CN112876083B - Microcrystalline glass material, preparation method thereof and application thereof in semiconductor device - Google Patents
Microcrystalline glass material, preparation method thereof and application thereof in semiconductor device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
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Abstract
The invention relates to a microcrystalline glass material, a preparation method thereof and application thereof in a semiconductor device. The microcrystalline glass material comprises base glass, a crystal nucleus agent, a clarifying agent and an additive. The microcrystalline glass material provided by the invention has multiple crystal phases by constructing a specific polycrystalline phase system, overcomes the defect of the performance of the microcrystalline glass with a single crystal phase, ensures the high hardness of the microcrystalline glass, improves the transparency and the impact strength of the microcrystalline glass, and is suitable for the use requirements of semiconductor devices, particularly high-end mobile phone (including 5G) panel and back panel materials.
Description
Technical Field
The invention belongs to the technical field of semiconductor devices, and particularly relates to a microcrystalline glass material, a preparation method thereof and application thereof in a semiconductor device.
Background
The wireless frequency spectrum of more than 3GHz is adopted in 5G communication, the antenna structure is more complex than that of 4G, and the existing antenna layout structure cannot meet the requirement of 5G. Therefore, in the 5G era, the smart phone will abandon the existing metal rear cover with signal shielding property, and the ceramic rear cover and the glass rear cover become the alternatives of 5G communication products. The glass rear cover made of the microcrystalline glass has excellent wear resistance, is easy to clean and color-adjust, and becomes a hotspot of current research.
The microcrystalline glass has various types, glass products with different purposes can be produced by different component proportions and different processes, most of the existing microcrystalline glass products are single crystal phases, and the existing microcrystalline glass products are mainly used as building decorative materials, biological materials, technical products or small heating products and the like. At present, the production of high-hardness, high-strength and high-transparency glass ceramics is not found in domestic markets, and the glass ceramics are blank for semiconductor devices such as mobile phone panels and back plates. Only American Corning company produces the apple fruit internationally.
Patent CN110217985A discloses a microcrystalline glass, which is a polycrystalline phase system, has a lower expansion coefficient, higher hardness and strength, but the transparency thereof still needs to be improved, and the impact performance and the mohs hardness thereof are not tested, and the transparency, the impact performance and the mohs hardness are exactly the most interesting properties for preparing the mobile phone panel or the back plate.
Therefore, the development of a microcrystalline glass with high hardness, high strength and high transparency, which can be applied to semiconductor devices, has important research significance and great economic value.
Disclosure of Invention
The invention aims to overcome the defects of high hardness, high strength and high transparency of microcrystalline glass in the prior art and provide a microcrystalline glass material. The microcrystalline glass material provided by the invention has multiple crystal phases by constructing a polycrystalline phase system, overcomes the defect of the performance of microcrystalline glass with a single crystal phase, ensures the high hardness of the microcrystalline glass, improves the transparency and the impact strength of the microcrystalline glass, and is suitable for the use requirements of semiconductor devices, especially high-end mobile phone (including 5G) panel and back panel materials.
The invention also aims to provide a preparation method of the microcrystalline glass material.
The invention also aims to provide application of the microcrystalline glass material in a semiconductor device.
In order to achieve the purpose, the invention adopts the following technical scheme:
a microcrystalline glass material comprises base glass, a crystal nucleus agent, a clarifying agent and additives, wherein the weight percentage of the total weight of the microcrystalline glass material is as follows:
the base glass comprises the following components in parts by weight: li2O 0.5~3.2%，Al2O3 25.0~35.0%，SiO245.0~60.0%，MgO 2.0~14.0%；
The crystal nucleus agent comprises the following components in parts by weight: SnO20.1~1.0%，ZrO21.0~5.0%；
The additive comprises the following components in parts by weight: la2O3 0.1~1.0%，Y2O30.1~1.0%。
The microcrystalline glass material comprises a glass matrix and a polycrystalline phase system dispersed in the glass matrix; the polycrystalline phase system takes magnesium aluminate spinel as a main part and tetragonal zirconia, eucryptite and quartz solid solution as an auxiliary part; wherein the weight fraction of the magnesium aluminate spinel is not less than 15%; the sum of the weight fractions of tetragonal zirconia, eucryptite and quartz solid solutions is less than 3%.
We have conducted many years of research on glass ceramics. In the previous research work (patent CN 110217985A), a microcrystalline glass has been developed, which has a low expansion coefficient and high hardness and strength, and can be used for preparing thick products such as astronomical telescope lens blanks. In addition, the preparation method can also be used for preparing ultrathin glass ceramics products, and is expected to be applied to 5G mobile phone backboards and the like. But the transparency thereof is still to be improved; and when the impact property and the Mohs hardness are tested, the impact strength of the glass is basically close to that of high-alumina glass. If the performance of the semiconductor device is required to be really applied to a semiconductor device such as a 5G mobile phone backboard and the like, the performance of the semiconductor device is still required to be improved.
