Tunable electronic and magnetic properties of transition-metal atoms doped CrBr<sub>3</sub> monolayer

Chen Xu-Fan; Yang Qiang; Hu Xiao-Hui

doi:10.7498/aps.70.20210936

Abstract

The CrBr₃ monolayer is a two-dimensional semiconductor material with intrinsic ferromagnetism. However, the low Curie temperature of CrBr₃ monolayer limits its practical development in innovative spintronic devices. The electronic and magnetic properties of transition-metal atoms doped CrBr₃ monolayer have been systematically investigated by using the density functional theory calculations. The formation energy elucidates that all 3d transition metal (TM) atoms prefer to be doped in the middle of a hexagon (H) site of CrBr₃ monolayer. And all the TM atoms, except the Zn atom, can bond strongly to the surrounding Cr atoms with sizable formation energy. The results also indicate that the magnetic moment of TM-CrBr₃ system changes as a result of the charge transfer between TM atom and adjacent Cr atom. In addition, comparing with the intrinsic CrBr₃, the T_C of TM-CrBr₃ system increases significantly, which means that the ferromagnetic stability of CrBr₃ monolayer is enhanced. In particular, the T_C of CrBr₃ with Sc atom can be increased by 159%. The enhancement of ferromagnetism is mainly due to the competition between the direct exchange and the superexchange interaction. We also find that the electronic properties of the TM-CrBr₃ systems are diverse. For example, Sc-, Ti-, V-, Mn-, Fe-, Co-, Ni-, Cu- and Zn-CrBr₃ exhibit spin gapless semiconductor (SGS) properties with 100% spin polarization at Fermi level. The TM-CrBr₃ system can be adjusted from semiconductor to half-metal when Cr atoms are doped into the CrBr₃ monolayer. This work, together with recent achievements in the field of two-dimensional ferromagnetic materials, provides an experimentally achievable guide for realizing the preparation of TM-CrBr₃ system with high Curie temperature. Moreover, the possibility of application of these systems in nanoelectronics and spintronics is increased.

Keywords:

Authors and contacts

1.
College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211816, China
2.
Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, Nanjing Tech University, Nanjing 211816, China

Corresponding author: Hu Xiao-Hui, xiaohui.hu@njtech.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11604047), the Natural Science Foundation of Jiangsu Province, China (Grant No. BK20160694), the Jiangsu Planned Projects for Postdoctoral Research Funds, China (Grant No. 2019K010A), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), China

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References

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Cited By

图 1 (a) 单层CrBr₃的结构示意图; (b) 单层CrBr₃的能带结构和态密度. 能带结构中自旋向上和自旋向下分别用红色实线和蓝色实线表示

Figure 1. (a) Structural diagram of CrBr₃ monolayer; (b) band structure and density of states of CrBr₃ monolayer. The red and blue solid lines indicate spin-up and spin-down channels in the band structures, respectively.

DownLoad: Full-Size Img PowerPoint

图 2 (a)−(c) TM原子分别掺杂在H, Cr-Top和Br-Top位点时TM-CrBr₃晶体结构的俯视图和侧视图; (d) TM-CrBr₃的形成能; (e) 在H构型中, TM原子到CrBr₃表层Br原子的高度以及TM原子与最邻近Br原子共价键的键长

Figure 2. Top and side views of the crystalline structure of three different doped positions of TM atoms labeled as (a) H, (b) Cr-Top and (c) Br-Top; (d) the formation energy of TM-CrBr₃; (e) the height of the TM to Br on the surface of CrBr₃ and the length of covalent bond between TM and nearest Br atom.

DownLoad: Full-Size Img PowerPoint

图 3 在300 K下, TM-CrBr₃掺杂体系的H构型在5 ps后分子动力学模拟的结构示意图

Figure 3. Snapshots of TM-CrBr₃ on the H site taken after 5 ps of DFT-MD simulations at 300 K.

DownLoad: Full-Size Img PowerPoint

图 4 (a) H构型的TM-CrBr₃中TM原子的磁矩以及与TM原子最近邻的Cr原子的磁矩; (b) TM-CrBr₃中Cr和TM原子的电荷转移; (c) TM-CrBr₃体系的总磁矩(M_total)

Figure 4. (a) Magnetic moments of TM atom and Cr atom nearest to TM atom in TM-CrBr₃ of H configuration; (b) charge transfer between Cr and TM atoms in TM-CrBr₃; (c) the total magnetic moments (M_total) of TM-CrBr₃.

DownLoad: Full-Size Img PowerPoint

图 5 (a) 本征CrBr₃和TM-CrBr₃体系的AFM构型与FM构型的能量差E_AFM – E_FM和居里温度T_C; (b) 本征CrBr₃和TM-CrBr₃的Cr—Cr距离和Cr—I—Cr键角

Figure 5. (a) The E_AFM – E_FM and Curie temperature of pristine CrBr₃ and TM-CrBr₃; (b) the Cr—Cr distance and Cr—I—Cr bond angle in pristine CrBr₃ and TM-CrBr₃.

