Cr silicate as a prototype for engineering magnetic phases in air-stable two-dimensional transition-metal silicates

Doudin, Nassar; Saritas, Kayahan; Zheng, Jin-Cheng; Boscoboinik, J. Anibal; Sadowski, Jerzy T.; Shafer, Padraic; N’Diaye, Alpha T.; Li, Min; Ismail-Beigi, Sohrab; Altman, Eric I.

doi:10.1088/2053-1583/acf0d1

Title: Cr silicate as a prototype for engineering magnetic phases in air-stable two-dimensional transition-metal silicates

Journal Article · Tue Aug 29 00:00:00 EDT 2023 · 2D Materials

DOI:https://doi.org/10.1088/2053-1583/acf0d1· OSTI ID:1997292

;

; Li, Min;

;

Abstract Identifying environmentally inert, ferromagnetic two-dimensional (2D) materials with high Curie temperatures ( T _c ) down to the single layer limit has been an obstacle to fundamental studies of 2D magnetism and application of 2D heterostructures to spin-polarized devices. To address this challenge, the growth, structure and magnetic properties of a 2D Cr-silicate single layer on Pt(111) was investigated experimentally and theoretically. The layer was grown by sequentially depositing SiO and Cr followed by annealing in O ₂ . Scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and low energy electron microscopy all indicated a well-ordered layer that uniformly covered the surface, with STM and LEED indicating that the silicate relaxed to its favored lattice constant. Further experimental characterizations demonstrated that the Cr was nominally 3+ but with a lower electron density than typical trivalent Cr compounds. Comparison with theory identified a Cr ₂ Si ₂ O ₉ structure that resembles a single layer of a dehydrogenated dioctahedral silicate. Magnetic circular dichroism in x-ray absorption spectroscopy revealed a ferromagnetically ordered state up to at least 80 K. Theoretical analysis revealed that the Cr in a dehydrogenated Cr-silicate/Pt(111) is more oxidized than Cr in freestanding Cr ₂ Si ₂ O ₉ H ₄ layers. This greater oxidation was found to enhance ferromagnetic coupling and suggests that the magnetism may be tuned by doping. The 2D Cr-silicate is the first member of a broad series of possible layered first-row transition metal silicates with magnetic order; thus, this paper introduces a new platform for investigating 2D ferromagnetism and the development of magnetoelectronic and spintronic devices by stacking 2D atomic layers.

View Journal Article

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); US Army Research Office (ARO)

Grant/Contract Number:: SC0012704; AC02-05CH11231; W911NF19-1-0371

OSTI ID:: 1997292

Alternate ID(s):: OSTI ID: 1996614

Report Number(s):: BNL-224708-2023-JAAM

Journal Information:: 2D Materials, Journal Name: 2D Materials Vol. 10 Journal Issue: 4; ISSN 2053-1583

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (63)

