Zero-expansion glass-ceramics based on wide temperature range and preparation method and application thereof

Abstract

The application belongs to the technical field of germanate glass-ceramics, and discloses a zero-expansion glass-ceramic based on a wide temperature range and a preparation method and application thereof, wherein the zero-expansion glass-ceramic based on a wide temperature range comprises 40%<=GeO2<=52%; 3%<=Ga2O3<=5%; 26%<=SiO2<=35%; 10%<=Al2O3<=13%; 1.5%<=Y2O3<=3%; 3%<=B2O3<=5%; the crystal phase of the zero-expansion glass-ceramic comprises a beta-(Ga, Y)2GeO5 solid solution phase and a germanate quartz phase, wherein the beta-(Ga, Y)2GeO5 solid solution phase is determined by the mole percentage of Ge elements, Y elements and Ga elements; the application does not contain lithium elements and phosphorus elements, can significantly shorten the heat treatment time, and can also have a thermal expansion coefficient <=0.05 ppm / ℃ in a wide temperature range of -50~100 DEG C, so as to realize a near-zero expansion characteristic.

Description

Technical Field

[0001] This invention relates to the field of germanate microcrystalline glass technology, specifically to a zero-expansion microcrystalline glass based on a wide temperature range, its preparation method, and its applications. Background Technology

[0002] Zero-expansion glass is a special type of glass with a coefficient of thermal expansion close to zero over a wide temperature range. The core technology of zero-expansion glass lies in offsetting the inherent thermal expansion effect of the material through composition design and process control.

[0003] Current mainstream near-zero expansion glasses (as described in Chinese patent application CN108929040B) are primarily based on a lithium aluminum silicon system (Li2O-Al2O3-SiO2, LAS). The core mechanism utilizes the negative thermal expansion characteristics of the high-quartz solid solution (β-quartz solid solution) to offset the positive expansion of the glass matrix, thereby achieving overall near-zero expansion performance. This lithium aluminum silicon system typically uses Li2O, Al2O3, and SiO2 as the main components, with small amounts of nucleating agents such as MgO, ZnO, and P2O5 added to promote microcrystallization. During heat treatment, crystal nuclei precipitate in the glass at 500–600 °C, followed by a prolonged holding at 750–830 °C (4.5–10 days) to allow the β-quartz solid solution to grow fully and reach the ideal crystalline phase ratio (typically 30%–50%).

[0004] It is evident that, to achieve near-zero expansion characteristics with a target crystalline phase ratio of 30% to 50%, heat treatment at 750 to 830 °C for 4.5 to 10 days is required. This process is inefficient and cannot cover the full temperature range of -50 to 100 °C required for aerospace or quantum devices. Summary of the Invention

[0005] The purpose of this invention is to provide a wide-temperature-range zero-expansion microcrystalline glass, its preparation method, and its applications, to overcome the problems existing in the prior art. This invention adopts a unique nucleation-growth mechanism, which can complete the crystallization process within 3 hours, significantly shortening the heat treatment time compared with traditional processes. Secondly, it has excellent thermal stability, achieving a coefficient of thermal expansion (CTE) ≤0.05 ppm / ℃ in a wide temperature range of -50~100 ℃, reaching near-zero expansion characteristics. In addition, it does not contain lithium and phosphorus elements, avoiding the environmental sensitivity problems of traditional materials, and obtaining a wide-temperature-range near-zero expansion microcrystalline glass specifically for emerging fields such as quantum computing and biochips.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a zero-expansion microcrystalline glass based on a wide temperature range, which is prepared from raw materials of the following components in molar percentage:

[0008] 40%≤GeO2≤52%; 3%≤Ga2O3≤5%; 26%≤SiO2≤35%; 10%≤Al2O3≤13%; 1.5%≤Y2O3≤3%; 3%≤B2O3≤5%;

[0009] The crystal phases of the zero-expansion microcrystalline glass include a β-(Ga,Y)2GeO5 solid solution phase and a germanium quartz phase, wherein the β-(Ga,Y)2GeO5 solid solution phase is determined by the molar percentages of Ge, Y and Ga elements.

[0010] Furthermore, the volume fraction of the germanium-quartz phase is 42%~48%;

[0011] The absolute value of the coefficient of thermal expansion of the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase in the temperature range of -50~100 ℃ is ≤0.05 ppm / ℃;

[0012] The grain size of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is 80~230 nm, and the standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is ≤3%.

[0013] The ratio of [SiO4] / [GeO4] tetrahedral structures or types in the zero-expansion microcrystalline glass is 0.569~0.642;

[0014] The molar ratio of Al2O3 / Ga2O3 is 2.1~3.714;

[0015] Furthermore, it is prepared from raw materials containing the following components in molar percentage:

[0016] 46.2% GeO2, 4.2% Ga2O3, 32% SiO2, 12.1% Al2O3, 2.3% Y2O3, 3.2% B2O3.

[0017] Secondly, the present invention provides a method for preparing a wide-temperature-range zero-expansion microcrystalline glass, comprising the following steps:

[0018] Weigh the raw materials according to the composition and molar percentage of the zero-expansion microcrystalline glass;

[0019] The raw materials are melted under an inert atmosphere to obtain molten raw materials;

[0020] The molten raw material is nucleated in two steps to obtain nucleated raw material;

[0021] The nucleated raw material is subjected to selective laser crystallization to obtain crystalline raw material;

[0022] The crystallized raw materials are annealed to obtain zero-expansion microcrystalline glass;

[0023] Further, the raw materials are weighed according to the composition and molar percentage of the zero-expansion microcrystalline glass, specifically including: converting the molar percentage of each component of the zero-expansion microcrystalline glass into a mass percentage, and further weighing the raw materials corresponding to each oxide component according to the weight of the zero-expansion microcrystalline glass to be melted.

