Nanotechnology

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Tuning electronic and optical properties of arsenene/C3N van der Waals

heterostructure by vertical strain and external electric field
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Page 1 of 14 AUTHOR SUBMITTED MANUSCRIPT - NANO-115847.R1

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Tuning electronic and optical properties of
11 arsenene/C3N van der Waals heterostructure by
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13 vertical strain and external electric field

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16 Hui Zeng1 ‡, Jun Zhao2 §, Ai-Qiang Cheng1 , Lei Zhang1 , Zi He1
17 and Ru-Shan Chen1
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19 School of Electronic and Optical Engineering, Nanjing University of Science and
20 Technology, Nanjing, Jiangsu 210094, China

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21 School of Science, Nanjing University of Posts and Telecommunications, Nanjing,
22 Jiangsu 210023, China
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E-mail: eerschen@njust.edu.cn
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25 December 2017
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Abstract. Searching for new van der Waals (vdW) heterostructure with novel
electronic and optical properties is of great interest and importance for the next
30 generation devices. By using first-principles calculations, we show that the electronic
31 and optical properties of the arsenene/C3 N vdW heterostructure can be effectively
32 modulated by applying vertical strain and external electric field. Our results suggest
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33 that this heterostructure has an intrinsic type-II band alignment with an indirect
34 bandgap of 0.16 eV, facilitating the separation of photogenerated electron-hole pairs.
35 The bandgap in the heterostructure can be tuned from zero to 0.35 eV via the strain,
36 experiencing an indirect-to-direct bandgap transition. Moreover, the bandgap of the
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heterostructure varies linearly with respect to a moderate external electric field, and the
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semiconductor-to-metal transition can be realized in the presence of a strong electric
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40 field. The calculated band alignment and the optical absorption reveal that the
41 arsenene/C3 N heterostructure could present excellent light-harvesting performance.
42 Our designed vdW heterostructure is expected to have great potential applications in
43 nanoelectronic devices and photovoltaics.
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Keywords: heterostructure, arsenene/C3 N, vertical strain, external electric field,
47 optoelectronic devices Submitted to: Nanotechnology
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52 1. Introduction
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54 The pioneering work of Geim and Novoselov has demonstrated that the two-dimensional
55 (2D) graphene crystal can be stable under ambient conditions and it has unique electrical
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properties deriving from its truly 2D nanostructure[1]. Inspired by the boom of 2D
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‡ These authors contributed equally to this work.
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§ These authors contributed equally to this work.
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5 graphene, tremendous efforts have been focused on the synthesis, characterization, and
6 theoretical exploration of various 2D nanomaterials beyond graphene, including IV-
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group analogues, V-group analogues, transition metal dichalcogenides, III-VI layered
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9 semiconductors, MXenes, metal-organic frameworks (MOF), metal halides, and so
10 on[2, 3, 4]. Very Recently, the two dimensional carbon-based nanostructure C3 N
11 has been successfully fabricated, and the measurements at room temperature have
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13 shown that C3 N is an indirect semiconductor with 0.39 eV bandgap and high carrier

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14 mobility[5]. Most importantly, large-scale and controllable fabrication of C3 N single
15 crystalline sheets have pave the way of great potentials for both fundamental research
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17 and technological applications in the field of nanoelectronics. Meanwhile, the group-V
18 analogies, monolayered- or multilayered-phosphene, antimonene, and bismuthene have
19 become rising stars in 2D material community for their appropriate bandgaps within the
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21 range of optoelectronic applications and the excellent electronic properties such as a high
22 carrier mobility[6, 7, 8, 9, 10, 11, 12, 13, 14, 15]. Arsenene, another group-V elemental
23 2D material, is demonstrated to have an indirect bandgap of 2.3 eV by hybrid functional,
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25 and its electronic structure can be tuned by strain engineering[16, 17] and organic
26 molecular doping[18]. To date, multilayered-arsenene and antimonene nanoribbons have
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been successfully synthesized on various substrates[19, 20, 21].
To modulate the electronic and optical performance for optoelectronic devices,
30 many 2D nanomaterials have been vertically stacked to fabricate a van der Waals
31 (vdW) heterostructure, especially for the individual monolayer (ML) with different
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33 bandgaps[22, 23]. Owing to the weak interaction arising from the vdW, the
34 vertical heterostructure could generally preserve each individual electronic and optical
35 properties[24, 25]. But the meantime, some new physics may be obtained at the
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37 interface. For instance, the graphene stacked to the hexagonal boron nitride (h-BN)
38 insulator creates a tiny bandgap, as a result of inversion symmetry breaking induced by
39 the h-BN[26]. In recent years, various 2D heterostructures have been experimentally
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41 fabricated and characterized with great potentials in the fields of electronic and
42 optoelectronic applications[27]. The electronic and optical properties of 2D vertical
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heterostructure can be further modulated by strain engineering, chemical doping and

