CN114873918B - Photosensitive glass material - Google Patents
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- CN114873918B CN114873918B CN202210722719.0A CN202210722719A CN114873918B CN 114873918 B CN114873918 B CN 114873918B CN 202210722719 A CN202210722719 A CN 202210722719A CN 114873918 B CN114873918 B CN 114873918B
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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 rate and lower etching loss rate. The photosensitive glass material comprises the following components in percentage by weight: siO (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 to 0.5 percent, wherein SiO 2 /Li 2 O is 7.6-10.6, 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 rate 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 rate and lower etching loss rate.
Background
Photosensitive glass ceramics are glass materials that undergo structural changes upon irradiation with light of a specific wavelength to exhibit a particular property. Under the irradiation of ultraviolet light, the inside of the photosensitive microcrystalline glass is structurally changed to generate crystal nuclei, and a large number of microcrystalline glass with specific components can be generated in an irradiation area after heat treatment is continued at a certain temperature. The glass through hole (TGV) technology is a key technology for preparing glass adapter plates, integrated passive devices and MEMS vacuum devices, is structurally characterized in that vertical interconnection through holes are formed by being contained in different materials, can be regarded as a package body of the vertical interconnection through holes, and has the function of building bridges for interconnection between I/O ports with different pitches between chips and package substrates. Meanwhile, through the mounting of the chips or the wafers on the upper surface and the lower surface of the adapter plate, the vertical interconnection of the chips and the wafers in the structure and the signal is realized, so that 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 common glass materials is easy to cause edge breakage, cracks and low yield of the side wall of the through hole, and after ultraviolet exposure and heat treatment, the photosensitive microcrystalline glass can form crystals which are easy to dissolve in acid in an exposure area, the crystal etching speed is high, compared with the substrate glass of an unexposed part, the method has the characteristic of high etching selectivity, the TGV manufacturing method based on the photosensitive microcrystalline glass can realize parallel manufacturing of a hole array, and is easy to realize through holes with smaller diameter/interval and larger depth-to-width ratio. In the prior art, researches on photosensitive microcrystalline glass materials are mainly focused on reducing dielectric constants and dielectric losses of the materials, and in the TGV processing and application processes, problems of high crystallization shrinkage rate, high matrix glass etching loss rate and the like also occur in the TGV processing process of the photosensitive microcrystalline glass, and the problems of excessive warping, strength reduction, microcrack, device cold welding, layering, breakage and the like of a TGV adapter plate in subsequent applications can be caused.
CN106746606a discloses a sensitized photosensitive glass with reduced dielectric loss and a production method thereof by introducing a glass component B with low polarization rate 2 O 3 Achieve the effect of reducing dielectric constant and dielectric loss, but B 2 O 3 The introduction of (a) increases the refractive index of the glass, resulting in an increase in reflectivity, thereby decreasing transmittance at ultraviolet exposure wavelength, resulting in an increase in taper of the glass via hole, and (B) 2 O 3 The introduction of (a) causes an increase in the crystallization shrinkage of the glass, resulting in warpage or deformation of the glass substrate. The research on dense hole array glass substrate carrier materials in the scientific literature Ruan Jian, the university of martial arts, shuoshi institute paper, P36, (2006) has been found through experiments that excessive reduction of the substrate thickness and obvious reduction of the strength are caused by discomfort of the concentration of dilute HF acid, and the too low or too high concentration of the dilute HF acid can cause great damage to the glass substrate matrix. The literature does not quantify the etching loss rate of the photosensitive microcrystalline glass matrix material, and does not study the influence of the photosensitive microcrystalline glass component on the etching loss rate, while the photosensitive microcrystalline glass component has a critical influence on the etching loss rate.
Disclosure of Invention
The invention aims to provide a photosensitive glass material with lower crystallization shrinkage and lower etching loss rate.
The invention solves the technical problems by adopting the following solution:
the photosensitive glass material comprises the following components in percentage by weight: siO (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 to 0.5 percent, wherein SiO 2 /Li 2 O is 7.6-10.6, 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 to 0.06 percent; 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 components of which are represented by weight percentage by 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 7.6-10.6, R is 2 O is Na 2 O、K 2 One or two of O, MO is one or two of MgO and CaO.