The inventors of the present application have made repeated studies to improve the formulation of the glass ceramics from several aspects, such as the transparency, the impact resistance and the mohs hardness. Specifically, the method comprises the following steps:
the microcrystalline glass in patent CN110217985A is Li2O-Al2O3-SiO2The crystal phase of the microcrystalline glass is mainly spodumene, and part of the crystalline phase is eucryptite and quartz solid solution; the microcrystalline glass material provided by the application constructs a new crystalline phase system, and particularly, the microcrystalline glass material provided by the application takes magnesium aluminate spinel as a main material and takes tetragonal zirconia, eucryptite and quartz solid solution as an auxiliary material (the weight fraction of the magnesium aluminate spinel is greater than that of other crystalline phases, so that a polycrystalline phase system is obtained and is dispersed in a glass matrix, and the hardness, transparency and impact strength of the microcrystalline glass can be effectively improved; simultaneously, the material property is increased, the forming temperature is reduced, and the mobile phone cover plate is more suitable for various products of mobile phone cover platesAnd (4) the type requirement.
Specifically, the formula of the base glass, the crystal nucleating agent and the additive is optimized to construct a specific polycrystalline phase system, so that the hardness, the transparency and the impact strength of the microcrystalline glass are improved, and the forming performance is improved.
Wherein Al is increased by increasing Al in the base glass2O3And MgO, and simultaneously adopting a plurality of nucleating agents, so that the microcrystalline glass takes magnesium aluminate spinel as a main part and tetragonal zirconia, eucryptite and quartz solid solution as auxiliary parts to obtain a polycrystalline phase system.
For the nucleating agent and the additive, ZrO is adjusted in the application2By weight ratio of ZrO2The toughened glass ceramics is an important way for improving the toughness, and ZrO in the glass ceramics2The toughening mechanism mainly induces phase change toughening, crack toughening and microcrack toughening by stress, and the toughening effect is influenced by ZrO in the microcrystalline glass2The volume content of the ZrO2, the crystal form, the crystal size and the crystal morphology of the ZrO2, and simultaneously adding SnO2The crystal growth can be effectively controlled to be too fast, and the size and uniformity of crystal particles are ensured, so that the transparency of the glass is ensured. But ZrO2When the amount is larger, the defects of difficult melting and poor uniformity of the glass are caused, and the problem of easy crystallization in the production process is caused. The inventor of the present application has found that Y is introduced into the glass ceramics2O3Can solve the problems of melting and crystallization and effectively improve the bending strength of the glass. In addition, La2O3The introduction of (2) enables the crystal phase to develop into complete columnar and plate-shaped crystals, and can increase the strength and toughness of the glass.
The microcrystalline glass obtained by the invention has higher transparency, hardness and strength, and is suitable for the use requirements of semiconductor devices, especially high-end mobile phone (including 5G) panel and backboard materials. The specific performance indexes are as follows:
(1) density: 2.60-2.80 g/cm3；
(2) Coefficient of thermal expansion: 52.8 to 53.8X 10-7/DEG C (0 to 50 ℃); 53.5 to 60.8X 10-7/DEG C (30 to 500 ℃);
(3) visible light transmittance: more than or equal to 91.5 percent (thickness is 1 mm);
(4) sheet glass vickers hardness: HV 823 + 898 + -20 kg/mm2(load 100 g);
mohs hardness of 7.0-8.0
(5) Chemical strengthening expansion ratio: 0.03 percent
(6) Enhancing the warping rate: 0.05 percent
(7) Modulus of elasticity: (8.8. + -. 0.1). times.105 kg/cm2
(8) Impact strength (132 g steel ball drop): 80 cm.
Preferably, the mass fraction of the magnesium aluminate spinel in the microcrystalline glass material is 15-20%; the sum of the mass fractions of tetragonal zirconia, eucryptite and quartz solid solution is 3-5%.
Specifically, the mass fraction of the tetragonal zirconia can be 1-1.5%; the mass fraction of eucryptite can be 0.5-1.5%; the mass fraction of the quartz solid solution can be 0.5-1.5%.
Preferably, the magnesium aluminate spinel, tetragonal zirconia, eucryptite and quartz solid solutions all develop into intact columnar or plate-like crystals; the solid solutions of magnesium aluminate spinel, tetragonal zirconia, eucryptite and quartz are uniform and uniformly dispersed in the glass matrix.
