Polymorphic Control of CsGaE2 (E = S, Se) Using Diorganyl Dichalcogenide Precursors

Sun, Zhaohong; Pakhanyan, Christopher P.; Saleem, Usama; Feldman, Eitan I.; Sharada, Shaama Mallikarjun; Brutchey, Richard L.

doi:10.1021/acs.inorgchem.5c04153

Polymorphic Control of CsGaE₂ (E = S, Se) Using Diorganyl Dichalcogenide Precursors

Journal Article · Fri Oct 24 00:00:00 EDT 2025 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5c04153· OSTI ID:3015137

^[1]; ^[1]; Saleem, Usama ^[1]; ^[2]; ^[1]; ^[1]

University of Southern California, Los Angeles, CA (United States)
Rice University, Houston, TX (United States)

Diorganyl dichalcogenides (R–E–E–R; R = organyl, E = S, Se, Te) are widely employed for the polymorphic control of diamond-like crystal structures owing to their tunable C–E bond reactivity. In this work, we extend their application to non-close-packed alkali metal-based chalcogenides by demonstrating the selective synthesis of CsGaE₂ (E = S, Se) polymorphs. Weaker C–E bonds or higher temperatures promote the formation of the thermodynamically stable mC64 phases, while stronger C–E bonds or lower temperatures allow for the isolation of the metastable mC16 phases. Furthermore, heat-treatment studies reveal the pronounced metastability of CsGaSe₂-mC16 particles and the irreversible phase transition of CsGaS₂ analogous to its bulk counterpart.

View Accepted Manuscript (DOE)

Research Organization:: University of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0006812

OSTI ID:: 3015137

Alternate ID(s):: OSTI ID: 3013926

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 44 Vol. 64; ISSN 0020-1669; ISSN 1520-510X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (38)

