CN110937805B - Photoetching lithium-aluminum-silicon glass material and preparation method and application thereof - Google Patents
Photoetching lithium-aluminum-silicon glass material and preparation method and application thereof Download PDFInfo
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- CN110937805B CN110937805B CN201911063645.9A CN201911063645A CN110937805B CN 110937805 B CN110937805 B CN 110937805B CN 201911063645 A CN201911063645 A CN 201911063645A CN 110937805 B CN110937805 B CN 110937805B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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Abstract
The invention relates to a photoetching lithium-aluminum-silicon glass material and a preparation method and application thereof, wherein the lithium-aluminum-silicon glass material comprises the following components in percentage by weight: SiO 2272～76wt％；Li2O 10～15wt％；K2O 3～4wt％；Al2O36～8wt％；Na2O 2～3wt％；ZnO 1～1.2wt％；Sb2O30.8～1.5wt％；Ce2O30.04～0.08wt％；Ag20.04-0.08 wt% of O. The photoetching lithium-aluminum-silicon glass material prepared by the invention has simple and clear material components and convenient production process, and the prepared glass material has the same photosensitivity with the same type of glass.
Description
Technical Field
The invention belongs to the field of glass materials, and particularly relates to a photoetching lithium-aluminum-silicon glass material and a preparation method and application thereof.
Background
The photoetchable lithium-aluminum-silicon glass is a functional glass material compatible with microelectronic technology, can be prepared into a specific microstructure on the surface or inside through ultraviolet photoetching and wet etching technology, and is widely applied to the fields of communication, aerospace, biomedicine and the like.
The processing characteristics of the photoetchable lithium-aluminum-silicon glass come from the micro light in the glass componentsSensitizers (Ce)2O3) Crystal nucleus agent (Ag)2O) and a weak reducing agent (Sb)2O3). Wherein the cerium ion having photosensitivity is Ce3+And Ce4+Is present in the glass network, and the weak reducing agent Sb2O3Then maintain Ce3+Relative amounts of (c). Under ultraviolet light (about 312nm), Ce3+Absorb photon energy to release free electrons, Ag+And combining with one free electron to form silver atom, and diffusing and aggregating a plurality of silver atoms to form the colloidal silver nano-particles. In the glass network structure, the colloidal silver particles act as nucleating agents, inducing the growth of the lithium metasilicate crystal phase. In dilute HF solutions, the rate of dissolution of the lithium metasilicate crystalline phase is about 30 times the rate of dissolution of the glassy phase. Thus, the lithium metasilicate crystal phase in the exposed regions will be preferentially etched away, and the unexposed regions will remain, thereby producing a particular structure consisting of a glass phase.
The Schottky company discloses a Foturan photoetching glass which comprises SiO2 75～85wt％，Li2O 7～11wt％，K2O and Al2O3 3～6wt％，Na2O 1～2wt％，ZnO＜2wt％，Sb2O3 0.2～0.4wt％，Ce2O30.01～0.04wt％，Ag20.05-0.15 wt% of O, and the photoetching glass has large dielectric constant and large dielectric loss, so that the photoetching glass is difficult to meet the application in the field of electronic devices. University of electronic technology discloses photoetching glass with SiO as component2 63～72wt％，Li2O 6～12wt％，Na2O 1～5wt％，K2O 3～9wt％，Al2O3 2～5wt％，ZnO 1～4wt％，Sb2O3 0.5～0.9wt％，Ce2O3 0.02～0.06wt％，Ag2O 0.09～0.16wt％，B2O32 to 5 wt%, BaO 0.5 to 2 wt% or (and) CaO 0.5 to 3 wt%, MgO 1 to 5 wt%, and at 1MHz, the dielectric coefficient is 4.2 to 5.6, and the dielectric loss is 2 to 4 x 10-3The photodefinable glass is improved and greatly improved in dielectric properties, but found in applications due to the Si in the glass2Mass% of OThe ratio is greatly reduced, the ratio of alkali metal oxide is larger, the glass strength is also greatly reduced, the photoetching glass substrate is easy to crack after being subjected to microstructure processing, and the Young modulus is less than 10GPa, so that the use requirement cannot be met.
