Photosensitive microcrystalline glass and manufacturing method thereof

Abstract

The invention provides a photosensitive glass ceramic with lower visible light absorption loss, which comprises the following components in molar percentage: cation components: 50-65% of Si < 4 + >; 25 to 38% of Na < + >; 2-6% of Zn < 2 + >; 3-9% of Al < 3 + >; 0.001 to 0.1% of Ag < + >; 0.001 to 0.08% of Ce < 4 + >; 0.02 to 0.2 percent of Sb < 3 + >; the negative ion component comprises 88 to 98 percent of O < 2->, 0.001 to 0.09 percent of Sn < 4 + > and 88 to 98 percent of Sn < 4 + >; f-: 2 to 10%; and 0.05 to 2 percent of Br <->. Through reasonable component design, the obtained photosensitive microcrystalline glass is low in visible light absorption loss and can be used for preparing glass elements such as volume Bragg gratings with low optical loss and high diffraction efficiency.

Description

Technical Field

[0001] The present invention relates to glass, in particular to a photosensitive microcrystalline glass with low visible light absorption loss. Background Art

[0002] The development of photosensitive glass-ceramics dates back to the 1940s, when American scientist Stookey discovered that by adding metal nucleating agents and sensitizers, glass could become sensitive to light after exposure to ultraviolet (UV) or even higher wavelength radiation. This led to the creation of photoopalescent glass, photosensitive tinted glass, and panchromatic photosensitive glass, laying the foundation for the subsequent development of photosensitive glass for volume holographic recording. In the late 1980s, Glebov et al., building on Stookey's proposal, first melted photosensitive glass using the Li-Si-Al system. The crystallites precipitated from this type of glass were primarily [Li₂O·SiO₂]. However, the volume Bragg gratings fabricated from this type of glass exhibited low diffraction efficiency and were not suitable for spatial filtering of laser beams.

[0003] Silver clusters formed during UV exposure and nucleation heat treatment of photosensitive glass-ceramics are a significant factor in the absorption loss of photosensitive glass-ceramics. The absorption bands of silver atoms and clusters typically peak near 350-500nm in the visible light spectrum, exhibiting broadband absorption. As the clusters grow, their absorption bands undergo a redshift, extending to the 1μm band. Silver cluster formation is essential for realizing volume Bragg grating (VBR) devices in photosensitive glass-ceramics. While optical absorption in the visible light range is unavoidable, the optical loss of VBR devices is a key performance indicator. Reducing the optical loss of VBR devices is crucial and remains a challenge in this field, one for which effective solutions have been lacking. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a photosensitive microcrystalline glass with low visible light absorption loss and a manufacturing method thereof.

[0005] The technical solution adopted by the present invention to solve the technical problem is:

[0006] (1) Photosensitive glass-ceramics, whose components are expressed in molar percentages, the cationic components contain: Si 4+ :50~65%;Na + :25~38%; Zn 2+ :2~6%;Al 3+ :3~9%;Ag + :0.001~0.1%;Ce 4+ :0.001~0.08%;Sb 3+ :0.02~0.2%;Sn 4+: 0.001~0.09%, the anion component contains: O 2- :88~98%;F - :2~10%;Br - :0.05~2%.

[0007] (2) The photosensitive glass-ceramics according to (1), wherein the components are expressed in molar percentages, and the cationic component further comprises: Ge 4+ :0~0.5%;and / or K + :0~2%.

[0008] (3) Photosensitive glass-ceramics, whose components are expressed in molar percentages, the cationic component is Si 4+ :50~65%;Na + :25~38%; Zn 2+ :2~6%;Al 3+ :3~9%;Ag + :0.001~0.1%;Ce 4+ :0.001~0.08%;Sb 3+ :0.02~0.2%;Sn 4+ :0.001~0.09%;Ge 4+ :0~0.5%;K + : 0~2%, the anion component is O 2- :88~98%;F - :2~10%;Br - : 0.05~2% composition.

[0009] (4) The photosensitive glass-ceramics according to any one of (1) to (3), wherein the components are expressed in molar percentages, wherein: (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~79.8×10 -7 , preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~13.2×10 -7 , more preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.2×10 -7 ~1.4×10 -7 .

[0010] (5) The photosensitive glass-ceramics according to any one of (1) to (3), wherein the components are expressed in molar percentages, wherein: (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 11 to 2150, preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 50 to 861, more preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ It is 68 to 356.

