JPS62128991A - Metallizing composition for nitride ceramic body and processtherefor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a metallizing composition, and more particularly, a metallizing composition containing an oxynitride glass component and forming a metallized layer on the surface of a nitride ceramic body. The present invention relates to a metallizing composition useful for. Furthermore, the present invention relates to a method of metallizing a nitride ceramic body using this composition.

[Prior art and its problems]

In recent years, the bonding of ceramic bodies and metals has played an extremely important role in the composite industrial technology of both materials. With the development of new materials for ceramic bodies, silicon nitride ceramics, which have excellent properties not found in conventional oxide ceramic bodies, such as high-temperature and high-strength properties, are attracting attention. Excellent strength is required.

The metallization method used for the above bonding includes the high temperature metal method (
For example, the Telefunken method) is known.

However, even if the nitride ceramic body is metallized by the conventionally well-known high-temperature metal method, there is a problem in that the adhesive strength is poor and it easily peels off.

[Means to solve problems]

In view of the above circumstances, the present inventors conducted intensive research and found that a composition containing oxynitride glass with a specific composition and high melting point metal powder, which will be described in detail below, firmly adheres to the nitride ceramic body and peels off. It has been found that a metallized layer with excellent strength can be formed on this ceramic body.

That is, according to the present invention, it is characterized in that it essentially consists of at least one selected from group IIa elements or group IIIa elements of the periodic table, oxynitride glass of aluminum and silicon, and high melting point metal powder. A composition for metallizing a nitride ceramic body is provided.

Furthermore, according to the present invention, an element of group na or group I of the periodic table
A metallizing composition consisting essentially of an oxynitride glass of at least one selected from Group IIa elements, aluminum and silicon, and a high melting point metal powder was made into a paste form, and this was applied to the required locations on a nitride ceramic body. A method for metallizing a nitride ceramic body is provided, which is characterized in that the process is then baked at a temperature of 1000 to 1600°C in a non-oxidizing atmosphere.

As already pointed out, the present invention is characterized in that the oxynitride glass having the above composition is used as a glass binder for metallization. That is, by using this oxynitride glass, it is possible to form a metallized layer with excellent adhesive strength to a nitride ceramic body, which is completely unexpected from metallized compositions using conventional oxide glass. .

Oxynitride glass The oxynitride glass used in the metallized composition of the present invention is conventionally known as Mg-5i-AI-0-N glass or Y-3i-AI-0-N glass. A notable difference from conventional glass binders for metallization is that a portion of oxygen is replaced with nitrogen. In general, the nitrogen content in oxynitride glass in terms of adhesion to nitride ceramic bodies is
It is preferably in the range of 2 to 19% by weight, particularly 2 to 15% by weight, based on the total weight.

In the oxynitride glass of the present invention, the Group 1) a elements of the periodic table include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or two or more of these. Among these combinations, magnesium is the most preferred. In terms of adhesion to ceramic bodies, the Ua group elements of the periodic table, AI and Si, are in the composition range surrounded by the four straight lines I, ■, ■, and ■ in Figure 1 in atomic ratio percentage based on the three components. (Hereinafter, the first [a
Type (i) oxynitride glass containing group elements
).

That is, this type of oxynitride glass (i
) is expressed as the 3-component standard atomic ratio %, and the following formula % formula % () In the formula, × is the atomic ratio % of the Ua group element of the periodic table based on the 3-component standard, Y is the atomic ratio % of aluminum, Z is the atomic ratio % of silicon, and it is assumed that 2, :,, :, teX+Y+Z=100te.

It is desirable that the value be within the range expressed by .

Note that the lines 41), ■, ■, and ■ in FIG. 1 correspond to the equations in the case of an equal sign in the above equations.

According to experiments by the present inventors, the above straight lines ■, ■, ■, and ■
It has been found that a more desirable range within the composition range surrounded by is set to the following formula.

That is, Z≧0.37X-0,66Y... (I) Z≧-〇,
06X+0.80Y... (II)Y≧10
... (II)×≧IO... (
IV) In the oxynitride glass of the present invention, the Group IIIa elements of the periodic table include scandium (Sc), indolium (Y), lanthanum (La), and cerium (Ce).
, praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (t
! u), gadolinium (Gd), televisionram (Td)
, dysprosium (DV), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu), among which yttrium, lanthanum, and cerium are preferred.

III of the periodic table in terms of adhesion to ceramic bodies.
Group A elements, AI and Si have the second highest atomic ratio based on the three components.
Type (ii
).

