Glass material

Abstract

The application provides a glass material with a proper thermal expansion coefficient and suitable for application in the field of semiconductor manufacturing. The glass material contains, in terms of percentage by weight, SiO2: 43-63%; B2O3: 0-15%; Al2O3: 2-15%; BaO: 11-30%; and CaO: 3-18%. Through reasonable component design, the glass material obtained by the application has a proper thermal expansion coefficient and is suitable for application in the field of semiconductor manufacturing.

Description

TECHNICAL FIELD

[0001] The present application relates to a glass material, in particular to a glass material used in the field of semiconductor manufacturing. BACKGROUND

[0002] In the prior art, metal, ceramic and monocrystalline silicon materials with good mechanical strength and acid and alkali corrosion resistance are usually used as substrates for wafers in the manufacturing process to prevent the wafer from deforming in the processes of photolithography, cleaning and packaging. However, since the metal, ceramic and monocrystalline silicon substrate materials are not transparent, a heated stripping process is needed in the substrate and wafer stripping process. If a transparent glass material is used as a manufacturing substrate, a light stripping process can be used. Compared with the heated stripping process, the light stripping process can greatly reduce the process time and stripping cost, and avoid baking the chip wafer at high temperature, thereby improving the yield of the chip manufacturing process. On the other hand, the substrate material is usually combined with a resin material, which requires that the thermal expansion coefficient of the substrate material matches that of the resin material. Otherwise, the wafer will be warped and deformed during the high and low temperature changes in the chip manufacturing process, resulting in chip scrap.

[0003] For the above reasons, it is of great significance to develop a glass material with a suitable thermal expansion coefficient for the development of the field of semiconductor manufacturing. SUMMARY

[0004] The technical problem to be solved by the present application is to provide a glass material with a suitable thermal expansion coefficient to meet the application in the field of semiconductor manufacturing.

[0005] The technical solution adopted by the present application to solve the technical problem is:

[0006] The glass material contains, in terms of weight percentage, SiO2: 43-63%; B2O3: 0-15%; Al2O3: 2-15%; BaO: 11-30%; and CaO: 3-18%.

[0007] Further, the glass material contains, in terms of weight percentage, SrO: 0-12%; and / or ZrO2: 0-8%; and / or MgO: 0-10%; and / or Rn2O: 0-8%; and / or Ln2O3: 0-8%; and / or ZnO: 0-8%; and / or TiO2: 0-5%; and / or P2O5: 0-5%; and / or clarifying agent: 0-2%, wherein the Rn2O is one or more of Li2O, Na2O and K2O, the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3 and Yb2O3, and the clarifying agent is one or more of Sb2O3, SnO2 and CeO2.

[0008] A glass material, the components of which consist of, expressed in percentage by weight: SiO2: 43-63%; B2O3: 0-15%; Al2O3: 2-15%; BaO: 11-30%; CaO: 3-18%; SrO: 0-12%; ZrO2: 0-8%; MgO: 0-10%; Rn2O: 0-8%; Ln2O3: 0-8%; ZnO: 0-8%; TiO2: 0-5%; P2O5: 0-5%; fining agent: 0-2%, said Rn2O being one or more of Li2O, Na2O, K2O, Ln2O3 being one or more of La2O3, Gd2O3, Y2O3, Yb2O3, the fining agent being one or more of Sb2O3, SnO2, CeO2.

[0009] Further, the glass material, the components of which consist of, expressed in percentage by weight: SiO2: 46-60%, preferably SiO2: 49-56%; and / or B2O3: 0.5-10%, preferably B2O3: 1-7%; and / or Al2O3: 4-13%, preferably Al2O3: 6-11%; and / or BaO: 15-25%, preferably BaO: 17-23%; and / or CaO: 5-15%, preferably CaO: 7-12%; and / or SrO: 0.5-10%, preferably SrO: 1-7%; and / or ZrO2: 0-5%, preferably ZrO2: 0-2%; and / or MgO: 0-5%, preferably MgO: 0-2%; and / or Rn2O: 0-5%, preferably Rn2O: 0-1%; and / or Ln2O3: 0-5%, preferably Ln2O3: 0-2%; and / or ZnO: 0-5%, preferably ZnO: 0-2%; and / or TiO2: 0-3%, preferably TiO2: 0-1%; and / or P2O5: 0-3%, preferably P2O5: 0-1%; and / or fining agent: 0-1%, preferably fining agent: 0-0.8%, said Rn2O being one or more of Li2O, Na2O, K2O, Ln2O3 being one or more of La2O3, Gd2O3, Y2O3, Yb2O3, the fining agent being one or more of Sb2O3, SnO2, CeO2.

[0010] Further, the glass material, the components of which consist of, expressed in percentage by weight: RO: 16-60%, preferably RO: 20-50%, more preferably RO: 25-45%, further preferably RO: 28-40%, said RO being the total content of MgO, CaO, SrO, BaO.

[0011] Further, the glass material, the components of which consist of, expressed in percentage by weight:

[0012] (Al2O3 + CaO) / SiO2 is 0.1 to 0.65, preferably (Al2O3 + CaO) / SiO2 is 0.15 to 0.55, more preferably (Al2O3 + CaO) / SiO2 is 0.2 to 0.5, further preferably (Al2O3 + CaO) / SiO2 is 0.25 to 0.45.

[0013] Further, the glass material, the components of which are expressed in percentage by weight, wherein: SiO2 / (BaO + CaO) is 1.0 to 4.0, preferably SiO2 / (BaO + CaO) is 1.2 to 3.0, more preferably SiO2 / (BaO + CaO) is 1.3 to 2.5, further preferably SiO2 / (BaO + CaO) is 1.5 to 2.0.