Observing the oxidation of platinum van Spronsen, Matthijs A.; Frenken, Joost W. M.; Groot, Irene M. N. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00643-z	journal	September 2017
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
Room-temperature intrinsic ferromagnetism in epitaxial CrTe2 ultrathin films Zhang, Xiaoqian; Lu, Qiangsheng; Liu, Wenqing Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22777-x	journal	May 2021
Piezoelectric properties in two-dimensional materials: Simulations and experiments Hinchet, Ronan; Khan, Usman; Falconi, Christian Materials Today, Vol. 21, Issue 6 https://doi.org/10.1016/j.mattod.2018.01.031	journal	July 2018
Epitaxial Growth of CrO ₂ Thin Films on TiO ₂ (110) Surfaces Bullen, Heather A.; Garrett, Simon J. Chemistry of Materials, Vol. 14, Issue 1 https://doi.org/10.1021/cm0105256	journal	January 2002
Work function of Pt(111) Derry, G. N.; Ji-Zhong, Zhang Physical Review B, Vol. 39, Issue 3 https://doi.org/10.1103/PhysRevB.39.1940	journal	January 1989
Ab Initio Prediction of Piezoelectricity in Two-Dimensional Materials Blonsky, Michael N.; Zhuang, Houlong L.; Singh, Arunima K. ACS Nano, Vol. 9, Issue 10 https://doi.org/10.1021/acsnano.5b03394	journal	September 2015
A Tidal Disruption Event Candidate Discovered in the Active Galactic Nucleus SDSS J022700.77-042020.6 Liu, Zhu; Li, Dongyue; Liu, He-Yang The Astrophysical Journal, Vol. 894, Issue 2 https://doi.org/10.3847/1538-4357/ab880f	journal	May 2020
Perspectives for spintronics in 2D materials Han, Wei APL Materials, Vol. 4, Issue 3 https://doi.org/10.1063/1.4941712	journal	March 2016
Interface-induced phenomena in magnetism Hellman, Frances; Hoffmann, Axel; Tserkovnyak, Yaroslav Reviews of Modern Physics, Vol. 89, Issue 2 https://doi.org/10.1103/RevModPhys.89.025006	journal	June 2017
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
Two-dimensional valleytronic semiconductor with spontaneous spin and valley polarization in single-layer Cr2Se3 He, Zhonglin; Peng, Rui; Feng, Xiangyu Physical Review B, Vol. 104, Issue 7 https://doi.org/10.1103/PhysRevB.104.075105	journal	August 2021
2D materials and van der Waals heterostructures Novoselov, K. S.; Mishchenko, A.; Carvalho, A. Science, Vol. 353, Issue 6298 https://doi.org/10.1126/science.aac9439	journal	July 2016
Chemically Exfoliated VSe ₂ Monolayers with Room‐Temperature Ferromagnetism Yu, Wei; Li, Jing; Herng, Tun Seng Advanced Materials, Vol. 31, Issue 40 https://doi.org/10.1002/adma.201903779	journal	August 2019
A high-speed variable-temperature ultrahigh vacuum scanning tunneling microscope Nakakura, C. Y.; Phanse, V. M.; Zheng, G. Review of Scientific Instruments, Vol. 69, Issue 9 https://doi.org/10.1063/1.1149224	journal	September 1998
Determination of chromium valence over the range Cr(0)–Cr(VI) by electron energy loss spectroscopy Daulton, Tyrone L.; Little, Brenda J. Ultramicroscopy, Vol. 106, Issue 7 https://doi.org/10.1016/j.ultramic.2006.02.005	journal	May 2006
Toward Complete Exfoliation of the Chemisorbed Two-Dimensional Iron Silicates on Ru(0001) via Hydrogenation Saritas, Kayahan; Altman, Eric I.; Ismail-Beigi, Sohrab The Journal of Physical Chemistry C, Vol. 126, Issue 28 https://doi.org/10.1021/acs.jpcc.2c02376	journal	July 2022
The Magnetic Genome of Two-Dimensional van der Waals Materials Wang, Qing Hua; Bedoya-Pinto, Amilcar; Blei, Mark ACS Nano, Vol. 16, Issue 5 https://doi.org/10.1021/acsnano.1c09150	journal	April 2022
Defect induced, layer-modulated magnetism in ultrathin metallic PtSe2 Avsar, Ahmet; Ciarrocchi, Alberto; Pizzochero, Michele Nature Nanotechnology, Vol. 14, Issue 7 https://doi.org/10.1038/s41565-019-0467-1	journal	June 2019
Two-dimensional magnetic materials: structures, properties and external controls Zhang, Shuqing; Xu, Runzhang; Luo, Nannan Nanoscale, Vol. 13, Issue 3 https://doi.org/10.1039/D0NR06813F	journal	January 2021
Linear spin wave theory for single-Q incommensurate magnetic structures Toth, S.; Lake, B. Journal of Physics: Condensed Matter, Vol. 27, Issue 16 https://doi.org/10.1088/0953-8984/27/16/166002	journal	March 2015
Time-dependent density functional theory applied to x-ray absorption spectroscopy Bunău, Oana; Joly, Yves Physical Review B, Vol. 85, Issue 15 https://doi.org/10.1103/PhysRevB.85.155121	journal	April 2012
Magnetic properties of sheet silicates; 2:1 layer minerals Ballet, O.; Coey, J. M. D. Physics and Chemistry of Minerals, Vol. 8, Issue 5 https://doi.org/10.1007/BF00309481	journal	October 1982
NIH Image to ImageJ: 25 years of image analysis Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W. Nature Methods, Vol. 9, Issue 7 https://doi.org/10.1038/nmeth.2089	journal	June 2012
Degradation Chemistry and Kinetic Stabilization of Magnetic CrI₃ Zhang, Taiming; Grzeszczyk, Magdalena; Li, Jing Journal of the American Chemical Society, Vol. 144, Issue 12 https://doi.org/10.1021/jacs.1c08906	journal	March 2022
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Raman spectroscopy of atomically thin two-dimensional magnetic iron phosphorus trisulfide (FePS ₃ ) crystals Wang, Xingzhi; Du, Kezhao; Fredrik Liu, Yu Yang 2D Materials, Vol. 3, Issue 3 https://doi.org/10.1088/2053-1583/3/3/031009	journal	August 2016
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Two-dimensional magnetic crystals and emergent heterostructure devices Gong, Cheng; Zhang, Xiang Science, Vol. 363, Issue 6428 https://doi.org/10.1126/science.aav4450	journal	February 2019
Support effects on the atomic structure of ultrathin silica films on metals Yu, Xin; Yang, Bing; Anibal Boscoboinik, Jorge Applied Physics Letters, Vol. 100, Issue 15 https://doi.org/10.1063/1.3703609	journal	April 2012
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
X-ray absorption near-edge structure calculations beyond the muffin-tin approximation Joly, Y. Physical Review B, Vol. 63, Issue 12 https://doi.org/10.1103/PhysRevB.63.125120	journal	March 2001
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
