Glass seal material and use thereof

Abstract

Provided in the embodiments of the present application are a glass seal material and the use thereof. On the basis that the total mole of metal and metalloid elements in the glass seal material is 100%, the glass seal material comprises the following metal and metalloid elements in mole percentages: 0.5%-15% of lithium, 2%-15% of aluminum, 60%-80% of silicon, 5%-20% of boron, 0.1%-1% of potassium, and more than 0 and less than or equal to 15% of rare earth elements and an R element in total, the molar percentages of the rare earth elements and the R element being all greater than 0, wherein R comprises one or more of Ba, Ca, Mg, Zn and Ti. The glass seal material can be used for hermetic sealing of electronic components, has the characteristics of low dielectric constant, high coefficient of thermal expansion, moderate seal temperature, relatively high strength and relatively high temperature impact resistance, can improve the signal transmission rate of devices, and achieves dense and zero-gas-leakage packaging with high gas tightness.

Description

Glass sealing material and application thereof

[0001] This application claims priority to the Chinese patent application No. 202411392674.0 filed on September 30, 2024, and titled "Glass sealing material and application thereof", the entire content of which is incorporated herein by reference. TECHNICAL FIELD

[0002] Embodiments of the present application relate to the technical field of sealing materials, in particular to a glass sealing material and application thereof. BACKGROUND

[0003] With the continuous development of information technology, 50G PON (Passive Optical Network) is becoming a key supporting technology for building the next generation of gigabit networks and gigabit services. The Combo OLT ((Optical Line Terminal) small-sized optical device of 50G PON application optimizes the radio frequency link design and special packaging process to ensure signal quality at a rate of 50G. Compared with BOX packaging, COB (Chips on Board, Chip on Board packaging) and other packaging forms, TO (Transistor Outline, coaxial packaging) packaging can better adapt to harsh environments and has cost advantages. However, for TO radio frequency connectors, how to optimize the TO socket process and design to make the single-channel transmission rate reach 50G baud, and the packaging meets the air tightness requirements, is the biggest challenge faced by TO packaging.

[0004] At present, the shell and pin of the TO radio frequency connector are mostly Kovar alloy, and the sealing material is sealing glass with different dielectric constants. Under normal circumstances, the dielectric constant of the sealing glass of the TO radio frequency connector directly affects the propagation rate of the transmission signal, therefore, the sealing glass needs to have a relatively low dielectric constant. In addition, in order to ensure the reliable air tightness of the TO sealing, the sealing glass needs to have a thermal expansion coefficient compatible with Kovar alloy. However, with the continuous increase of the working frequency and power of the optical module, higher requirements are put forward for the heat dissipation and signal propagation rate of the TO socket. The existing Kovar alloy socket has far failed to meet the heat dissipation requirements, and materials such as cold-rolled steel with higher heat dissipation capacity are needed to replace them. Compared with the commonly used Kovar alloy, cold-rolled steel has a higher thermal expansion coefficient (about 12 ppm / k), and the existing sealing glass material is difficult to meet the requirements of low dielectric constant, high thermal expansion coefficient, high strength and high temperature impact resistance to match the application of cold-rolled steel. SUMMARY

[0005] In view of this, the embodiment of the present application provides a glass sealing material which can be used for air-tight sealing of electronic components (such as TO packaging), and the glass sealing material has low dielectric constant, high thermal expansion coefficient, suitable sealing temperature, and high strength and high temperature impact resistance, which can improve the signal transmission rate of the device, realize high air-tight sealing with no air leakage, improve the reliability of the device, and prolong the service life of the device.

[0006] In a first aspect, the embodiment of the present application provides a glass sealing material, wherein the total moles of metal and semi-metal elements in the glass sealing material are 100%, and the glass sealing material comprises the following metal and semi-metal elements in the following mole percentage:

[0007] 0.5%-15% of lithium element, 2%-15% of aluminum element, 60%-80% of silicon element, 5%-20% of boron element, 0.1%-1% of potassium element, and a total of greater than 0 and less than or equal to 15% of rare earth elements and R elements; and the mole percentage of the rare earth elements and the R elements is greater than 0;

[0008] The R comprises one or more of Ba, Ca, Mg, Zn, and Ti.

[0009] The glass sealing material provided by the embodiment of the present application can be used for air-tight sealing of electronic components, such as TO packaging of radio frequency devices. Under the synergistic effect of the specific content of lithium, aluminum, silicon, boron, potassium, rare earth elements, and R elements, the glass sealing material can have low dielectric constant and high thermal expansion coefficient, so as to meet the sealing requirements of metals with high thermal expansion coefficient such as cold-rolled steel, thereby improving the air-tightness while ensuring high signal transmission rate of the device, prolonging the service life of the device, and obtaining suitable sealing temperature, facilitating sealing operation.

[0010] In the embodiment of the present application, the mole percentage of the lithium element is 2%-10%. The suitable content of lithium element is conducive to reducing the high-temperature viscosity of the glass system, reducing the melting temperature, and improving the thermal expansion coefficient of the glass.

[0011] In the embodiment of the present application, the mole percentage of the aluminum element is 5%-12%. The suitable content of aluminum element can improve the compactness of the glass network structure, reduce the dielectric constant, improve the thermal stability of the glass, and improve the chemical stability and mechanical strength of the glass, thereby being conducive to improving the sealing strength and temperature impact resistance.

[0012] In the embodiment of the present application, the mole percentage of the silicon element is 65%-75%. A higher proportion of the silicon element is conducive to the construction of the glass base skeleton, improves the chemical stability and thermal stability of the glass, and can reduce the dielectric constant and dielectric loss. In addition, under the action of rare earth, the silicon dioxide SiO2 can be crystallized to form α-cristobalite phase and / or β-cristobalite phase, and can also form a cristobalite-like phase LiAlSi.

[0013] In the embodiment of the present application, the mole percentage of the boron element is 5%-15%. The boron with a suitable mole percentage can reduce the high-temperature viscosity of the glass system, reduce the melting temperature, and B2O3 itself has a lower ion polarization rate, which can reduce the dielectric constant of the glass.

[0014] In the embodiment of the present application, the mole percentage of the rare earth element is 0.5%-10%. An appropriate amount of rare earth element can act as a nucleating agent to induce the formation of a microcrystalline phase with low dielectric constant and high thermal expansion coefficient during the sealing process, thereby facilitating the reduction of the dielectric constant while obtaining a high thermal expansion coefficient and improving the sealing strength.

[0015] In the embodiment of the present application, the mole percentage of the rare earth element is 1%-8%.

[0016] In the embodiment of the present application, the rare earth element includes one or more of Y (yttrium), La (lanthanum), Ce (cerium), Nd (neodymium), and Sm (samarium).

[0017] In the embodiment of the present application, the mole percentage of the R element is 0.5%-5%. The presence of an appropriate amount of R element is conducive to improving the chemical stability and mechanical strength of the glass.

[0018] In the embodiment of the present application, the mole percentage of the R element is 1%-3%.

[0019] In the embodiment of the present application, the glass sealing material is a glass raw material mixed powder, or a glass frit formed by the glass raw material mixed powder, and the glass frit includes glass particles, or granulated mixed powder, or a preformed shaped piece. The glass sealing material can exist in the above four forms to meet different application requirements.

