Photosensitive glass, method for its production, strengthened photosensitive glass and use

Abstract

A photosensitive glass, a method for preparing the same, a strengthened photosensitive glass, and a use thereof, by controlling a raw material composition of the photosensitive glass, not only can ensure the stability of the glass composition during melting of the photosensitive glass containing Ag2O, but also can solve the problem of silver atom Ag 0 The problem of loss and damage of noble metal containers, and also can ensure that the optical transmittance of the exposed region of the photosensitive glass in the visible light and near-infrared wavelength range is extremely low after radiation treatment and heat treatment, and the shielding of the optical signal can be realized.

Description

Technical Field

[0001] This application relates to the field of glass technology, and more specifically, to a photosensitive glass, a method for preparing the same, a reinforced photosensitive glass, and its applications. Background Technology

[0002] Photosensitive glass responds to external light stimuli. Under certain lighting conditions, its structure and phases change, exhibiting different mechanical and optical properties. Ag-containing photosensitive glass is the most common type of photosensitive glass, and Ag is usually combined with Ce and Sb ions. During the melting process, Sb... 3+ Electrons can be transferred to Ce 4+ Reduce it to Ce 3+ In further UV exposure, Ce 3+ Electrons can be transferred to Ag + Restore it to Ag 0 Ag 0 As growth centers for colloidal Ag crystals, subsequent heat treatment can lead to the precipitation and growth of Ag colloids. Due to the similar lattice constants, Ag colloidal crystals can induce the precipitation of lithium metasilicate crystals. Based on the above reaction chain principle, Corning and Schott have developed Fotoform / Fotoceram and Foturan products, respectively. Through subsequent etching of the glass, micro-area machining of the glass can be achieved, which can be used in MEMS, TGV, and microfluidic glass chips, etc.

[0003] Ag-containing photosensitive glass presents numerous challenges during the melting process. For instance, using corundum or quartz containers during high-temperature melting significantly impacts the final glass composition, and the containers are also prone to breakage. Conversely, using precious metal containers (especially platinum and rhodium) allows the Ag in the glass to corrode the container, leading to severe wear and damage over prolonged melting (melting containers include crucibles, furnaces, and channels). Therefore, ensuring melting stability, maintaining glass composition stability, and minimizing or avoiding damage to the container during melting are urgent technical problems that need to be addressed.

[0004] The applications of this photosensitive glass system are mainly concentrated in glass micromachining, while its optical applications have not yet been reported. In fact, in the UV exposure region, the optical transmittance of the photosensitive glass decreases significantly with the precipitation of colloidal Ag crystals and lithium silicate crystals. This characteristic allows Ag photosensitive microcrystalline glass to be used for optical signal shielding. By combining UV exposure with masking of specific areas, shielding of optical signals within a certain wavelength range can be achieved in specific regions.

[0005] It should be noted that this part of the present invention only provides background technology related to the present invention, and does not necessarily constitute prior art or known technology. Summary of the Invention

[0006] The purpose of this application is to provide a photosensitive glass that not only ensures the stability of the glass composition during the melting process of Ag₂O-containing photosensitive glass, but also solves the problem of silver atoms (Ag) generated due to the decomposition of Ag₂O. 0 It addresses the issues of damage and destruction to precious metal containers and ensures that, when photosensitive glass is obtained after radiation and heat treatment, the optical transmittance of its exposed area in the visible and near-infrared wavelength range is extremely low, thus achieving shielding of optical signals.

[0007] To achieve the above objectives, this application provides the following technical solution:

[0008] In a first aspect, a photosensitive glass is provided, comprising the following components according to the mass percentage of each component in the photosensitive glass: 50wt% to 60wt% silica sand, 15wt% to 22wt% lithium carbonate, 6wt% to 10wt% aluminum hydroxide, 3wt% to 6wt% potassium nitrate, 3wt% to 6wt% sodium nitrate, 3wt% to 5wt% zirconium oxide, 0.3wt% to 0.6wt% silver nitrate, 0.05wt% to 0.10wt% cerium oxide, and pentavalent antimony salt; wherein, based on sodium antimony, the mass percentage of pentavalent antimony salt in the composition of the photosensitive glass is 0.3wt% to 0.8wt%.

[0009] As an optional implementation, based on the mass percentage of each component in the photosensitive glass, the photosensitive glass comprises the following components:

[0010] The silica sand content is 53 wt% to 59 wt%, preferably 54.00 wt% to 58.96 wt%, and / or,

[0011] The lithium carbonate content is 17 wt% to 20 wt%, preferably 17.43 wt% to 19.94 wt%, and / or,

[0012] The aluminum hydroxide content is 8 wt% to 10 wt%, preferably 8.22 wt% to 9.97 wt%, and / or,

[0013] The potassium nitrate content is 4 wt% to 6 wt%, preferably 4.07 wt% to 5.97 wt%, and / or,

[0014] The sodium nitrate content is 3.5 wt% to 5.5 wt%, preferably 3.77 wt% to 5.45 wt%, and / or,

[0015] The zirconium oxide content is 3.33 wt% to 5 wt%, preferably 3.33 wt% to 4.96 wt%, and / or,

[0016] The silver nitrate content is 0.3wt% to 0.5wt%, preferably 0.32wt% to 0.49wt%, and / or,

[0017] The cerium oxide content is 0.05 wt% to 0.09 wt%, preferably 0.06 wt% to 0.09 wt%, and / or,

[0018] The content of pentavalent antimony salt is 0.3wt% to 0.7wt%, preferably 0.3wt% to 0.5wt%.

[0019] As an alternative implementation, the pentavalent antimony salt includes at least one of NaSbO3, KSbO3, NH4SbO3, and their hydrates.

[0020] As an alternative implementation, the thickness of the photosensitive glass is 0.4-2.0 mm.

[0021] As an optional implementation, the photosensitive glass includes an exposed area and a non-exposed area. When the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T1 of the exposed area of ​​the photosensitive glass at a wavelength of 850 nm is 0.00% to 5.00%, preferably 0.00% to 3%, and / or, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T2 of the exposed area of ​​the photosensitive glass at a wavelength of 550 nm is 0.00% to 5.00%, preferably 0.00% to 2%, and / or, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T3 of the non-exposed area of ​​the photosensitive glass at a wavelength of 850 nm is 90% or more, and / or, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T4 of the non-exposed area of ​​the photosensitive glass at a wavelength of 550 nm is 90% or more.

[0022] Secondly, a method for preparing photosensitive glass as described above is provided, comprising:

[0023] The raw material components are prepared, then mixed and melted in a precious metal container, then shaped, and then annealed to obtain the substrate glass;

[0024] The substrate glass includes a first region and a second region. The first region is masked, while the second region is not masked, to obtain the masked substrate glass.

[0025] After the masked substrate glass is subjected to radiation treatment and heat treatment, a photosensitive glass with a non-exposed area and an exposed area is obtained; wherein the non-exposed area corresponds to the first area and the exposed area corresponds to the second area.

[0026] As an alternative implementation, the precious metal container is a container made of at least one metal selected from gold, platinum, and rhodium.

[0027] As an optional implementation, the melting temperature is 1400℃~1650℃, and the melting time is 6h~48h.

[0028] As an optional implementation, the annealing temperature is 400℃~500℃ and the annealing time is 8h~24h.

[0029] As an alternative implementation, the masking process includes masking using masking inks and / or photomasks.

[0030] As an alternative implementation, radiation treatment methods include ultraviolet irradiation.

[0031] As an optional implementation, the wavelength of the ultraviolet irradiation treatment is 300 nm to 320 nm, and the intensity of the ultraviolet irradiation treatment is 20 mW / cm². 2 ~360mw / cm 2 The ultraviolet irradiation treatment time is 5 min to 60 min.

[0032] As an alternative implementation, heat treatment includes nucleation and crystallization.

[0033] As an optional implementation, the heating rate of the nucleation treatment is 1℃ / min to 10℃ / min; and / or,

[0034] The nucleation treatment temperature is 430℃~540℃; and / or,

[0035] The nucleation treatment time is 30 min to 360 min, and / or,

[0036] The heating rate for crystallization treatment is 1℃ / min to 10℃ / min; and / or,

[0037] The crystallization treatment temperature is 540℃~800℃; and / or,

[0038] The crystallization treatment time is 30 min to 480 min.

