CN115793342B - All-solid-state multichannel dynamic adjustable spectrum filter device and preparation method thereof - Google Patents
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Abstract
The invention discloses an all-solid-state multichannel dynamic adjustable spectrum filter device, which comprises a basal layer, a lower conductive layer, an electrochromic layer, a structural color layer, a solid electrolyte layer, an ion storage layer and an upper conductive layer which are sequentially arranged from bottom to top, wherein the structural color layer is of a periodic micro-nano structure or a multi-layer film spectrum filter structure.
Description
Technical Field
The invention belongs to the field of micro-nano electronics, and particularly relates to an all-solid-state multichannel dynamic adjustable spectrum filter device and a preparation method thereof.
Background
The spectrum imaging technology is a novel imaging technology formed by perfectly combining the spectrum analysis technology and the optical imaging technology, can realize the qualitative and quantitative analysis function of the spectrum analysis technology, can acquire more accurate and visual target object information through the optical imaging technology, provides more accurate technical means for analysis, detection, monitoring, measurement and other applications, and has been widely applied to the fields of deep space exploration, remote sensing and telemetry, military national defense, biomedicine and the like.
Spectral filtering is one of the core functions of spectral imaging, and the filter element that implements this function is a critical component in a spectral imaging system. Currently, the most commonly used spectral filtering elements are grating/prism type, filtering wheel type, liquid crystal tunable (Liquid Crystal Tunable Filter, LCTF) and Acousto-optic tunable (Acousto-Optic Tunable Filter, AOTF) type, and micro electro mechanical system (Micro Electro Mechanical Systems, MEMS) tunable filtering type. However, the imaging system based on the grating/prism type and the filtering wheel type beam splitting element has large volume, heavy weight and low working frequency, and is difficult to integrate, lighten and miniaturize; although the hyperspectral imaging system based on LCTF and AOTF has wide-amplitude modulation and high-resolution filtering capability, the working spectrum is limited due to material limitation, and the influence of environment is remarkable; the MEMS adjustable spectrum filter chip realizes the leap of the optical element from static to dynamic, but vibration, impact and the like in the use environment have great influence on the working stability due to the existence of micro-mechanical movable components.
The chameleon, the chameleon bird and the like in the natural world generate inspiration, scientists propose the concept of 'structural color', and the chameleon color is generated by physical phenomena such as scattering, diffraction and the like of a micro-nano structure, and has the advantages of stable physical and chemical properties, easiness in integration with a photoelectric device, environmental protection and the like. The micro-nano structure array with the sub-wavelength scale has strong light field control capability and presents unique advantages in the aspect of spectral filtering. With the rapid development of micro-nano processing technology and electromagnetic wave theory numerical algorithm, the micro-nano structure filter based on different optical principles and different structural forms is also sequentially proposed by making various sub-wavelength structures into an important spectrum filtering implementation mode, and the micro-nano structure filter has excellent spectrum customization capability, such as a silicon nanowire, a photonic crystal, a metal grating, a multilayer film structure and the like. The optical function filter chip based on the micro-nano structure has the advantages of high integration level, light weight, stable performance, high resolution, strong customization capability, and has remarkable application potential in the aspects of photoelectric detection, spectral imaging and the like. However, for structural color films prepared under fixed conditions, they can only exhibit one color state and cannot be dynamically tunable.
The electrochromic device has the advantages of strong adjustability, short switching time, high contrast, low driving energy and the like, and is generally composed of five continuous layers, namely an upper conductive layer, a lower conductive layer, an electrochromic layer, an ion conductor layer and an ion storage layer. The electrochromic layer is mainly composed of electrochromic materials, electrons and ions are injected and extracted from the electrochromic materials under the action of an external electric field, so that chemical components and valence states of the materials are changed, and the optical characteristics (refractive index, extinction coefficient and the like) of the materials are changed stably and reversibly, and the phenomena of changing the color and transparency of the materials are expressed in appearance. At present, electrochromic materials are mainly divided into inorganic electrochromic materials and organic electrochromic materials, wherein the inorganic electrochromic materials are stable in structure, are not influenced by ultraviolet light basically, are good in cycling stability and high in response speed, and have the defects of single color change, small light modulation range and the like; the organic electrochromic material has more abundant color change, can be flexibly switched, and has relatively simple preparation process, but poor environment and electrochemical stability. Therefore, common electrochromic devices are also difficult to use in the tunable spectral filtering field.
