CN115407574B - Electrochromic structure for realizing multiband compatible dynamic regulation and control - Google Patents
Electrochromic structure for realizing multiband compatible dynamic regulation and control Download PDFInfo
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- 230000000737 periodic effect Effects 0.000 claims abstract description 66
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 claims description 51
- 239000004332 silver Substances 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000004070 electrodeposition Methods 0.000 claims description 13
- 238000002834 transmittance Methods 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002923 metal particle Substances 0.000 claims description 9
- 230000002441 reversible effect Effects 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- -1 silver ions Chemical class 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000001465 metallisation Methods 0.000 claims 1
- 230000003068 static effect Effects 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 48
- 230000008859 change Effects 0.000 description 18
- 239000002245 particle Substances 0.000 description 13
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000005855 radiation Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 230000003044 adaptive effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical class O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Classifications
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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
-
- 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
- G02F1/1533—Constructional details structural features not otherwise provided for
-
- 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
- G02F1/155—Electrodes
-
- 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
- G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
Abstract
The invention discloses an electrochromic structure for realizing multiband compatible dynamic regulation, which comprises a first conductive unit, an electrochromic unit and a second conductive unit, wherein the electrochromic unit is clamped between the first conductive unit and the second conductive unit; the electrochromic cell comprises, from top to bottom, a first periodic microstructure layer, a gel electrolyte layer, and a second periodic microstructure layer. Compared with the traditional multiband compatible structure, the novel electrochromic structure capable of achieving dynamic regulation and control is not limited to a static structure, and can only achieve fixed camouflage requirements.
Description
Technical Field
The invention relates to the field of multiband spectrum compatible regulation and control, in particular to an electrochromic structure for realizing multiband compatible dynamic regulation and control.
Background
With the development of detection technology, battlefield viability of ground background targets is severely tested. The camouflage technology is successfully applied to the ground background target and has great success, and multi-region background combat gradually becomes the combat form of the ground background target, but most of the existing camouflage technology is designed aiming at specific backgrounds, and when the combat background changes, the existing camouflage cannot be replaced in real time, so that the camouflage is invalid. There is therefore an urgent need to study adaptive camouflage techniques that can vary with background.
The multi-band fusion is a development trend of a detection technology, the self-adaptive camouflage effect of a single band is good, and the single band is also unprecedented under the detection technology of the multi-band fusion. Two main detection wave bands of visible light and infrared as land targets are researched, and the adaptive camouflage technology compatible with the visible light and infrared in multiple wave bands is researched, so that the better dynamic spectrum characteristic regulation and control effect is obtained.
The spectrum characteristic control based on the periodic microstructure is to utilize the basic principle of interaction of electromagnetic waves and the surface of the structure, such as surface plasmons (SPPs), localized plasmons (LSPs), fabry-Perot resonance, forbidden band effect and the like, to realize the absorption, reflection and transmission control of radiation with specific wavelength, thereby controlling the spectrum characteristic of the surface of the periodic microstructure. However, the structural style and geometric parameters of conventional microstructures cannot be changed once determined. At this time, the static microstructure designed by the coupling action between the excitation microstructure and the electromagnetic wave can excite one or more electromagnetic actions only at a certain position/wave band, shows a fixed and non-adjustable structural color or infrared radiation characteristic, and cannot meet the requirement of multi-wave-band compatible self-adaptive camouflage. Therefore, in order to obtain the effect of dynamically tuning the visible and infrared spectral characteristics, it is important to use smart materials that are responsive to external stimuli (electric field, temperature, mechanical, etc.).
