journal article·2024-11-30Open access

Materials beyond monolayers: The magnetic quasi-1D semiconductor CrSBr

Julian Klein, Frances M. Ross

Journal of Materials Research· Volume 39· Issue 22

Abstract

Abstract The all-surface nature of atomically thin van der Waals materials can present challenges for practical applications. Fortunately, new layered materials are on the horizon that preserve their useful properties even when thicker than a monolayer. Here, we summarize our interest in one of these emergent materials, the magnetic semiconductor CrSBr. We describe monolayer properties exhibited by this material in its bulk form, discussing how the quasi-1D electronic structure of CrSBr allows mono- or bilayer physics to be displayed even in thick crystals. Long-range magnetic order offers additional tuning with the coupled lattice, spin, orbit, and charge degrees of freedom enabling magneto-correlated phenomena. We discuss the stability of CrSBr in air and show atomic scale structural manipulation through electron beam-driven transformations. We conclude that the stability and structural amenability of CrSBr provide opportunities for imagining devices that use bulk crystals yet exploit unique magnetic and quantum confinement effects. Graphical abstract
Source: crossref · Quality: baseline

Research context

OpenAlex topics: 2D Materials and Applications · MXene and MAX Phase Materials · Heusler alloys: electronic and magnetic properties

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (85)

