CN112180646A

CN112180646A - Patterned multi-color film, its production method and application

Info

Publication number: CN112180646A
Application number: CN201910594027.0A
Authority: CN
Inventors: 赵志刚; 王振; 丛杉; 陈健
Original assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Current assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Priority date: 2019-07-03
Filing date: 2019-07-03
Publication date: 2021-01-05
Anticipated expiration: 2039-07-03
Also published as: CN112180646B

Abstract

The invention discloses a patterned colorful film and a manufacturing method thereof. The patterned multicolor film comprises at least two different medium layers formed by in-situ oxidation of at least two pattern areas of a metal layer. Each dielectric layer may be formed by a laser direct writing technique or the like, and the colors exhibited by the different dielectric layers are different. The invention also discloses a colorful electrochromic structure based on the patterned colorful film. Compared with the prior art, the patterned colorful film provided by the invention has the characteristics of high precision, high pixel and the like, can realize fine colorful patterns, can be applied to electrochromic devices, and can realize the fusion of optical structure colors and electrochromism by adjusting the voltage, thereby presenting rich color modes.

Description

Patterned multi-color film, its production method and application

Technical Field

The invention relates to a colorful film, in particular to a high-precision patterned colorful film, a manufacturing method thereof and application thereof in the field of colorful electrochromism, and belongs to the technical field of photoelectricity.

Background

Color coatings, thin films, and the like based on metal oxides have been applied in various fields of displays, decorations, and the like. At present, the color coatings, films and the like are mainly manufactured by modes of magnetron sputtering, electron beam evaporation, thermal evaporation, electrochemical deposition and the like. In the manufacturing method, the metal oxide is deposited for multiple times through a masking method, and the metal oxide layers with different thicknesses can be prepared in different areas to realize colorful patterns. However, these methods produce films with poor precision and, due to edge effects, large uncontrolled mottling occurs near the edge of the mask. In addition, in each pixel area of such color coatings and films, the color presented is often single and unchangeable, which makes the color effect presented by the whole color coating and film monotonous and stiff.

Disclosure of Invention

The invention mainly aims to provide a patterned colorful film, a manufacturing method and application thereof, so as to overcome the defects in the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a patterned colorful film, which comprises:

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

each medium 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 medium layer, the second reflecting surface is the combined interface of the second surface of the medium 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.

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

The embodiment of the invention also provides a method for manufacturing the patterned colorful film, which comprises the following steps:

providing a metal layer;

and oxidizing at least two pattern areas of the metal layer in situ to form at least two dielectric layers capable of presenting different colors in the at least two pattern areas, wherein each dielectric layer is matched with a first reflecting surface and a second reflecting surface to form an optical cavity, and further the patterned colorful film is prepared.

Further, the manufacturing method further comprises the following steps: and in an oxygen-containing atmosphere, at least two areas of the at least one metal layer are oxidized in situ by adopting a laser direct writing mode to form a dielectric layer.

The embodiment of the invention also provides a colorful electrochromic structure which comprises a working electrode, an electrolyte and a counter electrode, wherein the working electrode comprises the patterned colorful film.

Compared with the prior art, the metal oxide layers with different thicknesses and/or materials are directly formed on the metal layer through in-situ etching (oxidation) by the laser direct writing technology to form the patterned colorful film with the metal-medium structure, the process is simple, the precision is high, the pixel of the pattern can reach the submicron level, and the patterned colorful film can present rich and variable optical structural colors by adjusting the thicknesses, materials and the like of other optical structure layers in the patterned colorful film.

Drawings

FIG. 1 is a schematic diagram of a process for forming a high-precision patterned multi-color film according to an exemplary embodiment of the present invention.

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 description of the embodiments or 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 for those skilled in the art, other drawings can be obtained according to 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 "at least one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.

One aspect of the embodiments of the present invention provides a method for manufacturing a patterned multicolor film, including:

providing a metal layer;

In some embodiments, the method of making comprises: and in an oxygen-containing atmosphere, at least two regions of the at least one metal layer are subjected to in-situ oxidation by adopting a laser direct writing mode to form at least two different dielectric layers.

The oxygen-containing atmosphere may be an oxygen atmosphere, or may be a mixed atmosphere of oxygen and another inert gas (e.g., nitrogen, an inert gas, etc.), and for example, an air atmosphere may be preferable.

