Yttrium bisilicate microcrystalline glass material and preparation method thereof

Abstract

The invention relates to an yttrium disilicate glass ceramic material and a preparation method thereof. The glass material comprises base glass, a nucleating agent, a modifier and an additive, the base glass is prepared from the following components in percentage by weight: 25 to 40 weight percent of SiO2, 20 to 30 weight percent of Al2O3, 20 to 35 weight percent of Y2O3 and 3 to 15 weight percent of B2O3; the nucleating agent comprises the following components in percentage by weight: 1 to 4 percent of ZrO2, 0 to 6 percent of TiO2 and 1 to 2 percent of P2O5; the modifier comprises 0 to 4 wt% of BaO; and the additive comprises 0 to 5 wt% of La2O3. And carrying out micro-crystallization treatment on the glass material to obtain the double-yttrium silicate glass ceramic material. The yttrium bisilicate glass ceramic material provided by the invention has extremely high elastic modulus and fracture toughness and low dielectric loss, and is expected to be used as a next-generation novel glass material in the advanced packaging field.

Description

Technical Field

[0001] This invention belongs to the field of microcrystalline glass technology, and relates to a yttrium bissilicate microcrystalline glass material and its preparation method. Background Technology

[0002] Integrated circuits are the core and foundation of modern information technology. As the technological system and industrial ecosystem are gradually established, integrated chips will develop into the third main path for improving chip performance. Packaging substrates play a crucial role in the iterative upgrading of integrated chip performance.

[0003] As an emerging substrate material, glass packaging substrates have unique advantages over traditional substrates in terms of dimensional stability, thermal stability, electrical performance, and mechanical performance. This provides a "new platform" for high-performance, highly integrated, and energy-efficient chips in the post-Moore era to achieve a better balance between electrical performance, thermal performance, mechanical performance, and cost-effectiveness.

[0004] Despite their numerous advantages, integrating glass substrates into mainstream applications still faces significant hurdles. Schott's BF33 and AF32 glasses, as high-performance specialty glasses, possess excellent thermal stability, chemical inertness, and electrical insulation properties. However, their high dielectric loss and low modulus lead to reliability issues during the encapsulation process. Summary of the Invention

[0005] To address the technical problems existing in glass products in the prior art, this invention provides a glass material with extremely high elastic modulus, fracture toughness, and low dielectric loss, which is expected to be used as a next-generation novel glass material in the field of advanced packaging. To improve the strength and reliability of the glass as a substrate material while maintaining good electrical properties, this invention provides a yttrium bissilicate microcrystalline glass material and its preparation method.

[0006] In a first aspect, the present invention provides a glass material comprising a base glass, a nucleating agent, a modifier, and additives, in weight percentages as follows: The base glass comprises: 25–40 wt% SiO2, 20–30 wt% Al2O3, 20–35 wt% Y2O3, and 3–15 wt% B2O3; The nucleating agents include: 1–4 wt% ZrO2, 0–6 wt% TiO2, and 1–2 wt% P2O5; Modifiers include: 0–4 wt% BaO; Additives include: 0–5 wt% La2O3; Preferably, the total amount of Al2O3 and B2O3 is not higher than 40 wt%, preferably 20-30 wt%; Al2O3 / B2O3 = 1.4-20; SiO2 / Al2O3 = 1-1.4; B2O3 / Y2O3 = 0-0.4; SiO2 / Y2O3 = 0.9-1.8; wherein La2O3 / (ZrO2+TiO2) = 0-0.6; ZrO2 / TiO2 = 0.4-1; The glass material does not contain Na2O, Li2O, or K2O.

[0007] Preferably, the glass material further includes a clarifying agent, which is Sb2O3; preferably, the amount of the clarifying agent added is 0 to 1 wt% of the total mass of the base glass, nucleating agent, modifier and additives, and more preferably 0 to 0.5 wt%.

