CN109400175B - Preparation method of high-thermal-conductivity silicon nitride ceramic substrate material - Google Patents
Preparation method of high-thermal-conductivity silicon nitride ceramic substrate material Download PDFInfo
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- CN109400175B CN109400175B CN201811358422.0A CN201811358422A CN109400175B CN 109400175 B CN109400175 B CN 109400175B CN 201811358422 A CN201811358422 A CN 201811358422A CN 109400175 B CN109400175 B CN 109400175B
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 85
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000000919 ceramic Substances 0.000 title claims abstract description 79
- 239000000758 substrate Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005520 cutting process Methods 0.000 claims abstract description 74
- 238000005245 sintering Methods 0.000 claims abstract description 73
- 235000015895 biscuits Nutrition 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000748 compression moulding Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 33
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 30
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 21
- 229910003460 diamond Inorganic materials 0.000 claims description 18
- 239000010432 diamond Substances 0.000 claims description 18
- 239000000395 magnesium oxide Substances 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 15
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 14
- 238000005121 nitriding Methods 0.000 claims description 13
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 12
- 150000002602 lanthanoids Chemical class 0.000 claims description 12
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
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- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 9
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 9
- 229940117972 triolein Drugs 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000462 isostatic pressing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001272 pressureless sintering Methods 0.000 claims description 4
- 241000252203 Clupea harengus Species 0.000 claims description 3
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- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
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- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 235000019514 herring Nutrition 0.000 claims description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000009694 cold isostatic pressing Methods 0.000 description 11
- 238000003825 pressing Methods 0.000 description 10
- 238000005498 polishing Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 229910002114 biscuit porcelain Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000010345 tape casting Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000007569 slipcasting Methods 0.000 description 4
- 241001391944 Commicarpus scandens Species 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- RMAOWVAWWPWUIZ-UHFFFAOYSA-N [O-2].[Mg+2].[O-2].[Dy+3] Chemical compound [O-2].[Mg+2].[O-2].[Dy+3] RMAOWVAWWPWUIZ-UHFFFAOYSA-N 0.000 description 1
- BPEGXYJAEMXYBP-UHFFFAOYSA-N [O-2].[Mg+2].[O-2].[Yb+3] Chemical compound [O-2].[Mg+2].[O-2].[Yb+3] BPEGXYJAEMXYBP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
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Abstract
The invention relates to a preparation method of a high-thermal-conductivity silicon nitride ceramic substrate material, which comprises the following steps: mixing silicon nitride powder or/and silicon powder serving as raw material powder with a sintering aid to obtain mixed powder; mixing the mixed powder and a binder, granulating, and performing compression molding to obtain a biscuit; and after the obtained biscuit is subjected to de-bonding and sintering, cutting into a specified thickness to obtain the silicon nitride ceramic substrate material.
Description
Technical Field
The invention relates to a preparation method of a silicon nitride ceramic substrate material, belonging to the field of preparation process and application of ceramics.
Background
The high-thermal-conductivity silicon nitride ceramic substrate is a key thermal management material for ensuring the safe operation of a high-power electronic device. The power electronic device is a core unit for converting and controlling electric energy in power equipment, and the application field covers various fields such as energy, traffic, basic industry and the like. Commonly used power electronics include IGBTs, inverters, and the like. China has become the largest global power electronic device demand market, the total market amount is nearly 2000 million yuan in 2013, 2020 is estimated to reach 5000 million yuan, and the annual growth rate is nearly 20%. The corresponding demand for ceramic substrates is also enormous. It is estimated that the demand for ceramic substrates will reach 60 billion dollar bills for only one electric vehicle.
The development of high power, high frequency and integration is the direction of power electronic devices. The power of the device can reach KW level and even more than tens of GW. Due to high energy density and serious heating, the working temperature rises continuously, and the working stability and the service life of the device are seriously influenced. The heat dissipation problem has become a key to be solved. At present, aluminum oxide and aluminum nitride base materials are commonly used, and the aluminum oxide cannot effectively dissipate heat due to low thermal conductivity; aluminum nitride ceramics have high thermal conductivity, but are poor in mechanical properties, and are prone to cracking caused by thermal shock during use. Silicon nitride ceramics have the advantages of high thermal conductivity and high reliability, and are the only candidate materials at present.