[0014] Further, the glass material, the components of which are expressed in percentage by weight, wherein: (BaO + SrO) / SiO2 is 0.2 to 0.8, preferably (BaO + SrO) / SiO2 is 0.25 to 0.7, more preferably (BaO + SrO) / SiO2 is 0.3 to 0.65, further preferably (BaO + SrO) / SiO2 is 0.35 to 0.6.

[0015] Further, the glass material, the components of which are expressed in percentage by weight, wherein: BaO / Al2O3 is 1.0 to 10.0, preferably BaO / Al2O3 is 1.2 to 8.0, more preferably BaO / Al2O3 is 1.5 to 5.0, further preferably BaO / Al2O3 is 1.8 to 3.0.

[0016] Further, the glass material, the components of which are expressed in percentage by weight, wherein: Rn2O / BaO is 0.6 or less, preferably Rn2O / BaO is 0.5 or less, more preferably Rn2O / BaO is 0.3 or less, further preferably Rn2O / BaO is 0.1 or less, the Rn2O being one or more of Li2O, Na2O, K2O.

[0017] Further, the glass material, the components of which are expressed in percentage by weight, wherein:

[0018] (Ln2O3 + CaO) / BaO is 0.15 to 1.5, preferably (Ln2O3 + CaO) / BaO is 0.2 to 1.0, more preferably (Ln2O3 + CaO) / BaO is 0.25 to 0.8, further preferably (Ln2O3 + CaO) / BaO is 0.3 to 0.7, the Ln2O3 being one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0019] Further, the glass material, the components of which are represented by weight percentage, wherein: SrO / BaO is 0.02-0.8, preferably SrO / BaO is 0.05-0.6, more preferably SrO / BaO is 0.1-0.5, further preferably SrO / BaO is 0.1-0.4.

[0020] Further, the glass material, the components of which are represented by weight percentage, wherein:

[0021] (ZnO+TiO2) / SrO is 2.0 or less, preferably (ZnO+TiO2) / SrO is 1.5 or less, more preferably (ZnO+TiO2) / SrO is 1.0 or less, further preferably (ZnO+TiO2) / SrO is 0.5 or less.

[0022] Further, the glass material, the components of which are represented by weight percentage, wherein:

[0023] (SiO2+Al2O3) / (BaO+B2O3) is 1.2-5.0, preferably (SiO2+Al2O3) / (BaO+B2O3) is 1.5-4.0, more preferably (SiO2+Al2O3) / (BaO+B2O3) is 1.7-3.5, further preferably (SiO2+Al2O3) / (BaO+B2O3) is 2.0-3.0.

[0024] Further, the glass material, the components of which do not contain MgO; and / or do not contain ZnO; and / or do not contain P2O5; and / or do not contain TiO2; and / or do not contain Rn2O, the Rn2O being one or more of Li2O, Na2O, K2O; and / or do not contain Ln2O3, the Ln2O3 being one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0025] Further, the glass material has a thermal expansion coefficient α 20-300℃ of 50x10 -7 / K-68x10 -7 / K, preferably 51x10 -7 / K-65x10 -7 / K, more preferably 52x10 -7 / K-64x10 -7 / K; and / or a transition temperature T g of 620℃-760℃, preferably 650℃-750℃, more preferably 680℃-740℃; and / or a Young's modulus E of 6500x10 7 Pa or more, preferably 7000x10 7 Pa or more, more preferably 7500x10 7Pa or more; and / or acid resistance stability D A is 2 or more, preferably 1; and / or water resistance stability D W is 2 or more, preferably 1; and / or the bubble degree is A class or more, preferably A0 class or more, more preferably A 00 class or more, preferably B class or more.

[0026] Further, the glass material has a viscosity of 250 dPaS or less at 1450°C, preferably a viscosity of 220 dPaS or less at 1450°C, more preferably a viscosity of 200 dPaS or less at 1450°C; and / or a viscosity of 400 dPaS or more at 1300°C, preferably a viscosity of 500 dPaS or more at 1300°C, more preferably a viscosity of 600 dPaS or more at 1300°C; and / or a coefficient of thermal expansion precision of ±3x10 -7 / K or less, preferably ±2x10 -7 / K or less.

[0027] A packaging container made of the above glass material.

[0028] A glass element made of the above glass material.

[0029] An apparatus containing the above glass material.

[0030] The present application has the following beneficial effects: through reasonable component design, the glass material obtained by the present application has a suitable coefficient of thermal expansion, and is suitable for the field of semiconductor manufacturing. DETAILED DESCRIPTION

[0031] Hereinafter, the embodiments of the glass material of the present application will be described in detail, but the present application is not limited to the following embodiments, and can be implemented by appropriately changing within the scope of the object of the present application. Furthermore, regarding the repeatedly described parts, although there are appropriately omitted descriptions, the gist of the present application will not be limited thereby. In the present specification, the glass material of the present application will be sometimes referred to simply as glass.

[0032] [GLASS MATERIAL]

[0033] Hereinafter, the range of each component of the glass material of the present application will be described. In the present application, if not otherwise specified, the content of each component, the total content are all expressed in terms of weight percentage (wt%), i.e., the content of each component, the total content are expressed in terms of weight percentage with respect to the total amount of the glass material in terms of oxide composition. Here, the "oxide composition" refers to the case where the total amount of the oxide is 100% when the oxide, the complex salt, the hydroxide, and the like, which are used as raw materials for the glass material composition of the present application, are decomposed and converted into oxides upon melting.

