high modulus glass

Abstract

The application provides a high modulus glass with high Young's modulus and light transmittance. The high modulus glass contains, in terms of weight percentage, SiO2: 34-46%; B2O3: 2-10%; Al2O3: 20-32%; ZnO: 5-15%; MgO: 5-15%; Y2O3: 1-10%; TiO2: 0.5-8%, wherein Y2O3 / (B2O3+ZnO) is 0.1-1.2. Through reasonable component design, the glass obtained by the application has high Young's modulus and light transmittance, and is suitable for the field of semiconductor manufacturing and the like.

Description

Technical Field

[0001] This invention relates to a glass, and more particularly to a glass with high Young's modulus and high light transmittance. Background Technology

[0002] With the development of the times, glass has been widely used in various fields, such as construction, imaging, and medicine. Due to its excellent mechanical and chemical stability, light transmittance, and the ability to achieve ultra-large sizes at a relatively low cost, glass is a material with great development potential for semiconductor chip packaging carriers.

[0003] Glass used as a carrier is often fabricated into large-sized glass sheets. The higher the Young's modulus of the glass, the less prone it is to deformation during application. In particular, a higher Young's modulus means less likelihood of warping and breakage during the stress phase of the packaging process, thus improving yield. When glass is used in semiconductor packaging, ultraviolet (UV) laser lift-off technology is commonly employed. Compared to traditional lift-off techniques, UV laser lift-off offers advantages such as high yield and low cost. However, it requires the carrier glass to possess high transmittance in the UV band. Higher UV transmittance leads to higher debonding efficiency during packaging and a lower risk of wafer warpage. Simultaneously, high visible light transmittance allows for more efficient and precise optical inspection during the packaging process. Therefore, developing glass with high Young's modulus and high light transmittance is of great significance to the semiconductor manufacturing industry. Summary of the Invention

[0004] Based on the above reasons, the technical problem to be solved by the present invention is to provide a high modulus glass with high Young's modulus and high light transmittance.

[0005] The technical solution adopted by this invention to solve the technical problem is:

[0006] (1) High modulus glass, the composition of which is expressed as a weight percentage, contains: SiO2: 34-46%; B2O3: 2-10%; Al2O3: 20-32%; ZnO: 5-15%; MgO: 5-15%; Y2O3: 1-10%; TiO2: 0.5-8%, of which Y2O3 / (B2O3+ZnO) is 0.1-1.2.

[0007] (2) The high modulus glass according to (1) further comprises, by weight percentage: ZrO2: 0-4%; and / or BaO: 0-4%; and / or SrO: 0-4%; and / or CaO: 0-4%; and / or La2O3: 0-5%; and / or Gd2O3: 0-4%; and / or Nb2O5: 0-3%; and / or WO3: 0-3%; and / or Ta2O5: 0-3%; and / or GeO2: 0-3%; and / or Rn2O: 0-3%; and / or clarifying agent: 0-2%, wherein Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifying agent is one or more of Sb2O3, SnO2, and CeO2.

[0008] (3) A high-modulus glass containing SiO2, B2O3, Al2O3, ZnO, MgO, Y2O3, and TiO2, expressed as a weight percentage, wherein the ratio of Y2O3 / (B2O3+ZnO) is 0.1–1.2, the high-modulus glass has a Young's modulus E of 91 GPa or higher, and a light transmittance T at 550 nm. 550nm The light transmittance at 355nm is above 85.0% (T). 355nm It is above 80.0%.

[0009] (4) The high-modulus glass according to (3) comprises, by weight percentage: SiO2: 34-46%; and / or B2O3: 2-10%; and / or Al2O3: 20-32%; and / or ZnO: 5-15%; and / or MgO: 5-15%; and / or Y2O3: 1-10%; and / or TiO2: 0.5-8%; and / or ZrO2: 0-4%; and / or BaO: 0-4%; and / or SrO: 0-4%; and / or CaO: 0–4%; and / or La2O3: 0–5%; and / or Gd2O3: 0–4%; and / or Nb2O5: 0–3%; and / or WO3: 0–3%; and / or Ta2O5: 0–3%; and / or GeO2: 0–3%; and / or Rn2O: 0–3%; and / or clarifying agent: 0–2%, wherein Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifying agent is one or more of Sb2O3, SnO2, and CeO2.

[0010] (5) The high-modulus glass according to any one of (1) to (4) has a composition expressed as a weight percentage that satisfies one or more of the following nine conditions:

[0011] 1) The MgO / Y2O3 ratio is 0.7 to 8.0, preferably 1.0 to 6.0, more preferably 1.2 to 4.0, and even more preferably 1.3 to 3.0;

[0012] 2) The Al2O3 / SiO2 ratio is 0.46 to 0.85, preferably 0.50 to 0.80, and more preferably 0.53 to 0.73;

[0013] 3) The Al2O3 / Y2O3 ratio is 2.5 to 10.0, preferably 3.0 to 8.0, more preferably 3.5 to 7.0, and even more preferably 4.0 to 6.0;

[0014] 4) The MgO / B2O3 ratio is 0.7 to 6.0, preferably 1.0 to 5.0, more preferably 1.0 to 3.5, and even more preferably 1.2 to 2.5;

[0015] 5) The MgO / (ZrO2+TiO2) ratio is 0.5 to 10.0, preferably 1.0 to 8.0, more preferably 1.5 to 5.0, and even more preferably 1.5 to 3.5.

