Electroreflective working electrode

Abstract

The utility model provides a kind of electroreflective working electrode, the electrode includes substrate layer, the functional layer of metal material and the first stable layer of sulfide material, and first stable layer forms strong chemical bonding interface with functional layer by metal-sulfur bond. By constructing strong chemical bonding metal-sulfur bond, effectively solve the problem of weak interlayer adhesion, easy to peel off, significantly enhance the mechanical stability and interface integrity of electroreflective working electrode, thereby substantially prolong the service life and optical performance durability of electroreflective working electrode.

Description

Technical Field

[0001] This utility model relates to the field of electroluminescent devices, and in particular to an electroluminescent working electrode. Background Technology

[0002] Electroluminescence technology is a type of intelligent optoelectronic technology based on electrochemical principles. Its core lies in the reversible redox reaction that occurs in functional materials when an external electric field is applied, leading to significant changes in their optical constants (such as refractive index and extinction coefficient). Macroscopically, this manifests as dynamic and reversible control of transmittance, reflectance, or color. Compared to traditional liquid crystal or electrophoretic display technologies, this technology offers unique advantages such as a wide viewing angle, no need for polarizers, and open-circuit memory (zero-power state retention). These characteristics give it enormous application potential in cutting-edge fields such as smart windows (energy-saving dimming), anti-glare rearview mirrors, low-power displays, and photoelectric sensors, making it one of the current research hotspots at the intersection of new materials and optoelectronics.

[0003] However, the commercialization of current electroluminescent technology still faces some challenges: First, poor interface stability: the physical adhesion or weak chemical bonding (bond energy usually below 300 kJ / mol) between the functional layer and the metal electrode layer is prone to failure during long-term ion insertion / extraction cycles, leading to interface peeling. This manifests as rapid decay of the device's optical contrast and a lifespan that is difficult to exceed 2000 cycles. Second, insufficient environmental tolerance: the metal functional layers (such as silver and copper) used to ensure high conductivity are easily corroded or undergo unnecessary side reactions in liquid or gel electrolytes, resulting in a continuous increase in sheet resistance, a rise in driving voltage, and ultimately device failure. Third, low compatibility of fabrication processes: existing technologies often require multiple deposition processes (such as sputtering, evaporation, and solution methods) to prepare multilayer films stepwise. The process is complex and easily introduces impurities and defects, resulting in poor film density, numerous pinholes, and difficulty in controlling uniformity, which seriously affects product yield and performance consistency.

[0004] Therefore, there is currently no good solution to this problem. Utility Model Content

[0005] In order to overcome the above-mentioned technical defects, the purpose of this utility model is to provide an electroluminescent working electrode.

[0006] This utility model discloses an electroluminescent working electrode. The electroluminescent working electrode includes a substrate layer, a functional layer made of a metal material, and a first stabilizing layer made of a sulfide material; the substrate layer and the functional layer are fixed relative to each other; the first stabilizing layer is attached to and fixed on the surface of the functional layer away from the substrate layer, and a metal-sulfur bond is formed between the first stabilizing layer and the functional layer.

[0007] Preferably, the electroluminescent working electrode further includes a second stabilizing layer, which is disposed between the substrate layer and the functional layer, with one side attached and fixed to the substrate layer and the other side attached and fixed to the functional layer.

[0008] Preferably, the material of the functional layer includes one or more of elemental platinum, gold, copper, and their alloys.

[0009] Preferably, the thickness of the functional layer is 1nm-20nm.

[0010] Preferably, the materials of the first stabilizing layer and the second stabilizing layer include one or more of Ag2S, ZnS, and Bi2S3.

[0011] Preferably, the thickness of the first stabilizing layer and the second stabilizing layer is 1 nm to 30 nm.

[0012] Preferably, the first stabilizing layer and the second stabilizing layer are formed by physical vapor deposition.

[0013] Preferably, the substrate layer is a flexible conductive substrate layer.

[0014] Preferably, the substrate layer includes a flexible substrate layer and a conductive layer;

[0015] The flexible substrate is made of polyethylene terephthalate, and the conductive layer is made of indium tin oxide.

