JPH0244789B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to titanates, silicates, arsenides, silicides, tellurides, phosphides, nitrides (excluding boron nitride) of metals or metalloids or mixtures thereof;
Base or foundation of oxides (excluding alumina, zirconia, saphire, quartz, and beryllia), borides (excluding titanium diboride), carbides (excluding silicon carbide), steel, or mixtures or compression molded bodies thereof Concerning complexes as elements.

In these composites, alloys of tin, lead, indium, or their alloys with metals that tend to form carbides or carbonyls, such as Cr, Ni, and V, in which some or all of them form carbides or carbonyls. If the layer is used as a coating, film, layer or interlayer, and the coating is bonded to the substrate in a carbon monoxide atmosphere, it is not dewettable even when heated, and the coating and the substrate are bonded together in a carbon monoxide atmosphere. The wetting angle, that is, the contact angle between the two is zero to negative, and a composite is formed with no voids at the interface. As used herein, "reducing wettability" means a state in which the coating hardens into a hemispherical shape when the coating is in a liquid state due to heating.

We filed the previous application (Patent Application No. 88741/1988)
No. 63-32759), tin, lead, indium or their alloys are mixed with the aforementioned carbide- or carbonyl-forming metals which have been found to be particularly useful for producing adhesive coatings. disclosed substrates and adhesive coatings. The present invention was made while utilizing and investigating various aspects of the invention of the above-mentioned application, and it has been known for a long time that it is very difficult to bond different materials to a substrate. It is based on the following discoveries which have been found to be particularly useful when applied to substrates.

As disclosed in the earlier application,
The combination of tin, lead, indium or their alloys with metals that tend to form carbides and carbonyls is hitherto unknown when they are suitably mixed and then bonded to a substrate in a carbon monoxide atmosphere. However, it was discovered that unexpected results were obtained, and this discovery opened the door to the possibility of bonding metals with substrates that had been extremely difficult to bond to. Traditionally, there has been virtually no vacancy,
It has been found that good bonds with great adhesion and an unmeasurable increase in resistance can be formed in excellent yields by carrying out the above method on various substrates on which it was not possible to form easily. It was done. This is possible for a variety of substrates, and the tin, lead, and indium alloys on the substrate can be further combined with other substrates or metals in various ways, making it ideal for applications such as those in the electronics industry where heat dissipation, current conduction, etc. are desired. They are useful in many applications, provide novel and previously unknown substrates, and form contamination-free, virtually pore-free (by microscopic examination) bonds between these devices. . That is, devices such as piezoelectric materials, such as barium titanate, and laser beam generators, such as those based on aluminum gallium arsenide, have been shown to be effective for electrically conductive materials or base elements or for thermally conductive but still electrically insulating base elements. It can be easily bonded and manufactured by simple means at a fraction of the cost for useful applications and uses.

In view of the foregoing, the disclosure in the earlier application is hereby incorporated by reference, but will not be repeated in detail. Generally, the same atmospheric conditions are applied, along with the same temperature ranges, and these are established for the substrate at the required conditions. Similarly, the residence time provided by the reducing atmosphere of carbon monoxide for suitable bonding is established as necessary, but is generally within the ranges described in the earlier application. The particular temperatures and residence times used are those that are optimal for the particular substrate and the mere predetermined establishment of the necessary conditions when carried out in the industrial installation to which the practice of the invention is sought to be applied. , is carried out in either case.

Although carbon monoxide is an excellent reducing agent, it can also be mixed with other compatible reducing agents. Similarly, it can be diluted with other gases compatible with carbon monoxide which do not affect the reaction mechanism or reducibility of carbon monoxide. After a reducing atmosphere has been established and a suitable bond has been formed, e.g. by substantially pore-free, sufficient wetting and intimate adhesion as described above, the reducing atmosphere is suitably removed and other The inert atmosphere is replaced to cool the formed composite. Although preheating of the substrate and material can likewise be done in a reducing gas such as hydrogen, the initial heating can be done in an inert atmosphere by the same means as the subsequent cooling. However, the most effective means, and the most advantageous, are to form substrates, layers, etc. with tin, lead, indium and/or their alloys and carbides or carbonyl-forming metals, tin, etc. and/or carbides or carbonyl-forming metals. It is in the presence of carbon monoxide that the body metals somehow interact synergistically.