[0016] 6) The ratio of Y2O3 / (B2O3+ZnO) is 0.1 to 1.0, preferably 0.15 to 0.8, and more preferably 0.2 to 0.6;

[0017] 7) The TiO2 / ZnO ratio is 0.1 to 1.5, preferably 0.15 to 1.0, more preferably 0.2 to 0.8, and even more preferably 0.25 to 0.6;

[0018] 8) The CaO / ZnO ratio is 0.6 or less, preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less;

[0019] 9) The ratio of Rn2O / Al2O3 is 0.13 or less, preferably 0.1 or less, more preferably 0.08 or less, and even more preferably 0.05 or less, wherein Rn2O is one or more of Li2O, Na2O, and K2O.

[0020] (6) The high-modulus glass according to any one of (1) to (4), wherein the composition is expressed in weight percentage, wherein: SiO2: 36-45%, preferably SiO2: 37-43%; and / or B2O3: 3-9%, preferably B2O3: 4-8%; and / or Al2O3: 21-30%, preferably Al2O3: 23-28%; and / or ZrO2: 0-3%, preferably ZrO2: 0-2%; and / or TiO2: 1-7%, preferably TiO2: 2-6%; and / or ZnO: 6-13%, preferably ZnO: 8-12%; and / or BaO: 0-2%, preferably BaO: 0-1%; and / or SrO: 0-2%, preferably SrO: 0-1%; and / or CaO: 0-2%, preferably CaO: 0-1%; and / or MgO: 6-13%, preferably MgO: 8-12%. %; and / or La2O3: 0–3%, preferably La2O3: 0–2%; and / or Y2O3: 2–8%, preferably Y2O3: 3–7%; and / or Gd2O3: 0–3%, preferably Gd2O3: 0–1%; and / or Nb2O5: 0–2%, preferably Nb2O5: 0–1%; and / or WO3: 0–2%, preferably WO3: 0–1%; and / or Ta2O5: 0–2% The preferred components are Ta2O5: 0-1%; and / or GeO2: 0-2%, preferably GeO2: 0-1%; and / or Rn2O: 0-2%, preferably Rn2O: 0-1%; and / or clarifying agent: 0-1%, preferably clarifying agent: 0-0.5%, wherein the Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifying agent is one or more of Sb2O3, SnO2, and CeO2.

[0021] (7) The high modulus glass according to any one of (1) to (4) is free from BaO; and / or free from CaO; and / or free from SrO; and / or free from Gd2O3; and / or free from Nb2O5; and / or free from WO3; and / or free from Ta2O5; and / or free from GeO2; and / or free from Li2O; and / or free from Na2O; and / or free from K2O; and / or free from P2O5; and / or free from Fe2O3; and / or free from F.

[0022] (8) The high-modulus glass according to any one of (1) to (4), wherein the coefficient of thermal expansion of the high-modulus glass is α 20 / 300℃ 30×10 -7 / K~45×10 -7 / K, preferably 32×10 -7 / K~42×10 -7 / K, more preferably 35×10 -7 / K~40×10 -7 / K; and / or acid resistance stability DA Class 3 or more, preferably Class 2 or more; and / or water resistance stability D W It is of class 3 or more, preferably class 2 or more; and / or refractive index n d The Abbe number is 1.56–1.61, preferably 1.57–1.60, more preferably 1.58–1.60; and / or the Abbe number ν. d The value is 49–55, preferably 50–54, more preferably 51–53.5; and / or the Young's modulus E is 91 GPa or more, preferably 93 GPa or more, more preferably 95 GPa or more; and / or the transition temperature T g The temperature is 680°C or higher, preferably 700°C or higher, more preferably 710°C or higher, and even more preferably 710–735°C; and / or the density ρ is 3.00 g / cm³. 3 The preferred value is 2.90 g / cm³. 3 The preferred value is 2.85 g / cm³. 3 The following; and / or 550nm light transmittance T 550nm The transmittance is 85.0% or more, preferably 87.0% or more, more preferably 89.0% or more; and / or the light transmittance T at 355 nm. 355nm The content is 80.0% or more, preferably 82.0% or more, more preferably 84.0% or more; and / or Knoop hardness H K 520×10 7 Pa or higher, preferably 540 × 10 Pa 7 Pa or higher, more preferably 560 × 10 Pa 7 Pa or above.

[0023] (9) A packaging carrier made of any of the high modulus glass described in (1) to (8).

[0024] (10) A glass element made of any of the high modulus glass described in (1) to (8).

[0025] (11) An apparatus comprising any one of the high modulus glass described in (1) to (8), or comprising the glass element described in (10).

[0026] The beneficial effects of this invention are: through reasonable component design, the glass obtained by this invention has high Young's modulus and light transmittance, and is suitable for semiconductor manufacturing and other fields. Detailed Implementation

[0027] The embodiments of the high-modulus glass of the present invention will now be described in detail. However, the present invention is not limited to the embodiments described below, and appropriate modifications can be made to implement it within the scope of the purpose of the present invention. Furthermore, while there are appropriate omissions in the repeated descriptions, this does not limit the spirit of the invention. In this specification, "high modulus" refers to a glass with a high Young's modulus, and the high-modulus glass of the present invention is sometimes simply referred to as glass.