[0011] (6) The photosensitive glass-ceramics according to any one of (1) to (3), wherein the components are expressed in molar percentages, wherein: Si 4+ : 53.5~61.5%, preferably Si 4+ :56.5~60.9%;and / or Na + : 27.5~36.5%, preferably Na + : 27.7-33.2%; and / or Zn 2+ : 2.6~5%, preferably Zn 2+ : 3.55-4.55%; and / or Al 3+ : 4-8%, preferably Al 3+ :4.2~5.7%; and / or Ag + : 0.004~0.045%, preferably Ag + :0.005~0.027%;and / or Ce 4+ : 0.003~0.025%, preferably Ce 4+ :0.006~0.015%; and / or Sb 3+ : 0.027~0.197%, preferably Sb 3+ :0.049~0.115%; and / or Sn 4+ : 0.003~0.03%, preferably Sn 4+ :0.007~0.018%;and / or Ge 4+ : 0.02~0.3%, preferably Ge 4+ :0.05~0.23%;and / or K + : 0.4~1.8%, preferably K + :0.94~1.55%.

[0012] (7) The photosensitive glass-ceramics according to any one of (1) to (3), wherein the components are expressed in molar percentages, wherein: 2- : 91~96.7%, preferably O 2- : 93-96.2%; and / or F - : 2.73~8.21%, preferably F - :4.2~6.37%;and / or Br - : 0.13~1.1%, preferably Br - :0.26~0.87%.

[0013] (8) The photosensitive glass-ceramics according to any one of (1) to (3), wherein the photosensitive glass-ceramics contains a sodium fluoride crystal phase.

[0014] (9) According to any one of (1) to (3), the photosensitive glass-ceramics has a light absorption coefficient of 1.2 to 5.5 cm at 450 nm. -1 , preferably 1.2 to 4.5 cm -1 , more preferably 1.2 to 2.3 cm -1 .

[0015] (10) Matrix glass, whose components are expressed in molar percentages, the cationic component contains: Si 4+ :50~65%;Na + :25~38%; Zn 2+ :2~6%;Al 3+ :3~9%;Ag + :0.001~0.1%;Ce 4+ :0.001~0.08%;Sb 3+ :0.02~0.2%;Sn 4+ : 0.001~0.09%, the anion component contains: O 2- :88~98%;F - :2~10%;Br - :0.05~2%.

[0016] (11) According to the matrix glass described in (10), its components are expressed in molar percentages, and the cationic component further contains: Ge 4+ :0~0.5%;and / or K + :0~2%.

[0017] (12) The matrix glass according to (10) or (11), wherein the components are expressed in molar percentages, wherein: (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10-7 ~79.8×10 -7 , preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~13.2×10 -7 , more preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.2×10 -7 ~1.4×10 -7 ; and / or (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 11 to 2150, preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 50 to 861, more preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ It is 68 to 356.

[0018] (13) The matrix glass according to (10) or (11), wherein the components are expressed in molar percentages, wherein: Si 4+ : 53.5~61.5%, preferably Si 4+ :56.5~60.9%;and / or Na + : 27.5~36.5%, preferably Na + : 27.7-33.2%; and / or Zn 2+ : 2.6~5%, preferably Zn 2+ : 3.55-4.55%; and / or Al 3+ : 4-8%, preferably Al 3+ :4.2~5.7%; and / or Ag + : 0.004~0.045%, preferably Ag + :0.005~0.027%;and / or Ce 4+ : 0.003~0.025%, preferably Ce 4 + :0.006~0.015%; and / or Sb 3+ : 0.027~0.197%, preferably Sb3+ :0.049~0.115%; and / or Sn 4+ : 0.003~0.03%, preferably Sn 4+ :0.007~0.018%;and / or Ge 4+ : 0.02~0.3%, preferably Ge 4+ :0.05~0.23%;and / or K + : 0.4~1.8%, preferably K + :0.94~1.55%.

[0019] (14) The matrix glass according to (10) or (11), wherein the components are expressed in molar percentages, wherein: 2- : 91~96.7%, preferably O 2- : 93-96.2%; and / or F - : 2.73~8.21%, preferably F - :4.2~6.37%;and / or Br - : 0.13~1.1%, preferably Br - :0.26~0.87%.

[0020] (15) The matrix glass according to (10) or (11), wherein the crystallization temperature of the matrix glass is T c The temperature is 550 to 680°C, preferably 570 to 658°C, and more preferably 583 to 641°C.