Preferably, based on the total weight of the microcrystalline glass material:
the base glass comprises the following components in parts by weight: li2O 0.5~3.2%，Al2O3 25.0~35.0%，SiO245.0~60.0%，MgO 2.0~14.0%，ZnO 1.0~12.0%，CaO0.2~4.5%，SrO0.3~3.0%，BaO0.2~3.0%，R2O 1.1~10.2%；
The crystal nucleus agent comprises the following components in parts by weight: SnO20.1~1.0%，ZrO21.0~5.0%，TiO20.2~2.0%，P2O5 0~2.0%；
The clarifying agent comprises the following components in parts by weight: sb2O30.1~0.5%、NaCl0.2~0.6%；
The additive comprises the following components in parts by weight: la2O3 0.1~1%%，Y2O30.1~1.0%；
The sum of the weight fractions of the components is 100 percent.
More preferably, based on the total weight of the microcrystalline glass material: the base glass comprises the following components in parts by weight: li2O 2.0~3.1%，Al2O3 25.5~32.0%，SiO2 45.5~57.0%，MgO 3.0~12.0%，ZnO 3.0~11.5%，CaO 0.5~4.0%，SrO 0.5~2.0%，BaO 0.5~2.0%，R2O 3.0~8.0%。
More preferably, based on the total weight of the microcrystalline glass material: the crystal nucleus agent comprises the following components in parts by weight: SnO20.2~0.7%，ZrO2 2.0~4.7%；TiO2 0.25~1.9%，P2O5 0.1~1.9%。
More preferably, based on the total weight of the microcrystalline glass material: the clarifying agent comprises the following components in parts by weight: sb2O30.2~0.48%，NaCl 0.3~0.58%。
More preferably, based on the total weight of the microcrystalline glass material: the additive comprises the following components in parts by weight: la2O30.15~0.9%，Y2O3 0.12~0.95%。
Preferably, said R is2O comprises K2O、Na2O and Li2O。
More preferably, based on the total weight of the microcrystalline glass material: the R is2O comprises the following components K in percentage by weight2O0.1~2.5%，Na2O1.0~ 7.7%。
The preparation method of the microcrystalline glass material comprises the following steps: mixing base glass, a nucleating agent, a clarifying agent and an additive, melting, cooling, molding, annealing and crystallizing to obtain the microcrystalline glass; the crystallization treatment adopts multi-stage heat preservation treatment, and the temperature of each stage is gradually increased.
The invention adopts multiple temperature sections to carry out crystallization treatment, forms various crystal structures, and controls the size of the crystal through different temperatures and time, thereby ensuring the strength and hardness of the glass ceramics and the transparency of the glass ceramics.
The microcrystalline glass mainly comprises a glass matrix and nano-scale crystal particles dispersed in the glass matrix, wherein the crystal particles comprise magnesium aluminate spinel (as a main component), eucryptite, tetragonal zirconia crystal particles and quartz crystal particles.
Preferably, the melting temperature is 1600-1660 ℃, and the melting time is 6-12 h.
Preferably, the cooling temperature is 1440 ℃ to 1500 ℃, and the cooling time is 2 h to 4 h.
Preferably, the preparation method comprises the following steps: rolling forming, overflow forming or float forming.
Preferably, the crystallization treatment is a 2-stage heat preservation treatment: treating at 600-650 ℃ for 1-3 h, and then treating at 730-790 ℃ for 1-3 h; or the crystallization treatment is a 3-stage heat preservation treatment: treating at 600-650 ℃ for 1-3 h, then treating at 700-750 ℃ for 1-3 h, and then treating at 780-830 ℃ for 1-3 h.
Preferably, the annealing temperature is 550-580 ℃ and the time is 2-5 h.
The application of the microcrystalline glass in a semiconductor device (such as preparing a mobile phone panel or a mobile phone back panel) is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
the microcrystalline glass material provided by the invention has multiple crystal phases by constructing a polycrystalline phase system, overcomes the defect of the performance of microcrystalline glass with a single crystal phase, ensures the high hardness of the microcrystalline glass, improves the transparency and the impact strength of the microcrystalline glass, and is suitable for the use requirements of high-end mobile phone (including 5G) panel and back panel materials.
