CN111574049A - Glass composition - Google Patents

Abstract

The invention provides a glass composition, the components of which are expressed by mole percent and comprise: SiO 2₂：55～80％；B₂O₃：2～15％；TiO₂：0.5～10％；ZnO：0.5～12％；Al₂O₃：0～10％；Na₂O：1～15％；K₂O: 1 to 12 percent. Through reasonable component design, the glass composition obtained by the invention has proper thermal expansion coefficient, higher ultraviolet transmittance, excellent water resistance, acid resistance and alkali resistance, meets the requirement of large-caliber high-quality processing, and is suitable for the fields of semiconductor manufacturing and the like.

Description

glass composition

technical field

The present invention relates to a glass composition, in particular to a glass composition that can be used in the field of semiconductor manufacturing.

Background technique

In the field of semiconductor manufacturing, materials such as metals, ceramics and monocrystalline silicon are usually used as substrates in the manufacturing process of wafers to prevent deformation of wafers during lithography, cleaning, packaging and other processes. Although metal, ceramic and single crystal silicon substrate materials have good mechanical strength and acid and alkali corrosion resistance, because the above substrate materials are not light-transmitting, a heating peeling process is required in the peeling process of the substrate and the wafer. If a light-transmitting glass composition is used as the fabrication substrate, a light lift-off process can be used. Compared with the thermal peeling process, the light peeling process can greatly reduce the process time and peeling cost, and at the same time avoid the chip wafer baking at high temperature, and improve the yield of the chip manufacturing process. The light lift-off process generally uses an ultraviolet laser, which requires the glass substrate material to have a high transmittance for the working wavelength.

The substrate material is generally combined with the resin material, which requires the thermal expansion coefficient of the substrate material to match the resin material. Otherwise, when the chip manufacturing process undergoes high and low temperature changes, the wafer will warp and deform, causing the chip to be scrapped. At the same time, the glass substrate material is also required to have strong thermal shock resistance when undergoing high and low temperature changes.

The chip manufacturing process will undergo multiple acid and alkali cleaning, which requires the glass substrate material to have excellent water resistance, acid resistance and alkali resistance, otherwise the glass substrate will dissolve into the process solution, causing great losses. In addition, in view of the current mainstream large-scale manufacturing process in the semiconductor field, the preferred glass substrate material also needs to meet the needs of large-scale and high-quality processing.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a glass composition with suitable thermal expansion coefficient, high ultraviolet light transmittance, excellent water resistance, acid resistance and alkali resistance, which can meet the needs of large-diameter and high-quality processing.

The technical scheme adopted by the present invention to solve the technical problem is:

A glass composition, whose components are expressed in mole percentage, containing: SiO ₂ : 55-80%; B ₂ O ₃ : 2-15%; TiO ₂ : 0.5-10%; ZnO: 0.5-12%; Al ₂ O ₃ : 0 to 10%; Na ₂ O: 1 to 15%; K ₂ O: 1 to 12%.

Further, the above-mentioned glass composition, whose components are expressed in molar percentage, further contains: MgO+CaO+SrO+BaO: 0-10%; Li ₂ O: 0-5%; P ₂ O ₅ : 0-5 %; ZrO ₂ : 0-5%; Clarifying agent: 0-1%.

Further, the above-mentioned glass composition, its components are expressed in mole percent, and the content of each component satisfies one or more of the following 9 situations:

1) B ₂ O ₃ /SiO ₂ is 0.03 to 0.25;

2) Al ₂ O ₃ /B ₂ O ₃ is 0.2 to 2.0;

3) TiO ₂ /Al ₂ O ₃ is below 3.0;

4) ZnO/B ₂ O ₃ is 0.1～5.0;

5) Na ₂ O+K ₂ O is 4～25%;

6) Na ₂ O/K ₂ O is 0.8 to 5.0;

7) (Na ₂ O+K ₂ O)/Al ₂ O ₃ is 0.5 to 8.0;

8) (Na ₂ O + K ₂ O)/(B ₂ O ₃ +ZnO) is 0.2 to 5.0;

9) (SiO ₂ +TiO ₂ )/(Na ₂ O+ZnO) is 2.5 to 15.0.

Further, the above-mentioned glass composition, whose components are expressed in mole percent, contains: SiO ₂ : 60-78%; and/or B ₂ O ₃ : 3-12%; and/or TiO ₂ : 1-8% and/or ZnO: 1-10%; and/or Al ₂ O ₃ : 0.5-8%; and/or Na ₂ O: 2-12%; and/or K ₂ O: 2-10%; and/or or MgO+CaO+SrO+BaO: 0-5%; and/or Li ₂ O: 0-3%; and/or P ₂ O ₅ : 0-3%; and/or ZrO ₂ : 0-3%; and/or clarifying agent: 0 to 0.5%.

Further, the above-mentioned glass composition, its components are expressed in mole percent, and the content of each component satisfies one or more of the following 9 situations:

1) B ₂ O ₃ /SiO ₂ is 0.04 to 0.2;

2) Al ₂ O ₃ /B ₂ O ₃ is 0.25 to 1.5;

3) TiO ₂ /Al ₂ O ₃ is below 2.5;

4) ZnO/B ₂ O ₃ is 0.2 to 4.0;

5) Na ₂ O+K ₂ O is 5-20%;

6) Na ₂ O/K ₂ O is 0.85～4.0;

7) (Na ₂ O+K ₂ O)/Al ₂ O ₃ is 1.0 to 6.0;

8) (Na ₂ O + K ₂ O)/(B ₂ O ₃ +ZnO) is 0.3 to 4.0;

9) (SiO ₂ +TiO ₂ )/(Na ₂ O+ZnO) is 3.0 to 10.0.

