WO2020173065A1 - Structure de film optique, son procédé de fabrication et son utilisation - Google Patents

Structure de film optique, son procédé de fabrication et son utilisation Download PDF

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Publication number
WO2020173065A1
WO2020173065A1 PCT/CN2019/103280 CN2019103280W WO2020173065A1 WO 2020173065 A1 WO2020173065 A1 WO 2020173065A1 CN 2019103280 W CN2019103280 W CN 2019103280W WO 2020173065 A1 WO2020173065 A1 WO 2020173065A1
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Prior art keywords
layer
optical
optical structure
film structure
structure layer
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PCT/CN2019/103280
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English (en)
Chinese (zh)
Inventor
赵志刚
陈健
王振
丛杉
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Priority claimed from CN201910594027.0A external-priority patent/CN112180646B/zh
Priority claimed from CN201910594037.4A external-priority patent/CN112180647B/zh
Priority claimed from CN201910594031.7A external-priority patent/CN112180648B/zh
Application filed by Suzhou Institute of Nano Tech and Nano Bionics of CAS filed Critical Suzhou Institute of Nano Tech and Nano Bionics of CAS
Publication of WO2020173065A1 publication Critical patent/WO2020173065A1/fr
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices

Definitions

  • 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.
  • optical film structure 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.
  • 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.
  • 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, ⁇ 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 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.
  • 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.
  • 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:
  • 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.
  • the optical film structure of the embodiment of the present application adopts electrochromic material to form 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.
  • 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.
  • 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;
  • FIG. 3 is a schematic diagram of a manufacturing process of a high-precision patterned colorful film in a typical embodiment of the present application
  • FIG. 4 is a schematic structural diagram of a novel optical film structure in Embodiment 1 of the present application.
  • Example 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;
  • Example 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;
  • FIG. 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;
  • Example 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;
  • Example 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;
  • Example 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;
  • Example 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.
  • 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.
  • 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 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.
  • 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, Is the refractive index of the medium layer, ⁇ 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 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.
  • 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.
  • the reflection coefficient of the optical film structure is expressed as:
  • the reflectivity is expressed as:
  • 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 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.
  • 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 transmission coefficient of the optical film structure is expressed as:
  • the transmittance is expressed as:
  • 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.
  • the optical film structure has an optical transmission mode, an optical reflection mode, or an optical transmission and reflection mode.
  • the optical film structure has a double-sided asymmetric structure color.
  • the optical film structure in the optical transmission working mode, has a transparent structural color.
  • 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.
  • the optical film structure includes multiple first optical structure layers and/or multiple second optical structure layers and multiple medium layers.
  • the material of at least one of the first optical structure layer and the second optical structure layer includes a metal material.
  • the first optical structure layer or the second optical structure layer is a metal layer.
  • the first optical structure layer and the second optical structure layer are both metal layers.
  • the first optical structure layer or the second optical structure layer is directly air.
  • the first optical structure layer or the second optical structure layer is not present.
  • the metal material includes tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, palladium, etc., but is not limited thereto.
  • 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.
  • the material of the medium layer is selected from organic materials or inorganic materials.
  • 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.
  • non-metallic element includes any one or a combination of single crystal silicon, polycrystalline silicon, and diamond, but is not limited thereto.
  • the inorganic salt includes any one or a combination of fluoride, sulfide, selenide, chloride, bromide, iodide, arsenide, or telluride, but is not limited thereto.
  • 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.
  • 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.
  • the sulfide includes any one or a combination of ZnS, GeS, MoS 2 , and Bi 2 S 3 , but is not limited thereto.
  • the selenide includes any one or a combination of ZnSe, GeSe, MoSe 2 , PbSe, and Ag 2 Se, but is not limited thereto.
  • the chloride includes any one or a combination of AgCl, NaCl, and KCl, but is not limited thereto.
  • the bromide includes any one or a combination of AgBr, NaBr, KBr, TlBr, and CsBr, but is not limited thereto.
  • the iodide includes any one or a combination of AgI, NaI, KI, RbI, and CsI, but is not limited thereto.
  • the arsenide includes GaAs, etc., but is not limited thereto.
  • the antimony compound includes GdTe and the like, but is not limited thereto.
  • 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.
  • the material of the medium layer includes liquid crystal material or MOF material, but is not limited thereto.
  • the organic material includes small organic molecular compounds and/or polymers, but is not limited thereto.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the first optical structure layer or the second optical structure layer is combined with a substrate.
  • the substrate is transparent or translucent.
  • 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.
  • the aforementioned optimized medium layer may be disposed between the first optical structure layer or the second optical structure layer and the substrate.
  • 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.
  • the thickness of the optimized dielectric layer is preferably 0-2000 nm, preferably 100-500 nm.
  • 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.
  • the first optical structure layer 4 can also be directly air.
  • the second optical structure layer 2 may not exist.
  • 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.
  • the first optical or second optical structure layer and the medium layer may be sequentially formed on the substrate.
  • 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.
