Probing Defects and Spin‐Phonon Coupling in CrSBr via Resonant Raman Scattering

Torres, Kierstin; Kuc, Agnieszka; Maschio, Lorenzo; Pham, Thang; Reidy, Kate; Dekanovsky, Lukas; Sofer, Zdenek; Ross, Frances M.; Klein, Julian

doi:10.1002/adfm.202211366

Title: Probing Defects and Spin‐Phonon Coupling in CrSBr via Resonant Raman Scattering

Journal Article · Sun Jan 08 00:00:00 EST 2023 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202211366· OSTI ID:1908278

^[1];

^[2];

^[3];

^[1];

^[4];

^[1];

^[1]

Department of Materials Science and Engineering Massachusetts Institute of Technology Cambridge MA 02139 USA
Helmholtz‐Zentrum Dresden‐Rossendorf Abteilung Ressourcenökologie Forschungsstelle Leipzig Permoserstr. 15 04318 Leipzig Germany
Dipartimento di Chimica and NIS Centre Università di Torino via P. Giuria 5 I‐10125 Turin Italy
Department of Inorganic Chemistry University of Chemistry and Technology Prague Technická 5 166 28 Prague 6 Czech Republic

Abstract Understanding the stability limitations and defect formation mechanisms in 2D magnets is essential for their utilization in spintronic and memory technologies. Here, defects in mono‐ to multilayer CrSBr are correlated with structural, vibrational, and magnetic properties. Resonant Raman scattering is used to reveal distinct vibrational defect signatures. In pristine CrSBr, it is shown that bromine atoms mediate vibrational interlayer coupling, allowing for distinguishing between surface and bulk defect modes. Environmental exposure is shown to cause drastic degradation in monolayers, with the formation of intralayer defects. This is in contrast to multilayers that predominantly show bromine surface defects. Through deliberate ion irradiation, the formation of defect modes is tuned: these are strongly polarized and resonantly enhanced, reflecting the quasi‐‐1D electronic character of CrSBr. Strikingly, pronounced signatures of spin‐phonon coupling of the intrinsic phonon modes and the ion beam‐induced defect modes are observed throughout the magnetic transition temperature. Overall, defect engineering of magnetic properties is possible, with resonant Raman spectroscopy serving as a direct fingerprint of magnetic phases and defects in CrSBr.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE

OSTI ID:: 1908278

Alternate ID(s):: OSTI ID: 1961888

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Vol. 33 Journal Issue: 12; ISSN 1616-301X

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (70)

