CN115572072A - Sealing glass powder and preparation method thereof - Google Patents
Sealing glass powder and preparation method thereof Download PDFInfo
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- CN115572072A CN115572072A CN202211230469.5A CN202211230469A CN115572072A CN 115572072 A CN115572072 A CN 115572072A CN 202211230469 A CN202211230469 A CN 202211230469A CN 115572072 A CN115572072 A CN 115572072A
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- C—CHEMISTRY; METALLURGY
- 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
- C03C12/00—Powdered glass; Bead compositions
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- C—CHEMISTRY; METALLURGY
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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- C—CHEMISTRY; METALLURGY
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
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Abstract
The application provides sealing glass powder and a preparation method thereof, wherein the sealing glass powder comprises glass powder (a) and glass powder (b); the original composition of the glass powder (a) is: bi 2 O 3 、B 2 O 3 、ZnO、SrO、Ga 2 O 3 、GeO 2 Kaolin, cuO, sb 2 O 3 (ii) a The original composition of the glass powder (b) was: siO 2 2 、Al 2 O 3 、B 2 O 3 、Li 2 O、Na 2 O、K 2 O、MgO、SrO、Ga 2 O 3 、ZrO 2 、SrF 2 、NaCl/SnO 2 . The sealing glass powder formed by regulating and controlling the original compositions of the glass powder (a) and the glass powder (b) and the mixing ratio of the glass powder (a) and the glass powder (b) has lower thermal expansion coefficient and lower sealing performanceThe temperature and the smaller sealing shrinkage rate can be better matched with the expansion coefficients of different MEMS parts such as silicon wafers, low-expansion glass and the like, and the sealing strength is high, so that the sealing material is suitable for sealing and sealing MEMS devices and electronic components.
Description
Technical Field
The application relates to the technical field of electronic glass powder, in particular to sealing glass powder and a preparation method thereof.
Background
MEMS (Micro-Electro-Mechanical Systems, micro electromechanical Systems) relates to various subjects such as microelectronics, micromachines, materials science, information and control, and specifically applied device fields include semiconductor chips, sensors, accelerometers, resonators, gyroscopes, and the like. With the rapid iterative upgrade of electronic products, the MEMS has higher and higher requirements on the airtightness and reliability of sealing products, and thus, higher requirements on sealing materials are also put forward.
Most of the traditional MEMS sealing materials are lead-containing sealing glass powder, but with the development requirements of green, environmental protection and lead-free in the electronic manufacturing industry, the lead-free MEMS glass powder has great market potential. The prior lead-free MEMS glass powder also has the problems of higher sealing temperature, mismatched thermal expansion coefficient with the sealed material, poorer sealing strength and the like.
Disclosure of Invention
The application aims to provide sealing glass powder and a preparation method thereof so as to reduce the sealing temperature of the lead-free MEMS glass powder. The specific technical scheme is as follows:
a first aspect of the present application provides a sealing glass frit comprising a glass frit (a) and a glass frit (b); the glass powder (a) comprises the following raw components in percentage by mol:
the glass powder (b) comprises the following raw components in percentage by mol:
wherein,
the content of the glass frit (b) is 0 to 50% based on the mass of the sealing glass frit.
Preferably, the glass frit (a) has the original composition, in terms of mole percent, of:
preferably, the glass frit (b) has the original composition, in terms of mole percent, of:
preferably, the content of the glass frit (b) is 1 to 15% based on the mass of the sealing glass frit.
A second aspect of the present invention provides a method for preparing the sealing glass frit according to any one of the above embodiments, which comprises the steps of:
1) Preparing a raw material (a) and a raw material (b) according to the original compositions of the glass powder (a) and the glass powder (b), respectively, and mixing and grinding the raw material (a) and the raw material (b) to form a mixture (a) and a mixture (b);
2) Respectively heating and melting the mixture (a) and the mixture (b), fully melting the mixture, and then quenching the mixture with water to form cullet (a) and cullet (b);
3) Respectively grinding the cullet (a) and the cullet (b) to form glass powder (a) and glass powder (b);
4) Mixing the glass powder (a) and the glass powder (b) to form sealing glass powder;
wherein,
the heating and melting process of the mixture (a) comprises the following steps: heating the mixture from room temperature to 1000-1300 ℃ for 2-4 h, and keeping the temperature for 0.5-1.5 h;
the heating and melting process of the mixture (b) comprises the following steps: heating from room temperature to 1550-1650 ℃ after 6-9 h, and keeping the temperature for 1-3 h.