[0039] As an alternative implementation, the thickness of the substrate glass is 0.4-2.0 mm.

[0040] Thirdly, a reinforced photosensitive glass is provided, characterized in that it has a thickness of t, and includes a reinforcing layer and a tensile stress layer, wherein the reinforcing layer extends from the surface of the reinforced photosensitive glass inward, and the thickness of the reinforcing layer is 0 to 0.22t.

[0041] At the center of the tensile stress layer and / or the strengthened photosensitive glass, the following components are contained, by mass percentage of oxides:

[0042] SiO2: 65%–74.00%, Al2O3: 5.00%–10.00%, Li2O: 7.90%–12.00%, Na2O: 1.00%–3.00%, K2O: 1.50%–3.80%, ZrO2: 3.5%–6.50%, Ag2O: 0.20%–0.50%, CeO2: 0.07%–0.13%, and Sb2O3: 0.2%–0.50%;

[0043] The reinforcing layer, by mass percentage of oxides, comprises the following components:

[0044] SiO2: 65%–74.00%, Al2O3: 5.00%–10.00%, Na2O: 4.00%–16.00%, K2O: 2.0%–5.0%, ZrO2: 3.5%–6.50%, Ag2O: 0.20%–0.50%, CeO2: 0.07%–0.13%, and Sb2O3: 0.2%–0.50%; the Li2O content in the reinforcing layer is lower than that in the tensile stress layer and / or the Li2O content at the center of the reinforced photosensitive glass;

[0045] Among them, Na2O is obtained by sodium nitrate, K2O is obtained by potassium nitrate, Ag2O is obtained by silver nitrate, and Sb2O3 is obtained by pentavalent antimony salt;

[0046] Strengthened photosensitive glass includes non-exposed areas and exposed areas.

[0047] As an optional implementation, t is 0.4-2.0 mm.

[0048] As an optional implementation, the static compressive strength of the photosensitive glass is above 200N, preferably 200N to 500N, and more preferably 200N to 490N.

[0049] Fourthly, a cover glass is provided, which is made of photosensitive glass prepared by a method for preparing photosensitive glass according to any embodiment of the first aspect, photosensitive glass prepared by a method for preparing photosensitive glass according to any embodiment of the second aspect, or reinforced photosensitive glass according to any embodiment of the third aspect.

[0050] Fifthly, an electronic device is provided, comprising a photosensitive glass according to any embodiment of the first aspect, a photosensitive glass prepared by a method for preparing a photosensitive glass according to any embodiment of the second aspect, or a reinforced photosensitive glass according to any embodiment of the third aspect.

[0051] As an alternative embodiment, the electronic device includes a housing having a top and a bottom, the bottom housing comprising photosensitive glass prepared by a method for preparing photosensitive glass as provided in any embodiment of the first aspect or any embodiment of the second aspect, or a reinforced photosensitive glass as provided in the third aspect.

[0052] As an alternative implementation, the electronic device also includes a camera assembly, and the housing of the electronic device includes a camera protective cover, which is disposed on the camera assembly. The camera protective cover includes photosensitive glass prepared by the method of preparing photosensitive glass as provided in any embodiment of the first aspect or any embodiment of the second aspect, or a reinforced photosensitive glass of the third aspect.

[0053] The sixth aspect provides the use of photosensitive glass according to any embodiment of the first aspect, photosensitive glass prepared by the method for preparing photosensitive glass according to any embodiment of the second aspect, or reinforced photosensitive glass according to any embodiment of the third aspect in components used in mobile phones, smartwatches, wearable devices, camera modules, or vehicles.

[0054] One or more of the technical solutions provided in this application have the following advantages compared with the prior art:

[0055] By controlling the raw material composition of photosensitive glass, it is possible to ensure the stability of the glass composition during the melting process of Ag₂O-containing photosensitive glass, and to solve the problem of silver atoms (Ag) generated by the decomposition of Ag₂O. 0 It addresses the issues of damage and destruction to precious metal containers and ensures that, when photosensitive glass is obtained after radiation and heat treatment, the optical transmittance of its exposed area in the visible and near-infrared wavelength range is extremely low, thus achieving shielding of optical signals. Attached Figure Description

[0056] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0057] Figure 1 A schematic diagram of the structure of the substrate glass after being masked with masking ink, provided for an embodiment of this application.

[0058] Figure 2 This is a schematic diagram of the structure of the photosensitive glass provided in the embodiments of this application.

[0059] Figure 3 The electronic device provided in this application is a mobile phone.

[0060] Figure 4 This is a schematic diagram of the structure of a smartwatch mentioned in the embodiments of this application.

[0061] Figure 5 The images are photographs of the inner side of the crucible after melting in Examples 9-10 and Comparative Examples 1-2 of this application; wherein a. is a photograph of the bottom of the crucible in Comparative Example 1, b. is a photograph of the bottom of the crucible in Comparative Example 2, c. is a photograph of the bottom of the crucible in Example 9, and d. is a photograph of the bottom of the crucible in Example 10.

[0062] Figure 6 These are physical images of the shielded areas of Examples 9-10 and Comparative Examples 1-3 of this application within the visible light range. In Comparative Examples 1-3, the bright spots transmit red light.

[0063] Reference numerals: 11-Light-transmitting area; 12-Light-blocking area; 21-Exposure area; 22-Non-exposure area; 31-Camera protective cover; 32-Camera assembly; 33-Back cover; 41-Bottom casing of the smartwatch. Detailed Implementation

[0064] The embodiments of this application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of this application. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0065] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the ranges, the endpoint values ​​of the ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. The terms "optional" and "optional" mean that they may or may not be included (or may or may not be present). The term "and / or" as used herein is inclusive; for example, "A and / or B" means only A, or only B, or both A and B.

[0066] Terminology and testing methods:

[0067] In this application, the main surface refers to the surface with the largest surface area, such as the upper or lower surface of a horizontally placed substrate glass.

[0068] In this application, when light of a certain wavelength is irradiated onto the main surface of the photosensitive glass, the light will be reflected, absorbed, and transmitted. The ratio of the intensity of the transmitted portion to the intensity of the incident light is the transmittance.

[0069] In this application, the thickness of the glass was obtained by micrometer measurement.

[0070] In this application, the dimensions of the glass slides were measured using a two-dimensional measuring machine (instrument model: MiyuMY~YXCL~4030).

[0071] Main surface Ag / Ag2O concentration test

[0072] In this application, the surface Ag / Ag₂O concentration of the photosensitive glass was measured using X-ray fluorescence spectrometry (XRF), and the testing equipment used was Thermo Scientific ARL. TM PERFORM'X. The target material is Rh (rhodium), the photodiode voltage is 40KW, the current is 60mA, the collimator is 0.15, the crystal is LiF200, the detector is FPC, the test range is a 29mm circle, and the analysis software is UniQuant scale-free analysis. Scale-free XRF testing was used, which did not measure the concentration of elements with atomic numbers 6 and below, or their oxides, in the glass. Specifically, elements such as SiO2, Al2O3, Na2O, and K2O can be accurately measured, while elements such as Li2O and B2O3 cannot. Therefore, in this application, when measuring the Ag / Ag2O concentration on the surface using XRF, the total mass of the surface elements or their oxides does not include the mass of elements with atomic numbers 6 and below, or their oxides, in the glass.

[0073] In this application, a UV-Vis spectrophotometer is used to test the transmittance of the exposed and unexposed areas of the glass under test. The UV-Vis spectrophotometer used in this application is a Shimadzu UV-2000 UV-Vis spectrophotometer.

[0074] The specific method for testing the exposure area of ​​the glass under test is as follows: First, a blank sample is used as a fixture with the same shape and size as the glass under test, where the area corresponding to the exposure area is a cutout area and the area corresponding to the non-exposure area is an opaque area. The connection point between the cutout area and the opaque area is also opaque. This fixture is then used for test calibration. Next, a sample with the exposure area of ​​the glass under test cut out to match the shape of the cutout area of ​​the fixture is placed into the cutout area of ​​the fixture and the transmittance is tested. The transmittance of the exposure area of ​​five pieces of glass under test from the same batch to different wavelengths of light is measured using a UV-Vis spectrophotometer. The average value is then recorded as the transmittance result of the exposure area of ​​the glass under test at that wavelength.

