First-principles study of structural and electronic properties of substitutionally doped arsenene

Journal Pre-proof First-principles study of structural and electronic properties of substitutionally doped arsenene Zhiwei Liu, Xiaodan Li, Congcong Zhou, Taotao Hu, LiYao Zhang, Ruixia Niu, Yue Guan, Ningxia Zhang PII:

S1386-9477(19)31347-5

DOI:

https://doi.org/10.1016/j.physe.2020.114018

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PHYSE 114018

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Physica E: Low-dimensional Systems and Nanostructures

Received Date: 16 September 2019 Revised Date:

16 January 2020

Accepted Date: 10 February 2020

Please cite this article as: Z. Liu, X. Li, C. Zhou, T. Hu, L. Zhang, R. Niu, Y. Guan, N. Zhang, Firstprinciples study of structural and electronic properties of substitutionally doped arsenene, Physica E: Low-dimensional Systems and Nanostructures (2020), doi: https://doi.org/10.1016/j.physe.2020.114018. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2020 Published by Elsevier B.V.

First-principles study of structural and electronic properties of substitutionally doped arsenene Zhiwei Liua, XiaodanLia,*, Congcong Zhoua, Taotao Hub, LiYao Zhanga, Ruixia Niua, Yue Guana, Ningxia Zhanga a

College of Science, University of Shanghai for Science and Technology, Shanghai 200093, P.R.China b

School of Physics, Northeast Normal University, Changchun 130024, P.R.China

ABSTRACT: Arsenene has been found to have a suitable band gap and high mobility, making it a great prospect for electronic device applications. In order to make the material widely used in more fields, we need to make its electronic properties more diverse. For monolayer arsenene, which is a two-dimensional material, atom doping is the most effective and feasible method to change its electronic properties. In this paper, the structural and electronic properties of the substitutionally doped arsenene have been studied by first-principles calculations. The substitutional atoms cover group III to group VII. The calculated results indicate that the electronic properties of all doped systems in this paper are mainly controlled by impurity atoms. Magnetic states were obtained in C-, Si-, Ge- and Br-doped arsenene monolayer. Metallic behavior can be found in O-, S- and Se-doped arsenene. Through the substitutional doping of B, Al, Ga, N, F and Cl atoms, the arsenene sheets are transformed into direct bandgap semiconductors. The Br-doped system is a zero band gap material. These studies can provide some useful information for the study of two-dimensional arsenene doping systems. Our studies not only bring us some useful information for the theoretical understanding, but also provide the potential applications of future arsenene-based devices.

Keywords: first-principles; electronic properties; arsenene; substitutional doping

1.Introduction Since graphene was successfully fabricated experimentally [1], the two-dimensional (2D) materials have become the focus of scientific research. 2D graphene, a zero gap semiconductor [2], is renowned for its excellent properties, such as high carrier mobility, high strength, high electrical and thermal conductivity [3-6]. Since the band gap is an essential property in the fabrication of field effect transistors for logic circuit [7], we have to find some other promising materials to replace graphene. As typical graphene-like materials, graphyne [8], hexagonal BN [9, 10] and transition metal dichalcogenides (TMD) [11-16] have also attracted plenty of attention. Studies show that hexagonal BN is an insulator with a band gap of about 6.0 eV, which is not suitable for application of semiconductor devices [17]. Transition metal dichalcogenides, such as MoS2 [18, 19] and WS2 [20, 21], have also been widely used in the fields of optoelectronics, physics and chemical catalysis because of its unique optical and electrical properties. The study shows that, with reduced layer number, most TMD changes from an indirect band gap semiconductor with a moderate band gap to a direct band gap semiconductor [22]. However, the carrier mobility of TMD has declined substantially [23]. In 2014, Zhang et al’s have succeeded in fabricating p-type FETs based on few-layer black phosphorus crystals [24]. The results show that the monolayer black phosphorus band gap is about 2.0 eV and has high carrier mobility [25]. However, black phosphorus has poor stability and can be oxidized when exposed to air, which limits its future application [26, 27]. After phosphorene, Group-VA 2D materials (such as arsenene, antimonene and bismuthene) arouse broad interest because of the unique electronic properties and stability [28-35]. Both arsenic (As) and phosphorus (P) belong to group V and have the same outer shell electron distribution. Moreover, arsenic ranks below phosphorus in the periodic table, so it has better chemical stability. It is gratifying that Zhang et al discovered a promising two-dimensional material made of arsenic (namely arsenene) through theoretical calculation [31]. This single layer material, consists of pleated hexagonal rings, is the most common grey arsenic in the five allotropes of bulk arsenic [32]. Its layered structures are weakly coupled by van der Waals interactions [33]. In monolayer arsenic, there are three σ-bonding orbitals and a lone pair of electrons. It is proved that the monolayer arsenene satisfies the stable structure with

