CN111574049B

CN111574049B - Glass composition

Info

Publication number: CN111574049B
Application number: CN202010460648.2A
Authority: CN
Inventors: 毛露路; 匡波; 刘振禹; 聂小兵; 范少华; 司合帅; 王�华; 翟玉山
Original assignee: Huawei Technologies Co Ltd; CDGM Glass Co Ltd
Current assignee: Huawei Technologies Co Ltd; CDGM Glass Co Ltd
Priority date: 2020-05-27
Filing date: 2020-05-27
Publication date: 2022-04-15
Anticipated expiration: 2040-05-27
Also published as: CN111574049A

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, and more particularly to a glass composition useful in the field of semiconductor manufacturing.

Background

In the field of semiconductor manufacturing, materials such as metal, ceramic, and single crystal silicon are generally used as substrates for wafers during the manufacturing process, so as to prevent the wafers from being deformed during the processes of photolithography, cleaning, packaging, and the like. Although the substrate material of metal, ceramic and monocrystalline silicon has better mechanical strength and acid-base corrosion resistance, the substrate material is opaque, so a heating stripping process is required in the process of stripping the substrate and the wafer. If a light-transmitting glass composition is used as the production substrate, a photo-lift-off process may be used. Compared with a heating stripping process, the light stripping process can greatly reduce the process time and the stripping cost, simultaneously avoid the chip wafer from being baked at high temperature, and improve the yield of the chip manufacturing process. The optical lift-off process generally uses ultraviolet laser, which requires the glass substrate material to have a high transmittance to the working wavelength.

The substrate material is generally combined with the resin material, which requires that the thermal expansion coefficient of the substrate material is matched with that of the resin material, otherwise, when the wafer undergoes high-temperature and low-temperature changes in the chip manufacturing process, the wafer is warped and deformed, and the chip is discarded. Meanwhile, the glass substrate material is required to have stronger thermal shock resistance when undergoing high and low temperature changes.

The chip manufacturing process can be subjected to acid-base cleaning for many times, so that the glass substrate material is required to have excellent water resistance, acid resistance and alkali resistance, otherwise, the glass substrate can be dissolved in the process solution, and great loss is caused. In addition, for the mainstream large-size manufacturing process in the semiconductor field at present, the material of the glass substrate is preferably selected to meet the requirements of large-size and high-quality processing.

Disclosure of Invention

The invention aims to solve the technical problem of providing a glass composition which has a proper thermal expansion coefficient, higher ultraviolet transmittance, excellent water resistance, acid resistance and alkali resistance and meets the requirements of large-caliber high-quality processing.

The technical scheme adopted by the invention for solving the technical problem is as follows:

a glass composition having the components, expressed in mole percent, comprising: SiO 2₂：55～80％；B₂O₃： 2～15％；TiO₂：0.5～10％；ZnO：0.5～12％；Al₂O₃：0～10％；Na₂O：1～15％； K₂O：1～12％。

Further, the above glass composition, whose components are expressed in mole percent, further comprises: 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.

Further, the above glass composition has components expressed by mole percent, and the content of each component satisfies one or more of the following 9 cases:

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.

Further, the above glass composition, whose components are expressed in mole percent, contains: 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.

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.

Further, the above glass composition, whose components are expressed in mole percent, contains: 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.

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) of 4.0 to 8.0。

Further, the above glass composition has the components expressed in mole percent, 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)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.

Further, the above glass composition, whose components are expressed in mole percent, contains: 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.

Further, the above glass composition, whose components are expressed in mole percent, contains: 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％。

Further, the above glass composition has a thermal expansion coefficient α_20-300℃Is 60X 10^-7/K～90 ×10^-7Preferably 65X 10,/K^-7/K～85×10^-7K, more preferably 68X 10^-7/K～80×10^-7K; and/or light transmission rate tau_360nmIs 75% or more, preferably 80% or more, more preferablyPreferably more than 85%; and/or a Young's modulus E of 6500X 10⁷Pa or more, preferably 6800X 10⁷Pa～8500×10⁷Pa, more preferably 7000X 10⁷Pa～8000×10⁷Pa; and/or transition temperature T_g520 ℃ to 600 ℃, preferably 530 ℃ to 590 ℃, more preferably 540 ℃ to 570 ℃.

