A semimetal nanowire rectifier: balancing quantum confinement and surface electronegativity

TL;DR

This paper explores how quantum confinement and surface electronegativity influence the electronic properties of semimetal nanowires, enabling the creation of junctions within a single material without doping or heterojunctions.

Contribution

It demonstrates that surface chemistry can counteract quantum confinement effects, allowing for the design of semimetal-semiconductor junctions in nanowires without doping.

Findings

Quantum confinement induces a band gap in nanowires below 10 nm.

Surface electronegativity shifts energy levels comparable to quantum confinement.

Abrupt surface changes create internal semimetal-semiconductor junctions.

Abstract

For semimetal nanowires with diameters smaller than a few tens of nanometers, a semimetal-to-semiconductor transition is observed as the emergence of an energy band gap resulting from quantum confinement. Quantum confinement in a semimetal results in either lifting of the degeneracy of the conduction and valence bands in a zero gap semimetal, or shifting of bands with a negative energy overlap to form conduction and valence bands. For semimetal nanowires with diameters below 10 nanometer, the magnitude of the band gap can become significantly larger than the thermal energy at room temperature resulting in a new class of semiconductors relevant for nanoelectronics with critical dimensions on the order of a few atomic lengths. The smaller a nanowire's diameter, the larger its surface-to-volume ratio thus leading to an increasing impact of surface chemistry on its electronic structure. Energy level shifts to states in the vicinity of the Fermi level due to the electronegativity of surface terminating species are shown to be comparable in magnitude to quantum confinement effects at nanowire diameters of a few nanometer; these two effects can be used to counteract one another leading to semimetallic behavior for nanowire cross sections at which the quantum confinement effect would otherwise dominate. Abruptly changing the surface terminating species along the length of a nanowire leads to an abrupt change in the surface electronegativity. This can result in the formation of a semimetal-semiconductor junction within a monomaterial nanowire, without the need for impurity doping nor requiring the formation of a heterojunction.