CN101186442B - A kind of high resistance glass for metal sealing - Google Patents
A kind of high resistance glass for metal sealing Download PDFInfo
- Publication number
- CN101186442B CN101186442B CN2007101787029A CN200710178702A CN101186442B CN 101186442 B CN101186442 B CN 101186442B CN 2007101787029 A CN2007101787029 A CN 2007101787029A CN 200710178702 A CN200710178702 A CN 200710178702A CN 101186442 B CN101186442 B CN 101186442B
- Authority
- CN
- China
- Prior art keywords
- glass
- sealing
- metal
- high resistance
- resistance glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011521 glass Substances 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 238000007789 sealing Methods 0.000 title claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 15
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 239000000956 alloy Substances 0.000 abstract description 9
- 229910000833 kovar Inorganic materials 0.000 abstract description 9
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract description 8
- 239000011810 insulating material Substances 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010953 base metal Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004018 waxing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
一种金属封接用高阻玻璃，属于玻璃领域，涉及适用于微电子封装中与金属封接的绝缘材料，特别是用于金属外壳或密封继电器。其特征在于按质量百分比含有SiO235％～55％、Al2O35％～20％、B20310％～20％、CaO5％～15％、BaO10％～25％、ZnO3％～8％、Cr2O30％～2％，保证线膨胀系数在45×10-7～54×10-7/℃，能与可伐合金或铁镍合金封接，封接件的绝缘电阻高、气密性好。The invention relates to a high-resistance glass for metal sealing, which belongs to the field of glass and relates to an insulating material suitable for sealing with metal in microelectronic packages, especially for metal shells or sealed relays. It is characterized in that it contains SiO2 35%-55%, Al2O3 5%-20 % , B203 10 %-20%, CaO5%-15%, BaO10%-25%, ZnO3%- 8%, Cr 2 O 3 0% ~ 2%, the guaranteed linear expansion coefficient is 45×10 -7 ~ 54×10 -7 /℃, can be sealed with Kovar alloy or iron-nickel alloy, and the insulation resistance of the sealing parts High, good air tightness.
Description
Technical field
The present invention is a kind of high resistance glass, it be can with the insulating material of metal hermetic seal, be mainly used in metal shell or sealed relay in the microelectronics Packaging.
Background technology
The used metal shell of electronic devices and components uses the glass insulator of hollow cylinder usually, and its outside is the base or the side wall of metal, and the inboard is through metal lead wire, and provides enclosure and outside being electrically connected by lead-in wire.Wherein glass is to make the main material that insulate between case body and the lead-in wire and realize the vacuum tight sealing-in, the work-ing life of its quality direct relation components and parts.More and more higher along with electronic devices and components are required, also more and more higher to the glass material performance demands, particularly need to have high insulation resistance, high chemical stability, the glass for sealing that moisture resistance is separated performance.
The metal current shell extensively adopts the borosilicate glasses such as DM-305, DM-308 with the kovar alloy matched seal, and the main component of these two kinds of glass is: Al
2O
3, B
2O
3, SiO
2, Na
2O, K
2O, but the sealing-in quality is difficult to satisfy the demand.Though also used the glass powder or the glass base of various imports in recent years, the sealing-in quality makes moderate progress, and belongs to borosilicate glass after all together, one of shortcoming that this class glass exists is exactly that insulation resistance is lower, generally can only reach 10
11About Ω, after electroplate and hectic fever etc. tested, insulation resistance reduced an order of magnitude toward the contact meeting.
The resistivity of glass itself is very high, and what influence insulation resistance mainly is surface resistivity, and it is because conductive ion easily due to the migration, particularly monovalent base metal ion Na that surface resistivity reduces
+And K
+Moisture in the easy absorbed air of glass surface is with the Na in the glass
+Exchange generates NaOH or Na
2CO
3Solution forms one deck successive solution film, the Na in the liquid film at glass surface at last
+, K
+The transfer ability that tool is higher is as document
Smit.W.Modelling of interdiffusionof hydrogen and alkali ions in glass surfaces:electrical resistivity.Journal of Non-CrystallineSolids, 1982,50 (2): 183～187 Hes
Tomozawa.M.,
Takata.M.Electrical resistivity of glass surfacereacted with water.Journal of Non-Crystalline Solids, 1981,45 (1): the report in 141～144 has caused the reduction of surface resistivity.If can reduce or cancel the monovalent base metal content in the glass, just can effectively improve the electrical insulation capability of glass.
Summary of the invention
The object of the present invention is to provide a kind of high resistance glass for sealing metal, this glass does not contain the monovalent base metal oxide, and has added a certain amount of divalent alkaline-earth metal oxide compound, by adjusting each component concentration, guarantees that expansion coefficient of glass thread is 45 * 10
-7～54 * 10
-7/ ℃, and have good and metal wetting property.Shortcomings such as the insulation resistance that it can solve the used glass of metal current shell is low, poor chemical stability can hermetic seal with kovar alloy or iron-nickel alloy, and insulation resistance height, resistance to air loss are good.
