CN112180647B - Device comprising a multicoloured film structure - Google Patents
Device comprising a multicoloured film structure Download PDFInfo
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- CN112180647B CN112180647B CN201910594037.4A CN201910594037A CN112180647B CN 112180647 B CN112180647 B CN 112180647B CN 201910594037 A CN201910594037 A CN 201910594037A CN 112180647 B CN112180647 B CN 112180647B
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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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1524—Transition metal compounds
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices
Abstract
The invention discloses a device comprising a colorful film structure, which comprises a substrate, wherein the colorful film structure is connected with or integrally formed on the substrate and comprises at least one dielectric layer, each dielectric layer is matched with a first reflecting surface and a second reflecting surface to form an optical cavity, the first reflecting surface is the first surface of the dielectric layer, the second reflecting surface is the combined interface of the second surface of the dielectric layer and a second optical structure layer, and the first surface and the second surface are arranged oppositely. Further, the dielectric layer is formed of an electrochromic material. The improved colorful film structure is applied to consumer electronics, household appliances, buildings, vehicles, clothes and the like, and the colorful film structure has the characteristics of electrochromism and physical color fusion, so that colorful regulation and control of colors can be realized, the devices can present colorful changes, and the requirements of practical application, especially the personalized requirements of different crowds, can be fully met.
Description
Technical Field
The present invention relates to a multicolored optical structure, and more particularly to a device, such as a consumer electronic product, a household appliance, a building, a vehicle, a garment, etc., that includes a multicolored film structure.
Background
With the improvement of living standard, people have higher and higher requirements on color changes of various devices in daily life and working environments, such as consumer electronics, household appliances, buildings, vehicles, clothes and the like. For example, for consumer electronics such as mobile phones, various mobile phone shells capable of changing color have been proposed in the industry to meet different personalized requirements. Existing color changeable mobile phone shells are typically implemented by the following schemes, for example: a layer of color-changing material is sprayed or printed on the mobile phone shell, but the color-changing material is easy to wear or fall off, and the color-changing effect is single; alternatively, a multilayer structure is adopted, for example, a photochromic layer, a primer layer, a heat dissipation layer, an abrasion resistant layer, a transparent coating layer and the like are formed into a multilayer composite structure, but the multilayer composite structure is not easy to process, has low photochromic efficiency and also has the defects of single photochromic effect and the like.
In recent years, color-changeable optical structures based on electrochromic materials have also become more and more widely used. For example, the industry has attempted to apply electrochromic optical structures to commercially available cell phone cases, appliance housings, architectural or vehicular windows, and the like. However, the color modulation of the existing electrochromic structure is chemical color modulation, and the color thereof depends on the intrinsic property of the material, so that the color is monotonous and difficult to well meet the actual requirement.
Disclosure of Invention
It is a primary object of the present invention to provide a device including a multicolored film structure that overcomes the deficiencies of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a device comprising a colorful film structure, which comprises a substrate, wherein the substrate is connected with or integrally formed with the colorful film structure, the colorful film structure comprises at least one dielectric layer, each dielectric layer is matched with a first reflecting surface and a second reflecting surface to form an optical cavity, the first reflecting surface is a first surface of the dielectric layer, the second reflecting surface is a combined interface of a second surface of the dielectric layer and a second optical structure layer, and the first surface and the second surface are arranged oppositely;
when incident light enters the optical cavity, the phase shift of the reflected light formed on the first reflecting surface and the reflected light formed on the second reflecting surface
d is the thickness of the dielectric layer,
is the refractive index of the dielectric layer, lambda is the wavelength of the incident light,
the refraction angle of the incident light when the incident light passes through the first reflecting surface is shown.
Further, if the refractive index of the medium material on the first surface of the medium layer is defined as
The reflection coefficient of the first reflection surface
Wherein
Is the incident angle of the incident light; and if the refractive index of the medium material on the second surface of the medium layer is defined as
The reflection coefficient of the second reflection surface
Wherein
The refraction angle of the incident light when the incident light passes through the second reflecting surface; the reflection coefficient of the multicolor film structure mainly composed of the dielectric layer and the second optical structure layer is expressed as follows:
the reflectance is expressed as:
furthermore, the material of the dielectric layer is selected from organic materials or inorganic materials, and electrochromic materials are preferred.
Further, the first reflecting surface is a joint surface of the first surface of the dielectric layer and the first optical structure layer, and the refractive index of the first optical structure layer is
The refractive index of the second optical structure layer is
Further, the transmission coefficient of the first optical structure layer
Wherein
The transmission coefficient of the second optical structure layer is the incident angle of the incident light on the first surface
Wherein
The transmission coefficient of the colorful thin film structure mainly composed of the first optical structure layer, the medium layer and the second optical structure layer is expressed as follows:
the transmittance is expressed as:
furthermore, the colorful thin film structure mainly composed of the first optical structure layer, the dielectric 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 colorful film structure has double-sided asymmetric structural colors, and in the optical transmission working mode, the colorful film structure has transparent structural colors.
