High-alumina-silica glass etching anti-reflection method and application
By forming a dense network structure on the surface of high-alumina-silicon glass and etching micropores, the problems of high manufacturing cost and narrow transmittance of high-alumina-silicon glass in the prior art are solved, and a low-cost, wide-band anti-reflection and anti-transmittance effect is achieved.
Patent Information
- Application Number
- CN202511145561.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-15
- Publication Date
- 2025-11-21
AI Technical Summary
Existing technologies for preparing high-alumina-silicon glass suffer from high costs, complex processes, and narrow transmittance bands, making it difficult to achieve wide-band anti-reflection and anti-reflection effects.
A dense K+-Si-O-Al network structure is formed on the glass surface through chemical strengthening treatment, and a microporous structure is formed by mixed acid etching treatment. By adjusting the acid concentration and reaction time, the pore size and depth of the micropores are controlled to form a microstructure similar to the eye structure of a moth.
It achieves high light transmittance of over 99%, wide-band anti-reflection and anti-reflection effects, low cost, and superior optical performance. The transmittance is over 99% in the range of 380-1100nm, which is far lower than the cost of vacuum coating equipment.
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Figure CN120987571A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of optical glass preparation technology, and more specifically to a method and application for preparing high-alumina-silicon glass through etching for anti-reflection and anti-reflection. Background Technology
[0002] Currently, to reduce reflection and improve light transmittance on glass surfaces, high- and low-refractive-index materials are commonly used to stack layers of varying thicknesses in a vacuum, achieving this function through the interference effect of the layers. However, due to limitations in material refractive index and the requirements of the coating process, achieving a wide-band anti-reflection and anti-reflection effect is extremely expensive and very difficult to control. With existing materials, at least 4-6 layers of alternating high- and low-refractive-index dielectric films of varying thicknesses are required using vacuum coating equipment to achieve an anti-reflection and anti-reflection effect in the visible light 380-780nm range. Moreover, this process has a narrow transmission spectral width, generally only showing good anti-reflection and anti-reflection effects in the 450-650nm range.
[0003] Therefore, how to provide a high-aluminosilicate glass that is simple to prepare, low in cost, and has high transmittance over a wide wavelength range is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0004] In view of this, the present invention provides a method and application for etching high-alumina-silicon glass with anti-reflection and anti-reflection properties that is simple to prepare, low in cost, and has a wide range of high transmittance. Firstly, a dense K-type silicate is formed on the glass surface through chemical strengthening treatment. + -Si-O-Al network structure. Then, etching is performed using mixed acid to form an etched layer, obtaining high aluminosilicate glass with antireflective and anti-reflective properties.
[0005] To achieve the above objectives, the present invention first provides a method for anti-reflection and anti-reflection etching of high-alumina-silicon glass, specifically including the following steps:
[0006] S1 high aluminosilicate glass strengthening treatment
[0007] A high-alumina-silicon glass substrate is immersed in KNO3 molten salt for chemical strengthening treatment to obtain strengthened high-alumina-silicon glass.
[0008] Its beneficial effect is that high-alumina silica glass undergoes Na oxidation in KNO3 molten salt. + and K + Ion exchange generates a dense K+ layer on the glass surface. + The -SI-O-Al network structure improves the strength of the glass.
[0009] S2 Mixed Acid Solution Preparation
[0010] Sulfuric acid solution, hydrofluoric acid solution, phosphoric acid solution, hydrochloric acid solution, and nitric acid solution are mixed in proportion and allowed to stand to obtain a mixed acid solution.
[0011] S3 etching process
[0012] The reinforced high-aluminosilicate glass was etched by immersing it in a mixed acid solution. After etching, it was removed, rinsed with water, and then immersed in a cleaning solution. After removal, it was cleaned by an ultrasonic cleaner to obtain etched anti-reflective and anti-reflective high-aluminosilicate glass.
[0013] Its beneficial effects are as follows: sulfuric acid in the mixed acid solution reacts with Al2O3 in the high-alumina-silica glass to form micropores of a certain depth; simultaneously, hydrofluoric acid reacts with silicon dioxide in the high-alumina-silica glass, rapidly dissolving the glass; phosphoric acid, nitric acid, and hydrochloric acid also participate in the dissolution of other trace alkali metals in the high-alumina-silica glass. After a period of reaction, a microporous structure with a certain pore size and depth gradually forms on the surface of the high-alumina-silica glass, causing the refractive index to gradually increase from n0 = 1 at the glass surface to n0 = 1 inside the glass. s =1.5, the transmittance increases from 92% (specifically referring to 0.33mm high aluminosilicate glass) to more than 99%, with the peak value even exceeding 99.5%, achieving the effect of reducing reflection and increasing transmittance.
