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Effects of interstitial dopings of 3d transition metal atoms on antimonene: A first-principles study
Applied Surface Science 458 (2018) 572–579
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Effects of interstitial dopings of 3d transition metal atoms on antimonene: A first-principles study
T
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Yungang Zhou , Xudong Lin School of Physics, University of Electronic Science and Technology of China, Chengdu 610054, PR China
A R T I C LE I N FO
A B S T R A C T
Keywords: Antimonene Dopings Electronic and magnetic properties Density functional theory
Antimonene, a new elemental two-dimensional (2D) material, attracts extensive attention recently. In particular, such 2D structure has been successfully fabricated by various strategies experimentally (Nat. Commun. 7 (2016) 13352; Adv. Mater. 28 (2016) 6332–6336; Angew. Chem. Int. Ed. 55 (2016) 14345–14349; Nano Lett. 17 (2017) 4970–4975). In this report, we, using first-principles calculations based on density functional theory (DFT), studied the effects of interstitial dopings of 3d transition metal (TM) atoms on antimonene. Our calculations revealed that the geometric structure of antimonene can be well kept after dopings of the TM atoms. Due to the relatively large values of the binding energies, TM atoms can robustly occupy at the interstitial site of antimonene. Interestingly, we found interstitial doping can make nonmagnetic antimonene system exhibit novel magnetic behavior. Moreover, interstitial doping also can effectively functionalize the electronic property of antimonene that antimonene system can be a half-metal, metal or spin-polarized semiconductor depending on the kind of impure atoms. In addition, the effect of doping of two TM atoms on antimonene was also checked. It was found that TM atoms prefer to dope at the adjacent sites due to the strong magnetic coupling, which associates with the new electronic and magnetic properties. All these results demonstrate that interstitial doping is a feasible method to tune the properties of antimonene, which is important for designing and developing new antimonene-based electronic devices.
1. Introduction Due to the ultrathin nature and rather unique properties, more and more attention has been paid to the 2D materials. Among these, antimonene, a monolayer honeycomb buckled structure, attracts tremendous interest in most recent years [1–3]. It was first proposed by Zhang et al in 2015 [4]. The study shows that antimonene can be thermodynamically stable and exhibit a semiconducting property with a gap of 2.28 eV [4]. Meanwhile, Zhang et al. [5] and Sharma et al. [6] also revealed the high carrier mobility and the excellent thermoelectric performance for the antimonene, respectively. In addition, strain-induced high temperature quantum spin hall effect [7], electronic fieldinduced indirect-direct band gap transition [8], defect-induced spin splitting [9,10] and chemical functionalization-induced topological insulator property [11] also have been reported. It should be noted that some strategies, such as van der waals epitaxy growth [12], mechanical isolation [13], liquid-phase exfoliation [14] and solid-source molecular beam epitaxy [15], have been proposed to synthesize such a honeycomb structure. Moreover, the possible applications of antimonene, such as thermoelectric devices [16], photovoltaics [17,18] and Na-ion
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battery [19], also have been proposed. Application of 2D material often requires functionalization to modify or optimize its properties. Due to the large surface ratio, the properties of 2D structure can be easily functionalized through dopings of impurity atoms. Krasheninnikov et al. [20], Huang et al. [21] and Ma et al. [22] have studied the effects of substitutional dopings of 3d-TM atoms on graphene, BN sheet and MoS2 sheet, respectively, and Hu et al. [23], Ma et al. [24] and Wang et al. [25] have explored the influences of adsorptional dopings of 3d-TM atoms on graphene, BN sheet and MoS2 sheet, respectively. These studies show that most metallic atoms can effectively modulate the electronic and magnetic properties of the 2D structures. To date, like to other 2D structures, some groups have provided systematical discussions for the effects of substitutional doping [26,27] and adsorptional doping [28] on the properties of antimonene. Note that, comparing with most 2D structures, such graphene (2.46 Å) [23], BN sheet (2.51 Å) [24], MoS2 sheet (3.19 Å) [22], the lattice constant of antimonene (4.05 Å) [26] is much larger. Remarkable lattice constant leads to a large size of honeycomb cavity, which may be suitable for the occupation of external atoms in antimonene. It should be noted that, such occupation, denoted as the
Corresponding author. E-mail address: [email protected] (Y. Zhou).
https://doi.org/10.1016/j.apsusc.2018.07.126 Received 14 April 2018; Received in revised form 12 July 2018; Accepted 19 July 2018 Available online 19 July 2018 0169-4332/ © 2018 Published by Elsevier B.V.
