CN102452794A - Crystalline low-melting-point sealing glass and preparation method thereof - Google Patents
Crystalline low-melting-point sealing glass and preparation method thereof Download PDFInfo
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- CN102452794A CN102452794A CN2010105215321A CN201010521532A CN102452794A CN 102452794 A CN102452794 A CN 102452794A CN 2010105215321 A CN2010105215321 A CN 2010105215321A CN 201010521532 A CN201010521532 A CN 201010521532A CN 102452794 A CN102452794 A CN 102452794A
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Abstract
The invention relates to crystalline low-melting-point sealing glass and a preparation method thereof. The sealing glass consists of the following raw materials in percentage by weight: 50-70 percent of SiO2, 10-30 percent of ZnO, 1-10 percent of B2O3, 1-8 percent of CaO, 1-10 percent of Na2O, 1-10 percent of Li2O and 0.1-1 percent of Sb2O3. The preparation method comprises the following steps of: weighing, mixing, founding, tableting/quenching, ball milling and packing. The sealing glass has the advantages of high heat resistance, high chemical stability, high strength after sealing, superior electric performance and low expansion coefficient, and is suitable for silicon element encapsulation type molybdenum sealing.
Description
[technical field]
The present invention relates to the frit field, specifically, is a kind of crystal type low-melting point sealing glass and preparation method thereof.
[background technology]
Low-melting sealing glass is a kind of advanced person's a welding material; This material has lower temperature of fusion and sealing temperature (＜600 ℃); Good thermotolerance and chemicalstability; High physical strength is widely used in various fields such as electrovacuum and microelectronics, laser and infrared technique, high energy physics, the energy, aerospace, automobile, has realized the mutual sealing-in between glass, pottery, metal, semi-conductor.The product of using has CRD, vacuum fluorescent display, plasma display, vacuum glass, solar energy heat collection pipe, laser apparatus, magneticsubstance magnetic head and magneticsubstance film etc.
Because great majority are high pbo glass in the commercial seal glass that uses at present, lead is very harmful to human body and environment.American-European, day has all formulated the unleaded mandatory implementation date of electronic product.China Ministry of Information Industry has also issued relevant regulations.Therefore; The successful exploitation of nuisanceless low-melting sealing glass such as lead-free and cadmium-free will form the product technology barrier; The industry face that it relates to very extensively; Consumption is big, and industries such as China's household electrical appliances, precision parts, 3C (computingmachine, communication, consumer electronics product) electronic product are had crucial strategic importance.
In recent years, along with microelectronics, electronics show, the development of photoelectron technology, to the performance of sealing-in goods and technology require increasingly highly, also make the seal glass industry obtain certain development.Owing to reasons such as technical know-hows, much the document about seal glass all is confined to the research to the structure and the performance of seal glass system, and other aspect reports are less.In addition, the research of China aspect seal glass also has certain distance with Japan, Korea S, America and Europe, and except that a few kind, other are dependence on import all now.
The crystal type solder glass is meant complete crystallization or part crystallization in the sealing-in process; Adopt the advantage of crystal type seal glass: (1) can be separated out the kind and the quantity of crystalline phase through adjusting; Thereby regulate the coefficient of expansion and expansion characteristics greatly, make it with by the matched coefficients of thermal expansion of closure.(2) in the seal glass after the crystallization; The small crystal of many densifications is surrounded by thin glassy phase; The general crystallization phases coefficient of expansion is low, thereby glassy phase receives stress, and crystallization phases receives tension stress; And the intensity of fine and close crystallization phases is higher than glassy phase usually, and the total intensity of sealing layer is improved like this.In a single day in addition, glassy phase can play the effect of stress relaxation, even occur tiny crack in the glass coating, just is passivated but extend to the crystallization phases interface, suppressed the development of tiny crack.Thereby improve sealing strength, heat-shock resistance and chemicalstability.
The crystallinity seal glass is the seal, sealing materials that contains the stable crystalline body, and people liken the crystallinity seal glass to thermosetting material.This glass is after sealing-in, and reheat does not soften to comparatively high temps.In order to reach suitable crystal growth and maximum sealing strength, first sintering and curing cycle are extremely important.The method of use of crystallinity seal glass is that glass powder is processed the paste shape, adopts the method identical with the amorphism seal glass to carry out sealing-in then.When the crystallinity seal glass of heating powder shape, it at first is fused into glass, and this moment, its mobile fairly good can soak into the material that is sealed, and formed very strong bonding force, and when continuation was heated, glass began crystallization.Its crystalline size and type of generating of temperature decision of heating.Crystalline size and type determine the thermal expansivity of glass again.Therefore, under the different heating conditions, the final thermal expansivity of seal glass is also different.Under the temperature of regulation, time enough must be arranged, make the abundant crystallization of glass, otherwise during reheat, will cause sealing-in to burst because of producing stress.Sealing-in can be carried out being higher than under the temperature of crystallization, but the sealing strength of this moment descends significantly.
