Super-hydrophobic anti-dazzle vehicle-mounted cover plate glass based on micro-nano composite structure

Abstract

The invention discloses super-hydrophobic anti-glare vehicle-mounted cover plate glass based on a micro-nano composite structure, and relates to the field of optical glass elements. The anti-glare layer is provided with micron pits; an indium tin oxide conductive layer; a zinc oxide nanorod array layer; a silicon dioxide antireflection layer; through the synergistic effect of the micron-sized anti-dazzle structure and the nano-sized zinc oxide nanorod array, a composite surface with super-hydrophobic and oleophobic characteristics is constructed, the residual area of fingerprints is reduced, the fingerprints are easy to wipe, meanwhile, the zinc oxide nanorod array enhances the adhesive force of the anti-fingerprint film, and the anti-dazzle performance of the anti-fingerprint film is improved. The wear resistance is improved; the multi-layer thin film design effectively balances the anti-dazzle and high-definition display requirements, and provides a technical scheme with functionality and durability for vehicle-mounted display.

Description

Technical Field

[0001] This invention relates to the field of optical glass components, specifically to a superhydrophobic anti-glare automotive cover glass based on a micro-nano composite structure. Background Technology

[0002] As the core interactive carrier of the smart cockpit, the surface performance of the in-vehicle touch screen directly affects driving safety and user experience. When the glass panel of the screen is exposed to strong outdoor light, the screen surface is prone to strong glare, which can cause driver visual fatigue or even temporary blindness, greatly increasing driving risks. In addition, frequent daily touch operations will leave fingerprints, oil stains and dust on the surface, which not only blurs the displayed content and reduces information reading efficiency, but also affects the interior texture due to the stains, lowering the perceived product quality.

[0003] To address the aforementioned issues, the mainstream solution in the industry is to construct a composite functional coating of "anti-glare (AG) + anti-fingerprint (AF)" on the surface of the cover glass.

[0004] Among them, the AG coating scatters ambient light through its micro-rough structure, reducing specular reflection; while the AF coating uses fluorine-containing compounds to form a hydrophobic and oleophobic film on the surface, reducing the adhesion of pollutants. However, the inherent defects of traditional manufacturing processes make it difficult for the two to achieve synergistic performance: On the one hand, although the current mainstream spraying process can quickly form micron-level (usually 1-5μm) rough AG surfaces, the irregular uneven structure and huge specific surface area it forms actually provide "anchoring points" for macromolecules such as grease and protein in fingerprints. Experimental data shows that under the same conditions, the amount of fingerprint residue on AG surfaces is 30%-50% higher than that on ordinary glass. Moreover, due to the complex structure, more force is required to wipe during cleaning, which can easily cause secondary scratches. On the other hand, traditional AF solutions rely on solvent evaporation to form a uniform film layer. However, on rough AG surfaces, the solution will preferentially fill the concave areas, resulting in insufficient film thickness at the protrusions. Ultimately, the film layer will have "hydrophobic and oleophobic blind zones". The contact angle drops sharply from 110°-120° on flat surfaces to 60°-70°. The wear resistance also decreases by more than 50% due to the weak film-substrate adhesion, and local failure occurs after a period of use. Summary of the Invention

[0005] The purpose of this invention is to provide a superhydrophobic anti-glare automotive cover glass, a light-uniforming module, and electronic equipment based on a micro-nano composite structure, in order to solve the problems of impurities in cooling water and heat waste mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a superhydrophobic anti-glare automotive cover glass based on a micro-nano composite structure, comprising, from the bottom substrate upwards: a sodium-calcium-silicon glass substrate; An anti-glare layer with micron-sized pits; Indium tin oxide conductive layer; Zinc oxide nanorod array layer; Silicon dioxide antireflective layer; Anti-fingerprint layer deposited by vapor deposition of perfluoroalkylsilane compounds.

