阅读说明：本技术 一种氮化铝烧结体及应用 (aluminum nitride sintered body and application ) 是由 黄雪云 江楠 于 2019-08-29 设计创作，主要内容包括：本发明公开了一种氮化铝烧结体,包含以下质量百分含量的成分：氮化锆0.5-20wt％、氟化钙0-3wt％、含钇化合物(以氧化钇形式计算)0-5wt％、含硅化合物(以氧化硅形式计算)0-0.5wt％、含镁化合物(以氧化镁形式计算)0-3wt％；其中,在所述氮化铝烧结体中,氮化铝的质量百分含量大于75％。本发明利用原位合成的方法,生成的氮化锆可均匀的分散在基底材料中,并能与AlN晶粒紧密结合,达到弥散增韧基板的效果；可有效提升基板强度,使基板强度高达600Mpa,在市场上能与Si<Sub>3</Sub>N<Sub>4</Sub>竞争,可应用于IGBT模块中。同时,本发明还公开一种包含上述烧结体的氮化铝基板。(The invention discloses an aluminum nitride sintered body, which comprises the following components in percentage by mass: zirconium nitride 0.5-20 wt%, calcium fluoride 0-3 wt%, yttrium-containing compound (calculated as yttrium oxide) 0-5 wt%, silicon-containing compound (calculated as silicon oxide) 0-0.5 wt%, magnesium-containing compound (calculated as magnesium oxide) 0-3 wt%; wherein, in the aluminum nitride sintered body, the mass percentage of the aluminum nitride is more than 75 percent. By utilizing the in-situ synthesis method, the generated zirconium nitride can be uniformly dispersed in the base material and can be tightly combined with AlN grains, so that the effect of dispersing and toughening the substrate is achieved; the strength of the substrate can be effectively improved to be as high as 600Mpa, and the substrate can compete with Si3N4 in the market and can be applied to IGBT modules. Meanwhile, the invention also discloses an aluminum nitride substrate containing the sintered body.)

1. An aluminum nitride sintered body is characterized by comprising the following components in percentage by mass: zirconium nitride 0.5-20 wt%, calcium fluoride 0-3 wt%, yttrium-containing compound (calculated as yttrium oxide) 0-5 wt%, silicon-containing compound (calculated as silicon oxide) 0-0.5 wt%, magnesium-containing compound (calculated as magnesium oxide) 0-3 wt%; wherein, in the aluminum nitride sintered body, the mass percentage of the aluminum nitride is more than 75 percent.

2. The aluminum nitride sintered body as set forth in claim 1, which comprises the following components in percentage by mass: 1-8 wt% of zirconium nitride, 0.05-2.5 wt% of calcium fluoride, 0.05-3 wt% of yttrium-containing compound (calculated as yttrium oxide), 0.01-0.4 wt% of silicon-containing compound (calculated as silicon oxide), and 0.05-2.5 wt% of magnesium-containing compound (calculated as magnesium oxide); wherein, in the aluminum nitride sintered body, the mass percentage of the aluminum nitride is more than 75 percent.

3. The aluminum nitride sintered body as claimed in claim 1, further comprising first crystal grains, wherein the average size of the zirconium nitride crystal grains is not less than 20% of the average size of the first crystal grains; preferably, the average size of the zirconium nitride grains is 20% to 66% of the average size of the first grains.

4. The aluminum nitride sintered body as claimed in claim 1, wherein the average size of the zirconium nitride crystal grains is not less than 10% of the average size of the aluminum nitride crystal grains; preferably, the average size of the zirconium nitride grains is 10% to 35% of the average size of the aluminum nitride grains.

5. The aluminum nitride sintered body as claimed in any one of claims 1 to 4, wherein the average grain diameter of the zirconium nitride crystal grains is 0.1 to 5.0 μm; preferably, the average grain diameter of the zirconium nitride crystal grains is 0.6 to 1.5 μm.

6. The aluminum nitride sintered body as claimed in any one of claims 1 to 4, wherein the average particle diameter of the aluminum nitride crystal grains is 0.1 to 10 μm; preferably, the average grain diameter of the aluminum nitride crystal grains is 3 to 8 μm.

7. the aluminum nitride sintered body as claimed in any one of claims 1 to 4, further comprising first crystal grains, wherein the first crystal grains are yttrium aluminate, and the first crystal grains have an average grain diameter of 0.5 to 5 μm; preferably, the average grain size of the first crystal grains is 1.25 to 3.5 μm.

8. The aluminum nitride sintered body as claimed in any one of claims 1 to 4, further comprising first crystal grains which are yttrium aluminate and have a number of crystal grains of zirconium nitride 1 to 7 times as large as the number of the first crystal grains per 100 μm 2; preferably, the number of grains of the zirconium nitride is 2 to 5 times the number of the first grains per unit area of 100 μm 2.