[0075] In addition, the transmittance of the unexposed areas of five glass samples from the same batch to different wavelengths of light was measured using a UV-Vis spectrophotometer. The average transmittance of the unexposed areas of the five glass samples under different wavelengths of light was taken as the transmittance result of the unexposed area of ​​the glass sample under that wavelength of light.

[0076] In this application, the single-bar static compressive strength test can be performed as follows: Place the glass sample to be tested on the bottom ring of a tensile testing machine (LT-850A), start the testing software, and set the moving speed of the compression bar (8mm diameter, 10mm indenter radius) to 50mm / min. Click "Start Test." The compression bar will apply force to the center of the glass sample at the set moving speed until the glass sample cracks and breaks. The testing software will automatically read the force (N) at the time of glass sample breakage as the test result. Ten glass samples in the same condition are tested, and the average value of the test results is taken as the single-bar static compressive strength of the glass sample under test.

[0077] In this application, the wavelength range of visible light and near-infrared light refers to 400nm to 1000nm.

[0078] In this application, the glass composition contains Ag₂O, which undergoes the following reversible reaction during the melting process:

[0079]

[0080] The silver atoms Ag produced by the decomposition 0 Therefore, in order to prevent Ag2O decomposition from producing Ag 0 To prevent corrosion and damage to precious metal containers containing mixed molten raw materials, this application employs various raw material components other than Ag₂O that can provide an oxygen atmosphere during melting, thereby inhibiting the conversion of Ag₂O to Ag. 0The preferred raw material components that can provide an oxygen atmosphere include nitrates and / or pentavalent antimony salts. Specifically, nitrates are used as raw material components, including NaNO3, KNO3, AgNO3, etc. Nitrates decompose to produce O2 during the melting process, and the specific reaction is as follows, thereby providing an oxidizing atmosphere that can inhibit the decomposition of Ag2O.

[0081]

[0082] In addition, pentavalent antimony salts, including NaSbO3, KSbO3, NH4SbO3, and their hydrates, can also decompose during the melting process to generate an oxygen atmosphere, thereby inhibiting the conversion of Ag2O to Ag. 0 Taking NaSbO3 as an example, the specific reaction is as follows:

[0083] 2NaSbO3→Na2O+Sb2O3+O2↑

[0084] In addition, Sb 5+ Sb is produced during the decomposition of antimony salts in the melting process. 3+ It can act as a reducing agent to convert Ce in glass. 4 + Restored to Ce 3+ Maintain Ce 3+ The effective content; and then in the later exposure area of ​​the photosensitive glass under radiation conditions such as ultraviolet irradiation, Ce 3+ Ag + Restored to Ag 0 Ag 0 As a growth center, Ag can then undergo heat treatment. 0 Clustered crystal nuclei induce the precipitation of lithium metasilicate crystals.

[0085] This application controls the composition of the photosensitive glass to ensure that the Ag₂O-containing photosensitive glass remains stable during the melting process, without any Ag₂O. 0 This leads to the generation and resolution of Ag produced by the decomposition of Ag2O. 0 It eliminates the problem of corrosion and damage to molten precious metal containers, and also ensures that after radiation and heat treatment, the exposed area of ​​the photosensitive glass forms an opaque area, achieving shielding of optical signals in the visible and near-infrared wavelength range.

[0086] In some embodiments of this application, a photosensitive glass is provided, comprising the following components by mass percentage in the photosensitive glass: 50wt%–60wt% silica sand, 15wt%–22wt% lithium carbonate, 6wt%–10wt% aluminum hydroxide, 3wt%–6wt% potassium nitrate, 3wt%–6wt% sodium nitrate, 3wt%–5wt% zirconium oxide, 0.3wt%–0.6wt% silver nitrate, 0.05wt%–0.10wt% cerium oxide, and pentavalent antimony salt; wherein, based on sodium antimonate, the mass percentage of pentavalent antimony salt in the composition of the photosensitive glass is 0.3wt%–0.8wt%.

[0087] The crystals precipitated during the crystallization process of photosensitive glass are mainly lithium metasilicate (Li2SiO3). The precipitation of Li2SiO3 helps to reduce the optical transmittance of the exposed area of ​​the photosensitive glass and is beneficial for the shielding of optical signals in the visible and near-infrared wavelength range. In this application, SiO2 is a glass-forming oxide, serving as the network framework of the glass, and it is derived from silica sand. In some embodiments of this application, the content of silica sand, based on the mass percentage of each component in the photosensitive glass, is 53wt% to 60wt%, preferably 53wt% to 59wt%, and more preferably 54.00wt% to 58.96wt%.

[0088] In some embodiments of this application, the content of silica sand, based on the mass percentage of each component of the raw material in the photosensitive glass, can be 53wt%, 53.5wt%, 54wt%, 54.5wt%, 55wt%, 55.5wt%, 56wt%, 56.5wt%, 57wt%, 57.5wt%, 58wt%, 58.5wt%, 58.96wt%, 59wt%, or 60wt%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0089] In some embodiments of this application, the mass percentage of lithium carbonate in the photosensitive glass is 15 wt% to 22 wt%, preferably 15 wt% to 20 wt%, and more preferably 17 wt% to 20 wt%. In some embodiments of this application, the content of lithium carbonate in the photosensitive glass can be 15 wt%, 16 wt%, 17 wt%, 17.43 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt%, 19.5 wt%, 19.94 wt%, 20 wt%, 21 wt%, or 22 wt%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0090] In this application, Al2O3 serves as an intermediate in the glass network, entering the glass network structure as [AlO4] tetrahedra. Alumina, derived from aluminum hydroxide, increases the stability of the photosensitive glass. In some embodiments of this application, the content of aluminum hydroxide, based on the mass percentage of each component in the photosensitive glass, is 6 wt% to 10 wt%, preferably 8 wt% to 10 wt%, and more preferably 8.22 wt% to 9.97 wt%. In some embodiments of this application, the content of aluminum hydroxide, based on the mass percentage of each component in the photosensitive glass, can be 6 wt%, 7 wt%, 8 wt%, 8.22 wt%, 8.5 wt%, 8.7 wt%, 9 wt%, 9.2 wt%, 9.5 wt%, 9.7 wt%, 9.97 wt%, or 10 wt%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0091] In this application, zirconium oxide (ZrO2) can improve the chemical stability of photosensitive glass. However, ZrO2 has a high melting point, and excessive addition will lead to a higher melting temperature of the photosensitive glass. In some embodiments of this application, the zirconium oxide content is 3 wt% to 5 wt%, preferably 3.33 wt% to 5 wt%, and more preferably 3.33 wt% to 4.96 wt%, based on the mass percentage of each component in the photosensitive glass. In some embodiments of this application, the zirconium oxide content can be 3.0 wt%, 3.2 wt%, 3.33 wt%, 3.5 wt%, 3.7 wt%, 4.0 wt%, 4.2 wt%, 4.5 wt%, 4.8 wt%, 4.96 wt%, or 5.0 wt%, or a value within the range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0092] In this application, Na₂O and K₂O are the outer components of the glass network, acting as fluxes to lower the melting temperature of the glass. + K + In the case of existence, Na + K + The lithium will be preferentially fed into the aluminum-silicon-oxygen network to compensate for the electricity price, which to some extent maintains the lithium content in the lithium-rich region, making the Si / Li ratio in the lithium-rich region closer to the chemical ratio of Li₂SiO₃. This results in the precipitated crystalline phase of the photosensitive glass containing Na₂O and K₂O being lithium metasilicate; Na₂O originates from sodium nitrate, and K₂O from potassium nitrate. In this application, nitrates such as sodium nitrate, potassium nitrate, and / or silver nitrate, combined with antimonates, provide better clarification, thus affecting the transmittance and other properties of the finished product. Carbonates cannot achieve the transmittance effect of the finished product involved in this application.