Furthermore, the multicolor film structure comprises a working electrode, a counter electrode and electrolyte distributed between the working electrode and the counter electrode, wherein the working electrode comprises a dielectric layer formed by electrochromic materials.
Further, the device is a consumer electronic product or a household appliance, and the colorful film structure is connected and/or integrally formed on a shell and/or a display screen of the device.
Further, the device is a building, and the colorful film structure is connected and/or integrally formed on any one of an inner wall, an outer wall and a window of the building.
Further, the device is a vehicle, and the colorful film structure is connected and/or integrally formed on any one of an outer shell, an inner wall and a window of the vehicle.
Further, the device is a shoe, a cap or a piece of clothes, and the colorful film structure is connected and/or integrally formed on the surface of the device.
Furthermore, the colorful film structure is a set image-text structure.
Compared with the prior art, the improved colorful film structure is applied to devices such as consumer electronics, household appliances, buildings, vehicles, clothes and the like, and has the characteristics of electrochromism and physical color fusion, namely, the advantages of electrochromism, adjustable color and wide physical color are organically combined, so that the colorful adjustment and control of the color can be realized, the controllability is good, the devices have rich and colorful color changes, and the requirements of practical application, especially the individual requirements of different crowds can be fully met.
Drawings
Fig. 1 is a schematic structural diagram of a mobile phone according to embodiment 1 of the present invention;
fig. 2 is a schematic diagram of the structure of the multicolor film forming Logo of fig. 1.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Moreover, it is noted that, in this specification, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising at least one of a 8230, a" do 8230, "does not exclude the presence of additional like elements in a process, method, article, or apparatus comprising the element.
One aspect of the embodiments of the present invention provides a device including a colorful film structure, including a substrate, the substrate being connected to or integrally formed with the colorful film structure, the colorful film structure including at least one dielectric layer, each of the dielectric layers cooperating with a first reflective surface and a second reflective surface to form an optical cavity, the first reflective surface being a first surface of the dielectric layer, the second reflective surface being a bonding interface between the second surface of the dielectric layer and a second optical structure layer, the first surface being opposite to the second surface;
when the incident light enters the optical cavity, the phase shift of the reflected light formed on the first reflecting surface and the reflected light formed on the second reflecting surface
d is the thickness of the dielectric layer,
is the refractive index of the dielectric layer, lambda is the wavelength of the incident light,
the refraction angle of the incident light when the incident light passes through the first reflecting surface is shown.
Further, if the refractive index of the medium material on the first surface of the medium layer is defined as
The reflection coefficient of the first reflecting surface
Wherein
Is the incident angle of the incident light; and if the refractive index of the medium material on the second surface of the medium layer is defined as
The reflection coefficient of the second reflecting surface
Wherein
The refraction angle of the incident light when the incident light passes through the second reflecting surface; mainly composed of the dielectric layer and the second optical structure layerThe reflectance of the resulting multicolored film structure is expressed as:
the reflectance is expressed as:
in some embodiments, the second optical structure layer is a metal material layer with a thickness of 20nm or more, and preferably, the metal reflective layer has a thickness of 50 to 3000nm. That is, the second optical structure layer may be considered as a metal reflective layer. At this time, reflected light formed by incident light on the first surface (i.e., the first reflecting surface) of the dielectric layer and reflected light formed by incident light transmitted through the dielectric layer on the surface (i.e., the second reflecting surface) of the metal layer are superimposed by interference.
Further, the material of the metal reflective layer may be selected from non-active metals, such as chromium, gold, silver, copper, tungsten, titanium, or alloys thereof, and the like, without being limited thereto.
In some embodiments, if the dielectric layer in the multicolor thin film structure is formed of an electrochromic material, so that the multicolor thin film structure is an electrochromic structure, the metal reflective layer also serves as a current collector of the dielectric layer. Accordingly, the metal reflective layer may be preferably formed of a metal material having high conductivity, for example, may be formed of a material having high conductivity, such as silver (Ag) or copper (Cu).
In some embodiments, the second optical structure layer is a metal material layer with a thickness greater than 0 and less than 20nm.
In some embodiments, the first reflective surface is a 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
Furthermore, the reflection coefficient and the reflectivity of the multicolor film structure are also suitable for the condition that the incident light enters the optical cavity from the second optical structure layer.
Further, the first optical structure layer and the second optical structure layer are arranged in parallel and have optical reflectivity and/or optical transmissivity.