[0014] Preferably, the thickness of the high-alumina-silicon glass substrate in step S1 is 0.1 to 200 mm, wherein the Al2O3 content is greater than 10%.
[0015] The temperature of the KNO3 molten salt is 385–420°C, and the soaking time is 3–5 hours.
[0016] The chemical enhancement treatment requires an ion exchange depth of 5–20 μm.
[0017] In step S2, the concentration of the sulfuric acid solution is 5%–30%, the concentration of the hydrofluoric acid solution is 0.5%–5%, the concentration of the phosphoric acid solution is 1.5%–7%, the concentration of the hydrochloric acid solution is 0.5%–5%, and the concentration of the nitric acid solution is 0.5%–1.5%.
[0018] Its beneficial effect is that by adjusting the concentration of different acids and the reaction time, the pore size and depth of the micropores can be controlled, thereby obtaining the desired etching effect.
[0019] The volume ratio of the sulfuric acid solution, hydrofluoric acid solution, phosphoric acid solution, hydrochloric acid solution, and nitric acid solution is 30:5:10:5:2.
[0020] The settling time is 8 hours.
[0021] The etching process in step S3 is carried out at a temperature of 28–50°C for 4–12 minutes.
[0022] The cleaning solution is a 10% ammonium acetate solution or a 1:1 mixture of a 10% ammonium acetate solution and a 10% glycerol solution.
[0023] The soaking time is 0.5 to 2 minutes.
[0024] The present invention also provides an etched antireflective and anti-reflective high-alumina-silicon glass prepared by the above method, wherein the etched antireflective and anti-reflective high-alumina-silicon glass is composed of an upper surface etched layer, an intermediate layer, and a lower surface etched layer; the upper and lower surface etched layers have a microporous structure, similar to the structure of a moth's eye.
[0025] This invention provides the application of the aforementioned etched antireflective and anti-reflective high-aluminosilicate glass in the manufacture of displays, cameras, lidar, exhibition windows, office spaces, and solar panels.
[0026] As can be seen from the above technical solution, the present invention discloses a method for anti-reflection and anti-reflection etching of high-alumina-silicon glass, which has the following advantages compared with the prior art:
[0027] (1) In this invention, sulfuric acid is used to dissolve Al2O3, forming an ultraporous structure on the glass surface. Then, hydrofluoric acid is used to dissolve silicon dioxide, and hydrochloric acid, phosphoric acid, and nitric acid are used to dissolve other trace amounts of alkali metals, expanding the microporous structure. This results in a honeycomb structure on the surface of the high-alumina-silicon glass. From the optical formula: D=k*λ / (4*n), where: D is the pore depth, K is an odd number (1, 3, 5...), λ is the wavelength, and n is the equivalent refractive index, this experiment, combined with transmittance, can estimate that n is approximately between 1.25 and 1.3. Combined with the analysis of the measured spectral curve, it can be deduced that the micropore depth is greater than 300nm, exhibiting a microstructure similar to the eye structure of a moth. The refractive index gradually increases from n0=1.0 on the glass surface to n inside the glass. s =1.5, light does not reflect off the glass surface, transmittance is greater than 99%, peak transmittance is greater than 99.5%, achieving the effect of reducing reflection and increasing transmittance.
[0028] (2) The anti-reflection and anti-reflection coating layer produced by the present invention can achieve anti-reflection and anti-reflection in a wide wavelength range of 380-1100nm, and the cost is low, which is almost impossible to achieve with coating equipment. The optical performance is excellent, and the cost is less than one-tenth of the coating cost, which has great promotional value. Attached Figure Description
[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0030] Figure 1 Schematic diagram of etched antireflective and antitransmittance high aluminosilicate glass structure.
[0031] Figure 2 Spectral curve of high aluminosilicate glass treated with mixed acid solution 1 at room temperature (28℃).
[0032] Figure 3 Spectral curve of high aluminosilicate glass treated with mixed acid solution 2 at 35℃.
[0033] Figure 4 Spectral curve of high aluminosilicate glass treated with mixed acid solution 3 at 40℃.
