Ligand Tuning of Localized Surface Plasmon Resonances in Antimony-Doped Tin Oxide Nanocrystals.

Aliovalent-doped metal oxide nanocrystals exhibiting localized surface plasmons (LSPRs) are applied in systems that require reflection/scattering/absorption in infrared and optical transparency in visible. Indium tin oxide (ITO) is currently leading the field, but indium resources are known to be very restricted. Antimony-doped tin oxide (ATO) is a cheap candidate to substitute the ITO, but it exhibits less advantageous electronic properties and limited control of the LSPRs. To date, LSPR tuning in ATO NCs has been achieved electrochemically and by aliovalent doping, with a significant decrease in doping efficiency with an increasing doping level. Here, we synthesize plasmonic ATO nanocrystals (NCs) via a solvothermal route and demonstrate ligand exchange to tune the LSPR energies. Attachment of ligands acting as Lewis acids and bases results in LSPR peak shifts with a doping efficiency overcoming those by aliovalent doping. Thus, this strategy is of potential interest for plasmon implementations, which are of potential interest for infrared upconversion, smart glazing, heat absorbers, or thermal barriers.

Tuning the localized surface plasmon resonance in Cu(2-x)Se nanocrystals by postsynthetic ligand exchange.

Nanoparticles exhibiting localized surface plasmon resonances (LSPR) are valuable tools traditionally used in a wide field of applications including sensing, imaging, biodiagnostics and medical therapy. Plasmonics in semiconductor nanocrystals is of special interest because of the tunability of the carrier densities in semiconductors, and the possibility to couple the plasmonic resonances to quantum confined excitonic transitions. Here, colloidal Cu2-xSe nanocrystals were synthesized, whose composition was shown by Rutherford backscattering analysis and electron dispersive X-ray spectroscopy, to exhibit Cu deficiency. The latter results in p-type doping causing LSPRs, in the present case around a wavelength of 1100 nm, closely matching the indirect band gap of Cu2-xSe. By partial exchange of the organic ligands to specific electron trapping or donating species the LSPR is fine-tuned to exhibit blue or red shifts, in total up to 200 nm. This tuning not only provides a convenient tool for post synthetic adjustments of LSPRs to specific target wavelength but the sensitive dependence of the resonance wavelength on surface charges makes these nanocrystals also interesting for sensing applications, to detect analytes dressed by functional groups.

The chemical exfoliation phenomena in layered GaSe-polyaniline composite.

To elucidate the nature of polyaniline (PANI)-GaSe mutual interaction, we carried out structural studies of nano-GaSe powders encapsulated by PANI, exploiting X-ray diffraction and high resolution transmission electron microscopy (HRTEM). Mechanically and ultrasonically dispersed GaSe crystals were mixed with aniline, which then underwent polymerization. After such treatment, GaSe nanocrystals (as shown by HRTEM) consist of few elementary monolayer sandwiches of hexagonal GaSe structure along the crystallographic axis c with a mean diameter of 9.2 nm. There was a significant expansion of interplanar distances (up to 0.833 nm) for all of the nanocrystals observed compared to 0.796 nm for the single crystals.