Further, the stability of the acid resistance of the above glass composition 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.

A package carrier made from any of the glass compositions described above.

A device comprising the glass composition of any of the above.

The invention has the beneficial effects that: 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 field of semiconductor manufacturing.

Detailed Description

The following describes in detail embodiments of the glass composition of the present invention, but the present invention is not limited to the embodiments described below, and can be carried out with appropriate modifications within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. In the following, the glass composition of the present invention is sometimes referred to simply as glass.

[ glass composition ]

The ranges of the components of the glass composition of the present invention are described below. In the present specification, unless otherwise specified, the contents and total contents of the respective components are all expressed in terms of mole percent (mol%) relative to the total amount of glass substances in terms of composition of oxides. Here, the "composition in terms of oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the constituent components (components) of the glass composition of the present invention are decomposed in the melt and converted into oxides, the total amount of the oxides is defined as 100%.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.

< essential Components and optional Components >

SiO₂Is one of the main components of the glass of the present invention in which an appropriate amount of SiO is present₂Can ensure that the glass has higher water resistance and acid resistance, and can realize high ultraviolet transmittance at the same time. If SiO₂The content of the glass is less than 55 percent, and the water resistance and the acid resistance of the glass and the ultraviolet transmittance of the glass are lower than the design requirements. If SiO₂The content of (b) is more than 80%, the melting temperature of the glass is sharply increased, high-quality glass is not easily obtained in production, and the thermal expansion coefficient of the glass is lower than that expected by design. Thus, SiO in the present invention₂The content of (b) is limited to 55 to 80%, preferably 60 to 78%, more preferably 65 to 75%.

Appropriate amount of B₂O₃When the glass is added into glass, the structure of the glass can be converted to a compact direction, the water resistance and the acid resistance of the glass are improved, and if the content of the glass is lower than 2%, the effect is not obvious. If B is₂O₃The content of the glass is higher than 15%, and the water resistance and acid resistance of the glass are rapidly reduced. Thus, B₂O₃The content of (b) is limited to 2 to 15%, preferably 3 to 12%, more preferably 4 to 10%.

In some embodiments of the invention, B₂O₃/SiO₂The value of (A) affects the difficulty of glass production, when B₂O₃/SiO₂When the glass melting temperature is less than 0.03, the glass melting temperature is increased, and the glass is suitable for refractory materialsThe corrosion is intensified, more coloring impurities and inclusions are easily introduced into the glass, the short-wave transmittance of the glass cannot meet the design requirement, and the probability of generating defects on the surface of a product is increased. When B is present₂O₃/SiO₂Above 0.25, the melting temperature does not drop significantly, while B₂O₃The increased erosion of the refractory material also leads to the easy introduction of more colored impurities and inclusions into the glass, the short-wave transmittance of the glass does not meet the design requirements, and the probability of generating defects on the surface of the product is increased. Thus, in the present invention, B₂O₃/SiO₂When the value of (A) is between 0.03 and 0.25, preferably between 0.04 and 0.2, and more preferably between 0.05 and 0.15, the smelting temperature can be lower, and the corrosion of the glass to refractory materials in the smelting process can be ensured to be lower.

Appropriate amount of P₂O₅The glass can be added into the glass to increase the strength of the glass, but if the content of the glass exceeds 5 percent, micro-phase is easily generated in the glass, and a part of short-wave wavelength can be scattered by the micro-phase, so that the transmittance can not meet the design requirement. Thus, P₂O₅The content of (B) is limited to 0 to 5%, preferably 0 to 3%. In some embodiments, it is more preferred not to add P when the glass strength is designed to meet the use requirements₂O₅。

An appropriate amount of Al₂O₃The addition of the glass into the glass can improve the water resistance and acid resistance of the glass and simultaneously can reduce the thermal expansion coefficient of the glass, especially in the presence of alkali metal oxide. If Al is present₂O₃The content of (A) is higher than 10%, the thermal expansion coefficient of the glass is rapidly reduced, and the design requirement cannot be met. Thus, Al₂O₃The content of (b) is limited to 0 to 10%, preferably 0.5 to 8%, more preferably 1 to 6%.