Applied Surface Science 458 (2018) 572–579
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for the antimonene. Thus, in this work, we mainly consider the dopings of Ti, V, Mn, Fe and Co atoms in antimonene. Optimized geometric structures for the doped systems are depicted in Fig. 2, and corresponding structural parameters are listed in Table 1. Clearly, compared with the binding length of 2.89 Å of pristine antimonene, the values of d1 in Ti-, V-, Mn-, Fe- and Co-doped antimonene systems are somewhat increased. It should be noted that the values of d2, d3, d4 and d5 in Ti-, V-, Mn-, Fe- and Co-doped antimonene systems are very close to the value of 2.89 Å of pure antimonene. Moreover, calculated lattice constants of Ti-, V-, Mn-, Fe- and Co-doped antimonene systems on the basic of 4 × 4 supercell are also very close to the value of 16.5 Å found in pristine antimonene. Consequently, we can conclude that, after dopings of the TM atoms, the geometry of antimonene can be well kept here.
interstitial doping here, was neglected in previous studies. In this work, by means of first-principles calculations, we present an extensive analysis of the effects of interstitial dopings of 3d-TM atoms on antimonene. The formwork of our work is clear. It was arranged as follow: firstly we investigated the geometric structures of TM-doped antimonene systems; secondly we examined the stabilities of TM-doped antimonene systems; thirdly we studied the magnetic behaviors of TMdoped antimonene systems; and fourthly the electronic properties of TM-doped antimonene systems were explored. In addition, we also explored the effect of doping of two magnetic atoms on antimonene. Full understanding of these results is important for designing and developing new antimonene-based electronic devices. 2. Methods
3.2. Stabilities of TM-doped antimonene systems
First-principles calculations are performed within the DFT framework, as implemented in the Vienna ab initio Simulation Package (VASP). The electronic exchange-correlation interaction is treated using the Perdew-Burke-Ernzerhof functional (PBE) within the generalized gradient approximation (GGA). The kinetic-energy cutoff for the valence electron wave functions is set as 500 eV. Considering the localization character of 3d electrons of TM atoms, GGA+U formalism is adopted to describe the strong on-site Coulomb interaction. The effective Coulomb exchange interaction, Ueff = U-J, is set as 3 for the TM atoms here and its veracity has been confirmed in previous studies [29,30]. We choose a 4 × 4 supercell of antimonene as the host for the doping of 3d-TM atoms. A 8 × 8 × 1 k-grid mesh in the brillouin zone is used for the geometric optimization of single TM atom doped antimonene, and 4 × 4 × 1 k-grid mesh in the brillouin zone is used for the geometric optimization of two TM atoms doped antimonene. Note that, the k-grid mesh is extended up to a large value for the self consistent calculations to obtain more precise electronic structure. During the calculations, the atomic positions and the geometric structure of the cell are optimized until the atomic forces are less than 0.02 eVÅ−1.
Then we analyze the stability of the dopings of TM atoms in antimonene. The binding energy in the calculations was defined as follows:
Eb = Eantimonene + E TM - E TM - antimonene where ETM-antimonene is the total energy of antimonene system with TM doping and Eantimonene is the energy of pristine antimonene. ETM is the energy of an isolated TM atom. According to this concept, the doped system was assumed to be stable when the quantity was positive. Calculated binding energies for Ti-, V-, Mn-, Fe- and Co-doped antimonene systems are about 1.396, 1.999, 0.708, 2.057 and 2.533 eV, respectively, which are comparable with that found in TM-adsorbed arsenene systems (0.39–2.37 eV) and TM-adsorbed germanene systems (1.39–4.46 eV) under the DFT+U calculations [31,32]. It should be mentioned that the binding energies obtained from the DFT+U calculations are usually lower than that from the DFT calculations. In order to further understand the interaction between the TM atom and the antimonene, we also examined the binding energies of the doped systems with the DFT calculations. On the basic of DFT calculations, binding energies of Ti-, V-, Mn-, Fe- and Co-doped antimonene systems become about 3.496, 2.784, 2.168, 3.063 and 4.088 eV, respectively. These values are also comparable with that found in TM-adsorbed arsenene systems (1.96–3.53 eV) [31], TM-adsorbed phosphorene systems (1.78–3.56 eV) [33], TM-adsorbed germanene systems (2.48–4.35 eV) [34] and TM-adsorbed silicene systems (3.48–5.61 eV) [35] on the basic of DFT calculations. Thus, TM atoms can stably occupy at the interstitial site of antimonene. Robust stabilities of TMdoped antimonene systems also can be attributed to the interaction between the TM atom and its neighboring Sb atoms. One can see that, in all doped systems, the TM atoms display an almost perfect C6v symmetric configuration. It means that each TM atom in the doped system can bond with 6 neighboring Sb atoms. Besides, calculated the TM-Sb binding lengths are about 2.76, 2.77, 2.71, 2.66 and 2.62 Å for Ti-, V-, Mn-, Fe- and Co-doped antimonene systems, respectively. Obviously, these values are smaller than the Sb-Sb binding length of 2.89 Å found in pristine antimonene. Moreover, as shown in Fig. 3, a remarkable hybridization between the TM atom and the antimonene host, located at the energy region from −6 to 3 eV, was observed for the doped systems. These results explain why TM atom can robustly occupy at the interstitial site of the antimonene.
