skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl 3 crystals

Abstract

CrCl 3 is a layered insulator that undergoes a crystallographic phase transition below room temperature and orders antiferromagnetically at low temperature. Weak van der Waals bonding between the layers and ferromagnetic in-plane magnetic order make it a promising material for obtaining atomically thin magnets and creating van der Waals heterostructures. In this work we have grown crystals of CrCl 3, revisited the structural and thermodynamic properties of the bulk material, and explored mechanical exfoliation of the crystals. We find two distinct anomalies in the heat capacity at 14 and 17 K confirming that the magnetic order develops in two stages on cooling, with ferromagnetic correlations forming before long-range antiferromagnetic order develops between them. This scenario is supported by magnetization data. A magnetic phase diagram is constructed from the heat capacity and magnetization results. We also find an anomaly in the magnetic susceptibility at the crystallographic phase transition, indicating some coupling between the magnetism and the lattice. First-principles calculations accounting for van der Waals interactions also indicate spin-lattice coupling, and find multiple nearly degenerate crystallographic and magnetic structures consistent with the experimental observations. Lastly, we demonstrate that monolayer and few-layer CrCl 3 specimens can be produced from the bulk crystals bymore » exfoliation, providing a path for the study of heterostructures and magnetism in ultrathin crystals down to the monolayer limit.« less

Authors:
 [1];  [2]; ORCiD logo [1];  [3];  [1];  [1];  [2];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Washington, Seattle, WA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); The Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1376459
Alternate Identifier(s):
OSTI ID: 1364213; OSTI ID: 1376530
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 1; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

McGuire, Michael A., Clark, Genevieve, KC, Santosh, Chance, W. Michael, Jellison, Jr., Gerald E., Cooper, Valentino R., Xu, Xiaodong, and Sales, Brian C. Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl3 crystals. United States: N. p., 2017. Web. doi:10.1103/PhysRevMaterials.1.014001.
McGuire, Michael A., Clark, Genevieve, KC, Santosh, Chance, W. Michael, Jellison, Jr., Gerald E., Cooper, Valentino R., Xu, Xiaodong, & Sales, Brian C. Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl3 crystals. United States. doi:10.1103/PhysRevMaterials.1.014001.
McGuire, Michael A., Clark, Genevieve, KC, Santosh, Chance, W. Michael, Jellison, Jr., Gerald E., Cooper, Valentino R., Xu, Xiaodong, and Sales, Brian C. Mon . "Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl3 crystals". United States. doi:10.1103/PhysRevMaterials.1.014001. https://www.osti.gov/servlets/purl/1376459.
@article{osti_1376459,
title = {Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl3 crystals},
author = {McGuire, Michael A. and Clark, Genevieve and KC, Santosh and Chance, W. Michael and Jellison, Jr., Gerald E. and Cooper, Valentino R. and Xu, Xiaodong and Sales, Brian C.},
abstractNote = {CrCl3 is a layered insulator that undergoes a crystallographic phase transition below room temperature and orders antiferromagnetically at low temperature. Weak van der Waals bonding between the layers and ferromagnetic in-plane magnetic order make it a promising material for obtaining atomically thin magnets and creating van der Waals heterostructures. In this work we have grown crystals of CrCl3, revisited the structural and thermodynamic properties of the bulk material, and explored mechanical exfoliation of the crystals. We find two distinct anomalies in the heat capacity at 14 and 17 K confirming that the magnetic order develops in two stages on cooling, with ferromagnetic correlations forming before long-range antiferromagnetic order develops between them. This scenario is supported by magnetization data. A magnetic phase diagram is constructed from the heat capacity and magnetization results. We also find an anomaly in the magnetic susceptibility at the crystallographic phase transition, indicating some coupling between the magnetism and the lattice. First-principles calculations accounting for van der Waals interactions also indicate spin-lattice coupling, and find multiple nearly degenerate crystallographic and magnetic structures consistent with the experimental observations. Lastly, we demonstrate that monolayer and few-layer CrCl3 specimens can be produced from the bulk crystals by exfoliation, providing a path for the study of heterostructures and magnetism in ultrathin crystals down to the monolayer limit.},
doi = {10.1103/PhysRevMaterials.1.014001},
journal = {Physical Review Materials},
number = 1,
volume = 1,
place = {United States},
year = {2017},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The Magnetic Properties of the Iron Group Anhydrous Chlorides at Low Temperatures. I. Experimental
journal, December 1940