Appropriate amount of TiO₂The glass has the advantages of improving the water resistance, acid resistance and alkali resistance of the glass, reducing the thermal expansion coefficient of the glass and improving the thermal shock resistance of the glass when being added into the glass. If TiO₂The content of (a) is less than 0.5%, the above effects are not obvious; if TiO₂The content of (A) is more than 10%The short-wave transmittance of the glass is rapidly reduced, especially in an environment where the smelting atmosphere is unstable. More importantly, a high content of TiO₂The refractive index of the glass can be rapidly increased, the reflection loss of short-wave wavelength can be increased under the condition of not plating an antireflection film, the short-wave transmittance is further reduced, and meanwhile, the thermal expansion coefficient of the glass is reduced, so that the design requirement cannot be met. Thus, TiO in the present invention₂The content of (b) is limited to 0.5 to 10%, preferably 1 to 8%. In some embodiments, TiO is more preferred in view of the difficulty of controlling the atmosphere during glass melting₂The content of (A) is 1-5%.

Ti ions and Al ions in the glass belong to positive ions with stronger electronegativity, and complex synergistic effect can occur in the alkali-containing glass of the system, and especially the anti-crystallization performance of the glass can be influenced. The inventors have discovered that, in some embodiments, when TiO is used₂/Al₂O₃When the value of (A) is 3.0 or less, the tendency of devitrification of the glass is reduced, which is particularly important in producing a product having a specification exceeding 340mm in width and 50mm in thickness, or a product having a diameter larger than 340mm in which the raw glass blank is press-molded by heat treatment again. Therefore, if it is desired to obtain a low defect product with a caliber of more than 340mm, TiO is preferred₂/Al₂O₃A value of (D) is 3.0 or less, and TiO is more preferable₂/Al₂O₃Is 2.5 or less, and TiO is more preferable₂/Al₂O₃Is 2.0 or less.

Appropriate amount of ZrO₂The chemical stability and the thermal shock resistance of the glass can be improved by adding the glass into the glass, but the glass is characterized in that the melting temperature of the glass is obviously increased, and if the content of the glass is higher than 5 percent, inclusion defects are easy to appear in the glass. Thus ZrO₂The content of (b) is limited to 5% or less, preferably 3% or less. In some embodiments, where the glass is chemically stable and has a margin in strength, it is more preferred not to add ZrO₂。

The field strength of ZnO in divalent metal oxide is high, the ZnO added into the glass can improve the acid resistance, water resistance and alkali resistance of the glass, and can reduce the thermal expansion coefficient of the glass, especially in a glass system containing alkali metal. If the content of ZnO is less than 0.5%, the above effect is not significant. If the content of ZnO exceeds 12%, the transition temperature of the glass is rapidly lowered, so that the glass is easily softened and deformed in a high-temperature working environment, thereby adversely affecting 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%.

Through a great deal of experimental research of the inventor, the glass contains B₂O₃In the meantime, the existence of ZnO can further reduce the melting temperature of the glass, and a high-quality product can be more easily obtained, if ZnO/B₂O₃The above effect is not significant, if the value of (A) is less than 0.1; if ZnO/B₂O₃Above 5.0, the glass transition temperature is rapidly lowered and the heat resistance does not meet the design requirements. On the other hand, when ZnO/B₂O₃When the value of (A) is 0.1-5.0, the water resistance, acid resistance and alkali resistance of the glass are compared with those of the glass which is singly added with B₂O₃The time is more excellent. Thus, ZnO/B in the present invention₂O₃The value of (b) 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 belong to alkaline earth metal oxides, and when the MgO, CaO, SrO and BaO are added into glass, the refractive index and the transition temperature of the glass can be improved, and the stability and the thermal expansion coefficient of the glass can be adjusted. However, the addition of the alkaline earth metal oxide causes a rapid increase in the Young's modulus of the glass, and when the glass materials have the same coefficient of thermal expansion, the glass having a low Young's modulus has better thermal shock resistance. Therefore, in view of the above, the total amount of addition of MgO + CaO + SrO + BaO of the alkaline earth metal oxide is preferably 10% or less, more preferably 5% or less. In some embodiments, it is further preferred that no alkaline earth oxide be added if the glass has a stability, coefficient of thermal expansion and transition temperature that meet design requirements.

