Cation–Eutectic Transition via Sublattice Melting in CuInP2S6/In4/3P2S6 van der Waals Layered Crystals
Abstract
Single crystals of the van der Waals layered ferrielectric material CuInP2S6 spontaneously phase separate when synthesized with Cu deficiency. In this paper, we identify a route to form and tune intralayer heterostructures between the corresponding ferrielectric (CuInP2S6) and paraelectric (In4/3P2S6) phases through control of chemical phase separation. We conclusively demonstrate that Cu-deficient Cu1–xIn1+x/3P2S6 forms a single phase at high temperature. We also identify the mechanism by which the phase separation proceeds upon cooling. Above 500 K both Cu+ and In3+ become mobile, while P2S64– anions maintain their structure. We therefore propose that this transition can be understood as eutectic melting on the cation sublattice. Such a model suggests that the transition temperature for the melting process is relatively low because it requires only a partial reorganization of the crystal lattice. As a result, varying the cooling rate through the phase transition controls the lateral extent of chemical domains over several decades in size. At the fastest cooling rate, the dimensional confinement of the ferrielectric CuInP2S6 phase to nanoscale dimensions suppresses ferrielectric ordering due to the intrinsic ferroelectric size effect. Finally, intralayer heterostructures can be formed, destroyed, and re-formed by thermal cycling, thus enabling the possibility of finely tuned ferroic structuresmore »
- Authors:
-
[1];
[2];
[3];
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States). Aerospace Systems Directorate; UES Inc., Beavercreek, OH (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
- Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division
- Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR); National Research Council (United States)
- Contributing Org.:
- UES Inc., Beavercreek, OH (United States); Georgia Inst. of Technology, Atlanta, GA (United States)
- OSTI Identifier:
- 1376461
- Grant/Contract Number:
- AC05-00OR22725; AC02-06CH11357; 14RQ08COR
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 7; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 2D ferrielectric; 2D heterostructures; chalcogenides; sublattice melting; transition metal thiophosphate
Citation Formats
Susner, Michael A., Chyasnavichyus, Marius, Puretzky, Alexander A., He, Qian, Conner, Benjamin S., Ren, Yang, Cullen, David A., Ganesh, Panchapakesan, Shin, Dongwon, Demir, Hakan, McMurray, Jacob W., Borisevich, Albina Y., Maksymovych, Petro, and McGuire, Michael A. Cation–Eutectic Transition via Sublattice Melting in CuInP2S6/In4/3P2S6 van der Waals Layered Crystals. United States: N. p., 2017.
Web. doi:10.1021/acsnano.7b02695.
Susner, Michael A., Chyasnavichyus, Marius, Puretzky, Alexander A., He, Qian, Conner, Benjamin S., Ren, Yang, Cullen, David A., Ganesh, Panchapakesan, Shin, Dongwon, Demir, Hakan, McMurray, Jacob W., Borisevich, Albina Y., Maksymovych, Petro, & McGuire, Michael A. Cation–Eutectic Transition via Sublattice Melting in CuInP2S6/In4/3P2S6 van der Waals Layered Crystals. United States. https://doi.org/10.1021/acsnano.7b02695
Susner, Michael A., Chyasnavichyus, Marius, Puretzky, Alexander A., He, Qian, Conner, Benjamin S., Ren, Yang, Cullen, David A., Ganesh, Panchapakesan, Shin, Dongwon, Demir, Hakan, McMurray, Jacob W., Borisevich, Albina Y., Maksymovych, Petro, and McGuire, Michael A. Fri .
"Cation–Eutectic Transition via Sublattice Melting in CuInP2S6/In4/3P2S6 van der Waals Layered Crystals". United States. https://doi.org/10.1021/acsnano.7b02695. https://www.osti.gov/servlets/purl/1376461.
@article{osti_1376461,
title = {Cation–Eutectic Transition via Sublattice Melting in CuInP2S6/In4/3P2S6 van der Waals Layered Crystals},
author = {Susner, Michael A. and Chyasnavichyus, Marius and Puretzky, Alexander A. and He, Qian and Conner, Benjamin S. and Ren, Yang and Cullen, David A. and Ganesh, Panchapakesan and Shin, Dongwon and Demir, Hakan and McMurray, Jacob W. and Borisevich, Albina Y. and Maksymovych, Petro and McGuire, Michael A.},
abstractNote = {Single crystals of the van der Waals layered ferrielectric material CuInP2S6 spontaneously phase separate when synthesized with Cu deficiency. In this paper, we identify a route to form and tune intralayer heterostructures between the corresponding ferrielectric (CuInP2S6) and paraelectric (In4/3P2S6) phases through control of chemical phase separation. We conclusively demonstrate that Cu-deficient Cu1–xIn1+x/3P2S6 forms a single phase at high temperature. We also identify the mechanism by which the phase separation proceeds upon cooling. Above 500 K both Cu+ and In3+ become mobile, while P2S64– anions maintain their structure. We therefore propose that this transition can be understood as eutectic melting on the cation sublattice. Such a model suggests that the transition temperature for the melting process is relatively low because it requires only a partial reorganization of the crystal lattice. As a result, varying the cooling rate through the phase transition controls the lateral extent of chemical domains over several decades in size. At the fastest cooling rate, the dimensional confinement of the ferrielectric CuInP2S6 phase to nanoscale dimensions suppresses ferrielectric ordering due to the intrinsic ferroelectric size effect. Finally, intralayer heterostructures can be formed, destroyed, and re-formed by thermal cycling, thus enabling the possibility of finely tuned ferroic structures that can potentially be optimized for specific device architectures.},
doi = {10.1021/acsnano.7b02695},
journal = {ACS Nano},
number = 7,
volume = 11,
place = {United States},
year = {Fri Jul 07 00:00:00 EDT 2017},
month = {Fri Jul 07 00:00:00 EDT 2017}
}
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