CN115925399B - Thermal shock resistant ceramic substrate and preparation method thereof - Google Patents
Thermal shock resistant ceramic substrate and preparation method thereof Download PDFInfo
- Publication number
- CN115925399B CN115925399B CN202211353541.3A CN202211353541A CN115925399B CN 115925399 B CN115925399 B CN 115925399B CN 202211353541 A CN202211353541 A CN 202211353541A CN 115925399 B CN115925399 B CN 115925399B
- Authority
- CN
- China
- Prior art keywords
- ceramic substrate
- sintering
- alumina
- mass
- ball milling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 113
- 239000000758 substrate Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 230000035939 shock Effects 0.000 title abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005245 sintering Methods 0.000 claims abstract description 56
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000000292 calcium oxide Substances 0.000 claims abstract description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000015895 biscuits Nutrition 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005452 bending Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 235000010944 ethyl methyl cellulose Nutrition 0.000 claims 1
- 235000010981 methylcellulose Nutrition 0.000 claims 1
- 229920003087 methylethyl cellulose Polymers 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 11
- 235000012255 calcium oxide Nutrition 0.000 description 10
- 229910010293 ceramic material Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000013022 formulation composition Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The invention discloses a thermal shock resistant ceramic substrate and a preparation method thereof. The ceramic substrate comprises the following components in percentage by mass: 96-97% of aluminum oxide, 0.8-3.5% of magnesium oxide, 0.2-2.5% of silicon oxide and 0.3-1.0% of calcium oxide. The preparation method of the ceramic substrate comprises the following steps: s1: mixing alumina powder and a grinding solvent, performing ball milling to obtain slurry, and mixing the slurry with a binder, a plasticizer and a sintering aid to obtain a mixture; s2: removing grinding solvent from the mixture, casting and forming into a biscuit, and then manufacturing a biscuit sheet; s3: and sintering the blank to obtain the ceramic substrate. The ceramic substrate with excellent thermal shock resistance provided by the invention has the advantages of low thermal expansion coefficient and high strength, simple preparation process, easiness in operation control and wide application prospect.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a thermal shock resistant ceramic substrate and a preparation method thereof.
Background
Alumina ceramics have many advantages such as higher strength, greater hardness, good wear and high temperature resistance, better thermal conductivity, chemical resistance and electrical insulation, and thus are widely used in many fields.
However, the existing alumina ceramics have the defect of poor thermal shock resistance, which limits the application range of the ceramic. Therefore, how to improve the thermal shock resistance of alumina ceramics becomes a technical problem to be solved by the person skilled in the art.
Disclosure of Invention
The present invention aims to solve the above-mentioned technical problems existing in the prior art. It is therefore an object of the present invention to provide a ceramic substrate having excellent thermal shock resistance, a method for producing the ceramic substrate, and a third object of the present invention to provide an application of the ceramic substrate.
Thermal shock resistance refers to the ability of a material to withstand rapid changes in temperature without being damaged. The calculation formula for the thermal shock resistance R of the precision ceramic is as follows:
in the formula, R-thermal shock resistance coefficient; sigma (sigma) f -flexural strength; k-thermal conductivity; e-modulus of elasticity; alpha-poisson ratio; gamma-thermal expansion coefficient.
The mechanical properties related to the thermal shock resistance of the alumina ceramic material mainly comprise bending strength, elastic modulus and the like. Thermal properties related to thermal shock resistance of alumina ceramic materials are mainly thermal expansion coefficient and thermal conductivity. Therefore, the thermal shock resistance of the alumina ceramic material can be improved by improving the flexural strength and the thermal conductivity of the material and reducing the elastic modulus and the thermal expansion coefficient of the material.
In addition to the influence of the properties of the material itself, the properties of the ceramic material are mainly influenced by the porosity and the grain size. The greater the porosity, the lower the strength and thermal conductivity of the material, the greater the grain size and the lower the strength.
Therefore, the invention considers the formula of the alumina ceramic, controls the grain size, the phase and the porosity of the ceramic material by a ball milling process and a sintering process, reduces the thermal expansion coefficient of the ceramic material and improves the strength, thereby obtaining the ceramic substrate with excellent thermal shock resistance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a ceramic substrate, which comprises the following components in percentage by mass: 96-97% of aluminum oxide, 0.8-3.5% of magnesium oxide, 0.2-2.5% of silicon oxide and 0.3-1.0% of calcium oxide.
The ratio of calcium oxide to magnesium oxide affects the grain size and porosity. When the content of calcium oxide exceeds 1.0wt%, the porosity of the sintered product at the grain boundary is larger; when the content of calcium oxide is less than 0.3wt%, the ceramic dielectric properties are poor; when the content of magnesium oxide is more than 3.5wt%, enrichment is easy, secondary phases are generated, resulting in low strength; when the content of magnesium oxide is less than 0.8wt%, the porosity on the crystal face is large. Therefore, the thermal shock resistance of the alumina ceramic can be effectively improved by controlling the mass content of the magnesium oxide to be 0.8-3.5% and the mass content of the calcium oxide to be 0.3-1.0%.
