Size-dependent spectroscopy of InP quantum dots

The spectroscopic behavior of colloidal InP quantum dots (QDs) has been investigated as a function of the mean QD diameter (which ranged from 26 to 60 Angstrom). Absorption spectra show up to three peaks or shoulders which reflect excited state transitions in the QDs. Global photoluminescence (PL) spectra (excitation well to the blue of the absorption onset and which consequently excites most of the QDs in the size distribution) show broad PL emission. The emission and absorption features shift to higher energy with decreasing QD size. Resonant PL spectra (size-selective excitation into the tail of the absorption onset) show increasing fluorescence line narrowing with increasing excitation wavelength PL and photoluminescence excitation spectroscopy were used to derive the PL red shift as a function of QD size. The resonant red shifts for QDs of a single size were extracted from PL data that reflect the emission from an ensemble of QD diameters. An analysis of the single-dot resonant red shift (difference between PL peak and the first absorption peak) as a function of the single QD diameter indicate that the results are consistent with a model in which the emission occurs from an intrinsic, spin-forbidden state, split from its singlet counterpart, due to screened electron-hole exchange.