Silicon nitride ceramics are a conventional structural ceramic material. Has the advantages of high strength, high toughness and excellent high-temperature performance, and has a great amount of application in the industrial and civil fields all the time. In recent years, the silicon nitride ceramic has high heat conductivity and good microwave permeability, and is an ideal ceramic substrate material for high-power electronics by combining good mechanical properties and high-temperature properties. However, for efficient heat transfer, the silicon nitride ceramic substrate is typically only 0.32mm thick, and a common method is tape casting combined with gas pressure sintering.
However, the casting molding has the disadvantages of more added raw materials, complex process, long period and high cost. Moreover, the substrate prepared by the tape casting process often needs high-temperature flattening treatment, and because the number of stacked layers of the substrate material is limited, the number of silicon nitride substrates loaded each time is also very limited, and finally, the preparation cost is increased.
Disclosure of Invention
Aiming at the problems of the traditional tape casting process for preparing the silicon nitride ceramic substrate material, a new scheme of adopting block cutting is provided, and two approaches are mainly provided: one is to prepare a block silicon nitride ceramic biscuit, cut the biscuit before sintering and then sinter the biscuit; the other method is to cut the silicon nitride ceramic substrate after sintering.
On one hand, the invention also provides a preparation method of the high-thermal-conductivity silicon nitride ceramic substrate material, which comprises the following steps:
mixing silicon nitride powder or/and silicon powder serving as raw material powder with a sintering aid to obtain mixed powder;
mixing the mixed powder and a binder, granulating, and performing compression molding to obtain a biscuit;
when the raw material powder is only silicon nitride powder, the obtained biscuit is subjected to de-bonding and biscuit firing treatment, then is cut into a given thickness, and is sintered to obtain the silicon nitride ceramic substrate material, wherein the biscuit firing treatment temperature is 1200-1600 ℃ and the biscuit firing treatment time is 1-12 hours;
or when the raw material powder contains silicon powder, cutting the biscuit into a specified thickness after de-bonding and nitriding treatment, and sintering to obtain the silicon nitride ceramic substrate material, wherein the nitriding treatment is performed in nitrogen atmosphere at 1380-1500 ℃ for 2-48 hours;
or the obtained biscuit is subjected to de-bonding and sintering and then is cut into a specified thickness, so as to obtain the silicon nitride ceramic substrate material.
Preferably, the sintering aid is magnesium oxide, titanium oxide, Y2O3At least two of lanthanide rare earth oxides; the mass ratio of the raw material powder to the sintering aid is (80-97): (20-3) when the raw material powder contains silicon powder (silicon powder), the mass of the silicon powder is calculated as the mass of the silicon nitride powder.
Further, it is preferable that when the sintering aid comprises titanium oxide, Y2O3At least one of lanthanide rare earth oxides, and magnesium oxide; the titanium oxide and Y2O3The ratio of the molar content of at least one of the lanthanide rare earth oxides to the molar content of the magnesium oxide is (2-5): 5.
further, it is preferable that when the sintering aid includes Y2O3At least two of lanthanide rare earth oxides, and magnesium oxide; said Y is2O3The ratio of the molar contents of at least two of the lanthanide rare earth oxides to the molar content of magnesium oxide is (2-5): 5.
preferably, the sintering aid comprises Y2O3And at least two of lanthanide rare earth oxides.
Preferably, the particle size of the silicon nitride powder is 0.5 to 5 μm, and the particle size of the silicon powder is 1 to 20 μm.
Preferably, the cutting process is a multi-chip cutting process or a multi-wire cutting process, preferably a multi-wire cutting process; more preferably, the multi-wire cutting process comprises: cutting by using a diamond wire with the diameter of 0.4-0.6 mm as a cutting line and adopting a swinging wire supply mode; the running speed of the cutting line is set to be less than or equal to 10m/s, and the feeding speed is set to be 0.005-0.05 mm/min. In the present disclosure, the multi-sheet cutting process includes: a plurality of blades are adopted, the blade spacing is controlled, and cutting is carried out simultaneously; the multi-line cutting process comprises the following steps: and (3) adopting a plurality of cutting lines, controlling the distance between the cutting lines (basically consistent with the thickness of the obtained green body substrate or ceramic substrate), and cutting simultaneously. Multi-wire cutting is commonly used.