In the ceramic substrate, the sum of the mass percentages of aluminum oxide, magnesium oxide, silicon oxide and calcium oxide is 100%.
Preferably, in the ceramic substrate, the alumina crystal in the ceramic substrate has the following characteristics: the alumina crystal is a long rod-shaped crystal.
Preferably, in the ceramic substrate, the alumina crystal in the ceramic substrate has the following characteristics: the alumina crystal with the diameter of more than 10 mu m accounts for less than or equal to 3 percent of the total alumina crystal by mass.
Preferably, in the ceramic substrate, the alumina crystal in the ceramic substrate has the following characteristics: the particle diameter D50 of the alumina crystal is 3.2 μm to 3.8 μm.
Preferably, the ceramic substrate has a flexural strength >350MPa; further preferably, the ceramic substrate has a flexural strength of 351MPa to 400MPa.
Preferably, the porosity of the ceramic substrate is less than or equal to 2%; further preferably, the porosity of the ceramic substrate is 0.9% to 2%.
Preferably, the porosity of the ceramic substrate is less than or equal to 1.7%; further preferably, the porosity of the ceramic substrate is 0.9% to 1.7%.
Preferably, the thermal conductivity of the ceramic substrate is > 20W/(mK); further preferably, the thermal conductivity of the ceramic substrate is not less than 21W/(mK); still more preferably, the thermal conductivity of the ceramic substrate is 21W/(mK) to 23W/(mK).
Preferably, the ceramic substrate has a thermal expansion coefficient of < 7.0X10 at 20 ℃ to 400 DEG C -6 a/DEG C; further preferably, the ceramic substrate has a thermal expansion coefficient of 6.00×10 at 20 ℃ to 400 DEG C -6 /℃～6.99×10 -6 /℃。
Preferably, the density of the ceramic substrate is more than or equal to 3.7g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Further preferably, the ceramic substrate has a density of 3.7g/cm 3 ～4.0g/cm 3 。
A second aspect of the present invention provides a method for preparing a ceramic substrate according to the first aspect of the present invention, comprising the steps of:
s1: mixing alumina powder and a grinding solvent, performing ball milling to obtain slurry, and mixing the slurry with a binder, a plasticizer and a sintering aid to obtain a mixture; the sintering aid comprises magnesium oxide, silicon oxide and calcium oxide;
s2: removing grinding solvent from the mixture, casting and forming into a biscuit, and then manufacturing a biscuit sheet;
s3: and sintering the blank to obtain the ceramic substrate.
Preferably, in step S1 of the ceramic substrate preparation method, the particle size of the alumina powder is submicron; further preferably, the alumina powder has a particle diameter of 0.5 μm to 1. Mu.m.
Preferably, in step S1 of the method for producing a ceramic substrate, the particle diameter D50 of the magnesium oxide is 2 μm to 6 μm.
Preferably, in the ball milling of the step S1 of the preparation method of the ceramic substrate, the mass ratio of the alumina powder to the grinding balls is 1: (0.8-2.3); further preferably, the mass ratio of the alumina powder to the grinding ball is 1: (0.9-1.2).
Preferably, in the ball milling of the step S1 of the preparation method of the ceramic substrate, the diameter of the grinding balls is 8-20 mm.
Preferably, in the ball milling of the step S1 of the preparation method of the ceramic substrate, the grinding balls are zirconia balls.
Preferably, in the ball milling of the step S1 of the preparation method of the ceramic substrate, the mass of the grinding solvent is 5% -20% of the mass of the alumina powder; further preferably, the mass of the grinding solvent is 5 to 12% of the mass of the alumina powder.
Preferably, in the ball milling of the step S1 of the preparation method of the ceramic substrate, the rotation speed of the ball milling is 200 r/min-1200 r/min; further preferably, the rotation speed of the ball mill is 600r/min to 1000r/min.
Preferably, in the ball milling of the step S1 of the preparation method of the ceramic substrate, the ball milling time is 10 hours to 30 hours; further preferably, the ball milling time is 10 to 20 hours.
Preferably, in the ball milling of the step S1 of the preparation method of the ceramic substrate, the ball milling is carried out until the powder particle diameter D50 of the slurry is 0.6-1.2 mu m; further preferably, the powder particle diameter D50 of the slurry obtained by ball milling is 0.8 μm to 1. Mu.m.
Preferably, in step S1 of the ceramic substrate preparation method, the grinding solvent includes at least one of ethanol, isopropanol, glycerol, and n-hexane; further preferably, the milling solvent comprises at least one of isopropyl alcohol and glycerol.
Preferably, in step S1 of the method for preparing a ceramic substrate, the binder includes at least one of polyvinyl butyral Ding Quanzhi (PVB), polyacrylate, methylcellulose, ethylcellulose, and polyvinyl alcohol; further preferably, the binder includes at least one of polyvinyl alcohol Ding Quanzhi and polyvinyl alcohol.