[0024] Furthermore, the inert atmosphere includes one of argon, nitrogen, helium, and neon;

[0025] The melting temperature is 1120~1250 ℃, the melting time is 2.5~3.5 h, and the volatilization rate of GeO2 during the melting process is ≤3%;

[0026] Furthermore, the two-step nucleation includes a first-stage nucleation and a second-stage nucleation;

[0027] The temperature for the first stage of nucleation is 750~780 ℃, and the holding time for the first stage of nucleation is 1 h.

[0028] The temperature for the second stage of nucleation is 800~820 ℃, and the holding time for the second stage of nucleation is 1 h.

[0029] Furthermore, the step of performing laser selective crystallization on the nucleated raw material to obtain crystalline raw material specifically includes:

[0030] Using laser at 6~9 J / cm 2 The surface of the nucleated raw material was treated with an energy density and a scanning speed of 2~4 mm / s for 2.7~2.9 h to form a temperature gradient field on the nucleated raw material, thereby obtaining crystallized raw material;

[0031] Furthermore, the wavelength of the laser is 1064 nm;

[0032] The surface temperature of the temperature gradient field is 1000 ℃, and the internal temperature of the temperature gradient field is 850 ℃;

[0033] In the crystallized raw material obtained after laser selective crystallization, the phase ratio of the β-(Ga,Y)2GeO5 solid solution phase is determined by the laser energy density E (J / cm²). 2 )control:

[0034] V β =50+1.2(E-6);

[0035] In the formula, V β Indicates the phase ratio of the β-(Ga,Y)2GeO5 solid solution phase; 6≤E≤9;

[0036] Furthermore, the annealing specifically includes cooling to room temperature at a rate of less than 1 °C / min, wherein the room temperature is 25 °C.

[0037] Thirdly, the present invention provides an application of the above-mentioned wide-temperature-range zero-expansion microcrystalline glass in quantum bit carriers and biochip substrates, excluding application scenarios such as astronomical telescopes, photolithography equipment, and laser gyroscopes.

[0038] The above technical solution has the following advantages or beneficial effects:

[0039] In the first aspect, the present invention provides a zero-expansion microcrystalline glass based on a wide temperature range, which abandons the traditional LAS system microcrystalline glass, strictly controls Li, P and Zn impurities below the detection limit, completely eliminates quantum bit decoherence caused by ion migration and infrared absorption interference of phosphorus oxygen bond, and meets the optical and electromagnetic purity requirements of quantum computing substrates and biochips.

[0040] Furthermore, by precisely controlling the ratio of β-(Ga,Y)2GeO5 solid solution phase to germanium quartz phase, the absolute value of the coefficient of thermal expansion is ≤0.05 ppm / ℃ in the full temperature range of -50~100℃, which is more than 5 times wider than the traditional LAS glass (temperature range of only 20~50 ℃), especially covering the core working temperature range of biochips and the low temperature environment of superconducting quantum computing.

[0041] Furthermore, by setting the above components, the zero-expansion microcrystalline glass of the present invention exhibits a coefficient of thermal expansion (CTE) ≤0.05 ppm / ℃ over a wide temperature range of -50 to 100 ℃, demonstrating excellent near-zero expansion characteristics. These superior characteristics enable the zero-expansion microcrystalline glass obtained by the present invention to maintain minimal dimensional changes in environments with drastic temperature variations, greatly improving the stability and reliability of the zero-expansion microcrystalline glass in high-precision applications. Secondly, it achieves a lithium-free and phosphorus-free formulation design, avoiding a series of problems that lithium and phosphorus elements may bring. Lithium may have high chemical reactivity in certain situations, easily reacting with other substances and affecting the performance and stability of the glass. The presence of phosphorus may adversely affect the glass melting process and optical properties. The lithium-free and phosphorus-free formulation of the present invention not only simplifies the production process but also improves the consistency of product quality and performance. In addition, the present invention can employ 3... This revolutionary process, which completes crystallization within hours, significantly shortens the production cycle and improves production efficiency. Compared with traditional crystallization processes, it significantly reduces energy consumption and production costs, while also reducing the risk of glass performance degradation that may result from prolonged crystallization treatment, thus facilitating large-scale industrial production.

[0042] Secondly, this invention provides a method for preparing a zero-expansion microcrystalline glass based on a wide temperature range. First, by providing a two-step nucleation process, composite crystal nuclei can be pre-fabricated, reducing the activation energy during crystallization. Second, by using laser selective crystallization to form a temperature gradient field, a directional phase transition is driven, enabling the crystallization process to be completed within 3 hours, which is significantly more efficient than the traditional one-step or two-step method (4.5-10 hours), thus significantly shortening the processing time. In addition, this invention does not contain lithium or phosphorus, avoiding the environmental sensitivity issues of traditional materials. Furthermore, it can also achieve precise control of the crystal phase ratio, avoiding the phase separation risk of traditional annealing processes.