Further, the above-mentioned glass composition, whose components are expressed in mole percent, contains: SiO ₂ : 65-75%; and/or B ₂ O ₃ : 4-10%; and/or TiO ₂ : 1-5% and/or ZnO: 1-7%; and/or Al ₂ O ₃ : 1-6%; and/or Na ₂ O: 4-10%; and/or K ₂ O: 3-8%; and/or Or clarifying agent: 0～0.2%.

Further, the above-mentioned glass composition, its components are expressed in mole percent, and the content of each component satisfies one or more of the following 9 situations:

1) B ₂ O ₃ /SiO ₂ is 0.05 to 0.15;

2) Al ₂ O ₃ /B ₂ O ₃ is 0.3 to 1.0;

3) TiO ₂ /Al ₂ O ₃ is below 2.0;

4) ZnO/B ₂ O ₃ is 0.4～3.0;

5) Na ₂ O+K ₂ O is 8-18%;

6) Na ₂ O/K ₂ O is 0.9 to 3.0;

7) (Na ₂ O+K ₂ O)/Al ₂ O ₃ is 2.0 to 5.0;

8) (Na ₂ O + K ₂ O)/(B ₂ O ₃ +ZnO) is 0.5 to 2.0;

9) (SiO ₂ +TiO ₂ )/(Na ₂ O+ZnO) is 4.0 to 8.0.

Further, the above-mentioned glass composition, its components are expressed in mole percentage, wherein: (MgO+CaO+SrO+BaO)/ZnO is 1.0 or less, preferably (MgO+CaO+SrO+BaO)/ZnO is 0.8 or less, More preferably (MgO+CaO+SrO+BaO)/ZnO is 0.5 or less; and/or (MgO+CaO+SrO+BaO)/(Na ₂ O+K ₂ O) is 1.0 or less, preferably (MgO+CaO+SrO +BaO)/(Na ₂ O+K ₂ O) is 0.5 or less, more preferably (MgO+CaO+SrO+BaO)/(Na ₂ O+K ₂ O) is 0.3 or less.

Further, the above-mentioned glass composition, whose components are expressed in mole percent, contains: MgO: 0-5%, preferably MgO: 0-4%, more preferably MgO: 0-3%; and/or CaO: 0-5% 5%, preferably CaO: 0-4%, more preferably CaO: 0-3%; and/or SrO: 0-5%, preferably SrO: 0-4%, more preferably SrO: 0-3%; and/or BaO: 0 to 5%, preferably BaO: 0 to 4%, more preferably BaO: 0 to 3%.

Further, the above-mentioned glass composition, whose components are expressed in molar percentage, contains: La ₂ O ₃ : 0-5%, preferably La ₂ O ₃ : 0-3%, more preferably La ₂ O ₃ : 0-1 %; and/or Y ₂ O ₃ : 0-5%, preferably Y ₂ O ₃ : 0-3%, more preferably Y ₂ O ₃ : 0-1%; and/or Gd ₂ O ₃ : 0-5% , preferably Gd ₂ O ₃ : 0-3%, more preferably Gd ₂ O ₃ : 0-1%; and/or Nb ₂ O ₅ : 0-5%, preferably Nb ₂ O ₅ : 0-3%, more preferably Nb ₂ O ₅ : 0-1%; and/or WO ₃ : 0-5%, preferably WO ₃ : 0-3%, more preferably WO ₃ : 0-1%.

Further, the thermal expansion coefficient α _20-300°C of the above-mentioned glass composition is 60×10 ^-7 /K～90×10 ^-7 /K, preferably 65×10 ^-7 /K～85×10 ^-7 /K , more preferably 68×10 ^-7 /K to 80×10 ^-7 /K; and/or light transmittance τ _360nm is 75% or more, preferably 80% or more, more preferably 85% or more; and/or The Young's modulus E is 6500×10 ⁷ Pa or more, preferably 6800×10 ⁷ Pa to 8500×10 ⁷ Pa, more preferably 7000×10 ⁷ Pa to 8000×10 ⁷ Pa; and/or the transition temperature T _g is 520°C to 600°C, preferably 530°C to 590°C, more preferably 540°C to 570°C.

Further, the acid resistance stability D _A of the above-mentioned glass composition is 2 or more types, preferably 1 type; and/or the water resistance stability D _W is 2 types or more, preferably 1 type; and/or alkali resistance The stability of the glass sample measured according to the test conditions and requirements of ISO 10629 is less than 10 mg, preferably less than 8 mg, more preferably less than 5 mg.

The packaging carrier is made of any one of the glass compositions described above.

A device comprising any of the glass compositions described above.

The beneficial effects of the present invention are: through reasonable component design, the glass composition obtained by the present invention has a suitable thermal expansion coefficient, high ultraviolet light transmittance, excellent water resistance, acid resistance and alkali resistance, and meets the requirements of large diameter and high Quality processing, suitable for semiconductor manufacturing.