Preferably, in step S1 of the preparation method of a ceramic substrate, the mass of the binder is 5% -10% of the mass of the alumina powder.
Preferably, in step S1 of the ceramic substrate preparation method, the plasticizer includes at least one of phthalate, o-xylene dibutyl ester, and polymethyl methacrylate.
Preferably, in step S1 of the method for preparing a ceramic substrate, the mass of the plasticizer is 2% -15% of the mass of the binder.
Preferably, in step S1 of the method for preparing a ceramic substrate, the slurry is mixed with the binder, the plasticizer and the sintering aid for 10-30 hours; it is further preferred that the slurry is mixed with the binder, plasticizer and burn aid for a period of 10 to 20 hours.
Preferably, in step S1 of the preparation method of a ceramic substrate, the mass ratio of calcium oxide to magnesium oxide is 1: (1-1.5).
Preferably, in step S2 of the preparation method of a ceramic substrate, the solid content of the mixture after the grinding solvent is removed is 70wt% to 80wt%.
Preferably, in step S2 of the method for preparing a ceramic substrate, the method for removing the polishing solvent is vacuum removal.
Preferably, in step S2 of the method for preparing a ceramic substrate, the thickness of the biscuit is 0.56mm to 0.64mm; further preferably, the thickness of the biscuit is 0.58mm to 0.62mm.
Preferably, in step S2 of the method for preparing a ceramic substrate, the green sheet is formed by molding a green body with a mold and punching the green body into a green sheet.
Preferably, in the sintering of the step S3 of the preparation method of the ceramic substrate, the heating rate is 2 ℃/min-10 ℃/min. When the temperature rising rate is less than 2 ℃/min, the temperature rising rate is too slow, and a foreign phase is easy to generate; when the temperature rising rate is more than 10 ℃/min, the temperature rising rate is too high, crystal grains are not burned, the size difference of the crystal grains is large, and the uniformity is poor.
Further preferably, in the sintering of the step S3 of the method for preparing a ceramic substrate, the heating rate is 4 ℃/min to 7 ℃/min.
Preferably, in the sintering of the step S3 of the ceramic substrate preparation method, the gas flow is 20m 3 /h～80m 3 And/h. When the gas flow is less than 20m 3 And/h, the internal heat flow is difficult to enter, so that the product is heated unevenly and broken crystals exist, and the compactness and strength are affected; when the gas flow is more than 80m 3 And/h, the product can slide easily in the sintering process, and the sample sliding phenomenon exists.
Preferably, in step S3 of the method for preparing a ceramic substrate, the gas used for sintering is air.
Preferably, in the sintering of the step S3 of the preparation method of the ceramic substrate, the sintering temperature is 1500-1700 ℃. When the sintering temperature is lower than 1500 ℃, the sintering temperature is too low, more broken crystals in the ceramic are generated, the strength is low, and the compactness is poor; when the sintering temperature is higher than 1700 ℃, the sintering temperature is too high, local overburning exists, and abnormal large grains are easy to generate, so that the compactness and the strength are poor.
Further preferably, in the sintering of the step S3 of the preparation method of the ceramic substrate, the sintering temperature is 1650 ℃ to 1700 ℃; still more preferably, the sintering temperature is 1650℃to 1675 ℃.
Preferably, in the sintering of the step S3 of the preparation method of the ceramic substrate, the heat preservation time at the sintering temperature is 2-4 h. The heat preservation time is too short, which can lead to insufficient sintering; the heat preservation time is too long, and the burning is easy. Therefore, the holding time is in a proper range of 2 to 4 hours.
Preferably, in the sintering of the step S3 of the preparation method of the ceramic substrate, the cooling rate is 3 ℃/min-15 ℃/min. When the cooling rate is more than 15 ℃/min, the cooling rate is too fast, and ceramic forming fracture is caused by uneven sintering; when the cooling rate is less than 3 ℃/min, the cooling rate is too slow, the energy consumption is high, and the cost is high.
Further preferably, in the sintering of the step S3 of the preparation method of the ceramic substrate, the cooling rate is 4 ℃/min to 5 ℃/min.
In a third aspect, the present invention provides a use of a ceramic substrate according to the first aspect of the present invention or a ceramic substrate according to the second aspect of the present invention in the manufacture of an electronic device or a semiconductor device.
Preferably, the ceramic substrate is applied to preparing MOSFET, IGBT, transistor, chip, electronic heater or high-frequency switch power supply.
The beneficial effects of the invention are as follows:
the ceramic substrate with excellent thermal shock resistance provided by the invention has the advantages of low thermal expansion coefficient and high strength, simple preparation process, easiness in operation control and wide application prospect.