In some embodiments, the manufacturing method may further include: in the laser direct writing process, the thicknesses and/or materials of different dielectric layers are different at least by regulating and controlling the laser power and/or the laser irradiation time.

Referring to fig. 1, in an exemplary embodiment of the present invention, a method for manufacturing a patterned multi-color film may include the following steps:

providing a metal layer 12 disposed on a substrate 11, wherein the metal layer can be formed on the substrate surface by physical/chemical deposition (such as magnetron sputtering, electroplating, etc.), or can be formed by transferring a self-supporting metal film onto the substrate surface; and

providing a laser direct writing device, and enabling a laser beam emitted by a laser head 2 of the laser direct writing device to irradiate a preset area (also called as a pixel area 13) on the metal layer in an oxygen-containing atmosphere, wherein the laser head and the metal layer can move relatively, and the motion 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 medium layer.

Wherein, the laser spot formed on the metal layer by the laser beam can be controlled at the micron or submicron level. And the shape of the laser spot may be arbitrary, such as circular, rectangular, etc.

The power of the laser, the irradiation time, the relative movement speed of the laser head and the metal layer, etc. can be properly adjusted according to the requirements of practical application. For example, the respective process conditions may be controlled within the following ranges: 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, the size of a rectangular laser spot is 0.5mm multiplied by 1mm-4mm multiplied by 5mm, the laser action time is 1s-5s, the defocusing amount is 0.01mm-10mm, and the overlapping rate of the laser spots is 10% -50%.

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

Another aspect of the embodiments of the present invention provides a patterned multicolor film including:

d is the thickness of the dielectric layer,

In the foregoing embodiment of the present invention, during the laser direct writing process, due to the photo-thermal-chemical effect of the laser, each pattern region of the metal layer is oxidized to generate metal oxide thin films with different types and different thicknesses, and different color effects can be exhibited by different dielectric layers through the color of the metal oxide itself, etc.

Further, the aforementioned graphic regions may be characters, continuous or discontinuous patterns, and the like, and are not limited thereto.

Furthermore, the dielectric layer may be a thin film structure composed of one metal oxide, or a thin film structure formed by compounding a plurality of metal oxides.

In some embodiments of the present invention, in the laser direct writing process, the degree of in-situ oxidation of different pattern areas of the metal layer is different by adjusting the relative movement speed of the laser spot and the metal layer, so that the thicknesses and/or materials of different dielectric layers are different.

Furthermore, in the laser direct writing process, the size of the laser spot can be adjusted, for example, can be controlled to be in a submicron level, so that the pattern pixels formed on the metal layer can reach the submicron level, the precision is high, and the occurrence of mottle can be avoided.

Moreover, the laser direct writing method has the advantage that the method has almost no limit on the shape of the metal layer, for example, the metal layer can be a continuous plane, a curved surface or other irregular surfaces. This makes the final patterned multicolor film meet the application requirements of various scenes.

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

In some embodiments, the color exhibited by two different optical cavities based on two different layers of media may also be the same.

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

In some embodiments, the second optical structure layer is a metal material layer with a thickness of 20nm or more, and preferably, the metal reflective layer has a thickness of 50 to 3000 nm.

Further, in the patterned multicolor film provided by the foregoing embodiment of the invention, the reflected light formed by the incident light on the first reflecting surface interferes and overlaps with the reflected light formed by the incident light transmitted through the dielectric layer on the second reflecting surface.

Further, in some embodiments, 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; the reflection coefficient of the optical film structure mainly composed of the dielectric layer and the second optical structure layer is expressed as follows:

the reflectance is expressed as:

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

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

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

Further, reflected light formed at the first surface by incident light incident from the first optical structure layer and reflected light formed at the second surface by incident light transmitted through the dielectric layer are superimposed by interference. 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.

Further, the first optical structure layer has a transmittance

Wherein

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

Wherein

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

the transmittance is expressed as:

further, the transmittance and transmittance of the optical film structure are also suitable for the case that the incident light enters the optical cavity from the second optical structure layer.

