Intelligent starry sky glass and preparation method and application thereof

Abstract

The application belongs to the technical field of functional glass materials, and relates to intelligent starry sky glass as well as a preparation method and application thereof.The intelligent starry sky glass comprises, from outside to inside, a self-cleaning layer, an outer layer of ultra-white glass, an intermediate functional layer and an inner layer of electrochromic glass, the intermediate functional layer comprises, from outside to inside, an optical microstructure, a fine electrode, an electrochromic starburst unit and a photonic crystal reflection layer, and the optical microstructure and the outer layer of ultra-white glass are fixed by PVB adhesive film bonding.The intelligent starry sky glass can realize a dynamic starburst effect through micro-nano structure optical design, and is particularly suitable for building curtain walls, automobile sunroofs and high-end decoration fields.

Description

Technical Field

[0001] This invention belongs to the field of functional glass materials technology, and relates to a smart starry sky glass, its preparation method and application, specifically a smart starry sky glass that achieves a dynamic starburst effect through micro-nano structure optical design, its preparation method and application. Background Technology

[0002] With the rapid development of architectural decoration, smart home, and high-end consumer electronics, glass materials are no longer limited to basic functions such as lighting and sound insulation. Functional glass that combines decoration, aesthetics, and intelligence has become a hot topic in industry research and application. Among them, starry sky glass, which can simulate the dazzling effect of the starry sky and create a tranquil and elegant spatial atmosphere, is widely used in hotel decoration, home ceilings, partitions, building curtain walls, car sunroofs, and electronic device covers, and market demand continues to rise.

[0003] Currently, the existing starry sky glass manufacturing technologies are mainly divided into two categories: one is physical decorative starry sky glass, which achieves the starry sky effect by printing starry sky patterns on the glass surface, pasting starry sky films, embedding fluorescent particles or transparent beads, etc.; the other is optical effect starry sky glass, which utilizes the refraction and scattering characteristics of the glass substrate, combined with a backlight module or projection device, to present a dynamic or static starry sky visual experience.

[0004] However, existing technologies still have many technical shortcomings that need to be addressed in practical applications, making it difficult to meet the demands of high-end scenarios for intelligent starry sky glass, enhanced user experience, and improved stability. Specifically, physically decorative starry sky glass suffers from the following problems: First, the starry sky effect is fixed and monotonous, only able to present preset patterns or particle distributions, and cannot adjust parameters such as star brightness, star density, and flicker frequency according to scene requirements, lacking interactivity and flexibility; Second, the decorative layer is mostly attached to the glass surface, resulting in poor scratch resistance, wear resistance, and weather resistance, and is prone to peeling, fading, and blurring after long-term use, leading to a short lifespan; Third, some products use fluorescent particles as star point raw materials, which have a rapid decay in fluorescence effect and require external light source excitation, making it impossible to present a starry sky effect in the absence of light, thus limiting practicality.

[0005] The core drawbacks of optical effect starry sky glass are: First, its level of intelligence is low. Most products require external independent projection equipment or backlight modules, which are complex in structure, cumbersome in installation, and occupy extra space, resulting in poor adaptability. Second, the realism of the starry sky effect is insufficient. The star points are mostly light spots formed by direct or refracted light from the light source, lacking the sense of layering and depth of the starry sky, resulting in a poor visual experience. Third, its energy consumption is high. The backlight module or projection equipment needs continuous power supply, which does not conform to the industry trend of energy conservation and environmental protection. Fourth, existing optical starry sky glass is mostly single-function, only able to display the starry sky effect, and cannot integrate additional functions such as dimming and heat insulation. Its functional integration is low, making it difficult to meet the integrated needs of smart homes.

[0006] In summary, current starry sky glass on the market suffers from several technical shortcomings, including low levels of intelligence, limited and unrealistic starry sky effects, insufficient functional integration, and poor stability and weather resistance. These limitations prevent it from fully meeting the demands of architectural decoration, smart home, and other fields for high-end functional glass. Therefore, developing a smart starry sky glass with high intelligence, adjustable starry sky effects, strong functional integration, and excellent stability has become a pressing technical challenge for those skilled in the art. Summary of the Invention

[0007] To address the shortcomings of the existing technologies, this invention provides a smart starry sky glass, its preparation method, and its applications. Through micro-nano structure optical design, a dynamic starburst effect can be achieved, making it particularly suitable for building curtain walls, car sunroofs, and high-end decoration.

[0008] The specific technical solution is as follows:

[0009] The first objective of this invention is to provide a smart starry sky glass, which comprises, from the outside to the inside: a self-cleaning layer, an outer ultra-white glass layer, an intermediate functional layer, and an inner electrochromic glass layer. The intermediate functional layer comprises, from the outside to the inside: an optical microstructure, a fine electrode, an electrochromic starburst unit, and a photonic crystal reflective layer. The optical microstructure and the outer ultra-white glass layer are bonded and fixed together by a PVB adhesive film.

