We present results on electrical resistance of metal contacts to ZnSb. We synthesized the thermoelectric semiconductor ZnSb with specific doping concentrations by adding Cu as an acceptor to the melt, followed by solidification, crushing, ball-milling, hot-pressing, sawing, and polishing yielding wafers suitable for substrates for further processing. Many batches were made yielding different doping concentrations. We defined transmission line geometries in deposited metal films for specific contact resistance measurements. We prepared sets of Cu, Ti, and Ni films, respectively. We measured the contact resistance vs annealing temperatures. For Cu/ZnSb samples, we observed a specific contact resistance from 5 × 10−7 to 4 × 10−5 Ω cm2. We also measured the carrier concentration of ZnSb. The measurement data of the specific contact resistance had systematic dependence on doping concentration and annealing temperature and were analyzed by a model incorporating different transport mechanisms across the energy barrier at the metal–semiconductor interface. The data were discussed in terms of systematic variation in barrier height and density of states effective mass. We proposed these arising as a consequence of interactions at the interface and a nonparabolic valence band. We have also monitored the interface of the ZnSb substrate and metal films with transmission electron microscopy.

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