Visible-infrared narrow-spectrum dynamic regulation and control device based on reversible metal electrodeposition and construction method of visible-infrared narrow-spectrum dynamic regulation and control device

Abstract

The invention relates to a visible-infrared narrow spectrum dynamic regulation and control device based on reversible metal electrodeposition and a construction method thereof. The device is sequentially provided with a top substrate layer, a multilayer film structure, an electrolyte layer and a bottom transparent electrode layer from top to bottom; the top substrate layer and the multi-layer film structure jointly form a working electrode, and reversible deposition and metal dissolution are carried out on the working electrode by controlling external voltage; the multi-layer film structure comprises a micro-nano structure and a conductive layer, and narrow spectrum regulation and control are carried out in a visible-infrared band by regulating and controlling the multi-layer film structure. The device provided by the invention can realize narrow spectrum dynamic regulation and control of a specific wavelength in a visible-infrared band range, and is low in energy consumption, simple in structure and relatively low in cost.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermal radiation control, and in particular relates to a visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition and a construction method thereof. Background Art

[0002] In recent years, micro-nanostructures have demonstrated tremendous potential in the field of thermal radiation control, leveraging their unique size and surface effects. Compared to traditional methods, these methods offer advantages such as high reliability and stability. They are considered one of the most effective methods for thermal radiation control in the future, and hold significant significance for achieving efficient energy utilization and technological innovation across multiple fields.

[0003] However, while spectral manipulation based on micro-nanostructure design offers numerous advantages, it only enables static control and is unable to meet today's complex and diverse thermal radiation control needs. Therefore, achieving precise and efficient dynamic thermal radiation control based on micro-nanostructures remains an urgent challenge. Current approaches to dynamic spectral manipulation based on micro-nanostructures primarily exploit the stimulus-responsive properties of certain materials, such as thermochromics, phase-change materials, and electrochromics. These materials, with their low energy consumption and fast response times, are widely used in smart windows, displays, energy-saving glass, thermal management, and other fields. However, they currently suffer from numerous drawbacks.

[0004] Electrochromic devices based on organic materials face many challenges in the organic material preparation process. On the one hand, the preparation cycle is lengthy, and it often takes a lot of time from raw material preparation to obtaining the final product; on the other hand, the preparation method is extremely complex, involving a variety of sophisticated chemical reactions and operating procedures, which undoubtedly increases the difficulty and cost of production. Secondly, these problems of these electrochromic materials seriously limit the widespread application of such electrochromic devices. Electrochromic materials based on inorganic materials such as WO3 and VO2 require high-precision equipment and strict process control for the processing of conductive layer films, which increases the cost. At the same time, these materials share the problems of precise control of the spectrum, poor controllable performance, low spectral modulation amplitude, inability to achieve complete opacity, and poor controllability of the spectrum and thermal radiation.

[0005] In addition, spectral devices based on reversible metal electrodeposition utilize metal deposition on the working electrode to control light entry. Due to the large extinction coefficient of metal, light propagation can be completely blocked, and large-area devices can be fabricated. However, due to the high reflectivity of metals in both the visible and infrared regions, reversible metal electrodeposition can only achieve broad-spectrum control. With the increasing sophistication of thermal radiation control, the development of this broad-spectrum control technology is subject to certain development limitations. How to leverage the advantages of reversible metal electrodeposition in dynamic spectral control while also achieving narrow-spectrum dynamic control is a problem that needs to be solved. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition and a construction method thereof. The device has the advantages of simple structure, strong controllability, large modulation amplitude, and the ability to achieve narrow spectrum dynamic switching.

[0007] The present invention provides a visible-infrared narrow-spectrum dynamic control device based on reversible metal electrodeposition, wherein a top substrate layer, a multilayer film structure, an electrolyte layer and a bottom transparent electrode layer are sequentially arranged from top to bottom; the top substrate layer and the multilayer film structure together constitute a working electrode, and reversible deposition and dissolution of metal are performed on the working electrode by controlling an external voltage; the multilayer film structure includes a micro-nano structure and a conductive layer, and narrow-spectrum control is performed in the visible-infrared band by regulating the multilayer film structure.

[0008] Preferably, the top substrate layer is one or more of soda-lime glass, quartz glass, BaF2, CaF2, PP, PE, and PET.

[0009] Preferably, the electrolyte in the electrolyte layer contains at least one metal salt; and the thickness of the electrolyte layer is 1.5 mm to 2.0 mm.

[0010] Preferably, the electrolyte further comprises an auxiliary agent, and the auxiliary agent is one or more of chloride, iodide, bromide, pyridine, and imidazole.

[0011] Preferably, the transparent electrode in the bottom transparent electrode layer comprises one or more of ITO, AZO, and FTO, and the square resistance of the transparent electrode is ≤100Ωsq -1 .