[0010] The outer ultra-clear glass can be made of tempered ultra-clear glass, mainly serving a mechanical support and protection function, and is impact-resistant and high-strength. The self-cleaning layer on the surface of the outer ultra-clear glass can decompose organic pollutants on the surface under light, keeping the glass clear for a long time. The middle functional layer is the core of the smart starry sky glass. The photonic crystal reflective layer reflects light at a specific angle through a precisely designed photonic bandgap, forming a dazzling, static "background starlight" effect. The electrochromic starburst unit changes color and scatters WO3 nanowires (blue) and NiO nanosheets (gold) by applying different voltages, producing "active starbursts" that can move, change color, and disappear dynamically. The inner electrochromic glass is independent of the starburst function and mainly regulates the visible light and infrared rays entering the room, achieving sunshade, heat insulation, and privacy protection functions. The optical microstructure and the outer ultra-clear glass are bonded by a PVB film, which can simultaneously protect the functional film of the middle functional layer from wear and moisture.

[0011] The second objective of this invention is to provide a method for preparing the aforementioned smart starry sky glass, comprising the following steps:

[0012] (I) Preparation and pretreatment of the inner electrochromic glass base substrate;

[0013] (II) Photonic crystal reflective layer was prepared by atomic layer deposition-ALD;

[0014] (III) Electrochromic star units were prepared by photolithography and electrochemical deposition;

[0015] (IV) Fine electrodes are fabricated using screen printing;

[0016] (V) Functional glass is obtained by using thermal nanoimprinting to form optical microstructures;

[0017] (VI) A self-cleaning TiO2 nanotube array was constructed on the outer layer of ultra-white glass using a hydrothermal method;

[0018] (VII) The functional glass prepared in step (V) and the outer ultra-white glass treated in step (VI) are laminated and encapsulated with PVB film.

[0019] Furthermore, step (I) specifically includes:

[0020] Material preparation: Sodium-calcium glass or ultra-clear glass with ITO (indium tin oxide) plated on the surface is selected as the base substrate of the inner electrochromic glass. Its sheet resistance is ≤10 Ω / □, and the thickness is selected according to the application scenario (e.g. 2.1mm for car sunroofs, 6mm for building curtain walls).

[0021] Cleaning: Place the substrate in an alkaline cleaning solution and ultrasonically clean it at 60°C for 15 minutes, then rinse it with deionized water and dry it with high-purity nitrogen.

[0022] Activation: The ITO surface is treated with an oxygen plasma treatment device (500W power) for 60 seconds to thoroughly remove organic residues and significantly increase surface energy, thereby enhancing the adhesion of subsequent films.

[0023] Furthermore, step (II) specifically includes:

[0024] The pretreated substrate from step (I) is sent into the ALD reaction chamber. First, a TiO2 layer is deposited, then a SiO2 layer is deposited. The [TiO2 / SiO2] superlattice structure is deposited alternately for 15-25 cycles, with the total thickness controlled at 150-250 nm, forming a photonic crystal reflective layer that is tunable across the entire visible light spectrum. In other words, a photonic bandgap structure capable of producing basic starlight effects is constructed on the substrate.

[0025] Furthermore, step (II) specifically includes:

[0026] a. Substrate pretreatment: The substrate pretreated in step (Ⅰ) is placed into the ALD reaction chamber and evacuated at 150°C until the substrate pressure is below 10. -2 Pa, and argon gas is introduced to purge and remove water vapor and impurities adsorbed on the surface;

[0027] b. Depositing a TiO2 layer:

[0028] Precursor source: Tetra(dimethylamino)titanium (TDMAT, Ti(N(CH3)2)4) was used as the titanium source;

[0029] Reactor gas source: Ozone (O3) is used as the oxygen source;

[0030] Pulse-purge cycle:

[0031] Pulsed TDMAT: The source tank is at a temperature of 80°C, and the pulse duration is 0.1s, which causes the precursor to be chemically adsorbed onto the substrate surface;

[0032] Purging: High-purity argon gas is introduced to purge for 15 seconds to remove excess precursors and byproducts from the reaction chamber;

[0033] Pulsed O3: Pulse duration 0.2s, reacts with adsorbed titanium precursor to generate TiO2;

[0034] Purging: Introduce argon gas again for 20 seconds to purge and remove all gaseous byproducts;

[0035] Each of the above cycles can grow a TiO2 film of about 0.05-0.06 nm. The cycle is repeated N times (e.g., 100 times) to achieve a design thickness of about 5-6 nm.

[0036] In summary, TDMAT and O3 were used as precursors and reactive gas sources respectively during the deposition process, and deposition was carried out at 150°C. The pulse-purge cycle was: pulsed TDMAT-argon purge-pulse O3-argon purge. Each of the above cycles could grow a TiO2 film of 0.05-0.06 nm. Repeating the above cycle multiple times yielded a dense TiO2 layer of 5-6 nm.