  • 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.
  • the device further includes an electrolyte distributed between the working electrode and the counter electrode.
  • the type of the electrolyte is not particularly limited, and liquid electrolyte, gel polymer electrolyte or inorganic solid electrolyte can be used.
  • 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.
  • 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.
  • 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.
  • 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.
  • the electrolyte may be a liquid electrolyte, such as aqueous LiCl, AlCl 3 , HCl, and H 2 SO 4 aqueous solutions.
  • 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.
  • 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).
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC carbonic acid Ethyl methyl
  • organic LiClO 4 , Na(ClO 4 ) 3 propylene carbonate electrolyte, etc. can be used.
  • 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.
  • 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.
  • the electrolyte when an inorganic solid electrolyte is used as the electrolyte, the electrolyte may include LiPON or Ta 2 O 5 .
  • the electrolyte may be, but is not limited to, a Li-containing metal oxide film, such as LiTaO or LiPO.
  • 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.
  • it may be LiBO 2 +Li 2 SO 4 , LiAlF 4 , LiNbO 3 , Li 2 OB 2 O 3 etc.
  • the device further includes an ion storage layer.
  • the ion storage layer is in contact with the electrolyte.
  • the first optical structure layer or the second optical structure layer is also combined with a substrate.
  • the working electrode may include a substrate.
  • 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.
  • 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.
  • a conductive layer is also provided on the substrate.
  • 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.
  • 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;
  • the working electrode, the electrolyte and the counter electrode are assembled to form a device.
  • FIG. 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.
  • 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.
  • 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.
  • the thickness of the aforementioned second optical structure layer is greater than 0 and less than 20 nm.
  • the reflection/transmission structure color of the optical film structure can be changed.
  • 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:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the device further includes a power supply, which can be electrically connected with the device to form a working circuit.
  • a power supply which can be electrically connected with the device to form a working circuit.
  • 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.
  • the device is a consumer electronic product or a household appliance
  • the optical film structure is connected and/or integrally formed on the housing and/or display screen of the device.
  • 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.
  • 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.
  • the optical film structure presents a set graphic structure.
  • 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
  • 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;
  • the phase shift between the reflected light formed on the first reflective surface and the reflected light formed on the second reflective surface d is the thickness of the dielectric layer, Is the refractive index of the medium layer, ⁇ is the wavelength of the incident light, Is the refraction angle of the incident light when passing through the first reflecting surface.
  • 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 second optical structure layer adopts a metal material layer with a thickness of 20 nm or more.
  • 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.
  • 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.
  • 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).
  • the second optical structure layer adopts a metal material layer with a thickness greater than 0 and less than 20 nm.
  • 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
  • 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.
  • first optical structure layer and the second optical structure layer are arranged in parallel, and have optical reflectivity and/or optical transmittance.
  • 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 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.
  • 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:
  • 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.
  • 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.
  • the colorful film structure includes multiple first optical structure layers and/or multiple second optical structure layers and multiple medium layers.
  • the first optical structure layer is a metal material layer or consists of gas.
  • the thickness of the first optical structure layer is preferably 0-20 nm, preferably greater than 0 but less than 20 nm.
  • the first optical structure layer is a metal layer.
  • the first optical structure layer is formed of air.
  • the first optical structure layer or the second optical structure layer is not present.
  • 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.
  • 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.
  • 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.
  • 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.
  • adding a semiconductor material of a suitable thickness can increase the intensity difference of the reflectance curve, thereby increasing the color saturation.
  • 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.
  • the colorful film structure has an optical transmission mode, an optical reflection mode, or an optical transmission and reflection mode.
  • the colorful film structure in the optical reflection working mode, has a double-sided asymmetric structure color.
  • the colorful film structure In the optical transmission mode, has a transparent structural color.
  • 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.
  • the material of the medium layer is selected from organic materials or inorganic materials.
  • 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.
  • non-metallic element includes any one or a combination of single crystal silicon, polycrystalline silicon, and diamond, but is not limited thereto.
  • the inorganic salt includes any one or a combination of fluoride, sulfide, selenide, chloride, bromide, iodide, arsenide, or telluride, but is not limited thereto.
  • 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.
  • the sulfide includes any one or a combination of ZnS, GeS, MoS 2 , and Bi 2 S 3 , but is not limited thereto.
  • the selenide includes any one or a combination of ZnSe, GeSe, MoSe 2 , PbSe, and Ag 2 Se, but is not limited thereto.
  • the chloride includes AgCl, but not limited thereto.
  • the bromide includes any one or a combination of AgBr and TlBr, but is not limited thereto.
  • the iodide includes AgI, etc., but is not limited thereto.
  • the arsenide includes GaAs, etc., but is not limited thereto.
  • the antimony compound includes GdTe and the like, but is not limited thereto.
  • 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.
  • the material of the medium layer includes liquid crystal material or MOF material, but is not limited thereto.
  • the organic material includes small organic molecular compounds and/or polymers, but is not limited thereto.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the electrochromic material may be selected from organic electrochromic materials or inorganic electrochromic materials.
