High-valence metal ion assisted reversible electrodeposition dot matrix display device and method thereof

Abstract

The invention relates to the field of reversible electro-deposition dot matrix display, in particular to a reversible electro-deposition dot matrix display device assisted by high-valence metal ions and a method of the reversible electro-deposition dot matrix display device. The high-valence metal ions serve as electrolyte additives, and the deposition behavior process of the metal ions is assisted by the high-valence metal ions. By adopting the technical scheme, the electric bilayer and ion adsorption behaviors are regulated and controlled through introduction of high-valence metal ions, metal deposition is improved, and the optical regulation and control performance is improved.

Description

Technical Field

[0001] The present invention relates to the field of reversible electrodeposition dot matrix display, and particularly to a reversible electrodeposition dot matrix display device and method assisted by high-valent metal ions. Background Art

[0002] An electrochromic display device is a device that can present specific colors or patterns under voltage stimulation, and its optical properties can reversibly change under voltage stimulation. Under the background of the increasingly urgent low-carbon demand, it has gradually become a display technology that has received extensive attention. Among them, the electrochromic technology based on reversible metal electrodeposition has broader application prospects than metal oxide-based electrochromic display devices due to advantages such as color neutrality, simple structure, and low cost.

[0003] The reversible metal electrodeposition technology depends on a liquid electrolyte and a transparent conductive substrate, so its encodability, patterning ability, and customizability are poor, and due to the voltage difference caused by the electrode voltage drop, its zonal control and encoding regulation have become a major problem. Currently, electrodeposition optical devices based on metals or alloys such as Ag, Bi, and Zn exhibit excellent performance in visible light and near-infrared modulation. Through the deposition / stripping behavior of metals, dynamic regulation of optical reflection, transmission, etc. is achieved. However, due to reasons such as dendritic growth, uncontrollable nucleation behavior, and the formation of "dead" metals, the morphology of the electrodeposited metal is uncontrollable, which severely restricts the light field modulation ability of reversible metal electrodeposition devices.

[0004] In the prior art, since the conductive layer and the electrochromic layer of an electrochromic display device are independent of each other, it can be achieved by processing the electrochromic layer or the conductive layer through methods such as a mask plate and etching. For an optical display device based on reversible metal electrodeposition, to achieve pixelated regulation requires that each part can independently modulate the deposition / stripping behavior of the metal. And the electrochromic layer of a metal reversible electrodeposition device depends on the conductive layer. To achieve its pixelated regulation, reasonable circuit design must be carried out to avoid voltage drop, crosstalk, and short circuit, etc. Currently, although the device voltage drop can be effectively alleviated through a metal mesh grid structure, there is still a lack of effective design means for device pixel regulation. In addition, since the growth nucleation mode during metal deposition is dominated by Volmer-Weber, the morphology of the deposited metal thin film is usually not dense and smooth enough, and it does not have good optical display performance in a dot matrix display device, and its open-circuit stability is poor, which greatly limits its application prospects as a display device.

[0005] Therefore, a display device based on reversible metal electrodeposition is needed, which not only meets the uniformity and smoothness of metal film formation, but also designs a reasonable circuit configuration to ensure the independent regulation of each part. Summary of the Invention

[0006] To solve the above problems, the present invention provides a high-valent metal ion-assisted reversible electrodeposition dot matrix display device and method, which are used to regulate the electric double layer and ion adsorption behavior by introducing high-valent metal ions, improve metal deposition, and enhance optical regulation performance.

[0007] To achieve the above object, the technical solution of the present invention is as follows: A high-valent metal ion-assisted reversible electrodeposition dot matrix method, using high-valent metal ions as an electrolyte additive to assist the metal ion deposition behavior process.