In view of the foregoing, it is desirable to provide a spectral filter device that meets the needs of spectral imaging systems.
Disclosure of Invention
The invention aims to provide an all-solid-state multichannel dynamic adjustable spectrum filter device, which is constructed by combining structural colors with electrochromic devices, integrates the characteristics of the micro-nano structure on the spectrum which can be customized randomly and the performance advantage of adjustable photoelectric coefficients of electrochromic materials, applies different voltage external excitation to the filter device, changes material properties, external environment and the like, realizes the dynamic adjustment of the spectrum of the filter device, achieves the effects of real-time dynamic adjustment and control of the spectrum and displays colorful display.
In order to achieve the above purpose, the invention adopts the following technical scheme: the utility model provides an all-solid-state multichannel developments adjustable spectrum filter, includes stratum basale, lower floor conducting layer, electrochromic layer, structure colour layer, solid electrolyte layer, ion storage layer and upper conductive layer that from the bottom up set gradually, the structure colour layer is periodic micro-nano structure or multilayer film spectrum filter structure.
The filtering structure of the present invention includes: a base layer, a lower conductive layer, an electrochromic layer, a structural color layer, a solid electrolyte layer, an ion storage layer and an upper conductive layer. According to interaction mechanisms of light and substances such as a surface plasma resonance effect, an FP resonance effect, a Fano resonance effect and the like, filtering effects of different wave bands can be obtained by adjusting size parameters, shapes, film layer configuration and the like of the generated structural color micro-nano structure; the change of dielectric properties of the surrounding environment of the structural color layer can cause the change of the resonance frequency of the micro-nano structure, so that the resonance wavelength position is correspondingly changed, and the working wave band and the color are changed; the color layer micro-nano structure of the structure is fused with the performance advantages of the spectrum with the characteristics capable of being customized at will and the adjustable photoelectric coefficient of the electrochromic layer material, the effects of dynamic regulation and control of multi-channel spectrum filtering, multicolor display and the like can be obtained, and the indexes of the spectrum such as regulation and control range, optical contrast and the like can be improved.
Preferably, the material of the substrate layer is glass or PET.
Preferably, the material of the lower conductive layer is selected from one of Al, ag, ni, cr, ti, ITO and FTO.
Preferably, the electrochromic layer is made of a material selected from WO 3 、TiO、NiO、V 2 O 5 One of them.
Preferably, the solid electrolyte layer is a ceramic solid electrolyte or a polymer solid electrolyte, and the ceramic solid electrolyte is selected from LiF, liAlOx, liPON, liTaO 3 、LiNbO 3 One of them.
Preferably, the material of the ion storage layer is selected from NiO and WO 3 One of TiO.
Preferably, the upper conductive layer is a transparent electrode and the material of the upper conductive layer is ITO or FTO.
The invention further aims at providing a preparation method of the all-solid-state multichannel dynamic tunable spectral filter device, which specifically comprises the following steps:
s1, cleaning a basal layer: sequentially performing ultrasonic cleaning on a substrate by using acetone and alcohol, washing the substrate by using deionized water, and drying the substrate by using nitrogen;
s2, depositing a lower conductive layer: depositing a lower conductive layer on the substrate layer cleaned in the step S1 by using a physical vapor deposition method or a chemical vapor deposition method;
s3, depositing an electrochromic layer: depositing an electrochromic layer on the surface of the lower conductive layer obtained in the step S2 by using a physical vapor deposition method or a chemical vapor deposition method;
s4, preparing a structural color layer: preparing a structural color layer on the surface of the electrochromic layer obtained in the step S3;
s5, depositing a solid electrolyte layer: sputtering a solid electrolyte layer on the surface of the structural color layer obtained in the step S4 by using a physical vapor deposition method or a chemical vapor deposition method;
s6, depositing an ion storage layer: depositing an ion storage layer on the surface of the solid electrolyte layer obtained in the step S5 by using a physical vapor deposition method or a chemical vapor deposition method;
s7, depositing an upper conductive layer: and (3) depositing an upper conductive layer on the surface of the ion storage layer obtained in the step (S6) by using a physical vapor deposition method or a chemical vapor deposition method to obtain the all-solid-state multichannel dynamic adjustable spectrum filter device.