Further, with the multicolor film structure, the reflected light formed on the first surface by the incident light from the first optical structure layer interferes and superposes the reflected light formed on the second surface by the incident light transmitted through the dielectric layer. The reverse is true, namely, the reflected light formed on the second surface by the incident light from the second optical structure layer and the reflected light formed on the first surface by the incident light transmitted through the dielectric layer are superimposed by interference.
Specifically, the transmission coefficient of the first optical structure layer
Wherein
The transmission coefficient of the second optical structure layer is the incident angle of the incident light on the first surface
Wherein
The transmission coefficient of the multicolor film structure mainly composed of the first optical structure layer, the medium layer and the second optical structure layer is expressed as follows:
the transmittance is expressed as:
furthermore, the transmission coefficient and the transmittance of the colorful film structure are also suitable for the condition that the incident light enters the optical cavity from the second optical structure layer.
In some embodiments, the multicolored film structure includes one or more first optical structure layers, one or more dielectric layers, and one or more second optical structure layers.
In some embodiments, the multicolored film structure includes a plurality of first optical structure layers and/or a plurality of second optical structure layers and a plurality of dielectric layers.
In some embodiments, the first optical structure layer is a layer of metallic material or consists of a gas.
Further, the thickness of the first optical structure layer is preferably 0 to 20nm, and is preferably greater than 0 and less than 20nm.
In some embodiments, the first optical structure layer is a metal layer.
In some embodiments, the first optical structure layer is formed of air.
In some embodiments, the first or second optical structure layer is absent.
Further, the material of the metal material layer includes any one or a combination of more of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, and palladium, but is not limited thereto.
Furthermore, an optimization dielectric layer can be added between the first optical structure layer or the second optical structure layer and the dielectric layer to optimize the color of the multicolor film structure.
Further, an optimization medium layer may be added on the first optical structure layer or the second optical structure layer, or the first optical structure layer or the second optical structure layer may be disposed on the optimization medium layer, so as to optimize the color of the multicolor film structure.
Further, the material of the optimized dielectric layer includes but is not limited to WO 3 、NiO、TiO 2 、Nb 2 O 5 、Fe 2 O 3 、V 2 O 5 、Co 2 O 3 、Y 2 O 3 、Cr 2 O 3 、MoO 3 、Al 2 O 3 、SiO 2 、MgO、ZnO、MnO 2 、CaO、ZrO 2 、Ta 2 O 5 、Y 3 Al 5 O 12 、Er 2 O 3 、ZnS、MgF 2 、SiN x (silicon nitride), and the like, but is not limited thereto.
For example, for some specific materials or multi-color films with appropriate thickness in the embodiments of the present invention, the intensity difference of the reflectivity curve can be increased by adding semiconductor materials with appropriate thickness, so as to increase the saturation of the color.
Furthermore, the thickness of the optimized dielectric layer is preferably 0 to 2000nm, preferably 0 to 500nm, preferably 0 to 300nm, and particularly preferably 1 to 100nm.
Further, the multi-color thin film structure has an optical transmission operation mode, an optical reflection operation mode or an optical transmission and reflection operation mode.
And in the optical reflection working mode, the colorful film structure has double-sided asymmetric structural colors. And in the optical transmission working mode, the colorful film structure has transparent structural color.
In some embodiments, the dielectric layer has a thickness greater than 0 and less than or equal to 2000nm, preferably between 50 and 2000nm, and more preferably between 100 and 500nm, to provide greater color saturation of the multicolor film structure.
In some embodiments, the material of the dielectric layer is selected from organic materials or inorganic materials.
Further, the inorganic material includes a metal or a combination of any one or more of a non-metal element, an inorganic salt, and an oxide, but is not limited thereto.
Further, the elemental nonmetal includes any one or a combination of monocrystalline silicon, polycrystalline silicon and diamond, but is not limited thereto.
Further, the inorganic salt includes any one or a combination of more of fluoride, sulfide, selenide, chloride, bromide, iodide, arsenide, or telluride, but is not limited thereto.
Further, the oxide includes WO 3 、NiO、TiO 2 、Nb 2 O 5 、Fe 2 O 3 、V 2 O 5 、Co 2 O 3 、Y 2 O 3 、Cr 2 O 3 、MoO 3 、Al 2 O 3 、SiO 2 、MgO、ZnO、MnO 2 、CaO、ZrO 2 、Ta 2 O 5 、Y 3 Al 5 O 12 、Er 2 O 3 、IrO 2 Any one or more of these, but not limited thereto.
Further, the sulfide includes ZnS, geS, moS 2 、Bi 2 S 3 Any one or more of these, but not limited thereto.
Further, the selenide includes ZnSe, geSe, moSe 2 、PbSe、Ag 2 Se is any one or combination of Se, but not limited thereto.
Further, the chloride includes AgCl and the like, but is not limited thereto.
