Dynamic crystallography reveals spontaneous anisotropy in cubic GeTe

Kimber, Simon J.; Zhang, Jiayong; Liang, Charles H.; Guzmán-Verri, Gian G.; Littlewood, Peter B.; Cheng, Yongqiang; Abernathy, Douglas L.; Hudspeth, Jessica M.; Luo, Zhong-Zhen; Kanatzidis, Mercouri G.; Chatterji, Tapan; Ramirez-Cuesta, Anibal J.; Billinge, Simon L.

doi:10.1038/s41563-023-01483-7

Dynamic crystallography reveals spontaneous anisotropy in cubic GeTe

Journal Article · Sun Feb 19 23:00:00 EST 2023 · Nature Materials

DOI:https://doi.org/10.1038/s41563-023-01483-7· OSTI ID:1963580

^[1]; Zhang, Jiayong ^[2]; Liang, Charles H. ^[3]; ^[4]; Littlewood, Peter B. ^[5]; Cheng, Yongqiang ^[2]; ^[2]; Hudspeth, Jessica M. ^[6]; Luo, Zhong-Zhen ^[7]; ^[7]; Chatterji, Tapan ^[8]; ^[2]; ^[9]

Université de Bourgogne, Dijon (France)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
University of Chicago, IL (United States)
Universidad de Costa Rica, San José (Costa Rica)
University of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
European Synchrotron, Grenoble (France)
Northwestern University, Evanston, IL (United States)
Institut Laue-Langevin, Grenoble (France)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Condensed Matter Physics; Columbia University, New York, NY (United States)

Cubic energy materials such as thermoelectrics or hybrid perovskite materials are often understood to be highly disordered. In GeTe and related IV–VI compounds, this is thought to provide the low thermal conductivities needed for thermoelectric applications. Since conventional crystallography cannot distinguish between static disorder and atomic motions, we develop the energy-resolved variable-shutter pair distribution function technique. This collects structural snapshots with varying exposure times, on timescales relevant for atomic motions. In disagreement with previous interpretations, we find the time-averaged structure of GeTe to be crystalline at all temperatures, but with anisotropic anharmonic dynamics at higher temperatures that resemble static disorder at fast shutter speeds, with correlated ferroelectric fluctuations along the <100>_c direction. We show that this anisotropy naturally emerges from a Ginzburg–Landau model that couples polarization fluctuations through long-range elastic interactions. By accessing time-dependent atomic correlations in energy materials, we resolve the long-standing disagreement between local and average structure probes and show that spontaneous anisotropy is ubiquitous in cubic IV–VI materials.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF); University of Costa Rica; ISITE-BFC