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45 external electric fields[28, 29]. Following this strategy, since the C3 N and arsenene both
46 have hexagonal lattice that similar to graphene, what will happen if we combine the
47 C3 N monolayer with the arsenene monolayer?
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49 The vertical heterostructure consisting of C3 N and arsenene monolayer is
50 anticipated to exhibit the desired electronic and optical properties arising from different
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bandgaps for the two individuals. What about the performance of the vertical
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53 arsenene/C3 N heterostructure? What about the electronic and optical properties of
54 the heterostructure under vertical strain and external electric field? In this work, we
55 have carried out first-principle calculations to investigate the structural and electronic
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properties of vertical heterostructures composed of C3 N and arsenene monolayers, which
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58 is referred to as arsenene/C3 N hereafter. Moreover, the influences of vertical strain
59 and external electric field on the structural, electronic and optical properties of the
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5 arsenene/C3 N heterostructure have been evaluated.
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8 2. Computational methods

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10 We have performed the first-principles calculations within density functional theory
11 (DFT) to study the electronic structures of the ground state for the ML arsenene
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and ML C3 N and the arsenene/C3 N heterostructure, which are implemented in the

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14 Vienna ab initio simulation package (VASP)[30, 31]. Projector augmented wave (PAW)
15 pseudopotentials in the form of Perdew-Burke-Ernzerhof (PBE) are used for electronic
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exchange-correlation potential[32]. The electronic wave functions were expanded using
18 a plane-wave basis set with a cutoff energy of 500 eV. Considering that the electronic
19 properties of the arsenene/C3 N vertical heterostructure are sensitive to the in-plane
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lattice constant, we thus have carried out fully structural optimizations for both in-plane
22 lattice parameters and ion position. The convergence criteria for the ionic relaxation
23 are such that the remnant force on each atom is below 0.01 eV/Å, and the energy is
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converged to within 10−6 eV per atom. For structural optimizations, the exchange-
26 correlation potential is described by the generalized gradient approximation (GGA)[32].
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A vacuum layer of 30 Å is set in the plane normal direction, which is sufficient to
eliminate the cell-to-cell interactions. The gamma centered Monkhorst-Pack set of
30 7×7×1 k-mesh is used to sample the Brillouin zone (BZ) for the geometry optimization
31 and a denser grid of 17 × 17 × 1 is used for electronic structure computations[33].
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To include the van der Waals interaction between the arsenene and the C3 N, we
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34 make use of vdW-DF dispersion interactions proposed by Dion et al. to describe the
35 non-local correlation[34, 35, 36]. Taken account of the fact that the vertical distance
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between the arsenene and C3 N are not experimentally available, we have tested the
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38 hexagonal graphene/BN heterostructure and found that the simulation value reported
39 by the optB86b functional is close to the experimental value. We thus choose this
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functional for our calculations. The optimized in-plane lattice constant and the buckling
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42 distance for the arsenene are a=3.61 Å and δ=1.38 Å[37], and the in-plane lattice
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constant for the C3 N is a=4.86 Å. Both are in good agreement with the values reported
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previously[5, 13, 16]. Furthermore, we have used a 4 × 4 supercell for the ML arsenene
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46 and a 3 × 3 supercell for the ML C3 N to restrict the in-plane lattice mismatch. The
47 mismatch for the arsenene/C3 N heterostructure is merely 1%. The optimized in-plane
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lattice constant for the arsenene/C3 N heterostructure is 14.55 Å, as shown in Figure 1.
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50 To investigate the optical properties of the arsenene/C3 N heterostructure, we
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have calculated the frequency-dependent dielectric function ϵ(ω), and evaluated the
52 absorption coefficient α(ω)[38]. The optical properties of the 2D nanomaterials are
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54 determined by in-plane dielectric function for the normal incidence. The imaginary
55 part ϵ2 (ω) of the dielectric function is calculated by a summation of optical transition
56 matrix element over empty states:
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58 4π 2 e2 1
59 ϵ2 (ω) = lim 2 Σc,v,k 2Wk δ(ϵck −ϵvk −ω)×⟨uck+eα q |uvk ⟩⟨uck+eβ q |uvk ⟩∗ (1)
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Ω q→0 q
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32 Figure 1. (Color Online) : (a) The ball-and-stick model for the arsenene/C3 N vertical
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33 heterostructure after structural optimization. (b) The total energy as a function of
34 in-plane lattice constant for this heterostructure. (c) The plane-averaged electrostatic
35 potential along the z direction for the heterostructure. The potential difference between
36 the two monolayers is denoted as ∆. (d) The plane-averaged charge density difference
37 of the heterostructure obtained by: ∆ρ = ρheterostructure − ρC3 N − ρarsenene . The inset
38 shows the corresponding isosurface of charge density difference, and the yellow and
39 cyan ares represent electrons accumulation and depletion, respectively.
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where the indices c and v refer to conduction and valence band states, respectively.
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44 The real part ϵ1 (ω) then can be calculated from the obtained imaginary part
45 ϵ2 (ω) through the Kramer-Kroning transformation[39]. Furthermore, the frequency-
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dependent optical absorption coefficient α(ω) is computed by:
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48 √ √ 1
49 α(ω) = 2ω[ ϵ21 (ω) + ϵ22 (ω) − ϵ1 (ω)] 2 (2)
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52 3. Results and Discussion