Disclosure of Invention
Aiming at the defects of dielectric property and mechanical property of photoetching glass in the prior art, the invention aims to provide a photoetching lithium-aluminum-silicon glass material with low dielectric loss and high mechanical strength, a preparation method and application thereof, which reduce the dielectric loss of a glass substrate during high-frequency working on the premise of ensuring the excellent photoetching property of the glass, ensure that certain mechanical strength is achieved to meet the subsequent processing and assembly requirements, and finally realize the application of photoetching glass in the field of microelectronics.
In order to achieve the above object, the present invention provides a lithographically-processable lithium aluminum silicon glass material, which comprises the following components by weight:
SiO2 72～76wt％；Li2O 10～15wt％；K2O 3～4wt％；Al2O3 6～8wt％；Na2O 2～3wt％；ZnO 1～1.2wt％；Sb2O3 0.8～1.5wt％；Ce2O3 0.04～0.08wt％；Ag20.04-0.08 wt% of O; wherein SiO is2Being network formers for glass, Li+、Na+、K+As a crystallization promoter, Al3+、Zn2+、Sb3+Is an anti-crystallizing agent, and cerium and silver are nucleating agents.
Further, the dielectric constant of the photo-etching Li-Al-Si glass material is 4.9-5.0 at a frequency of 1MHz, and the dielectric loss is 4.5-4.9 × 10-3。
In order to achieve the above object, one aspect of the present invention provides a method for preparing a lithographically-processable lithium aluminum silicon glass material, comprising the following steps:
1) weighing the corresponding raw materials according to the following formula: 72-76 wt% of high-purity quartz sand, 24.73-37.09 wt% of lithium carbonate, 3.42-5.13 wt% of anhydrous sodium carbonate, 3.42-5.13 wt% of anhydrous potassium carbonate, 9.18-12.24 wt% of aluminum hydroxide, 1-1.2 wt% of zinc oxide, 0.8-1.5 wt% of antimony trioxide, 0.11-0.21 wt% of cerium nitrate hexahydrate and 0.06-0.12 wt% of silver nitrate, and uniformly mixing to obtain a batch mixture;
2) putting the batch materials obtained in the step 1) into a mixer for full grinding and mixing, and sieving by a 40-mesh sieve; placing the mixture into a high-temperature melting furnace for melting, stirring the mixture for 4 to 5 hours at the speed of 15 to 30r/min, completely melting the batch mixture into a liquid state, and clarifying and homogenizing the liquid state;
3) slowly cooling the glass liquid to 1250-.
Further, in the step 2), the melting temperature is 1500-1550 ℃, and the melting time is 1-2 hours.
Further, in the step 2), the stirring speed is 15 r/min-30 r/min, and the stirring time is 4-5 hours.
Further, in the step 3), the preheating temperature is 400-500 ℃.
Further, in the step 3), the temperature of the annealing furnace is 400-440 ℃; the heat preservation time is 2-3 hours.
The invention also provides a glass through hole, which comprises the following components in percentage by weight:
SiO2 72～76wt％；Li2O 10～15wt％；K2O 3～4wt％；Al2O3 6～8wt％；Na2O 2～3wt％；ZnO 1～1.2wt％；Sb2O3 0.8～1.5wt％；Ce2O3 0.04～0.08wt％；Ag2O 0.04～0.08wt％。
further, the elastic modulus of the glass through hole is 60-70 GPa.
