CN102276152A - Composition for metallization of alumina ceramic surface - Google Patents
Composition for metallization of alumina ceramic surface Download PDFInfo
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- CN102276152A CN102276152A CN201110175857A CN201110175857A CN102276152A CN 102276152 A CN102276152 A CN 102276152A CN 201110175857 A CN201110175857 A CN 201110175857A CN 201110175857 A CN201110175857 A CN 201110175857A CN 102276152 A CN102276152 A CN 102276152A
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Abstract
The invention provides slurry for reducing sheet resistance of tungsten metallization layers of alumina ceramics and a preparation process thereof, belonging to the technical field of ceramic-to-metal seal. A tungsten metallization layer comprises tungsten powder and a glass phase. According to the invention, good gradation of tungsten powder and compact piling of tungsten particles are formed mainly by changing particle size distribution of tungsten powder; ultrafine glass powder prepared by the sol-gel method is added at the same time, and after the glass powder is fused in the process of sintering, tungsten particles are enabled to be rearranged rapidly and to fill gaps effectively, thereby promoting densification of the tungsten metallization layer. The invention enables the density of an alumina ceramic tungsten metallization layer to be improved substantially and surface sheet resistance of the tungsten metallization layer to be reduced to 7 to 9 m omega per square, and is mainly applicable to packaging housings for hybrid integrated circuits, millimeter wave/micron wave integrated circuits, multi-chip modules and high power devices in microelectronic packaging.
Description
Technical field
The invention belongs to ceramic-metal sealing technology field, relate to and be used for Al
2O
3Formula of size of ceramic surface tungsten metallization and preparation method thereof.Mainly containing the content of two aspects, at first is to adopt the tungsten powder of certain grating to guarantee metal layer lower porosity to be arranged; Next is to adopt sol-gel method to prepare the glass powder of ultra-fine grain, promotes the densification of tungsten metallization layer, thereby reduces surface side's resistance of tungsten metallization layer.
Background technology
Al
2O
3Pottery has the physical strength height, and insulation resistance is big, and the coefficient of expansion and chip characteristic such as be complementary is modal baseplate material in microelectronics Packaging field or encapsulating housing material.In order to make electron device or encapsulating housing have high strength and high-air-tightness, Al
2O
3Pottery often need carry out soldering with package metals such as kovar alloys.And common metal solder and Al
2O
3The pottery wettability is poor, so need be at Al
2O
3Ceramic surface metallizes, and one of modal method is burnt the tungsten metallization layer altogether on its surface exactly, will have the Al of tungsten metallization layer then
2O
3Pottery carries out electroplated Ni or Au, so just can adopt traditional solder brazing Al such as Ag-Cu
2O
3Pottery and kovar alloy, thus level Hermetic Package obtained.
The tungsten metallization layer of alumina-ceramic mainly is made up of tungsten powder and glass powder, wherein the quality percentage composition of tungsten powder is about 95 ~ 97%, its size range is 0.2 μ m ~ 10 μ m, and glass powder contains 3 ~ 5% approximately, and the main effect of glassy phase is the effect that connects tungsten powder and aluminium oxide ceramic substrate.The traditional technological process of alumina-ceramic tungsten metallization is: each powder is by the burning → metallized product performance test altogether of slurry → silk screen printing → under atmosphere protection that obtains metallizing of proportioning mixing and ball milling → adding additives.
Alumina-ceramic tungsten metallization slurry glassy phase commonly used is generally the silicate glass material of high softening-point.The common preparation method of glass powder is the glass powder sintering process, and the fusion process temperature of sintering process is higher, and some component volatilization easily causes departing from of composition, and the glass of making is very difficult levigate, and the glass powder particle diameter made from sintering process is about 5 μ m.
Because the tungsten powders that adopt a kind of granularity of the tungsten powder in the traditional method more, and the particle size of glass powder with the sintering process preparation is bigger, thus there are defectives such as structure is not fine and close, porosity height with the tungsten metallization layer of traditional method preparation, as shown in Figure 1, its side's resistance is higher, is about 10 ~ 20 m Ω/.
Along with the continuous development of microelectronic packaging technology, the performance of the tungsten metallization layer of traditional method preparation can't satisfy the requirement of resistance to air loss or surface side resistance so Al
2O
3The density of ceramic surface metallization layer and the resistance of surface side just become the key factor that influences its use.Although by changing the density that technology that ceramic-metal burns altogether can improve metal layer to a certain extent, can not fundamentally solve the low and surface side of its density and hinder high problem.