[0016] Preferably, the substrate layer has a resistance of <15 Ω / □ and a visible light transmittance of >70%.

[0017] Compared with existing technologies, the above technical solution has the following advantages:

[0018] 1. This application fundamentally solves the problem of weak bonding and easy peeling between the functional layer and the stabilizing layer by constructing a strong chemical bond of metal-sulfur. This strong chemical bond can effectively suppress interlayer peeling caused by long-term electrochemical cycling, greatly improve the mechanical stability and interface integrity of the working electrode, thereby significantly extending the service life of the device and the durability of its optical performance;

[0019] 2. By introducing a second stabilizing layer and selecting specific sulfide materials, a symmetrical "sandwich" protective structure was constructed. This design constrains and protects the functional layers from both sides, suppressing stress deformation during operation and enhancing overall mechanical stability. The physical vapor deposition process forms a dense, uniform, and pure film, avoiding impurities and pinhole defects, significantly improving film quality and density. This ensures the excellent barrier protection effect and ion conductivity of the stabilizing layer, guaranteeing the high efficiency, uniformity, and stability of the electrochemical reaction.

[0020] 3. By using highly chemically stable metals and alloys for the functional layer and designing its thickness accordingly, the corrosion resistance and optical transmittance of the electrodes in the electrolyte are significantly improved. This avoids rapid decay of conductivity, ensuring a stable, low-resistance current path while providing a foundation for achieving high-contrast optical switching, and guaranteeing the stability of the device's driving voltage and the consistency of its response speed.

[0021] 4. By combining low resistance, high transmittance, and flexibility in the substrate layer, the application scenarios of the device have been successfully expanded. A specific flexible composite substrate structure is employed, combining the flexibility of polymer materials with the conductivity and transmittance of metal oxides. This allows the working electrode to maintain the integrity and functional stability of the conductive layer even under bending, curling, and other deformations, providing an ideal solution for realizing high-performance, high-reliability flexible electrochromic devices. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of one implementation of the electroluminescent working electrode provided in this application;

[0023] Figure 2 This is a schematic diagram of the structure in which the first stabilizing layer and the functional layer generate chemical bonds in the electroluminescent working electrode provided in this application;

[0024] Figure 3 This is a schematic diagram of another implementation of the electroluminescent working electrode provided in this application. Detailed Implementation

[0025] The advantages of this utility model are further illustrated below with reference to the accompanying drawings and specific embodiments.

[0026] Exemplary embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings. When the following description relates to the drawings, unless otherwise indicated, the same numerals in different drawings denote the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this disclosure as detailed in the appended claims.

[0027] The terminology used in this disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The singular forms “a,” “the,” and “the” as used in this disclosure and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” as used herein refers to and includes any and all possible combinations of one or more of the associated listed items.

[0028] It should be understood that although the terms first, second, third, etc., may be used in this disclosure to describe various information, such information should not be limited to these terms. These terms are used only to distinguish information of the same type from one another. For example, without departing from the scope of this disclosure, first information may also be referred to as second information, and similarly, second information may also be referred to as first information. Depending on the context, the word "if" as used herein may be interpreted as "when," "when," or "in response to determination."

[0029] In the description of this utility model, it should be understood that the terms "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this utility model and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this utility model.

[0030] In the description of this utility model, unless otherwise specified and limited, it should be noted that the terms "installation", "connection" and "linking" should be interpreted broadly. For example, they can refer to mechanical or electrical connections, or internal connections between two components. They can be direct connections or indirect connections through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms according to the specific circumstances.

[0031] In the following description, the use of suffixes such as "module," "part," or "unit" to denote elements is solely for the purpose of illustrating this invention and has no specific meaning in itself. Therefore, "module" and "part" can be used interchangeably.

[0032] Please see Figures 1-2 , Figure 1 This is a schematic diagram of one implementation of the electroluminescent working electrode provided in this application; Figure 2 This is a schematic diagram of the structure in which the first stabilizing layer and the functional layer generate chemical bonds in the electroluminescent working electrode provided in this application.