Detailed ways

Hereinafter, although the embodiment of the glass composition of this invention is demonstrated in detail, this invention is not limited to the following embodiment, It can change suitably within the range of the objective of this invention, and can implement. In addition, although description is abbreviate|omitted suitably about the repeated description part, it does not limit the meaning of invention by this. In the following, the glass composition of the present invention is sometimes simply referred to as glass.

[glass composition]

The range of each component of the glass composition of the present invention will be described below. In this specification, unless otherwise specified, the content of each component and the total content are all expressed in mole percent (mol %) relative to the total amount of glass substances in the composition converted into oxides. Here, the "composition in terms of oxides" means that oxides, complex salts, hydroxides, etc., which are used as raw materials of the constituent components (components) of the glass composition of the present invention, are decomposed and converted into In the case of an oxide, the total amount of the oxide is taken as 100%.

Unless otherwise indicated in a specific case, the numerical ranges recited herein include upper and lower limits, "above" and "below" include the endpoints, and all integers and fractions included within the range without limitation The specific value listed in the range. As used herein, "and/or" is inclusive, eg, "A; and/or B", and means only A, or only B, or both.

<Essential Components and Optional Components>

SiO ₂ is one of the main components of the glass of the present invention. In the glass of the present invention, an appropriate amount of SiO ₂ can ensure that the glass has high water resistance and acid resistance, and can achieve high transmittance of ultraviolet light. If the content of SiO ₂ is lower than 55%, the water resistance, acid resistance and UV transmittance of the glass are lower than the design requirements. If the content of SiO ₂ is higher than 80%, the melting temperature of the glass increases sharply, it is difficult to obtain high-quality glass in production, and the thermal expansion coefficient of the glass is lower than the design expectation. Therefore, in the present invention, the content of SiO ₂ is limited to 55 to 80%, preferably 60 to 78%, and more preferably 65 to 75%.

Adding an appropriate amount of B ₂ O ₃ to the glass can transform the structure of the glass into a dense direction and improve the water resistance and acid resistance of the glass. If the content of B 2 O 3 is less than 2%, the above effect is not obvious. If the content of B ₂ O ₃ is higher than 15%, the water resistance and acid resistance of glass will decrease rapidly. Therefore, the content of B ₂ O ₃ is limited to 2 to 15%, preferably 3 to 12%, and more preferably 4 to 10%.

In some embodiments of the present invention, the value of B ₂ O ₃ /SiO ₂ will affect the production difficulty of glass. When B ₂ O ₃ /SiO ₂ is less than 0.03, the melting temperature of glass will increase, and the erosion of refractory materials will be intensified. Introducing more colored impurities and inclusions into the glass will cause the short-wave transmittance of the glass to fail to meet the design requirements, and at the same time will lead to an increase in the probability of defects on the surface of the product. When B ₂ O ₃ /SiO ₂ is greater than 0.25, the smelting temperature does not drop significantly, and at the same time, the erosion of B ₂ O ₃ to refractory materials increases, which also leads to easy introduction of more coloring impurities and inclusions into the glass, resulting in the loss of glass. The short-wave transmittance does not meet the design requirements, and at the same time, the probability of defects on the surface of the product will increase. Therefore, in the present invention, when the value of B ₂ O ₃ /SiO ₂ is between 0.03 and 0.25, preferably between 0.04 and 0.2, and more preferably between 0.05 and 0.15, a lower melting temperature can be obtained, and the It can ensure that the erosion of the glass to the refractory material is small during the smelting process.

Adding a suitable amount of P ₂ O ₅ to the glass can increase the strength of the glass, but if its content exceeds 5%, a differential phase is likely to be generated inside the glass, and the differential phase will scatter part of the short-wave wavelength, so that the transmittance cannot meet the design requirements. . Therefore, the content of P ₂ O ₅ is limited to 0 to 5%, preferably 0 to 3%. In some embodiments, when the strength of the glass is designed to meet the usage requirements, it is more preferable not to add P ₂ O ₅ .

A suitable amount of Al ₂ O ₃ added to the glass can improve the water resistance and acid resistance of the glass, and at the same time can reduce the thermal expansion coefficient of the glass, especially in the presence of alkali metal oxides. If the content of Al ₂ O ₃ is higher than 10%, the thermal expansion coefficient of the glass decreases rapidly, which fails to meet the design requirements. Therefore, the content of Al ₂ O ₃ is limited to 0 to 10%, preferably 0.5 to 8%, and more preferably 1 to 6%.

Adding a suitable amount of TiO ₂ to the glass can improve the water resistance, acid resistance and alkali resistance of the glass, at the same time, it can reduce the thermal expansion coefficient of the glass and improve the thermal shock resistance of the glass. If the content of TiO ₂ is less than 0.5%, the above effect is not obvious; if the content of TiO ₂ exceeds 10%, the short-wave transmittance of the glass decreases rapidly, especially in the environment of unstable melting atmosphere. More importantly, high content of TiO ₂ will lead to a rapid increase in the refractive index of the glass, which will increase the reflection loss of short-wave wavelengths without anti-reflection coating, resulting in a further decrease in short-wave transmittance, and the thermal expansion of the glass. The coefficient is reduced and the design requirements are not met. Therefore, in the present invention, the content of TiO ₂ is limited to 0.5 to 10%, preferably 1 to 8%. In some embodiments, considering the difficulty of controlling the atmosphere during glass melting, the content of TiO ₂ is more preferably 1-5%.

