Continuous Nucleation and Size Dependent Growth Kinetics of Indium Phosphide Nanocrystals

Aminophosphines derived from N,N′-disubstituted ethylenediamines (R–N(H)CH2CH2N(H)–R; R = ortho-tolyl, phenyl, benzyl, iso-propyl, and n-octyl) were used to adjust the kinetics of InP nanocrystal formation by more than 1 order of magnitude. Ultraviolet–visible absorption and 31P nuclear magnetic resonance measurements demonstrate that the rate of nanocrystal formation is limited by the precursor reactivity. At low temperature (180 °C), crystal nucleation is concurrent with growth throughout the reaction, rather than occurring in a burst at early times. The low temperature produces a narrow range of small sizes (d = 4.2–4.9 nm) regardless of the precursor used. Higher temperatures (up to 270 °C) promote growth to larger sizes (d ≤ 7.8 nm), shorten the nucleation period, and create conditions where the final size is controlled by the precursor conversion reactivity. The temperature dependence is proposed to arise from growth kinetics that slow as the nanocrystal size increases, a novel surface attachment limited size distribution-focusing mechanism. Such a mechanism supports a narrow size distribution without separating the nucleation and growth phases.