That is, this type of oxynitride glass (ii)
is expressed as 3-component standard atomic ratio %, and the following formula 2% () In the formula, It is assumed here that X+y+z=t o o.

It is desirable to have a composition expressed by:

Incidentally, the straight lines ■, ■, ■, ■ in FIG. 2 correspond to each equation in the case of an equal sign in the above equation.

According to experiments by the present inventors, the above straight lines ■, ■, ■, and ■
It has been found that it is preferable to set the following formula as a more desirable composition range within the composition range surrounded by .

That is, Z≧0.28X+0.14Y... (V)Z≧-0,
29X+0.59Y... (Vl)Y≧10
... (I[[)×≧10
(IV) The oxynitride glass used in the present invention is made by blending each nitride and oxide raw material or a raw material compound that becomes oxynitride under melting conditions so that the composition falls within the above range, and then homogeneously It is obtained by mixing, melting these components, and vitrifying them.

Silica (Si(h) and silicon nitride (SiJ4) can be used as silicon raw materials, and alumina (AhO:+) and aluminum nitride (SiJ4) can be used as aluminum raw materials.
AIN), aluminum nitrate, or the like can be used. In addition, raw materials from Group IVa of the periodic table or IIIa
As the group raw materials, oxides, hydroxides, nitrides, nitrates, carbonates, etc. can be used. Of course, nitrides must be used as at least part of the at least one raw material so that the final glass contains the aforementioned amounts of nitrogen.

In the present invention, it is desirable to use aluminum nitride as at least a part of the aluminum raw material. That is, by using aluminum nitride, more homogeneous and uniform vitrification can be achieved, and nitrogen can be effectively fixed in the final glass.

Although the glass used in the present invention essentially contains the above-mentioned components, it is not excluded that other components may be mixed therein. For example, there are -〇, ZrO□, etc., which are inevitably mixed in due to the abrasion of grinding media such as balls as the glass composition is prepared, and these are contained within 10% by weight of the total composition. Permissible. Also,
For example, if a grinding medium such as AlzOz or AIM is used,
Components required for the glass composition of the present invention can be mixed.

Furthermore, in the present invention, the above-mentioned raw materials were prepared in a predetermined mixing ratio, heated and melted in a non-oxidizing atmosphere, and cooled. It is desirable to set this heating temperature in the temperature range of 1500 to 1900°C; if it is less than 1500°C, it will not melt easily, and if it exceeds 1900°C, it will decompose and volatilize. It is then pulverized to a particle size of 100 mesh or less to facilitate coating or screen printing.

The non-oxidizing atmosphere can be selected from either a vacuum atmosphere or an inert atmosphere consisting of a gas such as nitrogen or argon;
When nitrogen gas is used, it is possible to control the equilibrium of glass decomposition according to the nitrogen gas partial pressure, and there is an advantage that glass gasification can be controlled and manufacturing without waste can be achieved.

The glasses of types (i) and (ii) of the present invention may be completely amorphous glasses, or may contain some of the components in a crystallized form depending on the composition. For example, 40% by volume or less based on the whole glass,
Silicon oxynitride, sialon compound, N
It may be contained in the glass in the form of crystals such as silicates.

The oxynitride glass used in the present invention is of type (i
) and type (ii) can also be used in a mixed form. In this case, glass (i) and glass (ii) may be mixed in powder form and contained in the metallizing composition, or glass (i) and glass (ii) may be melted and mixed in advance. It may also be used in glass form.

) 9 (,Q) The high melting point metal powder to be dispersed and mixed in the oxynitride glass is basically a metal, metal silicide, nitride, or boride powder that does not melt or vaporize at the baking temperature. When the glass is baked, it is sufficient that it exists as a metal, a metal silicide, nitride, boride, or a mixture thereof, such as titanium (Ti), zirconium (Zr),
Hafnium (Hf), vanadium (V), niobium (Nb)
), tantalum (Ta), chromium (Cr), molybdenum (
Mo), tungsten (-), etc. of the periodic table ■, ■, ■
Group A metal element powder is preferred. Among these, tungsten, molybdenum, tungsten silicide, molybdenum silicide, tungsten carbide, molybdenum carbide, niobium silicide, tantalum silicide, or a combination of two or more of these are particularly preferred. Further, it is desirable that the metal powder has a particle size of 100 mesh or less.

Although the blending ratio of glass and high melting point metal powder can vary over a fairly wide range, PQ contains 35 to 90 volume % glass powder, especially 40 to 75 volume %, and metal powder I
It is preferable to use a mixture of O to 65% by volume, especially 60 to 25% by volume.