Further, the photosensitive glass material comprises the following components in percentage by weight: siO (SiO) 2 /Li 2 O is 7.9-10.3.
Further, the photosensitive glass material comprises the following components in percentage by weight: al (Al) 2 O 3 /(TiO 2 +ZrO 2 ) From 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 MO is 0.6 to 19, preferably Al 2 O 3 And MO is 1.2-6.5, and MO is one or two of MgO and CaO.
Further, the photosensitive glass material comprises the following components in percentage by weight: siO (SiO) 2 :74.6 to 79.5 percent; and/or Li 2 O:7.1 to 9.3 percent; and/or R 2 O: 2-5%; and/or Al 2 O 3 :2.1 to 4.2 percent; and/or TiO 2 +Ag 2 O:0.13 to 0.26 percent; and/or CeO 2 :0.032 to 0.042 percent; and/or Sb 2 O 3 :0.3 to 0.7 percent; and/or MO:0.6 to 2.2 percent; and/or ZnO:1.1 to 1.9 percent; and/or ZrO 2 :0.1 to 0.6 percent, R is as follows 2 O is Na 2 O、K 2 One or two of O, 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 to 4%, preferably Na 2 O:1.1 to 4 percent; and/or K 2 O:0.9 to 4.7%, preferably K 2 O:1.5 to 4.3 percent; and/or MgO:0 to 3%, preferably MgO:0.6 to 2.2 percent; and/or CaO:0 to 3%, preferably CaO:0.2 to 1.2 percent; and/or TiO 2 :0 to 0.2%, preferably TiO 2 :0 to 0.1 percent; and/or Ag 2 O:0.02 to 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 dielectric loss of 4.7X10 -3 ～9.2×10 -3 Preferably 7.8X10 -3 ～9.0×10 -3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the etching loss rate is 1.45% -2.60%, preferably 1.5% -2.0%; and/or a crystallization shrinkage of 2.0X10 -4 ～13.2×10 -4 Preferably 3.0X10 -4 ～8.0×10 -4 。
The beneficial effects of the invention are as follows: through reasonable component design, the photosensitive glass material obtained by the invention has lower crystallization shrinkage rate and lower etching loss rate, and is suitable for preparing glass adapter plates, MEMS vacuum devices and the like.
Detailed Description
The following describes embodiments of the present invention in detail, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In the repeated explanation, explanation is omitted appropriately, but the gist of the invention is not limited thereto.
[ photosensitive glass Material ]
In the following, the constituent components (components) of the photosensitive glass material of the present invention and their functions will be described in detail, and it should be noted that, in the present specification, unless otherwise specified, the content of each component, the total amount, are expressed in weight percent (wt%), that is, the content of each component is expressed in weight percent with respect to the total amount of glass substance converted into the composition of oxide. The term "composition converted into oxide" as used herein means that the total amount of oxide used as a raw material of the glass composition of the present invention is 100% when the oxide, composite salt, hydroxide, or the like is decomposed and converted into oxide by melting. The photosensitive glass material of the present invention is sometimes referred to simply as a glass material, or photosensitive glass, or glass.
Unless otherwise indicated in a particular context, numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "and/or" as used herein is inclusive, e.g. "a and/or B", meaning either a alone, B alone, or both a and B.
SiO 2 Is a glass-forming oxide, forms an irregular continuous network with structural units of silicon oxygen tetrahedra, forms a framework of glass, and is Si 4+ Has lower electron displacement polarization ratio (1.64×10) 3 m -3 ) And thus has a low dielectric constant. When SiO 2 When the content is less than 74.6%, glassThe 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 (2) is higher than 82.5%, the etching selectivity of the glass decreases. Thus, siO 2 The content of (2) is in the range of 74.6 to 82.5%, preferably 74.6 to 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 the photosensitive glass material to form crystals, and can reduce the melting temperature of the glass. When Li 2 When the O content is less than 7.1%, the crystal content of the glass is reduced, and the glass is insufficient in crystal content and difficult to etch into a through hole after passing through an ultraviolet exposure area; when Li 2 When the O content is more than 10.4%, the glass in the unexposed portion is liable to devitrify during the heat treatment, the etching loss rate of the matrix glass increases, and the dielectric constant and dielectric loss of the glass increase. Thus Li 2 The O content is limited to 7.1 to 10.4%, preferably 7.1 to 9.3%.