Further, the bromide includes any one or more of AgBr and TlBr, but is not limited thereto.
Further, the iodide includes AgI, etc., but is not limited thereto.
Further, the arsenide includes GaAs and the like, but is not limited thereto.
Further, the antimonide includes GdTe and the like, but is not limited thereto.
Furthermore, the material of the dielectric layer comprises SrTiO 3 、Ba 3 Ta 4 O 15 、Bi 4 Ti 3 O 2 、CaCO 3 、CaWO 4 、CaMnO 4 、LiNbO 4 Any one or more of Prussian blue, prussian black, prussian white and Prussian green, but notAnd is limited thereto.
Further, the material of the dielectric layer includes, but is not limited to, a liquid crystal material or an MOF material.
Further, the organic material includes an organic small molecule compound and/or a polymer, but is not limited thereto.
Further, the organic material includes any one or a combination of more of viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthalyl ester, dimethyldiphenylamine, tetrathiafulvene, alkyl bipyridine, phenothiazine, polyamide, epoxy resin, and polydiacetylene, but is not limited thereto.
In some embodiments, the dielectric layer may consist essentially of an electrochromic material. The electrochromic material can be selected from inorganic and organic materials or liquid crystal materials, MOF materials and the like. For example, the inorganic material may include WO 3 、NiO、TiO 2 、Nb 2 O 5 、Fe 2 O 3 、V 2 O 5 、Co 2 O 3 、Y 2 O 3 、MoO 3 、IrO 2 Prussian blue, prussian black, prussian white, prussian green, etc., without being limited thereto. The organic material may include viologen, polypyrrole, polyaniline, polythiophene, polycarbazole, phthalocyanine, terephthaloyl, dimethyldiphenylamine, tetrathiafulvene, alkyl bipyridine, phenothiazine, polydiacetylene, and the like, but is not limited thereto.
In some embodiments, the thickness and/or material of the first optical structure layer, the second optical structure layer, the dielectric layer, etc. may also be adjusted, so as to adjust the color of the multicolor film structure.
In some embodiments, the multicolored film structure includes a working electrode including a dielectric layer formed from an electrochromic material, a counter electrode, and an electrolyte disposed between the working electrode and the counter electrode.
Further, the electrochromic material may be selected from an organic electrochromic material or an inorganic electrochromic material. Wherein the inorganic electrochromic material can be Co, rh, ir, ni, cr, mn, fe, ti, or Ti,Oxides of V, nb, ta, mo, W, e.g. LiNiO 2 (lithium nickelate), irO 2 、NiO、V 2 O 5 、LixCoO 2 (lithium cobaltate), rh 2 O 3 、CrO 3 、WO 3 、MoO 3 、Nb 2 O 5 、Ta 2 O 5 Or TiO 2 Etc., without being limited thereto. The organic electrochromic material may be an organic polymer, an organic small molecule, a metal supramolecular polymer, a metal organic compound, and the like, such as methyl viologen, polyaniline, polythiophene, polypyrrole, prussian blue, a metal organic chelate (e.g., a cyanine compound), polydiacetylene, and the like, but is not limited thereto.
Further, the type of the electrolyte is not particularly limited, and a liquid electrolyte, a gel polymer electrolyte, or an inorganic solid electrolyte may be used.
In some embodiments, the electrolyte is in contact with the dielectric layer and provides a mobile environment for ions, such as hydrogen ions or lithium ions, to color or decolorize the electrochromic material.
In some embodiments, the electrolyte may comprise one or more compounds, for example containing H + 、Li + 、Al 3+ 、Na + 、K + 、Rb + 、Ca 2+ ，Zn 2+ 、Mg 2+ Or Cs + The compound of (1). In one embodiment, the electrolyte layer may comprise a lithium salt compound, such as LiClO 4 、LiBF 4 、LiAsF 6 Or LiPF 6 . Ions contained in the electrolyte may contribute to a color change or a light transmittance change of the device when being inserted into or removed from the dielectric layer according to the polarity of the applied voltage.
In some embodiments, the electrolyte may be a mixed electrolyte, such as aqueous LiCl, alCl 3 、HCl、MgCl 2 、ZnCl 2 And mixed electrolytes composed of two or more salts among the salts. When an electrolytic solution containing two or more kinds of ions is used, the foregoing implementation of the present invention can be made as compared with the case where an electrolytic solution containing only a single kind of ions is usedThe colorful film structure of the embodiment has more abundant color change and higher color saturation.
In some embodiments, the electrolyte may be a liquid electrolyte, such as aqueous LiCl, alCl 3 、HCl、H 2 SO 4 Aqueous solutions, and the like.