In some applications of semiconductor processing, higher refractive index is required to achieve matching of the optical system, or higher transition temperature is required, which requires the addition of small amounts of alkaline earth oxides. In order to avoid rapid deterioration of the water-, acid-and alkali-resistance properties of the glass while adding the alkaline earth metal oxide, it is conceivable to add MgO, CaO, SrO, BaO singly or in combination in this order. If the content of the alkaline earth metal oxides such as MgO, CaO, SrO, BaO and the like is more than 5 percent, the devitrification resistance of the glass is rapidly reduced, and a large-caliber high-quality product is not easy to obtain. Therefore, the contents of MgO, CaO, SrO, and BaO are each limited to 5% or less, preferably 4% or less, and more preferably 3% or less.

As a result of extensive experimental studies by the inventors, it has been found that when a certain amount of alkaline earth metal oxide is present in the glass, it is considered that the ZnO content can be adjusted to reduce the loss of the chemical stability and thermal shock resistance of the glass. When the value of (MgO + CaO + SrO + BaO)/ZnO is 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less, a glass having a higher refractive index and satisfying the chemical stability, thermal expansion coefficient, heat resistance and thermal shock resistance required for the design of the present invention can be obtained relatively easily.

In some embodiments of the invention, when it is desired to raise the glass refractive index and transition temperature, a suitable amount of La may be added₂O₃、Y₂O₃、Gd₂O₃、Nb₂O₅、WO₃Etc., but when the content thereof alone or in combination exceeds 5%, devitrification resistance and short-wave transmittance of the glass are deteriorated. Thus, La₂O₃、 Y₂O₃、Gd₂O₃、Nb₂O₅、WO₃The content of (b) is 5% or less, preferably 3% or less, more preferably 1% or less, and further preferably not contained. Further, La is preferable₂O₃、Y₂O₃、Gd₂O₃、Nb₂O₅、 WO₃The total content of (a) is 5% or less, more preferably 3% or less, and still more preferably 1% or less.

Li₂O、Na₂O、K₂O is an alkali metal oxide, and its content in the glass of the present invention is closely related to the thermal expansion coefficient, chemical stability and dielectric constant of the glass.

Li₂The addition of O to the glass can lower the glass melting temperature and has chemical stability to the glass compared with other two alkali metal oxidesThe losses are minimal. However, if Li₂The content of O is more than 5 percent, and the solidification speed of the glass is slow in the forming process, namely the process flow of cooling the molten glass from a liquid state to a solid state, which is unfavorable for producing products with the width (or diameter) of more than 340mm and the thickness of more than 40mm, and the delamination and the crystallization are easy to occur, which is fatal to the production of large-size high-quality products. On the other hand, the glass transition temperature is lowered, and the heat resistance does not meet the design requirements. Thus, Li₂The content of O is limited to 5% or less, preferably 3% or less, and more preferably no Li is added₂O。

Na₂The addition of O into the glass can obviously improve the thermal expansion coefficient of the glass, and simultaneously can reduce the high-temperature viscosity of the glass, so that the large-caliber high-quality product can be obtained more easily. If however Na₂The content of O exceeds 15%, the chemical stability of the glass is rapidly reduced, and the design requirement cannot be met. If Na₂The content of O is less than 1%, the thermal expansion coefficient of the glass does not meet the design requirements, and the chemical stability is also deteriorated. Thus, Na₂The content of O is limited to 1 to 15%, preferably 2 to 12%, more preferably 4 to 10%.