[0028] [Glass]

[0029] The component ranges of the high-modulus glass of the present invention are described below. In this invention, unless otherwise specified, the content of each component, the total content, and the total content are all expressed as weight percentages (wt%), that is, the weight percentage of the content of each component, the total content, and the total content relative to the total amount of glass material converted into oxide composition. Here, "converted into oxide composition" means that when the oxides, complex salts, and hydroxides used as raw materials for the high-modulus glass of the present invention decompose and transform into oxides upon melting, the total amount of such oxides is taken as 100%.

[0030] Unless otherwise specified in the specific context, the numerical ranges listed in this invention include upper and lower limits, and "above" and "below" include endpoint values ​​and all integers and fractions included in the range, but are not limited to the specific values ​​listed when the range is defined. The term "and / or" as used herein is inclusive; for example, "A and / or B" means only A, or only B, or both A and B.

[0031] <Essential and Optional Components>

[0032] SiO2 is a major component constituting the glass framework and has a significant impact on the high-temperature viscosity and coefficient of thermal expansion of glass. If its content is below 34%, the coefficient of thermal expansion of the glass increases, making it difficult to achieve the desired coefficient of thermal expansion as described in this invention, and the transition temperature and devitrification resistance decrease. If the SiO2 content exceeds 46%, the high-temperature viscosity of the glass increases, which is not conducive to obtaining large-size, high-quality glass. Therefore, the SiO2 content in this invention is 34–46%, preferably 36–45%, and more preferably 37–43%.

[0033] Al₂O₃ can increase the Young's modulus of glass, which is beneficial for improving the glass's resistance to warping and breakage. It can also reduce the coefficient of thermal expansion of glass. In this invention, the above effects are achieved by containing more than 20% Al₂O₃. However, if the Al₂O₃ content is too high, the glass's meltability decreases, and its resistance to crystallization declines. Therefore, in this invention, the Al₂O₃ content is 20-32%, preferably 21-30%, and more preferably 23-28%.

[0034] In some embodiments, controlling the Al2O3 / SiO2 ratio (Al2O3 / SiO2) within the range of 0.46 to 0.85 can improve the Young's modulus of the glass while obtaining a suitable coefficient of thermal expansion. Therefore, an Al2O3 / SiO2 ratio of 0.46 to 0.85 is preferred, 0.50 to 0.80 is more preferred, and 0.53 to 0.73 is even more preferred.

[0035] B2O3 can improve the melt flow properties and devitrification resistance of glass. This invention achieves these effects by containing more than 2% B2O3. However, if the B2O3 content exceeds 10%, it is difficult to achieve the desired coefficient of thermal expansion of the glass. Therefore, the B2O3 content in this invention is 2–10%, preferably 3–9%, and more preferably 4–8%.

[0036] ZnO can improve the melting properties of glass and adjust its high-temperature viscosity. However, if its content is too high, the glass transition temperature will decrease, making the glass unsuitable for use in high-temperature environments, and its chemical stability will also decrease. Therefore, the ZnO content is 5–15%, preferably 6–13%, and more preferably 8–12%.

[0037] MgO can improve the light transmittance of glass and reduce its density, but if its content is too high, the chemical stability of the glass will deteriorate. Therefore, the MgO content in this invention is 5-15%, preferably 6-13%, and more preferably 8-12%.

[0038] In some embodiments, controlling the ratio of MgO to B2O3 content (MgO / B2O3) within the range of 0.7 to 6.0 can improve the glass's acid resistance while maintaining a suitable coefficient of thermal expansion. Therefore, a MgO / B2O3 ratio of 0.7 to 6.0 is preferred, more preferably 1.0 to 5.0, even more preferably 1.0 to 3.5, and still more preferably 1.2 to 2.5.

[0039] CaO can improve the meltability of glass, but if its content is too high, the glass's resistance to crystallization will decrease. Therefore, the CaO content is 0-4%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is even more preferable that the glass does not contain CaO.

[0040] In some embodiments, controlling the ratio of CaO content to ZnO content (CaO / ZnO) to below 0.6 can reduce the glass density while preventing a deterioration in the glass's water resistance. Therefore, it is preferable that the CaO / ZnO ratio is below 0.6, more preferably below 0.5, even more preferably below 0.3, and still more preferably below 0.1.

[0041] SrO can adjust the high-temperature viscosity and melting properties of glass, but if its content is too high, the chemical stability of the glass will decrease. Therefore, the SrO content is 0-4%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is even more preferable that the glass does not contain SrO.

[0042] BaO can increase the refractive index of glass and adjust its high-temperature viscosity, but if its content is too high, the coefficient of thermal expansion and density of the glass will increase. Therefore, the BaO content in this invention is 0-4%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that BaO is not present.

[0043] TiO2 can improve the refractive index and dispersion of glass, and adjust its coefficient of thermal expansion. However, if the TiO2 content exceeds 8%, the light transmittance of the glass decreases rapidly, making subsequent laser stripping difficult, and the coefficient of thermal expansion of the glass is hard to meet design requirements. Therefore, the TiO2 content is 0.5–8%, preferably 1–7%, and more preferably 2–6%.