Preferably, the binder is polyvinyl butyral or/and polymethyl methacrylate, and the addition amount of the binder is 0.5-10 wt% of the total mass of the mixed powder; preferably, the mixed powder, the organic solvent, the dispersant and the binder are dried and granulated after being mixed, and then the biscuit is obtained after compression molding; more preferably, the organic solvent is at least one of ethanol, butanone, toluene, n-hexane, methanol, xylene, n-propanol and n-butanol, and the addition amount is 14-50 wt% of the total mass of the mixed powder; the dispersing agent is at least one of triolein, phosphate ester, castor oil herring oil, ascorbic acid and terpineol, and the adding amount of the dispersing agent is 0.5-4 wt% of the total mass of the silicon nitride powder and the sintering aid system.
Preferably, the temperature for debonding is 600-900 ℃ and the time is 2-48 hours.
Preferably, the sintering mode is pressureless sintering, air pressure sintering, hot pressing sintering or isostatic pressing sintering; preferably, the sintering atmosphere is nitrogen atmosphere, the temperature is 1600-1950 ℃, the air pressure is 0.1-10 MPa, and the time is 1-24 hours; more preferably, the temperature rise rate of the sintering is 1-5 ℃ for minutes.
Preferably, the biscuit is formed in at least one of dry pressing, cold isostatic pressing, dry pressing-cold isostatic pressing, gel injection molding, slip casting, pressure slip casting and extrusion molding; preferably, the pressure of the dry pressing is 10-60 MPa, and the pressure of the cold isostatic pressing is 150-200 MPa.
Preferably, the predetermined thickness is 0.32mm to 2mm, preferably 0.4mm to 2 mm.
On the other hand, the invention also provides the high-thermal-conductivity silicon nitride ceramic substrate material prepared by the preparation method, and the thickness of the high-thermal-conductivity silicon nitride ceramic substrate material is generally 0.32 mm-2 mm. The preparation method of the silicon nitride ceramic substrate provided by the invention has the following characteristics. First, a silicon nitride biscuit can be obtained by a variety of manufacturing techniques including dry pressing, cold isostatic pressing, dry-cold isostatic pressing, gel casting, slip casting, pressure slip casting, extrusion molding, and the like. Therefore, the common ceramic preparation technology can be applied to the preparation of the high-thermal-conductivity silicon nitride ceramic substrate. Also, various sintering techniques such as pressureless sintering, gas pressure sintering, hot pressed sintering, and hot isostatic pressing sintering may be employed. The cutting can be carried out after biscuit firing or nitriding or after sintering, the process is more diversified, the time is short, the cost is low, and the large-scale product preparation is convenient.
Compared with the conventional tape casting preparation scheme, the preparation scheme of the silicon nitride ceramic substrate material provided by the invention has the advantages of simple process, short period and low cost. The basic properties of the silicon nitride ceramic substrate material prepared by the invention are as follows: the density is 3.2 to 3.5g/cm3Toughness of 6 to 9MPa m1/2And above, the bending strength is 600 to 900MPa, and the thermal conductivity is 90 to 100W/m.K. The size of the prepared silicon nitride ceramic substrate material is 114mm x 0.32 mm. Surface roughness: ra is less than or equal to 0.3 mu m; surface warping degree: is less than 0.1 percent.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The preparation technology of the silicon nitride ceramic substrate material provided by the invention is different from the common technology for preparing the ceramic substrate by tape casting, can adopt various traditional ceramic preparation technologies to prepare a biscuit, and has the advantages of simple process, short period, convenient operation and low cost. Can be combined with the traditional ceramic preparation process and is a feasible scheme for preparing the silicon nitride ceramic substrate. In particular for thicker ceramic substrates, but also for other types of ceramic substrates.
The invention adopts the cutting technology, can cut the biscuit after biscuit firing treatment or nitriding treatment, and then sinter at high temperature, or cut the silicon nitride ceramics after sintering at high temperature, the process is more diversified, the time is short, the cost is low, and the invention is convenient for large-scale product preparation. And finally, polishing the two surfaces to obtain the silicon nitride ceramic substrate material with proper thickness, surface roughness and surface warping degree. In addition, compared with the cutting of the silicon nitride ceramics after high-temperature sintering, the cutting of the biscuit after the biscuit firing treatment or the biscuit after the nitriding treatment is easier and the cost is lower. The following will illustrate the preparation method of the high thermal conductive silicon nitride ceramic substrate material provided by the present invention by embodiments.