In some embodiments of the present application, the average particle size (D50) of the glass frit (a) is 50 to 75 μm, and the average particle size (D50) of the glass frit (b) is 30 to 60 μm.
In some embodiments of the present application, the sealing glass frit has a coefficient of thermal expansion of (60 to 80). Times.10 -7 /℃。
In some embodiments of the present application, the sealing glass frit has a softening point T s Is 340 to 400 ℃.
In some embodiments of the present application, the sealing glass frit has a shear strength of 25 to 30N.
The application has the beneficial effects that:
the sealing glass powder provided by the application comprises glass powder (a) and glass powder (b), and by regulating and controlling the original components in the glass powder (a) and the glass powder (b) and the mixing proportion of the glass powder (a) and the glass powder (b), the formed sealing glass powder has a lower thermal expansion coefficient, a lower sealing temperature and a smaller sealing shrinkage rate, can be better matched with the expansion coefficients of different MEMS parts such as a silicon wafer, low-expansion glass and the like, has high sealing strength, and is suitable for sealing and sealing MEMS devices and electronic components; the sealing glass powder does not contain harmful elements such as lead, vanadium, thallium, tellurium and the like, and meets the requirement of environmental protection. Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
Detailed Description
The technical solutions in the present application will be described clearly and completely with reference to the embodiments in the present application, and it should be apparent that the described embodiments are only a part of the embodiments in the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application are within the scope of protection of the present application.
A first aspect of the present application provides a sealing glass frit which comprises a glass frit (a) and a glass frit (b); the glass powder (a) comprises the following raw components in percentage by mol:
the glass powder (b) comprises the following raw components in percentage by mol:
wherein,
the content of the glass frit (b) is 0 to 50%, preferably 5 to 15%, based on the mass of the sealing glass frit.
In the glass frit (a) of the present application,
Bi 2 O 3 a body oxide is generated for the glass network, and when the content thereof is low, the softening point of the glass cannot be sufficiently lowered; when the content is too high, devitrification of the glass is likely to occur and the thermal expansion coefficient of the glass is significantly increased. Thus, this application regulates Bi 2 O 3 The molar percentage of the component (A) is between 40 and 50, so that the softening point of the glass can be reduced, and the thermal expansion coefficient of the glass can be reduced.
B 2 O 3 A body oxide is generated for the glass network, and when the content thereof is too low, it is not favorable for forming glass; when the content is too high, the tendency of phase separation of the glass increases and the amount of boron volatilization increases, so that it is difficult to homogenize the glass, which is disadvantageous in improving the stability of the glass. Thus, the present application regulates B 2 O 3 The molar percentage of (b) is between 15 and 30, so that the glass melting property can be improved, and the viscosity of the glass can be reduced.
ZnO is a glass network intermediate oxide, when the content of ZnO is too low, glass is not easy to form, and the thermal expansion coefficient of the formed glass is obviously larger; when the content is too high, the glass is liable to devitrify and the softening point is elevated. Therefore, the mol percentage of ZnO is regulated to be between 20 and 30, and the thermal expansion coefficient and the softening point of the glass can be reduced.
SrO is an oxide of the outer body of the glass network, and when the content of SrO is too low, the effect of lowering the melting temperature of the glass is not obvious, and when the content of SrO is too high, the thermal expansion coefficient of the glass is increased, and the glass is easy to crystallize and become brittle during sealing. Therefore, the mol percentage of SrO is regulated and controlled to be 0.1-10, the softening point of the glass can be reduced, and the fluidity of the glass in a low-temperature area can be improved.
