JP4060822B2 - Ceramic composite material - Google Patents

Description

  The present invention relates to a ceramic composite material.

  Conventionally, a silicon carbide (SiC) sintered body, which is a ceramic composite material, has occupied an industrially important position due to its excellent heat resistance and fire resistance, such as insulators, sanitary ware, tableware, picture frames and ceramic tubes, etc. It is often used as a shelf for firing ceramics and tiles. Among such SiC sintered bodies, a Si—SiC composite material containing SiC and Si as constituent components is known. This Si—SiC composite material is mainly composed of a furnace core tube for semiconductor firing, a roller for a roller hearth kiln, In recent years, not only is it used for tubes for heat exchangers, but in recent years there has been an increasing need for heat dissipation materials that efficiently discharge the heat generated in semiconductor elements and prevent degradation of the performance and reliability of semiconductor elements. Yes.

  In particular, a heat dissipation material for a semiconductor element is indispensable to bond the element and the heat dissipation material with high accuracy for efficient heat discharge. Further, when the IC chip is increased in size, a semiconductor substrate (silicon substrate) is required. The stress generated by the difference in thermal expansion between the GaAs substrate and the heat radiating material increases, and there is a risk that the adhesion accuracy between the IC chip and the heat radiating material is lowered, and a peeling phenomenon or mechanical breakage occurs.

  The Si-SiC composite material (product) used in such applications is, for example, molding raw material powder by casting or press molding, and heat-treating (recrystallizing) the resulting molded body at 1800 to 2500 ° C for 1 to 5 hours. After heat impregnating metal silicon (Si) in a reduced-pressure atmosphere at 1450 to 1800 ° C. in a firing container, argon (Ar) was introduced to atmospheric pressure and cooled at the transition to cooling, The obtained fired product is taken out from the firing jig, both surfaces of the fired product (semi-finished product) are sandblasted, and further polished.

  At this time, since the surface of the fired product after impregnation with Si has good wettability with Si, a large amount of unnecessary Si deposits are stuck, and this Si deposit has an acute contact angle with the fired product (for example, 55 °), when removing Si deposits from the surface of the fired product by sandblasting, there was a problem that corner portions of the fired product were missing together with Si. Furthermore, since the contact area between the Si deposit and the fired product is large, a great deal of labor is required to completely remove the deposit.

  In addition, since silicon undergoes volume expansion when it changes from the liquid phase to the solid phase during the cooling process, when this Si deposit is volume expanded on the surface of the fired product when solidified during the cooling process after impregnation with Si, This will affect the basic structure of the surface (a structure in which metal silicon is impregnated in a void formed by bonding silicon carbide crystals to each other), resulting in surface defects. For this reason, there has been a problem that the surface defects of the product are not eliminated even if both sides of the fired product (semi-finished product) are sandblasted and further polished.

  Furthermore, when the fired product is taken out from the firing jig, Si sticks to the contact portion between the fired product and the firing jig, and it is difficult to peel the fired product from the firing jig. There was a problem that the fired product would be missing. In addition, the above phenomenon was the same even when not only the recrystallized base material but a base material was used as a molded object.

  The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to easily remove deposits formed on the surface of the ceramic composite material after firing the ceramic composite material. Another object is to provide a ceramic composite material capable of preventing surface defects of the obtained ceramic composite material.

  In order to achieve the above object, the present invention provides the following ceramic composite material.

[1] Ceramics having a metal-impregnated layer in which silicon carbide is impregnated with 60 to 98% by mass, metal silicon is 2 to 40% by mass, and voids formed by bonding the silicon carbide crystals to each other are impregnated. A rough surface that suppresses wettability to impregnated metal silicon by a chemical reaction using a gaseous substance containing Al and N elements on the surface of the metal-impregnated layer is a composite material. It is formed on the whole or a part of the outer surface of the composite material, and all the Ra of the outer surface of the ceramic composite material is a rough surface of 3 μm or more, or the Ra on the front surface and / or the back surface of the outer surface. It consists of a combination of a flat surface of 1 μm or less and a rough surface of 3 μm or more at the periphery thereof, and the surface layer of the rough surface contains Al and N elements, and the Al element is 0.01 to 10% by mass. N element is 0. Ceramic composite material in which 02 to 30% by mass is present.

