Concentration-Dependent Layer-Stacking and the Influence on Phase-Conversion in Colloidally Synthesized WSe2 Nanocrystals

We report a synthesis of WSe2 nanocrystals in which the number of layers is controlled by varying the precursor concentration. By altering the ratios and concentrations of W­(CO)6 and Ph2Se2 in trioctylphosphine oxide, we show that high [Se] and large Se/W ratios lead to an increased number of layers per nanocrystal. As the number of layers per nanocrystal is increased, the nanocrystal ensembles show less phase-conversion from the metastable 2M phase to the thermodynamically favored 2H phase. Density functional theory calculations indicate that the interlayer binding energy increases with the number of layers, indicating that the stronger interlayer interactions in multilayered nanocrystals may increase the energy barrier to phase-conversion. The results presented herein provide insights for directing phase-conversion in solution-phase syntheses of transition metal dichalcogenides.