[0034] Unless otherwise indicated in specific instances, the numerical ranges set forth in the present application include the upper and lower values, "above" and "below" include the endpoint values, and all integers and fractions within the range, without being limited to the specific values listed in the defined range. As referred to herein, "and / or" is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0035] <essential components and optional components>

[0036] SiO2 is the main component of the glass skeleton, which has a great influence on the high temperature viscosity and chemical stability of the glass, especially water resistance. If the content of SiO2 is less than 43%, it is difficult to achieve the design requirements of water resistance of the glass. The high temperature viscosity of the glass has an important influence on the intrinsic quality of the glass and the forming of large size. The glass of the system of the present application is usually refined at a temperature above 1450°C to obtain better bubble degree. If the viscosity of the glass at 1450°C is too large, it is difficult for the glass to remove bubbles, and the bubble degree of the product is low. On the other hand, in order to obtain a glass blank with a larger diameter, the glass usually needs to be formed at a suitable viscosity to be smoothly spread and cooled to obtain a large diameter product with better striation. If the content of SiO2 is higher than 63%, the high temperature viscosity of the glass is difficult to meet the design requirements. Therefore, the content of SiO2 in the present application is 43% to 63%, preferably 46% to 60%, and more preferably 49% to 56%.

[0037] B2O3 can further enhance the glass network in the glass and improve the chemical stability of the glass, and can also adjust the thermal expansion coefficient of the glass. If the content of B2O3 is more than 15%, B2O3 is easy to volatilize under high temperature melting conditions. When the melting environment changes, the thermal expansion coefficient of the glass changes, resulting in that the precision of the expansion coefficient of the glass is difficult to meet the design requirements. Therefore, the content of B2O3 in the present application is 0 to 15%, preferably 0.5 to 10%, and more preferably 1 to 7%.

[0038] Al2O3 can improve the chemical stability of the glass and reduce the thermal expansion coefficient of the glass, especially in the case of containing more alkaline earth metal oxides in the glass system. If the content of Al2O3 is less than 2%, the above effect is not obvious, and if the content of Al2O3 is more than 15%, the melting of the glass becomes very difficult, which is not conducive to improving the bubble degree and striation of the glass. Therefore, the content of Al2O3 in the present application is 2% to 15%, preferably 4% to 13%, and more preferably 6% to 11%.

[0039] MgO, CaO, SrO and BaO are alkaline earth metal oxides, which can enhance the stability of the glass, reduce the high temperature viscosity of the glass, adjust the expansion coefficient and transition temperature of the glass. In the present application, the total content of MgO, CaO, SrO and BaO, RO, is controlled in the range of 16-60% to obtain the above effects, preferably RO is 20-50%, more preferably RO is 25-45%, and further preferably RO is 28-40%.

[0040] The inventors have found through a large number of experimental studies that the type, content and relative content of alkaline earth metal oxides have a great influence on the chemical stability, thermal expansion coefficient, transition temperature and anti-crystallization performance of the glass.

[0041] MgO has the strongest ability to reduce the thermal expansion coefficient of the glass compared to other alkaline earth metal components, and thus can be appropriately contained in scenarios where it is necessary to reduce the thermal expansion coefficient. If the content of MgO exceeds 10%, the anti-crystallization performance of the glass deteriorates rapidly. Therefore, the content of MgO in the present application is 0-10%, preferably 0-5%, and more preferably 0-2%. In some embodiments, it is further preferred that MgO is not contained.

[0042] CaO can greatly reduce the high temperature viscosity of the glass. If the content of CaO exceeds 18%, the thermal expansion coefficient of the glass is higher than the design requirement. Therefore, the content of CaO is 3-18%, preferably 5-15%, and more preferably 7-12%.

[0043] In some embodiments, the ratio between the total content of Al2O3 and CaO, Al2O3+CaO, and the content of SiO2, (Al2O3+CaO) / SiO2, is controlled in the range of 0.1-0.65, so that the glass can more easily obtain appropriate high temperature viscosity and transition temperature, and the precision of the thermal expansion coefficient of the glass is optimized. Therefore, (Al2O3+CaO) / SiO2 is preferably 0.1-0.65, and more preferably (Al2O3+CaO) / SiO2 is 0.15-0.55. Further, controlling (Al2O3+CaO) / SiO2 in the range of 0.2-0.5 can further optimize the bubble degree and chemical stability of the glass. Therefore, (Al2O3+CaO) / SiO2 is further preferably 0.2-0.5, and more further preferably (Al2O3+CaO) / SiO2 is 0.25-0.45.

[0044] BaO can reduce the high temperature viscosity of the glass and adjust the transition temperature of the glass. If the content of BaO is less than 11%, the stability of the glass decreases and the high temperature viscosity is higher than the design requirement. If the content of BaO is higher than 30%, the thermal expansion coefficient of the glass is higher than the design requirement, the chemical stability of the glass is poor, and the density increases. Therefore, the content of BaO is 11-30%, preferably 15-25%, and more preferably 17-23%.

[0045] In some embodiments, the ratio BaO / Al2O3 between the content of BaO and the content of Al2O3 is controlled in the range of 1.0-10.0, which is beneficial for the glass to obtain a suitable coefficient of thermal expansion and high temperature viscosity. Therefore, it is preferred that BaO / Al2O3 is in the range of 1.0-10.0, more preferably BaO / Al2O3 is in the range of 1.2-8.0. Further, controlling BaO / Al2O3 in the range of 1.5-5.0 can further improve the striation and chemical stability of the glass. Therefore, it is further preferred that BaO / Al2O3 is in the range of 1.5-5.0, more further preferred that BaO / Al2O3 is in the range of 1.8-3.0.