DownLoad: Full-Size Img PowerPoint

图 6 3d TM原子掺杂单层CrBr₃的自旋极化能带结构, 插图是费米能级附近能带结构的放大图. 自旋向上和自旋向下分别用红色实线和蓝色实线表示

Figure 6. Spin-polarized band structures of 3d TM atoms doped CrBr₃ monolayer. The illustration is an enlarged picture of the band structures near the Fermi level. The red and blue solid lines indicate spin-up and spin-down channels in the band structures, respectively.

DownLoad: Full-Size Img PowerPoint

表 1 本征CrBr₃和TM-CrBr₃体系中的交换耦合参数 (J )

Table 1. Exchange coupling parameter (J ) of pristine CrBr₃ and TM-CrBr₃.

CrBr₃ Sc Ti V Cr Mn Fe Co Ni Cu Zn

J/meV 2.39 5.95 3.95 5.10 2.66 3.96 2.80 1.25 2.97 3.27 4.73

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map

[1]	Hu X H, Björkman T, Lipsanen H, Sun L T, Krasheninnikov A V 2015 J. Phys. Chem. Lett. 6 3263 Google Scholar
[2]	Hu X H, Wang Y F, Shen X D, Krasheninnikov A V, Sun L T, Chen Z F 2018 2D Mater. 5 031012 Google Scholar
[3]	Duan X D, Wang C, Pan A L, Yu R Q, Duan X F 2015 Chem. Soc. Rev. 44 8859 Google Scholar
[4]	Kou L Z, Ma Y D, Sun Z Q, Heine T, Chen C F 2017 J. Phys. Chem. Lett. 8 1905 Google Scholar
[5]	Hu X H, Zhao Y H, Shen X D, Krasheninnikov A V, Chen Z F, Sun L T 2020 ACS Appl. Mater. Interfaces 12 26367 Google Scholar
[6]	Ai W, Kou L Z, Hu X H, Wang Y F, Krasheninnikov A V, Sun L T, Shen X D 2019 J. Phys. Condens. Matter 31 445301 Google Scholar
[7]	Hu X H, Wan N, Sun L T, Krasheninnikov A V 2014 J. Phys. Chem. C 118 16133 Google Scholar
[8]	Hu X H, Zhang W, Sun L T, Krasheninnikov A V 2012 Phys. Rev. B 86 195418 Google Scholar
[9]	艾雯, 胡小会, 潘林, 陈长春, 王一峰, 沈晓冬 2019 68 197101 Google Scholar Ai W, Hu X H, Pan L, Chen C C, Wang Y F, Shen X D 2019 Acta Phys. Sin. 68 197101 Google Scholar
[10]	Hu X H, Sun L T, Krasheninnikov A V 2012 Appl. Phys. Lett. 100 263115 Google Scholar
[11]	Zhang S L, Yan Z, Li Y F, Chen Z F, Zeng H B 2015 Angew. Chem. -Int. Ed. 54 3112 Google Scholar
[12]	Chen X P, Yang Q, Meng R S, Jiang J K, Liang Q H, Tan C J, Sun X 2016 J. Mater. Chem. C 4 5434 Google Scholar
[13]	Yang Q, Kou L Z, Hu X H, Wang Y F, Lu C H, Krasheninnikov A V, Sun L T 2020 J. Phys. Condens. Matter 32 365302 Google Scholar
[14]	Karthikeyan J, Komsa H P, Batzill M, Krasheninnikov A V 2019 Nano Lett. 19 4581 Google Scholar
[15]	Yang Q, Hu X H, Shen X D, Krasheninnikov A V, Chen Z F, Sun L T 2021 ACS Appl. Mater. Interfaces 13 21593 Google Scholar
[16]	Wang J X, Kou L Z, Ni Y R, Hu X H 2021 J. Phys. Condens. Matter 33 235502 Google Scholar
[17]	Kou L, Tang C, Guo W, Chen C 2011 ACS Nano 5 1012 Google Scholar
[18]	Liu L F, Kou L Z, Wang Y F, Lu C H, Hu X H 2020 Nanotechnology 31 455702 Google Scholar
[19]	Tao P, Guo H H, Zhang Z D, Yang T 2014 J. Appl. Phys. 115 054305 Google Scholar
[20]	Jiang C H, Zhou R Q, Peng Z H, Zhu J F, Chen Q 2016 Phys. Chem. Chem. Phys. 18 32528 Google Scholar
[21]	Huang B, Clark G, Navarro-Moratalla E, Klein D R, Cheng R, Seyler K L, Zhong D, Schmidgall E, McGuire M A, Cobden D H, Yao W, Xiao D, Jarillo-Herrero P, Xu X D 2017 Nature 546 270 Google Scholar
[22]	Gong C, Li L, Li Z L, Ji H W, Stern A, Xia Y, Cao T, Bao W, Wang C Z, Wang Y A, Qiu Z Q, Cava R J, Louie S G, Xia J, Zhang X 2017 Nature 546 265 Google Scholar