eight electrons [31]. Arsenene is an indirect semiconductor with a band gap of arsenene is 2.49 eV, which corresponds to the blue-light spectral range [31]. When a small external strain is applied, arsenene transforms from an indirect band gap into a direct band gap [33, 34]. What’s more, the carrier mobility of arsenene can reach several thousand square centimeters per volt-second [35]. These electronic structure characteristics show that arsenene has potential applications in blue-light detectors, LEDs, etc. Very recently, through plasma-assisted process, Tsai et al. successfully synthesized multilayer arsenene on InAs substrate. The interlayer interaction of multilayer arsenene is van der Waals force, which is easily overwhelmed. Its thickness could be changed by altering the plasma exposure time in this low-cost approach [36]. All of these properties indicate that the 2D arsenene could provide a precondition for functionalization at nanoscale. In this work, we have studied the structural characteristics, electronic properties and magnetism of substitutionally doped arsenene by using first principle calculations. The van der Waals interaction is taken into account for a better understanding of weak interlayer attractions in layered materials. Substitutional doping in 2D materials is also expected to exhibit some abnormal behaviors due to the strong electron confinement effect. The electronic properties of doped systems will be fundamentally affected by the number of valence electrons of dopants. Thus we choose dopant atoms from group III (B, Al, Ga) and group IV (C, Si, Ge) due to two and one less electron. However, the group VI (O, S, Se) and group VII (F, Cl, Br) dopants were selected because of the one or two more electrons. For comparison, the group V (N, P) (with same electrons as As atom) doped arsenene is also calculated. Our results show that, by introducing foreign atom to the arsenene, the electronic structure of the system can be modified, which could lead to appealing character. Since the interaction within corresponding layered bulk materials is weak van der Waals interaction, our results are also has the guiding meaning to understand the mechanism of the substitutional doping of bulk arsenic.

2. Methods In this work, all calculations were performed by using a first-principles method based on the density functional theory (DFT), as implemented in the Vienna Ab Initio Simulation

Package (VASP) code [37, 38]. The generalized gradient approximation (GGA) in the parameterization of Perdew-Burke-Ernzerhof (PBE) was employed to describe the exchange–correlation interactions [39]. Since the DFT-GGA calculation generally fails to predict the interlayer distances of layered structures [40], we chose to perform -D2 calculations [41], in which the van der Waals (vdW) interaction is taken into account by adding a semi-empirical dispersion potential to the conventional Kohn-Sham DFT energy. In order to obtain a more accurate band gap, the Heyd–Scuseria–Ernzerhof (HSE06) [42] screened hybrid functional was employed. The electronic wave function is developed by the plane wave function, and the integration of the Brillouin zone (BZ) is performed by the Monkhorst-Pack special k-point sampling method [43]. In view of the special hexagonal lattice structure of arsenene, we select 5×5×1 Г-centered Monkhorst-Pack grid in the calculations. We define the x and y axes to be within the arsenene plane, while the z-axis perpendicular to it. In the x-y plane we used a 4×4×1supercellto make sure the interaction between substitutional doping atoms in the periodic arrangement is negligible. A vacuum of 15 Å in the z direction was set in this work to ensure that the interaction between the layers was small enough. For ionic relaxation, the convergence criterion between two consecutive steps in our self-consistent calculation chosen as 10−5 eV and relaxation stops when the force acting on each atom are less than 0.01 eV/Å.