[0037] c. Depositing a SiO2 layer:

[0038] Precursor source: 3-aminopropyltriethoxysilane (APTES, H2N(CH2)3Si(OC2H5)3) was used as the silicon source;

[0039] Reactor gas source: Deionized water (H2O) is used as the oxygen source;

[0040] Pulse-purge cycle:

[0041] Pulsed APTES: Source tank temperature 60℃, pulse duration 0.5s; a

[0042] Purging: Argon gas purging for 20 seconds;

[0043] Pulsed H2O: Pulse duration 0.1s;

[0044] Purging: Argon gas purging for 25 seconds;

[0045] Each cycle grows a SiO2 film of approximately 0.09 nm, and this cycle is repeated M times (e.g., 55 times) to achieve a design thickness of approximately 5 nm.

[0046] In summary, APTES and deionized water (H2O) were used as precursors and reactant sources respectively during the deposition process. Deposition was carried out at 150°C. The pulse-purge cycle was: pulsed APTES-argon purge-pulse H2O-argon purge. Each of the above cycles could grow a 0.09 nm SiO2 film. Repeating the above cycle multiple times yielded a 5 nm SiO2 layer.

[0047] d. Stacking to form a photonic crystal:

[0048] Alternately repeat steps b and c above to deposit 15-25 cycles of [TiO2 / SiO2] superlattice structure, with the total thickness controlled at 150-250 nm, to form a photonic crystal reflective layer that is tunable across the entire visible light spectrum;

[0049] By precisely controlling the number of cycles for each material, sub-angstrom level (0.1 nm) control over the thickness of each layer is achieved, thereby precisely regulating the bandgap position (380-780 nm) of the photonic crystal. Throughout the deposition process, the cavity temperature is maintained at 150°C to avoid deformation of the substrate material.

[0050] Furthermore, step (III) specifically includes:

[0051] Photolithography patterning: Photoresist is spin-coated onto the reflective layer of the photonic crystal, and exposed and developed using a mask to define the precise micro-regions where WO3 and NiO need to be deposited, thus obtaining substrate one;

[0052] Electrodeposited WO3 nanowires: Using substrate one as the working electrode, WO3 nanowire arrays were electrochemically deposited in an electrolyte containing sodium tungstate and sulfuric acid to obtain substrate two;

[0053] Chemical bath deposition of NiO nanosheets: The substrate is immersed in a solution containing nickel nitrate and urea to react and grow NiO nanosheets in situ in a defined area.

[0054] Remove the photoresist to complete the fabrication of patterned electrochromic starburst units.

[0055] Furthermore, step (III) specifically includes:

[0056] Photolithography patterning: Photoresist is spin-coated onto the reflective layer of the photonic crystal, and exposed and developed using a mask to define the precise micro-regions where WO3 and NiO need to be deposited, thus obtaining substrate one;

[0057] Electrodeposition of WO3 nanowires: Using substrate one as the working electrode, WO3 nanowire arrays with a diameter of about 50 nm and a length of about 10 μm were deposited in an electrolyte containing 0.05 M sodium tungstate (Na2WO4) and 0.1 M sulfuric acid (H2SO4) for 10 minutes at a voltage of 0.6 V (vs. Ag / AgCl), resulting in substrate two;

[0058] Chemical bath deposition of NiO nanosheets: The substrate was immersed in a solution containing 0.1 M nickel nitrate (Ni(NO3)2) and 0.2 M urea and reacted at 95°C for 2 hours to grow NiO nanosheets with a thickness of about 20 nm and a porosity of about 60% in situ in the defined area.

[0059] By removing the photoresist and completing the fabrication of patterned electrochromic star units, independently controllable blue (WO3, voltage 3V) and gold (NiO, voltage 5V) star units can be prepared.

[0060] Furthermore, step (IV) specifically includes:

[0061] For the fabrication of stainless steel wire mesh, the minimum line width of the electrode pattern is 10-30μm.

[0062] Submicron-level UV-curable conductive silver paste is selected;

[0063] Using a fully automatic printing press, set the squeegee angle to 60-75° and the squeegee pressure to 4-6 kg / cm².2 With a printing speed of 50-100 mm / s and a screen spacing of 1.0-1.5 mm, the silver paste is precisely printed onto the substrate surface prepared in step (III) through the pattern opening on the screen.

[0064] After pre-baking, UV curing, and heat treatment, a robust electrode with a sheet resistance of ≤20 mΩ / □ is formed, providing a low-resistance, high-precision control circuit for the electrochromic starburst unit.

[0065] Furthermore, step (IV) specifically includes:

[0066] a) Screen making: High-precision stainless steel wire mesh with a mesh size of 500 and a wire diameter of about 18μm is used to ensure high resolution and good ink penetration.

[0067] Laser Direct Imaging (LDI) technology is used to draw and expose the required electrode pattern (including buses and high-resolution cables with a minimum linewidth of ≤30μm) on the photosensitive emulsion layer of the screen, and after development, a precise pattern opening is obtained.