[0008] The beneficial effects of adopting the above solution are as follows:

[0009] In this solution, due to the presence of high-valent metal ions, which have extra charges compared to the other two metal ions, when the initial voltage bias is applied, they can preferentially occupy the electrode surface sites, thus generating a strong repulsive force on the metal ions that are not adsorbed on the electrode. This repulsive phenomenon is most prominent at the sites of dendrite growth. Therefore, at the position of dendrite growth, this repulsive force on the deposited metal ions can effectively prevent ion aggregation and selective deposition, and effectively inhibit dendrite growth. On the other hand, this competitive high-valent ion can reduce the Debye length, thereby weakening the repulsive force between ions in the electric double layer and inducing a uniform metal deposition behavior.

[0010] Using high-valent metal ions as an electrolyte additive can regulate the charge balance relationship of the electric double layer, assist the metal ion deposition behavior process, and thus improve the performance of the reversible metal electrodeposition device. The reversible electrodeposition dot matrix display device has a dense and smooth metal deposition film layer, a larger optical contrast, a longer open-circuit stability, and a higher optical reflection intensity.

[0011] A high-valent metal ion-assisted reversible electrodeposition dot matrix display device, characterized in that it includes a dot matrix electrode layer, an electrolyte layer, and a bottom electrode layer. The composition of the electrolyte layer includes CuCl 2 , NiCl 2 , LiClO 4 , high-valent metal ions, and DMSO.

[0012] Beneficial effects: Both the dot matrix electrode layer and the bottom electrode layer adopt conventional electrode materials, and by adding high-valent metal ions to the electrolyte layer, the deposition process is improved to obtain a better deposition effect.

[0013] Furthermore, the high-valent metal ions include Gd 3+ , Ga 3+ , Ce 3+ , Al 3+ , Dy 3+ , Cr 3+ , Tb 3+ , Tm 3+, Ho 3+ , Eu 3+ , Nd 3 + , Sm 3+ , Lu 3+ , Yb 3+ , Er 3+ , Hf 4+ , Ta 5+ , Pr 3+ , Y 3+ , La 3+ , Sc 3+ at least one of

[0014] Advantageous effect: A variety of high-valence metal ions can all assist in the metal ion deposition behavior, so the type of high-valence metal ions selected can be adjusted according to the cost requirements.

[0015] Furthermore, the molar ratio of Cu 2+ and Ni 2+ in the electrolyte is between 1:1 and 1:5, and the added content of the high-valence metal ions is 5%-20% of the total molar amount of Cu 2+ and Ni 2+ .

[0016] Advantageous effect: By reasonable Cu 2+ and Ni 2+ , a better metal precipitation effect can be obtained. At the same time, the added content of the high-valence metal ions is 5%-20% of the total molar amount of Cu 2+ and Ni 2+ , which can ensure that the high-valence metal ions will not overly affect the performance of the CuNi alloy.

[0017] Furthermore, the bottom electrode layer is one of ITO, FTO, and AZO, and the dot-matrix electrode layer is one of ITO, FTO, and AZO after laser etching.

[0018] Advantageous effect: ITO is doped tin oxide, FTO is fluorine-doped tin oxide, and AZO is aluminum-doped zinc oxide, all of which can be the constituent materials of the bottom electrode layer and the dot-matrix electrode layer.

[0019] Furthermore, the area of a single array square in the dot-matrix electrode layer is between 1-3 cm 2 .

[0020] Advantageous effect: Through the design of array squares with appropriate sizes, the deposition uniformity of the display device and the fineness of dot-matrix display can be ensured.

[0021] Further, the dot matrix electrode layer further includes a plurality of wires, the spacing between the wires is 0.2 mm - 0.5 mm, one end of each wire is respectively connected to an array block, and the other end of each wire is provided with a pin having an area of 1 cm 2 2.

[0022] Beneficial effects: Through appropriate wire design, effective conduction of current can be ensured.

[0023] Further, the wires are arranged on the substrate surface in the shortest path.

[0024] Beneficial effects: Arranging in the shortest path can minimize the voltage drop effect and ensure the uniformity of deposition.

[0025] Further, the shortest path is designed to achieve the lowest voltage drop effect, and the calculation formula for the voltage drop effect reduction is:

[0026]

[0027] Among them, J represents the confined diffusion deposition current density, R sh is the sheet resistance of the electrode surface, L represents the maximum length of the electrode surface, and V represents the deposition voltage magnitude.