Specifically, compared with the prior art, the invention has the following advantages:
1. the slurry with uniform particle size is obtained by controlling the adding amount, size and ball milling time of the grinding balls. The process can achieve the proportion of alumina grains in the ceramic substrate below 3%, and improves the uniformity of grain size.
2. The ceramic substrate with excellent thermal shock property is obtained by adopting an in-situ sintering method through one-step synthesis, and the method is simple, easy to operate and convenient to control.
3. The invention obtains small grain size by controlling the conditions of gas flow, heating rate, heat preservation time, cooling rate and the like. A ceramic substrate with a bottom and a uniform phase.
Drawings
FIG. 1 is a scanning electron microscope image of a ceramic substrate of example 2;
FIG. 2 is a graph showing the grain size distribution of alumina grains of the ceramic substrate of example 2;
FIG. 3 is a scanning electron microscope image of the ceramic substrate of comparative example 2;
FIG. 4 is a graph showing the grain size distribution of alumina grains of the ceramic substrate of comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were either commercially available from conventional sources or may be obtained by prior art methods unless specifically indicated. Unless otherwise indicated, assays or testing methods are routine in the art.
Table 1 shows the formulation compositions of the ceramic substrates of the examples and comparative examples. The alumina used was a high purity submicron alumina powder having a particle diameter D50 of 1 μm. The particle diameter D50 of the magnesium oxide is 2-6 mu m.
Table 1 formulation composition of the ceramic substrates of examples and comparative examples
Example 1
Example 1 the formulation composition of the alumina ceramic substrate is shown in table 1.
The preparation method of the alumina ceramic substrate comprises the following steps:
1) Ball milling: mixing alumina powder in a zirconia ball milling tank to obtain powder: zirconia balls were added to a ball mill pot at a mass ratio of=1:1, then glycerol was added as a milling solvent, wherein the amount of glycerol was 10wt% of the amount of powder, zirconia balls (diameter 20 mm) were used as milling media, ball milling was performed at 800r/min for 15 hours, the slurry particle size was measured, the particle size D50 of the powder was controlled at 1 μm, and then binder PVB, plasticizer polymethyl methacrylate, and sintering aid (such as the added amounts of magnesium oxide, silicon oxide and calcium oxide in table 1) were added and blended for 20 hours. Wherein the addition amount of the adhesive is 5% of the mass of the alumina powder, and the addition amount of the plasticizer is 8% of the mass of the adhesive.
2) Removing the solvent in vacuum after discharging to ensure that the solid content of the slurry reaches 70wt%;
3) Casting: controlling casting parameters, and forming into a biscuit with the thickness of 0.6mm by casting;
4) And (3) forming: forming by a mould, and punching into blank sheets with corresponding sizes;
5) Sintering: the product is prepared by adopting an in-situ sintering method, and the gas (air) flow is 40m 3 And (3) at the temperature of/h, heating from the room temperature to the sintering temperature of 1700 ℃ at a heating rate of 6 ℃/min, preserving heat for 2h, and then cooling to the room temperature at a cooling rate of 4 ℃/min to finish sintering, thereby obtaining the alumina ceramic substrate of the embodiment.
Examples 2 to 12
Examples 2 to 12 are different from example 1 in the content of alumina powder and sintering aid (magnesia, silica and calcia), and the rest is the same as example 1. The ceramic substrate formulations of examples 2-12 are detailed in Table 1.
Examples 13 to 19
Examples 13 to 19 differ from example 1 in the sintering process.
The temperature rise rate of the curve in example 13 was 4℃per minute, and the rest was the same as in example 1.
The temperature rise rate of the curve in example 14 was 7℃per minute, and the rest was the same as in example 1.
The gas (air) flow rate in example 15 was 20m 3 And/h, the remainder being the same as in example 1.
The gas (air) flow rate in example 16 was 80m 3 And/h, the remainder being the same as in example 1.
The sintering temperature in example 17 was kept at 1500℃for 4 hours, and the rest was the same as in example 1.
The cooling rate in example 18 was 3℃per minute, and the rest was the same as in example 1.
The cooling rate in example 19 was 15℃per minute, and the rest was the same as in example 1.
Comparative examples 1 to 9
Comparative examples 1 to 9 are different from example 1 in the content of alumina powder and the content of a sintering aid, and the rest is the same as example 1. The formulation of the ceramic substrates of comparative examples 1-9 are detailed in Table 1.
Comparative examples 10 to 16
Comparative examples 10 to 16 differ from example 1 in the sintering process.
The temperature rise rate of the curve in comparative example 10 was 3℃per minute, and the rest was the same as in example 1.
The temperature rise rate of the curve in comparative example 11 was 12℃per minute, and the rest was the same as in example 1.
Comparative example 12 gas (air) flow 5m 3 And/h, the remainder being the same as in example 1.
Comparative example 13 gas (air) flow 100m 3 And/h, the remainder being the same as in example 1.
The sintering temperature of comparative example 14 was 1450℃for 6 hours, and the remainder was the same as in example 1.
