Liquid-Phase Syntheses and Material Properties of Two-Dimensional Nanocrystals of Rare Earth–Selenium Compound Containing Planar Se Layers: RESe2 Nanosheets and RE4O4Se3 Nanoplates

Abstract

Synthesis of diverse two-dimensional nanostructures with unique material properties is of current interest and multidisciplinary importance but remains a challenge for trivalent rare earth (RE)-selenium (Se) compounds because of the weak affinity between hard rare earth cations and soft selenium anions. In this article, for the first time, we report a mild solution approach toward a series of two-dimensional trivalent RE-selenium compound nanocrystals, namely RESe2 nanosheets (RE = La to Nd, for EuSe2, nanobars were obtained) and RE4O4Se3 nanoplates (RE = Nd, Sm, Gd to Ho), under a high chemical potential of selenium obtained by activating SeO2 powder with oleylamine in high boiling point organic solvents. Both kinds of nanocrystals contain Se with -1 valence in planar Se layers, allowing for a great variability in their crystal structures. Satellite diffraction peaks were observed in the electron diffraction pattern of LaSe2 nanosheets, indicating the presence of Peierls distortion in the Se layers. In the RE4O4Se3 nanoplates, the interaction between Se(2-) ions and [Se-Se](2-) dumbbells in the Se layers increases when the radii of the RE(3+) ions decrease along the lanthanide series, resulting in a narrower optical band gap (from 1.96 to 1.73 eV). The LaSe2 nanosheet films fabricated by drop-casting exhibited good electrical conductivity at room temperature (about 1 Ω·cm(-1)). Further, the RE4O4Se3 nanoplates showed very high light extinction capacity in the visible region (extinction coefficient μi: 4.4 × 10(5) cm(-1) for Nd4O4Se3, and 3.1 × 10(5) cm(-1) for Gd4O4Se3), comparable to that (5 × 10(5) cm(-1)) of CuInS2 commonly used in solar cells.