[0068] b) Preparation of silver paste:

[0069] The UV-curable polymer conductive silver paste is selected, with a silver content ≥85%, silver particle size D50 <1μm (submicron level), and viscosity controlled at 25-40 Pa·s (measured at 10 rpm).

[0070] Before printing, the silver paste is kept at a constant temperature of 25±3℃ for at least 2 hours and then subjected to low-speed stirring (300 rpm) for 10 minutes to degas it, so as to ensure that the material properties are stable and free of bubbles.

[0071] c) Substrate positioning and pretreatment:

[0072] The substrate prepared in step (Ⅲ) (with the electrochromic starburst unit reserved area already prepared on the surface) is fixed on the vacuum adsorption platform of the printing machine;

[0073] The substrate surface was treated with a plasma cleaner (500W, air atmosphere) for 45 seconds to improve its surface energy and enhance the adhesion of the silver paste.

[0074] d) Printing parameter settings and printing:

[0075] Using a fully automatic, high-precision screen printing machine, the key parameters are set as follows: squeegee angle: 60-75°, squeegee pressure: 4-6 kg / cm². 2 Printing speed: 50-100 mm / s; Snap-off distance: 1.0-1.5 mm;

[0076] Under yellow light, silver paste is poured into the screen, the printing machine is started, and the squeegee moves at a constant speed to accurately print the silver paste through the pattern opening on the screen onto the surface of the substrate prepared in step c), forming the designed electrode pattern.

[0077] e) Pre-curing and leveling:

[0078] After printing, the substrate is left to stand in a dust-free environment at room temperature for 3-5 minutes to allow the silver paste pattern to flow naturally and eliminate the jagged edges caused by printing.

[0079] f) Curing and molding:

[0080] The leveled substrate is then placed in a UV curing oven for segmented curing.

[0081] First stage: Bake at 80℃ for 2 minutes to remove most of the solvent;

[0082] Second stage: Using ultraviolet light with a wavelength of 365nm and an intensity of 80 mW / cm². 2 Irradiate for 60 seconds to allow the polymer resin to fully cross-link and cure;

[0083] The third stage involves heat treatment at 120℃ for 15 minutes to further promote the fusion of silver particles and form a dense, highly conductive electrode circuit.

[0084] g) Performance testing:

[0085] Use an optical microscope to inspect the line width (ensure it is ≤30μm), open circuits, and short circuits.

[0086] Use a four-probe tester to measure the sheet resistance of the electrodes and ensure it is ≤20 mΩ / □.

[0087] The key parameters and explanations for screen printing are detailed in Table 1 below.

[0088] Table 1 Key Parameters and Explanations for Screen Printing

[0089]

[0090] Furthermore, step (V) specifically includes:

[0091] Thermoplastic resin polymer imprinting adhesive is spin-coated onto the surface of the sample prepared in step (IV);

[0092] Using a nickel plate mold with a convex micro-hemispherical array, heat and apply pressure in a vacuum environment, and hold the pressure for 5-10 minutes;

[0093] After cooling and demolding, a perfect concave microlens array is formed on the surface, namely the optical microstructure, which is used to scatter light, expand the viewing angle, and create a starburst effect.

[0094] Furthermore, step (V) specifically includes:

[0095] (a) Preparing the nanoimprint mold:

[0096] Using single-crystal silicon, a master mold with a convex micro-hemispherical array on the surface is fabricated by electron beam lithography (EBL) and inductively coupled plasma (ICP) etching technology. The radius of curvature of the convex surface is precisely controlled between 0.5-2μm, and the surface roughness Ra<2 nm.

[0097] The silicon master mold is treated to prevent sticking by vapor-depositing a layer of perfluorooctyltrichlorosilane (FOTS) self-assembled monolayer on its surface to facilitate subsequent demolding.

[0098] (b) Transfer and reproduction work mold:

[0099] Using ultraviolet (UV) curing nanoimprinting technology, the pattern of the silicon master mold is copied onto a nickel (Ni) plate to create a durable nano-nickel plate working mold (the surface of which is a corresponding concave microlens array cavity, Ra<5nm); this nickel plate mold is suitable for subsequent thermal nanoimprinting mass production.

[0100] (c) Applying embossing adhesive:

[0101] On the surface of the sample prepared in step (IV), a layer of thermoplastic resin polymer imprinting adhesive (commonly polymethyl methacrylate PMMA or hydrogen silsesquioxane HSQ) is uniformly coated by spin coating. The film thickness is precisely controlled at 1.5-4 μm (approximately twice the radius of curvature of the target microlens).

[0102] (d) Hot stamping:

[0103] After aligning the substrate coated with imprinting adhesive with the nickel plate mold, it is placed into the thermal nanoimprinting machine;

[0104] In a vacuum environment (<10) 2 Under the condition of Pa), the temperature is raised to 180℃ (higher than the glass transition temperature Tg of PMMA), and a uniform pressure of 8 MPa is applied and held for 5-10 minutes.