[0021] (16) A glass element made of the photosensitive microcrystalline glass described in any one of (1) to (9), or made of the matrix glass described in any one of (10) to (15).

[0022] (17) A device comprising the photosensitive glass-ceramics described in any one of (1) to (9), or the matrix glass described in any one of (10) to (15), or the glass element described in (16).

[0023] (18) A method for manufacturing a photosensitive glass-ceramic according to any one of (1) to (9), comprising the following steps: 1) forming a matrix glass; 2) forming the photosensitive glass-ceramic from the matrix glass by a hypercrystallization process.

[0024] (19). According to the method for manufacturing photosensitive microcrystalline glass described in (18), the crystallization process includes exposing the matrix glass to exposure treatment and heat treatment, the exposure treatment is to expose the matrix glass to ultraviolet light of 300 to 320 nm, the exposure time is 2 to 20 minutes, preferably the exposure time is 2 to 10 minutes, the heat treatment temperature is 490 to 550°C, preferably the heat treatment temperature is 500 to 520°C, the heat treatment time is 10 to 180 minutes, preferably the heat treatment time is 30 to 90 minutes.

[0025] The beneficial effects of the present invention are: through reasonable component design, the photosensitive microcrystalline glass obtained by the present invention has low visible light absorption loss and can be used to prepare glass elements such as low optical loss and high diffraction efficiency volume Bragg gratings. DETAILED DESCRIPTION

[0026] The following describes embodiments of the present invention in detail. However, the present invention is not limited to the embodiments described below and can be implemented with appropriate modifications within the scope of the present invention. Furthermore, although some overlapping descriptions may be omitted as appropriate, this does not limit the scope of the invention. In this specification, when referred to simply as glass, it refers to the matrix glass before crystallization (i.e., crystallization process). After crystallization (i.e., crystallization process), the matrix glass is referred to as photosensitive glass-ceramics.

[0027] In some embodiments, the photosensitive glass-ceramic of the present invention contains a sodium fluoride crystal phase. The photosensitive glass-ceramic with a sodium fluoride crystal phase is a special glass-ceramic in which the matrix glass is subjected to ultraviolet light exposure treatment and further heat treatment, resulting in the precipitation of sodium fluoride crystals in the ultraviolet light exposure area, causing refractive index modulation and forming a hologram inside. Compared with traditional volume holographic materials, the photosensitive glass-ceramic of the present invention, as a new type of photosensitive volume holographic material, has good thermal stability and a high laser damage threshold. It is an ideal material for preparing volume Bragg gratings and has important application prospects in the fields of volume diffraction optical devices, structural optical devices, high-density optical storage media, high-resolution and high-speed holographic recording media, etc.

[0028] The following describes the ranges of the various components (ingredients) that make up the photosensitive glass-ceramics and matrix glass of the present invention. In this specification, unless otherwise specified, the content of a cationic component is expressed as the molar percentage (mol%) of the cationic component relative to the total cationic components, and the content of an anionic component is expressed as the molar percentage (mol%) of the anionic component relative to the total anionic components. The ratio of the cationic component contents is the ratio of the molar percentages of the contents of the various cationic components; the ratio of the anionic component contents is the ratio of the molar percentages of the contents of the various anionic components; and the ratio of the anionic and cationic components is the ratio of the molar percentages of the contents of the cationic component relative to the molar percentages of the contents of the various anionic components. The product of the cationic component contents is the product of the corresponding values of the molar percentages of the contents of the various cationic components. For example, if the content of component A is 1% and the content of component B is 2%, the value of "A×B" referred to herein is 1%×2%, or 0.0002.

[0029] Unless otherwise indicated in specific circumstances, the numerical ranges listed herein include upper and lower limits, and "above" and "below" include the endpoints, as well as all integers and fractions included in the range, without limitation to the specific values listed when defining the range. The term "and / or" herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0030] It should be noted that the ionic valences of the components described below are representative values used for convenience and are not different from other ionic valences. The ionic valences of the components in the glass may be other than the representative values. For example, Ce usually exists in the glass with an ionic valence of +4, so in this specification, "Ce 4+ " is used as a representative value, but there is the possibility of existing in other ionic valence states, which is also within the scope of protection of this patent.

