All-solid-state electrochromic lens and preparation method thereof, electrochromic glasses

Abstract

The application discloses a kind of all-solid-state electrochromic lenses and preparation method thereof, electrochromic glasses belong to electrochromic device preparation technical field.Preparation method includes: the surface of transparent lens substrate is deposited bottom transparent conductive layer;On bottom transparent conductive layer, deposit electrochromic functional layer;Using the same composite transparent conductive layer mask plate is deposited composite transparent conductive layer on the surface of ion storage layer in stages;Form metal external electrode;When using composite transparent conductive layer mask plate for deposition, the hollow area of composite transparent conductive layer mask plate is less than the deposition area corresponding to electrochromic functional layer, so that the edge of composite transparent conductive layer is located in the edge of electrochromic functional layer, and a predetermined insulating interval is formed between the two.The application can effectively reduce the risk of random conduction and edge short circuit of top transparent conductive layer, improve the preparation yield, working stability and cycle reliability of all-solid-state electrochromic lenses.

Description

Technical Field

[0001] This invention relates to the field of electrochromic technology, and more specifically, to an all-solid-state electrochromic lens and its preparation method, as well as electrochromic glasses. Background Technology

[0002] In recent years, as smart wearable devices have developed towards lightweight, intelligent, and multifunctional designs, smart dimming glasses that can adjust their transmittance according to changes in ambient light intensity have attracted increasing attention and show promising application prospects in fields such as visual protection, outdoor sports, medical assistance, and augmented reality displays. Currently, the commonly used technologies for smart dimming glasses mainly include photochromic, liquid crystal dimming, and electrochromic technologies. Among them, electrochromic technology uses an applied voltage to drive ions to reversibly migrate within the functional layer, achieving continuous adjustment of lens transmittance. It boasts advantages such as low driving voltage, low energy consumption, wide adjustment range, and retention even after power failure, and is gradually becoming an important technological development direction for smart dimming glasses.

[0003] Existing all-solid-state electrochromic devices typically consist of a multi-layered structure including a transparent substrate, a bottom transparent conductive layer, an electrochromic layer, a solid-state ion-conducting layer, an ion storage layer, and a top transparent conductive layer. This type of all-solid-state structure eliminates the need for a liquid electrolyte and offers good encapsulation, making it an important research direction for electrochromic lenses.

[0004] However, in the actual fabrication process of all-solid-state electrochromic lenses, especially when the lens area is large and the substrate shape is curved or irregular, the surface of the underlying functional film often exhibits microscopic irregularities such as particle defects, local roughness, deposition steps, and edge undulations. Traditional fabrication processes typically use a mask to continuously deposit a thick top transparent conductive layer on the surface of the functional layer in a single operation. The transparent conductive material can easily cross the aforementioned defect areas, forming local low-resistance conduction paths, which can lead to local leakage or even short circuits, severely affecting device fabrication yield and product consistency.

[0005] Furthermore, during the patterning process, the fit between the edge of the top transparent conductive layer and the edge of the electrochromic functional layer also affects the device's insulation performance. If the patterned area of ​​the top transparent conductive layer is too close to the edge of the underlying functional layer or extends directly to cover the edge of the functional layer, local electric field concentration and abnormal conduction are more likely to occur in the edge step region, thereby increasing the risk of edge leakage and short circuits. For curved or irregularly shaped substrates such as eyeglass lenses, structural control of the aforementioned edge regions is even more difficult, and existing solutions lack effective inward isolation designs for the edge of the top transparent conductive layer.

[0006] Meanwhile, existing research on smart electrochromic glasses focuses more on peripheral improvements such as control systems, drive circuits, sensing modules, and intelligent interactive functions. It has not effectively addressed the problems of random short circuits caused by one-time deposition of the top conductive layer, leakage caused by lack of edge isolation, and insufficient consistency in batch production by focusing on the interlayer structure design and patterned fabrication process of the electrochromic lens itself.

[0007] Therefore, optimizing the patterning fabrication process of all-solid-state electrochromic lenses to avoid random short circuits caused by the top transparent conductive layer crossing defects in the lower layer, while effectively improving the insulation performance of the edge region, thereby improving the fabrication yield and long-term stability while ensuring the conductivity and effective dimming area of ​​the device, has become a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0008] To overcome the shortcomings of existing all-solid-state electrochromic lenses, such as the top transparent conductive layer easily crossing defects in the lower layer to form random conductions leading to short circuits and low yield, this invention provides a method for preparing all-solid-state electrochromic lenses. The method involves sequentially depositing each functional layer and electrode using four different masks. The composite transparent conductive layer is deposited in stages using a seed layer and a main layer to form a continuous conductive network. Furthermore, the edge of the composite transparent conductive layer is recessed within the edge of the electrochromic functional layer to form an insulating gap region.

[0009] The first aspect of this invention provides a method for preparing an all-solid-state electrochromic lens, comprising the following steps: Step S1: Deposit a bottom transparent conductive layer on the surface of the transparent lens substrate using a bottom mask; Step S2: Using an electrochromic mask, an electrochromic layer, a solid ion conduction layer, and an ion storage layer are sequentially deposited on the bottom transparent conductive layer to form an electrochromic functional layer. Step S3: Using the same composite transparent conductive layer mask, a composite transparent conductive layer is deposited in stages on the surface of the ion storage layer. The composite transparent conductive layer includes a seed transparent conductive layer and a main transparent conductive layer deposited sequentially. Step S4: Using an electrode mask, external metal electrodes are formed in the lead-out areas of the bottom transparent conductive layer and the composite transparent conductive layer, respectively. In step S3, the thickness of the seed transparent conductive layer is 5-50 nm, the thickness of the main transparent conductive layer is 100-500 nm, and the main transparent conductive layer and the seed transparent conductive layer are interconnected to form a continuous conductive network. When the composite transparent conductive layer mask is used for deposition, the cutout area of ​​the composite transparent conductive layer mask is smaller than the deposition area corresponding to the electrochromic functional layer, so that the edge of the composite transparent conductive layer is located inside the edge of the electrochromic functional layer, and a preset insulating gap area is formed between the two, the width of the insulating gap area is 0.5-1 mm.

