the building; or, the device is For a vehicle, the optical film structure is connected to and/or integrally formed with any one of the housing, inner wall, and window of the vehicle; or, the device is shoes, hats or clothing, and the surface of the device is connected And/or integrally formed with the optical film structure.

In some embodiments, the optical film structure presents a set graphic structure.

Another aspect of the embodiments of the present application also provides a device including a colorful film structure, including a substrate, the substrate is connected to or integrally formed with a colorful film structure, the colorful film structure includes at least one dielectric layer, wherein Each dielectric 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 dielectric layer, and the second reflective surface is the second surface of the dielectric layer and A bonding interface of the second optical structure layer, the first surface and the second surface are arranged opposite to each other;

When 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 refraction angle of the incident light when passing through the first reflecting surface.

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

Then the reflection coefficient of the first reflecting surface

among them

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

Then the reflection coefficient of the second reflecting surface

among them

Is the refraction angle of incident light when passing through the second reflecting surface; the reflection coefficient of the colorful film structure mainly composed of the dielectric layer and the second optical structure layer is expressed as:

The reflectivity is expressed as:

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

Further, the material of the metal reflective layer can 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 film structure is formed of electrochromic material, so that the colorful film structure is an electrochromic structure, the metal reflective layer also serves as the current collector of the dielectric layer. Therefore, the metal reflective layer may preferably be formed of a metal material having high conductivity, for example, may be formed of a material having 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.

In some embodiments, the first reflective surface is the junction surface between the first surface of the dielectric 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 reflectivity and reflectivity of the colorful film structure are also applicable to the case where 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 from the first optical structure layer and the reflected light formed on the second surface by the incident light passing through the dielectric layer Reflected light interference and superposition. The reverse is also true, that is, the reflected light formed on the second surface by the incident light incident from the second optical structure layer and the reflected light formed on the first surface by the incident light passing through the medium layer are interfered and superposed.

Specifically, the transmission coefficient of the first optical structure layer

among them

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

among them

Is the refraction angle of incident light when passing through the second surface, 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 film structure are also applicable to the case where incident light enters the optical cavity from the second optical structure layer.

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

In some embodiments, the colorful film structure includes multiple first optical structure layers and/or multiple second optical structure layers and multiple medium 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 but less than 20 nm.

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

In some embodiments, the first optical structure layer is formed of air.

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, and palladium, but is not limited to this.

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

Further, an optimized medium layer may be added to the first optical structure layer or the second optical structure layer, or the first optical structure layer or the second optical structure layer may also be arranged on the optimized medium layer, To optimize the color of the colorful film structure.

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

Further, the thickness of the optimized dielectric layer is preferably 0 to 2000 nm, preferably 0 to 500 nm, preferably 0 to 300 nm, and particularly preferably 1 to 100 nm.

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

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

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

Further, the chloride includes AgCl, 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 is not limited thereto.

Further, the arsenide includes GaAs, etc., but is 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 to adjust the color of the colorful film structure.

In some embodiments, 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 electrochromic material may be selected from organic electrochromic materials or inorganic electrochromic materials. Among them, the inorganic electrochromic material may be 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 cobalt oxide), Rh ₂ O ₃ , CrO ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ or TiO _2, etc., and not limited thereto. Among them, the organic electrochromic material can be organic polymers, small organic molecules, metal supramolecular polymers, metal organic compounds, etc., such as methyl viologen, viologen, polyaniline, polythiophene, polypyrrole, Prussian blue , Metal organic chelates (such as phthalocyanine compounds), polydiynes, etc., and are not limited thereto.

Further, the type of the electrolyte is not particularly limited, and liquid electrolyte, gel polymer electrolyte or inorganic solid electrolyte can be used.

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

In some embodiments, the electrolyte may contain one or more compounds, for example containing H ⁺ , Li ⁺ , Al ³⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Ca ²⁺ , Zn ²⁺ , Mg ^{2 +} Or Cs ⁺ compound. In one embodiment, the electrolyte layer may include 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 of the device or the change in light transmittance when being inserted into 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 of water-based LiCl, AlCl ₃ , HCl, MgCl ₂ , ZnCl ₂ and the like. When an electrolyte containing two or more kinds of ions is used, compared to the case of using an electrolyte containing only a single ion, the color change of the colorful film structure of the foregoing embodiment of the application can be more abundant, and the color is saturated. Degree higher.

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.

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 a material having characteristics such as high light transmittance and low sheet resistance. For example, it can be formed by including any one 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 conductive oxide of NTO (niobium doped titanium oxide), ZnO, OMO (oxide/metal/oxide) and CTO; silver (Ag) nanowires; metal mesh; or OMO (oxide metal oxide) .

The method of forming the transparent conductive electrode or the transparent conductive layer is not particularly limited, and any known method can 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 be in the range of 10 nm to 500 nm, and in the case of the printing method, the thickness may be in the range of 0.1 μm to 20 μm. In an example, the visible light transmittance of the transparent conductive electrode layer may be 70% to 95%.

In some preferred embodiments, the electrolyte adopts 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 electrolyte in the all-solid colorful film structure may be in the form of a solid ion conductive layer. The color change principle of this kind of all-solid colorful film structure is: the metal reflective layer and other layer materials constitute a metal-medium structure, and may also include other layers, such as ion conductive layer, ion storage layer, and transparent conductive layer, etc., by adjusting the If the thickness of each layer material is in the appropriate range, an electrochromic structure with structural color can be prepared. Further, by applying voltage, the refractive index of the electrochromic material can be adjusted, and the color of the all-solid colorful film structure can be further adjusted .

In some embodiments, in addition to adjusting the thickness and/or material of the first optical structure layer, the second optical structure layer, the dielectric layer, etc., to adjust the color (structure color) of the colorful film structure, you can also adjust The electric potential difference applied between the working electrode and the counter electrode is adjusted to at least change the refractive index of the electrochromic material in the dielectric layer, thereby adjusting the color of the colorful film structure. This control process can be dynamic, so that the fusion of colorful structural colors and electrochromic is realized, which greatly enriches the color modulation of colorful film structures.

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

In some embodiments of the present application, 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, medium 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 it is not limited thereto. For example, the metal material can be processed by laser direct writing, chemical etching, etc., to form the dielectric layer.

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

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

The embodiment of the present application also provides a manufacturing method of the patterned colorful film, including:

Provide a metal layer;

At least two pattern areas of the one metal layer are oxidized in situ, thereby forming at least two dielectric layers capable of showing different colors in the at least two pattern areas, wherein each dielectric layer is connected to a first The reflection surface and a second reflection surface cooperate to form an optical cavity, and then a patterned colorful film is produced.