[0033] like Figures 1-2 As shown, this utility model discloses an electroluminescent working electrode. The electroluminescent working electrode includes a substrate layer, a functional layer made of a metal material, and a first stabilizing layer made of a sulfide material; the substrate layer and the functional layer are fixed relative to each other; the first stabilizing layer is attached to and fixed on the surface of the functional layer away from the substrate layer, and a metal-sulfur bond is formed between the first stabilizing layer and the functional layer.

[0034] The principle needs to be described here: Generally speaking, electroluminescence technology is a type of intelligent optoelectronic technology based on electrochemical principles. Its core lies in the fact that when an external electric field is applied to a functional material, a reversible redox reaction occurs, which leads to a significant change in its optical constants (such as refractive index and extinction coefficient). Macroscopically, this is manifested as dynamic and reversible control of transmittance, reflectance, or color.

[0035] Therefore, when adjusting the transmittance, it is necessary to apply an electric current to the functional layer. In this application, a metal-sulfur bond can be formed between the functional layer composed of metal and the first stabilizing layer composed of sulfides, with a bond energy ≥400 kJ / mol (e.g., Pt-S bond energy ≥650 kJ / mol, Au-S bond energy ≥580 kJ / mol, Cu-S bond energy ≥480 kJ / mol). Compared to the typical bond energy of 300 kJ / mol in the prior art, this significantly improves the bonding force between the interfaces, thereby preventing interlayer delamination. Furthermore, the metal functional layer can provide a highly conductive channel, effectively reducing the internal resistance of the functional layer and extending its color-changing cycles. Additionally, the first stabilizing layer of sulfides can, to some extent, inhibit the corrosion of the electrode by the electrolyte, thereby further improving its service life. Finally, an electroreflective working electrode with significantly improved cycle life (exemplarily, in one possible implementation, cycle life ≥3000 times, transmittance decay <10%, while traditional WO3 electrode decays >30% after 2000 cycles), lower cost, and better environmental adaptability (in one possible implementation, resistance change <8% after 30 days at 60℃ / 90% humidity) is obtained.

[0036] The above is an explanation of the basic concept of this application. Those skilled in the art will understand that there are no limitations on the specific implementation of this application. The following will be explained in conjunction with the accompanying drawings.

[0037] First, this application may have more layers to achieve better results.

[0038] Please see Figure 3 , Figure 3 This is a schematic diagram of another implementation of the electroluminescent working electrode provided in this application.

[0039] like Figure 3 As shown, in another possible implementation, the electroluminescent working electrode further includes a second stabilizing layer disposed between the substrate layer and the functional layer, with one side attached and fixed to the substrate layer and the other side attached and fixed to the functional layer.

[0040] This can be understood as follows: the second implementation of this application also provides a symmetrical protective structure of a first stabilizing layer, a functional layer, and a second stabilizing layer. This design can simultaneously constrain and protect the functional layer from both the top and bottom, greatly suppressing stress deformation and structural failure caused by volume changes during operation, and enhancing the overall mechanical stability of the electrode. Simultaneously, this structure provides a more uniform interface for ion migration, helping to improve the uniformity and reversibility of electrochemical reactions, thereby obtaining more stable and consistent optical modulation performance.

[0041] Secondly, the specific material and thickness of the functional layer are also not limited.

[0042] In one possible implementation, the material of the functional layer includes one or more of elemental platinum, gold, copper, and their alloys.

[0043] This claim, by specifying that the functional layer is made of a noble metal or its alloy with high chemical stability, significantly improves the corrosion and oxidation resistance of the working electrode in the electrolyte environment. This avoids the problem of rapid conductivity decay caused by corrosion of the metal layer, ensuring that the working electrode can maintain a stable and low-resistance current path during long-term service, thereby guaranteeing the stability of the device's driving voltage and the consistency of its response speed.

[0044] Regarding thickness, in one possible implementation, the thickness of the functional layer is 1nm-20nm. Specifically, it can be 1nm, 5nm, 10nm, 15nm, and 20nm. This application does not impose any specific limitations here.