U.S. Pat 20020019303 has proposed a kind of seal glass of phosphor tin Zn system, 430 ℃～500 ℃ of sealing temperatures, but owing to contain a large amount of SnO; Need under reducing atmosphere, produce and sealing-in; Be unfavorable for commercial application, and the SnO cost is more expensive; Thereby the application of this seal glass has significant limitation.
USP P5153151 has announced a kind of phosphate seal glass, 300～340 ℃ of transition temperatures, thermal expansivity 135～180 * 10
-7/ ℃, the thermal expansivity of this glass is bigger, can not be used for, low-expansion sealing-in.
The spy of Hitachi opens flat 2-267137 and has announced a kind of vanadium oxide (V
2O
5) be seal glass, sealing temperature is less than 400 ℃, thermal expansivity 90 * 10
-7/ ℃ below, but in this glass, plumbous oxide is necessary component, can not satisfy unleaded requirement, simultaneously, also contains the oxide compound of hypertoxic thallium.
[summary of the invention]
The objective of the invention is to overcome the deficiency of existing low-melting point sealing glass, a kind of crystal type low-melting point sealing glass and preparation method thereof is provided, have low-expansion characteristics, be applicable to the sealing-in of silicon cell packaged type molybdenum.
The objective of the invention is to realize through following technical scheme:
A kind of crystal type low-melting point sealing glass, raw materials by weight consists of, SiO
2Be 50～70%, ZnO is 10～30%, B
2O
3Be 1～10%, CaO is 1～8%, Na
2O is 1～10%, Li
2O is 1～10%, Sb
2O
3Be 0.1～1%;
Described SiO
2Be preferably 55～65%, the best is 59%;
Described ZnO is preferably 15～25%, and the best is 19%;
Described B
2O
3Be preferably 3～7%, the best is 5%;
Described CaO is preferably 2～5%, and the best is 3%;
Described Na
2O is preferably 3～8%, and the best is 5.5%;
Described Li
2O is preferably 5～10%, and the best is 8%;
Described Sb
2O
3Be preferably 0.3～0.7%, the best is 0.5%;
Described SiO
2, ZnO, B
2O
3Summation be 70%～90%;
Described Na
2O, Li
2O, Sb
2O
3Summation be 10%～17%.
Each raw material of the present invention is CP level raw material, wherein SiO
2, ZnO, Sb
2O
3All introduce B with oxide compound
2O
3Introduce CaO, Na with boric acid
2O, Li
2O all introduces with the form of carbonate.
A kind of crystal type low-melting point sealing glass of the present invention and preparation method thereof may further comprise the steps:
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1200 ℃～1400 ℃ electric furnace, insulation 2～7h;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice or pours quenching in the cold water into;
(5) sheet or granular glass are put into the ball mill ball milling together;
(6) glass powder behind the ball milling is sieved, detects, packs.
The positively effect of a kind of crystal type low-melting point sealing glass of the present invention and preparation method thereof is:
(1) thermotolerance of the present invention, to change stability good;
(2) intensity after the sealing-in of the present invention is big;
(3) superior electrical property of the present invention.
[description of drawings]
The DSC curve of Fig. 1 embodiment 2.
[embodiment]
The embodiment of a kind of crystal type low-melting point sealing glass of the present invention and preparation method thereof below is provided.
Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The present invention adopts the heat effect in the TAS2100 type differential analysis appearance tested glass crystallization process of Japanese RIGAKU company; The free-running property that compares glass with the button experiment; Take by weighing 0.3g glass powder and place the pressing mold of the hollow cylindrical of 76YP-24B powder compressing machine; Apply the pressure of 30MPa, be pressed into drug sheet, place then on the bright and clean glass substrate; In electric furnace,, observe its free-running property by predetermined sealing temperature insulation 30min; Simultaneously seal glass is contrasted with metal sealing in atmosphere and protective atmosphere.