Synthesis of Wurtzite Cu₂ZnGeSe₄ Nanocrystals and their Thermoelectric Properties Xue, Ding‐Jiang; Jiao, Fei; Yan, Hui‐Juan Chemistry – An Asian Journal, Vol. 8, Issue 10 https://doi.org/10.1002/asia.201300425	journal	June 2013
Polymorphic Metastability in Colloidal Semiconductor Nanocrystals Tappan, Bryce A.; Brutchey, Richard L. ChemNanoMat, Vol. 6, Issue 11 https://doi.org/10.1002/cnma.202000406	journal	September 2020
Use and misuse of the Kubelka-Munk function to obtain the band gap energy from diffuse reflectance measurements Landi, Salmon; Segundo, Iran Rocha; Freitas, Elisabete Solid State Communications, Vol. 341 https://doi.org/10.1016/j.ssc.2021.114573	journal	January 2022
Diorganyl Dichalcogenides as Useful Synthons for Colloidal Semiconductor Nanocrystals Brutchey, Richard L. Accounts of Chemical Research, Vol. 48, Issue 11 https://doi.org/10.1021/acs.accounts.5b00362	journal	October 2015
Synthesis, Crystal Structure, and Physical Properties of Two Polymorphs of CsGaSe ₂ , and High-Temperature X-ray Diffraction Study of the Phase Transition Kinetics Friedrich, Daniel; Schlosser, Marc; Pfitzner, Arno Crystal Growth & Design, Vol. 16, Issue 7 https://doi.org/10.1021/acs.cgd.6b00532	journal	May 2016
Colloidal Nanoparticles of a Metastable Copper Selenide Phase with Near-Infrared Plasmon Resonance Lord, Robert W.; Fanghanel, Julian; Holder, Cameron F. Chemistry of Materials, Vol. 32, Issue 23 https://doi.org/10.1021/acs.chemmater.0c04058	journal	November 2020
High-Pressure Phase Transition of Metastable Wurtzite-Like CuInSe₂ Nanocrystals Bang, Shinhyo; Liu, Juejing; Wang, Bipeng Chemistry of Materials, Vol. 37, Issue 7 https://doi.org/10.1021/acs.chemmater.5c00152	journal	March 2025
Phase-Controlled Colloidal Syntheses of Iron Sulfide Nanocrystals via Sulfur Precursor Reactivity and Direct Pyrite Precipitation Rhodes, Jordan M.; Jones, Caleb A.; Thal, Lucas B. Chemistry of Materials, Vol. 29, Issue 19 https://doi.org/10.1021/acs.chemmater.7b03550	journal	September 2017
Utilizing Diselenide Precursors toward Rationally Controlled Synthesis of Metastable CuInSe ₂ Nanocrystals Tappan, Bryce A.; Barim, Gözde; Kwok, Jacky C. Chemistry of Materials, Vol. 30, Issue 16 https://doi.org/10.1021/acs.chemmater.8b02205	journal	July 2018
Direct Synthesis of Novel Cu _{2– x} Se Wurtzite Phase Hernández-Pagán, Emil A.; Robinson, Evan H.; La Croix, Andrew D. Chemistry of Materials, Vol. 31, Issue 12 https://doi.org/10.1021/acs.chemmater.9b02019	journal	May 2019
Synthesis and Characterization of CuZnSe₂ Nanocrystals in Wurtzite, Zinc Blende, and Core–Shell Polytypes Ren, Huan; Wang, Miao; Li, Zhe Chemistry of Materials, Vol. 31, Issue 24 https://doi.org/10.1021/acs.chemmater.9b03063	journal	November 2019
Ligand-Mediated Phase Control in Colloidal AgInSe ₂ Nanocrystals Tappan, Bryce A.; Horton, Matthew K.; Brutchey, Richard L. Chemistry of Materials, Vol. 32, Issue 7 https://doi.org/10.1021/acs.chemmater.9b05163	journal	March 2020
Formation Pathway of Wurtzite-like Cu₂ZnSnSe₄ Nanocrystals Tappan, Bryce A.; Crans, Kyle D.; Brutchey, Richard L. Inorganic Chemistry, Vol. 60, Issue 22 https://doi.org/10.1021/acs.inorgchem.1c02506	journal	November 2021
Molecular Decomposition Routes of Diaryl Diselenide Precursors in Relation to the Phase Determination of Copper Selenides Koziel, Alexandra C.; Goldfarb, Ralston B.; Endres, Emma J. Inorganic Chemistry, Vol. 61, Issue 37 https://doi.org/10.1021/acs.inorgchem.2c02042	journal	September 2022
In Situ X-ray Diffraction Study of the Thermal Decomposition of Selenogallates Cs ₂ [Ga ₂ (Se ₂ ) _{2– x} Se _{2+ x} ] ( x = 0, 1, 2) Friedrich, Daniel; Schlosser, Marc; Näther, Christian Inorganic Chemistry, Vol. 57, Issue 9 https://doi.org/10.1021/acs.inorgchem.8b00324	journal	April 2018
Polytypic Zn–(In,Ga)–Se Nanocrystals with Tunable Emission Sun, Zhaohong; Baluyot-Reyes, Nina; Zamarripa, Karla Nano Letters, Vol. 25, Issue 39 https://doi.org/10.1021/acs.nanolett.5c03311	journal	September 2025
General Synthesis of Wurtzite Cu-Based Quaternary Selenide Nanocrystals via the Colloidal Method Chen, Song; Zu, Bingqian; Jin, Qiren ACS Applied Materials & Interfaces, Vol. 17, Issue 16 https://doi.org/10.1021/acsami.5c04244	journal	April 2025
Discovery of a Wurtzite-like Cu ₂ FeSnSe ₄ Semiconductor Nanocrystal Polymorph and Implications for Related CuFeSe ₂ Materials Tappan, Bryce A.; Chu, Weibin; Mecklenburg, Matthew ACS Nano, Vol. 15, Issue 8 https://doi.org/10.1021/acsnano.1c03974	journal	August 2021
Alkaline Earth-Based Ternary Chalcogenide Nanocrystals: Cadmium- and Lead-Free Optical Materials Pavel, Md Riad Sarkar; Santhiran, Anuluxan; Dalberg, Seth ACS Nano, Vol. 19, Issue 37 https://doi.org/10.1021/acsnano.5c10309	journal	September 2025
Colloidal AInSe₂ (A = K, Rb, Cs) Nanocrystals with Tunable Crystal and Band Structures Sun, Zhaohong; Perez, Carlos Mora; Prezhdo, Oleg V. ACS Nanoscience Au, Vol. 4, Issue 6 https://doi.org/10.1021/acsnanoscienceau.4c00022	journal	October 2024