3. Results and discussion 3.1 Structural and electronic properties of pristine arsenene In order to set up a proper unit cell for the calculated system, we first calculated the structural parameters and electronic structure of the 4×4×1 arsenene supercell, which contains 32 arsenic atoms (Fig.1 (a) and (b)). After relaxation, the optimized lattice parameter ‘a’ of arsenene supercell is 14.49 Å. The calculated As-As bond length, sheet thickness and bond angle, are 2.513 Å, 1.393 Å and 92.226°, respectively. As shown in Table 1, a good agreement was obtained between our results and those of previously published articles, which shows the reliability of our calculation [31, 43-47]. The electronic band structure and the total density of states of a 4×4×1 arsenene are shown in Fig. 1 (b). It can be seen from Fig. 2 that the valence band maximum (VBM) lies at Γ point and the conduction band minimum (CBM)

lies between Γ and Μ point. It suggests that the material is an indirect band gap semiconductor with a band gap of 1.616 eV. This result is consistent with the reported value of 1.635 eV [44]. Table I. Calculated geometry of Arsenene, including the lattice constants (a), arsenene thickness (h), As-As bond length (d) and band gap (Eg). system

a(Å)

d(Å)

Eg(eV)

3.623

1.393

2.513

1.616

a

a

a

1.635a

3.607 Arsenene

h(Å) 1.389

2.503

3.610b

1.398b

2.510b

1.601b

3.6c

1.39c

2.505c

1.590c

3.61d

1.40d

2.51d

1.60d

a

Ref. [44] bRef. [45] cRef. [46] dRef. [47]

Fig. 1. (a) Top view, (b) side view and (c) the band structure of a 4×4×1 arsenene supercell. The As-As bond length (2.513 Å), height of the As-As bond (1.393 Å) and the band gap (1.616 eV) are displayed in the graph.

3.2 Structural and electronic properties of doped arsenene For substitutionally doped arsenene system, we first consider a vacancy-containing arsenene, in which a single As atom being removed from each 4×4 supercell. Then we put the substitutional atom in the vacancy. In this paper, the substitutional doped atom is marked as D (D = B, Al, Ga, C, Si, Ge, N, P, O, S, Se, F, Cl and Br). The structure of substitutionally

doped material (D1As31) is shown in Fig. 2. We found that the structure of the substituted doped system could generally maintain its original hexagonal structure in the pristine arsenene. However, the introduction of doped atoms breaks the symmetry of arsenene monolayer.

Fig. 2. (a) Top view and (b) side view of substitutionally doped arsenene. The substitutional doped atoms D and arsenic atoms are shown in red and purple, respectively.

The geometry of substitutionally doped D1As31 is obtained from the positions of the atoms after relaxation. The arrangement of extranuclear electrons, lattice constants, magnetic moment, formation energy (Ef) and structural configurations of substitutionally doped D1As31 obtained from our calculations are listed in Table II. After relaxation, we found that the lattice constants of all doped D1As31 arsenene did not change significantly, indicating that the structures of the doped materials are very similar to that before doping. However, the length of As-D bonds all changed with different degrees. For the same group, the length of the As-D bond increases with increasing atomic number. We attribute this phenomenon to the effect of the ionic radius on the bond length. Based on Bader analysis, the charge transferred of substitutional atom D from its adjacent three As atoms are -1.15, -0.22, -0.05, 1.67, 0.51, -0.92, 0.57, 0.29, -0.98, -0.49, -0.27, -0.68, -0.44, -0.37, respectively. We found that there is obvious charge transfer between the substitutional atom D and its three neighboring As atoms, which indicates the strong coupling between them.