In some embodiments, the manufacturing method includes: in an oxygen-containing atmosphere, using laser direct writing to oxidize at least two regions of the at least one metal layer in situ to form at least two different dielectric layers.

Wherein, the oxygen-containing atmosphere may be an oxygen atmosphere, or a mixed atmosphere of oxygen and other inactive gases (for example, nitrogen, inert gas, etc.), for example, it may be preferably an air atmosphere.

In some embodiments, the manufacturing method may further include: in the laser direct writing process, at least the laser power and/or laser irradiation time are adjusted to make the thickness and/or material of different dielectric layers different.

Please refer to FIG. 3. In a typical implementation case of the present application, a method for manufacturing a patterned colorful film may include the following steps:

A metal layer is provided, and the metal layer 120 is disposed on a substrate 110. The metal layer can be formed on the surface of the substrate by physical/chemical deposition (such as magnetron sputtering, electroplating, etc.), or it can be a self-supporting metal The film is transferred to the substrate surface to form; and

Provide laser direct writing equipment. In an oxygen-containing atmosphere, the laser beam emitted by the laser head 20 of the laser direct writing equipment irradiates a predetermined area (also referred to as a pixel area 130) on the metal layer. In this process, the laser The head moves relative to the metal layer, and its movement track can be linear, two-dimensional, or three-dimensional, so that each pixel area on the metal layer is oxidized in situ to form a patterned dielectric layer.

Wherein, the laser spot formed by the laser beam on the metal layer can be controlled at the micron level or sub-micron level. The shape of the laser spot can be arbitrary, such as a circle, a rectangle, and so on.

Among them, the power of the laser, the irradiation time, the relative movement speed of the laser head and the metal layer, etc. can be adjusted appropriately according to the requirements of the actual application. For example, the corresponding process conditions can be controlled within the following range: the relative movement speed of the laser head and the metal layer is controlled to be 2mm/s-20mm/s, the continuous laser power is 50W-500W, and the laser rectangular spot size is 0.5mm×1mm -4mm×5mm, the laser action time is 1s-5s, the defocus amount is 0.01mm-10mm, and the spot overlap rate is 10%-50%.

The aforementioned laser direct writing process can be carried out in a closed container or in air.

Another aspect of the embodiments of the present application provides a patterned colorful film including:

At least two different dielectric layers formed by in-situ oxidation of at least two pattern areas of a metal layer;

Wherein, each dielectric 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 dielectric layer, and the second reflective surface is the second reflective surface of the dielectric layer. A bonding interface between the surface and a second optical structure layer, the first surface and the second surface are arranged opposite to each other;

d is the thickness of the dielectric layer,

Further, at least two pattern areas of the metal layer are oxidized in situ by laser direct writing to form a dielectric layer.

In the foregoing embodiments of the present application, in the process of laser direct writing, due to the photo-thermo-chemical effect of the laser, each pattern area of the metal layer is oxidized to generate metal oxide films of different types and thicknesses. Through the color of the metal oxide itself, different dielectric layers can show different color effects.

Further, the aforementioned graphic area may be text, continuous or discontinuous patterns, etc., and is not limited thereto.

Further, the dielectric layer can be a thin film structure composed of one metal oxide, or a thin film structure composed of multiple metal oxides.

In some implementations of the embodiments of the present application, the relative movement speed of the laser spot and the metal layer can be adjusted during the aforementioned laser direct writing process, so that different pattern areas of the metal layer are oxidized in situ to different degrees, and then Make the thickness and/or material of different dielectric layers different.

Furthermore, in the aforementioned laser direct writing process, the size of the laser spot can also be adjusted, for example, it can be controlled at the sub-micron level, so that the patterned pixels formed on the metal layer can reach the sub-micron level with high accuracy and avoid occurrence Variegated.

Moreover, the advantage of using the aforementioned laser direct writing method is that it has almost no limitation on the shape of the metal layer. For example, the metal layer may be a continuous plane, curved surface or other irregular surface. This allows the final patterned colorful film to meet the application requirements of a variety of scenarios.

In some embodiments, two different optical cavities based on two different dielectric layers exhibit different colors.

In some embodiments, the colors presented by two different optical cavities based on two different dielectric layers may also be the same.

In some embodiments, two different dielectric layers are spaced apart from each other or adjacent to each other.

In some embodiments, the second optical structure layer adopts a metal material layer with a thickness of 20 nm or more. Preferably, the thickness of the metal reflective layer is 50-3000 nm.

Further, in the patterned colorful film provided by the foregoing embodiment of the present application, the reflected light formed by the incident light on the first reflective surface and the reflected light formed on the second reflective surface by the incident light passing through the medium layer interfere and superimpose .

Furthermore, in some embodiments, if the refractive index of the media material on the first surface of the media layer is defined as

Then the reflection coefficient of the first reflecting surface

among them

Then the reflection coefficient of the second reflecting surface

among them

Is the refraction angle of incident light when passing through the second reflecting surface; the reflection coefficient of the optical film structure mainly composed of the dielectric layer and the second optical structure layer is expressed as:

The reflectivity is expressed as:

Further, the material of the metal layer includes a transition metal, for example, it can be selected from but not limited to any one or a combination of W, Ni, Ti, Nb, Fe, Co, and Mo elements.

The refractive index of the second optical structure layer is

Further, 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 passing through the medium layer are interfered and superposed. The reverse is also true, that is, the reflected light formed on the second surface by the incident light incident from the second optical structure layer and the reflected light formed on the first surface by the incident light passing through the medium layer are interfered and superposed.

Furthermore, the transmission coefficient of the first optical structure layer

among them

Is the refraction angle of incident light when passing through the second surface, the transmission coefficient of the optical 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 transmission coefficient and transmittance of the optical film structure are also applicable to the case where incident light enters the optical cavity from the second optical structure layer.

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

In some embodiments, the thickness of the first optical structure layer is preferably 0-20 nm.

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

In some embodiments, the optical 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; In the optical reflection working mode, the optical film structure has a double-sided asymmetric structural color, and in the optical transmission working mode, the optical film structure has a transparent structural color.

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

In some embodiments, a thin layer of metal may be added on the dielectric layer to optimize the color of the patterned colorful film. Specifically, for certain materials or patterned colorful films with a suitable thickness, adding a metal material with a suitable thickness can increase the intensity difference of the reflectance curve, thereby increasing the color saturation. Wherein, the material of the thin layer metal can be selected from Ag, Al, Cu, Ni, etc., but is not limited thereto. The thickness of the metal layer may preferably be 0 to 30 nm, particularly preferably 1 to 10 nm.