The invention also provides a preparation method of the glass through hole, which comprises the following steps:
s1, exposure: using a quartz mask with a pore size of 100 μm and a pitch of 100 μm at 316nm7.5J/cm2Exposing the lithium aluminosilicate glass material according to claim 1 or 2 for 30 min;
s2, heat treatment: heating at 10 deg.C/min from room temperature to 400 deg.C, heating at 1 deg.C/min from 400 deg.C to 500 deg.C, maintaining at 500 deg.C for 1 hr, heating at 1 deg.C/min from 500 deg.C to 560 deg.C, maintaining at 560 deg.C for 1 hr, cooling at 0.5 deg.C/min from 560 deg.C to 400 deg.C, and furnace cooling to room temperature;
s3, etching: and etching the material obtained in the step S2 for 20min by using 10wt% hydrofluoric acid solution, and cleaning to obtain the glass through hole.
The invention has the following beneficial effects:
the photoetching lithium-aluminum-silicon glass material prepared by the invention has simple and clear material components and convenient and fast production process, and the prepared glass material has the same photosensitivity with the same type of glass, such as glass prepared by Schottky company or electronic technology university.
The photoetching lithium-aluminum-silicon glass material prepared by the invention reduces the addition of modifiers such as boron and alkaline earth metal elements by adjusting Al2O3The content of (A) is such that the glass enters a glass silica network in the form of aluminum tetrahedrons, thus playing the roles of repairing the network and reducing the number of non-bridging oxygens, weakening the integral polarizability and ionic polarization of the glass and improving the dielectric properties of the glass material.
The prepared photoetching lithium-aluminum-silicon glass material improves Sb2O3The content of (2) and antimony oxide in the glass as a reducing agent for exposure and heat treatment can promote the growth of crystal nuclei and reduce the grain size of precipitated crystals, thereby not only improving the surface quality after etching, but also greatly improving the efficiency of the exposure process (the exposure time can be reduced to 24 min).
The prepared photoetching lithium-aluminum-silicon glass material has the advantages that the content of Ag ions is reduced as much as possible on the premise of ensuring the photosensitivity, the tendency of the Ag ions to separate out clusters is reduced in the engineering melting process, and the corrosion to a platinum crucible is reduced.
The lithium-aluminum-silicon glass material has a dielectric constant of 4.9 to 5.0 at a frequency of 1MHzThe electrical loss is 4.5 to 4.9 x 10-3(ii) a And the elastic modulus of the glass through hole prepared by the lithium-aluminum-silicon glass material is 60-70 GPa.
Drawings
FIG. 1 is a graph showing the change of dielectric constant and dielectric loss with alumina content at 1MHz in the examples of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Materials, reagents and the like used in the following examples are commercially available.
The following table 1 shows the specific raw material composition of the lithographically printable lithium-aluminum-silicon glass material of examples 1-5 of the present invention.
The method for preparing the lithographically printable lithium aluminum silicon glass material of the above embodiment 1 to embodiment 5 comprises the following steps:
1) respectively and uniformly mixing high-purity quartz sand, lithium carbonate, anhydrous potassium carbonate, aluminum hydroxide, anhydrous sodium carbonate, zinc oxide, antimony trioxide, cerium nitrate hexahydrate and silver nitrate according to the formula in the table 1 to obtain a batch mixture;
2) putting the batch materials obtained in the step 1) into a mixer for full grinding and mixing, and sieving by a 40-mesh sieve; placing the mixture in a high-temperature melting furnace, melting for 1 hour at 1520 ℃, stirring for 1 hour at the speed of 15r/min, then stirring for 2 hours at the speed of 30r/min, and stirring for 1 hour at the speed of 15r/min (so that the clarifying and homogenizing effects are better) to completely melt the batch into a liquid state for clarifying and homogenizing;
3) and (3) slowly cooling the molten glass to 1250 ℃, pouring the molten glass into a preheated mold at 400 ℃, cooling and molding, putting the molten glass into an annealing furnace at 440 ℃, preserving the heat for 2 hours, and cooling the molten glass to room temperature along with the furnace to obtain the photoetching lithium-aluminum-silicon glass material, wherein the specific components of the photoetching lithium-aluminum-silicon glass material are shown in Table 2.