Preferably, in the step S4, the preparation method of the structural color layer is as follows:
s41: firstly, depositing a dielectric film on an electrochromic layer, spin-coating photoresist, baking, setting a rotating speed and spin-coating time, completing spin-coating of the photoresist, placing the photoresist on a hot plate, baking a substrate, curing the photoresist, placing the substrate with the spin-coated photoresist in a cavity of a photoetching device, setting exposure dose according to a photoetching pattern, and completing exposure; finally, placing the substrate in a developing solution for developing, cleaning by isopropanol, and drying by nitrogen;
s42: and placing the substrate in a cavity of etching equipment, etching the dielectric film by taking the photoresist periodic sub-wavelength structure as a mask to obtain a sub-wavelength hole array, then placing the sub-wavelength hole array in acetone for cleaning, and removing the photoresist to obtain a structural color layer.
Preferably, in the step S41, the photoresist is PMMA positive photoresist or HSQ negative photoresist.
Preferably, in the step S41, the thin film deposition apparatus is a magnetron sputtering machine or an evaporation machine.
Preferably, in the step S41, the lithographic apparatus is a laser direct writing machine or an EUV lithography machine.
Preferably, in the step S42, the etching apparatus is selected from one of a RIE etching apparatus, an ICP etching apparatus, and an IBE apparatus.
Preferably, in the step S4, the preparation method of the structural color layer is as follows:
s41, spin-coating photoresist on the substrate, performing proper curing, placing the spin-coated photoresist substrate in nano imprinting equipment for imprinting and demolding, and curing to obtain a structural color mask;
s42, coating: placing the substrate in a chamber of a film deposition device, and depositing a corresponding structural color film layer on the substrate;
s43, stripping: and (3) putting the device into stripping liquid such as acetone and the like for stripping, and removing photoresist to obtain the structural color layer.
Preferably, in the step S41, the photoresist is nano imprint resist or PMMA.
Preferably, in the step S41, the imprint apparatus is a nanoimprint lithography apparatus or a roll-to-roll nanoimprint machine;
preferably, in the step S42, the thin film deposition apparatus is an electron beam evaporation apparatus or a thermal evaporation apparatus.
Compared with the prior art, the invention has the following advantages:
firstly, the working wave band, the center wavelength and the bandwidth of the filter device provided by the invention are easy to regulate and control by adjusting the structural parameters and the external driving voltage, so that the filter device is convenient to integrate in a spectrum imaging system; the substrate provides support for the filtering structure; the structural color layer provides an initial color or an initial filtering wave band, and the electrochromic device provides a good color-changing environment for the structural color layer; by changing the structure size of each unit in the structure color layer, the spectrum of different wave bands can be obtained; the photoelectric coefficient (such as refractive index) of the electrochromic layer can be controlled by applying external voltage, and the change of the photoelectric coefficient of the material can change the resonance frequency and the central wavelength position;
secondly, the all-solid-state device provided by the invention has good performance stability and weather resistance, cannot influence the optical filtering due to external environment change, and is convenient to package; the filtering structure disclosed by the invention combines the performance advantages of the micro-nano structure on the spectrum, such as the optional customizable characteristic of the spectrum and the adjustable photoelectric coefficient of the electrochromic material, and can obtain the effects of dynamic regulation and control of multi-channel spectrum filtering, multicolor display and the like;
thirdly, the filtering structure proposed in the invention adopts WO 3 An electrochromic material has low regulation voltage and low energy consumption; the filtering structure is made of aluminum and the like, and is convenient to integrate with a CMOS circuit, thereby being convenient to integrate with an imaging system.