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

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

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

In some embodiments, the optical film structure consisting essentially of the first optical structure layer, the dielectric layer, and the second optical structure layer has an optical transmissive mode of operation, an optical reflective mode of operation, or an optical transmissive and reflective mode of operation; wherein in the optically reflective mode of operation the optical film structure has a two-sided asymmetric structural color and in the optically transmissive mode of operation the optical film structure has a transparent structural color.

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

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 optical film structure.

In some embodiments, a thin layer of metal may also be added on the dielectric layer to optimize the color of the patterned multicolored film. Specifically, for some materials or patterned multicolor films with appropriate thickness, the addition of metal materials with appropriate thickness can improve the intensity difference of the reflectivity curve, thereby improving the saturation of the color. The material of the thin metal layer may be selected from Ag, Al, Cu, Ni, and the like, but is not limited thereto. The thickness of the metal layer may be preferably 0 to 30nm, and particularly preferably 1 to 10 nm.

In some embodiments, a semiconductor material may be added to the dielectric layer to optimize the color of the patterned multicolored film. For some specific materials or patterned colorful films with proper thicknesses, the intensity difference of the reflectivity curve can be improved by adding semiconductor materials with proper thicknesses, and further, the saturation of colors is improved. Wherein the semiconductor may be selected from Al₂O₃、SiO₂、ZnS、MgF₂Silicon nitride, etc., but not limited thereto. The thickness of the semiconductor can be preferably 0 to 300nm, and particularly preferably 1 to 100 nm.

Further, an optimization dielectric 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 dielectric layer, so as to optimize the color of the patterned multicolor film.

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

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

Further, the material of the optimized dielectric layer includes but is not limited to WO₃、NiO、TiO₂、Nb₂O₅、Fe₂O₃、V₂O₅、Co₂O₃、Y₂O₃、Cr₂O₃、MoO₃、Al₂O₃、SiO₂、MgO、ZnO、MnO₂、CaO、ZrO₂、Ta₂O₅、Y₃Al₅O₁₂、Er₂O₃、ZnS、MgF₂、SiN_x(nitridingSilicon), and the like, but is not limited thereto.

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

Wherein the substrate is transparent or translucent.

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

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

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

Another aspect of an embodiment of the present invention provides a multicolor electrochromic structure comprising a working electrode, an electrolyte, and a counter electrode, wherein the working electrode comprises any one of the patterned multicolor films described above.

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

In some embodiments, the electrolyte may comprise one or more compounds, for example containing H⁺、Li⁺、Al³ ⁺、Na⁺、K⁺、Rb⁺Or Cs⁺The compound of (1). In one example, the electrolyte layer may include a lithium salt compound, such as LiClO₄、LiBF₄、LiAsF₆Or LiPF₆. 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 electrolysis is performedThe electrolyte may be a liquid electrolyte, such as aqueous LiCl or AlCl₃、HCl、H₂SO₄Aqueous solutions, and the like.

In some embodiments, the electrolyte may be a mixed electrolyte, such as aqueous LiCl, AlCl₃、HCl、MgCl₂、ZnCl₂And mixed electrolytes composed of two or more salts among the salts. When the electrolyte containing two or more ions is used, the electrochromic structure of the foregoing embodiment of the present invention can be made more rich in color change and higher in color saturation than when the electrolyte containing only a single ion is used.

In some embodiments, the electrolyte may further include a carbonate compound-based electrolyte. The carbonate-based compound has a high dielectric constant, and can increase ionic conductivity provided by a lithium salt. As the carbonate 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 used₄、Na(ClO₄)₃And propylene carbonate electrolyte, and the like.

In some embodiments, the electrolyte can be a gel electrolyte, such as PMMA-PEG-LiClO₄，PVDF-PC-LiPF₆And the like, but are not limited thereto.

In some preferred embodiments, when an inorganic solid electrolyte is used as the electrolyte, the electrolyte may include LiPON or Ta₂O₅. 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 therein₂O₅The electrolyte to which components such as B, S and W are added may be LiBO, for example₂+Li₂SO₄、LiAlF₄、LiNbO₃、Li₂O-B₂O₃And the like.

In some preferred embodiments, the electrolyte is an all-solid electrolyte, which can be combined to form an all-solid multicolor electrochromic structure by using patterned multicolor films, counter electrodes and the like in a solid state.