In some embodiments, a semiconductor material may be added on the dielectric layer to optimize the color of the patterned colorful film. For patterned colorful films with specific materials or thicknesses, adding a suitable thickness of semiconductor materials can increase the intensity difference of the reflectance curve, thereby increasing the color saturation. Wherein, the semiconductor may be selected from Al ₂ O ₃ , SiO ₂ , ZnS, MgF ₂ , silicon nitride, etc., but is not limited thereto. The thickness of the semiconductor may preferably be 0 to 300 nm, particularly preferably 1 to 100 nm.

Further, an optimized medium layer may be added to the first optical structure layer or the second optical structure layer, or the first optical structure layer or the second optical structure layer may also be arranged on the optimized medium layer, To optimize the color of the patterned colorful film.

In some embodiments, the first optical structure layer or the second optical structure layer is further combined with a substrate.

Wherein, the substrate is transparent or translucent.

Further, the material of the substrate includes but is not limited to any one or a combination of metal, glass, organic glass, PET, PES, PEN, PC, PMMA, and PDMS.

In some embodiments, the first optical structure layer is integrated with the substrate.

Another aspect of the embodiments of the present application provides a colorful electrochromic structure comprising a working electrode, an electrolyte and a counter electrode, and the working electrode includes any of the aforementioned patterned colorful films.

Further, the type of the electrolyte is not particularly limited, and liquid electrolyte, gel polymer electrolyte or inorganic solid electrolyte can be used. In some embodiments, the electrolyte is in contact with the dielectric layer, and provides a material for a mobile environment for discoloring or decolorizing metal oxides as electrochromic materials, such as hydrogen ions or lithium ions.

In some embodiments, the electrolyte may include one or more compounds, such as compounds containing H ⁺ , Li ⁺ , Al ³⁺ , Na ⁺ , K ⁺ , Rb ⁺ or Cs ⁺ . In one example, the electrolyte layer may include a lithium salt compound, such as LiClO ₄ , LiBF ₄ , LiAsF ₆ or LiPF ₆ . The ions contained in the electrolyte may exert an effect on the discoloration of the device or the change in light transmittance when being inserted into 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 of water-based LiCl, AlCl ₃ , HCl, MgCl ₂ , and ZnCl ₂ . When an electrolyte containing two or more kinds of ions is used, compared to the case of using an electrolyte containing only a single ion, the color changes of the electrochromic structure of the foregoing embodiments of the present application can be more abundant. The saturation is higher.

In some embodiments, the electrolyte may further include a carbonate compound-based electrolyte. The carbonate-based compound has a high dielectric constant and can increase the ionic conductivity provided by the lithium salt. As the carbonate compound, at least one of the following can be used: PC (propylene carbonate), EC (ethylene carbonate), DMC (dimethyl carbonate), DEC (diethyl carbonate), and EMC (ethylene carbonate) Methyl ester). For example, organic LiClO ₄ , Na(ClO ₄ ) ₃ propylene carbonate electrolyte, etc. can be used.

In some embodiments, the electrolyte may be a gel electrolyte, such as PMMA-PEG-LiClO ₄ , PVDF-PC-LiPF _6, etc., but is not limited thereto.

In some preferred embodiments, the electrolyte adopts an all-solid electrolyte, which can be combined into a solid-state patterned colorful film, a counter electrode, etc., to form an all-solid colorful electrochromic structure.

In some embodiments, the metal material layer serving as the first optical structure layer may also serve as a current collector of the dielectric layer. Therefore, the metal material layer may preferably be formed of a metal material having high conductivity, for example, may be formed of a material having high conductivity such as silver (Ag) or copper (Cu).

In some embodiments, an ion storage layer is further provided between the counter electrode and the dielectric layer, and its material can be selected from but not limited to NiO, Fe ₂ O ₃ , TiO ₂ and the like. The ion storage layer is in contact with the electrolyte.

In some embodiments, the counter electrode may be a transparent conductive electrode, which may be formed by including a material having characteristics such as high light transmittance and low sheet resistance. For example, it may 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), Transparent conductive oxides of IZO (indium-doped zinc oxide), NTO (niobium-doped titanium oxide), ZnO, OMO (oxide/metal/oxide) and CTO; silver (Ag) nanowires; metal Mesh; or OMO (Oxide Metal Oxide).

The method of forming the transparent conductive electrode is not particularly limited, and any known method can 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 be in the range of 10 nm to 500 nm, and in the case of the printing method, the thickness may be in the range of 0.1 m to 20 m. In an example, the visible light transmittance of the transparent conductive electrode layer may be 70% to 95%.

Another aspect of the embodiments of the present application also provides a method for adjusting and controlling the colorful electrochromic structure, which includes:

The potential difference between the working electrode and the counter electrode is adjusted to at least change the refractive index of the metal oxide as the electrochromic material in the dielectric layer, thereby adjusting the color of the colorful electrochromic structure.

Wherein, the working voltage of the colorful electrochromic structure can be adjusted according to actual conditions, for example, it can be -4V to 4V, but is not limited to this.

In the foregoing embodiments of the present application, the colorful electrochromic structure integrates the structural color of the patterned colorful film with electrochromic, enriches the color modulation of the electrochromic structure, and realizes multi-color dynamic control. Specifically, the colorful structural colors can be obtained by adjusting the thickness and material of the first optical structure layer, the second optical structure layer, and the dielectric layer in the patterned colorful film. At the same time, the patterned colorful film is used as a working electrode, and by applying a voltage, the refractive index of the metal oxide as an electrochromic material in the dielectric layer is changed (which can be caused by the insertion or extraction of ions in the electrolyte layer of the electrochromic It is caused by the material), resulting in the change of the optical parameters of the medium layer and the change of the color, and finally can realize multiple working modes of electrochromism (such as the aforementioned dual mode of reflection/transmission) and brilliant and rich color modulation.

The embodiments of the application also provide the use of the patterned colorful film or the colorful electrochromic structure, for example in electronic equipment, optical equipment, construction, automobiles, art decoration, filters, anti-counterfeiting, solar cells, displays, LED screen, communication, sensor, lighting and other fields.

Another aspect of the embodiments of the present application also provides a device, which includes the colorful electrochromic structure. Further, the device further includes a power supply, which can be electrically connected with the colorful electrochromic structure to form a working circuit.

In some embodiments, the device may also include additional packaging structures, control modules, power modules, and other components, and these accessory components may be combined with the colorful electrochromic structure in a conventional manner.

The technical solution of the present application will be further described in detail below through several embodiments in conjunction with the drawings. However, the selected embodiments are only used to illustrate the application, and do not limit the scope of the application.

Example 1:

An optical film structure provided in this embodiment includes a first optical structure layer, a second optical structure layer, a medium layer, and a base layer, which can be referred to as shown in FIG. 1.