In recent years, electrochromic materials have been attracting attention due to the advantages of fast response speed, simple implementation mode and the like, however, conventional electrochromic materials, such as tungsten trioxide and polyaniline, realize regulation and control of infrared emissivity and simultaneously usually accompany fixed color change, and one infrared radiation characteristic can only correspondingly display one color and cannot meet the requirement of multiband compatible self-adaptive camouflage. The reversible metal electrodeposition is used as a novel electrochromic material, the deposition and dissolution of metal on a transparent electrode can be controlled by adjusting the size and the direction of an applied voltage, the limitation of the traditional electrochromic material is broken through, and the possibility is provided for realizing the dual-dynamic adjustment of structural color and infrared radiation characteristics. Li et al achieved reversible dynamic modulation of 3-14 μm band emissivity Δε=0.8 using reversible silver electrodeposition (Li M, liu D, cheng H, et al, modeling metals for adaptive thermal cam uflag, science Advances,6 (22): eaba 3494). On the basis, a series of chromium oxide in the visible wavelength range is added between the substrate and the nano platinum film electrode, so that the film interference effect is excited, and the structural color is displayed. The structure realizes the structural color change while the infrared radiation characteristic changes, but the structure has a narrow regulation range in the aspect of structural color change, and once the thickness of the chromium oxide layer is determined, the structural color can only realize the brightness change.
Disclosure of Invention
The invention aims to provide an electrochromic structure for realizing multi-band compatible dynamic regulation, aiming at realizing compatible dynamic regulation on spectral characteristics of a plurality of bands, coping with different types of background environments and improving the self-adaptive camouflage capability of a target.
The technical scheme for realizing the aim of the invention is as follows: an electrochromic structure for realizing multiband compatible dynamic regulation comprises a first conductive unit, an electrochromic unit and a second conductive unit, wherein the electrochromic unit is clamped between the first conductive unit and the second conductive unit; the first conductive unit comprises a first substrate and a first transparent conductive layer formed on the lower surface of the first substrate; the electrochromic unit comprises a first periodic microstructure layer arranged on the lower surface of the first transparent conductive layer, a gel electrolyte layer formed on the lower surface of the first periodic microstructure layer and a second periodic microstructure layer arranged on the lower side of the gel electrolyte layer; the second conductive unit is covered on the surface of the electrochromic unit far away from the first conductive unit and comprises a second substrate and a second transparent conductive layer which is formed on the surface of the second substrate and is connected with the second periodic microstructure layer in the electrochromic unit.
In some examples, the first periodic microstructured layer and the second periodic microstructured layer act as templates for electrodeposition of metal particles, controlling the shape of the metal deposit; the metal ions are reduced to metal particles and deposited in the grooves/holes of the first and second periodic microstructures by applying voltage to form the metal microstructures. The reverse voltage is applied, the deposited metal particles start to be oxidized into metal ions, the metal microstructure is dissolved and restored to the original state, and then the metal ions are reduced to the metal particles to be deposited in the holes/grooves of the second/first periodic microstructure, so that the metal microstructure is formed.
In some examples, the first periodic microstructured layer is selected from one of: grating, round hole, rectangular hole, square hole.
In some examples, the first periodic microstructure layer period p=1-3 μm, the duty cycle f is less than or equal to 0.2, the height H 1 ＝40～80nm。
In some examples, the second periodic microstructured layer is selected from one of: round holes, rectangular holes, square holes.
In some examples, the second periodic microstructured layer hole diameter/side length d=20-90 nm, the center-to-center distance d=65-125 nm, the hole height H 2 ＝40～100nm。
In some examples, the first periodic microstructure layer and the second periodic microstructure layer have a transmittance of at least 90% in both visible and infrared bands, and the material selected is silica.
In some examples, the gel electrolyte layer has a transmittance of 90% or more in the visible band and an absorptivity of 80% or more in the infrared band, the gel electrolyte provides metal cations required for electrodeposition, the thickness is 250 μm or more, and the gel electrolyte layer includes silver nitrate, silver ions as electrodeposited/dissolved metal ions.
In some examples, the first transparent conductive layer and the second transparent conductive layer each have a transmittance of 90% or more in the visible and infrared bands, the materials being selected from the group of: platinum, gold, and combinations thereof, the first transparent conductive layer and the second transparent conductive layer having a thickness of 1 to 3nm.