9. An aluminum nitride substrate comprising the aluminum nitride sintered body according to any one of claims 1 to 8.

10. The method for preparing the aluminum nitride substrate according to claim 9, comprising the steps of:

The method comprises the following steps: preparing slurry; firstly, uniformly mixing an yttrium-containing compound and a zirconium-containing compound, then adding aluminum nitride and other components, and dispersing and mixing to obtain slurry;

Step two: tape casting;

Step three: and (5) sintering.

Technical Field

The invention relates to the field of nitride ceramics, in particular to an aluminum nitride sintered body and application thereof.

Background

The aluminum nitride ceramic material has the characteristics of high thermal conductivity, low dielectric constant, low dielectric loss, excellent insulating property, corrosion resistance, thermal expansion coefficient matched with silicon and the like, and is an ideal packaging material in the fields of high-power-density circuits and IGBTs. Moreover, as the application field of electronic packaging products is more and more extensive, the application environment is more and more complex, and the requirement for the strength of the aluminum nitride substrate is increased, so that it is very necessary to prepare a substrate with excellent mechanical properties.

At present, the aluminum nitride substrate generally adopts rare earth metal oxide, alkaline earth metal oxide and the like as sintering aids, and is formed by dry pressing, tape casting and other processes, and is combined with a proper sintering process to obtain a ceramic matrix with certain thermal and mechanical properties. After a conventional green body taking yttrium oxide as a sintering aid is sintered in a nitrogen atmosphere, the strength of a substrate can only reach about 450MPa, and excellent heat conduction performance and high strength performance cannot be realized at the same time, so that the application of the green body in the fields of high strength and high shock resistance is limited. The main problems are that 1) AIN is a strong covalent bond compound, the atomic self-diffusion coefficient is small, the AIN is difficult to sinter and compact, and the strength of the AIN ceramic substrate obtained by the existing preparation method is not high; 2) at present, the sintering temperature of the AIN ceramic substrate is higher and is more than 1700 ℃, so that the requirements on sintering equipment are higher and the energy consumption is higher.

Disclosure of Invention

Based on this, the object of the present invention is to overcome the above-mentioned disadvantages of the prior art and to provide an aluminum nitride sintered body.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: an aluminum nitride sintered body comprises the following components in percentage by mass: zirconium nitride 0.5-20 wt%, calcium fluoride 0-3 wt%, yttrium-containing compound (calculated as yttrium oxide) 0-5 wt%, silicon-containing compound (calculated as silicon oxide) 0-0.5 wt%, magnesium-containing compound (calculated as magnesium oxide) 0-3 wt%; wherein, in the aluminum nitride sintered body, the mass percentage of the aluminum nitride is more than 75 percent.

Preferably, the aluminum nitride sintered body comprises the following components in percentage by mass: 1-8 wt% of zirconium nitride, 0.05-2.5 wt% of calcium fluoride, 0.05-3 wt% of yttrium-containing compound (calculated as yttrium oxide), 0.01-0.4 wt% of silicon-containing compound (calculated as silicon oxide), and 0.05-2.5 wt% of magnesium-containing compound (calculated as magnesium oxide); wherein, in the aluminum nitride sintered body, the mass percentage of the aluminum nitride is more than 75 percent.

In the aluminum nitride sintered body, because of the difference between the elastic modulus and the thermal expansion coefficient of zirconium nitride and aluminum nitride, a residual stress field exists between zirconium nitride particles and a surrounding matrix, and the residual stress field can change a crack propagation path, so that cracks are deflected, crack propagation power is weakened, and the strength is improved.

In the aluminum nitride sintered body, when the content of zirconium nitride is too high, the compatibility among particles is poor, the particles are easy to agglomerate and cannot play a role in dispersion strengthening, and meanwhile, the grains among the particles are difficult to completely develop, so that the sintered body is difficult to compact, and the strength is reduced. Furthermore, according to SEM, too much zirconium nitride tends to be distributed around the YAG phase (Y3Al5O12) affecting the effect of the liquid phase during sintering.

Preferably, the aluminum nitride sintered body further contains first crystal grains, and the first crystal grains are yttrium aluminate, such as Y3Al5O12, Y4Al2O9, YAlO 3.

more preferably, the average size of the zirconium nitride grains is not less than 20% of the average size of the first grains; preferably, the average size of the zirconium nitride grains is 20% to 66% of the average size of the first grains.

Preferably, the average size of the zirconium nitride grains is not less than 10% of the average size of the aluminum nitride grains; more preferably, the average size of the zirconium nitride grains is 10% to 35% of the average size of the aluminum nitride grains.