[0010] Compared with existing technologies, this invention achieves staged deposition of composite transparent electrodes through a mask-confined process. First, an ultrathin seed layer is formed as the conductive base, and then the main conductive layer is grown on top of it. This prevents the top conductive material from directly crossing the particle defects and edge steps on the surface of the electrochromic functional layer, fundamentally blocking the generation of random conduction paths. Simultaneously, by controlling the pattern size of the composite transparent conductive layer mask, its deposition area is made smaller than the functional layer area, forming an inward-shrinking insulating gap between them. This effectively avoids high-defect areas at the edge of the functional layer, reducing the risk of edge leakage and short circuits. The synergistic effect of the above structural design and process significantly improves device fabrication yield, operational stability, and long-term cycle reliability, while also ensuring the uniformity of current distribution and effective dimming area in the color-changing region. Furthermore, the overall solution is compatible with existing thin-film fabrication processes and has promising prospects for engineering mass production.

[0011] Furthermore, when the width of the insulating gap is less than 0.5 mm, the gap between the composite transparent conductive layer and the edge of the electrochromic functional layer is small, making it difficult to fully avoid particle defects, film steps, and local rough areas at the edge of the electrochromic functional layer. During the deposition of the composite transparent conductive layer, a cross-conduction path may still be formed, resulting in limited suppression of edge leakage and random short circuits. When the width of the insulating gap is greater than 1 mm, although it increases the edge isolation distance, it reduces the effective coverage area of ​​the composite transparent conductive layer, decreasing the effective area of ​​the electrochromic functional region. It may also increase the lateral current transmission distance, leading to uneven current distribution in the working area and affecting the uniformity of lens color change. Therefore, considering short-circuit suppression effect, effective color change area, and current distribution uniformity, the width of the insulating gap is 0.5-1 mm.

[0012] In one possible implementation, the composite transparent conductive layer mask, the bottom mask, the electrochromic mask, and the electrode mask are all provided with positioning slots that match the contour of the transparent lens substrate, so as to realize the positioning and repeated clamping of the lens substrate.

[0013] Compared with the prior art, the present invention sets up positioning slots that match the contour of the transparent lens substrate, so that each mask can adapt to the clamping and positioning requirements of curved or irregularly shaped lens substrates, ensuring the relative position accuracy and repeatability accuracy during the patterned deposition of multilayer thin films, thereby improving the consistency of device structure and reducing batch fabrication errors.

[0014] In one possible implementation, in step S1, the material of the transparent lens substrate is selected from one of PC lenses, CR39 lenses, PMMA lenses and glass lenses, and the material of the bottom transparent conductive layer is ITO with a thickness of 80-300nm.

[0015] Compared with the prior art, the present invention limits the material and thickness range of the transparent lens substrate and the bottom transparent conductive layer, so that the lens can have good conductivity and mechanical stability while meeting the requirements of light transmission performance, thereby providing a stable foundation for the subsequent construction of electrochromic functional layer and composite transparent conductive layer.

[0016] In one possible implementation, in step S2, the electrochromic layer is made of WO3 and / or MoO3, the solid ion conduction layer is made of LiTaO3 and / or LiNbO3, and the ion storage layer is made of NiO and / or V2O5.

[0017] Compared with the prior art, the present invention defines the material system of the electrochromic layer, the solid-state ion conduction layer and the ion storage layer, so that the electrochromic functional layer has stable ion transport capability and reversible electrochromic performance, thereby ensuring that the all-solid-state electrochromic lens has good transmittance adjustment effect and cycle operation stability.

[0018] In one possible implementation, in step S3, both the seed transparent conductive layer and the main transparent conductive layer are made of ITO.

[0019] Compared with existing technologies, this invention uses ITO to form the seed transparent conductive layer and the main transparent conductive layer respectively. While maintaining high light transmittance and good conductivity, it also takes into account the process compatibility with existing all-solid-state electrochromic material systems, which is conducive to the stable construction and engineering application of composite transparent conductive layers.

[0020] In one possible implementation, the method for depositing the bottom transparent conductive layer, the electrochromic layer, the solid ion conduction layer, the ion storage layer, the seed transparent conductive layer, and the main transparent conductive layer is a vacuum evaporation method or a magnetron sputtering method; the external metal electrode is formed using vacuum evaporation, magnetron sputtering, screen printing, or inkjet printing processes.

[0021] Compared with the prior art, the present invention provides adaptability limitations for the fabrication processes of each functional layer and the metal external electrode, enabling the composite transparent conductive layer and the electrochromic functional layer to be formed using mature thin film deposition processes. At the same time, the metal external electrode can flexibly select patterning processes according to actual production needs, thereby improving the compatibility of the fabrication process and the convenience of industrial implementation.

[0022] In one possible implementation, in step S4, the thickness of the external metal electrode is 50-1000 nm, and the material of the external metal electrode is selected from one or more of Ag, Au, Cr, Ti and Cu.

[0023] Compared with the prior art, the present invention, by limiting the material and thickness range of the external metal electrode, enables the external electrode to meet the requirements of low contact resistance while taking into account the pattern formation quality and the reliability of the connection with the upper and lower conductive layers, thereby improving the stability of the lens when connected to the external driving circuit.

[0024] A second aspect of the present invention provides an all-solid-state electrochromic lens, comprising, from bottom to top, a transparent lens substrate, a bottom transparent conductive layer, an electrochromic functional layer, and a composite transparent conductive layer. The lead-out areas of the bottom transparent conductive layer and the composite transparent conductive layer respectively form external metal electrodes. The electrochromic functional layer comprises, sequentially arranged, an electrochromic layer, a solid-state ion-conducting layer, and an ion-storage layer. The composite transparent conductive layer comprises, sequentially arranged, a seed transparent conductive layer and a main transparent conductive layer. The thickness of the seed transparent conductive layer is 5-50 nm, and the thickness of the main transparent conductive layer is 100-500 nm. The main transparent conductive layer and the seed transparent conductive layer are interconnected to form a continuous conductive network. The edge of the composite transparent conductive layer is located inside the edge of the electrochromic functional layer, and a predetermined insulating gap region is formed between the composite transparent conductive layer and the edge of the electrochromic functional layer. The width of the insulating gap region is 0.5-1 mm.