Summary of the invention
The present invention seeks to and to prepare the density that two kinds of approach of ultra-fine grain glass powder improve the tungsten metallization layer by grating and the employing novel method that changes tungsten powder, improve its side's resistance.The present invention solves Al by the grain composition dual mode for preparing glass powder and adjustment tungsten powder with sol-gel method
2O
3Low and the high shortcoming of side's resistance of ceramic surface tungsten metallization layer density, its preparation method is simple simultaneously, and good repeatability is arranged, and is suitable for suitability for industrialized production.
Technical scheme of the present invention is:
(1) composition of the surperficial tungsten metallization layer of a kind of alumina-ceramic is characterized in that it is made of following metallizing formula: 95% ~ 97% tungsten powder is arranged by weight percentage, 3% ~ 5% MgO-Al
2O
3-SiO
2Glass powder.
(2) tungsten powder that adopts two kinds of different grain sizes to distribute represents with A and B that respectively wherein the D50 of A is 0.8 ~ 1.2 μ m, B for D50 is 2 ~ 3 μ m., the weight percent of A and B is respectively 30% ~ 50% and 50% ~ 70%.
The unsound major cause of metal layer is that the tungsten powder particles grating is improper, there are many spaces in inside, the present invention is by regulating the ratio row of two kinds of tungsten powders, make tungsten powder form good grating, space between the macrobead is well filled by small-particle, make between the tungsten particle to form tightly packedly, reduce the metal layer porosity effectively, thereby reduce the resistance of metal layer side.
(3) MgO-Al of the present invention's use
2O
3-SiO
2Glass powder, the content of each oxide compound has by weight percentage: 61% ~ 63% SiO
2, 19% ~ 21%MgO, 16% ~ 18% Al
2O
3, the particle diameter of glass powder is 0.5 ~ 1 μ m.
(4) MgO-Al of the present invention's use
2O
3-SiO
2Glass powder is prepared by sol-gel method, and its preparation method is:
1) calculates weighing magnesium nitrate hexahydrate, nine water aluminum nitrate and tetraethoxys by the amount of each oxide compound in the preparation powder;
2) magnesium nitrate hexahydrate, nine water aluminum nitrates are dissolved in dehydrated alcohol respectively, the ethanol consumption reaches magnesium nitrate hexahydrate, the dissolving of nine water aluminum nitrates is got final product: join in the tetraethoxy magnesium nitrate and aluminum nitrate solution and stirring, made mixing solutions prehydrolysis 8 ~ 12 minutes;
3) with above-mentioned solution 80 ℃ ~ 90 ℃ water-baths, stir to form vitreosol, static back forms gel;
4) with gel 60 ℃ ~ 70 ℃ dryings, ball milling is 3 ~ 4 hours then, obtains dry gel powder;
5) with the dry gel powder that obtains 650 ℃ ~ 750 ℃ calcinings, obtain MgO-Al
2O
3-SiO
2Glass powder.
During the Prepared by Sol Gel Method powder, can be at the material of lower temperature synthetic molecules level, it is accurate to have chemical constitution, the purity height, advantage such as homogeneity is strong, and also the synthetic diameter of particle is controlled easily, can make the glass powder of suitable particle size, it can make tungsten particle arrange rapidly and intensive effectively filling space in sintering process again after fusion, promote the densification of rete, finally causes the reduction of rete side's resistance.
After obtaining tungsten powder and glass powder, can be according to Al
2O
3The process system of ceramic surface tungsten metallization is prepared, and its concrete technology is: above-mentioned raw materials is weighed, mixed in the ratio of metallizing formula, is medium with the dehydrated alcohol, places the planetary ball mill ball milling 12 hours, then dry for standby; With the metallization powder for preparing, add an amount of organic binder bond, ball milling 72 hours mixes it, obtains the tungsten metallization slurry.Method with silk screen printing covers on the aluminium oxide ceramics green ceramic chip then; To be coated with ceramic chips sintering under wet hydrogen atmosphere of metallization powder, dew point of hydrogen is in 20 ± 10 ℃ of scopes, and 1600 ℃ of sintering temperatures are incubated 40 ~ 60min.
The present invention compares with existing tungsten metallization slurry, being used of the tungsten powder that distributes by two kinds of different grain sizes, add the density that has significantly increased the tungsten metallization layer with the palladium powder of Prepared by Sol Gel Method simultaneously, the side's resistance with the tungsten metallization layer simultaneously is reduced to 7 ~ 9 m Ω/.
Figure of description
Fig. 1 prepares the micro-structure diagram of alumina-ceramic tungsten metallization layer for traditional method;
The sem photograph of the glass powder that Fig. 2 makes with sol-gel method for the present invention;
The XRD diffractogram of the glass powder that Fig. 3 makes with sol-gel method for the present invention;
Fig. 4 is the micro-structure diagram of the alumina-ceramic tungsten metallization layer of the method for the invention preparation;
Fig. 5 is the surface topography map of the alumina-ceramic tungsten metallization layer of the method for the invention preparation.