The first optical structure layer is air, the second optical structure is a metal tungsten (W) layer, the dielectric layer is formed of tungsten oxide, and the base layer may be a PET film.

The preparation method of the optical thin film structure is as follows: On a clean PET substrate, a layer of tungsten film is sputtered by a magnetron sputtering method. Preferably, the thickness of the tungsten film is selected to be about 10 nm by sputtering. Then, a tungsten oxide layer is sputtered on the tungsten film by magnetron sputtering. Preferably, the thickness of the tungsten oxide layer is set at 100 nm to 400 nm.

Of course, the aforementioned tungsten film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation. The aforementioned tungsten oxide layer can be prepared by methods known in the industry such as electron beam evaporation, thermal evaporation, electrochemical deposition, sol-gel technology, and the like.

Referring to FIG. 3, the thickness of the tungsten oxide layer is controlled to be different. From the side of the first optical structure layer, an optical thin film structure with rich and brilliant colors can be obtained.

Referring to Figure 4, under different tungsten oxide thicknesses (in Figure 3), from the direction of the base layer, the corresponding reflection color also presents a rich and brilliant color, and this color is the same as the color seen from the direction of the first optical structure layer Quite different.

Referring to FIG. 5, under different tungsten oxide thicknesses shown in FIG. 3, through the optical film structure of this embodiment, a transmission structure color can be obtained, and the transmission structure color also presents a rich and brilliant color. Therefore, the transmittance of the transmission color of the optical film structure of this embodiment is determined by the thickness of the metal tungsten layer and the tungsten oxide layer.

Comparative example 1:

The optical film structure provided by the comparative example includes a first optical structure layer, a second optical structure layer, a medium layer and a base layer.

Among them, the first optical structure layer is air, the second optical structure does not exist (no tungsten film), the dielectric layer is formed of tungsten oxide, and the base layer may be a PET film.

The preparation method of the optical thin film structure is as follows: on a clean PET substrate, a tungsten oxide layer is sputtered by magnetron sputtering. Preferably, the thickness of the tungsten oxide layer is set at 100 nm to 400 nm.

The thickness of the tungsten oxide layer is controlled to be different, and when viewed from one side of the first optical structure layer, a transparent and colorless optical film structure is obtained.

Under different thicknesses of tungsten oxide, the corresponding color is also transparent and colorless when viewed from the direction of the base layer, and this color is exactly the same as the color viewed from the direction of the first optical structure layer.

Under different thicknesses of tungsten oxide, through the optical film structure of this comparative example, a transparent and colorless optical film structure is still obtained.

Comparative Example 2:

The preparation method of the optical thin film structure is as follows: On a clean PET substrate, a layer of tungsten film is sputtered by a magnetron sputtering method. Preferably, the thickness of the tungsten film is selected to be about 100 nm by sputtering. After that, a tungsten oxide layer is sputtered on the tungsten film by magnetron sputtering. Preferably, the thickness of the tungsten oxide layer is set at 100 nm to 400 nm.

The thickness of the tungsten oxide layer is controlled to be different, and when viewed from the side of the first optical structure layer, an optical film structure with rich and brilliant colors can be obtained.

Under different tungsten oxide thicknesses, when viewed from the direction of the base layer, the corresponding reflection color only presents the color of the metallic tungsten film (silver white).

Under different thicknesses of tungsten oxide, through the optical thin film structure of this comparative example, no permeability is found.

Example 2:

Wherein, the first optical structure layer is air, the second optical structure is a metallic silver (Ag) layer, the dielectric layer is formed of titanium dioxide, and the base layer may be a PET film.

The preparation method of the optical thin film structure is as follows: on a clean PET substrate, a layer of silver film is sputtered by a magnetron sputtering method. Preferably, the thickness of the silver film is selected to be about 2 nm by sputtering. After that, a layer of titanium dioxide is sputtered on the tungsten film by magnetron sputtering. Preferably, the thickness of the titanium dioxide layer is set at 100 nm to 400 nm.

Of course, the aforementioned silver film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation. The aforementioned titanium dioxide layer can be prepared by methods known in the industry such as electron beam evaporation, thermal evaporation, electrochemical deposition, and sol-gel technology.

The optical film structure of this embodiment exhibits similar properties to the optical film structure of Embodiment 1, that is, when viewed from two sides, it exhibits different colors. It also has a transmissive structural color.

Example 3:

An optical film structure provided in this embodiment includes a first medium layer, a second optical structure layer, a second medium layer, and a first optical structure layer sequentially formed on a substrate.

Among them, the added second medium layer can improve color brightness and saturation.

As shown in FIG. 6, the first optical structure layer of the optical film structure is air, the second optical structure layer is metal tungsten (W), the first and second dielectric layers are formed of tungsten oxide, and the base layer may be PET membrane.

The preparation method of the optical thin film structure is as follows: on a clean PET substrate, a tungsten oxide layer is sputtered by a magnetron sputtering method. Preferably, the thickness of the tungsten oxide layer is set at 1 nm to 400 nm. Then a layer of tungsten film is sputtered by a magnetron sputtering method. Preferably, the thickness of the tungsten film is about 10 nm. After that, a tungsten oxide layer is sputtered on the tungsten film by magnetron sputtering. Preferably, the thickness of the tungsten oxide layer is set at 100 nm to 400 nm.

Referring to FIG. 7, the thickness of the tungsten oxide layer between the control tungsten layer and the PET substrate is different. From the side of the first optical structure layer, an optical film structure with rich and brilliant colors can be obtained.

Referring to Figure 8, under the different tungsten oxide thicknesses shown in Figure 7, the corresponding reflection color also presents a rich and brilliant color from the side of the base layer, and this color is completely different from the color seen from the film direction different.

Please refer to FIG. 9 again. Under the different tungsten oxide thicknesses shown in FIG. 7, the transmission structure color can be obtained through the optical film structure, and the transmission structure color also presents rich and brilliant colors. The transmittance of the transmission color of the optical film structure is determined by the thickness of the metal tungsten layer and the tungsten oxide layer.

Example 4:

An optical film structure provided by this embodiment includes a second optical structure layer, a medium layer, and a first optical structure layer formed on a substrate in sequence.

Among them, the first optical structure layer is a metal tungsten (W) film, the second optical structure layer is a metal aluminum (Al) film, the dielectric layer is formed of zinc sulfide (ZnS), and the base layer may be a PET film.

The preparation method of the optical thin film structure is as follows: on a clean PET substrate, a layer of metal aluminum film is sputtered by a magnetron sputtering method. Preferably, the thickness of the aluminum film is set at 15 nm. Then, a zinc sulfide layer is sputtered by a magnetron sputtering method. Preferably, the thickness of the zinc sulfide is selected to be 100 nm to 400 nm by sputtering. Afterwards, a tungsten film layer is sputtered on the zinc sulfide layer by magnetron sputtering. Preferably, the thickness of the tungsten film layer is set to 0-50 nm.