In some embodiments, the metal material layer as the first optical structure layer may also serve as a current collector of the dielectric layer. Therefore, the metal material 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, an ion storage layer is further disposed between the counter electrode and the dielectric layer, and the material of the ion storage layer may be selected from, but not limited to, NiO and Fe₂O₃、TiO₂And the like. The ion storage layer is in contact with the electrolyte.

In some embodiments, the counter electrode may be a transparent conductive electrode, which may be formed by including a material having characteristics of high light transmittance, low sheet resistance, and the like, for example, by including any one 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 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%.

Another aspect of the embodiments of the present invention further provides a method for controlling the multicolor electrochromic structure, including:

connecting the working electrode, the counter electrode and a power supply to form a working circuit;

and adjusting the potential difference between the working electrode and the counter electrode to change the refractive index of at least the metal oxide serving as the electrochromic material in the dielectric layer, thereby regulating and controlling the color of the multicolor electrochromic structure.

The operating voltage of the multi-color electrochromic structure may be adjusted according to actual conditions, and may be, for example, from-4V to 4V, but is not limited thereto.

In the foregoing embodiment of the present invention, the multicolor electrochromic structure fuses structural colors of the patterned multicolor thin film and electrochromism, so as to enrich color modulation of the electrochromic structure and realize dynamic control of multiple colors. Specifically, the thickness, material, and the like of the first optical structure layer, the second optical structure layer, the dielectric layer, and the like in the patterned multicolor film can be adjusted to obtain a colorful structural color. Meanwhile, the patterned colorful film is used as a working electrode, and voltage is applied to change the refractive index of the metal oxide serving as the electrochromic material in the dielectric layer (which can be caused by the insertion or extraction of ions in the electrolyte layer into or from the electrochromic material), so that the optical parameters of the dielectric layer are changed, the color is changed, and finally, a plurality of electrochromic working modes (such as the reflection/transmission dual mode) and gorgeous and rich color modulation can be realized.

The embodiment of the invention also provides application of the patterned multicolor film or the multicolor electrochromic structure, such as application in the fields of electronic equipment, optical equipment, buildings, automobiles, artistic decoration, optical filters, anti-counterfeiting, solar cells, displays, LED screens, communication, sensing, illumination and the like.

Another aspect of the embodiments of the present invention also provides a device including the multicolor electrochromic structure. Furthermore, the device also comprises a power supply, and the power supply can be electrically connected with the colorful electrochromic structure to form a working loop.

In some embodiments, the device may also include additional packaging structures, control modules, power modules, etc. that may be incorporated with the multicolored electrochromic structure in a conventional manner.

The devices include, but are not limited to, mechanical devices, optoelectronic devices, electronic devices, buildings, vehicles, outdoor billboards, and the like.

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 this embodiment provides a method for making a high precision patterned multicolor film.

Referring to fig. 1, the high-precision patterned multicolor film comprises a substrate and a metal layer arranged 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 each dielectric layer can be 10nm to 300nm, and each dielectric layer is formed by metal oxide generated in situ. The substrate may be a PET plastic plate. The metal layer may be a tungsten film deposited on the substrate and may have a thickness of about 500 nm.

Specifically, a method for manufacturing the patterned multicolor film can comprise the following steps: a layer of tungsten film is firstly sputtered by magnetron sputtering on a clean PET plastic plate with the size of 3cm by 3cm, and the thickness of the tungsten film is preferably selected to be about 500 nm. Then, a laser direct writing method is used for sequentially carrying out laser oxidation on each pixel point (namely a graph area) on the tungsten film to form tungsten oxide layers with different required thicknesses. 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 200W, the size of a laser rectangular light spot is 1.4mm multiplied by 1.4mm, the defocusing amount is 5mm, the overlap ratio of the light spot is 40%, when the laser action time is 6.5s, the thickness of the obtained medium layer is 163nm, the area shows pink, when the laser action time is 8s, the thickness of the obtained medium layer is 200nm, and the area shows blue.

Of course, the tungsten film can be prepared by electron beam evaporation, thermal evaporation, and the like known in the art.

