CN111484333A - Aluminum nitride ceramic with high thermal conductivity and high strength and preparation method thereof - Google Patents

Aluminum nitride ceramic with high thermal conductivity and high strength and preparation method thereof Download PDF

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CN111484333A
CN111484333A CN201910081721.2A CN201910081721A CN111484333A CN 111484333 A CN111484333 A CN 111484333A CN 201910081721 A CN201910081721 A CN 201910081721A CN 111484333 A CN111484333 A CN 111484333A
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aluminum nitride
ceramic
nitride ceramic
thermal conductivity
oxidation treatment
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汪小红
姜海
吕文中
范桂芬
雷文
付明
王晓川
梁飞
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Huazhong University of Science and Technology
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Abstract

The invention belongs to the technical field of ceramic materials, and particularly relates to a preparation method of pressureless sintering aluminum nitride ceramic with high heat conductivity and high strength. The aluminum nitride ceramics is prepared by oxidizing the aluminum nitride sintered body obtained by pressureless sintering, an oxidation layer with proper thickness and compactness can be formed on the surface of the aluminum nitride sintered body by proper oxidation treatment, the formation of the oxidation layer can increase the residual compressive stress in the aluminum nitride matrix, and the change of the residual stress is helpful to prevent the expansion of cracks in the aluminum nitride ceramics and reduce the contact thermal resistance of aluminum nitride crystal boundaries. The invention providesThe thermal conductivity of the aluminum nitride ceramic after oxidation treatment can be improved to 185-210W/(m.K), the bending strength can be improved to 390-460 MPa, the dielectric constant is 9-10, and the dielectric loss is 0.8 × 10‑3～2.4×10‑3Can meet the application requirements of industries such as semiconductor devices, integrated circuits and the like.

Description

Aluminum nitride ceramic with high thermal conductivity and high strength and preparation method thereof
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a preparation method of pressureless sintering aluminum nitride ceramic with high heat conductivity and high strength.
Background
With the rapid development of microelectronic technology, devices are required to develop towards the direction of high capacity, high density, high speed and high power output, and more complex devices put higher and higher requirements on the heat dissipation of substrates and packaging materials. The traditional resin substrate and the alumina ceramic substrate have the highest thermal conductivity of only about 30W/(m.K), and can not meet the heat dissipation requirement of the current devices. Beryllium oxide ceramic materials, although having a thermal conductivity of 350W/(m · K), are expensive and toxic during the manufacturing process. The aluminum nitride ceramic has the excellent characteristics of excellent heat-conducting property, thermal expansion coefficient close to that of silicon, good insulating property, moderate dielectric constant and dielectric loss, good room-temperature and high-temperature mechanical properties, no toxicity and the like, and has wide application prospect when being used as a substrate material and an electronic packaging material of integrated circuits and high-power devices.
AlN belongs to a compound with a strong covalent bond, has high melting point and small atomic self-diffusion coefficient, causes difficult sintering and is difficult to realize sintering densification; in addition, since AlN has a strong affinity for oxygen, the AlN powder surface generally adsorbs oxygen to form Al2O3When the ceramic is prepared by sintering, partial oxygen can be dissolved into crystal lattices of AlN in a solid solution mode, the formed aluminum vacancies have a strong scattering effect on phonons, and the mean free path of the phonons is greatly reduced, so that the thermal conductivity of AlN is reduced. Further, the bending strength of AlN ceramics is generally less than 300MPa, which limits the industrial application of AlN ceramics.
At present, a great deal of research is carried out on the modification of the performance of aluminum nitride ceramics at home and abroad, and in Chinese patent CN201310315911.9, Korean Meerkrasia and the like adopt Y2O3、CaSiO3And CaMgSi2O6As a sintering aid, AlN ceramics can be sintered and molded in vacuum or nitrogen atmosphere at 1550-1600 ℃, but the sample thermal conductivity is very low and is only 60-80W/(m.K); in the Chinese patent CN03100287.0, the Zhouyi selects alkaline earth oxide and alkaline earth fluoride as mixed sintering aids, and adopts the tape casting process to prepare the AlN blank, and the thermal conductivity of the sintered sample can reach 140-200W/(m.K). Most of the methods provide one or more sintering aids, and the method of utilizing the reaction of the sintering aids and oxygen impurities to improve the thermal conductivity of the aluminum nitride is utilized, but the method of improving the thermal conductivity is only utilized, so that the mechanical property of the ceramic matrix is not greatly improved finally. In the chinese patent CN201310531348.9, wushanghua and the like select molybdenum, tungsten, niobium, molybdenum carbide, tungsten carbide and niobium carbide as the particle dispersion toughening phase, and the bending strength and fracture toughness of the AlN substrate are effectively improved through the toughening mechanisms such as crack deflection bending and crack bridging. However, this method results in a decrease in the resistivity of AlN ceramics and a thermal conductivity of only 150-. Therefore, the new method is developed to ensure that the AlN ceramic has high thermal conductivity and high bending strength simultaneously, and has important application prospect.