The metallizing composition of the present invention can use an auxiliary agent to impart applicability and adhesion to a ceramic body. For example, an organic binder and an organic solvent are added to the composition of the present invention to prepare a coating composition. As the organic binder, for example, nitrocellulose or ethylcellulose can be used, and as the organic solvent, for example, α-chilbionel or petyl-caldetol acetate can be used. In terms of coatability and adhesion, based on the total amount of glass and metal,
1 to 10% by weight of an organic binder, and 10 to 20% by weight of an organic binder;
It is desirable to use % by weight of organic solvent.

Metallized ceramic Bison manufacturing method - Example 3
The figure shows a partially vertical perspective view of a metallized structure obtained by the method of the present invention.

The metallized composition fixed over the area necessary for bonding on the nitride ceramic body 1 is baked to form a metallized part 2, and on this metallized part 2, nickel (Ni)N3 is applied by plating, and then gold is applied by plating. A (Au) layer 4 is formed on the gold layer 4 so that it can be soldered.

As the nitride ceramic body, silicon nitride (SisN4
), aluminum nitride (AIN), sialon, boron nitride (BN), titanium nitride (TiN), zirconium nitride (ZrN), and the like. Of course, these sintered bodies can be used within the scope of not departing from the essence of nitride ceramic bodies.
It may contain other components, such as oxide ceramics, and may also contain various sintering aids.

As the sintering aid, elements of groups IIa and IIIa of the periodic table, oxides such as aluminum and silicon, and aluminum nitride (AIN) are used alone or in combination. These auxiliary agents form the main phase of the intergranular phase by sintering, and the intergranular phase is usually composed of oxynitride glass or oxynitride glass obtained by crystallizing this glass.

The surface to be metalized of the ceramic body 1 which has been molded into a predetermined shape and sintered is polished to make the metallized surface easier. The metallizing coating composition described above is applied to this surface by silk screen printing or other coating means. This coating layer is heated to 1000 to 1600°C, preferably 1300°C.
It may be baked by heating in a non-oxidizing atmosphere set within a temperature range of 1,600°C. This non-oxidizing atmosphere may be either a vacuum atmosphere or an inert atmosphere consisting of a gas such as nitrogen or argon. In particular, when nitrogen gas is used, the equilibrium of glass decomposition can be controlled according to the nitrogen gas partial pressure. In addition to controlling the gasification of the glass, the metallized layer is free of bubbles and superior metallized ceramic bodies can be efficiently produced.

The thickness of the metallized layer is generally 5 to 50 mm, especially 10 mm.
The distance is preferably in the range of 30 mm to 30 mm.

In the present invention, when oxynitride glass is used to form the metallized layer, substances can easily move between the ceramics in contact with the glass, and the low temperature allows the equilibrium vapor pressure of the ceramics to be set low, thereby preventing decomposition of the ceramic interface. It was possible to significantly reduce the generation of bubbles. In addition, this glass has excellent wettability with the nitride ceramic body, and the high concentration of nitrogen in the glass suppresses the generation of bubbles due to reactions compared to oxide glass, resulting in the formation of nitrides in the metallized layer. This significantly improves the bonding strength to the ceramic body.

Furthermore, oxynitride glass has superior strength and hardness compared to other glasses, and has high viscosity at high temperatures.
It also has excellent water resistance and chemical resistance. This results in
The metallized ceramic body of the present invention is suitable as a high-temperature structural material.

On the obtained metallized part, the metal to be joined can be soldered as a structural material as described above, or a highly conductive metal such as Au or Ni can be plated to form a printed circuit board. It can be applied to electrical materials by forming conductor wiring.

Regarding the metallized ceramic body of the present invention, a method for measuring the bonding strength after soldering described later will be explained with reference to FIG.

That is, the nitride ceramic body 1, which is the test piece S, is firmly fixed with a compressive force [large arrow] applied toward the center by vices 8 from the left and right sides, and the hanging fitting 5 is soldered onto the gold 1i4. 6, and a push-pull gauge (spring spring balance) 7 is attached to the upper end of this hanging fitting 5. In this state, the hanging fixture 5 is pulled upward at a speed of 30 mm/min, and the strength at the moment the metallized portion 2 is separated from the ceramic body 1 is read using the gauge 7.

〔Example〕

(1) Nitride ceramic body Starting materials for nitride ceramics containing sintering aids as shown in Table 1 are pulverized and mixed, formed into a desired shape, and after debinding, in a nitrogen atmosphere as shown in Table 1. After firing under the following firing conditions, the metallized surface of this sintered body was heated to 250
The test piece (
Samples tlh a-1 to a-7) were obtained.