Drawings
FIG. 1 is an X-ray diffraction pattern of a series of glass-ceramics provided in example 1;
FIG. 2 is a scanning electron micrograph of a series of glass-ceramics provided in example 1;
FIG. 3 is a scanning electron micrograph of the crystallized glass provided in comparative example 2;
fig. 4 is a scanning electron micrograph of the crystallized glass provided in comparative example 4.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The microcrystalline glasses of the examples and comparative examples of the present invention were pressed to a sample size of 164.45 x 71.36 x 0.7mm and tested as follows:
(1) density: 2.60-2.80 g/cm3(GB/T2540 pycnometer method);
(2) coefficient of thermal expansion: 52.8 to 53.8X 10-7/DEG C (0 to 50 ℃); 53.5 to 60.8X 10-7/DEG C (30 to 500 ℃ C.) (TMA static thermomechanical analysis);
(3) visible light transmittance (thickness 1 mm): more than or equal to 91.5 percent (GB 5433-85);
(4) plate glass vickers hardness (load 100 g): HV 823 + 898 + -20 kg/mm2(load 100 g) (micro vickers hardness tester);
mohs hardness: 7.0 to 8.0 (scratch method);
(5) chemical strengthening expansion ratio: 0.03% (comparative method);
(6) enhancing the warping rate: 0.05 percent. (comparative method);
(7) modulus of elasticity: (8.8 +/-0.1) multiplied by 105 kg/cm2 (GB/T37788-2019);
(8) impact strength (132 g steel ball drop): 80cm (GB 9622.7-88).
Example 1
This example provides a series of glass-ceramics consisting of the following components (in weight fraction, the same applies below): 2.0wt% Li2O、25.5wt%A2lO3、51.5%wtSiO2、0.5wt%CaO、0.5wt%SrO、3.0wt%ZnO、8.1wt%MgO、0.5wt%BaO、0.4wt%K2O、1.0wt%Na2O、5.0wt%ZrO2、0.1wt%Y2O3、0.4wt%Sb2O3、0.4wt%NaCl、0.5wt%SnO2、 0.3% TiO2、0.2% P2O5、0.1wt% La2O3。
The preparation process comprises the following steps:
(1) the components are mixed and melted for 10 hours at the temperature of 1655 ℃, then cooled for 3 hours at 1460 ℃, and then cast and molded to obtain the common glass.
(2) Crystallizing common glass to obtain microcrystalline glass, wherein the crystallization treatment is divided into three stages, the temperature of the first stage is 640 ℃, the time is 2 hours, the temperature of the second stage is 710 ℃, the time is 1 hour, and the temperature of the third stage is 780 ℃ and the time is 2 hours respectively; and annealing treatment is carried out after crystallization treatment, wherein the annealing treatment temperature is 560 ℃, and the time is 3 h.
Meanwhile, the treatment temperatures of the third stage of the step (2) are respectively adjusted to 640 ℃, 740 ℃ and 980 ℃, and the rest conditions are consistent with the above operation, so as to carry out comparative analysis.
The series of glass-ceramics was characterized by means of X-ray diffraction (XRD) analysis techniques, and assisted by the Scanning Electron Microscope (SEM) method. The results are shown in FIGS. 1 and 2. As can be seen from FIG. 2, when the microcrystalline glass is treated at 640 ℃, only a small amount of crystals are scattered, and at 740 ℃, crystal particles are opened and grown in a glass phase, but the glass structure is loose and the strength and the hardness are poor. After 780 ℃, the crystal and the glass phase are combined perfectly. However, if the treatment temperature is too high, for example, 980 ℃, the glass-ceramic is completely devitrified due to the growth of crystal grains. Specifically, as can be seen from the analysis (fig. 1) of the crystal phase of the crystallized glass subjected to the temperature holding treatment, the crystallized glass mainly consists of a glass matrix and nano-scale crystal particles dispersed therein, wherein the crystal particles of the crystallized glass obtained by the treatment at 640 ℃ and 740 ℃ are mainly magnesia alumina spinel, and have very low contents of eucryptite, tetragonal zirconia crystal particles and quartz crystal particles and almost no diffraction peak; the crystal particles of the microcrystalline glass obtained by 780 ℃ treatment are mainly magnesium aluminate spinel, about 18% by weight, eucryptite (about 1.5% by weight), tetragonal zirconia crystal particles (about 1% by weight) and quartz crystal particles (about 0.5% by weight) as auxiliary materials, and are 3-5% in total; the content of magnesia-alumina spinel, tetragonal zirconia crystal particles and quartz crystal particles in the crystal particles of the microcrystalline glass obtained by treatment at 980 ℃ is further increased, the content of eucryptite crystal particles is greatly reduced, and almost no diffraction peak exists. This is primarily because eucryptite gradually transitions to spodumene as the temperature increases.
Example 2
The embodiment provides a microcrystalline glass, which consists of the following components: 51.7wt% SiO2、25.1wt% Al2O3、3.0wt% ZnO、5.0wt% ZrO2、0.6wt% Y2O3、0.3wt% Sb2O3、1.0wt% BaO、0.5wt%SrO、1wt% La2O3、5.5wt%Na2O、1.0wt%K2O、0.5wt%Li2O、0.5wt% CaO、0.5 wt % SnO2、0.3 wt % TiO2、0.2% P2O5、3.0 wt% MgO, 0.3wt% NaCl.
The preparation process comprises the following steps:
(1) the components are mixed and melted for 8.3 hours at the temperature of 1650 ℃, cooled for 2 hours at 1450 ℃, and then cast and molded to obtain the common glass.
