Superstructural Ordering in Hexagonal CuInSe 2 Nanoparticles
Résumé
Chalcogenide semiconducting nanoparticles are promising building blocks for solution-processed fabrication of optoelectronic devices. In this work, we report a new large-scale colloidal synthesis of metastable CuInSe 2 nanoparticles with hexagonal plate-like morphology. Powder X-ray diffraction analysis of the nanoparticles showed that the structure of the nanoparticles is not simple hexagonal wurtzite-type CuInSe 2 (space group P6 3 mc), indicating the formation of an ordered superstructure. Detailed insight into this structural aspect was explored by high-resolution electron microscopy, and the results evidence an unreported chemical ordering within the synthesized CuInSe 2 nanoparticles. Specifically, while the Se sublattice is arranged in perfect wurtzite subcell, Cu and In are segregated over distinct framework positions, forming domains with lower symmetry. The arrangement of these domains within the hexagonal Se substructure proceeds through the formation of a number of planar defects, mainly twins and antiphase boundaries. As a semiconductor, the synthesized material exhibits a direct optical transition at 0.95 eV, which correlates well with its electronic structure assessed by density functional theory calculations. Overall, these findings may inspire the design and synthesis of other nanoparticles featuring unique chemical ordering; thus, providing an additional possibility of tuning intrinsic transport properties. © 2018 American Chemical Society.
Mots clés
Powder X ray diffraction
Ordered superstructures
Hexagonal wurtzite
Copper compounds
Density functional theory
Electronic structure
High resolution electron microscopy
Indium compounds
Nanoparticles
Optoelectronic devices
Selenium
Sols
X ray powder diffraction
Zinc sulfide
Antiphase boundaries
Colloidal synthesis
Semi-conducting nanoparticles
Structural aspects
Synthesized materials
Synthesis (chemical)
Scanning transmission electron microscopy
Wurtzite
Physical and chemical processes
Electrical conductivity