[0043] Furthermore, by precisely controlling the inert atmosphere and melting parameters (1120~1250 ℃, 2.5~3.5h), this method effectively suppresses the high-temperature volatilization of GeO2 (vaporization rate ≤3%), ensuring component stability and melt uniformity. This not only improves the consistency of the thermal expansion coefficient of zero-expansion glass-ceramics over a wide temperature range, but also significantly enhances the thermal stability and mechanical properties of zero-expansion glass-ceramics, making it suitable for the fabrication of high-precision optical devices.

[0044] Furthermore, by employing a two-stage nucleation process at 750~780 ℃ and 800~820 ℃, with each stage held for 1 h, the gradual formation and controllable growth of crystal nuclei were achieved. This effectively promoted the precipitation of uniform and fine crystals, avoided the generation of microcracks, significantly improved the zero-expansion characteristics and dimensional stability of the zero-expansion glass-ceramic over a wide temperature range, and enhanced the mechanical strength and thermal shock resistance of the material.

[0045] Furthermore, selective laser crystallization (energy density 6~9 J / cm²) is employed. 2 (Scanning speed 2~4 mm / s, processing time 2.7~2.9 h) A precise and controllable temperature gradient field is formed on the surface of the nucleated raw material, which realizes the precise induction of micro-region crystallization, promotes the precipitation of fine and uniform crystals, significantly improves the zero expansion performance, structural consistency and dimensional stability of the zero expansion glass-ceramic in a wide temperature range, and avoids thermal damage.

[0046] Furthermore, a precise temperature gradient field (1000 ℃ on the surface / 850 ℃ inside) was constructed using a 1064 nm laser, and the energy density (6~9 J / cm²) was measured. 2 Linear regulation of the phase ratio (V) of the β-(Ga,Y)2GeO5 solid solution phase β =50+1.2(E-6)), which enables programmable and precise design of crystal phase composition, significantly optimizes the zero expansion characteristics of glass-ceramics, and enables zero expansion glass-ceramics to have excellent thermal stability and mechanical properties in a wide temperature range, making them suitable for high-precision optical systems.

[0047] Furthermore, by controlling the annealing cooling rate to be less than 1 ℃ / min, residual stress inside the glass-ceramic is effectively eliminated, cracks and deformation are avoided, the integrity and uniformity of the material structure are ensured, and the dimensional stability, mechanical strength and thermal shock resistance of the zero-expansion glass-ceramic are significantly improved in a wide temperature range, making it suitable for the manufacture of high-precision optical devices.

[0048] Thirdly, this invention provides an application of a wide-temperature-range zero-expansion microcrystalline glass in quantum bit carriers and biochip substrates. Phosphorus-oxygen bonds can cause infrared absorption interference, affecting the accurate detection and analysis of signals by biochips. The zero-expansion microcrystalline glass of this invention effectively avoids the above-mentioned problems, ensuring that biochips can work stably in complex environments and accurately acquire biological information. In addition, the wide temperature range and zero-expansion characteristics of the zero-expansion microcrystalline glass make the material stable under different temperature environments, broadening the application scenarios and showing broad application prospects in high-tech fields. Attached Figure Description

[0049] Figure 1 This is a schematic diagram of the preparation method of the zero-expansion microcrystalline glass based on a wide temperature range according to the present invention. Detailed Implementation

[0050] In the following description, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments can be modified in various ways without departing from the spirit or scope of the invention. Therefore, the drawings and description are considered to be exemplary in nature and not restrictive.

[0051] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0052] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0053] This invention provides a zero-expansion microcrystalline glass based on a wide temperature range, prepared from raw materials of the following components in mole percentage (mol%):

[0054] 40%≤GeO2≤52%; 3%≤Ga2O3≤5%; 26%≤SiO2≤35%; 10%≤Al2O3≤13%; 1.5%≤Y2O3≤3%; 3%≤B2O3≤5%; In practical operation, considering the possibility of impurities, the following percentages are permissible: 0.00%<Li2O≤0.01%, 0.00%<P2O5≤0.01%, 0.00%<ZnO≤0.01%.

[0055] The zero-expansion glass-ceramic comprises a β-(Ga,Y)₂GeO₅ solid solution phase and a germanium quartz phase. The β-(Ga,Y)₂GeO₅ solid solution phase is determined by the molar percentages of Ge, Y, and Ga elements, and by subsequent heat treatment processes such as two-step nucleation and laser selective crystallization. The volume fraction of the germanium quartz phase is 42%–48%. The grain size of both the β-(Ga,Y)₂GeO₅ solid solution phase and the germanium quartz phase is 80–230 nm. The standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)₂GeO₅ solid solution phase and the germanium quartz phase is ≤3%. The absolute value of the coefficient of thermal expansion (CTE) of both the β-(Ga,Y)₂GeO₅ solid solution phase and the germanium quartz phase in the temperature range of -50–100 °C is ≤0.05. The ratio of [SiO4] / [GeO4] tetrahedral structures or types in zero-expansion microcrystalline glass is 0.569~0.642 at ppm / ℃.

[0056] This invention also provides an application of a wide-temperature-range zero-expansion microcrystalline glass in quantum bit carriers and biochip substrates, excluding applications in astronomical telescopes, photolithography equipment, and laser gyroscopes.

