Part II - Papers - Diffusion and Electrotransport of Solutes in Molten Germanium-Implications for Producing p-n Junctions

The diffusion coefficients and electrotralzsport mobilities of aluminum, gallium, and arsenic have been determined in molten germanium with the capillary reservoir technique. The diffusion coefficients are slightly higher than those determined by the solidification technique of Brirton et a1.1 It was found that aluminium and gallium migrate to the cathode in molten germanium) whereas arsenic migrates to the anode under an electric field. A possible technique for producing p-n junctions by means of electric field freezing is discussed in view of the experimental data. In the past decade or so the literature has abounded with articles concerning the solid-state properties of the semiconducting elements germanium and silicon. It is surprising by comparison how little has been published concerning the liquid-state properties of these materials. In the production of doped germanium or silicon the diffusion coefficient of the dopant in liquid germanium or silicon is an important quantity. Yet, to the best of our knowledge, no one has ever made a direct measurement of the diffusion coefficient of solutes in either molten germanium or silicon. A number of authors'-4 have determined some diffusion coefficients by the indirect technique developed by Burton et al.1 This technique appears to give numbers of the correct order of magnitude but it does depend upon a number of assumptions in the analysis and also requires prior knowledge of the viscosity of the melt. In the present work a more direct measure of the diffusion coefficients of arsenic, gallium: and aluminum in molten germanium has been made. It has been shown independently by two groups of authors5, 6 that, when an electric current is passed through the interface of a solidifying metal containing an impurity, the resulting electrotransport in the liquid boundary layer at the interface offers a mechanism for control over the redistribution of the impurity accompanying the solidification. These authors show that the degree of control is proportional to the mobility, U of the impurity atoms in the liquid boundary layer, where the mobility is defined as the drift velocity relative to the solvent per unit electric field. In principle the results apply to the solidification of a doped semiconductor and offer an interesting technique for control of the doping of a semiconductor. In the present work the mobilities of aluminum, gallium, and arsenic were determined in molten germanium in order to evaluate the potential usefulness of electro-transport as a technique for solute control when applied to the solidification of doped germanium. EXPERIMENTAL PROCEDURE Both the diffusion coefficients and the mobilities were measured using high-purity alumina capillaries and a resistivity technique for analysis. A schematic diagram of the electrotransport apparatus is shown in Fig. 1 and the details of the cell design are shown in Fig. 2. For the mobility experiments electrical contact with the bottom of the capillary was made with graphite, as shown in Fig. 2. In order to prevent electrical contact with the melt the graphite was coated with a thin layer of alumina using a plasma spray torch. The cell assembly, a graphite electrode, and another assembly containing two blank capillaries were fastened to the lavite disk shown in Fig. 1. To make a run the system was evacuated and the doped germanium was outgassed at the operating temperature of 1030°C. The cell and blank capillaries were then submerged beneath the melt and a slightly positive pressure of helium was introduced to fill them. After passing current through the cell for a given time the cell and blank capillaries were raised from the melt and the furnace was shut off. The temperature of the cells dropped below the freezing point of germanium within 1 to 2 min after the furnace was shut off.