Each constituent mass percentage composition of high resistance glass for sealing metal of the present invention is: SiO
2: 35%～55%, Al
2O
3: 3%～17%, B
2O
3: 8%～20%, CaO:5%～15%, BaO:10%～25%, ZnO:0%～8%, Cr
2O
3: 0%～2%.
The preferable range of said components is: SiO
2: 42%～50%, Al
2O
3: 8%～15%, B
2O
3: 12%～18%, CaO:8%～12%, BaO:11%～16%, ZnO:0%～5%, Cr
2O
3: 0%～0.8%.
Adopt sealing process of the present invention to be:
1, batch mixes, each constituent mass percentage composition is: SiO
2: 35%～55%, Al
2O
3: 3%～17%, B
2O
3: 8%～20%, CaO:5%～15%, BaO:10%～25%, ZnO:0%～8%, Cr
2O
3: 0%～2%.
2, above-mentioned preparing glass charge was mixed on ball mill 4～8 hours, make it to mix; Mixed glass powder ℃ was founded 4～6 hours in platinum crucible internal heating to 1400～1600, and chilling is poured glass metal in the deionized water into then, with gained glass ball milling once more, make the granularity≤2 μ m of glass powder, then glass powder is carried out granulation, make the glass base.
3, the glass base is carried out de-waxing at 670～780 ℃; Ripe base behind the de-waxing and the kovar alloy after the preoxidation or the iron-nickel alloy speed with 8～15 ℃/min is heated up, carry out sealing-in at 960～1050 ℃, highest temperature district soaking time is 20～50 minutes, reduce to room temperature with the rate of temperature fall of 15～20 ℃/min then, sealing-in atmosphere is micro-oxidizing atmosphere, as the general nitrogen of industry.
The high resistance glass coefficient of expansion 45 * 10 of the present invention
-7～54 * 10
-7/ ℃, after kovar alloy, iron-nickel alloy sealing-in, the insulation resistance of closure is 5.0 * 10
12Ω～5.0 * 10
13Ω, leakage rate≤0.1 * 10
-10Pam
3/ s.
High resistance glass of the present invention is compared with electric-vacuum glasses such as BH-G/K with DM-305, DM-308 has following advantage:
1, high resistance glass of the present invention does not contain the monovalent base metal oxide, and has very high insulation resistance after kovar alloy or the iron-nickel alloy sealing-in, is packaged on the shell of model of the same race, measures under the identical situation of ambient moisture, and its insulation resistance can reach 5.0 * 10
12Ω～5.0 * 10
13Ω, high two orders of magnitude of more present common seal glass.
2, high resistance glass of the present invention does not contain the monovalent base metal oxide, under the bigger environment of ambient moisture, can not form one deck successive Na at glass surface
+, K
+Solution film still can keep higher insulation resistivity, makes the shell of sealing-in still can keep high insulation resistance at plum rain season.
3, high resistance glass of the present invention does not contain the monovalent base metal oxide, and has very high chemical stability after kovar alloy or the iron-nickel alloy sealing-in.
4, having very low leakage rate after high resistance glass of the present invention and kovar alloy or the iron-nickel alloy sealing-in, leakage rate can reach≤and 0.1 * 10
-10Pam
3/ s.
Embodiment
The invention will be further described below in conjunction with embodiment.
The component of embodiments of the invention 1～4, performance perameter, processing parameter are as shown in table 1.
The manufacturing process program of the various embodiments described above of the present invention is basic identical, and just processing parameter is slightly different, is illustrated with embodiment 1.
The manufacturing process of embodiment 1: each constituent mass percentage composition is: SiO
245%, B
2O
315%, Al
2O
310%, CaO10%, BaO15%, ZnO4.5%, Cr
2O
30.5%; Each component was mixed on ball mill 6 hours, join in the platinum crucible after mixing, founded 4 hours on 1539 ℃ on electric furnace, chilling then, the glass metal that melts is poured in the deionized water, obtained glass block, with granulation behind the glass block ball milling, at 740 ℃ of de-waxings, speed with 10 ℃/min heats up, and insulation 5min in highest temperature district is in the mould of packing into, push in the micro-oxidizing atmosphere at 1020 ℃ of sealings by fusing highest temperature district insulation 20min.After kovar alloy, iron-nickel alloy sealing-in, the insulation resistance of closure is 5.0 * 10
12Ω～5.0 * 10
13Ω, leakage rate≤0.1 * 10
-10Pam
3/ s.