The inventors have found that in some embodiments, the substrate glass etch loss rate is a function of SiO 2 /Li 2 The value of O is increased and decreased, when SiO 2 /Li 2 When O is lower than 7.6, the etching loss rate of the matrix glass is increased, and the etching selectivity of the glass is reduced; when SiO 2 /Li 2 When O exceeds 10.6, the etching loss rate of the matrix glass is low, but the crystalline content of the crystallized portion is low, and the through hole cannot be etched on the glass substrate. Thus, in some embodiments, siO is preferred 2 /Li 2 When O is in the range of 7.6-10.6, the etching loss rate of the matrix glass is lower, meanwhile, the crystallization part can keep higher crystal content, etching through holes are easy to form, the glass substrate has higher strength, microcrack is not easy to generate or substrate breakage phenomenon is not easy to generate, the effect of protecting a circuit is achieved, and the glass substrate is particularly suitable for preparing glass adapter plates, and more preferably SiO 2 /Li 2 O is 7.9-10.3.
Alkali metal oxide R 2 O(R 2 O is Na 2 O、K 2 One or two of O) can improve the forming property of the glass and promote the precipitation of lithium metasilicate crystals. When R is 2 O content is less thanWhen the content of the glass is 1.4%, the crystal content of the glass is reduced, and the etching loss rate of a crystallization 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 are increased, and Na is easily generated 2 SiO 3 And K 2 SiO 3 And other crystals, leading to Li readily soluble in acid 2 SiO 3 The content is reduced, and the etching selectivity of the glass is reduced. Thus, R is 2 The content of O is limited to 1.4 to 8.7%, preferably 2 to 5%. In some embodiments, na 2 The O content is preferably 0.1 to 4%, more preferably 1.1 to 4%; k (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 crystallization performance of glass, improve strength and hardness of glass, and Al 2 O 3 The existence of the glass can enlarge the molding range of the glass in the three-dimensional phase diagram, enhance the chemical stability of the glass, and simultaneously improve the transmittance of the glass at the ultraviolet exposure wavelength of 313 nm. When Al is 2 O 3 When the content of (2) is less than 2.1%, the crystallization shrinkage of the glass increases; when Al is 2 O 3 When the content of (2) is higher than 6%, the etching selectivity of the glass decreases. Thus, the Al of the present invention 2 O 3 The content of (2) is limited to 2.1 to 6%, preferably 2.1 to 4.2%.
The alkaline earth metal oxide MO (MO is one or both of MgO and CaO) can improve dielectric properties and crystallization properties of the glass, and when the MO content is higher than 4%, the crystal content of the glass decreases and the dielectric constant and dielectric loss of the glass increase. The MO content of 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 found that, in some embodiments, when Al 2 O 3 MO is less than 0.6 or Al 2 O 3 When the MO is more than 19, the dielectric constant and dielectric loss of the glass are increased, and when Al 2 O 3 When the MO is more than 19, the etching selectivity of the glass decreases. Therefore, al is preferable 2 O 3 MO is 0.6 to the whole within 19The dielectric constant and 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 MO is 1.2 to 6.5.
ZnO can increase the alkali resistance of the glass, alkaline solution can be used for cleaning the photosensitive glass, and when the content of ZnO is higher than 3%, the etching selectivity of the glass is reduced. Accordingly, 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 is used as a composite crystal nucleus agent of photosensitive glass material, and TiO is used as a material of the photosensitive glass material 2 Can increase the crystal content of glass, refine the grain size and make TiO 2 And Ag 2 Too little O content can not function as a crystal nucleus agent, and 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 O content is too high, so that the O is easy to deposit in the high-temperature melting process, and the crystallization performance of the photosensitive glass material is affected. The invention adopts TiO 2 And Ag 2 O is used as a composite crystal nucleus agent, when TiO 2 +Ag 2 When the O content is lower than 0.1%, the content of precipitated crystals is lower, and the etching selectivity of glass is reduced; when TiO 2 +Ag 2 When O exceeds 0.5%, the etching loss rate of the matrix glass increases. Thus, tiO 2 +Ag 2 The O content is limited to 0.1 to 0.5%, preferably 0.13 to 0.26%. In some embodiments, the TiO 2 The content of (2) is preferably 0 to 0.2%, more preferably 0 to 0.1%; ag (silver) 2 The content of O is preferably 0.02 to 0.3%, more preferably 0.11 to 0.17%.