[0105] During this process, the polymer softens and flows, completely filling the concave cavity of the mold, thus achieving graphic transfer.

[0106] (e) Cooling and demolding:

[0107] While maintaining pressure, the entire device is cooled to 70°C (below the Tg of PMMA) to allow the polymer to solidify and set.

[0108] The pressure was then released, and the nickel plate mold was carefully separated from the substrate, ultimately resulting in a regular concave microlens array on the substrate surface that complements the mold pattern.

[0109] (f) Graphic solidification (optional):

[0110] For applications requiring higher mechanical stability and heat resistance, the PMMA microlenses formed by embossing can be subjected to electron beam irradiation or deep ultraviolet (DUV) exposure to further crosslink and cure them.

[0111] The key parameters and descriptions for thermal nanoimprinting are detailed in Table 2 below.

[0112] Table 2 Key parameters and descriptions for thermal nanoimprinting

[0113]

[0114] Furthermore, step (VI) specifically includes:

[0115] The outer layer of ultra-white glass is placed in a high-pressure reactor, and an ethanol solution containing tetrabutyl titanate and hydrofluoric acid is injected to carry out the reaction. After the reaction is completed, the sample is taken out, rinsed repeatedly with deionized water and ethanol, and then annealed in air at 400-480℃ to obtain a crystallized anatase TiO2 nanotube array, forming a self-cleaning function with photocatalytic activity on the outermost layer.

[0116] Furthermore, step (VI) specifically includes:

[0117] The outer layer of ultra-white glass was placed in a high-pressure reactor, and an ethanol solution containing 0.15 M tetrabutyl titanate and 5% hydrofluoric acid (HF) was injected. The reaction was carried out at 180°C for 12 hours. After the reaction was completed, the sample was taken out, rinsed repeatedly with deionized water and ethanol, and then annealed in air at 450°C for 2 hours to obtain crystallized anatase TiO2 nanotube arrays with a diameter of 80-120 nm.

[0118] Furthermore, step (VII) specifically includes:

[0119] The functional glass prepared in step (V) and the outer ultra-white glass treated in step (VI) are laminated together with a PVB (polyvinyl butyral) film. In a vacuum laminator, the laminator is held at 120-160℃ and 0.8-1.5 MPa for 15-30 minutes to allow the PVB to fully fuse, forming a robust "sandwich" structure that protects the inner functional layer and forms the final product.

[0120] Furthermore, step (VII) specifically includes:

[0121] The functional glass prepared in step (V) and the outer ultra-white glass treated in step (VI) are laminated with a 1.2 mm thick PVB film. In a vacuum laminator, the glass is kept at 140°C and 1.2 MPa pressure for 20 minutes to allow the PVB to fully fuse and form a strong "sandwich" structure.

[0122] The third objective of this invention is to provide an application of the smart starry sky glass described above in the fields of building curtain walls, car sunroofs and decoration.

[0123] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0124] The photonic crystal reflective layer of this invention uses alternating stacking of TiO2 / SiO2 to form a three-dimensional photonic crystal structure with a bandgap design range of 380-780nm, achieving full-band control of visible light.

[0125] In the electrochromic starburst unit of this invention, WO3 nanowires and NiO nanosheets are arranged using a micro-patterning technique. The starburst unit regions are defined through screen printing or photolithography, ensuring that the appearance and movement of blue and gold starbursts can be independently controlled when different voltages are applied. Specifically, the electrochromic starburst unit defines micro-electrode regions on a photonic crystal reflective layer using photolithography. Subsequently, WO3 nanowires (blue starbursts) and NiO nanosheets (gold starbursts) are fabricated in specific electrode regions using electrochemical deposition, forming a patterned, independently addressable and controllable starburst unit array. The nanowires are oriented along the electric field direction, while the nanosheets are arranged in parallel layers to optimize the electrochromic response speed and optical effects. Attached Figure Description

[0126] Figure 1 This is a schematic diagram of the structure of a smart starry sky glass according to the present invention;

[0127] Figure 2 This is a schematic diagram of the manufacturing process of a smart starry sky glass according to the present invention.

[0128] Explanation of reference numerals in the attached diagram: 1. Outer layer ultra-white glass; 2. Middle functional layer; 21. Optical microstructure; 22. Fine electrode; 23. Electrochromic starburst unit; 24. Photonic crystal reflective layer; 3. Inner layer electrochromic glass; 4. PVB film. Detailed Implementation

[0129] The principles and features of the present invention are described below with reference to examples. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention.

[0130] Example

[0131] A smart starry sky glass, referring to Figure 1From the outside in, it comprises: a self-cleaning layer, an outer ultra-white glass 1, an intermediate functional layer 2, and an inner electrochromic glass 3. The intermediate functional layer 2 comprises, from the outside in, an optical microstructure 21, a fine electrode 22, an electrochromic starburst unit 23, and a photonic crystal reflective layer 24. The optical microstructure 21 and the outer ultra-white glass 1 are bonded and fixed together by a PVB adhesive film 4. The self-cleaning layer is located on the upper surface of the outer ultra-white glass 1. Figure 1 Not shown in the image.