3. Results and discussion 3.1. Geometric structures of TM-doped antimonene systems The geometric structures of TM-doped antimonene systems are firstly studied. Fig. 1 displays a schematic illustration of top and side views of a 4 × 4 supercell of interstitially doped antimonene. After optimization, we found that Ti-, V-, Mn-, Fe- and Co-dopings can remain the geometric structure of antimonene very well while other dopings, such as Sc- and Cr-dopings, give rise to a noticeable local deformation
3.3. Magnetic properties of TM-doped antimonene systems Pristine arsenene is a nonmagnetic material. Thus, one important objective for the dopings is to discuss the magnetic properties of TMinteracted antimonene systems. Calculated energy differences between the magnetic state and the nonmagnetic state for V-, Mn-, Fe- and Codoped antimonene systems are about 1.20, 2.45, 1.68 and 0.56 eV, respectively. Thus, these systems exhibit a magnetic behavior. Note that, due to the relatively large values of the energy differences between
Fig. 1. The schematic illustration of top and side views of a 4 × 4 supercell of interstitially doped antimonene. 573
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Fig. 2. Optimized geometries of Ti-, V-, Mn-, Fe- and Co-doped antimonene systems. Table 1 Structures parameters of single TM atom doped antimonene. dTM-Sb is the binding length of TM-Sb bond. dx (X = 1, 2, 3, 4, 5) is the binding length of Sb-Sb bond. a is the lattice constant of the doped system with 4 × 4 supercell.
dTM-Sb (Å) d1 (Å) d2 (Å) d3 (Å) d4 (Å) d5 (Å) a (Å)
antimonene-Ti
antimonene-V
antimonene-Mn
antimonene-Fe
antimonene-Co
2.76 3.15 2.87 2.90 2.89 2.89 16.6
2.77 3.08 2.87 2.90 2.89 2.89 16.6
2.71 3.06 2.87 2.90 2.89 2.90 16.6
2.66 3.02 2.89 2.90 2.89 2.89 16.5
2.62 2.98 2.88 2.90 2.89 2.89 16.5
shown in Figs. 5 and 6, respectively. Pristine antimonene is a semiconductor with a gap value of 1.26 eV. TM-dopins give rise to some localized states in the fundamental band gap of antimonene, which modify the electronic property of antimonene. For example, the majority spin channel in V-doped system and the minority spin channels in Mn- and Fe-doped systems show a metallic behavior. Meanwhile, the other spin channel in these systems is found to be semiconducting. It implies that V-, Mn- and Fe-doped antimonene systems are half-metallic. Note that, for these systems, the size of band gap in the semiconducting spin channel is larger than 0.95 eV, which indicates a robustly stability of the half-metallic property. In the case of the Codoping, the spin polarization was also observed. Note that, both the majority and minority spin channels were found to be semiconducting. Thus, the spin-polarized semiconducting state can be realized in Codoped antimonene. This finding is also interesting because most of the conventional dilute magnetic semiconductors like to exhibit the metallic band structure after the dopings. When doped by Ti atom, the situation was quite different. Ti-doped antimonene system represents a metallic characteristic and no magnetism was found in this case. As a result, the electronic property of antimonene can be effectively tuned. Depending on the kind of impure atoms, TM-doped antimonene system can be a half-metal, spin-polarized semiconductor or metal.
the magnetic state and the nonmagnetic state, the magnetic states of these systems should be rather stable that the magnetic behavior will not be influenced by the external conditions, such as thermal fluctuation. Our calculations suggest that V- and Mn-doped antimonene systems that associate with the high magnetic state can carry the magnetic moments of 5.0 and 3.0 μB, respectively, and Fe- and Co-doped antimonene systems that associate with the low magnetic state present the magnetic moments of 2.0 and 1.0 μB, respectively. Similar phenomenon was also found in TM-adsorbed arsenene and germanene that calculated magnetic moments for V-, Mn-, Fe- and Co-doped arsenene systems are about 5, 5, 2 and 1 μB, respectively, and calculated magnetic moments for V-, Mn-, Fe- and Co-doped germanene systems are about 3, 5, 3 and 1 μB, respectively [31,32]. In contrast, the Ti-doped antimonene system was found to be nonmagnetic. To further clearly understand the magnetic states of the doped systems, the spin charge density distributions with the isosurface value of 0.01 eÅ−1 are plotted in the Fig. 4a. Clearly, in all doped systems, the spin density is entirely localized at TM impurity and no spin density is induced even in the nearest Sb atoms. Fig. 4b illustrates the partial density of states (PDOS) of the magnetic atoms. We found that the major source of spin polarization for the TM atom originates from the 3d-orbitals. Further examination shows that all 3d-orbitals of the TM atom including dxy, dyz, dz2, dxz and dx2 are responsible for the magnetism. As a result, the V-, Mn-, Fe- and Codoped antimonene systems may be useful for the applications of spintronics and magnetic storage.
3.5. Influence of two magnetic atoms on antimonene In order to understand the interaction between the impure atoms and its influence for the electronic and magnetic properties of antimonene, we finally investigated the doping of two magnetic atoms in 4 × 4 antimonene supercell. We considered three possible independent configurations, namely 1–2, 1–3 and 1–4 configurations, as shown in Fig. 7. Here we use 1- j to denote the doped pair, in which one TM atom occupies at the fixed 1 position and the other TM atom occupies at the j
3.4. Electronic properties of TM-doped antimonene systems Another prime objective of doping is the modification of electronic property of 2D structure. To this end, we turn to check the electronic properties of TM-doped antimonene systems now. Calculated band structures and total density of states (TDOS) of the doped systems are 574
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Fig. 3. TDOS of the TM atoms and antimonene host in Ti-, V-, Mn-, Fe- and Co-doped antimonene systems.