[0093] In some embodiments of this application, the sodium nitrate content, based on the mass percentage of each component of the raw material in the photosensitive glass, is 3.0–6.0 wt%, preferably 3.5–5.5 wt%, and more preferably 3.77 wt%–5.45 wt%. In some embodiments of this application, the sodium nitrate content, based on the mass percentage of each component of the raw material in the photosensitive glass, can be 3.0 wt%, 3.5 wt%, 3.77 wt%, 4.0 wt%, 4.2 wt%, 4.5 wt%, 4.8 wt%, 5 wt%, 5.3 wt%, 5.45 wt%, or 5.5 wt%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0094] In some embodiments of this application, the potassium nitrate content, based on the mass percentage of each component of the raw material in the photosensitive glass, is 3 wt% to 6 wt%, preferably 4 wt% to 6 wt%, and more preferably 4.07 wt% to 5.97 wt%. In some embodiments of this application, the potassium nitrate content, based on the mass percentage of each component of the raw material in the photosensitive glass, can be 3.0 wt%, 4.0 wt%, 4.07 wt%, 4.2 wt%, 4.5 wt%, 4.7 wt%, 5.0 wt%, 5.2 wt%, 5.5 wt%, 5.8 wt%, 5.97 wt%, or 6.0 wt%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0095] In some embodiments of this application, the silver nitrate content, based on the mass percentage of each component of the raw material in the photosensitive glass, is 0.3wt% to 0.6wt%, preferably 0.30wt% to 0.5wt%, more preferably 0.32wt% to 0.49wt%. In some embodiments of this application, the silver nitrate content, based on the mass percentage of each component of the raw material in the photosensitive glass, can be 0.30wt%, 0.32wt%, 0.35wt%, 0.37wt%, 0.40wt%, 0.43wt%, 0.45wt%, 0.49wt%, 0.50wt%, or 0.60wt%, or a value within the range defined by any two of the above specific values ​​as endpoints. It should be understood that, in the embodiments, any of the above ranges can be combined with any other range.

[0096] Cerium oxide (CeO2) is used as a photosensitizer, and in the UV exposure process, it is represented by Ag. + Provides electronics. In some embodiments of this application, the cerium oxide content, based on the mass percentage of each component of the raw material in the photosensitive glass, is 0.05 wt% to 0.10 wt%, preferably 0.05 wt% to 0.09 wt%, more preferably 0.06 wt% to 0.09 wt%. In some embodiments of this application, the cerium oxide content, based on the mass percentage of each component of the raw material in the photosensitive glass, can be 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, or 0.10 wt%, or a value within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0097] In some embodiments of this application, in order to ensure Sb 5+The amount is sufficient. In this application, based on sodium antimonate and the mass percentage of each component of the raw material in the photosensitive glass, the content of pentavalent antimony salt is 0.3wt% to 0.8wt%, preferably 0.31wt% to 0.5wt%, and more preferably 0.31wt% to 0.49wt%.

[0098] In some embodiments of this application, the content of pentavalent antimony salt, calculated as sodium antimonate and based on the mass percentage of each component of the raw material in the photosensitive glass, can be 0.30 wt%, 0.31 wt%, 0.33 wt%, 0.35 wt%, 0.38 wt%, 0.40 wt%, 0.43 wt%, 0.45 wt%, 0.48 wt%, 0.49 wt%, or 0.50 wt%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0099] It should be noted that pentavalent antimony salts include, but are not limited to, sodium antimonate, potassium antimonate, ammonium antimonate and / or their hydrates. In this application, different types of pentavalent antimony salts are converted to sodium antimonate.

[0100] In some embodiments of this application, the pentavalent antimony salt includes at least one of NaSbO3, KSbO3, NH4SbO3 and their hydrates.

[0101] In this application, the photosensitive glass includes an exposed area and a non-exposed area. The exposed area has low transmittance in the visible and near-infrared wavelength range, while the non-exposed area has high transmittance in the visible and near-infrared wavelength range. In some embodiments of this application, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T1 of the exposed area of ​​the photosensitive glass at a wavelength of 850 nm is 0.00% to 5.00%, preferably 0.00% to 3%. In some embodiments of this application, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T1 of the exposure area of ​​the photosensitive glass at a wavelength of 850 nm can be 0.00%, 0.22%, 0.50%, 0.88%, 0.96%, 1.00%, 1.27%, 1.55%, 1.59%, 1.64%, 2.00%, 2.30%, 2.51%, 3.00%, 3.50%, 4.00%, 4.50%, 4.80%, or 5.00%; or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0102] In some embodiments of this application, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T2 of the exposure area of ​​the photosensitive glass at a wavelength of 550 nm is 0.00% to 5.00%, preferably 0.00% to 2%. In some embodiments of this application, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T2 of the exposure area of ​​the photosensitive glass at a wavelength of 550 nm can be 0.00%, 0.20%, 0.50%, 0.70%, 0.90%, 1.00%, 1.35%, 1.50%, 1.70%, 2.00%, 2.50%, 3.00%, 3.50%, 4.00%, 4.20%, 4.50%, 4.90%, or 5.00%; or a value within the range of any two of the above specific values ​​as endpoints. It should be understood that, in the implementation plan, any of the above scopes can be combined with any other scopes.

[0103] In some embodiments of this application, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T3 of the non-exposed area of ​​the photosensitive glass at a wavelength of 850 nm is 90% or higher. In some embodiments of this application, when the thickness of the photosensitive glass is 0.40 mm to 1.00 mm, the transmittance T3 of the non-exposed area of ​​the photosensitive glass at a wavelength of 850 nm can be 90.00%, 90.50%, 91.00%, 91.69%, 91.92%, 92.03%, 92.21%, 93.00%, 93.50%, 94.00%, 94.80%, or 95.00%; or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0104] In some embodiments of this application, when the thickness of the photosensitive glass is 0.40–1.00 mm, the transmittance T4 of the non-exposed area of ​​the photosensitive glass at a wavelength of 550 nm is 90% or higher. In some embodiments of this application, when the thickness of the photosensitive glass is 0.40–1.00 mm, the transmittance T4 of the non-exposed area of ​​the photosensitive glass at a wavelength of 550 nm can be 90.00%, 90.74%, 91.05%, 91.60%, 92.03%, 92.50%, 93.00%, 93.50%, 94.00%, 94.80%, or 95.00%; or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0105] In some embodiments of this application, a method for preparing the above-mentioned photosensitive glass is provided, which includes:

[0106] The raw material components are prepared, then mixed and melted in a precious metal container, then shaped, and then annealed to obtain the substrate glass;

[0107] The substrate glass includes a first region and a second region. The first region is masked, while the second region is not masked, to obtain the masked substrate glass.

[0108] After the masked substrate glass is subjected to radiation treatment and heat treatment, a photosensitive glass with a non-exposed area and an exposed area is obtained; wherein the non-exposed area corresponds to the first area and the exposed area corresponds to the second area.

[0109] In this application, the container includes, but is not limited to, crucibles, furnaces, channels, etc., wherein a precious metal container refers to a container in which at least the part in contact with the raw material is made of a precious metal, including, but not limited to, gold, platinum, rhodium, etc. In some embodiments of this application, the precious metal container is a container made of at least one metal selected from gold, platinum, and rhodium.

[0110] In this application, the substrate glass can be prepared using the forming methods in the prior art. This application does not limit this in any way. For example, the forming method of the substrate glass may include, but is not limited to, float glass, overflow glass, traction glass, rolling glass or casting process.

[0111] For example, the raw materials are prepared according to a defined set of ingredients and corresponding weight proportions. After the raw materials are mixed evenly, they are added to a precious metal container in stages and continuously for melting. The method of adding the materials can be adjusted according to the type of precious metal container. After the glass is melted, it is shaped into a glass brick. The glass brick is then transferred to an annealing furnace for annealing. After annealing, it is naturally cooled to room temperature to obtain the base glass.

[0112] In some embodiments of this application, the composition of the substrate glass is the same as or substantially the same as that of the photosensitive glass; the specific composition is as described above.

[0113] In some embodiments of this application, the melting temperature is 1400℃~1650℃, and the melting time is 6h~48h. In some embodiments of this application, the melting temperature can be 1400℃, 1475℃, 1500℃, 1525℃, 1550℃, 1575℃, 1600℃, 1625℃, or 1650℃, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0114] In some embodiments of this application, the melting time can be any value among 6h, 9h, 12h, 15h, 18h, 21h, 24h, 27h, 30h, 33h, 36h, 39h, 42h, 45h, and 48h, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the photosensitive glass with the desired performance of this application is obtained.

[0115] In some embodiments of this application, the annealing temperature is 400℃ to 500℃, and the annealing time is 8 hours to 24 hours. In some embodiments of this application, the annealing temperature is 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 490℃, or 500℃, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0116] In some embodiments of this application, the annealing time can be 5h, 6h, 7h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, or 24h, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0117] In some embodiments of this application, the masking process includes masking using masking ink and / or a mask plate.

