Patent Application
20070256783
A detailed description of the principal components of the adhesive pastes of the present invention are described in U.S. Pat. Nos. 6,111,005 and 6,265,471. The key difference is the substitution of spherical shaped silver powders for the silver flakes in the adhesive composition, preferably in the presence of a sintering aid. The spherical powders produced a highly sintered, more dense structure than the same paste with silver flakes. This produces an unexpected decrease in the bulk electrical resistivity and an increase in thermal conductivity. Furthermore, the adhesion was increased which allowed for a decrease in the resin content (higher silver-to-resin ratio) which further increases the thermal conductivity.
The inorganic filler used in the adhesive pastes of the present invention is present in particulate form. At least about 80% of the filler particles, and preferably substantially all of the filler particles, are characterized by round edges, and substantially free from flat surfaces. Substantially spherical particles are especially preferred. It is also preferred that the inorganic filler be substantially free from surfactant. Representative of filler particles which can be use in the present invention are those available from Metalor Technologies USA of Attlebro, Mass. K82P and P318-8.
The inorganic filler is preferably used in combination with at least one sintering aid, that is, any additive that enhances the sintering of the filler. Representative sintering aids include metal resinates and silver oxides. The sintering aid is generally present in a concentration of about from 0.1 to 0.5 weight percent of the cured materials.
The unexpected increase in electrical and thermal properties is not fully understood, but is believed to be due to the better packing and point contacts of the spheres as compared to the geometry of the flakes previously used in plastics of this type. Also believed to be significant is the absence of a surfactant or lubricant present in the flaking process, which leaves a residue on the surface of the flake. This organic layer tends to thermally isolate one flake from another.
In the powder resin technology previously described, when the assembly is heated, the resin powder melts and coalesces with other particles and migrates toward the bondline interfaces. This melting of the powders leaves a void in the bondline, hereafter referred to “bond drop out” (BDO). This distribution of BDO voiding or porosity is considered a key property of the bondline and controls the shear stresses created by the mismatch in expansion of the two components being bonded. The size and amount of these pores is a direct function of the amount of resin an the size distribution of the polymer powders. Without the pores, the present invention provides a highly sintered silver filler which by itself is high in modulus of elasticity. The distribution of pores from the powdered resin melting reduces the modulus of elasticity of the cured bondline. Resin leaving creates pores. The final porosity is accordingly a function of the initial volume of the powdered resin.
The sphere has the smallest surface area among all surfaces enclosing a given volume, and it encloses the largest volume among all closed surfaces with a given surface area. Thus, the number of contacts between spheres would be lower in number than a flake for a given volume of filler. Since the primary path of thermal conductivity is through the bulk of the filler, for the highest flow of heat, the number of particle contacts per unit volume of filler should be kept to a minimum. The packing density of the filler is the other key factor in determining the heat flow. This packing density can be enhanced by the particle size distribution of the spheres as illustrated in the examples to follow.
The present adhesive pastes preferably further comprise up to about 3.0 weight % reducing agent. A wide variety of reducing agents can be used, including organic, inorganic, organometallic, or salt compounds. Representative of reducing agents which can be used are hydrazine, phenylhydrazine, N,N-diethylhydroxylamine, hydroxylamine phosphate (HAP), hydroxylamine sulfate (HAS), ammonium hydrogen sulfate, ammonium hydrogen phosphate (AUP), ammonium dihydrogen phosphate, ammonium nitrate, and ammonium sulfate.
Other sphere-like shapes can also be use in the present invention. In mathematics, a spheroid is a quadratic surface in three dimensions obtained by rotating an ellipse about one of its principal axes. Thus, a sphere is a special case of the spheroid in which the generating ellipse is a circle.
To illustrate the invention, combinations of filler, resin and fugitive liquid were combined in a paste. The preparation of the adhesive from its principal components, and its methods of application and use, take advantage of the various methods and employ equipment well known in the art. The principal components can be mixed in equipment known in the art for paste preparation. Details of this process are described in the prior art cited and referenced above.
The die attach adhesives of the present invention are typically used for attaching microcircuit electronic components to a substrate. In general, this comprises making an adhesive paste of the present invention; followed by applying the paste to a surface of a substrate to form a bond line and placing the electronic component on the bond line so that the paste is between the electronic component and the substrate; followed by heating the assembly to a sufficiently high temperature for a sufficient time that the organic thermoplastic resin softens and becomes fluid, but does not degrade, and the liquid devolatilizes from the paste; followed by cooling the heat-treated assembly to a temperature below which the thermoplastic polymer becomes solid, whereby the microcircuit electronic component is bonded to the substrate by a void-free bond line. When thermoset resin is used, rather than as a particle, as part or all of the organic polymer, the processing temperature should be sufficiently high to crosslink the resin.
For purposes of demonstrating the invention, the pastes are doctor bladed on a glass side, as well as deposited on a ceramic substrate before the die is placed on the wet adhesive. All curing was done at 200° C. peak for 30 minutes. After curing, a force perpendicular to the side of the die was applied until the die was sheared off the substrate. This force was recorded in psi as the adhesion value for the particular composition being test. The strips of adhesive on the glass slides were measured for resistance and recorded as a bulk resistivity in micro ohm-cm. This resisitivity value has a strong relationship to the thermal conductivity since the mechanism for thermal transport is by electrons, the same mechanism as in electrical conductivity. Because of the relationship between electrical resistance and thermal conductivity, the resisitivity value served as an indicator of which compositions would be further tested for thermal conductivity. The thermal conductivity measurements were done by the known laser flash method.
As used herein, the expression “consists essentially of” means that the composition may include additional components other than the principal, named components, provided that the additional components are not present in an amount sufficient to detract from the operability of the present invention.
The present invention is now illustrated by examples of certain representative embodiments thereof, where all parts, proportions, and percentages are by weight unless otherwise indicated. The examples are intended to be illustrative only, and modifications and equivalents of the invention will be evident to those skilled in the art.
In the Examples in Table 1 below, pastes were prepared by the procedure described above, and illustrate the impact of filler morphology on resistivity.
Examples in Table 2 below illustrate the impact of metal resinate on resistivity and thermal conductivity of the adhesive paste.
Examples in Table 3 below illustrate the impact of filler loading on resistivity.
Examples in Table 4 below illustrate the impact of filler morphology in powdered resin system on resistivity and thermal conductivity. Example 14 represents the most preferred embodiment of the present invention.
Examples in Table 5 below illustrate the impact of filler morphology in epoxy resin system on resistivity and thermal conductivity.
Examples in Table 6 below illustrate the impact of filler morphology in another epoxy resin system on resistivity and thermal conductivity.
As the examples illustrate, the inclusion of a sphere shaped particles of Ag, in the presence of a Ag resinate as a sintering aid, yielded significantly lower electrical resistance and higher thermal conductivity, although the relationship was not always linear.
This application is based on Provisional Application 60/799,068, filed on May 8, 2006.
| Number | Date | Country | |
|---|---|---|---|
| 60799068 | May 2006 | US |
