Glass powder, glass slurry and preparation method and application thereof

Abstract

The invention discloses glass powder, glass slurry and a preparation method and application thereof, belongs to the technical field of electronic packaging, and particularly relates to glass powder, glass slurry and a preparation method and application thereof, the glass powder comprises the following components in parts by mass: 60-68.5% of silicon dioxide, 25-30% of boric oxide, 0.5-2% of divalent alkaline earth metal oxide, 2-6% of monovalent alkaline earth metal oxide and 2-4% of an auxiliary agent; the monovalent alkaline earth metal oxide comprises sodium oxide and potassium oxide in a mass ratio of (1-3): (1-3); the divalent alkaline earth metal oxide comprises magnesium oxide; the auxiliary agent comprises calcium fluoride and beta-eucryptite in a mass ratio of (0.5-5): 1. Under the combined action of all the components, the glass powder with a low-temperature sintering effect and a low thermal expansion coefficient is obtained, and the glass powder has an excellent high-humidity and high-heat resistant effect and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electronic packaging, and particularly relates to a glass powder, a glass paste, and a preparation method and application thereof. BACKGROUND

[0002] Glass is commonly used as a protective glaze layer of electronic components, and aluminum nitride, silicon oxide, and single-crystal silicon and materials with low thermal expansion coefficients are used as important components of electronic components. The glass glaze used in the electronic components requires low sintering temperature and low thermal expansion coefficient.

[0003] Glass with low sintering temperature (500-600 DEG C) needs to add sufficient network modifiers to break the network and chain in the Si-O bond in the network structure of the glass, and the thermal vibration amplitude of the glass particles is increased, and the thermal expansion coefficient of the glass is also increased accordingly. Therefore, the thermal expansion coefficient of the conventional low-softening-point glass is generally high. Glass glaze with low sintering temperature and low thermal expansion coefficient is a new material with great application prospect.

[0004] In view of this, the application is provided. SUMMARY

[0005] The application aims to overcome the deficiencies in the prior art and provides a glass powder, a glass paste, and a preparation method and application thereof. The glass powder has low-temperature sintering (500-600 DEG C) effect and low thermal expansion coefficient, has excellent high-humidity and high-temperature resistance effect, and has wide application prospect.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the application is as follows. A glass powder comprises the following components in parts by mass: 60-68.5% of silicon dioxide, 25-30% of boron oxide, 0.5-2% of divalent alkaline earth metal oxide, 2-6% of monovalent alkaline earth metal oxide, and 2-4% of an additive. The monovalent alkaline earth metal oxide comprises sodium oxide and potassium oxide in a mass ratio of (1-3):(1-3). The divalent alkaline earth metal oxide comprises magnesium oxide. The additive comprises calcium fluoride and beta-lithia in a mass ratio of (0.5-5):1.

[0007] The glass powder provided by the application adopts silicon dioxide and boron oxide as the network formers of the glass; and adopts divalent alkali earth metal oxide (magnesium oxide), monovalent alkali earth metal oxide (sodium oxide and potassium oxide) as the network modifiers. The raw materials, silicon dioxide and boron oxide, are used as the main network formers. In the composition, a large amount of low-melting-point boron oxide plays a role in reducing the softening point of the glass, and a small amount of added sodium oxide and potassium oxide are used as the network modifiers to break the network structure of the glass formers, so that the powder containing a large amount of silicon oxide and boron oxide can form a liquid glass with fluidity when melted. The divalent alkali earth metal, magnesium oxide, is a relatively high-valence metal oxide, which has a certain accumulation effect in the glass and improves the mechanical strength of the glass to a certain extent, so that the prepared glass glaze is not easy to crack. The glass system of the application is mainly based on network formers, and by adding the specific additives, the viscosity of the specific glass system (mainly network formers) of the application can be reduced, the O 2- ions in the network formation can be replaced, the integrity of the glass network structure can be improved, the rigidity of the glass network can be enhanced, the hydrolysis reaction in a humid and hot environment can be inhibited, the abnormal growth of crystal grains can be inhibited, and the sintering densification can be promoted. Under the joint action of the components, the glass powder with low-temperature sintering (500-600℃) effect and low thermal expansion coefficient is obtained. The glass powder has excellent high-humidity and high-temperature resistance effect and has a wide application prospect.

