JPS60151292A - Metallization of non-oxide ceramic - 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 Application of the Invention] The present invention particularly relates to a method for metallizing non-oxide ceramics, and in particular to a method for metallizing non-oxide ceramics, particularly for forming a metallized layer having a bonding interface with high bonding strength at a relatively low temperature and in a short time. The present invention relates to a method of metallizing non-oxide ceramics suitable for forming.

Specifically, a method for forming a chromium-containing metal layer with strong adhesion in a relatively short time on a desired surface of a non-oxide ceramic containing a t-triple compound capable of reacting with chromium-11 at a temperature lower than the melting point of chromium. and a method of forming another metal on the chromium-containing metal layer.

[Background of the invention]

Conventionally, oxide ceramics, especially alumina ceramics, have been metallized for a long time.

For example, the metallization of ceramics is extremely important in the electronics industry, such as electrical firing of ceramic capacitors, hermetic sealing of electron tubes, and semiconductor element bonding technology in conductor devices. In particular, oxide ceramics such as alumina and beryllia have been studied for a long time, and various gold, ρ and other methods have been established at 7iF. For example, in the total bending method for alumina ceramics, a paste of manganese powder and molybdenum 9 powder is applied, sintered in hydrogen to create a metallized layer, and then Ni plating or C11 plating is applied. The most common method is brazing. In addition, as methods for metallizing oxide-based ceramics, active metal methods, oxide solder methods, copper oxide methods, and various metallization methods improved on these methods have been established.

On the other hand, silicon nitride ip (S i 3 N4),
Not much is known about metallization methods for non-oxide ceramics such as silicon carbide (S i C).

According to Ushi, 5 Kaisho 55-1 I 368:3,
As a method for converting silicon carbide ceramics, powdered IV
a.

Va, Vla and ■1 suppression of group a metal name -1- from 10 to +
00ffTEt part and Ta+ II a, III,
1r IV a and 90 parts by weight of one or more of the group elements z4 and 1. It is applied to the surface of two-wing ceramics and heated (1 [100-1.
800° C.) to form a metal film on the ceramic surface. For example, 1 copper powder (20% copper powder) and 80% manganese powder
A base plate consisting of silicon carbide is coated on three nicks (−j
' L, I'm baking the 2 pieces in a vacuum. The bulletin states that base baking (1 hour is not specified, but it uses metal diffusion, J), and requires a long period of time.

JP-A-55-51771 also states that silicon nitride ceramics are metallized with a diffusion frame at 1550 DEG C. using a base material containing tungsten powder and manganese powder.

Furthermore, in JP-A-56-191522, Cr-N1-F
Metallization is carried out by a method in which an e-Mn-Si alloy is fused onto the surface of nitride silicon ceramics.

In JP-A No. 57-85423, a manganese-containing metal layer is formed on the surface of flame-set ceramics, the metal is heated to a temperature lower than the melting point of manganese, and a bonding reaction between the manganese and the carbon dioxide is used to form silicon carbide. He states that it is possible to turn ceramics into metals.

As mentioned above, patent applications are being filed for methods of metallizing non-oxide ceramics. Oxide-based ceramics are physically and chemically stable, so they have extremely poor wettability with metals. 1l (jl) A metallization method with sufficient adhesion strength has not been established.

[Purpose of the invention]

An object of the present invention is to provide a metallization method that can metallize non-oxide ceramics containing silicon compounds such as silicon nitride and silicon carbide at a relatively low temperature and in a short time, and has strong adhesion properties. Surunian).

[Summary of the invention]

In the present invention, a completely new bonding mechanism 11, which could not be achieved conventionally, is created due to the state of the metal contained in chromium formed on the surface of a non-oxide ceramic containing a silicon compound. It is based on the new discovery that metal reactions occur easily at low temperatures.

More specifically, chromium-containing gold is brought into close contact with the surface of the ceramic, and heated in a non-oxidizing atmosphere to a temperature higher than the melting point of the chromium-containing gold. A bonding reaction with the silicon atoms inside is carried out to form chloro\\silicide at the bonding interface to increase the adhesion strength.

