CN110451805B - Sealing glass - Google Patents
Sealing glass Download PDFInfo
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- CN110451805B CN110451805B CN201910886572.7A CN201910886572A CN110451805B CN 110451805 B CN110451805 B CN 110451805B CN 201910886572 A CN201910886572 A CN 201910886572A CN 110451805 B CN110451805 B CN 110451805B
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- glass
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- sealing glass
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
Abstract
The invention provides a sealing glass with higher resistivity and lower sealing temperature, and a group of the sealing glassIn mol%, contains V2O5：10～20％；TeO2：35～60％；PbO：15～40％；PbF2: 4-15%. Through reasonable component design, the sealing glass obtained by the invention has higher resistivity and lower sealing temperature, and can be widely applied to sealing in the fields of semiconductors, microelectronic technology, new energy and the like.
Description
Technical Field
The invention relates to the field of glass, in particular to sealing glass suitable for semiconductors, microelectronic technology, new energy and the like.
Background
The sealing glass is intermediate glass capable of sealing glass, ceramic, metal and composite materials, and is an advanced welding material. Because the low-temperature sealing glass has the properties of lower sealing temperature, good stability and mechanical property, lower conductivity and magnetic conductivity and the like, the low-temperature sealing glass is widely applied to the fields of electric vacuum and microelectronic technologies, aerospace, new energy sources and the like.
In the prior art, PbO-B is mainly adopted2O3-SiO2、PbO-ZnO-B2O3、Bi2O3-B2O3The sealing glass prepared by systems such as-ZnO and the like has the advantages of high resistivity, good chemical stability and the like, but the sealing temperature is generally higher. Sealing glass having a relatively low sealing temperature, due to V2O5The content of the components is high, or the components such as alkali metal and the like are introduced, so that the resistivity of the glass is low, and the insulation resistance is difficult to meet the sealing requirements of some devices. For example, CN101289279A realizes lower sealing temperature, but the component contains 25-55 mol% of V2O5And a certain amount of alkali metal oxide is introduced, the resistivity of the glass is reduced to 107Omega m or less.
Disclosure of Invention
The invention aims to provide sealing glass with higher resistivity and lower sealing temperature.
The technical scheme adopted by the invention for solving the technical problem is as follows: sealing glass having a composition, expressed in mol%, comprising: v2O5：10～20％；TeO2：35～60％；PbO：15～40％；PbF2：4～15％。
Further, the sealing glass has a composition expressed in mol%, and further comprises: ZnO: 0 to 7 percent; b is2O3：0～10％。
Sealing glass having a composition in mol% of V2O5：10～20％；TeO2：35～60％；PbO：15～40％；PbF2：4～15％；ZnO：0～7％；B2O3: 0 to 10% of the composition.
Further, the sealing glass has a composition expressed by mol%, wherein: v2O5: 12-18%; and/or TeO2: 35-50%; and/or PbO: 20-35%; and/or PbF2: 7-15%; and/or ZnO: 0 to 5 percent; and/or B2O3：0～5％。
Further, the sealing glass has a composition expressed by mol%, wherein: v2O5/TeO20.20 to 0.45, preferably V2O5/TeO20.25 to 0.40.
Further, the sealing glass has a composition expressed by mol%, wherein: PbF2/(PbF2+ PbO) is 0.15 to 0.45, preferably PbF2/(PbF2And + PbO) is 0.20 to 0.40.
Further, the sealing glass has a resistivity of 1.0 × 109Omega · m or more, preferably 1.0 to 95.0 × 109Omega. m, more preferably 24.0 to 83.0X 109Ω·m。
Further, the sealing temperature of the sealing glass is 370 ℃ or lower, preferably 365 ℃ or lower, more preferably 300 to 360 ℃, and further preferably 300 to 350 ℃.
Further, the softening temperature of the sealing glass is 300 ℃ or lower, preferably 280 ℃ or lower, more preferably 225 to 275 ℃, and further preferably 225 to 265 ℃.
Further, the sealing glass has an expansion coefficient of 220 × 10-7Preferably 155 to 210X 10 at a temperature of not more than/° C-7/℃。
The invention has the beneficial effects that: through reasonable component design, the sealing glass obtained by the invention has higher resistivity and lower sealing temperature, and can be widely applied to sealing in the fields of semiconductors, microelectronic technology, new energy and the like.