[0044] In some embodiments, controlling the TiO2 / ZnO ratio (TiO2 / ZnO) within the range of 0.1 to 1.5 can improve the hardness of the glass while preventing a decrease in its acid resistance. Therefore, a TiO2 / ZnO ratio of 0.1 to 1.5 is preferred, more preferably 0.15 to 1.0, even more preferably 0.2 to 0.8, and still more preferably 0.25 to 0.6.

[0045] ZrO2 can improve the refractive index and chemical stability of glass, reduce its coefficient of thermal expansion, and optimize its high-temperature viscosity. However, when the ZrO2 content is too high, the glass's resistance to devitrification decreases, and its ultraviolet light transmittance drops. Therefore, the ZrO2 content is 0–4%, preferably 0–3%, and more preferably 0–2%.

[0046] In some embodiments, the ratio of MgO content to the total content of ZrO2 and TiO2 (ZrO2+TiO2), MgO / (ZrO2+TiO2), is controlled within the range of 0.5 to 10.0. This can improve the water resistance of the glass while reducing its density. Therefore, it is preferable that MgO / (ZrO2+TiO2) is 0.5 to 10.0, more preferably 1.0 to 8.0, even more preferably 1.5 to 5.0, and still more preferably 1.5 to 3.5.

[0047] La2O3 can increase the refractive index and Abbe number of glass, improve its chemical stability and devitrification resistance, but if its content is too high, the ultraviolet light transmittance of the glass will decrease. Therefore, the content of La2O3 is 0-5%, preferably 0-3%, and more preferably 0-2%.

[0048] Y₂O₃ can improve the refractive index and devitrification resistance of glass, as well as its Young's modulus. However, if its content is too high, the chemical stability and ultraviolet light transmittance of the glass will decrease. Therefore, the Y₂O₃ content is 1–10%, preferably 2–8%, and more preferably 3–7%.

[0049] In some embodiments, controlling the ratio of Al2O3 content to Y2O3 content (Al2O3 / Y2O3) within the range of 2.5 to 10.0 can improve the hardness of the glass while preventing a decrease in the glass transition temperature. Therefore, it is preferable that the Al2O3 / Y2O3 ratio is 2.5 to 10.0, more preferably 3.0 to 8.0, even more preferably 3.5 to 7.0, and even more preferably 4.0 to 6.0.

[0050] In some embodiments, controlling the ratio of MgO content to Y2O3 content (MgO / Y2O3) within the range of 0.7 to 8.0 is beneficial for improving the light transmittance of the glass and reducing its density. Therefore, a MgO / Y2O3 ratio of 0.7 to 8.0 is preferred, a MgO / Y2O3 ratio of 1.0 to 6.0 is more preferred, a MgO / Y2O3 ratio of 1.2 to 4.0 is even more preferred, and a MgO / Y2O3 ratio of 1.3 to 3.0 is still preferred.

[0051] In some embodiments, the ratio Y2O3 / (B2O3+ZnO), between the content of Y2O3 and the total content of B2O3 and ZnO (B2O3+ZnO), is controlled within the range of 0.1 to 1.2. This can improve the Young's modulus of the glass while preventing a decrease in the light transmittance of the glass. Therefore, it is preferable that Y2O3 / (B2O3+ZnO) is 0.1 to 1.2, more preferably 0.1 to 1.0, even more preferably 0.15 to 0.8, and even more preferably 0.2 to 0.6.

[0052] Gd₂O₃ can improve the refractive index and chemical stability of glass, but if its content is too high, the glass's devitrification resistance will decrease and its density will increase. Therefore, the content of Gd₂O₃ is 0-4%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is even more preferable that the glass does not contain Gd₂O₃.

[0053] Nb₂O₅ is a high-refractive-index and high-dispersion component that can improve the refractive index and devitrification resistance of glass, and reduce the coefficient of thermal expansion of glass. However, if its content is too high, the ultraviolet light transmittance of the glass will decrease, and the coefficient of thermal expansion of the glass will be too low. Therefore, the content of Nb₂O₅ is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that the glass does not contain Nb₂O₅.

[0054] WO3 is a high-refractive-index and high-dispersion component that can improve the refractive index and devitrification resistance of glass. However, if its content is too high, the visible light transmittance of the glass will decrease. Therefore, the WO3 content is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is even more preferable that the glass does not contain WO3.

[0055] Ta₂O₅ can increase the refractive index of glass, but a high content will significantly increase the cost of the glass and worsen its melting performance and increase its density. Therefore, the content of Ta₂O₅ is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is even more preferable that Ta₂O₅ is not present.

[0056] GeO2 can improve the refractive index and devitrification resistance of glass. However, the presence of GeO2 in glass is detrimental to the control of glass raw material costs, and its high content reduces the chemical stability of the glass. Therefore, the GeO2 content is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that the glass does not contain GeO2.

[0057] Rn₂O (which can be one or more of Li₂O, Na₂O, and K₂O) can lower the glass melting temperature and density, but a high content of Rn₂O will decrease the glass transition temperature. On the other hand, when glass containing Rn₂O is used as a carrier, the alkali metal ions Li₂O… + Na + K + It can enter the single-crystal silicon substrate and contaminate the chip circuit. Therefore, the content of Rn2O in this invention is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that it does not contain Li2O; and / or does not contain Na2O; and / or does not contain K2O.