Both Ti ions and Al ions in the glass are positive ions with strong electronegativity, and complex synergistic effects will appear in the alkali-containing glass in this system, especially affecting the anti-devitrification properties of the glass. _The inventors have found that, in some embodiments, when the value of _TiO2 / _Al2O3 is below 3.0, the devitrification tendency of the glass is reduced, which is important for the production of products with specifications exceeding 340mm wide and 50mm thick, or raw glass blanks It is especially important for products that require re-heat treatment to be formed into products with a diameter greater than 340mm. Therefore, if it is necessary to obtain a low-defect product with a diameter exceeding 340 mm, the value of TiO ₂ /Al ₂ O ₃ is preferably 3.0 or less, more preferably TiO ₂ /Al ₂ O ₃ is 2.5 or less, and further preferably TiO ₂ /Al ₂ O ₃ is 2.0 or less.

Adding an appropriate amount of ZrO ₂ to the glass can improve the chemical stability and thermal shock resistance of the glass, but its characteristic is that it will significantly increase the melting temperature of the glass. If its content is higher than 5%, inclusion defects are prone to appear in the glass. . Therefore, the content of ZrO ₂ is limited to 5% or less, preferably 3% or less. In some embodiments, when the chemical stability and strength of the glass are excessive, it is more preferable not to add ZrO ₂ .

ZnO has a large field strength in divalent metal oxides. Adding ZnO to glass can improve the acid resistance, water resistance and alkali resistance of glass, and can reduce the thermal expansion coefficient of glass, especially in glass systems containing alkali metals. . If the content of ZnO is less than 0.5%, the above effect is not obvious. If the content of ZnO exceeds 12%, the transition temperature of the glass decreases rapidly, so that the glass is easily softened and deformed in a high temperature working environment, which has an adverse effect on the semiconductor manufacturing process. Therefore, the content of ZnO is limited to 0.5 to 12%, preferably 1 to 10%, and more preferably 1 to 7%.

The inventors have found that when the glass contains B ₂ O ₃ , the presence of ZnO will further reduce the melting temperature of the glass, making it easier to obtain high-quality products. If the value of ZnO/B ₂ O ₃ is lower than 0.1, the above The effect is not obvious; if ZnO/B ₂ O ₃ is higher than 5.0, the transition temperature of the glass decreases rapidly, and the heat resistance cannot meet the design requirements. On the other hand, when the value of ZnO/B ₂ O ₃ is 0.1 to 5.0, the water resistance, acid resistance and alkali resistance of the glass are more excellent than when B ₂ O ₃ is added alone. Therefore, in the present invention, the value of ZnO/B ₂ O ₃ is 0.1 to 5.0, preferably 0.2 to 4.0, and more preferably 0.4 to 3.0.

MgO, CaO, SrO, and BaO are alkaline earth metal oxides. Adding them to glass can increase the refractive index and transition temperature of the glass, and adjust the stability and thermal expansion coefficient of the glass. However, the addition of alkaline earth metal oxides will lead to a rapid increase in the Young's modulus of the glass. When the thermal expansion coefficient of the glass material is the same, the glass with a lower Young's modulus has better thermal shock resistance. Therefore, considering the above-mentioned factors, the total addition amount of the alkaline earth metal oxides, MgO+CaO+SrO+BaO, is preferably 10% or less, and more preferably 5% or less. In some embodiments, if the stability, thermal expansion coefficient and transition temperature of the glass meet the design requirements, it is further preferred not to add alkaline earth metal oxides.

In some applications in semiconductor processing, a higher refractive index is required to achieve optical system matching, or a higher transition temperature is required, which requires the addition of small amounts of alkaline earth metal oxides. When adding alkaline earth metal oxides, in order to avoid the rapid decline of the water resistance, acid resistance and alkali resistance of the glass, it can be considered to add MgO, CaO, SrO, BaO individually or in combination in the order. If the content of alkaline earth metal oxides such as MgO, CaO, SrO, and BaO alone exceeds 5%, the anti-devitrification performance of the glass will drop rapidly, and it is difficult to obtain large-diameter high-quality products. Therefore, the contents of MgO, CaO, SrO, and BaO are respectively limited to 5% or less, preferably 4% or less, and more preferably 3% or less.

The inventors have found through a large number of experiments that if there is a certain amount of alkaline earth metal oxides in the glass, it is possible to consider adjusting the ZnO content to reduce the loss of chemical stability and thermal shock resistance of the glass. When the value of (MgO+CaO+SrO+BaO)/ZnO is below 1.0, preferably below 0.8, more preferably below 0.5, a higher refractive index can be easily obtained, and the chemical stability, Glass with coefficient of thermal expansion, heat resistance and thermal shock resistance.

In some embodiments of the present invention, when it is necessary to increase the refractive index and transition temperature of the glass, an appropriate amount of oxides such as La ₂ O ₃ , Y ₂ O ₃ , Gd ₂ O ₃ , Nb ₂ O ₅ , WO ₃ and the like can be added , but when its single or combined content exceeds 5%, the anti-devitrification performance and short-wave transmittance of the glass will deteriorate. Therefore, the contents of La ₂ O ₃ , Y ₂ O ₃ , Gd ₂ O ₃ , Nb ₂ O ₅ , and WO ₃ are respectively 5% or less, preferably 3% or less, more preferably 1% or less, and further preferably not contained. Further, the total content of La ₂ O ₃ , Y ₂ O ₃ , Gd ₂ O ₃ , Nb ₂ O ₅ , and WO ₃ is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less.

