CN110451805A - Seal glass - Google Patents
Seal glass Download PDFInfo
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- CN110451805A CN110451805A CN201910886572.7A CN201910886572A CN110451805A CN 110451805 A CN110451805 A CN 110451805A CN 201910886572 A CN201910886572 A CN 201910886572A CN 110451805 A CN110451805 A CN 110451805A
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- glass
- seal glass
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Classifications
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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 present invention provides a kind of seal glass with higher electric resistivity, lower sealing temperature, and the composition of the seal glass is indicated with mol%, contains V2O5: 10~20%；TeO2: 35~60%；PbO:15~40%；PbF2: 4~15%.It is designed by reasonable component, the seal glass that the present invention obtains resistivity with higher and lower sealing temperature can be widely applied to the sealing-in in the fields such as semiconductor, microelectric technique, new energy.
Description
Technical field
The present invention relates to glass arts, more particularly, to a kind of envelope suitable for semiconductor, microelectric technique, new energy etc.
Connect glass.
Background technique
Seal glass is the middle layer glass for referring to glass, ceramics, metal and composite material to seal up each other,
It is a kind of advanced welding material.Because low temperature sealing glass has lower sealing temperature, good stability and mechanicalness
The performances such as energy, lower conductivity and magnetic conductivity, are widely used in electrovacuum and microelectric technique, aerospace, new energy
Etc. various fields.
PbO-B is mainly used in the prior art2O3-SiO2、PbO-ZnO-B2O3、Bi2O3-B2O3The systems such as-ZnO preparation envelope
Glass is connect, there is resistivity height, good chemical stability, but sealing temperature is generally all higher.Sealing temperature is relatively low
Seal glass, because of V2O5Constituent content is higher, or introduces the components such as alkali metal, so that glass resistor rate is smaller, insulated electro is thwarted
To meet the sealing-in requirement of some devices.As although CN101289279A realizes lower sealing temperature, but contain in its component
There is the V of 25~55mol%2O5, and a certain amount of alkali metal oxide is introduced, the resistivity of glass will drop to 107Ω m with
Under.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of sealing-in glass with higher electric resistivity, lower sealing temperature
Glass.
The present invention solve technical problem the technical solution adopted is that: seal glass, composition indicated with mol%, contain:
V2O5: 10~20%；TeO2: 35~60%；PbO:15~40%；PbF2: 4~15%.
Further, the seal glass, composition is indicated with mol%, is also contained: ZnO:0~7%；B2O3: 0~
10%.
Seal glass, composition is indicated with mol%, by V2O5: 10~20%；TeO2: 35~60%；PbO:15~40%；
PbF2: 4~15%；ZnO:0~7%；B2O3: 0~10% composition.
Further, the seal glass, composition are indicated with mol%, in which: V2O5: 12~18%；And/or
TeO2: 35~50%；And/or PbO:20~35%；And/or PbF2: 7~15%；And/or ZnO:0~5%；And/or B2O3: 0
~5%.
Further, the seal glass, composition are indicated with mol%, in which: V2O5/TeO2It is 0.20~0.45,
It is preferred that V2O5/TeO2It is 0.25~0.40.
Further, the seal glass, composition are indicated with mol%, in which: PbF2/(PbF2+ PbO) be 0.15~
0.45, preferably PbF2/(PbF2+ PbO) it is 0.20~0.40.
Further, the resistivity of the seal glass is 1.0 × 109Ω m or more, preferably 1.0~95.0 × 109
Ω m, more preferably 24.0~83.0 × 109Ω·m。
Further, the sealing temperature of the seal glass is for 370 DEG C hereinafter, preferably 365 DEG C hereinafter, more preferably
300~360 DEG C, further preferably 300~350 DEG C.
Further, the softening temperature of the seal glass is for 300 DEG C hereinafter, preferably 280 DEG C hereinafter, more preferably
225~275 DEG C, further preferably 225~265 DEG C.
Further, the coefficient of expansion of the seal glass is 220 × 10-7/ DEG C hereinafter, preferably 155~210 × 10-7/℃。
The beneficial effects of the present invention are: being designed by reasonable component, the seal glass that the present invention obtains is with higher
Resistivity and lower sealing temperature, can be widely applied to the sealing-in in the fields such as semiconductor, microelectric technique, new energy.
Specific embodiment
In the following, the embodiment of seal glass of the invention is described in detail, but the present invention is not limited to following realities
Mode is applied, change appropriate can be carried out in the range of the object of the invention to be implemented.In addition, about repetitive specification,
Although there is the case where omitting the description appropriate, but not therefore limit the purport invented.Sometimes this is sent out in the following contents
Bright seal glass is referred to as glass.