[0025] Compared with existing technologies, the all-solid-state electrochromic lens provided by this invention, by adopting a top transparent conductive layer with a layered composite structure and an edge-recessed graphic design, effectively reduces the probability of random conduction of the top conductive layer and edge short circuit in large-area all-solid-state electrochromic lenses without changing the basic structure of existing electrochromic material systems, thereby improving the working stability, cycle reliability and batch production consistency of the lens.

[0026] A third aspect of the present invention provides all-solid-state electrochromic glasses, including the above-mentioned all-solid-state electrochromic lens.

[0027] Compared with the prior art, the all-solid-state electrochromic glasses provided by the present invention, by adopting the above-mentioned all-solid-state electrochromic lenses, can improve the reliability and durability of the lenses in actual use while maintaining good optical adjustment performance, and have good application prospects. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the structure of the all-solid-state electrochromic lens of the present invention.

[0029] Figure 2 This is a schematic diagram of the structure of a composite transparent conductive layer mask, a bottom mask, an electrochromic mask, and an electrode mask.

[0030] Figure 3 This is a schematic diagram of the assembly structure of the all-solid-state electrochromic glasses of the present invention.

[0031] Figure 4 (a) is a photograph of the solid-state electrochromic glasses prepared in Example 1 before they change color when energized.

[0032] Figure 4 (b) is a photograph of the solid-state electrochromic glasses prepared in Example 1 after they change color when energized.

[0033] Figure 5 This is a schematic diagram showing the transmittance change of the all-solid-state electrochromic lens prepared in Example 1 after cyclic testing at a wavelength of 550 nm.

[0034] The structure includes: 1. Base layer; 1-1. Transparent lens base; 1-2. Bottom transparent conductive layer; 2. Electrochromic functional layer; 2-1. Electrochromic layer; 2-2. Solid ion conduction layer; 2-3. Ion storage layer; 3. Composite transparent conductive layer; 3-1. Seed transparent conductive layer; 3-2. Main transparent conductive layer; 4. External metal electrode; 4-1. Upper external metal electrode; 4-2. Lower external metal electrode; 5. Lens frame; a. Bottom mask; b. Electrochromic mask; c. Composite transparent conductive layer mask; d. Electrode mask. Detailed Implementation

[0035] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter range described in the present invention. Reasonable variations derived therefrom are still within the protection scope of the claims of the present invention.

[0036] It should be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0037] Unless otherwise defined, all terms, symbols, and other scientific terms used herein are intended to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In some instances, terms having a conventional meaning are defined herein for clarification or ease of reference, and such definitions should not be construed as indicating a significant difference from conventional understanding in the art. The technical methods described or referenced herein are generally well understood by those skilled in the art and employed by conventional methods. Unless otherwise stated, the use of commercially available kits, reagents, and instruments shall be performed according to the manufacturer's instructions and parameters.

[0038] like Figure 1 As shown, the present invention provides an all-solid-state electrochromic lens, which comprises, from bottom to top, a substrate layer 1, an electrochromic functional layer 2, and a composite transparent conductive layer 3. The substrate layer 1 includes a transparent lens substrate 1-1 and a bottom transparent conductive layer 1-2 disposed on the surface of the transparent lens substrate 1-1; the electrochromic functional layer 2 includes an electrochromic layer 2-1, a solid-state ion conduction layer 2-2, and an ion storage layer 2-3 disposed sequentially on the bottom transparent conductive layer 1-2; the composite transparent conductive layer 3 includes a seed transparent conductive layer 3-1 and a main transparent conductive layer 3-2 disposed on the surface of the ion storage layer 2-3, the main transparent conductive layer 3-2 and the seed transparent conductive layer 3-1 being interconnected to form a continuous conductive network, the lead-out area of ​​the bottom transparent conductive layer 1-2 being provided with an upper external metal electrode 4-1, and the lead-out area of ​​the composite transparent conductive layer 3 being provided with a lower external metal electrode 4-2. The edge of the composite transparent conductive layer 3 is located inside the edge of the electrochromic functional layer 2, and a preset insulating gap is formed between the composite transparent conductive layer 3 and the edge of the electrochromic functional layer 2. The width of the insulating gap is 0.5-1mm, so as to reduce the risk of leakage and short circuit in the edge area.

[0039] The "continuous conductive network" described in this invention refers to a network where both the main transparent conductive layer 3-2 and the seed transparent conductive layer 3-1 are made of transparent conductive materials, and they are in direct contact during deposition, forming a good ohmic contact. This together constitutes a complete and uninterrupted transparent conductive path extending from the electrochromic working region to the lead-out region of the composite transparent conductive layer 3. Specifically, the seed transparent conductive layer 3-1 first forms an initial thin conductive film on the surface of the ion storage layer 2-3. Subsequently, the deposited main transparent conductive layer 3-2 continues to grow on the surface of this initial conductive film and is tightly connected to it, enabling free electron transport between the two transparent conductive materials at the interface. This results in a continuous conductive network with low resistance and high transmittance throughout the entire composite transparent conductive layer 3, providing a uniform and stable electron transport channel for the device.

[0040] This invention also provides a method for preparing an all-solid-state electrochromic lens. The method includes the following steps: Step S1: Deposit a bottom transparent conductive layer 1-2 on the surface of the transparent lens substrate 1-1; Step S2: Electrochromic layer 2-1, solid ion conduction layer 2-2 and ion storage layer 2-3 are sequentially deposited on the bottom transparent conductive layer 1-2 to form electrochromic functional layer 2; Step S3: Using the same composite transparent conductive layer mask c, a composite transparent conductive layer 3 is deposited in stages on the surface of the ion storage layer 2-3. The composite transparent conductive layer 3 includes a seed transparent conductive layer 3-1 and a main transparent conductive layer 3-2 deposited sequentially. Step S4: Metal external electrodes 4 are formed in the lead-out areas of the bottom transparent conductive layer 1-2 and the lead-out areas of the composite transparent conductive layer 3, respectively.

[0041] When a bottom transparent conductive layer 1-2 is deposited on the surface of a transparent lens substrate 1-1 using a vacuum evaporation method, the evaporation rate is 3-6 Å / s and the working pressure is 2.5 × 10⁻⁶ Å / s. -2 -5×10 -2 Pa, temperature is 250-450℃.

