Quantum Confined High-Entropy Lanthanide Oxysulfide Colloidal Nanocrystals.

Ward-O'Brien, Brendan; McNaughter, Paul D; Cai, Rongsheng; Chattopadhyay, Amrita; Flitcroft, Joseph M; Smith, Charles T; Binks, David J; Skelton, Jonathan M et al. · Nano Lett · 2022

basic_science · Level V

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Abstract

We have synthesized the first reported example of quantum confined high-entropy (HE) nanoparticles, using the lanthanide oxysulfide, Ln<sub>2</sub>SO<sub>2</sub>, system as the host phase for an equimolar mixture of Pr, Nd, Gd, Dy, and Er. A uniform HE phase was achieved <i>via</i> the simultaneous thermolysis of a mixture of lanthanide dithiocarbamate precursors in solution. This was confirmed by powder X-ray diffraction and high-resolution scanning transmission electron microscopy, with energy dispersive X-ray spectroscopic mapping confirming the uniform distribution of the lanthanides throughout the particles. The nanoparticle dispersion displayed a significant blue shift in the absorption and photoluminescence spectra relative to our previously reported bulk sample with the same composition, with an absorption edge at 330 nm and a λ<sub>max</sub> at 410 nm compared to the absorption edge at 500 nm and a λ<sub>max</sub> at 450 nm in the bulk, which is indicative of quantum confinement. We support this postulate with experimental and theoretical analysis of the bandgap energy as a function of strain and surface effects (ligand binding) as well as calculation of the exciton Bohr radiii of the end member compounds.