[0008] Preferably, the glass material has an elastic modulus of 110–135 GPa and a fracture toughness of 1.2–1.5 MPa·m. 1 / 2 The dielectric loss (10GHz) is 3.5–5.3 × 10⁻⁶. -3 .

[0009] Secondly, the present invention provides a yttrium bissilicate microcrystalline glass material, which is obtained by microcrystallizing the above-mentioned glass material.

[0010] Preferably, the microcrystallization treatment is a heat treatment; the heat treatment includes a first heat treatment, a second heat treatment, and a third cooling treatment; Preferably, the temperature of the first heat treatment stage is 800-850℃, the holding time is 1-2h, and the heating rate is 3-5℃ / min; Preferably, the temperature of the second heat treatment stage is 900–1050°C, the holding time is 2–5 h, and the heating rate is 1–2°C / min; Preferably, the cooling rate of the third cooling stage is 1 to 10 °C / min.

[0011] Preferably, the main crystalline phase of the yttrium bissilicate microcrystalline glass material is Y₂Si₂O₇; the elastic modulus of the yttrium bissilicate microcrystalline glass material is 120–135 GPa, and the fracture toughness is 1.2–1.5 MPa·m. 1 / 2 The dielectric loss (10GHz) is 4.0–5.2 × 10⁻⁶. -3 .

[0012] Thirdly, the present invention provides a method for preparing the above-mentioned glass material, comprising: mixing raw material powders of base glass, nucleating agent, modifier, clarifying agent and additive, pouring them into a crucible, placing them in a high-temperature furnace, and obtaining the glass material through melting, clarification, molding and annealing.

[0013] Preferably, in the composition of the base glass, B2O3 is introduced in the form of boric acid, and Al2O3 is introduced in the form of Al(OH)3 or AlCl3; in the composition of the nucleating agent, P2O5 is introduced in the form of NH4H2PO4; in the composition of the modifier, BaO is introduced in the form of at least one of Ba(NO3)2, BaCO3, and BaSO4; and the remaining raw material components are introduced in the form of oxides.

[0014] Preferably, the raw material powder is added when the high-temperature furnace is heated to 1350-1450°C; the melting temperature is 1600-1650°C and the holding time is 3-10 hours.

[0015] Preferably, the clarification temperature is 1500–1550°C, and the clarification time is 2–5 hours.

[0016] Preferably, the forming process includes: pouring the clarified molten glass into a preheated mold, then covering the mold with an upper plate, introducing compressed air through the upper and lower plates of the mold for cooling, and inserting a thermocouple in the center of the mold to ensure that the glass is formed at a certain cooling rate; preferably, the preheating temperature of the mold is 300-500°C; and the air intake rate of the compressed air is 1-10 m / s. 3 / min; the cooling rate is 10-15℃ / min.

[0017] Preferably, the annealing temperature is 750–800°C and the annealing time is 2–5 hours.

[0018] Beneficial effects: Compared with the prior art, the present invention has the following beneficial effects: This invention solves the problem of forming transparent and uniform precursor glasses from high rare-earth element glasses in the preparation of precursor glasses. In terms of performance, it also addresses the issue of insufficient strength and reliability of packaging substrate materials, which makes it difficult to meet the rapidly evolving performance requirements of integrated chips. Through the rational design of the microcrystalline glass composition, Y2Si2O7 crystals are precipitated in the glass, resulting in microcrystalline glass with extremely high elastic modulus, fracture toughness, and low dielectric loss. It holds promise for application in next-generation adapter boards and substrate materials in the chip packaging field. Attached Figure Description

[0019] Figure 1 The image shows the DSC curve of the glass material prepared in Example 1 of this invention. Figure 2 The image shows the DSC curve of the glass material prepared in Example 2 of this invention. Figure 3 A photograph of the glass material prepared in Comparative Example 1; Figure 4 A photograph of the glass material prepared in Comparative Example 5; Figure 5 A photograph of the glass material prepared in Comparative Example 6; Figure 6 The image shows the XRD pattern of the yttrium silicate microcrystalline material prepared in Example 15 of this invention. Figure 7 This is a photograph of the yttrium silicate microcrystalline glass material prepared in Example 15 of the present invention. Figure 8 This is a physical image of the yttrium bissilicate microcrystalline glass material prepared in Comparative Example 8 of this invention. Detailed Implementation