[0012] Preferably, the micro-nano structure is a distributed Bragg reflector DBR; the DBR is composed of alternating high-refractive index materials and low-refractive index materials; wherein the high-refractive index material is one or more of Ge, Si, TiO2, SiN (Si3N4), HfO2, Ta2O5, AlN, Nb2O5, Y2O3, TeO2, ZnO, and ZrO2, with a thickness range of 40 to 1000 nm; the low-refractive index material is one or more of SiO2, Al2O3, MgF2, CaF2, and BaF2, with a thickness range of 60 to 1400 nm.

[0013] Preferably, the conductive layer is located at the bottom of the distributed Bragg reflector DBR and contacts the electrolyte layer, and includes one or more of metal Pt or ITO, AZO, and FTO; the sheet resistance of the conductive layer does not exceed 200Ωsq -1 .

[0014] The present invention also provides a method for constructing a visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition, comprising the following steps:

[0015] Step S1: Select the top substrate layer and the bottom transparent electrode layer and clean and dry them;

[0016] Step S2: Designing a micro-nanostructure for narrow spectrum control of specific wavelengths in the visible-infrared band based on the principle of optical resonance;

[0017] Step S3: using multi-target magnetron sputtering technology or electron beam evaporation technology to prepare the above-mentioned micro-nano structure and conductive layer on the top substrate layer to form a working electrode;

[0018] Step S4: preparing an electrolyte, and sandwiching the electrolyte between the working electrode and the bottom transparent electrode layer to obtain an electrolyte layer;

[0019] Step S5: Lead out the wire terminals to obtain a visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition.

[0020] Preferably, the cleaning and drying method in step S1 is: ultrasonic cleaning with acetone, isopropyl alcohol and deionized water in sequence, and drying with nitrogen.

[0021] Preferably, the optical resonance principle in step S2 is the Tamm resonance principle, and a reconfigurable metal layer is constructed by reversible metal electrodeposition to dynamically excite Tamm resonance, thereby achieving dynamic narrow spectrum control of specific wavelengths in the visible-infrared band. According to the wavelength to be adjusted, a suitable dielectric material is selected, and λ / 4=n is used. L d L =n H d H Calculate the thickness of the DBR high and low refractive index materials, and then use The resonant wavelength is precisely controlled by regulating the thickness (d) of the high-refractive-index material immediately adjacent to the conductive layer. By varying the thickness d while satisfying the Tamm resonance condition, the electric field phase shifts, thereby controlling the resonant wavelength, which now resides within the DBR bandgap.

[0022] Furthermore, the spectrum of the micro-nanostructure before and after metal electroplating is calculated according to the transfer matrix method (TMM), and the structure is numerically simulated to verify whether it meets the narrow spectrum control requirements, and then optimized based on the simulation results.

[0023] Furthermore, the high refractive index material included in the DBR is processed using electron beam evaporation technology, atomic layer deposition technology, or multi-target magnetron sputtering technology. The low refractive index material included in the DBR is processed using electron beam evaporation technology, multi-target magnetron sputtering technology, chemical vapor deposition technology, or inductively coupled plasma chemical vapor deposition technology.

[0024] During specific processing, plasma-enhanced chemical vapor deposition systems and inductively coupled plasma chemical vapor deposition equipment are planned to be used to deposit low-refractive index materials. The specific preparation principle is as follows: PECVD technology operates in a low-pressure environment. At the cathode of the process chamber (that is, the tray where the sample is placed), a glow discharge is generated by low-temperature plasma. At the same time, the sample is heated to a predetermined temperature by means of glow discharge or the addition of a heating element. Subsequently, an appropriate amount of process gas is introduced. These gases undergo a series of chemical reactions and plasma reactions, ultimately forming a solid film on the sample surface. ICPCVD technology is an improvement on PECVD technology. It uses inductive coupling to form plasma at lower temperatures (below 150°C), thereby achieving the growth of chemical vapor deposition films. For multi-target magnetron sputtering technology, a multi-target magnetron sputtering coating system is planned to be used for sputtering deposition. The multi-target magnetron sputtering coating system is capable of sputtering and depositing Pt, Ag, Cu, Au, ITO, and related composite films. The specific preparation principle is: argon (Ar) is introduced into the vacuum chamber of the magnetron sputtering system as a sputtering gas, and a sufficiently high voltage is applied to the cathode target to induce glow discharge and form plasma. The charged particles generated in the plasma move under the action of the Lorentz force. The sputtering gas argon is ionized to produce argon positive ions (Ar + ) and electrons (e). Under the action of the electric field, the positive argon ions are accelerated to fly toward the cathode target, bombarding the target surface with high energy, sputtering the target atoms and eventually depositing them into a film on the substrate.