[0020] In the embodiments of the present application, the glass raw material mixed powder comprises a lithium-containing compound, an aluminum-containing compound, a silicon-containing compound, a boron-containing compound, a potassium-containing compound, a rare earth element-containing compound, and an R element-containing compound. Understandably, the lithium-containing compound can provide lithium, the aluminum-containing compound can provide aluminum, the silicon-containing compound can provide silicon, the boron-containing compound can provide boron, the potassium-containing compound can provide potassium, the rare earth element-containing compound can provide a rare earth element, and the R element-containing compound can provide an R element. Each of the above raw material components is proportioned according to the molar percentage of each metal and semi-metal element.

[0021] In the embodiments of the present application, the aluminum-containing compound comprises one or more of an oxide of aluminum Al2O3, a hydroxide of aluminum Al(OH)3, a carbonate of aluminum Al2(CO3)3, and a nitrate of aluminum Al(NO3)3.

[0022] And / or, the silicon-containing compound comprises one or more of SiO, SiO2, and H2SiO3.

[0023] And / or, the boron-containing compound comprises one or more of B2O3 and H3BO3.

[0024] In the embodiments of the present application, the lithium-containing compound comprises one or more of an oxide of lithium (Li2O), a carbonate of lithium (Li2CO3), a hydroxide of lithium (LiOH), a chloride of lithium (LiCl), a nitride of lithium (Li3N), and a sulfide of lithium (Li2S).

[0025] And / or, the potassium-containing compound comprises one or more of K2O, K2CO3, KHCO3, KNO3, and K2SO4.

[0026] In the embodiments of the present application, the rare earth element-containing compound comprises one or more of an oxide of a rare earth element, a carbonate of a rare earth element, a nitrate of a rare earth element, and a hydroxide of a rare earth element; and / or, the R element-containing compound comprises one or more of an oxide of an R element, a carbonate of an R element, a nitrate of an R element, and a hydroxide of an R element.

[0027] The above compounds are readily available and facilitate the preparation of the glass sealing material as a raw material.

[0028] In the embodiments of the present application, the glass sealing material can be used to prepare a glass-ceramic, and the glass-ceramic prepared by the glass sealing material comprises a glass matrix and a crystalline phase, and the crystalline phase comprises a cristobalite phase and / or a cristobalite-like phase. The crystalline phase can comprise nanoscale and / or sub-micron scale crystalline grains. The nanocrystals and sub-micron scale crystalline grains with small size are dispersed in the glass matrix, which can not only achieve the requirements of low dielectric constant and high thermal expansion coefficient, but also improve the glass transition temperature, enhance the temperature shock resistance, and improve the sealing strength and sealing reliability.

[0029] In the embodiments of the present application, the cristobalite phase comprises an alpha cristobalite phase and / or a beta cristobalite phase, and the cristobalite-like phase comprises a LiAlSi crystalline phase and / or a LiZnSi crystalline phase. The cristobalite phase and the cristobalite-like phase are beneficial to the glass sealing material to achieve low dielectric constant and high thermal expansion coefficient.

[0030] In the embodiments of the present application, the glass sealing material has a dielectric constant of 3.5-5 and a thermal expansion coefficient of 7 ppm / K-15 ppm / K. The glass sealing material has a low dielectric constant, which is beneficial to ensure a high signal transmission rate and improve the performance of the device when used for the hermetic sealing of electronic components. The glass sealing material has a high thermal expansion coefficient, which can be well thermally matched with metals such as cold-rolled steel having a high thermal expansion coefficient, to achieve high hermetic sealing and improve the sealing reliability.

[0031] In the embodiments of the present application, the glass sealing material has a glass transition temperature of 600-950℃, a softening temperature of 700-1000℃, and a sealing temperature of greater than 700℃ and less than 1100℃. The glass sealing material has a high glass transition temperature, which can improve the temperature shock resistance and improve the service reliability. The softening temperature of the glass sealing material is in a suitable temperature range, which is beneficial to subsequent compression molding into various required shapes. The suitable sealing temperature is beneficial to achieve sealing at a controllable temperature and prevent the crystalline phase from being affected by remelting, which is beneficial to obtain high-performance and high-reliability sealing.

[0032] The second aspect of the embodiments of the present application provides a glass-ceramic formed by the glass sealing material of the first aspect of the embodiments of the present application. The glass-ceramic can be used as a connecting piece between metals, to improve the sealing reliability of the metals.

[0033] The third aspect of the embodiments of the present application provides an application of the glass sealing material of the first aspect or the glass-ceramic of the second aspect in the hermetic packaging of electronic components.

[0034] The fourth aspect of the embodiments of the present application provides a joint, comprising a first metal piece, a second metal piece and a connecting piece, the connecting piece connects the first metal piece and the second metal piece together and keeps the first metal piece and the second metal piece electrically insulated, and the connecting piece comprises the glass sealing material of the first aspect. The glass sealing material can improve the sealing reliability of the joint.

[0035] In the embodiments of the present application, the material of the first metal piece and the second metal piece comprises a metal with a coefficient of thermal expansion of 7 ppm / K-15 ppm / K.

[0036] In the embodiments of the present application, the joint comprises a radio frequency connector.

[0037] The embodiments of the present application also provide a sealing method, comprising:

[0038] The glass sealing material of the first aspect prepared into a preformed piece is arranged between the first metal piece and the second metal piece, and sealing is performed under a protective atmosphere and at a sealing temperature, so as to connect the first metal piece and the second metal piece together and keep the first metal piece and the second metal piece electrically insulated.

[0039] The sealing method is simple in process, can realize automatic crystallization and is convenient for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0040] FIG. 1 is a structural schematic diagram of a joint 100 provided by the embodiments of the present application;

[0041] FIG. 2 is an XRD (X-ray diffraction) picture of the glass sealing material of the embodiments of the present application 1. DETAILED DESCRIPTION

[0042] The embodiments of the present application will be described below in combination with the drawings in the embodiments of the present application.

[0043] Compared with 10G PON, 50G PON will bring 5 times bandwidth improvement, with low latency, low jitter, high reliability and other characteristics, through bandwidth exchange time delay, bandwidth conversion force, it can provide extreme service experience, and promote more new applications and new services, better meet the typical application requirements of the gigabit era of digital life, digital transformation of industry and urban digital infrastructure. The Combo OLT small optical device of 50G PON application needs to meet the characteristics of small size, high coupling efficiency, high structural reliability and strong mass production manufacturability. The most critical is that the optimized radio frequency link design and special packaging process ensure the signal quality under 50G rate, especially the device bandwidth under 50G PON downlink, to achieve the best user experience. TO package can adapt to harsh environment and has cost advantage, which is a common sealing structure of radio frequency connector.

[0044] At present, the shell and pin of TO radio frequency connector are usually Kovar alloy, and the sealing material is sealing glass with different dielectric constants. Generally, the dielectric constant of the sealing glass of TO radio frequency connector directly affects the signal transmission rate, therefore, the sealing glass needs to have a lower dielectric constant. In addition, in order to ensure the reliable air tightness of TO sealing, the sealing glass needs to have a thermal expansion coefficient compatible with Kovar alloy. Among them, air tightness refers to a kind of vacuum sealing state, and water vapor and harmful gas cannot penetrate into the sealed package, which can greatly prolong the service life of the device.