Of course, the aforementioned tungsten film and aluminum film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation. The aforementioned zinc sulfide layer can be prepared by methods known in the industry such as electron beam evaporation, thermal evaporation, electrochemical deposition, and sol-gel technology. The optical film structure of this embodiment shows different colors when viewed from two sides, and also has a transmission structure color.

Example 5:

Wherein, the first optical structure layer is air, the second optical structure layer is a metal aluminum (Al) film, the dielectric layer is formed of silicon simple substance, and the base layer may be a PET film.

The preparation method of the optical thin film structure is as follows: On a clean PET substrate, a layer of metal aluminum film is sputtered by a magnetron sputtering method. Preferably, the thickness of the aluminum film is set at 5 nm. Then, a silicon film layer is deposited by a magnetron sputtering method. Preferably, the thickness of the silicon film layer is selected to be sputtered from 100 nm to 400 nm.

Of course, the aforementioned aluminum film and silicon film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation. The optical film structure of this embodiment shows different colors when viewed from two sides, and also has a transmission structure color.

Example 6:

The first optical structure layer is a metallic silver (Ag) film, the second optical structure layer is a metallic aluminum (Al) film, the dielectric layer is formed of Prussian blue, and the base layer may be a PET/ITO film.

The preparation method of the optical thin film structure is as follows: on a clean PET/ITO substrate, a layer of metal aluminum film is sputtered by a magnetron sputtering method. Preferably, the thickness of the aluminum film is set at 10 nm. Then a layer of Prussian blue layer is deposited by electrodeposition method. Preferably, the thickness of Prussian blue is selected to be 100 nm to 2000 nm. Then, a layer of silver film is sputtered on the Prussian blue layer by magnetron sputtering. Preferably, the thickness of the silver film is set at 0-50 nm.

Of course, the aforementioned silver film and aluminum film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation. The aforementioned Prussian blue layer can be prepared by electrochemical deposition, sol-gel technology and other methods known in the industry.

The optical film structure of this embodiment shows different colors when viewed from two sides, and also has a transmission structure color.

Example 7:

This embodiment provides a device, which can be regarded as a reflection/transmission dual-mode colorful electrochromic device, comprising a working electrode, an electrolyte layer and a counter electrode, and the electrolyte layer is arranged between the working electrode and the counter electrode.

As shown in FIG. 12, the working electrode includes an optical film structure arranged on a conductive substrate. The optical film structure includes a first and second optical structure layers and a medium layer. Air is used as the first optical structure layer and the second optical structure layer It is formed of metal tungsten (W), and the dielectric layer is formed of tungsten oxide. The substrate can be PET/ITO, etc.

The preparation method of the working electrode is as follows: On a clean PET/ITO film, a layer of tungsten film is sputtered by a magnetron sputtering method. Preferably, the thickness of the tungsten film is selected to be about 10 nm by sputtering. After that, a tungsten oxide layer is sputtered by magnetron sputtering on the tungsten film. Preferably, the thickness of the tungsten oxide layer is set to 100 nm to 400 nm.

Of course, the aforementioned tungsten film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation. The aforementioned tungsten oxide layer can be prepared by methods known in the industry such as electron beam evaporation, thermal evaporation, and electrochemical deposition.

The working electrode of this embodiment shows different colors when viewed from two sides, and also has a transmissive structure color.

Then, the aforementioned working electrode is matched with a pair of electrodes (for example, NiO counter electrode), and AlCl ₃ electrolyte is encapsulated between the two, and then leads are drawn out to prepare the colorful electrochromic device of this embodiment. By applying voltage to the colorful electrochromic device, the color of the working electrode can be further modulated to change between more colors, especially the color changes on both sides of the working electrode are not completely the same. See the figure for details. 13 shown.

Example 8:

This embodiment provides an optical device, which can be regarded as a reflection/transmission dual-mode colorful electrochromic device, comprising 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 an optical thin film structure arranged on a conductive substrate. The optical thin film structure includes first and second optical structure layers and a dielectric layer. The first optical structure layer is formed of metal tungsten (W), and the second optical structure layer is formed by Metal silver (Ag) is formed, and the dielectric layer is formed of titanium dioxide (TiO ₂ ). The substrate can be PET/AgNWs.

The preparation method of the working electrode is as follows: on the clean PET/AgNWs film, a layer of silver film is sputtered by magnetron sputtering method. Preferably, the thickness of the silver film is selected to be about 10 nm. Afterwards, a layer of titanium oxide is sputtered on the silver film by magnetron sputtering. Preferably, the thickness of the titanium dioxide layer is set to 100 nm to 400 nm. Then a layer of tungsten film is sputtered by magnetron sputtering on the titanium dioxide layer. Preferably, the thickness of the tungsten film is selected to be about 5 nm by sputtering.

The optical device can be assembled and formed by referring to Embodiment 7.

Of course, the aforementioned silver film and tungsten film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation. The aforementioned titanium oxide layer can be prepared by methods known in the industry such as electron beam evaporation, thermal evaporation, and electrochemical deposition.

Then, the aforementioned working electrode is matched with a pair of electrodes (for example, a NiO counter electrode), and LiCl/PVA gel electrolyte is arranged between the two, and then the wires are drawn out to prepare the colorful electrochromic device of this embodiment. By applying voltage to the colorful electrochromic device, and by adjusting the voltage range, the color of the working electrode can be further modulated to change between more colors, especially the color change on both sides of the working electrode is not complete the same. The color change of the colorful electrochromic device of the present embodiment is similar to the color change of Example 7 caused by voltage application.

Example 9:

The working electrode includes an optical thin film structure arranged on a conductive substrate. The optical thin film structure includes first and second optical structure layers and a dielectric layer, wherein the first optical structure layer is air, and the second optical structure is a metallic copper (Cu) layer , The dielectric layer is formed of vanadium oxide (V ₂ O ₅ ), and the base layer can be PET/ITO.

The preparation method of the optical thin film structure is as follows: On a clean PET substrate, a layer of copper film is sputtered by a magnetron sputtering method. Preferably, the thickness of the copper film is selected to be about 15 nm by sputtering. Then, a vanadium oxide layer is sputtered on the copper film by magnetron sputtering. Preferably, the thickness of the vanadium oxide layer is set at 100 nm to 400 nm.

Of course, the aforementioned copper film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation. The aforementioned vanadium oxide layer can be prepared by methods known in the industry such as electron beam evaporation, thermal evaporation, electrochemical deposition, sol-gel technology, and the like.