(1) Racemic phase material The ceramic material that is the object of the present invention is produced by the silicon component contained therein reacting with chromium silica r.
In particular, silicon nitride and silicon carbide are used as BtJ-dioxide-based ceramitas.

(11) Chromium-containing metal layer In order to achieve the object of the present invention, it is necessary to form a condition in which chromium-15 easily reacts with soil, silicon nitride, and silicon carbide. Such an IP, The following method is available as a means for forming fl.

(a) Chromium-containing alloy is brought into close contact with the desired surface of the ceramics in the form of foil, mesh, powder, or film;
When this is heated above the melting point of the alloy in a non-oxidizing atmosphere, a liquid phase is formed. The liquid phase containing chlorine \\ thus formed approaches the silicon compound of the ceramic substrate, and the silicon atoms and chromium atoms easily combine'!
Experimentally confirmed that G +11'? ',did.

A particularly preferred alloy composition is 1 ] −15 gravity (% Cr
and 9 to 11 tons (% P) and an alloy consisting of 1 and 11 (melting point 890°C) and 18 to 20 weight % C1 and 9 to
An alloy consisting of 11% Si and the balance Ni (melting point 12%)
00"C), an alloy consisting of 39~41wt% C", 28~31wt%Ge, and the balance Ni (melting point approximately 1000%).
°C), 19%Cr-24%I”d-39%Ni-4%Si (melting point approximately 1050°C), 18
~20 heavy supernatant 'lo L'-, r 47''-57 heavy μ%
Ge-4 to 5 times μ'''<11. i is an alloy in which the remainder is Ni (approximately 1000" C), especially preferred 1: the above alloy is amorphous; It is desirable that

In particular, it is a new fact that the adhesion strength of the ceramics is dramatically improved in +4J, which makes an alloy consisting of 11=]5%, t%Cr and 9~j1weight-%1] and the balance Ni, to an amorphous state. Brother 1. Ta.

Furthermore, the object of the present invention can also be achieved by adding a small amount of chlorine to various eutectic alloys.

For example, 25 to 45 heavy weight lvl n -C', u alloy (melting point 870°C ± about 10°C) and 50 to 70 heavy weight %
By adding several weight percent of chromium to the extent that eutectic alloys such as M n -N i alloy (melting point 10] 8°C ± 10°C) do not become brittle, temperatures considerably lower than the circle I point of chromium can be achieved. By forming a melt, a metallized layer with high adhesion can be obtained.

Figure 1 shows the relationship between the chromium content in the alloy foil and the adhesion strength when a metallized layer is formed on the silicon nitride surface using an alloy foil in which chromium is added to a 40% by weight λ4 n -Cu base metal. shows.

In addition, the metallization method of the 11th director is JIfsa21n+1),
vertical.

Noa 5 on the silicon nitride ceramic surface with a width of 20nnn
A 0μm alloy λ) was placed on the sample in an argon atmosphere. ,/c6i (after applying 7CIJI pressure and heating it to the melting point of the alloy foil, naturally)ilj
The adhesion strength of the metallized layer formed by the above method was measured by the method shown in FIG. That is, as shown in Section 2M, a 5 Q 7 foil 1 was bonded with silver solder to the metallized layer 2 formed on the nitrided nitride ceramic according to the method d above. , Cu
The free tM of M3 is 1 nail (#, which strengthens the adhesion strength of the separated layer).6 As shown in Figure 1, when the alloy foil glue rJ A Jγ- is 2 weight Q+ (the strength is This decrease in adhesion strength is due to the excessive amount of the alloy foil, which becomes brittle due to the entanglement of the ROM, and a desirable amount is 3%.

In addition, when Chloro 11 was added to a 50=70% M ri -N i alloy (melting point about 1018° C.), the same results as in FIG. 1 were obtained.

(B)-I-Create a powder from an alloy with a Jlx of 1゛T, and prepare it into the shape of a base for other uses. Print.

By heating this in a non-oxidizing atmosphere to a temperature higher than that of the alloy, a melt is formed, and the chromium atoms in the powder and the silicon JJX J' in the ceramics come close to each other and can easily react.

(d) Chromium or gold containing chromium is adhered to the desired surface of the ceramic by vacuum deposition or sputtering.