[0034] Figure 5 Spectral curve of high aluminosilicate glass treated with mixed acid solution 4 at 45℃.
[0035] Figure 6 Spectral curve of high aluminosilicate glass treated with mixed acid solution 5 at 50℃.
[0036] Figure 7 Spectral curve of untreated high-aluminosilicate glass. Detailed Implementation
[0037] 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 skilled in the art without creative effort are within the scope of protection of the present invention.
[0038] Example 1
[0039] High aluminosilicate glass strengthening treatment
[0040] High-alumina-silicon glass with a thickness of 0.33 mm and an Al2O3 content of 17% was selected and immersed in KNO3 molten salt at 400℃ for 4 hours to obtain reinforced high-alumina-silicon glass. Measurements showed that its ion exchange depth was 12 μm.
[0041] Example 2
[0042] Preparation of mixed acid solution
[0043] Five mixed acid solutions were obtained by mixing sulfuric acid, hydrofluoric acid, phosphoric acid, hydrochloric acid, and nitric acid solutions of different concentrations in a volume ratio of 30:5:10:5:2 and letting them stand for 8 hours. These were designated as mixed acid solutions 1-5, as shown in Table 1 below.
[0044]
[0045]
[0046] Example 3
[0047] Etching
[0048] The reinforced high-aluminosilicate glass obtained in Example 1 was immersed in the mixed acid solution 1 in Example 2 for etching treatment. The solution temperature was room temperature 28°C, and the immersion time was 4 minutes, 6 minutes, 8 minutes, 10 minutes and 12 minutes respectively.
[0049] After etching, the glass was removed, rinsed with water, and then immersed in a 1:1 mixture of 10% glycerol and 10% ammonium acetate for 1 minute. After removal, it was cleaned using an ultrasonic cleaner to obtain etched antireflective and anti-reflective high-alumina-silicon glass. Spectral curve testing was then performed, and the results are shown below. Figure 2 .
[0050] The etched antireflective and anti-reflective high-aluminosilicate glass consists of an upper surface etched layer, a middle layer, and a lower surface etched layer; the upper and lower surface etched layers have a microporous structure with a pore depth greater than 300nm, similar to the structure of a moth's eye.
[0051] Example 4
[0052] Etching
[0053] The reinforced high-aluminosilicate glass obtained in Example 1 was immersed in the mixed acid solution 2 in Example 2 for etching treatment. The solution temperature was 35°C, and the immersion time was 4 minutes, 6 minutes, 8 minutes, 10 minutes, and 12 minutes, respectively.
[0054] After etching, the glass was removed, rinsed with water, and then immersed in a 1:1 mixture of 10% glycerol and 10% ammonium acetate for 1 minute. After removal, it was cleaned using an ultrasonic cleaner to obtain etched antireflective and anti-reflective high-alumina-silicon glass. Spectral curve testing was then performed, and the results are shown below. Figure 3 .
[0055] Example 5
[0056] Etching
[0057] The reinforced high-aluminosilicate glass obtained in Example 1 was immersed in the mixed acid solution 3 in Example 2 for etching treatment. The solution temperature was 40°C, and the immersion time was 4 minutes, 6 minutes, 8 minutes, 10 minutes, and 12 minutes, respectively.
[0058] After etching, the glass was removed, rinsed with water, and then immersed in a 1:1 mixture of 10% glycerol and 10% ammonium acetate for 1 minute. After removal, it was cleaned using an ultrasonic cleaner to obtain etched antireflective and anti-reflective high-alumina-silicon glass. Spectral curve testing was then performed, and the results are shown below. Figure 4 .
[0059] Example 6
[0060] Etching
[0061] The reinforced high-aluminosilicate glass obtained in Example 1 was immersed in the mixed acid solution 4 in Example 2 for etching treatment. The solution temperature was 45°C, and the immersion time was 4 minutes, 6 minutes, 8 minutes, 10 minutes, and 12 minutes, respectively.
[0062] After etching, the glass was removed, rinsed with water, and then immersed in a 1:1 mixture of 10% glycerol and 10% ammonium acetate for 1 minute. After removal, it was cleaned using an ultrasonic cleaner to obtain etched antireflective and anti-reflective high-alumina-silicon glass. Spectral curve testing was then performed, and the results are shown below. Figure 5 .
