Coupled HgSe Colloidal Quantum Wells through a Tunable Barrier: A Strategy To Uncouple Optical and Transport Band Gap

Among semiconductor nanocrystals (NCs), 2D nanoplatelets (NPLs) are a special class of nanomaterials with well controlled optical features. So far, most of the efforts have been focused on wide band gap materials such as cadmium chalcogenide semiconductors. However, optical absorption can be pushed toward the infrared (IR) range using narrow band gap materials such as mercury chalcogenides. Here we demonstrate the feasibility of a core/shell structure made of a CdSe core with two HgSe external wells. We demonstrate that the optical spectrum of the heterostructure is set by the HgSe wells and this, despite the quasi type II band alignment, makes the band edge energy independent of the inner core thickness. On the other hand, these core/shell NPLs behave, from a transport point of view, as a wide band gap material. We demonstrate that the introduction of a wide band gap CdSe core makes the material less conductive and with a larger photoresponse. Hence, the heterostructure presents an effective electric band gap wider than the optical band gap. This strategy will be of utmost interest to design infrared effective colloidal materials for which the reduction of the carrier density and the associated dark current is a critical property

Intraband Mid-Infrared Transitions in Ag₂Se Nanocrystals: Potential and Limitations for Hg-Free Low-Cost Photodetection

Infrared photodetection based on colloidal nanoparticles is a promising path toward low-cost devices. However, mid-infrared absorption relies on interband transitions in heavy metal-based materials, which is a major flaw for the development toward mass market. In the quest of mercury-free infrared active colloidal materials, we here investigate Ag₂Se nanoparticles presenting intraband transition between 3 and 15 μm. With photoemission and infrared spectroscopy, we are able to propose an electronic spectrum of the material in the absolute energy scale. We also investigate the origin of doping and demonstrate that it results from a cation excess under the Ag⁺ form. We demonstrate photoconduction into this material under resonant excitation of the intraband transition. However, performances are currently quite weak with (i) a slow photoresponse (several seconds) and (ii) some electrochemical instabilities at room temperature