Li ₂ O, Na ₂ O and K ₂ O belong to alkali metal oxides, and in the glass of the present invention, their content is closely related to the thermal expansion coefficient, chemical stability and dielectric constant of the glass.

The addition of Li ₂ O to the glass can reduce the melting temperature of the glass, and at the same time, compared with the other two alkali metal oxides, the chemical stability loss of the glass is minimal. However, if the content of Li ₂ O exceeds 5%, the solidification speed of the glass during the forming process, that is, the process of cooling the glass liquid from liquid to solid, will be slow, which is not suitable for production width (or diameter) greater than 340mm and thickness greater than 340mm. 40mm products are unfavorable, and are prone to delamination and crystallization, which is fatal to the production of large-scale high-quality products. On the other hand, it will also cause the transition temperature of the glass to drop, and the heat resistance will not meet the design requirements. Therefore, the content of Li ₂ O is limited to 5% or less, preferably 3% or less, and more preferably, no Li ₂ O is added.

The addition of Na ₂ O to the glass can significantly increase the thermal expansion coefficient of the glass, and at the same time can reduce the high temperature viscosity of the glass, making it easier to obtain large-diameter high-quality products. However, if the content of Na ₂ O exceeds 15%, the chemical stability of the glass decreases rapidly, which cannot meet the design requirements. If the content of Na ₂ O is less than 1%, the thermal expansion coefficient of the glass cannot meet the design requirements, and the chemical stability will also deteriorate. Therefore, the content of Na ₂ O is limited to 1 to 15%, preferably 2 to 12%, and more preferably 4 to 10%.

Adding K ₂ O to the glass can increase the thermal expansion coefficient of the glass and reduce the high temperature viscosity of the glass, especially in the case of coexisting with Na ₂ O, adding an appropriate amount of K ₂ O to the glass will not significantly damage the chemical stability of the glass sex. However, if the content of K ₂ O exceeds 12%, the water resistance, acid resistance and alkali resistance of the glass deteriorate. If the content of K ₂ O is less than 1%, the effect of increasing the thermal expansion coefficient and reducing the high temperature viscosity is not obvious. Therefore, the content of K ₂ O is limited to 1 to 12%, preferably 2 to 10%, and more preferably 3 to 8%.

In some embodiments of the present invention, if the total content of Na ₂ O and K ₂ O exceeds 25%, the thermal expansion coefficient of the glass exceeds the design requirement, and the dielectric constant of the glass rises rapidly, resulting in a rapid decline in the insulating properties of the glass. It is disadvantageous for some applications where insulation is required. If the total content is less than 4%, the thermal expansion coefficient of the glass will not meet the design requirements, and at the same time, the coloring ability of the valence-changing components in the glass will be enhanced, and the short-wave transmittance of the glass will not meet the design requirements. Therefore, the total content of Na ₂ O and K ₂ O, Na ₂ O+K ₂ O, is preferably 4 to 25%, more preferably 5 to 20%, and further preferably 8 to 18%.

In some embodiments of the present invention, when the value of (Na ₂ O + K ₂ O)/(B ₂ O ₃ +ZnO) is lower than 0.2, the free oxygen in the glass system is insufficient, resulting in B ₂ O ₃ , ZnO, etc. The probability of components entering the glass network is reduced, resulting in a decrease in chemical stability, and at the same time, the thermal expansion coefficient of the glass is reduced, which cannot meet the design requirements. When the value of (Na ₂ O+K ₂ O)/(B ₂ O ₃ +ZnO) is greater than 5.0, the free oxygen in the glass system is excessive, the chemical stability of the glass drops sharply, and the thermal expansion coefficient of the glass exceeds the design requirement. Therefore, the value of (Na ₂ O+K ₂ O)/(B ₂ O ₃ +ZnO) is preferably 0.2 to 5.0, more preferably 0.3 to 4.0, and even more preferably 0.5 to 2.0.

In the prior art, it is generally believed that the addition of alkaline earth metal oxides MgO, CaO, SrO, BaO, etc. to glass is more conducive to the improvement of chemical stability than alkali metal oxides Li ₂ O, Na ₂ O, K ₂ O, etc. The inventor found through experiments that in the glass of this system, since the ability of alkaline earth metal oxides to provide free oxygen is weaker than that of alkali metal oxides, when the ratio of (MgO+CaO+SrO+BaO)/(Na ₂ O+K ₂ O) When the value is greater than 1.0, the internal network of the glass is severely fractured, thereby reducing the chemical stability of the glass, especially when immersed in a strong alkaline solution, if (MgO+CaO+SrO+BaO)/(Na ₂ O+K ₂ O ) is greater than 1.0, the alkaline earth metal ions are more likely to be eroded and precipitated, which is very unfavorable for certain processes in the semiconductor manufacturing process. Therefore, in some embodiments of the present invention, the value of (MgO+CaO+SrO+BaO)/(Na ₂ O+K ₂ O) is preferably 1.0 or less, more preferably 0.5 or less, and still more preferably 0.3 or less.

