A high-resolution patterned electrochromic display device and a method for making the same

Abstract

The present application relates to a kind of high-resolution patterning electrochromic display device and its preparation method.The high-resolution patterning electrochromic display device, including the first transparent electrode layer, buffer layer, electrochromic layer containing multiple hole array arrangement, gel electrolyte layer filled in aperture and second transparent electrode layer arranged in sequence.

Description

Technical Field

[0001] This invention relates to a high-resolution patterned electrochromic display device and its preparation method, belonging to the technical fields of chemical material synthesis and functional materials. Background Technology

[0002] Energy is a crucial foundation for maintaining a nation's sustained economic development and ensuring people's material living standards. Today, energy shortages and environmental pollution are becoming increasingly severe. While developing new energy sources, scientists are also striving to find ways to conserve energy and reduce consumption. Buildings are one of the main places for human production and living activities, and they account for a large proportion of total energy consumption. Within building energy consumption, the energy consumption of lighting and air conditioning systems, used to improve building comfort, accounts for over 75% of total building energy consumption. Both of these energy consumption components are related to windows and doors; therefore, developing energy-efficient building glass is an important way to achieve building energy conservation. Current methods for controlling energy loss in building glass are static. For example, Low-E glass, which has high reflectivity in the infrared band, can block infrared rays from passing through windows; double-glazed windows utilize the low thermal conductivity of air to reduce heat conduction between the indoor and outdoor spaces. In the 1980s, scientists proposed the concept of "smart windows" based on electrochromic materials—a type of architectural window structure material that actively regulates the intensity of visible and near-infrared transmitted light. It can dynamically adjust the intensity of light entering the room according to the differences between indoor and outdoor environments, reducing the use of air conditioning and lighting systems. Combined with Low-E and insulated glass, it can achieve better energy-saving effects. The performance of electrochromic materials determines the light-regulating ability of "smart windows," thus attracting widespread attention. Electrochromism refers to the reversible color change phenomenon of a material's optical properties, such as transmittance and reflectivity, under low voltage, manifesting as a reversible transformation between a blue and transparent state. Electrochromism is currently a hot research topic with wide applications. Electrochromic devices and technologies are mainly used in energy-saving building glass, other moving vehicle windows, automotive anti-glare rearview mirrors, displays, electronic paper, and camouflage applications. Low-E is a type of low-emissivity glass that works by reflecting most infrared radiation, reducing heat entering the room. Insulated glass reduces heat exchange between the indoor and outdoor environments. The purpose of both is to reduce indoor cooling energy consumption. However, both types of windows and their combinations only facilitate cooling, not temperature regulation. That is, in cold winters, heat still has difficulty entering the room.

[0003] Traditional electrochromic devices mainly consist of five thin film layers: two transparent conductive layers, an ion storage layer, an electrochromic layer, and an ion conduction layer. The ion storage layer assists the electrochromic layer in achieving the electrochromic reaction by applying a low voltage to the first and second conductive layers. The ion conduction layer provides lithium ions and diffuses the thin film, ensuring ion conductivity under an electric field; its structure and fabrication process are among the most important technologies for guaranteeing the electrochromic performance of the device. Because all-solid-state electrochromic devices are structurally stable and have good resistance to water, oxygen, and ultraviolet radiation, they avoid the drawbacks of liquid and quasi-solid-state devices, such as leakage, instability, and poor cycle stability, and are therefore widely used.

[0004] All-solid-state electrochromic devices offer advantages such as high contrast, high transparency, and high cycle durability, demonstrating broad application prospects in the display field. However, current electrochromic display devices exhibit some degree of blurring at the edges of patterns or text during the fading / coloring process, resulting in relatively low resolution. Summary of the Invention

[0005] To address the issue of low resolution in existing electrochromic display devices, this invention optimizes the edge sharpness of the display pattern during the color-changing / fading process by designing an electrochromic layer with an array aperture structure and a gel-based ion storage layer with good fluidity, thereby achieving high-resolution display.

[0006] Specifically, the present invention provides a high-resolution patterned electrochromic display device, the electrochromic device comprising a first transparent electrode layer, a buffer layer, an electrochromic layer containing an array of multiple holes arranged in sequence, a gel electrolyte layer filling the holes and covering the electrochromic layer, and a second transparent electrode layer.