Using the colored film prepared as described above as an electrochromic layer, and additionally preparing a pair of electrodes, e.g. NiO pairA pole layer encapsulating LiClO therebetween₄And leading out a lead after the PC electrolyte is used, thus the multicolor electrochromic device can be prepared. The color of the multicolor electrochromic device can be further modulated by applying voltage to the multicolor electrochromic device. When a power supply with the voltage of-2.5V- +2.5V is switched on, 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.

Example 2: the embodiment provides a method for manufacturing a high-precision patterned colorful film.

Referring to fig. 1, the high-precision patterned multicolor film comprises a substrate and a metal layer arranged 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 each dielectric layer can be 10nm to 300nm, and each dielectric layer is formed by metal oxide generated in situ. The substrate may be a PET plastic plate. The metal layer may be a titanium film deposited on the substrate and may have a thickness of about 500 nm.

Specifically, a method for manufacturing the patterned multicolor film can comprise the following steps: a layer of titanium film is firstly sputtered by magnetron sputtering on a clean PET plastic plate with the size of 3cm by 3cm, and the thickness of the titanium film is preferably selected to be about 500 nm. Then, a laser direct writing method is used for sequentially carrying out laser oxidation on all pixel points (namely graph areas) on the titanium film to form titanium oxide layers with different required thicknesses. Wherein the moving speed of the workbench controlled by the X-Y computer is 15mm/s, the continuous laser power is 300W, the size of a laser rectangular spot is 1.4mm multiplied by 1.4mm, the defocusing amount is 5mm, the overlapping rate of the spot is 40%, and the acting time of the laser is 3-10 s.

Of course, the titanium film can be prepared by electron beam evaporation, thermal evaporation, etc. in a manner known in the art.

Example 3: the embodiment provides a method for manufacturing a high-precision patterned colorful film.

Referring to fig. 1, the high-precision patterned multicolor film comprises a substrate and a metal layer arranged on the substrate, wherein a plurality of continuous or interval distributed dielectric layers formed by laser direct writing are distributed on the metal layer, the thickness of each dielectric layer is 0-20nm, and each dielectric layer is formed by metal oxide generated in situ. The substrate may be a PET plastic plate. The metal layer may be a copper film deposited on the substrate and may have a thickness of about 0-20 nm.

Specifically, a method for manufacturing the patterned multicolor film can comprise the following steps: a clean PET plastic plate with the size of 3cm by 3cm is sputtered by magnetron sputtering with a copper film, and the thickness of the copper film is preferably selected to be about 15 nm. And then, sequentially carrying out laser oxidation on each pixel point (namely a pattern area) on the copper film by using a laser direct writing method to form copper oxide layers with different required thicknesses. Wherein the moving speed of the workbench controlled by the X-Y computer is 15mm/s, the continuous laser power is 100W, the size of a laser rectangular spot is 1.4mm multiplied by 1.4mm, the defocusing amount is 5mm, the overlapping rate of the spot is 40%, and the acting time of the laser is 0-5 s.

Example 4: the embodiment provides a method for manufacturing a high-precision patterned colorful film.

Specifically, a method for manufacturing the patterned multicolor film can comprise the following steps: a layer of tungsten film is firstly sputtered by magnetron sputtering on a clean PET plastic plate with the size of 3cm by 3cm, and the thickness of the tungsten film is preferably selected to be about 500 nm. Then, a laser direct writing method is used for sequentially carrying out laser oxidation on each pixel point (namely a graph area) on the tungsten film to form tungsten oxide layers with different required thicknesses. Wherein, the moving speed of a workbench controlled by an X-Y computer is 15mm/s, the continuous laser power is 200W, the size of a laser rectangular spot is 1.4mm multiplied by 1.4mm, the defocusing amount is 5mm, the overlapping rate of the spots is 40%, when the laser action time is 6s, the thickness of the obtained medium layer is 150nm, the area is yellow, when the laser action time is 10s, the thickness of the obtained medium layer is about 250nm, and the area is green.

The prepared color film is used as an electrochromic layer, a pair of electrodes, such as NiO counter electrode layers, are additionally prepared, PMMA-PEG-LiPF6 gel electrolyte is packaged between the electrodes, and then a lead is led out, so that the high-precision patterned multi-color electrochromic device can be prepared. By applying voltage to the high-precision patterned multi-color electrochromic device, the color of the device can be further modulated. When a power supply with the voltage of-2.5V- +2.5V is switched on, the yellow area of the working electrode is converted among yellow, green and blue in real time; the green color area will shift between green, cyan, blue in real time.