Drawings
FIG. 1 is a three-dimensional schematic diagram of an all-solid-state multichannel dynamically tunable spectral filter structure of the present invention;
FIG. 2 is a flow chart of the processing technique of the all-solid-state multichannel dynamic tunable spectral filter structure of the embodiment 1 of the invention;
FIG. 3 is a flow chart of the processing technique of the all-solid-state multichannel dynamic tunable spectral filter structure of embodiment 2 of the present invention;
FIG. 4 shows a multi-channel mosaic filter structure corresponding to a circular-hole rectangular array arrangement with different structural dimensions;
FIG. 5 is a graph of reflection spectra corresponding to different sizes of filter structures;
fig. 6 is a CIE chromaticity diagram corresponding to colors exhibited by filter structures of different structure sizes.
In the figure:
1: a base layer; 2: a lower conductive layer; 3: an electrochromic layer; 4: a structural color layer; 4-1: a dielectric film; 4-2: a photoresist periodic sub-wavelength structure; 4-3: a structural color mask; 4-4: a structural color film layer; 5: a solid electrolyte layer; 6: an ion storage layer; 7: an upper conductive layer.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
The embodiment provides an all-solid-state multichannel dynamic adjustable spectrum filter device, which comprises a substrate layer 1, a lower conductive layer 2, an electrochromic layer 3, a structural color layer 4, a solid electrolyte layer 5, an ion storage layer 6 and an upper conductive layer 7 which are sequentially arranged from bottom to top, wherein the structural color layer 4 is a periodic micro-nano structure or a multi-layer film spectrum filter structure, and the substrate provides support for the filter structure; the structural color layer 4 provides an initial color or an initial filtering wave band, and the electrochromic device provides a good color-changing environment for the structural color layer 4; by changing the structural dimensions of the units in the structural color layer 4, spectra of different wavebands can be obtained; the photoelectric coefficient (such as refractive index) of the electrochromic layer 3 can be controlled by applying external voltage, the change of the photoelectric coefficient of the material can change the resonance frequency and the central wavelength position, the change of the dielectric property of the surrounding environment of the structural color layer 4 can change the resonance frequency of the micro-nano structure, the resonance wavelength position can correspondingly change, the working wave band and the color can change, the performance advantages of the micro-nano structure of the structural color layer 4 on the spectrum, such as the optional custom characteristic of the spectrum and the adjustable photoelectric coefficient of the material of the electrochromic layer 3 can be fused, the effects of dynamic regulation and control of multi-channel spectral filtering, multicolor display and the like can be obtained, and the indexes of the regulation range, optical contrast and the like of the spectrum can be improved.
In this embodiment, the material of the base layer 1 is glass or PET.
In this embodiment, the material of the lower conductive layer 2 is selected from one of Al, ag, ni, cr, ti, ITO and FTO.
In this embodiment, the material of the electrochromic layer 3 is selected from WO 3 、TiO、NiO、V 2 O 5 One of them.
In the present embodiment, the solid electrolyte layer 5 is a ceramic solid electrolyte or a polymer solid electrolyte, and the ceramic solid electrolyte is selected from LiF, liAlOx, liPON, liTaO 3 、LiNbO 3 One of them. The solid electrolyte layer 5 has good stability and weather resistance, is convenient for packaging and large-scale preparation, and adopts tungsten oxide, nickel oxide and V 2 O 5 And the like; li is selected as the material of the solid electrolyte layer 5 + The material, the ion implantation and the ion output, change the refractive index of the material of the solid electrolyte layer 5.
In the present embodiment, the material of the ion storage layer 6 is selected from NiO, WO 3 One of TiO.
In this embodiment, the upper conductive layer 7 is a transparent electrode and the material of the upper conductive layer 7 is ITO or FTO.
