Cyclotron Splittings in the Plasmon Resonances of Electronically Doped Semiconductor Nanocrystals Probed by Magnetic Circular Dichroism Spectroscopy

Abstract

A fundamental understanding of the rich electronic structures of electronically doped semiconductor nanocrystals is vital for assessing the utility of these materials for future applications from solar cells to redox catalysis. Here, we examine the use of magnetic circular dichroism (MCD) spectroscopy to probe the infrared localized surface plasmon resonances of p-Cu2-xSe, n-ZnO, and tin-doped In2O3 (n-ITO) nanocrystals. We demonstrate that the MCD spectra of these nanocrystals can be analyzed by invoking classical cyclotron motions of their excess charge carriers, with experimental MCD signs conveying the carrier types (n or p) and experimental MCD intensities conveying the cyclotron splitting magnitudes. The experimental cyclotron splittings can then be used to quantify carrier effective masses (m∗), with results that agree with bulk in most cases. MCD spectroscopy thus offers a unique measure of m∗ in free-standing colloidal semiconductor nanocrystals, raising new opportunities to investigate the influence of various other synthetic or environmental parameters on this fundamentally important electronic property.