Show source-provided references
1. K.S. Novoselov, Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004). https://doi.org/10.1126/science.110289610.1126/science.1102896 ↗
2. K.F. Mak, C. Lee, J. Hone, J. Shan, T.F. Heinz, Atomically thin MoSe2: a new direct-gap semiconductor. Phys. Rev. Lett. 105, 136805 (2010). https://doi.org/10.1103/physrevlett.105.13680510.1103/physrevlett.105.136805 ↗
3. A. Splendiani et al., Emerging photoluminescence in monolayer MoS2. Nano Lett. 10, 1271–1275 (2010). https://doi.org/10.1021/nl903868w10.1021/nl903868w ↗
4. D. Rhodes, S.H. Chae, R. Ribeiro-Palau, J. Hone, Disorder in van der Waals heterostructures of 2d materials. Nat. Mater. 18, 541–549 (2019). https://doi.org/10.1038/s41563-019-0366-810.1038/s41563-019-0366-8 ↗
5. A. Chernikov et al., Exciton binding energy and nonhydrogenic Rydberg series in monolayer WS2. Phys. Rev. Lett. (2014). https://doi.org/10.1103/PhysRevLett.113.07680210.1103/PhysRevLett.113.076802 ↗
6. A. Raja et al., Coulomb engineering of the bandgap and excitons in two-dimensional materials. Nat. Commun. (2017). https://doi.org/10.1038/ncomms1525110.1038/ncomms15251 ↗
7. Y. Cao, et al., Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43–50 (2018). http://www.nature.com/articles/nature26160.10.1038/nature26160 ↗
8. Y. Cao et al., Correlated insulator behaviour at half-filling in magic-angle graphene superlattices. Nature 556, 80–84 (2018). https://doi.org/10.1038/nature2615410.1038/nature26154 ↗
9. R. Decker et al., Local electronic properties of graphene on a BN substrate via scanning tunneling microscopy. Nano Lett. 11, 2291–2295 (2011). https://doi.org/10.1021/nl200511510.1021/nl2005115 ↗
10. B.G. Shin et al., Indirect bandgap puddles in monolayer mos2 by substrate-induced local strain. Adv. Mater. 28, 9378–9384 (2016). https://doi.org/10.1002/adma.20160262610.1002/adma.201602626 ↗
11. A. Raja et al., Dielectric disorder in two-dimensional materials. Nat. Nanotechnol. 14, 832–837 (2019). https://doi.org/10.1038/s41565-019-0520-010.1038/s41565-019-0520-0 ↗
12. C.R. Dean et al., Boron nitride substrates for high quality graphene electronics. Nat. Nanotechnol. 5, 722–726 (2010). https://doi.org/10.1038/nnano.2010.17210.1038/nnano.2010.172 ↗
13. F. Cadiz et al., Excitonic linewidth approaching the homogeneous limit in MoS2-based van der Waals heterostructures. Phys. Rev. X 7, 021026 (2017). https://doi.org/10.1103/physrevx.7.02102610.1103/physrevx.7.021026 ↗
14. O.A. Ajayi et al., Approaching the intrinsic photoluminescence linewidth in transition metal dichalcogenide monolayers. 2D Mater. 4, 031011 (2017). https://doi.org/10.1088/2053-1583/aa6aa110.1088/2053-1583/aa6aa1 ↗
15. J. Wierzbowski, et al., Direct exciton emission from atomically thin transition metal dichalcogenide heterostructures near the lifetime limit. Sci. Rep. 7, 12383 (2017). http://www.nature.com/articles/s41598-017-09739-4.10.1038/s41598-017-09739-4 ↗
16. K.S. Kim et al., The future of two-dimensional semiconductors beyond Moore’s law. Nat. Nanotechnol. (2024). https://doi.org/10.1038/s41565-024-01695-110.1038/s41565-024-01695-1 ↗
17. A.A. Balandin, F. Kargar, T.T. Salguero, R.K. Lake, One-dimensional van der Waals quantum materials. Mater. Today 55, 74–91 (2022). https://doi.org/10.1016/j.mattod.2022.03.01510.1016/j.mattod.2022.03.015 ↗
18. P.A. Lee, T.M. Rice, P.W. Anderson, Fluctuation effects at a Peierls transition. Phys. Rev. Lett. 31, 462–465 (1973). https://doi.org/10.1103/PhysRevLett.31.46210.1103/PhysRevLett.31.462 ↗
19. P. Monçeau, N.P. Ong, A.M. Portis, A. Meerschaut, J. Rouxel, Electric field breakdown of charge-density wave-induced anomalies in NbSe3. Phys. Rev. Lett. 37, 602–606 (1976). https://doi.org/10.1103/PhysRevLett.37.60210.1103/PhysRevLett.37.602 ↗
20. X. Chen et al., Thickness-dependent anisotropic superconductivity and charge density wave in ZrTe3 down to the two-dimensional limit. Phys. Rev. B (2024). https://doi.org/10.1103/PhysRevB.109.14451310.1103/PhysRevB.109.144513 ↗
21. H. Katscher, H. Hahn, Über Chalkogenidhalogenide des dreiwertigen Chroms. Die Nat. 53, 361–361 (1966). https://doi.org/10.1007/bf0062187510.1007/bf00621875 ↗
