Etching solution for anti-reflection of aluminosilicate glass and preparation method of etching solution, aluminosilicate glass with anti-reflection effect and preparation method of aluminosilicate glass
By using an etching solution composed of concentrated sulfuric acid, hydrogen peroxide, and hydrofluoric acid to form nanoscale roughness on the surface of aluminosilicate glass, the problems of complex and high cost of traditional AR coating processes are solved, achieving low-cost anti-reflection and anti-reflection effects, which are suitable for consumer electronics products.
Patent Information
- Application Number
- CN202511083417.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-04
- Publication Date
- 2025-11-14
AI Technical Summary
Existing technologies struggle to create nanoscale roughness on aluminosilicate glass surfaces to achieve anti-reflective and anti-reflective effects. Furthermore, traditional AR coating processes are complex and costly, making them unsuitable for widespread application in low-end consumer electronics.
An etching solution composed of concentrated sulfuric acid, hydrogen peroxide, and hydrofluoric acid is used to form nanoscale roughness on the surface of aluminosilicate glass through wet etching, thereby achieving anti-reflection and anti-reflection effects by combining the effective medium theory.
It achieves low-cost formation of nanoscale roughness on the surface of aluminosilicate glass, improving transmittance to ≥95% and reflectance to ≤4.5%, while maintaining anti-reflection effect at large normal angles. The process is simple and suitable for mass production.
Smart Images
Figure CN120943535A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of silicate glass technology, specifically relating to an etching solution for anti-reflection and anti-reflection of aluminosilicate glass and its preparation method, as well as an aluminosilicate glass with anti-reflection and anti-reflection effects and its preparation method. Background Technology
[0002] In the rapidly developing consumer electronics industry, anti-reflection on screen covers is often achieved by utilizing the light interference effect of thin films, such as covering the substrate surface with an AR film that has anti-reflection properties. However, due to the complexity of multi-layer AR film deposition processes and the high cost of materials, the cost of AR films remains high, preventing their widespread application in relatively low-end consumer electronics products. Furthermore, traditional processes for achieving anti-reflection using AR film systems are complex and costly, and due to the inherent characteristics of AR film systems, their anti-reflection effect cannot be maintained at large normal angles (>30°).
[0003] Reducing light reflection is not limited to light interference effects; the Effective Medium Theory (EMT) offers another solution. The fundamental approach to antireflection and anti-reflection in EMT theory is to structurally (with nanoscale surface structures) separate the two media (air and glass), causing the refractive index of the region separated by the glass surface structure to change asymptotically (referred to as the "RI distribution").
[0004] In the consumer electronics industry, the glass used in the industry generally belongs to the broad category of silicate glass (SG), which can be further divided into aluminosilicate glass systems (AGS) and soda-lime glass systems (SLG). Among them, aluminosilicate glass is mainly used for screen covers.
[0005] Compared to soda-lime glass, aluminosilicate glass has a higher molar percentage of aluminum oxide, ranging from 8 mol% to 12 mol%. Unlike soda-lime glass, which contains less Al2O3 (2 mol% to 3 mol%) as a stabilizing agent, aluminosilicate glass's Al2O3 directly participates in the construction of the glass network framework, resulting in better connectivity. This leads to a higher hardness than soda-lime glass, which is the basis for its application in the consumer electronics industry.
[0006] However, this also results in a more complex network bonding structure in aluminosilicate glass, with three different energy barriers. For directly bonded Si-O-Si, the bonding energy barrier is 1.22 eV; while in the Al-O-Si structural chain, the Al-O bond bonding energy is 0.49 eV, and the Si-O bond bonding energy is 1.34 eV. Since the silicon and aluminum network forgings constituting the glass network are randomly and homogeneously distributed within the glass's spatial structure, these differences in bonding energy barriers are not directly reflected when traditional glass etchants, such as hydrofluoric acid and sodium hydroxide, react with aluminosilicate glass. This makes it impossible to etch a surface with nanoscale roughness and achieve antireflective and anti-reflective effects. Summary of the Invention
[0007] To address the aforementioned technical problems, this invention provides an etching solution for anti-reflection and anti-reflection of aluminosilicate glass and its preparation method. The solution has a simple composition and low cost, and can form nanoscale roughness on the surface of aluminosilicate glass to achieve anti-reflection and anti-reflection effects while maintaining a good glass appearance.