[0007] This invention fabricates a high-resolution electrochromic display device by optimizing the device structure and controlling the edges of patterns or text during coloring. Specifically, according to the desired display pattern, a highly fluid ion storage layer precursor solution can fully fill the electrochromic layer with an array of apertures. This structure not only shortens the migration distance of ions but also restricts ion movement within the electrochromic layer, thereby improving the device's response speed and display resolution. To prevent short circuits, a buffer layer is inserted between the electrode and the electrochromic layer to improve the device's internal electronic insulation. The electrochromic display device exhibits excellent resolution during the coloring / fading process.

[0008] Preferably, the materials of the first transparent electrode layer and the second transparent electrode layer are independently selected from at least one of transparent conductive oxide and metal nanowires; the sheet resistance of the first transparent electrode layer and the second transparent electrode layer is 10 to 40 Ω / cm. 2 Visible light transmittance ≥75%.

[0009] Preferably, the material of the buffer layer is at least one of SiO2, Si3N4, Al2O3, and SnO2; the film thickness of the buffer layer is 5 to 50 nm.

[0010] Preferably, the electrochromic layer is made of at least one of WO3, MoO3, and TiO2; the cross-sectional shape of the pores is rectangular or circular; the diameter of the pores is 1–20 μm, the minimum spacing between adjacent pores is 1–20 μm, and the height of the pores is 500–1000 nm. If the pore size is too large, the amount of electrochromic layer material will be reduced, affecting the device's performance and structural stability; if the pore size is too small, the intended purpose will not be achieved, affecting the device's bonding strength; if the pore spacing is too large, the interfacial bonding strength of the device will be reduced; if the pore spacing is too small, the improvement in device resolution will be insignificant, failing to achieve the intended purpose.

[0011] Preferably, the gel electrolyte layer is a lithium-containing gel-based solid electrolyte; the lithium salt is selected from at least one of lithium chloride, lithium perchlorate, lithium phosphate, lithium silicate, and LiPON; without calculating the pore height, the thickness of the gel electrolyte layer is 1.5 nm to 9 μm.

[0012] Preferably, the method for preparing the gel electrolyte layer includes:

[0013] (1) Weigh the UV resin monomer, stabilizer, organic precursor and lithium salt according to the mass ratio of 1:(0.05~0.2):(0.5~2):(1~3) and stir until completely dissolved to obtain mixed solution 1;

[0014] (2) Add an initiator to mixed solution 1 to obtain mixed solution 2;

[0015] (3) The obtained mixed solution 2 was spin-coated and then cured under ultraviolet light to obtain a gel electrolyte layer.

[0016] Preferably, the UV resin monomer is selected from at least one of HDDA (hexanediol diacrylate), pentaerythritol triacrylate (PETA), dipropylene glycol diacrylate (DPGDA), and dipropylene glycol diacrylate (TPGDA); the photocurable resin monomer is used in the gel electrolyte layer of the device due to its good flowability.

[0017] The stabilizer is a transition metal organometallic compound, preferably ferrocene or its derivatives;

[0018] The organic precursor includes an acid ester compound, preferably ethoxylated trimethylolpropane triacrylate (ETPTA).

[0019] The initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile, cumene hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxide, dicyclohexyl peroxide, di-tert-butyl peroxide, diisopropyl peroxide, tert-butyl peroxybenzoate, and tert-butyl peroxyvalerate, and is added in an amount of 0.1% to 0.3% of the total mass.

[0020] The spin coating speed is 1000-3000 rpm, and the time is 10-30 seconds;

[0021] The photocuring process involves irradiation with a 100-300W ultraviolet lamp for 5-60 seconds.

[0022] Preferably, at least one of a leveling agent, an adhesion promoter, and a defoamer is added to the mixed solution 1, and this is referred to as mixed solution 3;

[0023] The leveling agent is selected from at least one of BYK333, BYK358N, BYK306 and BYK378, and the amount added is 0.5% to 2% of the total mass;

[0024] The adhesion promoter is selected from at least one of BYK4500, BYK4509, BYK4510, BYK4511 and BYK4512, and is added in an amount of 0.05 to 2% of the total mass.