The embodiment also provides a preparation method of the all-solid-state multichannel dynamic adjustable spectrum filter device, which specifically comprises the following steps:
s1, cleaning a basal layer 1: sequentially performing ultrasonic cleaning on a substrate by using acetone and alcohol, washing the substrate by using deionized water, and drying the substrate by using nitrogen;
s2, depositing a lower conductive layer 2: depositing a lower conductive layer 2 on the substrate layer 1 cleaned in the step S1 by using a physical vapor deposition method or a chemical vapor deposition method;
s3, depositing an electrochromic layer 3: depositing an electrochromic layer 3 on the surface of the lower conductive layer 2 obtained in the step S2 by using a physical vapor deposition method or a chemical vapor deposition method;
s4, preparing a structural color layer 4: preparing a structural color layer 4 on the surface of the electrochromic layer 3 obtained in the step S3;
s5, depositing a solid electrolyte layer 5: sputtering a solid electrolyte layer 5 on the surface of the structural color layer 4 obtained in the step S4 by using a physical vapor deposition method or a chemical vapor deposition method;
s6, depositing an ion storage layer 6: depositing an ion storage layer 6 on the surface of the solid electrolyte layer 5 obtained in the step S5 by using a physical vapor deposition method or a chemical vapor deposition method;
s7, depositing an upper conductive layer 7: and (3) depositing an upper conductive layer 7 on the surface of the ion storage layer 6 obtained in the step S6 by using a physical vapor deposition method or a chemical vapor deposition method to obtain the all-solid-state multichannel dynamic adjustable spectrum filter device.
As shown in fig. 2: in this embodiment, in step S4, the preparation method of the structural color layer 4 is as follows:
s41: firstly, depositing a dielectric film 4-1 on an electrochromic layer 3, spin-coating photoresist, baking, setting a rotating speed and spin-coating time, completing spin-coating of the photoresist, placing the photoresist on a hot plate, baking a substrate, curing the photoresist, placing the substrate with the spin-coated photoresist in a cavity of a photoetching device, setting exposure dose according to a photoetching pattern, and completing exposure; finally, placing the substrate in a developing solution for developing, cleaning by isopropanol, and drying by nitrogen;
s42: and placing the substrate in an etching equipment chamber, etching the dielectric film 4-1 by taking the photoresist periodic sub-wavelength structure 4-2 as a mask to obtain a sub-wavelength hole array, then placing the sub-wavelength hole array in acetone for cleaning, and removing the photoresist to obtain the structural color layer 4.
In this embodiment, in step S41, the photoresist is PMMA positive photoresist or HSQ negative photoresist.
In this embodiment, in step S41, the thin film deposition apparatus is a magnetron sputtering machine or an evaporation machine.
In this embodiment, in step S41, the lithographic apparatus is a laser direct writing machine or an EUV lithography machine.
In this embodiment, in step S42, the etching apparatus is selected from one of an RIE etcher, an ICP etcher, and an IBE apparatus.
As shown in fig. 3: in other embodiments, in step S4, the preparation method of the structural color layer 4 is as follows:
s41, spin-coating photoresist on the substrate, performing proper curing, placing the spin-coated photoresist substrate in nano imprinting equipment for imprinting and demolding, and curing to obtain a structural color mask 4-3;
s42, coating: placing the substrate in a chamber of a film deposition device, and depositing a corresponding structural color film layer 4-4 on the substrate;
s43, stripping: the device is placed in stripping liquid such as acetone for stripping, and photoresist is removed to obtain the structural color layer 4.
Specifically, in step S41, the photoresist is nano imprint resist or PMMA.
Specifically, in step S41, the imprint apparatus is a nanoimprint lithography apparatus or a roll-to-roll nanoimprint machine;
specifically, in step S42, the thin film deposition apparatus is an electron beam evaporation apparatus or a thermal evaporation apparatus.
The technical effects of the present invention will be described below with reference to specific examples.
Example 1
As shown in fig. 1, the spectral filter device based on the combination of structural color and electrochromic device according to the present embodiment mainly includes a base layer 1, a lower conductive layer 2, an electrochromic layer 3, a structural color layer 4, a solid electrolyte layer 5, an ion storage layer 6, and an upper conductive layer 7.