The optical device can be assembled and formed by referring to Embodiment 7.

Then, the aforementioned working electrode is matched with a pair of electrodes (for example, NiO counter electrode), and LiCl/HCl/AlCl ₃ /NaCl/PVA mixed ion gel electrolyte is set between the two. By applying voltage to the colorful electrochromic device, and by adjusting the voltage range, the color of the working electrode can be further modulated to change between more colors, especially the color change on both sides of the working electrode is not complete the same. The color change of the colorful electrochromic device of the present embodiment is similar to the color change of Example 7 caused by voltage application.

Example 10:

The working electrode includes an optical thin film structure arranged on a conductive substrate. The optical thin film structure includes first and second optical structure layers and a dielectric layer. Air is used as the first optical structure layer, and the second optical structure layer is made of metal tungsten (W). Formed, the dielectric layer is formed of tungsten oxide (WO ₃ ). The substrate can be PET/ITO.

The preparation method of the working electrode is as follows: On a clean PET/ITO film, a silver film is sputtered by magnetron sputtering. Preferably, the thickness of the tungsten film is selected to be about 10nm sputtered. Afterwards, a tungsten oxide layer is sputtered by magnetron sputtering on the silver film. Preferably, the thickness of the tungsten oxide layer is set to 100 nm to 400 nm.

A layer of lanthanum lithium titanate film is sputtered on the aforementioned working electrode as a solid electrolyte by a magnetron sputtering method, and the thickness of the lanthanum lithium titanate film is preferably 500 nm.

Then, the working electrode and the solid electrolyte are matched with a pair of electrodes (for example, an IrO ₂ pair of electrodes), and then the wires are drawn out to prepare the colorful electrochromic device of this embodiment. By applying voltage to the colorful electrochromic device, the color of the working electrode can be further modulated to change between more colors, especially the color changes on both sides of the working electrode are not completely the same. The color change of the colorful electrochromic device of the present embodiment is similar to the color change of Example 7 caused by voltage application.

In addition, the applicant of the present application also used other dielectric materials, metal reflective materials, base materials, etc. listed in this specification to replace the corresponding materials in the foregoing embodiments for experiments, and found that the obtained optical film structures all have similar advantages.

Example 11

As shown in FIG. 3, the high-precision patterned colorful film includes a substrate and a metal layer disposed on the substrate, wherein a plurality of continuous or spaced dielectric layers formed by laser direct writing are distributed on the metal layer. The thickness of the layer can be 10 nm-300 nm, and each dielectric layer is formed of metal oxide generated in situ. Among them, the substrate can be a PET plastic plate. The metal layer may be a tungsten film deposited on the substrate, and its thickness may be about 500 nm.

Specifically, a method for making the patterned colorful film may include: magnetron sputtering sputtering a layer of tungsten film on a clean, 3cm*3cm PET plastic plate, preferably, a tungsten film The thickness of the sputtering is chosen to be about 500nm. Then, a laser direct writing method is used to sequentially laser oxidize tungsten oxide layers of different required thicknesses on each pixel (ie, pattern area) on the tungsten film. Among them, the tungsten film can be placed on a worktable controlled by an XY computer, with a moving speed of 15mm/s, a continuous laser power of 200W, a laser rectangular spot size of 1.4mm×1.4mm, a defocusing distance of 5mm, and a spot overlap rate 40%, when the laser action time is 6.5s, the obtained dielectric layer thickness is 163nm, the area is pink, and when the laser action time is 8s, the obtained dielectric layer thickness is 200nm, and the area appears blue.

Of course, the aforementioned tungsten film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation.

The color film prepared above is used as an electrochromic layer, and a pair of electrodes, such as a NiO counter electrode layer, is additionally prepared, and LiClO ₄ -PC electrolyte is encapsulated between the two and lead wires are drawn to prepare colorful electrochromic devices. By applying voltage to the colorful electrochromic device, its color can be further modulated. When the power supply with a voltage of -2.5V～+2.5V is switched on, 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.

Example 12

As shown in FIG. 3, the high-precision patterned colorful film includes a substrate and a metal layer disposed on the substrate, wherein a plurality of continuous or spaced dielectric layers formed by laser direct writing are distributed on the metal layer. The thickness of the layer can be 10 nm-300 nm, and each dielectric layer is formed of metal oxide generated in situ. Among them, the substrate can be a PET plastic plate. The metal layer may be a titanium film deposited on the substrate, and its thickness may be about 500 nm.

Specifically, a method for making the patterned colorful film may include: magnetron sputtering sputtering a layer of titanium film on a clean PET plastic plate with a size of 3cm*3cm, preferably, a titanium film The thickness of the sputtering is chosen to be about 500nm. Then, the laser direct writing method is used to sequentially laser oxidize the titanium oxide layer of different required thickness on each pixel point (ie, the pattern area) on the titanium film. Among them, the moving speed of the worktable controlled by the XY computer is 15mm/s, the continuous laser power is 300W, the laser rectangular spot size is 1.4mm×1.4mm, the defocus is 5mm, the spot overlap rate is 40%, and the laser action time is 3 -10s.

Of course, the aforementioned titanium film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation.

Example 13

As shown in FIG. 3, the high-precision patterned colorful film includes a substrate and a metal layer disposed on the substrate, wherein a plurality of continuous or spaced dielectric layers formed by laser direct writing are distributed on the metal layer. The thickness of the dielectric layer is 0-20 nm, and each dielectric layer is formed of metal oxide generated in situ. Among them, the substrate can be a PET plastic plate. The metal layer may be a copper film deposited on the substrate, and its thickness may be about 0-20 nm.

Specifically, a method of making the patterned colorful film may include: first magnetron sputtering sputtering a copper film on a clean PET plastic plate with a size of 3cm*3cm, preferably a copper film The thickness of the sputtering is chosen to be about 15nm. Then, the laser direct writing method is used to sequentially laser oxidize the copper oxide layers of different required thicknesses on each pixel point (that is, the pattern area) on the copper film. Among them, the moving speed of the worktable controlled by the XY computer is 15mm/s, the continuous laser power is 100W, the laser rectangular spot size is 1.4mm×1.4mm, the defocus is 5mm, the spot overlap rate is 40%, and the laser action time is 0 -5s.

Example 14

As shown in FIG. 3, the high-precision patterned colorful film includes a substrate and a metal layer disposed on the substrate, wherein a plurality of continuous or spaced dielectric layers formed by laser direct writing are distributed on the metal layer. The thickness of the dielectric layer may be 10 nm to 300 nm, and each dielectric layer is formed of metal oxide generated in situ. Among them, the substrate can be a PET plastic plate. The metal layer may be a tungsten film deposited on the substrate, and its thickness may be about 500 nm.