2D Quantum materials: Magnetism and superconductivity Milošević, M. V.; Mandrus, D. Journal of Applied Physics, Vol. 130, Issue 18 https://doi.org/10.1063/5.0075774	journal	November 2021
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
Intrinsic Piezoelectricity in Two-Dimensional Materials Duerloo, Karel-Alexander N.; Ong, Mitchell T.; Reed, Evan J. The Journal of Physical Chemistry Letters, Vol. 3, Issue 19 https://doi.org/10.1021/jz3012436	journal	September 2012
Piezoelectric ferromagnetism in two-dimensional materials via materials screening Saritas, Kayahan; Ismail-Beigi, Sohrab Physical Review B, Vol. 106, Issue 13 https://doi.org/10.1103/PhysRevB.106.134421	journal	October 2022
Tuning two-dimensional phase formation through epitaxial strain and growth conditions: silica and silicate on Ni _x Pd _1−x (111) alloy substrates Zhou, Chao; Liang, Xin; Hutchings, Gregory S. Nanoscale, Vol. 11, Issue 44 https://doi.org/10.1039/C9NR05944J	journal	January 2019
Ambient pressure x-ray photoelectron spectroscopy study of water formation and adsorption under two-dimensional silica and aluminosilicate layers on Pd(111) Jhang, Jin-Hao; Boscoboinik, J. Anibal; Altman, Eric I. The Journal of Chemical Physics, Vol. 152, Issue 8 https://doi.org/10.1063/1.5142621	journal	February 2020
Magnetic Two-Dimensional Chromium Trihalides: A Theoretical Perspective Soriano, D.; Katsnelson, M. I.; Fernández-Rossier, J. Nano Letters, Vol. 20, Issue 9 https://doi.org/10.1021/acs.nanolett.0c02381	journal	July 2020
Quantum Density Oscillations in an Inhomogeneous Electron Gas Kohn, W.; Sham, L. J. Physical Review, Vol. 137, Issue 6A https://doi.org/10.1103/PhysRev.137.A1697	journal	March 1965
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
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Band theory and Mott insulators: Hubbard U instead of Stoner I Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K. Physical Review B, Vol. 44, Issue 3, p. 943-954 https://doi.org/10.1103/PhysRevB.44.943	journal	July 1991
Vanishing Fe 3d orbital moments in single-crystalline magnetite Goering, E.; Gold, S.; Lafkioti, M. Europhysics Letters (EPL), Vol. 73, Issue 1 https://doi.org/10.1209/epl/i2005-10359-8	journal	January 2006
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
Ising-Type Magnetic Ordering in Atomically Thin FePS ₃ Lee, Jae-Ung; Lee, Sungmin; Ryoo, Ji Hoon Nano Letters, Vol. 16, Issue 12 https://doi.org/10.1021/acs.nanolett.6b03052	journal	November 2016
Photoreduction of Hexavalent Chromium during X‐Ray Photoelectron Spectroscopy Analysis of Electrochemical and Thermal Films Halada, Gary P.; Clayton, Clive R. Journal of The Electrochemical Society, Vol. 138, Issue 10 https://doi.org/10.1149/1.2085340	journal	October 1991
Two-Dimensional Ultrathin Silica Films Zhong, Jian-Qiang; Freund, Hans-Joachim Chemical Reviews, Vol. 122, Issue 13 https://doi.org/10.1021/acs.chemrev.1c00995	journal	June 2022
X-ray photoelectron spectroscopic studies of CrO2 and some related chromium compounds Ikemoto, Isao; Ishii, Kikujiro; Kinoshita, Shuichi Journal of Solid State Chemistry, Vol. 17, Issue 4 https://doi.org/10.1016/S0022-4596(76)80012-6	journal	January 1976
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
Evolution of interlayer and intralayer magnetism in three atomically thin chromium trihalides Kim, Hyun Ho; Yang, Bowen; Li, Siwen Proceedings of the National Academy of Sciences, Vol. 116, Issue 23 https://doi.org/10.1073/pnas.1902100116	journal	May 2019
Magnetism and piezoelectricity in stable transition metal silicate monolayers Saritas, Kayahan; Doudin, Nassar; Altman, Eric I. Physical Review Materials, Vol. 5, Issue 10 https://doi.org/10.1103/PhysRevMaterials.5.104002	journal	October 2021
Experimental and theoretical investigation of the formation of two-dimensional Fe silicate on Pd(111) Doudin, Nassar; Saritas, Kayahan; Ismail-Beigi, Sohrab Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 39, Issue 6 https://doi.org/10.1116/6.0001397	journal	November 2021
Correlations in the electronic structure of half-metallic ferromagnetic ${CrO}_{2}$ films: An x-ray absorption and resonant photoemission spectroscopy study Dedkov, Yu. S.; Vinogradov, A. S.; Fonin, M. Physical Review B, Vol. 72, Issue 6 https://doi.org/10.1103/PhysRevB.72.060401	journal	August 2005
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) Neugebauer, Jörg; Scheffler, Matthias Physical Review B, Vol. 46, Issue 24 https://doi.org/10.1103/PhysRevB.46.16067	journal	December 1992
Atomic Structure of an Ultrathin Fe-Silicate Film Grown on a Metal: A Monolayer of Clay? Włodarczyk, Radosław; Sauer, Joachim; Yu, Xin Journal of the American Chemical Society, Vol. 135, Issue 51 https://doi.org/10.1021/ja408772p	journal	December 2013
Doping a Mott insulator: Physics of high-temperature superconductivity Lee, Patrick A.; Nagaosa, Naoto; Wen, Xiao-Gang Reviews of Modern Physics, Vol. 78, Issue 1 https://doi.org/10.1103/RevModPhys.78.17	journal	January 2006
Room-Temperature Ferromagnetism at an Oxide-Nitride Interface Jin, Qiao; Wang, Zhiwen; Zhang, Qinghua Physical Review Letters, Vol. 128, Issue 1 https://doi.org/10.1103/PhysRevLett.128.017202	journal	January 2022
Structure of a Two-Dimensional Silicate Layer Formed by Reaction with an Alloy Substrate Zhou, Chao; Liang, Xin; Hutchings, Gregory S. Chemistry of Materials, Vol. 31, Issue 3 https://doi.org/10.1021/acs.chemmater.8b03988	journal	January 2019
On the Hohenberg–Mermin–Wagner Theorem and Its Limitations Halperin, Bertrand I. Journal of Statistical Physics, Vol. 175, Issue 3-4 https://doi.org/10.1007/s10955-018-2202-y	journal	December 2018
Ultrathin Ti-Silicate Film on a Ru(0001) Surface Fischer, Frank Daniel; Sauer, Joachim; Yu, Xin The Journal of Physical Chemistry C, Vol. 119, Issue 27 https://doi.org/10.1021/acs.jpcc.5b04291	journal	June 2015
X-ray Magnetic Circular Dichroism: Historical Perspective and Recent Highlights Rogalev, Andrei; Wilhelm, Fabrice; Jaouen, Nicolas Magnetism: A Synchrotron Radiation Approach https://doi.org/10.1007/3-540-33242-1_4	book	January 2006