Ceramic greenware (biscuit) is prepared. Mixing silicon nitride powder and sintering aid, and dispersing in organic solvent. Specifically, silicon nitride powder and the sintering aid system are dispersed in an organic solvent, then a dispersing agent and a binding agent are added and uniformly mixed, and after drying, the mixture is pressed and formed to obtain a biscuit. Wherein the binder is polyvinyl butyral or/and polymethyl methacrylate, and the addition amount of the binder is 0.5-10 wt% of the total mass of the mixed powder. The organic solvent can be at least one of ethanol, butanone, toluene, n-hexane, methanol, xylene, n-propanol and n-butanol, and the addition amount of the organic solvent is 14-50 wt% of the total mass of the mixed powder. The dispersing agent is at least one of triolein, phosphate ester, castor oil herring oil, ascorbic acid and terpineol, and the adding amount of the dispersing agent is 0.5-4 wt% of the total mass of the silicon nitride powder and the sintering aid system. The biscuit may also include a plasticizer. Wherein, the sintering aid system can be magnesium oxide and rare earth oxide, or magnesium oxide and double rare earth compound, or single rare earth compound (rare earth oxide), or at least two or more rare earth compounds. And then forming by dry pressing, isostatic pressing, dry pressing-isostatic pressing, grouting, pressure grouting, gel casting and other processes, wherein the mass ratio of the silicon nitride powder to the sintering aid system is (80-97): (20-3). Wherein the particle size of the silicon nitride powder is between 0.5 and 5 mu m. The particle size of the silicon powder is 1-20 μm. Or preparing silicon powder or mixed powder of silicon powder and silicon nitride powder, and the technological process is similar. When calculating the raw material powder, the mass of the silicon powder is calculated by converting the silicon powder into the mass of the silicon nitride powder. The second step is a de-binding and bisque firing treatment, the de-binding temperature typically being 900 ℃. After the bonding is removed, if biscuit cutting is needed, the temperature is continuously increased to 1600 ℃ for biscuit firing treatment, and then cutting is carried out. Bisque firing is to improve the strength of the ceramic body, the body must have a certain strength during cutting, and the body will not fracture (or crack) until the body is cut to a specified thickness, and the strength of the body is much lower than that of the sintered silicon nitride ceramic, so that the body can be cut more easily. Of course, the ceramic biscuit can not be cut before biscuit firing, and at the moment, the ceramic biscuit is of a porous structure, generally has low strength, is easy to break during cutting and is difficult to operate. If not cut, bisque firing is not required. Silicon powder and biscuit prepared by mixing the silicon powder and silicon nitride powder are subjected to nitridation treatment of the silicon powder after debonding. The de-bonding temperature is similar to that of silicon nitride powder, the de-bonding temperature is 600-900 ℃, and the time is 2-48 hours. Wherein the temperature of the nitridation treatment is usually 1380-1500 ℃. If dicing, dicing may follow the nitriding process. The nitriding treatment is to improve the strength of the ceramic body, and the body must have a certain strength during cutting, not break (or crack) until it is cut to a predetermined thickness, and have a strength much lower than that of the sintered silicon nitride ceramic, thereby facilitating cutting. Of course, the ceramic biscuit can not be cut before the nitriding treatment, and the ceramic biscuit has a porous structure, is generally low in strength, is easy to break during cutting and is difficult to operate.
And (5) sintering. The method adopts pressureless sintering, air pressure sintering, hot pressing sintering and high temperature isostatic pressing sintering processes. The sintering temperature of the silicon nitride ceramic substrate material is 1600-1950 ℃, the air pressure is 0.1-10 MPa, the sintering time is 1-24 h, and the atmosphere is nitrogen atmosphere.