Although the carbide or carbonyl-forming metals are used in a variety of forms, they are most advantageously used in fine particles starting from colloids to fine particles up to 1/8 inch. These fine particles are dispersed in a metal such as tin under conditions conducive to it, for example by forging and/or hot molding or similar methods; likewise on the other hand in their extremely fine form. The dispersoid is suitably mixed in a vehicle such as rosin oil or a variety of Freon that evaporates more easily than the dispersion. The dispersion is then coated onto the substrate or applied to it by screening or printing, depending on the thickness of the substrate. The material is then inserted under appropriate conditions in a reducing atmosphere as described above. Thus, different patterns, such as conductive paths or the like, are formed on the substrate to form circuits and the like.

Some of the example substrates given in the earlier application combine equally well with substrates not previously disclosed in this application. Accordingly, the various substrates as disclosed and claimed in this application can be combined in distinct and novel combinations useful for purposes as disclosed herein.
Thus, lanthanum boride, _LaB6 , useful as a highly effective electron source used in electron microscopy, can be significantly bonded to electrical devices when first coated with tin-vanadium. This substrate is successfully bonded or coated with a mixture of about 15-2% vanadium, balance tin, at about 1000 DEG C. in an atmosphere of carbon monoxide.

The homogeneous mixing of these powders, their easy dispersibility in finely divided form and their easy application to substrates contribute to the purpose of applying these combinations to a variety of other substrates as mentioned above.

Other equally easy methods for forming films, layers, etc. on gallium arsenide or aluminum gallium arsenide and/or bonding gallium arsenide or aluminum gallium arsenide with various substrates include tin and carbides. or when used in combination with carbonyl-forming metals. Some of these are for example
Cr-Sn, V-Sn, Mo-Sn, W-Sn, Fe-Sn,
Ti-Sn, Ta-Sn, Mn-Sn, Ni-Sn and Co-
Sn.

The percentage of the above combination is about 15-2% carbide or carbonyl-forming metal, balance tin, with a preferred range being about 10-15% carbide- or carbonyl-forming metal when combined with gallium arsenide or aluminum gallium arsenide. be. Similar to the above, Sn-V combinations in particular are readily used to form adhesive coatings on silicon nitride or silicon oxide, thus forming various layer combinations (besides these, in turn, etc.). bonded to the aforementioned substrate). In addition to the carbide- or carbonyl-forming metals mentioned above, mixtures thereof are useful as well. For example, Cr, V, Mo and
The addition of 10% nickel to a cobalt mixture of 90% Sn to 10% Co produces similarly pronounced adhesion to substrates such as tungsten carbide in combination with the substrates described herein.

In addition, a light cutting diode (Light
Gallium phosphide used at high frequencies such as for cutting diodes is a tin, indium, lead alloy with carbide or carbonyl forming metals e.g. 90%
of Sn, 5% V and 5% Ni at 900° C. in a carbon monoxide atmosphere. A highly adhesive bond was formed. In a similar manner, vanadium is used in the same proportions as above to tin, etc.
Also, nickel, zirconium ortho-silicate itself or in mixtures with magnesium silicate and also with aluminum silicate are well coated with remarkable adhesion properties in carbon monoxide under the same conditions.

In addition, in the same way as above, various titanates such as barium titanate; silicates such as borosilicate glass, sodalime-silicate glass;
Nitrides such as silicon nitride, aluminum nitride, titanium nitride; oxides such as oxides of boron, silicon, iron, titanium, zinc, oxides of aluminum such as ruby; arsenides; silicides; tellurides, carbides such as tungsten carbide, Titanium carbide, boron carbide, steel such as stainless steel and the like are bonded with tin-containing carbides or carbonyl-forming metals.

According to the method, the composite has excellent mechanical and/or electrical and/or thermal conductive properties.
No new metals are required, no sputtering is required, and a very solid and strong bond is formed. Because the temperature can be adjusted on a variety of substrates, high temperature demands can be encountered in specially made cases, for example when bonding to stainless steel, where heretofore these temperature limits have not been achievable. can.

In general, the present invention relates to oxides, nitrides, arsenides, titanates, tellurides, silicides of metals or metalloids, including ceramic-type materials known as cermets, which consist of mixtures of ceramics and metals; It has been discovered that the present invention can be applied to the same effective substances including borides, phosphides and carbides. When these are in powder form, for example, when compressed isostatically into a very solid mass under very high pressure (in powder irons and when subjected to high isostatic pressures as in the well-known art) , has been found to be particularly useful as a substrate material.