Double-slit photoelectron interference in strong-field ionization of the neon dimer Kunitski, Maksim; Eicke, Nicolas; Huber, Pia Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07882-8	journal	January 2019
U1 snRNP regulates cancer cell migration and invasion in vitro Oh, Jung-Min; Venters, Christopher C.; Di, Chao Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-13993-7	journal	January 2020
Resonance Raman scattering from defects in CdSe Arora, Akhilesh K.; Ramdas, A. K. Physical Review B, Vol. 35, Issue 9 https://doi.org/10.1103/PhysRevB.35.4345	journal	March 1987
Strong Photoluminescence Enhancement of MoS ₂ through Defect Engineering and Oxygen Bonding Nan, Haiyan; Wang, Zilu; Wang, Wenhui ACS Nano, Vol. 8, Issue 6 https://doi.org/10.1021/nn500532f	journal	May 2014
Robust valley polarization of helium ion modified atomically thin MoS ₂ Klein, J.; Kuc, A.; Nolinder, A. 2D Materials, Vol. 5, Issue 1 https://doi.org/10.1088/2053-1583/aa9642	journal	November 2017
Strong Spin-Phonon Coupling in Two-Dimensional Magnetic Semiconductor CrSBr Xu, Xiaomin; Wang, Xiaohu; Chang, Pu The Journal of Physical Chemistry C, Vol. 126, Issue 25 https://doi.org/10.1021/acs.jpcc.2c02742	journal	June 2022
Spin-Selective Hole–Exciton Coupling in a V-Doped WSe₂ Ferromagnetic Semiconductor at Room Temperature Nguyen, Lan-Anh T.; Dhakal, Krishna P.; Lee, Yuhan ACS Nano, Vol. 15, Issue 12 https://doi.org/10.1021/acsnano.1c08375	journal	November 2021
The one phonon Raman spectrum in microcrystalline silicon Richter, H.; Wang, Z. P.; Ley, L. Solid State Communications, Vol. 39, Issue 5 https://doi.org/10.1016/0038-1098(81)90337-9	journal	August 1981
Dynamic magnetic crossover at the origin of the hidden-order in van der Waals antiferromagnet CrSBr López-Paz, Sara A.; Guguchia, Zurab; Pomjakushin, Vladimir Y. Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32290-4	journal	August 2022
Precision cutting and patterning of graphene with helium ions Bell, D. C.; Lemme, M. C.; Stern, L. A. Nanotechnology, Vol. 20, Issue 45 https://doi.org/10.1088/0957-4484/20/45/455301	journal	October 2009
Defect-Induced Magnetic Skyrmion in a Two-Dimensional Chromium Triiodide Monolayer Beck, Ryan A.; Lu, Lixin; Sushko, Peter V. JACS Au, Vol. 1, Issue 9 https://doi.org/10.1021/jacsau.1c00142	journal	July 2021
Helium ion microscopy of graphene: beam damage, image quality and edge contrast Fox, D.; Zhou, Y. B.; O’Neill, A. Nanotechnology, Vol. 24, Issue 33 https://doi.org/10.1088/0957-4484/24/33/335702	journal	July 2013
Reversible strain-induced magnetic phase transition in a van der Waals magnet Cenker, John; Sivakumar, Shivesh; Xie, Kaichen Nature Nanotechnology, Vol. 17, Issue 3 https://doi.org/10.1038/s41565-021-01052-6	journal	January 2022
Defect Engineering in 2D Materials: Precise Manipulation and Improved Functionalities Jiang, Jie; Xu, Tao; Lu, Junpeng Research, Vol. 2019 https://doi.org/10.34133/2019/4641739	journal	December 2019
SRIM – The stopping and range of ions in matter (2010) Ziegler, James F.; Ziegler, M. D.; Biersack, J. P. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 268, Issue 11-12 https://doi.org/10.1016/j.nimb.2010.02.091	journal	June 2010
Ferromagnetic Order at Room Temperature in Monolayer WSe ₂ Semiconductor via Vanadium Dopant Yun, Seok Joon; Duong, Dinh Loc; Ha, Doan Manh Advanced Science, Vol. 7, Issue 9 https://doi.org/10.1002/advs.201903076	journal	March 2020
n-Type Behavior of Graphene Supported on Si/SiO ₂ Substrates Romero, Hugo E.; Shen, Ning; Joshi, Prasoon ACS Nano, Vol. 2, Issue 10 https://doi.org/10.1021/nn800354m	journal	September 2008
Near-unity photoluminescence quantum yield in MoS2 Amani, M.; Lien, D. -H.; Kiriya, D. Science, Vol. 350, Issue 6264 https://doi.org/10.1126/science.aad2114	journal	November 2015
Defect engineering of two-dimensional transition metal dichalcogenides Lin, Zhong; Carvalho, Bruno R.; Kahn, Ethan 2D Materials, Vol. 3, Issue 2 https://doi.org/10.1088/2053-1583/3/2/022002	journal	April 2016