[0020] To further illustrate the invention's content, features, and practical effects, the invention will be described in detail below with reference to embodiments. It should be noted that the modification methods of the invention are not limited to these specific implementation methods. Equivalent substitutions and modifications made by those skilled in the art based on their reading of the invention's content, without departing from the spirit and essence of the invention, are also within the scope of protection claimed by this invention.

[0021] First, this invention provides a glass material comprising: a base glass composition of 25–40 wt% SiO2, 20–30 wt% Al2O3, 20–35 wt% Y2O3, and 3–15 wt% B2O3; a nucleating agent of 1–4 wt% ZrO2, 0–6 wt% TiO2, and 1–2 wt% P2O5; a modifier of 0–4 wt% BaO; and an additive of 0–5 wt% La2O3. In this invention, the interaction between Y2O3, Al2O3, SiO2, and B2O3 in the formulation is controlled to fully utilize the role of each oxide in the glass structure, resulting in a high-performance precursor glass. Subsequently, a Y2Si2O7 crystalline phase is precipitated through crystallization, thereby obtaining a high-strength, low-dielectric yttrium bissilicate microcrystalline glass material.

[0022] In this invention, a quaternary system of Y₂O₃-Al₂O₃-SiO₂-B₂O₃ (containing no alkali, Li₂O, K₂O, etc.) is employed, and a nucleating agent combination of P₂O₅ (1-2 wt%) and ZrO₂ and TiO₂ is precisely introduced to achieve directional control of the glass structure. This design aims to preferentially form a uniform glass phase separation, thereby specifically inducing the directional precipitation of the Y₂Si₂O₇ phase during heat treatment, ultimately obtaining a high-strength, low-dielectric microcrystalline glass. The control logic of the microcrystalline glass components in this invention is as follows: by strictly excluding alkali metal oxides to ensure network stability, and utilizing the phase separation effect of P₂O₅ and the synergistic effect of the nucleating agent, the crystallization behavior is precisely controlled, which is fundamentally different from general-purpose yttrium aluminum silicate glasses that only pursue melting and mechanical properties.

[0023] In the optional implementation scheme, the composition design is explained as follows: In the composition of yttrium bissilicate glass-ceramics, SiO2, Al2O3, Y2O3, and B2O3 are the main components. While ensuring the normal melting of the base glass, they also improve the stoichiometric ratio of Y / Si to be as close as possible to Y2Si2O7. Al2O3 is used to stabilize the glass network and improve chemical stability. Too little Al2O3 results in weak glass-forming ability, while too much Al2O3 can easily lead to the formation of other crystalline phases, which is not conducive to the final preparation of yttrium bissilicate glass-ceramics with yttrium bissilicate as the main crystalline phase. B2O3, as a flux, is mainly used to reduce the high-temperature viscosity and melting temperature of the glass. Too much B2O3 will weaken the glass network, making the crystallization process difficult to control and reducing the mechanical strength and other properties of the final product.

[0024] SiO2 is the core material constituting the glass network. Within the glass, it forms an irregular, continuous network of silicon-oxygen tetrahedral [SiO4] structural units, serving as the framework of the glass structure. It is also one of the components that form the Y2Si2O7 crystalline phase after crystallization. SiO2 can improve the melting temperature, high-temperature viscosity, chemical stability, thermal stability, and mechanical strength of the glass. In some embodiments, the weight percentage of SiO2 in the glass matrix is ​​25–40 wt%, preferably 25–35 wt%, and more preferably 25–30 wt%.