Ga 2 O 3 Is a glass network intermediate oxide, and when the content of the glass network intermediate oxide is too low, the effect of reducing the glass melting temperature is not obvious; and when the content thereof is too high, the glass tends to be devitrified and the cost thereof tends to be high. Thus, the present application regulates Ga 2 O 3 The mole percentage of the glass is between 0.1 and 5, the liquid phase temperature can be reduced, the glass melting temperature can be reduced, and the chemical stability of the glass can be improved.
GeO 2 Is a glass network-forming body oxide, and when the content thereof is too low, the effects of reducing the thermal expansion coefficient of the glass and improving the strength of the glass are not obvious; and when the content thereof is too high, devitrification of the glass may be caused. Thus, the present application regulates GeO 2 The mol percentage content of the glass is between 1 and 10, the thermal expansion coefficient of the glass can be reduced, the elastic modulus and the strength of the glass are improved, and the melting point of the glass is obviously lower than that of SiO 2 And the melting is easier.
When the content of the kaolin is too low, the generated water vapor can not be fused with bubbles in the glass melt, and the effect of playing a role is not obvious; when the content is too high, the viscosity of the glass increases and the softening point increases. Therefore, the molar percentage of kaolin regulated and controlled by the method is between 0.1 and 10, so that glass can be decomposed to generate Al in the high-temperature melting stage 2 O 3 、SiO 2 The generated water vapor can be fused with bubbles in the glass melt, so that the diameter of the bubbles is effectively increased, the glass clarification time is favorably shortened, the energy consumption of glass production is saved, and the glass melting quality is improved; and Al generated by decomposition of kaolin 2 O 3 、SiO 2 Can reduce the thermal expansion coefficient of the glass, and improve the mechanical strength and chemical resistance.
CuO is an external oxide of a glass network, and when the content of CuO is too low, the effect of reducing the softening point of glass is not obvious; and when the content thereof is too high, devitrification of the glass may be caused. Therefore, the mol percentage content of CuO is regulated and controlled to be between 4 and 12, the softening point of glass can be reduced, and the absorption rate of infrared spectrum of the sealing glass can be improved as a coloring agent, so that the sealing temperature is reduced.
Sb 2 O 3 Sb is regulated and controlled by the application as a glass network exosomatic oxide 2 O 3 The mole percentage of the glass is between 0.1 and 3, and the crystallization of the glass can be inhibited in the sealing process.
In the glass frit (b) of the present application, siO 2 Is an important glass network generation body oxide, forms a skeleton structure of the glass, and when the content of the oxide is too low, the formation of the skeleton structure of the glass is influenced, so that the mechanical property of the glass is reduced; however, when the content is too high, the viscosity of the molten glass rapidly increases and melting becomes difficult. Thus, the present application regulates SiO 2 The molar percentage of the glass is between 68 and 81, so that the reduction of the thermal expansion coefficient of the glass can be reduced, and the mechanical property of the glass can be improved.
Al 2 O 3 The glass is a glass network intermediate oxide, and when the content of the glass network intermediate oxide is too low, the thermal property of the glass is not obviously improved; when the content is too high, the viscosity of the molten glass rapidly increases and melting becomes difficult. Thus, the present application regulates Al 2 O 3 The molar percentage of the glass is 3-6, the precipitation tendency of the glass can be reduced, and the thermal property of the glass can be improved.
B 2 O 3 The glass is oxide formed by a glass network, when the content of the oxide is too low, the effect of reducing the viscosity of the glass can not be achieved, and the thermal expansion coefficient of the glass is large; when the content is too high, phase separation or devitrification of the glass may occur, resulting in lowering of chemical resistance of the glass. Thus, the present application regulates B 2 O 3 The mol percentage content of the glass is between 13 and 22, which not only can reduce the thermal expansion coefficient and high-temperature viscosity of the glass, but also can play a role in well fluxing and accelerating the melting of the glassPreparation and clarification.