[0045] With the continuous increase of the working frequency and power of optical modules, higher requirements are put forward for the heat dissipation and signal transmission rate of TO tube seat. The existing Kovar alloy tube seat has far failed to meet the heat dissipation demand, and needs to be replaced by cold rolled steel with higher heat dissipation capacity. Compared with Kovar alloy, cold rolled steel has a higher thermal expansion coefficient (about 12 ppm / k). The existing sealing glass material mainly selects high borosilicate system glass, which still has a large dielectric constant and generally has problems such as low strength, small thermal expansion coefficient, poor temperature impact resistance and mechanical impact resistance, etc., which is difficult to meet the requirements of low dielectric constant, high thermal expansion coefficient, high strength and high temperature impact resistance to match the application of cold rolled steel. Moreover, inorganic materials generally have the rule that the lower the dielectric constant, the lower the thermal expansion coefficient, making it more difficult to obtain sealing glass materials with low dielectric constant and high thermal expansion coefficient. For example, the existing sealing glass on the market, such as Corning 7070 sealing glass, has a dielectric constant of about 4, but its thermal expansion coefficient is only 3.1 ppm / k; some sealing glasses have high thermal expansion coefficient, but their dielectric constant is also high.

[0046] In order to better match the sealing of the TO package with high thermal expansion coefficient, the embodiment of the present application provides a glass sealing material, which can be used for the air-tight sealing of electronic components such as TO package. The glass sealing material has low dielectric constant, high thermal expansion coefficient, and high strength and high temperature impact resistance, which can improve the signal transmission rate of the device, realize high air-tight sealing with no air leakage, improve the reliability of the device, and prolong the service life of the device.

[0047] The embodiment of the present application provides a glass sealing material, wherein the total moles of metal and semi-metal elements in the glass sealing material are 100%, and the glass sealing material comprises the following metal and semi-metal elements in the following mole percentage:

[0048] 0.5%-15% of lithium element, 2%-15% of aluminum element, 60%-80% of silicon element, 5%-20% of boron element, 0.1%-1% of potassium element, and the sum of rare earth elements and R elements is greater than 0 and less than or equal to 15%; and the mole percentage of the rare earth elements and R elements is greater than 0;

[0049] Wherein, R includes one or more of Ba, Ca, Mg, Zn, and Ti.

[0050] The semi-metal element is a substance between metal and non-metal. In the above-mentioned composition elements of the glass sealing material, lithium, aluminum, potassium, rare earth elements and R elements are metal elements, and silicon and boron are semi-metal elements.

[0051] The glass sealing material provided in the embodiments of the present application can be used for air-tight sealing of electronic components, for example, TO packaging of radio frequency devices; the glass sealing material has a low dielectric constant, which can improve the signal transmission rate of the device and enable the radio frequency device to have good radio frequency performance; and the glass sealing material has a high thermal expansion coefficient, which can form a high thermal expansion coefficient matching with metals such as cold-rolled steel, so that high air-tight packaging without air leakage can be achieved, water vapor and harmful gas can be prevented from penetrating into the device, the reliability of the device can be improved, and the service life of the device can be prolonged; the glass sealing material also has high strength and high temperature impact resistance, which can better resist external force impact and cold and hot temperature impact, further improve the stability and reliability of the device, and prolong the service life of the device. The glass sealing material provided in the embodiments of the present application can meet the basic sealing performance requirements under the synergistic effect of lithium, aluminum, silicon, boron, potassium, rare earth elements and R elements in a specific content ratio, can be applied to air-tight sealing of electronic components, and can have low dielectric constant and high thermal expansion coefficient to meet the sealing requirements of metals such as cold-rolled steel with high thermal expansion coefficient, so that the device has high signal transmission rate, air-tightness is improved, and the service life of the device is prolonged; in addition, a high glass transition temperature can be obtained, temperature impact resistance is improved, a high sealing strength can be obtained, sealing reliability is improved, device performance is improved, and a suitable sealing temperature can be obtained. The glass sealing material provided in the embodiments of the present application has a high content of silicon, boron and aluminum, which is beneficial to obtaining low dielectric constant, and the introduced rare earth elements can be used as nucleating agents to dope the material, which can promote in-situ generation of low-dielectric high-thermal-expansion microcrystalline phases during the sealing process. These microcrystalline phases are dispersedly distributed in the glass matrix, which not only meets the requirements of low dielectric constant and high thermal expansion coefficient, but also improves the glass transition temperature, improves the temperature impact resistance, and improves the sealing strength and sealing reliability.

[0052] In the embodiments of the present application, the glass sealing material can have different forms, specifically, the glass sealing material can be glass raw material mixed powder, or glass material formed by further processing of the glass raw material mixed powder, and the glass material specifically can include glass particles, or granulated mixed powder, or preformed pieces. The glass sealing material in the embodiments of the present application can be used to prepare glass, specifically, can be microcrystalline glass.

[0053] In the present application, the metal sealing of the glass sealing material is specifically that the metal and the glass sealing material with a certain shape (such as a preformed piece) are combined by surface diffusion melting at high temperature.

[0054] In the embodiments of the present application, the glass sealing material further comprises oxygen element. In the mixed powder of the glass raw materials, the oxygen element constitutes a raw material component, and in the glass formed by the mixed powder of the glass raw materials, the oxygen element can constitute metal oxides and semi-metal oxides, etc. The metal oxides can include Al2O3, Li2O, K2O, rare earth element oxides, and R element oxides, and the semi-metal oxides can include SiO2and B2O3. In the frit formed by the mixed powder of the glass raw materials, the oxygen element can also constitute the above-mentioned metal oxides and semi-metal oxides.

[0055] In some embodiments of the present application, the glass sealing material comprises a mixed powder of glass raw materials, which comprises a lithium-containing compound, an aluminum-containing compound, a silicon-containing compound, a boron-containing compound, a potassium-containing compound, a rare earth element-containing compound, and an R element-containing compound. The mixed powder of glass raw materials can be obtained by mixing the above-mentioned raw material components, i.e., the glass sealing material is a mixed powder comprising the above-mentioned raw material components. The lithium-containing compound can provide lithium element, the aluminum-containing compound can provide aluminum element, the silicon-containing compound can provide silicon element, the boron-containing compound can provide boron element, the potassium-containing compound can provide potassium element, the rare earth element-containing compound can provide rare earth element, and the R element-containing compound can provide R element. The above-mentioned raw material components are proportioned according to the molar percentage of each metal and semi-metal element. In the embodiments of the present application, the glass sealing material mainly comprises the silicon-containing compound and the boron-containing compound, and by adding the lithium-containing compound, the aluminum-containing compound, the potassium-containing compound, and the rare earth element-containing compound and the R element-containing compound in specific contents, and through the synergistic effect of the components in specific content ratio, the glass sealing material has low dielectric constant, high thermal expansion coefficient, and high strength and high temperature shock resistance. High content of the silicon-containing compound, the boron-containing compound, and the aluminum-containing compound is beneficial to obtain low dielectric constant, and the introduced rare earth element-containing compound can promote the formation of microcrystalline phase as a nucleating agent.