In this embodiment: the substrate layer 1 is a glass hard substrate, and provides support for the filter structure; the lower conducting layer 2 is made of metal layer Al, and the lower conducting layer 2 can be used as a reflecting mirror layer of a structural color part FP cavity, and the thickness of the reflecting mirror layer exceeds 100nm; electrochromic layer 3, WO 3 A material; the electrochromic layer 3 can be used as an intermediate dielectric layer of the structural color part FP cavity, and the thickness is between 50nm and 150nm; the structural color layer 4 is made of a periodic nano-pore structure based on coupling of a surface plasmon resonance effect and an FP resonance effect, and the like, and the structural color layer 4 is made of Al with the thickness of 10-50nm;
the structural color layer 4 in the present embodiment can be set to 4 channels by changing the structural shape and size parameters, as shown in fig. 4, corresponding to (1) radius r=116 nm; period p=350 nm; (2) radius r=66 nm; period p=200 nm; (3) radius r=50 nm; period p=150 nm; the structural dimension parameters of the channel (1) and the channel (4) are consistent; the solid electrolyte layer 5 is selected from solid electrolyte LiNbO3;
the ion storage layer 6 of the embodiment adopts NiO; the upper conducting layer 7 is an ITO transparent electrode;
as shown in fig. 2, the specific preparation steps of the dynamically tunable spectral filter structure of this embodiment are as follows:
(a) Cleaning the substrate layer 1: ultrasonically cleaning the basal layer 1 by using acetone, then ultrasonically cleaning the basal layer in alcohol, then washing the basal layer by using deionized water, and drying by using nitrogen;
(b) Depositing an underlying conductive layer 2: placing the cleaned substrate layer 1 in a chamber of a magnetron sputtering device, and depositing a conductive film Al with the thickness of 100nm;
(c) Depositing an electrochromic layer 3: placing the above substrate in a magnetron sputtering device, and depositing a 100nm thick electrochromic layer WO 3 ；
(d) Photoresist periodic sub-wavelength structures 4-2 required for preparing structural color layer 4: firstly, depositing a dielectric film 4-1 with the thickness of 20nm on a lower conductive layer 2 in magnetron sputtering equipment, spin-coating PMMA positive photoresist, and baking, wherein the material of the dielectric film 4-1 is Al, setting the rotating speed and the spin-coating time, completing spin-coating of the PMMA positive photoresist, placing the PMMA positive photoresist on a hot plate, baking a substrate, curing the PMMA positive photoresist, placing the substrate spin-coated with the PMMA positive photoresist in an EUV photoetching machine chamber, setting exposure dose according to photoetching patterns, and completing exposure; finally, placing the substrate in a developing solution for developing, cleaning with isopropyl alcohol (IPA), and drying with nitrogen to obtain a PMMA positive photoresist periodic sub-wavelength structure 4-2 (figure 4), wherein P is the period of the periodic sub-wavelength hole array; r is the radial dimension of the hole, which is (1) the radius r=116 nm; period p=350 nm; (2) radius r=66 nm; period p=200 nm; (3) radius r=50 nm; period p=150 nm; the structural dimension parameters of the channel (1) and the channel (4) are consistent;
(e) Etching the structural color layer 4: placing the substrate in an IBE equipment chamber, and etching the dielectric film 4-1 by taking the photoresist periodic sub-wavelength structure 4-2 as a mask to obtain a sub-wavelength hole array; then placing the mixture in acetone for cleaning to remove PMMA positive photoresist;
(f) Depositing a solid electrolyte layer 5: placing the substrate in a chamber of a magnetron sputtering device, and sputtering solid electrolyte LiNbO 3 ；
(g) Depositing an ion storage layer 6: placing the substrate in a chamber of a magnetron sputtering device, and depositing an ion storage layer 6;
(h) Depositing an upper conductive layer 7: placing the substrate in a chamber of a magnetron sputtering device, and depositing an upper conductive layer 7 to obtain an all-solid-state multichannel dynamic adjustable spectrum filter;
example 2
The spectral filter device based on the combination of structural color and electrochromic device provided by the embodiment mainly comprises a substrate layer 1, a lower conductive layer 2, an electrochromic layer 3, a structural color layer 4, a solid electrolyte layer 5, an ion storage layer 6 and an upper conductive layer 7.