[0058] In some embodiments, controlling the ratio of Rn2O content to Al2O3 content, Rn2O / Al2O3, to be below 0.13 can ensure that the glass has a good coefficient of thermal expansion while preventing a deterioration in the Young's modulus. Therefore, it is preferable that Rn2O / Al2O3 is below 0.13, more preferably below 0.1, further preferably below 0.08, and even more preferably below 0.05.

[0059] In this invention, one or more of the following components containing 0-2% Sb2O3, SnO2, and CeO2 are used as clarifiers to improve the clarification effect of the glass. Preferably, the content of the clarifier is 0-1%, more preferably 0-0.5%.

[0060] <Components that should not be present>

[0061] P2O5 tends to form differential phases inside the glass, which scatter some short-wavelength wavelengths, making it difficult to achieve the designed transmittance. Therefore, in some embodiments, it is preferable to exclude P2O5.

[0062] Fe2O3 can cause glass discoloration, which is detrimental to achieving excellent light transmittance. Therefore, in some embodiments, it is preferable to avoid the presence of Fe2O3.

[0063] Fluorine (F) lowers the glass transition temperature and volatilizes during the glass melting process, causing instability in the glass composition and reducing glass quality. Therefore, in some embodiments, it is preferable to omit F.

[0064] In the glass of the present invention, even if oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained in small amounts, either alone or in combination, the glass will be colored and absorb at specific wavelengths in the visible light region, thereby weakening the property of the present invention to improve visible light transmittance. Therefore, it is preferable that the glass does not actually contain the above-mentioned components, especially for glasses that require transmittance in the visible light region.

[0065] Oxides of Th, Cd, Tl, Os, Be, and Se have been increasingly subject to controlled use in recent years due to their status as hazardous chemicals. Environmental protection measures are essential not only in glass manufacturing but also in processing and post-product disposal. Therefore, given the importance of environmental impact, it is preferable to avoid the presence of these substances, except where their contamination is unavoidable. This results in glass that is virtually free of pollutants. Consequently, the glass of this invention can be manufactured, processed, and disposed of even without specific environmental countermeasures.

[0066] To achieve environmental friendliness, the glass of the present invention preferably does not contain As2O3 and PbO.

[0067] The terms "not containing" and "0%" as used herein mean that the compound, molecule, or element was not intentionally added to the glass of this invention as a raw material. However, as raw materials and / or equipment used in the production of glass, there may be some impurities or components that are not intentionally added, which may be present in small or trace amounts in the final glass. Such cases are also within the scope of protection of this patent.

[0068] The performance of the high-modulus glass of the present invention will now be described.

[0069] <Refractive Index and Abbe Number>

[0070] The refractive index (n) of glass d ) and Abbe number (ν d According to the national standard GB / T 7962.1-2010

[0071] Test using the prescribed methods.

[0072] In some embodiments, the refractive index (n) of the high-modulus glass of the present invention is... d The lower limit for the refractive index (n) is 1.56, preferably 1.57, and more preferably 1.58. In some embodiments, the refractive index (n) of the high-modulus glass of the present invention is... d The upper limit for () is 1.61, and the preferred upper limit is 1.60.

[0073] In some embodiments, the Abbe number (ν) of the high-modulus glass of the present invention is... dThe lower limit for the Abbe number (ν) is 49, preferably 50, and more preferably 51. In some embodiments, the Abbe number (ν) of the high-modulus glass of the present invention is... d The upper limit of ) is 55, the preferred upper limit is 54, and the more preferred upper limit is 53.5.

[0074] Coefficient of thermal expansion

[0075] The coefficient of thermal expansion of glass (α) 20 / 300℃ Data from 20 to 300℃ were tested according to the method specified in the national standard GB / T 7962.16-2010. The coefficient of thermal expansion of the glass should not be too high or too low, and it needs to be thermally matched with the encapsulation medium (such as resin material) to prevent excessive difference in the coefficient of thermal expansion from causing stress rise in the interface layer and leading to cracking.

[0076] In some embodiments, the coefficient of thermal expansion (α) of the high-modulus glass of the present invention is... 20 / 300℃ ) is 30×10 -7 / K~45×10 -7 / K, preferably 32×10 -7 / K~42×10 -7 / K, more preferably 35×10 -7 / K~40×10 -7 / K.

[0077] <Stability under acid conditions>

[0078] Acid resistance stability of glass (D) A (Powder method) Tested according to the method specified in the national standard GB / T 17129. In this specification, acid resistance stability is sometimes simply referred to as acid resistance or acid stability. During application, in highly acidic environments, the better the acid resistance, the less likely the glass is to fail.

[0079] In some embodiments, the acid resistance stability (D) of the high modulus glass of the present invention is... A It should be of 3 or more categories, preferably 2 or more categories.

[0080] <Stability under water resistance>

[0081] Water resistance stability of glass (D) W (Powder method) Tested according to the method specified in the national standard GB / T 17129. In this specification, water resistance stability is sometimes simply referred to as water resistance or water stability. The better the water resistance of the glass, the more it can avoid water erosion during application. In particular, excellent water resistance of glass can better prevent water erosion during the encapsulation process. If the water resistance of the glass is poor, it may cause a decrease in glass transmittance and debonding efficiency, and in severe cases, it may lead to carrier plate cracking and failure.

[0082] In some embodiments, the water resistance stability (D) of the high modulus glass of the present invention is... W It should be of 3 or more categories, preferably 2 or more categories.

