Commentary

Phase Diagrams

Phase Diagrams of Important Electronic Materials

C.R. Kao

A phase diagram is the most concise representation of the phase equilibria present in a system. Phase diagrams are indispensable in understanding phase transformations, solidification, interfacial reactions, and the accompanying changes in microstructure. Knowledge of the phase equilibria of a material system is, therefore, critical for the improvement of existing materials and the development of new materials. More significantly, with the rapid development of thermodynamic modeling of phase diagrams, information that can be obtained from phase diagrams is no longer limited to the phase stability of a single phase or the chemical (interfacial) stability between multiple phases. The driving forces for phase transformations, chemical reactions, and diffusion processes can now be estimated quantitatively once the proper thermodynamic modeling of a materials system has been performed. The knowledge of the driving forces can then be used to rationalize observed phenomena, or even to serve as inputs of kinetic models for quantitative predictions. With appropriate thermodynamic modeling, even the metastable phase equilibria and the driving forces involving metastable phase(s) can be accurately calculated. Thermodynamic modeling of phase diagrams is also quite helpful in simplifying the time-consuming experimental determination of phase diagrams. Moreover, thermodynamic modeling combined with kinetic modeling, such as solidification modeling and diffusion modeling, can significantly cut down the development time of new products. The electronics industry faces accelerating demands for products with higher functionality and greater portability at lower prices. At the same time, environmental regulations
44

demand the elimination of certain toxic elements, such as lead, from electronic products. Central to these issues is the development of new and better material systems in a minimum amount of time. Phases diagrams, thermodynamic modeling, and appropriate kinetic modeling combined together can serve as a powerful tool to achieve this goal. The following articles address issues related to the thermodynamic modeling of phase diagrams for electronic materials, the combined use of the thermodynamic and kinetic modeling, and the applications of phase diagrams in developing electronic materials. The first article, by U.R. Kattner, discusses thermodynamic modeling for the development of an important class of electronic materials, lead-free solder alloys. Phase diagrams and thermodynamic modeling are especially useful for the development of lead-free solder alloys and their matching metallizations because, in these systems, very good agreement between modeling and experimental observation can be achieved. This is because for most of the solder alloys, which usually melt below 230C, even room temperature is at relatively high homologous temperatures, and local thermodynamic equilibrium can be established rather easily. In this article, the CALPHAD (CALculation of PHAse Diagram) approach is introduced first. All the important binary systems related to soldering are reviewed. Important ternary and higher-order systems are also covered. This paper clearly shows that the electronic solders and related materials as a whole combine to form one of the best-characterized materials systems in terms of the thermodynamic description, and offer a great potential to demonstrate the usefulness of phase diagrams and thermodynamic modeling.

The second article, by J.K. Kivilahti, presents an excellent discussion on the applications of combined thermodynamic and diffusion kinetic modeling to the development of new electronic materials, including lead-free solders, their matching metallizations, and the appropriate diffusion barrier layers. In this article, the theoretical background is discussed first. An important new concept of local nominal composition is introduced. The local nominal-composition concept combined with a diffusion-couple experiment is shown to be very useful for studying compatibility issues in electronic packages. Examples, including the effect of a zinc addition on reactions and stabilities of diffusion barrier layers between copper and silicon, are given. The third article, by T. Studnitzky and R. Schmid-Fetzer, describes the advantages of combining studies on phase equilibration in powder samples with bulk and thin-film diffusion couples for systematic investigation of new materials for high-temperature bonding. In contrast to low-temperature bonding processes such as soldering, there are relatively few studies on materials for high-temperature bonding. This is rather surprising considering the importance of high-temperature bonding processes for the manufacturing of electronic devices. The article is a timely and important contribution to this field, and is an excellent example of applying phase equilibrium study to the development of electronic materials.

C.R. Kao is a professor with the Department of Chemical & Materials Engineering at National Central University in Chungli City, Taiwan and is the advisor to JOM from the Alloy Phases Committee of the TMS Electronic, Magnetic & Photonic Materials and the Structural Materials Divisions.

JOM December 2002