CN106631039A - Preparation method of silicon nitride ceramic substrate - Google Patents
Preparation method of silicon nitride ceramic substrate Download PDFInfo
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Abstract
The invention discloses a preparation method of a silicon nitride ceramic substrate. The preparation method comprises steps as follows: silica powder, silicon nitride powder, a sintering aid and a dispersing agent are mixed, a solvent is added, all components are subjected to ball milling for the first time, then an adhesive and a plasticizer are added, all components are subjected to the ball milling the second time and subjected to vacuum defoamation, slurry is obtained, and a mass ratio of the silica powder to the silicon nitride powder is (1:10)-(10:1); the slurry is subjected to tape casting and dried, a biscuit is obtained and subjected to vacuum adhesive discharging, and a green body is obtained; the green body is sintered, and the silicon nitride ceramic substrate is obtained. The silicon nitride powder and the cheap silica powder are adopted as main raw materials, the silicon nitride ceramic substrate is prepared with a tape casting technology, and the silicon nitride ceramic substrate with low cost and excellent comprehensive performance is obtained.
Description
Technical field
The invention belongs to ceramic substrate material technical field, is related to a kind of preparation method of silicon nitride ceramic substrate.
Technical background
Semi-conductor power module is one of most important power device in field of power electronics, is applied to electric automobile, rail
The fields such as road traffic.Wherein, the copper-clad base plate for encapsulating power model is indispensable key foundation material, and covers cuprio
Insulating barrier in plate is typically ceramic material.At present, widely used dielectric substrate material is mainly aluminium oxide and aluminium nitride, but
The bending strength and fracture toughness of aluminium oxide and aluminum nitride ceramic substrate is all relatively low, causes to weld after oxygen-free copper in thermal cycle
During be easy to cracking, the reliability of whole power model is affected, while when semi-conductor power module in vehicle etc. using existing
Frequently on the MOVING STRUCTURE of vibrations, easily there is fracture in the not enough ceramic substrate of mechanical property, reduces semi-conductor power module
Reliability in use.Silicon nitride ceramics has excellent mechanical property, and its bending strength and fracture toughness are nitridations
More than 2 times of aluminum and aluminium oxide, and there is high heat conductance, low thermal coefficient of expansion and high-heat resistance shock resistant, it is more suitable for
It is live in the application of high power semi-conductor power model, particularly apply and prepared in the power model for having vibration occasion.
Preparing the method for silicon nitride ceramic substrate includes, first sinters out silicon nitride ceramics block using beta-silicon nitride powder, cuts
Cut and obtain final product ceramic substrate, as described in patent CN 1192989C and CN 1139117C.In addition can be using silicon nitride powder by curtain coating
The method of molding prepares silicon nitride ceramic substrate, needs not move through machine cuts, the such as A of patent CN 103781742, patent CN
Described in 100398491C, the A of patent CN 102105418A and CN 103922746.Above prior art is all using air pressure or heat
Pressure sintering, while raw material be silicon nitride powder so that silicon nitride board it is with high costs.In order to reduce production cost, ensureing power
On the premise of learning performance and thermal conductivity, can be using cheap high-purity silicon powder as primary raw material, using flowing nitrogen gas
The mode of atmosphere sintering prepares silicon nitride ceramics, but, during laminar ceramic substrate is prepared, using silica flour flow casting molding and
The mode of high-temperature ammonolysis prepares silicon nitride board, easily occurs producing showing for molten silicon because exothermic reaction causes local temperature too high
As so as to affect the yields of product.
The content of the invention
To overcome the deficiencies in the prior art, the present invention provides a kind of preparation method of silicon nitride ceramic substrate, the present invention with
Silicon nitride powder and cheap silica flour are primary raw material, by adding dispersant, plasticizer and bonding agent, and using curtain coating work
Skill prepares the silicon nitride ceramic substrate of low cost, excellent combination property.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of silicon nitride ceramic substrate, comprises the following steps：
By silica flour, silicon nitride powder, sintering aid, dispersant, solvent is added, carry out first time ball milling, added viscous
Agent and plasticizer are connect, second ball milling is carried out, Jing after vacuum defoamation, the mass ratio of slurry, the silica flour and silicon nitride powder is obtained
For (1：10)～(10:1)；
By slurry Jing flow casting moldings, it is dried, obtains biscuit, Jing after vacuum dumping green compact is obtained；By green sintering, nitrogen is obtained
SiClx ceramic substrate.