In some embodiments, the electrolyte may further comprise a carbonate compound. Since the carbonate-based compound has a high dielectric constant, the ionic conductivity provided by the lithium salt may be increased. As the carbonate-based compound, at least one of the following may be used: PC (propylene carbonate), EC (ethylene carbonate), DMC (dimethyl carbonate), DEC (diethyl carbonate) and EMC (ethyl methyl carbonate). For example, organic LiClO can be used 4 、Na(ClO 4 ) 3 And propylene carbonate electrolyte, and the like.
In some embodiments, the electrolyte can be a gel electrolyte, such as PMMA-PEG-LiClO 4 ，PVDF-PC-LiPF 6 ，LiCl/PVA，H 2 SO 4 PVA, etc., but are not limited thereto.
In some preferred embodiments, when an inorganic solid electrolyte is used as the electrolyte, the electrolyte may comprise LiPON or Ta 2 O 5 . For example, the electrolyte may be, but is not limited to, a Li-containing metal oxide thin film, such as a LiTaO or LiPO thin film. Further, the inorganic solid electrolyte may be LiPON or Ta therein 2 O 5 The electrolyte to which components such as B, S and W are added may be LiBO, for example 2 +Li 2 SO 4 、LiAlF 4 、LiNbO 3 、Li 2 O-B 2 O 3 And the like.
Preferably, the device further comprises an ion storage layer.
Further, the ion storage layer is in contact with the electrolyte.
Further, the counter electrode may include a substrate, a transparent conductive layer, and an ion storage layer.
Further, the material of the ion storage layer may be selected from, but not limited to, niO and Fe 2 O 3 、TiO 2 Prussian blue and IrO 2 And the like.
In some embodiments, the counter electrode is transparent or translucent.
In some embodiments, a transparent conductive electrode or the like may also be included within the working electrode. The transparent conductive electrode may be formed by containing a material having characteristics such as high light transmittance, low sheet resistance, and the like, and may be formed by containing any of: a transparent conductive oxide 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), NTO (niobium-doped titanium oxide), znO, OMO (oxide/metal/oxide), and CTO; silver (Ag) nanowires; a 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 may be used without limitation. For example, a thin film electrode layer containing transparent conductive oxide particles may 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 10nm to 500nm in the case of the vacuum method, and may be in the range of 0.1 μm to 20 μm in the case of the printing method. In one example, the visible light transmittance of the transparent conductive electrode layer may be 70% to 95%.
In some preferred embodiments, the electrolyte is an all-solid-state electrolyte, which can be combined to form an all-solid-state colorful thin film structure by a dielectric layer, a first optical structure layer, a second optical structure layer, a counter electrode, and the like, which are in a solid state. For example, the all-solid electrolyte within the all-solid multicolor film structure can be in the form of a solid ionically conductive layer. The color change principle of the all-solid-state multicolor film structure is as follows: the metal reflecting layer and other layer materials form a metal-medium structure, and can also comprise other layers, such as an ion conducting layer, an ion storage layer, a transparent conducting layer and the like, the electrochromic structure with structural color can be prepared by adjusting the thickness of each layer material to a proper range, further, the refractive index of the electrochromic material can be adjusted by applying voltage, and the color of the all-solid-state multicolor thin film structure can be further adjusted.
In some embodiments, in addition to adjusting the color (structural color) of the multicolor film structure by adjusting the thickness and/or material of the first optical structure layer, the second optical structure layer, the dielectric layer, and the like, the color of the multicolor film structure can be adjusted by adjusting the potential difference applied between the working electrode and the counter electrode to change at least the refractive index of the electrochromic material in the dielectric layer. The regulation and control process can be dynamic, so that the fusion of colorful structural colors and electrochromism is realized, and the color modulation of the colorful thin film structure is greatly enriched.
Of course, the device may also include components such as a control module, a power module, etc. that cooperate with the multicolored film structure, and these accessory components may be self-contained or otherwise added to the device.
In some embodiments of the present invention, at least one of the first optical structure layer, the second optical structure layer, the dielectric layer, and the like may be formed by any one of magnetron sputtering, ion plating, electron beam evaporation, thermal evaporation, chemical vapor deposition, and electrochemical deposition.
More specifically, the dielectric layer may be prepared by magnetron sputtering, ion plating, electron beam evaporation, thermal evaporation, chemical vapor deposition, electrochemical deposition, and the like, but is not limited thereto. For example, the dielectric layer may be formed by processing a metal material or the like by laser direct writing, chemical etching, or the like.
More specifically, the first optical structure layer, the second optical structure layer, and the like may be prepared by magnetron sputtering, ion plating, electron beam evaporation, thermal evaporation, chemical vapor deposition, and the like.
In addition, the first or second optical structure layer, the dielectric layer, and the like may also be formed by coating, printing, casting, atomic force deposition, sol-gel technique, and the like, without being limited thereto.