Binding energies for antimonene-(V-V)-AFM1-2, antimonene-(Fe-Fe)AFM1-2, antimonene-(Mn-Mn)-FM1-2 and antimonene-(Co-Co)-FM1-2 structures are about 2.711, 2.401, 1.275 and 2.669 eV, respectively. Note that, these values are larger than that of single TM-doped antimonene systems. It means that when another TM atom dopes in the antimonene, the stability can be enhanced largely due to the coupling interaction between the TM atoms. It manifests a feasibility of the occupation of TM at relatively high concentration. TDOS and spin charge density plots of these structures are shown in Fig. 8. One can see that, comparing with the electronic and magnetic properties of single TMdoped antimonene systems, the situations here are somewhat different. As observed, the net magnetic moment is found to be 0 μB for antimonene-(V-V)-AFM1-2 and antimonene-(Fe-Fe)-AFM1-2 systems while antimonene-(Mn-Mn)-FM1-2 and antimonene-(Co-Co)-FM1-2 structures can present relatively large magnetism. Besides, we also found antimonene-(V-V)-AFM1-2 and antimonene-(Fe-Fe)-AFM1-2 systems exhibit semiconducting property while antimonene-(Mn-Mn)-FM1-2 and antimonene-(Co-Co)-FM1-2 systems can possess half-metallic property.
position. Besides, for each configuration, the ferromagnetic (FM) and antiferromagnetic (AFM) couplings were also considered. The binding energies for the doped systems are listed in Table 2. Here the binding energy in the calculation was defined as follows:
Eb = (Eantimonene + 2E TM - E TM - antimonene)/2 where ETM-antimonene and Eantimonene are the energies of antimonene systems with and without TM dopings, respectively. ETM is the energy of an isolated TM impurity. Large binding energy indicates that the doping is energetically favorable. Clearly, TM atoms prefer to dope as a 1–2 configuration, in which two TM atoms occupy at the adjacent positions. For 1–2 configuration, we further found that V- and Fe-dopings prefer the AFM coupling while Mn- and Co-dopings prefer the FM coupling. Similar coupled behaviors also have been reported in TM-adsorbed arsenene systems that V- and Fe-dopings prefer the AFM coupling while Mn- and Co-dopings prefer the FM coupling [31]. As a result, antimonene-(V-V)-AFM1-2, antimonene-(Fe-Fe)-AFM1-2, antimonene-(MnMn)-FM1-2 and antimonene-(Co-Co)-FM1-2 structures are favorable. 575
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Fig. 4. (a) The spin charge density distributions with the isosurface value of 0.01 eÅ−1 for V-, Mn-, Fe- and Co-doped antimonene systems. (b) PDOS of the magnetic atoms in V-, Mn-, Fe- and Co-doped antimonene systems.
Fig. 5. Band structures for the Ti-, V-, Mn-, Fe- and Co-doped antimonene systems.
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Fig. 6. TDOS for the Ti-, V-, Mn-, Fe- and Co-doped antimonene systems.
Fig. 7. Schematic illustration of top and side views two TM atoms doped antimonene systems.
4. Conclusion
Table 2 Binding energies of two TM atoms doped antimonene.
AFM1-2 (eV) FM1-2 (eV) AFM1-3 (eV) FM1-3 (eV) AFM1-4 (eV) FM1-4 (eV)
antimonene(V-V)
antimonene(Mn-Mn)
antimonene(Fe-Fe)
antimonene(Co-Co)
2.711
1.269
2.401
2.665
2.643
1.275
2.187
2.669
2.107
0.693
2.030
2.495
2.014
0.693
1.914
2.494
2.055
0.768
1.978
2.544
2.018
0.757
1.978
2.543
Using first-principles calculations, we have investigated the effects of interstitial dopings of 3d-TM atoms on antimonene. Our conclusions include the follow: (1) the geometry of antimonene can be well kept after the dopings of the TM atoms; (2) TM atoms can robustly occupy at the interstitial site of the antimonene; (3) due to the relatively large energy differences between the magnetic state and the nonmagnetic state, TM-doped antimonene systems can exhibit a robustly magnetic behavior; (4) TM-dopins give rise to some localized states in the fundamental band gap of antimonene that, depending on the kind of impure atoms, TM-doped antimonene system can be a half-metal, spinpolarized semiconductor or metal; (5) we also checked the effect of doping of two TM atoms on antimonene and observed some new electronic and magnetic properties. All these results demonstrate that interstitial doping is a feasible method to tune the properties of antimonene. We believe our results will give some guidances for the design 577
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Fig. 8. (a) TDOS for the antimonene-(V-V)-AFM1-2, antimonene-(Mn-Mn)-FM1-2, antimonene-(Fe-Fe)AFM1-2 and antimonene-(Co-Co)-FM1-2 structures. (b) Spin charge density distributions with the isosurface value of 0.01 eÅ−1 for antimonene-(V-V)AFM1-2, antimonene-(Mn-Mn)-FM1-2, antimonene(Fe-Fe)-AFM1-2 and antimonene-(Co-Co)-FM1-2 structures.
of new antimonene-based electronic devices. [13]
Acknowledgements
[14]
This project was supported by the National Natural Science Foundation of China (No. 11504044).