In some examples, the first substrate and the second substrate have a transmittance of 90% or more in both the visible and infrared bands, the materials being selected from the group of: barium fluoride, calcium fluoride, lithium fluoride, and combinations thereof.
The invention has the gain effects that: (1) According to the invention, two layers of different periodic microstructures are introduced into the electrochromic unit to serve as metal electrodeposition templates, when silver is deposited in the grooves/holes of the first periodic microstructures, the structure has structural color while high reflection is realized in an infrared band, the thickness of deposited silver is changed, the infrared high reflection characteristic is unchanged, and the structural color can be changed in depth; when silver is deposited in the holes of the second periodic microstructure, the structure has structural color while realizing low reflection in the infrared band, the thickness of deposited silver is changed, the infrared low reflection characteristic is unchanged, the structural color can realize wide-range change, the structure realizes compatible dynamic regulation and control of the spectral characteristics of visible and infrared bands, and meets the compatible self-adaptive camouflage requirement of visible light and infrared multiband; (2) According to the invention, a first periodic microstructure layer is introduced at the lower side of a first transparent conductive layer to serve as a metal electrodeposition template, and reversible metal electrodeposition is combined with microstructure regulation and control infrared radiation characteristics, so that the dynamic regulation and control of the infrared radiation characteristics is realized; (3) The first periodic microstructure layer designed by the invention has proper form and size, can ensure that the whole structure realizes infrared high reflection characteristic during silver deposition, and can also present bright structural color; (4) According to the invention, the second periodic microstructure layer is introduced to the upper side of the second transparent conductive layer as a metal electrodeposition template, and the reversible metal electrodeposition is combined with the microstructure regulation and control structure color, so that the dynamic regulation and control structure color is realized; (5) The second periodic microstructure layer designed by the invention has proper size, the silver structure deposited in the microstructure holes can excite local plasmons, the position of a formant can be tuned by changing the silver deposition thickness, and the wide-range change of structural color is realized; (6) The thickness change of deposited silver in the grooves/holes of the first periodic microstructure and the second periodic microstructure can be controlled by controlling the application size, time and direction of the applied voltage, so that the infrared radiation characteristic/structural color can be reversibly regulated and controlled; (7) The invention adopts the ultrathin noble metal film as the transparent conductive layer, not only has high transmittance to incident light in visible and infrared wave bands, but also has adsorption effect on silver particles, and can promote the silver particles to be deposited at the bottoms of the grooves/holes of the template structure.
Drawings
The foregoing and other objects, features and advantages of the present application will become more apparent from the following more particular description of embodiments of the present application, as illustrated in the accompanying drawings. The accompanying drawings are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate the application and not constitute a limitation to the application.
Fig. 1 is a schematic diagram showing the front view of the novel electrochromic structure without silver deposition in example 1 of the present invention.
Fig. 2 is a schematic diagram showing the front view of the novel electrochromic structure when silver is deposited in the grooves of the first periodic microstructure in example 1 of the present invention.
Fig. 3 is a graph showing the visible light reflection characteristics and corresponding structural color change of the novel electrochromic structure when silver is deposited in the grooves of the first periodic microstructure in example 1 of the present invention.
Fig. 4 is a graph showing the change in infrared reflection characteristics of the novel electrochromic structure when silver is deposited in the grooves of the first periodic microstructure in example 1 of the present invention.
Fig. 5 is a schematic diagram showing the front view of the novel electrochromic structure when silver is deposited in the holes of the second periodic microstructure in example 1 of the present invention.
Fig. 6 is a graph showing the visible light reflection characteristics and corresponding structural color change of the novel electrochromic structure when silver is deposited in the holes of the second periodic microstructure in example 1 of the present invention.
Fig. 7 shows the color change and corresponding RGB values of the novel electrochromic structure when silver is deposited in the holes of the second periodic microstructure of different hole diameters in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples, which are, however, to be understood only for the purpose of more detailed description and are not to be construed as limiting the invention in any way.