These substrate materials are either compatible or incompatible but strong, distributed as powders in the form of fine dispersions of each other or other similar forms, and then very dense particles of remarkable nature. Can be evenly compressed into shape. They can thus be made into ceramics or cermets (ceramics, metal combinations) which are subsequently bonded to other metals, ceramics, cermets and the like by means of tin etc. and carbides or carbonyl-forming metals. can. When subsequently bonded with tin, lead, indium, or alloys thereof mixed with carbides or carbonyl-forming metals as described herein, these substrates have strong bonds with each other or with other metals and cermets and Used for the various purposes mentioned above.

Next, examples of the present invention will be shown, but the present invention is not limited thereto.

Example 1 For a substrate consisting of lanthanum boride ( _LaB6 ) 5% Cr-Sn, 5% Ni-5% V-Sn, 2.5%
Cr-2.5%V-Sn, 5%Cr-5%Ni-5%V-
Sn, 2.0%Cr-2.0%V-2%Ni-Sn, 2.5%Ni-
Using each mixture of 2.5% V-Sn and heating at 800 °C for 3 minutes under a 10-100 Vol% CO atmosphere,
An adhesive coating can be formed on the surface of the lanthanum boride. These mixtures do not degrade in wetting and are usefully used, for example, in electron microscopy.

Example 2 A substrate made of gallium arsenide, gallium phosphorus arsenide, and aluminum gallium phosphide, such as those used in a laser beam electric oscillator, contains 5% Cr-Sn and 5% Cr-Sn.
Cr-5%Ni-5%V-Sn, 5%V-Sn, 2.5%
A mixture of Cr-2.5% V-Sn, 5% Ni-5% V-Sn was used, and 10 to 100 vol% was used at 580°C for 10 minutes.
Heat under CO atmosphere.

Example 3 Piezoelectric material made of barium titanate and strontium titanate contains 5% Cr-Sn, 5% V-Sn, 2.5
%Cr-2.5%V-Sn, 2.5%Fe-2.5%Cr-Sn, 2.5
A mixture of %Ni-2.5%V-Sn was used at 800℃
Heat for 4-6 minutes at 1-10 vol% CO atmosphere.

5% for other substrates made of aluminum silicate, telluride, nitride and other ceramics.
Cr-Sn, 5%V-Sn, 2.5%Cr-2.5%V-Sn,
A mixture consisting of 2.5%Ni-2.5%V-Sn was used, and 10-100vol% of
Upon heating under a CO atmosphere, an adhesive coating can be formed on the substrate.

Similarly, 5%Ni-5%V-Sn or 5%Cr-
5%Ni-5%V-Sn is boron carbide, titanium carbide,
Tungsten carbide, aluminum nitride, titanium nitride, silicon nitride, oxides of iron, silicon, titanium, zinc and oxides of aluminum such as ruby, borosilicate such as indium phosphide, gallium phosphide, zirconium silicate, pyrex glass. Used when the substrate is soda-quartz-silicate glass such as salt glass and window glass, and 3%
Cr-3%V-Sn can be used when the substrate is glass.

Furthermore, the above-mentioned composite may be provided with an overlay made of Ni, Cu, or Mo.

Claims (1)