Table 1
| Component, performance perameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| SiO 2(mass percent) | 45 | 46 | 45 | 45 |
| B 2O 3(mass percent) | 15 | 16 | 15 | 16 |
| Al 2O 3(mass percent) | 10 | 9 | 12 | 13 |
| CaO (mass percent) | 10 | 9 | 10 | 8 |
| BaO (mass percent) | 15 | 16 | 15 | 15 |
| ZnO (mass percent) | 4.5 | 3.5 | 2.5 | 2.5 |
| Cr 2O 3(mass percent) | 0.5 | 0.5 | 0.5 | 0.5 |
| Density (g/cm 3) | 2.637 | 2.640 | 2.614 | 2.561 |
| Temperature of fusion (℃) | 1539 | 1539 | 1547 | 1558 |
| Clarifying temp (℃) | 1468 | 1458 | 1481 | 1491 |
| Thermal expansivity (10 -7/℃) (200～500℃) | 51.1 | 50.1 | 50.2 | 47.0 |
Claims (2)
1. high resistance glass for sealing metal, it is characterized in that: the quality percentage composition of high resistance glass component is: SiO
2: 35%～55%, Al
2O
3: 3%～17%, B
2O
3: 8%～20%, CaO:5%～15%, BaO:10%～25%, ZnO:0%～8%, Cr
2O
3: 0%～2%.
2. high resistance glass for sealing metal according to claim 1 is characterized in that: the quality percentage composition of high resistance glass preferred ingredient is: SiO
2: 42%～50%, Al
2O
3: 8%～15%, B
2O
3: 12%～18%, CaO:8%～12%, BaO:11%～16%, ZnO:0%～5%, Cr
2O
3: 0%～0.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101787029A CN101186442B (en) | 2007-12-04 | 2007-12-04 | A kind of high resistance glass for metal sealing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101787029A CN101186442B (en) | 2007-12-04 | 2007-12-04 | A kind of high resistance glass for metal sealing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101186442A CN101186442A (en) | 2008-05-28 |
| CN101186442B true CN101186442B (en) | 2010-12-08 |
Family
ID=39479103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101787029A Expired - Fee Related CN101186442B (en) | 2007-12-04 | 2007-12-04 | A kind of high resistance glass for metal sealing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101186442B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265176B (en) * | 2013-05-20 | 2015-10-14 | 京东方科技集团股份有限公司 | A kind of sealing glass ceramic, its method for sealing and purposes |
| CN106882922B (en) * | 2015-12-16 | 2019-09-27 | 辽宁省轻工科学研究院有限公司 | A kind of seal glass and preparation method thereof of resistance to 550 DEG C of high temperature |
| CN112624616B (en) * | 2021-01-06 | 2022-02-11 | 中国科学院新疆理化技术研究所 | A kind of glass ceramic material for encapsulating high temperature resistant vacuum thermistor and preparation method thereof |
| DE102023126243A1 (en) | 2023-09-27 | 2025-03-27 | Schott Ag | Use of a glass for passivating an electronic component and passivated electronic component |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4349635A (en) * | 1981-10-26 | 1982-09-14 | Motorola, Inc. | Lower temperature glass and hermetic seal means and method |
| JPS63107838A (en) | 1986-10-24 | 1988-05-12 | Matsushita Electric Works Ltd | Glass-ceramic sintered body |
| JPH0397634A (en) | 1989-06-15 | 1991-04-23 | Medtronic Inc | Glass-metal sealed article and apparatus consisting of electrochemical cell making use thereof, equipment and vessel capable of being embedded, and external lead wire |
| US5104755A (en) * | 1989-06-15 | 1992-04-14 | Medtronic, Inc. | Glass-metal seals |
| CN1413930A (en) * | 2002-09-26 | 2003-04-30 | 北京亚康特种玻璃有限责任公司 | Electronic component seal glass |
-
2007
- 2007-12-04 CN CN2007101787029A patent/CN101186442B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4349635A (en) * | 1981-10-26 | 1982-09-14 | Motorola, Inc. | Lower temperature glass and hermetic seal means and method |
| JPS63107838A (en) | 1986-10-24 | 1988-05-12 | Matsushita Electric Works Ltd | Glass-ceramic sintered body |
| JPH0397634A (en) | 1989-06-15 | 1991-04-23 | Medtronic Inc | Glass-metal sealed article and apparatus consisting of electrochemical cell making use thereof, equipment and vessel capable of being embedded, and external lead wire |
| US5104755A (en) * | 1989-06-15 | 1992-04-14 | Medtronic, Inc. | Glass-metal seals |
| CN1413930A (en) * | 2002-09-26 | 2003-04-30 | 北京亚康特种玻璃有限责任公司 | Electronic component seal glass |
Non-Patent Citations (4)
| Title |
|---|
| Smit.W.Moldelling of interdiffusion of alkali ions in glass surfaces electrical resistivity.Journal of Non-crystalline solids.1982,50(2),183-187. * |
| 刘联宝等.氧化物焊接配方.陶瓷-金属封接技术指南.国防工业出版社,1990,190-195页. * |
| 童震松、沈卓身.金属封接材料的现状及发展.电子与封接.2005,5(3),全文. * |
| 西北轻工业学院.玻璃的电学、磁学性质.玻璃工艺学.中国轻工业出版社,2007,126、127、130. * |
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| Publication number | Publication date |
|---|---|
| CN101186442A (en) | 2008-05-28 |
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