22. O. Göser, W. Paul, H. Kahle, Magnetic properties of CrSBr. J. Magn. Magn. Mater. 92, 129–136 (1990). https://linkinghub.elsevier.com/retrieve/pii/030488539090689N10.1016/0304-8853(90)90689-N ↗
23. J. Beck, Über Chalkogenidhalogenide des Chroms Synthese, Kristallstruktur und Magnetismus von Chromsulfidbromid CrSBr. Z. anorg. allgemeine Chem. 585, 157–167 (1990). https://doi.org/10.1002/zaac.1990585011810.1002/zaac.19905850118 ↗
24. E.J. Telford et al., Layered antiferromagnetism induces large negative magnetoresistance in the van der Waals semiconductor CrSBr. Adv. Mater. 32, 2003240 (2020). https://doi.org/10.1002/adma.20200324010.1002/adma.202003240 ↗
25. H. Wang, J. Qi, X. Qian, Electrically tunable high Curie temperature two-dimensional ferromagnetism in van der Waals layered crystals. Appl. Phys. Lett. 117, 083102 (2020). https://doi.org/10.1063/5.001486510.1063/5.0014865 ↗
26. J. Klein et al., Sensing the local magnetic environment through optically active defects in a layered magnetic semiconductor. ACS Nano 17, 288–299 (2022). https://doi.org/10.1021/acsnano.2c0765510.1021/acsnano.2c07655 ↗
27. J. Klein et al., Control of structure and spin texture in the van der Waals layered magnet CrSBr. Nat. Commun. (2022). https://doi.org/10.1038/s41467-022-32737-810.1038/s41467-022-32737-8 ↗
28. K. Yang, G. Wang, L. Liu, D. Lu, H. Wu, Triaxial magnetic anisotropy in the two-dimensional ferromagnetic semiconductor CrSBr. Phys. Rev. B 104, 144416 (2021). https://doi.org/10.1103/PhysRevB.104.14441610.1103/PhysRevB.104.144416 ↗
29. A.N. Rudenko, M. Rösner, M.I. Katsnelson, Dielectric tunability of magnetic properties in orthorhombic ferromagnetic monolayer CrSBr. NPJ Comput. Mater. (2023). https://doi.org/10.1038/s41524-023-01050-310.1038/s41524-023-01050-3 ↗
30. A. Scheie et al., Spin waves and magnetic exchange Hamiltonian in CrSBr. Adv. Sci. 9, 2202467 (2022). https://doi.org/10.1002/advs.20220246710.1002/advs.202202467 ↗
31. K. Lee et al., Magnetic order and symmetry in the 2D semiconductor CrSBr. Nano Lett. 21, 3511–3517 (2021). https://doi.org/10.1021/acs.nanolett.1c0021910.1021/acs.nanolett.1c00219 ↗
32. C. Boix-Constant et al., Probing the spin dimensionality in single-layer CrSBr van der Waals heterostructures by magneto-transport measurements. Adv. Mater. (2022). https://doi.org/10.1002/adma.20220494010.1002/adma.202204940 ↗
33. Y. Zur et al., Magnetic imaging and domain nucleation in CrSBr down to the 2d limit. Adv. Mater. (2023). https://doi.org/10.1002/adma.20230719510.1002/adma.202307195 ↗
34. M.A. Tschudin et al., Imaging nanomagnetism and magnetic phase transitions in atomically thin CrSBr. Nat. Commun. (2024). https://doi.org/10.1038/s41467-024-49717-910.1038/s41467-024-49717-9 ↗
35. R. Loudon, The Raman effect in crystals. Adv. Phys. 13, 423–482 (1964). https://doi.org/10.1080/0001873640010105110.1080/00018736400101051 ↗
36. K. Torres et al., Probing defects and spin–phonon coupling in CrSBr via resonant Raman scattering. Adv. Funct. Mater. 33, 2211366 (2023). https://doi.org/10.1002/adfm.20221136610.1002/adfm.202211366 ↗
37. C. Ye et al., Layer-dependent interlayer antiferromagnetic spin reorientation in air-stable semiconductor CrSBr. ACS Nano (2022). https://doi.org/10.1021/acsnano.2c0115110.1021/acsnano.2c01151 ↗
38. J. Cenker et al., Reversible strain-induced magnetic phase transition in a van der Waals magnet. Nat. Nanotechnol. (2022). https://doi.org/10.1038/s41565-021-01052-610.1038/s41565-021-01052-6 ↗
39. A. Pawbake et al., Raman scattering signatures of strong spin–phonon coupling in the bulk magnetic van der Waals material CrSBr. Phys. Rev. B (2023). https://doi.org/10.1103/PhysRevB.107.07542110.1103/PhysRevB.107.075421 ↗
40. D. Fausti et al., Symmetry disquisition on the TiOX phase diagram (X = Br, Cl). Phys. Rev. B (2007). https://doi.org/10.1103/physrevb.75.24511410.1103/physrevb.75.245114 ↗
41. M. Bykov et al., High-pressure behavior of FeOCl. Phys. Rev. B (2013). https://doi.org/10.1103/physrevb.88.01411010.1103/physrevb.88.014110 ↗
42. T. Zhang et al., Magnetism and optical anisotropy in van der Waals antiferromagnetic insulator CrOCl. ACS Nano 13, 11353–11362 (2019). https://doi.org/10.1021/acsnano.9b0472610.1021/acsnano.9b04726 ↗
