Theoretical prediction of C- and O-doped Hittorf’s violet phosphorene as bipolar magnetic semiconductor material

Lu Yi-Lin; Dong Sheng-Jie; Cui Fang-Chao; Zhang Kai-Cheng; Liu Chun-Mei; Li Jie-Sen; Mao Zhuo

doi:10.7498/aps.73.20231279

Abstract

Hittorf’s violet phosphorene is a novel two-dimensional material with stable structure and excellent optoelectronic properties. Studying the doping effect helps to understand its physical essence and is of great significance in further developing nanoelectronic devices. In this paper, the first-principles method based on density functional theory is used to study the electromagnetic properties of the non-metallic element B-, C-, N-, and O-doped single-layer violet phosphene. The results show that there is no magnetism after having doped boron and nitrogen, and the system still behaves as a nonmagnetic semiconductor, while carbon doping and oxygen doping cause spin splitting, and the violet phosphorene transforms from a nonmagnetic semiconductor to a bipolar magnetic semiconductor, and its spin density is mainly distributed in the P atom and gap region, rather than on the impurity. The direction of spin polarization of its carrier can be reversed by adjusting the electric field of O-doped violet phosphorene. When a certain size of forward or reverse electrostatic field is applied, the band dispersion becomes stronger, and the O-doped violet phosphorene transforms into a half-metallic magnet with 100% downward or upward spin polarization at the Fermi level. The field effect spin filter based on O-doped violet phosphorene can reverse the direction of spin-polarized current by changing the direction of the gate voltage. This study shows that O-doped violet phosphorene is expected to be an ideal candidate material for two-dimensional spin field-effect transistors, bipolar magnetic spintronic devices, dual channel field effect spin filters, and field-effect spin valves.

Keywords:

Authors and contacts

1.
Institute of Ocean, College of Physical Science and Technology, Bohai University, Jinzhou 121007, China
2.
Faculty of Electronic Information Engineering, Guangdong Baiyun University, Guangzhou 510450, China
3.
College of Food Science and Engineering, Bohai University, Jinzhou 121007, China
4.
School of Environment and Chemical Engineering, Foshan University, Foshan 528000, China
5.
Peking Union Medical College, Chinese Academy of Medical Sciences, Tianjin 300192, China

Corresponding author: Lu Yi-Lin, yilinlu@tju.edu.cn ; Dong Sheng-Jie, shengjiedong@tju.edu.cn ;

Funds: Project supported by the Scientific Research Fund of the Education Department of Liaoning Province, China (Grant No. LJKQZ20222272) and the Open Project of the Institute of Ocean Research, Bohai University, China. (Grant No. BDHYYJY2023015).

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References

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图 1 不同掺杂位点掺杂单层紫磷烯的几何结构模型. 紫色和红色小球分别表示磷原子和掺杂原子. 标记的1, 2和3分别代表与杂质原子距离最近的3个磷原子P1, P2和P3

Figure 1. Geometric structure of the doped Hittorf’s violet phosphorene with different doping sites. The violet and red spheres represent the phosphorus atoms and the dopant atom, respectively. The marked 1, 2, and 3 denote the sites of three nearest-neighboring P atoms P1, P2, and P3.

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图 2 掺杂体系键长、形成能与掺杂位置的关系图　(a)键长d_X-P1; (b)键长d_X-P2; (c)键长d_X-P3; (d)形成能

Figure 2. Calculated bond length, forming energy of doping system as a function of differential substitutional sites: (a) Bond length d_X-P1; (b) bond length d_X-P2; (c) bond length d_X-P3; (d) formation energy.

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图 3 掺杂体系的能带结构　(a) B掺杂; (b) C掺杂; (c) N掺杂; (d) O掺杂

Figure 3. Energy band structures of doping system: (a) B doping; (b) C doping; (c) N doping; (d) O doping.

DownLoad: Full-Size Img PowerPoint

图 4 掺杂体系的态密度, 其中每一张图的上半部分和下半部分分别为P原子和X原子的分态密度　(a) B掺杂; (b) C掺杂; (c) N掺杂; (d) O掺杂

Figure 4. Density of states for doping system, and the graphs above and below indicate the partial density of states for the P atoms and X atom, respectively: (a) B doping; (b) C doping; (c) N doping; (d) O doping.

DownLoad: Full-Size Img PowerPoint

图 5 C掺杂(a)和O掺杂(b)紫磷烯的自旋密度图. 等值面为0.003 e/Å, 上图为侧视图, 下图为俯视图

Figure 5. Spatial spin density for C doping (a) and O doping (b), respectively. Isovalue is set to 0.003 e/Å, and the upper panel is the side view and the down panel is the top view.