Each component (composition) range of seal glass of the present invention is illustrated below.In the present specification, if do not had
Specified otherwise, the content of each component all use molar percentage (mol%) to indicate.Unless in particular situations it is further noted that
Listed numberical range includes upper and lower bound value in the present invention and this specification, " more than " and " following " include endpoint value,
And including all integers and score in the range, and it is not limited to occurrence listed when limited range.It is herein referred
"and/or" is inclusive, such as " A；And/or B ", refer to only A, perhaps only B or has A and B simultaneously.
V2O5It is the Network former of glass in the present invention.V2O5Glass cannot be independently formed, but can be with many oxidations
Object is formed together glass, and has bigger forming area of glass.Vanadium ion is with VO6Octahedral form enters glass
Network structure can be significantly reduced the fusion temperature and the coefficient of expansion of glass, pass through the V of 10% or more introducing in the present invention2O5With
Obtain said effect, preferably V2O5Content 12% or more.V2O5The mobility that will lead to glass when content is excessive reduces, and
Volume resistivity reduces, therefore V is controlled in the present invention2O5Content 20% hereinafter, it is preferred that below 18%.
TeO2It is also a kind of glass former, with V2O5It is combined with very big glass formation regions.Pass through introducing in the present invention
35% or more TeO2To improve the devitrification resistance energy of glass；Work as TeO2Content is more than 60%, the softening temperature of glass and expansion system
Number increases.Therefore in the present invention, TeO2Content range be 35~60%, preferred scope be 35~50%.
In some embodiments, V is controlled2O5And TeO2Introducing ratio V2O5/TeO2It, can in 0.20~0.45 range
Reduce the softening temperature of glass, preferably V2O5/TeO2It is 0.25~0.40.
PbO is a part of with extra-network ion Pb in glass2+Into glass structure, a part is with [PbO4] pyramid into
Enter network, under conditions of unobvious raising glass transition temperature, can improve glass at stability, glass, and improve glass
Resistivity, the present invention in by introduce 15% or more PbO to obtain said effect.When the content of PbO is more than 40%, glass
Softening temperature rise, it is difficult to meet design requirement.Therefore, the content of PbO is 15~40%, and preferred scope is 20~35%.
PbF2Suitable F is introduced in glass-, effect be interrupt glass network structure bridging oxygen it is strong, reach reduction glass
The purpose of sealing temperature.But with F-The coefficient of expansion of the increase of introduction volume, glass will increase, and mechanical strength reduces, and chemistry is steady
Qualitative variation, resistivity are also substantially reduced, and are unfavorable for improving the insulation resistance of glass.Therefore, PbF in the present invention2Content be 4
~15%, preferably 7~15%.
In some embodiments, by making PbF2With PbO and PbF2Total content (PbF2+ PbO) introducing ratio
PbF2/(PbF2+ PbO) in 0.15~0.45 range, glass volume resistivity with higher and lower softening temperature are excellent
Select PbF2/(PbF2+ PbO) 0.20~0.40.
ZnO has inhibition devitrification of glass in glass, reduces glass expansion coefficient, improves glass machinery intensity, improves glass
The effect of glass chemical stability.When its content is more than 7%, the softening temperature of glass is increased.Therefore, ZnO content is 0 in the present invention
~7%, preferably 0~5%.
B2O3Have in glass and inhibit devitrification of glass, reduce glass expansion coefficient, improve glass machinery intensity, improves glass
The effect of glass chemical stability.When its content is more than 10%, the softening temperature of glass is increased.Therefore, B in the present invention2O3Content is
0~10%, preferably 0~5%.
In the present invention, to obtain excellent resistivity, preferably do not introduce in some embodiments alkali metal oxide or
Alkali metal fluoride, the alkali metal oxide refer to that the oxide of Li, Na, K, Rb, Cs etc., the alkali metal fluoride refer to
The fluoride of Li, Na, K, Rb, Cs etc..
" 0% " described herein, which refers to, is not deliberately added to this as raw material for the compound, molecule or element etc.
In invention glass, but raw material and/or equipment as production glass, can exist certain is not the impurity deliberately added or group
Point, a small amount of or trace it can contain in final glass, such situation is also in the scope of protection of the patent of the present invention.
In the following, being illustrated to the performance of seal glass of the invention.
<coefficient of expansion>
The coefficient of expansion of seal glass of the present invention tests 20~120 DEG C according to method as defined in GB/T 7962.16-2010
Data.The heretofore described coefficient of expansion is linear expansion coefficient.
In certain embodiments of the present invention, the coefficient of expansion (α) of seal glass is 220 × 10-7/ DEG C hereinafter, it is preferred that
It is 155~210 × 10-7/℃。
<softening temperature>
The softening temperature of seal glass of the present invention is tested according to method as defined in SJ690-83.
In certain embodiments of the present invention, the softening temperature of seal glass be 300 DEG C hereinafter, preferably 280 DEG C with
Under, more preferably 225~275 DEG C, further preferably 225~265 DEG C.
