The effect of nanocrystal surface structure on the luminescence properties: Photoemission study of HF-etched InP nanocrystals

InP nanocrystals with narrow size distribution and mean particle diameter tunable from ∼2 up to ∼7nm were synthesized via the dehalosilylation reaction between InCl3 and tris(trimethylsilyl)phosphine. Specific capping of the nanocrystal surface with a shell of organic ligands protects the nanocrystals from oxidation and provides solubility of the particles in various organic solvents. InP nanocrystals with enhanced photoluminescence (PL) efficiency were obtained from the initial nanocrystals by photoassisted etching of the nanocrystal surface with HF. The resulting PL quantum efficiency of InP nanocrystals dispersed in n-butanol is about three orders of magnitude higher when compared to the nonetched InP samples and approaches ∼40% at room temperature. High-resolution photoelectron spectroscopy with the use of synchrotron radiation was applied to reveal the changes of the nanocrystal surface responsible for the dramatic improvement of the PL efficiency. The analysis of high-resolution P 2p core-level spectra confirmed significant changes of the nanocrystal surface structure induced by the postpreparative treatments and allowed us to propose the description of the etching mechanism. In the nonetched InP nanocrystals, some surface P atoms generate energy states located inside the band gap which provide nonradiative recombination pathways. Photoassisted treatment of InP nanocrystals with HF results in selective removal of these phosphorous atoms from the nanocrystal surface. The reconstructed surface of the etched InP nanocrystals is terminated mainly with In atoms and is efficiently passivated with tri-n-octylphosphine oxide ligands.