The cooling rate in comparative example 15 was 2℃per minute, and the rest was the same as in example 1.
The cooling rate in comparative example 16 was 20℃per minute, and the rest was the same as in example 1.
The alumina ceramic substrates prepared in examples 1 to 19 and comparative examples 1 to 16 were subjected to performance test, and the performance test method is described as follows:
flexural strength: using an electronic universal material tester, three-point bending test, preparing a sample by using laser scribing, wherein the size of the sample is bxl x h=24 x 40 x 1mm, and the span is as follows: 30mm, test speed: 0.5mm/min.
Porosity: FE-SEM pictures were taken and calculated analytically.
Coefficient of thermal expansion: sample dicing was a 10mm diameter wafer test using TMA.
Density: using the drainage principle. The test samples were >2g and the instrument used a densitometer.
Surface roughness: the roughness meter was used for testing.
Thermal conductivity: specific heat capacity was measured using low temperature DSC: scribing the sample, namely testing a wafer with the diameter of 5 mm; specific heat diffusion coefficient was measured using a heat conduction instrument: the sample was diced into 10mm diameter discs for testing. Thermal conductivity λ=thermal diffusivity α density ρ specific heat c.
Thermal shock resistance test: placing the plate with the impression face facing upwards, adding the plate at 180 ℃, preserving heat for 30 seconds, pushing the plate into a water tank at 25 ℃, drying water in a drying oven at 100 ℃, coating red, and counting the cracking condition. Specifically, 8000-10000 samples are prepared in each batch, 100 samples are randomly sampled in each batch, 20 batches are tested in total, and finally, the ratio of the number of fragments to the total number of tests is counted.
The results of the performance tests of the ceramic substrates of the examples and comparative examples are given in Table 2.
Table 2 results of performance testing of example and comparative ceramic substrates
As is clear from the results of Table 2, the alumina ceramic substrate prepared in the examples of the present invention has flexural strength>350MPa, porosity less than 1.7%, thermal conductivity more than 20W/(m.K), thermal expansion coefficient less than 7.0X10 -6 Per DEG C (20-400 ℃). The alumina ceramic substrate prepared by the embodiment of the invention has the thermal shock resistance of less than or equal to 12 percent.
FIG. 1 is a scanning electron microscope image of a ceramic substrate of example 2. FIG. 2 is a graph showing the grain size distribution of alumina grains in the ceramic substrate of example 2. As is clear from FIGS. 1 to 2, in the alumina ceramic substrate obtained in the examples, the crystal grain shape of the alumina crystal is a long rod-like crystal, the crystal grain ratio of more than 10 μm is 3% or less, the size distribution (D50) is in the range of 3.2 to 3.8. Mu.m, and the sintering is uniform. FIG. 3 is a scanning electron microscope image of the ceramic substrate of comparative example 2. FIG. 4 is a graph showing the grain size distribution of alumina grains in the ceramic substrate of comparative example 2. As can be seen from FIGS. 3 to 4, the alumina ceramic substrate obtained in the comparative example was unevenly sintered, and alumina grains larger than 10 μm accounted for about 10%. The ceramic substrate manufactured by the existing sintering process has the advantages that most of crystal grains larger than 10 mu m account for more than 10%, the proportion of the crystal grains can be less than 3% by adopting the preparation process provided by the invention, and the uniformity of the crystal grain size is greatly improved.
The glass phase content of the alumina ceramic substrate prepared by the embodiment of the invention is below 2%. The impact of glass on ceramic substrate performance is as follows: 1. the glass phase strength is low, and when the glass phase strength is more than 2%, the ceramic forming overall strength is lower, and the compactness of the material is poor. 2. The glassy phase is amorphous and when the ratio exceeds 2%, it results in poor dielectric properties of the material.
According to the experimental results, the grain size, the phase and the porosity of the ceramic material are controlled through the ball milling process and the sintering process, so that the thermal expansion coefficient of the ceramic material is reduced, the strength is improved, and the ceramic substrate with excellent thermal shock resistance is prepared.
The ceramic substrate provided by the invention can be applied to the field of semiconductors, such as a main stream power device represented by MOSFET, IGBT and transistor, and can replace GTR to become an inverter, a UPS, a frequency converter, a motor drive and the like; but also in chips such as LED chips; the method can also be applied to the preparation of electronic heaters, high-frequency switching power supplies and the like.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The ceramic substrate is characterized by comprising the following components in percentage by mass: 96-97% of aluminum oxide, 0.8-3.5% of magnesium oxide, 0.2-2.5% of silicon oxide and 0.3-1.0% of calcium oxide;
the ceramic substrate is prepared by a preparation method comprising the following steps:
s1: mixing alumina powder and a grinding solvent, performing ball milling to obtain slurry, and mixing the slurry with a binder, a plasticizer and a sintering aid to obtain a mixture; the sintering aid comprises magnesium oxide, silicon oxide and calcium oxide;
s2: removing grinding solvent from the mixture, casting and forming into a biscuit, and then manufacturing a biscuit sheet;
s3: sintering the blank to obtain the ceramic substrate;
in the step S3, sintering conditions are as follows: heating upThe speed is 2 ℃/min-10 ℃/min; the gas used for sintering is air; the gas flow rate is 20m 3 /h～80m 3 /h; the sintering temperature is 1500-1700 ℃; the heat preservation time at the sintering temperature is 2-4 h; the cooling rate is 3 ℃/min to 15 ℃/min.