Table II. Calculated geometry of substitutionally doped system D1As31, including the arrangement of extranuclear electrons (AEE), lattice constants (a=b), As-D bond length (d), total magnetic moment of the system (M), formation energy (Ef), As-As bond length (d1, d2), arsenene thickness (h1, h2) and band gap (Eg) calculated by using PBE/HSE06. D1As31

AEE

a=b (Å)

d (Å)

Ef (eV)

d1 (Å)

d2 (Å)

h1 (Å)

h2 (Å)

Eg (eV)

M(µB)

D=N

2

2s 2p

3

14.36

2.01

-0.298

2.55

2.50

0.82

1.40

1.27/1.89

NM

D=P

2

3s 3p

3

14.44

2.41

-0.393

2.52

2.50

1.29

1.39

1.62/2.22

NM

D = As

4s24p3

14.49

2.51

/

2.52

2.51

1.39

1.39

1.62/2.21

NM

D=B

2s22p1

14.44

2.06

-5.104

2.51

2.51

0.46

1.39

1.26/1.87

NM

D = Al

3s23p1

14.51

2.43

-0.324

2.50

2.52

0.51

1.43

1.46/2.06

NM

D = Ga

4s24p1

14.54

2.44

0.676

2.50

2.52

0.49

1.43

1.46/2.06

NM

D=C

2s22p2

14.41

2.00

-5.948

2.55

2.50

0.54

1.40

0.49/1.36

1.00

D = Si

2

3s 3p

2

14.48

2.40

-0.507

2.51

2.51

1.02

1.40

0.68/1.49

1.00

D = Ge

2

4s 4p

2

14.53

2.49

0.161

2.50

2.52

1.12

1.40

0.49/1.24

1.00

D=O

2

2s 2p

4

14.38

2.09

0.102

2.51

2.50

0.66

1.39

/

NM

D=S

2

3s 3p

4

14.47

2.43

0.794

2.49

2.51

1.00

1.41

/

NM

D = Se

4s24p4

14.51

2.54

1.226

2.49

2.52

1.11

1.41

/

NM

D=F

2s22p5

14.41

2.31

1.368

2.47

2.50

0.57

1.41

0.60/0.81

NM

D = Cl

3s23p5

14.53

2.65

2.769

2.47

2.51

0.24

1.44

0.65/0.83

NM

D = Br

4s24p5

14.58

2.95

3.545

2.46

2.52

1.93

1.37

0.00/0.20

2.00

To discuss the stability and feasibility of the substitutionally doped arsenene, the formation energy (Ef) in Table 1 is defined as [48]: E f = E D1 As31 − E Arsenene − µ D + µ As

(1)

Where ED1 As31 stands for the total energy of the substitutionally doped system, in which one of the As atoms is replaced with D (D = B, Al, Ga, C, Si, Ge, N, P, O, S, Se, F, Cl and Br) atom. E Arsenene represents the total energy of the pristine 4×4×1 arsenene.

µD

and µ As are

the chemical potentials of D and As atoms, respectively. We can see that the formation energies of these doping systems are very small except Cl1As31 and Br1As31. Especially, the formation energies of N-, P-, B-, Al-, C-, Si-doped systems are negative, which indicates that the doping process of these systems is exothermic and relatively stable. To check the deformation of the arsenene, the As-As bond length (d1, d2) and the

thickness of arsenene sheet (h1, h2) are also shown in table 1. The subscript 1 and 2 means the structure parameters near and far from the doping position, respectively. Compared with the bond length of As-As in pristine arsenene, the N1As31 and C1As31 systems have the longest d1 (both increased by 1.2%), while the F1As31, Cl1As31 and Br1As31 systems have the shortest d1 (decreased by 2.0%, 2.0% and 2.4%, respectively). Due to the introduction of dopant atoms, the amplitudes of the sheet thickness near the doping position (denoted by h1, shown in Fig. 2) have pronounced change. Except for Br1As31 system, the sheet thickness ‘h1’ decreased by 7.2%~82.7% from their free standing values (1.39 Å). However, in view of the bond length d2 and the sheet thickness h2 which are representative parameters of the substitutionally doped system, we could tell that the configuration distortions caused by dopant atoms are almost localized.