Liquid Exfoliation of Layered Materials
journal, June 2013

  • Nicolosi, V.; Chhowalla, M.; Kanatzidis, M. G.
  • Science, Vol. 340, Issue 6139, p. 1226419
  • DOI: 10.1126/science.1226419

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

X‐Ray Diffraction and Nuclear Quadrupole Resonance Studies of Chromium Trichloride
journal, April 1964

  • Morosin, Bruno; Narath, Albert
  • The Journal of Chemical Physics, Vol. 40, Issue 7
  • DOI: 10.1063/1.1725428

Projector augmented-wave method
journal, December 1994


Some Magnetic Properties of the Chromium ( III ) Halides at 4.2°K
journal, April 1959

  • Hansen, Wilford N.
  • Journal of Applied Physics, Vol. 30, Issue 4
  • DOI: 10.1063/1.2185944

Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks
journal, September 2015


Coupling of Crystal Structure and Magnetism in the Layered, Ferromagnetic Insulator CrI 3
journal, January 2015

  • McGuire, Michael A.; Dixit, Hemant; Cooper, Valentino R.
  • Chemistry of Materials, Vol. 27, Issue 2
  • DOI: 10.1021/cm504242t

Chemical accuracy for the van der Waals density functional
journal, December 2009

  • Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
  • Journal of Physics: Condensed Matter, Vol. 22, Issue 2
  • DOI: 10.1088/0953-8984/22/2/022201

Heat Capacity of Cr Br 3 from 14 to 360°K
journal, August 1965


CrXTe 3 (X = Si, Ge) nanosheets: two dimensional intrinsic ferromagnetic semiconductors
journal, January 2014

  • Li, Xingxing; Yang, Jinlong
  • Journal of Materials Chemistry C, Vol. 2, Issue 34
  • DOI: 10.1039/C4TC01193G

Crystallographic, magnetic and electronic structures of a new layered ferromagnetic compound Cr 2 Ge 2 Te 6
journal, January 1995


Spin-Wave Analysis of the Sublattice Magnetization Behavior of Antiferromagnetic and Ferromagnetic Cr Cl 3
journal, January 1965


Magnetic structure and phase stability of the van der Waals bonded ferromagnet Fe 3 x GeTe 2
journal, January 2016


Computational discovery of ferromagnetic semiconducting single-layer CrSnTe 3
journal, July 2015


Doping enhanced ferromagnetism and induced half-metallicity in CrI 3 monolayer
journal, May 2016


On the Magnetic Properties of a CrBr 3 Single Crystal
journal, September 1960

  • Tsubokawa, Ichiro
  • Journal of the Physical Society of Japan, Vol. 15, Issue 9
  • DOI: 10.1143/JPSJ.15.1664

Unusual Dirac half-metallicity with intrinsic ferromagnetism in vanadium trihalide monolayers
journal, January 2016

  • He, Junjie; Ma, Shuangying; Lyu, Pengbo
  • Journal of Materials Chemistry C, Vol. 4, Issue 13
  • DOI: 10.1039/C6TC00409A

Intrinsic Optical Properties of CrCl3
journal, January 1970


Van der Waals engineering of ferromagnetic semiconductor heterostructures for spin and valleytronics
journal, May 2017


van der Waals Bonding in Layered Compounds from Advanced Density-Functional First-Principles Calculations
journal, June 2012


Low-temperature crystal and magnetic structure of α RuCl 3
journal, April 2016


Two-Dimensional Materials from Data Filtering and Ab Initio Calculations
journal, July 2013


Magnetization, Resonance, and Optical Properties of the Ferromagnet CrI 3
journal, March 1965

  • Dillon, J. F.; Olson, C. E.
  • Journal of Applied Physics, Vol. 36, Issue 3
  • DOI: 10.1063/1.1714194

Exfoliating biocompatible ferromagnetic Cr-trihalide monolayers
journal, January 2016