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54 3.1. Equilibrium geometrical structure
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56 Figure 1 illustrates the optimized nanostructure of the arsenene/C3 N heterostructure.
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57 The optimized vertical distance between the planar C3 N and the buckled arsenene is
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59 3.42 Å (Figure 1 (a,b)). The work function (defined as the energy difference between
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5 Table 1. The calculated lattice constants a and b, energy gaps Eg , and work function
6 Φ.
7 Structure a=b (Å) Eg (eV) Φ (eV)
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9 arsenene 3.61 1.59 4.55
10 C3 N 4.86 0.39 2.94
11 supercell-arsenene/C3 N 14.55 0.16 3.58
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15 the vacuum level Evacuum and the Fermi level EF ) of the C3 N is smaller than that of
16 the arsenene, as listed in Table 1. When the arsenene/C3 N vertical heterostructure
17 is formed, the electrons are expected to spontaneously transfer from C3 N to arsenene,
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19 owing to the higher work function for arsenene (arsenene: 4.55 eV; C3 N: 2.94 eV).
20 Therefore, a remarkable charge redistribution emerges at the interface. The presence of

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21 the built-in electric field Eint at the interface is accompanied by the electron transfer,
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23 and in turn hinders the electron transfer. Not until the equilibrium is achieved,
24 the increase of the built-in electric field will persist as a result of more and more
25 electrons accumulation/depletion at the opposite sides. As shown in Figure 1 (c), the
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C3 N has a deeper average electrostatic potential when the equilibrium is realized in
the heterostructure. The significant potential difference between the opposite sheets
suggests a strong Eint across the interface, which may lead to extensive modifications
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31 on the electronic structure around EF .
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33 3.2. Electronic structures
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35 In order to understand the electronic band structure of the heterostructure, we first
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37 investigate the corresponding results of the two individual monolayers, arsenene and
38 C3 N. For the ML arsenene, its valence band maximum (VBM) is at Γ-point while its
39 conduction band minimum (CBM) is located at about half of Γ-K direction, resulting in
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41 an indirect bandgap of 1.59eV. In the case of the C3 N monolayer, the VBM and CBM is
42 found at M- and Γ-points, respectively. The calculated electronic band structures shown
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in Figure 2 (a)-(b) agrees well with the reported values[5, 16]. When we consider the
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45 arsenene/C3 N vdW heterostructure (Figure 2 (c)), the electronic structures of arsenene
46 and C3 N are well preserved. However, due to the vdW interlayer coupling, remarkable
47 changes at the VBM and CBM are observed when compared to the electronic structures
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49 of the free-standing arsenene and C3 N. The CBM and VBM of the arsenene/C3 N
50 heterostructure is comprised by the arsenene and C3 N, respectively, in good accordance
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with the projected density of states (PDOS) results. The obtained arsenene/C3 N
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53 heterostructure is an indirect semiconductor with 0.16 eV bandgap.
54 The semiconductor based heterostructure can be analyzed on the basis of band
