CN102276152B - Composition for metallization of alumina ceramic surface - Google Patents
Composition for metallization of alumina ceramic surface Download PDFInfo
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- CN102276152B CN102276152B CN 201110175857 CN201110175857A CN102276152B CN 102276152 B CN102276152 B CN 102276152B CN 201110175857 CN201110175857 CN 201110175857 CN 201110175857 A CN201110175857 A CN 201110175857A CN 102276152 B CN102276152 B CN 102276152B
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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 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 the sheet resistivity of tungsten metallization layer.
Background technology
Al
2O
3Pottery has the physical strength height, and insulation resistance is large, and the coefficient of expansion and the chip characteristic such as be complementary is the 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 to carry out soldering with package metals such as kovar alloys.And common metal solder and Al
2O
3The pottery wettability is poor, so need to be at Al
2O
3Ceramic surface metallizes, and one of modal method is burnt the tungsten metallization layer altogether on its surface exactly, then will have the Al of tungsten metallization layer
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 comprised 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 Function 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 obtains Metal slurry → silk screen printing → altogether burning → metallized product performance test under atmosphere protection by 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 melting process temperature of sintering process is higher, and some component easily volatilization 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 larger, thus there are the defectives such as structure is not fine and close, porosity is high with the tungsten metallization layer of traditional method preparation, as shown in Figure 1, its sheet resistance is higher, is about 10 ~ 20 m Ω/.
Along with the 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 sheet resistivity so Al
2O
3The density of ceramic surface metallization layer and sheet resistivity just become the key factor that affects its use.Although can improve to a certain extent the density of metal layer by changing technique that ceramic-metal burns altogether, can not fundamentally solve the low and high problem of sheet resistivity of its density.
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 sheet 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 sheet 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, effectively reduce the metal layer porosity, thereby reduce the metal layer sheet resistance.
(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 respectively dehydrated alcohol, 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 mentioned solution 80 ℃ ~ 90 ℃ water-baths, stir to form vitreosol, static rear formation gel;
4) with gel 60 ℃ ~ 70 ℃ dryings, then ball milling is 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.
When sol-gel method prepares powder, can be at the material of lower temperature synthetic molecules level, it is accurate to have chemical constitution, the advantages such as purity is high, and homogeneity is strong, and 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 filling space effectively in sintering process again after melting, promote the densification of rete, finally causes the reduction of rete sheet 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, take dehydrated alcohol as medium, placed 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.Then the method with silk screen printing covers on the aluminium oxide ceramics green ceramic chip; 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 simultaneously the density that has significantly increased the tungsten metallization layer with the palladium powder of sol-gel method preparation, the sheet resistance with the tungsten metallization layer is reduced to 7 ~ 9 m Ω/ simultaneously.
Figure of description
Fig. 1 is the micro-structure diagram that traditional method prepares alumina-ceramic tungsten metallization layer;
The scanning electron microscope (SEM) photograph of Fig. 2 glass powder that to be the present invention make with sol-gel method;
The XRD diffractogram of Fig. 3 glass powder that to be the present invention make with sol-gel method;
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
The present invention is described in detail below in conjunction with embodiment.
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.
Be 20g by oxide aggregate, calculate and the required magnesium nitrate hexahydrate of weighing, nine water aluminum nitrate and tetraethoxys.Magnesium nitrate hexahydrate, nine water aluminum nitrates are dissolved in respectively dehydrated alcohol, 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 mentioned solution, constantly stir until the viscosity of solution obviously increases, form 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 lower calcinings, obtain the said glass powder of the present invention, be the scanning electron microscope (SEM) photograph of glass powder such as Fig. 2, can find out that glass powder has certain reunion, 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 Fig. 3 glass powder that to be the present invention make with sol-gel method, diffraction peak is obvious steamed bun peak among the figure, does not have the diffraction peak of crystal, the powder that hence one can see that makes is glass.
Embodiment 2: the sheet resistivity of used tungsten powder prescription (weight percent) and metal layer is as shown in table 1.Specific implementation process is (take the 2# sample as example):
The sheet resistivity 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 |
| Sheet resistivity | 8.66 | 7.94 | 7.13 | 7.58 |
Take by weighing altogether 97g of two kinds of tungsten powders of A, B 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 namely 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 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 sheet resistivity that obtains the tungsten metallization layer of 3# sample is 7.13 m Ω/, significantly be lower than sheet resistance 10 ~ 20 m Ω/ of present tungsten metallization layer, so can obviously reduce the metal layer sheet resistance with tungsten metallization slurry provided by the invention.
Fig. 1 is the ceramic metallized layer microstructure electromicroscopic photograph that is obtained by traditional method, can find out tungsten metallization layer short texture, has a lot of holes.Fig. 4 and Fig. 5 are respectively microtexture and the surface topography map of 3# sample, can find out tungsten metallization layer and Al
2O
3Ceramic bond is tight, and tungsten metallization layer compact structure, combines closely between the tungsten particle, and porosity is very low.
Claims (1)
1. the composition of a metallization of alumina ceramic surface is characterized in that the composition of metallization of alumina ceramic surface 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, and the D50 of B is 2 ~ 3 μ m, and 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; Adopt 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 respectively dehydrated alcohol, 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 mentioned solution 80 ℃ ~ 90 ℃ water-baths, stir to form vitreosol, static rear formation 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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| CN102276152B true CN102276152B (en) | 2013-04-24 |
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| 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 |
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 |
-
2011
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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 |
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