Disclosure of Invention
In view of the above drawbacks or needs for improvement in the prior art, the present invention provides an aluminum nitride ceramic having both high thermal conductivity and high strength, and a method for preparing the same, in which an aluminum nitride ceramic is prepared by subjecting an aluminum nitride sintered body obtained by pressureless sintering to oxidation treatment, thereby solving the technical problem that the existing aluminum nitride ceramic cannot achieve both high thermal conductivity and high bending strength.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing an aluminum nitride ceramic, comprising the steps of:
(1) mixing aluminum nitride powder and a sintering aid to obtain a mixture;
(2) granulating, pressing and molding the mixture, and carrying out pressureless sintering to obtain an aluminum nitride sintered body;
(3) and carrying out oxidation treatment on the aluminum nitride sintered body to obtain aluminum nitride ceramic, wherein an oxidation layer is arranged on the surface of the aluminum nitride ceramic, and the main component of the oxidation layer is aluminum oxide.
Preferably, the sintering aid in step (1) is yttrium oxide powder and yttrium fluoride powder.
Preferably, the mass of the yttrium oxide powder in the step (1) accounts for 2-3% of the total mass of the mixture, and the mass of the yttrium fluoride powder accounts for 1-2% of the total mass of the mixture.
Preferably, the oxidation treatment of step (3) is performed in an air or oxygen atmosphere.
Preferably, the oxidation treatment temperature in the step (3) is 1000-1200 ℃, and the oxidation treatment time is 1-3 h.
In many cases, the thickness of the oxide layer in step (3) is 1 to 10 μm.
According to another aspect of the invention, an aluminum nitride ceramic with high thermal conductivity and high strength is provided, and is prepared according to the preparation method.
Preferably, the aluminum nitride ceramic comprises aluminum nitride, yttrium oxide and yttrium fluoride, wherein the mass percent of the yttrium oxide is 2-3%, and the mass percent of the yttrium fluoride is 1-2%; the ceramic surface has an oxide layer, and the main component of the oxide layer is alumina.
Preferably, the thickness of the oxide layer on the surface of the ceramic is 1-10 μm.
Preferably, the thermal conductivity of the aluminum nitride ceramic is 185-210W/(m.K), the bending strength is 390-460 MPa, the dielectric constant is 9-10, and the dielectric loss is 0.8 × 10-3～2.4×10-3。
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
1. the aluminum nitride ceramics is prepared by oxidizing the aluminum nitride sintered body obtained by pressureless sintering, an oxidation layer with proper thickness and compactness can be formed on the surface of the aluminum nitride sintered body by proper oxidation treatment, the formation of the oxidation layer can increase the residual compressive stress in the aluminum nitride matrix, and the change of the residual stress is helpful for preventing the expansion of cracks in the aluminum nitride ceramics and reducing the contact thermal resistance of an aluminum nitride crystal boundary;
2. the oxidation treatment also has the effect of annealing heat treatment, and can further eliminate surface defects of the sintered body and further reduce the oxygen content in the aluminum nitride crystal lattice.
3. Due to the multiple functions of the oxidation treatment, the aluminum nitride ceramic provided by the invention has excellent thermal property, mechanical property and dielectric property, the thermal conductivity can reach 185-210W/(m.K), the bending strength can reach 390-460 MPa, the dielectric constant is 9-10, and the dielectric loss is 0.8 × 10-3～2.4×10-3。
4. According to the invention, the sintering aid yttrium oxide is added, so that the oxygen atoms in the aluminum nitride crystal are reduced, the lattice oxygen defect is eliminated, and meanwhile, the yttrium fluoride with low melting point is added into the aluminum nitride powder, so that the sintering temperature can be reduced, and the sintering densification of the main crystal phase is promoted. An oxidation layer with proper thickness and compactness can be formed on the surface of the aluminum nitride sintered body through proper oxidation treatment, the formation of the oxidation layer can increase the residual compressive stress in the aluminum nitride matrix, and the change of the residual stress is helpful to prevent the expansion of cracks in the aluminum nitride ceramic and reduce the contact thermal resistance of an aluminum nitride crystal boundary; meanwhile, the oxidation treatment also has the function of annealing heat treatment, so that the surface defects of the sintered body can be further eliminated, and the oxygen content in the aluminum nitride crystal lattice can be further reduced. Therefore, the aluminum nitride ceramic after oxidation treatment has the advantages of high thermal conductivity and high bending strength.