[0007] Preferably, the zinc oxide nanorod array is grown inside and on the surface of the micron-sized pits in the anti-glare layer, forming a micron-nano composite rough structure.

[0008] Preferably, the anti-fingerprint layer is formed by vacuum evaporation and is coated on the surface of the zinc oxide nanorod array layer and the silicon dioxide antireflection layer.

[0009] Preferably, the sheet resistance of the indium tin oxide conductive layer is 80-100 Ω / sq, and the light transmittance exceeds 85%.

[0010] Preferably, the optical thickness of the silicon dioxide antireflection layer is optimized so that the reflectivity at a wavelength of 550 nm does not exceed 1.5%.

[0011] Preferably, the depth of the micron-sized pits in the anti-glare layer is 10-15 μm, and the surface roughness is 3-5 μm.

[0012] Preferably, the zinc oxide nanorod array layer has a diameter of 50-80 nm, a height of 300-500 nm, and a spacing of 20-50 nm between the rods.

[0013] This invention also provides a preparation method, comprising the following steps: S1. Etch the glass substrate with a mixed acid of HF / H2SO4 to form an anti-glare layer; S2. A magnetron sputtering layer of indium tin oxide conductive layer is deposited on the surface of the anti-glare layer; S3. A zinc oxide nanorod array layer is grown on the surface of indium tin oxide by an electrochemical method; S4. Magnetron sputtering deposition of silicon dioxide antireflection layer; S5. Vacuum-deposited anti-fingerprint layer; Preferably, the electrolyte in the electrochemical deposition process of zinc oxide nanorod array layers is a mixed aqueous solution of zinc nitrate and hexamethylenetetramine, the temperature is 70-90 °C, a constant potential of -1.0V to -1.2V is applied, and the deposition time is 40-60 minutes.

[0014] Preferably, the etching solution has a composition of HF:H2SO4=1:(2-4), an etching temperature of 50-60℃, and an etching time of 5-12 minutes.

[0015] Compared with the prior art, the beneficial effects of the present invention are: This invention utilizes the synergistic effect of a micron-level anti-glare structure and a nano-level zinc oxide nanorod array to construct a composite surface with superhydrophobic and oleophobic properties, reducing the area of ​​fingerprint residue and making it easy to wipe away. At the same time, the zinc oxide nanorod array enhances the adhesion of the anti-fingerprint film and improves wear resistance. The multi-layer thin film design effectively balances the requirements of anti-glare and high-definition display, providing a functional and durable technical solution for automotive displays. Attached Figure Description

[0016] Figure 1 Glass structure diagram In the figure: Glass substrate-101; Anti-glare layer-102; Indium tin oxide conductive layer - 103; Zinc oxide nanorod array layer - 104; Silicon dioxide antireflective layer -105; Anti-fingerprint layer - 106. Detailed Implementation

[0017] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] Please see Figure 1 The present invention provides a technical solution: a superhydrophobic anti-glare vehicle cover glass based on a micro-nano composite structure, comprising, from the bottom substrate upwards: a sodium-calcium-silicon glass substrate 101; Anti-glare layer 102 with micron-sized pits; Indium tin oxide conductive layer 103; Zinc oxide nanorod array layer 104; 105 silicon dioxide antireflective layer; Anti-fingerprint layer 106, formed by vapor deposition of perfluoroalkyl silane compounds.

[0019] In this embodiment, the zinc oxide nanorod array 104 is grown inside and on the surface of the micron-sized pits of the anti-glare layer 102, forming a micron-nano composite rough structure.

[0020] In this embodiment, the anti-fingerprint layer 106 is formed by vacuum evaporation and is coated on the surface of the zinc oxide nanorod array layer 104 and the silicon dioxide anti-reflection layer 105.

[0021] In this embodiment, the sheet resistance of the indium tin oxide conductive layer 103 is 80-100 Ω / sq, and the light transmittance exceeds 85%.

[0022] In this embodiment, the optical thickness of the silicon dioxide antireflection layer 105 is optimized so that the reflectivity at a wavelength of 550 nm does not exceed 1.5%.