2. A ceramic substrate according to claim 1, characterized in that the alumina crystals in the ceramic substrate have the following characteristics:
the alumina crystal is a long rod-shaped crystal;
and/or, the alumina crystals with the mass percentage of more than 10 μm account for less than or equal to 3% of the total alumina crystals;
and/or the particle diameter D50 of the alumina crystal is 3.2 μm to 3.8 μm.
3. A ceramic substrate according to claim 1 or 2, wherein,
the bending strength of the ceramic substrate is more than 350MPa;
and/or the porosity of the ceramic substrate is less than or equal to 2%;
and/or the thermal conductivity of the ceramic substrate is > 20W/(mK);
and/or the ceramic substrate has a thermal expansion coefficient of < 7.0X10 at 20 ℃ to 400 DEG C -6 /℃。
4. A method of producing the ceramic substrate according to any one of claims 1 to 3, comprising the steps of:
s1: mixing alumina powder and a grinding solvent, performing ball milling to obtain slurry, and mixing the slurry with a binder, a plasticizer and a sintering aid to obtain a mixture; the sintering aid comprises magnesium oxide, silicon oxide and calcium oxide;
s2: removing grinding solvent from the mixture, casting and forming into a biscuit, and then manufacturing a biscuit sheet;
s3: sintering the blank to obtain the ceramic substrate;
in the step S3, sintering conditions are as follows: the temperature rising rate is 2 ℃/min-10 ℃/min; the gas used for sintering is air; the gas flow rate is 20m 3 /h～80m 3 /h; the sintering temperature is 1500-1700 ℃; the heat preservation time at the sintering temperature is 2-4 h; the cooling rate is 3 ℃/min to 15 ℃/min.
5. The method of manufacturing according to claim 4, wherein: in the step S1, the ball milling conditions are as follows:
the mass ratio of the alumina powder to the grinding ball is 1: (0.8-2.3);
and/or the diameter of the grinding ball is 8 mm-20 mm;
and/or the grinding balls are zirconia balls;
and/or the mass of the grinding solvent is 5% -20% of the mass of the alumina powder;
and/or the rotation speed of ball milling is 200 r/min-1200 r/min;
and/or ball milling time is 10-30 h;
and/or ball milling to obtain slurry with a powder particle diameter D50 of 0.6-1.2 μm.
6. The method of manufacturing according to claim 4, wherein: in the step S1 of the above-mentioned process,
the grinding solvent comprises at least one of ethanol, isopropanol, glycerol and n-hexane;
and/or the binder comprises at least one of polyvinyl alcohol Ding Quanzhi, polyacrylate, methyl cellulose, ethyl cellulose and polyvinyl alcohol;
and/or the plasticizer comprises at least one of phthalate, o-xylene dibutyl ester and polymethyl methacrylate.
7. The method of manufacturing according to claim 4, wherein: in the step S1 of the above-mentioned process,
the mass of the binder is 5-10% of that of the alumina powder;
and/or the mass of the plasticizer is 2-15% of the mass of the binder.
8. The method of manufacturing according to claim 4, wherein: in the step S2 of the above-mentioned process,
the solid content of the mixture after the grinding solvent is removed is 70 to 80 weight percent;
and/or the thickness of the biscuit is 0.56 mm-0.64 mm.