(2) The common glass is crystallized to prepare the microcrystalline glass, the crystallization treatment is divided into two stages, the temperature of the first stage is 640 ℃, the time is 3 hours, the temperature of the second stage is 750 ℃, the time is 2 hours, the annealing treatment is carried out after the crystallization treatment, the temperature of the annealing treatment is 578 ℃, and the time is 2.5 hours.
The X-ray diffraction pattern of this glass-ceramic is consistent with that of the glass-ceramic obtained by 780 ℃ treatment in fig. 1, consisting essentially of a glass matrix with nano-scale crystal particles dispersed therein, the crystal particles consisting essentially of magnesium aluminate spinel (about 20% by weight), eucryptite (about 1.2% by weight), tetragonal zirconia crystal particles (about 1.3% by weight), and quartz crystal particles (about 1% by weight).
Example 3
The embodiment provides a microcrystalline glass, which consists of the following components: 45.2 wt% SiO2、33.1 wt% Al2O3、1.0 wt% ZnO、4.0 wt% ZrO2、0.5 wt% Y2O3、0.2 wt% Sb2O3、0.6 wt% BaO、0.5 wt% SrO、0.8 wt% La2O3、3.5 wt% Na2O、1.2 wt%K2O、1.5 wt% Li2O、0.4 wt% CaO、0.5 wt % SnO2、0.3 wt % TiO2、0.4 wt % P2O56.0 wt% MgO and 0.3wt% NaCl.
The preparation process comprises the following steps:
(1) the components are mixed and melted for 8 hours at 1660 ℃, cooled for 2 hours at 1450 ℃, and then cast and molded to obtain the common glass.
(2) The common glass is crystallized to prepare the microcrystalline glass, the crystallization treatment is divided into 3 stages, the temperature of the first stage is 620 ℃, the time is 1.5 h, the temperature of the second stage is 730 ℃, the time is 1.5 h, the annealing treatment is needed after the crystallization treatment, and the temperature of the annealing treatment is 790 ℃, and the time is 1 h.
The X-ray diffraction pattern of this glass-ceramic was consistent with that of the glass-ceramic obtained by 780 ℃ treatment in FIG. 1, consisting essentially of a glass matrix and nano-sized crystal particles dispersed therein, the crystal particles being composed mainly of magnesium aluminate spinel (weight fraction of about 19%), and eucryptite (weight fraction of about 1.5%), tetragonal zirconia crystal particles (weight fraction of about 1.2%) and quartz crystal particles (weight fraction of about 1%).
Example 4
The embodiment provides a microcrystalline glass, which consists of the following components: 52.2 wt% SiO2、30.2 wt% Al2O3、6.0 wt% ZnO、2.0 wt% ZrO2、0.1 wt% Y2O3、0.3 wt% Sb2O3、0.5 wt% BaO、0.5 wt% SrO、0.1 wt% La2O3、1.0 wt% Na2O、0.7 wt% K2O、1.8 wt% Li2O、0.5 wt% CaO、0.2 wt % SnO2、0.3 wt% TiO2、0.4 wt% P2O53.0 wt% MgO and 0.2 wt% NaCl.
The preparation process comprises the following steps:
(1) the components are mixed and melted for 12 hours at the temperature of 1655 ℃, then cooled for 3 hours at the temperature of 1490 ℃, and then cast and molded to obtain the common glass.
(2) The common glass is crystallized to obtain the microcrystalline glass, the crystallization treatment is divided into 2 stages, the temperature of the first stage is 640 ℃, the time is 2.5 hours, the temperature of the second stage is 750 ℃, the time is 2 hours, the annealing treatment is carried out after the crystallization treatment, the temperature of the annealing treatment is 580 ℃, and the time is 4 hours.
The X-ray diffraction pattern of this glass-ceramic is consistent with that of the glass-ceramic obtained by 780 ℃ treatment in fig. 1, and is composed mainly of a glass matrix and nano-sized crystal grains dispersed therein, the crystal grains being composed of magnesia-alumina spinel (about 17% by weight) as a main component and eucryptite (about 1.5% by weight), tetragonal zirconia crystal grains (about 0.5% by weight) and quartz crystal grains (about 1.2% by weight).
Comparative example 1
This comparative example provides a glass-ceramic prepared according to example 1 of patent CN110217985A, having the same formulation as in example 1 of patent CN110217985A, and having the same size of the glass-ceramic chip as in each example.