[0118] For example, a schematic diagram of the structure of the substrate glass after being masked with masking ink is shown below. Figure 1 The composite circular hole has a light-transmitting area 11 with an inner diameter and a light-blocking area 12 excluding the inner diameter; the corresponding structural schematic diagram of the photosensitive glass is shown below. Figure 2 The position corresponding to the light-transmitting area 11 forms the exposure area 21, and the position corresponding to the light-blocking area 12 forms the non-exposure area 22.

[0119] In some embodiments of this application, the radiation treatment method includes ultraviolet irradiation treatment.

[0120] In some embodiments of this application, the wavelength of the ultraviolet irradiation treatment is 300 nm to 320 nm, and the intensity of the ultraviolet irradiation treatment is 20 mw / cm². 2 ~360mw / cm 2 The ultraviolet irradiation treatment time is 5 min to 60 min.

[0121] In some embodiments of this application, the wavelength of the ultraviolet irradiation treatment is 300nm, 302nm, 305nm, 308nm, 310nm, 312nm, 315nm, 317nm, or 320nm, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the intensity of the ultraviolet irradiation treatment is 20mw / cm². 2 40mw / cm 2 60mw / cm 2 80mw / cm 2 100mw / cm 2 120mw / cm 2 140mw / cm 2 160mw / cm 2 180mw / cm 2 200mw / cm 2 210mw / cm 2 220mw / cm 2 230mw / cm 2 240mw / cm 2 250mw / cm 2 260mw / cm 2 270mw / cm 2 280mw / cm 2 290mw / cm 2 300mw / cm 2 310mw / cm 2 320mw / cm 2 330mw / cm 2 340mw / cm 2 350mw / cm 2 Or 360mw / cm 2 The time for ultraviolet irradiation treatment is 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, or 60 min, or a value within the range defined by any two of the above specific values; as long as the photosensitive glass with the desired performance of this application is obtained, it is acceptable. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the photosensitive glass with the desired performance of this application is obtained.

[0122] In some embodiments of this application, the heat treatment includes nucleation and crystallization. Nucleation and crystallization are common processes in the art.

[0123] In some embodiments of this application, the heating rate of the nucleation treatment is 1℃ / min to 10℃ / min. In some embodiments of this application, the nucleation treatment time can be 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, or 10℃ / min, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the temperature of the nucleation treatment can be 430℃ to 500℃. In some embodiments of this application, the temperature of the nucleation treatment can be 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 490℃, or 500℃, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the nucleation treatment time is 30min to 360min. In some embodiments of this application, the nucleation treatment time can be 30 min, 45 min, 50 min, 55 min, 60 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 220 min, 240 min, 280 min, 300 min, 320 min, 340 min, or 360 min, or a value within a range of any two of the above specific values ​​as endpoints.

[0124] In this application, the crystallization process includes one-step crystallization and multi-step crystallization. In some embodiments of this application, the heating rate of the crystallization process is 1℃ / min to 10℃ / min. In some embodiments of this application, the crystallization time can be 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, or 10℃ / min, or a value within a range defined by any two of the above specific values ​​as endpoints.

[0125] In some embodiments of this application, the temperature of the one-step crystallization process can be 500℃ to 800℃. In some embodiments of this application, the temperature of the one-step crystallization process can be 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 600℃, 650℃, 700℃, 750℃, or 800℃, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the time for the one-step crystallization process is 30 min to 480 min. In some embodiments of this application, the crystallization treatment time can be 30 min, 45 min, 50 min, 55 min, 60 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 220 min, 240 min, 280 min, 300 min, 340 min, 380 min, 400 min, 430 min, 450 min, or 480 min, or a value within a range of values ​​defined by any two of the above specific values ​​as endpoints.

[0126] In some embodiments of this application, the multi-step crystallization process includes a two-step crystallization process. In some embodiments of this application, the temperature of the first crystallization step in the two-step crystallization process is 500°C to 560°C, and the temperature of the second crystallization step is 560°C to 800°C. It is understood that the temperature of the second crystallization step is higher than the temperature of the first crystallization step.

[0127] In some embodiments of this application, the temperature of the first crystallization step in the two-step crystallization process can be 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, or 560°C, or a value within a range defined by any two of the above specific values ​​as endpoints. In some embodiments of this application, the temperature of the second crystallization step in the two-step crystallization process can be 560°C, 570°C, 580°C, 600°C, 650°C, 700°C, 750°C, or 800°C, or a value within a range defined by any two of the above specific values ​​as endpoints.

[0128] In some embodiments of this application, the time for the first crystallization step in the two-step crystallization process is 30 min to 240 min, and the time for the second crystallization step is 30 min to 240 min. In some embodiments of this application, the time for the first crystallization step in the two-step crystallization process can be 30 min, 45 min, 50 min, 55 min, 60 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 220 min, or 240 min, or a value within the range of any two of the above specific values ​​as endpoints. In some embodiments of this application, the time for the second crystallization step in the two-step crystallization process can be 30 min, 45 min, 50 min, 55 min, 60 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 220 min, or 240 min, or a value within a range of any two of the above specific values ​​as endpoints.

[0129] Before and / or after heat treatment, those skilled in the art may perform other conventional steps to obtain photosensitive glass samples that meet the required specifications or requirements. These steps may include shaping, cutting (e.g., using a multi-wire cutting machine), CNC machining, thinning, or polishing. This application does not limit the dimensions of the photosensitive glass; for example, it can be 50mm × 50mm × 1.0mm, 300mm × 120mm × 0.7mm, etc.

[0130] In some embodiments of this application, the thickness of the substrate glass and / or photosensitive glass is not particularly limited, and can be, for example, 0.4 to 2.0 mm. In some embodiments of this application, the thickness of the photosensitive glass can be 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, or 2.0 mm, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0131] In some embodiments of this application, a reinforced photosensitive glass with a thickness of t is provided. It includes a reinforcing layer and a tensile stress layer. The reinforcing layer extends from the surface of the reinforced photosensitive glass inward and has a thickness of 0 to 0.22t.

[0132] At the center of the tensile stress layer and / or the strengthened photosensitive glass, the following components are contained, by mass percentage of oxides:

[0133] SiO2: 65%–74.00%, Al2O3: 5.00%–10.00%, Li2O: 7.90%–12.00%, Na2O: 1.00%–3.00%, K2O: 1.50%–3.80%, ZrO2: 3.5%–6.50%, Ag2O: 0.20%–0.50%, CeO2: 0.07%–0.13%, and Sb2O3: 0.2%–0.50%;

[0134] The reinforcing layer, by mass percentage of oxides, comprises the following components:

[0135] SiO2: 65%–74.00%, Al2O3: 5.00%–10.00%, Na2O: 4.00%–16.00%, K2O: 2.0%–5.0%, ZrO2: 3.5%–6.50%, Ag2O: 0.20%–0.50%, CeO2: 0.07%–0.13%, and Sb2O3: 0.2%–0.50%; the Li2O content in the reinforcing layer is lower than that in the tensile stress layer and / or the Li2O content at the center of the reinforced photosensitive glass;

[0136] Among them, Na2O is obtained by sodium nitrate, K2O is obtained by potassium nitrate, Ag2O is obtained by silver nitrate, and Sb2O3 is obtained by pentavalent antimony salt;

[0137] Strengthened photosensitive glass includes non-exposed areas and exposed areas.

[0138] In some embodiments of this application, a strengthened photosensitive glass with a thickness of t is provided. The strengthened photosensitive glass is obtained by chemically strengthening the photosensitive glass of any of the above embodiments.