In this embodiment: the substrate layer 1 is a glass hard substrate, and provides support for the filter structure; the lower conducting layer 2 is made of metal layer Al, and the lower conducting layer 2 can be used as a reflecting mirror layer of a structural color part FP cavity, and the thickness of the reflecting mirror layer exceeds 100nm; electrochromic layer 3, WO 3 A material; the electrochromic layer 3 can be used as an intermediate dielectric layer of the structural color part FP cavity, and the thickness is between 50nm and 150nm; the structural color layer 4 is made of a periodic nano-pore structure based on coupling of a surface plasmon resonance effect and an FP resonance effect, and the like, and the structural color layer 4 is made of Al with the thickness of 10-50nm;
the structural color layer 4 in the present embodiment can be set to 4 channels by changing the structural shape and size parameters, as shown in fig. 4, corresponding to (1) radius r=116 nm; period p=350 nm; (2) radius r=66 nm; period p=200 nm; (3) radius r=50 nm; period p=150 nm; the structural dimension parameters of the channel (1) and the channel (4) are consistent; the solid electrolyte layer 5 is selected from solid electrolyte LiNbO 3 ；
The ion storage layer 6 of the embodiment adopts NiO; the upper conducting layer 7 is an ITO transparent electrode;
as shown in fig. 3, the specific preparation steps of the dynamically tunable spectral filter structure of this embodiment are as follows:
(a) Cleaning the substrate layer 1: ultrasonically cleaning the basal layer 1 by using acetone, then ultrasonically cleaning the basal layer in alcohol, then washing the basal layer by using deionized water, and drying by using nitrogen;
(b) Depositing an upper conductive layer 2: placing the cleaned substrate layer 1 in a chamber of a magnetron sputtering device, and depositing a conductive film Al with the thickness of 100nm;
(c) Depositing an electrochromic layer 3: placing the above substrate in a magnetron sputtering device, and depositing a 100nm thick electrochromic material layer WO 3 ；
(d) Mask 4-3 required for preparing structural color layer 4: firstly, spin-coating nano-imprinting glue on the substrate, and carrying out proper curing, then placing the substrate spin-coated with the nano-imprinting glue in nano-imprinting lithography equipment for imprinting and demolding, and obtaining a structural color mask 4-3 after curing;
(e) Coating: placing the substrate in a chamber of an electron beam evaporation device, and depositing a 20nmAl structural color film layer 4-4 on the substrate;
(f) Stripping: the device is placed in acetone stripping liquid for stripping, photoresist is removed, and a periodic aluminum nano-pore structure is obtained;
(g) Depositing a solid electrolyte layer 5: placing the substrate in a chamber of a magnetron sputtering device, and sputtering solid electrolyte LiNbO 3 ；
(h) Depositing an ion storage layer 6: placing the substrate in a chamber of a magnetron sputtering device, and depositing an ion storage layer NiO;
(i) Depositing an upper conductive layer 7: placing the substrate in a chamber of a magnetron sputtering device, and depositing a conductive layer ITO;
as shown in fig. 5, four-channel reflective filters were fabricated based on examples 1 and 2, wherein the fabricated period was 150nm, and the center wavelength of the filter structure with a radius of 50nm was modulated from 473nm to 608nm; the center wavelength of the manufactured filter structure with the period of 200nm and the radius of 66nm can be modulated from 493nm to 641nm; the manufactured filter structure with the period of 350nm and the radius of 116nm has the central wavelength modulated from 522nm to 680nm, and the central wavelength position is regulated and controlled to be more than 150nm.
