Surface-Engineered MXenes: Electric Field Control of Magnetism and Enhanced Magnetic Anisotropy

Frey, Nathan C.; Bandyopadhyay, Arkamita; Kumar, Hemant; Anasori, Babak; Gogotsi, Yury; Shenoy, Vivek B.

doi:10.1021/acsnano.8b09201

Title: Surface-Engineered MXenes: Electric Field Control of Magnetism and Enhanced Magnetic Anisotropy

Journal Article · Thu Jan 17 00:00:00 EST 2019 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.8b09201· OSTI ID:1774202

^[1]; Bandyopadhyay, Arkamita ^[1]; Kumar, Hemant ^[1];

^[2]; Gogotsi, Yury ^[2]; Shenoy, Vivek B. ^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Drexel Univ., Philadelphia, PA (United States). A. J. Drexel Nanotechnology Inst.

Controlling magnetism in two-dimensional (2D) materials via electric fields and doping enables robust long-range order by providing an external mechanism to modulate magnetic exchange interactions and anisotropy. Here in this report, we predict that transition metal carbide and nitride MXenes are promising candidates for controllable magnetic 2D materials. The surface terminations introduced during synthesis act as chemical dopants that influence the electronic structure, enabling controllable magnetic order. We show ground-state magnetic ordering in Janus M₂XO_xF_2–x (M is an early transition metal, X is carbon or nitrogen, and x = 0.5, 1, or 1.5) with asymmetric surface functionalization, where local structural and chemical disorder induces magnetic ordering in some systems that are nonmagnetic or weakly magnetic in their pristine form. The resulting magnetic states of these noncentrosymmetric structures can be robustly switched and stabilized by tuning the interlayer exchange couplings with small applied electric fields. Furthermore, bond directionality is enhanced by Janus functionalization, resulting in improved magnetic anisotropy, which is essential to stable 2D magnetic ordering. The mixed termination-induced anisotropy leads to robust Ising ferromagnetism with an out-of-plane easy axis over the full range of relevant termination compositions for Janus Mn₂N. Janus Cr₂C, V₂C, and Ti₂C were found to be robustly antiferromagnetic. Our results provide a strategy for exploiting asymmetric surface functionalization to achieve room-temperature nanoscale magnetism under ambient conditions in MXenes with currently available synthesis techniques.

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Research Organization:: Drexel Univ., Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Army Research Office (ARO); National Science Foundation (NSF)

Grant/Contract Number:: SC0018618; W911NF-16-1-0447; CMMI-1727717; EFMA-542879

OSTI ID:: 1774202

Journal Information:: ACS Nano, Vol. 13, Issue 3; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 92 works

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References (42)