Metal treatment is carried out by heating the alloy to just above it (5 is the peak point of the alloy or 1 or Q).

In the method of J-Note (a) and (d), a melt is formed at a lower temperature than the Qi+ of RiU-no, and chromium 12 reacts with the silicon in the ceramic, Good money J
r'SIIζ(3, where r'm and sh)jcon react and form '1m silicide at the bonding interface.
to be accomplished. This T! f' was confirmed by x-ray analysis and X-ray diffraction of the bonding interface between the racemic and the metallized layer.

[Embodiments of the invention]

The present invention will be explained in detail below. .

Real jj' (Example 1 of 1 Thickness 2111:11, @, 19 wt% Cr and 11 heavy electric P with a thickness of 30 μl'n on the surface of the silicon nitride of the horizontal 30 cylinder.
, an amorphous alloy foil with the remainder made of Ni is placed; 1. Approximately 1 from the melting point (890″C) of the alloy foil in an argon atmosphere
) O"CL was heated to a low temperature for 30 seconds and then allowed to cool naturally. Thereafter, the gold formed by the above method was prepared.

In order to examine the adhesion strength of the ceramic layer to the ceramic surface,
1 by brazing 50 μm of Ni foil onto the surface of the metal layer.
Four matched. The adhesion strength of this was examined in the same manner as shown in FIG. 2, and as a result, the adhesion strength was 25 kg f /n+m', and it broke at the silver soldered part.

Example 2 19% heavy nails were applied to the surface of silicon nitride having the same shape as in Example 1.
The particle size is approximately 20% consisting of Cr, 11% P, and the balance Ni.
Apply a paste of μm powder with an organic solvent and heat it for 30 seconds at a temperature approximately 50°C higher than the melting point (890°C) of the powder in an argon atmosphere.
Shita. In order to examine the bonding strength on the surface of the 11-metalized ceramic material obtained by the method described in -1-0, 50/1. +11 (7,1Ni foil was coated with silver solder and the adhesion strength was investigated using the same method as shown in Figure 2.) As a result, the adhesion strength was found to be 28 to 1/1'. I was more decisive.

Example 3 19% by weight Cr was added to the surface of nitrided silicon having the same shape as Example 1.
and 10% Si, the balance is Ni, thickness 251L
Place a T11 alloy foil and add 50 u on top of it.
Overlap N i i'i-i of n+, Q , 5 kIX
/w+' pressure is applied, and the melting point of the alloy foil (12o
oc) for about 1 second. Heating is done with argon'1
The mixture was heated in a high-frequency coil for 5' and then cooled naturally.

The adhesion strength of the gold oxide layer obtained by the above method was measured by the method shown in FIG. 2. As a result, an adhesion strength of 30 dazzling f/+nm was obtained, which was 1Q higher than that of the Ni layer.

Implementation 6 4 Thickness l jIjI11. my jIj 2 On+,
An alloy consisting of carbonized weight % Cr, 30 weight % Si, and the balance Ni was deposited with a surface roughness of 2 μm. In this case, the ceramic was heated to 300'C during deposition. Furthermore, this sample was heated in a vacuum of 3
℃ for 5 minutes to perform metallization treatment.

A 30 μm Ni foil was bonded to the surface of the metallized layer formed by the above method by silver brazing, and the adhesion strength was examined using the method shown in Figure 2. As a result, a 4 bond strength of 20 kgf/myu” or more was obtained. Ta.

〔Effect of the invention〕

According to the present invention, metallization treatment of non-oxide ceramics can be performed at a relatively low temperature and in a short time. As a result, the properties of ceramics are not degraded.

A metallized layer with high adhesion strength is obtained.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between the degree of chromium addition and adhesion strength, and FIG. 2 is an explanatory diagram showing the adhesion strength and the Δ1 constant force method. Fork 1,

Claims (1)

[Claims] 1. A chromium-containing metal layer is formed in advance in close contact with the desired circular surface of a non-oxide ceramic whose main component is a silicon compound, and then the metal layer is applied to the gold) M W' . 1. A method for metallizing non-oxide ceramics, which comprises heating to a temperature above the melting point of chromium to cause a bonding reaction between chromium in the metal layer and silicon in the ceramic.