We report a tunable library of N,N,N'-trisubstituted selenourea precursors and their reaction with lead oleate at 60-150 °C to form carboxylate-terminated PbSe nanocrystals in quantitative yields. Single exponential conversion kinetics can be tailored over 4 orders of magnitude by adjusting the selenourea structure. The wide range of conversion reactivity allows the extent of nucleation ([nanocrystal] = 4.6-56.7 μM) and the size following complete precursor conversion (d = 1.7-6.6 nm) to be controlled. Narrow size distributions (σ = 0.5-2%) are obtained whose spectral line widths are dominated (73-83%) by the intrinsic single particle spectral broadening, as observed using spectral hole burning measurements. The intrinsic broadening decreases with increasing size (fwhm = 320-65 meV, d = 1.6-4.4 nm) that derives from exciton fine structure and exciton-phonon coupling rather than broadening caused by the size distribution.

Control over particle surfaces and interfaces is a principal requirement to fully take advantage of semiconducting Quantum Dot (QDs) properties. In the case of indium phosphide, the sensitivity of the material to water renders it challenging to synthesize oxide-free particles. We demonstrate the ability to achieve complete control over the surface by developing synthetic strategies based on a novel reactive indium precursor, tris(N,N'diisopropylacetamidinato) indium(III). This complex permits the synthesis of InP QDs at temperatures as low as 150°C with no inherent surface oxidation. At higher temperatures (230°C), the concomitant use of an H 2 atmosphere yields oxide-free InP QDs. The prevention of such an amorphous oxide layer provides a clean surface suitable for subsequent growth. An extensive solid-state 2 H NMR spectroscopy study demonstrates an unprecedented H 2 bond dissociation at the QD surface yielding QDs-H species and in so doing protecting the surface from oxidation. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Experimental section, TEM, UV-Vis, XRD and solid state NMR data of InP QDs 1-4, and the ZnScoated versions 5-6.