[0025] The defoamer is selected from at least one of BYK011, BYK012, BYK014, BYK018 and BUK019, and the amount added is 0.1 to 0.5% of the total mass.

[0026] On the other hand, the present invention provides a method for fabricating the above-mentioned high-resolution patterned electrochromic display device, wherein the method for fabricating the electrochromic layer containing a plurality of aperture arrays includes:

[0027] (1) An unetched electrochromic layer was deposited on the buffer layer using a magnetron sputtering process;

[0028] (2) Near-infrared laser is used for etching to obtain an electrochromic layer containing multiple aperture arrays.

[0029] Preferably, in step (1), the parameters of the magnetron sputtering process include: deposition power of 50-100W, deposition gas pressure of 1-2Pa, and deposition time of 15-60 minutes.

[0030] Preferably, in step (2), the etching parameters include: a near-infrared laser power of 10–100 W and a wavelength of 1200 nm; a hole diameter of 1–20 μm; and a minimum hole spacing of 1–20 μm between adjacent holes. Studies using laser etching of arrayed holes on an electrochromic surface have shown that hole spacing and hole diameter are closely related to the device resolution.

[0031] Beneficial effects:

[0032] 1. This patent designs a device structure with an array of holes, which can precisely restrict the flow of liquid precursor liquid, thereby achieving high-precision application / fading of the electrochromic layer of the device;

[0033] 2. The high-resolution patterned electrochromic display device of the present invention has a simple structure, is easy to manufacture, has a low cost, and meets the display requirements of high precision. Attached Figure Description

[0034] Figure 1 This is a schematic diagram of the structure of the high-resolution patterned electrochromic display device of the present invention.

[0035] Figure 2 This is a schematic diagram illustrating the evaluation of the display resolution of the high-resolution patterned electrochromic display device in Example 1. Detailed Implementation

[0036] The present invention will be further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0037] In this field, all-solid-state electrochromic devices offer advantages such as high contrast, high transparency, and high cycle durability, demonstrating broad application prospects in the display industry. However, current electrochromic display devices exhibit some degree of blurring at the edges of patterns or text during the fading / coloring process, resulting in lower resolution.

[0038] In this disclosure, a high-resolution electrochromic display device is fabricated by optimizing the device structure and controlling the edges of patterns or text during coloring. Specifically, the high-resolution patterned electrochromic display device comprises: a first transparent electrode layer, a buffer layer, an electrochromic layer containing an array of multiple holes, a gel electrolyte layer, and a second transparent electrode layer, which are sequentially stacked. The desired pattern is formed by filling some or all of the holes with gel electrolyte layer material.

[0039] In this invention, the high-resolution patterned electrochromic display device has a simple structure, is easy to fabricate, and has a low cost, meeting the display requirements for high precision. In this invention, a buffer layer and an unetched electrochromic layer are prepared using magnetron sputtering deposition. The DC magnetron sputtering system used for magnetron sputtering deposition may include a deposition chamber, a sample inlet chamber, several target heads, a substrate, a DC current source, and a series of mechanical pumps and vacuum pumps. The target head is at a certain angle to the substrate and separated by a certain distance, and the DC power supply is connected to the target head. The substrate is ultrasonically cleaned with acetone, anhydrous ethanol, and deionized water for 20 minutes each, and then dried with compressed air. A portion of the conductive substrate is covered with high-temperature tape as an electrode and fixed on the substrate tray. The substrate is placed in the sample inlet chamber, and the mechanical pump is turned on to pump the pressure to below 5 Pa. Then, the baffle valve is opened, and the vacuum level (baseline vacuum) reaches 10 Pa. -4 Splash chambers with Pa and below.

[0040] The specific sputtering deposition process is as follows: High-purity argon and oxygen are introduced into the sputtering chamber, with the purity of the argon and oxygen being 99.99% or higher. The total pressure and oxygen partial pressure within the chamber are controlled within the ranges of 0.5–2.0 Pa and 0–50%, respectively, with the oxygen partial pressure preferably being 0–25%. The vertical distance between the target and the substrate is controlled to be 10–20 cm, and the initial substrate temperature is room temperature. The DC power supply is turned on, and the power is controlled to be 30–200 W. The pre-sputtering time is 5–30 min, the sputtering time is 10–60 min, and the substrate temperature is room temperature. After sputtering, the substrate is removed after the substrate temperature has cooled to room temperature.