[0056] Silicon dioxide SiO2 can be used as a glass network former and is the backbone of the glass. SiO2 is formed by silicon and oxygen elements. In the glass sealing material, the molar percentage of silicon element is controlled to be 60-80% of the total molar number of metal and semi-metal elements, which is conducive to the construction of the glass basic skeleton and improves the chemical stability and thermal stability of the glass. SiO2 is not easy to be polarized under the action of an external electric field, which can reduce the dielectric constant and dielectric loss. Under the action of the nucleating agent containing rare earth element compounds, silicon dioxide SiO2 can be crystallized to form alpha-cristobalite phase and / or beta-cristobalite phase, and can also form LiAlSi-like cristobalite phase. For example, the molar percentage of silicon element is 60%, 62%, 64%, 65%, 67%, 69%, 69.5%, 70%, 72%, 74%, 75%, 77%, 78%, 79%, 80% of the total molar number of metal and semi-metal elements in the glass sealing material. In some embodiments of the present application, the molar percentage of silicon element is 65%-80%. In some embodiments of the present application, the molar percentage of silicon element is 65%-75%. It can be understood that the silicon-containing compound in the glass raw material mixed powder can be added according to the above-mentioned molar percentage of silicon element.

[0057] In the embodiments of the present application, the silicon-containing compound can specifically be one or more silicon and oxygen-containing compounds including SiO, SiO2, and H2SiO3. In some embodiments, the silicon-containing compound can specifically include SiO and / or SiO2. In some embodiments, the silicon-containing compound includes SiO2. In some embodiments, the silicon-containing compound includes SiO.

[0058] Boron oxide B2O3 can be used as a glass network former and is also a good fluxing agent. B2O3 is formed by boron and oxygen elements. In the glass sealing material, the molar percentage of boron element is controlled to be 5%-20% of the total molar number of metal and semi-metal elements, which is suitable for the molar percentage of boron to reduce the high-temperature viscosity of the glass system, reduce the melting temperature, and B2O3 itself has a low ion polarization rate, which can reduce the dielectric constant of the glass. For example, the molar percentage of boron element is 5%, 6%, 7%, 8%, 9%, 10%, 12%, 13%, 15%, 16%, 18%, 19%, 20% of the total molar number of metal and semi-metal elements in the glass sealing material. In some embodiments of the present application, the molar percentage of boron element is 5%-15%. It can be understood that the boron-containing compound in the glass raw material mixed powder can be added according to the above-mentioned molar percentage of boron element.

[0059] In some embodiments, the boron-containing compound can be one or more boron- and oxygen-containing compounds including B2O3, H3BO3. In some embodiments, the boron-containing compound includes B2O3. In some embodiments, the boron-containing compound includes H3BO3.

[0060] Al2O3 can act as a glass network intermediate, and the molar percentage of aluminum in the glass sealing material is controlled in a suitable range of 2%-15%, based on 100% of the total moles of metal and semimetal elements in the glass sealing material, which can improve the compactness of the glass network structure, reduce the dielectric constant, and also improve the thermal stability of the glass, and improve the chemical stability and mechanical strength of the glass, thereby facilitating the improvement of the sealing strength and temperature shock resistance. Exemplarily, the molar percentage of aluminum can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, based on 100% of the total moles of metal and semimetal elements in the glass sealing material. In some embodiments of the present application, the molar percentage of aluminum is 5%-12%. Understandably, the aluminum-containing compound in the mixed glass raw material powder can be added according to the above-mentioned molar percentage of aluminum.

[0061] In some embodiments of the present application, the aluminum-containing compound can be one or more aluminum- and oxygen-containing compounds including an oxide of aluminum Al2O3, a hydroxide of aluminum Al(OH)3, a carbonate of aluminum Al2(CO3)3, a nitrate of aluminum Al(NO3)3. In some embodiments, the aluminum-containing compound can be one or more of an oxide of aluminum Al2O3, a hydroxide of aluminum Al(OH)3. In some embodiments, the aluminum-containing compound can include Al2O3. In some embodiments, the aluminum-containing compound can include Al(OH)3.

[0062] Lithium oxide Li2O can be used as a modifier of the glass network, Li2O is formed by lithium element and oxygen element, and the molar percentage of lithium element in the glass sealing material is controlled in a suitable range of 0.5% to 15%, based on 100% of the total moles of metal and semimetal elements in the glass sealing material, which is beneficial to reduce the high-temperature viscosity of the glass system, reduce the melting temperature, and improve the thermal expansion coefficient of the glass. For example, the molar percentage of lithium element can be 0.5%, 1%, 2%, 3%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, based on 100% of the total moles of metal and semimetal elements in the glass sealing material. In some embodiments of the present application, the molar percentage of lithium element is 2% to 10%. In some embodiments of the present application, the molar percentage of lithium-containing compound is 1% to 8%. It can be understood that the lithium-containing compound in the mixed glass raw material powder can be added according to the above-mentioned molar percentage of lithium element.

[0063] In the embodiments of the present application, the lithium-containing compound can be one or more of lithium oxide (Li2O), lithium carbonate (Li2CO3), lithium hydroxide (LiOH), lithium chloride (LiCl), lithium nitride (Li3N), and lithium sulfide (Li2S). In some embodiments, the lithium-containing compound includes one or more of Li2O, Li2CO3, and LiOH. In some embodiments, the lithium-containing compound includes one or more of Li2O and Li2CO3. In some embodiments, the lithium-containing compound includes Li2O. In some embodiments, the lithium-containing compound includes Li2CO3.

[0064] Potassium oxide K2O can be used as a modifier of the glass network, K2O is formed by potassium element and oxygen element, and the molar percentage of potassium element in the glass sealing material is controlled in a suitable range of 0.1% to 1%, based on 100% of the total moles of metal and semimetal elements in the glass sealing material, which is beneficial to reduce the high-temperature viscosity of the glass system, reduce the melting temperature, control the crystallization of the glass, and improve the chemical stability of the glass. For example, the molar percentage of potassium element can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, based on 100% of the total moles of metal and semimetal elements in the glass sealing material. It can be understood that the potassium-containing compound in the mixed glass raw material powder can be added according to the above-mentioned molar percentage of potassium element.

[0065] In some embodiments, the potassium-containing compound can be one or more potassium- and oxygen-containing compounds including K2O, K2CO3, KHCO3, KNO3, K2SO4. In some embodiments, the potassium-containing compound can be one or more of K2O, K2CO3, KHCO3. In some embodiments, the potassium-containing compound can be one or more of K2O, K2CO3. In some embodiments, the potassium-containing compound includes K2O. In some embodiments, the potassium-containing compound includes K2CO3.

[0066] The presence of R element oxide in an appropriate amount is beneficial to improve the chemical stability and mechanical strength of the glass, and R can be one or more selected from Ba, Ca, Mg, Zn, Ti. The R element oxide is formed from R element and oxygen element. In some embodiments, the mole percentage of R element in the glass sealing material is 0.5% to 5%, based on 100% of the total moles of metal and semi-metal elements in the glass sealing material. Illustratively, the mole percentage of R element can be 0.5%, 1%, 2%, 3%, 4%, 5%. In some embodiments, the mole percentage of R element is 1% to 3%. It can be understood that the R element-containing compound in the glass raw material mixed powder can be added according to the above-mentioned mole percentage of R element.