55 alignment[40]. The band edges of the ML arsenene, the ML C3 N, and the arsenene/C3 N
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heterostructure are presented in Figure 2 (d). The calculated band alignment suggests
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58 the formation of the type-II heterojuction, which is promising to achieve practical
59 applications in photoelectric devices. In addition, the work function Φ is used to evaluate
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Figure 2. (Color Online) : The electronic band structures for (a) the ML
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31 arsenene, (b) the ML C3 N. (c) The projected band structure of the arsenene/C3 N
32 heterostructure with the projected density of states (PDOS) shown on the right
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33 side. The subbands contributed by arsenene and C3 N are represented by red and
34 green colors, respectively. The Fermi level (EF ) is set to zero and indicated by
35 the gray dashed line. (d) Schematic representation of the band alignment of the
36 arsenene/C3 N heterostructure. (e) Isosurface plots of the band decomposed charge
37 densities (isosurface unit: 0.001e/Bohr3 ) corresponding to the VBM and the CBM are
38 shown on the left-side and right-side, respectively.
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41 the potential barrier at the interface and determine the electron flowing direction.
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43 The work functions of the ML C3 N and the ML arsenene are 2.94 eV and 4.55 eV,
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44 respectively, which is consistent with the calculated results reported previously[41]. The
45 work function of the heterostructure is 3.58 eV. When the arsenene/C3 N heterostructure
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47 is formed, the electrons are lost from the C3 N region (cyan colored area in Figure
48 1 (d)) and they are piled up on the arsenene region (yellow colored area). Thus,
49 significant electron accumulation and depletion take place at the arsenene and the C3 N,
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51 respectively. To gain further insight, we also explore band decomposed charge densities
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52 of the arsenene/C3 N heterostructure, as shown in Figure 2 (e). The calculated results

53 clearly demonstrate that the electrons and holes are mainly localized on the arsenene
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55 region and C3 N region, respectively. Therefore, the photogenerated electron in the C3 N
56 can easily move to the conducting band of the arsenene due to CBM offset[42]. Here, the
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57 CBM/VBM offset is defined as the CBM/VBM difference between arsenene and C3 N

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monolayers. In analogy to the photogenerated electron, the VBM offset also gives rise to
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5 photogenerated holes. As a result, the efficient separation of photogenerated electron-
6 hole pairs is anticipated in the arsenene/C3 N heterostructure, which is crucial to the
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performance of optoelectronic devices[29]. The separation of the electron-hole pairs
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9 ultimately leads to the formation of Eint . The direction of Eint is from C3 N to arsenene.
10 Moreover, sufficient built-in electric field is a key gradient to reduce the recombination
11 of electron-hole pairs.
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14 3.3. Electronic structure modified by vertical strain
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Figure 3. (Color Online) : The electronic properties of the arsenene/C3 N
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heterostructure varied with respect to the vertical strain ε = d0 − d, where d0 is the