The preparation process comprises the following steps: the paint consists of the following components in percentage by weight: li2O：3.7%；Al2O3：22%；SiO2：60.3%；CaO：1.8%；MgO：0.7%；ZnO：2.2%；BaO：1.0%；K2O：0.5%；Na2O：0.5% ；TiO2：1.8%；ZrO2： 2.0%；P2O5：2.0%；As2O3：0.5%；Sb2O3：0.5%；NaCl：0.5%。
The process flow comprises the following steps:
(1) preparing the materials according to the provided formula; (2) mixing ofCombining; (3) melting: 4.8M 2 heat exchange type fuel oil or natural gas is melted in a tank furnace at the temperature of 1560 ℃; (4) and (3) cooling: 1440 ℃ to 1520 ℃; (5) casting and molding, wherein the temperature is 1370-1440 ℃, large glass (phi 2.2 m, thickness 0.35 m and weight 4 tons) is cast after 20 minutes, crystallization does not occur at the temperature of more than 1330 ℃, crystallization does not occur at the temperature reduction process of 1330 ℃ -600 ℃ for 60 minutes, heat treatment is carried out at the temperature of 630 ℃, and the temperature is controlled according to a temperature reduction curve 3; (6) precise heat treatment and annealing, cooling the glass from 1330 ℃ → 750 ℃ within 60 minutes after casting, and cooling to 630 ℃ from the following heat treatment system
750℃
770℃
770℃
800℃
800℃
600℃
600℃
At room temperature, the color of the glass plate is brown and transparent; (7) slicing to the desired size (consistent with the test sample) (8) preparing: grinding, polishing and finish machining; (9) and packaging and warehousing for later use.
The microcrystalline glass consists essentially of a glass matrix and crystals of beta-eucryptite crystals and beta-quartz solid solutions dispersed therein.
Comparative example 2
Comparative exampleA glass ceramics is provided, which does not contain Y in its composition2O3And is ZrO2Except that the content of (B) was 5.1wt%, the rest was the same as in example 2, and the preparation method was the same as in example 2. The glass-ceramic consists essentially of a glass matrix with nanoscale crystal grains dispersed therein, the X-ray diffraction pattern being consistent with that of the glass-ceramic obtained by 780 ℃ treatment in FIG. 1, the crystal grains consisting essentially of magnesium aluminate spinel (weight fraction of about 20%), eucryptite (weight fraction of about 1.2%), tetragonal zirconia crystal grains (weight fraction of about 1.5%) and quartz crystal grains (weight fraction of about 1.1%). FIG. 3 is a scanning electron micrograph showing that Y is not contained2O3Result in ZrO2The zirconium oxide is difficult to melt, the size and the distribution of zirconium oxide crystal particles are not uniform, and even zirconium oxide stripes appear.
Comparative example 3
This comparative example provides a microcrystalline glass having a composition excluding La2O3And SiO2Except that the content of (B) was 51.6wt%, the rest was the same as in example 2, and the preparation method was the same as in example 2. The X-ray diffraction pattern of this glass-ceramic was consistent with that of the glass-ceramic obtained by 780 ℃ treatment in fig. 1, consisting essentially of a glass matrix and nano-sized crystal particles dispersed therein, the crystal particles consisting of magnesia-alumina spinel (about 19% by weight) as the main and eucryptite (about 1.5% by weight), tetragonal zirconia crystal particles (about 1.2% by weight) and quartz crystal particles (about 1.0% by weight). La is visible2O3Has little influence on the composition of the crystal due to La2O3The method is favorable for the development of the crystal phase in the microcrystalline glass into complete columnar and plate-shaped crystals, and influences the performance of the microcrystalline glass.
Comparative example 4
This comparative example provides a microcrystalline glass having a composition excluding SnO2And SiO2Except that the content of (A) was 52.0wt%, the rest was the same as in example 2, and the preparation method was the same as in example 2. The X-ray diffraction pattern of the microcrystalline glass is consistent with that of the microcrystalline glass obtained by 780 ℃ treatment in figure 1, and the microcrystalline glass mainly comprises a glass matrix and nano particles dispersed in the glass matrixA composition of primary crystal grains consisting essentially of magnesium aluminate spinel (about 17% by weight) and eucryptite (about 1.5% by weight), tetragonal zirconia crystal grains (about 0.5% by weight) and quartz crystal grains (about 1.2% by weight). SnO2The crystal growth can be effectively controlled to be too fast, and the size and uniformity of crystal particles are ensured, so that the transparency and the strength of the glass are ensured.
FIG. 4 is a scanning electron micrograph. As is clear from the figure, SnO was not added2The size and uniformity of the crystal grains of the obtained glass-ceramics are poor.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention. Table 1 shows the test results of the glass ceramics of examples and comparative examples.