[0023] In this embodiment, the anti-glare layer 102 has a micron-deep pit of 10-15 μm and a surface roughness of 3-5 μm.

[0024] In this embodiment, the zinc oxide nanorod array layer 104 has a diameter of 50-80 nm, a height of 300-500 nm, and a spacing of 20-50 nm between the rods.

[0025] Example 1 Anti-glare layer preparation: The sodium-calcium-silicon glass substrate was immersed in a mixed etching solution of HF:H2SO4=1:3 and treated at 50℃ for 8 minutes to form a micron-deep pit structure with a depth of 12μm.

[0026] Indium tin oxide conductive layer deposition: DC magnetron sputtering was used to sputter at 3kW power for 30 minutes in an argon atmosphere at 0.5Pa to obtain an indium tin oxide conductive layer with a sheet resistance of 90Ω / sq.

[0027] Zinc oxide nanorod growth: Prepare a 0.01 mol / L Zn(NO3)2+ 0.02 mol / L HMTA aqueous solution and electrodeposit at a constant potential of -1.15V for 50 minutes in an 85℃ water bath.

[0028] Preparation of silicon dioxide antireflection layer: In an Ar / O2=3:1 mixed gas, SiO2 target material was sputtered by magnetron sputtering, and the optical thickness was controlled to achieve a reflectivity of 1.2% at a wavelength of 550nm.

[0029] Anti-fingerprint layer deposition: Perfluorodecyltrimethoxysilane is dissolved in isopropanol and vacuum evaporation is used to form a continuous thin film.

[0030] The performance results of the finished product are shown in the table below:

[0031] Table 1 Example 2 Improved preparation of anti-glare layer: HF:H2SO4=1:4 etching solution was used, and the layer was treated at 60℃ for 12 minutes to form a honeycomb microstructure with a depth of 15μm.

[0032] Indium tin oxide conductive layer optimization: sputtering power was increased to 4kW, working pressure was 0.8Pa, and a transparent conductive layer with sheet resistance of 85Ω / sq was obtained after 40 minutes of deposition.

[0033] Zinc oxide nanorod array: Electrodeposition was performed at a constant potential of -1.2V for 60 minutes at 75℃ using a 0.015 mol / L Zn(NO3)2+ 0.03 mol / L HMTA solution.

[0034] Enhanced antireflective layer with silicon dioxide: A dual-target co-sputtering system was used to deposit SiO2 and TiO2 in a 3:1 ratio, achieving a 550nm reflectivity of 0.8%.

[0035] Improved anti-fingerprint layer: Plasma-assisted vapor deposition was used, reducing the deposition pressure to 5×10⁻⁶. -3 Pa increases the film density.

[0036] The performance results of the finished product are shown in the table below:

[0037] Table 2 A preparation method comprising the following steps: S1. The glass substrate 101 is etched with a mixed acid of HF / H2SO4 to form an anti-glare layer 102; S2. A magnetron sputtering deposition of an indium tin oxide conductive layer 103 is performed on the surface of the anti-glare layer 102; S3. A zinc oxide nanorod array layer 104 is grown on the surface of indium tin oxide by an electrochemical method; S4. Magnetron sputtering deposition of silicon dioxide antireflection layer 105; S5. Vacuum-deposited anti-fingerprint layer 106; In this embodiment, the electrolyte in the electrochemical deposition process of zinc oxide nanorod array layer 104 is a mixed aqueous solution of zinc nitrate and hexamethylenetetramine, the temperature is 70-90 °C, a constant potential of -1.0V to -1.2V is applied, and the deposition time is 40-60 minutes.

[0038] In this embodiment, the etching solution has a composition of HF:H2SO4=1:(2-4), the etching temperature is 50-60℃, and the etching time is 5-12 minutes.

