Abstract
Complex pnictides such as I-II4-V3 compounds (I = alkali metal; II = divalent transition metal; V = pnictide element) display rich structural chemistry and interesting optoelectronic properties, but can be challenging to synthesize using traditional high-temperature solid-state synthesis. Soft chemistry methods can offer control over particle size, morphology, and properties. However, the synthesis of multinary pnictides from solution remains underdeveloped. Here, we report the colloidal hot-injection synthesis of ACd4P3 (A = Na, K) nanostructures from their alkali metal hydrides (AH). Control studies indicate that NaCd4P3 forms from monometallic Cd0 seeds and not from binary Cd3P2 nanocrystals. IR and ssNMR spectroscopy reveal tri-n-octylphosphine oxide (TOPO) and related ligands are coordinated to the ternary surface. Computational studies show that competing phases with space group symmetries R3¯ m and Cm differ by only 30 meV/formula unit, indicating that synthetic access to either of these polymorphs is possible. Our synthesis unlocks a new family of nanoscale multinary pnictide materials that could find use in optoelectronic and energy conversion devices.
Original language | English (US) |
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Pages (from-to) | 130-139 |
Number of pages | 10 |
Journal | ACS Materials Au |
Volume | 1 |
Issue number | 2 |
DOIs | |
State | Published - Nov 10 2021 |
Funding
J.V. gratefully acknowledges funding from the U.S. National Science Foundation, Division of Chemistry, Macromolecular, Supramolecular, and Nanochemistry Program (1905066). Y.C. and A.J.R. (solid-state NMR spectroscopy) were supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. The Ames Laboratory is operated for the U.S. DOE by Iowa State University under Contract DE-AC02-07CH11358. This photoluminescence part of this work was performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract DE-AC02-06CH11357.
Keywords
- I-II-V
- hydride
- nanostructures
- solution phase
- ternary semiconductor
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Materials Chemistry
- Polymers and Plastics
- Biomaterials