Oxide-bondable solder

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Reexamination Certificate

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C228S101000, C228S903000, C420S501000, C420S507000, C420S513000, C420S555000, C420S557000, C420S563000, C420S576000, C420S577000, C420S580000, C420S589000, C420S505000, C420S511000, C420S524000, C420S558000, C420S559000, C420S562000, C420S566000, C420S570000, C420S571000, C420S572000, C420S574000, C428S450000, C428S432000, C428S433000, C428S434000, C427S123000

Reexamination Certificate

active

06319617

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to solder compositions, particularly solder compositions useful for bonding to oxides.
2. Discussion of the Related Art
Electronic solders such as Pb—Sn, Sn—Ag, Bi—Sn, and Au—Sn are widely used for bonding of components and circuits in electronic and optoelectronic devices. Numerous other solder compositions, as well as a variety of processing and assembly procedures, are also known. See, e.g., H. H. Manko,
Solders and Soldering
, McGraw-Hill Inc. (1992).
It is generally accepted that the nonmetallic surfaces of oxide materials prohibit direct wetting of conventional solder materials, and therefore require an intermediate bonding layer, also known as a metallization layer, to allow soldering to occur. typically, a thin metallic film layer is deposited onto the oxide surface, and any solder bonding is carried out on that metallic film. For example, soldering on silica optical fiber is able to be accomplished by forming a nickel-containing intermediate layer, e.g., by electroless plating, on the silica surface. (See, e.g., R. W. Filas, “Metallization of Silica Optical Fibers”,
MRS Symposium Proc
., Vol. 531, 263 (1998)). Soldering on ceramic substrates, such as Al
2
O
3
, in hybrid circuits is conventionally accomplished by first metallizing the oxide surface using either a thick-film technique relying on firing of a metal-glass mixture frit at elevated temperatures or a thin film technique relying on sputtering or evaporation of a metal layer. The use of such an intermediary metallization layer, however, is not always desirable due to the added complexity and cost, as well as concerns over bond reliability since there is often no strong chemical bond at the oxide-metal interface.
One approach to these metal-oxide bonding problems has been to incorporate reactive elements, such as rare earth elements, into the solder. The rare earth elements improve the bond by inducing chemical reactions at the interface between the metal and the oxide. See, e.g., U.S. Pat. No. 3,949,118. Unfortunately, the matrix materials of these solders—Sn and Pb—lack solid solubility for the rare earths. And this lack of solubility makes the solders susceptible to significant loss of bonding ability, due to the tendency of the rare earths and the matrix solder to form intermetallics. These intermetallics make the rare earths less available to aid in the bonding process due to the time required to re-dissolve the intermetallic particles into the molten solder, particularly where the intermetallic particles are coarse. This intermetallic formation occurs both during the manufacture of the solders—when the melt is cooled to room temperature, and also later—due to time-dependent reactions of the reactive elements during storage. Also, due to the presence of easily-oxidizable rare earths, oxidation of the molten solder surface during soldering and of the solder joint surface after soldering tends to reduce the reliability of the solder bond. For example, during the process of intermetallic re-dissolution in molten solder, the oxidation of the rare earth tends to produce oxide skin on the solder surface.
Thus, improved solder materials capable of providing reliable bonds to oxides, yet which avoid problems of previous solders, are desired.
SUMMARY OF THE INVENTION
The invention relates to use of solders containing rare earth metals. While the use of rare earths has previously been contemplated in solder, as mentioned above, problems related to rare earth's easy oxidation and the near-zero solubility in conventional solder metals have not been solved. The invention overcomes these problems by providing a solder material having microstructure that contains a solder matrix in which is distributed fine, micron-scale islands of rare-earth-containing intermetailic particles, i.e., islands having an effective diameter less than 60 &mgr;m, advantageously less than 20 &mgr;m. (Effective diameter indicates the diameter of a sphere having the same volume as a non-spherical island.) It is possible for a matrix to consist of one or more phases.
Advantageously, the solder contains Au and/or Ag, in which the rare earth elements tend to have some solid solubility. Due to this solubility, the Au and/or Ag tend to provide some protection of the rare earths against oxidation, and to accelerate dissolution of the rare earth into the molten solder. The solders of the invention contain typical solder metals, e.g. Sn, Pb, Sb, In, Bi, about 0.02 to about 20 wt. % rare earth metals, and optionally some gold and/or silver. To attain the micron-scale islands containing the rare earths, the solders are generally prepared by rapid solidification from the molten state, to induce formation of relatively small islands and avoid substantial coarsening of the islands.
The resultant solder provides excellent bonding to oxide materials such as glass optical fibers.


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Manko, H.H.Solders and Soldering, McGraw-Hill Inc. (Dec. 1992).
Filas, R.W., “Metallization of Silica Optical Fibers”,MRS Symposium Proc., vol. 531, (Dec. 1998).
Mavoori, H. et al., “Enhanced Thermal and Magnetic Actuation for Broad-Range Tuning of FBG-Based Reconfigurable Add/Drop Devices”,Optics Lett., vol. 24, No. 11, 714 (Jun. 1999).

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