[0031] <Cationic Component>

[0032] Si 4+ It is the network forming component of the glass and photosensitive microcrystalline glass of the present invention, forming an irregular continuous network with the structural unit of silicon-oxygen tetrahedron, forming the skeleton of glass and photosensitive microcrystalline glass. 4+ Too much content will lead to high viscosity of the glass, making the melting temperature high, making it difficult to smelt the material and forming glass. At the same time, high temperature melting will cause the components of the glass to volatilize, especially affecting the F content in the glass. - Br - The content of volatile components such as Si 4+ If the content is too low, the glass will be easy to crystallize and separate, which will affect the transmittance of the glass. 4+The content of is 50 to 65%, preferably 53.5 to 61.5%, more preferably 56.5 to 60.9%.

[0033] Ge 4+ It is also a network former component of the glass and photosensitive glass-ceramics of the present invention, and can replace part of the Si in the glass [Si-O-Si] structure. 4+ It can reduce the visible light absorption loss of photosensitive glass-ceramics, but excessive Ge 4+ It will make the glass difficult to crystallize during the crystallization process, affect the crystallization performance of the matrix glass, and cause the refractive index modulation performance of the photosensitive micro-ceramic glass to decrease. 4+ The content of is 0 to 0.5%, preferably 0.02 to 0.3%, more preferably 0.05 to 0.23%.

[0034] Zn 2+ 、Al 3+ It is a network intermediate component of glass and photosensitive micro-ceramic glass, entering the network structure of glass and photosensitive micro-ceramic glass as [ZnO4] and [AlO4] tetrahedron respectively, and can provide network channels for the formation of sodium fluoride crystal phase. 2+ It can reduce the thermal expansion coefficient of glass and improve chemical stability and thermal stability. 3+ It has the function of inhibiting the phase separation of glass during the forming and crystallization process, and can also improve the strength and hardness of glass and photosensitive micro-ceramic glass. 3+ The presence of Zn increases the molding range of glass in the three-dimensional phase diagram, enhances the chemical stability of glass, and improves the transparency of glass. 2+ 、Al 3+ Excessive content will increase Na + 、F - Br - The solubility of Zn in glass is not conducive to the formation of sodium fluoride crystal phase, which affects the refractive index modulation ability of photosensitive microcrystalline glass. 2+ The content of Al is 2-6%, preferably 2.6-5%, more preferably 3.55-4.55%; 3+ The content of is 3 to 9%, preferably 4 to 8%, and more preferably 4.2 to 5.7%.

[0035] Alkali metal component Na + , K + It is the network outer body of glass and photosensitive microcrystalline glass. It can reduce the viscosity of glass during high temperature melting, lower the melting temperature of glass, reduce the volatilization of glass components, and increase the F content in glass. - Br - The stability of volatile components such as Na +It is a component of the photosensitive glass-ceramic phase, which is conducive to the formation of sodium fluoride crystal phase. + , K + Excessive content of Na will increase the tendency of crystallization and phase separation of glass, induce the transmittance of glass to decrease, and on the other hand will reduce the chemical stability of glass; + , K + Too little content of Na will reduce the crystallization tendency of the glass during the crystallization process, which is not conducive to improving the refractive index modulation ability of the photosensitive micro-ceramic glass. + The content of K is 25-38%, preferably 27.5-36.5%, more preferably 27.7-33.2%; + The content of is 0 to 2%, preferably 0.4 to 1.8%, more preferably 0.94 to 1.55%.

[0036] The inventors have found through a lot of experimental studies that if (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ If it is lower than 11, the crystallization temperature of the glass is high, and the glass is not easy to crystallize during the process of manufacturing photosensitive micro-ceramics, which will lead to low refractive index modulation ability of the photosensitive micro-ceramics; if (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ If the temperature is higher than 2150, the crystallization temperature of the glass will be low, and spontaneous crystallization will easily occur during glass melting, which will affect the refractive index modulation effect of the photosensitive micro-ceramic glass. Therefore, it is preferred to (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 11 to 2150, more preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 50 to 861, more preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ It is 68 to 356.

[0037] Ag + It is a crystal nucleating agent for glass. The higher its content, the easier it is to form silver atoms (Ag 0 ), which is beneficial to improve the photosensitivity of glass. +Too much content of Ag can easily cause spontaneous crystallization in the unexposed area of the photosensitive microcrystalline glass, and the absorption of silver clusters in the exposed area will also be enhanced, resulting in increased absorption loss of the photosensitive microcrystalline glass. + The content of is 0.001 to 0.1%, preferably 0.004 to 0.045%, more preferably 0.005 to 0.027%.