[0025] Al₂O₃ is a glass intermediate oxide that can improve the chemical stability and mechanical strength of glass. Y₂O₃ is a network modifier with a high valence and moderate ionic radius, which can provide stable charge compensation for the [AlO₄] network structure, thereby making the glass structure more stable and greatly increasing the elastic modulus of the glass. In some embodiments, the weight percentage of Al₂O₃ in the glass matrix is ​​20–30 wt%, preferably 20–26 wt%, more preferably 20–23 wt%; the weight percentage of Y₂O₃ is 20–35 wt%, preferably 25–35 wt%, more preferably 30–35 wt%.

[0026] B2O3 is an important glass-forming oxide that can lower the melting temperature and improve the mechanical strength, toughness, and chemical stability of glass. In some embodiments, the weight percentage of B2O3 in the glass matrix is ​​5–15 wt%, preferably 5–10 wt%, and more preferably 7–10 wt%.

[0027] ZrO2 is a nucleating agent, which not only promotes nucleation but also refines grains and improves glass stability. In some embodiments, the weight percentage of ZrO2 in the glass matrix is ​​1–4 wt%. TiO2 is also a nucleating agent, which effectively promotes the precipitation of nuclei during nucleation. In some embodiments, the weight percentage of TiO2 in the glass matrix is ​​0–6 wt%, preferably 0–4 wt%, and more preferably 0–2 wt%. The ZrO2 / TiO2 ratio is 0.4–1, and the ZrO2 to TiO2 mass ratio should be greater than 0.5 to suppress the formation of the Y2[Ti2O7] crystal phase.

[0028] P2O5 acts as a nucleating agent, its introduction facilitating the formation of crystal nuclei in the glass and promoting uniform crystal growth. In some embodiments, the weight percentage of P2O5 in the glass matrix is ​​1–2 wt%.

[0029] BaO is a modifier that can break the silicon-oxygen network, thus having a certain fluxing effect. At the same time, as a nitrate carrier, it decomposes and releases gas at high temperature to help remove bubbles and can play a certain clarifying role. In some embodiments, the weight ratio of BaO in the glass matrix is ​​0 to 4 wt%, preferably 0 to 2 wt%.

[0030] Sb₂O₃ is a clarifying agent, and its introduction is beneficial to the clarification and homogenization of the glass. In some embodiments, the weight percentage of Sb₂O₃ in the glass matrix is ​​0–1 wt%.

[0031] Among them, La2O3 is a glass network modifier, and the large La 3+Ions can cause the expansion and distortion of local structures, altering the free volume of the network, thereby affecting ion diffusion and migration, increasing the nucleation and growth barriers during the cooling process of the glass melt, thus improving the glass's resistance to crystallization and inhibiting the formation of solid solution-like crystals. In some embodiments, the weight percentage of La2O3 in the glass matrix is ​​0–5 wt%, preferably 2–5 wt%.

[0032] In some embodiments, SiO2 / Al2O3 = 1–1.4, with the mass ratio of SiO2 to Al2O3 not exceeding 1.4, to prevent devitrification; in some embodiments, Al2O3 / B2O3 = 1.4–20, with the mass ratio of Al2O3 to B2O3 not less than 1.4, to prevent devitrification; in some embodiments, B2O3 / Y2O3 = 0–0.4, with the mass ratio of B2O3 to Y2O3 not greater than 0.4, to prevent devitrification. SiO2 / Y2O3 = 0.9–1.8 improves glass forming ability; La2O3 / (ZrO2+TiO2) = 0–0.6 inhibits the formation of solid solution-like crystals.

[0033] In some embodiments, the main crystalline phase of the yttrium bissilicate microcrystalline glass material prepared by the present invention is Y₂Si₂O₇, with a content of approximately 90% (calculated by integrating the XRD peak area). Although it also contains other crystalline forms, such as Y₂Ti₂O₇ and Al₆Si₂O₇, it is not the only crystalline material. 13 However, their contents were only 3.6% and 6.1% respectively, which can be ignored.