(2) Oxynitride glass S made by intimately mixing raw materials with the ingredients and proportions shown in Table 2 and coating the inner surface with orthogonal BN.
It was put into an iC crucible. Then, a second
The material was heated and melted under the melting conditions shown in the table, and then allowed to cool.

The current thus obtained was coarsely ground in a mortar and adjusted to a particle size of 325 mesh or less using a vibrating mill.

In addition, in Table 2, MgO and CaO+ SrO are each M
g(OH)t.

CaC0t+ 5rCO:+ were used as raw materials, respectively.

(3) Fixing and baking: Mix the high-melting point metal powder adjusted to a particle size of 325 mS or less and the oxynitride glass in the mixing ratio shown in Table 3, and further add an organic binder and an organic solvent to metallize. It was made into a composition.

This composition was placed on the ceramic body obtained in (1) for 4 m.
The coating was applied to a thickness of 20 to 30 .mu.m over an area of 1.5 m", and baked under the conditions shown in Table 3 in a nitrogen atmosphere to obtain a metallized part.

Furthermore, Ni electroless plating was applied to the metallized portion, a hanging fitting was soldered to the metallized portion in accordance with the method described above, and the peel strength between the metallized portion and the ceramic body was measured.

Note that this measurement was performed using 20 test pieces for each test.

The results are shown in Table 3.

As is clear from Table 3, test light 1 to 7.14 to 1
No. 9 has excellent peel strength, showing a high value of 51 MPa or more.

On the other hand, the test magnet 8.9 shows significantly deteriorated characteristic values because the blending ratio of glass and metal is outside the desirable range of the present invention, and the test light 10 to 13 shows significantly deteriorated characteristic values.
In this case, excellent peel strength could not be obtained because the glass composition deviated from the desired glass composition of the present invention.

Furthermore, in addition to the above examples, T a S is used as a high melting point metal powder.
I Z I T i N + T t B z +
Even when Z r B z + Z r N was used, the same effect as the main idea of the present invention was obtained.

Furthermore, other than the above, Group 1) a and Group 1) 1 of the periodic table
The effects of the present invention could be achieved even when a group a element was used and even when a nitride ceramic body other than those mentioned above was hemetallized.

In addition, based on the conventionally well-known high-temperature metal method, Mo85%-M
A metallizing composition containing 5% by weight of n10 weight%-3ing was baked and its peel strength was measured as described above to be about 50 MPa, but it did not adhere to the nitride ceramic body and was easily peeled off.

However, when the metallizing composition of the present invention was used, it was possible to obtain strength that exceeded the adhesion to alumina ceramics.

〔Effect of the invention〕

As mentioned above, when the metallizing composition of the present invention was used, the bonding strength between the nitride ceramic body and the metal could be significantly improved. Furthermore, this metallized composition has excellent water resistance and chemical resistance, so it is suitable for a wide range of uses.

Thus, the ceramic-metal bonded body obtained according to the present invention can be used for various parts for industrial machinery and electronic parts such as semiconductor packages and various ceramic substrates.

[Brief explanation of drawings]

FIG. 1 is a diagram showing a preferred three-component composition range of an oxynitride glass containing group 1) a elements of the periodic table, aluminum, and silicon according to the present invention, and FIG. FIG. 3 is a diagram showing a preferred three-component composition range of an oxynitride glass containing Group IIIa elements, aluminum, and silicon; FIG. 3 is a partially vertical perspective view of a metallized structure according to the present invention; FIG. FIG. 2 is a schematic diagram illustrating the intensity measurement method used in the example. 1... Nitride ceramic body 2... Metallized portion 3... Nickel layer 4... Gold layer Agent Patent attorney 1) Katsuhiko Hara Figure 0

Claims (2)

[Claims] (1) A nitride ceramic body consisting essentially of at least one element selected from group IIa or IIIa elements of the periodic table, oxynitride glass of aluminum and silicon, and high melting point metal powder. Metallizing composition. (2) A metallized composition consisting essentially of at least one element selected from Group IIa or Group IIIa elements of the periodic table, oxynitride glass of aluminum and silicon, and high melting point metal powder is made into a paste form, and this is made into a paste. A method for metallizing a nitride ceramic body, which comprises coating the nitride ceramic body at required locations and then baking the body at a temperature of 1000 to 1600°C in a non-oxidizing atmosphere.