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Effects of interstitial dopings of 3d transition metal atoms on antimonene: A first-principles study
T
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Yungang Zhou , Xudong Lin School of Physics, University of Electronic Science and Technology of China, Chengdu 610054, PR China
A R T I C LE I N FO
A B S T R A C T
Keywords: Antimonene Dopings Electronic and magnetic properties Density functional theory
Antimonene, a new elemental two-dimensional (2D) material, attracts extensive attention recently. In particular, such 2D structure has been successfully fabricated by various strategies experimentally (Nat. Commun. 7 (2016) 13352; Adv. Mater. 28 (2016) 6332–6336; Angew. Chem. Int. Ed. 55 (2016) 14345–14349; Nano Lett. 17 (2017) 4970–4975). In this report, we, using first-principles calculations based on density functional theory (DFT), studied the effects of interstitial dopings of 3d transition metal (TM) atoms on antimonene. Our calculations revealed that the geometric structure of antimonene can be well kept after dopings of the TM atoms. Due to the relatively large values of the binding energies, TM atoms can robustly occupy at the interstitial site of antimonene. Interestingly, we found interstitial doping can make nonmagnetic antimonene system exhibit novel magnetic behavior. Moreover, interstitial doping also can effectively functionalize the electronic property of antimonene that antimonene system can be a half-metal, metal or spin-polarized semiconductor depending on the kind of impure atoms. In addition, the effect of doping of two TM atoms on antimonene was also checked. It was found that TM atoms prefer to dope at the adjacent sites due to the strong magnetic coupling, which associates with the new electronic and magnetic properties. All these results demonstrate that interstitial doping is a feasible method to tune the properties of antimonene, which is important for designing and developing new antimonene-based electronic devices.
1. Introduction Due to the ultrathin nature and rather unique properties, more and more attention has been paid to the 2D materials. Among these, antimonene, a monolayer honeycomb buckled structure, attracts tremendous interest in most recent years [1–3]. It was first proposed by Zhang et al in 2015 [4]. The study shows that antimonene can be thermodynamically stable and exhibit a semiconducting property with a gap of 2.28 eV [4]. Meanwhile, Zhang et al. [5] and Sharma et al. [6] also revealed the high carrier mobility and the excellent thermoelectric performance for the antimonene, respectively. In addition, strain-induced high temperature quantum spin hall effect [7], electronic fieldinduced indirect-direct band gap transition [8], defect-induced spin splitting [9,10] and chemical functionalization-induced topological insulator property [11] also have been reported. It should be noted that some strategies, such as van der waals epitaxy growth [12], mechanical isolation [13], liquid-phase exfoliation [14] and solid-source molecular beam epitaxy [15], have been proposed to synthesize such a honeycomb structure. Moreover, the possible applications of antimonene, such as thermoelectric devices [16], photovoltaics [17,18] and Na-ion
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battery [19], also have been proposed. Application of 2D material often requires functionalization to modify or optimize its properties. Due to the large surface ratio, the properties of 2D structure can be easily functionalized through dopings of impurity atoms. Krasheninnikov et al. [20], Huang et al. [21] and Ma et al. [22] have studied the effects of substitutional dopings of 3d-TM atoms on graphene, BN sheet and MoS2 sheet, respectively, and Hu et al. [23], Ma et al. [24] and Wang et al. [25] have explored the influences of adsorptional dopings of 3d-TM atoms on graphene, BN sheet and MoS2 sheet, respectively. These studies show that most metallic atoms can effectively modulate the electronic and magnetic properties of the 2D structures. To date, like to other 2D structures, some groups have provided systematical discussions for the effects of substitutional doping [26,27] and adsorptional doping [28] on the properties of antimonene. Note that, comparing with most 2D structures, such graphene (2.46 Å) [23], BN sheet (2.51 Å) [24], MoS2 sheet (3.19 Å) [22], the lattice constant of antimonene (4.05 Å) [26] is much larger. Remarkable lattice constant leads to a large size of honeycomb cavity, which may be suitable for the occupation of external atoms in antimonene. It should be noted that, such occupation, denoted as the
Corresponding author. E-mail address: [email protected] (Y. Zhou).
https://doi.org/10.1016/j.apsusc.2018.07.126 Received 14 April 2018; Received in revised form 12 July 2018; Accepted 19 July 2018 Available online 19 July 2018 0169-4332/ © 2018 Published by Elsevier B.V.