Preferably, the silica flour and the mass ratio of silicon nitride powder are (1：10)～(4:1).
Preferably, the median particle diameter of the silica flour is 3-25 μm, and the median particle diameter of silicon nitride powder is 0.2 μm～3 μm.It is more excellent
Choosing, the median particle diameter of the silica flour is more than the median particle diameter of silicon nitride powder.
Preferably, described sintering aid is ZrO2、MxOyWith Re2O3Mixture, MxOyFor metal-oxide, M is Mg
Or Al, Re2O3For rare earth oxide, Re is Gd, Lu, Y, Yb, Eu, the ZrO2、MxOyWith Re2O3Mass ratio be (2-3)：1：
(3-5).It is furthermore preferred that silica flour is (4～10) with the mass ratio of sintering aid with the quality sum of silicon nitride powder:1.
Preferably, the dispersant is Oleum Ricini.
It is furthermore preferred that the silica flour is (40～80) with the ratio of the quality of dispersant with the quality sum of silicon nitride powder：
1。
The solvent is used for dispersant, bonding agent and the plasticizer that dissolving is added, and concrete material is not particularly limited, preferably
, the solvent is the mixed solvent that dehydrated alcohol is mixed to get with butanone, and its quality is silica flour, silicon nitride powder, sintering aid
1～2 times of quality sum.
Preferably, the bonding agent is polyvinyl butyral resin.
It is furthermore preferred that the quality of the bonding agent is (5～25) with the ratio of silica flour, the quality sum of silicon nitride powder:
100。
Preferably, described plasticizer is dibutyl phthalate, diisobutyl phthalate, dibutyl sebacate
In at least two mixture.It is furthermore preferred that it is 1 that the plasticizer is mass ratio:1 di-n-octyl sebacate and phthalic acid
The mixture of diisobutyl ester, quality and the ratio of silica flour, the quality sum of silicon nitride powder of plasticizer are (5～25):100.
Preferably, 25 DEG C of dynamic viscosities of the slurry are 3000mPaS～50000mPaS.
Preferably, the thickness of the biscuit is 0.1mm～2.2mm.
Preferably, the first time ball milling is with 50-100 rev/min of ball milling speed ball milling 12-48h, second ball milling
It is with 50-100 rev/min of ball milling speed ball milling 12-48h.
Preferably, the temperature of the drying is 25 DEG C～70 DEG C, and the time is 0.5h-4h.
Preferably, the operation of the vacuum dumping is：Under conditions of vacuum is 0.04Pa～0.1Pa, with the speed that heats up
By room temperature to 600 DEG C～650 DEG C, constant temperature is processed as 0.5h-2h to 25 DEG C/h～80 DEG C/h.
Preferably, the concrete operations of the sintering are：In the flowing nitrogen atmosphere of 1atm, with 5 DEG C/min～20 DEG C/
The heating rate of min is warmed up to 1350 DEG C～1420 DEG C insulation 0.5-4h, then with the heating rate liter of 5 DEG C/min～10 DEG C/min
Then temperature is warming up to 1780 DEG C～1850 DEG C insulations to 1580 DEG C～1620 DEG C with the heating rate of 5 DEG C/min～10 DEG C/min
2-5h, cools to 1600 DEG C～1200 DEG C, cooling with the rate of temperature fall of 1 DEG C/min～20 DEG C/min.
The invention has the advantages that：
(1) present invention is mixed as primary raw material using silica flour with silicon nitride powder, with reference to silica flour reaction-sintered and silicon nitride powder
Sintering prepares silicon nitride ceramics, effectively relaxes silicon powder nitride response speed, is effectively utilized the heat produced during silicon powder nitride
Amount, promotes the nitridation of silica flour and the densification of product, turn avoid the product crack caused because melting silicon, improves the property of product
Energy and yields.