[0067] In some embodiments, the R element-containing compound includes one or more of Ba-containing compound, Ca-containing compound, Mg-containing compound, Zn-containing compound, Ti-containing compound. The Ba-containing compound can be barium oxide BaO; the Ca-containing compound can be calcium oxide CaO; the Mg-containing compound can be magnesium oxide MgO; the Zn-containing compound can be zinc oxide ZnO; the Ti-containing compound can be titanium oxide TiO2. In some embodiments, the R element-containing compound includes one or more of BaO, CaO, MgO, ZnO, TiO2. In some embodiments, the R element-containing compound includes ZnO. In some embodiments, the R element-containing compound includes TiO2. Among them, the R element-containing compound including ZnO and / or TiO2 is beneficial to better improve the coefficient of thermal expansion of the glass sealing material. In some embodiments, the R element-containing compound includes ZnO, and in some embodiments, the R element-containing compound includes ZnO and TiO2.

[0068] In the glass sealing material, the appropriate addition of the rare earth element compound can serve as a nucleating agent to induce the formation of a microcrystalline phase with low dielectric constant and high thermal expansion coefficient during the sealing process, thereby facilitating the reduction of the dielectric constant while achieving a higher thermal expansion coefficient and improving the sealing strength. In the embodiments of the present application, the molar percentage of the rare earth element in the glass sealing material is 0.5% to 10%, based on 100% of the total moles of metal and semi-metal elements in the glass sealing material. In some embodiments, the molar percentage of the rare earth element is 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%. In some embodiments, the molar percentage of the rare earth element is 1% to 8%. Understandably, the rare earth element compound in the mixed glass raw material powder can be added according to the above-mentioned molar percentage of the rare earth element.

[0069] In the embodiments of the present application, the rare earth element can be one or more of Y (yttrium), La (lanthanum), Ce (cerium), Nd (neodymium), and Sm (samarium). The rare earth element compound can be one or more of an oxide of the rare earth element, a carbonate of the rare earth element, a nitrate of the rare earth element, and a hydroxide of the rare earth element, which are compounds containing the rare earth element and oxygen. In some embodiments, the rare earth element compound can be one or more of a Y-containing compound, a La-containing compound, a Ce-containing compound, a Nd-containing compound, and a Sm-containing compound. The Y-containing compound can be yttrium oxide Y2O3; the La-containing compound can be lanthanum oxide La2O3; the Ce-containing compound can be cerium oxide CeO; the Nd-containing compound can be neodymium oxide Nd2O3; and the Sm-containing compound can be samarium oxide Sm2O3. In some embodiments, the rare earth element compound includes one or more of Y2O3, La2O3, CeO, Nd2O3, and Sm2O3. In some embodiments, the rare earth element compound includes Y2O3 and La2O3. In some embodiments, the rare earth element compound includes Y2O3 and Nd2O3. In some embodiments, the rare earth element compound includes CeO.

[0070] In the embodiments of the present application, the mixed glass raw material powder can be obtained by mixing the above-mentioned raw material components, i.e., the glass sealing material is a mixed powder including the above-mentioned raw material components. For example, the glass sealing material includes a mixed powder of the lithium-containing compound, the aluminum-containing compound, the silicon-containing compound, the boron-containing compound, the potassium-containing compound, the rare earth element compound, and the R element-containing compound.

[0071] In the embodiments of the present application, the glass particles can be obtained by melting and water quenching the mixed glass raw material powder, specifically, by the following method:

[0072] S101, mixing the above-mentioned mixed glass raw material powder with water to obtain a mixed slurry;

[0073] S102, melting the mixed slurry obtained in S101 to obtain a melt, and then water quenching the obtained melt to obtain glass particles.

[0074] In step S102, the melting temperature can be 1500-1700℃, for example, 1500℃, 1550℃, 1600℃, 1650℃, 1700℃, and the melting time can be 1-3 hours, for example, 1 hour, 2 hours, 3 hours. The water quenching can be pouring the melt into deionized water at 0℃. The glass particles can be glass fragments and / or glass slag.

[0075] The granulated mixed powder can be obtained by mixing the glass particles after grinding with a binder, and specifically, can be obtained by the following method:

[0076] The glass particles described above are ground, dried, sieved, mixed with a binder and a solvent, and then spray granulated to obtain the granulated mixed powder. The grinding can be ball milling, the ball milling can use zirconium oxide, the ball milling medium can be ethanol, and the ball milling time can be 1-5 hours. The glass particles can be ground to a particle size of 10-50μm.

[0077] Based on the above preparation method, the granulated mixed powder contains a binder. The binder can be polyvinyl butyral PVB, polyethylene glycol PEG, polyvinyl alcohol PVA, etc., and the binder needs to be able to be smoothly removed during the de-binding process. The particle size of the granulated mixed powder can be 100-300μm. Exemplarily, the particle size of the granulated mixed powder can be 100μm, 150μm, 200μm, 250μm, 300μm.

[0078] The pre-formed piece can be obtained by pressing the granulated mixed powder using a molding die. Specifically, the pressing can be performed at a temperature of less than 400-700℃ and a pressure of 15-40MPa for 10-60 seconds. Exemplarily, the pressing temperature can be 400℃, 500℃, 600℃, 700℃. In one embodiment, the pressing is performed at a temperature of 700℃ and a pressure of 20MPa for 30 seconds. It can be understood that the molding die can be selected according to actual needs.

[0079] The present application also provides a glass sealing material formed by the above-mentioned glass sealing material, i.e., the glass sealing material of the present application can be microcrystallized to obtain a glass-ceramic, and the glass-ceramic can be obtained by microcrystallizing the pre-formed piece described above after de-binding at a sealing temperature of greater than 700℃ and less than 1100℃ for 1-4 hours, i.e., after completing the sealing operation.

[0080] The glass sealing material of the embodiments of the present application is used to prepare a glass-ceramic, which comprises a glass matrix and a crystalline phase. The crystalline phase is uniformly distributed in the glass matrix. The crystalline phase can comprise nanocrystals with a size of 1-100 nm and / or submicron grains with a size of greater than 100 nm and less than or equal to 1000 nm. Exemplarily, the size of the nanocrystals is 1 nm, 2 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm. The size of the submicron grains can be 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm or 1000 nm. In the embodiments of the present application, the crystalline phase can comprise cristobalite and / or cristobalite-like phase. In some embodiments, the crystalline phase comprises cristobalite; in some embodiments, the crystalline phase comprises cristobalite-like phase; and in some embodiments, the crystalline phase comprises both cristobalite and cristobalite-like phase. The cristobalite can comprise alpha cristobalite and / or beta cristobalite. In some embodiments, the cristobalite comprises alpha cristobalite; in some embodiments, the cristobalite comprises beta cristobalite; and in some embodiments, the cristobalite comprises both alpha cristobalite and beta cristobalite. The cristobalite-like phase can comprise LiAlSi crystalline phase and / or LiZnSi crystalline phase. The nanocrystals and submicron grains with small sizes are dispersed in the glass matrix, which not only meets the requirements of low dielectric constant and high thermal expansion coefficient, but also improves the glass transition temperature, enhances the temperature shock resistance, and improves the sealing strength and reliability.