[0083] Young's Modulus

[0084] The Young's modulus (E) of glass is obtained by ultrasonic testing of its longitudinal wave velocity and transverse wave velocity, and then calculated according to the following formula.

[0085] The following formula is used to calculate:

[0086]

[0087] Where G = V S 2 ρ

[0088] In the formula:

[0089] E is Young's modulus, in Pa;

[0090] G is the shear modulus, Pa;

[0091] V T The longitudinal wave velocity is given in m / s.

[0092] V S The transverse wave velocity is in m / s;

[0093] ρ is the density of glass, in g / cm³ 3 .

[0094] The higher the Young's modulus of glass, the less likely it is to deform during application. In particular, the higher the Young's modulus of glass, the less likely it is to warp or break under stress during the packaging process.

[0095] In some embodiments, the Young's modulus (E) of the high-modulus glass of the present invention is 91 GPa or more, preferably 93 GPa or more, and more preferably 95 GPa or more.

[0096] <Transition Temperature>

[0097] Glass transition temperature (T) g Test according to the method specified in the national standard GB / T 7962.16-2010.

[0098] If the glass transition temperature is too low, its heat resistance decreases, making it prone to softening and deformation during high-temperature processes. If the glass transition temperature is too high, it will create design difficulties for the heat resistance of precision annealing equipment, resulting in a decrease in the reliability of the equipment. This is especially true when precision annealing large-diameter glass blanks, which require prolonged holding at temperatures near the transition temperature. If the transition temperature is too high, it will significantly reduce the reliability of the precision annealing equipment.

[0099] In some embodiments, the transition temperature (T) of the high-modulus glass of the present invention is... g The temperature is 680°C or higher, preferably 700°C or higher, more preferably 710°C or higher, and even more preferably 710-735°C.

[0100] <Density>

[0101] The density (ρ) of the glass was tested according to the method specified in the national standard GB / T 7962.20-2010. Lower glass density is more conducive to achieving lightweight application terminals. In particular, lower glass density means less weight is borne by the support equipment in the packaging process, enabling higher precision and efficiency.

[0102] In some embodiments, the density (ρ) of the high-modulus glass of the present invention is 3.00 g / cm³. 3 The preferred value is 2.90 g / cm³. 3 The preferred value is 2.85 g / cm³. 3 the following.

[0103] <Light transmittance>

[0104] The light transmittance of glass is tested using the following method: The glass sample to be tested is processed to a certain thickness and its opposing surfaces are polished parallel to each other. The test is then performed according to the method specified in the national standard GB / T 7962.12-2010. In this invention, the glass is processed to a thickness of 1±0.1 mm, and its light transmittance at 550 nm (T) is tested. 550nm ) and light transmittance at 355nm (T 355nm The higher the light transmittance of the glass at 550nm, the more efficient and accurate the optical inspection equipment can achieve in the packaging process; the higher the light transmittance of the glass at 355nm, the higher the debonding efficiency in the packaging process, and the lower the risk of wafer warpage.

[0105] In some embodiments, the light transmittance (T) of the high-modulus glass of the present invention at 550 nm is... 550nm The content is 85.0% or more, preferably 87.0% or more, and more preferably 89.0% or more.

[0106] In some embodiments, the light transmittance (T) of the high-modulus glass of the present invention at 355 nm is... 355nm The content is 80.0% or more, preferably 82.0% or more, and more preferably 84.0% or more.

[0107] Knoop Hardness

[0108] Knoop hardness (H) of glass KTest according to the test methods specified in the national standard GB / T 7962.18-2010.

[0109] In some embodiments, the Knoop hardness (H) of the high modulus glass of the present invention is... K ) is 520×10 7 Pa or higher, preferably 540 × 10 Pa 7 Pa or higher, more preferably 560 × 10 Pa 7 Pa or above.

[0110] The high-modulus glass of this invention, due to its superior properties, can be used to manufacture packaging carriers (substrate materials) for semiconductor manufacturing processes.

[0111] The high-modulus glass of this invention can be used to manufacture various glass components, providing a variety of lenses, prisms, and other glass components with high optical value. Examples of lenses include concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, plano-concave lenses, and other lenses with spherical or aspherical lens surfaces.

[0112] The high-modulus glass and glass elements of this invention can be used to manufacture various devices (the devices described in this invention include instruments, equipment, etc.), such as imaging equipment, sensors, microscopes, medical technology, digital projection, communication, optical communication technology / information transmission, optics / lighting in the automotive field, photolithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for use in the automotive field, and in the field of surveillance and security imaging equipment and devices.

[0113] [Manufacturing Method]

[0114] The manufacturing method of the high-modulus glass of this invention is as follows: The high-modulus glass of this invention uses carbonates, nitrates, sulfates, hydroxides, oxides, fluorides, etc. as raw materials. After being batched according to conventional methods, the batched furnace charge is put into a melting furnace at 1300-1500°C for melting. After clarification, stirring, and homogenization, a homogeneous molten glass without bubbles and undissolved substances is obtained. This molten glass is then cast in a mold and annealed. Those skilled in the art can appropriately select raw materials, process methods, and process parameters according to actual needs.

[0115] [Example]

[0116] To further illustrate and explain the technical solution of the present invention, the following non-limiting embodiments are provided.