K₂The addition of O to the glass can raise the thermal expansion coefficient of the glass and lower the high temperature viscosity of the glass, especially in the presence of Na₂In the case where O coexists, an appropriate amount of K₂The addition of O to the glass does not significantly impair the chemical stability of the glass. But if K₂The content of O exceeds 12%, and the water resistance, acid resistance and alkali resistance of the glass are deteriorated. If K₂The content of O is less than 1%, and the effects of increasing the thermal expansion coefficient and reducing the high-temperature viscosity are not obvious. Thus, K₂The content of O is limited to 1 to 12%, preferably 2 to 10%, more preferably 3 to 8%.

In some embodiments of the invention, Na₂O and K₂If the total content of O exceeds 25%, the thermal expansion coefficient of the glass exceeds the design requirement, and the dielectric constant of the glass rapidly increases, resulting in rapid deterioration of the insulating properties of the glass, which is disadvantageous for some applications requiring insulation. If the total content is less than 4%, the thermal expansion coefficient of the glass does not meet the design requirement, and the glass has a thermal expansion coefficient of less than 4%The coloring capability of the valence-variable components in the glass is enhanced, and the short-wave transmittance of the glass does not meet the design requirement. Thus, Na₂O and K₂Total content Na of O₂O+K₂O is preferably 4 to 25%, more preferably 5 to 20%, and further preferably 8 to 18%.

In some embodiments of the invention, (Na) is₂O+K₂O)/(B₂O₃+ ZnO) below 0.2, the glass system is deficient in free oxygen, resulting in B₂O₃And the probability of components such as ZnO entering the glass network is reduced, so that the chemical stability is reduced, and meanwhile, the thermal expansion coefficient of the glass is reduced, and the design requirement cannot be met. When (Na)₂O+K₂O)/(B₂O₃+ ZnO) is greater than 5.0, the free oxygen in the glass system is excessive, the chemical stability of the glass is drastically reduced, and the thermal expansion coefficient of the glass exceeds the design requirements. Therefore, (Na) is preferred₂O+K₂O)/(B₂O₃+ ZnO) is 0.2 to 5.0, more preferably 0.3 to 4.0, and still more preferably 0.5 to 2.0.

It is generally accepted in the art that the alkaline earth oxides MgO, CaO, SrO, BaO, etc. are added to the glass as compared to the alkali oxides Li₂O、Na₂O、K₂O and the like are more favorable for improving the chemical stability, and the inventor finds through experiments that in the glass of the system, the capability of providing free oxygen is weaker than that of alkali metal oxide due to alkaline earth metal oxide, when (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) value greater than 1.0 causes severe breakage of the internal network of the glass, which in turn reduces the chemical stability of the glass, especially if (MgO + CaO + SrO + BaO)/(Na) is immersed in strongly alkaline solutions₂O+K₂O) is greater than 1.0, alkaline earth metal ions are more easily precipitated by etching, which is very disadvantageous for some processes in semiconductor processing. Thus, in some embodiments of the invention, (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is preferably 1.0 or less, more preferably 0.5 or less, and still more preferably 0.3 or less.

In the present invention, Na is used for obtaining a suitable thermal expansion coefficient₂O and K₂O is necessary to the glass but leads to a decrease in the chemical stability of the glass. The inventor of the invention has found that Al exists in the glass₂O₃When present, the type and relative content of alkali metal oxide can change the microstructure of the glass, and have a large influence on the chemical stability of the glass. In some embodiments, when Na is satisfied₂O/K₂The value of O is 0.8-5.0, preferably 0.85-4.0, and more preferably 0.9-3.0; and/or satisfy (Na)₂O+K₂O)/Al₂O₃When the value of (a) is 0.5 to 8.0, preferably 1.0 to 6.0, more preferably 2.0 to 5.0, the chemical stability of the glass can be significantly optimized.

