Exciton Fine Structure and Lattice Dynamics in InP/ZnSe Core/Shell Quantum Dots

Nanocrystalline InP quantum dots (QDs) hold promise for heavy-metal free opto-electronic applications due to their bright and size-tunable emission in the visible range. Photochemical stability and high photoluminescence (PL) quantum yield are obtained by a diversity of epitaxial shells around the InP core. To understand and optimize the emission line shapes, the exciton fine structure of InP core/shell QD systems needs be investigated. Here, we study the exciton fine structure of InP/ZnSe core/shell QDs with core diameters ranging from 2.9 to 3.6 nm (PL peak from 2.3 to 1.95 eV at 4 K). PL decay measurements as a function of temperature in the 10 mK to 300 K range show that the lowest exciton fine structure state is a dark state, from which radiative recombination is assisted by coupling to confined acoustic phonons with energies ranging from 4 to 7 meV, depending on the core diameter. Circularly polarized fluorescence line-narrowing (FLN) spectroscopy at 4 K under high magnetic fields (up to 30 T) demonstrates that radiative recombination from the dark F = ±2 state involves acoustic and optical phonons, both from the InP core and the ZnSe shell. Our data indicate that the highest-intensity FLN peak is an acoustic phonon replica rather than a zero-phonon line, implying that the energy separation observed between the F = ±1 state and the highest-intensity peak in the FLN spectra (6 to 16 meV, depending on the InP core size) is larger than the splitting between the dark and bright fine structure exciton states