CN103395993A - Aluminium-nitride-based glass ceramic and preparation method thereof - Google Patents
Aluminium-nitride-based glass ceramic and preparation method thereof Download PDFInfo
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- CN103395993A CN103395993A CN2013103159123A CN201310315912A CN103395993A CN 103395993 A CN103395993 A CN 103395993A CN 2013103159123 A CN2013103159123 A CN 2013103159123A CN 201310315912 A CN201310315912 A CN 201310315912A CN 103395993 A CN103395993 A CN 103395993A
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Abstract
The invention discloses aluminium-nitride-based glass ceramic. The aluminium-nitride-based glass ceramic comprises the following components in parts by weight: 30-35 parts of aluminium nitride, 8-12 parts of calcium oxide, 7-11 parts of diboron trioxide, 17-24 parts of silicon dioxide, 1-2 parts of zinc oxide, 13-18 parts of magnesium oxide and 1-2 parts of zirconium dioxide. The preparation process is as follows: firstly adopting CaO, B2O3, SiO2 and ZnO as raw materials, and obtaining CBSZ glass powder with the softening point of 650-700 DEG C by a fusion method; then adopting MgO, B2O3, SiO2 and ZrO3 as raw materials, and obtaining MBSZ glass powder with the softening point of 720-770 DEG C by the fusion method; and carrying out mixing, granulation, forming and glue discharging on the two types of glass powder and the aluminium nitride, and sintering. The aluminium-nitride-based glass ceramic disclosed by the invention has the advantages that the preparation process is simple, the price of raw materials is low, sintering densification can be achieved under normal pressure and the temperature lower than 800 DEG C, and good heat conductivity is obtained.
Description
Technical field
The present invention relates to a kind of aluminum-nitride-based glass-ceramic and preparation method thereof, belong to materials science field.
Background technology
Along with innovation and the development of modern microelectronics, electron device is just towards highly integrated, microminiaturized, modularization, high reliability and future development cheaply.The electron device that becomes increasingly complex has proposed requirements at the higher level to the over-all properties of base plate for packaging material, requires it to have higher heat conductivility, suitable thermal expansivity, and lower specific inductivity and dielectric loss.Due to the fusing point lower (Cu is 1083 ℃, and Ag is 961 ℃) of metal electrode, in the electron device preparation process, for making substrate, can burn altogether with metal electrode (as Cu or Ag) simultaneously, require baseplate material to have lower sintering temperature.
Al
2O
3Base glass-ceramic system is the comparatively ripe electronic substrate of development at present, and its sintering temperature can be low to moderate 800-900 ℃, can realize and the common burning of metal electrode, but its thermal conductivity is generally not high, is only 2-4W/ (mK).Lead borosilicate/Al as serial as DuPont company 951
2O
3Substrate, its sintering temperature are 900 ℃ of left and right, but thermal conductivity is only 3.0W/ (mK) left and right.Therefore, how to prepare sintering temperature lower than 900 ℃, to reach the purpose of burning altogether with metal electrode, the better baseplate materials of over-all properties such as while heat conductivility, be that current electron device is to key highly integrated and the modularization development.