ZrO 2 Can improve crystallization performance of glass, refine grain size and reduce crystallization shrinkage of matrix glass. When ZrO (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 (2) is limited to 0 to 1%, preferably 0.1 to 0.6%.
The inventors have found that, in some embodiments, when Al 2 O 3 /(TiO 2 +ZrO 2 ) When the glass is in the range of 2.4 to 34.6, the crystallization shrinkage rate of the glass is low, which is beneficial to reducingAnd the excessive warping of the glass adapter plate after the small TGV processing solves the problems of cold joint, layering, failure and the like of the device. Therefore, al is preferable 2 O 3 /(TiO 2 +ZrO 2 ) From 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 + Providing electrons when CeO 2 When the content is less than 0.02%, sufficient electrons cannot be provided, so that the crystal content is too low, the etching selectivity of the glass is lowered, and when CeO 2 When the content is higher than 0.06%, the transmittance of the glass in the ultraviolet exposure wave band of 313nm is reduced, the penetration depth of ultraviolet light is reduced, and the taper of the through hole of the glass is increased. Thus, ceO 2 The content of (2) is limited to 0.02 to 0.06%, preferably 0.032 to 0.042%.
Sb 2 O 3 As a reducing agent, ce in the glass can be maintained 3+ And Ce (Ce) 4+ Meanwhile, the glass also plays a role of a clarifying agent, improves the transmittance of the glass and Sb 2 O 3 The content of (2) is limited to 0 to 1%, preferably 0.3 to 0.7%.
The term "not containing" or "0%" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the glass of the present invention; however, it is within the scope of the present invention that certain impurities or components may be present as raw materials and/or equipment for producing the glass that are not intentionally added, and that may be present in minor or trace amounts in the final glass.
The properties of the photosensitive glass material of the present invention will be described below.
< dielectric constant >
Dielectric constant (. Epsilon.) of glass r ) The data under the condition of 1GHz are tested according to the measurement of the national standard GB/T7265.1-1987 test method of microwave complex dielectric constant, namely the perturbation method.
In some embodiments, the glass of the present invention has a dielectric constant (. Epsilon.) 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 test method of microwave complex dielectric constant of 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 delta) of 4.7X10 -3 ～9.2×10 -3 Preferably 7.8X10 -3 ～9.0×10 -3 。
< substrate glass etching loss Rate >
Two-sided polished samples (30X 1mm in the sample specification of this example) were heat treated at 560 ℃. After the heat treatment is finished, the glass sample is put into an HF acid solution with the mass ratio of 5%, the sample is etched for 10min under the ultrasonic condition of 50kHz, distilled water is adopted for cleaning and drying 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 Deltal of the matrix glass, is calculated according to the formula (1).
Δ1＝(m 1 -m 2 )/m 1 (1)
Wherein m is 1 For the 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 is not exposed to ultraviolet light, and in addition, the etching loss rate generally increases with the increase of the acid etching time, the HF acid concentration and the ultrasonic frequency, so that the index requires clear test conditions.
In some embodiments, the glass of the present invention has an etch loss rate (Δl) of 1.45% to 2.60%, preferably 1.5% to 2.0%.
< crystallization shrinkage >
The crystallization shrinkage rate refers to the ratio of the size change of glass to the original size of glass after ultraviolet irradiation and heat treatment of a photosensitive glass material, and represents the size change of glass before and after crystallization, wherein the change of glass before and after heat treatment/the length before heat treatment is the crystallization shrinkage rate (eta) of glass.
In some embodiments, the glass of the present invention has a crystallization shrinkage (. Eta.) of 2.0X10 -4 ～13.2×10 -4 Preferably 3.0X10 -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 according to the weight percentage of the raw materials corresponding to the components, fully mixing, adding into a platinum crucible, melting at 1450-1600 ℃ (attention is paid to atmosphere control), 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 is not devitrified; and (3) placing the formed glass and the metal mold into an annealing furnace for heat preservation and annealing, and then powering off and cooling along with the furnace to obtain the transparent glass.