Li 2 O、Na 2 O、K 2 O is used as an alkali metal oxide and is a glass network external oxide, and when the content of O is too low, the melting temperature of the glass is too high; when the content is too high, the thermal expansion coefficient is rapidly increased and the overall glass properties are deteriorated. Thus, the present application regulates Li 2 O、Na 2 O、K 2 The mol percentage of O is in the range of the application, which is beneficial to the melting of glass and the formation of glass state, and the mixed alkali effect is formed through the mixture ratio and the difference of the alkali metal ion radius, thereby improving the thermal and mechanical properties of the borosilicate glass.
MgO is an oxide of a glass network outer body, and when the content of MgO is too low, the low-temperature viscosity of the glass is high, and the sealing temperature is high; and when the content thereof is too high, glass brittleness increases. Therefore, the MgO mole percentage content is regulated and controlled to be between 1 and 6, which is beneficial to reducing the low-temperature viscosity of the glass, reducing the sealing temperature of the glass powder and improving the stability of the glass.
SrO is a glass network exo-oxide, and when the content is too high, the thermal expansion coefficient and the tendency to devitrify of the glass increase. Therefore, the mol percentage content of SrO is regulated and controlled to be 0-8, the softening point of glass can be reduced, the mobility of the glass in a low-temperature area is improved, and the reduction of the sealing temperature of glass powder is facilitated.
Ga 2 O 3 Is a glass network intermediate oxide, and when the content of the oxide is too low, the effect of reducing the thermal expansion coefficient of the glass is not obvious; when the content is too high, the cost is increased and devitrification of the glass is liable to occur. Thus, the present application regulates Ga 2 O 3 The mole percentage of the Ga is between 0.1 and 5, the liquid phase temperature and the melting temperature can be reduced, the chemical stability of the glass is improved, and the Ga 3+ The large ionic radius enables a network structure to be compact, and is beneficial to reducing the thermal expansion coefficient of the glass powder.
ZrO 2 The glass is an oxide outside the glass network, and when the content of the oxide is too low, the effects of reducing the thermal expansion coefficient of the glass and improving the chemical stability of the glass are not obvious; and when the content thereof is too high, the high-temperature viscosity of the glass is significantly increased. Therefore, this applicationPlease control ZrO 2 The molar percentage of the glass powder is between 0.1 and 5, the thermal expansion coefficient can be properly reduced, the chemical resistance of the glass is obviously improved, the acid resistance, the alkali resistance and the water resistance of the glass powder can be effectively improved after the glass powder is used for MEMS sealing, and the sealing service life of the glass is prolonged.
When SrF 2 When the content is too low, the effect of reducing the viscosity and the surface tension of the glass liquid is not obvious; and when the content is too high, it results in a rapid increase in the thermal expansion coefficient of the glass. Thus, the present application regulates SrF 2 The molar percentage of the glass transition metal is between 0.1 and 2, the reaction of glass formation can be accelerated, the viscosity and the surface tension of glass liquid can be reduced, and the clarification and the homogenization of the glass liquid can be promoted.
NaCl/SnO 2 When the content of the clarifying agent is too low as a clarifying agent, the clarifying effect is not obvious; when the content is too high, the glass strength is lowered and coloring occurs. Therefore, the application regulates and controls NaCl/SnO 2 The mole percentage of the glass powder is between 0.1 and 1.5, so that the glass powder can be vaporized and decomposed to release gas at high temperature, and the bubble removing effect in the glass powder (b) is good. NaCl/SnO in the present application 2 Expressed as NaCl or SnO 2 As a clarifying agent alone; alternatively, naCl and SnO 2 Jointly used as a clarifying agent, wherein NaCl and SnO are used 2 When used together as a fining agent, naCl and SnO 2 The mass ratio of the components is 1: 0.1-1.
In the application, the mass contents of the glass powder (a) and the glass powder (b) in the sealing glass powder are in the ranges, the thermal expansion coefficient of the sealing glass powder can be regulated and controlled, the sealing glass powder is matched with the expansion coefficients of different MEMS parts such as silicon wafers, low-expansion glass and the like, and the applicability is high.