Similar Records

Real-time scanning tunneling microscopy observations of the oxidation of a Ti/Pt(111)-(2x2) surface alloy using O{sub 2} and NO{sub 2}

Journal Article · Mon Sep 15 00:00:00 EDT 2008 · Journal of Vacuum Science and Technology. A, International Journal Devoted to Vacuum, Surfaces, and Films · OSTI ID:1997292

Shuchen, Hsieh; Liu, G F; Koel, Bruce E

The growth of epitaxial iron oxides on platinum (111) as studied by X-ray photoelectron diffraction, scanning tunneling microscopy, and low energy electron diffraction

Thesis/Dissertation · Mon May 01 00:00:00 EDT 1995 · OSTI ID:1997292

Kim, Yong -Joo

Adsorption of oxygen on Pt{sub 3}Sn(110) studied by STM and LEED

Journal Article · Sat Jan 15 00:00:00 EST 2005 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:1997292

Hoheisel, M; Speller, S; Atrei, A; +2 more

Related Subjects

36 MATERIALS SCIENCE
2D materials
transition metal silicates
air stable
intrinsic magnetic order
ferromagnetism
spintronic devices

Title: Cr silicate as a prototype for engineering magnetic phases in air-stable two-dimensional transition-metal silicates

Citation Formats

References (63)

Similar Records

Related Subjects