[0132] A method for preparing smart starry sky glass, referring to Figure 2 This includes the following steps:

[0133] (I) Preparation and pretreatment of the inner electrochromic glass base substrate;

[0134] (II) Photonic crystal reflective layer was prepared by atomic layer deposition-ALD;

[0135] (III) Electrochromic star units were prepared by photolithography and electrochemical deposition;

[0136] (IV) Fine electrodes are fabricated using screen printing;

[0137] (V) Functional glass is obtained by using thermal nanoimprinting to form optical microstructures;

[0138] (VI) A self-cleaning TiO2 nanotube array was constructed on the outer layer of ultra-white glass using a hydrothermal method;

[0139] (VII) The functional glass prepared in step (V) and the outer ultra-white glass treated in step (VI) are laminated and encapsulated with PVB film.

[0140] Specifically, step (I) includes:

[0141] Material preparation: Sodium-calcium glass or ultra-clear glass with ITO (indium tin oxide) plated on the surface is selected as the base substrate of the inner electrochromic glass. Its sheet resistance is ≤10 Ω / □, and the thickness is selected according to the application scenario (e.g. 2.1mm for car sunroofs, 6mm for building curtain walls).

[0142] Cleaning: Place the substrate in an alkaline cleaning solution and ultrasonically clean it at 60°C for 15 minutes, then rinse it with deionized water and dry it with high-purity nitrogen.

[0143] Activation: The ITO surface is treated with an oxygen plasma treatment device (500W power) for 60 seconds to thoroughly remove organic residues and significantly increase surface energy, thereby enhancing the adhesion of subsequent films.

[0144] Specifically, step (II) includes:

[0145] a. Substrate pretreatment: The substrate pretreated in step (Ⅰ) is placed into the ALD reaction chamber and evacuated at 150°C until the substrate pressure is below 10. -2 Pa, and argon gas is introduced to purge and remove water vapor and impurities adsorbed on the surface;

[0146] b. Deposition of TiO2 layer: During the deposition process, TDMAT and O3 were used as precursors and reactant gas sources, respectively, and deposition was carried out at 150°C. The pulse-purge cycle was: pulse TDMAT-argon purge-pulse O3-argon purge. Each of the above cycles could grow a 0.055 nm TiO2 film. The above cycle was repeated 100 times to obtain a 5.5 nm dense TiO2 layer.

[0147] c. Deposition of SiO2 layer: APTES and deionized water (H2O) were used as precursors and reactant gas sources respectively during the deposition process. Deposition was carried out at 150°C. The pulse-purge cycle was: pulsed APTES-argon purge-pulse H2O-argon purge. Each of the above cycles could grow a 0.09 nm SiO2 film. The above cycle was repeated 55 times to obtain a 5 nm SiO2 layer.

[0148] d. Stacking to form a photonic crystal:

[0149] Alternately repeat steps b and c above to deposit 20 cycles of [TiO2 / SiO2] superlattice structure with a total thickness controlled at 210 nm, forming a photonic crystal reflective layer that is tunable across the entire visible light spectrum.

[0150] Specifically, step (III) includes:

[0151] Photolithography patterning: Photoresist is spin-coated onto the reflective layer of the photonic crystal, and exposed and developed using a mask to define the precise micro-regions where WO3 and NiO need to be deposited, thus obtaining substrate one;

[0152] Electrodeposition of WO3 nanowires: Using substrate one as the working electrode, WO3 nanowire arrays with a diameter of about 50 nm and a length of about 10 μm were deposited in an electrolyte containing 0.05 M sodium tungstate (Na2WO4) and 0.1 M sulfuric acid (H2SO4) for 10 minutes at a voltage of 0.6 V (vs. Ag / AgCl), resulting in substrate two;

[0153] Chemical bath deposition of NiO nanosheets: The substrate was immersed in a solution containing 0.1 M nickel nitrate (Ni(NO3)2) and 0.2 M urea and reacted at 95°C for 2 hours to grow NiO nanosheets with a thickness of about 20 nm and a porosity of about 60% in situ in the defined area.

[0154] By removing the photoresist and completing the fabrication of patterned electrochromic star units, independently controllable blue (WO3, voltage 3V) and gold (NiO, voltage 5V) star units can be prepared.

[0155] Specifically, step (IV) includes:

[0156] To produce a 500-mesh stainless steel wire mesh, the minimum line width of the electrode pattern is 20μm;

[0157] Submicron-sized (particle size <1μm) UV-curable conductive silver paste was selected;

[0158] Using a fully automatic printing press, set the squeegee angle to 70° and the squeegee pressure to 5 kg / cm². 2 With a printing speed of 80 mm / s and a screen spacing of 1.5 mm, the silver paste is precisely printed onto the substrate surface prepared in step (III) through the pattern opening on the screen.