  • Liu, Junyi; Sun, Qiang; Kawazoe, Yoshiyuki
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 13
  • DOI: 10.1039/C5CP04835D

Proximate Kitaev quantum spin liquid behaviour in a honeycomb magnet
journal, April 2016

  • Banerjee, A.; Bridges, C. A.; Yan, J. -Q.
  • Nature Materials, Vol. 15, Issue 7
  • DOI: 10.1038/nmat4604

Magnetic structure of the new layered ferromagnetic chromium hexatellurosilicate Cr2Si2Te6
journal, March 1991

  • Carteaux, V.; Ouvrard, G.; Grenier, J. C.
  • Journal of Magnetism and Magnetic Materials, Vol. 94, Issue 1-2
  • DOI: 10.1016/0304-8853(91)90121-P

Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals
journal, April 2017


Magnetic Ordering in CrCl3 at the Phase Transition
journal, July 1982


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Further measurements of the magnetic properties of some salts of the iron group at low temperatures
journal, January 1940


Van der Waals heterostructures
journal, July 2013

  • Geim, A. K.; Grigorieva, I. V.
  • Nature, Vol. 499, Issue 7459, p. 419-425
  • DOI: 10.1038/nature12385

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Fe3GeTe2 and Ni3GeTe2 – Two New Layered Transition-Metal Compounds: Crystal Structures, HRTEM Investigations, and Magnetic and Electrical Properties
journal, April 2006

  • Deiseroth, Hans-Jörg; Aleksandrov, Krasimir; Reiner, Christof
  • European Journal of Inorganic Chemistry, Vol. 2006, Issue 8
  • DOI: 10.1002/ejic.200501020

Heat Capacities of CrF 3 and CrCl 3 from 15 to 300°K
journal, May 1958

  • Hansen, Wilford N.; Griffel, Maurice
  • The Journal of Chemical Physics, Vol. 28, Issue 5
  • DOI: 10.1063/1.1744294

Magnetic Properties of Layered Itinerant Electron Ferromagnet Fe 3 GeTe 2
journal, December 2013

  • Chen, Bin; Yang, JinHu; Wang, HangDong
  • Journal of the Physical Society of Japan, Vol. 82, Issue 12
  • DOI: 10.7566/JPSJ.82.124711

Crystal and Magnetic Structures in Layered, Transition Metal Dihalides and Trihalides
journal, April 2017


Static and dynamic critical properties of the quasi-two-dimensional antiferromagnet MnPS 3
journal, September 2006


Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
journal, September 2007


Magnetic ground state of semiconducting transition-metal trichalcogenide monolayers
journal, June 2015


Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit
journal, June 2017

  • Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén
  • Nature, Vol. 546, Issue 7657
  • DOI: 10.1038/nature22391

Ultrathin nanosheets of CrSiTe 3 : a semiconducting two-dimensional ferromagnetic material
journal, January 2016

  • Lin, Ming-Wei; Zhuang, Houlong L.; Yan, Jiaqiang
  • Journal of Materials Chemistry C, Vol. 4, Issue 2
  • DOI: 10.1039/C5TC03463A

Electronic structure and magnetic ordering of the semiconducting chromium trihalides CrCl 3 , CrBr 3 , and CrI 3
journal, March 2011


Strong spin-lattice coupling in CrSiTe 3
journal, April 2015

  • Casto, L. D.; Clune, A. J.; Yokosuk, M. O.
  • APL Materials, Vol. 3, Issue 4
  • DOI: 10.1063/1.4914134

Paramagnetic Susceptibilities of the Chromium (III) Halides
journal, April 1959

  • Hansen, Wilford N.; Griffel, Maurice
  • The Journal of Chemical Physics, Vol. 30, Issue 4
  • DOI: 10.1063/1.1730125

Neutron diffraction investigation of antiferromagnetism in CrCl3
journal, April 1961

  • Cable, J. W.; Wilkinson, M. K.; Wollan, E. O.
  • Journal of Physics and Chemistry of Solids, Vol. 19, Issue 1-2
  • DOI: 10.1016/0022-3697(61)90053-1

Magnetic properties and specific heat of MPS3 (M=Mn, Fe, Zn)
journal, May 2004