[0028] Beneficial effects: The formula shows that there is a large voltage drop phenomenon on the entire electrode surface from the center to the edge region. Only by minimizing the actual length of each unit region from the voltage excitation as much as possible can effective, high-quality, and fast-response metal electrodeposition be ensured.

[0029] A manufacturing method of a high-valent metal ion-assisted reversible electrodeposition dot matrix display device, including:

[0030] Step 1, prepare a plurality of dot matrix electrode layer electrodes to be processed and bottom electrode layer electrodes to be processed. Etch microstructures on the surface of the dot matrix electrode layer electrodes by laser etching, and clean them with acetone solution after etching; use a plasma cleaner to clean the dot matrix electrode layer electrodes and the bottom electrode layer electrodes for 8 min - 15 min for surface hydrophilic treatment;

[0031] Step 2, dissolve CuCl 2 , NiCl 2 , LiClO 4 , high-valent metal ions and polyvinyl alcohol in a DMSO solution in a preset ratio to obtain an electrolyte solution;

[0032] Step 3, package the dot matrix electrode layer electrodes and the bottom electrode layer electrodes in a sandwich configuration, use 3M tape as a spacer layer, package them into a single device, inject the electrolyte solution into the device with a syringe, and deposit CuNi alloy by constant voltage.

[0033] Additional aspects and advantages of the present invention will be given in part in the following description, become apparent in part from the following description, or be learned by practice of the present invention. Description of the Drawings

[0034] Figure 1 Schematic diagram of the dot matrix electrode layer of the high-valent metal ion-assisted reversible electrodeposition dot matrix display device of the present invention;

[0035] Figure 2 Schematic diagram of AFM in the performance test of the high-valent metal ion-assisted reversible electrodeposition dot matrix display device of the present invention;

[0036] Figure 3 Schematic diagram of SEM in the performance test of the high-valent metal ion-assisted reversible electrodeposition dot matrix display device of the present invention;

[0037] Figure 4 Schematic diagram of the dynamic deposition spectrum test in the performance test of the high-valent metal ion-assisted reversible electrodeposition dot matrix display device of the present invention;

[0038] Figure 5 Schematic diagram of the current change and energy spectrum in the performance test of the high-valent metal ion-assisted reversible electrodeposition dot matrix display device of the present invention;

[0039] Figure 6 Schematic diagram of the change of transparency with time in the performance test of the high-valent metal ion-assisted reversible electrodeposition dot matrix display device of the present invention;

[0040] Figure 7 Schematic diagram of the patterned display of the present invention.

[0041] Reference numerals in the drawings of the specification include: 1, array square; 2, wire; 3, pin. Detailed Embodiments

[0042] The technical solutions of the present invention will be clearly and completely described below with reference to the drawings. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0043] In the description of the present invention, it should be noted that the orientation or positional relationship indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation to the present invention. In addition, the terms "first", "second", "third" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance.

[0044] In the description of the present invention, it should be noted that unless otherwise clearly specified and defined, the terms "mounted", "connected", "coupled" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection, an electrical connection; it can be directly connected, or indirectly connected through an intermediate medium, and it can be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations.

[0045] The following is a further detailed description through specific embodiments:

[0046] As shown in the Figures 1-7 accompanying drawings: A method for reversibly electro-depositing a lattice assisted by a high-valent metal ion, using the high-valent metal ion as an electrolyte additive to utilize the process of the high-valent metal ion assisting the metal ion deposition behavior.

[0047] Due to the presence of the high-valent metal ion, it has extra charges compared to the other two metal ions. When the initial voltage bias is applied, it can preferentially occupy the electrode surface sites, thereby generating a strong repulsive force on the metal ions not adsorbed on the electrode. This repulsive phenomenon is most prominent at the sites of dendrite growth. Therefore, at the position of dendrite growth, this repulsive force phenomenon on the deposited metal ions can effectively prevent ion aggregation and selective deposition, and effectively inhibit dendrite growth. On the other hand, this competitive high-valent ion can reduce the Debye length, thereby weakening the repulsive force between ions in the double electric layer and inducing a uniform metal deposition behavior.