[0034] The yttrium silicate microcrystalline material of this invention has an elastic modulus of 120–135 GPa and a fracture toughness of 1.2–1.5 MPa·m. 1 / 2 The dielectric loss (10GHz) is 4.0–5.2 × 10⁻⁶. -3 .

[0035] The following exemplarily illustrates the preparation method of the yttrium silicate microcrystalline glass material provided by the present invention.

[0036] The raw material powders of base glass, nucleating agent, modifier, clarifying agent and additives are mixed evenly.

[0037] In an optional embodiment, in the composition of the base glass, B2O3 is introduced in the form of boric acid, and Al2O3 is introduced in the form of Al(OH)3 or AlCl3; in the composition of the nucleating agent, P2O5 is introduced in the form of NH4H2PO4; in the composition of the modifier, BaO is introduced in the form of at least one of Ba(NO3)2, BaCO3, and BaSO4; and the remaining raw material components are introduced in the form of oxides.

[0038] When the high-temperature furnace is heated to 1350-1450℃, the raw material powder is added, and after melting, clarifying, shaping and annealing, glass material is obtained.

[0039] In an optional embodiment, the melting temperature is 1600–1650°C, and the holding time is 3–10 hours. The clarification temperature is 1500–1550°C, and the clarification time is 2–5 hours.

[0040] In an optional embodiment, the forming process includes: pouring the clarified molten glass into a preheated mold, then covering the mold with an upper plate, introducing compressed air through the upper and lower plates of the mold for cooling, and inserting a thermocouple in the center of the mold to ensure that the glass is formed at a certain cooling rate; preferably, the preheating temperature of the mold is 300–500°C; and the air intake rate of the compressed air is 1–10 m / s. 3 / min; the cooling rate is 10-15℃ / min.

[0041] In an optional embodiment, the annealing temperature is 750–800°C and the annealing time is 2–5 hours.

[0042] The obtained glass material was subjected to microcrystallization treatment to obtain yttrium bissilicate microcrystalline glass material.

[0043] In an optional embodiment, the microcrystallization treatment is a heat treatment; the heat treatment includes a first heat treatment, a second heat treatment, and a third cooling treatment; wherein, the temperature of the first heat treatment is 800-850℃, the holding time is 1-2h, and the heating rate is 3-5℃ / min; the temperature of the second heat treatment is 900-1050℃, the holding time is 2-5h, and the heating rate is 1-2℃ / min; the cooling rate of the third cooling treatment is 1-10℃ / min.

[0044] This invention utilizes a casting mold with intelligent temperature control to form a glass precursor, and then prepares a microcrystalline glass with yttrium bissilicate as the main crystalline phase through nucleation crystallization. This solves the problem of the difficulty in forming transparent and uniform precursor glasses from high rare earth element glasses, and further induces the formation of yttrium bissilicate by introducing a specific proportion of nucleating agent. This glass exhibits extremely high elastic modulus, fracture toughness, and low dielectric loss, and holds promise for application as a next-generation novel glass material in advanced packaging fields.

[0045] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below. Example 1

[0046] 27.5 wt% SiO2, 25.9 wt% Al2O3, 3.6wt%B2O3, 29.8 wt%Y2O3, 3.8 wt% ZrO2, 1.4wt% P2O5, 4.9 wt% TiO2, 3.1wt% BaO, 0.2 wt% After the Sb₂O₃ is thoroughly mixed, it is poured into a platinum crucible. Once the muffle furnace is heated to 1380°C, the crucible is placed inside. The mixture is then heated at a rate of 10°C / min to 1650°C for melting, and held at this temperature for 6 hours. The temperature is then lowered to 1530°C to begin the refining stage, which lasts for 3 hours. Next, the refined glass melt is poured into a preheated mold, and the upper mold plate is installed. Compressed air is circulated through the upper and lower mold plates for cooling. A thermocouple is inserted in the center of the mold to ensure the glass is formed at a controlled cooling rate. The mold preheating temperature is 440°C, and the compressed air intake rate is 10 m / s. 3 The cooling rate is 10℃ / min; finally, the formed glass is annealed at 750℃ for 4 hours to obtain the glass material (or glass-ceramic precursor). Example 2