[0139] In some embodiments of this application, the above-mentioned reinforced photosensitive glass comprises a reinforcing layer and a tensile stress layer. The reinforcing layer, by mass percentage of oxides, comprises the following components:

[0140] SiO2: 65%–74.00%, Al2O3: 5.00%–10.00%, Na2O: 4.00%–16.00%, K2O: 2.0%–5.0%, ZrO2: 3.5%–6.50%, Ag2O: 0.20%–0.50%, CeO2: 0.07%–0.13%, and Sb2O3: 0.2%–0.50%; the Li2O content in the reinforcing layer is lower than that in the tensile stress layer and / or the Li2O content at the center of the reinforced photosensitive glass;

[0141] Among them, Na2O is obtained by sodium nitrate, K2O is obtained by potassium nitrate, Ag2O is obtained by silver nitrate, and Sb2O3 is obtained by pentavalent antimony salt;

[0142] At the center of the tensile stress layer and / or the strengthened photosensitive glass, the following components are contained, by mass percentage of oxides:

[0143] SiO2: 65%–74.00%, Al2O3: 5.00%–10.00%, Li2O: 7.90%–12.00%, Na2O: 1.00%–3.00%, K2O: 1.50%–3.80%, ZrO2: 3.5%–6.50%, Ag2O: 0.20%–0.50%, CeO2: 0.07%–0.13%, and Sb2O3: 0.2%–0.50%.

[0144] In this application, SiO2 is a glass-forming oxide that forms an irregular, continuous network of silicon-oxygen tetrahedral structural units, serving as the framework for glass formation. In some embodiments of this application, the SiO2 content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of the oxide, is 65.00% to 74.00%, preferably 66.00% to 73.20%.

[0145] In some embodiments of this application, the SiO2 content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxides, can be 65.00%, 66.00%, 67.00%, 68.00%, 69.00%, 70.00%, 71.00%, 72.00%, 73.00%, or 74.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0146] In this application, Al2O3 serves as an intermediate in the glass network, entering the glass network structure as [AlO4] tetrahedra. Increasing the amount of Al2O3 can improve the glass's temperature (T). g Temperature and thermal stability are enhanced, and it is beneficial to suppress phase separation during the glass heat treatment process, but excessive amounts will increase the melting temperature of the glass. In some embodiments of this application, the Al2O3 content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxides, is 5.00% to 10.00%, preferably 5.10% to 9.70%, and more preferably 5.20% to 9.40%.

[0147] In some embodiments of this application, the Al2O3 content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxides, can be 5.00%, 5.50%, 6.00%, 6.50%, 7.00%, 7.50%, 8.00%, 8.50%, 9.00%, 9.50%, 10.00%, 7.25%, 5.83%, 8.76%, 7.62%, 7.89%, 6.47%, or 8.96%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0148] In some embodiments of this application, the content of Li2O in the strengthening layer of the photosensitive glass is 7.90% to 12.00% by mass percentage of oxides.

[0149] In some embodiments of this application, the Li₂O content in the tensile stress layer or center of the strengthened photosensitive glass, based on the mass percentage of oxides, can be 7.90%, 8.00%, 8.50%, 9.00%, 9.50%, 10.00%, 10.50%, 11.00%, 11.50%, or 12.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0150] In some embodiments of this application, the Li2O content in the strengthening layer is lower than the Li2O content at the center of the tensile stress layer and / or the strengthening photosensitive glass, based on the mass percentage of oxides.

[0151] In some embodiments of this application, the Na₂O content in the tensile stress layer or center of the strengthened photosensitive glass, based on the mass percentage of oxide, is 1.00% to 3.00%, preferably 1.00% to 2.80%. In some embodiments of this application, the Na₂O content in the tensile stress layer or center of the strengthened photosensitive glass, based on the mass percentage of oxide, can be 1.00%, 1.10%, 1.20%, 1.30%, 1.40%, 1.50%, 1.60%, 1.70%, 1.80%, 1.90%, 2.00%, 2.10%, 2.20%, 2.30%, 2.40%, 2.50%, 2.60%, 2.70%, 2.80%, 2.90%, or 3.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0152] In some embodiments of this application, the Na₂O content in the strengthening layer of the photosensitive glass, based on the mass percentage of oxides, is 4.00% to 16.00%, preferably 4.00% to 15%. In some embodiments of this application, the Na₂O content in the strengthening layer of the photosensitive glass, based on the mass percentage of oxides, can be 4.00%, 4.50%, 4.80%, 5.00%, 5.40%, 5.80%, 6.60%, 6.90%, 7.00%, 7.20%, 7.80%, 8.00%, 8.50%, 8.90%, 9.00%, or 9.50%. The values ​​may be 10.0%, 10.30%, 10.80%, 11.00%, 11.50%, 12.00%, 12.50%, 12.90%, 13.00%, 13.50%, 14.00%, 14.50%, 15.00%, 15.60%, 15.90%, or 16.00%, or values ​​within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in the implementation scheme, any of the above ranges may be combined with any other range.

[0153] In some embodiments of this application, the K2O content in the tensile stress layer or center of the strengthened photosensitive glass, based on the mass percentage of oxide, is 1.50% to 3.80%, preferably 1.80% to 3.50%. In some embodiments of this application, the K2O content in the tensile stress layer or center of the strengthened photosensitive glass, based on the mass percentage of oxide, can be 1.50%, 1.80%, 2.00%, 2.30%, 2.40%, 2.80%, 3.00%, 3.30%, 3.40%, 3.50%, 3.60%, 3.70%, or 3.80%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0154] In some embodiments of this application, the K2O content in the strengthening layer of the photosensitive glass, based on the mass percentage of oxide, is 2.00% to 5.00%, preferably 2.20% to 4.90%. In some embodiments of this application, the K2O content in the strengthening layer of the photosensitive glass, based on the mass percentage of oxide, can be 2.00%, 2.50%, 2.80%, 3.00%, 3.40%, 3.80%, 4.00%, 4.30%, 4.80%, or 5.00%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0155] In some embodiments of this application, the ZrO2 content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxide, is 3.50% to 6.50%, preferably 3.80% to 6.40%. In some embodiments of this application, the ZrO2 content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxide, can be 3.50%, 3.80%, 4.00%, 4.30%, 4.80%, 5.00%, 5.30%, 5.70%, 5.80%, 5.90%, 6.00%, 6.20%, or 6.50%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0156] In some embodiments of this application, the Ag₂O content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxide, is 0.20% to 0.50%, preferably 0.20% to 0.49%. In some embodiments of this application, the Ag₂O content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxide, can be 0.20%, 0.22%, 0.24%, 0.26%, 0.28%, 0.30%, 0.32%, 0.34%, 0.36%, 0.38%, 0.40%, 0.42%, 0.44%, 0.46%, 0.48%, or 0.50%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0157] In some embodiments of this application, the mass percentage of CeO2 in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass is 0.07% to 0.13%, preferably 0.08% to 0.12%, based on the mass percentage of oxides.

[0158] In some embodiments of this application, the CeO2 content in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxide, can be 0.07%, 0.08%, 0.09%, 0.10%, 0.11%, 0.12%, or 0.13%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0159] In this application, Sb₂O₃ is a weak reducing agent and also acts as a clarifying agent. 3+ During the glass melting process, it will react with Ce. 4+A redox reaction occurs, maintaining Ce 3+ The effective content. In some embodiments of this application, the mass percentage of Sb2O3 in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxides, is 0.20% to 0.50%, preferably 0.22% to 0.49%.

[0160] In some embodiments of this application, the content of Sb₂O₃ in the strengthening layer, tensile stress layer, or center of the strengthened photosensitive glass, based on the mass percentage of oxide, can be 0.20%, 0.22%, 0.25%, 0.28%, 0.30%, 0.34%, 0.37%, 0.39%, 0.40%, 0.42%, 0.45%, 0.47%, 0.49%, or 0.50%, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0161] In this application, chemical strengthening can be carried out by existing known methods; for example, chemical strengthening includes single-step chemical strengthening or multi-step chemical strengthening.

[0162] In some embodiments of this application, single-step chemical enhancement uses a salt bath containing NaNO3; preferably, the content of NaNO3 in the salt bath is 30wt% to 100wt%; preferably, single-step chemical enhancement uses a mixed salt bath containing NaNO3 and KNO3, preferably, the content of KNO3 in the mixed salt bath is greater than or equal to 80wt% and less than 100wt%, and the content of NaNO3 is greater than 0 and less than or equal to 20wt%.

[0163] In some embodiments of this application, the temperature for single-step chemical enhancement is 380°C to 480°C; preferably, the ion exchange time for single-step chemical enhancement is 5h to 20h.

[0164] In some embodiments of this application, multi-step chemical strengthening includes two-step chemical strengthening, wherein the first step of chemical strengthening uses a salt bath containing NaNO3, preferably with a NaNO3 content of 30wt% to 100wt%; and the second step of chemical strengthening uses a salt bath containing KNO3, preferably with a KNO3 content of 60wt% to 100wt%.