(2) compared with silicon nitride ceramics is prepared as raw material with silicon nitride powder, the present invention mixes work with silicon nitride powder with silica flour
For primary raw material, silicon nitride ceramics is prepared with reference to silica flour reaction-sintered and silicon nitride powder sintering, be effectively improved the property of product
Can, while reducing the production cost of product.
Description of the drawings
Fig. 1 is the surface scan electromicroscopic photograph of green compact in embodiment 3
Fig. 2 is the profile scanning electromicroscopic photograph of ceramic substrate in embodiment 4
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.Specific embodiment described herein only to explain the present invention, is not used to limit
The present invention.
Embodiment 1
The preparation method of silicon nitride ceramic substrate is as follows：
A：By 15.75g silica flours (median particle diameter is 10 μm), 68.25g silicon nitride powders (median particle diameter is 0.2 μm), 5.7g oxygen
Change zirconium powder (ZrO2), 2g magnesia powders (MgO) and 8.3g Gadolinia. powder (Gd2O3) mixing, 1.68g Oleum Ricini is added, add
(dehydrated alcohol is 1 with the mass ratio of butanone to 120g dehydrated alcohol-butanone mixed solvent:2), enter by ball-milling medium of silicon nitride ball
Row first time ball milling, ball milling speed is 80 revs/min, and the time is 24h；Be subsequently adding 4.2g bonding agents polyvinyl butyral resin and
6.72g plasticizers carry out second ball milling, and ball milling speed is 80 revs/min, and the time is 24h, wherein, plasticizer is mass ratio 1:
1 di-n-octyl sebacate and diisobutyl phthalate, the deaeration under conditions of vacuum is 0.1Pa, obtains after the completion of ball milling
To 25 DEG C of dynamic viscosities for 3000mPaS slurry, 25 DEG C of dynamic viscosities obtain by rotating cylinder viscometer test；
B：Slurry is carried out into flow casting molding, at 25 DEG C 4h is dried, obtain biscuit, carried out very in vacuum degreasing stove after cutting
Idle discharge glue, the vacuum during dumping is 0.06Pa, 600 DEG C is warmed up to by 80 DEG C/h of heating rate during dumping, at 600 DEG C
After insulation 0.5h, drop to room temperature and obtain green compact；
C：Green compact are put in graphite crucible, in being placed in the flowing nitrogen atmosphere sintering furnace that sintering atmosphere is 1atm, with 10
DEG C/temperature is raised to 1400 DEG C of insulation 2h by the heating rate of min, is then warming up to 1600 DEG C with the programming rate of 10 DEG C/min,
Then temperature is raised to into 1800 DEG C with the heating rate of 5 DEG C/min, after insulation 2h, is dropped temperature with the rate of temperature fall of 1 DEG C/min
To 1600 DEG C, furnace cooling is carried out afterwards, obtain silicon nitride ceramic substrate.
Jing is tested, and the three-point bending resistance intensity of silicon nitride ceramic substrate manufactured in the present embodiment is 800MPa, SENB
Method measurement fracture toughness is 8MPam1/2, laser shine method measurement thermal conductivity be 60Wm-1·K-1。
Embodiment 2
The preparation method of silicon nitride ceramic substrate is as follows：
A：By 47.25g silica flours (median particle diameter is 6.5 μm), 36.75g silicon nitride powders (median particle diameter is 0.2 μm), 5.7g
ZrO2Powder, 2g MgO powder and 8.3g Gd2O3Powder mixes, and adds 1.68g Oleum Ricini, adds 150g dehydrated alcohol-butanone mixing
(dehydrated alcohol is 1 with the mass ratio of butanone to solvent:2), first time ball milling, ball milling speed are carried out by ball-milling medium of silicon nitride ball
For 100 revs/min, the time is 20h；Being subsequently adding 14.28g bonding agents polyvinyl butyral resin and 10.5g plasticizers carries out
Secondary ball milling, ball milling speed is 100 revs/min, and the time is 24h, wherein, it is 1 that plasticizer is mass ratio:1 decanedioic acid two is pungent
Ester and diisobutyl phthalate, the deaeration under conditions of vacuum is 0.1Pa, obtains 25 DEG C of dynamic viscosities after the completion of ball milling
For the slurry of 20000mPaS, 25 DEG C of dynamic viscosities are obtained by rotating cylinder viscometer test；
B:Slurry is carried out into flow casting molding, through 70 DEG C, the drying of 0.5h, biscuit is obtained, in vacuum degreasing stove after cutting
In carry out vacuum dumping, vacuum is 0.1Pa, and by 25 DEG C/h of heating rate 650 DEG C are raised to, 650 DEG C be incubated 1h after, drop to
Room temperature, obtains green compact；
C：Green compact are put into into graphite crucible to be built in the flowing nitrogen atmosphere sintering furnace that sintering atmosphere is 1atm, with 10
DEG C/temperature is raised to 1400 DEG C of insulation 2h by the heating rate of min, is then warming up to 1600 DEG C with the programming rate of 10 DEG C/min,
Then temperature is raised to into 1800 DEG C with the heating rate of 5 DEG C/min, after insulation 2h, is dropped temperature with the rate of temperature fall of 10 DEG C/min
To 1600 DEG C, furnace cooling is carried out afterwards, obtain silicon nitride ceramic substrate.