Further, the device is a consumer electronic product or a household appliance, and the colorful film structure is connected and/or integrally formed on a shell and/or a display screen of the device.
The consumer electronic product includes a mobile phone, a bracelet, a tablet computer or a notebook computer, and the like, but is not limited thereto.
Wherein the household appliances include, but are not limited to, a television, a refrigerator, an electric fan, an air conditioner, or the like.
Further, the device is a building having the multicolored film structure attached to and/or integrally formed on any of an interior wall, an exterior wall, a ceiling, a window of the building.
Further, the device is a vehicle, and the colorful film structure is connected and/or integrally formed on any one of an outer shell, an inner wall and a window of the vehicle.
The vehicle may be various motor vehicles such as an automobile, a motorcycle, an electric vehicle, etc., or a yacht, an airplane, etc., and is not limited thereto.
Further, the device is a shoe, hat or piece of apparel (including but not limited to clothing, belts, scarves, wristbands, hair bands, etc.) having the multicolored film structure attached to and/or integrally formed with a surface of the device.
Further, the colorful film structure can be presented as a set graphic structure, such as a pattern, a text, etc., without being limited thereto.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Embodiment 1 referring to fig. 1 to 2, the embodiment discloses a mobile phone, which includes a mobile phone body 1 and a mobile phone shell 2, and includes a housing 10, where a Logo3 formed by a colorful film structure is integrally disposed on the housing. The colorful film structure is an all-solid-state electrochromic structure and comprises a working electrode, an electrolyte layer and a counter electrode, wherein the electrolyte layer is arranged between the working electrode and the counter electrode. The workThe electrode comprises a metal tungsten layer 11 with the thickness of about 100nm and a tungsten oxide dielectric layer 12 with the thickness of about 150 nm-400 nm which are sequentially deposited on the shell of the mobile phone shell in a magnetron sputtering mode. The electrolyte 13 adopts LiNbO with the thickness of about 600nm 3 . The pair of electrodes 15 uses ITO with a thickness of about 200 nm. An ion storage layer NiO14 with the thickness of about 200nm is arranged between the counter electrode and the electrolyte. Of course, the tungsten film and the tungsten oxide layer can be prepared by electron beam evaporation, thermal evaporation, ion plating, and the like.
The Logo is in a single color when not powered on, and after the power supply (a mobile phone power supply) is powered on, the color of the Logo can be converted among various colors along with the change of the voltage by adjusting the voltage (the voltage can be adjusted by the voltage adjusting function of the mobile phone or a voltage adjusting element can be additionally arranged), for example, the color can be changed from red to yellow, then from yellow to green, and can also be in blue, purple and the like, and the hue, saturation, brightness and the like can be adjusted in real time.
Example 2: the embodiment discloses a refrigerator panel, which comprises a transparent cover plate covered on a front side box body of a refrigerator, wherein a colorful film structure is covered on the inner wall of the transparent cover plate. The colorful film structure is an all-solid-state electrochromic structure and comprises a working electrode, an electrolyte layer and a counter electrode, wherein the electrolyte layer is arranged between the working electrode and the counter electrode. The working electrode comprises a metal Cr layer with the thickness of about 50nm, which is sequentially deposited on the shell of the mobile phone shell in a magnetron sputtering mode, and a Prussian blue layer with the thickness of about 100nm is electrochemically deposited on the metal Cr layer. The Prussian blue layer is provided with a ZnS layer with the thickness of about 1 nm-15 nm by magnetron sputtering. The ZnS layer is formed with LiAlF having a thickness of about 300nm 4 An electrolyte layer. Fe with a thickness of about 100nm is formed on the electrolyte layer 2 O 3 A layer. The Fe 2 O 3 AZO with a thickness of about 80nm was provided on the layer as a counter electrode.
When the power supply (the power supply module of the refrigerator) is switched on, the color of the colorful thin film structure can be switched among red, yellow and blue colors at will by adjusting the voltage (the additionally arranged voltage regulating element).
Example 3: the embodiment discloses a building, which is provided with more than one window, wherein some windows comprise a window frame and glass fixed on the window frame, the glass is covered with a colorful film structure, and the colorful film structure comprises a first medium layer, a second optical structure layer, a second medium layer and a first optical structure layer which are sequentially formed on the glass. The first optical structure layer is air, the second optical structure layer is a metal tungsten film, and the first medium layer and the second medium layer are formed by tungsten oxide layers.
The tungsten oxide layer as the first dielectric layer may be formed by magnetron sputtering or the like, and has a thickness of about 1nm to 400nm. The thickness of the metal tungsten film was about 10nm. The tungsten oxide layer as the second dielectric layer has a thickness of about 100nm to 400nm, and may be formed on the metal tungsten film by magnetron sputtering.