9. An application of a ceramic substrate in preparing an electronic device or a semiconductor device, which is characterized in that: the ceramic substrate is a ceramic substrate according to any one of claims 1 to 3 or is produced by the production method according to any one of claims 4 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211353541.3A CN115925399B (en) | 2022-11-01 | 2022-11-01 | Thermal shock resistant ceramic substrate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211353541.3A CN115925399B (en) | 2022-11-01 | 2022-11-01 | Thermal shock resistant ceramic substrate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115925399A CN115925399A (en) | 2023-04-07 |
| CN115925399B true CN115925399B (en) | 2023-12-12 |
Family
ID=86699728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211353541.3A Active CN115925399B (en) | 2022-11-01 | 2022-11-01 | Thermal shock resistant ceramic substrate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115925399B (en) |
Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0329349A (en) * | 1989-06-26 | 1991-02-07 | Mitsubishi Electric Corp | Material for ceramic substrate |
| JPH0789759A (en) * | 1993-07-27 | 1995-04-04 | Sumitomo Chem Co Ltd | Alumina for tape cast, alumina composition, alumina green sheet, alumina sintered plate and its production |
| WO2002033019A1 (en) * | 2000-10-16 | 2002-04-25 | 3M Innovative Properties Company | Method of making ceramic aggregate particles |
| JP2006137618A (en) * | 2004-11-10 | 2006-06-01 | Sanyo Electric Co Ltd | Dielectric ceramic substrate |
| WO2008004386A1 (en) * | 2006-06-05 | 2008-01-10 | Tohoku University | Highly functional composite material and method for producing the same |
| CN102782089A (en) * | 2010-02-04 | 2012-11-14 | 日东电工株式会社 | Light emissive ceramic laminate and method of making same |
| CN103058633A (en) * | 2011-10-18 | 2013-04-24 | 中国科学院福建物质结构研究所 | Method of YAG composite transparent laser ceramic |
| CN103183500A (en) * | 2011-12-27 | 2013-07-03 | 比亚迪股份有限公司 | Aluminium oxide ceramic substrate and preparation method for same |
| CN103492345A (en) * | 2011-07-14 | 2014-01-01 | 株式会社东芝 | Ceramic circuit board |
| CN103626478A (en) * | 2012-08-22 | 2014-03-12 | 新化县亚泰鑫瓷业发展有限责任公司 | 96% alumina ceramic substrate and preparation method thereof |
| JP2016040209A (en) * | 2014-08-12 | 2016-03-24 | 株式会社ノリタケカンパニーリミテド | Ceramic substrate |
| CN105906331A (en) * | 2016-05-26 | 2016-08-31 | 郑州中瓷科技有限公司 | Large-size ceramic substrate, and preparation method and production line thereof |
| CN107001148A (en) * | 2014-11-28 | 2017-08-01 | 日本碍子株式会社 | Alumina sintered body and basal substrate used for optical elements |
| CN107311666A (en) * | 2017-05-23 | 2017-11-03 | 福建华清电子材料科技有限公司 | The shaping of low-temperature co-fired ceramic substrate and sintering method |
| CN108137411A (en) * | 2015-09-30 | 2018-06-08 | 日本碍子株式会社 | Epitaxial growth orientation aluminum oxide substrate |
| CN108585802A (en) * | 2018-06-28 | 2018-09-28 | 南京大学 | A kind of sintering preparation method of high dielectric property ceramics |
| CN111470522A (en) * | 2020-03-31 | 2020-07-31 | 洛阳中超新材料股份有限公司 | Spherical alumina and preparation method and application thereof |
| CN112441821A (en) * | 2020-11-06 | 2021-03-05 | 南充三环电子有限公司 | Ceramic packaging base and preparation method thereof |
| CN113860889A (en) * | 2021-09-26 | 2021-12-31 | 深圳技术大学 | Low-temperature rapid degreasing sintering method for alumina ceramic biscuit |
| CN114180980A (en) * | 2021-12-28 | 2022-03-15 | 德阳三环科技有限公司 | Self-toughening 99 aluminum oxide ceramic substrate and preparation method thereof |
| WO2022072705A2 (en) * | 2020-10-03 | 2022-04-07 | Heraeus Conamic North America Llc | Sintered ceramic body of large dimension and method of making |
-
2022
- 2022-11-01 CN CN202211353541.3A patent/CN115925399B/en active Active
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0329349A (en) * | 1989-06-26 | 1991-02-07 | Mitsubishi Electric Corp | Material for ceramic substrate |
| JPH0789759A (en) * | 1993-07-27 | 1995-04-04 | Sumitomo Chem Co Ltd | Alumina for tape cast, alumina composition, alumina green sheet, alumina sintered plate and its production |
| WO2002033019A1 (en) * | 2000-10-16 | 2002-04-25 | 3M Innovative Properties Company | Method of making ceramic aggregate particles |
| JP2006137618A (en) * | 2004-11-10 | 2006-06-01 | Sanyo Electric Co Ltd | Dielectric ceramic substrate |
| WO2008004386A1 (en) * | 2006-06-05 | 2008-01-10 | Tohoku University | Highly functional composite material and method for producing the same |
| CN102782089A (en) * | 2010-02-04 | 2012-11-14 | 日东电工株式会社 | Light emissive ceramic laminate and method of making same |
| CN103492345A (en) * | 2011-07-14 | 2014-01-01 | 株式会社东芝 | Ceramic circuit board |