[0038] Ce 4+ It is a photosensitive component in glass and is partially converted into Ce during the glass melting process. 3+ ions, during the 300-325nm ultraviolet light exposure process, Ce in the glass 3+ Photons excite and generate photoelectrons, which are + Capture electrons to form silver atoms (Ag 0 During the heat treatment process, silver atoms (Ag 0 ) will nucleate to form Ag 0 Cluster nucleus. Ce 4+ The more the content of Ce, the more Ce 3+ The more, the better to improve the photosensitivity of glass, forming more silver atoms (Ag 0 ), which is beneficial to improve the refractive index modulation ability of photosensitive glass-ceramics. 4+ The content of is too much, so 3+ The intrinsic broadband absorption at 300-325nm will make the corresponding band absorption too strong, affecting the exposure uniformity of the photosensitive micro-ceramic glass in the depth during the grating writing process. 4+ The content of is 0.001 to 0.08%, preferably 0.003 to 0.025%, more preferably 0.006 to 0.015%.

[0039] Sn 4+ 、Sb 3+ In the present invention, both are sensitizers. During the melting process, Sb 3+ Part of Ce can be 4+ Reduction to Ce 3+ , part of Sn 4+ Reduction to Sn 2+ , part of itself is converted into Sb 5+ 。 Ce 3+ Increasing the content is beneficial to improving the photosensitivity of the glass. 2+ 、Sb 3+ It can release electrons during heat treatment to promote Ag + To Ag 0 transformation, which is conducive to nucleation. 4+ With Sb 5+ During the exposure process, Ag +At the same time, Sn 4+ 、Sb 3+ Too high a content of Sn will cause defects in the form of accelerated operating temperature rise of the photosensitive microcrystalline glass product after it is made into a component, affecting the working stability. 4+ The content of Sb is 0.001 to 0.09%, preferably 0.003 to 0.03%, more preferably 0.007 to 0.018%; 3+ The content of is 0.02 to 0.2%, preferably 0.027 to 0.197%, and more preferably 0.049 to 0.115%.

[0040] <Anion Component>

[0041] O 2- It is the main anion component of the glass and photosensitive glass-ceramics of the present invention, and is the key component of the silicon-oxygen tetrahedron, forming a continuous silicon-oxygen backbone. 2- With Br - 、F - Together, they balance the charges of the glass and the photosensitive glass-ceramics cation components. 2- The content of is 88 to 98%, preferably 91 to 96.7%, more preferably 93 to 96.2%.

[0042] F - As the main component of sodium fluoride crystal phase, the higher its content, the more conducive it is to improving the refractive index modulation ability of photosensitive microcrystalline glass. - It has the effect of reducing the high temperature viscosity of glass and lowering the melting temperature. - Too much content can easily lead to crystallization being difficult to control during the crystallization process, causing the grain size to grow too large, and easily leading to phase separation during the glass crystallization process, resulting in increased absorption loss of the photosensitive micro-ceramic glass. - The content of is 2 to 10%, preferably 2.73 to 8.21%, and more preferably 4.2 to 6.37%.

[0043] Br - It is a nucleation component in the manufacturing process of photosensitive microcrystalline glass, and it also has the effect of reducing the high-temperature viscosity of the glass and lowering the melting temperature. In addition, an appropriate amount of Br - It can generate AgBr components in silver clusters, and sodium fluoride crystal phase is more likely to precipitate on AgBr, which is beneficial to the crystallization characteristics of photosensitive micro-ceramics; but Br - Too much content will make the glass more likely to separate into phases during crystallization, which will reduce the transmittance of the photosensitive micro-ceramic glass. - The content of is 0.05 to 2%, preferably 0.13 to 1.1%, and more preferably 0.26 to 0.87%.

[0044] After extensive research and repeated experiments, the inventors found that the light absorption caused by the silver clusters of the photosensitive glass-ceramics obtained after exposure and heat treatment of the matrix glass is affected by the composition of the silver clusters, the silver content in the glass, the amount of electrons released by the photosensitizer during the exposure process, the state of the glass network structure, etc. In some embodiments of the present invention, by controlling (Br - ×Ag + ×Ce 4+ ) / Ge 4+ In 0.1×10 -7 ~79.8×10 -7 range, which is beneficial to the regulation of the state of silver clusters in photosensitive glass-ceramics. - ×Ag + ×Ce 4+ ) / Ge 4+ Less than 0.1×10 -7 , the amount of silver clusters precipitated in the photosensitive glass-ceramics is small, which makes it difficult for the photosensitive glass-ceramics to crystallize during the manufacturing process, which is not conducive to the refractive index modulation performance of the photosensitive glass-ceramics; if (Br - ×Ag + ×Ce 4 + ) / Ge 4+ Higher than 79.8×10 -7 , which will lead to strong absorption of silver clusters in the photosensitive microcrystalline glass and large visible light loss of the photosensitive microcrystalline glass. Therefore, it is preferred that (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~79.8×10 -7 , more preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~13.2×10 -7 , further preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.2×10 -7 ~1.4×10 -7 .

[0045] The "0%" recorded in this article means that the component is not intentionally added as a raw material to the matrix glass and photosensitive microcrystalline glass of the present invention; however, as raw materials and / or equipment for producing glass and / or photosensitive microcrystalline glass, there will be certain impurities or components that are not intentionally added, which will be contained in small amounts or trace amounts in the final glass and / or photosensitive microcrystalline glass. This situation is also within the scope of protection of the patent of this invention.

[0046] [Manufacturing method]

[0047] The method for manufacturing the photosensitive glass-ceramics of the present invention comprises the following steps:

[0048] Step 1: Forming matrix glass. Using salts (such as carbonates, nitrates, phosphates, etc.), hydroxides, oxides, fluorides, bromides, etc. as raw materials, according to the content of glass components, after the ingredients are prepared according to the conventional method, the prepared furnace charge is put into a melting furnace (such as a platinum crucible) at 1350-1500°C for melting, and after clarification, stirring and homogenization, a homogeneous molten glass is obtained, and the molten glass is formed in a mold and annealed. During the molding process, it is preferred to introduce circulating cooling air to ensure that the glass does not crystallize. Those skilled in the art can reasonably and appropriately select raw materials, process methods and process parameters according to actual needs.

[0049] Step 2: Use a crystallization process to form a photosensitive glass-ceramic from the matrix glass. The crystallization process of the present invention includes exposing the matrix glass to light and heat treatment. Depending on the application requirements of the photosensitive glass-ceramic, the matrix glass can be subjected to partial exposure or full exposure. The partial exposure process refers to shielding or masking a portion of the matrix glass, exposing the portion that needs to be crystallized directly to ultraviolet light; the full exposure process refers to not shielding or masking the matrix glass, but exposing the entire matrix glass to ultraviolet light. The exposure process refers to exposing the matrix glass to ultraviolet light of 300 to 320 nm for 2 to 20 minutes, preferably 2 to 10 minutes. After the exposure process is completed, heat treatment is performed. The heat treatment temperature is 490 to 550°C, preferably 500 to 520°C, and the heat treatment time is 10 to 180 minutes, preferably 30 to 90 minutes.

[0050] Next, the properties of the matrix glass and photosensitive glass-ceramics of the present invention are described.

[0051] <Crystallization Temperature>

[0052] The crystallization temperature (T c ), 15 mg of sample was weighed during the test, and the heating rate was 10 K / min.

[0053] In some embodiments, the crystallization temperature (T c ) is 550-680°C, preferably 570-658°C, more preferably 583-641°C.

[0054] <Light Absorption Coefficient>

[0055] The photosensitive glass-ceramics was processed into a thickness of 2 mm, and the light absorption coefficient of the photosensitive glass-ceramics was tested in accordance with the national standard "GB / T 7962.9-2010".

[0056] In some embodiments, the light absorption coefficient of the photosensitive glass-ceramics of the present invention at 450 nm is 1.2 to 5.5 cm -1 , preferably 1.2 to 4.5 cm -1 , more preferably 1.2 to 2.3 cm -1 .

[0057] [Glass elements]

[0058] The photosensitive glass-ceramic of this invention can be used to fabricate glass components such as volume Bragg grating devices, which are used for near-field beam quality control, pulse broadening and compression, spectral control, and spectral synthesis. These devices are ideal for high-power laser systems. For example, reflective volume Bragg grating devices can be used to lock and narrow the output spectrum of semiconductor laser pump sources in high-power laser devices; transmissive volume Bragg grating devices can be used to optimize near-field laser beam quality; and chirped volume Bragg grating devices can be used for pulse compression and broadening.

[0059] The matrix glass and photosensitive microcrystalline glass of the present invention can be used to manufacture glass elements such as lenses and prisms. Examples of lenses include various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses with spherical or aspherical lens surfaces.

[0060] The photosensitive glass-ceramics and matrix glass of the present invention can be used to make glass components such as glass cover plates due to their excellent properties.

[0061] [equipment]

[0062] The photosensitive glass-ceramics of the present invention and the glass components made thereof can be widely used in various types of lasers and other equipment due to their excellent properties.