In the present invention, in order to obtain a suitable thermal expansion coefficient, it is necessary to add Na ₂ O and K ₂ O to the glass, but the chemical stability of the glass will decrease. The inventors have found through research that when Al ₂ O ₃ exists in the glass, the type and relative content of the alkali metal oxides will change the microstructure of the glass and have a greater impact on the chemical stability of the glass. In some embodiments, when the value of Na ₂ O/K ₂ O is 0.8-5.0, preferably 0.85-4.0, more preferably 0.9-3.0; and/or (Na ₂ O+K ₂ O)/Al When the value of ₂ O ₃ is 0.5 to 8.0, preferably 1.0 to 6.0, and more preferably 2.0 to 5.0, the chemical stability of the glass can be significantly optimized.

In order to obtain high-quality glass products, the inventors found that, in some embodiments, if the value of (SiO ₂ +TiO ₂ )/(Na ₂ O + ZnO) is greater than 15.0, the glass becomes difficult to melt and clarify, and the inside of the glass becomes difficult to melt and clarify. It is very difficult to remove air bubbles and inclusions, and it is impossible to obtain products with an internal quality of A ₀ and above, and the internal fringes of the glass are serious. If (SiO ₂ +TiO ₂ )/(Na ₂ O+ZnO) is lower than 2.5, the thermal expansion coefficient of the glass increases rapidly, exceeding the design requirements. Therefore, in the present invention, the value of (SiO ₂ +TiO ₂ )/(Na ₂ O+ZnO) is preferably 2.5 to 15.0, more preferably 3.0 to 10.0, and even more preferably 4.0 to 8.0.

In some embodiments, if the glass contains more alkali metal oxides, Al ₂ O ₃ and B ₂ O ₃ form a complex synergistic effect, so that the structure of the glass undergoes nonlinear changes within a certain range. The inventors found that when the value of Al ₂ O ₃ /B ₂ O ₃ is 0.2 to 2.0, the synergistic effect of the above two oxides can significantly improve the alkali resistance stability of the glass, preferably Al ₂ O ₃ /B ₂ The value of O ₃ is 0.25 to 1.5, and the value of Al ₂ O ₃ /B ₂ O ₃ is more preferably 0.3 to 1.0.

In some embodiments of the present invention, by adding 0-1% of one or more components of Sb ₂ O ₃ , SnO ₂ , SnO, NaCl, sulfate and CeO ₂ as a clarifying agent, preferably Sb ₂ is used As a clarifying agent, O ₃ can improve the clarifying effect of glass, and it is preferable to add 0-0.5% of the clarifying agent, more preferably 0-0.2% of the clarifying agent.

The addition of F into the glass will increase the volatilization of the glass raw material, which is likely to cause environmental pollution and deterioration of the glass streak. Therefore, the glass of the present invention preferably does not contain F. The addition of Ta ₂ O ₅ to the glass will greatly increase the cost of the glass and deteriorate the melting performance of the glass, so the glass of the present invention preferably does not contain Ta ₂ O ₅ .

<Ingredients that should not be contained>

Oxides of Th, Cd, Tl, Os, Be, and Se tend to be used in a controlled manner as harmful chemical substances in recent years, not only in the glass manufacturing process, but also in the processing process and disposal after productization. Action is required. Therefore, when considering the influence on the environment, it is preferable not to actually contain them except for unavoidable mixing. Thereby, the glass becomes practically free of substances that pollute the environment. Therefore, the glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental measures.

In order to achieve environmental friendliness, the glass of the present invention does not contain As ₂ O ₃ and PbO. Although As ₂ O ₃ has the effect of eliminating bubbles and preventing glass coloration, the addition of As ₂ O ₃ will increase the platinum erosion of the glass to the furnace, especially the platinum furnace, resulting in more platinum ions entering the glass. The service life of the platinum furnace is adversely affected. PbO can significantly improve the high refractive index and high dispersion properties of glass, but both PbO and As ₂ O ₃ are substances that cause environmental pollution.

"Does not contain", "does not add" and "0%" as described herein means that the compound, molecule or element, etc. is not intentionally added as a raw material to the glass of the present invention; however, as a raw material and/or equipment for producing glass, there may be Some impurities or components that are not intentionally added will be contained in a small or trace amount in the final glass, and this situation is also within the protection scope of the present invention.

Next, the properties of the glass composition of the present invention will be described.

<Acid resistance stability>

The acid resistance stability of glass (D _A ) (powder method) is tested according to the method specified in GB/T 17129. Acid resistance stability is sometimes referred to herein simply as acid resistance or acid resistance stability.

The acid resistance stability (D _A ) of the glass of the present invention is two or more types, preferably one type.

<Water resistance stability>

The water resistance stability of glass (D _W ) (powder method) is tested according to the method specified in GB/T 17129. Water resistance stability is sometimes referred to herein simply as water resistance or water resistance stability.

The water resistance stability (D _W ) of the glass of the present invention is two or more types, preferably one type.

<Alkali resistance stability>

The alkali resistance stability of glass is measured in accordance with the test conditions and requirements of ISO 10629 and is expressed as the weight loss of the glass sample. Alkali action stability is sometimes referred to herein simply as alkali resistance or alkali stability.