[0057] Preferably, in the oxide composition of the zero-expansion microcrystalline glass of the present invention: GeO2 is the main network former, providing a negative thermal expansion germanium quartz phase framework, and providing GeO2 for the formation of the β-(Ga,Y)2GeO5 solid solution phase. 3+ The content of GeO2 directly affects the amount of β-(Ga,Y)2GeO5 solid solution phase formed. When the content of GeO2 is too high, it can easily lead to a sharp increase in melt viscosity and increase the risk of devitrification of the zero-expansion glass-ceramic. When the content is too low, it is impossible to ensure the formation of a sufficient amount of crystalline phase. In the following embodiments, the zero-expansion glass-ceramic of the present invention includes 40~52 mol% GeO2 or any sub-range contained therein.

[0058] SiO2 is also a network former, forming the framework of zero-expansion glass-ceramics together with GeO2, enhancing the network stability of the zero-expansion glass-ceramics (reducing the tendency for high-temperature crystallization). Simultaneously, it synergistically forms a low-expansion germanium-quartz phase with GeO2. When the SiO2 content is less than 27 mol%, it cannot provide sufficient component content for crystal phase formation; when the SiO2 content is greater than 33 mol%, [SiO4] tetrahedra compete with GeO2 for the form of the [SiO4] tetrahedron. 3+ The site will inhibit the nucleation and precipitation of the β-(Ga,Y)2GeO5 solid solution phase, disrupt the crystal phase balance, and cause an excessive total network formation, resulting in excessively high melt viscosity. In the following embodiments, the zero-expansion microcrystalline glass of the present invention includes 26~35 mol% SiO2 or any sub-range contained therein.

[0059] Al2O3, as an intermediate oxide, can play a role in charge compensation, which is beneficial for promoting Ga... 3+ and Y 3+ Entering the crystal lattice to form a solid solution can also increase the transition temperature of zero-expansion glass-ceramics and enhance their mechanical strength. However, when its content is too low (<10 mol%), it cannot effectively stabilize the amorphous network. When it is too high (>13 mol%), it will form the Al4GeO8 phase, which will lead to an increased tendency for melt crystallization and disrupt the expansion balance. In the following embodiments, the zero-expansion glass-ceramics of the present invention includes 10~13 mol% of Al2O3 or any sub-range contained therein.

[0060] Both Ga₂O₃ and Y₂O₃ are essential structural units for forming the β-(Ga,Y)₂GeO₅ solid solution phase with negative expansion characteristics. The β-(Ga,Y)₂GeO₅ solid solution phase is provided by Ga₂O₃ as the lattice host; Y₂O₃ is formed through Y₂O₃... 3+ Replace 10-15% of Ga 3 + The formation of solid solution distortion at the site further improves and enhances the negative expansion characteristics of the pure β-(Ga,Y)2GeO5 solid solution phase. In the following embodiments, the zero expansion microcrystalline glass of the present invention comprises 3~5 mol% Ga2O3, 1.5~3 mol% Y2O3 or any sub-range contained therein.

[0061] B2O3, as a melt modifier, is beneficial for reducing the high-temperature viscosity of zero-expansion glass-ceramic melt and inhibiting the volatilization of GeO2. When the content of B2O3 is too low, it will not reduce the high-temperature viscosity of the zero-expansion glass-ceramic melt. When the content of B2O3 is too high, it is easy to induce boron anomalies, leading to phase separation of the zero-expansion glass-ceramic. In the following embodiments, the zero-expansion glass-ceramic of the present invention includes 3 to 5 mol% of B2O3 or any sub-range contained therein.

[0062] Furthermore, the zero-expansion microcrystalline glass of this invention limits the content of impurities such as Li2O, P2O5, and ZnO, and Li + and Zn 2+ These impurities can easily cause ion migration and interfere with qubits, and the infrared absorption of phosphorus-oxygen bonds can interfere with optical detection in biochip applications. Therefore, the total amount of such impurities is controlled below 300 ppm.

[0063] The formation mechanism of the β-(Ga,Y)₂GeO₅ solid solution phase (CTE≈-2.8 ppm / ℃) in this invention is as follows: First, Ga₂O₃ provides octahedral sites, and GeO₄ fills the tetrahedral interstices to form a lattice; second, Y₂O₃ introduces Y... 3+ Replace ≤15% Ga 3+ Octahedral solid solution is formed, and at the same time, Y 3+ The substitution alters the twist angle of the GaO6 octahedron, further enhancing its negative expansion characteristics. In this invention, the germanium-quartz phase structure is formed by GeO2-SiO2-rich regions, and its low positive expansion (+0.9 ppm / ℃) originates from the restricted bond angle vibration between [GeO4] and [SiO4].

[0064] Unless otherwise stated, the "β-(Ga,Y)2GeO5 solid solution phase" in this invention is simply referred to as the "β phase". β This refers to the phase ratio, proportion, or volume fraction of the β-(Ga,Y)2GeO5 solid solution phase (after laser crystallization).

[0065] Unless otherwise stated, the coefficient of thermal expansion (CTE) in this invention represents the measured value within a temperature range of -50°C to 100°C, and the unit of the coefficient of thermal expansion is "×10". -7 " / ℃" or "ppm / ℃", where 1ppm = 10 -6 / ℃; All temperatures mentioned in this invention are expressed in degrees Celsius (℃).

