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Chemical Interface Damping in Nonstoichiometric Semiconductor Plasmonic Nanocrystals: An Effect of the Surrounding Environment.

Nandan GhoraiHirendra N Ghosh
Published in: Langmuir : the ACS journal of surfaces and colloids (2022)
Semiconductor plasmonic nanocrystals (NCs) have been utilized for an enormous number of plasmon-enhanced spectroscopic and energy conversion applications. Plasmonic NCs are extremely high light absorbers, and optical properties can be easily manipulated across the UV-vis-NIR spectrum region by changing mere chemical compositions and the surrounding environment of the NCs. This feature article focuses on reassessing plasmon dynamics by changing the interface composition between NCs and the surrounding medium to ascertain the damping contribution from chemical interface damping (CID). Also, this feature article deciphers a fundamental understanding of hot-carrier relaxation and extraction from plasmonic materials. On the route to determining the different relaxation dynamics of nonstoichiometric Cu 2- x S/Se NCs, we have employed a transient ultrafast pump-probe broadband spectrometer. First, we have described the ultrafast plasmon relaxation dynamics of nonstoichiometric Cu 2- x S NCs by varying the copper to sulfur ratio, and then we carefully compare how two surface ligands (oleylamine and 3-mercaptopropionic acid) lead to significantly different transient kinetics of the same plasmonic (Cu 2- x Se) NCs because of different capping agents. Along with this, we have described the impact of a molecular adsorbate (methylene blue) on ultrafast plasmon relaxation dynamics of the nonstoichiometric Cu 2- x Se NCs system. Finally, the chemical interface damping effect has been compared in the Cu 2- x S NCs system after capping with two distinct capping ligands: oleylamine and oleic acid. For the proof of concept, plasmonic thin-film devices were fabricated and exhibited higher conductivity/photoconductivity performance in oleic acid-capped NCs because of a deprotonated carboxyl functional group. We have also introduced a model and mechanism of chemical interface damping in a nonstoichiometric plasmonic semiconductor (Cu 2- x S/Se) NC system. This feature article highlights the importance of the surface functionalization of nonstoichiometric plasmonic semiconductors to develop new advanced semiconductor-based devices such as infrared photodetectors, plasmonic solar cells, and efficient NIR phototransistors.
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