  The ceramic composite material of the present invention can easily remove deposits formed on the surface of the ceramic composite material after firing the ceramic composite material and can prevent surface defects of the obtained ceramic composite material.

  Hereinafter, the ceramic composite material of the present invention will be described in detail. However, the present invention is not construed as being limited thereto, and various modifications can be made based on the knowledge of those skilled in the art without departing from the scope of the present invention. Changes, corrections and improvements can be added.

In the ceramic composite material according to the present invention, 60 to 98% by mass of silicon carbide and 2 to 40% by mass of metal silicon are impregnated with the metal silicon in voids formed by bonding the silicon carbide crystals to each other . A ceramic composite material having a metal-impregnated layer , wherein the surface of the metal-impregnated layer further suppresses wettability to impregnated metal silicon by a chemical reaction using a gaseous substance containing Al and N elements. The rough surface is formed on the whole or a part of the outer surface of the ceramic composite material, and all the Ra of the outer surface of the ceramic composite material is a rough surface of 3 μm or more, or among the outer surface, the surface and / Or a rear surface Ra is a combination of a flat surface of 1 μm or less and a rough surface of 3 μm or more at the peripheral edge thereof, and the surface layer of the rough surface contains Al and N elements, and the Al element is 0.1%. 01 And 10 wt%, in which N elements are present 0.02 to 30% by weight. Note that Ra is a surface parameter defined by JIS and indicates the surface roughness, in which the arithmetic average height is expressed as Ra. This arithmetic average height is in accordance with JIS B 0601-2001.

Ceramic composite material of the present invention, if example embodiment, which has a characteristics adapted to the balance between the actual electronic components (including semiconductor devices) thermal expansion coefficient obtained by such a thermal conductivity, have a high thermal conductivity.

  Here, the main feature of the ceramic composite material of the present invention is that the surface of the metal impregnated layer in which the silicon silicon crystal is impregnated in the voids formed by bonding silicon carbide crystals to each other is further impregnated with the metal ( In particular, a layer (rough surface) that suppresses wettability to Si) is formed on the whole or a part of the outer surface.

  As a result, the ceramic composite material of the present invention can make the contact angle with the deposit on the metal impregnated layer an obtuse angle of 90 ° or more, that is, the contact surface between the metal impregnated layer and the deposit is minimized. Therefore, it is possible to easily remove deposits from the metal-impregnated layer, and it does not affect the metal-impregnated layer due to volume expansion of the deposits. Surface defects of the material can be prevented.

  Moreover, the ceramic composite material of the present invention does not stick to the contact portion between the fired product and the firing jig, for example, when the ceramic composite material (fired product) is taken out from the firing jig. Therefore, it is possible to easily take out the fired product from the firing container (saya).

  In order to obtain the above effects, the ceramic composite material of the present invention has 0.01 to 10% by mass (more preferably 0.1 to 6% by mass) of Al element and N element on the surface of the rough surface. Is preferably 0.2 to 30% by mass (more preferably 2 to 25% by mass).

  This is because the surface of the metal-impregnated layer of the ceramic composite material contains a small amount of AlN with suppressed wettability with respect to Si, so that the contact angle with Si, which is a deposit, is increased with respect to the metal-impregnated layer. Presumed to be.

  The ceramic composite material of the present invention may be a rough surface having an Ra of 3 μm or more on the entire outer surface, a flat surface having an Ra of the surface and / or the back surface of 1 μm or less, A combination with a rough surface having a Ra of 3 μm or more at the peripheral edge may be used.

  The ceramic composite material of the present invention is often used in a state related to heat due to its excellent heat resistance. In this case, when the Ra of the rough surface is less than 3 μm, the heat radiation rate of the surface is low, but by increasing Ra to 3 μm or more, the heat radiation rate can be increased. When the thermal emissivity increases, the thermal uniformity improves when used at high temperatures, and the heat dissipation characteristics improve when used as a heat dissipation material. In addition, the flat surface is often used as an adhesive surface when bonded to an IC chip or another device. When Ra is 1 μm or less, this adhesive property is good, but when it exceeds 1 μm, it is not preferable because peeling occurs after bonding.