Examples
In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided. Embodiments of the present invention take numerous efforts to ensure accuracy with respect to numbers but some errors and deviations should be accounted for.
The photosensitive glass materials having the compositions shown in tables 1 to 2 were obtained by the above-described manufacturing method of the photosensitive glass material, and the properties of the glasses were tested by the above-described test method.
Table 1.
Table 2.
Claims (12)
1. The photosensitive glass material is characterized by comprising the following components in percentage by weight: siO (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 to 0.5 percent, wherein SiO 2 /Li 2 O is 7.6-10.6, al 2 O 3 /(TiO 2 +ZrO 2 ) 4.8 to 34.6, R is as follows 2 O is Na 2 O、K 2 One or two of O.
2. The photosensitive glass material according to claim 1, wherein the composition thereof is expressed in weight percent, further comprising: ceO (CeO) 2 :0.02 to 0.06 percent; 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. A photosensitive glass material characterized in that the components thereof are represented by weight percentage by 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 7.6-10.6, al 2 O 3 /(TiO 2 +ZrO 2 ) 4.8 to 34.6, R is as follows 2 O is Na 2 O、K 2 One or two of O, MO is one or more of MgO and CaOTwo kinds.
4. A photosensitive glass material according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: siO (SiO) 2 /Li 2 O is 7.9-10.3.
5. A photosensitive glass material according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: al (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 components thereof are expressed in weight percent, wherein: al (Al) 2 O 3 And MO is 0.6-19, and 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 components thereof are expressed in weight percent, wherein: al (Al) 2 O 3 And MO is 1.2-6.5, 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 components thereof are expressed in weight percent, wherein: siO (SiO) 2 :74.6 to 79.5 percent; and/or Li 2 O:7.1 to 9.3 percent; and/or R 2 O: 2-5%; and/or Al 2 O 3 :2.1 to 4.2 percent; and/or TiO 2 +Ag 2 O:0.13 to 0.26 percent; and/or CeO 2 :0.032 to 0.042 percent; and/or Sb 2 O 3 :0.3 to 0.7 percent; and/or MO:0.6 to 2.2 percent; and/or ZnO:1.1 to 1.9 percent; and/or ZrO 2 :0.1 to 0.6 percent, R is as follows 2 O is Na 2 O、K 2 One or two of O, MO is one or two of MgO and CaO.
9. A photosensitive glass material according to any one of claims 1 to 3, whereinThe components are expressed in weight percent, wherein: na (Na) 2 O:0.1 to 4 percent; and/or K 2 O:0.9 to 4.7 percent; and/or MgO:0 to 3 percent; and/or CaO:0 to 3 percent; and/or TiO 2 :0 to 0.2 percent; and/or Ag 2 O：0.02～0.3％。
10. A photosensitive glass material according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: na (Na) 2 O:1.1 to 4 percent; and/or K 2 O:1.5 to 4.3 percent; and/or MgO:0.6 to 2.2 percent; and/or CaO:0.2 to 1.2 percent; and/or TiO 2 :0 to 0.1 percent; and/or Ag 2 O：0.11～0.17％。
11. A photosensitive glass material according to any of claims 1-3, wherein the dielectric constant of said photosensitive glass material is 3.2-7.2; and/or dielectric loss of 4.7X10 -3 ～9.2×10 -3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the etching loss rate is 1.45% -2.60%; and/or a crystallization shrinkage of 2.0X10 -4 ～13.2×10 -4 。
12. A photosensitive glass material according to any of claims 1-3, wherein the dielectric constant of said photosensitive glass material is 5.9-7.0; and/or dielectric loss of 7.8X10 -3 ～9.0×10 -3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the etching loss rate is 1.5% -2.0%; and/or a crystallization shrinkage of 3.0X10 -4 ～8.0×10 -4 。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5098915A (en) * | 1973-12-29 | 1975-08-06 | ||
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| US7799711B2 (en) * | 2007-08-31 | 2010-09-21 | Corning Incorporated | Photomachinable glass compositions having tunable photosensitivity |
| US20170003421A1 (en) * | 2014-01-24 | 2017-01-05 | 3D Glass Solutions, Inc | Methods of Fabricating Photoactive Substrates for Micro-lenses and Arrays |
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