5. The aluminum nitride ceramic provided by the invention has high thermal conductivity and high bending strength, is suitable for substrate materials and electronic packaging materials, does not contain heavy metal elements, meets the environmental protection requirement of the electronic industry, and has the advantages of simple preparation process and no pollution in the process.
Drawings
FIG. 1 is an XRD spectrum of the high thermal conductivity and high strength aluminum nitride ceramic provided by the present invention.
FIG. 2 is an SEM image of the high thermal conductivity and high strength aluminum nitride ceramic provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of aluminum nitride ceramic, which comprises the following steps:
(1) mixing aluminum nitride powder and a sintering aid to obtain a mixture;
(2) granulating, pressing and molding the mixture, and carrying out pressureless sintering to obtain an aluminum nitride sintered body;
(3) and carrying out oxidation treatment on the aluminum nitride sintered body to obtain aluminum nitride ceramic, wherein the surface of the aluminum nitride ceramic is provided with an oxidation layer, and the main component of the oxidation layer is aluminum oxide.
The sintering aid can be selected from commonly used sintering aids, and in some preferred embodiments, the sintering aid is yttrium oxide powder and yttrium fluoride powder. Y is2O3Has strong oxygen-expelling capability and is mixed with Al on the surface of AlN particles in the sintering process2O3One or more yttrium aluminates are generated in a combined manner, so that oxygen dissolved in AlN crystal lattices can be migrated to a crystal boundary, and oxygen atoms are reduced to enter the AlN crystal lattices to form defects; and YF3The melting point of the material is low, a liquid phase can be formed in the sintering process, the sintering densification of a main crystal phase can be promoted, and the sintering temperature is reduced. Thus, Y is added2O3And YF3As a sintering aid, the sintering temperature of the AlN ceramic is reducedThe formation of defects by oxygen atoms into the crystal lattice of AlN can be reduced to improve the thermal conductivity of AlN ceramic and maintain its excellent dielectric properties. In some embodiments, the yttrium oxide powder in step (1) accounts for 2-3% of the total mass of the mixture, and the yttrium fluoride powder accounts for 1-2% of the total mass of the mixture.
The invention firstly carries out pressureless sintering on the mixed powder of aluminum nitride and sintering auxiliary agent, the pressureless sintering process is the same as the conventional pressureless sintering of the aluminum nitride, namely, the mixed powder is sintered in the nitrogen atmosphere, the sintering temperature can be selected to be 1600-1800 ℃, and the sintering time can be 3-10 h.
The aluminum nitride sintered body can form an oxidation layer with proper thickness and compactness on the surface of the aluminum nitride sintered body through proper oxidation treatment, the formation of the oxidation layer can increase the residual compressive stress in the aluminum nitride sintered body, and the change of the residual stress is helpful to prevent the expansion of cracks in the aluminum nitride ceramic and reduce the contact thermal resistance of an aluminum nitride crystal boundary; meanwhile, the oxidation treatment also has the function of annealing heat treatment, so that the surface defects of the sintered body can be further eliminated, and the oxygen content in the aluminum nitride crystal lattice can be further reduced. Therefore, the aluminum nitride ceramic after oxidation treatment has the advantages of high thermal conductivity and high bending strength, and can meet the application requirements of substrate materials and electronic packaging materials.
The oxidation treatment in step (3) may be performed in any oxygen-containing atmosphere, such as air or an oxygen atmosphere. The aluminum nitride sintered body prepared in the step (2) is subjected to oxidation treatment, the oxidation degree of the sintered body has great influence on the heat conductivity and the strength performance of the final aluminum nitride ceramic, the oxidation degree is too low, the surface aluminum oxide layer is too thin, and the strength of the aluminum nitride sintered body is not obviously enhanced; the oxide layer is too thick, so that the oxide layer becomes not dense, a plurality of air holes are formed, and the mechanical strength and the thermal conductivity are reduced; the oxide layer is composed of alumina, which has a much lower thermal conductivity than aluminum nitride, so that the oxide layer is too thick, resulting in a significant reduction in thermal conductivity. The invention carries out oxidation treatment on the sintered body, and the oxidation condition is harsh. The thickness of the aluminum oxide on the surface of the aluminum nitride ceramic obtained after the oxidation treatment is preferably 1-10 micrometers. Correspondingly, in some embodiments, the oxidation treatment temperature in the step (3) is 1000 ℃ to 1200 ℃, and the oxidation treatment time is 1h to 3 h. The proper oxidation temperature can form a dense oxide layer with proper thickness on the surface of the sintered body. The proper oxidation time can improve the degree of compactness of the oxide layer on the surface of the sintered body and has the annealing heat treatment effect on the aluminum nitride sintered body.