[0046] In some embodiments, the ratio SiO2 / (BaO+CaO) between the content of SiO2 and the total content of BaO and CaO (BaO+CaO) is controlled in the range of 1.0-4.0, which is beneficial for the glass to obtain a suitable coefficient of thermal expansion while improving the bubble degree of the glass. Therefore, it is preferred that SiO2 / (BaO+CaO) is in the range of 1.0-4.0, more preferably SiO2 / (BaO+CaO) is in the range of 1.2-3.0. Further, controlling SiO2 / (BaO+CaO) in the range of 1.3-2.5 can further optimize the Young's modulus and the coefficient of thermal expansion precision of the glass. Therefore, it is further preferred that SiO2 / (BaO+CaO) is in the range of 1.3-2.5, more further preferred that SiO2 / (BaO+CaO) is in the range of 1.5-2.0.

[0047] In some embodiments, the ratio (BaO+SrO) / SiO2 between the total content of BaO and SrO (BaO+SrO) and the content of SiO2 is controlled in the range of 0.2-0.8, which is beneficial for improving the Young's modulus of the glass and preventing the chemical stability of the glass from decreasing. Therefore, it is preferred that (BaO+SrO) / SiO2 is in the range of 0.2-0.8, more preferably (BaO+SrO) / SiO2 is in the range of 0.25-0.7. Further, controlling (BaO+SrO) / SiO2 in the range of 0.3-0.65 can further optimize the bubble degree and anti-crystallization performance of the glass. Therefore, it is further preferred that (BaO+SrO) / SiO2 is in the range of 0.3-0.65, more further preferred that (BaO+SrO) / SiO2 is in the range of 0.35-0.6.

[0048] In some embodiments, the ratio of the total content of SiO2and Al2O3to the total content of BaO and B2O3, (SiO2+ Al2O3) / (BaO + B2O3), is controlled in the range of 1.2 to 5.0, the glass has a high Young's modulus while having a suitable coefficient of thermal expansion. Therefore, it is preferred that (SiO2+ Al2O3) / (BaO + B2O3) is in the range of 1.2 to 5.0, more preferably (SiO2+ Al2O3) / (BaO + B2O3) is in the range of 1.5 to 4.0. Further, controlling (SiO2+ Al2O3) / (BaO + B2O3) in the range of 1.7 to 3.5, the high temperature viscosity and the transition temperature of the glass can be further optimized, and the coefficient of thermal expansion of the glass can be optimized with precision. Therefore, it is further preferred that (SiO2+ Al2O3) / (BaO + B2O3) is in the range of 1.7 to 3.5, and more further preferred that (SiO2+ Al2O3) / (BaO + B2O3) is in the range of 2.0 to 3.0.

[0049] SrO can adjust the high temperature viscosity and the transition temperature of the glass, and increase the Young's modulus of the glass, but if its content is too high, the glass crystallization resistance is reduced. Therefore, the content of SrO is in the range of 0 to 12%, preferably in the range of 0.5 to 10%, and more preferably in the range of 1 to 7%.

[0050] In some embodiments, the ratio of the content of SrO to the content of BaO, SrO / BaO, is controlled in the range of 0.02 to 0.8, the glass can obtain a suitable transition temperature while preventing the glass crystallization resistance from being reduced. Therefore, it is preferred that SrO / BaO is in the range of 0.02 to 0.8, and more preferably SrO / BaO is in the range of 0.05 to 0.6. Further, controlling SrO / BaO in the range of 0.1 to 0.5, the chemical stability and the coefficient of thermal expansion of the glass can be further optimized. Therefore, it is further preferred that SrO / BaO is in the range of 0.1 to 0.5, and more further preferred that SrO / BaO is in the range of 0.1 to 0.4.

[0051] ZnO can improve the chemical stability of the glass and reduce the coefficient of thermal expansion of the glass, but if its content is higher than 8%, it becomes particularly difficult to remove bubbles during the high temperature fining process. Therefore, the content of ZnO is in the range of 0 to 8%, preferably in the range of 0 to 5%, and more preferably in the range of 0 to 2%. In some embodiments, it is further preferred that ZnO is not contained.

[0052] ZrO2 can improve the chemical stability of the glass. More importantly, the system glass melts at a relatively high temperature. A small amount of ZrO2 in the glass can significantly reduce the corrosion of the glass liquid to the refractory material of the melting tank, greatly improve the service life of the melting tank, and reduce the risk of generating unfused substances. If the content of ZrO2 is higher than 8%, unfused substances are likely to appear in the glass, resulting in poor internal quality of the glass. Therefore, the content of ZrO2 is limited to 8% or less, preferably 5% or less, and more preferably 2% or less.

[0053] A suitable amount of P2O5 can increase the strength of the glass, but if its content exceeds 5%, microphase separation is likely to occur in the glass, which will scatter a part of the short wavelength, so that the light transmittance cannot meet the design requirements. Therefore, the content of P2O5 is limited to 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred to not contain P2O5.

[0054] TiO2 can improve the crystallization resistance and mechanical strength of the glass. If the content of TiO2 exceeds 5%, the light transmittance of the glass decreases rapidly, making it difficult for subsequent laser stripping, and the coefficient of thermal expansion of the glass decreases, which is difficult to meet the design requirements. Therefore, the content of TiO2 is 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, it is further preferred to not contain TiO2.