[0081] The glass sealing material of the embodiments of the present application and the glass-ceramic prepared therefrom can be analyzed for composition by electron microscope composition analysis, XRD analysis, EDS (Energy Dispersive Spectrometer) analysis, XRF (X-ray fluorescence) analysis, etc. The crystalline phase can be characterized by SEM (scanning electron microscope) observation and XRD, etc.

[0082] The dielectric constant of the glass sealing material of the embodiments of the present application is between 3.5 and 5. The dielectric constant reflects the polarization degree of the material under the action of an applied electric field. Exemplarily, the dielectric constant of the glass sealing material can be 3.5, 3.6, 3.8, 4.0, 4.2, 4.5, 4.8 or 5. The glass sealing material has a low dielectric constant, which is beneficial to ensuring a high signal transmission rate and improving the performance of the device when used for the hermetic sealing of electronic components. The dielectric constant of the glass sealing material can be obtained by analyzing the glass-ceramic prepared after sealing by using a network analyzer system.

[0083] The coefficient of thermal expansion of the glass sealing material of the embodiments of the present application is in the range of 7 ppm / K-15 ppm / K. Illustratively, the coefficient of thermal expansion of the glass sealing material can be 7 ppm / K, 8 ppm / K, 9 ppm / K, 10 ppm / K, 11 ppm / K, 12 ppm / K, 13 ppm / K, 14 ppm / K, 15 ppm / K. The glass sealing material of the embodiments of the present application has a relatively high coefficient of thermal expansion, and can be well thermally matched with metals such as cold-rolled steel having a high coefficient of thermal expansion, to achieve high airtight sealing and improve sealing reliability. The coefficient of thermal expansion of the glass sealing material can be obtained by testing the glass-ceramic obtained after sealing using a thermal dilatometer.

[0084] The glass sealing material of the embodiments of the present application has a glass transition temperature (Tg) greater than or equal to 600°C, and in some embodiments, the glass transition temperature (Tg) is 600°C-950°C. The glass transition temperature (Tg) refers to the temperature corresponding to the transition from a glass state to a high-elasticity state. The glass sealing material having a relatively high glass transition temperature can improve temperature shock resistance and improve service reliability. In some embodiments, the glass sealing material has a glass transition temperature (Tg) of 600°C, 650°C, 700°C, 750°C, 800°C, 820°C, 830°C, 850°C, 880°C, 900°C, 920°C, 950°C.

[0085] The glass sealing material of the embodiments of the present application has a softening temperature of 700°C-1000°C. The glass sealing material has a softening temperature in a suitable temperature range, which is conducive to subsequent compression molding into various required shapes. The softening temperature of the glass sealing material can be obtained by testing the glass particles obtained after melting using a glass softening point tester. Illustratively, the softening temperature of the glass sealing material can be 700°C, 750°C, 800°C, 850°C, 860°C, 880°C, 900°C, 920°C, 930°C, 950°C, 980°C, 1000°C.

[0086] The sealing temperature of the glass sealing material of the embodiments of the present application is greater than 700°C and less than 1100°C. A suitable sealing temperature is conducive to achieving sealing at a controllable temperature, and can prevent remelting and affect the microcrystalline phase, which is conducive to obtaining high-performance and high-reliability sealing. Illustratively, the sealing temperature of the glass sealing material is 720°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C, 1090°C. In order to achieve sealing, the sealing temperature can be greater than or equal to the softening temperature of the glass sealing material.

[0087] The application further provides the glass sealing material and the application of the glass sealing material in the air-tight packaging of electronic components. The electronic components can be components in the field of optical networks (such as passive optical networks) and the like. The air-tight packaging of electronic components can be packaging of radio frequency components, packaging of solid oxide fuel cells, packaging of relays and the like. The radio frequency components can be, but are not limited to, radio frequency connectors.

[0088] The application of the glass sealing material in the packaging of radio frequency connectors is described below as an example.

[0089] Referring to FIG. 1, the application provides a joint 100, which includes a first metal piece 101, a second metal piece 102 and a connecting piece 103. The connecting piece 103 connects the first metal piece 101 and the second metal piece 102 together and keeps the first metal piece 101 and the second metal piece 102 electrically insulated. The connecting piece 103 includes the glass sealing material described above to form a glass sealing material. The joint 100 is sealed by the glass sealing material described above, which can realize high air-tight sealing of the first metal piece 101 and the second metal piece 102 with high thermal expansion coefficients such as cold-rolled steel, and at the same time, can achieve low dielectric, high signal transmission rate and high sealing strength and high temperature impact resistance.

[0090] In the application, the material of the first metal piece 101 and the second metal piece 102 can be a metal with a thermal expansion coefficient of 7 ppm / K-15 ppm / K. The metal can be a metal element or an alloy. For example, the material of the first metal piece 101 and the second metal piece 102 can be a metal with a thermal expansion coefficient of 7 ppm / K, 8 ppm / K, 9 ppm / K, 10 ppm / K, 11 ppm / K, 12 ppm / K, 13 ppm / K, 14 ppm / K or 15 ppm / K. In some embodiments, the material of the first metal piece 101 and the second metal piece 102 is cold-rolled steel. The first metal piece 101 and the second metal piece 102 can be various metal structural pieces that need to be sealed, and can have various shapes and sizes. The joint 100 can be various electronic components, such as radio frequency components and the like.

[0091] FIG. 1 specifically shows a radio frequency connector. The first metal piece 101 is a TO can of the radio frequency connector, the second metal piece 102 is a pin (i.e., a lead), and the connecting piece 103 is sealing glass. The sealing glass has good thermal expansion matching with the TO can, can realize dense and air-tight sealing, and can realize high radio frequency performance of the radio frequency connector.

[0092] Correspondingly, the application further provides a sealing method, which includes:

[0093] The glass sealing material prepared into the preformed shape according to the embodiment of the application is arranged between the first metal piece 101 and the second metal piece 102, and the sealing is performed under a protective atmosphere and at a sealing temperature, so that the first metal piece 101 and the second metal piece 102 are bonded together and the electrical insulation between the first metal piece 101 and the second metal piece 102 is maintained.

[0094] It can be understood that the preformed shape can be prepared into a specific shape and size according to actual needs to meet the sealing requirements. Before being arranged between the first metal piece 101 and the second metal piece 102, the preformed shape can be subjected to a degassing treatment at 300-550°C for 1-3 hours to remove the binder.

[0095] The protective atmosphere can be nitrogen or the like. The sealing temperature can be greater than 700°C and less than 1100°C. During the sealing process, the preformed shape is diffusively melted at the interface where the preformed shape is in contact with the first metal piece 101 and the second metal piece 102 to complete the bonding, and after the sealing is completed, the preformed shape is crystallized to form the connecting piece 103. In some embodiments, as shown in FIG. 1, the second metal piece 102 is arranged in the hole formed in the first metal piece 101, and the preformed shape can be designed as a ring structure. The preformed shape is first arranged in the hole formed in the first metal piece 101, and then the second metal piece 102 is inserted into the hole of the preformed shape. In this way, the inner side surface of the ring structure is in contact with the second metal piece 102 and is melted during the sealing process, and the outer side surface of the ring structure is in contact with the first metal piece 101 and is melted during the sealing process. After the sealing is completed, the second metal piece 102 is fixed.