TABLE 2
For different Al of examples 1, 2, 4 and 52O3The dielectric property of the glass sample is tested, and as can be seen from fig. 1, the dielectric constant and the dielectric loss of the glass are increased along with the increase of the Al content, and the dielectric property of the glass is reduced along with the increase of the Al content.
When Al is introduced into the glass component2O3Of (i) is Al3+In the case of sufficient free oxygen, [ AlO ]4]5-The form of (A) enters a silicon-oxygen network to play a role of a network generation body; and hexa-coordinated Al in the case of insufficient free oxygen3+In octahedral form, acting as an extra-network entity. When the aluminum oxide structure is increased, metal cations are needed to compensate the electrovalence, and the ionic radius is larger+It causes distortion of the glass network and increases the polarization of the dipole moment, resulting in an increase in the dielectric constant of the glass.
When Al is present2O3When the content is proper, the glass acts as a network former to bind a loose silicon-oxygen network, so that the structural loss and the resonance loss of the glass are reduced, and the dielectric loss of the glass is further reduced. On the other hand, [ AlO ]4]5-Greater than [ SiO ] by volume4]4-In contrast, alkali metal cations are more readily in [ AlO ]4]5-To be migrated. When Al is present2O3When the content is too high, the dielectric loss of the glass increases.
The Al content of example 3 is the same as that of example 1, but due to Li+Higher content, enhanced ionic polarization in the glass, higher dielectric constant, weakened mixed alkali effect and higher dielectric loss.
Example 6:
this example provides a method for preparing a lithographically acceptable lithium-aluminum-silicon-based glass material, which differs from the preparation method of example 1 above in that the melting temperature of step 2) of this example is 1500 ℃. The specific composition of the prepared lithium-aluminum-silicon glass material was the same as in example 1.
The photoetching glass can be obtained by reducing the melting temperature, but the formed glass block is occasionally provided with unmelted objects, and the glass obtained by the process is proved to have photosensitive property, but impurities such as the unmelted objects and the like need to be avoided in the subsequent processing process.
Example 7:
this example provides a method for preparing a lithographically-acceptable lithium-aluminum-silicon glass material, which is different from the preparation method of example 1 in that the annealing furnace temperature in step 3) of this example is 400 ℃ and the holding time is 3 hours. The specific composition of the prepared lithium-aluminum-silicon glass material was the same as in example 1.
Lowering the annealing temperature will result in a slower stress relief process and may require special optimization of the process parameters. If the temperature continues to decrease, residual stress may be excessive and the subsequent glass cold working process may not be completed.
Example 8:
this example provides a method for preparing a lithographically-usable lithium-aluminum-silicon glass material, which is different from the preparation method of example 1 in that the melting temperature of step 2) in this example is 1550 ℃, the glass material is placed in a high-temperature melting furnace, and stirring and clarification are performed after melting for 30min at 1550 ℃; slowly cooling the molten glass in the step 3) to 1300 ℃, and pouring the molten glass into a die preheated at 400 ℃. The specific composition of the prepared lithium-aluminum-silicon glass material was the same as in example 1.
Higher melting temperatures can also result in a well-performing photodefinable glass, but with some degradation in the optical quality inherent in the glass. As the melting temperature increases, the melting time can be shortened, but bubbles and striae increase in the formed glass. For applications with less demanding usage, the temperature can be increased to increase production efficiency.