And when the first optical structure layer is seen from one side, a colorful film structure with rich and gorgeous colors can be obtained. And when viewed from one side of the glass, the corresponding reflection color of the glass also presents rich and gorgeous colors, and the color is quite different from the color viewed from the direction of the film. And the colorful film structure is penetrated, so that the transmission structure color can be obtained, the transmission structure color also presents rich and gorgeous colors, and the reflection color and the transmission rate of the transmission color of the colorful film structure are determined by the thicknesses of the metal tungsten layer and the tungsten oxide layer.
Example 4: the embodiment discloses an automobile, wherein a window glass of the automobile is conformally covered with a reflection/transmission dual-mode colorful film structure, and the reflection/transmission dual-mode colorful film structure comprises a working electrode, an electrolyte layer and a counter electrode, wherein the electrolyte layer is arranged between the working electrode and the counter electrode.
The working electrode comprises a first optical structure layer, a second optical structure layer and a dielectric layer, wherein the first optical structure layer is a tungsten film with the thickness of about 5nm, the second optical structure layer is a silver film with the thickness of about 10nm, and the dielectric layer is a titanium oxide layer with the thickness of 100 nm-400 nm. The window glass of the automobile is also provided with a transparent conductive layer formed by nano silver wires, and the first or the second optical structure layer is formed on the transparent conductive layer.
The glass of the present embodiment will appear different colors when viewed from both sides, and additionally has a transmissive structural color.
And then the working electrode is matched with a pair of electrodes (such as NiO pair electrodes), liCl/PVA gel electrolyte is arranged between the working electrode and the pair of electrodes, then a lead is led out to be connected with an automobile power supply, voltage is loaded on the colorful film structure, and the color of the colorful film structure can be further modulated by adjusting the voltage range, so that the colorful film structure can be changed among a plurality of colors, particularly the color change of two sides of the window glass is not completely the same.
Example 5: the embodiment discloses a sunbonnet, wherein a local area of a cap body of the sunbonnet is made of a PET (polyethylene terephthalate) film, a colorful pattern with a colorful film structure is formed on the PET film, the colorful film structure comprises 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 and the counter electrode are also electrically connected with an organic photovoltaic cell arranged on the sun hat through a voltage control module.
The working electrode comprises a tungsten film with the thickness of about 500nm, wherein the tungsten film is formed on a PET (polyethylene terephthalate) film in a magnetron sputtering mode, and each pixel point (corresponding to the colorful pattern) of the tungsten film is oxidized in a laser direct writing mode to form tungsten oxide layers with different thicknesses as dielectric layers. The dielectric layer has a thickness of about 0-300nm. The process conditions of the laser direct writing include: the tungsten film can be placed on a workbench controlled by an X-Y computer, the moving speed of the tungsten film is 15mm/s, the continuous laser power is 100W, the size of a rectangular laser spot is 1.4mm multiplied by 1.4mm, the defocusing amount is 5mm, the overlap ratio of the laser spot is 40%, and the acting time of the laser is 0-5s. The counter electrode may be a NiO counter electrode layer. LiBO is packaged between working electrode and counter electrode 2 +Li 2 SO 4 Solid electrolyte, and then lead out. The colorful thin film structure is loaded with voltage through the organic photovoltaic cell, and the color of the colorful thin film structure can be further modulated. When the voltage is-2.5V- +2.5V, the red area of the working electrode is converted among red, orange and yellow in real time; the blue area will shift between blue, violet and red in real time.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (28)
1. A device comprising a multicolored film structure, said device being selected from the group consisting of consumer electronics, household appliances, buildings, vehicles, shoes, hats, and apparel, and said device comprising a substrate having a multicolored film structure attached to or integrally formed thereon, wherein: the colorful thin film structure comprises at least one dielectric layer, wherein the material of the dielectric layer is selected from inorganic electrochromic materials and/or organic electrochromic materials, each dielectric layer is matched with a first reflecting surface and a second reflecting surface to form an optical cavity, the first reflecting surface is the first surface of the dielectric layer, the second reflecting surface is the combined interface of the second surface of the dielectric layer and a second optical structure layer, and the first surface and the second surface are arranged oppositely;
when the incident light enters the optical cavity, the phase shift of the reflected light formed on the first reflecting surface and the reflected light formed on the second reflecting surface
d is the thickness of the dielectric layer,
is the refractive index of the dielectric layer, lambda is the wavelength of the incident light,
the refraction angle of the incident light when the incident light passes through the first reflecting surface is shown;
a reflection coefficient of the first reflection surface
Wherein
Is the angle of incidence of the incident light,
is the refractive index of the medium material on the first surface of the medium layer;
a reflection coefficient of the second reflecting surface
Wherein
Is the refraction angle of the incident light when passing through the second reflective surface,
is the refractive index of the medium material on the second surface of the medium layer;
the reflectance of the multicolor film structure is expressed as:
the reflectance is expressed as:
the second optical structure layer adopts a metal reflecting layer.
