Ward-O'Brien Brendan, McNaughter Paul D, Cai Rongsheng, Chattopadhyay Amrita, Flitcroft Joseph M, Smith Charles T, Binks David J, Skelton Jonathan M, Haigh Sarah J, Lewis David J
Department of Materials, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Nano Lett. 2022 Oct 26;22(20):8045-8051. doi: 10.1021/acs.nanolett.2c01596. Epub 2022 Oct 4.
We have synthesized the first reported example of quantum confined high-entropy (HE) nanoparticles, using the lanthanide oxysulfide, LnSO, system as the host phase for an equimolar mixture of Pr, Nd, Gd, Dy, and Er. A uniform HE phase was achieved 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 at 410 nm compared to the absorption edge at 500 nm and a λ 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.
我们合成了首个报道的量子限域高熵(HE)纳米颗粒实例,使用氧硫化镧(LnSO)体系作为镨(Pr)、钕(Nd)、钆(Gd)、镝(Dy)和铒(Er)等摩尔混合物的主体相。通过溶液中镧系二硫代氨基甲酸盐前体混合物的同步热解,实现了均匀的HE相。粉末X射线衍射和高分辨率扫描透射电子显微镜证实了这一点,能量色散X射线光谱映射证实了镧系元素在整个颗粒中的均匀分布。相对于我们之前报道的具有相同组成的块状样品,纳米颗粒分散体在吸收光谱和光致发光光谱中显示出显著的蓝移,块状样品的吸收边缘在500 nm,λ在450 nm,而纳米颗粒分散体的吸收边缘在330 nm,λ在410 nm,这表明存在量子限域效应。我们通过对带隙能量作为应变和表面效应(配体结合)函数的实验和理论分析以及对端元化合物激子玻尔半径的计算,支持了这一假设。