Specifically, a method for making the patterned colorful film may include: magnetron sputtering sputtering a layer of tungsten film on a clean, 3cm*3cm PET plastic plate, preferably, a tungsten film The thickness of the sputtering is chosen to be about 500nm. Then, a laser direct writing method is used to sequentially laser oxidize tungsten oxide layers of different required thicknesses on each pixel (ie, pattern area) on the tungsten film. Among them, the moving speed of the worktable controlled by the XY computer is 15mm/s, the continuous laser power is 200W, the laser rectangular spot size is 1.4mm×1.4mm, the defocus is 5mm, the spot overlap rate is 40%, and the laser action time is 6s. When the thickness of the obtained dielectric layer is 150nm, the area appears yellow, when the laser action time is 10s, the thickness of the obtained dielectric layer is about 250nm, and this area appears green.

The color film prepared above is used as the electrochromic layer, and a pair of electrodes, such as a NiO counter electrode layer, is prepared, and the PMMA-PEG-LiPF6 gel electrolyte is encapsulated between the two, and then the wires are led out, then high-precision patterning can be prepared Multi-color electrochromic devices. By applying voltage to the high-precision patterned multicolor electrochromic device, its color can be further modulated. When the power supply voltage is -2.5V～+2.5V, the yellow area of the working electrode will change in real time between yellow, green and blue; the green area will change in real time between green, cyan and blue.

Example 15

Referring to FIGS. 14-15, this embodiment discloses a mobile phone, which includes a mobile phone body 200 and a mobile phone case 300, which includes a housing 210 on which a Logo 400 formed of a colorful film structure is integrally provided. The colorful film structure is an all-solid 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 210 with a thickness of about 100 nm and a tungsten oxide dielectric layer 220 with a thickness of about 150 nm to 400 nm that are sequentially deposited on the mobile phone shell by magnetron sputtering. The electrolyte 230 uses LiNbO ₃ with a thickness of about 600 nm. The pair of electrodes 250 uses ITO with a thickness of about 200 nm. An ion storage layer NiO 240 with a thickness of about 200 nm is arranged 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.

The logo appears as a single color when it is not powered on, and after the power (mobile phone power supply) is turned on, the voltage can be adjusted (this can be achieved through the voltage control function of the mobile phone or a voltage control component can also be added). The color can be switched between a variety of colors with the change of voltage, for example, it can change from red to yellow, then from yellow to green, or it can be blue, purple, etc., and the hue, saturation, brightness, etc. are all Can be adjusted in real time.

Example 16

This embodiment discloses a refrigerator panel, which includes a transparent cover plate covering the front box of the refrigerator, and a colorful film structure is covered on the inner wall of the transparent cover plate. The colorful film structure is an all-solid 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 50nm sequentially deposited on the mobile phone shell by magnetron sputtering, and a Prussian blue layer with a thickness of about 100nm is electrochemically deposited on the metal Cr layer. The Prussian blue layer is magnetron sputtered with a ZnS layer with a thickness of about 1 nm to 15 nm. A LiAlF4 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 is formed on the electrolyte layer. AZO with a thickness of about 80 nm is provided on the Fe ₂ O ₃ layer as a counter electrode.

The colorful film structure presents a single color when it is not energized, and after the power supply (the power module of the refrigerator) is turned on, the color of the colorful film structure can be changed by adjusting the voltage (which can be added by an additional voltage control element). Switch between red, yellow and blue at will.

Example 17

This embodiment discloses a building with more than one window, some of the windows include a window frame and glass fixed on the window frame, the glass is covered with a colorful film structure, the colorful film structure includes successively The first medium layer, the second optical structure layer, the second medium layer, and the first optical structure layer are formed on the glass. Wherein, the first optical structure layer is air, the second optical structure layer is a metal tungsten film, and the first and second dielectric layers are formed of tungsten oxide layers.

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

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

Example 18

This embodiment discloses an automobile. The window glass of the automobile is conformally covered with a reflection/transmission dual-mode colorful film structure, which includes a working electrode, an electrolyte layer and a counter electrode. The electrolyte layer is arranged on the working electrode and the counter electrode. between.

The working electrode includes first and second optical structure layers and a dielectric layer. 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 thickness of 100 nm to 400 nm. Titanium oxide layer. A transparent conductive layer formed by nano silver 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 shows different colors when viewed from two sides, and also has a transmission structure 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 car power supply. By applying voltage 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 car window glass are not completely the same.

Example 19

This embodiment discloses a sun visor cap, a partial area of the sun visor cap body is made of PET film, and a colorful pattern with a colorful film structure is formed on the PET film. The colorful film structure includes a working electrode, an electrolyte layer and For the 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 on the PET film by magnetron sputtering. Each pixel of the tungsten film (corresponding to the colorful pattern) is oxidized by laser direct writing to form a tungsten oxide layer of different thicknesses as a dielectric layer . The thickness of the dielectric layer is about 0-300 nm. The process conditions of the laser direct writing include: the tungsten film can be placed on a worktable controlled by an XY computer, the moving speed is 15mm/s, the continuous laser power is 100W, the laser rectangular spot size is 1.4mm×1.4mm, and it is out of focus. The amount 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 encapsulated between the working electrode and the counter electrode, and then leads are drawn. The color of the colorful thin film structure can be further modulated by applying voltage to the colorful film structure through organic photovoltaic cells. When the voltage is -2.5V～+2.5V, the red area of the working electrode will change between red, orange and yellow in real time; the blue area will change between blue, purple and red in real time.

It should be understood that the above-mentioned embodiments only illustrate the technical ideas and features of the application, and their purpose is to enable those familiar with the technology to understand the content of the application and implement them accordingly, and cannot limit the protection scope of the application. All equivalent changes or modifications made according to the spirit and essence of this application shall be covered by the protection scope of this application.