Grant/Contract Number:: SC0012704; AC05-00OR22725; AC02-06CH11357; SC0014520

OSTI ID:: 1963580

Alternate ID(s):: OSTI ID: 1969333
OSTI ID: 1976009

Report Number(s):: BNL-224181-2023-JAAM

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 3 Vol. 22; ISSN 1476-1122

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Electric Control of the Giant Rashba Effect in Bulk GeTe Di Sante, Domenico; Barone, Paolo; Bertacco, Riccardo Advanced Materials, Vol. 25, Issue 4 https://doi.org/10.1002/adma.201203199	journal	October 2012
Short-Range Order of Methylammonium and Persistence of Distortion at the Local Scale in MAPbBr ₃ Hybrid Perovskite Page, Katharine; Siewenie, Joan E.; Quadrelli, Paolo Angewandte Chemie International Edition, Vol. 55, Issue 46 https://doi.org/10.1002/anie.201608602	journal	October 2016
Dynamics of the phase-change material GeTe across the structural phase transition Chatterji, T.; Rols, S.; Wdowik, U. D. Frontiers of Physics, Vol. 14, Issue 2 https://doi.org/10.1007/s11467-018-0864-1	journal	October 2018
Soft phonon mode and ferroelectricity in GeTe Steigmeier, E. F.; Harbeke, G. Solid State Communications, Vol. 8, Issue 16 https://doi.org/10.1016/0038-1098(70)90619-8	journal	August 1970
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Simulation of Inelastic Neutron Scattering Spectra Using OCLIMAX Cheng, Y. Q.; Daemen, L. L.; Kolesnikov, A. I. Journal of Chemical Theory and Computation, Vol. 15, Issue 3 https://doi.org/10.1021/acs.jctc.8b01250	journal	January 2019
Elastic Constants, Optical Phonons, and Molecular Relaxations in the High Temperature Plastic Phase of the CH ₃ NH ₃ PbBr ₃ Hybrid Perovskite Létoublon, Antoine; Paofai, Serge; Rufflé, Benoît The Journal of Physical Chemistry Letters, Vol. 7, Issue 19 https://doi.org/10.1021/acs.jpclett.6b01709	journal	September 2016
Resonant bonding leads to low lattice thermal conductivity Lee, Sangyeop; Esfarjani, Keivan; Luo, Tengfei Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4525	journal	April 2014
Phase-change materials for rewriteable data storage Wuttig, Matthias; Yamada, Noboru Nature Materials, Vol. 6, Issue 11 https://doi.org/10.1038/nmat2009	journal	November 2007
Resonant bonding in crystalline phase-change materials Shportko, Kostiantyn; Kremers, Stephan; Woda, Michael Nature Materials, Vol. 7, Issue 8 https://doi.org/10.1038/nmat2226	journal	July 2008
Giant anharmonic phonon scattering in PbTe Delaire, O.; Ma, J.; Marty, K. Nature Materials, Vol. 10, Issue 8, p. 614-619 https://doi.org/10.1038/nmat3035	journal	June 2011
Ferroelectric large polarons Miyata, Kiyoshi; Zhu, X. -Y. Nature Materials, Vol. 17, Issue 5 https://doi.org/10.1038/s41563-018-0068-7	journal	April 2018
Cooperative elastic fluctuations provide tuning of the metal–insulator transition Guzmán-Verri, G. G.; Brierley, R. T.; Littlewood, P. B. Nature, Vol. 576, Issue 7787 https://doi.org/10.1038/s41586-019-1824-9	journal	December 2019
Structural disorder in the high-temperature cubic phase of GeTe Xu, Ming; Lei, Zhenyu; Yuan, Junhui RSC Advances, Vol. 8, Issue 31 https://doi.org/10.1039/C8RA02561D	journal	January 2018
Numerical Evaluation of X‐Ray Absorption Factors for Cylindrical Samples and Annular Sample Cells Paalman, H. H.; Pings, C. J. Journal of Applied Physics, Vol. 33, Issue 8 https://doi.org/10.1063/1.1729034	journal	August 1962
The order-disorder transition in GeTe: Views from different length-scales Matsunaga, T.; Fons, P.; Kolobov, A. V. Applied Physics Letters, Vol. 99, Issue 23 https://doi.org/10.1063/1.3665067	journal	December 2011
Design and operation of the wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source Abernathy, D. L.; Stone, M. B.; Loguillo, M. J. Review of Scientific Instruments, Vol. 83, Issue 1 https://doi.org/10.1063/1.3680104	journal	January 2012
Electronic and thermal transport in GeTe: A versatile base for thermoelectric materials Levin, E. M.; Besser, M. F.; Hanus, R. Journal of Applied Physics, Vol. 114, Issue 8 https://doi.org/10.1063/1.4819222	journal	August 2013
A radial collimator for a time-of-flight neutron spectrometer Stone, M. B.; Niedziela, J. L.; Loguillo, M. J. Review of Scientific Instruments, Vol. 85, Issue 8 https://doi.org/10.1063/1.4891302	journal	August 2014
Design and operating characteristic of a vacuum furnace for time-of-flight inelastic neutron scattering measurements Niedziela, J. L.; Mills, R.; Loguillo, M. J. Review of Scientific Instruments, Vol. 88, Issue 10 https://doi.org/10.1063/1.5007089	journal	October 2017
The crystal structure of IV-VI compounds. I. Classification and description Littlewood, P. B. Journal of Physics C: Solid State Physics, Vol. 13, Issue 26 https://doi.org/10.1088/0022-3719/13/26/009	journal	September 1980
Neutron diffraction study on the structural phase transition in GeTe Chattopadhyay, T.; Boucherle, J. X.; vonSchnering, H. G. Journal of Physics C: Solid State Physics, Vol. 20, Issue 10 https://doi.org/10.1088/0022-3719/20/10/012	journal	April 1987
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals Farrow, C. L.; Juhas, P.; Liu, J. W. Journal of Physics: Condensed Matter, Vol. 19, Issue 33 https://doi.org/10.1088/0953-8984/19/33/335219	journal	July 2007
Anharmonic force constants extracted from first-principles molecular dynamics: applications to heat transfer simulations Tadano, T.; Gohda, Y.; Tsuneyuki, S. Journal of Physics: Condensed Matter, Vol. 26, Issue 22 https://doi.org/10.1088/0953-8984/26/22/225402	journal	May 2014