In some embodiments, the method for preparing the aluminum nitride ceramic with high thermal conductivity and high strength provided by the invention comprises the steps of mixing aluminum nitride powder, yttrium oxide and yttrium fluoride in a certain proportion, obtaining a powdery mixture by a wet ball milling method, and drying the powdery mixture, wherein the purities of the aluminum nitride powder, the yttrium oxide and the lanthanum fluoride are all more than 99.99%; granulating, pressing and molding the dried powdery mixture, and sintering under no pressure to obtain an aluminum nitride sintered body; and oxidizing the aluminum nitride sintered body in the air to prepare the final aluminum nitride ceramic.
The method for preparing the aluminum nitride ceramic with high thermal conductivity and high strength, provided by the invention, is beneficial to preventing the propagation of cracks in the aluminum nitride ceramic and reducing the contact thermal resistance of an aluminum nitride crystal boundary due to the addition of the oxidation treatment step, and meanwhile, the oxidation treatment also has the effect of annealing heat treatment, so that the surface defects of a sintered body can be further eliminated, and the oxygen content in the aluminum nitride crystal lattice can be further reduced. Therefore, the thermal conductivity and the bending strength of the aluminum nitride ceramic are simultaneously improved.
The aluminum nitride ceramic provided by the invention is an aluminum nitride ceramic with high thermal conductivity and high strength, and comprises aluminum nitride, yttrium oxide and yttrium fluoride, wherein the mass percent of the yttrium oxide is 2-3%, the mass percent of the yttrium fluoride is 1-2%, the thickness of an aluminum oxide film on the surface of the ceramic is 1-10 mu m, the thermal conductivity can reach 185-210W/(m.K), the bending strength can reach 390-460 MPa, the dielectric constant is 9-10, and the dielectric loss is 0.8 × 10-3～2.4×10-3。
The following are examples:
examples 1 to 6
Example 1: the mass percent of the AlN powder is 97 percent and the mass percent of Y2O32 percent of YF3The mass percent is 1 percent, the oxidation treatment temperature is 1000 ℃, and the oxidation time is 1 h.
Example 2: the mass percent of the AlN powder is 97 percent and the mass percent of Y2O32 percent of YF3The mass percent is 1 percent, the oxidation treatment temperature is 1100 ℃, and the oxidation time is 1 h.
Example 3: the mass percent of the AlN powder is 97 percent and the mass percent of Y2O32 percent of YF3The mass percent is 1 percent, the oxidation treatment temperature is 1200 ℃, and the oxidation time is 1 h.
Example 4: the mass percent of the AlN powder is 96 percent and the mass percent of Y is2O33 percent of YF3The mass percent is 1 percent, the oxidation treatment temperature is 1100 ℃, and the oxidation time is 1 h.
Example 5: the AlN powder accounts for 96 percent by mass, the Y2O3 accounts for 2 percent by mass, the YF3 accounts for 2 percent by mass, the oxidation treatment temperature is 1100 ℃, and the oxidation time is 1 h.
Example 6: 95 percent of AlN powder and Y2O33 percent of YF3The mass percent is 2 percent, the oxidation treatment temperature is 1100 ℃, and the oxidation time is 1 h.
The components and the component proportions of the above examples 1 to 6 are prepared according to the following preparation method, and the preparation method comprises the following steps:
(1) according to the composition components and the component proportion of the embodiments 1 to 6, the composition components are placed in a ball milling tank according to the proportion and mixed into a mixture, wherein the purity of each composition component is more than 99.99 percent; mixing the mixture with the mass percent of 33.3% and ethanol with the mass percent of 66.7%, adding a ball milling medium, performing wet ball milling for 5 hours to obtain a powdery mixture, and then drying the powdery mixture; and adding a binder into the dried powdery mixture for granulation, performing compression molding, performing cold static pressure treatment, and finally sintering in a nitrogen atmosphere at the heating rate of 10 ℃/min and the sintering temperature of 1700 ℃ to obtain the aluminum nitride sintered body.