The glass is processed into a test sample with a size of 30mm×30mm×2mm, polished on six sides, and put into 2000ml of NaOH solution. The concentration of the NaOH solution is 0.01mol/L and the pH value is 12.0. The test process is regularly monitored with a pH meter Change the pH value of the test solution, and replace the reaction test solution in time. After eroding for 100 hours at a temperature of 50 °C, an electronic balance is used to measure the weight loss of the sample, and the weight loss is expressed in mg.

The glass of the present invention has a weight loss of less than 10 mg after the above test method, preferably less than 8 mg, more preferably less than 5 mg.

<Coefficient of Thermal Expansion>

The thermal expansion coefficient mentioned in the present invention refers to the average thermal expansion coefficient of glass at 20-300°C, expressed as α _20-300°C , and tested according to the method specified in GB/T7962.16-2010.

The thermal expansion coefficient (α _20-300°C ) of the glass of the present invention is 60×10 ^-7 /K to 90×10 ^-7 /K, preferably 65×10 ^-7 /K to 85×10 ^-7 /K, more preferably It is 68×10 ^-7 /K to 80×10 ^-7 /K.

<Light transmittance>

The light transmittance in the present invention refers to the internal transmittance of a glass sample with a thickness of 10 mm at 360 nm, expressed as τ _{360 nm} , and tested according to the method specified in GB/T7962.12-2010.

The glass of the present invention has an internal transmittance (τ _360nm ) at 360 nm of 75% or more, preferably 80% or more, and more preferably 85% or more.

<Transition temperature>

The glass transition temperature (T _g ) is tested according to the method specified in GB/T7962.16-2010.

The transition temperature (T _g ) of the glass of the present invention is 520°C to 600°C, preferably 530°C to 590°C, and more preferably 540°C to 570°C.

<Young's modulus>

The Young's modulus (E) of glass is calculated using the following formula:

Among them, G=V _S ² ρ

where:

E is Young's modulus, Pa;

G is the shear modulus, Pa;

V _T is the longitudinal wave velocity, m/s;

V _S is the shear wave velocity, m/s;

ρ is the glass density, g/cm ³ .

The Young's modulus (E) of the glass of the present invention is 6500×10 ⁷ Pa or more, preferably 6800×10 ⁷ Pa to 8500×10 ⁷ Pa, and more preferably 7000×10 ⁷ Pa to 8000×10 ⁷ Pa.

Due to the above-mentioned excellent properties, the glass composition of the present invention can be applied to the packaging carrier (substrate material) of the semiconductor process, and can also be used to manufacture various devices or instruments, such as imaging equipment, sensors, microscopes, medical technology, digital projection, Communication, optical communication technology/information transmission, optics/illumination in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for automotive applications, monitoring Camera equipment and devices in the field of security.

[Manufacturing method]

The manufacturing method of the glass composition of the present invention is as follows: the glass of the present invention is produced by using conventional raw materials and conventional processes, using carbonates, nitrates, sulfates, hydroxides, oxides, etc. The prepared charge is put into a smelting furnace at 1300-1500°C for melting, and after clarification, stirring and homogenization, a homogeneous molten glass without bubbles and no undissolved substances is obtained, and the molten glass is cast in a mold. type and annealed. Those skilled in the art can appropriately select raw materials, process methods and process parameters according to actual needs.

[Example]

In order to further clearly illustrate and illustrate the technical solutions of the present invention, the following non-limiting Examples 1-20 are provided.

In this example, glass compositions having the compositions shown in Tables 1 to 2 were obtained by using the above-described method for producing a glass composition. In addition, the characteristics of each glass were measured by the test method according to the present invention, and the measurement results are shown in Tables 1 to 2.

Table 1

Table 2

Claims (14)

1. Glass composition, characterized in that its components, expressed in mole percentages, contain: SiO 2₂：55～80％；B₂O₃：2～15％；TiO₂：0.5～10％；ZnO：0.5～12％；Al₂O₃：0～10％；Na₂O：1～15％；K₂O：1～12％。

2. The glass composition according to claim 1, further comprising, in mole percent: MgO + CaO + SrO + BaO: 0 to 10 percent; li₂O：0～5％；P₂O₅：0～5％；ZrO₂: 0 to 5 percent; a clarifying agent: 0 to 1 percent.

3. The glass composition according to claim 1 or 2, wherein the components are present in mole percent in an amount satisfying one or more of the following 9 conditions:

1)B₂O₃/SiO₂0.03 to 0.25;

2)Al₂O₃/B₂O₃0.2 to 2.0;

3)TiO₂/Al₂O₃is 3.0 or less;

4)ZnO/B₂O₃0.1 to 5.0;

5)Na₂O+K₂o is 4-25%;

6)Na₂O/K₂o is 0.8 to 5.0;

7)(Na₂O+K₂O)/Al₂O₃0.5 to 8.0;

8)(Na₂O+K₂O)/(B₂O₃+ ZnO) is 0.2 to 5.0;

9)(SiO₂+TiO₂)/(Na₂o + ZnO) of 2.5 to 15.0.

4. Glass composition according to claim 1 or 2, characterized in that its composition, expressed in mole percentages, comprises: SiO 2₂: 60-78%; and/or B₂O₃: 3-12%; and/or TiO₂: 1-8%; and/or ZnO: 1-10%; and/or Al₂O₃: 0.5-8%; and/or Na₂O: 2-12%; and/or K₂O: 2-10%; and/or MgO + CaO + SrO + BaO: 0 to 5 percent; and/or Li₂O: 0 to 3 percent; and/or P₂O₅: 0 to 3 percent; and/or ZrO₂: 0 to 3 percent; and/or a clarifying agent: 0 to 0.5 percent.