[0008] As a preferred embodiment of the application, the components include the following mass parts: 64-67% silicon dioxide, 26-28% boron oxide, 1-1.5% divalent alkali earth metal oxide, 3-4% monovalent alkali earth metal oxide, and 2.5-3% additives.

[0009] As a preferred embodiment of the application, the additives include calcium fluoride and β-eucryptite in a mass ratio of (1-2):1.

[0010] As a preferred embodiment of the application, the mass ratio of the additives to the monovalent alkali earth metal oxide is 1:(1-2).

[0011] The application further provides a preparation method of the glass powder, which includes the following steps: The raw materials are mixed according to the ratio, melted, quenched with water, dried, ball milled, sieved through a 60-mesh sieve, ball milled again, dried, and then glass powder is obtained.

[0012] As a preferred embodiment of the application, the melting temperature is 1580-1620℃. The ball milling speed is 200-300 rpm, and the ball milling time is 2-6 h. The second ball milling speed is 250-400 rpm, and the second ball milling time is 6-8 h.

[0013] The application further provides a glass paste, comprising the following components in mass percentage: 55-65% glass powder, 20-25% organic solvent, 10-15% resin, 0-1% dispersant, 0-1% leveling agent, and 0-1% defoaming agent. The glass powder comprises the glass powder described above.

[0014] As a preferred embodiment of the application, the organic solvent comprises at least one of terpineol and diethylene glycol butyl ether. The resin comprises ethyl cellulose.

[0015] The leveling agent comprises a silicone leveling agent.

[0016] The leveling agent comprises at least one of BYK-333, BYK-345, BYK-306, BYK-358N and BYK-361N.

[0017] The defoaming agent comprises a silicone defoaming agent.

[0018] The defoaming agent comprises at least one of BYK-012, BYK-014, BYK-1794, BYK-A550 and BYK-066N.

[0019] The dispersant comprises at least one of a silane coupling agent and an organic acid.

[0020] The silane coupling agent comprises at least one of KH-550, KH-560, KH-570, KH-792, KH-2121, KH-2122, GPTES, APTES, VTMS, VTES and JH-N308.

[0021] The organic acid comprises at least one of citric acid, malic acid, tartaric acid, acetic acid, butyric acid, valeric acid, hexanoic acid, mercaptoacetic acid and mercaptopropionic acid.

[0022] The application further provides a preparation method of the glass paste, comprising the following steps: uniformly mixing raw materials according to a proportion to obtain the glass paste.

[0023] The application further provides application of the glass paste in preparation of electronic components.

[0024] The beneficial effects of this invention are as follows: In the glass powder described in this invention, silicon dioxide and boron oxide are used as the network forging bodies of the glass; divalent alkaline earth metal oxides (magnesium oxide) and monovalent alkaline earth metal oxides (sodium oxide and potassium oxide) are used as network modifiers. The raw materials silicon dioxide and boron oxide serve as the main network forging bodies. A large amount of low-melting-point boron oxide in the composition lowers the softening point of the glass, while small amounts of sodium oxide and potassium oxide act as network modifiers. The "broken network and open chain" network structure of the glass forging body allows the powder containing a large amount of silicon dioxide and boron oxide to form a fluid liquid glass when melted. Magnesium oxide, a divalent alkaline earth metal, is a relatively high-valence metal oxide, which has a certain accumulation effect in the glass, improving the mechanical strength of the glass to a certain extent and making the prepared glass glaze layer less prone to cracking. This glass system is mainly composed of network forging bodies. By adding the specific additives mentioned above, the viscosity of the specific glass system of this invention (mainly composed of network forging bodies) can be reduced, replacing the O in the network formation. 2- The ions improve the integrity of the glass network structure, enhance the rigidity of the glass network, inhibit hydrolysis reactions under humid and hot conditions, suppress abnormal grain growth, and promote densification sintering. Under the combined effect of the components, this invention yields a glass powder with low-temperature sintering effect (500~600℃) and low coefficient of thermal expansion. The glass powder has excellent resistance to high humidity and high heat and has broad application prospects. Attached Figure Description