[0008] This invention also provides an aluminosilicate glass with anti-reflective and anti-reflective effects and its preparation method. The aluminosilicate glass is obtained by immersing one or both sides of it in the etching solution described in this invention for 30 to 40 minutes, and then washing it with water. The preparation method is simple and low in cost.
[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0010] An etching solution for antireflection and anti-reflection of aluminosilicate glass, the etching solution being composed of the following components by volume percentage: 30%-40% concentrated sulfuric acid, 10%-20% hydrogen peroxide, 0.05%-0.2% hydrofluoric acid, with the remainder being water.
[0011] Furthermore, the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 60-80:40-20, preferably 75:25. Within this range, it is possible to ensure that nanoscale roughness is formed on the glass surface in a short time, thereby achieving the corresponding anti-reflection effect. If the volume ratio is lower than 60:40, the risk of preparing the solution is too high; if it is higher than 80:20, the etching reaction time is too long, greater than 4 hours, which is not beneficial to efficiency.
[0012] The concentrated sulfuric acid has a mass fraction of 98%.
[0013] The hydrogen peroxide has a mass fraction of 30-35%.
[0014] The hydrofluoric acid has a mass fraction of 40-50%.
[0015] The present invention also provides a method for preparing the etching solution, the method comprising the following steps:
[0016] (1) Slowly add hydrogen peroxide to the concentrated sulfuric acid of the formula amount and stir until well mixed;
[0017] (2) After the solution has cooled to room temperature, add water to it and stir well;
[0018] (3) After the solution has cooled to room temperature, add hydrofluoric acid and stir until homogeneous.
[0019] The present invention also provides a method for preparing aluminosilicate glass with anti-reflection and anti-reflection effects, the method comprising the following steps: immersing one or both sides of the aluminosilicate glass in the etching solution described in the present invention for 30 to 40 minutes, and then washing with water.
[0020] Furthermore, when immersing one side, the other side is protected with an acid-resistant film.
[0021] The present invention also provides an aluminosilicate glass with anti-reflection and anti-reflection effects, which is prepared by the method for preparing the aluminosilicate glass with anti-reflection and anti-reflection effects.
[0022] The aluminosilicate glass with anti-reflection and anti-reflection effects has a transmittance of ≥95% and a reflectance of ≤4.5%.
[0023] The etching solution for antireflection and anti-reflection of aluminosilicate glass provided by this invention is composed of concentrated sulfuric acid, hydrogen peroxide, hydrofluoric acid, and water. Concentrated sulfuric acid and hydrogen peroxide are components of the piranha solution, and together they can form carboxylic acid (H₂SO₄). Carboxylic acid is a stronger acid than typical strong acids, such as sulfuric acid. The pKa of the first dissociation of carboxylic acid is approximately -3.5, which is stronger than the first dissociation of sulfuric acid in aqueous solution (pKa[H₂SO₄] = -3.0). In solution, carboxylic acid undergoes complete first dissociation to form stable hydrated hydrogen ions (H₃O₂). + ) and carboxylate hydride anions (HSO5) - The equation is as follows:
[0024] H₂SO₅ + H₂O → HSO₅ - +H3O +
[0025] A stronger acidity means that within this mixed solution system, the solution itself has a better ability to retain protons. In aqueous solution, this proton stabilization manifests as hydrated hydrogen ions (H3O). + In strongly acidic solution systems, hydrated hydrogen ions (H3O) + These complex with active sites on the silicate surface, and the bound hydrated hydrogen ions (H3O) +The active sites of the glass matrix are preferentially attacked by substances in water that can react with the glass framework structure. In aluminosilicate glass frameworks, the bonding energies of the framework components are not the same. For directly connected Si-O-Si, their bonding energy is 1.22 eV; while in the Al-O-Si structural chain, the Al-O bond bonding energy is 0.49 eV and the Si-O bond bonding energy is 1.34 eV. This results in inconsistent destruction of these proton-bonded structures by the etching solution, thus forming nanoscale roughness on the glass surface.
[0026] In the Effective Medium Theory (EMT), the fundamental principle of anti-reflection and anti-reflection is to separate two media, such as air and glass, using nanoscale surface structures, causing an asymptotic change in the refractive index of the separated regions. In terms of EMT design standards, the core issue is that the glass surface must have nanoscale roughness. When the roughness is smaller than the wavelength, light interacts with the entire material surface. The roughness, at the nanoscale, separates the air from the material, achieving the effects of anti-reflection and anti-reflection.