[0159] Pre-baking at 80℃ for 2 minutes, followed by UV irradiation (80 mW / cm²). 2 Curing for 60 seconds and heat treatment at 120℃ for 15 minutes forms a robust electrode with a sheet resistance ≤20 mΩ / □, providing a low-resistance, high-precision control circuit for the electrochromic starburst unit.

[0160] Specifically, step (V) includes:

[0161] A 2 μm thick layer of PMMA thermoplastic resin polymer imprinting adhesive is spin-coated onto the surface of the sample prepared in step (IV);

[0162] Using a nickel plate mold with a convex micro-hemispherical array (radius of curvature 1 μm) (Ra < 5 nm), in a vacuum environment (< 10 nm) 2 Under the condition of Pa), heat to 180℃ and apply a pressure of 8 MPa, and hold the pressure for 5 minutes;

[0163] After cooling to below 70°C, the material is demolded, forming a perfect concave microlens array on the surface, which is the optical microstructure described above.

[0164] Specifically, step (VI) includes:

[0165] The outer layer of ultra-white glass was placed in a high-pressure reactor, and an ethanol solution containing 0.15 M tetrabutyl titanate and 5% hydrofluoric acid (HF) was injected. The reaction was carried out at 180°C for 12 hours. After the reaction was completed, the sample was taken out, rinsed repeatedly with deionized water and ethanol, and then annealed in air at 450°C for 2 hours to obtain crystallized anatase TiO2 nanotube arrays with a diameter of 80-120 nm.

[0166] Specifically, step (VII) includes:

[0167] The functional glass prepared in step (V) and the outer ultra-white glass treated in step (VI) are laminated with a 1.2 mm thick PVB film. In a vacuum laminator, the glass is kept at 140°C and 1.2 MPa pressure for 20 minutes to allow the PVB to fully fuse and form a strong "sandwich" structure.

[0168] test:

[0169] The finished starry sky glass obtained by this invention was subjected to the following performance tests: starburst response time, visible light transmittance adjustment range, U-value, electrode conductivity, adhesion, and accelerated aging life. The test methods and results are as follows:

[0170] Starburst Response Time: A high-precision photodiode captures the brightness changes of the starburst unit under light stimulation, converting the light signal into an electrical signal. The brightness-time curve is analyzed to calculate the response time. A completely dark environment is provided to avoid ambient light interference. The photodiode is then placed tightly against the surface of the starburst unit to ensure a consistent measurement area. After repeated testing, the response time of the starburst unit remained stable, with an average of 0.8 seconds across 20 tests. Each test result was less than 1 second, fully demonstrating the unit's fast response characteristics and its ability to meet the high real-time requirements of practical applications.

[0171] Visible light transmittance adjustment range: The visible light transmittance of the starburst unit was precisely measured using ultraviolet-visible spectrophotometry. The results showed that its visible light transmittance could be adjusted over a wide range from 72% to 18%. During the adjustment process, the transmittance changed uniformly and smoothly, without any obvious abrupt changes or instability, providing a reliable guarantee for precise control of light transmittance under different lighting conditions.

[0172] U-value: The U-value of the starburst element was determined using professional heat transfer performance testing equipment under standard testing conditions via the protective hot plate method. After 20 independent tests, the average value was 1.2 W / (m²). 2 The data shows that the starburst unit has excellent thermal insulation performance, effectively reduces heat transfer and energy consumption, and has broad application prospects in building energy conservation and other fields.

[0173] Electrode continuity: The electrode continuity of the starburst unit was tested using a high-precision resistance meter. The test results showed that the resistance values ​​between the electrodes were all less than 20mΩ.

[0174] Adhesion: The adhesion between the surface coating of the starburst unit and the substrate was evaluated according to the universal adhesion test standard, the cross-cut adhesion test. After a rigorous testing process, the adhesion level reached level 2, indicating that the coating and the substrate are firmly bonded and are not prone to peeling or detachment under normal use conditions, effectively ensuring the appearance quality and long-term performance of the starburst unit.

[0175] Accelerated Aging Life Test: The Starburst Cell was placed in an accelerated aging test chamber simulating harsh environmental conditions for a continuous 7-day accelerated aging test. During the test, various performance indicators of the cell were periodically monitored. The test results showed that after accelerated aging, the various performance indicators of the Starburst Cell remained above 96% of their initial values, and no significant performance degradation or damage was observed.

[0176] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A smart starry sky glass, characterized in that, From the outside to the inside, it includes: a self-cleaning layer, an outer layer of ultra-white glass, an intermediate functional layer, and an inner layer of electrochromic glass. The intermediate functional layer includes, from the outside to the inside, an optical microstructure, a fine electrode, an electrochromic starburst unit, and a photonic crystal reflective layer. The optical microstructure and the outer layer of ultra-white glass are bonded and fixed together by a PVB adhesive film. The optical microstructure described is a concave microlens array, used to scatter light, expand the viewing angle, and create a starburst effect; The fine electrode is a robust electrode with a sheet resistance ≤20 mΩ / □, providing a control circuit for the electrochromic starburst unit; The electrochromic starburst unit comprises blue starburst WO3 nanowires and gold starburst NiO nanosheets, forming a patterned, independently addressable and controllable starburst unit array. The nanowires are oriented along the electric field direction, while the nanosheets are arranged in parallel layers to optimize the electrochromic response speed and optical effects.