To obtain a high quality glass product, the inventors have found that, in some embodiments, (SiO) is₂+TiO₂)/(Na₂O + ZnO) of more than 15.0, the glass becomes difficult to melt and clarify, and the removal of bubbles, inclusions and the like inside the glass is very difficult, and the inherent quality A cannot be obtained₀The glass is a product of grade and above, and the inner stripes of the glass are serious. If (SiO)₂+TiO₂)/(Na₂O + ZnO) is less than 2.5, and the thermal expansion coefficient of the glass rapidly rises and exceeds the design requirement. Therefore, (SiO) is preferred in the present invention₂+TiO₂)/(Na₂O + ZnO) is 2.5 to 15.0, more preferably 3.0 to 10.0, and still more preferably 4.0 to 8.0.

In some embodiments, if the glass contains a relatively high content of alkali oxides, Al₂O₃And B₂O₃Complex synergistic effect is formed, and the structure of the glass is subjected to nonlinear change within a certain range. The inventor researches and discovers that when Al is used₂O₃/B₂O₃When the value of (A) is 0.2-2.0, the synergistic effect of the two oxides can obviously improve the alkali resistance stability of the glass, and Al is preferred₂O₃/B₂O₃The value of (A) is 0.25 to 1.5, more preferably Al₂O₃/B₂O₃The value of (b) is 0.3 to 1.0.

In some embodiments of the invention, 0-1% Sb is added₂O₃、SnO₂SnO, NaCl, sulfate and CeO₂As a clarifying agent, preferably Sb is used₂O₃As the clarifying agent, the clarifying effect of the glass can be improved, and 0-0.5% of the clarifying agent is preferably added, and 0-0.2% of the clarifying agent is more preferably added.

F is added into the glass, which can increase the volatilization of glass raw materials, easily cause environmental pollution and poor glass streak degree, so that the glass of the invention preferably does not contain F. Ta₂O₅Since the addition to the glass greatly increases the cost of the glass and deteriorates the melting property of the glass, it is preferable that Ta is not contained in the glass of the present invention₂O₅。

< component which should not be contained >

In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the glass becomes practically free from substances contaminating the environment. Therefore, the glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.

To achieve environmental friendliness, the glasses according to the invention do not contain As₂O₃And PbO. Although As₂O₃Has the effects of eliminating bubbles and better preventing the glass from coloring, but As₂O₃The addition of (b) increases the platinum attack of the glass on the furnace, particularly on the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace. PbO can significantly improve the high-refractivity and high-dispersion properties of the glass, but PbO and As₂O₃All cause environmental pollution.

The phrase "not containing", "not adding" or "0%" as used herein means that the compound, molecule, element or the like is not intentionally added to the glass of the present invention as a raw material; however, it is also within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the glass, and may be present in small or trace amounts in the final glass.

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

< stability against acid Effect >

Stability of the acid resistance of the glass (D)_A) (powder method) the test was carried out according to the method prescribed in GB/T17129. Acid resistance stability is sometimes referred to herein simply as acid resistance or acid resistance stability.

Stability of the acid resistance of the glasses according to the invention (D)_A) Is 2 or more, preferably 1.

< stability against Water action >

Stability of the glass to Water action (D)_W) (powder method) the test was carried out according to the method prescribed in GB/T17129. Stability to hydrolytic action is sometimes referred to herein simply as water resistance or hydrolytic stability.

Stability to Water action of the glasses according to the invention (D)_W) Is 2 or more, preferably 1.

< stability of alkali resistance action >

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

Processing glass into a test sample with the specification of 30mm multiplied by 2mm, polishing six surfaces, putting the test sample into 2000ml of NaOH solution, wherein the concentration of the NaOH solution is 0.01mol/L, the p H value is 12.0, monitoring the change condition of the p H value of the test solution by a p H meter in the test process, timely replacing the reaction test solution, and measuring the weight loss of the sample by an electronic balance after corroding for 100 hours at the temperature of 50 ℃, wherein the weight loss is expressed in mg.

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

< coefficient of thermal expansion >

The thermal expansion coefficient of the invention is the average thermal expansion coefficient of the glass at 20-300 ℃, so thatα_20-300℃The test is shown to be carried out according to the method specified in GB/T7962.16-2010.