[0165] In some embodiments of this application, the temperature of the first step of chemical strengthening is 380°C to 480°C, and the time of the first step of chemical strengthening is preferably 3h to 20h; and / or, the temperature of the second step of chemical strengthening is 380°C to 480°C, and the time of the second step of chemical strengthening is preferably 5min to 30min.

[0166] In some embodiments of this application, the photosensitive glass can undergo other conventional processing before chemical strengthening to obtain a photosensitive glass sample that meets the required specifications or requirements. These processing methods include one or more of CNC machining, grinding and polishing, cleaning, 3D hot bending, and sweeping. It should be noted that this application does not limit the size of the strengthened photosensitive glass sample; for example, it can be 50mm × 50mm × 1.0mm, 300mm × 120mm × 0.7mm, etc.

[0167] In some embodiments of this application, the reinforced photosensitive glass can be flat or curved.

[0168] In some embodiments of this application, the thickness t of the strengthened photosensitive glass is not particularly limited, and can be, for example, 0.4 to 2.0 mm. In some embodiments of this application, the thickness t of the strengthened photosensitive glass can be 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, or 2.0 mm, or a value within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0169] In some embodiments of this application, the surface pressure (CS) of the non-exposed area of ​​the strengthened photosensitive glass is 300 MPa or higher, preferably 350 MPa or higher, and more preferably 350 MPa to 600 MPa. In some embodiments of this application, the surface pressure (CS) of the non-exposed area of ​​the strengthened photosensitive glass can be 350 MPa, 351 MPa, 395 MPa, 438 MPa, 385 MPa, 391 MPa, 398 MPa, 402 MPa, 422 MPa, 450 MPa, 480 MPa, 500 MPa, 530 MPa, 550 MPa, 580 MPa, or 600 MPa, or a value within a range defined by any two of the above specific values ​​as endpoints; as long as the photosensitive glass with the performance required by this application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0170] In some embodiments of this application, the static compressive strength of a single rod of the strengthened photosensitive glass is above 200N, preferably 200N to 500N, and more preferably 200N to 490N. In some embodiments of this application, the static compressive strength of a single rod of the strengthened curved photosensitive glass can be 200N, 250N, 294N, 361N, 392N, 301N, 314N, 375N, 376N, 390N, 400N, 450N, 480N, or 500N, or a value within a range defined by any two of the above specific values ​​as endpoints; as long as the photosensitive glass with the performance required by this application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range.

[0171] The photosensitive glass and / or strengthened photosensitive glass provided in this application can be used in electronic devices, including but not limited to mobile phones, tablets, handheld game consoles, portable digital devices (such as digital cameras), smart home devices, and smart wearables (such as smart bracelets, smartwatches, and smart glasses). They can also be used in vehicles, aircraft, or spacecraft, and in any glass device requiring photosensitive glass. For example, they can be used for the back cover glass of mobile phones, the outer casing glass of smartwatches, etc.; and for the windshields of vehicles, aircraft, or spacecraft, such as front windshields or side windshields.

[0172] For example, the photosensitive glass and / or strengthened photosensitive glass provided in this application can be used to manufacture cover glass, which can be the back cover or camera protective cover of an electronic device such as a mobile phone. For example, the photosensitive glass and / or strengthened photosensitive glass with excellent performance provided in this application can be used in electronic devices. In some embodiments of this application, an electronic device is provided, which can be a mobile phone (such as...) Figure 3 As shown, photosensitive glass and / or tempered photosensitive glass can be used as the back cover of a mobile phone, or as a tablet computer, smart wearable device (such as...). Figure 4 As shown, photosensitive glass and / or reinforced photosensitive glass can be used as the casing at the bottom of smartwatches and other electronic products.

[0173] In some embodiments of this application, the electronic device includes a smart wearable device worn on the body, comprising a housing having a top and a bottom, the bottom housing comprising the photosensitive glass and / or reinforced photosensitive glass described above in this application. The bottom is designed to contact the user's skin when worn.

[0174] In some embodiments of this application, such as Figure 3As shown, the electronic device also includes a camera assembly 32 located inside the housing. The housing may include a camera protective cover 31, which covers the camera assembly 32 to protect it. The camera protective cover 31 is made of the aforementioned photosensitive glass and / or reinforced photosensitive glass. In some embodiments of this application, the camera protective cover 31 may be partially or entirely made of the aforementioned photosensitive glass. In some embodiments of this application, the location of the camera protective cover 31 depends on the location of the camera assembly 32; it may be located on the front side of the electronic device or on the rear side. In some embodiments of this application, the camera protective cover 31 may be a separate structure from the rear cover 33. In other embodiments of this application, the camera protective cover 31 may be an integral structure with the rear cover 33.

[0175] The technical solutions of this application will be further described in detail below with reference to the embodiments. The embodiments of this application described in detail below are exemplary and are only used to explain this application, and should not be construed as limiting this application.

[0176] Example 1

[0177] (1) Prepare each raw material according to the proportion of each component in Table 1. The total mass of the prepared raw materials is 2000g. Add 10g of clarifying agent sodium chloride (NaCl) to the prepared raw materials, and then mix with a V-type mixer for 30 minutes to obtain a uniformly mixed raw material mixture.

[0178] The raw material mixture is transferred to a platinum crucible at 1500℃ for melting. The melt is stirred with a platinum stirring rod for 10 hours, followed by drawing and shaping to continuously produce glass bricks of the required specifications. The glass bricks are then quickly placed in an annealing furnace at 500℃ and held for 10 hours, after which they are allowed to cool naturally to room temperature to obtain the base glass brick.

[0179] After the above-mentioned substrate glass brick is cut, CNC machined (the CNC instrument used in this application is model: RCG500S), and polished, a substrate glass with a size of 50mm×50mm×1.0mm can be obtained.

[0180] (2) The substrate glass obtained above is ultrasonically cleaned for 10 minutes and then dried in a drying oven;

[0181] After cleaning, apply masking ink to specific areas of the substrate glass, such as... Figure 1 As shown, the black area is the masked area; subsequently, it was irradiated for a total of 25 minutes under parallel ultraviolet light (UVHX800*850 drawer type) with a wavelength of 310nm, and the intensity of the ultraviolet irradiation treatment was 120mw / cm².2 ;

[0182] The UV-irradiated glass was heat-treated according to the heat treatment process in Table 1 to obtain photosensitive glass; the heat treatment included nucleation and crystallization; the heating rate for both nucleation and crystallization was 10℃ / min; the photosensitive glass was then subjected to cold working processes such as laser cutting, cleaving, polishing, and chamfering to obtain photosensitive glass with dimensions of φ30*1.0mm. Figure 2 As shown.

[0183] Examples 2 to 8

[0184] Each of these was carried out with reference to Example 1, except that the raw material composition ratio, heat treatment process parameters, and other parameters of Examples 1 to 8 were different.

[0185] The relevant performance tests were performed on Examples 1 to 8, and the results are shown in Table 1.

[0186] Table 1

[0187]

[0188]

[0189] The photosensitive glasses of Examples 1, 3 and 6 were subjected to chemical strengthening treatment. The chemical strengthening treatment was carried out by sequential chemical strengthening in a salt bath of 100wt% NaNO3 at 460℃ for 18h and chemical strengthening in a salt bath of 100wt% KNO3 at 440℃ for 20min to obtain strengthened photosensitive glasses.

[0190] The mass percentages of each component of the raw materials for the photosensitive glass in Examples 1, 3, and 6 converted to oxides are shown in Table 2 below; the surface CS and monobar static compressive strength of the non-exposed area of ​​the strengthened photosensitive glass were tested, and the results are shown in Table 3.

[0191] Table 2

[0192]

[0193]

[0194] Table 3

[0195] Example 1 Example 3 Example 6 Non-exposed area CS / MPa 372 398 426 Single rod static compressive strength / N 302 365 388

[0196] Examples 9-10 and Comparative Examples 1-3

[0197] The same procedure was followed as in Example 1, except that the raw material compositions of Examples 9-10 and Comparative Examples 1-3 were different, as shown in Table 4.