Claims

An optical film structure, characterized by comprising a first optical structure layer and a second optical structure layer arranged in parallel, the first optical structure layer and the second optical structure layer being optically reflective and/or optically transmissive, A medium layer is arranged between the first optical structure layer and the second optical structure layer, and the bonding interface between the medium layer and the first optical structure layer and the second optical structure layer is the first surface of the medium layer, A second surface, the first surface, the second surface and the dielectric layer 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 medium layer, λ is the wavelength of the incident light,
Is the refraction angle of the incident light when passing through the first surface or the second surface.
The optical film structure of claim 1, wherein if the refractive index of the first optical structure layer is defined as
The reflection coefficient of the first surface
among them
Is the incident angle of incident light on the first surface;

And/or, if the refractive index of the second optical structure layer is defined as
The reflection coefficient of the second surface
among them
Is the refraction angle of incident light when passing through the second surface.
3. The optical film structure of claim 2, wherein the reflection coefficient of the optical film structure is expressed as:
The reflectivity is expressed as:
The optical film structure according to any one of claims 1-3, wherein: if the refractive index of the first optical structure layer is defined as
The transmission coefficient of the first optical structure layer
among them
Is the incident angle of incident light on the first surface;

And/or, if the refractive index of the second optical structure layer is defined as
The transmission coefficient of the second optical structure layer
among them
Is the refraction angle of incident light when passing through the second surface.
The optical film structure according to claim 4, wherein the transmission coefficient of the optical film structure is expressed as:
The transmittance is expressed as:
The optical film structure according to claim 1, wherein the optical film structure has an optical transmission mode, an optical reflection mode, or an optical transmission and reflection mode; preferably, in the optical reflection mode, The optical film structure has a double-sided asymmetric structural color, and in the optical transmission working mode, the optical film structure has a transparent structural color.
The optical thin film structure of claim 1, wherein any one of the first optical structure layer and the second optical structure layer is a metal layer, and the other is composed of a gas, and the gas includes air; or, Both the first optical structure layer and the second optical structure layer are metal layers.
The optical film structure of claim 1, wherein the optical film structure comprises one or more first optical structure layers, one or more medium layers, and one or more second optical structure layers.
8. The optical film structure according to claim 8, wherein the optical film structure comprises a plurality of first optical structure layers and/or a plurality of second optical structure layers and a plurality of dielectric layers.
The optical thin film structure of claim 1, 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 comprises tungsten, gold, Any one or a combination of silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, and palladium; and/or, in the first optical structure layer and the second optical structure layer At least one has a thickness of 0-20 nm; or, at least one of the first optical structure layer and the second optical structure layer has a thickness of 20 nm or more; preferably, the first optical structure layer and the second optical structure The thickness of at least one of the layers is 50-3000 nm.
The optical film structure according to claim 1, wherein the material of the medium layer is selected from organic materials or inorganic materials;

Preferably, the inorganic material includes any one or a combination of metal element or non-metal element, inorganic salt, and oxide;

More optionally, the non-metallic element includes any one or a combination of single crystal silicon, polycrystalline silicon, and diamond;

More preferably, the inorganic salt includes any one or a combination of fluoride, sulfide, selenide, chloride, bromide, iodide, arsenide, or telluride;

More preferably, the oxide 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 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 ;

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 Kind or a combination of many;

More preferably, the sulfide includes any one or a combination of ZnS, GeS, MoS 2 , and Bi 2 S 3 ;

More preferably, the selenide includes any one or a combination of ZnSe, GeSe, MoSe 2 , PbSe, and Ag 2 Se;

More preferably, the chloride includes any one or a combination of AgCl, NaCl, and KCl;

More preferably, the bromide includes any one or a combination of AgBr, NaBr, KBr, TlBr, and CsBr;

More preferably, the iodide includes any one or a combination of AgI, NaI, KI, RbI, and CsI;

More preferably, the arsenide includes GaAs;

More preferably, the antimonide includes GdTe;

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, Prussian green Any one or a combination of

Preferably, the material of the medium layer includes liquid crystal material or MOF material;

Preferably, the organic material includes organic small molecule compounds and/or polymers;

More preferably, the organic material includes viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthalate, dimethylbenzidine, tetrathiafulvene, alkyl-linked Any one or a combination of pyridine, phenothiazole, polyamide, epoxy resin, and polydiyne;

And/or, the thickness of the dielectric layer is greater than 0 and less than or equal to 2000 nm, preferably 100 to 500 nm;

More preferably, the material of the dielectric layer is selected from inorganic electrochromic materials and/or organic electrochromic materials.
The optical film structure according to claim 1, wherein an optimized medium layer is also distributed between the medium layer and the first optical structure layer or the second optical structure layer; or, the first optical structure layer or An optimized medium layer is provided on the second optical structure layer;

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. 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 , any of silicon nitride One or more combinations;

Preferably, the thickness of the optimized dielectric layer is 0-2000 nm.
The optical film structure according to claim 1, wherein the first optical structure layer or the second optical structure layer is further combined with a substrate; preferably, the substrate is transparent or translucent; more preferably, The substrate includes any one or a combination of glass, organic glass, PET, PES, PEN, PC, PMMA, and PDMS.
A device comprising a working electrode and a counter electrode that cooperate with each other, characterized in that the working electrode comprises the optical film structure of any one of claims 1-13, and the dielectric layer in the optical film structure is mainly composed of Composed of electrochromic materials.
The device according to claim 14, characterized in that: the device further comprises an electrolyte distributed between the working electrode and the counter electrode; preferably, the electrolyte comprises a liquid electrolyte, a gel electrolyte or a solid electrolyte;

Preferably, the device further includes an ion storage layer, and the ion storage layer is in contact with the electrolyte;

Preferably, the first optical structure layer or the second optical structure layer is further combined with a substrate; preferably, the substrate is transparent or translucent; more preferably, the substrate includes materials including glass, organic glass, Any one or a combination of PET, PES, PEN, PC, PMMA, PDMS; more preferably, a conductive layer is provided on the substrate; preferably, the conductive layer includes FTO, ITO, Ag nano Any one or a combination of wires, Ag nano grids, carbon nanotubes, and graphene; and/or, the counter electrode is transparent or semi-transparent.
The device control method according to any one of claims 14-15, characterized by comprising: connecting the working electrode, the counter electrode and the power source to form a working circuit; adjusting the potential difference between the working electrode and the counter electrode to at least make the medium The refractive index of the electrochromic material within the layer changes, thereby regulating the color of the device.
A device, characterized by comprising the device according to any one of claims 14-15; preferably, the device further comprises a power supply, which can be electrically connected with the device to form a working circuit.
The device according to claim 17, wherein the device is a consumer electronic product or a household appliance, and the optical film structure is connected and/or integrally formed on the housing and/or display screen of the device.
The device according to claim 18, wherein the consumer electronic product comprises a mobile phone, a bracelet, a tablet computer or a notebook computer; or, the household appliance comprises a TV, a refrigerator, an electric fan or an air conditioner.
The device according to claim 17, wherein the device is a building, and any one of the inner wall, the outer wall, and the window of the building is connected to and/or integrally formed with the optical film structure Or, the device is a vehicle, and the optical film structure is connected to and/or integrally formed with any one of the housing, inner wall, and window of the vehicle; or, the device is shoes, hats or clothing The surface of the device is connected and/or integrally formed with the optical film structure.
17. The device of claim 17, wherein the optical film structure is a set graphic structure.