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45 equilibrium distance. (a) Bandgap Eg and binding energy Eb . The inset represents
46 the applied strain direction on the heterostructure. (b) The electronic band structures
47 of the heterostructure when ε = -0.8 Å, -0.4 Å, 0.4 Å, and 0.8 Å. The EF is set to zero
48 and indicated by the gray dashed line. (c) The average potential and (d) the isosurface
49 of the differential charge density. The isovalue of the plot is 0.0005e/Bohr3 .
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52 Strain has been widely used in layered semiconductors to modulate the electronic
53 band structure. For vdW heterostructures, in particular, the interlayer distance
54 determined by vdW interaction can be easily modified by introducing strain along the
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vertical direction[24, 43, 44, 45]. In the arsenene/C3 N heterostructure, we investigate
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57 the electronic band structure and the binding energy (Eb ) varied with respect to the
58 vertical strain ε. We define the vertical strain as ε = d0 − d, where d0 = 3.42 Å
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is the equilibrium interlayer distance. The energetic stability of the heterostructure
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5 Table 2. The potential drop ∆ (eV) across the arsenene/C3 N heterostructure varied
6 with respect to vertical strain ε = d0 − d (Å), which is quantitatively calculated based
7 on the average potential shown in Figure 3 (c).
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9 ε (Å) -0.8 -0.4 0.0 0.4 0.8
10 ∆ (eV) 20.919 20.928 20.947 21.243 21.694
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13 is evaluated in terms of the binding energy: Eb = Earsenene/C3 N − EC3 N − Earsenene .

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15 The calculated binding energy Eb curve in Figure 3 (a) shows that when ε = 0, the
16 heterostructure with interlayer distance 3.42 Å is the most stable configuration. It is
17 indicated that the vdW interaction plays an important role in describing the geometry of
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19 the arsenene/C3 N heterostructure. By exerting different vertical strains, the bandgaps
20 can be modulated from zero to 0.35 eV, as shown in Figure 3 (a). Specifically, the

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21 bandgap is completely closed since ε ≤ −0.5 Å, and an indirect-to-direct transition is
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23 realized when ε = 0.8 Å.
24 The variation on the electronic structures can be understood by the band alignment
25 influenced by vertical strain. In detail, the interlayer interaction between the C3 N and
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the arsenene is decreased with ε decreasing from 0 to -0.8 Å, leading to remarkable
reduction on charge transfer between C3 N and arsenene, as evidenced by the isosurface
of differential charge density in Figure 3 (d). Correspondingly, Eint and the obtained
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31 potential drop (∆) are also reduced, which is listed in Table 2 and shown in Figure
32 3 (c). When the interlayer distance is increased (ε < 0), based on the analysis of
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33 band alignment at equilibrium, we found that the VBM deriving from C3 N and the
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35 CBM deriving from arsenene is upward and downward shifted, respectively. Hence,
36 the bandgap is monotonously reduced as ε decreases, and it eventually closes when the
37 interlayer distance turns to be 3.92 Å.
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39 Conversely, the bandgap is monotonously increased as ε increases because the VBM
40 contributed by C3 N and CBM contributed by arsenene is continuously downward and
41 upward shifted, respectively. The electron transfer is also monotonously enhanced as the
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43 interlayer distance decreases. The maximum bandgap, in principle, can be approached
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44 when the CBM is lifted to the energy level above the CBM of the C3 N monolayer. It is
45 found that the bandgap reaches maximum value when ε = 0.7. Hence, the maximum Eg
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47 depends on the bandgap of C3 N monolayer because both VBM and CBM are localized
48 on C3 N, which can be verified by PDOS and charge density results shown in Figure
49 S1. It is worthy to notice that the CBM location in the moment space has been
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51 changed to Γ-point when ε is increased[46]. And the type-II to type-I transition can be
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52 realized in the arsenene/C3 N heterostructure by using vertical strain engineering[47].

53 The same conclusions have been achieved in the previous work[41, 43]. As ε is further
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55 increased, the bandgap of heterostructure is determined by the subband bending. This
56 subband bending is caused by the enhanced interaction between C3 N and arsenene MLs.
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57 Moreover, the indirect-to-direct transition is observed when ε ≥ 0.8. Taken the band
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structure of ε = 0.8 for example, as shown in Figure 3 (b), the VBM is shifted from M
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Figure 4. (Color Online) : The electronic properties of the arsenene/C3 N
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33 heterostructure varied with respect to the vertical electric field Eext . (a) The evolution
34 of the bandgaps, and the inset represents the positive direction of the electric field in
35 the heterostructure. (b) The electronic structures of the arsenene/C3 N heterostructure
36 under Eext . The EF is set to zero and indicated by the gray dashed line. (c) The
37 differential charge density under Eext . The isovalue of the plot is 0.0005e/Bohr3 . (d)
38 The integrated charge density difference of the heterostructure under Eext .
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41 to Γ. We ascribe such shift of the VBM to the enhancement of the interlayer coupling
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interaction. The arsenene/C3 N heterostructure with smaller and direct bandgaps tuned
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44 by vertical strain may have potential applications in solar energy conversion[4].