[0025] Preferably, the reflectivity of the entire device was measured using an integrating sphere. The measured reflectivity was found to be consistent with theoretically calculated reflectivity, demonstrating that multi-target magnetron sputtering, atomic layer deposition, and chemical vapor deposition techniques can produce high-quality nanofilms. Electroplating testing was performed on the device by connecting it to a three-electrode chemical workstation, setting a cycling voltage, and measuring spectral changes before and after electroplating.

[0026] Preferably, the electrolyte in step S4 is prepared by mixing an ionic salt containing metal ions, an auxiliary agent and a solvent.

[0027] Beneficial effects

[0028] (1) The control device of the present invention regulates the spectrum based on optical resonance stimulated by the metal layer. This inherits the advantages of reversible metal electrodeposition, such as large spectral modulation amplitude, simple manufacturing, and the ability to manufacture large-area devices, while solving the problem of dynamic control of narrow-spectrum thermal radiation. The device can also be customized to achieve target functions by designing micro-nanostructures based on specific needs.

[0029] (2) The processing and preparation of the control device of the present invention are all based on conventional coating technology, and multi-target magnetron sputtering can be used to complete the processing of all micro-nano structures, which reduces costs and is expected to achieve large-scale preparation.

[0030] (3) The control device of the present invention has a simple structure, no complex feed lines, and low manufacturing cost. At the same time, it has low driving voltage, low power, and low energy consumption. Thanks to the optical Tamm resonance, the resonant excitation of the device is independent of the electric field polarization, does not require additional auxiliary devices (such as prisms), and is angle-independent. By simply changing the size of the micro-nanostructure, dynamic spectral control of specific wavelengths in the visible-infrared band can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a schematic diagram of the overall structure of the present invention.

[0032] Figure 2 ab are schematic diagrams of the multilayer film structure of the present invention.

[0033] Figure 3 af are spectra before and after metal deposition of the present invention. DETAILED DESCRIPTION

[0034] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0035] Example 1

[0036] Depend on Figure 1 As shown, this embodiment provides a visible-infrared narrow-spectrum dynamic control device based on reversible metal electrodeposition, in which a top substrate layer, a multilayer film structure, an electrolyte layer and a bottom transparent electrode layer are arranged in sequence from top to bottom; the top substrate layer and the multilayer film structure together constitute a working electrode, and reversible deposition and dissolution of metal are performed on the working electrode by controlling the external voltage; the multilayer film structure includes a micro-nano structure and a conductive layer, and narrow-spectrum control is performed in the visible-infrared band by regulating the multilayer film structure.

[0037] The present invention also provides a method for constructing a visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition, comprising the following steps:

[0038] Step S1: Select the top substrate layer and the bottom transparent electrode layer and clean and dry them;

[0039] Step S2: Designing a micro-nanostructure for narrow spectrum control of specific wavelengths in the visible-infrared band based on the principle of optical resonance;

[0040] Step S3: using multi-target magnetron sputtering technology or electron beam evaporation technology to prepare the above-mentioned micro-nano structure and conductive layer on the top substrate layer to form a working electrode;

[0041] Step S4: preparing the electrolyte, sandwiching the electrolyte between the working electrode and the bottom transparent electrode layer and encapsulating it to obtain the electrolyte layer; Step S5: leading out the wire terminals to obtain a visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition.

[0042] In this embodiment, quartz glass is selected as the top substrate layer, and ITO conductive glass (square resistance ≤ 10Ωsq -1 ) as the bottom transparent electrode layer, and washed with acetone, isopropyl alcohol, and deionized water in sequence, and dried under a nitrogen flow.

[0043] The quartz glass is 1mm thick and 5cm x 5cm in size. The micro-nanostructure fabricated on the top substrate is a distributed Bragg reflector (DBR) consisting of alternating TiO2 / SiO2 layers, fabricated using inductively coupled plasma chemical vapor deposition. The conductive layer is a 5nm thick Pt layer, fabricated using multi-target magnetron sputtering.

[0044] Specifically, for the visible light band and near-infrared band, DBR adopts a four-period structure of TiO2 / SiO2 alternately stacked, and its structural diagram is shown as follows Figure 2 As shown in a. For the mid-infrared band, a three-period structure of alternating Si / SiO2 is used, and its structural diagram is shown as follows Figure 2 As shown in b.

[0045] The electrolyte layer is 1.8mm thick and is prepared by weighing 9.37% silver nitrate (AgNO3), 0.03% copper chloride (CuCl2), 80.6% tetrabutylammonium bromide (TBABr), and 10% polyvinyl butyral (PVB) in dimethyl sulfoxide (DMSO). The electrolyte layer is an encapsulated gel electrolyte sandwiched between the working electrode and the bottom transparent electrode layer.