[0096] The glass sealing material according to the embodiment of the application has a simple sealing process, can realize automatic crystallization, and has strong operability.

[0097] After the sealing is completed, the helium mass spectrometer leak detector can be used to measure the air tightness of the bonded piece under different environments and conditions. The radio frequency connector TO tube seat sealed by the glass sealing material according to the embodiment of the application can maintain the air tightness ≤10 -9 Pa·m 3 / s:

[0098] ① 300°C-ambient temperature cold and hot impact ≥5 times;

[0099] ② The pin is bent by 90° clockwise and counterclockwise;

[0100] ③ One meter drop once.

[0101] The glass sealing material according to the embodiment of the application can maintain high air tightness under the above different working conditions after the sealing is completed, which can improve the service reliability of the device and prolong the service life of the device.

[0102] The technical solutions of the present application are further described below in multiple embodiments.

[0103] Embodiment 1

[0104] (1) The raw material components of the glass sealing material are mixed uniformly after adding water to obtain a mixed slurry; the raw material components of the glass sealing material include the following molar percentages of each substance:

[0105] Li2CO3: 1 mol%, Al2O3: 5 mol%, SiO2: 69.5 mol%, B2O3: 5 mol%, K2O: 0.25 mol%, Y2O3: 1 mol%, La2O3: 2.5 mol%, TiO2: 1 mol%; wherein the total molar percentage of metal and semi-metal elements is 100%.

[0106] (2) The mixed slurry obtained in step (1) is melted at 1600°C for 1.5 hours to obtain a melt, and then the obtained melt is poured into deionized water at 0°C for water quenching to obtain glass fragments and / or glass slag, i.e. glass particles;

[0107] (3) The glass particles are ball milled (using zirconium oxide grinding, with ethanol as the medium) for 2 hours, then dried, sieved, mixed with PVB adhesive and ethanol, and then spray granulated to obtain a granulated mixed powder;

[0108] (4) The granulated mixed powder is pressed and formed using a forming mold at a temperature of 600°C and a pressure of 20 MPa for 30 seconds to obtain a pre-formed part;

[0109] (5) After the pre-formed part is degassed at 400°C for 2 hours, it is loaded into a pre-set hole in a cold-rolled steel TO tube seat of a radio frequency connector to be sealed, and a cold-rolled steel pin is inserted, and then co-fired at 960°C under nitrogen protection for 1.5 hours to crystallize the pre-formed part to obtain a glass-ceramic connector, the sealing is completed, and a joint is obtained.

[0110] Embodiment 2

[0111] The difference from Embodiment 1 is that the glass sealing material includes the following molar percentages of each raw material component: Li2O: 1 mol%, Al2O3: 5 mol%, SiO2: 69.5 mol%, B2O3: 5 mol%, K2O: 0.25 mol%, Y2O3: 3 mol%, La2O3: 0.5 mol%, TiO2: 1 mol%. The total molar percentage of metal and semi-metal elements is 100%.

[0112] Embodiment 3

[0113] The difference from Example 1 is that the glass sealing material comprises the following molar percentages of each raw material component: Li2CO3: 5 mol%, Al2O3: 2.5 mol%, SiO2: 69.5 mol%, H3BO3: 10 mol%, K2O: 0.25 mol%, Y2O3: 2.5 mol%, Nd2O3: 0.5 mol%, ZnO: 1 mol%. The total molar percentage of metal and semi-metal elements is 100%.

[0114] Example 4

[0115] The difference from Example 1 is that the glass sealing material comprises the following molar percentages of each raw material component: Li2CO3: 5 mol%, Al2O3: 3 mol%, SiO2: 69.5 mol%, H3BO3: 10 mol%, K2O: 0.25 mol%, CeO: 1 mol%, ZnO: 3 mol%. The total molar percentage of metal and semi-metal elements is 100%.

[0116] Example 5

[0117] The difference from Example 1 is that the glass sealing material comprises the following molar percentages of each raw material component: Li2CO3: 4 mol%, Al(OH)3: 6 mol%, SiO2: 69.5 mol%, H3BO3: 10 mol%, K2CO3: 0.25 mol%, CeO: 2 mol%, ZnO: 2 mol%. The total molar percentage of metal and semi-metal elements is 100%.

[0118] Example 6

[0119] The difference from Example 1 is that the glass sealing material comprises the following molar percentages of each raw material component: Li2O: 4 mol%, Al2O3: 4 mol%, SiO: 69.5 mol%, B2O3: 5 mol%, K2CO3: 0.25 mol%, Y2O3: 1 mol%, CeO: 1 mol%, ZnO: 1 mol%. The total molar percentage of metal and semi-metal elements is 100%.

[0120] The melting temperature, the pressing forming temperature, and the sealing temperature in Examples 2 to 6 can be adjusted according to actual needs.

[0121] The glass sealing materials in Examples 1 to 6 are subjected to the following performance tests:

[0122] 1. Glass transition temperature (Tg): obtained by testing the glass particles obtained after melting using a DSC analyzer.

[0123] 2. Glass softening temperature (Ts): The glass particles obtained after melting were tested using a glass softening point tester.

[0124] 3. Coefficient of thermal expansion:

[0125] The granulated mixed powders prepared in Examples 1 to 6 were respectively placed in a specific mold, pressed into a long bar using a hydraulic machine, and then placed in a muffle furnace. After degassing at 400°C for 2 hours, the temperature was increased to 960°C for 1.5 hours, and then the furnace was cooled to room temperature to obtain a glass-ceramic test sample. The coefficient of thermal expansion of the glass-ceramic test sample was measured using a thermal dilatometer.

[0126] 4. Dielectric constant:

[0127] The granulated mixed powders prepared in Examples 1 to 6 were respectively placed in a specific mold, pressed into a round sheet using a hydraulic machine, and then placed in a muffle furnace. After degassing at 400°C for 2 hours, the temperature was increased to 960°C for 1.5 hours, and then the furnace was cooled to room temperature to obtain a glass-ceramic test sample. The dielectric constant of the glass-ceramic test sample was measured using a network analyzer system.

[0128] 5. Air tightness:

[0129] The air tightness of the joints prepared in Examples 1 to 6 was measured using a helium mass spectrometer leak detector under three conditions: 20 times of cold and hot impact at 300°C to room temperature, bending of the pin by 90° clockwise and counterclockwise, and one-meter drop.

[0130] The performance test results are shown in Table 1.

[0131] Table 1

[0132] As can be seen from the results in Table 1, the glass sealing material of the present application has a dielectric constant of less than 5, thus ensuring high-quality and high-speed signal transmission. At the same time, it has a glass transition temperature higher than 800°C and a softening temperature less than 1000°C, which can ensure its high temperature impact resistance and a suitable sealing temperature. In addition, the glass sealing material has high sealing strength and a high coefficient of thermal expansion (greater than 7 ppm / K), which can obtain high air tightness sealing when used for cold-rolled steel sealing, thereby improving the reliability and service life of the device.