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for the antimonene. Thus, in this work, we mainly consider the dopings of Ti, V, Mn, Fe and Co atoms in antimonene. Optimized geometric structures for the doped systems are depicted in Fig. 2, and corresponding structural parameters are listed in Table 1. Clearly, compared with the binding length of 2.89 Å of pristine antimonene, the values of d1 in Ti-, V-, Mn-, Fe- and Co-doped antimonene systems are somewhat increased. It should be noted that the values of d2, d3, d4 and d5 in Ti-, V-, Mn-, Fe- and Co-doped antimonene systems are very close to the value of 2.89 Å of pure antimonene. Moreover, calculated lattice constants of Ti-, V-, Mn-, Fe- and Co-doped antimonene systems on the basic of 4 × 4 supercell are also very close to the value of 16.5 Å found in pristine antimonene. Consequently, we can conclude that, after dopings of the TM atoms, the geometry of antimonene can be well kept here.
interstitial doping here, was neglected in previous studies. In this work, by means of first-principles calculations, we present an extensive analysis of the effects of interstitial dopings of 3d-TM atoms on antimonene. The formwork of our work is clear. It was arranged as follow: firstly we investigated the geometric structures of TM-doped antimonene systems; secondly we examined the stabilities of TM-doped antimonene systems; thirdly we studied the magnetic behaviors of TMdoped antimonene systems; and fourthly the electronic properties of TM-doped antimonene systems were explored. In addition, we also explored the effect of doping of two magnetic atoms on antimonene. Full understanding of these results is important for designing and developing new antimonene-based electronic devices. 2. Methods
3.2. Stabilities of TM-doped antimonene systems
First-principles calculations are performed within the DFT framework, as implemented in the Vienna ab initio Simulation Package (VASP). The electronic exchange-correlation interaction is treated using the Perdew-Burke-Ernzerhof functional (PBE) within the generalized gradient approximation (GGA). The kinetic-energy cutoff for the valence electron wave functions is set as 500 eV. Considering the localization character of 3d electrons of TM atoms, GGA+U formalism is adopted to describe the strong on-site Coulomb interaction. The effective Coulomb exchange interaction, Ueff = U-J, is set as 3 for the TM atoms here and its veracity has been confirmed in previous studies [29,30]. We choose a 4 × 4 supercell of antimonene as the host for the doping of 3d-TM atoms. A 8 × 8 × 1 k-grid mesh in the brillouin zone is used for the geometric optimization of single TM atom doped antimonene, and 4 × 4 × 1 k-grid mesh in the brillouin zone is used for the geometric optimization of two TM atoms doped antimonene. Note that, the k-grid mesh is extended up to a large value for the self consistent calculations to obtain more precise electronic structure. During the calculations, the atomic positions and the geometric structure of the cell are optimized until the atomic forces are less than 0.02 eVÅ−1.
Then we analyze the stability of the dopings of TM atoms in antimonene. The binding energy in the calculations was defined as follows:
Eb = Eantimonene + E TM - E TM - antimonene where ETM-antimonene is the total energy of antimonene system with TM doping and Eantimonene is the energy of pristine antimonene. ETM is the energy of an isolated TM atom. According to this concept, the doped system was assumed to be stable when the quantity was positive. Calculated binding energies for Ti-, V-, Mn-, Fe- and Co-doped antimonene systems are about 1.396, 1.999, 0.708, 2.057 and 2.533 eV, respectively, which are comparable with that found in TM-adsorbed arsenene systems (0.39–2.37 eV) and TM-adsorbed germanene systems (1.39–4.46 eV) under the DFT+U calculations [31,32]. It should be mentioned that the binding energies obtained from the DFT+U calculations are usually lower than that from the DFT calculations. In order to further understand the interaction between the TM atom and the antimonene, we also examined the binding energies of the doped systems with the DFT calculations. On the basic of DFT calculations, binding energies of Ti-, V-, Mn-, Fe- and Co-doped antimonene systems become about 3.496, 2.784, 2.168, 3.063 and 4.088 eV, respectively. These values are also comparable with that found in TM-adsorbed arsenene systems (1.96–3.53 eV) [31], TM-adsorbed phosphorene systems (1.78–3.56 eV) [33], TM-adsorbed germanene systems (2.48–4.35 eV) [34] and TM-adsorbed silicene systems (3.48–5.61 eV) [35] on the basic of DFT calculations. Thus, TM atoms can stably occupy at the interstitial site of antimonene. Robust stabilities of TMdoped antimonene systems also can be attributed to the interaction between the TM atom and its neighboring Sb atoms. One can see that, in all doped systems, the TM atoms display an almost perfect C6v symmetric configuration. It means that each TM atom in the doped system can bond with 6 neighboring Sb atoms. Besides, calculated the TM-Sb binding lengths are about 2.76, 2.77, 2.71, 2.66 and 2.62 Å for Ti-, V-, Mn-, Fe- and Co-doped antimonene systems, respectively. Obviously, these values are smaller than the Sb-Sb binding length of 2.89 Å found in pristine antimonene. Moreover, as shown in Fig. 3, a remarkable hybridization between the TM atom and the antimonene host, located at the energy region from −6 to 3 eV, was observed for the doped systems. These results explain why TM atom can robustly occupy at the interstitial site of the antimonene.