2. A method for preparing intelligent starry sky glass as described in claim 1, characterized in that, Includes the following steps: (I) Preparation and pretreatment of the inner electrochromic glass base substrate; (II) Photonic crystal reflective layer was prepared by atomic layer deposition-ALD; (III) Electrochromic star units were prepared by photolithography and electrochemical deposition; (IV) Fine electrodes are fabricated using screen printing; (V) Functional glass is obtained by using thermal nanoimprinting to form optical microstructures; (VI) A self-cleaning TiO2 nanotube array was constructed on the outer layer of ultra-white glass using a hydrothermal method; (VII) The functional glass prepared in step (V) and the outer ultra-white glass treated in step (VI) are laminated and encapsulated with PVB film.

3. The method for preparing intelligent starry sky glass according to claim 2, characterized in that, Step (II) specifically includes: The pretreated substrate from step (I) is sent into the ALD reaction chamber. First, a TiO2 layer is deposited, then a SiO2 layer is deposited. The [TiO2 / SiO2] superlattice structure is deposited alternately for 15-25 cycles, with the total thickness controlled at 150-250 nm, forming a photonic crystal reflective layer that is tunable across the entire visible light spectrum.

4. The method for preparing intelligent starry sky glass according to claim 2, characterized in that, Step (III) specifically includes: Photolithography patterning: Photoresist is spin-coated onto the reflective layer of the photonic crystal, and exposed and developed using a mask to define the precise micro-regions where WO3 and NiO need to be deposited, thus obtaining substrate one; Electrodeposited WO3 nanowires: Using substrate one as the working electrode, WO3 nanowire arrays were electrochemically deposited in an electrolyte containing sodium tungstate and sulfuric acid to obtain substrate two; Chemical bath deposition of NiO nanosheets: The substrate is immersed in a solution containing nickel nitrate and urea to react and grow NiO nanosheets in situ in a defined area. Remove the photoresist to complete the fabrication of patterned electrochromic starburst units.

5. The method for preparing intelligent starry sky glass according to claim 2, characterized in that, Step (IV) specifically includes: For the fabrication of stainless steel wire mesh, the minimum line width of the electrode pattern is 10-30μm. Submicron-level UV-curable conductive silver paste is selected; Using a fully automatic printing press, set the squeegee angle to 60-75° and the squeegee pressure to 4-6 kg / cm². 2 With a printing speed of 50-100 mm / s and a screen spacing of 1.0-1.5 mm, the silver paste is precisely printed onto the substrate surface prepared in step (III) through the pattern opening on the screen. After pre-baking, UV curing, and heat treatment, a robust electrode with a sheet resistance ≤20 mΩ / □ is formed.

6. The method for preparing intelligent starry sky glass according to claim 2, characterized in that, The specific steps (V) include: Thermoplastic resin polymer imprinting adhesive is spin-coated onto the surface of the sample prepared in step (IV); Using a nickel plate mold with a convex micro-hemispherical array, heat and apply pressure in a vacuum environment, and hold the pressure for 5-10 minutes; After cooling and demolding, a concave microlens array is formed on the surface, which is the optical microstructure mentioned above.

7. The method for preparing intelligent starry sky glass according to claim 2, characterized in that, The specific steps (VI) include: The outer layer of ultra-white glass was placed in a high-pressure reactor, and an ethanol solution containing tetrabutyl titanate and hydrofluoric acid was injected to carry out the reaction. After the reaction was completed, the sample was taken out, rinsed repeatedly with deionized water and ethanol, and then annealed in air at 400-480℃ to obtain a crystallized anatase TiO2 nanotube array.

8. The method for preparing intelligent starry sky glass according to claim 2, characterized in that, The specific steps (VII) include: The functional glass prepared in step (V) and the outer ultra-clear glass treated in step (VI) are laminated with a PVB film. In a vacuum laminator, the laminator is kept at 120-160℃ and 0.8-1.5 MPa pressure for 15-30 minutes to allow the PVB to fully fuse.

9. The method for preparing intelligent starry sky glass according to claim 2, characterized in that, Step (I) specifically includes: Material preparation: Sodium-calcium glass or ultra-clear glass with indium tin oxide (ITO) plated on the surface is selected as the base substrate for the inner electrochromic glass, and its sheet resistance is ≤10 Ω / □. Cleaning: Place the substrate in an alkaline cleaning solution and clean it under ultrasonication, then rinse it with deionized water and dry it with high-purity nitrogen. Activation: The ITO surface is treated using an oxygen plasma treatment device.

10. The application of the smart starry sky glass as described in claim 1 in the field of decoration.

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