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3.4. Electronic structure modified by external electric field
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Another possible route to tune the electronic structure of the heterostructure is to apply
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50 a vertical external electric field Eext [28, 48, 49]. For this purpose, we have examined the
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influences of Eext on the electronic properties of the arsenene/C3 N heterostructure, and

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the corresponding results are displayed in Figure 4. The positive direction of the Eext ,
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54 as shown in the inset of Figure 4 (a), is opposite to the direction of Eint . It is found
55 that the geometrical structure of the heterojunction experiences negligible change under
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different Eext [50]. However, the electronic band structure is substantially changed. We
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58 stress that the combined effects of the Eint and the Eext make significant influence on
59 the modification of the electronic properties. Therefore, the physical mechanism of the
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5 Eext on the electronic structure is the shift of the band edge with respect to EF , as
6 demonstrated in Figure 4 (b). It is shown that the bandgap varies linearly with respect
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to the applied Eext , which may be understood by the Stark effect[51].
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9 When a negative electric field is applied, the bandgap is reduced in a linear way,
10 which is caused by the CBM band edge shifting toward to the VBM. Simultaneously,
11 the negative Eext induces more electrons to accumulate/deplete at the opposite side, as
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13 clearly visualized in Figure 4 (c). Accordingly, the quasi-Fermi level of C3 N monolayer

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14 as well as EV BM rises, and the quasi-Fermi level of arsenene monolayer and ECBM
15 decreases, producing a linear reduction on bandgap.
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17 Conversely, with the positive electric field exerting on the heterostructure, the
18 bandgap is linearly increased when Eext ≤ 0.3 V/Å is applied, which enhance the band
19 offsets so as to promote the separation of electron-hole pairs. The initial enlargement
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21 in bandgaps is attributed to the counterbalance of Eext to some extent by the Eint .
22 Correspondingly, the quasi-Fermi level of C3 N monolayer as well as EV BM is downward
23 shifted, and the quasi-Fermi level of arsenene monolayer and ECBM is lifted. Therefore,
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25 the bandgap of the heterostructure is increased under a moderate positive Eext . It is
26 interesting to point out that the heterostructure becomes a metal when it is subjected
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to a stronger electric field. This is originated from the dielectric breakdown as well as
charge tunneling, which is clearly shown in Figure 4 (c).
30 To examine in detail how Eext modulate the electric properties of the
31 heterostructure, the integrated charge density is shown in Figure 4 (d), which is
32
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33 calculated by:
34 ∫ ∫
35 ∆ρEext (z) = ρEext (x, y, z)dxdy − ρE0 (x, y, z)dxdy (3)
36
37 ∫ ∫
38
where ρEext (x, y, z)dxdy and ρE0 (x, y, z)dxdy are the charge density at (x, y,
39 z) point in the supercell of the arsenene/C3 N heterostructure with and without Eext ,
40 respectively. The Eext exerts influence on charge transfer in the heterostructure. The
41
42
integrated charge density quantitatively illustrates that the amount of transferring
43 charge increases with the strength of the Eext , and more importantly, positive electric
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44 field induces more prominent charge transfer than that of the negative electric field.
45
Further increase on the positive electric field gives rise to striking variation on the
46
47 integrated charge density difference as a result of dielectric breakdown, ultimately
48 leading to semiconductor-to-metal (SM) transition. These calculated results have
49
revealed that both bandgaps and SM transition of the arsenene/C3 N heterostructure are
50
51 dependent on electrostatic gating, which could be used in high-performance electronic
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52 and optoelectronic devices[51].