Embodiment
Below in conjunction with embodiment the present invention is done detailed explanation.
Embodiment is as follows:
Embodiment 1: the prescription of present embodiment consists of: 20.6 MgO, 17.5 Al
2O
3, 62.0 SiO
2, all be weight percentage.
By oxide aggregate is 20g, calculates the also required magnesium nitrate hexahydrate of weighing, nine water aluminum nitrate and tetraethoxys.Magnesium nitrate hexahydrate, nine water aluminum nitrates are dissolved in dehydrated alcohol respectively, and the ethanol consumption reaches magnesium nitrate hexahydrate, the dissolving of nine water aluminum nitrates is got final product: join in the tetraethoxy magnesium nitrate and aluminum nitrate solution and stirring, made mixing solutions prehydrolysis 10 minutes.With 90 ℃ of water-baths of above-mentioned solution, constantly the viscosity that stirs up to solution obviously increases, and forms gel.Gel 60 ℃ of dryings, is ground to powdery with block xerogel.With making abrading-ball with the agate ball of dry gel powder equivalent weight, ball milling 4 hours, taking-up is 700 ℃ of calcinings down, obtain the said glass powder of the present invention, as Fig. 2 is the sem photograph of glass powder, glass powder has certain reunion as can be seen, and its diameter of particle is about 0.5 ~ 1 μ m, significantly is lower than glass powder particle diameter 2 ~ 5 μ m that traditional melting mode prepares.The XRD diffracting spectrum of the glass powder that Fig. 3 makes with sol-gel method for the present invention, diffraction peak is tangible steamed bun peak among the figure, does not have the crystalline diffraction peak, the powder that hence one can see that makes is a glass.
Embodiment 2: surface side's resistance of used tungsten powder prescription (weight percent) and metal layer is as shown in table 1.Specific implementation process is (is example with the 2# sample):
Surface side's resistance of the proportioning of several tungsten powders of table 1 and tungsten metallization layer
| Specimen coding | 1# | 2# | 3# | 4# |
| A content (%) | 30．00 | 38.04 | 45.00 | 50.00 |
| B content (%) | 70.00 | 61.96 | 55.00 | 50.00 |
| The resistance of surface side | 8.66 | 7.94 | 7.13 | 7.58 |
Take by weighing two kinds of tungsten powders of A, B 97g altogether by 3# sample in the table 1, will add the glass powder that makes among the 3g embodiment 1 in the load weighted tungsten powder, obtain the mixture of tungsten powder and glass powder, powder promptly metallizes.The powder that will metallize places ball grinder, makes medium with dehydrated alcohol, makes abrading-ball with alumina balls, and ball milling 12 hours takes out and places the loft drier oven dry.
The metallization powder that mixes is added the 20g organic binder bond, and organic binder bond is a terpineol solution of ethyl cellulose, makes abrading-ball with tungsten-carbide ball, and ball milling obtained the tungsten metallization slurry in 72 hours.
Method with silk screen printing is printed on the above-mentioned slurry for preparing on the aluminium oxide ceramics green ceramic chip, and with ceramic chips sintering under wet hydrogen atmosphere, dew point of hydrogen is in 20 ± 10 ℃ of scopes, and 1600 ℃ of sintering temperatures are incubated 40 ~ 60min.
Sample is carried out performance test, the surface side's resistance that obtains the tungsten metallization layer of 3# sample is 7.13 m Ω/, significantly be lower than side's resistance 10 ~ 20 m Ω/ of present tungsten metallization layer, so can obviously reduce the resistance of metal layer side with tungsten metallization slurry provided by the invention.
Fig. 1 is the ceramic metallized layer microstructure electromicroscopic photograph that is obtained by traditional method, and there are a lot of holes in tungsten metallization layer short texture as can be seen.Fig. 4 and Fig. 5 are respectively the microtexture and the surface topography map of 3# sample, tungsten metallization layer and Al as can be seen
2O
3Pottery is in conjunction with tight, and tungsten metallization layer compact structure, combines closely between the tungsten particle, and porosity is very low.
Claims (2)
1. the composition of an alumina-ceramic surface metalation is characterized in that the composition of alumina-ceramic surface metalation is made of following metallizing formula: 95% ~ 97% tungsten powder is arranged by weight percentage, 3% ~ 5% MgO-Al
2O
3-SiO
2Glass powder; The tungsten powder that tungsten powder adopts two kinds of different grain sizes to distribute represents with A and B that respectively wherein the D50 of A is 0.8 ~ 1.2 μ m, B for D50 is 2 ~ 3 μ m, the weight percent of A and B is respectively 30% ~ 50% and 50% ~ 70%; Glass powder has 61% ~ 63% SiO by weight percentage
2, 19% ~ 21%MgO, 16% ~ 18% Al
2O
3, the particle diameter of glass powder is 0.5 ~ 1 μ m.