3. Results and discussion 3.1. Geometric structures of TM-doped antimonene systems The geometric structures of TM-doped antimonene systems are firstly studied. Fig. 1 displays a schematic illustration of top and side views of a 4 × 4 supercell of interstitially doped antimonene. After optimization, we found that Ti-, V-, Mn-, Fe- and Co-dopings can remain the geometric structure of antimonene very well while other dopings, such as Sc- and Cr-dopings, give rise to a noticeable local deformation
3.3. Magnetic properties of TM-doped antimonene systems Pristine arsenene is a nonmagnetic material. Thus, one important objective for the dopings is to discuss the magnetic properties of TMinteracted antimonene systems. Calculated energy differences between the magnetic state and the nonmagnetic state for V-, Mn-, Fe- and Codoped antimonene systems are about 1.20, 2.45, 1.68 and 0.56 eV, respectively. Thus, these systems exhibit a magnetic behavior. Note that, due to the relatively large values of the energy differences between
Fig. 1. The schematic illustration of top and side views of a 4 × 4 supercell of interstitially doped antimonene. 573
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Fig. 2. Optimized geometries of Ti-, V-, Mn-, Fe- and Co-doped antimonene systems. Table 1 Structures parameters of single TM atom doped antimonene. dTM-Sb is the binding length of TM-Sb bond. dx (X = 1, 2, 3, 4, 5) is the binding length of Sb-Sb bond. a is the lattice constant of the doped system with 4 × 4 supercell.
dTM-Sb (Å) d1 (Å) d2 (Å) d3 (Å) d4 (Å) d5 (Å) a (Å)
antimonene-Ti
antimonene-V
antimonene-Mn
antimonene-Fe
antimonene-Co
2.76 3.15 2.87 2.90 2.89 2.89 16.6
2.77 3.08 2.87 2.90 2.89 2.89 16.6
2.71 3.06 2.87 2.90 2.89 2.90 16.6
2.66 3.02 2.89 2.90 2.89 2.89 16.5
2.62 2.98 2.88 2.90 2.89 2.89 16.5
shown in Figs. 5 and 6, respectively. Pristine antimonene is a semiconductor with a gap value of 1.26 eV. TM-dopins give rise to some localized states in the fundamental band gap of antimonene, which modify the electronic property of antimonene. For example, the majority spin channel in V-doped system and the minority spin channels in Mn- and Fe-doped systems show a metallic behavior. Meanwhile, the other spin channel in these systems is found to be semiconducting. It implies that V-, Mn- and Fe-doped antimonene systems are half-metallic. Note that, for these systems, the size of band gap in the semiconducting spin channel is larger than 0.95 eV, which indicates a robustly stability of the half-metallic property. In the case of the Codoping, the spin polarization was also observed. Note that, both the majority and minority spin channels were found to be semiconducting. Thus, the spin-polarized semiconducting state can be realized in Codoped antimonene. This finding is also interesting because most of the conventional dilute magnetic semiconductors like to exhibit the metallic band structure after the dopings. When doped by Ti atom, the situation was quite different. Ti-doped antimonene system represents a metallic characteristic and no magnetism was found in this case. As a result, the electronic property of antimonene can be effectively tuned. Depending on the kind of impure atoms, TM-doped antimonene system can be a half-metal, spin-polarized semiconductor or metal.
the magnetic state and the nonmagnetic state, the magnetic states of these systems should be rather stable that the magnetic behavior will not be influenced by the external conditions, such as thermal fluctuation. Our calculations suggest that V- and Mn-doped antimonene systems that associate with the high magnetic state can carry the magnetic moments of 5.0 and 3.0 μB, respectively, and Fe- and Co-doped antimonene systems that associate with the low magnetic state present the magnetic moments of 2.0 and 1.0 μB, respectively. Similar phenomenon was also found in TM-adsorbed arsenene and germanene that calculated magnetic moments for V-, Mn-, Fe- and Co-doped arsenene systems are about 5, 5, 2 and 1 μB, respectively, and calculated magnetic moments for V-, Mn-, Fe- and Co-doped germanene systems are about 3, 5, 3 and 1 μB, respectively [31,32]. In contrast, the Ti-doped antimonene system was found to be nonmagnetic. To further clearly understand the magnetic states of the doped systems, the spin charge density distributions with the isosurface value of 0.01 eÅ−1 are plotted in the Fig. 4a. Clearly, in all doped systems, the spin density is entirely localized at TM impurity and no spin density is induced even in the nearest Sb atoms. Fig. 4b illustrates the partial density of states (PDOS) of the magnetic atoms. We found that the major source of spin polarization for the TM atom originates from the 3d-orbitals. Further examination shows that all 3d-orbitals of the TM atom including dxy, dyz, dz2, dxz and dx2 are responsible for the magnetism. As a result, the V-, Mn-, Fe- and Codoped antimonene systems may be useful for the applications of spintronics and magnetic storage.
3.5. Influence of two magnetic atoms on antimonene In order to understand the interaction between the impure atoms and its influence for the electronic and magnetic properties of antimonene, we finally investigated the doping of two magnetic atoms in 4 × 4 antimonene supercell. We considered three possible independent configurations, namely 1–2, 1–3 and 1–4 configurations, as shown in Fig. 7. Here we use 1- j to denote the doped pair, in which one TM atom occupies at the fixed 1 position and the other TM atom occupies at the j
3.4. Electronic properties of TM-doped antimonene systems Another prime objective of doping is the modification of electronic property of 2D structure. To this end, we turn to check the electronic properties of TM-doped antimonene systems now. Calculated band structures and total density of states (TDOS) of the doped systems are 574
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Fig. 3. TDOS of the TM atoms and antimonene host in Ti-, V-, Mn-, Fe- and Co-doped antimonene systems.