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图 6 缺陷引起的杂质能级的电子填充状态的示意图. 实心圆圈和空心圆圈分别表示电子和空穴

Figure 6. Schematic representations of the defect-induced impurity band electronic states. Filled and open circles denote electrons and holes, respectively.

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图 7 各原子掺杂紫磷烯的差分电荷密度图(等值面为0.02 e/Å^–3)　(a) B掺杂; (b) C掺杂; (c) N掺杂; (d) O掺杂

Figure 7. Charge density difference for atom doped violet phosphoene (Isovalue is set to 0.02 e/Å^–3): (a) B doping; (b) C doping; (c) N doping; (d) O doping.

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图 8 O掺杂浓度为2.38%时, 掺杂紫磷烯在外加电场下的能带结构

Figure 8. Energy band structures of the O-doped Hittorf’s violet phosphorene with effective O-concentration of 2.38% under different applied external electric fields.

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图 9 O掺杂浓度为1.19%时, 掺杂紫磷烯的能带(a)和态密度(b)

Figure 9. Energy band structures (a) and density of states (b) of the O-doped Hittorf’s violet phosphorene with effective O-concentration of 1.19%.

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图 10 O掺杂浓度为1.19%时, 掺杂紫磷烯在外加电场下的能带结构

Figure 10. Energy band structures of the O-doped Hittorf’s violet phosphorene with effective O-concentration of 1.19% under different applied external electric fields.

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图 11 (a)基于O掺杂紫磷烯材料的场效应自旋滤通器模拟示意图; (b)电场控制下O掺杂紫磷烯的能带结构示意图

Figure 11. (a) Schematic diagram of a field-effect spin filter based on O-doped Hittorf’s violet phosphorene; (b) schematic illustration of the electrical control of the band structure of O-doped Hittorf’s violet phosphorene.

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表 1 非金属原子掺杂单层紫磷烯的总磁矩M_tot, 非金属原子X的局部磁矩M_X, 磷原子的局部磁矩M_P以及间隙区域的局部磁矩M_int

Table 1. Total magnetic moment M_tot, the partial magnetic moment of the dopant M_X, the P atoms M_P, and the interstitial region M_int, respectively.

掺杂体系 M_tot/μ_B M_X/μ_B M_P/μ_B M_int/μ_B

B掺杂 0 0 0 0

C掺杂 0.988 0.262 0.229 0.497

N掺杂 0 0 0 0

O掺杂 0.991 0.012 0.471 0.520

DownLoad: CSV

表 2 掺杂紫磷烯中X, P1, P2和P3原子的Bader电荷值

Table 2. Bader charges of the dopant X, P1, P2, and P3 atoms, respectively.