[0025] Figure 1 This is a microscope image of the enamel layer in Example 1.

[0026] Figure 2 This is a microscope image of the enamel layer in Comparative Example 1. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0028] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0029] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0030] In this application, there are no particular restrictions on the specific dispersion and mixing methods.

[0031] Unless otherwise specified, all components, raw materials, or instruments used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0032] The following embodiments are provided to facilitate understanding of the invention. These embodiments are not intended to limit the scope of the claims.

[0033] Examples 1-10, Comparative Examples 1-7 The formulations of glass powder in Examples 1-10 and Comparative Examples 1-7 are shown in Tables 1 and 2 (all figures are parts by weight).

[0034] The preparation methods of the glass powders in Examples 1-10 and Comparative Examples 1-7 include the following steps: The components were mixed thoroughly in a mixer. The mixture was then transferred to a platinum crucible and melted at 1600°C for 2 hours in a high-temperature furnace. The molten glass was poured into a container of pure water and quenched to obtain a glass frit. The frit was then dried in an oven at 80°C. The dried frit was then placed in a zirconia planetary ball mill jar and ball-milled. 500g of 20mm diameter zirconia balls and 500g of 10mm diameter zirconia balls were used for ball milling. Using 300 ml of anhydrous ethanol, ball milling was performed at 250 rpm for 4 hours. The powder was then filtered through a 60-mesh sieve and dried at 60°C. The dried coarse powder was transferred to a ball mill jar for a second fine grinding. The second ball milling used 500 g of 5 mm and 3 mm diameter zirconium balls, with 300 ml of anhydrous ethanol as the milling fluid, at 300 rpm for 7 hours, ensuring the D50 particle size of the glass powder was controlled at 1.0 ± 0.1 μm. The molten glass was then dried at 60°C to obtain the glass powder.

[0035] Table 1 Table 2 Example 11 A glass slurry comprising the following components by weight percentage: 62% glass powder, 18% terpineol, 8% diethylene glycol dibutyl ether, 10% ethyl cellulose, 1% dispersant (γ-aminopropyltriethoxysilane), and 1% leveling agent BYK-333.

[0036] The method for preparing the glass slurry includes the following steps: mixing the raw materials evenly to obtain the glass slurry.

[0037] Test case 1. Test the DSC and CTE thermal analysis data of the glass, and analyze the softening point and coefficient of thermal expansion of the glass. Define the glass with a softening point below 600℃ as having low-temperature sintering properties.

[0038] 2. The glass powders from the examples and comparative examples were prepared into glass slurries according to the method of Example 11 for testing.

[0039] Glass paste was printed onto an aluminum nitride ceramic substrate and sintered at 600°C for 1 hour to form a 10μm thick glass glaze layer. The glaze layer sintered on the aluminum nitride substrate was washed three times with deionized water and dried at 80°C. The overall weight was measured and recorded. The glass glaze substrate was placed in a high-temperature and high-humidity chamber at 85°C and 85% humidity for a total test period of one week. After 14 days, it was removed and observed under a 10x microscope for any peeling, flaking, or flaking at the edges of the glaze layer. A pass was recorded as "OK" and a fail as "NG". The microscope image of the glaze layer in Example 1 is shown below. Figure 1 As shown, the microscope image of the glaze layer in Comparative Example 1 is as follows. Figure 2 As shown.