[0042] The bottom transparent conductive layer 1-2, electrochromic layer 2-1, solid-state ion-conducting layer 2-2, ion storage layer 2-3, seed transparent conductive layer 3-1, and main transparent conductive layer 3-2 can be formed by vacuum evaporation or magnetron sputtering. The material of the external metal electrode 4 can be selected from one or more of Ag, Au, Cr, Ti, and Cu, with a thickness of 50-1000 nm, and can be formed by vacuum evaporation, magnetron sputtering, screen printing, or inkjet printing.

[0043] When depositing a bottom transparent conductive layer of 1-2 using magnetron sputtering, the deposition power is 100-200W, the working pressure is 0.2-1.0Pa, the deposition time is 60-300min, the substrate temperature is room temperature, and the base vacuum is 1×10⁻⁶. -3 -5×10 -5 Pa.

[0044] When the electrochromic layer 2-1, the solid ion-conducting layer 2-2, and the ion storage layer 2-3 are sequentially deposited using a vacuum evaporation method, the evaporation rate of the electrochromic layer 2-1 is 3-6 Å / s, and the working pressure is 2.5 × 10⁻⁶ Å / s. -2 -5×10 -2 Pa, temperature 250-450℃; evaporation rate of solid ion-conducting layer 2-2 is 3-6 Å / s, working pressure is 2.5×10 -2 -5×10 -2 Pa, temperature 250-450℃; evaporation rate of ion storage layer 2-3 is 3-6 Å / s, working pressure is 2.5×10 -2 -5×10 -2 Pa, temperature is 250-450℃.

[0045] When the electrochromic layer 2-1, the solid ion conduction layer 2-2, and the ion storage layer 2-3 are sequentially deposited using magnetron sputtering, the deposition power of the electrochromic layer 2-1 is 150-200 W, the working pressure is 0.2-1.0 Pa, the deposition time is 200-300 min, and the substrate temperature is room temperature; the deposition power of the solid ion conduction layer 2-2 is 100-200 W, the working pressure is 0.2-1.0 Pa, the deposition time is 100-250 min, and the substrate temperature is room temperature; the deposition power of the ion storage layer 2-3 is 150-200 W, the working pressure is 0.2-1.0 Pa, the deposition time is 150-200 min, and the substrate temperature is room temperature.

[0046] When the seed transparent conductive layer 3-1 and the main transparent conductive layer 3-2 are deposited by vacuum evaporation, the evaporation rate of the seed transparent conductive layer 3-1 is 1-3 Å / s, and the working pressure is 2.5 × 10⁻⁶. -2 -5×10 -2 Pa, temperature 250-450℃; evaporation rate of the main transparent conductive layer 3-2 is 3-6 Å / s, working pressure is 2.5×10 -2 -5×10 -2 Pa, temperature is 250-450℃.

[0047] When depositing the seed transparent conductive layer 3-1 and the main transparent conductive layer 3-2 using magnetron sputtering, the deposition power of the seed transparent conductive layer 3-1 is 100-150W, the working pressure is 0.2-1.0Pa, the deposition time is 150-3000s, and the substrate temperature is room temperature; the deposition power of the main transparent conductive layer 3-2 is 150-200W, the working pressure is 0.2-1.0Pa, the deposition time is 25-500min, and the substrate temperature is room temperature.

[0048] When the external metal electrode 4 is formed by vacuum evaporation, the evaporation rate is 1-3 Å / s and the working pressure is 1×10⁻⁶. -2 -2×10 -2 Pa.

[0049] When depositing the external metal electrode 4 using magnetron sputtering, the deposition power is 200-300W, the working pressure is 0.2-1.0Pa, the deposition time is 20-40min, the substrate temperature is room temperature, and the background vacuum is 1×10⁻⁶. -3 -5×10 -5 Pa.

[0050] In step S3 above, the seed transparent conductive layer 3-1 has a thickness of 5-50 nm, and the main transparent conductive layer 3-2 has a thickness of 100-500 nm. The main transparent conductive layer 3-2 and the seed transparent conductive layer 3-1 are interconnected to form a continuous conductive network. When using a composite transparent conductive layer mask c for deposition, the cutout area of ​​the composite transparent conductive layer mask c is smaller than the deposition area corresponding to the electrochromic functional layer 2, so that the edge of the composite transparent conductive layer 3 is located inside the edge of the electrochromic functional layer 2, forming a predetermined insulating gap between them. By first forming a thinner seed transparent conductive layer 3-1 and then a thicker main transparent conductive layer 3-2, the probability of the transparent conductive material directly crossing particle defects, edge steps, and local rough areas to form random conductive paths can be reduced, thereby improving the device fabrication yield and operational stability.

[0051] In the specific fabrication process, to adapt to curved or irregularly shaped lens substrates and ensure the consistency of the dimensions and relative positions of the multilayer thin film pattern, each functional layer can be formed using a mask-confined deposition method. For example... Figure 2 As shown, when depositing the bottom transparent conductive layer 1-2, a bottom mask a that matches the contour of the transparent lens substrate 1-1 can be used; as Figure 2 As shown, when depositing the electrochromic layer 2-1, the solid-state ion-conducting layer 2-2, and the ion storage layer 2-3, the electrochromic mask b corresponding to the electrochromic functional layer 2 can be used; as shown Figure 2 As shown, a composite transparent conductive layer mask c can be used when depositing the seed transparent conductive layer 3-1 and the main transparent conductive layer 3-2; as shown Figure 2As shown, electrode mask d can be used when depositing the upper metal external electrode 4-1 and the lower metal external electrode 4-2. Each of the above masks can be provided with a positioning slot that matches the contour of the transparent lens substrate 1-1, so as to realize the rapid positioning and repeated clamping of the irregularly shaped lens substrate.