[0066] Example 1:

[0067] See Figure 1 This invention provides a method for preparing a wide-temperature-range zero-expansion microcrystalline glass, comprising the following steps:

[0068] Step 1: Weighing Raw Materials: Convert the molar percentages of each component of the zero-expansion glass-ceramic to mass percentages (mol%). Further weigh the raw materials corresponding to each oxide component according to the required weight of the zero-expansion glass-ceramic to be melted. The molar percentages of each component are: 46.2% GeO2, 4.2% Ga2O3, 32% SiO2, 12.1% Al2O3, 2.3% Y2O3, and 3.2% B2O3. (Note: The last part about Al2O3 is incomplete and likely refers to a different process.) The molar ratio of Ga2O3 is 2.881. The crystal phases of the zero-expansion glass-ceramic include a β-(Ga,Y)2GeO5 solid solution phase and a germanium quartz phase. The β-(Ga,Y)2GeO5 solid solution phase is determined by the molar percentages of Ge, Y, and Ga elements, as well as subsequent heat treatment processes such as two-step nucleation and laser selective crystallization. The volume fraction of the β-(Ga,Y)2GeO5 solid solution phase is 55%, and the volume fraction of the germanium quartz phase is 45%. The grain size of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is 150 nm. The standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is ≤2.5%.

[0069] Preferably, in the β-(Ga,Y)2GeO5 solid solution phase, Y 3+ The substitution amount was 13.23 at%;

[0070] Preferably, the ratio of [SiO4] / [GeO4] tetrahedral structure or species is 0.621;

[0071] Step 2, Cold crucible melting: The raw material is melted at 1200 °C for 3 h under an argon atmosphere to obtain molten raw material. During the melting process, the volatilization rate of GeO2 is 2.1%.

[0072] Step 3, two-step nucleation: The molten raw material is nucleated in two steps to obtain nucleated raw material. The two-step nucleation includes a first-stage nucleation and a second-stage nucleation. The temperature of the first-stage nucleation is 765 ℃ and the holding time of the first-stage nucleation is 1 h. The temperature of the second-stage nucleation is 810 ℃ and the holding time of the second-stage nucleation is 1 h.

[0073] Step 4, Selective Laser Crystallization: The nucleation material is nucleated using a laser with a wavelength of 1064 nm (near-infrared band) at a speed of 6~9 J / cm². 2 The surface of the nucleated raw material was treated with an energy density and a scanning speed of 3 mm / s for 2.8 h to form a temperature gradient field and obtain crystallized raw material. The surface temperature of the temperature gradient field was 1000 ℃ and the internal temperature of the temperature gradient field was 850 ℃.

[0074] Step 5, Annealing: Cool the crystallized raw material to room temperature at a rate of less than 1 °C / min, wherein the room temperature is 25 °C, to obtain zero-expansion microcrystalline glass.

[0075] The zero-expansion microcrystalline glass obtained in Example 1 of this invention has a fixed scanning speed of 3 mm / s and an adjusted laser energy density E (J / cm²). 2 ) respectively 6 J / cm 2 7 J / cm 2 8 J / cm 2 and 9 J / cm 2 The laser phase control verification was performed, and the results are shown in the table below:

[0076] Table 1. Results of Zero-Expansion Microcrystalline Glass Implementation in Example 1

[0077]

[0078] Example 2:

[0079] See Figure 1 This invention provides a method for preparing a wide-temperature-range zero-expansion microcrystalline glass, comprising the following steps:

[0080] Step 1: Weighing Raw Materials: Convert the molar percentages of each component of the zero-expansion glass-ceramic to mass percentages (mol%). Further weigh the raw materials corresponding to each oxide component according to the required weight of the zero-expansion glass-ceramic to be melted. The molar percentages of each component are: 40.5% GeO2, 3.5% Ga2O3, 35% SiO2, 13% Al2O3, 3% Y2O3, and 5% B2O3. (Note: The last part about Al2O3 / ... is incomplete and requires further context.) The molar ratio of Ga2O3 is 3.714. The crystal phases of the zero-expansion glass-ceramic include a β-(Ga,Y)2GeO5 solid solution phase and a germanium quartz phase. The β-(Ga,Y)2GeO5 solid solution phase is determined by the molar percentages of Ge, Y, and Ga elements, as well as subsequent heat treatment processes such as two-step nucleation and laser selective crystallization. The volume fraction of the β-(Ga,Y)2GeO5 solid solution phase is 52%, and the volume fraction of the germanium quartz phase is 48%. The grain size of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is 80 nm. The standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is ≤2.8%.

[0081] Preferably, in the β-(Ga,Y)2GeO5 solid solution phase, Y 3+ The substitution amount was 14.89 at%;

[0082] Preferably, the ratio of [SiO4] / [GeO4] tetrahedral structure or species is 0.569;

[0083] Step 2, Cold crucible melting: The raw material is melted at 1180 °C for 3.5 h under an argon atmosphere to obtain molten raw material. During the melting process, the volatilization rate of GeO2 is 2.8%.

[0084] Step 3, two-step nucleation: The molten raw material is nucleated in two steps to obtain nucleated raw material. The two-step nucleation includes a first-stage nucleation and a second-stage nucleation. The temperature of the first-stage nucleation is 780 ℃ and the holding time of the first-stage nucleation is 1 h. The temperature of the second-stage nucleation is 800 ℃ and the holding time of the second-stage nucleation is 1 h.

[0085] Step 4, Selective Laser Crystallization: The nucleation material is nucleated using a laser with a wavelength of 1064 nm (near-infrared band) at a speed of 6~9 J / cm². 2 The surface of the nucleated raw material was treated with an energy density and a scanning speed of 2 mm / s for 2.9 h to form a temperature gradient field and obtain crystallized raw material. The surface temperature of the temperature gradient field was 1000 ℃ and the internal temperature of the temperature gradient field was 850 ℃.