Detailed Description
The following describes in detail embodiments of the sealing glass of the present invention, but the present invention is not limited to the embodiments described below, and can be implemented by making appropriate changes within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. In the following, the sealing glass of the present invention may be simply referred to as glass.
The ranges of the respective components (compositions) of the sealing glass of the present invention are explained below. In the present specification, the contents of the respective components are all expressed in mole percent (mol%), if not specifically stated. Unless otherwise indicated herein or otherwise indicated herein, the numerical ranges set forth in this specification and this application include upper and lower values, and the "above" and "below" include end-point values, as well as all integers and fractions included in the ranges, and are not limited to the specific values recited in the defined ranges. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.
V2O5In the present invention, is a network former of glass. V2O5Glass cannot be formed alone, but can be formed with many oxides and has a relatively large glass forming region. Vanadium ion VO6The octahedron form enters the network structure of the glass, the melting temperature and the expansion coefficient of the glass can be obviously reduced, and more than 10 percent of V is introduced into the glass2O5To obtain the above effects, V is preferable2O5The content of (A) is more than 12%. V2O5When the content is too muchResulting in a decrease in the fluidity of the glass and a decrease in the volume resistivity, so that V is controlled in the present invention2O5The content of (B) is 20% or less, preferably 18% or less.
TeO2Is also a glass former, with V2O5Incorporating a large glass forming area. More than 35 percent of TeO is introduced into the invention2So as to improve the devitrification resistance of the glass; when TeO2The content exceeds 60%, and the softening temperature and the expansion coefficient of the glass increase. Thus, in the present invention, TeO2The content of (A) is in the range of 35-60%, and the preferable range is 35-50%.
In some embodiments, control V2O5And TeO2Introduction ratio V of2O5/TeO2In the range of 0.20 to 0.45, the softening temperature of the glass can be lowered, and V is preferably selected2O5/TeO20.25 to 0.40.
PbO is partially in the glass with external ions Pb2+Into a glass structure, partially with [ PbO ]4]The pyramid shape enters the network, the glass forming stability of the glass can be improved under the condition of not obviously increasing the softening temperature of the glass, and the resistivity of the glass is improved, wherein the effect is obtained by introducing more than 15 percent of PbO. When the content of PbO exceeds 40%, the softening temperature of the glass rises, and it is difficult to satisfy the design requirements. Therefore, the content of PbO is 15 to 40%, and the preferable range is 20 to 35%.
PbF2Introducing F into glass-The function of the glass sealing agent is to break the bridge oxygen bond of the glass network structure, thereby achieving the purpose of reducing the glass sealing temperature. But with F-The increase of the introduction amount increases the expansion coefficient of the glass, reduces the mechanical strength, deteriorates the chemical stability, remarkably reduces the resistivity, and is not beneficial to improving the insulation resistance of the glass. Thus, PbF in the present invention2The content of (b) is 4 to 15%, preferably 7 to 15%.
In some embodiments, the composition is prepared by reacting PbF2With PbO and PbF2Total content of (PbF)2+ PbO) introduction ratio PbF2/(PbF2+ PbO) in the range of 0.15 to 0.45In the enclosure, the glass has a higher volume resistivity and a lower softening temperature, and PbF is preferred2/(PbF2And + PbO) is 0.20 to 0.40.
ZnO in glass has the effects of inhibiting glass crystallization, reducing glass expansion coefficient, improving glass mechanical strength and improving glass chemical stability. When the content thereof exceeds 7%, the softening temperature of the glass rises. Therefore, the ZnO content in the present invention is 0 to 7%, preferably 0 to 5%.
B2O3The glass has the effects of inhibiting glass crystallization, reducing glass expansion coefficient, improving glass mechanical strength and improving glass chemical stability. When the content thereof exceeds 10%, the softening temperature of the glass rises. Thus, in the present invention B2O3The content is 0 to 10%, preferably 0 to 5%.
In the present invention, in order to obtain excellent resistivity, it is preferable in some embodiments that no alkali metal oxide, which is an oxide of Li, Na, K, Rb, Cs, or the like, or alkali metal fluoride, which is a fluoride of Li, Na, K, Rb, Cs, or the like, is introduced.