Jing is tested, and the three-point bending resistance intensity of silicon nitride ceramic substrate manufactured in the present embodiment is 700MPa, SENB
Method measurement fracture toughness is 7MPam1/2, laser shine method measurement thermal conductivity be 52Wm-1·K-1。
Embodiment 3
The preparation method of silicon nitride ceramic substrate is as follows：
A：By 47.25g silica flours (median particle diameter is 6.5 μm), 36.75g silicon nitride powders (median particle diameter is 0.2 μm), 5.7g
ZrO2Powder, 2g MgO powder and 8.3g Gd2O3Powder mixes, and adds 1.68g Oleum Ricini, adds 150g dehydrated alcohol-butanone mixing
(dehydrated alcohol is 1 with the mass ratio of butanone to solvent:2), first time ball milling, ball milling speed are carried out by ball-milling medium of silicon nitride ball
For 100 revs/min, the time is 20h；Being subsequently adding 14.28g bonding agents polyvinyl butyral resin and 10.5g plasticizers carries out
Secondary ball milling, ball milling speed is 100 revs/min, and the time is 24h, wherein, it is 1 that plasticizer is mass ratio:1 decanedioic acid two is pungent
Ester and diisobutyl phthalate, the deaeration under conditions of vacuum is 0.1Pa, obtains 25 DEG C of dynamic viscosities after the completion of ball milling
For the slurry of 30000mPaS, 25 DEG C of dynamic viscosities are obtained by rotating cylinder viscometer test；
B:Slurry is carried out into flow casting molding, through 70 DEG C, the drying of 0.5h, the biscuit of 2mm is obtained, it is de- in vacuum after cutting
Vacuum dumping is carried out in fat stove, specifically under the conditions of vacuum is 0.1Pa, by 25 DEG C/h of heating rate 650 DEG C is raised to,
650 DEG C of isothermal holding 1h, drop to room temperature, obtain green compact, and to gained green compact surface Scanning Electron microscopic examination is carried out, and obtain table
The structure chart in face is as shown in Figure 1, it is seen that the silica flour of big particle diameter and the silicon nitride powder coalition of small particle are distributed with green compact；
C：Green compact are put into into graphite crucible to be built in the flowing nitrogen atmosphere sintering furnace that sintering atmosphere is 1atm, with 20
DEG C/temperature is raised to 1400 DEG C of insulation 2h by the heating rate of min, is then warming up to 1600 DEG C with the programming rate of 10 DEG C/min,
Then temperature is raised to into 1800 DEG C with the heating rate of 10 DEG C/min, after insulation 2h, with the rate of temperature fall of 10 DEG C/min by temperature