In the present disclosure, the cutting process is divided into two types. Biscuit cutting and ceramic cutting. If biscuit cutting is adopted, two situations are divided: one is to cut a sample using silicon nitride powder as a starting material after bisque firing treatment (bisque firing). The biscuit prepared from the silicon powder and the mixed powder of the silicon powder and the silicon nitride is cut after the nitriding treatment (nitriding). And after cutting, heating and sintering, and then polishing the two sides of the sample to prepare the required ceramic substrate. The second is cutting after sintering. After cutting, double-side grinding is carried out to obtain the required substrate material, similar to the former case.
In the present disclosure, the dicing may employ a multi-chip dicing method or a multi-wire dicing method. And grinding the two sides of the substrate after cutting so as to meet the requirements of surface roughness and surface warping degree. Wherein, the multi-piece cutting process comprises: and grinding four sides of the sample, mounting the sample on a multi-piece cutting machine, and simultaneously cutting out a plurality of samples by adjusting the distance between cutting blades. The multi-line cutting process comprises the following steps: four sides of the sample are ground flat, and a plurality of samples are cut simultaneously by adjusting the line distance on the fixed multi-line cutting equipment. Among which is mainly multi-wire cutting. Because the silicon nitride ceramics have high hardness and toughness, the adopted multi-wire cutting equipment is easy to break wires, and surface tool marks can also appear. Therefore, technological parameters need to be carefully adjusted, the invention creatively adopts diamond wires with medium diameter to cut (the diameter can be 0.4-0.6 mm), and adopts a swinging wire supply mode to effectively improve the cutting efficiency, and meanwhile, chips are easy to discharge. The speed of the cutting wire is set to be less than or equal to 10m/s, and the feeding speed is set to be 0.005-0.05 mm/min, so as to avoid wire breakage as much as possible. If the wire is broken, the thick diamond wire (with the diameter of 0.4-0.6 mm) is led in by using the diamond wire (with the diameter of 0.25-0.3 mm) with the smaller diameter, and then the cutting is continued. Wherein the distance between the multiple diamond wires is generally 0.32 mm-2 mm (preferably 0.4-2 mm), which is the thickness value of the cut silicon nitride ceramic substrate. It should be noted that the above cutting multi-line cutting process parameters are also applicable to the biscuit-fired or nitrided blank.
The invention provides a method for preparing a silicon nitride ceramic substrate material by adopting a cutting method, which not only has the same performance as a tape casting process. And has the advantages of high preparation speed and low cost, and is a new preparation scheme of the ceramic substrate material.
The relative density of the silicon nitride ceramic substrate material measured by the Archimedes drainage method is 98-99.5%. The thermal conductivity of the silicon nitride ceramic substrate material is measured to be 90-100W/m.K by adopting a laser thermal conductivity meter method. Measuring the toughness of the silicon nitride ceramic substrate material by adopting a unilateral notched beam method to be 6-9 MPa-m1/2And the above. And the bending strength of the silicon nitride ceramic substrate material is 600-900 MPa measured by a three-point bending method. Measuring the surface roughness of the silicon nitride ceramic substrate material by using a surface roughness measuring instrument: ra is less than or equal to 0.3 mu m. MiningAnd measuring the surface warping degree of the silicon nitride ceramic substrate material by using a warping degree tester: is less than 0.1 percent.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. Unless otherwise specified, the particle diameters of the silicon nitride powder and the silicon powder in the following examples are generally 0.2 to 2 μm. The particle size distribution of the sintering aid system is 0.5-10 mu m.
Example 1
97g of silicon nitride powder and 3g of a sintering aid (magnesia-yttria) were added to a 50g ethanol/butanone solvent system (ethanol to butanone mass ratio 34: 66) with a molar ratio of magnesia to yttria of 5: 2. 1g of triolein is used as a dispersing agent, 0.5g of PVB is used as a bonding agent, and the materials are put into an oven to be dried for 24 hours at 60 ℃ after ball milling. Then, the mixture is taken out and sieved by a 100-mesh sieve. And putting the sieved powder into a mold for dry pressing and molding. Then cold isostatic pressing is adopted for treatment at 200MPa-1 min. After treatment, the mixture is put into a carbon tube furnace, heated to 900 ℃ at the speed of 1 ℃/min under vacuum, kept warm for 1h to complete the debonding, and continuously heated to 1500 ℃ and kept warm for 2h to complete the bisque firing. The sample after the biscuiting treatment is cut by adopting a multi-wire cutting device (CX8080 type diamond wire cutting machine, the slice thickness is 0.40mm), and the thickness is 0.45 mm. A diamond wire of 0.6mm was used, and the speed of travel of the cutting wire was set to 10m/s and the feed speed was set to 0.005mm/min in a swinging wire feed manner. Sintering the cut biscuit in a carbon tube furnace, and keeping the temperature for 2h at 0.9MPa and the temperature rising rate of 5 ℃/min to 1900 ℃ to realize sintering. Then the compact and complete silicon nitride ceramic substrate is prepared after double-side polishing.