As a whole, the glass frit (a) obtained using the raw components in the above range has a low softening point T s Higher chemical stability; the glass powder (b) prepared by adopting the original components in the range has lower thermal expansion coefficient, viscosity and higher chemical stability; according to the method, the mass percentage of the glass powder (b) in the sealing glass powder is regulated to be within the range, so that the prepared sealing glass powder has low thermal expansion coefficient, softening point and viscosity, and the strength of the glass after packagingLarge size, high chemical stability, small sealing shrinkage and good wettability with low-expansion coefficient glass in MEMS.
In the present application, the raw materials of the original components in the glass frit (a) and the glass frit (b) are not particularly limited as long as the object of the present application can be achieved, and for example, the raw materials of the original components in the glass frit (a) and the glass frit (b) may be oxides of each other, minerals corresponding to the oxides of each other, or compounds. The kaolin is not particularly limited as long as the purpose of the present invention can be achieved, and for example, the kaolin is soft kaolin, and the chemical composition of the kaolin is 2SiO 2 ·Al 2 O 3 ·2H 2 O。
Preferably, the glass frit (a) has the original composition, in terms of mole percent, of:
when the composition of the glass frit (a) is within the above range, it is more advantageous to obtain a glass frit having a low expansion coefficient, a low softening temperature and a high strength.
Preferably, the glass frit (b) has the original composition, in terms of mole percent, of:
when the composition of the glass frit (b) is within the above range, the obtained glass frit (b) has a lower expansion coefficient, viscosity and sealing temperature, and higher chemical stability and mechanical strength.
A second aspect of the present invention provides a method for preparing the sealing glass frit of any of the above embodiments, which comprises the steps of:
1) Preparing a raw material (a) and a raw material (b) according to the original compositions of the glass powder (a) and the glass powder (b), respectively mixing and grinding the raw material (a) and the raw material (b) to form a mixture (a) and a mixture (b);
2) Respectively heating and melting the mixture (a) and the mixture (b), fully melting the mixture, and then quenching the mixture with water to form cullet (a) and cullet (b);
3) Respectively grinding the cullet (a) and the cullet (b) to form glass powder (a) and glass powder (b);
4) And (b) mixing the glass powder (a) and the glass powder (b) to form the sealing glass powder.
Wherein,
the heating and melting process of the mixture (a) comprises the following steps: heating the mixture from room temperature to 1000-1300 ℃ for 2-4 h, and keeping the temperature for 0.5-1.5 h;
the heating and melting process of the mixture (b) comprises the following steps: heating from room temperature to 1550-1650 ℃ after 6-9 h, and keeping the temperature for 1-3 h.
In the application, the original compositions of the glass powder (a) and the glass powder (b) are adjusted, and the glass powder (a) and the glass powder (b) with different expansion coefficients and melting points can be formed by respectively heating and melting the mixture (a) and the mixture (b), wherein the glass powder (a) has a higher thermal expansion coefficient and a lower softening point, and the glass powder (b) has a lower thermal expansion coefficient and a higher softening point. Specifically, the thermal expansion coefficient of the glass frit (a) is (90 to 110). Times.10 -7 /. Degree.C., softening point T s 340-390 ℃, and the thermal expansion coefficient of the glass powder (b) is (30-36) multiplied by 10 -7 V. C, softening point T s Is 810-830 ℃. The sealing glass powder contains a high borosilicate component, so that the wettability of the glass powder and the low-expansion-coefficient glass in the MEMS device can be improved, and the sealing strength is enhanced.
The present application is not particularly limited to a grinding apparatus as long as the object of the present application can be achieved, for example, an agate grinder. The polishing time is not particularly limited as long as the object of the present invention can be achieved, and for example, the polishing time is 0.5 to 3 hours. The apparatus for heating and melting in step 2) is not particularly limited as long as the object of the present invention can be achieved, and for example, the apparatus for heating and melting is a high temperature electric furnace. The water quenching in the step 2) refers to a treatment process of pouring the melted and heat-preserved high-temperature glass liquid into cold water.