Strong ferromagnetism in hydrogenated monolayer MoS $_{2}$ tuned by strain Shi, Hongliang; Pan, Hui; Zhang, Yong-Wei Physical Review B, Vol. 88, Issue 20 https://doi.org/10.1103/PhysRevB.88.205305	journal	November 2013
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
Controlling magnetism in 2D CrI3 by electrostatic doping Jiang, Shengwei; Li, Lizhong; Wang, Zefang Nature Nanotechnology, Vol. 13, Issue 7 https://doi.org/10.1038/s41565-018-0135-x	journal	May 2018
Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes Dong, Liang; Kumar, Hemant; Anasori, Babak The Journal of Physical Chemistry Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acs.jpclett.6b02751	journal	January 2017
Absence of Ferromagnetism or Antiferromagnetism in One- or Two-Dimensional Isotropic Heisenberg Models Mermin, N. D.; Wagner, H. Physical Review Letters, Vol. 17, Issue 22 https://doi.org/10.1103/PhysRevLett.17.1133	journal	November 1966
Investigations on V ₂ C and V ₂ CX ₂ (X = F, OH) Monolayer as a Promising Anode Material for Li Ion Batteries from First-Principles Calculations Hu, Junping; Xu, Bo; Ouyang, Chuying The Journal of Physical Chemistry C, Vol. 118, Issue 42 https://doi.org/10.1021/jp507336x	journal	October 2014
Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals Gong, Cheng; Li, Lin; Li, Zhenglu Nature, Vol. 546, Issue 7657 https://doi.org/10.1038/nature22060	journal	April 2017
Robust isothermal electric control of exchange bias at room temperature He, Xi; Wang, Yi; Wu, Ning Nature Materials, Vol. 9, Issue 7 https://doi.org/10.1038/nmat2785	journal	June 2010
Mn ₂ C monolayer: a 2D antiferromagnetic metal with high Néel temperature and large spin–orbit coupling Hu, Lin; Wu, Xiaojun; Yang, Jinlong Nanoscale, Vol. 8, Issue 26 https://doi.org/10.1039/C6NR02417C	journal	January 2016
Evidence of the Existence of Magnetism in Pristine VX ₂ Monolayers (X = S, Se) and Their Strain-Induced Tunable Magnetic Properties Ma, Yandong; Dai, Ying; Guo, Meng ACS Nano, Vol. 6, Issue 2 https://doi.org/10.1021/nn204667z	journal	January 2012
Tuning Noncollinear Spin Structure and Anisotropy in Ferromagnetic Nitride MXenes Frey, Nathan C.; Kumar, Hemant; Anasori, Babak ACS Nano, Vol. 12, Issue 6 https://doi.org/10.1021/acsnano.8b03472	journal	May 2018
Electronic properties and applications of MXenes: a theoretical review Khazaei, Mohammad; Ranjbar, Ahmad; Arai, Masao Journal of Materials Chemistry C, Vol. 5, Issue 10 https://doi.org/10.1039/C7TC00140A	journal	January 2017
Reversible electric control of exchange bias in a multiferroic field-effect device Wu, S. M.; Cybart, Shane A.; Yu, P. Nature Materials, Vol. 9, Issue 9 https://doi.org/10.1038/nmat2803	journal	July 2010
Stacking-Dependent Magnetism in Bilayer CrI ₃ Sivadas, Nikhil; Okamoto, Satoshi; Xu, Xiaodong Nano Letters, Vol. 18, Issue 12 https://doi.org/10.1021/acs.nanolett.8b03321	journal	November 2018
Electric-Field-Induced Magnetization Reversal in a Ferromagnet-Multiferroic Heterostructure Heron, J. T.; Trassin, M.; Ashraf, K. Physical Review Letters, Vol. 107, Issue 21 https://doi.org/10.1103/PhysRevLett.107.217202	journal	November 2011
Two-Dimensional Nanocrystals Produced by Exfoliation of Ti₃AlC₂ Naguib, Michael; Kurtoglu, Murat; Presser, Volker Advanced Materials, Vol. 23, Issue 37, p. 4248-4253 https://doi.org/10.1002/adma.201102306	journal	August 2011
Tunable Magnetism and Transport Properties in Nitride MXenes Kumar, Hemant; Frey, Nathan C.; Dong, Liang ACS Nano, Vol. 11, Issue 8 https://doi.org/10.1021/acsnano.7b02578	journal	June 2017
High temperature spin-polarized semiconductivity with zero magnetization in two-dimensional Janus MXenes He, Junjie; Lyu, Pengbo; Sun, L. Z. Journal of Materials Chemistry C, Vol. 4, Issue 27 https://doi.org/10.1039/C6TC01287F	journal	January 2016
Hybrid density functional study of structural and electronic properties of functionalized Ti $_{n + 1} X_{n}$ ( $X = C$ , N) monolayers Xie, Yu; Kent, P. R. C. Physical Review B, Vol. 87, Issue 23 https://doi.org/10.1103/PhysRevB.87.235441	journal	June 2013
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
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
Electrical control of 2D magnetism in bilayer CrI3 Huang, Bevin; Clark, Genevieve; Klein, Dahlia R. Nature Nanotechnology, Vol. 13, Issue 7 https://doi.org/10.1038/s41565-018-0121-3	journal	April 2018
Magnetism of Ta dichalcogenide monolayers tuned by strain and hydrogenation Manchanda, Priyanka; Sharma, Vinit; Yu, Hongbin Applied Physics Letters, Vol. 107, Issue 3 https://doi.org/10.1063/1.4927286	journal	July 2015
First-principles prediction of redox potentials in transition-metal compounds with $LDA + U$ Zhou, F.; Cococcioni, M.; Marianetti, C. A. Physical Review B, Vol. 70, Issue 23 https://doi.org/10.1103/PhysRevB.70.235121	journal	December 2004