Example 2
95g of silicon nitride powder and 5g of sintering aid (magnesium oxide-ytterbium oxide) are added into a 50g ethanol/butanone solvent system (the mass ratio of ethanol to butanone is 34: 66), and the molar ratio of magnesium oxide to ytterbium oxide is 5: 2. 2g of triolein is used as a dispersing agent, 1g of PVB is used as a binder, and the mixture is put into an oven to be dried for 24 hours at 60 ℃ after ball milling. Then, the mixture is taken out and sieved by a 100-mesh sieve. And putting the sieved powder into a mold for dry pressing and molding. Then cold isostatic pressing is adopted for treatment at 200MPa-1 min. After treatment, the mixture is put into a carbon tube furnace, and the temperature is raised to 900 ℃ at the speed of 1 ℃/min under vacuum, and the temperature is preserved for 1h to complete the debonding. Sintering the disbonded biscuit in a carbon tube furnace, wherein the temperature rise rate reaches 1950 ℃ at 5 ℃/min, and the sintering is realized by preserving the heat for 2h under 2 MPa. And cutting the sintered ceramic by adopting multi-wire cutting equipment (CX8080 type diamond wire cutting machine with the slice thickness of 0.40mm), wherein the thickness is 0.38mm. A diamond wire of 0.6mm is adopted, the wire feeding speed is set to be 9m/s in a swinging wire feeding mode, and the feeding speed is set to be 0.008 mm/min. And preparing a compact and complete silicon nitride ceramic substrate after double-side polishing.
Example 3
90g of silicon nitride powder and 10g of sintering aid (magnesium oxide-lutetium oxide) are added into a 50g ethanol/butanone solvent system (the mass ratio of ethanol to butanone is 34: 66), and the molar ratio of magnesium oxide to lutetium oxide is 5: 2. 3g of triolein is used as a dispersing agent, 2g of PVB is used as a binder, and the mixture is put into an oven to be dried for 24 hours at 60 ℃ after ball milling. Then, the mixture is taken out and sieved by a 100-mesh sieve. And putting the sieved powder into a mold for dry pressing and molding. Then cold isostatic pressing is adopted for treatment at 200MPa-1 min. After treatment, the mixture is put into a carbon tube furnace, and the temperature is raised to 900 ℃ at the speed of 1 ℃/min under vacuum, and the temperature is preserved for 1h to complete the debonding. Sintering the disbonded biscuit in a carbon tube furnace, and keeping the temperature at 0.6MPa for 4h at the temperature rise rate of 4 ℃/min of 1900 ℃ to realize sintering. The sintered ceramic is cut by adopting a multi-wire cutting device (CX8080 type diamond wire cutting machine, the slice thickness is 0.40mm), the thickness is 0.38mm, a 0.4mm diamond wire is adopted, the wire feeding speed is set to be 8m/s in a swinging wire feeding mode, and the feeding speed is set to be 0.01 mm/min. Then the compact and complete silicon nitride ceramic substrate is prepared after double-side polishing.
Example 4
80g of silicon nitride powder and 20g of a sintering aid (magnesia-titania) were added to a 50g ethanol/butanone solvent system (ethanol to butanone mass ratio of 34: 66), the molar ratio of magnesia to titania being 5: 2. 3g of triolein is used as a dispersing agent, 2g of PVB is used as a binder, and the mixture is put into an oven to be dried for 24 hours at 60 ℃ after ball milling. Then, the mixture is taken out and sieved by a 100-mesh sieve. And putting the sieved powder into a mold for dry pressing and molding. Then cold isostatic pressing is adopted for treatment at 200MPa-1 min. After treatment, the mixture is put into a carbon tube furnace, and the temperature is raised to 900 ℃ at the speed of 1 ℃/min under vacuum, and the temperature is preserved for 1h to complete the debonding. Sintering the disbonded biscuit in a carbon tube furnace, wherein the temperature rise rate reaches 1800 ℃ at 3 ℃/min, and the sintering is realized by keeping the temperature for 6h in nitrogen atmosphere. The sintered ceramic is cut by adopting a multi-wire cutting device (CX8080 type diamond wire cutting machine, the slice thickness is 0.40mm), the thickness is 0.38mm, a 0.6mm diamond wire is adopted, the wire feeding speed is set to be 10m/s in a swinging wire feeding mode, and the feeding speed is set to be 0.05 mm/min. Then the compact and complete silicon nitride ceramic substrate is prepared after double-side polishing.