Fig. 3. The spin densities of (a) C, (b) Si, (c) Ge, and (d) Br-doped arsenene.

We now turn our attention to the magnetic moments of substitutionally doped system. The magnetism of two-dimensional materials, associated with strong intrinsic spin fluctuations, has long been the research emphases of condensed matter physics [49]. As we can see from Table I, only C-, Si-, Ge, Br-doped systems show magnetic behavior. In order to gain a further understanding of the magnetic D1As31 systems, the isosurface of spin density are presented in Fig. 3. We observed that the spin densities of Si- and Ge-doped arsenene are mainly distributed around the impurity atoms, indicating that the magnetic moments of these

systems are localized. However, for C- and Br-doped systems, the next nearest neighboring As atoms of host arsenene are also shown to be spin-polarized. This is due to the strong hybridization between the p orbitals (came from doapnts ) and the p and d orbitals (came from As). Magnetic materials, especially 2D materials, provide the ideal platform for exploring the area of data storage and electronics. The low-dimensional 2D arsenene, a tunable magnetism originates from defects of doping, offer spintronics and photoelectronic potentials. Since the spintronics is designed to control the spin of electrons, the magnetic states obtained in C-, Si-, Ge- and Br-doped systems make arsenene a potential candidate for application in spintronic devices.

Fig. 4. TDOS and PDOS of substitutionally doped system.

To illustrate the intrinsic mechanism behind magnetic properties in substitutionally doped system, the total and partial density of states (TDOS and PDOS) are presented in Fig. 4. Fig. 4(c) shows the total and partial density of states of group V atoms-doped arsenene. Since N, P and As atoms all belong to the fifth group of elements, they have same outer shell electron distribution. We observed that the group V atoms-doped system has similar TDOS and all three materials are semiconductors. What’s more, the PDOS shows that the electronic states near fermi level of the doping system are mainly controlled by impurity atoms. The TDOS and PDOS of group III and group IV atoms-doped arsenene are shown in Fig. 4(a)-(b). We can see that group III and group IV atoms-doped system still retain its semiconducting properties of the pristine arsenene. However, there is a significant change in TDOS. The group IV atoms-doped system has a magnetic moment, which is consistent with the data

shown in Table I. Fig. 4(d) and (e) are the TDOS and PDOS of group VI and group VII atoms-doped arsenene. Within substitutional doping of group VI atoms, the lowest unoccupied states drop below the Fermi level, indicating the n-type doping of arsenene. Fig. 5 illustrates the band structures obtained from the PBE as well as the HSE06 hybrid functional potentials, with Fermi level locates at zero bonding energy. It can be seen from Fig. 5 that the two approaches exhibit analogous band structures. Based on the PBE functional, for As32 system, the magnitude of the band gap is found to be 1.616 eV. The more accurate band gap obtained from HSE06 is 2.212 eV, which is nearly 1.4 times increase of the PBE-predicted band gap justifies the use of HSE06 functional. As presented in Fig. 5(a), the band structure of the P-doped system is very close to the pristine arsenene. However, the N-doped system transforms into a direct band gap (at Γ point) semiconductor with a reduced band gap. The group III atoms-doped systems are direct band gap semiconductors, while the group VI atoms-doped systems are found to be metallic with contributions from dopant atoms passing through the Fermi level. This means the n-type doping of arsenene increases its conductivity. As for the group IV atoms-doped arsenene, the systems behave as indirect band gap semiconductors. Around the Fermi level, the spin-up states are fully occupied while the spin-down states are unoccupied. Since the occupation situation of the spin-up and spin-down states is very uneven, the dopant atoms induced a relatively large magnetic moments in arsenene. Within substitutional doping of group VII atoms, both F- and Cl-doped arsenene systems are direct semiconductors with narrow band gaps. However, within DFT-D2 approach, the Br-doped system is half metal, its majority spin states are found to be semi-metallic (a zero band gap at Γ point) while the minority spin states are semiconducting. Through Fig. 5, we find that the impurity atoms determine the electronic properties of the D-doped arsenene systems.

