Ternary ACd4P3(A = Na, K) Nanostructures via a Hydride Solution-Phase Route

Alan M. Medina-Gonzalez; Philip Yox; Yunhua Chen; Marquix A.S. Adamson; Maranny Svay; Emily A. Smith; Richard D. Schaller; Aaron J. Rossini; Javier Vela

doi:10.1021/acsmaterialsau.1c00018

Ternary ACd₄P₃(A = Na, K) Nanostructures via a Hydride Solution-Phase Route

Alan M. Medina-Gonzalez, Philip Yox, Yunhua Chen, Marquix A.S. Adamson, Maranny Svay, Emily A. Smith, Richard D. Schaller, Aaron J. Rossini, Javier Vela^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

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)
Pages (from-to)	130-139
Number of pages	10
Journal	ACS Materials Au
Volume	1
Issue number	2
DOIs	https://doi.org/10.1021/acsmaterialsau.1c00018
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

Access to Document

10.1021/acsmaterialsau.1c00018

Cite this

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title = "Ternary ACd4P3(A = Na, K) Nanostructures via a Hydride Solution-Phase Route",

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.",

keywords = "I-II-V, hydride, nanostructures, solution phase, ternary semiconductor",

author = "Medina-Gonzalez, {Alan M.} and Philip Yox and Yunhua Chen and Adamson, {Marquix A.S.} and Maranny Svay and Smith, {Emily A.} and Schaller, {Richard D.} and Rossini, {Aaron J.} and Javier Vela",

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T1 - Ternary ACd4P3(A = Na, K) Nanostructures via a Hydride Solution-Phase Route

AU - Medina-Gonzalez, Alan M.

AU - Yox, Philip

AU - Chen, Yunhua

AU - Adamson, Marquix A.S.

AU - Svay, Maranny

AU - Smith, Emily A.

AU - Schaller, Richard D.

AU - Rossini, Aaron J.

AU - Vela, Javier

PY - 2021/11/10

Y1 - 2021/11/10

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AB - 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.

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