The advantages such as the thermal expansivity that the AlN pottery has high thermal conductivity, be complementary with silicon, low specific inductivity, good insulativity and environment-protecting asepsis, be current optimal electron device baseplate material, yet the sintering temperature of pure AlN pottery up to 1900 ℃ seriously limited its promotion and application.In order to take full advantage of the heat-conductive characteristic that aluminium nitride is good, avoid again simultaneously its high sintering temperature, some investigators, by in aluminium nitride powder, adding appropriate glass powder, prepare the aluminum-nitride-based glass-ceramic matrix material that thermal conductivity is higher under lower sintering temperature.As (J Mater Pro Techno, 1999,89,497-500) with (J Mater Sci, 2000,16,4137-4141) in the AlN powder, add appropriate cordierite glass powder, 1200 ℃ of hot pressed sinterings obtain the AlN/ glass of dense structure, and thermal conductivity is 4.4W/ (mK); (the investigation of materials journal, 2003,17,79-82) at 950 ℃ of hot pressed sinterings, obtained AlN/SiO
2-B
2O
3-ZnO-Bi
2O
3Matrix material, thermal conductivity are 5.1-9.3W/ (mK); (electronic component and material, 2008,27,58-61) using the lead borosilicate glass powder as additive, at 900 ℃ of hot pressed sinterings, obtained the glass-ceramic matrix material of thermal conductivity higher than 10W/ (mK).From result of study is as can be known both at home and abroad at present, take aluminium nitride powder and glass powder as raw material, can by hot pressed sintering, obtain the aluminum-nitride-based glass ceramic composite material of thermal conductivity greater than 5.0W/ (mK) at a lower temperature, than the thermal conductivity of alumina base glass-ceramic, have largely and improved.Yet the hot-pressing sintering technique that adopts in above-mentioned research is complicated, preparation cost is higher, and sintering temperature also only can be reduced to 900-950 ℃; Because aluminium nitride can be transformed into aluminum oxide under the oxidizing atmosphere higher than 850 ℃, therefore must in protective atmosphere, carry out sintering, increased again thus preparation cost.In addition, part Study person has selected the flint glass poisonous to environment, has also limited the industrial application of aluminum-nitride-based glass-ceramic.
Summary of the invention
The purpose of this invention is to provide a kind of can be in the air below 800 ℃ normal pressure-sintered and have aluminum-nitride-based glass-ceramic of good thermal conductivity and preparation method thereof.
Aluminum-nitride-based glass-ceramic of the present invention, its parts by weight consist of:
30～50 parts of aluminium nitride
8～12 parts, calcium oxide
7～11 parts of boron trioxides
7～24 parts of silica 1s
1～2 part, zinc oxide
13～18 parts, magnesium oxide
1～2 part of zirconium dioxide.
The method of the aluminum-nitride-based glass-ceramic of preparation that the present invention proposes comprises the following steps:
(1) take 8～12 parts, calcium oxide, 3～5 parts of boron trioxides, 7～10 parts of silicon-dioxide, 1～2 part, zinc oxide, after mixing, put into alumina crucible, in 1200 ℃～1300 ℃ insulations melting in 30 minutes, directly pour into the glass metal of melting in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m, obtains the CBSZ glass powder;
(2) take 13～18 parts, magnesium oxide, 4～6 parts of boron trioxides, 0～14 part of silica 1,1～2 part of zirconium dioxide, after mixing, put into alumina crucible, in 1250 ℃～1350 ℃ insulations melting in 30 minutes, directly pour into the glass metal of melting in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m, obtains the MBSZ glass powder;
(3) above-mentioned two kinds of glass powders are mixed, add 30～50 parts of aluminium nitride, then take dehydrated alcohol as medium, ball milling mixed 12～36 hours;
(4) to the ethanol solution that adds polyvinyl butyral acetal in above-mentioned mixed powder as tackiness agent, after mixing, carry out granulation, moulding, binder removal, then sintering 1～2 hour in the air of 750 ℃～800 ℃, obtain aluminum-nitride-based glass-ceramic.
The present invention has following beneficial effect: the softening temperature of CBSZ glass is between 650～700 ℃, the softening temperature of MBSZ glass is between 720～770 ℃, by utilizing the synergy of two kinds of different glass, promote aluminum-nitride-based glass-ceramic can be under normal pressure in the air of 800 ℃ densified sintering product, and obtain good thermal conductivity.
Embodiment
The invention will be further described below in conjunction with example.