[0086] Step 5, Annealing: Cool the crystallized raw material to room temperature at a rate of less than 1 °C / min, wherein the room temperature is 25 °C, to obtain zero-expansion microcrystalline glass.

[0087] Example 3:

[0088] See Figure 1 This invention provides a method for preparing a wide-temperature-range zero-expansion microcrystalline glass, comprising the following steps:

[0089] Step 1: Weighing Raw Materials: Convert the molar percentages of each component of the zero-expansion glass-ceramic to mass percentages (mol%). Further weigh the raw materials corresponding to each oxide component according to the required weight of the zero-expansion glass-ceramic to be melted. The molar percentages of each component are: 52% GeO2, 5% Ga2O3, 27% SiO2, 10.5% Al2O3, 1.5% Y2O3, and 4% B2O3. (Note: The last part about Al2O3 is incomplete and likely refers to a different step.) The molar ratio of Ga2O3 is 2.1. The crystal phases of the zero-expansion glass-ceramic include a β-(Ga,Y)2GeO5 solid solution phase and a germanium quartz phase. The β-(Ga,Y)2GeO5 solid solution phase is determined by the molar percentages of Ge, Y, and Ga elements, as well as subsequent heat treatment processes such as two-step nucleation and laser selective crystallization. The volume fraction of the β-(Ga,Y)2GeO5 solid solution phase is 58%, and the volume fraction of the germanium quartz phase is 42%. The grain size of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is 230 nm. The standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is ≤2.9%.

[0090] Preferably, in the β-(Ga,Y)2GeO5 solid solution phase, Y 3+ The substitution amount was 12.11 at%;

[0091] Preferably, the ratio of [SiO4] / [GeO4] tetrahedral structure or type is 0.6;

[0092] Step 2, Cold crucible melting: The raw material is melted at 1220 °C for 2.5 h under an argon atmosphere to obtain molten raw material. During the melting process, the volatilization rate of GeO2 is 2.9%.

[0093] Step 3, two-step nucleation: The molten raw material is nucleated in two steps to obtain nucleated raw material. The two-step nucleation includes a first-stage nucleation and a second-stage nucleation. The temperature of the first-stage nucleation is 750 ℃ ​​and the holding time of the first-stage nucleation is 1 h. The temperature of the second-stage nucleation is 820 ℃ and the holding time of the second-stage nucleation is 1 h.

[0094] Step 4, Selective Laser Crystallization: The nucleation material is nucleated using a laser with a wavelength of 1064 nm (near-infrared band) at a speed of 6~9 J / cm². 2 The surface of the nucleated raw material was treated with an energy density and a scanning speed of 4 mm / s for 2.7 h to form a temperature gradient field and obtain crystallized raw material. The surface temperature of the temperature gradient field was 1000 ℃ and the internal temperature of the temperature gradient field was 850 ℃.

[0095] Step 5, Annealing: Cool the crystallized raw material to room temperature at a rate of less than 1 °C / min, wherein the room temperature is 25 °C, to obtain zero-expansion microcrystalline glass.

[0096] The above oxide composition was used for batching, melting, and crystallization (including two-step nucleation and laser crystallization processes), and relevant detection and characterization were performed. Table 2 lists non-limiting examples 1-3 of the zero-expansion microcrystalline glass composition and corresponding relevant detection data, as follows:

[0097] Table 2. Relevant test data for Examples 1-3

[0098]

[0099] Example 4:

[0100] See Figure 1 This invention provides a method for preparing a wide-temperature-range zero-expansion microcrystalline glass, comprising the following steps:

[0101] Step 1: Weighing Raw Materials: Convert the molar percentages of each component of the zero-expansion glass-ceramic to mass percentages (mol%). Further weigh the raw materials corresponding to each oxide component according to the required weight of the zero-expansion glass-ceramic to be melted. The molar percentages of each component are: 40% GeO2, 5% Ga2O3, 35% SiO2, 13% Al2O3, 3% Y2O3, and 4%... B2O3, wherein the molar ratio of Al2O3 / Ga2O3 is 2.6, the crystal phases of the zero-expansion microcrystalline glass include β-(Ga,Y)2GeO5 solid solution phase and germanium quartz phase. The β-(Ga,Y)2GeO5 solid solution phase is determined by the molar percentages of Ge, Y, and Ga elements, as well as subsequent heat treatment processes such as two-step nucleation and laser selective crystallization. The volume fraction of the β-(Ga,Y)2GeO5 solid solution phase is 54%, and the volume fraction of the germanium quartz phase is 46%. The grain size of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is 210 nm. The standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is ≤3%.

[0102] Preferably, in the β-(Ga,Y)2GeO5 solid solution phase, Y 3+ The substitution amount was 13.51 at%;

[0103] Preferably, the ratio of [SiO4] / [GeO4] tetrahedral structure or species is 0.598;

[0104] Step 2, Cold crucible melting: The raw material is melted at 1250 °C for 2.5 h under a nitrogen atmosphere to obtain molten raw material. During the melting process, the volatilization rate of GeO2 is 3%.

[0105] Step 3, two-step nucleation: The molten raw material is nucleated in two steps to obtain nucleated raw material. The two-step nucleation includes a first-stage nucleation and a second-stage nucleation. The temperature of the first-stage nucleation is 750 ℃ ​​and the holding time of the first-stage nucleation is 1 h. The temperature of the second-stage nucleation is 820 ℃ and the holding time of the second-stage nucleation is 1 h.