The first crystal grain is yttrium aluminate formed by the reaction of yttrium oxide and aluminum oxide in the reaction process, and the yttrium aluminate is distributed among the aluminum nitride crystal grains in a liquid state during sintering to promote the densification of the aluminum nitride blank. When the zirconium nitride crystal grains are too small, the performance requirement on a zirconium-containing compound in the raw material is too high, extra cost is increased, the effect of deflecting cracks cannot be achieved, and the strength is not improved.

The crystal grains of zirconium nitride exceeding the upper limit of the defined range may decrease the uniformity of dispersion thereof at the grain boundaries of aluminum nitride, resulting in excessively large voids between the grain boundaries, limiting the improvement in strength of the aluminum nitride sintered body, and at the same time, increasing the porosity of the aluminum nitride sintered body. Therefore, it is the best choice to limit the average size of the zirconium nitride grains to 10% -35% of the average size of the AlN grains.

Further, when the particle size of zirconium nitride is too large, microcracks are induced in the matrix by stress concentration, and the strength is lowered. Moreover, the zirconium nitride with an excessively large particle size affects the function of the first crystal grains in the aluminum nitride sintering process, the rearrangement and densification of the aluminum nitride particles, and even the zirconium nitride particles are squeezed by the growth of the crystal grains in the green body and migrate to the surface of the sintered body. Therefore, it is the best choice to control the average size of the zirconium nitride grains to be 20% to 66% of the average size of the first grains.

Preferably, the average grain diameter of the zirconium nitride crystal grains is 0.1 to 5.0 μm; more preferably, the average grain diameter of the zirconium nitride crystal grains is 0.6 to 1.5 μm.

Preferably, the average grain diameter of the aluminum nitride crystal grains is 0.1 to 10 μm; more preferably, the average particle diameter of the aluminum nitride crystal grains is 3 to 8 μm; more preferably, the average grain diameter of the aluminum nitride crystal grains is 4 to 5 μm.

The zirconium nitride with too large or too small grain diameter can have negative influence on the improvement of the substrate strength. The aluminum nitride crystal grains of the present invention are selected to fall within the above-defined range, mainly as the main component of the sintered body, satisfying the strength requirement of the sintered body. From the viewpoint of sintering densification, the smaller the average grain size of the aluminum nitride crystal grains, the better, and the higher the strength of the sintered body formed, preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 5 μm or less. However, from the viewpoint of production, the larger the average grain size of the aluminum nitride crystal grains is, the easier the raw material preparation and production thereof are.

Preferably, the aluminum nitride sintered body further contains first crystal grains, the first crystal grains are yttrium aluminate, and the average grain diameter of the first crystal grains is 0.5-5 μm; more preferably, the average particle diameter of the first crystal grains is 1.25 to 3.5 μm; more preferably, the average grain size of the first crystal grains is 1.8 to 3 μm.

The first crystal grains are mainly and intensively distributed among the grain boundary surfaces of the aluminum nitride crystal grains and are gathered at the triangular grain boundaries of the aluminum nitride crystal grains. If the average grain size of the first crystal grains is too large, abnormal growth of aluminum nitride crystal grains can be caused, pores are generated in the sintered body due to the grain size problem of the first crystal grains, and the heat conductivity of the sintered body is reduced; moreover, the average grain size of the first crystal grains is too large, which may cause excessive liquid phase migration, resulting in too high substrate surface roughness and poor flatness. If the size of the first crystal grains is too small, densification of the sintered body cannot be effectively promoted, which is disadvantageous in improving the flexural strength of the sintered body.

Preferably, the aluminum nitride sintered body further contains first crystal grains, the first crystal grains are yttrium aluminate, and the number of crystal grains of the zirconium nitride is 1 to 7 times of the number of the first crystal grains per unit area of 100 μm 2; more preferably, the number of grains of the zirconium nitride is 2 to 5 times the first number of grains per unit area of 100 μm 2; more preferably, the number of grains of the zirconium nitride is 2 to 3.5 times the first number of grains per unit area of 100 μm 2.

The number of crystal grains of zirconia per unit area exceeds the above-defined ratio, and the compatibility between particles is deteriorated, whereby the sintered body is hard to be densified, and the strength is rather lowered. The number of crystal grains of zirconia per unit area is less than a defined multiple, and the aluminum nitride substrate cannot satisfy the reinforcing effect.

Meanwhile, the invention also provides an aluminum nitride substrate containing the aluminum nitride sintered body.

In addition, the invention also discloses a preparation method of the aluminum nitride substrate, which comprises the following steps:

The method comprises the following steps: preparing slurry; firstly, uniformly mixing an yttrium-containing compound and a zirconium-containing compound, then adding aluminum nitride and other components, and dispersing and mixing to obtain slurry;

Step two: tape casting;

Step three: and (5) sintering.