[0047] The preparation process of the glass material in Example 2 is the same as in Example 1, except that the raw material composition of the glass material includes: 28.3 wt% SiO2, 21.4 wt% Al2O3, 7.3 wt% B2O3, 30.8 wt% Y2O3, 2.5 wt% ZrO2, 1.5 wt% P2O5, 5.1 wt% TiO2, 3.1 wt% BaO, and 0.2 wt% Sb2O3. Example 3

[0048] The preparation process of the glass material in Example 3 is the same as in Example 1, except that the raw material composition of the glass material includes: 27.6 wt% SiO2, 20.6 wt% Al2O3, 7.3 wt% B2O3, 30.4 wt% Y2O3, 2.6 wt% ZrO2, 1.4 wt% P2O5, 4.9 wt% TiO2, 3.2 wt% BaO, 2.0 wt% La2O3, and 0.2 wt% Sb2O3. Example 4

[0049] The preparation process of the glass material in Example 4 is the same as in Example 1, except that the raw material composition of the glass material includes: 27.7 wt% SiO2, 20.7 wt% Al2O3, 7.3 wt% B2O3, 29.1 wt% Y2O3, 2.7 wt% ZrO2, 1.4 wt% P2O5, 4.9 wt% TiO2, 3.2 wt% BaO, 3.0 wt% La2O3, and 0.2 wt% Sb2O3. Comparative Example 1

[0050] The glass material preparation process in Comparative Example 1 is the same as in Example 1, except that the preheating temperature of the mold is 270°C. Comparative Example 2

[0051] The glass material preparation process in Comparative Example 2 is the same as in Example 1, except that the annealing temperature is 850°C. Comparative Example 3

[0052] The preparation process of the glass material in Comparative Example 3 is the same as in Example 1, except that the amount of Sb2O3 added is 2.5 wt%. Comparative Example 4

[0053] The preparation process of the glass material in Comparative Example 4 is the same as in Example 1, except that the raw material composition of the glass material includes: 31.2 wt% SiO2, 21.2 wt% Al2O3, 3.6 wt% B2O3, 30.5 wt% Y2O3, 3.8 wt% ZrO2, 1.5 wt% P2O5, 5.0 wt% TiO2, 3.2 wt% BaO, and 0.2 wt% Sb2O3. Comparative Example 5

[0054] The preparation process of the glass material in Comparative Example 5 is the same as in Example 1, except that the raw material composition of the glass material includes: 35.1 wt% SiO2, 16.3 wt% Al2O3, 3.7 wt% B2O3, 31.2 wt% Y2O3, 3.9 wt% ZrO2, 1.5 wt% P2O5, 5.0 wt% TiO2, 3.3 wt% BaO, and 0.2 wt% Sb2O3. Comparative Example 6

[0055] The preparation process of the glass material in Comparative Example 6 is the same as in Example 1, except that the raw material composition of the glass material includes: 27.8 wt% SiO2, 16.5 wt% Al2O3, 11.9 wt% B2O3, 30.2 wt% Y2O3, 3.9 wt% ZrO2, 1.5 wt% P2O5, 5.1 wt% TiO2, 3.1 wt% BaO, and 0.2 wt% Sb2O3. Comparative Example 7

[0056] The preparation process of the glass material in Comparative Example 7 is the same as in Example 1, except that the raw material composition of the glass material includes: 30.3 wt% SiO2, 22.8 wt% Al2O3, 10.9 wt% B2O3, 23.0 wt% Y2O3, 2.7 wt% ZrO2, 1.6 wt% P2O5, 5.3 wt% TiO2, 3.4 wt% BaO, and 0.2 wt% Sb2O3. Comparative Example 8

[0057] The preparation process of the glass material in Comparative Example 8 is the same as in Example 1, except that the raw material composition of the glass material includes: 28.5 wt% SiO2, 21.6 wt% Al2O3, 7.5 wt% B2O3, 31.1 wt% Y2O3, 2.7 wt% ZrO2, 5.3 wt% TiO2, 3.3 wt% BaO, and 0.2 wt% Sb2O3.