[0052] The transparent lens substrate 1-1 can be selected from PC lenses, CR39 lenses, PMMA lenses, and glass lenses. The bottom transparent conductive layer 1-2 is preferably made of ITO material with a thickness of 80-300 nm. The electrochromic layer 2-1 can be made of WO3 and / or MoO3 material with a thickness of 300-700 nm; the solid ion conducting layer 2-2 can be made of LiTaO3 and / or LiNbO3 material with a thickness of 200-500 nm; the ion storage layer 2-3 can be made of NiO and / or V2O5 material with a thickness of 100-300 nm. The seed transparent conductive layer 3-1 and the main transparent conductive layer 3-2 are preferably both made of ITO material, wherein the seed transparent conductive layer 3-1 has a thickness of 5-50 nm, and the main transparent conductive layer 3-2 has a thickness of 100-500 nm.

[0053] like Figure 3 As shown, after the all-solid-state electrochromic lens is fabricated, the upper metal external electrode 4-1 and the lower metal external electrode 4-2 can be connected to the external control circuit through wires or flexible circuit boards and assembled into the frame 5 to obtain all-solid-state electrochromic glasses.

[0054] The present invention will be further illustrated by specific embodiments below.

[0055] Example 1

[0056] This embodiment prepares an all-solid-state electrochromic lens with a composite transparent conductive layer structure.

[0057] First, an optical glass lens was selected as the transparent lens substrate 1-1. To remove surface organic contaminants and particulate impurities, the glass lens was first ultrasonically cleaned sequentially in acetone, anhydrous ethanol, and deionized water, with each cleaning step lasting 10 minutes. After cleaning, it was dried with nitrogen gas and then subjected to plasma activation treatment for 5 minutes. Subsequently, as... Figure 2 As shown, the processed transparent lens substrate 1-1 is mounted in the positioning slot of the bottom mask a corresponding to the bottom transparent conductive layer, so that the edge of the lens fits with the positioning structure of the bottom mask a. An ITO bottom transparent conductive layer 1-2 is deposited on the surface of the transparent lens substrate 1-1 using a vacuum evaporation method, with a deposition thickness of 200 nm, an evaporation rate of 4 Å / s, and a working pressure of 3 × 10⁻⁶. -2 Pa, temperature is 300℃.

[0058] After completing the deposition of the bottom transparent conductive layer 1-2, replace it with the electrochromic mask b corresponding to the electrochromic functional layer 2, and as follows... Figure 2 The transparent lens substrate 1-1 is remounted in the positioning slot. Subsequently, a WO3 electrochromic layer 2-1, a LiTaO3 solid-state ion-conducting layer 2-2, and a NiO ion-storage layer 2-3 are sequentially deposited using vacuum evaporation. The WO3 electrochromic layer 2-1 has a thickness of 690 nm, an evaporation rate of 4 Å / s, and an operating pressure of 3 × 10⁻⁶. -2 The working pressure is 3 × 10⁻⁶ Pa, the temperature is 300 °C; the thickness of the LiTaO₃ solid ion-conducting layer 2-2 is 400 nm, the evaporation rate is 4 Å / s, and the working pressure is 3 × 10⁻⁶ Pa. -2 The pressure is Pa, the temperature is 300℃; the thickness of the NiO ion storage layer 2-3 is 120 nm, the evaporation rate is 4 Å / s, and the working pressure is 3.5 × 10⁻⁶ Pa. -2 Pa, temperature 400℃; thus forming a complete electrochromic functional layer 2.

[0059] Then, the composite transparent conductive layer 3 is prepared. For example... Figure 2 As shown, the substrate forming the electrochromic functional layer 2 is mounted in the positioning slot of the composite transparent conductive layer mask c. The cutout area of ​​the composite transparent conductive layer mask c is smaller than the deposition area corresponding to the electrochromic functional layer 2 to ensure that the edge of the composite transparent conductive layer 3 is tapered inward from the edge of the electrochromic functional layer 2 and to reserve an insulating gap area. The width of the insulating gap area is 0.5 mm. First, an ITO seed transparent conductive layer 3-1 with a thickness of 10 nm is deposited using a vacuum evaporation method at an evaporation rate of 2 Å / s and a working pressure of 3 × 10⁻⁶. -2 Pa, temperature 280℃. The seed transparent conductive layer 3-1 forms the initial conductive connection basis on the surface of the ion storage layer 2-3. Subsequently, the ITO host transparent conductive layer 3-2 with a thickness of 200 nm is deposited by vacuum evaporation at a rate of 4 Å / s and a working pressure of 3 × 10 Pa. -2 Pa, at a temperature of 400℃, allows it to grow continuously on the surface of the seed transparent conductive layer 3-1 and form a continuous conductive network, thereby obtaining the composite transparent conductive layer 3.

[0060] After completing the deposition of the composite transparent conductive layer 3, such as Figure 2 As shown, metal external electrodes 4 are deposited in the lead-out regions of the bottom transparent conductive layer 1-2 and the composite transparent conductive layer 3 using electrode mask d. In this embodiment, Ag is selected as the material for the metal external electrode 4, and a metal external electrode 4 with a thickness of 800 nm is formed by vacuum evaporation at an evaporation rate of 1.5 Å / s and a working pressure of 1.5 × 10⁻⁶. -2At room temperature (Pa), the upper metal external electrode 4-1 is located in the lead-out area of ​​the bottom transparent conductive layer 1-2, and the lower metal external electrode 4-2 is located in the lead-out area of ​​the composite transparent conductive layer 3. After the external electrodes are fabricated, they are connected to an external control circuit via wires or a flexible circuit board and assembled into the frame 5 to obtain all-solid-state electrochromic glasses.

[0061] Further cyclic stability testing of the all-solid-state electrochromic glasses prepared in this embodiment showed that after more than 1,000 coloring / fading cycles at a wavelength of 550 nm, the device still maintained a stable transmittance modulation capability, indicating that the composite transparent conductive layer structure can effectively improve the cyclic stability of the device. Figure 4 (a) is a photograph of the all-solid-state electrochromic glasses prepared in this embodiment before they change color when energized. Figure 4 (b) is a photograph of the all-solid-state electrochromic glasses fabricated in this embodiment after they change color when powered on. It can be seen that the device can achieve stable optical state switching after being powered on.

[0062] like Figure 5 As shown, the all-solid-state electrochromic lens prepared in this embodiment was subjected to a cycle stability test. After more than 1,000 coloring / fading cycles at a wavelength of 550 nm, the device still maintained a stable transmittance modulation capability.