1600 DEG C are dropped to, furnace cooling is carried out afterwards, obtain silicon nitride ceramic substrate.
Jing is tested, and the three-point bending resistance intensity of silicon nitride ceramic substrate manufactured in the present embodiment is 700MPa, SENB
Method measurement fracture toughness is 7MPam1/2, laser shine method measurement thermal conductivity be 55Wm-1·K-1。
Embodiment 4
The preparation method of silicon nitride ceramic substrate is as follows：
A：By 47.25g silica flours (median particle diameter is 6.5 μm), 36.75g silicon nitride powders (median particle diameter is 0.2 μm), 5.7g
ZrO2Powder, 2g MgO powder and 8.3g Gd2O3Powder mixes, and adds 1.68g Oleum Ricini, adds 150g dehydrated alcohol-butanone mixing
(dehydrated alcohol is 1 with the mass ratio of butanone to solvent:2), first time ball milling, ball milling speed are carried out by ball-milling medium of silicon nitride ball
For 80 revs/min, the time is 20h；Being subsequently adding 16.8g bonding agents polyvinyl butyral resin and 4.2g plasticizers carries out second
Ball milling, ball milling speed is 80 revs/min, and the time is 24h, wherein, it is 1 that plasticizer is mass ratio:1 di-n-octyl sebacate and neighbour
Phthalic acid diisobutyl ester, the deaeration under conditions of vacuum is 0.1Pa after the completion of ball milling, obtaining 25 DEG C of dynamic viscosities is
The slurry of 40000mPaS, 25 DEG C of dynamic viscosities are obtained by rotating cylinder viscometer test；
B:Slurry is carried out into flow casting molding, through 70 DEG C, the drying of 0.5h, biscuit is obtained, in vacuum degreasing stove after cutting
In carry out vacuum dumping, specifically vacuum be 0.1Pa under the conditions of, 650 DEG C are raised to by 25 DEG C/h of heating rate, 650
After DEG C isothermal holding 2h, room temperature is dropped to, obtain green compact；
C：Green compact are put into into graphite crucible to be built in the flowing nitrogen atmosphere sintering furnace that sintering atmosphere is 1atm, with 20
DEG C/temperature is raised to 1400 DEG C of insulation 2h by the heating rate of min, is then warming up to 1600 DEG C with the programming rate of 10 DEG C/min,
Then temperature is raised to by 1835 DEG C of insulation 2h with the heating rate of 5 DEG C/min, is reduced the temperature to the rate of temperature fall of 10 DEG C/min
, furnace cooling is carried out afterwards, obtain silicon nitride ceramic substrate by 1400 DEG C.
Electronic scanner microscope detection is carried out to the section of silicon nitride ceramic substrate, obtain cross-section structure as shown in Fig. 2
It can be seen that gained substrate has high-compactness.Jing is tested, and the three-point bending resistance intensity of silicon nitride ceramic substrate manufactured in the present embodiment is
700MPa, Single edge notch beam measurement fracture toughness is 7MPam1/2, laser shine method measurement thermal conductivity be 55Wm-1·K-1。
Embodiment 5
The preparation method of silicon nitride ceramic substrate is as follows：
A：By 51.7g silica flours (median particle diameter is 10 μm), 28.8g silicon nitride powders (bimodal distribution, 0.2 μm and 2 μm), 6.9g
ZrO2Powder, 2.6gMgO powder and 10g luteium oxide (Lu2O3) powder mixing, 1.34g Oleum Ricini is added, add 150g dehydrated alcohol-fourth
(dehydrated alcohol is 1 with the mass ratio of butanone to ketone mixed solvent:2), first time ball milling, ball are carried out by ball-milling medium of silicon nitride ball
Mill speed is 80 revs/min, and the time is 20h；It is subsequently adding 6.44g bonding agents polyvinyl butyral resin and 6.44g plasticizers enters
Second ball milling of row, ball milling speed is 80 revs/min, and the time is 24h, wherein, it is 1 that plasticizer is mass ratio:1 decanedioic acid two
Monooctyl ester and diisobutyl phthalate, the deaeration under conditions of vacuum is 0.1Pa after the completion of ball milling, obtain 25 DEG C of power and glue
The slurry for 20000mPaS is spent, 25 DEG C of dynamic viscosities are obtained by rotating cylinder viscometer test；
B:Slurry is carried out into flow casting molding, through 35 DEG C, the drying of 1.5h obtains biscuit, in vacuum degreasing stove after cutting
In carry out vacuum dumping, dumping is under the conditions of vacuum is 0.1Pa, 650 DEG C to be raised to by 75 DEG C/h of heating rate, 650
After DEG C isothermal holding 0.5h, room temperature is dropped to, obtain green compact；
C：Green compact are put into into graphite crucible to be built in the flowing nitrogen atmosphere sintering furnace that sintering atmosphere is 1atm, with 20
DEG C/temperature is raised to 1400 DEG C of insulation 2h by the heating rate of min, is then warming up to 1800 DEG C with the programming rate of 10 DEG C/min,
After insulation 2h, 1600 DEG C are reduced the temperature to the rate of temperature fall of 20 DEG C/min, furnace cooling is carried out afterwards, obtain silicon nitride ceramics
Substrate.