Synthesis of Metastable Wurtzite CuInSe ₂ Nanocrystals Norako, Michelle E.; Brutchey, Richard L. Chemistry of Materials, Vol. 22, Issue 5 https://doi.org/10.1021/cm100341r	journal	March 2010
Solution-Phase Synthesis of Highly Conductive Tungsten Diselenide Nanosheets Antunez, Priscilla D.; Webber, David H.; Brutchey, Richard L. Chemistry of Materials, Vol. 25, Issue 12 https://doi.org/10.1021/cm400790z	journal	June 2013
Absolute electronegativity and hardness: application to inorganic chemistry Pearson, Ralph G. Inorganic Chemistry, Vol. 27, Issue 4 https://doi.org/10.1021/ic00277a030	journal	February 1988
Synthesis of Monodispersed Wurtzite Structure CuInSe ₂ Nanocrystals and Their Application in High-Performance Organic−Inorganic Hybrid Photodetectors Wang, Jian-Jun; Wang, Yong-Qing; Cao, Fei-Fei Journal of the American Chemical Society, Vol. 132, Issue 35 https://doi.org/10.1021/ja1057955	journal	September 2010
Synthesis of Shape-Controlled Monodisperse Wurtzite CuIn _x Ga _{1– x} S ₂ Semiconductor Nanocrystals with Tunable Band Gap Wang, Yu-Hsiang A.; Zhang, Xiaoyan; Bao, Ningzhong Journal of the American Chemical Society, Vol. 133, Issue 29 https://doi.org/10.1021/ja203933e	journal	July 2011
Synthesis and Characterization of Wurtzite-Phase Copper Tin Selenide Nanocrystals Norako, Michelle E.; Greaney, Matthew J.; Brutchey, Richard L. Journal of the American Chemical Society, Vol. 134, Issue 1 https://doi.org/10.1021/ja206929s	journal	December 2011
Complete Colloidal Synthesis of Cu ₂ SnSe ₃ Nanocrystals with Crystal Phase and Shape Control Wang, Jian-jun; Liu, Pai; Seaton, Colin C. Journal of the American Chemical Society, Vol. 136, Issue 22 https://doi.org/10.1021/ja501591n	journal	April 2014
Predictive Synthesis of Copper Selenides Using a Multidimensional Phase Map Constructed with a Data-Driven Classifier Williamson, Emily M.; Sun, Zhaohong; Tappan, Bryce A. Journal of the American Chemical Society, Vol. 145, Issue 32 https://doi.org/10.1021/jacs.3c05490	journal	August 2023
Band Gap Engineering and Metastable Phase Discovery in Cu₂BaSnS_4–xSe_x Nanocrystals via Topotactic Anion Exchange Sun, Zhaohong; Chen, Yizhen; Brutchey, Richard L. Journal of the American Chemical Society, Vol. 147, Issue 24 https://doi.org/10.1021/jacs.5c07324	journal	June 2025
Sequential Cation Exchange in Nanocrystals: Preservation of Crystal Phase and Formation of Metastable Phases Li, Hongbo; Zanella, Marco; Genovese, Alessandro Nano Letters, Vol. 11, Issue 11 https://doi.org/10.1021/nl202927a	journal	November 2011
Shape-Programmed Nanofabrication: Understanding the Reactivity of Dichalcogenide Precursors Guo, Yijun; Alvarado, Samuel R.; Barclay, Joshua D. ACS Nano, Vol. 7, Issue 4 https://doi.org/10.1021/nn400596e	journal	April 2013
Wurtzite Cu2ZnSnSe4 nanocrystals for high-performance organic–inorganic hybrid photodetectors Wang, Jian-Jun; Hu, Jin-Song; Guo, Yu-Guo NPG Asia Materials, Vol. 4, Issue 1 https://doi.org/10.1038/am.2012.2	journal	January 2012
Polymorphism of CsGaS ₂ – structural characterization of a new two-dimensional polymorph and study of the phase-transition kinetics Friedrich, D.; Schlosser, M.; Weihrich, R. Inorganic Chemistry Frontiers, Vol. 4, Issue 2 https://doi.org/10.1039/C6QI00462H	journal	January 2017
Using ligands to control reactivity, size and phase in the colloidal synthesis of WSe ₂ nanocrystals Geisenhoff, Jessica Q.; Tamura, Ashley K.; Schimpf, Alina M. Chemical Communications, Vol. 55, Issue 60 https://doi.org/10.1039/C9CC03326B	journal	January 2019
Colloidal synthesis of ultrathin KFeS₂ and RbFeS₂ magnetic nanowires with non-van der Waals 1D structures Sun, Zhaohong; Pham, Ngoc; Derakhshan, Shahab Chemical Science, Vol. 16, Issue 40 https://doi.org/10.1039/D5SC04592D	journal	January 2025
The Rietveld Method Young, R. A. https://doi.org/10.1093/oso/9780198555773.001.0001	book	April 1993
Profex : a graphical user interface for the Rietveld refinement program BGMN Doebelin, Nicola; Kleeberg, Reinhard Journal of Applied Crystallography, Vol. 48, Issue 5 https://doi.org/10.1107/S1600576715014685	journal	August 2015
Darstellung und Kristallstruktur des Cs₂Se₅ mit einer Anmerkung zum Rb₂TeSe₄ Kretschmann, Uwe; Böttcher, Peter Zeitschrift für Naturforschung B, Vol. 40, Issue 7 https://doi.org/10.1515/znb-1985-0708	journal	July 1985

Similar Records

Utilizing Diselenide Precursors toward Rationally Controlled Synthesis of Metastable CuInSe₂ Nanocrystals

Journal Article · Sun Jul 29 20:00:00 EDT 2018 · Chemistry of Materials · OSTI ID:1582646

Polymorphic Metastability in Colloidal Semiconductor Nanocrystals

Journal Article · Sun Aug 23 20:00:00 EDT 2020 · ChemNanoMat · OSTI ID:1780901

Related Subjects

Cancer
Chalcogenides
Nanocrystals
Phase transitions
Precursors

Polymorphic Control of CsGaE2 (E = S, Se) Using Diorganyl Dichalcogenide Precursors

Citation Formats

References (38)

Similar Records

Related Subjects

Polymorphic Control of CsGaE₂ (E = S, Se) Using Diorganyl Dichalcogenide Precursors