[0133] In addition, in order to analyze the internal structure of the glass obtained after sealing of the glass sealing material of the present application, the following tests were also performed:

[0134] The test sample of the glass-ceramic prepared from the granulated mixed powder of Example 1 was ground with a maroon mortar, sieved through a 200 mesh sieve, and tested by a high-resolution powder X-ray diffractometer at a voltage of 40 KV, a current of 40 mA, Cu / Ka rays, a scanning range of 10-80°, and a scanning speed of 5° / min. The obtained XRD pattern was searched for JCPDS cards by using Jade software to determine the types of crystal phases.

[0135] FIG. 2 is an XRD pattern of the glass-ceramic formed by the sealing glass material of Example 1 of the present application, from which it can be seen that there is a cristobalite microcrystal phase formed in the glass.

[0136] The glass sealing material provided by the embodiments of the present application can meet the basic sealing performance requirements under the synergistic effect of the components in a specific content ratio, can be applied to the air-tight sealing of electronic components, and can have a low dielectric constant and a high thermal expansion coefficient to meet the sealing requirements of metals such as cold-rolled steel with a high thermal expansion coefficient, so as to ensure a high signal transmission rate of the device, improve the air-tightness, and prolong the service life of the device; in addition, a high glass transition temperature can be obtained to improve the temperature shock resistance, a high sealing strength can be obtained to improve the sealing reliability and the performance of the device, and a suitable sealing temperature can be obtained.

[0137] It should be understood that the first, second, and various numerical designations referred to herein are only used for differentiation for the convenience of description, and do not limit the scope of the present application.

[0138] In the present application, the association relationship of the associated objects described by "and / or" indicates that there can be three kinds of relationships, for example, A and / or B can represent the following three cases: A exists alone, A and B exist simultaneously, and B exists alone, wherein A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0139] In the present application, "at least one" means one or more, and "a plurality of" means two or more. "At least one of the following" or the like means any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can represent a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0140] In the present application, "-" represents a range value, including the end point values at both ends, for example, the value of a can be 0.5-15, indicating that the value of a can be between 0.5 and 15, and the end point values 0.5 and 15 are included.

[0141] It should be understood that the size of the serial number of the above processes in various embodiments of the present application does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence, and the execution order of the processes should be determined according to its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

Claims

1. A glass sealing material, characterized by, The glass sealing material comprises the following metal and semi-metal elements in the following molar percentages, based on 100% of the total moles of the metal and semi-metal elements in the glass sealing material: 0.5%-15% of lithium element, 2%-15% of aluminum element, 60%-80% of silicon element, 5%-20% of boron element, 0.1%-1% of potassium element, total of greater than 0 and less than or equal to 15% of rare earth element and R element; and the molar percentages of the rare earth element and the R element are both greater than 0; The R comprises one or more of Ba, Ca, Mg, Zn, and Ti.

2. The glass seal material of claim 1, wherein, The molar percentage of the lithium element is 2%-10%.

3. The glass sealing material according to claim 1 or 2, wherein The molar percentage of the aluminum element is 5%-12%.

4. The glass sealing material according to any one of claims 1 to 3, wherein The molar percentage of the silicon element is 65%-75%.

5. The glass sealing material according to any one of claims 1 to 4, wherein The molar percentage of the boron element is 5%-15%.

6. The glass sealing material according to any one of claims 1 to 5, wherein The molar percentage of the rare earth element is 0.5%-10%.

7. The glass seal material of claim 6, wherein, The molar percentage of the rare earth element is 1%-8%.

8. The glass sealing material according to any one of claims 1 to 7, wherein The rare earth element comprises one or more of Y, La, Ce, Nd, and Sm.

9. The glass sealing material according to any one of claims 1 to 8, wherein The molar percentage of the R element is 0.5%-5%.

10. The glass sealing material of claim 9, wherein, The molar percentage of the R element is 1%-3%.

11. The glass sealing material of any one of claims 1-10, wherein, The glass sealing material is a glass raw material mixed powder, or a glass frit formed from the glass raw material mixed powder, the glass frit comprising glass particles, or granulated mixed powder, or a preformed shaped piece.

12. The glass sealing material of claim 11, wherein, The glass raw material mixed powder comprises a lithium-containing compound, an aluminum-containing compound, a silicon-containing compound, a boron-containing compound, a potassium-containing compound, a rare earth element-containing compound, and an R element-containing compound.

13. The glass sealing material of claim 12, wherein, The aluminum-containing compound comprises one or more of an oxide of aluminum, a hydroxide of aluminum, a carbonate of aluminum, and a nitrate of aluminum; and / or, the silicon-containing compound comprises one or more of SiO, SiO2, and H2SiO3; and / or, the boron-containing compound comprises one or more of B2O3 and H3BO3.

14. The glass sealing material according to claim 12 or 13, wherein The lithium-containing compound comprises one or more of an oxide of lithium, a carbonate of lithium, a hydroxide of lithium, a chloride of lithium, a nitride of lithium, and a sulfide of lithium; and / or, the potassium-containing compound comprises one or more of K2O, K2CO3, KHCO3, KNO3, and K2SO4.

15. The glass sealing material according to any one of claims 12 to 14, wherein The rare earth element-containing compound comprises one or more of an oxide of rare earth element, a carbonate of rare earth element, a nitrate of rare earth element, and a hydroxide of rare earth element; and / or, the R element-containing compound comprises one or more of an oxide of R element, a carbonate of R element, a nitrate of R element, and a hydroxide of R element.

16. The glass sealing material of any one of claims 1-15, wherein, The glass sealing material can be used to prepare a glass-ceramic, the glass-ceramic prepared from the glass sealing material comprising a glass matrix and a microcrystalline phase, the microcrystalline phase comprising a cristobalite phase and / or a cristobalite-like phase.

17. The glass sealing material of claim 16, wherein, The cristobalite phase comprises an alpha cristobalite phase and / or a beta cristobalite phase; and the cristobalite-like phase comprises a LiAlSi microcrystalline phase and / or a LiZnSi microcrystalline phase.

18. The glass sealing material of any one of claims 1-17, wherein, The glass sealing material has a dielectric constant of 3.5-5 and a coefficient of thermal expansion of 7-15 ppm / K.

19. The glass sealing material of any one of claims 1-18, wherein, The glass sealing material has a glass transition temperature of 600-950°C, a softening temperature of 700-1000°C, a sealing temperature of greater than 700°C and less than 1100°C.

20. A glass sealing material according to any one of claims 1-19, in the form of a glass-ceramic.

21. Use of a glass sealing material according to any one of claims 1-19, or a glass-ceramic according to claim 20, for the hermetic encapsulation of electronic components.

22. A joint, comprising: comprising a first metal piece, a second metal piece, and a connecting piece that joins the first metal piece to the second metal piece and maintains electrical insulation between the first metal piece and the second metal piece, the connecting piece comprising a glass-ceramic formed from a glass sealing material according to any one of claims 1-19.

23. The joint of claim 22, wherein, The first metal piece and the second metal piece comprise a metal having a coefficient of thermal expansion of 7-15 ppm / K.

24. The joint of claim 22 or 23, wherein, The connecting piece comprises a radio frequency connector.

25. A method of sealing, comprising: comprising: A glass sealing material according to any one of claims 1-19 is prepared into a preformed shape and placed between a first metal piece and a second metal piece, and is sealed under a protective atmosphere and at a sealing temperature to join the first metal piece to the second metal piece and maintain electrical insulation between the first metal piece and the second metal piece.

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