The invention discloses an electrochromic structure for realizing multiband compatible dynamic regulation, which comprises a first conductive unit, an electrochromic unit and a second conductive unit, wherein the electrochromic unit is clamped between the first conductive unit and the second conductive unit.
Wherein the first conductive unit comprises a first substrate 1 and a first transparent conductive layer 2 formed on the lower surface of the first substrate; the electrochromic unit comprises a first periodic microstructure layer 3 arranged on the lower surface of the first transparent conductive layer 2, a gel electrolyte layer 4 formed on the lower surface of the first periodic microstructure layer 3, and a second periodic microstructure layer 5 arranged on the lower side of the gel electrolyte layer 4; the second conductive unit is covered on the surface of the electrochromic unit far away from the first conductive unit and comprises a second substrate 7 and a second transparent conductive layer 6 which is formed on the surface of the second substrate 7 and is connected with the second periodic microstructure layer 5 in the electrochromic unit.
The first substrate 1 and the second substrate 7 are mainly used for transmitting incident light in visible light and infrared wavelength bands and serving as a support of a transparent conductive layer, and the materials are respectively selected from the following groups of materials: barium fluoride, calcium fluoride, lithium fluoride, and combinations thereof.
The first transparent conductive layer 2 and the second transparent conductive layer 6 have the thickness of 1-3 nm, are mainly used for conducting and transmitting incident light in visible light and infrared wave bands, and have adsorption effect on deposited silver particles at the same time, so that the silver particles are promoted to be deposited at the bottoms of grooves/holes of the periodic microstructure, and the materials are respectively selected from the following groups of materials: platinum, gold, and combinations thereof.
The first periodic microstructure layer 3 is mainly used for controlling the upward deposition shape of silver particles on the lower side of the first transparent conductive layer 2, and is used as a template for silver electrodeposition, so that silver ions in the gel electrolyte layer 4 are deposited in grooves/holes of the first periodic microstructure 3 when reduced into silver particles, so as to form a silver structure. The silver structure can not only play a role of a metal high-reflection film, but also excite a local plasmon effect to present a specific structural color. Wherein the first periodic microstructure layer 3 is selected from one of the following: grating, round hole, rectangular hole, square hole, microstructure period P=1-3 μm, duty ratio f is less than or equal to 0.2, height H 1 The transmittance of the microstructure in visible light and infrared wave bands is more than or equal to 90 percent, and the selected material is silicon dioxide.
The second periodic microstructure layer 5 is arranged on the upper side of the second transparent conductive layer 6 and is mainly used for controlling the downward deposition shape of silver particles, and is used as a template for silver electrodeposition, so that silver ions in the gel electrolyte layer 4 are deposited at the bottoms of holes of the second periodic microstructure layer 5 when reduced into silver particles, a silver disc/silver square array structure is formed, a local plasmon effect is excited, and structural colors are displayed. Wherein the second periodic microstructure layer 5 is selected from one of the following: round holes, rectangular holes, square holes, hole diameter/side length d=20-90nm, the center distance D=65-125 nm of adjacent holes, and the hole height H 2 The transmittance of the second periodic microstructure layer 5 in the visible light wave band is more than or equal to 90nm, and the selected material is silicon dioxide.
The gel electrolyte layer 4 is mainly used for providing electrodeposited silver ions, transmitting incident light in the visible light band and absorbing incident light in the infrared band. When no metal particles are deposited in the grooves/holes of the first periodic microstructure 3, incident light of an infrared wavelength band transmitted from the first substrate 1, the first transparent conductive layer 2, and the first periodic microstructure layer 3 is absorbed by the gel electrolyte layer 4, and the entire structure exhibits a low reflection state. The gel electrolyte comprises silver nitrate, silver ions as electrodeposited/dissolved metal cations.