[0117] In this embodiment, high-modulus glass with the compositions shown in Tables 1 to 3 was obtained using the high-modulus glass manufacturing method described above. Furthermore, the properties of each glass were measured using the testing method described in this invention, and the measurement results are shown in Tables 1 to 3.

[0118] Table 1.

[0119]

[0120]

[0121] Table 2.

[0122]

[0123]

[0124] Table 3.

[0125]

[0126]

Claims

1. A high-modulus glass, characterized in that, Its components, expressed as a weight percentage, contain: SiO2: 34–46%; B2O3: 2–10%; Al2O3: 20–32%; ZnO: 5–15%; MgO: 5–15%; Y2O3: 1–10%; TiO2: 0.5–8%; Rn2O: 0–3%, wherein the ratio of Y2O3 / (B2O3+ZnO) is 0.1–1.2, and the Rn2O is one or more of Li2O, Na2O, and K2O.

2. The high-modulus glass according to claim 1, characterized in that, Its components, expressed as a weight percentage, also contain: ZrO2: 0–4%; and / or BaO: 0–4%; and / or SrO: 0–4%; and / or CaO: 0–4%; and / or La2O3: 0–5%; and / or Gd2O3: 0–4%; and / or Nb2O5: 0–3%; and / or WO3: 0–3%; and / or Ta2O5: 0–3%; and / or GeO2: 0–3%; and / or clarifying agent: 0–2%, wherein the clarifying agent is one or more of Sb2O3, SnO2, and CeO2.

3. High-modulus glass, characterized in that, Its composition contains SiO2, B2O3, Al2O3, ZnO, MgO, Y2O3, and TiO2, expressed as a weight percentage, containing: SiO2: 34-45%; B2O3: 2-10%; Al2O3: 20-32%; ZnO: 5-15%; MgO: 5-15%; Y2O3: 1-10%; TiO2: 0.5-8%; Rn2O: 0-3%, wherein the ratio of Y2O3 / (B2O3+ZnO) is 0.1-1.2, and the Rn2O is one or more of Li2O, Na2O, and K2O. The high-modulus glass has a Young's modulus E of 91 GPa or higher, and a light transmittance T at 550 nm. 550nm The light transmittance at 355nm is above 85.0% (T). 355nm It is above 80.0%.

4. The high-modulus glass according to claim 3, characterized in that, Its components, expressed as a weight percentage, contain: ZrO2: 0–4%; and / or BaO: 0–4%; and / or SrO: 0–4%; and / or CaO: 0–4%; and / or La2O3: 0–5%; and / or Gd2O3: 0–4%; and / or Nb2O5: 0–3%; and / or WO3: 0–3%; and / or Ta2O5: 0–3%; and / or GeO2: 0–3%; and / or clarifying agent: 0–2%, wherein the clarifying agent is one or more of Sb2O3, SnO2, and CeO2.

5. The high-modulus glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage and meet one or more of the following nine conditions: 1) The MgO / Y2O3 ratio is 0.7–8.0; 2) The Al2O3 / SiO2 ratio is 0.46–0.85; 3) The Al2O3 / Y2O3 ratio is 2.5–10.0; 4) The MgO / B2O3 ratio is 0.7–6.0; 5) The ratio of MgO to (ZrO2 + TiO2) is 0.5–10.0; 6) The ratio of Y₂O₃ / (B₂O₃+ZnO) is 0.1–1.0; 7) The TiO2 / ZnO ratio is 0.1–1.5; 8) The CaO / ZnO ratio is below 0.6; 9) The ratio of Rn2O / Al2O3 is less than 0.13, and the Rn2O is one or more of Li2O, Na2O, and K2O.

6. The high-modulus glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage and meet one or more of the following nine conditions: 1) The MgO / Y2O3 ratio is 1.0–6.0; 2) The Al2O3 / SiO2 ratio is 0.50–0.80; 3) The Al2O3 / Y2O3 ratio is 3.0–8.0; 4) The MgO / B2O3 ratio is 1.0–5.0; 5) The ratio of MgO to (ZrO2 + TiO2) is 1.0–8.0; 6) The ratio of Y₂O₃ / (B₂O₃+ZnO) is 0.15–0.8; 7) The TiO2 / ZnO ratio is 0.15–1.0; 8) The CaO / ZnO ratio is below 0.5; 9) The ratio of Rn2O / Al2O3 is less than 0.1, and the Rn2O is one or more of Li2O, Na2O, and K2O.

7. The high-modulus glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage and meet one or more of the following nine conditions: 1) The MgO / Y2O3 ratio is 1.2–4.0; 2) The Al2O3 / SiO2 ratio is 0.53–0.73; 3) The Al2O3 / Y2O3 ratio is 3.5–7.0; 4) The MgO / B2O3 ratio is 1.0–3.5; 5) The ratio of MgO to (ZrO2 + TiO2) is 1.5–5.0; 6) The ratio of Y₂O₃ / (B₂O₃+ZnO) is 0.2–0.6; 7) The TiO2 / ZnO ratio is 0.2–0.8; 8) The CaO / ZnO ratio is below 0.3; 9) The ratio of Rn2O / Al2O3 is less than 0.08, and the Rn2O is one or more of Li2O, Na2O, and K2O.