[0039] Based on the above, this invention constructs a composite surface with superhydrophobic and oleophobic properties through the synergistic effect of a micron-level anti-glare structure and a nano-level zinc oxide nanorod array, which reduces the area of ​​fingerprint residue and makes it easy to wipe. At the same time, the zinc oxide nanorod array enhances the adhesion of the anti-fingerprint film and improves wear resistance. The multi-layer thin film design effectively balances the requirements of anti-glare and high-definition display, providing a technical solution for automotive displays that is both functional and durable.

[0040] As is known from common technical knowledge, this invention can be implemented through other embodiments that do not depart from its spirit or essential characteristics. Therefore, the disclosed embodiments described above are merely illustrative and not exhaustive. All modifications within the scope of this invention or its equivalents are included in this invention.

Claims

1. A micro-nano composite structure-based super-hydrophobic anti-glare vehicle cover plate glass, characterized in that: A sodium calcium silicon glass substrate (101) is provided on the bottom; A glare-proof layer (102) with micro-pits; An indium tin oxide conductive layer (103); A zinc oxide nanorod array layer (104); A silicon dioxide anti-reflective layer (105); A fingerprint-resistant layer (106) deposited by vapor deposition of perfluoroalkylsilane compounds.

2. The micro-nano composite structure-based super-hydrophobic anti-glare vehicle cover glass according to claim 1, characterized in that: The zinc oxide nanorod array (104) is grown inside and on the surface of the micro-pits of the glare-proof layer (102), forming a micro-nano composite rough structure.

3. The micro-nano composite structure-based super-hydrophobic anti-glare vehicle cover glass according to claim 1, characterized in that: The fingerprint-resistant layer (106) is formed by vacuum evaporation process, covering the surface of the zinc oxide nanorod array layer (104) and the silicon dioxide anti-reflective layer (105).

4. The micro-nano composite structure-based super-hydrophobic anti-glare vehicle cover glass according to claim 1, characterized in that: The sheet resistance of the indium tin oxide conductive layer (103) is 80-100 Ω / sq, and the light transmittance is more than 85%.

5. The micro-nano composite structure-based super-hydrophobic anti-glare vehicle cover glass according to claim 1, characterized in that: The optical thickness of the silicon dioxide anti-reflective layer (105) is optimized, and the reflectance at 550 nm wavelength is not more than 1.5%.

6. The micro-nano composite structure-based super-hydrophobic anti-glare vehicle cover glass according to claim 1, characterized in that: The depth of the micro-pits of the glare-proof layer (102) is 10-15 μm, and the surface roughness is 3-5 μm.

7. The micro-nano composite structure-based super-hydrophobic anti-glare vehicle cover glass according to claim 1, characterized in that: The diameter of the zinc oxide nanorod array layer (104) is 50-80 nm, the height is 300-500 nm, and the rod spacing is 20-50 nm.

8. A method of producing the cover glass according to any one of claims 1 to 7, characterized by, The following steps are included: S1. HF / H2SO4 mixed acid etching is performed on the glass substrate (101) to form a glare-proof layer (102); S2. Indium tin oxide conductive layer (103) is deposited on the surface of the glare-proof layer (102) by magnetron sputtering; S3. Zinc oxide nanorod array layer (104) is grown on the surface of the indium tin oxide by electrochemical method; S4. Silicon dioxide anti-reflective layer (105) is deposited by magnetron sputtering; S5. Fingerprint-resistant layer (106) is deposited by vacuum vapor deposition.

9. The method of claim 8, wherein: The electrolyte in the process of electrochemical deposition of zinc oxide nanorod array layer (104) is a mixed aqueous solution of zinc nitrate and hexamethylene tetramine, the temperature is 70-90 ℃, a constant potential of-1.0 V to-1.2 V is applied, and the deposition time is 40-60 minutes.

10. The method of claim 8, wherein: The etching solution composition is HF:H2SO4=1:(2-4), the etching temperature is 50-60 ℃, and the etching time is 5-12 minutes.

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