In some embodiments of the present application, the average particle size (D50) of the glass frit (a) is 50 to 75 μm, and the average particle size (D50) of the glass frit (b) is 30 to 60 μm. The sealing glass frit obtained by having the particle diameters of the glass frit (a) and the glass frit (b) within the above-mentioned ranges has a low thermal expansion coefficient and a low softening point.
In some embodiments of the present application, the sealing glass frit has a coefficient of thermal expansion of (60 to 80). Times.10 -7 V. C. The thermal expansion coefficient of the glass powder is 115 multiplied by 10 compared with the prior lead-free sealing glass powder -7 Compared with the temperature of about/° c, the sealing glass powder provided by the application has a lower thermal expansion coefficient, is wider and controllable in thermal expansion coefficient range, can be matched with MEMS (micro-electromechanical systems) parts with different thermal expansion coefficients, and is strong in applicability.
In some embodiments of the present application, the sealing glass frit has a softening point T s Is 340 to 400 ℃. Softening point T of the glass powder for lead-free sealing s Compared with the sealing glass powder generally higher than 450 ℃, the sealing glass powder provided by the application has lower softening point and low sealing temperature.
In some embodiments of the present application, the sealing glass frit has a shear strength of 25 to 30N. The application provides a sealing glass powder has higher shear strength, and sealing strength is high, and the leakproofness is strong, long service life.
The sealing glass powder provided by the application comprises glass powder (a) and glass powder (b), and by regulating and controlling the original components in the glass powder (a) and the glass powder (b) and the mixing ratio of the glass powder (a) and the glass powder (b), the formed sealing glass powder has lower thermal expansion coefficient, sealing temperature and smaller sealing shrinkage, can be matched with the expansion coefficients of different MEMS parts such as a silicon wafer, low-expansion glass and the like, has high sealing strength, and is suitable for sealing and sealing MEMS devices and electronic components; the sealing glass powder does not contain harmful elements such as lead, vanadium, thallium, tellurium and the like, and meets the requirement of environmental protection.
Test methods and apparatus:
coefficient of Thermal Expansion (CTE) test:
the thermal expansion coefficient of each example and the glass frit (a), the glass frit (b) and the sealing glass frit prepared in proportion were measured by a linear thermal expansion instrument according to the standard of GBT 169920-1997 glass average linear thermal expansion coefficient.
Softening point T s And (3) testing:
the glass powder (b) obtained in each example was subjected to softening point T by drawing in accordance with the Standard ASTM C338 Standard test method for glass softening Point s The glass powder (a) and sealing glass powder obtained in each of examples and comparative examples were subjected to a softening point T using a linear thermal expansion instrument according to the standard of GBT 169920-1997 determination of the mean linear thermal expansion coefficient of glass s And (6) testing.
Air tightness detection and shear strength detection:
the sealing glass powder prepared in each example and comparative example and an organic component (containing 85% of alpha-terpineol and 15% of hydroxymethyl cellulose) are uniformly mixed to form glass powder slurry (the mass ratio of the glass powder to the organic component is 88% and 12% respectively), the sealing glass powder slurry is formed on a silicon wafer through screen printing to form a closed ring, a device is positioned in the closed ring after presintering at the temperature of 410 ℃, and the device is placed in a bonding machine to be heated to the temperature of 440 ℃ for sintering to form a sealed cavity.
And detecting the air tightness of the sealed cavity through the fine helium leakage rate.