Half-Metallic Antiferromagnets van Leuken, H.; de Groot, R. A. Physical Review Letters, Vol. 74, Issue 7 https://doi.org/10.1103/PhysRevLett.74.1171	journal	February 1995
25th Anniversary Article: MXenes: A New Family of Two-Dimensional Materials Naguib, Michael; Mochalin, Vadym N.; Barsoum, Michel W. Advanced Materials, Vol. 26, Issue 7, p. 992-1005 https://doi.org/10.1002/adma.201304138	journal	December 2013
Manipulation of electronic and magnetic properties of M ₂ C (M = Hf, Nb, Sc, Ta, Ti, V, Zr) monolayer by applying mechanical strains Zhao, Shijun; Kang, Wei; Xue, Jianming Applied Physics Letters, Vol. 104, Issue 13 https://doi.org/10.1063/1.4870515	journal	March 2014
Low temperature solution synthesis of reduced two dimensional Ti ₃ C ₂ MXenes with paramagnetic behaviour Yoon, Yeoheung; Le, Thi Anh; Tiwari, Anand P. Nanoscale, Vol. 10, Issue 47 https://doi.org/10.1039/C8NR06854B	journal	January 2018
Formation enthalpies by mixing GGA and GGA $+$ $U$ calculations Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045115	journal	July 2011
Strong room-temperature ferromagnetism in VSe2 monolayers on van der Waals substrates Bonilla, Manuel; Kolekar, Sadhu; Ma, Yujing Nature Nanotechnology, Vol. 13, Issue 4 https://doi.org/10.1038/s41565-018-0063-9	journal	February 2018
Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén Nature, Vol. 546, Issue 7657 https://doi.org/10.1038/nature22391	journal	June 2017
New two-dimensional Mn-based MXenes with room-temperature ferromagnetism and half-metallicity He, Junjie; Lyu, Pengbo; Nachtigall, Petr Journal of Materials Chemistry C, Vol. 4, Issue 47 https://doi.org/10.1039/C6TC03917K	journal	January 2016
Cr ₂ TiC ₂ -based double MXenes: novel 2D bipolar antiferromagnetic semiconductor with gate-controllable spin orientation toward antiferromagnetic spintronics He, Junjie; Ding, Guangqian; Zhong, Chengyong Nanoscale, Vol. 11, Issue 1 https://doi.org/10.1039/C8NR07692H	journal	January 2019
Control of MXenes’ electronic properties through termination and intercalation Hart, James L.; Hantanasirisakul, Kanit; Lang, Andrew C. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-08169-8	journal	January 2019
Electronic and Optical Properties of 2D Transition Metal Carbides and Nitrides (MXenes) Hantanasirisakul, Kanit; Gogotsi, Yury Advanced Materials, Vol. 30, Issue 52 https://doi.org/10.1002/adma.201804779	journal	November 2018
Fully unconstrained noncollinear magnetism within the projector augmented-wave method Hobbs, D.; Kresse, G.; Hafner, J. Physical Review B, Vol. 62, Issue 17 https://doi.org/10.1103/PhysRevB.62.11556	journal	November 2000
Tensile strain induced switching of magnetic states in NbSe ₂ and NbS ₂ single layers Xu, Ying; Liu, Xiaofei; Guo, Wanlin Nanoscale, Vol. 6, Issue 21 https://doi.org/10.1039/C4NR01486C	journal	January 2014
2D metal carbides and nitrides (MXenes) for energy storage Anasori, Babak; Lukatskaya, Maria R.; Gogotsi, Yury Nature Reviews Materials, Vol. 2, Issue 2 https://doi.org/10.1038/natrevmats.2016.98	journal	January 2017
Electric-field control of local ferromagnetism using a magnetoelectric multiferroic Chu, Ying-Hao; Martin, Lane W.; Holcomb, Mikel B. Nature Materials, Vol. 7, Issue 6, p. 478-482 https://doi.org/10.1038/nmat2184	journal	April 2008
Control of magnetism by electric fields Matsukura, Fumihiro; Tokura, Yoshinori; Ohno, Hideo Nature Nanotechnology, Vol. 10, Issue 3 https://doi.org/10.1038/nnano.2015.22	journal	March 2015
Half-Metallic Ferromagnetism and Surface Functionalization-Induced Metal–Insulator Transition in Graphene-like Two-Dimensional Cr ₂ C Crystals Si, Chen; Zhou, Jian; Sun, Zhimei ACS Applied Materials & Interfaces, Vol. 7, Issue 31 https://doi.org/10.1021/acsami.5b05401	journal	August 2015
Monolayer MXenes: promising half-metals and spin gapless semiconductors Gao, Guoying; Ding, Guangqian; Li, Jie Nanoscale, Vol. 8, Issue 16 https://doi.org/10.1039/C6NR01333C	journal	January 2016

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Control of spintronic and electronic properties of bimetallic and vacancy-ordered vanadium carbide MXenes via surface functionalization Li, Shuo; He, Junjie; Nachtigall, Petr Physical Chemistry Chemical Physics, Vol. 21, Issue 46 https://doi.org/10.1039/c9cp05638f	journal	January 2019
Direction-control of anisotropic electronic behaviors via ferroelasticity in two-dimensional α-MPI (M = Zr, Hf) Zhang, Ting; Ma, Yandong; Yu, Lin Materials Horizons, Vol. 6, Issue 9 https://doi.org/10.1039/c9mh00633h	journal	January 2019
Control of spintronic and electronic properties of bimetallic and vacancy-ordered vanadium carbide MXenes via surface functionalization Li, Shuo; He, Junjie; Nachtigall, Petr arXiv https://doi.org/10.48550/arxiv.1910.01509	text	January 2019

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Title: Surface-Engineered MXenes: Electric Field Control of Magnetism and Enhanced Magnetic Anisotropy

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