[23]	Zhang Z W, Shang J Z, Jiang C Y, Rasmita A, Gao W B, Yu T 2019 Nano Lett. 19 3138 Google Scholar
[24]	Chen W J, Sun Z Y, Wang Z J, Gu L H, Xu X D, Wu S W, Gao C L 2019 Science 366 983 Google Scholar
[25]	Tang C L, Zhang Z W, Lai S, Tan Q H, Gao W B 2020 Adv. Mater. 32 1908498 Google Scholar
[26]	Lyons T P, Gillard D, Molina-Sanchez A, Misra A, Withers F, Keatley P S, Kozikov A, Taniguchi T, Watanabe K, Novoselov K S, Fernandez-Rossier J, Tartakovskii A I 2020 Nat. Commun. 11 6021 Google Scholar
[27]	Webster L, Yan J A 2018 Phys. Rev. B 98 144411 Google Scholar
[28]	Cheng Y C, Zhu Z Y, Mi W B, Guo Z B, Schwingenschlogl U 2013 Phys. Rev. 87 100401 Google Scholar
[29]	Li B, Xing T, Zhong M Z, Huang L, Lei N, Zhang J, Li J B, Wei Z M 2017 Nat. Commun. 8 1958 Google Scholar
[30]	Peng Y T, Wei S Y, Xia C X, Jia Y 2013 Mod. Phys. Lett. B 27 1350204 Google Scholar
[31]	Song C S, Xiao W, Li L, Lu Y, Jiang P, Li C, Chen A X, Zhong Z C 2019 Phys. Rev. B 99 214435 Google Scholar
[32]	Guo Y L, Yuan S J, Wang B, Shi L, Wang J L 2018 J. Mater. Chem. C 6 5716 Google Scholar
[33]	Kresse G, Furthmuller J 1996 Phys. Rev. B 54 11169 Google Scholar
[34]	Kresse G, Furthmuller J 1996 Comput. Mater. Sci. 6 15 Google Scholar
[35]	Blochl P E 1994 Phys. Rev. B 50 17953 Google Scholar
[36]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[37]	Chen S B, Huang C X, Sun H S, Ding J F, Jena P, Kan E 2019 J. Phys. Chem. C 123 17987 Google Scholar
[38]	Tang C, Zhang L, Du A J 2020 J. Mater. Chem. C 8 14948 Google Scholar
[39]	Bacaksiz C, Sabani D, Menezes R M, Milosevic M V 2021 Phys. Rev. B 103 125418 Google Scholar
[40]	Zhang H, Yang W, Ning Y, Xu X H 2020 Nanoscale 12 13964 Google Scholar
[41]	隋雪蕾 2017 博士学位论文 (北京: 清华大学) Sui X L 2017 Ph. D. Dissertation (Beijing: Tsinghua University) (in Chinese)
[42]	Krasheninnikov A V, Lehtinen P O, Foster A S, Pyykko P, Nieminen R M 2009 Phys. Rev. Lett. 102 126807 Google Scholar
[43]	Sui X L, Si C, Shao B, Zou X L, Wu J, Gu B L, Duan W H 2015 J. Phys. Chem. C 119 10059 Google Scholar
[44]	Tiwari S, Van-de-Put M L, Soree B, Vandenberghe W G 2021 Phys. Rev. B 103 014432 Google Scholar
[45]	Goodenough J B 1955 Phys. Rev. 100 564 Google Scholar
[46]	Kanamori J 1960 J. Appl. Phys. 31 S14 Google Scholar
[47]	Anderson P W 1959 Phys. Rev. 115 2 Google Scholar
[48]	Wang X L 2008 Phys. Rev. Lett. 100 156404 Google Scholar

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Tunable electronic and magnetic properties of transition-metal atoms doped CrBr₃ monolayer

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Corresponding author: Hu Xiao-Hui, xiaohui.hu@njtech.edu.cn

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	CrBr₃	Sc	Ti	V	Cr	Mn	Fe	Co	Ni	Cu	Zn
J/meV	2.39	5.95	3.95	5.10	2.66	3.96	2.80	1.25	2.97	3.27	4.73

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Tunable electronic and magnetic properties of transition-metal atoms doped CrBr3 monolayer

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Corresponding author: Hu Xiao-Hui, xiaohui.hu@njtech.edu.cn

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Tunable electronic and magnetic properties of transition-metal atoms doped CrBr₃ monolayer