[0048] Using the high-valent metal ion as an electrolyte additive can regulate the charge balance relationship of the electric double layer, assist the metal ion deposition behavior process, and thus improve the performance of the reversible metal electro-deposition device. Make the reversible electro-deposited lattice display device have a dense, smooth metal deposition film layer, a larger optical contrast, a longer open-circuit stability, and a higher optical reflection intensity.

[0049] A reversible electro-deposited lattice display device assisted by a high-valent metal ion, characterized in that it includes a lattice electrode layer, an electrolyte layer, and a bottom electrode layer, and the composition of the electrolyte layer includes CuCl2 , NiCl 2 , LiClO 4 , and a high-valent metal ion and DMSO. The high-valent metal ion includes Gd 3+ , Ga 3+ , Ce 3+ , Al 3+ , Dy 3+ , Cr 3+ , Tb 3+ , Tm 3+ , Ho 3+ , Eu 3+ , Nd 3+ , Sm 3+ , Lu 3+ , Yb 3+ , Er 3+ , Hf 4+ , Ta 5+ , Pr 3+ , Y 3+ , La 3+ , Sc 3+ at least one of. In the electrolyte, the molar ratio of Cu 2+ and Ni 2+ is between 1:1 and 1:5, and the addition content of the high-valent metal ion is 5%-20% of the total molar amount of Cu 2+ and Ni 2+ . The bottom electrode layer is one of ITO, FTO, and AZO, and the dot-matrix electrode layer is one of ITO, FTO, and AZO after laser etching.

[0050] Both the dot-matrix electrode layer and the bottom electrode layer use conventional electrode materials. By adding high-valent metal ions to the electrolyte layer, the deposition process is improved to obtain a better deposition effect. A variety of high-valent metal ions can all assist in the deposition behavior of metal ions, so the type of high-valent metal ions selected can be adjusted according to their own cost requirements.

[0051] The area of a single array square 1 in the dot-matrix electrode layer is between 1 and 3 cm 2 . The dot-matrix electrode layer further includes several wires 2, the spacing of the wires 2 is 0.2 mm - 0.5 mm, one end of each wire 2 is respectively connected to an array square 1, and the other end of each wire 2 is provided with a pin 3 with an area of 1 cm 2 . The wires 2 are all arranged on the substrate surface with the shortest path. The shortest path is designed to achieve the lowest voltage drop effect, and the calculation formula for the voltage drop effect is:

[0052]

[0053] where J represents the confined diffusion deposition current density, R shis the sheet resistance of the electrode surface, L represents the maximum length of the electrode surface, and V represents the deposition voltage magnitude.

[0054] The formula shows that there is a large voltage drop phenomenon across the entire electrode surface, from the center to the edge region. Only by minimizing the actual length of each unit region from the voltage excitation as much as possible can effective, high-quality, and fast-response metal electrodeposition be ensured.

[0055] Through the design of an array square 1 with appropriate dimensions, the deposition uniformity of the display device and the fineness of the dot matrix display can be ensured. Through the design of an appropriate wire 2, the effective conduction of current can be ensured. The shortest path layout can minimize the voltage drop effect and ensure deposition uniformity.

[0056] A method for fabricating a reversible electrodeposition dot matrix display device assisted by high-valent metal ions:

[0057] Select ITO as the material for the dot matrix electrode layer and the bottom electrode layer. First, microstructures are etched on the ITO electrode surface by laser etching, as Figure 1 shown. Then, the etched electrode is cleaned with acetone solution and surface hydrophilic treatment is performed by cleaning with a plasma cleaner for 10 min. The ITO electrode serving as the bottom electrode layer is also cleaned with the plasma cleaner for the same time. Then, an electrolyte is prepared by dissolving copper chloride (CuCl 2 ), nickel chloride (NiCl 2 ), lithium perchlorate (LiClO 4 ), gadolinium chloride (GdCl 3 ) and polyvinyl alcohol in DMSO solution in a preset ratio to obtain the electrolyte.