Preferably, in one embodiment of the present invention, zirconium nitride may be directly added to the raw material, and the high mechanical strength of the zirconium nitride material itself is used to improve the overall strength of the aluminum nitride sintered body.

More preferably, in another embodiment of the present invention, zirconia may be directly added to the raw material, and the zirconium nitride may be post-synthesized in situ, and the strength of the aluminum nitride may be improved as a whole.

During sintering, the added zirconium oxide reacts with aluminum nitride in the atmosphere of N2 to synthesize zirconium nitride in situ. The possible reaction process thereof is presumed as follows,

ZrO+N＝ZrN+NO (1)

2ZrO+2AlN＝2ZrN+AlO+0.5O (2)

Zirconium nitride particles synthesized in situ are dispersed in the aluminum nitride sintered body, and the aluminum nitride is obviously strengthened by a crack deflection mechanism.

In one scheme of the invention, nano-grade ZrO2 is used as a toughening phase, a fluxing agent Y2O3 and the toughening phase ZrO2 are uniformly mixed, AlN is added, and the mixture is ball-milled and dispersed into mixed slurry.

And carrying out tape casting on the mixed slurry to obtain a substrate with a certain size, synthesizing zirconium nitride in situ during sintering, wherein zirconium nitride particles are tightly combined with a base material, the risk that two phases cannot be well combined is reduced, and finally forming the particle dispersion toughened aluminum nitride ceramic substrate, wherein the toughened phase is zirconium nitride particles.

Compared with the prior art, the invention has the beneficial effects that:

The AIN ceramic substrate has obviously improved comprehensive performance, and mainly has good mechanical property, high density and certain electrical and thermal properties.

By utilizing the in-situ synthesis method, the generated zirconium nitride can be uniformly dispersed in the base material and can be tightly combined with AlN grains, so that the effect of dispersing and toughening the substrate is achieved; the strength of the substrate can be effectively improved to reach 600Mpa, and the substrate can compete with Si3N4 in the market. Meanwhile, the adopted toughening phase effectively improves the fracture toughness of the AIN substrate through crack deflection bending, crack bridging and a residual stress toughening mechanism. In addition, the adopted toughening phase particles have good chemical compatibility with the aluminum nitride matrix, can improve the thermal shock resistance of the aluminum nitride ceramic substrate, meet the thermal conductivity requirement of the substrate, improve the comprehensive performance of the aluminum nitride and increase the application field of the substrate.

Drawings

FIG. 1 is an SEM photograph of a sintered body of example 23 of the present invention;

FIG. 2 is a graph showing the distribution of zirconium nitride and a first crystal grain size in a sintered body according to example 14 of the present invention;

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.

In terms of the components of the sintered body, the invention provides examples 1-10 and comparative examples 1-3, and the specific preparation method comprises the following steps:

1) Preparing slurry; firstly, uniformly mixing yttrium oxide and zirconium oxide, adding aluminum nitride and other components including toluene and isopropanol serving as solvents, uniformly mixing by ball milling, and dispersing and mixing to form slurry;

2) Tape casting;

3) And (5) sintering.

According to the above method, the contents of the respective components in the sintered molded substrates of examples 1 to 10 and comparative examples 1 to 3 are specifically shown in Table 1.

TABLE 1 content (wt%) of each component in the sintered body

The flexural strength and thermal conductivity of the ceramic substrates were measured in examples 1 to 10 and comparative examples 1 to 3, respectively. The method for testing the bending strength comprises the steps of carrying out laser scribing and cutting on a sample into a rectangular sheet body with the thickness of L being 40mm and the thickness of b being 24mm, controlling the scribing depth to be 35-50% of the thickness of the sample, measuring the thickness h of each sample by using a micrometer screw, placing a scribing surface on an electronic universal testing machine, measuring the span L being 30mm, the diameter d of a roller rod being 3mm, the descending speed v of an upper roller rod being 0.5mm/min, measuring the critical bending resistance force F of the sample, and obtaining the strength result of the sample by using a strength calculation formula delta being 3FL/2bh 2.

The method for testing the heat conductivity coefficient can be according to the testing method in the national standard GB/T5598-2015, the sample is made into a wafer with the diameter d of 10mm, the sample and the standard sample with the same thickness are tested by a laser scintillation heat diffusion coefficient tester within a short time interval to obtain the heat diffusion coefficient alpha and the specific heat Cp of the sample, the volume density of the sample is obtained by the Archimedes method, and the heat conductivity coefficient of the sample is obtained by the heat conductivity coefficient formula lambda of alpha Cp rho.