Abstract
Introducing magnetic dopants into two-dimensional transition metal dichalcogenides has recently attracted considerable attention due to its promising applications in spintronics and valleytronics. Herein we realized manganese-doped molybdenum diselenide (MoSe2) single crystal via chemical vapor transport (CVT) reaction, containing up to 2.9% (atomic concentration) Mn dopants, and investigated the light-matter interaction in these samples. We observed a suppressed trion intensity, a longer photoluminescence lifetime, and prominent blue- and red-shift of E 22g (in-plane) and A1g (out-of-plane) Raman modes, respectively. Moreover, the Mn dopants increase the valley Zeeman splitting of the MoSe2 monolayer by ∼50%, while preserving the linear dependence on magnetic field. First-principles calculations indicate that the spin-polarized deep level defect states are formed due to the Mn substitutional dopants in the MoSe2 lattice. The resulting defect potential favors the funnelling of excitons towards the defects. The Mn dopants reduce the magnitude of the interatomic force constants, explaining the red-shift of the A1g mode. The Mn atoms and their immediate Mo and Se neighbors carry significant magnetic moments, which enhance the observed exciton g-factors due to the exchange interactions affecting defect-bound excitons.
摘要
最近, 将磁性掺杂引入到二维硫族化合物中从而调控自旋电子学及谷电子学的研究引起了科学界的广泛关注. 本文通过化学气相转移生长技术, 实现了二硒化钼高达2.9%原子丰度的锰掺杂,并采用光谱学技术研究了晶体及解理的少层样品中光与物质相互作用. 我们发现掺杂抑制了带电激子的发光, 激子发光具有更长的时间寿命, 同时面内E2g2和面外A1g声子振动模式分别呈现出显著的蓝移和红移. 此外, 锰掺杂增强了能谷塞曼劈裂约50%, 并保持了发光线偏振度对磁场的依赖关系. 第一性原理计算显示, 锰掺杂替代原子形成自旋极化的深能级, 导致缺陷势场更倾向于捕获激子. 锰掺杂降低了原子间的相互作用力常数, 可以解释面外A1g 声子振动模式的红移. 锰原子及最近邻的钼和硒原子带有显著的磁偶极, 其交换作用影响了缺陷捕获的激子, 从而增强了实验中观察到的g-因子.
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Acknowledgements
Xiong Q acknowledges the support from Singapore Ministry of Education via AcRF Tier3 Programme “Geometrical Quantum Materials” (MOE2018-T3-1-002), AcRF Tier2 grant (MOE2017-T2-1-040) and Tier1 grant (RG 194/17). Quek SY acknowledges the funding from the National Research Foundation, Prime Ministers Office, Singapore, under its Medium-Sized Centre Programme. Wu Y acknowledges computational support from Miguel dias Costa. Xuan F acknowledges the funding from MOE2017-T2-2-139. The calculations were performed on the clusters of the CA2DM and the National Supercomputing Centre (NSCC) Singapore.
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Liu S and Xiong Q conceived the idea and designed the experiments. Liu S and Chaturvedi A synthesized the Mndoped MoSe2 single crystal. Liu S prepared the atomically thin samples and performed the spectroscopic experiments. Wu Y performed the first principles calculations and analysis under the supervision of Quek SY. Liu X fabricated the FET devices and measured the transport properties. Liu S, Wu Y, Granados del Aguila A and Liu X analyzed the results. Liu S, Wu Y, Quek SY and Xiong Q wrote the manuscript. All authors discussed and commented on the manuscript. Quek SY and Xiong Q supervised this collaboration project.
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Experimental details and supporting data are available in the online version of the paper.
Yaze Wu received his BSc degree from the Physics Department of National University of Singapore and is currently a PhD candidate at the same department. His current research interest includes high-throughput first-principles calculations of piezoelectricity and optical properties in 2D materials.
Sheng Liu received his BSc and MSc degrees from the University of Science and Technology Beijing, and PhD degree from Nanyang Technological University (NTU), Singapore. He is currently a postdoctoral research fellow at Division of Physics and Applied Physics of NTU. His current research interest includes optical properties in 2D semiconductors and magnets.
Su Ying Quek is an Associate Professor at the Physics Department, National University of Singapore. She received a PhD in applied physics from Harvard University and a BA Honors (1st class) in Mathematics from the University of Cambridge. She leads a computation and theory group that studies the electronic structure and lattice dynamics of emerging materials. The group is active in advancing methodologies that address problems of experimental relevance and has strong collaborations with experimentalists.
Qihua Xiong is a Professor of physics at Tsinghua University. He received his PhD from Penn State University in 2006. In 2009–2020 he worked at NTU. His group is specialized in optical spectroscopy investigations of light-matter interactions in low-dimensional quantum materials. He currently serves as Associate Editor for Nano Letters and international advisory board for many prestigious journals, such as ACS Photonics, Nano Research, Science China Materials, etc.
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Liu, S., Wu, Y., Liu, X. et al. Light-matter interactions in high quality manganese-doped two-dimensional molybdenum diselenide. Sci. China Mater. 64, 2507–2518 (2021). https://doi.org/10.1007/s40843-020-1641-9
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DOI: https://doi.org/10.1007/s40843-020-1641-9