Jing is tested, and the three-point bending resistance intensity of silicon nitride ceramic substrate manufactured in the present embodiment is 650MPa, SENB
Method measurement fracture toughness is 7MPam1/2, laser shine method measurement thermal conductivity be 50Wm-1·K-1。
Finally it should be noted that above example is only to illustrate technical scheme rather than the present invention is protected
The restriction of scope.It will be understood by those of skill in the art that some deductions being carried out to technical scheme or being waited
With replacing, without deviating from the spirit and scope of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of silicon nitride ceramic substrate, comprises the following steps：
By silica flour, silicon nitride powder, sintering aid, dispersant, solvent is added, carry out first time ball milling, add bonding agent
And plasticizer, second ball milling is carried out, Jing after vacuum defoamation, slurry is obtained, the silica flour is (1 with the mass ratio of silicon nitride powder：
10)～(10:1)；
By slurry Jing flow casting moldings, it is dried, obtains biscuit, Jing after vacuum dumping green compact is obtained；By green sintering, silicon nitride is obtained
Ceramic substrate.
2. preparation method as claimed in claim 1, it is characterised in that the silica flour is (1 with the mass ratio of silicon nitride powder：10)
～(4:1).
3. preparation method as claimed in claim 1, it is characterised in that the median particle diameter of the silica flour is 3-25 μm, silicon nitride
The median particle diameter of powder is 0.2 μm～3 μm.
4. the preparation method as described in any one of claim 1-3, it is characterised in that described sintering aid is ZrO2、MxOyWith
Re2O3Mixture, MxOyFor metal-oxide, M is Mg or Al, Re2O3For rare earth oxide, Re is Gd, Lu, Y, Yb or Eu.
5. the preparation method as described in any one of claim 1-3, it is characterised in that the dispersant is Oleum Ricini.
6. preparation method as claimed in claim 5, it is characterised in that quality sum and dispersion of the silica flour with silicon nitride powder
The mass ratio of agent is (40～80)：1.
7. the preparation method as described in any one of claim 1-3, it is characterised in that the bonding agent is polyvinyl alcohol contracting fourth
Aldehyde.
8. preparation method as claimed in claim 7, it is characterised in that the quality of the bonding agent and silica flour, silicon nitride powder
The ratio of quality sum is (5～25):100.
9. the preparation method as described in any one of claim 1-3, it is characterised in that described plasticizer is phthalic acid two
At least two mixture in butyl ester, diisobutyl phthalate, dibutyl sebacate.
10. the preparation method as described in any one of claim 1-3, it is characterised in that 25 DEG C of dynamic viscosity values of the slurry
For 3000mPaS～50000mPaS.
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| CN108484150A (en) * | 2018-03-30 | 2018-09-04 | 胡果青 | A kind of preparation method of dense form high heat-conducting ceramic substrate |
| CN111253162A (en) * | 2019-02-22 | 2020-06-09 | 中国科学院上海硅酸盐研究所苏州研究院 | Method for preparing high-strength high-toughness high-thermal-conductivity silicon nitride ceramic |
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| CN113105252A (en) * | 2021-04-20 | 2021-07-13 | 中材高新氮化物陶瓷有限公司 | Sintering aid for preparing silicon nitride ceramic, application of sintering aid and preparation method of silicon nitride ceramic |
| CN113307631A (en) * | 2021-05-13 | 2021-08-27 | 广东工业大学 | Method for preparing silicon nitride ceramic with high comprehensive performance through pressureless sintering |
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