5. The glass composition according to claim 1 or 2, wherein the components are present in mole percent in an amount satisfying one or more of the following 9 conditions:

1)B₂O₃/SiO₂0.04 to 0.2;

2)Al₂O₃/B₂O₃0.25 to 1.5;

3)TiO₂/Al₂O₃is 2.5 or less;

4)ZnO/B₂O₃0.2 to 4.0;

5)Na₂O+K₂o is 5-20%;

6)Na₂O/K₂o is 0.85 to 4.0;

7)(Na₂O+K₂O)/Al₂O₃1.0 to 6.0;

8)(Na₂O+K₂O)/(B₂O₃+ ZnO) is 0.3 to 4.0;

9)(SiO₂+TiO₂)/(Na₂o + ZnO) is 3.0 to 10.0.

6. Glass composition according to claim 1 or 2, characterized in that its composition, expressed in mole percentages, comprises: SiO 2₂: 65-75%; and/or B₂O₃: 4-10%; and/or TiO₂: 1-5%; and/or ZnO: 1-7%; and/or Al₂O₃: 1-6%; and/or Na₂O: 4-10%; and/or K₂O: 3-8%; and/or a clarifying agent: 0 to 0.2 percent.

7. The glass composition according to claim 1 or 2, wherein the components are present in mole percent in an amount satisfying one or more of the following 9 conditions:

1)B₂O₃/SiO₂0.05 to 0.15;

2)Al₂O₃/B₂O₃0.3 to 1.0;

3)TiO₂/Al₂O₃is 2.0 or less;

4)ZnO/B₂O₃0.4 to 3.0;

5)Na₂O+K₂o is 8-18%;

6)Na₂O/K₂o is 0.9 to 3.0;

7)(Na₂O+K₂O)/Al₂O₃2.0 to 5.0;

8)(Na₂O+K₂O)/(B₂O₃+ ZnO) is 0.5 to 2.0;

9)(SiO₂+TiO₂)/(Na₂o + ZnO) is 4.0 to 8.0.

8. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (MgO + CaO + SrO + BaO)/ZnO is 1.0 or less, preferably (MgO + CaO + SrO + BaO)/ZnO is 0.8 or less, more preferably (MgO + CaO + SrO + BaO)/ZnO is 0.5 or less; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 1.0 or less, preferably (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 0.5 or less, more preferably (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 0.3 or less.

9. Glass composition according to claim 1 or 2, characterized in that its composition, expressed in mole percentages, comprises: MgO: 0-5%, preferably MgO: 0 to 4%, more preferably MgO: 0 to 3 percent; and/or CaO: 0-5%, preferably CaO: 0-4%, more preferably CaO: 0 to 3 percent; and/or SrO: 0 to 5%, preferably SrO: 0 to 4%, more preferably SrO: 0 to 3 percent; and/or BaO: 0-5%, preferably BaO: 0 to 4%, more preferably BaO: 0 to 3 percent.

10. Glass composition according to claim 1 or 2, characterized in that its composition, expressed in mole percentages, comprises: la₂O₃: 0 to 5%, preferably La₂O₃: 0 to 3%, more preferably La₂O₃: 0 to 1 percent; and/or Y₂O₃: 0 to 5%, preferably Y₂O₃: 0 to 3%, more preferably Y₂O₃: 0 to 1 percent; and/or Gd₂O₃: 0 to 5%, preferably Gd₂O₃: 0 to 3%, more preferably Gd₂O₃: 0 to 1 percent; and/or Nb₂O₅: 0 to 5%, preferably Nb₂O₅: 0 to 3%, more preferably Nb₂O₅: 0 to 1 percent; and/or WO₃: 0 to 5%, preferably WO₃: 0 to 3%, more preferably WO₃：0～1％。

11. The glass composition of claim 1 or claim 2, wherein the glass composition has a coefficient of thermal expansion of α_20-300℃Is 60 × 10^-7/K～90×10^-7Preferably 65 × 10K^-7/K～85×10^-7/K, more preferably 68 × 10^-7/K～80×10^-7K; and/or light transmission rate tau_360nm75% or more, preferably 80% or more, more preferably 85% or more, and/or a Young's modulus E of 6500 × 10⁷Pa or more, preferably 6800 × 10⁷Pa～8500×10⁷Pa, more preferably 7000 × 10⁷Pa～8000×10⁷Pa; and/or transition temperature T_g520 ℃ to 600 ℃, preferably 530 ℃ to 590 ℃, more preferably 540 ℃ to 570 ℃.

12. The glass composition according to claim 1 or 2, characterized in that the glass composition has an acid action resistance stability D_AIs 2 or more, preferably 1; and/or stability against water action D_WIs 2 or more, preferably 1; and/or alkali action resistance stability the glass samples after measurement according to the test conditions and requirements of ISO 10629 have a weight loss of less than 10mg, preferably a weight loss of less than 8mg, more preferably a weight loss of less than 5 mg.

13. A package carrier made of the glass composition according to any one of claims 1 to 12.

14. A device comprising the glass composition according to any one of claims 1 to 12.