As used herein, "0%" means that the compound, molecule, element, or the like is not intentionally added as a raw material to the glass of the present invention, but that certain impurities or components not intentionally added may be present as raw materials and/or equipment for producing the glass, and may be contained in the final glass in small or trace amounts, which is also within the scope of the present invention.
The performance of the sealing glass of the present invention will be described below.
< coefficient of expansion >
The expansion coefficient of the sealing glass is measured according to a method specified in GB/T7962.16-2010 at 20-120 ℃. The expansion coefficient in the invention is linear expansion coefficient.
In some embodiments of the invention, the sealing glass has a coefficient of expansion (α) of 220 × 10-7Preferably 155 to 210X 10 at a temperature of not more than/° C-7/℃。
< softening temperature >
The softening temperature of the sealing glass of the present invention was measured according to the method specified in SJ 690-83.
In some embodiments of the present invention, the softening temperature of the sealing glass is 300 ℃ or lower, preferably 280 ℃ or lower, more preferably 225 to 275 ℃, and still more preferably 225 to 265 ℃.
< resistivity >
The method for testing the resistivity of the sealing glass comprises the following steps: the glass was processed into a 30X 5mm glass sample and tested with a volume surface resistance tester (model ATI-212) at a test voltage of 1000V. The resistivity in the invention is volume resistivity.
In some embodiments of the invention, the sealing glass has a resistivity of 1.0X 109Omega · m or more, preferably 1.0 to 95.0 × 109Omega. m, more preferably 24.0 to 83.0X 109Ω·m。
< sealing temperature >
The sealing temperature of the sealing glass of the invention is tested according to the method specified in SJ/T3231-.
In some embodiments of the present invention, the sealing temperature of the sealing glass is 370 ℃ or lower, preferably 365 ℃ or lower, more preferably 300 to 360 ℃, and further preferably 300 to 350 ℃.
[ method for producing sealing glass ]
The manufacturing method of the sealing glass of the invention is as follows: after the raw materials with the content of each component are weighed in proportion, the raw materials are fully and uniformly mixed, and are put into a melting device (such as a quartz crucible or a ceramic crucible) to be melted at the temperature of 500-600 ℃ for 30-60 minutes. And after the raw materials are fully melted, fully and uniformly stirring the molten glass by using a ceramic rod, pouring the molten glass into a cast iron mold, cooling and shaping the molten glass, and then putting the molten glass into a muffle furnace for annealing to obtain the sealing glass.
Examples
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, sealing glasses having compositions shown in tables 1 to 2 were obtained by the above-described methods for producing sealing glasses. The characteristics of each glass were measured by the test method described in the present invention, and the test results are shown in tables 1 to 2.
TABLE 1
TABLE 2
Claims (21)
1. Sealing glass, characterized in that it has a composition, expressed in mol%, comprising: v2O5：10～20％；TeO2：35～60％；PbO：15～40％；PbF2：4～15％。
2. A sealing glass according to claim 1, characterized in that it has a composition, expressed in mol%, further comprising: ZnO: 0 to 7 percent; b is2O3：0～10％。
3. Sealing glass, characterized in that its composition, expressed in mol%, is represented by V2O5：10～20％；TeO2：35～60％；PbO：15～40％；PbF2：4～15％；ZnO：0～7％；B2O3: 0 to 10% of the composition.
4. A sealing glass according to any of claims 1 to 3, having a composition in mol%, wherein: v2O5: 12-18%; and/or TeO2: 35-50%; and/or PbO: 20-35%; and/or PbF2: 7-15%; and/or ZnO: 0 to 5 percent; and/or B2O3：0～5％。
5. A sealing glass according to any of claims 1 to 3, having a composition in mol%, wherein: v2O5/TeO20.20 to 0.45.
6. A sealing glass according to any of claims 1 to 3, having a composition in mol%, wherein: v2O5/TeO20.25 to 0.40.
7. A sealing glass according to any of claims 1 to 3, having a composition in mol%, wherein: PbF2/(PbF2And + PbO) is 0.15 to 0.45.
8. A sealing glass according to any of claims 1 to 3, having a composition in mol%, wherein: PbF2/(PbF2And + PbO) is 0.20 to 0.40.
9. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a resistivity of 1.0 x 109Omega · m or more.
10. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a resistivity of 1.0 to 95.0 x 109Ω·m。
11. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a resistivity of 24.0 to 83.0 x 109Ω·m。
12. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a sealing temperature of 370 ℃ or lower.
13. A sealing glass according to any of claims 1 to 3, wherein the sealing temperature of the sealing glass is 365 ℃.
14. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a sealing temperature of 300 to 360 ℃.
15. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a sealing temperature of 300 to 350 ℃.
16. A sealing glass according to any of claims 1 to 3, wherein the softening temperature of the sealing glass is 300 ℃ or lower.
17. A sealing glass according to any of claims 1 to 3, wherein the softening temperature of the sealing glass is 280 ℃ or lower.
18. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a softening temperature of 225 to 275 ℃.
19. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a softening temperature of 225 to 265 ℃.
20. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a coefficient of expansion of 220 x 10-7Below/° c.
21. A sealing glass according to any of claims 1 to 3, wherein the sealing glass has a coefficient of expansion of 155 to 210 x 10-7/℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910886572.7A CN110451805B (en) | 2019-09-19 | 2019-09-19 | Sealing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910886572.7A CN110451805B (en) | 2019-09-19 | 2019-09-19 | Sealing glass |
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| Publication Number | Publication Date |
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| CN110451805A CN110451805A (en) | 2019-11-15 |
| CN110451805B true CN110451805B (en) | 2021-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910886572.7A Active CN110451805B (en) | 2019-09-19 | 2019-09-19 | Sealing glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114180843B (en) * | 2021-12-28 | 2023-01-13 | 海南大学 | Sealing glass and preparation method thereof |
Citations (6)
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|---|---|---|---|---|
| EP1391437A1 (en) * | 2002-07-25 | 2004-02-25 | Nortel Networks Limited | Sealing glass composition |
| CN102947235A (en) * | 2010-05-04 | 2013-02-27 | E·I·内穆尔杜邦公司 | Thick-film pastes containing lead-tellurium-boron-oxides, and their use in the manufacture of semiconductor devices |
| CN103219063A (en) * | 2012-01-24 | 2013-07-24 | E·I·内穆尔杜邦公司 | Thick film silver paste containing copper and lead-tellurium-oxide and its use in the manufacture of semiconductor devices |
| CN103236281A (en) * | 2012-01-17 | 2013-08-07 | E.I.内穆尔杜邦公司 | Conductive paste for fine-line high-aspect-ratio screen printing in the manufacture of semiconductor devices |
| CN103578600A (en) * | 2012-08-03 | 2014-02-12 | E·I·内穆尔杜邦公司 | Thick-film paste containing lead-vanadium-based oxide glass and its use in the manufacture of semiconductor devices |
| WO2015171094A1 (en) * | 2014-05-07 | 2015-11-12 | Istanbul Teknik Universitesi | A thermochromic glass material and a production method thereof |
-
2019
- 2019-09-19 CN CN201910886572.7A patent/CN110451805B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1391437A1 (en) * | 2002-07-25 | 2004-02-25 | Nortel Networks Limited | Sealing glass composition |
| CN102947235A (en) * | 2010-05-04 | 2013-02-27 | E·I·内穆尔杜邦公司 | Thick-film pastes containing lead-tellurium-boron-oxides, and their use in the manufacture of semiconductor devices |
| CN103236281A (en) * | 2012-01-17 | 2013-08-07 | E.I.内穆尔杜邦公司 | Conductive paste for fine-line high-aspect-ratio screen printing in the manufacture of semiconductor devices |
| CN103219063A (en) * | 2012-01-24 | 2013-07-24 | E·I·内穆尔杜邦公司 | Thick film silver paste containing copper and lead-tellurium-oxide and its use in the manufacture of semiconductor devices |
| CN103578600A (en) * | 2012-08-03 | 2014-02-12 | E·I·内穆尔杜邦公司 | Thick-film paste containing lead-vanadium-based oxide glass and its use in the manufacture of semiconductor devices |
| WO2015171094A1 (en) * | 2014-05-07 | 2015-11-12 | Istanbul Teknik Universitesi | A thermochromic glass material and a production method thereof |
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