Table 1 test results of glass ceramics of examples and comparative examples
As can be seen from the above table, the microcrystalline glass provided by each embodiment of the present invention has high transparency, hardness and strength, wherein the visible light transmittance is more than 91.5%, the mohs hardness is high, the impact resistance is excellent, and the performance is far better than that of comparative example 1. Due to Y2O3And ZrO2Forming a substitutional solid solution to contain high ZrO2The melting temperature of the microcrystalline glass is reduced, the material structure is more compact, and Y is not added2O3The glass ceramics of (1) (as comparative example 2), resulting in a decrease in impact strength; due to La2O3Is beneficial to the development of the crystal phase in the glass ceramics into complete columnar and platy crystals, improves the strength of the glass ceramics without adding La2O3The modulus of elasticity and impact strength of the glass ceramics (as in comparative example 3) are reduced; SnO2The crystal growth can be effectively controlled to be too fast, and the size and uniformity of crystal particles are ensured, so that the transparency and the strength of the glass are ensured. Without the addition of SnO2The microcrystalline glass (as in comparative example 4) has reduced visible light transmittance, chemical strengthening expansion rate, strengthening warping rate, elastic modulus and impact strength.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (9)
1. A microcrystalline glass material, comprising a base glass, a crystal nucleus agent, a clarifying agent and an additive, wherein based on the total weight of the microcrystalline glass material:
the base glass comprises the following components in parts by weight: li2O 0.5~3.2%，Al2O3 25.0~35.0%，SiO2 45.0~60.0%，MgO 2.0~14.0%；
The crystal nucleus agent comprises the following components in parts by weight: SnO20.1~1.0%，ZrO21.0~5.0%；
The additive comprises the following components in parts by weight: la2O3 0.1~1.0%，Y2O30.1~1.0%；
The microcrystalline glass material comprises a glass matrix and a polycrystalline phase system dispersed in the glass matrix; the polycrystalline phase system takes magnesium aluminate spinel as a main part and tetragonal zirconia, eucryptite and quartz solid solution as an auxiliary part; wherein the mass fraction of the magnesium aluminate spinel is 15-20%, the sum of the mass fractions of tetragonal zirconia, eucryptite and quartz solid solution is not less than 3%, and the mass fraction of the tetragonal zirconia is 1-1.5%; the mass fraction of eucryptite is 0.5-1.5%; the mass fraction of the quartz solid solution is 0.5-1.5%;
the magnesium aluminate spinel, tetragonal zirconia, eucryptite and quartz solid solutions all developed into complete columnar or plate-like crystals.
2. The microcrystalline glass material of claim 1, wherein based on the total weight of the microcrystalline glass material:
the base glass comprises the following components in parts by weight: li2O 0.5~3.2%，Al2O3 25.0~35.0%，SiO2 45.0~60.0%，MgO 2.0~14.0%，ZnO 1.0~12.0%，CaO0.2~4.5%，SrO0.3~3.0%，BaO0.2~3.0%，R21.1-10.2% of O; the R is2O comprises K2O and Na2O；
The crystal nucleus agent comprises the following components in parts by weight: SnO20.1~1.0%，ZrO21.0~5.0%，TiO20.2~2.0%，P2O5 0~2.0%；
The clarifying agent comprises the following components in parts by weight: sb2O30.1~0.5%、NaCl0.2~0.6%；
The additive comprises the following components in parts by weight: la2O3 0.1~1%，Y2O30.1~1.0%；
The sum of the weight fractions of the components is 100 percent.
3. The microcrystalline glass material of claim 2, wherein based on the total weight of the microcrystalline glass material:
the base glass comprises the following components in parts by weight: li2O 2.0~3.1%，Al2O3 25.5~32.0%，SiO2 45.5~57.0%，MgO 3.0~12.0%，ZnO 3.0~11.5%，CaO 0.5~4.0%，SrO 0.5~2.0%，BaO 0.5~2.0%，R2O 3.0~8.0%；
The crystal nucleus agent comprises the following components in parts by weight: SnO2 0.2~0.7%，ZrO2 2.0~4.7%；TiO2 0.25~1.9%，P2O5 0.1~1.9%；
The clarifying agent comprises the following components in parts by weight: sb2O3 0.2~0.48%，NaCl 0.3~0.58%；
The additive comprises the following components in parts by weight: la2O30.15~0.9%，Y2O3 0.12~0.95%。
4. A microcrystalline glass material according to any one of claims 2-3, wherein based on the total weight of the microcrystalline glass material: the R is2O comprises the following components in parts by weight: k2O0.1~2.5%，Na2O1.0~ 7.7%。
5. A preparation method of the microcrystalline glass material as claimed in any one of claims 1 to 4, characterized by comprising the following steps: mixing base glass, a nucleating agent, a clarifying agent and an additive, melting, cooling, molding, crystallizing and annealing to obtain the microcrystalline glass; the crystallization treatment adopts multi-stage heat preservation treatment, and the temperature of each stage is gradually increased.