[0058] A three-electrode system is used for depositing a metal film on the ITO substrate. Among them, ITO is the working electrode, and a CuNi alloy is deposited on the ITO surface using a constant voltage. A Pt sheet is used as the counter electrode, and Ag / AgCl is used as the reference electrode. The device with dot matrix display is encapsulated in a "sandwich" configuration. 3M tape is used as the spacer layer to encapsulate the dot matrix-etched ITO and the unetched ITO into a single device, and the electrolyte is injected into the device with a syringe. The electrodeposition and cyclic performance tests of the device also use a two-electrode system. The dot matrix ITO is the working electrode, and the reference electrode and the counter electrode are both connected to the counter electrode ITO.

[0059] First, electrochemical and spectral modulation performance tests are carried out on the electrochromic device with the addition of high-valent ions. The deposition morphologies of the reversible electrodeposition devices with and without the addition of Gd 3+ are characterized respectively. Their AFM and SEM images are as 3+ shown in Figure 2 and 3 shown. Whether it is at 30 s or 60 s of deposition, with Gd3+ The added reversible metal electrodeposition device has more uniform nucleation sites and smaller roughness. Its surface morphology is smoother, the thin film quality is denser, and it can effectively inhibit dendrite growth. In contrast, the device without the addition of high-valent ions has a rough and uneven thin film surface with low density. The smoother, denser, and dendrite-free thin film is more favorable during dissolution and can more easily obtain a large optical contrast to achieve a wide range of spectral regulation. In addition, the reversible metal electrodeposition device with a uniform deposition morphology can make the ion concentration distribution near the electrode more uniform, effectively improving the overall stability and open-circuit retention.

[0060] The dynamic deposition spectra of the device were tested, and the deposition spectra and device photos at the initial state, 3 s, 5 s, 10 s, 20 s, 30 s, and 50 s were characterized respectively, as Figure 4 shown, Figure 4 where a is the device photo with the addition of Gd 3+ and b is the device photo without the addition of Gd 3+ . Due to the addition of Gd 3+ , it can better induce the uniform film formation of the deposited metal, showing a faster optical modulation response and a larger optical contrast (less than 0.3%). And it can show more obvious specular state characteristics, which is due to the dense and smooth deposited metal film, enhancing the spectral reflection.

[0061] Figure 5 where a is the graph of the current change with time of the device without the addition of Gd 3+ and the device with the addition of Gd 3+ , b is the graph of the current change with voltage of the device without the addition of Gd 3+ and the device with the addition of Gd 3+ , c is the energy spectrum diagram after the addition of Gd 3+ and d is the energy spectrum diagram without the addition of Gd 3+ . It is proved that during the metal deposition process, the high-valent Gd 3+ acts as an additive, effectively slowing down the metal deposition process, which is also an important reason for its uniform deposition. After the addition of Gd 3+ , the deposition system has a smaller current and a larger polarization voltage, which is strong evidence of the competition between Gd 3 + and other deposited metal ions in the reaction system. According to the energy spectra of the metal deposition before and after the addition of Gd 3+ , it can be seen that Gd 3+ does not participate in the deposition process but mainly acts as a regulatory factor in the whole system, playing its role as an electrolyte additive.

[0062] Figure 6 It shows that Gd 3+After addition, it can effectively improve the open-circuit stability of the device because the denser and smoother metal film proves that the deposited metal thin film has higher quality, its self-erasure effect can be effectively suppressed, more ions need to diffuse to the surface of the deposited metal and more reaction energy is required, which leads to the improvement of its bistable performance and can reach 50 minutes.

[0063] Figure 7 It is a schematic diagram of patterned display of a dot matrix display device, showing the displayed letters "K", "L", "M", "R". Through different voltage excitations and stimulations, the preparation of pixelated and dot matrix devices based on reversible metal electrodeposition can be realized.