The shear strength is detected on a bonding strength tester, and the area of a test silicon wafer is 4.13mm 2 。
Example 1
1) Weighing raw materials (a) and (b) according to the original compositions of the glass powder (a) and the glass powder (b) in the tables 1 and 2 respectively, and mixing and grinding the raw materials (a) and (b) for 2 hours respectively to form a mixture (a) and a mixture (b);
2) Putting the corundum crucible filled with the mixture (a) into a high-temperature electric furnace, and setting a temperature rise system as follows: heating to 1200 ℃ from room temperature for 3h, and keeping the temperature for 1h; putting the corundum crucible filled with the mixture (b) into a stirring high-temperature electric furnace, and setting a temperature rise system as follows: heating the mixture (a) and the mixture (b) from room temperature to 1600 ℃ for 7h, preserving heat for 2h to ensure that the mixture (a) and the mixture (b) are respectively and fully melted and homogenized, melting to form glass liquid (a) and glass liquid (b), and then respectively quenching with water to form cullet (a) and cullet (b);
3) Respectively putting the cullet (a) and the cullet (b) into an agate grinder to grind for 3 hours and 5 hours respectively to obtain glass powder (a) with the average particle size (D50) of 62 mu m and glass powder (b) with the average particle size (D50) of 45 mu m;
4) The glass powder (a) and the glass powder (b) were mixed well in the proportions shown in Table 3 to form a sealing glass powder.
Examples 2 to 11
The same as example 1 was repeated, except that the respective original components of the glass frit (a) and the glass frit (b) were adjusted in accordance with tables 1 and 2, respectively, and the addition ratios of the glass frit (a) and the glass frit (b) were adjusted in accordance with table 3.
Example 12 to example 13
The procedure was as in example 1 except that the temperature-raising system was adjusted as shown in Table 3.
Comparative examples 1 to 2
The procedure of example 1 was repeated except that the temperature rising system was adjusted as shown in Table 3.
Comparative example 3
The sealing glass powder is prepared from the following raw materials: glass powder (Bi of 44.7 mol%) with a mass fraction of 95% 2 O 3 21mol% of B 2 O 3 31.6mol% of ZnO, 2.6mol% of K 2 O) and 5% zircon, the average particle diameter D50 of the glass powder is 10 μm, and the thermal expansion coefficient of the obtained sealing glass powder is 96.4X 10 -7 V. C, softening point T s At 393 deg.C.
The sealing glass powders prepared in the examples and comparative examples were subjected to the performance test, and the results are shown in Table 4.
In table 4, as can be seen from examples 1 to 13 and comparative examples 1 to 3, the present application forms the glass frit of the mixed component by mixing the glass frit (a) and the glass frit (b) and synergistically adjusting the ratio between the glass frit (a) and the glass frit (b), and the sealing glass frit prepared has a smaller thermal expansion coefficient and a lower softening point than the glass frit of the single component, and has a high shear strength and a high sealing property when the sealing material is sealed after being mixed with a solvent and an adhesive, especially, the sealing glass frit of the present application has a smaller thermal expansion coefficient and a lower softening point than the sealing glass frit prepared by using the prior art raw material formulation (comparative example 3). Specifically, the sealing glass powder prepared in the examples of the present application has a coefficient of thermal expansion of (60 to 80). Times.10 -7 Between/° C, softening point T s Less than 400 deg.C, shear strength greater than 25N, helium fine leak rate less than 8 × 10 -7 Pa·cm 3 (s) and the sealing glass frit obtained in comparative example 3 had a thermal expansion coefficient of 96.4X 10 -7 V. C, softening point T s 393 deg.C, shear strength 25.8N, helium fine leak rate 3.5X 10 -7 Pa·cm 3 And(s) in the presence of a catalyst. It can be seen from examples 1 to 13 and comparative examples 1 to 2 that by controlling the temperature rise system within the range of the present application, a sealing glass frit having a small thermal expansion coefficient, a low softening point, a high shear strength and a high sealing property can be obtained, thereby improving the overall properties of the sealing glass frit.
As can be seen from tables 1, 2 and 4, the glass frit (a) has a small softening point T s But the thermal expansion coefficient is larger; the glass powder (b) has a small coefficient of thermal expansion but a softening point T s Is relatively high. According to the glass powder, the glass powder (a) and the glass powder (b) are mixed and the proportion of the glass powder (a) to the glass powder (b) is adjusted and controlled in a coordinated mode to form the glass powder with mixed components, and compared with the glass powder with single component, the softening point and the thermal expansion coefficient of the sealing glass powder can be in a proper range, so that the sealing glass powder can be matched with the expansion coefficients of different MEMS parts such as silicon wafers and low-expansion glass, and the adaptability is high.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (9)
1. A sealing glass frit comprising a glass frit (a) and a glass frit (b); the glass powder (a) comprises the following raw components in percentage by mol:
the glass powder (b) comprises the following raw components in percentage by mol:
wherein,
the content of the glass powder (b) is 0 to 50% based on the mass of the sealing glass powder.