  Moreover, it is preferable that the rough surface of the ceramic composite material of the present invention is formed by sandblasting. This is because, when a rough surface with Ra of 3 μm or more is formed, the method of polishing and / or grinding causes direction to fine irregularities generated on the surface, which may affect the heat radiation rate. This is because the processing by sandblasting not only forms the fine irregularities formed on the surface relatively uniformly, but also makes it possible to reduce the cost for the processing.

  Furthermore, it is preferable that the ceramic composite material of the present invention has a flat surface formed by grinding and / or polishing. This is because, when a flat surface with Ra of 1 μm or less is achieved, by processing the shape of fine irregularities on the surface by polishing and / or grinding, the adhesion is good, and the time and cost required for the processing This is because it is an effective means.

The method for producing a ceramic composite material according to the present invention includes a ceramic composite comprising a ceramic filled with a metal in a void portion of a porous ceramic body having a three-dimensional structure with a porosity of 2 to 60%. A method of manufacturing a material , wherein a metal impregnated layer is formed on the surface of a ceramic porous body after heat impregnation with molten metal silicon (metal silicon) in a void portion of the ceramic porous body composed of silicon carbide (SiC) and melted. until the metallic silicon is cooled and solidified below the melting point, the contact angle with respect to the metal-impregnated layer to form a deposit over 90 °, then by sand blasting, to remove deposits from metal-impregnated layer, the outer surface all Ra is to obtain a ceramic composite material having the above rough surface 3 [mu] m. Furthermore, in the method for producing a ceramic composite material of the present invention, by grinding and / or polishing the front surface and / or the back surface of the outer surface, the flat surface with an Ra of 1 μm or less and the Ra of the peripheral portion thereof are 3 μm. A ceramic composite material comprising a combination with the above rough surface can be obtained.

When forming a deposit having a contact angle of 90 ° or more with respect to the metal-impregnated layer, it is preferable to use a gaseous substance with a chemical reaction.

In this case, the gaseous substance preferably contains one or two elements selected from the group consisting of Al and N.

Further, the ceramic porous body, it is not preferable to be composed of silicon carbide.

Furthermore, the molten metal is not preferable to contain Si (metal silicon).

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

(Examples 1-6)
Silicon carbide powder (48% by mass of SiC coarse particles having an average particle size of 100 μm, 3% by mass of first intermediate particles having an average particle size of 30 μm, 2% by mass of second intermediate particles having an average particle size of 2 μm, An acrylic organic binder and a polycarboxylic acid dispersant were added to a composition comprising 47% by mass of SiC fine particles having an average particle diameter of 2 μm, and a slurry was prepared, and then a granulated powder was obtained with a spray dryer. The obtained granulated powder obtained the molded object by press molding (Examples 1-5). Moreover, the molded object was obtained by casting by the slurry obtained similarly (Example 6).

Each of the obtained compacts was heat-treated (recrystallized) at 2300 ° C. for 3 hours to obtain a ceramic porous substrate made of recrystallized SiC. In the firing vessel, simultaneously with the base material of the porous ceramic body made of recrystallized SiC, pellets in which metal aluminum or alumina and mullite were changed in the ratio shown in Table 1 as a film-forming substance were installed, and at 1500 ° C. under reduced pressure atmosphere After impregnating metallic silicon using the capillary phenomenon, nitrogen (N ₂ ) was introduced to the atmospheric pressure and cooled at the time of the transition to the cooling process to obtain a Si—SiC composite material. Table 2 shows the characteristics of the obtained Si-SiC composite material.

(Example 7 and Example 8)
Silicon carbide powder (48% by mass of SiC coarse particles having an average particle size of 100 μm, 3% by mass of first intermediate particles having an average particle size of 30 μm, 2% by mass of second intermediate particles having an average particle size of 2 μm, An acrylic organic binder and a polycarboxylic acid dispersant were added to a composition comprising 47% by mass of SiC fine particles having an average particle size of 2 μm, and a slurry was prepared, and then granulated powder was obtained with a spray dryer. The obtained granulated powder obtained a compact (porous ceramic substrate) by press molding (Example 7). Moreover, the molded object (base material of the ceramic porous body) was obtained by casting with the slurry similarly obtained (Example 8). In the firing container, a pellet made by changing metallic aluminum or alumina and mullite at the ratio shown in Table 1 at the same time as the film-forming material at the same time as the porous ceramic substrate is placed, and the metallic silicon is capillaryized at 1500 ° C. in a reduced pressure atmosphere. After impregnation by use, nitrogen was introduced to atmospheric pressure during cooling process transition and cooled to obtain a Si—SiC composite material. Table 2 shows the characteristics of the obtained Si-SiC composite material.