[0045] By optimizing the thickness range of the functional layer, high transmittance in the visible light band is achieved while ensuring excellent conductivity of the electrode. This thickness design enables the working electrode to achieve an optimal balance between optical transparency and electrical performance, providing a foundation for high-contrast optical switching in electroluminescent devices, while avoiding problems such as excessive internal stress and easy cracking caused by excessive film thickness.

[0046] Furthermore, the specific materials and thicknesses of the first and second stabilizing layers are also not limited.

[0047] In one possible implementation, the materials of the first stabilizing layer and the second stabilizing layer include one or more of Ag2S, ZnS, and Bi2S3.

[0048] Those skilled in the art will understand that the selected sulfides not only form robust metal-sulfur bonds with the functional layer, but also possess excellent electrochemical stability and ion conductivity. These sulfides are stable in the electrolyte, do not easily decompose, effectively protect the internal functional layer, and provide a smooth channel for the migration of working ions, ensuring the efficient and stable conduction of the electrochemical reaction, thereby achieving high performance and long service life cycling.

[0049] Regarding thickness, the thickness of the first stabilizing layer and the second stabilizing layer is 1nm-30nm. Specifically, it can be 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, and 30nm, etc., and this application does not impose any restrictions here.

[0050] By precisely controlling the thickness of the two stabilizing layers, it is ensured that they completely cover the surface of the functional layer to form a dense protective layer, effectively blocking the penetration and corrosion of the electrolyte, while avoiding excessive interfacial resistance or internal stress due to excessive thickness. This optimized thickness guarantees high efficiency in ion migration and mechanical reliability of interfacial bonding, which is beneficial for achieving rapid device response and improving long-term cycle stability.

[0051] Those skilled in the art will understand that the formation of the first and second stabilizing layers is also not limited.

[0052] In one possible implementation, the first and second stabilizing layers are deposited using physical vapor deposition (PVD). Specifically, the first stabilizing layer can be formed on the surface of the functional layer using PVD. This PVD process can create a dense, uniform, pure film with strong adhesion to the substrate. This method avoids defects such as impurities and pinholes that may be introduced by solution-based methods, significantly improving the quality and density of the film, thus ensuring the excellent barrier protection and ion conductivity of the stabilizing layer. Furthermore, it offers good process compatibility and facilitates large-scale uniform production. Similarly, the second stabilizing layer can be deposited on the surface of the substrate layer using PVD, which will not be elaborated further here.

[0053] Finally, the specific structure of the basal layer is also not limited.

[0054] In one possible implementation, the substrate layer is a flexible conductive substrate layer. By setting the substrate layer as a flexible conductive substrate, the limitations of traditional rigid glass substrates are overcome, giving the entire working electrode the characteristics of being bendable and foldable. This greatly expands the application scenarios of electroluminescent technology, enabling it to be applied to emerging fields such as flexible displays, wearable electronics, and curved smart windows, meeting the demands of modern electronic devices for lightweight, portability, and diverse forms.

[0055] Furthermore, the substrate layer includes a flexible substrate layer and a conductive layer;

[0056] The flexible substrate is made of polyethylene terephthalate, and the conductive layer is made of indium tin oxide.

[0057] By setting the substrate layer as two layers, the flexibility of the substrate layer is achieved through the flexibility of the polymer material. The conductivity and light transmittance of the substrate layer are achieved through the conductivity and light transmittance of the metal oxide, so that the working electrode can maintain the integrity of the conductive layer and the stability of its function even when subjected to mechanical deformation such as bending and curling. This provides an ideal substrate solution for realizing high-performance, high-reliability flexible electrochromic devices.

[0058] Furthermore, the substrate layer exhibits a resistance of <15 Ω / □ and a visible light transmittance >70%. By defining the substrate layer as possessing both low resistance and high transmittance, it is ensured that the working electrode, while acting as a highly efficient current conductor, does not significantly impact the overall light transmittance of the device. This provides the foundation for electroluminescent devices to achieve high transparency in bright conditions and high contrast in dark conditions, serving as a prerequisite for obtaining excellent optical performance.