Embodiment 1:
Take 8 parts, calcium oxide, 4 parts of boron trioxides, 8 parts of silicon-dioxide, 1 part, zinc oxide, after mixing, put into alumina crucible, in 1250 ℃ of insulations melting in 30 minutes, the glass metal of melting directly to be poured in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m.Take 15 parts, magnesium oxide, 6 parts of boron trioxides, 1 part of silica 1,1 part of zirconium dioxide, after mixing, put into alumina crucible, in 1300 ℃ of insulations melting in 30 minutes, the glass metal of melting directly to be poured in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m.Above-mentioned two kinds of glass powders are mixed, add 35 parts of aluminium nitride, then take dehydrated alcohol as medium, ball milling mixed 24 hours.In above-mentioned mixed powder, add the ethanol solution of 8 parts of polyvinyl butyral acetals as tackiness agent, after fully mixing, carry out granulation, then at the forming under the pressure of 150Mpa, after binder removal, in the air of 780 ℃, be incubated 2 hours and carry out sintering, namely obtain aluminum-nitride-based glass-ceramic of the present invention.Adopt the volume density of the above-mentioned glass-ceramic of drainage test, result is 2.88 gcm
-3Adopt laser conductometer to test its thermal conductivity, result is 5.72W/ (mK).
Embodiment 2:
Take 12 parts, calcium oxide, 5 parts of boron trioxides, 0 part of silica 1,2 parts, zinc oxide, after mixing, put into alumina crucible, in 1300 ℃ of insulations melting in 30 minutes, the glass metal of melting directly to be poured in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m.Take 18 parts, magnesium oxide, 6 parts of boron trioxides, 4 parts of silica 1s, 1 part of zirconium dioxide, after mixing, put into alumina crucible, in 1350 ℃ of insulations melting in 30 minutes, the glass metal of melting directly to be poured in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m.Above-mentioned two kinds of glass powders are mixed, add 45 parts of aluminium nitride, then take dehydrated alcohol as medium, ball milling mixed 18 hours.In above-mentioned mixed powder, add the ethanol solution of 10 parts of polyvinyl butyral acetals as tackiness agent, after fully mixing, carry out granulation, then at the forming under the pressure of 150Mpa, after binder removal, in the air of 800 ℃, be incubated 1 hour and carry out sintering, namely obtain aluminum-nitride-based glass-ceramic of the present invention.Adopt the volume density of the above-mentioned glass-ceramic of drainage test, result is 2.86 gcm
-3Adopt laser conductometer to test its thermal conductivity, result is 6.35W/ (mK).
Embodiment 3:
Take 10 parts, calcium oxide, 3 parts of boron trioxides, 8 parts of silicon-dioxide, 1 part, zinc oxide, after mixing, put into alumina crucible, in 1300 ℃ of insulations melting in 30 minutes, the glass metal of melting directly to be poured in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m.Take 13 parts, magnesium oxide, 4 parts of boron trioxides, 0 part of silica 1,1 part of zirconium dioxide, after mixing, put into alumina crucible, in 1300 ℃ of insulations melting in 30 minutes, the glass metal of melting directly to be poured in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m.Above-mentioned two kinds of glass powders are mixed, add 30 parts of aluminium nitride, then take dehydrated alcohol as medium, ball milling mixed 36 hours.In above-mentioned mixed powder, add the ethanol solution of 8 parts of polyvinyl butyral acetals as tackiness agent, after fully mixing, carry out granulation, then at the forming under the pressure of 150Mpa, after binder removal, in the air of 790 ℃, be incubated 1.5 hours and carry out sintering, namely obtain aluminum-nitride-based glass-ceramic of the present invention.Adopt the volume density of the above-mentioned glass-ceramic of drainage test, result is 2.92 gcm
-3Adopt laser conductometer to test its thermal conductivity, result is 5.51W/ (mK).
Embodiment 4:
Take 9 parts, calcium oxide, 4 parts of boron trioxides, 0 part of silica 1,2 parts, zinc oxide, after mixing, put into alumina crucible, in 1300 ℃ of insulations melting in 30 minutes, the glass metal of melting directly to be poured in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m.Take 16 parts, magnesium oxide, 5 parts of boron trioxides, 2 parts of silica 1s, 2 parts of zirconium dioxides, after mixing, put into alumina crucible, in 1350 ℃ of insulations melting in 30 minutes, the glass metal of melting directly to be poured in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m.Above-mentioned two kinds of glass powders are mixed, add 40 parts of aluminium nitride, then take dehydrated alcohol as medium, ball milling mixed 20 hours.In above-mentioned mixed powder, add the ethanol solution of 10 parts of polyvinyl butyral acetals as tackiness agent, after fully mixing, carry out granulation, then at the forming under the pressure of 150Mpa, after binder removal, in the air of 780 ℃, be incubated 2 hours and carry out sintering, namely obtain aluminum-nitride-based glass-ceramic of the present invention.Adopt the volume density of the above-mentioned glass-ceramic of drainage test, result is 2.81 gcm
-3Adopt laser conductometer to test its thermal conductivity, result is 5.83W/ (mK).
Claims (2)
1. aluminum-nitride-based glass-ceramic is characterized in that its parts by weight consist of:
30～50 parts of aluminium nitride
8～12 parts, calcium oxide
7～11 parts of boron trioxides
7～24 parts of silica 1s
1～2 part, zinc oxide
13～18 parts, magnesium oxide
1～2 part of zirconium dioxide.
2. the preparation method who prepares aluminum-nitride-based glass-ceramic claimed in claim 1 is characterized in that comprising the following steps:
(1) take 8～12 parts, calcium oxide, 3～5 parts of boron trioxides, 7～10 parts of silicon-dioxide, 1～2 part, zinc oxide, after mixing, put into alumina crucible, in 1200 ℃～1300 ℃ insulations melting in 30 minutes, directly pour into the glass metal of melting in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m, obtains the CBSZ glass powder;
(2) take 13～18 parts, magnesium oxide, 4～6 parts of boron trioxides, 0～14 part of silica 1,1～2 part of zirconium dioxide, after mixing, put into alumina crucible, in 1250 ℃～1350 ℃ insulations melting in 30 minutes, directly pour into the glass metal of melting in cold water, after the taking-up drying, being ground to particle diameter is 1～5 μ m, obtains the MBSZ glass powder;
(3) above-mentioned two kinds of glass powders are mixed, add 30～50 parts of aluminium nitride, then take dehydrated alcohol as medium, ball milling mixed 12～36 hours;
(4) to the ethanol solution that adds polyvinyl butyral acetal in above-mentioned mixed powder as tackiness agent, after mixing, carry out granulation, moulding, binder removal, then sintering 1～2 hour in the air of 750 ℃～800 ℃, obtain aluminum-nitride-based glass-ceramic.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600182A (en) * | 2014-12-23 | 2015-05-06 | 广州市尤特新材料有限公司 | Ceramic slurry for LED (light-emitting diode) metal substrate and preparation method of LED (light-emitting diode) metal substrate |
| CN111499389A (en) * | 2020-05-11 | 2020-08-07 | 陕西长石电子材料股份有限公司 | Preparation method of ceramic powder for metal-based ceramic copper-clad plate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000203878A (en) * | 1999-01-13 | 2000-07-25 | Asahi Glass Co Ltd | Glass ceramic composition |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000203878A (en) * | 1999-01-13 | 2000-07-25 | Asahi Glass Co Ltd | Glass ceramic composition |
Non-Patent Citations (1)
| Title |
|---|
| 赵宏生等: "AlN/SiO2-B2O3-ZnO-Bi2O3低温共烧玻璃陶瓷", 《电子元件与材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600182A (en) * | 2014-12-23 | 2015-05-06 | 广州市尤特新材料有限公司 | Ceramic slurry for LED (light-emitting diode) metal substrate and preparation method of LED (light-emitting diode) metal substrate |
| CN104600182B (en) * | 2014-12-23 | 2017-06-16 | 广州市尤特新材料有限公司 | The preparation method of LED metal substrates ceramic size and LED metal substrates |
| CN111499389A (en) * | 2020-05-11 | 2020-08-07 | 陕西长石电子材料股份有限公司 | Preparation method of ceramic powder for metal-based ceramic copper-clad plate |
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