Coefficient of thermal expansion (. alpha.) of the glass of the invention_20-300℃) Is 60X 10^-7/K～90×10^-7Preferably 65X 10,/K^-7/K～85×10^-7K, more preferably 68X 10^-7/K～80×10^-7/K。

< light transmittance >

The light transmittance of the invention refers to the internal transmittance at 360nm of a glass sample with the thickness of 10mm, and is shown as tau_360nmThe test is shown to be carried out according to the method specified in GB/T7962.12-2010.

Internal transmittance (τ) at 360nm of the glass of the invention_360nm) Is 75% or more, preferably 80% or more, and more preferably 85% or more.

< transition temperature >

Transition temperature (T) of glass_g) Testing according to the method specified in GB/T7962.16-2010.

Transition temperature (T) of the glasses according to the invention_g) 520 ℃ to 600 ℃, preferably 530 ℃ to 590 ℃, more preferably 540 ℃ to 570 ℃.

< Young's modulus >

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

wherein G ═ V_S ²ρ

In the formula:

e is Young's modulus, Pa;

g is shear modulus, Pa;

V_Tis the longitudinal wave velocity, m/s;

V_Sis the transverse wave velocity, m/s;

rho is the density of the glass, g/cm³。

The Young's modulus (E) of the glass of the invention is 6500X 10⁷Pa or more, preferably 6800X 10⁷Pa～ 8500×10⁷Pa, more preferably 7000×10⁷Pa～8000×10⁷Pa。

The glass composition of the present invention, because of the excellent properties described above, can be applied to packaging carriers (substrate materials) for semiconductor processes, and can also be used for manufacturing various devices or instruments, such as imaging apparatuses, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automotive field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for camera apparatuses and devices in the automotive field, monitoring security field.

[ production method ]

The method for producing the glass composition of the present invention is as follows: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace at 1300-1500 ℃ for smelting, and after clarification, stirring and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

[ examples ]

To further clearly illustrate and explain the technical solution of the present invention, the following non-limiting examples 1 to 20 are provided.

In this example, glass compositions having compositions shown in tables 1 to 2 were obtained by the above-described methods for producing glass compositions. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2.

TABLE 1

TABLE 2

Claims

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 to 12% of ZnO/B₂O₃0.1 to 1.5 (SiO)₂+TiO₂)/(Na₂O + ZnO) is 2.5 to 6.64.

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, characterized in that its components, expressed in mole percentages, are present in a content satisfying one or more of the following 7 cases:

1)B₂O₃/SiO₂0.03 to 0.25;

2)Al₂O₃/B₂O₃0.2 to 2.0;

3)TiO₂/Al₂O₃is 3.0 or less;

4)Na₂O+K₂o is 4-25%;

5)Na₂O/K₂o is 0.8 to 5.0；

6)(Na₂O+K₂O)/Al₂O₃0.5 to 8.0;

7)(Na₂O+K₂O)/(B₂O₃+ ZnO) is 0.2 to 5.0.

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 1.5;

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 6.64.

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 1.5;

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 6.64.

8. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: al (Al)₂O₃/B₂O₃0.2 to 1.0.

9. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: al (Al)₂O₃/B₂O₃0.2 to 0.88.

10. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: al (Al)₂O₃/B₂O₃0.25 to 0.53.

11. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: al (Al)₂O₃/B₂O₃0.25 to 0.45.

12. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: TiO 2₂/Al₂O₃0.4 to 2.5.

13. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: TiO 2₂/Al₂O₃0.7 to 2.0.

14. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: TiO 2₂/Al₂O₃Is 1.0 to 2.0.

15. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: TiO 2₂/Al₂O₃1.1 to 1.8.

16. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: ZnO/B₂O₃0.1 to 1.0.

17. Glass composition according to claim 1 or 2, characterised in thatIn that its components are expressed in mole percentages, in which: ZnO/B₂O₃0.2 to 1.0.

18. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: ZnO/B₂O₃0.3 to 0.8.

19. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: ZnO/B₂O₃0.4 to 0.7.

20. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/Al₂O₃Is 2.8 to 6.0.

21. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/Al₂O₃Is 3.2 to 5.3.

22. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/Al₂O₃Is 3.9 to 5.0.

23. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/Al₂O₃Is 4.1 to 5.0.

24. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/Al₂O₃2.8 to 4.6.

25. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/Al₂O₃Is 3.2 to 4.6.

26. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.64 to 1.56.

27. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.64 to 1.17.

28. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.78 to 1.15.

29. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.85 to 1.15.

30. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.85 to 1.

31. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (SiO)₂+TiO₂)/(Na₂O + ZnO) is 3.0 to 6.53.

32. Glass composition according to claim 1 or 2, characterised in thatThe composition is expressed in mole percent, wherein: (SiO)₂+TiO₂)/(Na₂O + ZnO) is 4.0 to 6.53.

33. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (SiO)₂+TiO₂)/(Na₂O + ZnO) is 4.62 to 6.53.

34. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (SiO)₂+TiO₂)/(Na₂O + ZnO) of 5.31 to 6.53.

35. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (SiO)₂+TiO₂)/(Na₂O + ZnO) is 5.73 to 6.53.

36. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (SiO)₂+TiO₂)/(Na₂O + ZnO) is 5.89 to 6.53.

37. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (SiO)₂+TiO₂)/(Na₂O + ZnO) is 6.13 to 6.53.

38. 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 less than 1.0; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 1.0 or less.

39. 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 less than 0.8; and/or (a)MgO+CaO+SrO+BaO)/(Na₂O+K₂O) is 0.5 or less.

40. 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 less than 0.5; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 0.3 or less.

41. Glass composition according to claim 1 or 2, characterized in that its composition, expressed in mole percentages, comprises: MgO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent.

42. Glass composition according to claim 1 or 2, characterized in that its composition, expressed in mole percentages, comprises: MgO: 0 to 4 percent; and/or CaO: 0 to 4 percent; and/or SrO: 0 to 4 percent; and/or BaO: 0 to 4 percent.

43. Glass composition according to claim 1 or 2, characterized in that its composition, expressed in mole percentages, comprises: MgO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent.

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

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

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

47. Glass composition according to claim 1 or 2, characterized in that the glass composition has a coefficient of thermal expansion α_20-300℃Is 60X 10^-7/K～90×10^-7K; and/or light transmission rate tau_360nmIs more than 75 percent; and/or a Young's modulus E of 6500X 10⁷Pa is above; and/or transition temperature T_gIs 520-600 ℃.

48. Glass composition according to claim 1 or 2, characterized in that the glass composition has a coefficient of thermal expansion α_20-300℃Is 65X 10^-7/K～85×10^-7K; and/or light transmission rate tau_360nmMore than 80 percent; and/or a Young's modulus E of 6800X 10⁷Pa～8500×10⁷Pa; and/or transition temperature T_gAt 530-590 ℃.

49. Glass composition according to claim 1 or 2, characterized in that the glass composition has a coefficient of thermal expansion α_20-300℃Is 68 x 10^-7/K～80×10^-7K; and/or light transmission rate tau_360nmMore than 85 percent; and/or a Young's modulus E of 7000X 10⁷Pa～8000×10⁷Pa; and/or transition temperature T_gIs 540-570 ℃.

50. The glass composition according to claim 1 or 2, characterized in that the glass composition has an acid action resistance stability D_AIs more than 2 types; and/or stability against water effectsD_WIs more than 2 types; and/or alkali action stability the glass samples have a weight loss of less than 10mg as measured according to the test conditions and requirements of ISO 10629.

51. The glass composition according to claim 1 or 2, characterized in that the glass composition has an acid action resistance stability D_AIs of type 1; and/or stability against water action D_WIs of type 1; and/or alkali action stability the glass sample loses less than 8mg weight after being measured according to the test conditions and requirements of ISO 10629.

52. Glass composition according to claim 1 or 2, wherein the glass composition has a stability to alkali action of less than 5mg loss in a glass sample as measured according to the test conditions and requirements of ISO 10629.

53. A package carrier made of the glass composition according to any one of claims 1 to 52.

54. A device comprising the glass composition of any of claims 1 to 52.