Binding energies for antimonene-(V-V)-AFM1-2, antimonene-(Fe-Fe)AFM1-2, antimonene-(Mn-Mn)-FM1-2 and antimonene-(Co-Co)-FM1-2 structures are about 2.711, 2.401, 1.275 and 2.669 eV, respectively. Note that, these values are larger than that of single TM-doped antimonene systems. It means that when another TM atom dopes in the antimonene, the stability can be enhanced largely due to the coupling interaction between the TM atoms. It manifests a feasibility of the occupation of TM at relatively high concentration. TDOS and spin charge density plots of these structures are shown in Fig. 8. One can see that, comparing with the electronic and magnetic properties of single TMdoped antimonene systems, the situations here are somewhat different. As observed, the net magnetic moment is found to be 0 μB for antimonene-(V-V)-AFM1-2 and antimonene-(Fe-Fe)-AFM1-2 systems while antimonene-(Mn-Mn)-FM1-2 and antimonene-(Co-Co)-FM1-2 structures can present relatively large magnetism. Besides, we also found antimonene-(V-V)-AFM1-2 and antimonene-(Fe-Fe)-AFM1-2 systems exhibit semiconducting property while antimonene-(Mn-Mn)-FM1-2 and antimonene-(Co-Co)-FM1-2 systems can possess half-metallic property.
position. Besides, for each configuration, the ferromagnetic (FM) and antiferromagnetic (AFM) couplings were also considered. The binding energies for the doped systems are listed in Table 2. Here the binding energy in the calculation was defined as follows:
Eb = (Eantimonene + 2E TM - E TM - antimonene)/2 where ETM-antimonene and Eantimonene are the energies of antimonene systems with and without TM dopings, respectively. ETM is the energy of an isolated TM impurity. Large binding energy indicates that the doping is energetically favorable. Clearly, TM atoms prefer to dope as a 1–2 configuration, in which two TM atoms occupy at the adjacent positions. For 1–2 configuration, we further found that V- and Fe-dopings prefer the AFM coupling while Mn- and Co-dopings prefer the FM coupling. Similar coupled behaviors also have been reported in TM-adsorbed arsenene systems that V- and Fe-dopings prefer the AFM coupling while Mn- and Co-dopings prefer the FM coupling [31]. As a result, antimonene-(V-V)-AFM1-2, antimonene-(Fe-Fe)-AFM1-2, antimonene-(MnMn)-FM1-2 and antimonene-(Co-Co)-FM1-2 structures are favorable. 575
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Fig. 4. (a) The spin charge density distributions with the isosurface value of 0.01 eÅ−1 for V-, Mn-, Fe- and Co-doped antimonene systems. (b) PDOS of the magnetic atoms in V-, Mn-, Fe- and Co-doped antimonene systems.
Fig. 5. Band structures for the Ti-, V-, Mn-, Fe- and Co-doped antimonene systems.
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Fig. 6. TDOS for the Ti-, V-, Mn-, Fe- and Co-doped antimonene systems.
Fig. 7. Schematic illustration of top and side views two TM atoms doped antimonene systems.
4. Conclusion
Table 2 Binding energies of two TM atoms doped antimonene.
AFM1-2 (eV) FM1-2 (eV) AFM1-3 (eV) FM1-3 (eV) AFM1-4 (eV) FM1-4 (eV)
antimonene(V-V)
antimonene(Mn-Mn)
antimonene(Fe-Fe)
antimonene(Co-Co)
2.711
1.269
2.401
2.665
2.643
1.275
2.187
2.669
2.107
0.693
2.030
2.495
2.014
0.693
1.914
2.494
2.055
0.768
1.978
2.544
2.018
0.757
1.978
2.543
Using first-principles calculations, we have investigated the effects of interstitial dopings of 3d-TM atoms on antimonene. Our conclusions include the follow: (1) the geometry of antimonene can be well kept after the dopings of the TM atoms; (2) TM atoms can robustly occupy at the interstitial site of the antimonene; (3) due to the relatively large energy differences between the magnetic state and the nonmagnetic state, TM-doped antimonene systems can exhibit a robustly magnetic behavior; (4) TM-dopins give rise to some localized states in the fundamental band gap of antimonene that, depending on the kind of impure atoms, TM-doped antimonene system can be a half-metal, spinpolarized semiconductor or metal; (5) we also checked the effect of doping of two TM atoms on antimonene and observed some new electronic and magnetic properties. All these results demonstrate that interstitial doping is a feasible method to tune the properties of antimonene. We believe our results will give some guidances for the design 577
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Fig. 8. (a) TDOS for the antimonene-(V-V)-AFM1-2, antimonene-(Mn-Mn)-FM1-2, antimonene-(Fe-Fe)AFM1-2 and antimonene-(Co-Co)-FM1-2 structures. (b) Spin charge density distributions with the isosurface value of 0.01 eÅ−1 for antimonene-(V-V)AFM1-2, antimonene-(Mn-Mn)-FM1-2, antimonene(Fe-Fe)-AFM1-2 and antimonene-(Co-Co)-FM1-2 structures.
of new antimonene-based electronic devices. [13]
Acknowledgements
[14]
This project was supported by the National Natural Science Foundation of China (No. 11504044).
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