掺杂体系 X P1 P2 P3

B掺杂 2.73 5.11 5.11 5.10

C掺杂 5.50 4.44 4.55 4.50

N掺杂 6.81 4.37 4.37 4.35

O掺杂 7.38 — 4.26 4.25

DownLoad: CSV

map

[1]	Novoselov K S, Geim A K, Morozov S V, Jiang D, Zhang Y, Dubonos S V, Grigorieva I V, Firsov A A 2004 Science 306 666 Google Scholar
[2]	Ni Z Y, Liu Q H, Tang K C, Zheng J X, Zhou J, Qin R, Gao Z X, Yu D P, Lu J 2012 Nano Lett. 12 113 Google Scholar
[3]	Chen L, Liu C C, Feng B, He X, Cheng P, Ding Z, Meng S, Yao Y, Wu K 2012 Phys. Rev. Lett. 109 056804 Google Scholar
[4]	Chiappe D, Grazianetti C, Tallarida G, Fanciulli M, Molle A 2012 Adv. Mater. 24 5088 Google Scholar
[5]	Zhu C, Shao R, Chen S, Cai R, Wu Y, Yao L, Xia W, Nie M, Sun L, Gao P, Xin H L, Xu F 2019 Small Methods 3 1900061 Google Scholar
[6]	Wu G, Wu X, Xu Y, Cheng H, Meng J, Yu Q, Shi X, Zhang K, Chen W, Chen S 2019 Adv. Mater. 31 1806492 Google Scholar
[7]	Feng B, Sugino O, Liu R Y, Zhang J, Yukawa R, Kawamura M, Iimori T, Kim H, Hasegawa Y, Li H, Chen L, Wu K, Kumigashira H, Komori F, Chiang T C, Meng S, Matsuda I 2017 Phys. Rev. Lett. 118 096401 Google Scholar
[8]	Kiraly B, Liu X, Wang L, Zhang Z, Mannix A J, Fisher B L, Yakobson B I, Hersam M C, Guisinger N P 2019 ACS Nano 13 3816 Google Scholar
[9]	Qiao J, Kong X, Hu Z X, Yang F, Ji W 2014 Nat. Commun. 5 4475 Google Scholar
[10]	Zhou Q, Chen Q, Tong Y, Wang J 2016 Angew. Chem. Int. Ed. 55 11437 Google Scholar
[11]	Chen Z, Zhu Y, Wang Q, Liu W, Cui Y, Tao X, Zhang D 2019 Electrochimica Acta 295 230 Google Scholar
[12]	Tsai H S, Lai C C, Hsiao C H, Medina H, Su T Y, Ouyang H, Chen T H, Liang J H, Chueh Y L 2015 ACS Appl. Mater. Interf. 7 13723 Google Scholar
[13]	Schusteritsch G, Uhrin M, Pickard C J 2016 Nano Lett. 16 2975 Google Scholar
[14]	Lu Y L, Dong S, Zhou W, Dai S, Zhou B, Zhao H, Wu P 2018 Phys. Chem. Chem. Phys. 20 11967 Google Scholar
[15]	Zhang L, Huang H, Zhang B, Gu M, Zhao D, Zhao X, Li L, Zhou J, Wu K, Cheng Y, Zhang J 2020 Angew. Chem. Int. Ed. 132 1090 Google Scholar
[16]	Zhang B, Wang Z, Huang H, Zhang L, Gu M, Cheng Y, Wu K, Zhou J, Zhang J 2020 J. Mater. Chem. A 8 8586 Google Scholar
[17]	Dai S, Zhou W, Liu Y, Lu Y L, Sun L, Wu P 2018 Appl. Surf. Sci. 448 281 Google Scholar
[18]	Han R, Qi M, Mao Z, Lin X, Wu P 2021 Appl. Surf. Sci. 541 148454 Google Scholar
[19]	Xue R, Han R, Lin X, Wu P 2023 Appl. Surf. Sci. 608 155240 Google Scholar
[20]	Lin X, Mao Z, Dong S, Jian X, Han R, Wu P 2021 Physica E 127 114524 Google Scholar
[21]	Han R, Qi M, Dong S, Mao Z, Lin X, Wu P 2021 Physica E 129 114667 Google Scholar
[22]	Lu Y L, Dong S, Li J, Wu Y, Zhao H 2022 Physica E 138 115068 Google Scholar
[23]	Baumer F, Ma Y, Shen C, Zhang A, Chen L, Liu Y, Pfister D, Nilges T, Zhou C 2017 ACS Nano 11 4105 Google Scholar
[24]	Lu Y L, Dong S, He H, Li J, Wang X, Zhao H, Wu P 2019 Comput. Mater. Sci. 163 209 Google Scholar
[25]	谭兴毅, 王佳恒, 朱祎祎, 左安友, 金克新 2014 63 207301 Google Scholar Tan X Y, Wang J H, Zhu Y Y, Zuo A Y, Jin K X 2014 Acta Phys. Sin. 63 207301 Google Scholar
[26]	Khan I, Hong J 2015 New J. Phys. 17 023056 Google Scholar
[27]	Zheng H, Zhang J, Yang B, Du X, Yan Y 2015 Phys. Chem. Chem. Phys. 17 16341 Google Scholar
[28]	Yang L, Mi W, Wang X 2016 J. Alloys Compd. 662 528 Google Scholar
[29]	Kresse G, Hafner J 1993 Phys. Rev. B 47 R558 Google Scholar
[30]	Kresse G, Hafner J 1994 Phys. Rev. B 49 14251 Google Scholar
[31]	Blochl P E 1994 Phys. Rev. B 50 17953 Google Scholar
[32]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[33]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
[34]	Grimme S 2006 J. Comput. Chem. 27 1787 Google Scholar
[35]	Lu Y L, Dong S, Zhou W, Liu Y, Zhao H, Wu P 2017 J. Magn. Magn. Mater. 441 799 Google Scholar
[36]	Safari F, Fathipour M, Goharrizi A Y 2018 J. Comput. Electron. 17 499 Google Scholar
[37]	Henkelman G, Arnaldsson A, Jónsson H 2006 Comput. Mater. Sci. 36 354 Google Scholar

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