2. The apparatus of claim 1, wherein: the thickness of the metal reflecting layer is more than 20nm.
3. The apparatus of claim 2, wherein: the thickness of the metal reflecting layer is 50-3000 nm.
4. The apparatus of claim 1, wherein: the thickness of the dielectric layer is greater than 0 and less than or equal to 2000nm.
5. The apparatus of claim 4, wherein: the thickness of the dielectric layer is 100-500 nm.
6. The apparatus of claim 1, wherein: the inorganic electrochromic material comprises oxides of Co, rh, ir, ni, cr, mn, fe, ti, V, nb, ta, mo or W.
7. The apparatus of claim 1, wherein: the organic electrochromic material comprises an organic polymer, an organic small molecule, a metal supramolecular polymer or a metal organic compound.
8. The apparatus of claim 7, wherein: the organic electrochromic material is selected from methyl viologen, polyaniline, polythiophene, polypyrrole, prussian blue, metal organic chelate or polydiacetylene.
9. The apparatus of claim 1, wherein: the first reflecting surface is a joint surface of the first surface of the dielectric layer and the first optical structure layer.
10. The apparatus of claim 9, wherein: transmission coefficient of the first optical structure layer
Transmission coefficient of the second optical structure layer
The transmission coefficient of the multicolor film structure is expressed as:
the transmittance is expressed as:
11. the apparatus of claim 9 or 10, wherein: the first optical structure layer is a metal material layer or is composed of gas.
12. The apparatus of claim 11, wherein: the first optical structure layer adopts a metal material layer with the thickness of more than 0 and less than or equal to 20nm.
13. The apparatus of claim 1, wherein: the material of the metal reflecting layer is selected from any one or combination of more of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium and palladium.
14. The apparatus of claim 1, wherein: and an optimized dielectric layer is distributed between the dielectric layer and the first optical structure layer or the second optical structure layer.
15. The apparatus of claim 14, wherein: the material of the optimized dielectric layer is selected from WO 3 、NiO、TiO 2 、Nb 2 O 5 、Fe 2 O 3 、V 2 O 5 、Co 2 O 3 、Y 2 O 3 、Cr 2 O 3 、MoO 3 、Al 2 O 3 、SiO 2 、MgO、ZnO、MnO 2 、CaO、ZrO 2 、Ta 2 O 5 、Y 3 Al 5 O 12 、Er 2 O 3 、ZnS、MgF 2 And silicon nitride.
16. The apparatus of claim 14, wherein: the thickness of the optimized dielectric layer is greater than 0 and less than or equal to 2000nm.
17. The apparatus of claim 16, wherein: the thickness of the optimized dielectric layer is more than 0 and less than or equal to 300nm.
18. The apparatus of claim 17, wherein: the thickness of the optimized dielectric layer is 1-100 nm.
19. The apparatus of claim 1, wherein: the colorful film structure comprises a working electrode, a counter electrode and electrolyte, wherein the working electrode comprises the dielectric layer, the counter electrode comprises a transparent conductive electrode and an ion storage layer, the electrolyte is distributed between the working electrode and the counter electrode, and the ion storage layer is distributed between the transparent conductive electrode and the dielectric layer.
20. The apparatus of claim 19, wherein: the electrolyte is selected from a liquid electrolyte, a gel electrolyte or a solid electrolyte.
21. The apparatus of claim 20, wherein: the electrolyte adopts a solid electrolyte, and the colorful thin film structure is of an all-solid-state structure.
22. The apparatus of claim 1, wherein: the device is a consumer electronic product or a household appliance, and the multicolor film structure is connected and/or integrally formed on a shell and/or a display screen of the device.
23. The apparatus of claim 22, wherein: the consumer electronic product comprises a mobile phone, a bracelet, a tablet computer or a notebook computer.
24. The apparatus of claim 22, wherein: the household appliances comprise a television, a refrigerator, an electric fan or an air conditioner.
25. The apparatus of claim 1, wherein: the device is a building, and the colorful film structure is connected and/or integrally formed on any one of an inner wall, an outer wall and a window of the building.
26. The apparatus of claim 1, wherein: the device is a vehicle having the multicolored film structure attached to and/or integrally formed on any of an exterior housing, interior wall, window of the vehicle.
27. The apparatus of claim 1, wherein: the device is a shoe, a hat or a piece of apparel, and the colorful film structure is connected and/or integrally formed on the surface of the device.
28. The apparatus of claim 1, wherein: the colorful film structure is a set image-text structure.
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| PCT/CN2019/103280 WO2020173065A1 (en) | 2019-02-27 | 2019-08-29 | Optical film structure, and manufacturing method therefor and use thereof |
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