6. The preparation method of the microcrystalline glass material as claimed in claim 5, wherein the melting temperature is 1600-1660 ℃, and the melting time is 6-12 h;
the cooling temperature is 1440 ℃ to 1500 ℃, and the cooling time is 2 h to 4 h;
the preparation method comprises the following steps: rolling, overflow forming or floating;
the crystallization treatment is 2-stage heat preservation treatment: treating at 600-650 ℃ for 1.0-3.0 h, and then treating at 730-790 ℃ for 1.0-3.0 h; or the crystallization treatment is a 3-stage heat preservation treatment: treating at 600-650 ℃ for 1.0-3.0 h, then treating at 700-750 ℃ for 1.0-3.0 h, and then treating at 780-830 ℃ for 1.0-3.0 h.
7. The method for preparing the microcrystalline glass material as claimed in claim 6, wherein the annealing temperature is 550-580 ℃ and the annealing time is 2.0-5.0 h.
8. Use of the microcrystalline glass material according to any one of claims 1 to 4 in a semiconductor device.
9. The application of the microcrystalline glass material as claimed in claim 8, wherein the microcrystalline glass material is used for preparing a mobile phone panel or a mobile phone back plate.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476821A (en) * | 1994-11-01 | 1995-12-19 | Corning Incorporated | High modulus glass-ceramics containing fine grained spinel-type crystals |
| CN103298760A (en) * | 2010-11-04 | 2013-09-11 | 康宁股份有限公司 | Arsenic-free spinel glass-ceramics with high visible transmission |
| CN109809696A (en) * | 2018-12-19 | 2019-05-28 | 温州市康尔微晶器皿有限公司 | A kind of magnalium silicon spinel devitrified glass |
| CN110156334A (en) * | 2019-06-19 | 2019-08-23 | 赵国祥 | A kind of devitrified glass and preparation method thereof |
| CN111377614A (en) * | 2018-12-27 | 2020-07-07 | 华为机器有限公司 | Aluminosilicate microcrystalline glass and preparation method and product thereof |
| CN111592224A (en) * | 2020-04-29 | 2020-08-28 | 深圳精匠云创科技有限公司 | Magnesium aluminum silicate nanocrystalline transparent ceramic, preparation method and product thereof |
| CN111615500A (en) * | 2017-11-30 | 2020-09-01 | 康宁股份有限公司 | Ion-exchangeable transparent gahnite-spinel glass ceramics with high hardness and modulus |
| CN111807705A (en) * | 2020-06-29 | 2020-10-23 | 成都光明光电股份有限公司 | Glass ceramics, glass ceramics product and manufacturing method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5968857A (en) * | 1997-03-31 | 1999-10-19 | Corning Incorporated | Glass-ceramics |
| CN111943513A (en) * | 2020-08-21 | 2020-11-17 | 广东科迪微晶玻璃实业有限公司 | Lithium-aluminum-silicon ceramic white microcrystalline glass and manufacturing method thereof |
| CN113024121B (en) * | 2021-04-26 | 2023-10-27 | 赵国祥 | Microcrystalline glass plate production process |
| CN112876083B (en) * | 2021-04-28 | 2021-09-10 | 深圳晶酝科技有限公司 | Microcrystalline glass material, preparation method thereof and application thereof in semiconductor device |
-
2021
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-
2022
- 2022-05-23 WO PCT/CN2022/094351 patent/WO2022228583A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476821A (en) * | 1994-11-01 | 1995-12-19 | Corning Incorporated | High modulus glass-ceramics containing fine grained spinel-type crystals |
| CN103298760A (en) * | 2010-11-04 | 2013-09-11 | 康宁股份有限公司 | Arsenic-free spinel glass-ceramics with high visible transmission |
| CN111615500A (en) * | 2017-11-30 | 2020-09-01 | 康宁股份有限公司 | Ion-exchangeable transparent gahnite-spinel glass ceramics with high hardness and modulus |
| CN109809696A (en) * | 2018-12-19 | 2019-05-28 | 温州市康尔微晶器皿有限公司 | A kind of magnalium silicon spinel devitrified glass |
| CN111377614A (en) * | 2018-12-27 | 2020-07-07 | 华为机器有限公司 | Aluminosilicate microcrystalline glass and preparation method and product thereof |
| CN110156334A (en) * | 2019-06-19 | 2019-08-23 | 赵国祥 | A kind of devitrified glass and preparation method thereof |
| CN111592224A (en) * | 2020-04-29 | 2020-08-28 | 深圳精匠云创科技有限公司 | Magnesium aluminum silicate nanocrystalline transparent ceramic, preparation method and product thereof |
| CN111807705A (en) * | 2020-06-29 | 2020-10-23 | 成都光明光电股份有限公司 | Glass ceramics, glass ceramics product and manufacturing method thereof |
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