[0063] Example 7
[0064] Etching
[0065] The reinforced high-aluminosilicate glass obtained in Example 1 was immersed in the mixed acid solution 5 in Example 2 for etching treatment. The solution temperature was 50°C, and the immersion time was 4 minutes, 6 minutes, 8 minutes, 10 minutes, and 12 minutes, respectively.
[0066] After etching, the glass was removed, rinsed with water, and then immersed in a 1:1 mixture of 10% glycerol and 10% ammonium acetate for 1 minute. After removal, it was cleaned using an ultrasonic cleaner to obtain etched antireflective and anti-reflective high-alumina-silicon glass. Spectral curve testing was then performed, and the results are shown below. Figure 6 .
[0067] Comparative Example 1
[0068] The spectral curves of untreated high-aluminosilicate glass were tested, and the results are shown below. Figure 7 .
[0069] pass Figure 2-7 The data clearly shows that the transmittance of the etched high-aluminosilicate glass increased from about 92% in the untreated glass to more than 99% in the treated glass, with a peak value of more than 99.5%, while the reflectance was less than 0.5% at the peak value.
[0070] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A method for anti-reflection and anti-reflection etching of high-alumina-silicon glass, characterized in that, Specifically, the steps include the following: S1 high aluminosilicate glass strengthening treatment A high-alumina-silicon glass substrate is immersed in KNO3 molten salt for chemical strengthening treatment to obtain strengthened high-alumina-silicon glass. S2 Mixed Acid Solution Preparation Sulfuric acid solution, hydrofluoric acid solution, phosphoric acid solution, hydrochloric acid solution, and nitric acid solution are mixed in proportion and allowed to stand to obtain a mixed acid solution. S3 etching process The reinforced high-aluminosilicate glass was etched by immersing it in a mixed acid solution. After etching, it was removed, rinsed with water, and then immersed in a cleaning solution. After removal, it was cleaned by an ultrasonic cleaner to obtain etched anti-reflective and anti-reflective high-aluminosilicate glass.
2. The method for anti-reflection and anti-reflection etching of high-alumina-silicon glass according to claim 1, characterized in that, The thickness of the high-alumina-silicon glass substrate mentioned in step S1 is 0.1 to 200 mm, and the Al2O3 content is greater than 10%.
3. The method for anti-reflection and anti-reflection etching of high-alumina-silicon glass according to claim 1, characterized in that, The temperature of the KNO3 molten salt in step S1 is 385-420°C, and the soaking time is 3-5 hours.
4. The method for anti-reflection and anti-reflection etching of high-alumina-silicon glass according to claim 1, characterized in that, The chemical enhancement treatment described in step S1 requires an ion exchange depth of 5–20 μm.
5. The method for anti-reflection and anti-reflection etching of high-alumina-silicon glass according to claim 1, characterized in that, In step S2, the concentration of the sulfuric acid solution is 5%–30%, the concentration of the hydrofluoric acid solution is 0.5%–5%, the concentration of the phosphoric acid solution is 1.5%–7%, the concentration of the hydrochloric acid solution is 0.5%–5%, and the concentration of the nitric acid solution is 0.5%–1.5%. The volume ratio of the sulfuric acid solution, hydrofluoric acid solution, phosphoric acid solution, hydrochloric acid solution, and nitric acid solution is 30:5:10:5:
2. The settling time is 8 hours.
6. The method for anti-reflection and anti-reflection etching of high-alumina-silicon glass according to claim 1, characterized in that, The etching process in step S3 is carried out at a temperature of 28–50°C for 4–12 minutes.
7. The method for anti-reflection and anti-reflection etching of high-alumina-silicon glass according to claim 1, characterized in that, The cleaning solution mentioned in step S3 is a 10% ammonium acetate solution or a 1:1 mixture of a 10% ammonium acetate solution and a 10% glycerol solution; The soaking time is 0.5 to 2 minutes.
8. An etched antireflective and anti-reflective high-alumina-silicon glass prepared by the method according to any one of claims 1 to 7, characterized in that, The etched antireflective and anti-reflective high-aluminosilicate glass consists of an upper surface etched layer, a middle layer, and a lower surface etched layer; the upper and lower surface etched layers have a microporous structure, similar to the structure of a moth's eye.
9. The application of an etched antireflective high-alumina-silicon glass prepared by the method of any one of claims 1 to 7, or the etched antireflective high-alumina-silicon glass as described in claim 8, in the manufacture of displays, cameras, lidar, exhibition windows, integrated office spaces, and solar panels.