[0059] The above is a complete description of the various implementations of the electroluminescent working electrode provided in this application. To enable those skilled in the art to better understand this application and facilitate its implementation, this application also provides two exemplary embodiments of the electroluminescent working electrode and its preparation method for reference.

[0060] Example 1: Pretreatment of substrate (ITO glass 8 Ω / □, 85% transmittance): ultrasonic cleaning with deionized water, ethanol and acetone in sequence, followed by ultraviolet ozone treatment and drying;

[0061] Functional layer fabrication: Magnetron sputtering (0.5 Pa, 100 W, 0.15 nm / s, 3 nm) Au layer;

[0062] Preparation of the first stabilizing layer: Electron beam evaporation (5×10⁻) 4 ZnS layer (Pa, 0.3 nm / s, 3 nm);

[0063] The electroreflective working electrode was obtained as "glass-ITO-Au-ZnS layer". The electrode film was tested using a transmittance meter. The measured transmittance was 65% / 10% (fading / coloring) and the reflectance was 10% / 65% (fading / coloring). The decay was 6% after 5000 cycles.

[0064] Example 2: Substrate layer: Flexible ITO-PET (10 Ω / □, 82% transmittance) pretreated;

[0065] Functional layer fabrication: Electron beam evaporation (3×10⁻)4 Pt layer (Pa, 0.25 nm / s, 2.5 nm);

[0066] Ag2S layer: magnetron sputtering (0.8 Pa, 120 W, 0.2 nm / s, 2 nm).

[0067] The electroreflective working electrode was obtained as a “PET-ITO-Pt-Ag2S layer”, with a measured reflectivity of 10% / 7% and a decay of 5% after 3000 cycles.

[0068] It should be noted that the embodiments of this utility model have better implementability and are not intended to limit this utility model in any way. Any person skilled in the art may use the above-disclosed technical content to change or modify it into equivalent effective embodiments. However, any modifications or equivalent changes and modifications made to the above embodiments based on the technical essence of this utility model without departing from the content of the technical solution of this utility model shall still fall within the scope of the technical solution of this utility model.

Claims

1. An electroluminescent working electrode, characterized in that, The electroluminescent working electrode includes a base layer, a functional layer made of metal, and a first stabilizing layer made of sulfide. The base layer and the functional layer are fixed relative to each other. The first stabilizing layer is attached to and fixed on the surface of the functional layer away from the base layer, and a metal-sulfur bond is formed between the first stabilizing layer and the functional layer.

2. The electroluminescent working electrode as described in claim 1, characterized in that, The electroluminescent working electrode further includes a second stabilizing layer, which is disposed between the substrate layer and the functional layer, with one side attached to and fixed to the substrate layer and the other side attached to and fixed to the functional layer.

3. The electroluminescent working electrode as described in claim 1, characterized in that, The material of the functional layer includes one or more of the following: elemental platinum, gold, copper, and their alloys.

4. The electroluminescent working electrode as described in claim 1, characterized in that, The thickness of the functional layer is 1nm-20nm.

5. The electroluminescent working electrode as described in claim 2, characterized in that, The materials of the first stabilizing layer and the second stabilizing layer include one or more of Ag2S, ZnS, and Bi2S3.

6. The electroluminescent working electrode as described in claim 2, characterized in that, The thickness of the first stabilizing layer and the second stabilizing layer is 1 nm-30 nm.

7. The electroluminescent working electrode as described in claim 2, characterized in that, The first stabilizing layer and the second stabilizing layer are formed by physical vapor deposition.

8. The electroluminescent working electrode as described in claim 1, characterized in that, The substrate layer is a flexible conductive substrate layer.

9. The electroluminescent working electrode as described in claim 1, characterized in that, The substrate layer includes a flexible substrate layer and a conductive layer; The flexible substrate is made of polyethylene terephthalate, and the conductive layer is made of indium tin oxide.

10. The electroluminescent working electrode as described in claim 9, characterized in that, The substrate layer has a resistance of <15 Ω / □ and a visible light transmittance of >70%.

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