<resistivity>
The test method of the resistivity of seal glass of the present invention are as follows: by glass processing at the glass sample of 30 × 30 × 5mm,
It is tested with volumetric surface resistance meter (model ATI-212), test voltage 1000V.Resistivity of the present invention is
Volume resistivity.
In certain embodiments of the present invention, the resistivity of seal glass is 1.0 × 109Ω m or more, preferably
1.0~95.0 × 109Ω m, more preferably 24.0~83.0 × 109Ω·m。
<sealing temperature>
The sealing temperature of seal glass of the present invention is tested according to method as defined in SJ/T 3231-2005.
In certain embodiments of the present invention, the sealing temperature of seal glass be 370 DEG C hereinafter, preferably 365 DEG C with
Under, more preferably 300~360 DEG C, further preferably 300~350 DEG C.
[manufacturing method of seal glass]
The manufacturing method of seal glass of the present invention is as follows: after each component is weighed finished in proportion containing content of starting materials, sufficiently
Be uniformly mixed, investment melting appartus (such as silica crucible or ceramic crucible) in, in 500~600 DEG C of at a temperature of material, material
Time 30~60 minutes.After raw material sufficiently melts, glass metal is stirred with ceramic rod, is poured into cast iron die,
It after cooling and shaping, is put into Muffle furnace and anneals, obtain seal glass.
Embodiment
In order to further clearly illustrate and illustrate technical solution of the present invention, non-limiting embodiment below is provided.
The present embodiment obtains having the seal glass formed shown in 1~table of table 2 using the manufacturing method of above-mentioned seal glass.
In addition, the test method measures the characteristic of each glass through the invention, and test result is indicated in 1~table of table 2.
Table 1
Table 2
Claims (10)
1. seal glass, which is characterized in that its composition is indicated with mol%, is contained: V2O5: 10~20%；TeO2: 35~60%；
PbO:15~40%；PbF2: 4~15%.
2. seal glass as described in claim 1, which is characterized in that its composition is indicated with mol%, is also contained: ZnO:0~
7%；B2O3: 0~10%.
3. seal glass, which is characterized in that its composition is indicated with mol%, by V2O5: 10~20%；TeO2: 35~60%；PbO:
15~40%；PbF2: 4~15%；ZnO:0~7%；B2O3: 0~10% composition.
4. the seal glass as described in claims 1 to 3 any claim, which is characterized in that its composition indicates with mol%,
Wherein: V2O5: 12~18%；And/or TeO2: 35~50%；And/or PbO:20~35%；And/or PbF2: 7~15%；With/
Or ZnO:0~5%；And/or B2O3: 0~5%.
5. the seal glass as described in claims 1 to 3 any claim, which is characterized in that its composition indicates with mol%,
Wherein: V2O5/TeO2It is 0.20~0.45, preferably V2O5/TeO2It is 0.25~0.40.
6. the seal glass as described in claims 1 to 3 any claim, which is characterized in that its composition indicates with mol%,
Wherein: PbF2/(PbF2+ PbO) it is 0.15~0.45, preferably PbF2/(PbF2+ PbO) it is 0.20~0.40.
7. the seal glass as described in claims 1 to 3 any claim, which is characterized in that the resistance of the seal glass
Rate is 1.0 × 109Ω m or more, preferably 1.0~95.0 × 109Ω m, more preferably 24.0~83.0 × 109Ω·m。
8. the seal glass as described in claims 1 to 3 any claim, which is characterized in that the sealing-in of the seal glass
Temperature is for 370 DEG C hereinafter, preferably 365 DEG C hereinafter, more preferably 300~360 DEG C, further preferably 300~350 DEG C.
9. the seal glass as described in claims 1 to 3 any claim, which is characterized in that the softening of the seal glass
Temperature is for 300 DEG C hereinafter, preferably 280 DEG C hereinafter, more preferably 225~275 DEG C, further preferably 225~265 DEG C.
10. the seal glass as described in claims 1 to 3 any claim, which is characterized in that the expansion of the seal glass
Coefficient is 220 × 10-7/ DEG C hereinafter, preferably 155~210 × 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110451805A true CN110451805A (en) | 2019-11-15 |
| CN110451805B CN110451805B (en) | 2021-11-26 |
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ID=68492368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910886572.7A Active CN110451805B (en) | 2019-09-19 | 2019-09-19 | Sealing glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110451805B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114180843A (en) * | 2021-12-28 | 2022-03-15 | 海南大学 | Sealing glass and preparation method thereof |
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 |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114180843A (en) * | 2021-12-28 | 2022-03-15 | 海南大学 | Sealing glass and preparation method thereof |
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| Publication number | Publication date |
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| CN110451805B (en) | 2021-11-26 |
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