[0041] A transparent conductive glass substrate was selected, and a buffer layer was continuously deposited on its surface. A magnetron sputtering method was used, with Si as the target material, argon and oxygen as the sputtering gases, a total pressure of 0.5–2.0 Pa, an oxygen partial pressure of 0–50%, a target-substrate distance of 10–20 cm, an initial substrate temperature of room temperature, and an applied radio frequency power of 30–150 W. A buffer layer film with a thickness of 5 nm–50 nm was deposited.

[0042] Preparation of inorganic electrochromic layers. Tungsten, molybdenum, or titanium is used as the target material. The sputtering gas is argon and oxygen, with a total pressure of 0.5–2.0 Pa and an oxygen partial pressure of 0–50%. The distance between the target and the substrate is 10–20 cm, and the initial substrate temperature is room temperature. The DC power applied to the target is 30–150 W, resulting in an electrochromic thin film with a thickness of 500 nm–1000 nm. A near-infrared laser is used, with an etching power of 10–100 W, a wavelength of 1200 nm, an aperture (hole diameter) of 1–20 μm, and a hole spacing of 1–20 μm.

[0043] The electrolyte uses UV-curable resin as a base material, with appropriate amounts of solvent, cationic salt, stabilizer, reducing agent, defoamer, leveling agent, adhesion promoter, and initiator added. A stable solution is obtained after thorough stirring and dissolution.

[0044] Prepare a precursor solution for a gel-based gel electrolyte layer. (1) Prepare a precursor solution of UV resin monomer, ferrocene, ETPTA and lithium salt in a mass ratio of 1:(0.05~0.2):(0.5~2):(1~3) and mix them. Heat the mixture to 50-80℃ (e.g. 60℃) and stir thoroughly until the solute is completely dissolved to obtain mixed solution 1. (3) Add (0.5~2)% leveling agent, (0.05~0.2)% adhesion promoter and (0.1~0.5)% defoamer to mixed solution 1 and continue stirring the solution until it is clear and transparent to obtain mixed solution 3. (4) Add an appropriate amount of azobisisobutyronitrile or the like as an initiator to mixed solution 3 and stir until it is clear and transparent to obtain mixed solution 2.

[0045] A spin-coating process was used to deposit the mixed solution 2 onto the etched electrochromic layer surface. After spin-coating (rotation speed can be 1000-3000 rpm), an uncured gel electrolyte layer with a film thickness of 2-10 μm was obtained (the thickness before and after curing is not significantly different and can be directly regarded as the thickness of the gel electrolyte layer). After covering with a second transparent electrode, the desired display pattern template was uniformly irradiated under a 100W UV lamp for 15 seconds. After the device cured, residual solvent was cleaned with ethyl acetate, and then encapsulated to finally obtain a high-resolution electrochromic display device.

[0046] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters such as time, temperature, pressure, and power in the following examples are merely examples within a suitable range; that is, those skilled in the art can select appropriate ranges based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0047] Example 1

[0048] (1) A transparent conductive glass substrate was selected, and a buffer layer and an inorganic electrochromic layer were continuously deposited on its surface. A buffer layer film with a thickness of 20 nm was deposited by magnetron sputtering with Si as the target material, argon and oxygen as the sputtering gases, a total pressure of 1.0 Pa, an oxygen partial pressure of 10%, a target-to-substrate distance of 15 cm, an initial substrate temperature of room temperature, and an applied RF power of 100 W. An electrochromic layer film with a thickness of 800 nm was deposited using tungsten as the target material, argon and oxygen as the sputtering gases, a total pressure of 1.5 Pa, an oxygen partial pressure of 15%, a target-to-substrate distance of 15 cm, an initial substrate temperature of room temperature, and an applied DC power of 100 W. A near-infrared laser was used with an etching power of 40 W, a wavelength of 1200 nm, an aperture of 12 μm, and a hole spacing of 12 μm.