[0055] In some embodiments, the ratio between the total content of ZnO and TiO2 (ZnO+TiO2) and the content of SrO (ZnO+TiO2) / SrO is controlled to be 2.0 or less, which can make the glass have a suitable transition temperature while preventing the crystallization resistance of the glass from decreasing. Therefore, it is preferred that (ZnO+TiO2) / SrO is 2.0 or less, and more preferably (ZnO+TiO2) / SrO is 1.5 or less. Further, controlling (ZnO+TiO2) / SrO to be 1.0 or less can further optimize the striation degree and chemical stability of the glass. Therefore, it is further preferred that (ZnO+TiO2) / SrO is 1.0 or less, and more preferably (ZnO+TiO2) / SrO is 0.5 or less.

[0056] Alkali metal oxides Rn2O (Rn2O is one or more of Li2O, Na2O, K2O) can quickly reduce the high-temperature viscosity of the glass, but after precipitation, it will have a greater impact on the electrical conductivity of the process liquid in the semiconductor process. Therefore, the content of Rn2O is 8% or less, preferably 5% or less, more preferably 1% or less, and further preferably does not contain Rn2O.

[0057] In some embodiments, the ratio Rn20 / BaO between the content of alkali metal oxide Rn20 and the content of BaO is controlled to be 0.6 or less, so that the glass can obtain a suitable high-temperature viscosity and thermal expansion coefficient while preventing the glass from having a reduced resistance to devitrification. Therefore, it is preferable that Rn20 / BaO be 0.6 or less, more preferable that Rn20 / BaO be 0.5 or less, further preferable that Rn20 / BaO be 0.3 or less, and still further preferable that Rn20 / BaO be 0.1 or less.

[0058] Ln203 (Ln203 is one or more of La203, Gd203, Y203, Yb203) can lower the high-temperature viscosity of the glass, and if the content thereof is too high, the resistance to devitrification of the glass rapidly decreases. Therefore, the content of Ln203 is 8% or less, preferably 5% or less, more preferably 2% or less, and further preferably the glass does not contain Ln203.

[0059] In some embodiments, the ratio (Ln203+CaO) / BaO between the total content of Ln203 and CaO (Ln203+CaO) and the content of BaO is controlled to be in the range of 0.15 to 1.5, so that the glass can easily obtain a desired high-temperature viscosity and improve the striation of the glass. Therefore, it is preferable that (Ln203+CaO) / BaO be in the range of 0.15 to 1.5, and more preferable that (Ln203+CaO) / BaO be in the range of 0.2 to 1.0. Further, controlling (Ln203+CaO) / BaO to be in the range of 0.25 to 0.8 can further optimize the Young's modulus of the glass. Therefore, it is further preferable that (Ln203+CaO) / BaO be in the range of 0.25 to 0.8, and still further preferable that (Ln203+CaO) / BaO be in the range of 0.3 to 0.7.

[0060] In the present application, one or more components selected from the group consisting of 0 to 2% of Sb203, Sn02, and Ce02 are contained as fining agents to improve the fining effect of the glass. It is preferable that the content of the fining agent be 0 to 1%, and more preferable that the content of the fining agent be 0 to 0.8%. In some embodiments, it is preferable to use Sb203 and / or Sn02 as the fining agent, and more preferable to use Sb203 as the fining agent.

[0061] <Components not to be contained>

[0062] The oxides of Th, Cd, Tl, Os, Be and Se have a tendency to be controlled in use as harmful chemical substances in recent years, and measures for environmental protection are necessary not only in the manufacturing process of glass but also in the processing process and disposal after productization. Therefore, in the case where the influence on the environment is taken into consideration, it is preferable that they are not contained in practice except for inevitable mixing. Thus, the glass becomes practically free from substances polluting the environment. Therefore, the glass of the present application can be manufactured, processed and discarded without taking special measures for environmental countermeasures.

[0063] In order to realize environmental friendliness, the glass of the present application does not contain As2O3and PbO. Although As2O3has the effect of eliminating bubbles and better preventing glass from coloring, the addition of As2O3increases 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 refractive index and high dispersion properties of the glass, but both PbO and As2O3are substances polluting the environment.

[0064] The "does not contain" "0%" described herein means that the compound, molecule or element, etc. is not intentionally added as a raw material to the glass of the present application; however, as a raw material and / or equipment for producing the glass, there can be some impurities or components that are not intentionally added and can be contained in a small amount or trace amount in the final glass, which is also within the scope of protection of the present patent.

[0065] Next, the properties of the glass material of the present application will be described.

[0066] <Acid action resistance>

[0067] The acid action resistance (D A ) of the glass was measured according to the method prescribed in GB / T 17129 (powder method). The acid action resistance is sometimes simply referred to as acid resistance or acid stability in this specification.

[0068] In some embodiments, the acid action resistance (D A ) of the glass material of the present application is Class 2 or more, preferably Class 1.

[0069] <Water action resistance>

[0070] The water action resistance (D W ) of the glass was measured according to the method prescribed in GB / T 17129 (powder method). The water action resistance is sometimes simply referred to as water resistance or water stability in this specification.

[0071] In some embodiments, the water action resistance (D W ) of the glass material of the present application is Class 2 or more, preferably Class 1.