Fig. 5. Band structures of the substitutionally doped systems calculated by using PBE (left panel) and HSE06 hybrid functional potentials (right panel).

The key point to understand the intrinsic mechanism of these 2D structures is to study the bonding nature between the dopant atom and the 2D monolayer system, which actually controls the dynamical behavior of growth process. The deformation charge density ( ∆ρ ) of planes passing through D and As atoms are shown in Fig. 6. The deformation charge density r r r r r is defined as ∆ρ (r ) = ρ (r ) − ∑ ρ atom (r − Rµ ) , where ρ (r ) represents the total charge µ

density of the atoms-doped arsenene and

∑µ ρ

atom

r r (r − Rµ ) are the superposition of atomic

charge densities. This ∆ρ can clearly demonstrate the charge transfer caused by the interaction between the dopant atoms and arsenene. The pink color and blue color in Fig. 6 indicate an increase (i.e. ∆ρ > 0) and decrease (i.e. ∆ρ < 0) in the electron density. For B-, C-, N-, O- and F-doped arsenene, there is obvious charge transfer from dopant atoms to its adjacent As atom. In the same main group, with the increasing atomic number, the ionic components of As-D bond decreases and the covalent components of As-D bond increases. What’s more, as the ratio of covalent bonding is lower, the formation energy and the As-D bond length of framework are both increased. In the case of group VII atoms doped arsenene, the binding distance of As-Br is much larger than the others, indicating the weak interaction between Br and the arsenene. As shown in Fig. 6, the Br atom is essentially neutral.

Fig. 6. Deformation charge density of the substitutionally doped systems

4. Conclusions Based on first-principles calculations, we have studied substitutionally doped arsenene. We replace one of the 32 arsenic atoms in the pristine arsenene with a D Atom. The dopant atoms cover group III (B, Al, Ga), group IV (C, Si, Ge), group V (N, P), group VI (O, S, Se) and group VII (F, Cl, Br) atoms. We have found that the electronic properties of all doped systems in this paper are mainly affected by impurity atoms. For dopant atoms from the same group with As, the P-doped system are very close to the pristine arsenene, while the N-doped system transforms into a direct band gap semiconductor. The group III atom doped arsenene systems are all direct band gap (at Γ point) semiconductors. The group IV atoms-doped arsenene sheets all have a magnetic moment and behave as indirect band gap semiconductors. The Group VI atoms-doped system exhibits the properties of the conductor. For group VI atoms-doped arsenene, F- and Cl-doped systems show that they are direct band gap semiconductors with narrow band gaps. while Br-doped arsenene is a zero band gap material with a introduced magnetic moment of 2.00 µ B. Magnetic states obtained in C-, Si-, Ge- and Br-doped systems make arsenene a promising material in spintronic devices.

Conflicts of interest There are no conflicts to declare.

Acknowledgments This work is supported by the Fundamental Research Funds for the Central Universities under grant No. 2412019FZ037.

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Structural and electrical properties of substitutionally doped arsenene are investigated using DFT-D2 and HSE06 functionals with GGA approximation. Functionalization induces semiconductor-to-metal transition in arsenene monolayer. Substitutional doping generates the tunability of the electronic band structures of arsenene. Magnetic states obtained in C-, Si-, Ge- and Br-doped systems make arsenene a promising material in spintronic devices.

Author Statement Zhiwei Liu: Writing - review & editing, Writing - original draft, Conceptualization. XiaodanLi: Project administration, Validation, Resources, Supervision, Writing review & editing. Congcong Zhou: Investigation, Formal analysis. Taotao Hu: Methodology, Writing - review & editing LiYao Zhang: Methodology, Writing - review & editing Ruixia Niu: Methodology, Investigation. Yue Guan: Methodology, Investigation. Ningxia Zhang: Methodology, Investigation.

Conflict of Interest We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled, “First-principles study of structural and electronic properties of substitutionally doped arsenene”