Fig. 1 is the DSC graphic representation of the glass sample of embodiment 2, among the figure, representes the transition temperature of solid glass with first heat absorption paddy starting point a; The pairing temperature of c point is called glass crystalline starting temperature, under this temperature, begins crystallization in the time of the glass nucleation; Along with the rising crystal of temperature increases gradually, and glassy phase constantly reduces, and the pairing temperature of exothermic peak d is called the crystallization summit temperature; This temperature representes that crystallization velocity reaches maximum temperature; Can find out that by Fig. 1 differential graphic representation and other glass of this group seal glass have very big difference, the tangible platform of none between heat absorption paddy and the exothermic peak; And between spacing very little, be the differential graphic representation of typical seal glass.
Must guarantee the glass solder fusing during sealing-in and have good flowability, could fully with by the seal, sealing materials infiltration contact, secondly after sealing-in, scolder has good thermotolerance, and is promptly before arriving heat-resistant limit, softening in advance.The eutectic sealing-in is under molten state; Must be to being sealed with good wettability by the material of sealing by fusing; Generally weigh, but for the crystal type glass solder, it makes it too early " freezing " because of crystallization is too fast and loses flowability in sealing-in heat-processed with the infiltration angle size of glass drop; So weigh with free-running property, it is a very important conventionally test index of glass solder and other material sealing-in.
Temperature is one of most important parameters in the glass-to-metal seal.Sealing temperature is too high, and closure is impaired easily, causes the closure quality to reduce; Sealing temperature is low excessively, and seal, sealing materials is difficult to carry out effectively fully sealing-in.For sealing-in, its maximum characteristic is that it has lower softening temperature, and sealing temperature is corresponding low.
Embodiment 1
One, the raw material composition is by weight percentage:
SiO
2Be 59%, ZnO is 19%, B
2O
3Be 5%, CaO is 3%, Na
2O is 5.5%, Li
2O is 8%, Sb
2O
3Be 0.5%.
Two, preparation method:
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1300 ℃ electric furnace, insulation 4h;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice or pours quenching in the cold water into;
(5) sheet or granular glass are put into the ball mill ball milling together;
(6) glass powder behind the ball milling is sieved, detects, packs.
Three, performance test:
Sealing temperature :≤600 ℃
Free-running property: 1.48/600 ℃
Sealing strength:＞5
Water-fast, oil resistant: sealing strength is constant
Thermal shocking: no abnormal phenomenon occurs.
Embodiment 2
One, the raw material composition is by weight percentage:
SiO
2Be 55%, ZnO is 21%, B
2O
3Be 7%, CaO is 2%, Na
2O is 5.6%, Li
2O is 9%, Sb
2O
3Be 0.4%.
Two, preparation method:
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1250 ℃ electric furnace, insulation 6h;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice or pours quenching in the cold water into;
(5) sheet or granular glass are put into the ball mill ball milling together;
(6) glass powder behind the ball milling is sieved, detects, packs.
Three, performance test:
Sealing temperature :≤600 ℃
Free-running property: 1.45/600 ℃
Sealing strength:＞5
Water-fast, oil resistant: sealing strength is constant
Thermal shocking: no abnormal phenomenon occurs.
Embodiment 3
One, the raw material composition is by weight percentage:
SiO
2Be 61%, ZnO is 16%, B
2O
3Be 4%, CaO is 3%, Na
2O is 6.3%, Li
2O is 9%, Sb
2O
3Be 0.7%.
Two, preparation method:
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1350 ℃ electric furnace, insulation 5h;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice or pours quenching in the cold water into;
(5) sheet or granular glass are put into the ball mill ball milling together;
(6) glass powder behind the ball milling is sieved, detects, packs.
Three, performance test:
Sealing temperature :≤600 ℃
Free-running property: 0.85/600 ℃
Sealing strength:＞5
Water-fast, oil resistant: sealing strength is constant
Thermal shocking: no abnormal phenomenon occurs.
Embodiment 4
One, the raw material composition is by weight percentage:
SiO
2Be 66%, ZnO is 11%, B
2O
3Be 5%, CaO is 3%, Na
2O is 5.4%, Li
2O is 9%, Sb
2O
3Be 0.6%.
Two, preparation method:
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1400 ℃ electric furnace, insulation 4h;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice or pours quenching in the cold water into;
(5) sheet or granular glass are put into the ball mill ball milling together;
(6) glass powder behind the ball milling is sieved, detects, packs.
Three, performance test:
Sealing temperature :≤600 ℃
Free-running property: 0.71/600 ℃
Sealing strength:＞5
Water-fast, oil resistant: sealing strength is constant
Thermal shocking: no abnormal phenomenon occurs.