[0072] <Anti-crystallization performance>

[0073] For the continuous production of large-scale and high-quality glass, the anti-crystallization performance of the glass is very important. If the anti-crystallization performance of the glass is poor, crystallization is likely to occur at the three-phase interface during the continuous forming process for several hundred or even several thousand hours, resulting in that the internal quality of the glass cannot meet the design requirements, and in severe cases, the forming device is blocked, the feeding, melting, and refining processes in the front stage are stopped, and the normal production is seriously affected.

[0074] The test method of the anti-crystallization performance of the present application is as follows: 1000ml of glass is placed in a crucible, the melting and refining processes are completed, and then the temperature is lowered to 1300℃, and after 48 hours of heat preservation, the glass is poured into a mold for forming, and after annealing and cooling, the crystallization on the surface and inside of the glass is observed using a microscope.

[0075] In some embodiments, the glass material of the present application does not show surface and internal crystallization after 48 hours of heat preservation at 1300℃, and the anti-crystallization performance of the glass material is excellent.

[0076] <Thermal expansion coefficient>

[0077] The thermal expansion coefficient of the present application refers to the average thermal expansion coefficient of the glass at 20-300℃, represented by α 20-300℃ , and tested according to the method specified in GB / T 7962.16-2010.

[0078] In some embodiments, the thermal expansion coefficient (α 20-300℃ ) of the glass material of the present application is 50×10 -7 / K-68×10 -7 / K, preferably 51×10 -7 / K-65×10 -7 / K, more preferably 52×10 -7 / K-64×10 -7 / K.

[0079] <Thermal expansion coefficient precision>

[0080] The test method of the thermal expansion coefficient precision is as follows: during the glass manufacturing process, a glass sample is taken every hour, annealed at-2℃ / hour, and then the thermal expansion coefficient (α 20-300℃The absolute value of the difference between the actual test value of the thermal expansion coefficient of the glass sample and the theoretical thermal expansion coefficient value of the glass (i.e., |the actual test value of the thermal expansion coefficient-the theoretical thermal expansion coefficient value of the glass|), when the absolute value of the difference is the largest, the difference is the thermal expansion coefficient accuracy. The smaller |the actual test value of the thermal expansion coefficient-the theoretical thermal expansion coefficient value of the glass| is, the more conducive to the application of the glass in semiconductor manufacturing.

[0081] In some embodiments, the thermal expansion coefficient accuracy of the glass material of the present application is ±3×10 -7 / K, preferably ±2×10 -7 / K.

[0082] <Transition temperature>

[0083] The transition temperature (T g ) of the glass is tested according to the method specified in GB / T 7962.16-2010.

[0084] If the transition temperature of the glass is low, the heat resistance of the glass decreases, and softening deformation easily occurs in high-temperature processing. If the transition temperature of the glass is too high, it will cause design difficulties in the heat resistance of the precision annealing equipment, resulting in a decrease in the reliability of the precision annealing equipment, especially when the glass blank with a caliber greater than 450 mm is precision annealed, it needs to be kept at the transition temperature for a long time. If the transition temperature is too high, the reliability of the precision annealing equipment will be greatly reduced, thereby affecting the thermal expansion coefficient and the thermal expansion coefficient accuracy.

[0085] In some embodiments, the transition temperature (T g ) of the glass material of the present application is 620℃ or higher, preferably 650℃ or higher, more preferably 680℃ or higher.

[0086] In some embodiments, the transition temperature (T g ) of the glass material of the present application is 760℃ or lower, preferably 750℃ or lower, more preferably 740℃ or lower.

[0087] <Young's modulus>

[0088] The Young's modulus (E) of the glass is calculated using the following formula:

[0089]

[0090] Wherein, G=V S 2 ρ

[0091] In the formula:

[0092] E is the Young's modulus, Pa;

[0093] G is the shear modulus, Pa;

[0094] V T Vp is the velocity of the longitudinal wave, m / s;

[0095] V S Vt is the velocity of the transverse wave, m / s;

[0096] p is the density of the glass, g / cm3. 3 .

[0097] In some embodiments, the Young's modulus (E) of the glass material of the present application is 6500 x 10 7 Pa or more, preferably 7000 x 10 7 Pa or more, more preferably 7500 x 10 7 Pa or more.

[0098] <Bubble degree>

[0099] The bubble degree of the glass is tested according to the method specified in GB / T 7962.8-2010.

[0100] In some embodiments, the bubble degree of the glass material of the present application is A class or more, preferably A0 class or more, more preferably A 00 class.

[0101] <Streak degree>

[0102] The streak degree of the glass is tested by using a streak instrument composed of a point light source and a lens, and is compared with a standard sample from the direction where the streaks are most easily seen, and is classified into 4 grades, as shown in Table 1 below.

[0103] Table 1. Streak degree classification table

[0104] grade degree of streaking A no visible streaks under prescribed test conditions. B fine and scattered streaks under prescribed test conditions. C slight parallel streaks under prescribed test conditions. D coarse parallel streaks under prescribed test conditions.

[0105] In some embodiments, the streak degree of the glass material of the present application is C class or more, preferably B class or more.

[0106] <Viscosity>

[0107] The viscosity of the glass is tested according to the following method: using a THETA Rheotronic II high temperature viscometer by the rotation method, and the numerical unit is dPaS (poise), and the smaller the value, the smaller the viscosity.

[0108] In some embodiments, the viscosity of the glass material at 1450°C is 250 dPaS or less, preferably the viscosity at 1450°C is 220 dPaS or less, more preferably the viscosity at 1450°C is 200 dPaS or less.

[0109] In some embodiments, the glass material of the present application has a viscosity of 400 dPaS or more at 1300°C, preferably a viscosity of 500 dPaS or more at 1300°C, and more preferably a viscosity of 600 dPaS or more at 1300°C.