  • 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.
  • 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.
  • the type of the electrolyte is not particularly limited, and liquid electrolyte, gel polymer electrolyte or inorganic solid electrolyte can be used.
  • 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.
  • 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.
  • 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.
  • 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.
  • a mixed electrolyte composed of two or more salts of water-based LiCl, AlCl 3 , HCl, MgCl 2 , ZnCl 2 and the like.
  • the electrolyte may be a liquid electrolyte, such as aqueous LiCl, AlCl 3 , HCl, and H 2 SO 4 aqueous solutions.
  • 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.
  • 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).
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC carbonic acid Ethyl methyl
  • organic LiClO 4 , Na(ClO 4 ) 3 propylene carbonate electrolyte, etc. can be used.
  • 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.
  • 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.
  • the electrolyte when an inorganic solid electrolyte is used as the electrolyte, the electrolyte may include LiPON or Ta 2 O 5 .
  • the electrolyte may be, but is not limited to, a Li-containing metal oxide film, such as LiTaO or LiPO.
  • 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.
  • it may be LiBO 2 +Li 2 SO 4 , LiAlF 4 , LiNbO 3 , Li 2 OB 2 O 3 etc.
  • the device further includes an ion storage layer.
  • the ion storage layer is in contact with the electrolyte.
  • the counter electrode may include a substrate, a transparent conductive layer and an ion storage layer.
  • 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.
  • the counter electrode is transparent or translucent.
  • 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.
  • 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.).
  • 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.
  • the visible light transmittance of the transparent conductive electrode layer may be 70% to 95%.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • the metal material can be processed by laser direct writing, chemical etching, etc., to form the dielectric layer.
  • the first optical structure layer 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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;
  • 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.
  • a predetermined area also referred to as a pixel area 130
  • 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.
  • 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.
  • 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.
  • 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.
  • At least two different dielectric layers formed by in-situ oxidation of at least two pattern areas of a metal layer
  • 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;
  • the phase shift between the reflected light formed on the first reflective surface and the reflected light formed on the second reflective surface d is the thickness of the dielectric layer, Is the refractive index of the medium layer, ⁇ is the wavelength of the incident light, Is the refraction angle of the incident light when passing through the first reflecting surface.
  • At least two pattern areas of the metal layer are oxidized in situ by laser direct writing to form a dielectric layer.
  • each pattern area of the metal layer is oxidized to generate metal oxide films of different types and thicknesses.
  • metal oxide films of different types and thicknesses.
  • different dielectric layers can show different color effects.
  • the aforementioned graphic area may be text, continuous or discontinuous patterns, etc., and is not limited thereto.
  • the dielectric layer can be a thin film structure composed of one metal oxide, or a thin film structure composed of multiple metal oxides.
  • 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.
  • 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.
  • the advantage of using the aforementioned laser direct writing method is that it has almost no limitation on the shape of the metal layer.
  • 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.
  • two different optical cavities based on two different dielectric layers exhibit different colors.
  • the colors presented by two different optical cavities based on two different dielectric layers may also be the same.
  • two different dielectric layers are spaced apart from each other or adjacent to each other.
  • the second optical structure layer adopts a metal material layer with a thickness of 20 nm or more.
  • the thickness of the metal reflective layer is 50-3000 nm.
  • 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 .
  • 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 optical film structure mainly composed of the dielectric layer and the second optical structure layer is expressed as: The reflectivity is expressed as:
  • 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 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
  • the second optical structure layer adopts a metal material layer with a thickness greater than 0 and less than 20 nm.
  • 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 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.
  • 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 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:
  • 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.
  • the first optical structure layer is a metal material layer or is composed of gas.
  • the thickness of the first optical structure layer is preferably 0-20 nm.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a semiconductor material may be added on the dielectric layer to optimize the color of the patterned colorful film.
  • adding a suitable thickness of semiconductor materials can increase the intensity difference of the reflectance curve, thereby increasing the color saturation.
  • 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.
  • 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.
  • the first optical structure layer or the second optical structure layer is further combined with a substrate.
  • the aforementioned optimized medium layer may be disposed between the first optical structure layer or the second optical structure layer and the substrate.
  • 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.
  • the thickness of the optimized dielectric layer is preferably 0-2000 nm, preferably 100-500 nm.
  • the substrate is transparent or translucent.
  • 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.
  • a conductive layer is also provided on the substrate.
  • 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.
  • the first optical structure layer is integrated with the substrate.
  • 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.
  • the type of the electrolyte is not particularly limited, and liquid electrolyte, gel polymer electrolyte or inorganic solid electrolyte can be used.
  • 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.
  • the electrolyte may include one or more compounds, such as compounds containing H + , Li + , Al 3+ , Na + , K + , Rb + or Cs + .
  • 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.
  • the electrolyte may be a liquid electrolyte, such as aqueous LiCl, AlCl 3 , HCl, and H 2 SO 4 aqueous solutions.
  • 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 .