2. A sealing glass frit according to claim 1, wherein the original composition of the glass frit (a) is, in terms of mole percent:
3. a sealing glass frit according to claim 1, wherein the original composition of the glass frit (b) is, in terms of mole percent:
4. a sealing glass frit according to claim 1, wherein the content of the glass frit (b) is 1 to 15% based on the mass of the sealing glass frit.
5. A method for producing a sealing glass frit according to any of claims 1 to 4, comprising the steps of:
1) Preparing a raw material (a) and a raw material (b) according to the original compositions of the glass powder (a) and the glass powder (b), respectively, and mixing and grinding the raw material (a) and the raw material (b) to form a mixture (a) and a mixture (b);
2) Respectively heating and melting the mixture (a) and the mixture (b), fully melting the mixture, and then quenching the mixture with water to form cullet (a) and cullet (b);
3) Grinding the cullet (a) and the cullet (b) respectively to form glass powder (a) and glass powder (b);
4) Mixing the glass powder (a) and the glass powder (b) to form the sealing glass powder;
wherein,
the heating and melting process of the mixture (a) comprises the following steps: heating the mixture from room temperature to 1000-1300 ℃ for 2-4 h, and keeping the temperature for 0.5-1.5 h;
the heating and melting process of the mixture (b) comprises the following steps: heating the mixture from room temperature to 1550-1650 ℃ after 6-9 h, and keeping the temperature for 1-3 h.
6. The production method according to claim 5, wherein the average particle size (D50) of the glass frit (a) is 50 to 75 μm, and the average particle size (D50) of the glass frit (b) is 30 to 60 μm.
7. A sealing glass frit according to claim 1, wherein the sealing glass frit has a thermal expansion coefficient of (60 to 80) × 10 -7 /℃。
8. A sealing glass frit according to claim 1, wherein the sealing glass frit has a softening point T s Is 340 to 400 ℃.
9. A sealing glass frit according to claim 1, wherein the shear strength of the sealing glass frit is 25 to 30N.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117361885A (en) * | 2023-10-13 | 2024-01-09 | 中建材玻璃新材料研究院集团有限公司 | Sealing glass powder for power lithium battery and preparation method thereof |
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| CN101723589A (en) * | 2008-10-29 | 2010-06-09 | 珠海彩珠实业有限公司 | Lead-free low-melting-point glass powder for PDP sealing and preparation method thereof |
| CN102515535A (en) * | 2011-12-21 | 2012-06-27 | 中国计量学院 | Lead-free low expansion coefficient glass powder for TFT-LCD sealing and preparation method thereof |
| CN114477768A (en) * | 2022-03-01 | 2022-05-13 | 中国建筑材料科学研究总院有限公司 | A kind of lead-free low melting point sealing glass doped with fusible metal alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101723589A (en) * | 2008-10-29 | 2010-06-09 | 珠海彩珠实业有限公司 | Lead-free low-melting-point glass powder for PDP sealing and preparation method thereof |
| CN102515535A (en) * | 2011-12-21 | 2012-06-27 | 中国计量学院 | Lead-free low expansion coefficient glass powder for TFT-LCD sealing and preparation method thereof |
| CN114477768A (en) * | 2022-03-01 | 2022-05-13 | 中国建筑材料科学研究总院有限公司 | A kind of lead-free low melting point sealing glass doped with fusible metal alloy and preparation method thereof |
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| CN117361885A (en) * | 2023-10-13 | 2024-01-09 | 中建材玻璃新材料研究院集团有限公司 | Sealing glass powder for power lithium battery and preparation method thereof |
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