The interplay between Peierls distortions and metavalent bonding in IV–VI compounds: comparing GeTe with related monochalcogenides Raty, Jean-Yves; Wuttig, Matthias Journal of Physics D: Applied Physics, Vol. 53, Issue 23 https://doi.org/10.1088/1361-6463/ab7e66	journal	April 2020
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
High-precision sampling for Brillouin-zone integration in metals Methfessel, M.; Paxton, A. T. Physical Review B, Vol. 40, Issue 6 https://doi.org/10.1103/PhysRevB.40.3616	journal	August 1989
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Dynamic radial distribution function from inelastic neutron scattering McQueeney, R. J. Physical Review B, Vol. 57, Issue 17 https://doi.org/10.1103/PhysRevB.57.10560	journal	May 1998
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Influence of phonons on the pair distribution function deduced from neutron powder diffraction Reichardt, W.; Pintschovius, L. Physical Review B, Vol. 63, Issue 17 https://doi.org/10.1103/PhysRevB.63.174302	journal	April 2001
Lattice dynamics and correlated atomic motion from the atomic pair distribution function Jeong, I. -K.; Heffner, R. H.; Graf, M. J. Physical Review B, Vol. 67, Issue 10 https://doi.org/10.1103/PhysRevB.67.104301	journal	March 2003
Phase transition in crystalline GeTe: Pitfalls of averaging effects Fons, Paul; Kolobov, Alexander V.; Krbal, Milos Physical Review B, Vol. 82, Issue 15 https://doi.org/10.1103/PhysRevB.82.155209	journal	October 2010
Lattice dynamics of anharmonic solids from first principles Hellman, O.; Abrikosov, I. A.; Simak, S. I. Physical Review B, Vol. 84, Issue 18 https://doi.org/10.1103/PhysRevB.84.180301	journal	November 2011
Temperature-dependent effective third-order interatomic force constants from first principles Hellman, Olle; Abrikosov, I. A. Physical Review B, Vol. 88, Issue 14 https://doi.org/10.1103/PhysRevB.88.144301	journal	October 2013
Local off-centering symmetry breaking in the high-temperature regime of SnTe Knox, K. R.; Bozin, E. S.; Malliakas, C. D. Physical Review B, Vol. 89, Issue 1 https://doi.org/10.1103/PhysRevB.89.014102	journal	January 2014
Anharmonicity and atomic distribution of SnTe and PbTe thermoelectrics Li, C. W.; Ma, J.; Cao, H. B. Physical Review B, Vol. 90, Issue 21 https://doi.org/10.1103/PhysRevB.90.214303	journal	December 2014
Strain coupling, microstructure dynamics, and acoustic mode softening in germanium telluride Yang, D.; Chatterji, T.; Schiemer, J. A. Physical Review B, Vol. 93, Issue 14 https://doi.org/10.1103/PhysRevB.93.144109	journal	April 2016
Emphanitic anharmonicity in PbSe at high temperature and anomalous electronic properties in the Pb Q ( Q = S , Se , Te ) system Yu, Runze; Bozin, Emil S.; Abeykoon, Milinda Physical Review B, Vol. 98, Issue 14 https://doi.org/10.1103/PhysRevB.98.144108	journal	October 2018
Emergence of Long-Range Order in BaTiO 3 from Local Symmetry-Breaking Distortions Senn, M. S.; Keen, D. A.; Lucas, T. C. A. Physical Review Letters, Vol. 116, Issue 20 https://doi.org/10.1103/PhysRevLett.116.207602	journal	May 2016
Dynamic Displacement Disorder of Cubic BaTiO3 Paściak, M.; Welberry, T. R.; Kulda, J. Physical Review Letters, Vol. 120, Issue 16 https://doi.org/10.1103/PhysRevLett.120.167601	journal	April 2018
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Soft-mode spectroscopy: Experimental studies of structural phase transitions Scott, J. F. Reviews of Modern Physics, Vol. 46, Issue 1 https://doi.org/10.1103/RevModPhys.46.83	journal	January 1974
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions Juhás, P.; Davis, T.; Farrow, C. L. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813005190	journal	March 2013
The fast azimuthal integration Python library: pyFAI Ashiotis, Giannis; Deschildre, Aurore; Nawaz, Zubair Journal of Applied Crystallography, Vol. 48, Issue 2 https://doi.org/10.1107/S1600576715004306	journal	March 2015
Applications of principal component analysis to pair distribution function data Chapman, Karena W.; Lapidus, Saul H.; Chupas, Peter J. Journal of Applied Crystallography, Vol. 48, Issue 6 https://doi.org/10.1107/S1600576715016532	journal	October 2015
PDFgetN3 : atomic pair distribution functions from neutron powder diffraction data using ad hoc corrections Juhás, Pavol; Louwen, Jaap N.; van Eijck, Lambert Journal of Applied Crystallography, Vol. 51, Issue 5 https://doi.org/10.1107/S1600576718010002	journal	August 2018
Entropically Stabilized Local Dipole Formation in Lead Chalcogenides Bozin, E. S.; Malliakas, C. D.; Souvatzis, P. Science, Vol. 330, Issue 6011 https://doi.org/10.1126/science.1192759	journal	December 2010
Computer Program for Varimax Rotation in Factor Analysis Kaiser, Henry F. Educational and Psychological Measurement, Vol. 19, Issue 3 https://doi.org/10.1177/001316445901900314	journal	October 1959
Local structure and phase transitions of KNbO₃ Yoneda, Yasuhiro; Ohara, Koji; Nagata, Hajime Japanese Journal of Applied Physics, Vol. 57, Issue 11S https://doi.org/10.7567/JJAP.57.11UB07	journal	September 2018

Similar Records

Thermoelectric properties of p-type cubic and rhombohedral GeTe

Journal Article · Mon May 21 00:00:00 EDT 2018 · Journal of Applied Physics · OSTI ID:1439412

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ferroelectrics
multiferroics
thermoelectrics

Dynamic crystallography reveals spontaneous anisotropy in cubic GeTe

Citation Formats

References (52)

Similar Records

Related Subjects