Colloidal Chemistry in Molten Inorganic Salts: Direct Synthesis of III-V Quantum Dots via Dehalosilylation of (Me3Si)3Pn (Pn = P, As) with Group III Halides

Zirui Zhou; Justin C. Ondry; Yi Chun Liu; Haoqi Wu; Ahhyun Jeong; Aritrajit Gupta; Yi Chen Chen; Jun Hyuk Chang; Richard D. Schaller; Dmitri V. Talapin

doi:10.1021/jacs.4c13568

Colloidal Chemistry in Molten Inorganic Salts: Direct Synthesis of III-V Quantum Dots via Dehalosilylation of (Me₃Si)₃Pn (Pn = P, As) with Group III Halides

Zirui Zhou, Justin C. Ondry, Yi Chun Liu, Haoqi Wu, Ahhyun Jeong, Aritrajit Gupta, Yi Chen Chen, Jun Hyuk Chang, Richard D. Schaller, Dmitri V. Talapin^*

^*Corresponding author for this work

Chemistry

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

Abstract

Gallium pnictides, such as GaAs and GaP, are among the most widely used semiconductors for electronic, optoelectronic, and photonic applications. However, solution syntheses of gallium pnictide nanomaterials are less developed than those of many other colloidal semiconductors, including indium pnictides, II-VI and IV-VI compounds, and lead halide perovskites. In this work, we demonstrate that the Wells dehalosilylation reaction can be carried out in molten inorganic salt solvents to synthesize colloidal GaAs, GaP, and GaP_1-xAs_x nanocrystals. We demonstrate that discrete colloidal nanocrystals can be nucleated and grown in a molten salt with control over their size and composition. Additionally, we found that reaction temperatures above 400 °C are crucial for annealing structural defects in GaAs nanocrystals. We also highlight the utility of the as-synthesized GaP nanocrystals by showing that GaP can be solution-processed into high-refractive-index coatings and patterned by direct optical lithography with micron resolution. Finally, we demonstrate that dehalosilylation reactions in molten salts can be generalized to synthesize indium pnictide (Pn = As, P) and ternary (In_1-xGa_xAs and In_1-xGa_xP) quantum dots.

Original language	English (US)
Pages (from-to)	9198-9209
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	147
Issue number	11
DOIs	https://doi.org/10.1021/jacs.4c13568
State	Published - Mar 19 2025

Funding

We acknowledge Dr. A. Nelson and R. Hotton for reading and editing the manuscript. We also thank Dr. J. Jureller and X. Shen for their help with Raman, film thickness, and PL measurements. We thank X. Shen, B. Li, and Prof. Philippe Guyot-Sionnest for their helpful discussions, Prof. P. Nealey for providing access to the spectroscopic ellipsometer, and Prof. A. P. Alivisatos for providing access to the PicoQuant spectrometer. The work on direct synthesis of III-V quantum dots was supported by the National Science Foundation under Award CHE-2404291. Structural and spectroscopic characterizations of novel III-V quantum dots were supported by the National Science Foundation Science and Technology Center (STC) for Integration of Modern Optoelectronic Materials on Demand (IMOD) under Award DMR-2019444. A. Jeong is partially supported by Kwanjeong Educational Foundation. This work made use of the shared facilities at the University of Chicago Materials Research Science and Engineering Center, supported by National Science Foundation under Award DMR-2011854. Parts of this work were carried out at the Soft Matter Characterization Facility of the University of Chicago. Work performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. We acknowledge Dr. A. Nelson and R. Hotton for reading and editing the manuscript. We also thank Dr. J. Jureller and X. Shen for their help with Raman, film thickness, and PL measurements. We thank X. Shen, B. Li, and Prof. Philippe Guyot-Sionnest for their helpful discussions, Prof. P. Nealey for providing access to the spectroscopic ellipsometer, and Prof. A. P. Alivisatos for providing access to the PicoQuant spectrometer. The work on direct synthesis of III\u2013V quantum dots was supported by the National Science Foundation under Award CHE-2404291. Structural and spectroscopic characterizations of novel III\u2013V quantum dots were supported by the National Science Foundation Science and Technology Center (STC) for Integration of Modern Optoelectronic Materials on Demand (IMOD) under Award DMR-2019444. A. Jeong is partially supported by Kwanjeong Educational Foundation. This work made use of the shared facilities at the University of Chicago Materials Research Science and Engineering Center, supported by National Science Foundation under Award DMR-2011854. Parts of this work were carried out at the Soft Matter Characterization Facility of the University of Chicago. Work performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.4c13568

Cite this

Zhou, Z., Ondry, J. C., Liu, Y. C., Wu, H., Jeong, A., Gupta, A., Chen, Y. C., Chang, J. H., Schaller, R. D., & Talapin, D. V. (2025). Colloidal Chemistry in Molten Inorganic Salts: Direct Synthesis of III-V Quantum Dots via Dehalosilylation of (Me₃Si)₃Pn (Pn = P, As) with Group III Halides. Journal of the American Chemical Society, 147(11), 9198-9209. https://doi.org/10.1021/jacs.4c13568

