HgSe Self-Doped Nanocrystals as a Platform to Investigate the Effects of Vanishing Confinement

Self-doped colloidal quantum dots (CQDs) attract a strong interest for the design of a new generation of low-cost infrared (IR) optoelectronic devices because of their tunable intraband absorption feature in the mid-IR region. However, very little remains known about their electronic structure which combines confinement and an inverted band structure, complicating the design of optimized devices. We use a combination of IR spectroscopy and photoemission to determine the absolute energy levels of HgSe CQDs with various sizes and surface chemistries. We demonstrate that the filling of the CQD states ranges from 2 electrons per CQD at small sizes (<5 nm) to more than 18 electrons per CQD at large sizes (≈20 nm). HgSe CQDs are also an interesting platform to observe vanishing confinement in colloidal nanoparticles. We present lines of evidence for a semiconductor-to-metal transition at the CQD level, through temperature-dependent absorption and transport measurements. In contrast with bulk systems, the transition is the result of the vanishing confinement rather than the increase of the doping level.