The photoetching lithium-aluminum-silicon glass material prepared by the invention adjusts the Al in the glass component2O3So that the aluminum oxide tetrahedron enters the glass silicon-oxygen network in the form of aluminum oxide tetrahedron, plays the roles of repairing the network and reducing the number of non-bridge oxygen, weakens the whole polarizability and the ionic polarization of the glass to a certain extent, reduces the dielectric constant and the dielectric loss of the glass, and simultaneously ensures that SiO2Above 72 wt%, the thermal expansion coefficient of the glass is reduced, the thermal stability and chemical stability are improved, and the hardness and mechanical strength of the glass are ensured. Increase of Sb2O3The content of the antimony oxide is used as a reducing agent for exposure and heat treatment in the glass, so that smooth photochemical reaction is ensured, the growth of crystal nuclei can be promoted, the grain size of precipitated crystals can be reduced, and the surface quality after etching is improved.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (3)
1. A photoetched lithium-aluminum-silicon glass material is characterized by comprising the following components in percentage by weight:
SiO2 72~76wt%；Li2O 10~15wt%；K2O 3~4wt%；Al2O3 6~8wt%；Na2O 2~3wt%；ZnO 1~1.2wt%；Sb2O3 0.8~1.5wt%；Ce2O3 0.04~0.08wt%；Ag2O 0.04~0.08wt%。
2. the lithographically printable lithium aluminosilicate glass material of claim 1, wherein the lithographically printable lithium aluminosilicate glass material has a dielectric constant of 4.9 to 5.0 and a dielectric loss of 4.5 to 4.9 x 10 at a frequency of 1MHz-3。
3. The preparation method of the glass through hole is characterized by comprising the following steps of:
s1, exposure: exposing the lithium alumino-silica based glass material of claim 1 or 2 to ultraviolet light at a dose of 316nm, 7.5J/cm for 30min using a quartz mask having an aperture of 100 μ ι η and a pitch of 100 μ ι η;
s2, heat treatment: heating at 10 deg.C/min from room temperature to 400 deg.C, heating at 1 deg.C/min from 400 deg.C to 500 deg.C, maintaining at 500 deg.C for 1 hr, heating at 1 deg.C/min from 500 deg.C to 560 deg.C, maintaining at 560 deg.C for 1 hr, cooling at 0.5 deg.C/min from 560 deg.C to 400 deg.C, and furnace cooling to room temperature;
s3, etching: and etching the material obtained in the step S2 for 20min by using 10wt% hydrofluoric acid solution, and cleaning to obtain the glass through hole.
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| CN114180831B (en) * | 2021-12-29 | 2024-04-02 | 中国建筑材料科学研究总院有限公司 | Photoetching glass and microstructure processing method thereof |
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| GB2398778A (en) * | 2003-02-03 | 2004-09-01 | Schott Glas | Photostructurable glass or glass-ceramic |
| CN1773274A (en) * | 2005-11-03 | 2006-05-17 | 武汉化工学院 | Method for producing miniflow control chip |
| CN106167355A (en) * | 2015-05-18 | 2016-11-30 | 肖特股份有限公司 | The photosensitive glass of sensitization and production method thereof |
| CN106746606A (en) * | 2017-03-13 | 2017-05-31 | 电子科技大学 | The be sensitized photosensitive glass and production method of a kind of low-dielectric loss |
| CN108698910A (en) * | 2016-01-26 | 2018-10-23 | 康宁公司 | Photosensitive glass and glass ceramics and the compound glass material made of them |
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| DE102005003594B4 (en) * | 2004-12-31 | 2016-02-18 | Schott Ag | Method for producing an optical component, component produced according to the method, and device comprising such components |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2398778A (en) * | 2003-02-03 | 2004-09-01 | Schott Glas | Photostructurable glass or glass-ceramic |
| CN1773274A (en) * | 2005-11-03 | 2006-05-17 | 武汉化工学院 | Method for producing miniflow control chip |
| CN106167355A (en) * | 2015-05-18 | 2016-11-30 | 肖特股份有限公司 | The photosensitive glass of sensitization and production method thereof |
| CN108698910A (en) * | 2016-01-26 | 2018-10-23 | 康宁公司 | Photosensitive glass and glass ceramics and the compound glass material made of them |
| CN106746606A (en) * | 2017-03-13 | 2017-05-31 | 电子科技大学 | The be sensitized photosensitive glass and production method of a kind of low-dielectric loss |
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