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title = "Colloidal Chemistry in Molten Inorganic Salts: Direct Synthesis of III-V Quantum Dots via Dehalosilylation of (Me3Si)3Pn (Pn = P, As) with Group III Halides",

abstract = "Gallium pnictides, such as GaAs and GaP, are among the most widely used semiconductors for electronic, optoelectronic, and photonic applications. However, solution syntheses of gallium pnictide nanomaterials are less developed than those of many other colloidal semiconductors, including indium pnictides, II-VI and IV-VI compounds, and lead halide perovskites. In this work, we demonstrate that the Wells dehalosilylation reaction can be carried out in molten inorganic salt solvents to synthesize colloidal GaAs, GaP, and GaP1-xAsx nanocrystals. We demonstrate that discrete colloidal nanocrystals can be nucleated and grown in a molten salt with control over their size and composition. Additionally, we found that reaction temperatures above 400 °C are crucial for annealing structural defects in GaAs nanocrystals. We also highlight the utility of the as-synthesized GaP nanocrystals by showing that GaP can be solution-processed into high-refractive-index coatings and patterned by direct optical lithography with micron resolution. Finally, we demonstrate that dehalosilylation reactions in molten salts can be generalized to synthesize indium pnictide (Pn = As, P) and ternary (In1-xGaxAs and In1-xGaxP) quantum dots.",

author = "Zirui Zhou and Ondry, {Justin C.} and Liu, {Yi Chun} and Haoqi Wu and Ahhyun Jeong and Aritrajit Gupta and Chen, {Yi Chen} and Chang, {Jun Hyuk} and Schaller, {Richard D.} and Talapin, {Dmitri V.}",

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Zhou, Z, Ondry, JC, Liu, YC, Wu, H, Jeong, A, Gupta, A, Chen, YC, Chang, JH, Schaller, RD & Talapin, DV 2025, 'Colloidal Chemistry in Molten Inorganic Salts: Direct Synthesis of III-V Quantum Dots via Dehalosilylation of (Me₃Si)₃Pn (Pn = P, As) with Group III Halides', Journal of the American Chemical Society, vol. 147, no. 11, pp. 9198-9209. https://doi.org/10.1021/jacs.4c13568

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T1 - Colloidal Chemistry in Molten Inorganic Salts

T2 - Direct Synthesis of III-V Quantum Dots via Dehalosilylation of (Me3Si)3Pn (Pn = P, As) with Group III Halides

AU - Zhou, Zirui

AU - Ondry, Justin C.

AU - Liu, Yi Chun

AU - Wu, Haoqi

AU - Jeong, Ahhyun

AU - Gupta, Aritrajit

AU - Chen, Yi Chen

AU - Chang, Jun Hyuk

AU - Schaller, Richard D.

AU - Talapin, Dmitri V.

PY - 2025/3/19

Y1 - 2025/3/19

N2 - Gallium pnictides, such as GaAs and GaP, are among the most widely used semiconductors for electronic, optoelectronic, and photonic applications. However, solution syntheses of gallium pnictide nanomaterials are less developed than those of many other colloidal semiconductors, including indium pnictides, II-VI and IV-VI compounds, and lead halide perovskites. In this work, we demonstrate that the Wells dehalosilylation reaction can be carried out in molten inorganic salt solvents to synthesize colloidal GaAs, GaP, and GaP1-xAsx nanocrystals. We demonstrate that discrete colloidal nanocrystals can be nucleated and grown in a molten salt with control over their size and composition. Additionally, we found that reaction temperatures above 400 °C are crucial for annealing structural defects in GaAs nanocrystals. We also highlight the utility of the as-synthesized GaP nanocrystals by showing that GaP can be solution-processed into high-refractive-index coatings and patterned by direct optical lithography with micron resolution. Finally, we demonstrate that dehalosilylation reactions in molten salts can be generalized to synthesize indium pnictide (Pn = As, P) and ternary (In1-xGaxAs and In1-xGaxP) quantum dots.

AB - Gallium pnictides, such as GaAs and GaP, are among the most widely used semiconductors for electronic, optoelectronic, and photonic applications. However, solution syntheses of gallium pnictide nanomaterials are less developed than those of many other colloidal semiconductors, including indium pnictides, II-VI and IV-VI compounds, and lead halide perovskites. In this work, we demonstrate that the Wells dehalosilylation reaction can be carried out in molten inorganic salt solvents to synthesize colloidal GaAs, GaP, and GaP1-xAsx nanocrystals. We demonstrate that discrete colloidal nanocrystals can be nucleated and grown in a molten salt with control over their size and composition. Additionally, we found that reaction temperatures above 400 °C are crucial for annealing structural defects in GaAs nanocrystals. We also highlight the utility of the as-synthesized GaP nanocrystals by showing that GaP can be solution-processed into high-refractive-index coatings and patterned by direct optical lithography with micron resolution. Finally, we demonstrate that dehalosilylation reactions in molten salts can be generalized to synthesize indium pnictide (Pn = As, P) and ternary (In1-xGaxAs and In1-xGaxP) quantum dots.

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