43. D. Shcherbakov et al., Raman spectroscopy, photocatalytic degradation, and stabilization of atomically thin chromium triiodide. Nano Lett. 18, 4214–4219 (2018). https://doi.org/10.1021/acs.nanolett.8b0113110.1021/acs.nanolett.8b01131 ↗
44. J. Klein et al., The bulk van der Waals layered magnet CrSBr is a quasi-1D material. ACS Nano 17, 5316–5328 (2023). https://doi.org/10.1021/acsnano.2c0731610.1021/acsnano.2c07316 ↗
45. C. Gong, et al., Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals. Nature 546, 265–269 (2017). http://www.nature.com/articles/nature22060.10.1038/nature22060 ↗
46. Y. Deng, et al. Gate-tunable room-temperature ferromagnetism in two-dimensional Fe3GeTe2. Nature 563, 94–99 (2018). http://www.nature.com/articles/s41586-018-0626-910.1038/s41586-018-0626-9 ↗
47. E.J. Telford, et al., Coupling between magnetic order and charge transport in a two-dimensional magnetic semiconductor. Nat. Mater. 21, 754–760 (2022). https://www.nature.com/articles/s41563-022-01245-x10.1038/s41563-022-01245-x ↗
48. F. Wu et al., Quasi-1D electronic transport in a 2D magnetic semiconductor. Adv. Mater. 34, 2109759 (2022). https://doi.org/10.1002/adma.20210975910.1002/adma.202109759 ↗
49. N.P. Wilson, et al., Interlayer electronic coupling on demand in a 2D magnetic semiconductor. Nat. Mater. (2021). http://www.nature.com/articles/s41563-021-01070-8
50. M. Bianchi et al., Paramagnetic electronic structure of CrSBr: comparison between ab initio GW theory and angle-resolved photoemission spectroscopy. Phys. Rev. B (2023). https://doi.org/10.1103/PhysRevB.107.23510710.1103/PhysRevB.107.235107 ↗
51. M. Bianchi et al., Charge transfer induced Lifshitz transition and magnetic symmetry breaking in ultrathin CrSBr crystals. Phys. Rev. B (2023). https://doi.org/10.1103/PhysRevB.108.19541010.1103/PhysRevB.108.195410 ↗
52. M.D. Watson et al., Giant exchange splitting in the electronic structure of a-type 2d antiferromagnet CrSBr. NPJ 2D Mater. Appl. (2024). https://doi.org/10.1038/s41699-024-00492-710.1038/s41699-024-00492-7 ↗
53. S. Smolenski, et al., Large exciton binding energy in the bulk van der Waals magnet CrSBr. arXiv (2024). arXiv:2403.13897
54. V. Tran, R. Soklaski, Y. Liang, L. Yang, Layer controlled band gap and anisotropic excitons in few-layer black phosphorus. Phys. Rev. B (2014). https://doi.org/10.1103/PhysRevB.89.23531910.1103/PhysRevB.89.235319 ↗
55. J. Klein et al., Impact of substrate induced band tail states on the electronic and optical properties of MoS2. Appl. Phys. Lett. 115, 261603 (2019). https://doi.org/10.1063/1.513127010.1063/1.5131270 ↗
56. G. Wang et al., Colloquium: excitons in atomically thin transition metal dichalcogenides. Rev. Mod. Phys. (2018). https://doi.org/10.1103/RevModPhys.90.02100110.1103/RevModPhys.90.021001 ↗
57. T.S. Ghiasi et al., Electrical and thermal generation of spin currents by magnetic bilayer graphene. Nat. Nanotechnol. 16, 788–794 (2021). https://doi.org/10.1038/s41565-021-00887-310.1038/s41565-021-00887-3 ↗
58. D.J. Rizzo, et al., Uniaxial plasmon polaritons via charge transfer at the graphene/CrSBr interface. arXiv (2024). arXiv:2407.07178
59. A. Spijkerman, J.L. de Boer, A. Meetsma, G.A. Wiegers, S. van Smaalen, X-ray crystal-structure refinement of the nearly commensurate phase of 1T-TaS2 in (3 + 2)-dimensional superspace. Phys. Rev. B 56, 13757–13767 (1997). https://doi.org/10.1103/physrevb.56.1375710.1103/physrevb.56.13757 ↗
60. M.-C. Heißenbüttel, et al., Quadratic optical response of CrSBr controlled by spin-selective interlayer coupling (2024). arXiv:2403.20174
61. S. Shree et al., Observation of exciton–phonon coupling in MoSe2 monolayers. Phys. Rev. B 98, 035302 (2018). https://doi.org/10.1103/physrevb.98.03530210.1103/physrevb.98.035302 ↗
62. K. Lin et al., Strong exciton–phonon coupling as a fingerprint of magnetic ordering in van der Waals layered CrSBr. ACS Nano 18, 2898–2905 (2024). https://doi.org/10.1021/acsnano.3c0723610.1021/acsnano.3c07236 ↗
63. F. Dirnberger, et al., Magneto-optics in a van der Waals magnet tuned by self-hybridized polaritons. Nature 620, 533–537 (2023). https://www.nature.com/articles/s41586-023-06275-210.1038/s41586-023-06275-2 ↗