[0027] Compared with the prior art, the present invention has the following beneficial effects:
[0028] The etching solution for anti-reflection and anti-reflection of aluminosilicate glass provided by this invention has a simple composition and low cost. It can form a surface with nanoscale roughness through etching of aluminosilicate glass to achieve the effect of anti-reflection and anti-reflection.
[0029] The aluminosilicate glass with anti-reflection and anti-reflection effects provided by this invention is obtained by wet etching of untreated aluminosilicate white glass with the etching solution provided by this invention. Based on the white glass surface, uncontrollable variables in the process can be eliminated to the greatest extent, and a surface with nanoscale roughness can be obtained in a controllable manner. This surface has an anti-reflection effect at large normal angles. Attached Figure Description
[0030] Figure 1 The reflectivity test data of the glass obtained in Examples 1 and 2 and Comparative Examples 1 and 2 are as follows;
[0031] Figure 2 The transmittance test data of the glass obtained in Examples 1 and 2 and Comparative Examples 1 and 2 are as follows;
[0032] Figure 3 Here is a SEM image of the glass surface obtained in Example 1;
[0033] Figure 4 This is a SEM image of the glass cross-section obtained in Example 1. Detailed Implementation
[0034] The present invention will now be described in detail with reference to the embodiments.
[0035] The concentrated sulfuric acid, hydrogen peroxide, and hydrofluoric acid used in the following examples and comparative examples have mass fractions of 98%, 30%, and 40%, respectively, and are all commercially available products.
[0036] Example 1
[0037] An etching solution for antireflection and anti-reflection of aluminosilicate glass is composed of the following components by volume percentage: 37.5% concentrated sulfuric acid, 12.5% hydrogen peroxide, 0.05%-0.2% hydrofluoric acid, and the remainder being water.
[0038] The method for preparing the etching solution includes the following steps:
[0039] (1) Slowly add 125 mL of hydrogen peroxide to 375 mL of concentrated sulfuric acid and stir until well mixed;
[0040] (2) After the solution has cooled to room temperature, add 500 mL of water and stir well; prepare multiple sets of such solutions.
[0041] (3) After the solution is cooled to room temperature, hydrofluoric acid is added to it in a gradient from 0.1 mL to 10 mL. Then the solution is stirred evenly to obtain the etching solution.
[0042] Immerse both sides of the aluminosilicate white glass in the etching solutions prepared in this example for 40 minutes, then rinse with running water and wipe dry with a lint-free cloth.
[0043] When the optimal amount of HF is 0.5 mL, the treated glass surface exhibits a double-sided transmittance of 96%, and appears clear without any iridescence.
[0044] As the amount of HF in the etching solution increases, the anti-reflection effect of the resulting glass becomes stronger. However, when the amount of HF exceeds 2 mL, severe iridescence appears on the surface of the glass. With the increase of hydrofluoric acid, the iridescence becomes more and more severe between 2.0 mL and 5.0 mL, even though the glass can exhibit a high transmittance of over 98%.
[0045] When the amount of hydrofluoric acid is increased to 10 mL, the amount of hydrofluoric acid in the etching solution is too high, and there is no differentiated etching for the bonding of the aluminosilicate glass network framework. After the reaction, the glass surface has no nano-roughness and no anti-reflection effect.
[0046] The test results of reflectance and transmittance of aluminosilicate glass with antireflective and anti-reflective effects obtained when the optimal amount of HF is 0.5 mL are as follows: Figure 1 , Figure 2 As shown in the figure, its transmittance is ≥95.5%, and its reflectance is ≤4.5%.
[0047] SEM images of the glass surface and cross-section are shown below. Figure 3 , Figure 4 As shown in the figure, nanoscale roughness is formed on the glass surface.
[0048] Example 2
[0049] An etching solution for antireflection and anti-reflection of aluminosilicate glass is composed of the following components by volume percentage: 37.5% concentrated sulfuric acid, 12.5% hydrogen peroxide, 0.1% hydrofluoric acid, and the remainder being water.
[0050] The method for preparing the etching solution includes the following steps:
[0051] (1) Slowly add 125 mL of hydrogen peroxide to 375 mL of concentrated sulfuric acid and stir until well mixed;
[0052] (2) After the solution has cooled to room temperature, add 500 mL of water and stir well; prepare multiple sets of such solutions.
[0053] (3) After the solution cools to room temperature, add 1 mL of hydrofluoric acid to each solution and stir until homogeneous to obtain the etching solution.