Consistent Gaussian basis sets of triple-zeta valence with polarization quality for solid-state calculations Peintinger, Michael F.; Oliveira, Daniel Vilela; Bredow, Thomas Journal of Computational Chemistry, Vol. 34, Issue 6 https://doi.org/10.1002/jcc.23153	journal	October 2012
Exciton-coupled coherent magnons in a 2D semiconductor Bae, Youn Jue; Wang, Jue; Scheie, Allen Nature, Vol. 609, Issue 7926 https://doi.org/10.1038/s41586-022-05024-1	journal	September 2022
Enhancement of defect-induced Raman modes at the fundamental absorption edge of electron-irradiated GaAs Berg, R. S.; Yu, P. Y. Physical Review B, Vol. 33, Issue 10 https://doi.org/10.1103/PhysRevB.33.7349	journal	May 1986
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
Electrically tunable high Curie temperature two-dimensional ferromagnetism in van der Waals layered crystals Wang, Hua; Qi, Jingshan; Qian, Xiaofeng Applied Physics Letters, Vol. 117, Issue 8 https://doi.org/10.1063/5.0014865	journal	August 2020
Raman spectroscopy in graphene Malard, L. M.; Pimenta, M. A.; Dresselhaus, G. Physics Reports, Vol. 473, Issue 5-6, p. 51-87 https://doi.org/10.1016/j.physrep.2009.02.003	journal	April 2009
Layered Antiferromagnetism Induces Large Negative Magnetoresistance in the van der Waals Semiconductor CrSBr Telford, Evan J.; Dismukes, Avalon H.; Lee, Kihong Advanced Materials, Vol. 32, Issue 37 https://doi.org/10.1002/adma.202003240	journal	August 2020
�ber Chalkogenidhalogenide des dreiwertigen Chroms Katscher, H.; Hahn, H. Die Naturwissenschaften, Vol. 53, Issue 14 https://doi.org/10.1007/BF00621875	journal	January 1966
Quasi‐1D Electronic Transport in a 2D Magnetic Semiconductor Wu, Fan; Gutiérrez‐Lezama, Ignacio; López‐Paz, Sara A. Advanced Materials, Vol. 34, Issue 16 https://doi.org/10.1002/adma.202109759	journal	March 2022
Structural Defects in Graphene Banhart, Florian; Kotakoski, Jani; Krasheninnikov, Arkady V. ACS Nano, Vol. 5, Issue 1 https://doi.org/10.1021/nn102598m	journal	November 2010
Phonons in single-layer and few-layer MoS $_{2}$ and WS $_{2}$ Molina-Sánchez, A.; Wirtz, L. Physical Review B, Vol. 84, Issue 15 https://doi.org/10.1103/PhysRevB.84.155413	journal	October 2011
MoS ₂ Memtransistors Fabricated by Localized Helium Ion Beam Irradiation Jadwiszczak, Jakub; Keane, Darragh; Maguire, Pierce ACS Nano, Vol. 13, Issue 12 https://doi.org/10.1021/acsnano.9b07421	journal	December 2019
Vacancy-Induced Ferromagnetism of MoS ₂ Nanosheets Cai, Liang; He, Jingfu; Liu, Qinghua Journal of the American Chemical Society, Vol. 137, Issue 7 https://doi.org/10.1021/ja5120908	journal	February 2015
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
Quantum-mechanical condensed matter simulations with CRYSTAL Dovesi, Roberto; Erba, Alessandro; Orlando, Roberto Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 4 https://doi.org/10.1002/wcms.1360	journal	March 2018
Anomalous Lattice Vibrations of Single- and Few-Layer MoS ₂ Lee, Changgu; Yan, Hugen; Brus, Louis E. ACS Nano, Vol. 4, Issue 5 https://doi.org/10.1021/nn1003937	journal	March 2010
Phonon Confinement Effect in Two-dimensional Nanocrystallites of Monolayer MoS ₂ to Probe Phonon Dispersion Trends Away from Brillouin-Zone Center Shi, Wei; Zhang, Xin; Li, Xiao-Li Chinese Physics Letters, Vol. 33, Issue 5 https://doi.org/10.1088/0256-307X/33/5/057801	journal	May 2016
Magnetic ordering effects in the Raman spectra of ${La}_{1 - x} {Mn}_{1 - x} O_{3}$ Granado, E.; García, A.; Sanjurjo, J. A. Physical Review B, Vol. 60, Issue 17 https://doi.org/10.1103/PhysRevB.60.11879	journal	November 1999
Probing the Spin Dimensionality in Single‐Layer CrSBr Van Der Waals Heterostructures by Magneto‐Transport Measurements Boix‐Constant, Carla; Mañas‐Valero, Samuel; Ruiz, Alberto M. Advanced Materials, Vol. 34, Issue 41 https://doi.org/10.1002/adma.202204940	journal	September 2022