64. T. Wang et al., Magnetically-dressed CrSBr exciton polaritons in ultrastrong coupling regime. Nat. Commun. (2023). https://doi.org/10.1038/s41467-023-41688-710.1038/s41467-023-41688-7 ↗
65. Q. Li, et al., Magnetic exciton–polariton with strongly coupled atomic and photonic anisotropies. arXiv (2023). arXiv:2306.11265
66. Y.J. Bae, et al., Exciton-coupled coherent magnons in a 2D semiconductor. Nature 609, 282–286 (2022). https://www.nature.com/articles/s41586-022-05024-110.1038/s41586-022-05024-1 ↗
67. G.M. Diederich et al., Tunable interaction between excitons and hybridized magnons in a layered semiconductor. Nat. Nanotechnol. 18, 23–28 (2022). https://doi.org/10.1038/s41565-022-01259-110.1038/s41565-022-01259-1 ↗
68. Y. Sun et al., Dipolar spin wave packet transport in a van der Waals antiferromagnet. Nat. Phys. 20, 794–800 (2024). https://doi.org/10.1038/s41567-024-02387-210.1038/s41567-024-02387-2 ↗
69. F. Tabataba-Vakili et al., Doping-control of excitons and magnetism in few-layer CrSBr. Nat. Commun. (2024). https://doi.org/10.1038/s41467-024-49048-910.1038/s41467-024-49048-9 ↗
70. P. Palvadeau, L. Coic, J. Rouxel, J. Portier, The lithium and molecular intercalates of FeOCl. Mater. Res. Bull. 13, 221–227 (1978). https://doi.org/10.1016/0025-5408(78)90226-x10.1016/0025-5408(78)90226-x ↗
71. S.R. Hwang, W.-H. Li, K.C. Lee, J.W. Lynn, C.-G. Wu, Spiral magnetic structure of Fe in Van der Waals gapped FeOCl and polyaniline-intercalated FeOCl. Phys. Rev. B 62, 14157–14163 (2000). https://doi.org/10.1103/physrevb.62.1415710.1103/physrevb.62.14157 ↗
72. F. Long et al., Ferromagnetic interlayer coupling in CrSBr crystals irradiated by ions. Nano Lett. 23, 8468–8473 (2023). https://doi.org/10.1021/acs.nanolett.3c0192010.1021/acs.nanolett.3c01920 ↗
73. H. Schulz, Wigner crystal in one dimension. Phys. Rev. Lett. 71, 1864 (1993)10.1103/PhysRevLett.71.1864 ↗
74. B. Spivak, S.A. Kivelson, Phases intermediate between a two-dimensional electron liquid and Wigner crystal. Phys. Rev. B (2004). https://doi.org/10.1103/physrevb.70.15511410.1103/physrevb.70.155114 ↗
75. V.J. Emery, E. Fradkin, S.A. Kivelson, T.C. Lubensky, Quantum theory of the smectic metal state in stripe phases. Phys. Rev. Lett. 85, 2160–2163 (2000). https://doi.org/10.1103/physrevlett.85.216010.1103/physrevlett.85.2160 ↗
76. D.L. Esteras, A. Rybakov, A.M. Ruiz, J.J. Baldoví, Magnon straintronics in the 2D van der Waals ferromagnet CrSBr from first-principles. Nano Lett. 22, 8771–8778 (2022). https://doi.org/10.1021/acs.nanolett.2c0286310.1021/acs.nanolett.2c02863 ↗
77. J. Cenker, et al., Strain-programmable van der Waals magnetic tunnel junctions. arXiv (2023). arXiv:2301.03759
78. K. Bagani, et al., Imaging strain-controlled magnetic reversal in thin CrSBr. arXiv (2024). arXiv:2408.0765710.1021/acs.nanolett.4c03919 ↗
79. F. Fei et al., Spin-mechanical coupling in 2d antiferromagnet CrSBr. Nano Lett. (2024). https://doi.org/10.1021/acs.nanolett.4c0175110.1021/acs.nanolett.4c01751 ↗
80. E.J. Telford et al., Designing magnetic properties in CrSBr through hydrostatic pressure and ligand substitution. Adv. Phys. Res. 2, 2300036 (2023). https://doi.org/10.1002/apxr.20230003610.1002/apxr.202300036 ↗
81. C. Boix-Constant et al., Multistep magnetization switching in orthogonally twisted ferromagnetic monolayers. Nat. Mater. 23, 212–218 (2023). https://doi.org/10.1038/s41563-023-01735-610.1038/s41563-023-01735-6 ↗
82. Y. Chen et al., Twist-assisted all-antiferromagnetic tunnel junction in the atomic limit. Nature (2024). https://doi.org/10.1038/s41586-024-07818-x10.1038/s41586-024-07818-x ↗
83. T.T. Tran, K. Bray, M.J. Ford, M. Toth, I. Aharonovich, Quantum emission from hexagonal boron nitride monolayers. Nat. Nanotechnol. 11, 37–41 (2016). https://www.nature.com/articles/nnano.2015.24210.1038/nnano.2015.242 ↗
84. P. Tonndorf, et al., Single-photon emission from localized excitons in an atomically thin semiconductor. Optica 2, 347 (2015). https://www.osapublishing.org/abstract.cfm?URI=optica-2-4-34710.1364/OPTICA.2.000347 ↗
85. J. Klein, et al., Site-selectively generated photon emitters in monolayer MoS2 via local helium ion irradiation. Nat. Commun. 10, 2755 (2019). http://www.nature.com/articles/s41467-019-10632-z10.1038/s41467-019-10632-z ↗