Quantum-confined InP nanocrystals from 20 to 50 Å in diameter have been synthesized via the reaction of InCl3 and P(Si(CH3)3)3 in trioctylphosphine oxide (TOPO) at elevated temperatures. The nanocrystals are highly crystalline, monodisperse, and soluble in various organic solvents. Improved size distributions have been obtained by size-selectively reprecipitating the nanocrystals. The UV/vis absorption spectra of the particles show the characteristic blue shift of the band gap of up to 1 eV due to quantum confinement, a moderately well-resolved first excitonic excited state, and, in some cases, the resolution of a higher excited state. Structurally, the nanocrystals are characterized with powder X-ray diffraction and transmission electron microscopy. Raman spectroscopy reveals TO and LO modes near the characteristic bulk InP positions as well a surface mode resulting from finite size. The Raman line widths, line positions, and relative intensities are all size-dependent . X-ray photoelectron spectroscopy (XPS) shows the nanocrystals have a nearly stoichiometric ratio of indium to phosphorus with TOPO surface coverages ranging from 30% to 100%. We have also used XPS to correlate the oxidation of the nanocrystal surface with photoluminescence intensity. Photoluminescence is observed as both band edge and deep trap emission with both features shifting with nanocrystal size. The luminescence is highly dependent on the surface of the nanocrystal with oxidation being a necessary condition for emission.
We report here on the size-dependent kinetics of exciton recombination in a III-V quantum dot system, InP. The measurements reported include various frequency dependent quantum yields as a function of temperature, frequency dependent luminescence decay curves, and time-gated emission spectra. This data is fit to a three-state quantum model which has been previously utilized to explain photophysical phenomena in II-VI quantum dots. The initial photoexcitation is assumed to place an electron in a ͑delocalized͒ bulk conduction band state. Activation barriers for trapping and detrapping of the electron to surface states, as well as activation barriers for surface-state radiationless relaxation processes are measured as a function of particle size. The energy barrier to detrapping is found to be the major factor limiting room temperature band-edge luminescence. This barrier increases with decreasing particle size. For 30 Å particles, this barrier is found to be greater than 6 kJ/mol-a barrier which is more than an order of magnitude larger than that previously found for 32 Å CdS nanocrystals.
The resonance Raman spectrum of InP nanocrystals is characterized by features ascribable to both longitudinal ͑LO͒ and transverse ͑TO͒ optical modes. The intensity ratio of these modes exhibits a strong size dependence. To calculate the size dependence of the LO and TO Raman cross sections, we combine existing models of Raman scattering, the size dependence of electronic and vibrational structure, and electron vibration coupling in solids. For nanocrystals with a radius Ͼ10 Å, both the LO and TO coupling strengths increase with increasing radius. This, together with an experimentally observed increase in the electronic dephasing rate with decreasing size, allows us to account for the observed ratio of LO/TO Raman intensities.
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