[0054] One side of the aluminosilicate white glass is covered with an acid-resistant film, then immersed in the etching solution prepared in this embodiment for 40 minutes, then rinsed with running water, and wiped dry with a lint-free cloth to obtain aluminosilicate glass with anti-reflective and anti-reflective effects.
[0055] The test results of reflectivity and transmittance of the aluminosilicate glass with antireflective and anti-reflective effects obtained in this embodiment are as follows: Figure 1 , Figure 2 As shown in the figure, its transmittance is ≥95.5%, and its reflectance is ≤4.5%.
[0056] Comparative Example 1
[0057] A method for preparing aluminosilicate glass with antireflective and anti-reflective effects, comprising the following steps:
[0058] An AR film, consisting of a magnesium fluoride coating on both sides of aluminosilicate clear glass, is applied. The test results for the glass's reflectivity and transmittance are as follows: Figure 1 , Figure 2 As shown.
[0059] Comparative Example 2
[0060] A method for preparing aluminosilicate glass with antireflective and anti-reflective effects, comprising the following steps:
[0061] An AR film, consisting of a magnesium fluoride coating on one side of aluminosilicate clear glass, was applied. The test results for the glass's reflectivity and transmittance are as follows: Figure 1 , Figure 2 As shown.
[0062] Comparative Example 3
[0063] The process is the same as in Example 1, except that the amounts of concentrated sulfuric acid and hydrogen peroxide are adjusted to 425 mL and 75 mL, respectively. When etching aluminosilicate glass, it takes more than 4 hours to achieve the desired anti-reflection and anti-reflection effect, resulting in low efficiency.
[0064] from Figure 1 , 2 It can be seen that the aluminosilicate glass with antireflective and anti-reflective effects prepared by the method of this invention can increase the transmittance of aluminosilicate glass by about 4.0% (the transmittance of aluminosilicate glass is about 91.5%). Although it does not reach the transmittance of over 98% of magnesium fluoride AR film system, the cost of nano-etching solution is much lower than the high cost of AR coating. Similarly, compared with additive manufacturing (such as nanoimprinting) or subtractive manufacturing (such as laser-induced), the formulation of nano-etching solution is more suitable for large-scale mass production.
[0065] The above-described detailed description of an etching solution for antireflection and anti-reflection of aluminosilicate glass and its preparation method, as well as an aluminosilicate glass with antireflection and anti-reflection effects and its preparation method, is illustrative rather than limiting. Several embodiments can be listed according to the defined scope. Therefore, changes and modifications without departing from the overall concept of the present invention should be within the protection scope of the present invention.
Claims
1. An etching solution for anti-reflection and anti-reflection of aluminosilicate glass, characterized in that, The etching solution is composed of the following components by volume percentage: 30%-40% concentrated sulfuric acid, 10%-20% hydrogen peroxide, 0.05%-0.2% hydrofluoric acid, and the remainder is water.
2. The etching solution according to claim 1, characterized in that: The volume ratio of concentrated sulfuric acid to hydrogen peroxide is 60–80:40–20.
3. The etching solution according to claim 1, characterized in that, The concentrated sulfuric acid has a mass fraction of 98%. The hydrogen peroxide has a mass fraction of 30-35%.
4. The etching solution according to claim 1, characterized in that, The hydrofluoric acid has a mass fraction of 40-50%.
5. The method for preparing the etching solution as described in claim 1, characterized in that, The preparation method includes the following steps: (1) Slowly add hydrogen peroxide to the concentrated sulfuric acid of the formula amount and stir until well mixed; (2) After the solution has cooled to room temperature, add water to it and stir well; (3) After the solution has cooled to room temperature, add hydrofluoric acid and stir until homogeneous.
6. A method for preparing aluminosilicate glass with antireflective and anti-reflective effects, characterized in that, The preparation method includes the following steps: immersing one or both sides of aluminosilicate glass in the etching solution described in any one of claims 1-4 for 30-40 minutes, and then rinsing with water.
7. The preparation method according to claim 6, characterized in that, When immersing one side, the other side is protected with an acid-resistant film.
8. An aluminosilicate glass with anti-reflective and anti-reflective effects, characterized in that, It is prepared using the preparation method described in claim 6 or 7.
9. The aluminosilicate glass with anti-reflective and anti-reflective effects according to claim 8, characterized in that, The aluminosilicate glass with anti-reflection and anti-reflection effects has a transmittance of ≥95.5% and a reflectance of ≤4.5%.