Nanopatterning and Electrical Tuning of MoS ₂ Layers with a Subnanometer Helium Ion Beam Fox, Daniel S.; Zhou, Yangbo; Maguire, Pierce Nano Letters, Vol. 15, Issue 8 https://doi.org/10.1021/acs.nanolett.5b01673	journal	July 2015
Magnetism in semiconducting molybdenum dichalcogenides Guguchia, Z.; Kerelsky, A.; Edelberg, D. Science Advances, Vol. 4, Issue 12 https://doi.org/10.1126/sciadv.aat3672	journal	December 2018
Resonant Raman studies of bound excitons in CdS Munz, D.; Pilkuhn, M. H. Solid State Communications, Vol. 36, Issue 3 https://doi.org/10.1016/0038-1098(80)90261-6	journal	October 1980
Ab initio analytical Raman intensities for periodic systems through a coupled perturbed Hartree-Fock/Kohn-Sham method in an atomic orbital basis. I. Theory Maschio, Lorenzo; Kirtman, Bernard; Rérat, Michel The Journal of Chemical Physics, Vol. 139, Issue 16 https://doi.org/10.1063/1.4824442	journal	October 2013
Coupling between magnetic order and charge transport in a two-dimensional magnetic semiconductor Telford, Evan J.; Dismukes, Avalon H.; Dudley, Raymond L. Nature Materials, Vol. 21, Issue 7 https://doi.org/10.1038/s41563-022-01245-x	journal	May 2022
Symmetry disquisition on theTiOXphase diagram(X=Br,Cl) Fausti, Daniele; Lummen, Tom T. A.; Angelescu, Cosmina Physical Review B, Vol. 75, Issue 24 https://doi.org/10.1103/PhysRevB.75.245114	journal	June 2007
Lattice Dynamics, Phonon Chirality, and Spin–Phonon Coupling in 2D Itinerant Ferromagnet Fe ₃ GeTe ₂ Du, Luojun; Tang, Jian; Zhao, Yanchong Advanced Functional Materials, Vol. 29, Issue 48 https://doi.org/10.1002/adfm.201904734	journal	September 2019
Effect of disorder on Raman scattering of single-layer $Mo S_{2}$ Mignuzzi, Sandro; Pollard, Andrew J.; Bonini, Nicola Physical Review B, Vol. 91, Issue 19 https://doi.org/10.1103/PhysRevB.91.195411	journal	May 2015
Substrate-induced strain and charge doping in CVD-grown monolayer MoS ₂ Chae, Woo Hyun; Cain, Jeffrey D.; Hanson, Eve D. Applied Physics Letters, Vol. 111, Issue 14 https://doi.org/10.1063/1.4998284	journal	October 2017
Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2 Lin, Yung-Chang; Dumcenco, Dumitru O.; Huang, Ying-Sheng Nature Nanotechnology, Vol. 9, Issue 5 https://doi.org/10.1038/nnano.2014.64	journal	April 2014
The effects of microcrystal size and shape on the one phonon Raman spectra of crystalline semiconductors Campbell, I. H.; Fauchet, P. M. Solid State Communications, Vol. 58, Issue 10 https://doi.org/10.1016/0038-1098(86)90513-2	journal	June 1986
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
Double-resonant LA phonon scattering in defective graphene and carbon nanotubes Herziger, Felix; Tyborski, Christoph; Ochedowski, Oliver Physical Review B, Vol. 90, Issue 24 https://doi.org/10.1103/PhysRevB.90.245431	journal	December 2014
The Raman effect in crystals Loudon, R. Advances in Physics, Vol. 13, Issue 52 https://doi.org/10.1080/00018736400101051	journal	October 1964
Wedging Transfer of Nanostructures Schneider, Grégory F.; Calado, Victor E.; Zandbergen, Henny Nano Letters, Vol. 10, Issue 5 https://doi.org/10.1021/nl1008037	journal	May 2010
Spin-phonon coupling in orthorhombic $R Mn O_{3}$ $(R = \Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y)$ : A Raman study Laverdière, J.; Jandl, S.; Mukhin, A. A. Physical Review B, Vol. 73, Issue 21 https://doi.org/10.1103/PhysRevB.73.214301	journal	June 2006
Endothelial ZEB1 promotes angiogenesis-dependent bone formation and reverses osteoporosis Fu, Rong; Lv, Wen-Cong; Xu, Ying Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-14076-3	journal	January 2020
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
Magnetism in MoS ₂ induced by proton irradiation Mathew, S.; Gopinadhan, K.; Chan, T. K. Applied Physics Letters, Vol. 101, Issue 10 https://doi.org/10.1063/1.4750237	journal	September 2012