[0106] Step 4, Selective Laser Crystallization: The nucleation material is nucleated using a laser with a wavelength of 1064 nm (near-infrared band) at a speed of 6~9 J / cm². 2 The surface of the nucleated raw material was treated with an energy density and a scanning speed of 4 mm / s for 2.9 h to form a temperature gradient field and obtain crystallized raw material. The surface temperature of the temperature gradient field was 1000 ℃ and the internal temperature of the temperature gradient field was 850 ℃.

[0107] Step 5, Annealing: Cool the crystallized raw material to room temperature at a rate of less than 1 °C / min, wherein the room temperature is 25 °C, to obtain zero-expansion microcrystalline glass.

[0108] Example 5:

[0109] See Figure 1 This invention provides a method for preparing a wide-temperature-range zero-expansion microcrystalline glass, comprising the following steps:

[0110] Step 1, Weighing Raw Materials: Convert the molar percentages of each component of the zero-expansion glass-ceramic to mass percentages (mol%). Further weigh the raw materials corresponding to each oxide component according to the required weight of the zero-expansion glass-ceramic to be melted. The molar percentages of each component are: 52% GeO2, 4% Ga2O3, 26% SiO2, 10% Al2O3, 3% Y2O3, and 5% B2O3. (Note: The last part, "Al2O3 / ", appears to be a typo and can be left as is.) The molar ratio of Ga2O3 is 2.5. The crystal phases of the zero-expansion glass-ceramic include a β-(Ga,Y)2GeO5 solid solution phase and a germanium quartz phase. The β-(Ga,Y)2GeO5 solid solution phase is determined by the molar percentages of Ge, Y, and Ga elements, as well as subsequent heat treatment processes such as two-step nucleation and laser selective crystallization. The volume fraction of the β-(Ga,Y)2GeO5 solid solution phase is 53%, and the volume fraction of the germanium quartz phase is 47%. The grain size of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is 160 nm. The standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is ≤2.8%.

[0111] Preferably, in the β-(Ga,Y)2GeO5 solid solution phase, Y 3+ The substitution amount was 14.01 at%;

[0112] Preferably, the ratio of [SiO4] / [GeO4] tetrahedral structure or species is 0.606;

[0113] Step 2, Cold crucible melting: The raw material is melted at 1120 °C for 3.5 h in a helium atmosphere to obtain molten raw material. During the melting process, the volatilization rate of GeO2 is 2.8%.

[0114] Step 3, two-step nucleation: The molten raw material is nucleated in two steps to obtain nucleated raw material. The two-step nucleation includes a first-stage nucleation and a second-stage nucleation. The temperature of the first-stage nucleation is 755 ℃ and the holding time of the first-stage nucleation is 1 h. The temperature of the second-stage nucleation is 815 ℃ and the holding time of the second-stage nucleation is 1 h.

[0115] Step 4, Selective Laser Crystallization: The nucleation material is nucleated using a laser with a wavelength of 1064 nm (near-infrared band) at a speed of 6~9 J / cm². 2 The surface of the nucleated raw material was treated with an energy density and a scanning speed of 4 mm / s for 2.8 h to form a temperature gradient field and obtain crystallized raw material. The surface temperature of the temperature gradient field was 1000 ℃ and the internal temperature of the temperature gradient field was 850 ℃.

[0116] Step 5, Annealing: Cool the crystallized raw material to room temperature at a rate of less than 1 °C / min, wherein the room temperature is 25 °C, to obtain zero-expansion microcrystalline glass.

[0117] Example 6:

[0118] See Figure 1 This invention provides a method for preparing a wide-temperature-range zero-expansion microcrystalline glass, comprising the following steps:

[0119] Step 1, Weighing Raw Materials: Convert the molar percentages of each component of the zero-expansion glass-ceramic to mass percentages (mol%). Further weigh the raw materials corresponding to each oxide component according to the required weight of the zero-expansion glass-ceramic to be melted. The molar percentages of each component are: 52% GeO2, 3% Ga2O3, 29% SiO2, 11% Al2O3, 2% Y2O3, and 3% B2O3. (Note: The last part, "Al2O3 / ", appears to be a typo and can be left as is.) The molar ratio of Ga2O3 is 3.667. The crystal phases of the zero-expansion glass-ceramic include a β-(Ga,Y)2GeO5 solid solution phase and a germanium quartz phase. The β-(Ga,Y)2GeO5 solid solution phase is determined by the molar percentages of Ge, Y, and Ga elements, as well as subsequent heat treatment processes such as two-step nucleation and laser selective crystallization. The volume fraction of the β-(Ga,Y)2GeO5 solid solution phase is 52%, and the volume fraction of the germanium quartz phase is 48%. The grain size of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is 200 nm. The standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is ≤2.9%.

[0120] Preferably, in the β-(Ga,Y)2GeO5 solid solution phase, Y 3+ The substitution amount was 12.88 at%;

[0121] Preferably, the ratio of [SiO4] / [GeO4] tetrahedral structure or species is 0.642;

[0122] Step 2, Cold crucible melting: The raw material is melted at 1220 °C for 2.5 h in a neon atmosphere to obtain molten raw material. During the melting process, the volatilization rate of GeO2 is 2.9%.

[0123] Step 3, two-step nucleation: The molten raw material is nucleated in two steps to obtain nucleated raw material. The two-step nucleation includes a first-stage nucleation and a second-stage nucleation. The temperature of the first-stage nucleation is 750 ℃ ​​and the holding time of the first-stage nucleation is 1 h. The temperature of the second-stage nucleation is 820 ℃ and the holding time of the second-stage nucleation is 1 h.