[0110] The glass material of the present application can be used to manufacture a packaging carrier (substrate material) for semiconductor processing due to its excellent properties described above.

[0111] The glass material of the present application can be used to manufacture various glass elements, and can provide various glass elements such as lenses, prisms, etc. with high optical value. As examples of lenses, various lenses such as concave meniscus lenses, convex meniscus lenses, lenticular lenses, double concave lenses, plano-convex lenses, and plano-concave lenses, etc. having spherical or aspherical lens surfaces can be given.

[0112] The glass material of the present application can also be used to manufacture various devices (devices described in the present application include instruments, apparatuses, etc.), such as imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology / information transmission, optics / illumination in the automotive field, photolithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or video recording devices and apparatuses used in the field of in-vehicle and surveillance security.

[0113] [Manufacturing method]

[0114] The manufacturing method of the glass material of the present application is as follows: the glass material of the present application uses carbonates, nitrates, sulfates, hydroxides, oxides, phosphates, metaphosphates, etc. as raw materials, and after batching according to conventional methods, the prepared batch is put into a melting furnace at 1300-1500°C for melting, and after refining, stirring, and homogenization, a homogeneous molten glass without bubbles and undissolved substances is obtained, which is cast in a mold and annealed to form. Those skilled in the art can appropriately select raw materials, process methods, and process parameters according to actual needs.

[0115] [Examples]

[0116] In order to further clearly illustrate and describe the technical solutions of the present application, the following non-limiting Examples 1#-24# are provided. The glass materials with the compositions shown in Tables 2-4 are obtained by the manufacturing method of the glass material described above. In addition, the properties of each glass are determined by the test methods described in the present application, and the test results are shown in Tables 2-4.

[0117] Table 2.

[0118]

[0119]

[0120] Table 3.

[0121]

[0122]

[0123]

[0124] Table 4.

[0125]

[0126]

Claims

1. Glass material, characterized in that Its components, expressed in weight percentage, contain: SiO2: 43-63%; B2O3: 0-7%; Al2O3: 2-15%; BaO: 15-30%; CaO: 7-18%, SiO2 / (BaO+CaO) is 1.0-2.5, BaO / Al2O3 is 1.5-10.0, and (BaO+SrO) / SiO2 is 0.35-0.

8.

2. The glass material according to claim 1, wherein Its components, expressed in weight percentage, further contain: SrO: 0-12%; and / or ZrO2: 0-8%; and / or MgO: 0-10%; and / or Rn2O: 0-8%; and / or Ln2O3: 0-8%; and / or ZnO: 0-8%; and / or TiO2: 0-5%; and / or P2O5: 0-5%; and / or clarifier: 0-2%, wherein the Rn2O is one or more of Li2O, Na2O, and K2O; the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3; and the clarifier is one or more of Sb2O3, SnO2, and CeO2.

3. Glass material, characterized in that Its components, expressed in weight percentage, are SiO2: 43-63%; B2O3: 0-7%; Al2O3: 2-15%; BaO: 15-30%; CaO: 7-18%; SrO: 0-12%; ZrO2: 0-8%; MgO: 0-10%; Rn2O: 0-8%; Ln2O3: 0-8%; ZnO: 0~8%; TiO2: 0~5%; P2O5: 0~5%; Clarifier: composition: 0-2%, SiO2 / (BaO+CaO) is 1.0-2.5, BaO / Al2O3 is 1.5-10.0, (BaO+SrO) / SiO2 is 0.35-0.8, Rn2O is one or more of Li2O, Na2O, K2O, Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, and the clarifier is one or more of Sb2O3, SnO2, and CeO2.

4. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: SiO2: 46-60%; and / or B2O3: 0.5-7%; and / or Al2O3: 4-13%; and / or BaO: 15-25%; and / or CaO: 7-15%; and / or SrO: 0.5-10%; and / or ZrO2: 0-5%; and / or MgO: 0-5%; and / or Rn2O: 0-5%; and / or Ln2O3: 0-5%; and / or ZnO: 0-5%; and / or TiO2: 0-3%; and / or P2O5: 0-3%; and / or clarifier: 0-1%, wherein Rn2O is one or more of Li2O, Na2O, and K2O, Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3, and the clarifier is one or more of Sb2O3, SnO2, and CeO2.

5. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: SiO2: 49-56%; and / or B2O3: 1-7%; and / or Al2O3: 6-11%; and / or BaO: 17-23%; and / or CaO: 7-12%; and / or SrO: 1-7%; and / or ZrO2: 0-2%; and / or MgO: 0-2%; and / or Rn2O: 0-1%; and / or Ln2O3: 0-2 %; and / or ZnO: 0-2%; and / or TiO2: 0-1%; and / or P2O5: 0-1%; and / or clarifier: 0-0.8%, wherein Rn2O is one or more of Li2O, Na2O, and K2O, Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3, and the clarifier is one or more of Sb2O3, SnO2, and CeO2.

6. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein RO is 16-60%, and the RO is the total content of MgO, CaO, SrO and BaO.

7. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: RO: 20-50%, and the RO is the total content of MgO, CaO, SrO and BaO.

8. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: RO: 25-45%, and the RO is the total content of MgO, CaO, SrO and BaO.

9. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein RO is 28-40%, and the RO is the total content of MgO, CaO, SrO and BaO.

10. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein (Al2O3+CaO) / SiO2 is 0.1 to 0.

65.

11. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein (Al2O3+CaO) / SiO2 is 0.15-0.