8. The high-modulus glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage and meet one or more of the following seven conditions: 1) The MgO / Y2O3 ratio is 1.3–3.0; 2) The Al2O3 / Y2O3 ratio is 4.0–6.0; 3) The MgO / B2O3 ratio is 1.2–2.5; 4) The ratio of MgO to (ZrO2 + TiO2) is 1.5–3.5; 5) The TiO2 / ZnO ratio is 0.25–0.6; 6) The CaO / ZnO ratio is below 0.1; 7) The ratio of Rn2O / Al2O3 is less than 0.05, and Rn2O is one or more of Li2O, Na2O, and K2O.

9. The high-modulus glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 36–45%; and / or B2O3: 3–9%; and / or Al2O3: 21–30%; and / or ZrO2: 0–3%; and / or TiO2: 1–7%; and / or ZnO: 6–13%; and / or BaO: 0–2%; and / or SrO: 0–2%; and / or CaO: 0–2%; and / or MgO: 6–13%; and / or La2O3: 0–3%; and / or Y2O3: 2-8%; and / or Gd2O3: 0-3%; and / or Nb2O5: 0-2%; and / or WO3: 0-2%; and / or Ta2O5: 0-2%; and / or GeO2: 0-2%; and / or Rn2O: 0-2%; and / or clarifying agent: 0-1%, wherein Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifying agent is one or more of Sb2O3, SnO2, and CeO2.

10. The high-modulus glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 37–43%; and / or B2O3: 4–8%; and / or Al2O3: 23–28%; and / or ZrO2: 0–2%; and / or TiO2: 2–6%; and / or ZnO: 8–12%; and / or BaO: 0–1%; and / or SrO: 0–1%; and / or CaO: 0–1%; and / or MgO: 8–12%; and / or La2O3: 0–2%; and / or Or Y2O3: 3-7%; and / or Gd2O3: 0-1%; and / or Nb2O5: 0-1%; and / or WO3: 0-1%; and / or Ta2O5: 0-1%; and / or GeO2: 0-1%; and / or Rn2O: 0-1%; and / or clarifying agent: 0-0.5%, wherein Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifying agent is one or more of Sb2O3, SnO2, and CeO2.

11. The high-modulus glass according to any one of claims 1 to 4, characterized in that, Its components do not contain BaO; and / or do not contain CaO; and / or do not contain SrO; and / or do not contain Gd2O3; and / or do not contain Nb2O5; and / or do not contain WO3; and / or do not contain Ta2O5; and / or do not contain GeO2; and / or do not contain Li2O; and / or do not contain Na2O; and / or do not contain K2O; and / or do not contain P2O5; and / or do not contain Fe2O3; and / or do not contain F.

12. The high-modulus glass according to any one of claims 1 to 2, characterized in that, The high-modulus glass has a Young's modulus E of 91 GPa or higher and a light transmittance T at 550 nm. 550nm The light transmittance at 355nm is above 85.0% (T). 355nm It is above 80.0%.

13. The high-modulus glass according to any one of claims 1 to 4, characterized in that, The high modulus glass has a thermal expansion coefficient α 20 / 300℃ 30×10 -7 / K~45×10 -7 / K; and / or acid resistance stability D A Class 3 or above; and / or water resistance stability D W Class 3 or above; and / or refractive index n d The value is 1.56–1.61; and / or the Abbe number ν. d The value is 49–55; and / or the Young's modulus E is 93 GPa or higher; and / or the transition temperature T g Temperature above 680℃; and / or density ρ of 3.00 g / cm³ 3 Below; and / or 550nm light transmittance T 550nm The transmittance is above 87.0%; and / or the light transmittance T at 355 nm. 355nm It is above 82.0%; and / or Knoop hardness H K 520×10 7 Pa or above.

14. The high-modulus glass according to any one of claims 1 to 4, characterized in that, The high modulus glass has a thermal expansion coefficient α 20 / 300℃ 32×10 -7 / K~42×10 -7 / K; and / or acid resistance stability D A Class 2 or above; and / or water resistance stability D W Class 2 or above; and / or refractive index n d The value is 1.57–1.60; and / or the Abbe number ν. d The value is 50–54; and / or the Young's modulus E is 95 GPa or higher; and / or the transition temperature T g Temperature above 700℃; and / or density ρ of 2.90 g / cm³ 3 Below; and / or 550nm light transmittance T 550nm The transmittance is above 89.0%; and / or the light transmittance T at 355 nm. 355nm It is above 84.0%; and / or Knoop hardness H K 540×10 7 Pa or above.

15. The high-modulus glass according to any one of claims 1 to 4, characterized in that, The high modulus glass has a thermal expansion coefficient α 20 / 300℃ 35×10 -7 / K~40×10 -7 / K; and / or refractive index n d The value is 1.58–1.60; and / or the Abbe number ν. d The temperature is 51–53.5°C; and / or the transition temperature T0. g Temperature above 710℃; and / or density ρ of 2.85 g / cm³ 3 The following; and / or Knoop hardness H K 560×10 7 Pa or above.

16. The high-modulus glass according to any one of claims 1 to 4, characterized in that, The transition temperature T of the high modulus glass g The temperature ranges from 710 to 735℃.

17. A packaging carrier, characterized in that, Made of the high modulus glass as described in any one of claims 1 to 16.

18. A glass element, characterized in that, Made of the high modulus glass as described in any one of claims 1 to 16.

19. An apparatus, characterized in that, It contains the high modulus glass according to any one of claims 1 to 16, or the glass element according to claim 18.

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