As shown in FIG. 6, the color development position of the manufactured filter structure with the period of 150nm and the radius of 50nm in the CIE chromaticity diagram is changed from a hollow five-pointed star to a solid five-pointed star, so that the modulation from yellow green to orange yellow is realized; the color development position of the manufactured filter structure with the period of 200nm and the radius of 66nm is changed from hollow hexagons to solid hexagons in the CIE chromaticity diagram, so that the modulation from green to red is realized; the manufactured filter structure with the period of 350nm and the radius of 116nm is changed from a hollow diamond to a solid diamond in the position of color development in the CIE chromaticity diagram, and the modulation from yellow to magenta is realized.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (6)
1. The all-solid-state multichannel dynamic adjustable spectrum filter device is characterized by comprising a substrate layer (1), a lower conductive layer (2), an electrochromic layer (3), a structural color layer (4), a solid electrolyte layer (5), an ion storage layer (6) and an upper conductive layer (7) which are sequentially arranged from bottom to top, wherein the structural color layer (4) is of a periodic micro-nano structure, the structural color layer (4) is made of Al, the thickness is 10-50nm, the structural color layer (4) is provided with 4 channels, and the radius r=116 nm of a first channel; period p=350 nm; radius r=66 nm of the second channel; period p=200 nm; radius r=50 nm of the third channel; period p=150 nm; radius r=116 nm of the fourth channel; period p=350 nm;
the preparation method of the all-solid-state multichannel dynamic adjustable spectrum filter device specifically comprises the following steps:
s1, cleaning a basal layer (1): sequentially performing ultrasonic cleaning on a substrate by using acetone and alcohol, washing the substrate by using deionized water, and drying the substrate by using nitrogen;
s2, depositing a lower conductive layer (2): depositing a lower conductive layer (2) on the substrate layer (1) cleaned in the step S1 by using a physical vapor deposition method or a chemical vapor deposition method;
s3, depositing an electrochromic layer (3): depositing an electrochromic layer (3) on the surface of the lower conductive layer obtained in the step S2 by using a physical vapor deposition method or a chemical vapor deposition method;
s4, preparing a structural color layer (4): preparing a structural color layer (4) on the surface of the electrochromic layer (3) obtained in the step S3;
s5, depositing a solid electrolyte layer (5): sputtering a solid electrolyte layer (5) on the surface of the structural color layer (4) obtained in the step S4 by using a physical vapor deposition method or a chemical vapor deposition method;
s6, depositing an ion storage layer (6): depositing an ion storage layer (6) on the surface of the solid electrolyte layer (5) obtained in the step S5 by using a physical vapor deposition method or a chemical vapor deposition method;
s7, depositing an upper conductive layer (7): depositing an upper conductive layer (7) on the surface of the ion storage layer (6) obtained in the step S6 by using a physical vapor deposition method or a chemical vapor deposition method to obtain an all-solid-state multichannel dynamic adjustable spectrum filter device;
in the step S4, the preparation method of the structural color layer (4) is as follows:
s41: firstly, depositing a dielectric film (4-1) on an electrochromic layer (3), spin-coating photoresist, baking, setting a rotating speed and spin-coating time, completing spin-coating of the photoresist, placing the photoresist on a hot plate, baking a substrate, curing the photoresist, placing the substrate with the spin-coated photoresist in a cavity of a photoetching device, setting exposure dose according to a photoetching pattern, and completing exposure; finally, placing the substrate in a developing solution for developing, cleaning by isopropanol, and drying by nitrogen;
s42: and placing the substrate in an etching equipment chamber, etching the dielectric film (4-1) by taking the photoresist periodic sub-wavelength structure (4-2) as a mask to obtain a sub-wavelength hole array, then placing the sub-wavelength hole array in acetone for cleaning, and removing the photoresist to obtain the structural color layer (4).
2. An all-solid-state multichannel dynamic tunable spectral filter device according to claim 1, characterized in that the material of the base layer (1) is glass or PET;
and/or the material of the lower conductive layer (2) is selected from one of Al, ag, ni, cr, ti, ITO and FTO.
3. An all solid state multichannel dynamic tunable spectral filter device according to claim 1, characterised in that the material of the electrochromic layer (3) is selected from WO 3 、TiO、NiO、V 2 O 5 One of the following;
and/or the solid electrolyte layer (5) is a ceramic solid electrolyte or a polymer solid electrolyte, and the ceramic solid electrolyte is selected from LiF, liAlOx, liPON, liTaO 3 、LiNbO 3 One of them.
4. An all solid state multichannel dynamic tunable spectral filter device according to claim 1, characterised in that the material of the ion storage layer (6) is selected from NiO, WO 3 One of TiO;
and/or, the upper conductive layer (7) is a transparent electrode and the material of the upper conductive layer (7) is ITO or FTO.
5. The all-solid-state multichannel dynamic tunable spectral filter device according to claim 1, wherein in step S41, the photoresist is PMMA positive gel or HSQ negative gel;
and/or, in the step S41, the thin film deposition device is a magnetron sputtering machine or an evaporation machine;
and/or, in the step S41, the lithographic apparatus is a laser direct writing machine or an EUV lithography machine.
6. The all-solid-state multichannel dynamic tunable spectral filter device according to claim 1, wherein in step S42, the etching apparatus is selected from one of a RIE etcher, an ICP etcher, and an IBE apparatus.
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