55.

12. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein (Al2O3+CaO) / SiO2 is 0.2-0.

5.

13. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein (Al2O3+CaO) / SiO2 is 0.25-0.

45.

14. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein SiO2 / (BaO+CaO) is 1.2 to 2.

5.

15. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein SiO2 / (BaO+CaO) is 1.3 to 2.

5.

16. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein SiO2 / (BaO+CaO) is 1.5-2.

0.

17. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein (BaO+SrO) / SiO2 is 0.35-0.

7.

18. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein (BaO+SrO) / SiO2 is 0.35-0.

65.

19. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein (BaO+SrO) / SiO2 is 0.35-0.

6.

20. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein BaO / Al2O3 is 1.5 to 8.

0.

21. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein BaO / Al2O3 is 1.5-5.

0.

22. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein BaO / Al2O3 is 1.8-5.

0.

23. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein BaO / Al2O3 is 1.8 to 3.

0.

24. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein Rn2O / BaO is less than 0.6, and the Rn2O is one or more of Li2O, Na2O, and K2O.

25. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: Rn2O / BaO is less than 0.5, and the Rn2O is one or more of Li2O, Na2O, and K2O.

26. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: Rn2O / BaO is less than 0.3, and the Rn2O is one or more of Li2O, Na2O, and K2O.

27. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: Rn2O / BaO is less than 0.1, and the Rn2O is one or more of Li2O, Na2O, and K2O.

28. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (Ln2O3+CaO) / BaO is 0.15-1.5, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

29. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (Ln2O3+CaO) / BaO is 0.2-1.0, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

30. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (Ln2O3+CaO) / BaO is 0.25-0.8, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

31. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (Ln2O3+CaO) / BaO is 0.3-0.7, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

32. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein SrO / BaO is 0.02-0.

8.

33. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein SrO / BaO is 0.05-0.

6.

34. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein SrO / BaO is 0.1-0.

5.

35. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein SrO / BaO is 0.1 to 0.

4.

36. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (ZnO+TiO2) / SrO is less than 2.

0.

37. The glass material according to any one of claims 1 to 3, characterized in that Its components are expressed in weight percentage, wherein: (ZnO+TiO2) / SrO is less than 1.

5.

38. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (ZnO+TiO2) / SrO is less than 1.

0.

39. The glass material according to any one of claims 1 to 3, characterized in that Its components are expressed in weight percentage, wherein: (ZnO+TiO2) / SrO is less than 0.

5.

40. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (SiO2+Al2O3) / (BaO+B2O3) is 1.2-5.

0.

41. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (SiO2+Al2O3) / (BaO+B2O3) is 1.5-4.

0.

42. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (SiO2+Al2O3) / (BaO+B2O3) is 1.7-3.

5.

43. The glass material according to any one of claims 1 to 3, characterized in that The components are expressed in weight percentage, wherein: (SiO2+Al2O3) / (BaO+B2O3) is 2.0-3.

0.

44. The glass material according to any one of claims 1 to 3, characterized in that Its components do not contain MgO; and / or do not contain ZnO; and / or do not contain P2O5; and / or do not contain TiO2; and / or do not contain Rn2O; and / or do not contain Ln2O3, wherein Rn2O is one or more of Li2O, Na2O, and K2O, and Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

45. The glass material according to any one of claims 1 to 3, characterized in that The thermal expansion coefficient of the glass material α 20-300℃ 50×10 -7 / K~68×10 -7 / K; and / or transition temperature T g 620℃~760℃;and / or Young's modulus E is 6500×10 7 Pa or above; and / or acid resistance stability D A Class 2 or above; and / or water resistance stability D W The degree of bubble is Class A or above; and / or the degree of streak is Class C or above.

46. ​​The glass material according to any one of claims 1 to 3, characterized in that The thermal expansion coefficient of the glass material α 20-300℃ 51×10 -7 / K~65×10 -7 / K; and / or transition temperature T g 650℃~750℃;and / or Young's modulus E is 7000×10 7 Pa or above; and / or acid resistance stability D A Class 1; and / or water resistance stability D W Class 1; and / or the bubble degree is A0 or above; and / or the streak degree is B or above.

47. The glass material according to any one of claims 1 to 3, characterized in that The thermal expansion coefficient of the glass material α 20-300℃ 52×10 -7 / K~64×10 -7 / K; and / or transition temperature T g 680℃~740℃;and / or Young's modulus E is 7500×10 7 Pa or above; and / or the bubble degree is A 00 class.

48. The glass material according to any one of claims 1 to 3, characterized in that The viscosity of the glass material at 1450°C is less than 250 dPaS; and / or the viscosity at 1300°C is greater than 400 dPaS; and / or the thermal expansion coefficient accuracy is ±3×10 -7 / K or less.

49. The glass material according to any one of claims 1 to 3, characterized in that The viscosity of the glass material at 1450°C is less than 220 dPaS; and / or the viscosity at 1300°C is greater than 500 dPaS; and / or the thermal expansion coefficient accuracy is ±2×10 -7 / K or less.

50. The glass material according to any one of claims 1 to 3, characterized in that The glass material has a viscosity of 200 dPaS or less at 1450° C. and / or a viscosity of 600 dPaS or more at 1300° C.

51. A packaging carrier, characterized in that Made of the glass material according to any one of claims 1 to 50.

52. Glass element, characterized in that Made of the glass material according to any one of claims 1 to 50.

53. A device, characterized in that Contains the glass material according to any one of claims 1 to 50.

Images