53
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55 3.5. Optical Properties
56
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57 We have also studied the optical properties of the arsenene/C3 N heterostructure under
58 vertical strain and external electric field, as illustrated in Figure 5. The absorption edge
59
of the heterostructure is located at about 0.2 eV, in good agreement with its bandgap.
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38 Figure 5. (Color Online) : The optical properties of the arsenene/C3 N
39 heterostructure. (a) The absorption coefficient and (b) the imaginary part ϵ2 (ω) of
40 dielectric functions as a function of photon energy. The absorption coefficient as a
41
function of (c) vertical strain ε and (d) external electric field Eext .
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45 Four absorption peaks at 0.56, 1.68, 2.00, and 2.30 eV are derived from different
46 interband transitions between the valence and conducting bands, respectively. The
47 arsenene/C3 N heterostructure exhibits wide absorption range and the ability to be used
48
49 in solar cells to absorb visible light. This phenomenon can be attributed to the overlap of
50 the electronic states, which is originated from the charge transfer and interlayer coupling
51
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discussed above. Thus, the optical transitions could be improved. With vertical strain
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53 increasing, the absorption edges are found to be significantly red-shifted, consistent
54 with the corresponding bandgap variations. The negative Eext gives rise to red-shift,
55 whereas the positive Eext lead to blue-shift toward visible light region and the obvious
56
enhancement of optical absorption peak. Therefore, the effective modulation of optical
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58 absorption characteristics by Eext suggests great potential applications of arsenene/C3 N
59 heterojunction in photodetector devices.
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5 It is worth to mention the potential applications of the arsenene/C3 N heterojunction
6 in the nanoelectronics. The contact resistance arising from the Schottky barrier
7
significantly degrades the electrical performance of devices[27]. Owing to the
8

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9 outstanding electrical conductivity, the 2D C3 N can be served as electrode to inject
10 carriers[52]. Therefore, we propose that the vertical hybrid contact consisting of metal-
11 C3 N-arsenene, as shown in Figure 6, could be favorable for planar 2D transistors, which
12
13 is similar to the metal-graphene-arsenene recently proposed by Wang et al [53]. The

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14 carrier injection at the metal-C3 N-arsenene interface is anticipated to be enhanced
15 and the Schottky barrier height can be substantially reduced by choosing appropriate
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17 metal electrode. For instance, using Ti-graphene-MoS2 as vertical hybrid contact, the
18 contact resistance is reduced by a factor of three when compared to the direct Ti-MoS2
19 contact[54]. Considering the fact that Sc, Ti, Ni, Pd, Pt metals have work functions
20

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21 ranging from 3.24∼5.82 eV and the arsenene/C3 N heterostructure is 3.58 eV, these
22 metal electrode can be used to form n-type and p-type Schottky contact[55]. As a
23 result, additional efforts based on computational design of 2D nanodevices should be
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25 devoted to reducing the Schottky barrier and improving the electrical performance.
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39 Figure 6. (Color Online) : Schematic diagram of a arsenene/C3 N electrical device
40 based on van der Waals vertical contacts, in which C3 N is inserted as interlayer buffer.
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43
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44 4. Conclusions
45
46
47 In summary, the density functional theory (DFT) calculations have been performed
48 to investigate the structural, electronic, and optical properties of the arsenene/C3 N
49 vdW heterostructure. The arsenene/C3 N heterostructure forms type-II heterojuction,
50
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which is favorable for efficient separation of photogenerated electron-hole pairs. The
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52 electronic structure properties of the arsenene/C3 N heterostructure are shown to be

53 significantly modulated by vertical strain. Furthermore, the bandgap varies linearly with
54
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respect to a moderate vertical electric field, and the heterostructure becomes a metal
56 when a strong field is applied. The arsenene/C3 N heterostructure with wide absorption
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57 range and remarkable visible light absorption is expected to have great potential to be
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functionalized as photovoltaic component in solar cells.
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5 5. Acknowledgments
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7 We are grateful to Dr. N. Xu for electronic structure simulations as well as inspirational
8 discussions. This work is financially supported by National Natural Science Foundation

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10 of China (Grant Nos. 11404037 and 61701232).
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