[0063] Example 2

[0064] This embodiment prepares an all-solid-state electrochromic lens based on a PC lens substrate.

[0065] First, a PC lens was selected as the clear lens substrate 1-1. The PC lens was then ultrasonically cleaned sequentially with isopropanol, anhydrous ethanol, and deionized water, each step lasting 8 minutes, followed by drying with nitrogen gas. The cleaned PC lens was then installed as follows: Figure 2 The bottom transparent conductive layer 1-2, corresponding to the positioning slot of the bottom mask a shown, is deposited using magnetron sputtering. The thickness of the ITO bottom transparent conductive layer 1-2 is 120 nm, the deposition power is 150 W, the working pressure is 0.8 Pa, the deposition time is 80 min, the substrate temperature is room temperature, and the base vacuum degree is 3 × 10⁻⁶. -5 Pa.

[0066] Next, the PC lens with the bottom transparent conductive layer 1-2 is installed on... Figure 2Within the positioning slot of the electrochromic mask b corresponding to the electrochromic functional layer 2 shown, a MoO3 electrochromic layer 2-1, a LiNbO3 solid-state ion-conducting layer 2-2, and a V2O5 ion-storage layer 2-3 are sequentially deposited by magnetron sputtering. Specifically, the MoO3 electrochromic layer 2-1 has a thickness of 300 nm, a deposition power of 180 W, an operating pressure of 0.75 Pa, a deposition time of 250 min, and a substrate temperature of room temperature; the LiNbO3 solid-state ion-conducting layer 2-2 has a thickness of 200 nm, a deposition power of 150 W, an operating pressure of 0.7 Pa, a deposition time of 200 min, and a substrate temperature of room temperature; the V2O5 ion-storage layer 2-3 has a thickness of 150 nm, a deposition power of 180 W, an operating pressure of 0.8 Pa, a deposition time of 175 min, and a substrate temperature of room temperature. Through the above deposition, an all-solid-state electrochromic functional layer 2 suitable for PC lens substrates is formed.

[0067] Subsequently, the sample was installed on such Figure 2 The composite transparent conductive layer mask c is positioned within the slot. The cutout area of ​​the composite transparent conductive layer mask c is also set smaller than the deposition area corresponding to the electrochromic functional layer 2, to ensure that the edge of the composite transparent conductive layer 3 is contracted inwards from the edge of the electrochromic functional layer 2 and to reserve an insulating gap area with a width of 1 mm. First, an ITO seed transparent conductive layer 3-1 with a thickness of 5 nm is deposited using magnetron sputtering at a deposition power of 125 W, a working pressure of 0.8 Pa, a deposition time of 180 s, and a substrate temperature of room temperature. Then, the ITO main transparent conductive layer 3-2 with a thickness of 150 nm is deposited at a deposition power of 160 W, a working pressure of 0.8 Pa, a deposition time of 30 min, and a substrate temperature of room temperature. After this staged deposition, a composite transparent conductive layer 3 that balances light transmittance and conductivity is formed.

[0068] Finally, adopting such Figure 2 The electrode mask d shown forms an external metal electrode 4 in the lead-out regions of the bottom transparent conductive layer 1-2 and the composite transparent conductive layer 3. In this embodiment, Au is selected as the material for the external metal electrode 4, and it is deposited using magnetron sputtering. The thickness of the external metal electrode 4 is 500 nm, the deposition power is 250 W, the working pressure is 0.7 Pa, the deposition time is 30 min, the substrate temperature is room temperature, and the base vacuum is 3 × 10⁻⁶. -5 Pa. After completion, a fully solid-state electrochromic lens is obtained.

[0069] Example 3

[0070] This embodiment prepares a large-area all-solid-state electrochromic lens based on a CR39 lens substrate.

[0071] First, a CR39 lens was selected as the clear lens substrate 1-1. The CR39 lens was then ultrasonically cleaned sequentially with acetone, anhydrous ethanol, and deionized water, each step lasting 15 minutes. Following this, it was dried with nitrogen and subjected to surface activation treatment. The treated lens was then mounted onto... Figure 2 The bottom transparent conductive layer 1-2, corresponding to the positioning slot of the bottom mask a, is deposited using magnetron sputtering. The thickness of the ITO bottom transparent conductive layer 1-2 is 300 nm, the deposition power is 180 W, the working pressure is 0.8 Pa, the deposition time is 300 min, the substrate temperature is room temperature, and the substrate vacuum degree is 1 × 10⁻⁶. -3 Pa.

[0072] Then changed to Figure 2 Electrochromic mask b corresponding to the electrochromic functional layer 2 is shown, and the sample is re-clamped. A WO3 electrochromic layer 2-1, a LiTaO3 solid-state ion-conducting layer 2-2, and a NiO ion-storage layer 2-3 are sequentially deposited using vacuum evaporation. The deposited WO3 electrochromic layer 2-1 has a thickness of 700 nm, an evaporation rate of 4.5 Å / s, and an operating pressure of 3 × 10⁻⁶. -2 The working pressure is 3 × 10⁻⁶ Pa, the temperature is 250℃; the thickness of the LiTaO₃ solid ion-conducting layer 2-2 is 500 nm, the evaporation rate is 5 Å / s, and the working pressure is 3 × 10⁻⁶ Pa. -2 Pa, temperature 350℃; NiO ion storage layer 2-3 thickness 300nm, evaporation rate 6Å / s, working pressure 2.5×10 Pa. -2 Pa, temperature 450℃. The thicker functional layer design improves the electrochromic capability and cycle stability of large-area lenses during use.

[0073] After the electrochromic functional layer 2 is completed, it is used as follows Figure 2 The composite transparent conductive layer 3 is deposited on the composite transparent conductive layer mask c shown. The cutout area of ​​the composite transparent conductive layer mask c is smaller than the corresponding area of ​​the electrochromic functional layer 2 to ensure that the edge of the composite transparent conductive layer 3 is contracted inward compared to the edge of the electrochromic functional layer 2 and to reserve an insulating gap area with a width of 0.75 mm. First, an ITO seed transparent conductive layer 3-1 with a thickness of 50 nm is deposited using magnetron sputtering at a deposition power of 150 W, a working pressure of 0.8 Pa, a deposition time of 30 min, and a substrate temperature of room temperature. Subsequently, an ITO main transparent conductive layer 3-2 with a thickness of 500 nm is deposited at a deposition power of 180 W, a working pressure of 0.7 Pa, a deposition time of 500 min, and a substrate temperature of room temperature. Due to the larger thickness of the main transparent conductive layer 3-2, the resulting top conductive network has a lower sheet resistance, which is more conducive to the uniform driving of large-area lenses.