Interlayer electronic coupling on demand in a 2D magnetic semiconductor Wilson, Nathan P.; Lee, Kihong; Cenker, John Nature Materials, Vol. 20, Issue 12 https://doi.org/10.1038/s41563-021-01070-8	journal	July 2021
Theory of Spin-Dependent Phonon Raman Scattering in Magnetic Crystals Suzuki, Naoshi; Kamimura, Hiroshi Journal of the Physical Society of Japan, Vol. 35, Issue 4 https://doi.org/10.1143/JPSJ.35.985	journal	October 1973
Raman Spectroscopy, Photocatalytic Degradation, and Stabilization of Atomically Thin Chromium Tri-iodide Shcherbakov, Dmitry; Stepanov, Petr; Weber, Daniel Nano Letters, Vol. 18, Issue 7 https://doi.org/10.1021/acs.nanolett.8b01131	journal	June 2018
A family of high-temperature ferromagnetic monolayers with locked spin-dichroism-mobility anisotropy: MnNX and CrCX (X = Cl, Br, I; C = S, Se, Te) Wang, Cong; Zhou, Xieyu; Zhou, Linwei Science Bulletin, Vol. 64, Issue 5 https://doi.org/10.1016/j.scib.2019.02.011	journal	March 2019
Hopping transport through defect-induced localized states in molybdenum disulphide Qiu, Hao; Xu, Tao; Wang, Zilu Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3642	journal	October 2013
Layer-Dependent Interlayer Antiferromagnetic Spin Reorientation in Air-Stable Semiconductor CrSBr Ye, Chen; Wang, Cong; Wu, Qiong ACS Nano, Vol. 16, Issue 8 https://doi.org/10.1021/acsnano.2c01151	journal	May 2022
Charge trapping at the MoS ₂ -SiO ₂ interface and its effects on the characteristics of MoS ₂ metal-oxide-semiconductor field effect transistors Guo, Yao; Wei, Xianlong; Shu, Jiapei Applied Physics Letters, Vol. 106, Issue 10 https://doi.org/10.1063/1.4914968	journal	March 2015
Magnetic Order and Symmetry in the 2D Semiconductor CrSBr Lee, Kihong; Dismukes, Avalon H.; Telford, Evan J. Nano Letters, Vol. 21, Issue 8 https://doi.org/10.1021/acs.nanolett.1c00219	journal	April 2021
Defect‐Engineered Magnetic Field Dependent Optoelectronics of Vanadium Doped Tungsten Diselenide Monolayers Nisi, Katharina; Kiemle, Jonas; Powalla, Lukas Advanced Optical Materials, Vol. 10, Issue 17 https://doi.org/10.1002/adom.202102711	journal	June 2022
Magnetism and Optical Anisotropy in van der Waals Antiferromagnetic Insulator CrOCl Zhang, Tianle; Wang, Yimeng; Li, Hexuan ACS Nano, Vol. 13, Issue 10 https://doi.org/10.1021/acsnano.9b04726	journal	September 2019
Photoluminescence Quenching in Single-Layer MoS ₂ via Oxygen Plasma Treatment Kang, Narae; Paudel, Hari P.; Leuenberger, Michael N. The Journal of Physical Chemistry C, Vol. 118, Issue 36 https://doi.org/10.1021/jp506964m	journal	August 2014
Microsecond Valley Lifetime of Defect-Bound Excitons in Monolayer WSe 2 Moody, Galan; Tran, Kha; Lu, Xiaobo Physical Review Letters, Vol. 121, Issue 5 https://doi.org/10.1103/PhysRevLett.121.057403	journal	August 2018
Magnetic properties of CrSBr Göser, O.; Paul, W.; Kahle, H. G. Journal of Magnetism and Magnetic Materials, Vol. 92, Issue 1 https://doi.org/10.1016/0304-8853(90)90689-N	journal	November 1990

Similar Records

Electrochemical Intercalation and Exfoliation of CrSBr into Ferromagnetic Fibers and Nanoribbons

Journal Article · Fri Dec 29 00:00:00 EST 2023 · Small Methods · OSTI ID:1908278

Mosina, Kseniia; Wu, Bing; Antonatos, Nikolas; +7 more

Designing Magnetic Properties in CrSBr through Hydrostatic Pressure and Ligand Substitution

Journal Article · Mon Aug 07 00:00:00 EDT 2023 · Advanced Physics Research · OSTI ID:1908278

Telford, Evan J.; Chica, Daniel G.; Ziebel, Michael E.; +10 more

Direct Imaging of Antiferromagnet‐Ferromagnet Phase Transition in van der Waals Antiferromagnet CrSBr

Journal Article · Thu Sep 28 00:00:00 EDT 2023 · Advanced Functional Materials · OSTI ID:1908278

Yu, Jingjing; Liu, Daxiang; Ding, Zhenyu; +16 more

Title: Probing Defects and Spin‐Phonon Coupling in CrSBr via Resonant Raman Scattering

Citation Formats

References (70)

Similar Records

Related Subjects