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紫磷烯是一种结构稳定且具有优异光电特性的新型二维材料, 研究掺杂效应有助于理解其物理本质, 对进一步开发纳米电子器件具有重要意义. 本文采用基于密度泛函理论的第一性原理方法, 研究了非金属元素B, C, N, O掺杂单层紫磷烯的电磁性质. 计算结果表明, B和N掺杂之后没有产生磁性, 体系依旧表现为非磁性半导体; 而C和O掺杂导致体系发生自旋劈裂, 紫磷烯由非磁性半导体转变成为双极磁性半导体, 其自旋密度主要分布在磷原子和间隙区域内而非杂原子上. 电场调控氧掺杂紫磷烯可使其载流子的自旋极化方向发生反转, 当施加一定大小的正向或反向的静电场时, 能带色散程度变强, 氧掺杂紫磷烯转变成100%自旋极化向下或向上的单自旋半金属磁体. 基于氧掺杂紫磷烯材料设计的场效应自旋滤通器可利用改变门电压方向的方法实现电流自旋极化方向的反转, 表明氧掺杂紫磷烯有望成为二维自旋场效应晶体管、双极磁性自旋电子学器件、双通道场效应自旋滤通器以及场效应自旋阀的理想候选材料.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.
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Keywords:
- violet phosphorene /
- doping /
- bipolar magnetic semiconductor /
- half-metallic magnet
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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
Fig. 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.
图 2 掺杂体系键长、形成能与掺杂位置的关系图 (a)键长dX-P1; (b)键长dX-P2; (c)键长dX-P3; (d)形成能
Fig. 2. Calculated bond length, forming energy of doping system as a function of differential substitutional sites: (a) Bond length dX-P1; (b) bond length dX-P2; (c) bond length dX-P3; (d) formation energy.
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
Fig. 3. Energy band structures of doping system: (a) B doping; (b) C doping; (c) N doping; (d) O doping.
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
Fig. 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.
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
Fig. 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.
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
Fig. 6. Schematic representations of the defect-induced impurity band electronic states. Filled and open circles denote electrons and holes, respectively.
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
Fig. 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.
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
Fig. 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.
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)
Fig. 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%.
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
Fig. 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.
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
Fig. 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.
表 1 非金属原子掺杂单层紫磷烯的总磁矩Mtot, 非金属原子X的局部磁矩MX, 磷原子的局部磁矩MP以及间隙区域的局部磁矩Mint
Table 1. Total magnetic moment Mtot, the partial magnetic moment of the dopant MX, the P atoms MP, and the interstitial region Mint, respectively.
掺杂体系 Mtot/μB MX/μB MP/μB Mint/μB 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 
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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
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[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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