(2) The aluminum nitride sintered body was subjected to oxidation treatment in air according to the oxidation temperature and oxidation time parameters of examples 1 to 6 to obtain a final aluminum nitride ceramic.
Phase composition and micro-morphology analysis are carried out on the surface of the aluminum nitride ceramic, and the results are shown in fig. 1 and fig. 2, fig. 1 shows an XRD (X-ray diffraction) spectrum of the aluminum nitride ceramic with high thermal conductivity and high strength provided by the invention, fig. 2 shows an SEM (scanning electron microscope) diagram of the aluminum nitride ceramic with high thermal conductivity and high strength provided by the invention, and in the diagrams, (a), (b) and (c) respectively correspond to the thicknesses of the aluminum nitride ceramic and the aluminum oxide layer on the surface of the aluminum nitride ceramic obtained by treatment under different temperature conditions. It can be seen that the surface oxide layer is mainly composed of alumina and has a thickness of 1-10 μm. The thermal conductivity and the bending strength of the aluminum nitride ceramic sample are increased and then reduced along with the increase of the thickness of the oxide layer, the thickness of the oxide layer is preferably 3-4 mu m, and the oxidation temperature and the oxidation time corresponding to the thickness are preferably 1100 ℃ and 1h respectively.
Table 1 shows the properties of the aluminum nitride ceramics prepared in examples 1 to 6, and the properties of the aluminum nitride ceramics were measured by phase analysis of the sintered ceramic sample by X-ray diffraction method, evaluation of thermal conductivity by a thermal conductivity meter, evaluation of bending strength by three-point bending method, and evaluation of high-frequency dielectric properties at 1MHz by an impedance analyzer.
Figure BDA0001960578190000081
The aluminum nitride ceramic provided by the invention has the thermal conductivity of 185-200W/(m.K), the bending strength of 390-460 MPa, the dielectric constant of 9-10 and the dielectric loss of 0.8 × 10-3～2.4×10-3. The high-thermal conductivity and high-strength aluminum nitride ceramic provided by the invention can effectively improve the thermal conductivity and the bending strength of the aluminum nitride ceramic at the same time, and meets the application requirements of substrate materials and electronic packaging materials of integrated circuits and high-power devices. Therefore, the present invention is industrially very valuable.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The preparation method of the aluminum nitride ceramic is characterized by comprising the following steps of:
(1) mixing aluminum nitride powder and a sintering aid to obtain a mixture;
(2) granulating, pressing and molding the mixture, and carrying out pressureless sintering to obtain an aluminum nitride sintered body;
(3) and carrying out oxidation treatment on the aluminum nitride sintered body to obtain aluminum nitride ceramic, wherein an oxidation layer is arranged on the surface of the aluminum nitride ceramic, and the main component of the oxidation layer is aluminum oxide.
2. The method according to claim 1, wherein the sintering aid in step (1) is yttrium oxide powder and yttrium fluoride powder.
3. The method according to claim 1, wherein the yttrium oxide powder in step (1) accounts for 2 to 3% by mass of the total mass of the mixture, and the yttrium fluoride powder accounts for 1 to 2% by mass of the total mass of the mixture.
4. The production method according to claim 1, wherein the oxidation treatment in the step (3) is carried out in an air or oxygen atmosphere.
5. The preparation method according to claim 1, wherein the oxidation treatment temperature in the step (3) is 1000 ℃ to 1200 ℃ and the oxidation treatment time is 1h to 3 h.
6. The method according to claim 1, wherein the thickness of the oxide layer in the step (3) is 1 to 10 μm.
7. An aluminum nitride ceramic having both high thermal conductivity and high strength, which is produced by the production method according to any one of claims 1 to 6.
8. The aluminum nitride ceramic according to claim 7, comprising aluminum nitride, yttrium oxide and yttrium fluoride, wherein the yttrium oxide is 2 to 3% by mass, and the yttrium fluoride is 1 to 2% by mass; the ceramic surface has an oxide layer, and the main component of the oxide layer is alumina.
9. The aluminum nitride ceramic according to claim 7, wherein the oxide layer on the surface of the ceramic has a thickness of 1 to 10 μm.
10. The aluminum nitride ceramic according to claim 7, wherein the thermal conductivity is 185 to 210W/(m-K), the bending strength is 390 to 460MPa, the dielectric constant is 9 to 10, and the dielectric loss is 0.8 × 10-3～2.4×10-3。
CN201910081721.2A 2019-01-28 2019-01-28 Aluminum nitride ceramic with high thermal conductivity and high strength and preparation method thereof Pending CN111484333A (en)

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