[0049] (2) Prepare the precursor solution for the gel-based gel electrolyte layer. (1) Prepare a precursor solution of tripropylene glycol acrylate (TPGDA), ferrocene, ETPTA and lithium perchlorate in a mass ratio of 1:0.1:1:1. Heat the mixed solution to 60°C and stir thoroughly until the solute is completely dissolved to obtain mixed solution 1. (3) Add 1% leveling agent, 0.1% adhesion promoter and 0.2% defoamer to the above mixed solution 1, and continue stirring the solution until it is clear and transparent to obtain mixed solution 3. (4) Add an appropriate amount of azobisisobutyronitrile as an initiator to mixed solution 3 and stir until it is clear and transparent to obtain mixed solution 2.

[0050] (3) The mixed solution 2 is deposited on the surface of the electrochromic layer using a spin-coating process, with the rotation speed controlled at 2500 rpm. The resulting film thickness is 2-10 μm (e.g., 5 μm). After covering with the second transparent electrode layer, the desired pattern template is uniformly irradiated under a 100W UV lamp for 15 seconds using ultraviolet light. After the device has cured, the residual solvent is cleaned with ethyl acetate, and then encapsulated to finally obtain a high-resolution electrochromic display device.

[0051] Example 2

[0052] The fabrication process of the high-resolution electrochromic display device in this embodiment 2 is the same as that in embodiment 1, except that in step (1), Si is used as the target material by magnetron sputtering, the sputtering gas is argon and oxygen, the total pressure is 1.0 Pa, the oxygen partial pressure is 10%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, and a buffer layer film with a thickness of 5 nm is deposited.

[0053] Example 3

[0054] The fabrication process of the high-resolution electrochromic display device in this embodiment 3 is the same as that in embodiment 1, except that in step (1), Si is used as the target material by magnetron sputtering, the sputtering gas is argon and oxygen, the total pressure is 1.0 Pa, the oxygen partial pressure is 10%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the radio frequency power applied to the target material is 100 W, and a buffer layer film with a thickness of 50 nm is deposited.

[0055] Example 4

[0056] The fabrication process of the high-resolution electrochromic display device in Example 4 is the same as that in Example 1, except that in step (1), a near-infrared laser is used with an etching power of 40W, a wavelength of 1200nm, an aperture of 1μm, and an aperture spacing of 12μm.

[0057] Example 5

[0058] The fabrication process of the high-resolution electrochromic display device in Example 5 is the same as that in Example 1, except that in step (1), a near-infrared laser is used with an etching power of 40W, a wavelength of 1200nm, an aperture of 20μm, and an aperture spacing of 12μm.

[0059] Example 6

[0060] The fabrication process of the high-resolution electrochromic display device in Example 6 is the same as that in Example 1, except that in step (1), a near-infrared laser is used with an etching power of 40W, a wavelength of 1200nm, an aperture of 12μm, and an aperture spacing of 1μm.

[0061] Example 7

[0062] The fabrication process of the high-resolution electrochromic display device in Example 7 is the same as that in Example 1, except that in step (1), a near-infrared laser is used with an etching power of 40W, a wavelength of 1200nm, an aperture of 12μm, and an aperture spacing of 20μm.

[0063] Example 8

[0064] The fabrication process of the high-resolution electrochromic display device in Example 8 is the same as that in Example 1, except that in step (1), tungsten metal is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 1.5 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the DC power applied to the target material is 100 W, and an electrochromic layer film with a thickness of 500 nm is deposited.

[0065] Example 9

[0066] The fabrication process of the high-resolution electrochromic display device in Example 9 is the same as that in Example 1, except that in step (1), tungsten metal is used as the target material, the sputtering gas is argon and oxygen, the total pressure is 1.5 Pa, the oxygen partial pressure is 15%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power applied to the target material is 100 W to deposit a 1000 nm electrochromic layer film.

[0067] Example 10

[0068] The preparation process of the high-resolution electrochromic display device in this embodiment 10 is the same as that in embodiment 1, except that in step (3), the above mixed solution 2 is deposited on the surface of the electrochromic layer by spin coating at a rotation speed of 3000 rpm and a film thickness of 2 μm.

[0069] Example 11

[0070] The preparation process of the high-resolution electrochromic display device in this embodiment 11 is the same as that in embodiment 1, except that in step (3), the above mixed solution 2 is deposited on the surface of the electrochromic layer by spin coating at a rotation speed of 1000 rpm and a film thickness of 10 μm.

[0071] Comparative Example 1

[0072] The fabrication process of the high-resolution electrochromic display device in Comparative Example 1 is the same as in Example 1, except that a buffer layer is not fabricated. In this patent, an insulating buffer layer is inserted between the electrochromic layer and the electrode. This is because the holes formed during etching would penetrate the electrochromic layer, and direct filling of the electrolyte would cause direct contact with the electrode, leading to a short circuit and affecting the device's performance. By inserting an insulating buffer layer, the filled electrolyte is prevented from directly contacting the electrode, ensuring the device's electrochromic performance. If the buffer layer is too thin, it is difficult to form a continuous film, thus affecting the device's insulation performance; if the buffer layer is too thick, it affects electron migration performance, leading to a decrease in the device's response speed.

[0073] Comparative Example 2

[0074] The fabrication process of the high-resolution electrochromic display device in Comparative Example 2 is the same as that in Example 1, except that in step (1), a near-infrared laser is used with an etching power of 40W, a wavelength of 1200nm, an aperture of 12μm, and an aperture spacing of 30μm.

[0075] Comparative Example 3

[0076] The fabrication process of the high-resolution electrochromic display device in Comparative Example 3 is the same as that in Example 1, except that in step (1), a near-infrared laser is used with an etching power of 40W, a wavelength of 1200nm, an aperture of 30μm, and an aperture spacing of 12μm. The effects of aperture and aperture spacing on resolution are as follows: if the aperture is too large, the electrochromic layer material will be reduced, affecting the performance of the device, and the structural stability of the device will also be affected; if the aperture is too small, the expected purpose will not be achieved, affecting the flexibility of the device; if the aperture spacing is too large, the flexibility and bending performance of the device will be reduced; if the aperture spacing is too small, the resolution improvement of the device will not be significant, and the expected purpose will not be achieved.

[0077] Table 1 shows the composition of a high-resolution electrochromic display device:

[0078]

[0079]

[0080] Table 2 shows the performance parameters of high-resolution electrochromic display devices:

[0081] Display resolution ratio Response speed (s) Cycle life (ten thousand cycles) Example 1 1.05 1.1 5 Example 2 1.1 2.5 3.2 Example 3 1.12 3.8 4.1 Example 4 1.4 1.6s 2.1 Example 5 1.08 3.2s 3.9 Example 6 1.06 2.2s 1.5 Example 7 2.0 1.9 3.4 Example 8 1.6 1.9 2.9 Example 9 1.8 3.5 1.9 Example 10 1.5 2.1 3.1 Example 11 2.6 5.6 4.1 Comparative Example 1 10.1 1.4 0.05 Comparative Example 2 4.6 4.5 0.4 Comparative Example 3 7.2 6.2 0.3

[0082] The resulting high-resolution electrochromic display device has a display resolution ratio of 1 to 3. The response time of the resulting high-resolution electrochromic display device is 1 to 6 seconds. The cycle life of the resulting high-resolution electrochromic display device is 20,000 to 50,000 cycles. Display resolution ratio: based on... Figure 2 As shown, during the coloring and fading process, the diffusion or dispersion of the pattern edges results in thicker actual pattern lines. The ratio of the number of grid cells occupied by the displayed pattern to the theoretical number of grid cells is the ratio of display resolution. Cycle life test method: Apply cyclic voltage to the device, with a high potential of 1.5V and a low potential of -3V, for 0.05s, and a hold time of 30s, for 1 minute per cycle. Response speed: The time required for the device to fully color from the faded state during cycle life testing.

[0083] Figure 2 The diagram below illustrates the display resolution evaluation of the device prepared in Example 1: the right image shows the target display pattern, and the left image shows the actual display pattern. During the color-changing process, the diffusion or dispersion of the pattern edges results in thicker lines in the actual pattern. Therefore, the left image occupies more grid cells than the right image. When the display grid sizes are consistent, the closer the ratio is to 1, the higher the display resolution.

Claims

1. A high-resolution patterned electrochromic display device, characterized in that, The electrochromic display device includes a first transparent electrode layer, a buffer layer, an electrochromic layer containing an array of multiple holes, a gel electrolyte layer filling the holes and covering the electrochromic layer, and a second transparent electrode layer, which are stacked sequentially. The electrochromic layer is made of at least one of WO3, MoO3, and TiO2. The cross-sectional shape of the holes is circular. The diameter of the holes is 1 to 20 μm, the shortest distance between adjacent holes is 1 to 20 μm, and the height of the holes is 500 to 1000 nm.

2. The high-resolution patterned electrochromic display device according to claim 1, characterized in that, The materials of the first and second transparent electrode layers are independently selected from at least one of transparent conductive oxides and metal nanowires; the sheet resistance of the first and second transparent electrode layers is 10–40 Ω / cm. 2 Visible light transmittance ≥75%.

3. The high-resolution patterned electrochromic display device according to claim 1, characterized in that, The material of the buffer layer is at least one of SiO2, Si3N4, Al2O3, and SnO2; the film thickness of the buffer layer is 5–50 nm.

4. The high-resolution patterned electrochromic display device according to claim 1, characterized in that, The gel electrolyte layer is a lithium-containing gel-based solid electrolyte; the lithium salt is selected from at least one of lithium chloride, lithium perchlorate, lithium phosphate, lithium silicate, and LiPON; without calculating the pore height, the thickness of the gel electrolyte layer is 1.5 μm to 9 μm.

5. The high-resolution patterned electrochromic display device according to claim 4, characterized in that, The method for preparing the gel electrolyte layer includes: (1) Weigh the UV resin monomer, stabilizer, organic precursor and lithium salt in a mass ratio of 1:(0.05~0.2):(0.5~2):(1~3) and stir until completely dissolved to obtain mixed solution 1; (2) Add an initiator to mixed solution 1 to obtain mixed solution 2; (3) The obtained mixed solution 2 was spin-coated and then cured under ultraviolet light to obtain a gel electrolyte layer.

6. The high-resolution patterned electrochromic display device according to claim 5, characterized in that, The UV resin monomer is selected from at least one of dipropylene glycol diacrylate (HDDA), pentaerythritol triacrylate (PETA), dipropylene glycol diacrylate (DPGDA), and tripropylene glycol diacrylate (TPGDA). The stabilizer is a transition metal organometallic compound; The organic precursor includes acid ester compounds; The initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile, cumene hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxide, dicyclohexyl peroxide, di-tert-butyl peroxide, diisopropyl peroxide, tert-butyl peroxide, and tert-butyl peroxide, and is added in an amount of 0.1 to 0.3 wt% of the total mass of the slurry. The spin coating speed is 1000-3000 rpm, and the time is 10-30 seconds; The photocuring process involves irradiation with a 100-300W ultraviolet lamp for 5-60 seconds.

7. The high-resolution patterned electrochromic display device according to claim 6, characterized in that, The stabilizer is ferrocene and its derivatives; the organic precursor is ethoxylated trimethylolpropane triacrylate (ETPTA).

8. The high-resolution patterned electrochromic display device according to claim 5, characterized in that, Add at least one of leveling agent, adhesion promoter and defoamer to mixed solution 1, and it is referred to as mixed solution 3; The leveling agent is selected from at least one of BYK333, BYK358N, BYK306 and BYK378, and the amount added is 0.5% to 2% of the total mass; The adhesion promoter is selected from at least one of BYK4500, BYK4509, BYK4510, BYK4511 and BYK4512, and is added in an amount of 0.05% to 2% of the total mass. The defoamer is selected from at least one of BYK011, BYK012, BYK014, BYK018 and BUK019, and the amount added is 0.1 to 0.5% of the total mass.

9. A method for fabricating a high-resolution patterned electrochromic display device as described in any one of claims 1-8, characterized in that, The method for preparing the electrochromic layer containing an array of multiple pores includes: (1) An unetched electrochromic layer is deposited on the buffer layer using a magnetron sputtering process; (2) Near-infrared laser is used for etching to obtain an electrochromic layer containing an array of multiple holes.

10. The preparation method according to claim 9, characterized in that, In step (1), the parameters of the magnetron sputtering process include: deposition power of 50-100 W, deposition gas pressure of 1-2 Pa, and deposition time of 15-60 minutes; In step (2), the etching parameters include: the power of the near-infrared laser is 10 to 100 W and the wavelength is 1200 nm; the diameter of the etched hole is 1 to 20 μm and the shortest hole spacing between adjacent holes is 1 to 20 μm.

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