[0046] The construction method of the micro-nanostructure designed for narrow spectrum control of specific wavelengths in the visible-infrared band based on the principle of optical resonance is as follows:

[0047] First, the resonant wavelength to be regulated is used as the central wavelength of the distributed Bragg reflector (DBR), and λ / 4=n L d L =n H d H(λ is the center wavelength) Calculate the thickness of the alternating medium of the distributed Bragg reflector (DBR) and design the spectrum before electroplating. Specifically, for center wavelengths of 0.6μm and 1μm, the thickness of the alternating TiO2 / SiO2 layer is calculated as follows: Figure 3 a.64 / 102nm, Figure 3 b.106 / 170nm, reflectivity spectrum as shown Figure 3 As shown in a and b; for the mid-infrared band with a wavelength of 4μm, the thickness of the alternating Si / SiO2 is calculated to be 680 / 288nm, and the reflection spectrum is shown in Figure 3 Then, adjust the spacer layer thickness to adjust the resonant wavelength position and the wavelength of resonance after metal deposition to meet the needs of narrow spectrum dynamic control. Figure 3 a: Spacer layer thicknesses of 50, 70, and 90 nm were selected for calculation, and their emissivity spectra are shown in the following figure: Figure 3 d, corresponding from left to right; for Figure 3 b: The spacer layer thicknesses of 70, 100, and 130 nm were selected for calculation, and the emissivity spectra are shown in the following figure. Figure 3 e, corresponding from left to right; for Figure 3 c: The spacer layer thicknesses of 210, 250, 290, and 330 nm were selected for calculation, and the emissivity spectra are shown in the following figure. Figure 3 f indicates, corresponding from left to right.

Claims

1. A visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition, characterized by: From top to bottom, a top substrate layer, a multilayer film structure, an electrolyte layer, and a bottom transparent electrode layer are sequentially arranged; the top substrate layer and the multilayer film structure together constitute a working electrode, and reversible deposition and dissolution of metal are performed on the working electrode by controlling an external voltage; the multilayer film structure includes a micro-nano structure and a conductive layer, and narrow spectrum regulation is performed in the visible-infrared band by regulating the multilayer film structure.

2. The visible-infrared narrow spectrum dynamic control device according to claim 1, characterized in that: The top substrate layer is one or more of soda-lime glass, quartz glass, BaF2, CaF2, PP, PE, and PET.

3. The visible-infrared narrow spectrum dynamic control device according to claim 1, characterized in that: The electrolyte in the electrolyte layer contains at least one metal salt; the thickness of the electrolyte layer is 1.5 mm to 2.0 mm.

4. The visible-infrared narrow spectrum dynamic control device according to claim 3, characterized in that: The electrolyte further comprises an auxiliary agent, which is one or more of chloride, iodide, bromide, pyridine, and imidazole.

5. The visible-infrared narrow spectrum dynamic control device according to claim 1, characterized in that: The transparent electrode in the bottom transparent electrode layer includes one or more of ITO, AZO, and FTO, and the square resistance of the transparent electrode is ≤100Ωsq -1 .

6. The visible-infrared narrow spectrum dynamic control device according to claim 1, characterized in that: The micro-nano structure is a distributed Bragg reflector DBR; the DBR is composed of alternating high-refractive index materials and low-refractive index materials; wherein the high-refractive index material is one or more of Ge, Si, TiO2, SiN, HfO2, Ta2O5, AlN, Nb2O5, Y2O3, TeO2, ZnO, and ZrO2, with a thickness range of 40 to 1000 nm; the low-refractive index material is one or more of SiO2, Al2O3, MgF2, CaF2, and BaF2, with a thickness range of 60 to 1400 nm.

7. The visible-infrared narrow spectrum dynamic control device according to claim 1, characterized in that: The conductive layer is located at the bottom of the distributed Bragg reflector DBR and contacts the electrolyte layer, and includes one or more of metal Pt or ITO, AZO, and FTO; the sheet resistance of the conductive layer does not exceed 200Ωsq -1 .

8. A method for constructing a visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition as claimed in claim 1, comprising the following steps: Step S1: Select the top substrate layer and the bottom transparent electrode layer and clean and dry them; Step S2: Designing a micro-nanostructure for narrow spectrum control of specific wavelengths in the visible-infrared band based on the principle of optical resonance; Step S3: using multi-target magnetron sputtering technology or electron beam evaporation technology to prepare the above-mentioned micro-nano structure and conductive layer on the top substrate layer to form a working electrode; Step S4: preparing an electrolyte, and sandwiching the electrolyte between the working electrode and the bottom transparent electrode layer to obtain an electrolyte layer; Step S5: Lead out the wire terminals to obtain a visible-infrared narrow spectrum dynamic control device based on reversible metal electrodeposition.

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