Andrew W. Wills

Electronic Impurity Doping in CdSe Nanocrystals

We dope CdSe nanocrystals with Ag impurities and investigate their optical and electrical properties. Doping leads not only to dramatic changes but surprising complexity. The addition of just a few Ag atoms per nanocrystal causes a large enhancement in the fluorescence, reaching efficiencies comparable to core-shell nanocrystals. While Ag was expected to be a substitutional acceptor, nonmonotonic trends in the fluorescence and Fermi level suggest that Ag changes from an interstitial (n-type) to a substitutional (p-type) impurity with increased doping.

Size control and quantum confinement in Cu2ZnSnS4 nanocrystals.

Starting with metal dithiocarbamate complexes, we synthesize colloidal Cu(2)ZnSnS(4) (CZTS) nanocrystals with diameters ranging from 2 to 7 nm. Structural and Raman scattering data confirm that CZTS is obtained rather than other possible material phases. The optical absorption spectra of nanocrystals with diameters less than 3 nm show a shift to higher energy due to quantum confinement.

Thermally degradable ligands for nanocrystals.

We exchanged the oleate ligands on as-prepared PbSe/CdSe core/shell nanocrystals with octyldithiocarbamate to enable the removal of insulating ligands by gentle heating. The octyldithiocarbamate ligand could readily be stripped from the surface by heating briefly to temperatures from 140 to 205 degrees C, which is substantially lower than the temperature (330 degrees C) required to remove oleate from the nanocrystal surface. X-ray diffraction and transmission electron microscopy reveal that the nanocrystals sinter around 250 degrees C, resulting in a loss of quantum confinement. Heating for 1 min to 205 degrees C removed 92% of the organics from the surface. We could therefore prepare densely packed films of quantum-confined nanocrystals via dithiocarbamate treatment. Conductivity increased by up to 4 orders of magnitude after annealing. In addition to PbSe/CdSe core/shell nanocrystals, we also examined the applicability of our ligand removal procedure to CdSe nanocrystals.

Imaging "invisible" dopant atoms in semiconductor nanocrystals

Nanometer-scale semiconductors that contain a few intentionally added impurity atoms can provide new opportunities for controlling electronic properties. However, since the physics of these materials depends strongly on the exact arrangement of the impurities, or dopants, inside the structure, and many impurities of interest cannot be observed with currently available imaging techniques, new methods are needed to determine their location. We combine electron energy loss spectroscopy with annular dark-field scanning transmission electron microscopy (ADF-STEM) to image individual Mn impurities inside ZnSe nanocrystals. While Mn is invisible to conventional ADF-STEM in this host, our experiments and detailed simulations show consistent detection of Mn. Thus, a general path is demonstrated for atomic-scale imaging and identification of individual dopants in a variety of semiconductor nanostructures.

The use of thermally decomposable ligands for conductive films of semiconductor nanocrystals

Poor conductivity is a bottleneck hindering the production of nanocrystal-based devices. In most nanocrystal syntheses, ligands with long alkyl chains are used to prepare monodisperse, crystalline particles. When these nanocrystals are incorporated into devices as films, the bulky ligands form an insulating layer that prevents charge transfer between particles. While annealing or post-deposition chemical treatments can be used to strip surface ligands, each of these approaches has disadvantages. Here we demonstrate the use of a novel family of ligands comprised of primary alkyl dithiocarbamates to stabilize PbSe/CdSe core-shell nanocrystals. Primary dithiocarbamates, which can bind to cadmium and lead, are known to decompose to the corresponding sulfides when heated under mild conditions. In our scheme, PbSe/CdSe core-shell nanocrystals are first synthesized with standard ligands. These ligands are then exchanged to short chain dithiocarbamates in solution. When a film is cast and annealed at low temperature, the dithiocarbamates are removed. Electron microscopy reveals that the particles move closer together, and, along with x-ray diffraction, shows that the nanocrystals remain quantum confined. Transport measurements show a 10,000-fold increase in conductivity after annealing.