The present invention generally relates to nanoscale heterostructures and, in some cases, to nanowire heterostructures exhibiting ballistic transport, and/or to metal-semiconductor junctions that that exhibit no or reduced Schottky barriers. One aspect of the invention provides a solid nanowire having a core and a shell, both of which are essentially undoped. For example, in one embodiment, the core may consist essentially of undoped germanium and the shell may consist essentially of undoped silicon. Carriers are injected into the nanowire, which can be ballistically transported through the nanowire. In other embodiments, however, the invention is not limited to solid nanowires, and other configurations, involving other nanoscale wires, are also contemplated within the scope of the present invention. Yet another aspect of the invention provides a junction between a metal and a nanoscale wire that exhibit no or reduced Schottky barriers. As a non-limiting example, a nanoscale wire having a core and a shell may be in physical contact with a metal electrode, such that the Schottky barrier to the core is reduced or eliminated. Still other aspects of the invention are directed to electronic devices exhibiting such properties, and techniques for methods of making or using such devices.