Examples
The material of the first substrate 1 and the second substrate 7 is barium fluoride; the material of the first transparent conductive layer 2 and the second transparent conductive layer 6 is platinum, and the thickness is 1nm; the first periodic microstructure 3 layer adopts a grating structure, the period P of the grating structure is=2.3 mu m, and the ridge width W 1 =0.2 μm, duty cycle f=w 1 P=0.087, groove width W 2 ＝P-W 1 =2.1 μm, grating height H 1 =50nm; the second periodic microstructure 5 adopts a round hole structure, the diameter d=70 nm of the holes, the center distance d=100 nm of the holes of adjacent discs, and the height H of the holes 2 =80 nm; gel electrolyte layer 4 was prepared by adding 0.5mM silver nitrate, 2.5mM tetrabutylammonium bromide, 0.1mM copper chloride and 10wt% polyvinyl butyral as the base polymer to 10ml dimethyl sulfoxide, with a thickness of 500. Mu.m. Referring to fig. 1, in an initial state, i.e., without silver deposition (h 1 ＝0nm，h 2 =0 nm), the structure exhibits a transparent color in the visible light band; incident light in the infrared band is absorbed by the gel electrolyte layer 4 and the structure exhibits a low reflection state.
When silver particles are deposited upwards in the grooves of the first periodic grating structure 3, a silver thickness h is deposited 1 See fig. 2. The thickness h of the deposited silver is calculated by a finite difference time domain method (FDTD) 1 Visible and infrared reflection characteristics of the structure at=0 to 40nm, see fig. 3 and 4. In the visible light range of the light source,thickness h of deposited silver 1 The reflection peak position is basically unchanged from 10nm to 40nm, the reflection intensity is gradually enhanced, the transition from dark green to light green is presented in color, and the structure color similar to the woodland background is realized. The structure can be changed from transparent color (h 1 =0 nm) to green (h) when silver is deposited 1 Not less than 10 nm), realizing reversible conversion from transparent to green; in the infrared band, silver thickness h is deposited 1 After the thickness of the deposited silver is more than 10nm, the change of the thickness of the deposited silver has no influence on the infrared reflection characteristic basically, the structure always presents an infrared high reflection state, and the ratio h is compared with 1 =0nm and h 1 The infrared reflection characteristic when the silver is 10nm, the average reflectivity of the wave band of 3-5 mu m is changed by 82.6 percent, the average reflectivity of the wave band of 8-14 mu m is changed by 64.2 percent, the reflectivity regulation amplitude of the structure before and after silver deposition is large, and the requirements of dynamic infrared stealth can be met. To sum up, comparison h 1 =0nm and h 1 When the spectrum characteristics of two wave bands are 10nm, the structure can be reversibly converted between two states of infrared wave band low reflection visible light wave band transparent color and infrared wave band high reflection visible light wave band dark green color, and the thickness h of silver is deposited 1 Above 10nm, the infrared band high reflection characteristic is unchanged, and the structural color can be changed from dark green to light green.
When silver particles are deposited downwards in the holes of the second periodic circular hole structure 5, a deposition thickness h 2 See fig. 5. The thickness h of the deposited silver is calculated by a time domain finite difference method 2 The visible light reflection characteristic of the structure when the structure is changed from 10nm to 70nm is calculated by a color space to obtain the structure color corresponding to different deposited silver thicknesses, and the structure can show a large-range reversible color change of tan, orange yellow, yellowish-turkish, coral, plum red and light purple, referring to fig. 6. When the diameter d of the circular hole is changed, the structure can present a new structural color, and referring to fig. 7, the diameter of the circular hole is reduced/increased, and the color change area moves toward the short wave/long wave direction, for example: the diameter d of the circular hole is reduced from 70nm to 40nm, and at h=20nm, the blue shift change of orange, olive, grass and azure glass green appears, so that a new color green appears; the diameter d of the circular holes increases from 70nm to 80nm, at h=70nAt m there is a redshift change from light purple to blue, a new color blue appears. The hole diameter d is changed according to different color requirements, so that the color change range can be adjusted to display the required color. When silver particles are deposited downward, incident light in the infrared band passes through the upper three layers (the first substrate 1, the first transparent conductive layer 2, and the first periodic microstructured layer 3) and is absorbed by the gel electrolyte layer 4 of the fourth layer, and the structure exhibits low reflection in the infrared band. In summary, by controlling the thickness h of the silver particles deposited downwards 2 The structure can exhibit a wide range of structural color changes while being low reflective in the infrared band.
