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Kinetics of Reactive Wetting

Scripta Materialia

Yost, Frederick G.

The importance of interfacial processes in materials joining has a long history. A significant amount of work has suggested that processes collateral to wetting can affect the extent of wetting and moderate or retard wetting rate. Even very small additions of a constituent, known to react with the substrate, cause pronounced improvement in wetting and are exploited in braze alloys, especially those used for joining to ceramics. The wide diversity of processes, such as diffusion, chemical reaction, and fluxing, and their possible combinations suggest that various rate laws should be expected for wetting kinetics depending on the controlling processes. These rate laws are expected to differ crucially from the standard fluid controlled wetting models found in the literature. Voitovitch et al. and Mortensen et al. have shown data that suggests diffusion control for some systems and reaction control for others. They also presented a model of wetting kinetics controlled by the diffusion of a constituent contained by the wetting fluid. In the following a model will be constructed for the wetting kinetics of a small droplet of metal containing a constituent that diffuses to the wetting line and chemically reacts with a flat, smooth substrate. The model is similar to that of Voitovitch et al. and Mortensen et al. but incorporates chemical reaction kinetics such that the result contains both diffusion and reaction kinetics. The model is constructed in the circular cylinder coordinate system, satisfies the diffusion equation under conditions of slow flow, and considers diffusion and reaction at the wetting line to be processes in series. This is done by solving the diffusion equation with proper initial and boundary conditions, computing the diffusive flux at the wetting line and equating this to both the convective flux and reaction flux. This procedure is similar to equating the current flowing in components of a series circuit. The wetting rate will be computed versus time for a variety of diffusion and reaction conditions. A transition is observed from nonlinear (diffusive) to linear (reactive) behavior as the control parameters (such as the diffusion coefficient) are modified. This is in agreement with experimental observations. The adequacy of the slow flow condition, used in this type of analysis, is discussed and an amended procedure is suggested.

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Stress Voiding During Wafer Processing

Yost, Frederick G.

Wafer processing involves several heating cycles to temperatures as high as 400 C. These thermal excursions are known to cause growth of voids that limit reliability of parts cut from the wafer. A model for void growth is constructed that can simulate the effect of these thermal cycles on void growth. The model is solved for typical process steps and the kinetics and extent of void growth are determined for each. It is shown that grain size, void spacing, and conductor line width are very important in determining void and stress behavior. For small grain sizes, stress relaxation can be rapid and can lead to void shrinkage during subsequent heating cycles. The effect of rapid quenching from process temperatures is to suppress void growth but induce large remnant stress in the conductor line. This stress can provide the driving force for void growth during storage even at room temperature. For isothermal processes the model can be solved analytically and estimates of terminal void size a nd lifetime are obtained.

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Model determination and validation for reactive wetting processes

Yost, Frederick G.

It is shown that dissolutive wetting initially yields a metastable equilibrium. A compact model for the kinetics of approach to this metastable state is described. The technique for constructing these kinetics stems from the early work of Onsager and begins with a relationship for the entropy production. From this, a coupled set of nonlinear, ordinary differential equations can be written directly. The equations are solved numerically for the wetted area and compared with experimental data. The model captures many of the subtle complexities of dissolutive wetting such as multiple metastable states. Sessile drop experiments involving a variety of Bi-Sn alloys on solid Bi substrates were performed. Substrates prepared from small and large-grained polycrystals and single crystals were used to measure equilibrium and metastable contact angles and estimate the surface tension and equilibrium contact angle of the solid-liquid interface. The substrates were also used to investigate the coupling of the dissolution and wetting processes and to investigate the effect of substrate grain size on wetting. It was determined that the equilibrium wetting geometry is independent of linear scale and that grain size has little influence on wetting or dissolution in the Bi-Sn system. To investigate the atomic behavior of liquids at interfaces during wetting, the authors simulated wetting in the Ag-Cu system using molecular dynamics with atomic potentials and observed both atomic dynamics and structural correlations of the liquid-solid interface. The authors found that spreading is prompted by interactions between the liquid and the substrate surface that cause the liquid layer in contact with the substrate to take on some of the symmetry of the substrate surface and result in the formation of a liquid monolayer that extends beyond the major part of the liquid droplet.

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The relevancy of current environmental issues to solder joints in microelectronic applications

Yost, Frederick G.

The technical issues brought about by recent federal mandates are reviewed and discussed. Progress made in the elimination of CFCs is briefly reviewed. The problems, implications, and status of pending anti-lead legislation and taxation are discussed at length. Recommendations are made for the enactment of rational, fair, and orderly legislation and taxation.

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Fundamentals of wetting and spreading with emphasis on soldering

Yost, Frederick G.

Soldering is often referred to as a mature technology whose fundamentals were established long ago. Yet a multitude of soldering problems persist, not the least of which are related to the wetting and spreading of solder. The Buff-Goodrich approach to thermodynamics of capillarity is utilized in a review of basic wetting principles. These thermodynamics allow a very compact formulation of capillary phenomena which is used to calculate various meniscus shapes and wetting forces. These shapes and forces lend themselves to experimental techniques, such as the sessile drop and the Wilhelmy plate, for measuring useful surface and interfacial energies. The familiar equations of Young, Wilhelmy, and Neumann are all derived with this approach. The force-energy duality of surface energy is discussed and the force method is developed and used to derive the Herring relations for anisotropic surfaces. The importance of contact angle hysteresis which results from surface roughness and chemical inhomogeneity is presented and Young's equation is modified to reflect these ever present effects. Finally, an analysis of wetting with simultaneous metallurigical reaction is given and used to discuss solder wetting phenomena. 60 refs., 13 figs.

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7 Results
7 Results