[0074] Finally, adopting such Figure 2 The electrode mask d shown forms Ag / Cu combined metal external electrodes 4 in the bottom transparent conductive layer 1-2 lead-out area and the composite transparent conductive layer 3 lead-out area, respectively. The total thickness of the metal external electrodes 4 is 1000nm. After formation, they are connected to the external driving circuit to obtain an all-solid-state electrochromic lens.

[0075] Comparative Example 1 This comparative example prepares an all-solid-state electrochromic lens with a composite transparent conductive layer structure. The preparation steps S1, S2, and S4 are the same as in Example 1, except that the width of the insulating gap region in step S3 is 0.4 mm. The rest are the same as in Example 1 and will not be repeated here.

[0076] Testing revealed that the 0.4 mm wide insulating gap used in this comparative example, which reduced the physical distance between the composite transparent conductive layer 3 and the electrochromic functional layer 2, was insufficient to completely avoid particle defects, film steps, and local rough areas at the edge of the functional layer. This is believed to be because, during the deposition of the composite transparent conductive layer 3, the transparent conductive material may still form a cross-conductive path across the aforementioned insufficiently isolated edge defect areas. Further electrical testing of the lens samples prepared according to this comparative example showed a significant increase in leakage current at the edge regions, with some samples exhibiting localized short-circuit failures. The device fabrication yield was lower than in Example 1, indicating that when the width of the insulating gap is less than the lower limit, the suppression effect on edge leakage and random short circuits is limited.

[0077] Comparative Example 2 This comparative example prepares an all-solid-state electrochromic lens with a composite transparent conductive layer structure. The preparation steps S1, S2, and S4 are the same as in Example 1, except that the width of the insulating gap region in step S3 is 1.1 mm. The rest are the same as in Example 1 and will not be described again here.

[0078] Testing revealed that the 1.1mm wide insulating gap in this comparative example increased the inward distance of the composite transparent conductive layer 3's edge, resulting in a significantly smaller effective coverage area compared to Example 1. This compressed the effective working area of ​​the electrochromic functional region. Simultaneously, the increased edge gap increased the lateral transmission distance of current from the external metal electrode to the distant working area, leading to uneven current distribution in the working area. Applying a driving voltage to the lens sample prepared in this comparative example and conducting a color-changing test revealed significant differences in color-changing gradients. The side closer to the electrode showed a darker color change, while the side farther from the electrode showed a lighter color change, indicating poor color-changing uniformity. This demonstrates that while a larger insulating gap enhances edge isolation, it sacrifices the effective color-changing area and color-changing uniformity.

[0079] Comparative Example 3 This comparative example prepares an all-solid-state electrochromic lens with a composite transparent conductive layer structure. The preparation steps S1, S2, and S4 are the same as in Example 1, except that the thickness of the seed transparent conductive layer 3-1 in step S3 is 2 nm. The rest are the same as in Example 1 and will not be repeated here.

[0080] Characterization tests revealed that, due to the seed transparent conductive layer 3-1's thickness of only 2 nm in this comparative example, it exhibited an island-like discontinuous distribution on the surface of the ion storage layer 2-3, failing to form a complete initial conductive film. During the subsequent deposition of the main transparent conductive layer 3-2, the main layer directly contacted particle defects and rough areas on the surface of the ion storage layer 2-3 in some regions, forming a cross-conduction path and failing to effectively prevent random short circuits. Furthermore, due to the discontinuity of the seed layer, the main transparent conductive layer 3-2 and the seed transparent conductive layer 3-1 could not form a good ohmic contact at the interface, and they failed to constitute a continuous conductive network penetrating the entire composite transparent conductive layer 3. Sheet resistance testing of the lens sample prepared in this comparative example showed that the overall sheet resistance of the composite transparent conductive layer 3 was approximately three times higher than that of Example 1; after applying a driving voltage, the lens's color-changing response time was significantly prolonged, and localized uncolored spots appeared in the working area, indicating a significant decrease in color-changing uniformity.

[0081] Comparative Example 4 This comparative example prepares an all-solid-state electrochromic lens with a composite transparent conductive layer structure. The preparation steps S1, S2, and S4 are the same as in Example 1, except that the thickness of the seed transparent conductive layer 3-1 in step S3 is 52 nm. The other steps are the same as in Example 1 and will not be repeated here.

[0082] Testing revealed that the excessively thick seed transparent conductive layer 3-1 in this comparative example caused two problems. First, it increased the overall thickness of the composite transparent conductive layer 3, significantly reducing the transmittance in the visible light band and decreasing the lens's ground-state transmittance, thus affecting the lens's optical performance. Second, the excessively thick seed ITO film increased residual stress and grain boundary defects, making it prone to microcracks and increasing the risk of film cracking and failure during cyclic coloring and fading. Optical testing of this comparative example showed that the initial visible light transmittance of the lens decreased by approximately 7% compared to Example 1. After hundreds of coloring and fading cycles, microcracks appeared in the composite transparent conductive layer 3 of some samples, resulting in the breakage of local conductive pathways, regional discoloration loss in the lens, and easy degradation of cycle durability.

[0083] Comparative Example 5 This comparative example prepares an all-solid-state electrochromic lens with a composite transparent conductive layer structure. The preparation steps S1, S2, and S4 are the same as in Example 1. The only difference is that in step S3, a SiO2 insulating layer is added between the seed transparent conductive layer 3-1 and the main transparent conductive layer 3-2. The rest are the same as in Example 1 and will not be described again here.