In addition, the inventors of the present application have also tested the corresponding materials in the foregoing examples with other materials and process conditions listed in the present specification, and found that the obtained patterned multicolor films all have similar advantages.

The patterned colorful film provided by the embodiment of the invention has the characteristics of simple manufacturing process, good controllability, high precision, high pixel and the like, can realize fine colorful patterns, can be applied to electrochromic devices, and can realize the modulation of the color mode of the electrochromic device only by adjusting voltage and the like.

It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. A patterned multicolor film, comprising:

d is the thickness of the dielectric layer,

2. The patterned multicolor film of claim 1, wherein: at least two pattern areas of the metal layer are oxidized in situ in a laser direct writing mode to form a dielectric layer.

3. The patterned multicolor film of claim 1, wherein: wherein the two different dielectric layers are different in thickness and/or material; and/or, two different optical cavities based on two different dielectric layers therein exhibit different colors; and/or wherein two different dielectric layers are spaced apart from each other or abut each other.

4. The patterned multicolor film of claim 1, wherein: the second optical structure layer is a metal material layer with the thickness of more than 20nm, and preferably, the thickness of the metal reflecting layer is 50-3000 nm; or, the second optical structure layer adopts a metal material layer with the thickness more than 0 and less than 20 nm.

5. The patterned multicolor film of claim 1, wherein: 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

The reflection coefficient of the second reflecting surface

Wherein

the reflectance is expressed as:

6. the patterned multicolor film of claim 1, wherein: the material of the metal layer comprises transition metal, and the transition metal comprises any one or combination of more of W, Ni, Ti, Nb, Fe, Co and Mo elements; and/or the thickness of the dielectric layer is 0-3000 nm, preferably 100-500 nm.

7. The patterned multicolor film of claim 5, wherein: the first reflecting surface is the 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

8. The patterned multicolor film of claim 7, wherein: transmission coefficient of the first optical structure layer

Wherein

Wherein

Is the folding of incident light when passing through the second surfaceAnd the transmission coefficient of an optical film structure mainly composed of the first optical structure layer, the dielectric layer and the second optical structure layer is expressed as follows:

the transmittance is expressed as:

9. the patterned multicolor film of claim 7, wherein: the first optical structure layer is a metal material layer or consists of gas; preferably, the thickness of the first optical structure layer is 0-20 nm.

10. The patterned multicolor film of claim 4 or 9, wherein: the material of the metal material layer comprises any one or combination of more of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium and palladium.

11. The patterned multicolor film of claim 7, 8 or 9, wherein: the optical 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; wherein in the optically reflective mode of operation the optical film structure has a two-sided asymmetric structural color and in the optically transmissive mode of operation the optical film structure has a transparent structural color.

12. The patterned multicolor film of claim 7, 8 or 9, wherein: the first optical structure layer or the second optical structure layer is also combined with the substrate; preferably, the substrate is transparent or translucent; more preferably, the material of the substrate comprises any one or a combination of more of metal, glass, organic glass, PET, PES, PEN, PC, PMMA and PDMS; more preferably, the first optical structure layer is integrally provided with the substrate.

13. A multi-color electrochromic structure comprising a working electrode, an electrolyte, and a counter electrode, characterized in that: the working electrode comprising the patterned multi-color film of any one of claims 1-12.

14. A multicolored electrochromic structure as recited in claim 13, wherein: the electrolyte comprises a liquid electrolyte, a gel electrolyte or a solid electrolyte; and/or, the dielectric layer is in contact with an electrolyte; and/or an ion storage layer is also arranged between the counter electrode and the dielectric layer.

15. The method of making a patterned multicolor film of any of claims 1-12, comprising:

providing a metal layer;

16. The method of manufacturing according to claim 15, comprising: and in an oxygen-containing atmosphere, at least two regions of the at least one metal layer are subjected to in-situ oxidation by adopting a laser direct writing mode to form at least two different dielectric layers.

17. The method of manufacturing according to claim 16, further comprising: in the laser direct writing process, the thicknesses and/or materials of different dielectric layers are different at least by regulating and controlling the laser power and/or the laser irradiation time.