[0058] Table 1 compares the composition (mass percentage) and performance data of the glass materials obtained in Examples 1-4 and Comparative Examples 1-2.

[0059] Table 1: .

[0060] Table 2 lists the composition (mass percentage) and performance data of the glass materials obtained in Comparative Examples 3-8.

[0061] Table 2: .

[0062] Table 3 compares the process parameters for preparing glass materials in Examples 1-4 and Comparative Examples 1-8.

[0063] Table 3: .

[0064] Figure 1 The figure shows the DSC curve of the glass material prepared in Example 1 of this invention. As can be seen from the figure, the Tg point of the glass material prepared in Example 1 is 810℃, and the Tc point is 1130℃.

[0065] Figure 2 The figure shows the DSC curve of the glass material prepared in Example 2 of this invention. As can be seen from the figure, the Tg point of the glass material prepared in Example 2 is 760℃, and the Tc point is 1110℃.

[0066] Combined with Table 1-3 and Figure 3-5 It can be seen that in Comparative Example 1, the low preheating temperature of the mold caused cracking at the edges and corners; in Comparative Example 2, the excessive annealing temperature caused glass crystallization; and in Comparative Example 3, the excessive amount of clarifying agent caused glass turbidity. As can be seen from Examples 1, 4, and 5, as the mass ratio of SiO2 to Al2O3 increases, when it exceeds 1.4, the glass undergoes significant devitrification. As can be seen from Examples 1 and 6, when the mass ratio of Al2O3 to B2O3 is less than 1.4, the glass also undergoes significant devitrification. As can be seen from Examples 2 and 7, it is found that when the mass ratio of B2O3 to Y2O3 is greater than 0.4, the glass gradually becomes devitrified.

[0067] As shown in Table 1, the glass material prepared in Example 2 exhibits the best overall performance. Therefore, the glass material from Example 2 was selected for microcrystallization treatment. By controlling the conditions of the microcrystallization treatment, the preparation of yttrium disilicate microcrystalline glass material was achieved. Table 4 lists a comparison of the process parameters for the microcrystallization treatment in Examples 5-16.

[0068] Table 4: .

[0069] Table 5 lists a comparison of the performance data of the yttrium silicate microcrystalline materials in Examples 5-16.

[0070] Table 5: .

[0071] Figure 6The image shows the XRD pattern of the yttrium bissilicate microcrystalline glass material prepared in Example 15 of this invention. As can be seen from the figure, the main crystalline phase of the yttrium bissilicate microcrystalline glass material prepared in Example 2 is Y₂Si₂O₇, with a content of approximately 90% (calculated by integrating the XRD peak areas). Although it also contains other crystalline forms, such as Y₂Ti₂O₇ and Al₆Si₂O₇, it does not contain other crystal forms. 13 However, their contents were only 3.6% and 6.1% respectively, which can be ignored.

[0072] Figure 7 This is a photograph of the yttrium silicate microcrystalline material prepared in Example 15 of this invention. Figure 8 This is a photograph of the yttrium bissilicate microcrystalline glass material prepared in Comparative Example 8 of this invention. As can be seen from the figure, the glass material containing P2O5 (Example 15) has a higher crystallinity and is easier to crystallize; while the glass material without P2O5 (Comparative Example 8) has a lower crystallinity and is more difficult to crystallize.

[0073] Combination Figure 6-8 As shown in Table 5, by controlling each process of microcrystallization, the preparation of yttrium silicate microcrystalline glass material is finally achieved, that is, a high-strength low-dielectric glass substrate with high elastic modulus, high fracture toughness, low dielectric constant and low dielectric loss is obtained.