It should be noted last that: above embodiment only is illustrative rather than definitive thereof technical scheme of the present invention; Although the present invention is specified with reference to the foregoing description; Those of ordinary skill in the art is to be understood that; Still can make amendment or be equal to replacement the present invention, and not break away from any modification or the local replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (10)
1. a crystal type low-melting point sealing glass is characterized in that raw materials by weight consists of, SiO
2Be 50～70%, ZnO is 10～30%, B
2O
3Be 1～10%, CaO is 1～8%, Na
2O is 1～10%, Li
2O is 1～10%, Sb
2O
3Be 0.1～1%.
2. a kind of crystal type low-melting point sealing glass as claimed in claim 1 is characterized in that described SiO2 is 55～65%, and described ZnO is 15～25%.
3. a kind of crystal type low-melting point sealing glass as claimed in claim 2 is characterized in that described SiO
2Be 59%, described ZnO is 19%.
4. a kind of crystal type low-melting point sealing glass as claimed in claim 1 is characterized in that described B
2O
3Be 3～7%, described CaO is 2～5%.
5. a kind of crystal type low-melting point sealing glass as claimed in claim 4 is characterized in that described B
2O
3Be 5%, described CaO is 3%.
6. a kind of crystal type low-melting point sealing glass as claimed in claim 1 is characterized in that described Na
2O is 3～8%, described Li
2O is 5～10%, described Sb
2O
3Be 0.3～0.7%.
7. a kind of crystal type low-melting point sealing glass as claimed in claim 6 is characterized in that described Na
2O is 5.5%, described Li
2O is 8%, described Sb
2O
3Be 0.5%.
8. a kind of crystal type low-melting point sealing glass as claimed in claim 1 is characterized in that described SiO
2, ZnO, B
2O
3Summation be 70%～90%.
9. a kind of crystal type low-melting point sealing glass as claimed in claim 1 is characterized in that described Na
2O, Li
2O, Sb
2O
3Summation be 10%～17%.
10. the preparation method of a crystal type low-melting point sealing glass is characterized in that, comprises the steps:
(1) weight percent according to each component takes by weighing each raw material;
(2) with the raw material thorough mixing that is taken by weighing;
(3) mixed compound is put into crucible, put into furnace temperature then and be 1200 ℃～1400 ℃ electric furnace, insulation 2～7h;
(4) glass metal after will melting is poured tabletting machine into and is pressed into thin slice or pours quenching in the cold water into;
(5) sheet or granular glass are put into the ball mill ball milling together;
(6) glass powder behind the ball milling is sieved, detects, packs.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105215321A CN102452794A (en) | 2010-10-27 | 2010-10-27 | Crystalline low-melting-point sealing glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105215321A CN102452794A (en) | 2010-10-27 | 2010-10-27 | Crystalline low-melting-point sealing glass and preparation method thereof |
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|---|---|
| CN102452794A true CN102452794A (en) | 2012-05-16 |
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ID=46036537
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539354A (en) * | 2013-10-25 | 2014-01-29 | 上海大学 | Frit composition of sealed light-emitting device, as well as preparation method and air-tight sealing method |
| CN103553336A (en) * | 2013-10-25 | 2014-02-05 | 上海大学 | Sealing material for air-tight sealing and preparation method thereof, and air-tight sealing method |
| CN107021635A (en) * | 2017-04-26 | 2017-08-08 | 苏州融睿电子科技有限公司 | Glass solder and preparation method thereof |
| CN112791801A (en) * | 2020-12-18 | 2021-05-14 | 中国振华集团云科电子有限公司 | Method for improving quality consistency of glass powder |
| CN115521072A (en) * | 2022-04-07 | 2022-12-27 | 西北工业大学 | Sealing glass for tantalum metal and preparation method thereof |
-
2010
- 2010-10-27 CN CN2010105215321A patent/CN102452794A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539354A (en) * | 2013-10-25 | 2014-01-29 | 上海大学 | Frit composition of sealed light-emitting device, as well as preparation method and air-tight sealing method |
| CN103553336A (en) * | 2013-10-25 | 2014-02-05 | 上海大学 | Sealing material for air-tight sealing and preparation method thereof, and air-tight sealing method |
| CN107021635A (en) * | 2017-04-26 | 2017-08-08 | 苏州融睿电子科技有限公司 | Glass solder and preparation method thereof |
| CN112791801A (en) * | 2020-12-18 | 2021-05-14 | 中国振华集团云科电子有限公司 | Method for improving quality consistency of glass powder |
| CN115521072A (en) * | 2022-04-07 | 2022-12-27 | 西北工业大学 | Sealing glass for tantalum metal and preparation method thereof |
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Application publication date: 20120516 |