| CN103058633A (en) * | 2011-10-18 | 2013-04-24 | 中国科学院福建物质结构研究所 | Method of YAG composite transparent laser ceramic |
| CN103183500A (en) * | 2011-12-27 | 2013-07-03 | 比亚迪股份有限公司 | Aluminium oxide ceramic substrate and preparation method for same |
| CN103626478A (en) * | 2012-08-22 | 2014-03-12 | 新化县亚泰鑫瓷业发展有限责任公司 | 96% alumina ceramic substrate and preparation method thereof |
| JP2016040209A (en) * | 2014-08-12 | 2016-03-24 | 株式会社ノリタケカンパニーリミテド | Ceramic substrate |
| CN107001148A (en) * | 2014-11-28 | 2017-08-01 | 日本碍子株式会社 | Alumina sintered body and basal substrate used for optical elements |
| CN108137411A (en) * | 2015-09-30 | 2018-06-08 | 日本碍子株式会社 | Epitaxial growth orientation aluminum oxide substrate |
| CN105906331A (en) * | 2016-05-26 | 2016-08-31 | 郑州中瓷科技有限公司 | Large-size ceramic substrate, and preparation method and production line thereof |
| CN107311666A (en) * | 2017-05-23 | 2017-11-03 | 福建华清电子材料科技有限公司 | The shaping of low-temperature co-fired ceramic substrate and sintering method |
| CN108585802A (en) * | 2018-06-28 | 2018-09-28 | 南京大学 | A kind of sintering preparation method of high dielectric property ceramics |
| CN111470522A (en) * | 2020-03-31 | 2020-07-31 | 洛阳中超新材料股份有限公司 | Spherical alumina and preparation method and application thereof |
| WO2022072705A2 (en) * | 2020-10-03 | 2022-04-07 | Heraeus Conamic North America Llc | Sintered ceramic body of large dimension and method of making |
| CN112441821A (en) * | 2020-11-06 | 2021-03-05 | 南充三环电子有限公司 | Ceramic packaging base and preparation method thereof |
| CN113860889A (en) * | 2021-09-26 | 2021-12-31 | 深圳技术大学 | Low-temperature rapid degreasing sintering method for alumina ceramic biscuit |
| CN114180980A (en) * | 2021-12-28 | 2022-03-15 | 德阳三环科技有限公司 | Self-toughening 99 aluminum oxide ceramic substrate and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 95%氧化铝陶瓷大型产品烧成工艺的研究;李景云 等;真空电子技术;第92-94、98页 * |
| 氧化铝陶瓷基板工艺研究;王吉刚;山东陶瓷;第9-12页 * |
| 熔融态氯化镁直接热解制备氧化镁粉体及表征;牛丽萍;张廷安;周爱平;吕国志;赫冀成;;中国有色金属学报(第06期);全文 * |
| 环境温度和湿度对96-Al_2O_3陶瓷电阻率的影响;刘建;程利霞;伍海东;谭毅成;向其军;伍尚华;;人工晶体学报(第06期);第1083-1087页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115925399A (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114149260B (en) | Low-thermal-conductivity high-entropy ceramic thermal barrier coating material | |
| JP2000058631A5 (en) | ||
| JP2013507526A (en) | Tin oxide ceramic sputtering target and method for producing the same | |
| JP2002171037A (en) | Ceramic circuit board and method of manufacturing the same | |
| CN1533999A (en) | Low temperature sintered 99 aluminium oxide ceramic and its production method and use | |
| JP2024500914A (en) | High thermal conductivity silicon nitride ceramic insulating board and method for manufacturing the same | |
| JP7062229B2 (en) | Plate-shaped silicon nitride sintered body and its manufacturing method | |
| CN115028460A (en) | Preparation method of high-thermal-conductivity silicon nitride ceramic substrate | |
| CN110540429B (en) | Aluminum nitride sintered body and application | |
| CN115925399B (en) | Thermal shock resistant ceramic substrate and preparation method thereof | |
| CN108101526A (en) | A kind of electric porcelain insulator and preparation method thereof | |
| CN112110740B (en) | Method for preparing aluminum oxide-based composite biological ceramic material through in-situ reaction and product prepared by method | |
| JP3126635B2 (en) | Alumina ceramic sintered body | |
| CN112979282A (en) | Alumina ceramic sintered body and preparation method and application thereof | |
| KR20210036141A (en) | Aluminum Nitride Sintered Body and Method for Preparing Aluminum Nitride Sintered Body | |
| KR101325509B1 (en) | Manufacturing method of ceramic ware with high plasticity and high strength | |
| KR20190023485A (en) | Aluminum nitride sintered body and method for manufacturing the same | |
| CN115594510A (en) | Silicon nitride heat-conducting substrate and preparation method thereof | |
| CN115286409A (en) | Silicon nitride whisker reinforced aluminum nitride composite ceramic material and preparation method thereof | |
| JP2002137962A (en) | Component for heat treatment consisting of mullite-based sintered compact | |
| JP2002220282A (en) | Aluminum nitride sintered compact and method of manufacture | |
| JP2006347802A (en) | Low-thermal expansion/high-specific rigidity ceramic, its production method, and electrostatic chuck | |
| CN108358628B (en) | Mullite-zirconia composite ceramic and preparation method thereof | |
| JP7339980B2 (en) | Manufacturing method of silicon nitride sintered body | |
| JP7339979B2 (en) | Manufacturing method of silicon nitride sintered body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |