CN114873918A - Photosensitive glass material - Google Patents
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- CN114873918A CN114873918A CN202210722719.0A CN202210722719A CN114873918A CN 114873918 A CN114873918 A CN 114873918A CN 202210722719 A CN202210722719 A CN 202210722719A CN 114873918 A CN114873918 A CN 114873918A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/04—Compositions for glass with special properties for photosensitive glass
Abstract
The invention provides a photosensitive glass material with lower crystallization shrinkage and lower etching loss rate. The photosensitive glass material comprises the following components in percentage by weight: SiO 2 2 ：74.6～82.5％；Li 2 O：7.1～10.4％；R 2 O：1.4～8.7％；Al 2 O 3 ：2.1～6％；TiO 2 +Ag 2 O: 0.1 to 0.5% of SiO 2 /Li 2 O is 7.6 to 10.6, and R is 2 O is Na 2 O、K 2 One or two of O. Through reasonable component design, the photosensitive glass material obtained by the invention has lower crystallization shrinkage and lower etching loss rate, and is suitable for preparing glass adapter plates, MEMS vacuum devices and the like.
Description
Technical Field
The invention relates to a glass material, in particular to a photosensitive glass material with lower crystallization shrinkage and lower etching loss rate.
Background
Photosensitive glass ceramics are glass materials which can generate structural change under the irradiation of light with specific wavelength so as to show a certain special performance. Under the irradiation of ultraviolet light, the structure inside the photosensitive glass ceramics is changed to generate crystal nucleus, and after heat treatment at a certain temperature, a large amount of glass with specific component microcrystals can be generated in an irradiation area. The glass through hole (TGV) technology is a novel high-density interconnection technology which is concerned with, and is a key technology for preparing a glass adapter plate, an integrated passive device and an MEMS (micro-electromechanical systems) vacuum device, the structure of the TGV technology is formed by containing vertical interconnection through holes by different materials, the TGV technology can be regarded as a packaging body of the vertical interconnection through holes, and the TGV technology has the function of building bridges for interconnection between I/O (input/output) ports with different pitches between a chip and a packaging substrate. Meanwhile, the chips or wafers are attached to the upper surface and the lower surface of the adapter plate, so that the chips and the wafers are interconnected in the vertical direction on the structure and the signal, the packaging circuit is expanded in the three-dimensional direction, and the miniaturization and high-density heterogeneous integration of the integrated circuit are facilitated.
The TGV through hole method adopting the common glass material is easy to cause edge breakage, cracks and low yield of the side wall of the through hole, the photosensitive glass ceramics can form crystals which are easy to dissolve in acid in an exposure area after ultraviolet exposure and heat treatment, the crystals have high etching speed, compared with the unexposed part of matrix glass, the crystal has the characteristic of high etching selection ratio, the TGV manufacturing method based on the photosensitive glass ceramics can realize the parallel manufacturing of the hole array, and the through holes with smaller diameter/space and larger depth-to-width ratio are easy to realize. In the prior art, researches on photosensitive glass-ceramic materials mainly focus on reducing the dielectric constant and dielectric loss of the materials, and in the TGV processing and application processes, the problems of high crystallization shrinkage rate, high matrix glass etching loss rate and the like in the TGV processing process of the photosensitive glass-ceramic may cause excessive warping, strength reduction and microcracks of a TGV adapter plate in subsequent application, and cause problems of insufficient soldering, delamination, fracture and the like of devices.
CN106746606A discloses a sensitizable photosensitive glass with reduced dielectric loss and a method for producing the same by introducing a glass component B of low polarizability 2 O 3 To achieve the effect of reducing dielectric constant and dielectric loss, but B 2 O 3 The introduction of (2) increases the refractive index of the glass, resulting in an increase in reflectivity, thereby reducing the transmittance at the ultraviolet exposure wavelength,causing an increase in the taper of the glass through-hole, and, in addition, B 2 O 3 The introduction of (2) causes an increase in crystallization shrinkage of the glass, resulting in warping or deformation of the glass substrate. Technical literature, "research on carrier materials of glass substrates with dense hole arrays, rujian, university of wuhan theory, university of majors academic thesis, P36, (2006)", experimentally observed that the phenomenon of excessive reduction in substrate thickness and significant decrease in strength is caused by inappropriate concentration of dilute HF acid, and that too low or too high concentration of dilute HF acid causes great damage to the glass substrate precursors. The reference does not quantify the etching loss rate of the photosensitive glass-ceramic matrix material, and does not study the influence of the photosensitive glass-ceramic component on the etching loss rate, which has a critical influence on the etching loss rate.
Disclosure of Invention
The invention aims to solve the technical problem of providing a photosensitive glass material with lower crystallization shrinkage and lower etching loss rate.
The technical problem to be solved by the invention is as follows:
the photosensitive glass material comprises the following components in percentage by weight: SiO 2 2 ：74.6～82.5％；Li 2 O：7.1～10.4％；R 2 O：1.4～8.7％；Al 2 O 3 ：2.1～6％；TiO 2 +Ag 2 O: 0.1 to 0.5% of SiO 2 /Li 2 O is 7.6 to 10.6, and R is 2 O is Na 2 O、K 2 One or two of O.
Further, the photosensitive glass material comprises the following components in percentage by weight: CeO (CeO) 2 : 0.02-0.06%; and/or Sb 2 O 3 : 0 to 1 percent; and/or MO: 0 to 4 percent; and/or ZnO: 0 to 3 percent; and/or ZrO 2 : 0-1%, wherein MO is one or two of MgO and CaO.
Photosensitive glass material, the composition of which is expressed by weight percentage of SiO 2 ：74.6～82.5％；Li 2 O：7.1～10.4％；R 2 O：1.4～8.7％；Al 2 O 3 ：2.1～6％；TiO 2 +Ag 2 O：0.1～0.5％；CeO 2 ：0.02～0.06％；Sb 2 O 3 ：0～1％；MO：0～4％；ZnO：0～3％；ZrO 2 : 0 to 1% of SiO 2 /Li 2 O is 7.6 to 10.6, and R is 2 O is Na 2 O、K 2 One or two of O, and MO is one or two of MgO and CaO.
Further, the photosensitive glass material comprises the following components in percentage by weight: SiO 2 2 /Li 2 O is 7.9 to 10.3.
Further, the photosensitive glass material comprises the following components in percentage by weight: al (Al) 2 O 3 /(TiO 2 +ZrO 2 ) 2.4 to 34.6, preferably Al 2 O 3 /(TiO 2 +ZrO 2 ) 5.9 to 21.6.
Further, the photosensitive glass material comprises the following components in percentage by weight: al (Al) 2 O 3 The ratio of Mo to Mo is 0.6-19, and Al is preferred 2 O 3 The ratio of/MO is 1.2-6.5, and the MO is one or two of MgO and CaO.
Further, the photosensitive glass material comprises the following components in percentage by weight: SiO 2 2 : 74.6-79.5%; and/or Li 2 O: 7.1-9.3%; and/or R 2 O: 2-5%; and/or Al 2 O 3 : 2.1-4.2%; and/or TiO 2 +Ag 2 O: 0.13-0.26%; and/or CeO 2 : 0.032-0.042%; and/or Sb 2 O 3 : 0.3-0.7%; and/or MO: 0.6-2.2%; and/or ZnO: 1.1-1.9%; and/or ZrO 2 : 0.1 to 0.6%, R 2 O is Na 2 O、K 2 One or two of O, and MO is one or two of MgO and CaO.
Further, the photosensitive glass material comprises the following components in percentage by weight: na (Na) 2 O: 0.1-4%, preferably Na 2 O: 1.1-4%; and/or K 2 O: 0.9-4.7%, preferably K 2 O: 1.5-4.3%; and/or MgO: 0-3%, preferably MgO: 0.6-2.2%; and/or CaO: 0-3%, preferably CaO: 0.2-1.2%; and/or TiO 2 : 0 to 0.2%, preferably TiO 2 : 0 to 0.1 percent; and/or Ag 2 O: 0.02-0.3%, preferably Ag 2 O：0.11～0.17％。
Further, the dielectric constant of the photosensitive glass material is 3.2-7.2, preferably 5.9-7.0; and/or a dielectric loss of 4.7X 10 -3 ～9.2×10 -3 Preferably 7.8X 10 -3 ～9.0×10 -3 (ii) a And/or the etching loss rate is 1.45% -2.60%, preferably 1.5% -2.0%; and/or a crystallization shrinkage of 2.0X 10 -4 ～13.2×10 -4 Preferably 3.0X 10 -4 ～8.0×10 -4 。
The invention has the beneficial effects that: through reasonable component design, the photosensitive glass material obtained by the invention has lower crystallization shrinkage and lower etching loss rate, and is suitable for preparing glass adapter plates, MEMS vacuum devices and the like.
Detailed Description
The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this.
[ photosensitive glass Material ]
The constituent components (components) of the photosensitive glass material of the present invention and the effects thereof will be described in detail below, and it should be noted that, in the present specification, the contents and the total amount of the respective components are expressed in weight percent (wt%), that is, the contents of the respective components are all expressed in weight percent with respect to the total amount of the glass substance converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%. The photosensitive glass material of the present invention is sometimes simply referred to as a glass material, or photosensitive glass, or glass.
Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include end-point values, as well as all integers and fractions within the range, and are not limited to the specific values recited in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
SiO 2 Is an oxide of glass former, forms an irregular continuous network with structural units of silicon-oxygen tetrahedron, forms the framework of glass, and is Si 4+ Has a low electron displacement polarizability (1.64X 10) 3 m -3 ) And thus has a lower dielectric constant. When SiO is present 2 When the content is less than 74.6%, the dielectric constant of the glass is increased, and the etching loss rate of the matrix glass is increased; but when SiO 2 When the content of (b) is more than 82.5%, the etching selectivity of the glass is lowered. Thus, SiO 2 The content of (b) is 74.6-82.5%, preferably 74.6-79.5%.
The main crystal phase of the precipitated crystal of the photosensitive glass material is lithium metasilicate (Li) 2 SiO 3 ) Alkali metal oxide Li 2 O is the main component of photosensitive glass material to form crystal, and can reduce the material melting temperature of the glass. When Li is present 2 When the O content is less than 7.1%, the crystal content of the glass is reduced, and in the area subjected to ultraviolet exposure, the glass crystal content is insufficient and is difficult to etch into a through hole; when Li is present 2 When the content of O is more than 10.4%, the glass of the unexposed portion is easily crystallized during the heat treatment, the etching loss rate of the matrix glass increases, and the dielectric constant and the dielectric loss of the glass increase. Thus, Li 2 The content of O is limited to 7.1 to 10.4%, preferably 7.1 to 9.3%.
The inventors have discovered that, in some embodiments, the rate of loss of substrate glass by etching is dependent on SiO 2 /Li 2 The value of O decreases as the SiO increases 2 /Li 2 When O is lower than 7.6, the etching loss rate of the matrix glass is increased, and the etching selection ratio of the glass is reduced; when SiO is present 2 /Li 2 When O exceeds 10.6, the etching loss rate of the matrix glass is low, but the crystal content of the crystallized portion is lowThe amount is low, and a through hole cannot be formed on the glass substrate by etching. Thus, in some embodiments, SiO is preferred 2 /Li 2 When the O is in the range of 7.6-10.6, the etching loss rate of the matrix glass is low, the high crystal content can be kept in a crystallization part, an etched through hole is easy to form, the glass substrate has high strength, microcracks are not easy to generate or the substrate is difficult to break, the circuit is protected, and the method is particularly suitable for preparing a glass adapter plate, and more preferably SiO 2 /Li 2 O is 7.9 to 10.3.
Alkali metal oxide R 2 O(R 2 O is Na 2 O、K 2 One or two of O) improves the formability of the glass and promotes the precipitation of lithium metasilicate crystals. When R is 2 When the O content is less than 1.4%, the crystal content of the glass is reduced, and the etching loss rate of a crystallized part is reduced; when R is 2 When the O content is more than 8.7%, the crystallization shrinkage, dielectric constant and dielectric loss of the glass increase, and Na is easily generated 2 SiO 3 And K 2 SiO 3 Etc. of other crystals, resulting in readily acid-soluble Li 2 SiO 3 The content is reduced, and the etching selection ratio of the glass is reduced. Thus, R 2 The content of O is limited to 1.4 to 8.7%, preferably 2 to 5%. In some embodiments, Na 2 The content of O is preferably 0.1-4%, more preferably 1.1-4%; k 2 The O content is preferably 0.9 to 4.7%, more preferably 1.5 to 4.3%.
Al 2 O 3 Can reduce the crystallization performance of the glass, improve the strength and the hardness of the glass, and Al 2 O 3 The glass has an enlarged forming range in a three-dimensional phase diagram, the chemical stability of the glass is enhanced, and the transmittance of the glass at an ultraviolet exposure wavelength of 313nm can be improved. When Al is present 2 O 3 When the content of (b) is less than 2.1%, the crystallization shrinkage of the glass increases; when Al is present 2 O 3 When the content of (b) is more than 6%, the etching selectivity of the glass is lowered. Thus, Al of the present invention 2 O 3 The content of (B) is limited to 2.1 to 6%, preferably 2.1 to 4.2%.
The alkaline earth metal oxide MO (MO is one or two of MgO and CaO) can improve the dielectric property and crystallization property of the glass, and when the content of MO is higher than 4%, the crystal content of the glass is reduced, and the dielectric constant and dielectric loss of the glass are increased. The content of MO in the present invention is limited to 0 to 4%, preferably 0.6 to 2.2%. In some embodiments, the MgO content is preferably 0 to 3%, more preferably 0.6 to 2.2%, and the CaO content is preferably 0 to 3%, more preferably 0.2 to 1.2%.
The inventors have discovered that, in some embodiments, Al is present when 2 O 3 MO is less than 0.6 or Al 2 O 3 When the ratio/MO is more than 19, the dielectric constant and dielectric loss of the glass increase, and when Al is contained 2 O 3 When the ratio/MO is larger than 19, the etching selectivity of the glass is lowered. Therefore, Al is preferable 2 O 3 When the/MO is within the range of 0.6-19, the dielectric constant and the dielectric loss of the glass are low, the glass has excellent dielectric property, can prevent signal distortion and reduce transmission power consumption, is beneficial to vertical transmission of high-frequency signals, and is more preferably Al 2 O 3 The ratio of MO to Mo is 1.2-6.5.
ZnO can increase the alkali resistance of the glass, and the photosensitive glass can be cleaned by adopting an alkali solution, and when the content of ZnO is higher than 3%, the etching selection ratio of the glass is reduced. Therefore, the content of ZnO in the present invention is limited to 0 to 3%, preferably 1.1 to 1.9%.
TiO 2 And Ag 2 O as a composite nucleating agent for photosensitive glass materials, TiO 2 Can increase the crystal content of the glass and refine the grain size, TiO 2 And Ag 2 Too low of O content to act as a nucleating agent, TiO 2 Too high a content causes crystallization of the unexposed portion, resulting in an increase in the etching loss rate of the matrix glass, while Ag 2 The excessive O content is easy to deposit in the high-temperature melting process, and the crystallization performance of the photosensitive glass material is influenced. The invention adopts TiO 2 And Ag 2 O as a composite nucleating agent when TiO 2 +Ag 2 When the O content is less than 0.1%, the content of precipitated crystals is low, and the etching selection ratio of the glass is reduced; when TiO is present 2 +Ag 2 When O exceeds 0.5%, the etching loss rate of the matrix glass increases. Thus, TiO 2 +Ag 2 The content of O is limited to 0.1 to 0.5%, preferably 0.13 to 0.26 percent. In some embodiments, the TiO 2 The content of (b) is preferably 0 to 0.2%, more preferably 0 to 0.1%; ag 2 The content of O is preferably 0.02 to 0.3%, more preferably 0.11 to 0.17%.
ZrO 2 Can improve the crystallization performance of the glass, refine the grain size and reduce the crystallization shrinkage of the matrix glass. When ZrO 2 When the content is higher than 1%, the content of glass crystals is reduced, and the taper of the glass through hole is increased. Thus, ZrO 2 The content of (B) is limited to 0 to 1%, preferably 0.1 to 0.6%.
The inventors have discovered that, in some embodiments, Al is present when 2 O 3 /(TiO 2 +ZrO 2 ) And in the range of 2.4-34.6, the crystallization shrinkage rate of the glass is low, so that the excessive warping of the glass adapter plate after TGV processing is reduced, and the problems of insufficient soldering, layering, failure and the like of devices are solved. Therefore, Al is preferable 2 O 3 /(TiO 2 +ZrO 2 ) 2.4 to 34.6, more preferably Al 2 O 3 /(TiO 2 +ZrO 2 ) 5.9 to 21.6.
CeO 2 Is a photosensitizer, is Ag + Donates electrons when CeO 2 When the content is less than 0.02%, sufficient electrons cannot be supplied, resulting in excessively low crystal content and lowering of etching selectivity of the glass, and when CeO is used 2 When the content is higher than 0.06%, the transmittance of the glass in an ultraviolet exposure wave band of 313nm is reduced, the penetration depth of ultraviolet light is reduced, and the through hole taper of the glass is increased. Thus, CeO 2 The content of (B) is limited to 0.02 to 0.06%, preferably 0.032 to 0.042%.
Sb 2 O 3 As a reducing agent, can maintain Ce in the glass 3+ And Ce 4+ Can also play a role of a clarifying agent and improve the transmittance of the glass, Sb 2 O 3 The content of (B) is limited to 0 to 1%, preferably 0.3 to 0.7%.
"0%" or "0%" is not included in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the glass of the present invention as a raw material; however, it is also within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the glass, and may be present in small or trace amounts in the final glass.
Next, the properties of the photosensitive glass material of the present invention will be described.
< dielectric constant >
Dielectric constant (. epsilon.) of glass r ) The measurement is carried out according to the national standard GB/T7265.1-1987 method for testing the complex dielectric constant of solid dielectric microwave-perturbation method, and the data under the condition of 1GHz is tested.
In some embodiments, the dielectric constant (. epsilon.) of the glasses of the invention r ) 3.2 to 7.2, preferably 5.9 to 7.0.
< dielectric loss >
The dielectric loss (tan delta) of the glass is measured according to the national standard GB/T7265.1-1987 method for testing the microwave complex dielectric constant of the solid dielectric, namely perturbation method, and data under the condition of 1GHz are tested.
In some embodiments, the glass of the present invention has a dielectric loss (tan δ) of 4.7 × 10 -3 ～9.2×10 -3 Preferably 7.8X 10 -3 ～9.0×10 -3 。
< etching loss ratio of matrix glass >
The samples with both polished sides (the sample of this example having a size of 30X 1mm) were subjected to heat treatment at 560 ℃. After the heat treatment is finished, the glass sample is placed into an HF acid solution with the mass ratio of 5%, the sample is etched for 10min under the ultrasonic condition of 50kHz, the sample is cleaned and dried by using distilled water after the etching is finished, the weight of the glass sample before and after the acid etching is respectively weighed, the weighing precision is 0.1mg, and the weight loss rate of the glass sample, namely the etching loss rate delta l of the matrix glass, is calculated according to the formula (1).
Δ1＝(m 1 -m 2 )/m 1 (1)
In the formula, m 1 Weight of the sample before acid etching, m 2 Is the weight of the sample after acid etching.
It should be noted that the sample was not subjected to uv exposure, and in addition, the etching loss rate generally increased with the increase of the acid etching time, HF acid concentration, and ultrasonic frequency, and therefore the index required definite test conditions.
In some embodiments, the glass of the present invention has an etch loss ratio (Δ l) of 1.45% to 2.60%, preferably 1.5% to 2.0%.
< crystallization shrinkage >
The crystallization shrinkage rate is the ratio of the glass size variation of a photosensitive glass material after ultraviolet irradiation and heat treatment to the original size of the glass, and represents the size variation of the glass before and after crystallization, and the variation of the glass before and after heat treatment/the length of the glass before heat treatment is the crystallization shrinkage rate (eta) of the glass.
In some embodiments, the glass of the present invention has a crystallization shrinkage (η) of 2.0 × 10 -4 ～13.2×10 -4 Preferably 3.0X 10 -4 ～8.0×10 -4 。
[ method for producing photosensitive glass Material ]
The method for manufacturing glass of the present invention comprises the steps of: selecting a glass formula, weighing the raw materials according to the weight percentage of the components, fully mixing, adding into a platinum crucible, melting at 1450-1600 ℃ (atmosphere control is needed), clarifying, homogenizing and cooling; pouring the molten glass into a metal mold preheated to about 450 ℃ for molding, and introducing circulating cooling air to ensure that the glass does not crystallize; and putting the formed glass and the metal mold into an annealing furnace for heat preservation and annealing, and then cooling along with the furnace after power failure to obtain the transparent glass.
Examples
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided. Many efforts have been made to ensure accuracy with respect to numbers in the embodiments of the invention, but some errors and deviations should be accounted for.
In examples 1 to 20# the photosensitive glass materials having the compositions shown in tables 1 to 2 were obtained by the above-mentioned manufacturing method of the photosensitive glass materials, and the properties of the glass were tested by the above-mentioned test method.
Table 1.
Table 2.
Claims (9)
1. Photosensitive glass material, characterized in that its composition, expressed in weight percent, contains: SiO 2 2 ：74.6～82.5％；Li 2 O：7.1～10.4％；R 2 O：1.4～8.7％；Al 2 O 3 ：2.1～6％；TiO 2 +Ag 2 O: 0.1 to 0.5% of SiO 2 /Li 2 O is 7.6 to 10.6, and R is 2 O is Na 2 O、K 2 One or two of O.
2. The photosensitive glass material according to claim 1, further comprising, in terms of weight percent: CeO (CeO) 2 : 0.02-0.06%; and/or Sb 2 O 3 : 0 to 1 percent; and/or MO: 0 to 4 percent; and/or ZnO: 0 to 3 percent; and/or ZrO 2 : 0-1%, wherein MO is one or two of MgO and CaO.
3. Photosensitive glass material, characterized in that its composition is represented by weight percent SiO 2 ：74.6～82.5％；Li 2 O：7.1～10.4％；R 2 O：1.4～8.7％；Al 2 O 3 ：2.1～6％；TiO 2 +Ag 2 O：0.1～0.5％；CeO 2 ：0.02～0.06％；Sb 2 O 3 ：0～1％；MO：0～4％；ZnO：0～3％；ZrO 2 : 0 to 1% of SiO 2 /Li 2 O is 7.6 to 10.6, and R is 2 O is Na 2 O、K 2 One or two of O, and MO is one or two of MgO and CaO.
4. A photosensitive glass material according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: SiO 2 2 /Li 2 O is 7.9 to 10.3.
5. A photosensitive glass material according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: al (Al) 2 O 3 /(TiO 2 +ZrO 2 ) 2.4 to 34.6, preferably Al 2 O 3 /(TiO 2 +ZrO 2 ) 5.9 to 21.6.
6. A photosensitive glass material according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: al (Al) 2 O 3 The ratio of/MO is 0.6 to 19, and Al is preferred 2 O 3 The ratio of/MO is 1.2-6.5, and the MO is one or two of MgO and CaO.
7. A photosensitive glass material according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: SiO 2 2 : 74.6-79.5%; and/or Li 2 O: 7.1-9.3%; and/or R 2 O: 2-5%; and/or Al 2 O 3 : 2.1-4.2%; and/or TiO 2 +Ag 2 O: 0.13-0.26%; and/or CeO 2 : 0.032-0.042%; and/or Sb 2 O 3 : 0.3-0.7%; and/or MO: 0.6-2.2%; and/or ZnO: 1.1-1.9%; and/or ZrO 2 : 0.1 to 0.6%, R 2 O is Na 2 O、K 2 One or two of O, and MO is one or two of MgO and CaO.
8. A photosensitive glass material according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: na (Na) 2 O: 0.1-4%, preferably Na 2 O: 1.1-4%; and/or K 2 O: 0.9-4.7%, preferably K 2 O: 1.5-4.3%; and/or MgO: 0-3%, preferably MgO: 0.6-2.2%; and/or CaO: 0-3%, preferably CaO: 0.2-1.2%; and/or TiO 2 : 0 to 0.2%, preferably TiO 2 : 0 to 0.1 percent; and/or Ag 2 O: 0.02-0.3%, preferably Ag 2 O：0.11～0.17％。
9. The photosensitive glass material according to any one of claims 1 to 3, wherein the dielectric constant of the photosensitive glass material is 3.2 to 7.2, preferably 5.9 to 7.0; and/or a dielectric loss of 4.7X 10 -3 ～9.2×10 -3 Preferably 7.8X 10 -3 ～9.0×10 -3 (ii) a And/or the etching loss rate is 1.45% -2.60%, preferably 1.5% -2.0%; and/or a crystallization shrinkage of 2.0X 10 -4 ～13.2×10 -4 Preferably 3.0X 10 -4 ～8.0×10 -4 。
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| CN111718120A (en) * | 2020-07-09 | 2020-09-29 | 电子科技大学 | Li-Al-Si photosensitive glass and preparation method thereof |
| CN112243430A (en) * | 2018-02-19 | 2021-01-19 | 康宁股份有限公司 | High-strength transparent glass ceramic container |
| WO2021238476A1 (en) * | 2020-05-27 | 2021-12-02 | 成都光明光电股份有限公司 | Glass material |
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| US20040180773A1 (en) * | 2003-02-03 | 2004-09-16 | Schott Glas | Photostructurable body and process for treating a glass and/or a glass-ceramic |
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| US20170003421A1 (en) * | 2014-01-24 | 2017-01-05 | 3D Glass Solutions, Inc | Methods of Fabricating Photoactive Substrates for Micro-lenses and Arrays |
| CN112243430A (en) * | 2018-02-19 | 2021-01-19 | 康宁股份有限公司 | High-strength transparent glass ceramic container |
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| CN114873918B (en) | 2023-08-08 |
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