2. the composition of a kind of alumina-ceramic surface metalation as claimed in claim 1 is characterized in that adopting sol-gel method to prepare MgO-Al
2O
3-SiO
2Glass powder; Preparation process is:
(1) presses MgO-Al
2O
3-SiO
2The amount of each oxide compound is calculated weighing magnesium nitrate hexahydrate, nine water aluminum nitrate and tetraethoxys in the glass powder;
(2) magnesium nitrate hexahydrate, nine water aluminum nitrates are dissolved in dehydrated alcohol respectively, the ethanol consumption reaches and makes magnesium nitrate hexahydrate, the dissolving of nine water aluminum nitrates: join in the tetraethoxy magnesium nitrate and aluminum nitrate solution and stirring, made mixing solutions prehydrolysis 10 minutes;
(3) with above-mentioned solution 80 ℃ ~ 90 ℃ water-baths, stir to form vitreosol, static back forms gel;
(4) with gel 60 ℃ ~ 70 ℃ dryings, ball milling 3 ~ 4 hours obtains dry gel powder;
(5) with the dry gel powder that obtains 650 ℃ ~ 750 ℃ calcinings, obtain MgO-Al
2O
3-SiO
2Glass powder.
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|---|---|---|---|
| CN 201110175857 CN102276152B (en) | 2011-06-28 | 2011-06-28 | Composition for metallization of alumina ceramic surface |
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| CN 201110175857 CN102276152B (en) | 2011-06-28 | 2011-06-28 | Composition for metallization of alumina ceramic surface |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314467A (en) * | 2018-04-11 | 2018-07-24 | 甘肃恒星特种陶瓷有限公司 | Heavy ion avcceleration ceramic-vacuum tube surface conductance layer formula and preparation method |
| CN109734480A (en) * | 2019-02-27 | 2019-05-10 | 常州联德陶业有限公司 | A kind of aluminium nitride ceramics heater cofiring high temperature exothermic slurry and preparation method thereof |
| CN115255347A (en) * | 2022-06-30 | 2022-11-01 | 南昌大学 | Tungsten-silicate micro zero-valent iron material and preparation method and application thereof |
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|---|---|---|---|---|
| CN1121499A (en) * | 1994-08-02 | 1996-05-01 | 住友电气工业株式会社 | Metallized ceramic substrate having smooth plating layer and method for producing the same |
| CN1887814A (en) * | 2006-07-16 | 2007-01-03 | 常熟市银洋陶瓷器件有限公司 | Powder for ceramic metallizing paste and its prepn |
| CN101200348A (en) * | 2007-12-21 | 2008-06-18 | 天津大学 | CaO-B2O3-SiO2 glass powder and preparation method |
| CN101318223A (en) * | 2008-07-14 | 2008-12-10 | 中南大学 | Method for manufacturing heavy pressure blank strength tungsten powder with ammonium metatungstate and ammonium paratungstate |
| CN101774826A (en) * | 2010-01-15 | 2010-07-14 | 电子科技大学 | 99BeO ceramic metallizing slurry and preparation method thereof |
-
2011
- 2011-06-28 CN CN 201110175857 patent/CN102276152B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121499A (en) * | 1994-08-02 | 1996-05-01 | 住友电气工业株式会社 | Metallized ceramic substrate having smooth plating layer and method for producing the same |
| CN1887814A (en) * | 2006-07-16 | 2007-01-03 | 常熟市银洋陶瓷器件有限公司 | Powder for ceramic metallizing paste and its prepn |
| CN101200348A (en) * | 2007-12-21 | 2008-06-18 | 天津大学 | CaO-B2O3-SiO2 glass powder and preparation method |
| CN101318223A (en) * | 2008-07-14 | 2008-12-10 | 中南大学 | Method for manufacturing heavy pressure blank strength tungsten powder with ammonium metatungstate and ammonium paratungstate |
| CN101774826A (en) * | 2010-01-15 | 2010-07-14 | 电子科技大学 | 99BeO ceramic metallizing slurry and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314467A (en) * | 2018-04-11 | 2018-07-24 | 甘肃恒星特种陶瓷有限公司 | Heavy ion avcceleration ceramic-vacuum tube surface conductance layer formula and preparation method |
| CN109734480A (en) * | 2019-02-27 | 2019-05-10 | 常州联德陶业有限公司 | A kind of aluminium nitride ceramics heater cofiring high temperature exothermic slurry and preparation method thereof |
| CN115255347A (en) * | 2022-06-30 | 2022-11-01 | 南昌大学 | Tungsten-silicate micro zero-valent iron material and preparation method and application thereof |
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| CN102276152B (en) | 2013-04-24 |
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