Example 5
54g of silicon powder (corresponding to 90g of silicon nitride powder) and 10g of sintering aid (magnesium oxide-dysprosium oxide) were added to 50g of ethanol/butanone solvent system (the mass ratio of ethanol to butanone was 34: 66), and the molar ratio of magnesium oxide to dysprosium oxide was 5: 2. 3g of triolein is used as a dispersing agent, 2g of PVB is used as a binder, and the mixture is put into an oven to be dried for 24 hours at 60 ℃ after ball milling. Then, the mixture is taken out and sieved by a 100-mesh sieve. And putting the sieved powder into a mold for dry pressing and molding. Then cold isostatic pressing is adopted for treatment at 200MPa-1 min. After treatment, the mixture is put into a carbon tube furnace, the temperature is increased to 900 ℃ at the speed of 1 ℃/min under vacuum, the heat preservation is carried out for 1h, the debonding is finished, the temperature is increased to 1400 ℃ at the speed of 2 ℃/min, and the heat preservation is carried out in 8h nitrogen atmosphere, so that the nitridation is finished. The biscuit after the nitriding treatment is cut by adopting a multi-wire cutting device (CX8080 type diamond wire cutting machine, the slice thickness is 0.40mm), and the thickness is 0.45 mm. A diamond wire of 0.6mm is adopted, the wire feeding speed is set to be 5m/s in a swinging wire feeding mode, and the feeding speed is set to be 0.05 mm/min. Sintering the cut biscuit in a carbon tube furnace, and keeping the temperature for 6h at 0.9MPa and the temperature rising rate of 2 ℃/min to 1900 ℃ to realize sintering. And preparing a compact and complete silicon nitride ceramic substrate after double-side polishing.
Example 6
45g of silicon nitride powder, 27g of silicon powder (equivalent to 45g of silicon nitride powder) and 10g of sintering aid (magnesia-erbium oxide) were added to 50g of ethanol/butanone solvent system (ethanol to butanone mass ratio 34: 66) with a molar ratio of magnesia to erbium oxide of 5: 2. 3g of triolein is used as a dispersing agent, 2g of PVB is used as a binder, and the mixture is put into an oven to be dried for 24 hours at 60 ℃ after ball milling. Then, the mixture is taken out and sieved by a 100-mesh sieve. And putting the sieved powder into a mold for dry pressing and molding. Then cold isostatic pressing is adopted for treatment at 200MPa-1 min. After treatment, the mixture is put into a carbon tube furnace, the temperature is increased to 900 ℃ at the speed of 1 ℃/min under vacuum, the heat is preserved for 1h to finish the debonding, the temperature is increased to 1400 ℃ at the speed of 2 ℃/min, and the heat is preserved for 8h in nitrogen atmosphere to finish the nitridation. And sintering the nitrided biscuit in a carbon tube furnace, wherein the temperature rise rate reaches 1900 ℃ at 1 ℃/min, and the temperature is kept at 1MPa for 12h to realize sintering. Then, the sintered ceramic is cut by using a multi-wire cutting device (CX8080 type diamond wire cutting machine, the slice thickness is 0.40mm), and the thickness is 0.38mm. A diamond wire of 0.45mm is adopted, the wire feeding speed is set to be 8m/s in a swinging wire feeding mode, and the feeding speed is set to be 0.02 mm/min. And cutting and polishing to prepare the compact and complete silicon nitride ceramic substrate.
