The
development of
applications for germanium nanocrystals has been hindered by the limited
availability of synthetic methods coupled with poorly understood ligand-exchange
chemistry. Herein we describe the synthesis of germanium nanocrystals
and ligand exchange experiments designed to establish facile routes
toward ligand replacement and, consequently, layers that are amenable
to charge-transfer. After assessing thiols, carboxylates, and dithiocarbamates,
sulfur dissolved in 1-ocatadecene was determined to be the most amenable
to ligand exchange, with over 95% of the initial alkylamine ligand
replaced as determined by Fourier transform infrared spectroscopy
(FTIR). These results were in good agreement with density functional
theory calculations showing a strong preference for Ge–S bonding.
The materials were fully characterized via powder X-ray diffraction,
FTIR, transmission electron microscopy, and X-ray and UV photoelectron
spectroscopy. This new ligand exchange procedure provides a possible
route toward the fabrication of thin films that may be employed in
such applications as photovoltaic devices.
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