Proceedings of nanoGe September Meeting 2017 (NFM17)
Publication date: 20th June 2016
Bulk HgSe is a zero-gap semiconductor, yet in the case of HgSe colloidal nanocrystals NCs, size quantization results in a non-zero gap. Possibility to cover whole infrared region by reducing the NC size down to a few nanometers makes HgSe QDs especially interesting for infrared photodetection. Recently, high quality syntheses to form HgSe QDs from HgCl2 dissolved in oleylamine have been developed for this purpose. To understand how general the prevailing (NC)[MX2] (where surface active group is placed between square brackets) binding motif is for as-synthesized II-VI and IV-VI QDs we introduced a solution nuclear magnetic resonance (NMR) spectroscopy to analyze HgSe QDs.
By combining elemental analysis and solution NMR spectroscopy we show that as-synthesized HgSe QDs are nearly stoichiometric, and terminated by pairs of oleylammonium and chloride ions that ensure charge neutrality. Specifically for this binding motif of HgSe QDs the ligand exchange characteristics shows that addition of dodecanethiol leads to the complete displacement of the ion pair (oleylammonium cloride) from the HgSe surface and at the same time carboxylic acid so no tendency to interact with the HgSe QDs. By means of DFT calculations, we attribute this markedly different binding motif as compared to other II-VI QDs to the low binding energy of HgCl2 to a stoichiometric HgSe QD.
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