  • a mixed electrolyte composed of two or more salts of water-based LiCl, AlCl 3 , HCl, MgCl 2 , and ZnCl 2 .
  • 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.
  • 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).
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylene carbonate Methyl ester
  • organic LiClO 4 , Na(ClO 4 ) 3 propylene carbonate electrolyte, etc. can be used.
  • the electrolyte may be a gel electrolyte, such as PMMA-PEG-LiClO 4 , PVDF-PC-LiPF 6, etc., but is not limited thereto.
  • the electrolyte when an inorganic solid electrolyte is used as the electrolyte, the electrolyte may include LiPON or Ta 2 O 5 .
  • the electrolyte may be, but is not limited to, a Li-containing metal oxide film, such as LiTaO or LiPO.
  • 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.
  • it may be LiBO 2 +Li 2 SO 4 , LiAlF 4 , LiNbO 3 , Li 2 OB 2 O 3 etc.
  • 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.
  • 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).
  • 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.
  • 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.
  • a transparent conductive electrode which may be formed by including a material having characteristics such as high light transmittance and low sheet resistance.
  • 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.
  • 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.).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 device includes, but is not limited to, mechanical equipment, optoelectronic equipment, electronic equipment, buildings, vehicles, outdoor billboards, etc., and is not limited thereto.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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 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 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.
  • 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.
  • the corresponding reflection color only presents the color of the metallic tungsten film (silver white).
  • 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 metallic silver (Ag) layer
  • the dielectric layer is formed of titanium dioxide
  • 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.
  • the thickness of the silver film is selected to be about 2 nm by sputtering.
  • a layer of titanium dioxide is sputtered on the tungsten film by magnetron sputtering.
  • the thickness of the titanium dioxide layer is set at 100 nm to 400 nm.
  • 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.
  • 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.
  • the added second medium layer can improve color brightness and saturation.
  • 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
  • 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.
  • the thickness of the tungsten oxide layer is set at 1 nm to 400 nm.
  • a layer of tungsten film is sputtered by a magnetron sputtering method.
  • the thickness of the tungsten film is about 10 nm.
  • a tungsten oxide layer is sputtered on the tungsten film by magnetron sputtering.
  • the thickness of the tungsten oxide layer is set at 100 nm to 400 nm.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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)
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • the thickness of the aluminum film is set at 10 nm.
  • a layer of Prussian blue layer is deposited by electrodeposition method.
  • the thickness of Prussian blue is selected to be 100 nm to 2000 nm.
  • a layer of silver film is sputtered on the Prussian blue layer by magnetron sputtering.
  • the thickness of the silver film is set at 0-50 nm.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a pair of electrodes for example, NiO counter electrode
  • AlCl 3 electrolyte is encapsulated between the two, and then leads are drawn out to prepare the colorful electrochromic device of this embodiment.
  • 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.
  • 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)
  • the second optical structure layer is formed by Metal silver (Ag) is formed
  • 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.
  • the thickness of the silver film is selected to be about 10 nm.
  • a layer of titanium oxide is sputtered on the silver film by magnetron sputtering.
  • the thickness of the titanium dioxide layer is set to 100 nm to 400 nm.
  • a layer of tungsten film is sputtered by magnetron sputtering on the titanium dioxide layer.
  • 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.
  • 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.
  • the working electrode of this embodiment shows different colors when viewed from two sides, and also has a transmissive structure color.
  • 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.
  • a pair of electrodes for example, a NiO counter electrode
  • 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.
  • 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, 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.
  • 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 working electrode of this embodiment shows different colors when viewed from two sides, and also has a transmissive structure color.
  • the optical device can be assembled and formed by referring to Embodiment 7.
  • 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.
  • a pair of electrodes for example, NiO counter electrode
  • LiCl/HCl/AlCl 3 /NaCl/PVA mixed ion gel electrolyte is set between the two.
  • 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. 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.
  • 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.
  • 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.
  • 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.
  • a pair of electrodes for example, an IrO 2 pair of electrodes
  • the wires are drawn out to prepare the colorful electrochromic device of this embodiment.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a pair of electrodes such as a NiO counter electrode layer
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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%
  • the laser action time is 3 -10s.
  • the aforementioned titanium film can also be prepared by methods known in the industry such as electron beam evaporation and thermal evaporation.
  • 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.
  • 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.
  • 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.
  • 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%
  • the laser action time is 0 -5s.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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%
  • the laser action time is 6s.
  • the thickness of the obtained dielectric layer is 150nm
  • the area appears yellow
  • the laser action time is 10s
  • the thickness of the obtained dielectric layer is about 250nm, and this area appears green.
  • 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 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.
  • a pair of electrodes such as a NiO counter electrode layer
  • High-precision patterning can be prepared Multi-color electrochromic devices.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the first optical structure layer is air
  • the second optical structure layer is a metal tungsten film
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • a pair of electrodes such as NiO counter electrode
  • LiCl/PVA gel electrolyte is set between the two, and then the lead wire is connected to the car power supply.
  • 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.
  • 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.