[0084] Characterization tests revealed that, due to the introduction of a SiO2 insulating layer between the seed transparent conductive layer 3-1 and the main transparent conductive layer 3-2 in this comparative example, the two transparent conductive materials are physically separated and cannot directly contact each other to form an ohmic contact. Therefore, they cannot interconnect to form a continuous conductive network. IV characteristic tests on the lens sample prepared in this comparative example showed that the overall resistance of the device increased by more than two orders of magnitude compared to Example 1. After applying a driving voltage, almost no current flowed, and the lens did not exhibit any coloring reaction. The electrochromic function was completely ineffective, indicating that the seed transparent conductive layer 3-1 and the main transparent conductive layer 3-2 must be in direct contact to form the continuous conductive network necessary for normal electrochromic actuation.

[0085] This invention utilizes a staged deposition process within confinement of a bottom mask (a), an electrochromic mask (b), a composite transparent conductive layer mask (c), and an electrode mask (d) to sequentially form a seed transparent conductive layer 3-1 and a main transparent conductive layer 3-2 on the surface of an ion storage layer 2-3, thereby constructing a composite transparent conductive layer 3. This allows the main transparent conductive layer 3-2 to preferentially grow continuously on the surface of the seed transparent conductive layer 3-1, effectively avoiding the formation of random conductive paths by the material of the composite transparent conductive layer 3 directly crossing particle defects and edge steps on the surface of the electrochromic functional layer 2. By using the composite transparent conductive layer 3... The edge of the seed transparent conductive layer 3-1 is recessed within the edge of the electrochromic functional layer 2 to form an insulating gap region. This achieves the best balance between fully avoiding the edge defects of the electrochromic functional layer 2 to suppress the risk of short circuits and ensuring the effective color-changing area and color-changing uniformity. At the same time, the seed transparent conductive layer 3-1 needs to have sufficient thickness to form its own continuous initial conductive film and to be in direct contact with the main transparent conductive layer 3-2 to form a continuous conductive network. This is necessary to simultaneously achieve random short circuit suppression and the construction of low-resistance transparent conductive pathways, thereby improving the preparation yield, working stability and cycle reliability of the all-solid-state electrochromic lens.

[0086] While the disclosure is as stated above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of this disclosure, and all such changes and modifications will fall within the protection scope of this invention.

Claims

1. A method for preparing an all-solid-state electrochromic lens, characterized in that, The preparation method specifically includes the following steps: Step S1: Deposit a bottom transparent conductive layer on the surface of the transparent lens substrate using a bottom mask; Step S2: Using an electrochromic mask, an electrochromic layer, a solid ion conduction layer, and an ion storage layer are sequentially deposited on the bottom transparent conductive layer to form an electrochromic functional layer. Step S3: Using the same composite transparent conductive layer mask, a composite transparent conductive layer is deposited in stages on the surface of the ion storage layer. The composite transparent conductive layer includes a seed transparent conductive layer and a main transparent conductive layer deposited sequentially. Step S4: Using an electrode mask, external metal electrodes are formed in the lead-out areas of the bottom transparent conductive layer and the composite transparent conductive layer, respectively. In step S3, the thickness of the seed transparent conductive layer is 5-50 nm, the thickness of the main transparent conductive layer is 100-500 nm, and the main transparent conductive layer and the seed transparent conductive layer are interconnected to form a continuous conductive network. When the composite transparent conductive layer mask is used for deposition, the cutout area of ​​the composite transparent conductive layer mask is smaller than the deposition area corresponding to the electrochromic functional layer, so that the edge of the composite transparent conductive layer is located inside the edge of the electrochromic functional layer, and a preset insulating gap area is formed between the two, the width of the insulating gap area is 0.5-1mm.

2. The preparation method according to claim 1, characterized in that, The composite transparent conductive layer mask, the bottom mask, the electrochromic mask, and the electrode mask are all provided with positioning slots that match the contour of the transparent lens substrate, so as to realize the positioning and repeated clamping of the lens substrate.

3. The preparation method according to claim 1, characterized in that, In step S1, the material of the transparent lens substrate is selected from one of PC lens, CR39 lens, PMMA lens and glass lens, and the material of the bottom transparent conductive layer is ITO with a thickness of 80-300nm.

4. The preparation method according to claim 1, characterized in that, In step S2, the electrochromic layer is made of WO3 and / or MoO3, the solid ion conduction layer is made of LiTaO3 and / or LiNbO3, and the ion storage layer is made of NiO and / or V2O5.

5. The preparation method according to claim 1, characterized in that, In step S3, both the seed transparent conductive layer and the main transparent conductive layer are made of ITO.

6. The preparation method according to claim 1, characterized in that, The methods for depositing the bottom transparent conductive layer, the electrochromic layer, the solid ion conduction layer, the ion storage layer, the seed transparent conductive layer, and the main transparent conductive layer are vacuum evaporation or magnetron sputtering; the external metal electrode is formed by vacuum evaporation, magnetron sputtering, screen printing, or inkjet printing.

7. The preparation method according to claim 1, characterized in that, In step S4, the thickness of the external metal electrode is 50-1000 nm, and the material of the external metal electrode is selected from one or more of Ag, Au, Cr, Ti and Cu.

8. A fully solid-state electrochromic lens, characterized in that, The all-solid-state electrochromic lens comprises, from bottom to top, a transparent lens substrate, a bottom transparent conductive layer, an electrochromic functional layer, and a composite transparent conductive layer. The lead-out areas of the bottom transparent conductive layer and the lead-out areas of the composite transparent conductive layer respectively form external metal electrodes. The electrochromic functional layer includes an electrochromic layer, a solid-state ion conduction layer, and an ion storage layer arranged sequentially. The composite transparent conductive layer includes a seed transparent conductive layer and a main transparent conductive layer arranged sequentially. The thickness of the seed transparent conductive layer is 5-50 nm, and the thickness of the main transparent conductive layer is 100-500 nm. The main transparent conductive layer and the seed transparent conductive layer are interconnected to form a continuous conductive network. The edge of the composite transparent conductive layer is located inside the edge of the electrochromic functional layer, and a preset insulating gap area is formed between the composite transparent conductive layer and the edge of the electrochromic functional layer. The width of the insulating gap area is 0.5-1mm.

9. A type of all-solid-state electrochromic glasses, characterized in that, Including the all-solid-state electrochromic lens as described in claim 8.

Images