Plasmon Spectroscopy and Chemical Structure of Small Bimetallic Cu_{(1–<i>x</i>)}Ag_<i>x</i> Clusters

The optical properties of small Cu–Ag bimetallic clusters have been experimentally and theoretically investigated in relation to their chemical structure analyzed by high resolution transmission electron microscopy (HRTEM). Cu _{(1–<i>x</i>)}Ag_<i>x</i> clusters of about 5 nm in diameter are produced in a laser vaporization source with a well-defined stoichiometry (<i>x</i> = 0, 25, 50, 75, and 100%) and dispersed in an alumina matrix. Absorption spectra are dominated by a broad and strong surface plasmon resonance whose shape and location are dependent on both cluster composition and sample aging. Detailed modeling and systematic calculations of the optical response of pure and oxidized mixed clusters of various chemical structures have been carried out in the framework of classical and semiquantal formalisms. Optical and HRTEM measurements combined with theoretical predictions lead to the conclusion that these bimetallic clusters are not alloyed at the atomic scale but rather present a segregation of chemical phases. Most likely, they adopt a Cu@Ag core–shell configuration. Moreover, the nanoparticle oxidation process is consistent with the formation of a copper oxide layer by dragging out inner copper atoms to the cluster surface

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

Material Perspective on HgTe Nanocrystal-Based Short-Wave Infrared Focal Plane Arrays

After the use of nanocrystals as light downconverters, infrared sensing appears to be one of the first market applications where they can be used while being both electrically and optically active. Over recent years, tremendous progress has been achieved, leading to an apparent rise in the technological-readiness level (TRL). So far, the efforts have been focused on PbS nanocrystals for operation in the near-infrared. Here, we focus on HgTe since its narrower band gap offers more flexibility to explore the extended short-wave and midwave infrared. We report a photoconductive strategy for the design of short-wave infrared focal plane arrays with enhanced image quality. An important aspect often swept under the rug at an early stage is the material stability. It appears that HgTe remains mostly unaffected by oxidation under air operation. The evaporation of Hg, a potentially dramatic aging process, only occurs at temperatures far beyond the focal plane array’s standard working temperature. The main bottleneck appears to be the particle sintering resulting from joule heating of focal plane arrays. This suggests that a cooling system is required, whose first role is to prevent the material from sintering even before targeting dark current reduction