[0040] Table 3 Therefore, in the glass powder of this invention, silicon dioxide and boron oxide are used as the network forgings of the glass; divalent alkaline earth metal oxides (magnesium oxide) and monovalent alkaline earth metal oxides (sodium oxide and potassium oxide) are used as network modifiers. The raw materials silicon dioxide and boron oxide serve as the main network forgings. A large amount of low-melting-point boron oxide in the composition lowers the softening point of the glass, while small amounts of sodium oxide and potassium oxide act as network modifiers. The "broken network and open chain" network structure of the glass forgings allows the powder containing a large amount of silicon dioxide and boron oxide to form a fluid liquid glass when melted. Magnesium oxide, a divalent alkaline earth metal, is a relatively high-valence metal oxide, which has a certain accumulation effect in the glass, improving its mechanical strength to a certain extent and making the prepared glass glaze layer less prone to cracking. This glass system is mainly composed of network forgings. By adding the specific additives mentioned above, the viscosity of the specific glass system of this invention (mainly composed of network forgings) can be reduced, replacing the O in the network formation.2- The ions improve the integrity of the glass network structure, enhance the rigidity of the glass network, inhibit hydrolysis reactions under humid and hot conditions, suppress abnormal grain growth, and promote densification sintering. Under the combined effect of the components, this invention yields a glass powder with low-temperature sintering effect (500~600℃) and low coefficient of thermal expansion. The glass powder has excellent resistance to high humidity and high heat and has broad application prospects.

[0041] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A glass powder, characterized in that, The composition includes the following components in parts by weight: 60-68.5% silicon dioxide, 25-30% boron oxide, 0.5-2% divalent alkaline earth metal oxide, 2-6% monovalent alkaline earth metal oxide, and 2-4% additives; The monovalent alkaline earth metal oxide comprises sodium oxide and potassium oxide in a mass ratio of (1~3):(1~3); The divalent alkaline earth metal oxides include magnesium oxide; The additives include calcium fluoride and β-nepheline in a mass ratio of (0.5~5):

1.

2. The glass powder according to claim 1, characterized in that, It comprises the following components by weight: 64-67% silicon dioxide, 26-28% boron oxide, 1-1.5% divalent alkaline earth metal oxide, 3-4% monovalent alkaline earth metal oxide, and 2.5-3% additives.

3. The glass powder according to claim 1, characterized in that, The additives include calcium fluoride and β-nepheline in a mass ratio of (1~2):

1.

4. The glass powder according to claim 1, characterized in that, The mass ratio of the auxiliary agent to the monovalent alkaline earth metal oxide is 1:(1~2).

5. The method for preparing the glass powder according to any one of claims 1 to 4, characterized in that, Includes the following steps: Mix the raw materials evenly according to the formula, melt them, quench the molten slurry with water, dry it, ball mill it, sieve it through a 60-mesh sieve, ball mill it a second time, dry it, and obtain glass powder.

6. The method for preparing glass powder according to claim 5, characterized in that, The melting temperature is 1580~1620℃; The ball milling speed is 200~300 rpm, and the ball milling time is 2~6 hours; The secondary ball milling speed is 250~400 rpm, and the secondary ball milling time is 6~8 hours.

7. A glass paste, characterized in that, It includes the following components by weight percentage: 55-65% glass powder, 20-25% organic solvent, 10-15% resin, 0-1% dispersant, 0-1% leveling agent, and 0-1% defoamer; The glass powder includes the glass powder according to any one of claims 1 to 4.

8. The glass slurry according to claim 7, characterized in that, The organic solvent includes at least one of terpineol and diethylene glycol butyl ether; The resin includes ethyl cellulose.

9. The method for preparing the glass slurry according to any one of claims 7-8, characterized in that, Includes the following steps: Mix the raw materials evenly according to the formula to obtain the glass slurry.

10. The use of the glass paste according to any one of claims 7 to 8 in the preparation of electronic components.

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