[0064] Obviously, the above embodiments are only examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or variations can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or variations derived therefrom are still within the protection scope of the present invention.

Claims

1. A high-valent metal ion-assisted reversible electrodeposition lattice method, characterized in that: High-valent metal ions are used as electrolyte additives to assist the metal ion deposition process.

2. A high-valent metal ion-assisted reversible electrodeposition dot matrix display device, characterized in that: It includes a dotted electrode layer, an electrolyte layer and a bottom electrode layer. The electrolyte layer comprises CuCl2, NiCl2, LiClO4, high-valent metal ions and DMSO.

3. The high-valent metal ion-assisted reversible electrodeposition dot matrix display device according to claim 2, characterized in that: High-valent metal ions include Gd 3+ , Ga 3+ 、Ce 3+ 、Al 3+ 、Dy 3+ Cr 3+ , Tb 3+ 、Tm 3+ 、Ho 3+ 、Eu 3+ 、Nd 3+ 、Sm 3+ 、Lu 3+ , Yb 3+ , Er 3+ , Hf 4+ 、 5+ , Pr 3+ , Y 3+ ,La 3+ Sc 3+ At least one of .

4. The high-valent metal ion-assisted reversible electrodeposition dot matrix display device according to claim 3, characterized in that: Cu in electrolyte 2+ and Ni 2+ The molar ratio is between 1:1-1:5, and the high-valent metal ion addition content is Cu 2+ and Ni 2+ 5%-20% of the total molar amount.

5. The high-valent metal ion-assisted reversible electrodeposition dot matrix display device according to claim 4, characterized in that: The bottom electrode layer is one of ITO, FTO and AZO, and the dot-matrix electrode layer is one of ITO, FTO and AZO after laser etching.

6. The high-valent metal ion-assisted reversible electrodeposition dot matrix display device according to claim 5, characterized in that: The area of ​​a single array block (1) in the dot-matrix electrode layer is 1-3 cm 2 between.

7. The high-valent metal ion-assisted reversible electrodeposition dot matrix display device according to claim 6, characterized in that: The dot matrix electrode layer also includes a plurality of wires (2), the spacing between the wires (2) is 0.2 mm to 0.5 mm, one end of each wire (2) is connected to an array block (1), and the other end of each wire (2) is provided with a 1 cm 2 pin (3).

8. The high-valent metal ion-assisted reversible electrodeposition dot matrix display device according to claim 7, characterized in that: The conductive wires (2) are arranged on the surface of the substrate in the shortest path.

9. The high-valent metal ion-assisted reversible electrodeposition dot matrix display device according to claim 8, characterized in that: The shortest path is designed to achieve the lowest voltage drop effect. The voltage drop effect is calculated as: Where J represents the confined diffusion deposition current density, R sh is the square resistance of the electrode surface, L represents the maximum length of the electrode surface, and V represents the deposition voltage.

10. A method for manufacturing a high-valent metal ion-assisted reversible electrodeposition dot matrix display device, based on the method for manufacturing a display device according to claims 2-9, characterized in that: include: Step 1: prepare a plurality of electrodes of the dotted electrode layer and the bottom electrode layer to be processed, etch a microstructure on the surface of the electrodes of the dotted electrode layer by laser etching, and clean them with acetone solution after etching; use a plasma cleaning machine to clean the electrodes of the dotted electrode layer and the bottom electrode layer for 8 minutes to 15 minutes to perform surface hydrophilic treatment; Step 2, dissolving CuCl2, NiCl2, LiClO4, high-valent metal ions and polyvinyl alcohol in a DMSO solution according to a preset ratio to obtain an electrolyte; Step three, encapsulating the electrodes of the dotted electrode layer and the bottom electrode layer in a sandwich configuration, using 3M tape as a spacer layer, encapsulating them into a single device, injecting the electrolyte into the device with a syringe, and depositing the CuNi alloy using a constant voltage.

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