Landscapes

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

Abstract

La présente invention concerne une structure de film optique, son procédé de fabrication et son utilisation. La structure de film optique comprend une première couche de structure optique (4) et une seconde couche de structure optique (2) qui sont agencées en parallèle ; la première couche de structure optique (4) et la seconde couche de structure optique (2) sont optiquement réfléchissantes et/ou transmissives ; une couche diélectrique (3) est disposée entre la première couche de structure optique (4) et la seconde couche de structure optique (2) ; les interfaces de liaison entre la couche diélectrique (3) et la première couche de structure optique (4) et entre la couche diélectrique (3) et la seconde couche de structure optique (2) sont une première surface et une seconde surface de la couche diélectrique (3) respectivement ; et la première surface, la seconde surface et la couche diélectrique (3) définissent une cavité optique. La structure de film optique présente des couleurs de réflexion/transmission colorées, et en particulier lorsqu'un matériau électrochromique est utilisé pour former la couche diélectrique (3), le réglage de l'amplitude de la tension appliquée à la couche diélectrique (3) peut également réaliser une fusion de la couleur structurale et de l'électrochromisme de la structure de film optique, de telle sorte que la structure de film optique présente des changements de couleur plus colorés, et peut donc être largement appliquée dans de multiples domaines.
PCT/CN2019/103280 2019-02-27 2019-08-29 Structure de film optique, son procédé de fabrication et son utilisation Ceased WO2020173065A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
CN201910146293 2019-02-27
CN201910146293.7 2019-02-27
CN201910594027.0 2019-07-03
CN201910594027.0A CN112180646B (zh) 2019-07-03 2019-07-03 图案化多彩薄膜，其制作方法及应用
CN201910594037.4A CN112180647B (zh) 2019-07-03 2019-07-03 包含多彩薄膜结构的装置
CN201910594031.7A CN112180648B (zh) 2019-07-03 2019-07-03 光学薄膜结构、其制备方法以及应用
CN201910594031.7 2019-07-03
CN201910594037.4 2019-07-03

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JPH09265005A (ja) * 1996-03-27 1997-10-07 Nikon Corp エキシマレーザー用ミラー
JP2001337210A (ja) * 2000-05-30 2001-12-07 Nippon Sheet Glass Co Ltd 光学反射鏡
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CN114253039A (zh) * 2020-09-22 2022-03-29 中国科学院苏州纳米技术与纳米仿生研究所 高亮度、饱和度、纯度的多彩电致变色结构、器件及制法
CN114253039B (zh) * 2020-09-22 2024-09-20 中国科学院苏州纳米技术与纳米仿生研究所 高亮度、饱和度、纯度的多彩电致变色结构、器件及制法

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