By combining the characteristics of silver particles in upward deposition, the structure can be reversibly switched between infrared low-reflection and high-reflection states, can display a large-range adjustable structural color in infrared low-reflection, and can display the change of the depth of a specific structural color in infrared high-reflection, so that the compatible dynamic regulation and control of the spectral characteristics of visible light and infrared two wave bands are realized, and the requirements of compatible self-adaptive camouflage of visible light and infrared multiband are met.
Claims (4)
1. An electrochromic structure for realizing multiband compatible dynamic regulation and control is characterized by comprising a first conductive unit, an electrochromic unit and a second conductive unit, wherein the electrochromic unit is clamped between the first conductive unit and the second conductive unit; the first conductive unit comprises a first substrate and a first transparent conductive layer formed on the lower surface of the first substrate; the electrochromic unit comprises a first periodic microstructure layer arranged on the lower surface of the first transparent conductive layer, a gel electrolyte layer formed on the lower surface of the first periodic microstructure layer and a second periodic microstructure layer arranged on the lower side of the gel electrolyte layer; the second conductive unit covers the surface of the electrochromic unit far away from the first conductive unit and comprises a second substrate and a second transparent conductive layer which is formed on the surface of the second substrate and is connected with a second periodic microstructure layer in the electrochromic unit;
the period P of the first periodic microstructure layer is 1-3 mu m,the duty ratio f is less than or equal to 0.2, the height H 1 =40 to 80nm; the diameter/side length of the holes of the second periodic microstructure layer is d=20-90 nm, the center distance of adjacent holes is d=65-125 nm, and the height H of the holes is 2 =40 to 100nm; the transmittance of the first periodic microstructure layer and the second periodic microstructure layer in visible light and infrared bands is more than or equal to 90%, and the selected material is silicon dioxide; the transmittance of the first transparent conductive layer and the second transparent conductive layer in visible light and infrared wave bands is more than or equal to 90%, and the materials are respectively selected from the following groups of materials: platinum, gold and combinations thereof, wherein the thicknesses of the first transparent conductive layer and the second transparent conductive layer are 1-3 nm; the first periodic microstructure layer is selected from one of the following: grating, round hole, rectangular hole, square hole; the second periodic microstructure layer is selected from one of the following: round holes, rectangular holes, square holes.
2. The electrochromic structure for achieving multiband compatible dynamic tuning of claim 1, wherein the first periodic microstructure layer and the second periodic microstructure layer serve as templates for metal particle electrodeposition to control the shape of metal deposition; applying a voltage to reduce the metal ions into metal particles to deposit in the grooves/holes of the first/second periodic microstructures to form metal microstructures; the reverse voltage is applied, the deposited metal particles start to be oxidized into metal ions, the metal microstructure is dissolved and restored to the original state, and then the metal ions are reduced to the metal particles to be deposited in the holes/grooves of the second/first periodic microstructure, so that the metal microstructure is formed.
3. The electrochromic structure for realizing multi-band compatible dynamic regulation according to claim 1 or 2, wherein the gel electrolyte layer has a transmittance of not less than 90% in a visible light band and an absorptivity of not less than 80% in an infrared band, the gel electrolyte provides metal cations required for electrodeposition, the thickness of not less than 250 μm, and the gel electrolyte layer comprises silver nitrate and silver ions as electrodeposited/dissolved metal ions.
4. The electrochromic structure for realizing multi-band compatible dynamic regulation according to claim 1 or 2, wherein the transmittance of the first substrate and the second substrate in the visible light and infrared bands is more than or equal to 90%, and the materials are respectively selected from the following materials: barium fluoride, calcium fluoride, lithium fluoride, and combinations thereof.
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