[Claims] 1 Titanates, silicates, arsenides, silicides, tellurides, phosphides, nitrides (excluding boron nitride), oxides (alumina, zirconia, A part or chromium, titanium, hafnium, zirconium, cobalt, iron, nickel, all forming their carbides or carbonyls;
An alloy coating layer consisting of manganese, rhenium, ruthenium, rhodium, osmium, iridium, vanadium, niobium, tantalum, tungsten, molybdenum or a mixture thereof and tin, lead, indium or their respective alloys as an adhesive coating, film or layer. complex with. 2 Cr, Ti, Hf, Zr, Co, Fe, Ni, some or all of which form carbide or carbonyl,
Mn, Re, Ru, Rh, Os, Ir, V, Nb, Ta, W,
The metal is composed of Mo or a mixture thereof and a tin group metal such as tin, lead, indium or their alloys, and the metal forms a carbide or carbonyl.
40%, with the remainder being a tin group metal, as a coating layer on the substrate. 3 2 to 15% of the above metal, some or all of which forms its carbide or carbonyl;
3. The composite according to claim 2, wherein the remainder is a tin group metal. 4. The composite according to claim 1, wherein the metal partially or wholly forming a carbide is chromium. 5. The composite according to claim 1, wherein the metal partially or wholly forming a carbide is vanadium. 6. The composite according to claim 1, wherein the metal partially or wholly forming a carbide is nickel mixed with vanadium. 7. The composite according to claim 1, wherein 5 to 15% of chromium is partially or wholly in the form of carbide, and the remainder is tin. 8. The composite according to claim 1, wherein molybdenum, partially or wholly forming carbide, accounts for 5 to 15%, and the remainder is tin. 9. The composite according to claim 1, wherein vanadium, partially or entirely forming a carbide, is mixed with indium. 10. The composite according to claim 1, wherein iron, partially or wholly forming a carbide or carbonyl, is mixed with tin in a ratio of 5:95. 11. The composite according to claim 1, wherein the tin alloy is a tin-lead alloy. 12. The composite according to claim 1, wherein the substrate structure is gallium arsenide, aluminum arsenide, aluminum gallium arsenide, gallium phosphide, aluminum gallium phosphide or gallium phosphorus arsenide. 13. The composite according to claim 1, wherein the boride substrate other than titanium diboride is lanthanum boride represented by LaB ₆ . 14. The composite according to claim 1, wherein the substrate is barium titanate, strontium titanate, zirconium orthosilicate, nickel orthosilicate, magnesium silicate, or aluminum silicate, or a mixture of these silicates. 15. The composite according to claim 1, wherein the nitride substrate other than boron nitride is silicon nitride. 16 The above alumina, zirconia, saphire,
2. The composite according to claim 1, wherein the oxide substrate other than quartz and beryllia is boron oxide. 17. The composite according to claim 1, wherein the carbide substrate other than silicon carbide is tungsten carbide. 18 Titanates, silicates, arsenides, silicides, tellurides, phosphides, nitrides (excluding boron nitride) of metals or metalloids or mixtures thereof;
On a substrate made of oxides (excluding alumina, zirconia, saphire, quartz, beryllia), borides (excluding titanium diboride), carbides (excluding silicon carbide), steel, mixtures thereof, or compression molded products thereof Cr, Ti, Hf, some or all of which form carbides or carbonyls,
Zr, Co, Fe, Ni, Mn, Re, Ru, Rh, Os, Ir,
V, Nb, Ta, W, Mo or a mixture thereof and tin;
A composite body comprising an alloy coating layer consisting of lead, indium or their respective alloys as an adhesive coating, film or layer, and further comprising an overlay thereon. 19. The composite of claim 18, wherein the overlay is a metal alloyable with the alloy coating layer on the substrate. 20. The composite according to claim 18, wherein the top layer is Cu, Ni, Mo or a composite material of these metals. 21. A composite according to claim 19, wherein the overlay is Cu on a Sn-Cr-arsenide composite. 22 Claim 1 in which the top lining is arsenic
The complex according to item 8. 23 Titanates, silicates, arsenides, silicides, tellurides, phosphides, nitrides (excluding boron nitride) of metals or metalloids or mixtures thereof;
Substrates made of oxides (excluding alumina, zirconia, saphire, quartz, and beryllia), borides (excluding titanium diboride), carbides (excluding silicon carbide), steel, mixtures thereof, or compression molded products thereof Cr, Ti, Hf, Zr, some or all of which form carbide or carbonyl,
Co, Fe, Ni, Mn, Re, Ru, Rh, Os, Ir, V,
Nb, Ta, W, Mo or a mixture thereof and tin, lead,
In a method for producing a composite having an adhesive coating, film or layer of an alloy coating layer consisting of indium or the respective alloy, granular tin;
mixing lead, indium or their respective alloys with finely divided carbide or carbonyl-forming metals to form a mixture in a vehicle suitable for forming dispersoids for dispersion on said substrate, carbon monoxide; reacting the mixture to and at the melting point of the mixture in the presence of an atmosphere of carbon monoxide or A method for producing a composite comprising cooling in the presence of a mixture of carbon and an inert gas or in an inert atmosphere of hydrogen or hydrogen and nitrogen. 24 350 mesh with colloidal particles (USA)
24. A method of producing a composite according to claim 23, wherein the composite is a mixture of particle sizes ranging from 1/8 inch (3.175 mm) to 1/8 inch (3.175 mm). 25. The method of claim 23, wherein the vehicle is a rosin oil, Freon composition or similar vehicle, and the dispersion is applied to the substrate by screen printing, painting, spraying or printing.