[0198] Examples 9-10 and Comparative Examples 1-3 all use molar percentages of oxides, with the same oxide provided by different raw materials. Taking Sb₂O₃ as an example, in Examples 9-10 and Comparative Examples 1-3, the content of Sb₂O₃ is 0.37% based on the molar percentage of oxides. The difference is that Example 9 uses sodium antimonate as a raw material to provide Sb₂O₃, Example 10 uses ammonium antimonate as a raw material to provide Sb₂O₃, and Comparative Examples 1-3 use antimony oxide (Sb₂O₃) as a raw material to provide Sb₂O₃. Thus; furthermore, the molar percentages of oxides in Examples 9 and 10, converted to the mass ratios of raw material components, are: 57.96 wt% silica sand, 18.34 wt% lithium carbonate, 8.89 wt% aluminum hydroxide, 5.30 wt% potassium nitrate, 5.05 wt% sodium nitrate, 3.62 wt% zirconium oxide, 0.43 wt% silver nitrate, 0.07 wt% cerium oxide, and pentavalent antimony salt; wherein, based on sodium antimonate, the content of pentavalent antimony salt is 0.34 wt%; which is within the mass ratio range of this application.

[0199] The Ag / Ag₂O concentration (converted to Ag₂O mass ratio) of the main surface of the photosensitive glasses prepared in Examples 9-10 and Comparative Examples 1-3 was tested, as well as the transmittance T₃ (850 nm) of their exposure areas. Additionally, the shielding patterns of the exposure areas of the photosensitive glasses prepared in Examples 9-10 and Comparative Examples 1-3 in the visible light range were obtained as follows: Figure 6 As shown in Table 5, the results are as follows.

[0200] Table 4

[0201]

[0202]

[0203] Table 5

[0204]

[0205] Photographs of the bottom of the crucible after melting in Examples 9-10 and Comparative Examples 1-2 are shown below. Figure 5 As shown, a. a photograph of the bottom of the crucible in Comparative Example 1, b. a photograph of the bottom of the crucible in Comparative Example 2, c. a photograph of the bottom of the crucible in Example 9, and d. a photograph of the bottom of the crucible in Example 10.

[0206] Figure 6 These are physical images of the shielded areas of Examples 9-10 and Comparative Examples 1-3 of this application within the visible light range. In Comparative Examples 1-3, the bright spots transmit red light.

[0207] According to Table 1 above and Figure 5 ,as well as Figure 6It is known that the photosensitive glass prepared in this application can ensure the stability of the glass composition during the melting process of Ag-containing photosensitive glass, without Ag precipitation corroding the noble metal container; and the exposure area of ​​the prepared photosensitive glass can achieve shielding of optical signals in the visible light and near-infrared wavelength range.

[0208] According to Table 4 above and Figure 5 It is known that, under the same molar ratio of oxides, the photosensitive glass prepared without nitrates causes severe corrosion to the platinum crucible; while the addition of some nitrates can reduce corrosion, but the direct use of silver oxide in the raw materials will still cause some corrosion to the platinum crucible. Furthermore, when sodium nitrate, potassium nitrate, silver nitrate, and sodium antimonate are used simultaneously in this application, it can be ensured that the platinum crucible will not be corroded.

[0209] As shown in Table 5 above, no Ag was present during the raw material melting and molding process in Examples 9-10. + The loss, comparative examples 1-3 have Ag + The loss is because in Examples 9-10, sodium nitrate, potassium nitrate, silver nitrate, and antimonate (sodium antimonate or ammonium antimonate) were used simultaneously as raw materials to prepare the photosensitive glass, and no Ag was present during the melting process. + The Ag is converted into Ag and precipitated, and the content of Ag₂O in the final product is almost the same as the content of Ag₂O in the initial composition; while in Comparative Examples 1-3, some Ag was present at the beginning of melting. + The Ag is converted into Ag and precipitated, resulting in a final product with a much lower Ag₂O content than the initial composition. Meanwhile, the photosensitive glass prepared in Examples 9-10 exhibits excellent shielding performance in the visible light region during exposure, while the photosensitive glass prepared in Comparative Examples 1-3 allows red light to pass through in the visible light region. Furthermore, the photosensitive glass prepared in Examples 9-10 has a lower transmittance at 850 nm in its exposure region, indicating good shielding performance.

[0210] The above are merely specific embodiments of this application and are not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing photosensitive glass, characterized in that, include: The raw material components are configured and, by mass percentage, include the following components: 50wt%~60wt% silica sand, 15wt%~22wt% lithium carbonate, 6wt%~10wt% aluminum hydroxide, 3wt%~6wt% potassium nitrate, 3wt%~6wt% sodium nitrate, 3wt%~5wt% zirconium oxide, 0.3wt%~0.6wt% silver nitrate, 0.05wt%~0.10wt% cerium oxide, and pentavalent antimony salt; wherein, based on sodium antimony, the pentavalent antimony salt accounts for 0.3wt%~0.8wt% of the composition in the photosensitive glass. The mixture is then mixed and melted in a precious metal container, shaped, and annealed to obtain the substrate glass. The substrate glass includes a first region and a second region. The first region is masked, while the second region is not masked, to obtain a masked substrate glass. After the masked substrate glass is subjected to radiation treatment and heat treatment, a photosensitive glass with a non-exposed area and an exposed area is obtained; wherein the non-exposed area corresponds to the first area and the exposed area corresponds to the second area.

2. The preparation method according to claim 1, characterized in that, The raw material components, based on mass percentage, comprise the following components: The silica sand content is 53wt%~59wt%, and / or, The lithium carbonate content is 17wt%~20wt%, and / or, The aluminum hydroxide content is 8wt%~10wt%, and / or, The potassium nitrate content is 4 wt% to 6 wt%, and / or, The sodium nitrate content is 3.5 wt% to 5.5 wt%, and / or, The zirconium oxide content is 3wt%~5wt%, and / or, The silver nitrate content is 0.3wt%~0.5wt%, and / or, The cerium oxide content is 0.05wt%~0.10wt%, and / or, The content of the pentavalent antimony salt is 0.3wt%~0.7wt%.

3. The preparation method according to claim 1, characterized in that, The raw material components, based on mass percentage, comprise the following components: The silica sand content is 54.00 wt%~58.96 wt%, and / or, The lithium carbonate content is 17.43 wt% to 19.94 wt%, and / or, The aluminum hydroxide content is 8.22wt%~9.97wt%, and / or, The potassium nitrate content is 4.07 wt% to 5.97 wt%, and / or, The sodium nitrate content is 3.77 wt% to 5.45 wt%, and / or, The zirconium oxide content is 3.33wt%~4.96wt%, and / or, The silver nitrate content is 0.32wt%~0.49wt%, and / or, The cerium oxide content is 0.06wt%~0.09wt%, and / or, The content of the pentavalent antimony salt is 0.3wt%~0.5wt%.

4. The preparation method according to claim 1, characterized in that, The pentavalent antimony salt includes at least one of NaSbO3, KSbO3, NH4SbO3, and their hydrates.

5. The preparation method according to claim 1, characterized in that, The precious metal container is a container made of at least one metal selected from gold, platinum, and rhodium.

6. The preparation method according to claim 1, characterized in that, The melting temperature is 1400℃~1650℃, and the melting time is 6h~48h; and / or, the annealing temperature is 400℃~500℃, and the annealing time is 8h~24h.

7. The preparation method according to any one of claims 1 to 6, characterized in that, The radiation treatment methods include ultraviolet irradiation treatment.

8. The preparation method according to claim 7, characterized in that, The wavelength of the ultraviolet irradiation treatment is 300nm~320nm, and the intensity of the ultraviolet irradiation treatment is 20mw / cm. 2 ~360mw / cm 2 The ultraviolet irradiation treatment time is 5 min to 60 min.

9. The preparation method according to any one of claims 1 to 6, characterized in that, The heat treatment includes nucleation and crystallization.

10. The preparation method according to claim 9, characterized in that, The heating rate of the nucleation treatment is 1℃ / min to 10℃ / min; and / or, The nucleation treatment is performed at a temperature of 430℃~540℃; and / or, The nucleation treatment time is 30 min to 360 min, and / or, The temperature rise rate for the crystallization treatment is 1℃ / min ~ 10℃ / min; and / or, The crystallization treatment temperature is 540℃~800℃; and / or, The crystallization process takes 30 to 240 minutes.

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