[0063] The photosensitive microcrystalline glass, matrix glass, and glass elements made thereof of the present invention can be used to manufacture various devices, including but not limited to electronic devices, medical devices, decorations or handicrafts, such as mobile phones, watches, computers, biomedical detection, etc., for manufacturing local light shielding glass or patterned cover glass for mobile phones, smart phones, tablets, laptops, televisions, etc., or optical signal channel glass for smart watches, biomedical devices, etc., or for manufacturing patterned decorations or handicrafts glass.

[0064] Example

[0065] In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.

[0066] <Matrix Glass Example>

[0067] This embodiment uses the above-mentioned method for producing matrix glass to obtain matrix glasses having the compositions shown in Tables 1 to 5. In addition, the properties of each matrix glass were measured using the testing method described in the present invention, and the measurement results are shown in Tables 1 to 5.

[0068] Table 1.

[0069]

[0070]

[0071] Table 2.

[0072]

[0073] Table 3.

[0074]

[0075] Table 4.

[0076]

[0077]

[0078] Table 5.

[0079]

[0080] <Photosensitive glass-ceramic example>

[0081] In this example, the matrix glasses listed in Tables 1 to 5 were treated through the crystallization process described in the present invention to obtain the photosensitive glass-ceramics shown in Tables 6 to 10. Furthermore, the properties of each photosensitive glass-ceramic were measured using the testing methods described in the present invention, and the results are shown in Tables 6 to 10.

[0082] Table 6.

[0083]

[0084] Table 7.

[0085]

[0086]

[0087] Table 8.

[0088]

[0089] Table 9.

[0090]

[0091]

[0092] Table 10.

[0093]

Claims

1. Photosensitive glass-ceramics, characterized in that: Its components are expressed in molar percentages, and the cationic component contains: Si 4+ :50~65%;Na + :25~38%; Zn 2+ :2~6%;Al 3+ :3~9%;Ag + :0.001~0.1%;Ce 4+ :0.001~0.08%;Sb 3+ :0.02~0.2%;Sn 4+ : 0.001~0.09%, the anion component contains: O 2- :88~98%;F - :2~10%;Br - :0.05~2%.

2. The photosensitive glass-ceramic according to claim 1, characterized in that: Its components are expressed in molar percentages, and the cationic component also contains: Ge 4+ :0~0.5%;and / or K + :0~2%.

3. Photosensitive glass-ceramics, characterized in that: Its components are expressed in molar percentages, and the cationic component consists of Si 4+ :50~65%;Na + :25~38%; Zn 2+ :2~6%;Al 3+ :3~9%;Ag + :0.001~0.1%;Ce 4+ :0.001~0.08%;Sb 3+ :0.02~0.2%;Sn 4+ :0.001~0.09%;Ge 4+ :0~0.5%;K + :0~2%, the anion component is O 2- :88~98%;F - :2~10%;Br - : 0.05~2% composition.

4. The photosensitive glass-ceramics according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentages, where: (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~79.8×10 -7 , preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~13.2×10 -7 , more preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.2×10 -7 ~1.4×10 -7 .

5. The photosensitive glass-ceramics according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentages, where: (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 11 to 2150, preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 50 to 861, more preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ It is 68 to 356.

6. The photosensitive glass-ceramics according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentages, where: Si 4+ : 53.5~61.5%, preferably Si 4+ :56.5~60.9%;and / or Na + : 27.5~36.5%, preferably Na + : 27.7-33.2%; and / or Zn 2+ : 2.6~5%, preferably Zn 2+ : 3.55-4.55%; and / or Al 3+ : 4-8%, preferably Al 3+ :4.2~5.7%; and / or Ag + : 0.004~0.045%, preferably Ag + :0.005~0.027%;and / or Ce 4+ : 0.003~0.025%, preferably Ce 4+ :0.006~0.015%; and / or Sb 3+ : 0.027~0.197%, preferably Sb 3+ :0.049~0.115%; and / or Sn 4+ : 0.003~0.03%, preferably Sn 4+ :0.007~0.018%;and / or Ge 4+ : 0.02~0.3%, preferably Ge 4+ :0.05~0.23%;and / or K + : 0.4~1.8%, preferably K + :0.94~1.55%.

7. The photosensitive glass-ceramics according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentages, where: 2- : 91~96.7%, preferably O 2- : 93-96.2%; and / or F - : 2.73~8.21%, preferably F - :4.2~6.37%;and / or Br - : 0.13~1.1%, preferably Br - :0.26~0.87%.