(Comparative Examples 1-4)
The porous ceramic substrates obtained in Example 1 and Examples 6 to 8 were each placed in a firing container, impregnated with metallic silicon using a capillary phenomenon at 1500 ° C. under reduced pressure, and then cooled. During the process transition, argon was introduced to atmospheric pressure and cooled to obtain a Si—SiC composite material. Table 2 shows the characteristics of the obtained Si-SiC composite material.

  At this time, for example, as shown in FIG. 1, the method for firing the Si—SiC composite material is such that the metal silicon 3 is disposed in the lower container 4 and is disposed at a predetermined position from the liquid surface of the metal silicon 3. A metallic porous substrate (fired body 1) is impregnated with metallic silicon 3 by capillary attraction. The arrangement of the metal silicon 3 may be the upper part or the inside of the object to be fired 1. In Examples 1 to 8, pellets 20 in which metallic aluminum or alumina and mullite are changed in the ratio shown in Table 1 are placed and fired in a firing container (sheath) 10.

(Discussion)
As shown in Table 2, in Examples 1 to 8, in order to suppress wettability of Si remaining in the metal-impregnated layer, spherical deposits (mainly Si ) Was confirmed (see FIG. 2). The ratio of alumina and mullite in the pellets arranged in the firing container (saya) has a large contact angle with respect to the metal-impregnated layer when the alumina ratio is 90% by mass or more and when metal aluminum is arranged (130 to 140 °). Furthermore, even if the base material of the ceramic porous body is a difference in molding method or a molded body or a product made of recrystallized SiC, the Si-SiC composite material of the present invention could be suitably manufactured.

  The blasting time is reduced by half compared to the comparative example because the contact angle with the impregnated metal layer is increased and the Si removal work is facilitated. In addition, the defect (chip) ratio and impregnated layer defects could be significantly reduced (see Table 2).

  On the other hand, in Comparative Examples 1 to 4, since the wettability of Si remaining in the metal-impregnated layer is good, sticking deposits (mainly Si) having a contact angle of 60 ° or less with respect to the metal-impregnated layer are formed. Was confirmed (see FIG. 3).

  The ceramic composite material of the present invention can be suitably used, for example, as a shelf plate for firing, a core tube for firing semiconductors, a roller for roller hearth kiln, a tube for heat exchanger, particularly a heat dissipation material for semiconductor elements.

It is sectional explanatory drawing which shows the baking method of the Si-SiC composite material in an Example. It is a photograph which shows the state in which the spherical deposit | attachment (mainly Si) with a contact angle of 90 degrees or more was formed with respect to the metal impregnation layer. It is a photograph which shows the state in which the stuck deposit | attachment (mainly Si) whose contact angle is 60 degrees or less with respect to the metal impregnation layer was formed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... To-be-fired body (base material of ceramic porous body), 3 ... Metallic silicon, 4 ... Container, 10 ... Firing container (sheath), 20 ... Pellet.

Claims (1)

A ceramic composite material having a metal-impregnated layer in which silicon carbide is impregnated with 60 to 98% by mass of silicon carbide and 2 to 40% by mass of metal silicon, and voids formed by bonding the silicon carbide crystals to each other. The surface of the metal-impregnated layer further has a rough surface that suppresses wettability with respect to the impregnated metal silicon by a chemical reaction using a gaseous substance containing Al and N elements. It is formed on the whole or a part of the outer surface, and all the Ra of the outer surface of the ceramic composite material is a rough surface of 3 μm or more, or, among the outer surfaces, the Ra of the surface and / or the back surface is 1 μm or less. It consists of a combination of a flat surface and a rough surface of 3 μm or more at the periphery thereof, and the surface layer of the rough surface contains Al and N elements, and Al element is 0.01 to 10% by mass, and N element Is 0.02- Ceramic composites 0 wt% is present.