Table 1 shows the performance parameters of the high thermal conductivity silicon nitride ceramic substrate materials prepared in examples 1 to 6 of the present invention:
Claims (12)
1. a preparation method of a high-thermal-conductivity silicon nitride ceramic substrate material is characterized by comprising the following steps:
mixing silicon nitride powder or/and silicon powder serving as raw material powder with a sintering aid to obtain mixed powder;
mixing the mixed powder and a binder, granulating, and performing compression molding to obtain a biscuit;
when the raw material powder is only silicon nitride powder, the obtained biscuit is subjected to de-bonding and biscuit firing treatment, then is cut into a given thickness, and is sintered to obtain the silicon nitride ceramic substrate material, wherein the biscuit firing treatment temperature is 1200-1600 ℃ and the biscuit firing treatment time is 1-12 hours;
or when the raw material powder contains silicon powder, cutting the biscuit into a specified thickness after de-bonding and nitriding treatment, and sintering to obtain the silicon nitride ceramic substrate material, wherein the nitriding treatment is performed in nitrogen atmosphere at 1380-1500 ℃ for 2-48 hours;
the cutting process is a multi-sheet cutting process or a multi-line cutting process; the predetermined thickness is 0.32mm to 2 mm.
2. The method according to claim 1, wherein the sintering aid is magnesium oxide, titanium oxide, Y2O3At least two of lanthanide rare earth oxides; the mass ratio of the raw material powder to the sintering aid is (80-97): (20-3) when the raw material powder contains silicon powder, the mass of the silicon powder is calculated by the mass converted into silicon nitride powder.
3. The method according to claim 2, wherein when the sintering aid comprises titanium oxide, Y2O3At least one of lanthanide rare earth oxides, and magnesium oxide; the titanium oxide and Y2O3The ratio of the molar content of at least one of the lanthanide rare earth oxides to the molar content of the magnesium oxide is (2-5): 5.
4. the method according to claim 3, wherein when the sintering aid comprises Y2O3At least two of lanthanide rare earth oxides, and magnesium oxide; said Y is2O3The ratio of the molar contents of at least two of the lanthanide rare earth oxides to the molar content of magnesium oxide is (2-5): 5.
5. the method of claim 2, wherein the sintering aid comprises Y2O3And at least two of lanthanide rare earth oxides.
6. The preparation method according to claim 1, wherein the particle size of the silicon nitride powder is in a range of 0.5 to 5 μm, and the particle size of the silicon powder is in a range of 1 to 20 μm.
7. The method of manufacturing of claim 1, wherein the dicing process is a multi-wire dicing process; the multi-line cutting process comprises the following steps: cutting by using a diamond wire with the diameter of 0.4-0.6 mm as a cutting line and adopting a swinging wire supply mode; the running speed of the cutting line is set to be less than or equal to 10m/s, and the feeding speed is set to be 0.005-0.05 mm/min.
8. The preparation method according to claim 1, wherein the binder is polyvinyl butyral or/and polymethyl methacrylate, and the addition amount is 0.5-10 wt% of the total mass of the mixed powder; mixing the mixed powder, an organic solvent, a dispersant and a binder, drying and granulating, and then performing compression molding to obtain a biscuit; the organic solvent is at least one of ethanol, butanone, toluene, n-hexane, methanol, xylene, n-propanol and n-butanol, and the addition amount of the organic solvent is 14-50 wt% of the total mass of the mixed powder; the dispersing agent is at least one of triolein, phosphate ester, castor oil herring oil, ascorbic acid and terpineol, and the adding amount of the dispersing agent is 0.5-4 wt% of the total mass of the silicon nitride powder and the sintering aid system.
9. The method according to claim 1, wherein the temperature of the de-binding is 600 to 900 ℃ and the time is 2 to 48 hours.
10. The production method according to claim 1, wherein the sintering is performed by pressureless sintering, gas pressure sintering, hot press sintering, or isostatic pressing sintering; the sintering atmosphere is nitrogen atmosphere, the temperature is 1600-1950 ℃, the air pressure is 0.1-10 MPa, and the time is 1-24 hours; the temperature rise rate of the sintering is 1-5 ℃/min.
11. The method according to any one of claims 1 to 10, wherein the predetermined thickness is 0.4 to 2 mm.
12. A high thermal conductive silicon nitride ceramic substrate material prepared according to the preparation method described in any one of claims 1 to 11.
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