8. The photosensitive glass-ceramics according to any one of claims 1 to 3, characterized in that: The photosensitive glass-ceramics contains a sodium fluoride crystal phase.

9. The photosensitive glass-ceramics according to any one of claims 1 to 3, characterized in that: The photosensitive glass-ceramic has a 450nm light absorption coefficient of 1.2 to 5.5 cm -1 , preferably 1.2 to 4.5 cm -1 , more preferably 1.2 to 2.3 cm -1 .

10. Matrix glass, characterized in that Its components are expressed in molar percentages, and the cationic component contains: Si 4+ :50~65%;Na + :25~38%; Zn 2+ :2~6%;Al 3+ :3~9%;Ag + :0.001~0.1%;Ce 4+ :0.001~0.08%;Sb 3+ :0.02~0.2%;Sn 4+ : 0.001~0.09%, the anion component contains: O 2- :88~98%;F - :2~10%;Br - :0.05~2%.

11. The matrix glass according to claim 10, characterized in that Its components are expressed in molar percentages, and the cationic component also contains: Ge 4+ :0~0.5%;and / or K + :0~2%.

12. The matrix glass according to claim 10 or 11, characterized in that Its components are expressed in molar percentages, where: (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~79.8×10 -7 , preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.1×10 -7 ~13.2×10 -7 , more preferably (Br - ×Ag + ×Ce 4+ ) / Ge 4+ 0.2×10 -7 ~1.4×10 -7 ; and / or (Na + +K + -3Al 3 + -2Zn 2+ ) / Ge 4+ 11 to 2150, preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ 50 to 861, more preferably (Na + +K + -3Al 3+ -2Zn 2+ ) / Ge 4+ It is 68 to 356.

13. The matrix glass according to claim 10 or 11, characterized in that Its components are expressed in molar percentages, where: Si 4+ : 53.5~61.5%, preferably Si 4+ :56.5~60.9%;and / or Na + : 27.5~36.5%, preferably Na + : 27.7-33.2%; and / or Zn 2+ : 2.6~5%, preferably Zn 2+ : 3.55-4.55%; and / or Al 3+ : 4-8%, preferably Al 3+ :4.2~5.7%; and / or Ag + : 0.004~0.045%, preferably Ag + :0.005~0.027%;and / or Ce 4+ : 0.003~0.025%, preferably Ce 4+ :0.006~0.015%; and / or Sb 3+ : 0.027~0.197%, preferably Sb 3+ :0.049~0.115%; and / or Sn 4+ : 0.003~0.03%, preferably Sn 4+ :0.007~0.018%;and / or Ge 4+ : 0.02~0.3%, preferably Ge 4+ :0.05~0.23%;and / or K + : 0.4~1.8%, preferably K + :0.94~1.55%.

14. The matrix glass according to claim 10 or 11, characterized in that Its components are expressed in molar percentages, where: 2- : 91~96.7%, preferably O 2- : 93-96.2%; and / or F - : 2.73~8.21%, preferably F - :4.2~6.37%;and / or Br - : 0.13~1.1%, preferably Br - :0.26~0.87%.

15. The matrix glass according to claim 10 or 11, characterized in that The crystallization temperature T of the matrix glass c The temperature is 550 to 680°C, preferably 570 to 658°C, and more preferably 583 to 641°C.

16. Glass element, characterized in that It is made of the photosensitive microcrystalline glass according to any one of claims 1 to 9, or made of the matrix glass according to any one of claims 10 to 15.

17. A device, characterized in that A glass element comprising the photosensitive glass-ceramic according to any one of claims 1 to 9, or the matrix glass according to any one of claims 10 to 15, or the glass element according to claim 16.

18. The method for manufacturing the photosensitive glass-ceramics according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: 1) forming matrix glass; 2) forming photosensitive micro-ceramic glass by using a hypercrystallization process on the matrix glass.

19. The method for manufacturing photosensitive glass-ceramics according to claim 18, characterized in that: The crystallization process includes exposing the matrix glass to an exposure treatment and a heat treatment. The exposure treatment is to expose the matrix glass to ultraviolet light of 300 to 320 nm for 2 to 20 minutes, preferably 2 to 10 minutes. The heat treatment temperature is 490 to 550° C., preferably 500 to 520° C., and the heat treatment time is 10 to 180 minutes, preferably 30 to 90 minutes.

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