[0074] The above description represents only some preferred embodiments of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention, without departing from the content and spirit of the present invention, shall still fall within the protection scope of the present invention.

Claims

1. A glass material comprising a base glass, a nucleating agent, a modifier, and additives, characterized in that, By weight percentage: The base glass comprises: 25–40 wt% SiO2, 20–30 wt% Al2O3, 20–35 wt% Y2O3, and 3–15 wt% B2O3; The nucleating agents include: 1–4 wt% ZrO2, 0–6 wt% TiO2, and 1–2 wt% P2O5; Modifiers include: 0–4 wt% BaO; Additives include: 0-5 wt% La2O3.

2. The glass material according to claim 1, characterized in that, in, The total amount of Al2O3 and B2O3 shall not exceed 40 wt%, preferably 20-30 wt%; Al2O3 / B2O3=1.4~20; SiO2 / Al2O3=1~1.4; B2O3 / Y2O3=0~0.4; SiO2 / Y2O3=0.9~1.

8.

3. The glass material according to claim 1 or 2, characterized in that, in, La2O3 / (ZrO2+TiO2)=0~0.6; ZrO2 / TiO2=0.4~1; The glass material does not contain Na2O, Li2O, or K2O.

4. The glass material according to any one of claims 1-3, characterized in that, The glass material further includes a clarifying agent, which is Sb2O3; preferably, the amount of the clarifying agent added is 0 to 1 wt% of the total mass of the base glass, nucleating agent, modifier and additives, and more preferably 0 to 0.5 wt%.

5. A yttrium silicate microcrystalline glass material, characterized in that, The yttrium bissilicate microcrystalline glass material is obtained by microcrystallization treatment of the glass material according to any one of claims 1-4.

6. The yttrium silicate microcrystalline material according to claim 5, characterized in that, The microcrystallization process is a heat treatment; the heat treatment includes a first heat treatment, a second heat treatment, and a third cooling treatment. Preferably, the temperature of the first heat treatment stage is 800-850℃, the holding time is 1-2h, and the heating rate is 3-5℃ / min; Preferably, the temperature of the second heat treatment stage is 900–1050°C, the holding time is 2–5 h, and the heating rate is 1–2°C / min; Preferably, the cooling rate of the third cooling stage is 1 to 10 °C / min.

7. The yttrium silicate microcrystalline material according to claim 5 or 6, characterized in that, The main crystalline phase of the yttrium silicate microcrystalline glass material is Y2Si2O7; The elastic modulus of the yttrium bissilicate microcrystalline glass material is 120–135 GPa, and the fracture toughness is 1.2–1.5 MPa·m. 1 / 2 The dielectric loss (10GHz) is 4.0–5.2 × 10⁻⁶. -3 .

8. A method for preparing a glass material according to any one of claims 1-4, characterized in that, The raw material powders of base glass, nucleating agent, modifier, clarifying agent and additive are mixed and poured into a crucible, placed in a high-temperature furnace, and then melted, clarified, shaped and annealed to obtain the glass material.

9. The preparation method according to claim 8, characterized in that, When the high-temperature furnace is heated to 1350-1450℃, the raw material powder is added. The melting temperature is 1600–1650℃, and the holding time is 3–10 hours; The clarification temperature is 1500–1550℃, and the clarification time is 2–5 hours.

10. The preparation method according to claim 8 or 9, characterized in that, The forming process includes: pouring clarified molten glass into a preheated mold, then covering the mold with an upper plate, introducing compressed air through the upper and lower plates of the mold for cooling, and inserting a thermocouple in the center of the mold to ensure that the glass is formed at a certain cooling rate; preferably, the preheating temperature of the mold is 300-500°C; and the air intake rate of the compressed air is 1-10 m / s. 3 / min; cooling rate is 10-15℃ / min; The annealing temperature is 750–800℃, and the annealing time is 2–5 hours.

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