[0124] Step 4, Selective Laser Crystallization: The nucleation material is nucleated using a laser with a wavelength of 1064 nm (near-infrared band) at a speed of 6~9 J / cm². 2 The surface of the nucleated raw material was treated with an energy density and a scanning speed of 4 mm / s for 2.9 h to form a temperature gradient field and obtain crystallized raw material. The surface temperature of the temperature gradient field was 1000 ℃ and the internal temperature of the temperature gradient field was 850 ℃.

[0125] Step 5, Annealing: Cool the crystallized raw material to room temperature at a rate of less than 1 °C / min, wherein the room temperature is 25 °C, to obtain zero-expansion microcrystalline glass.

[0126] The oxide composition of the aforementioned zero-expansion glass-ceramic was prepared, melted, and crystallized (including two-step nucleation and laser crystallization processes), and relevant detection and characterization were performed. Table 3 lists non-limiting examples 4-6 of the zero-expansion glass-ceramic composition and corresponding detection data, as follows:

[0127] Table 3. Relevant test data from Examples 4-6

[0128]

[0129] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered illustrative and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the scope of the invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0130] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can be appropriately combined to form other embodiments that can be understood by those skilled in the art. The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A zero-expansion microcrystalline glass based on a wide temperature range, characterized in that, It is prepared from the following raw materials in molar percentage: 40%≤GeO2≤52%; 3%≤Ga2O3≤5%; 26%≤SiO2≤35%; 10%≤Al2O3≤13%; 1.5%≤Y2O3≤3%; 3%≤B2O3≤5%; The crystal phases of the zero-expansion microcrystalline glass include a β-(Ga,Y)2GeO5 solid solution phase and a germanium quartz phase, wherein the β-(Ga,Y)2GeO5 solid solution phase is determined by the molar percentages of Ge, Y, and Ga elements.

2. The zero-expansion microcrystalline glass based on a wide temperature range according to claim 1, characterized in that, The volume fraction of the germanium-quartz phase is 42%~48%; The grain size of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is 80~230 nm, and the standard deviation of the uniformity of the crystal phase distribution of both the β-(Ga,Y)2GeO5 solid solution phase and the germanium quartz phase is ≤3%. The ratio of [SiO4] / [GeO4] tetrahedral structures or types in the zero-expansion microcrystalline glass is 0.569~0.

642.

3. The zero-expansion microcrystalline glass based on a wide temperature range according to claim 1, characterized in that, It is prepared from the following raw materials in molar percentage: 46.2% GeO2, 4.2% Ga2O3, 32% SiO2, 12.1% Al2O3, 2.3% Y2O3, 3.2% B2O3.

4. A method for preparing a wide-temperature-range zero-expansion microcrystalline glass according to any one of claims 1 to 3, characterized in that, Includes the following steps: Weigh the raw materials according to the composition and molar percentage of the zero-expansion microcrystalline glass; The raw materials are melted under an inert atmosphere to obtain molten raw materials; The molten raw material is nucleated in two steps to obtain nucleated raw material; The nucleated raw material is subjected to selective laser crystallization to obtain crystalline raw material; The crystallized raw materials are annealed to obtain zero-expansion microcrystalline glass.

5. The method for preparing a wide-temperature-range zero-expansion microcrystalline glass according to claim 4, characterized in that, The inert atmosphere includes one of argon, nitrogen, helium, and neon; The melting temperature is 1120~1250 ℃, the melting time is 2.5~3.5 h, and the volatilization rate of GeO2 during the melting process is ≤3%.

6. The method for preparing a wide-temperature-range zero-expansion microcrystalline glass according to claim 4, characterized in that, The two-step nucleation includes a first-stage nucleation and a second-stage nucleation; The temperature for the first stage of nucleation is 750~780 ℃, and the holding time for the first stage of nucleation is 1 h. The temperature for the second stage of nucleation is 800~820 ℃, and the holding time for the second stage of nucleation is 1 h.

7. The method for preparing a wide-temperature-range zero-expansion microcrystalline glass according to claim 4, characterized in that, The process of selectively crystallizing the nucleated raw material using laser to obtain crystalline raw material specifically includes: Using laser at 6~9 J / cm 2 The surface of the nucleated raw material was treated with an energy density and a scanning speed of 2~4 mm / s for 2.7~2.9 h to form a temperature gradient field on the nucleated raw material, thus obtaining crystallized raw material.

8. A method for preparing a wide-temperature-range zero-expansion glass-ceramic according to claim 7, characterized in that, The wavelength of the laser is 1064 nm; The surface temperature of the temperature gradient field is 1000 ℃, and the internal temperature of the temperature gradient field is 850 ℃; In the crystallized raw material obtained after laser selective crystallization, the phase ratio of the β-(Ga,Y)2GeO5 solid solution phase is controlled by the energy density E: V β =50+1.2(E-6); In the formula, V β E represents the phase ratio of the β-(Ga,Y)2GeO5 solid solution phase; 6≤E≤9.

9. A method for preparing a wide-temperature-range zero-expansion glass-ceramic according to claim 4, characterized in that, The annealing specifically includes cooling to room temperature at a rate of less than 1 °C / min.

10. The application of the wide-temperature-range zero-expansion microcrystalline glass according to any one of claims 1 to 3 in quantum bit carriers and biochip substrates.

Images