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Superlattices and Microstructures 73 (2014) 113–120

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Superlattices and Microstructures


journal homepage: www.elsevier.com/locate/superlattices

Electronic and magnetic properties of vanadium


doped AlN nanosheet under in-plane biaxial
strains
Huawei Cao a, Pengfei Lu a,⇑, Zhongyuan Yu a, Jun Chen b, Shumin Wang c,d
a
Key Laboratory of Information Photonics and Optical Communications (Beijing University of Posts and
Telecommunications), Ministry of Education, P.O. Box 49, Beijing 100876, China
b
Beijing Applied Physics and Computational Mathematics, Beijing 100088, China
c
State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology,
Chinese Academy of Sciences, Shanghai 200050, China
d
Photonics Laboratory, Department of Microtechnology and Nanoscience, Chalmers University of Technology, 41296
Gothenburg, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: First-principles calculations have been performed to investigate


Received 28 April 2014 the electronic and magnetic properties of V-doped AlN nanosheet
Received in revised form 4 May 2014 under in-plane biaxial strains. It is found that V atom favors to sub-
Accepted 6 May 2014
stitute for Al site with the lowest formation energy. The magnetic
Available online 27 May 2014
coupling of three different configurations are studied and configu-
ration I is demonstrated to possess room temperature ferromagne-
Keywords:
AlN nanosheet
tism. The stable ferromagnetic coupling is mediated by double
Magnetic properties exchange mechanism. In addition, the in-plane biaxial strains cor-
Biaxial strains responding to tensile and compressive strains can affect and
First-principles manipulate the magnetic interaction of V-doped AlN nanosheet
Spintronic in different ways. These results are conductive to design AlN based
two dimensional diluted magnetic semiconductors.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction

Recently, graphene and graphene-like two dimensional (2D) nanostructures have been widely
investigated to meet the demand of miniaturization of electronic devices [1–3]. The 2D systems have

⇑ Corresponding author. Address: P.O. Box 72, Xitucheng Road No. 10, Beijing 100876, China. Tel.: +86 10 61198062.
E-mail address: photon.bupt@gmail.com (P. Lu).

http://dx.doi.org/10.1016/j.spmi.2014.05.020
0749-6036/Ó 2014 Elsevier Ltd. All rights reserved.
114 H. Cao et al. / Superlattices and Microstructures 73 (2014) 113–120

specific structures and properties which differ from their bulk counterpart, as well have wide applica-
tions in chemistry and materials science [4]. Aluminium nitride (AlN) is a well-known group III nitride
with wide band gap (6.2 eV) and large exciting energy (70 meV). AlN based 2D nanostructures such as
thin films, nanosheets and nanoribbons have attracted much attention due to their good performances
in optics, electronics and magnetics [5–7]. Zhang et al. successfully synthesized uniform AlN nano-
sheet on Si substrates by a vapor-phase transport method, using At powder and ammonia as the
source materials [7]. It provides an opportunity to design novel spintronic devices by introducing fer-
romagnetism into the AlN nanosheet.
Dilute magnetic semiconductors (DMS) materials are considered potential candidates for future
magneto-electronic and spintronic devices owing to their unique properties, including high date-
processing speed, high density of magnetic recording and non-volatile storage [8,9]. However, the
major challenge for the application of DMS is that their Curie temperature is below room temperature.
In the past few years, many experimental and theoretical explorations have showed that 3d transition
metal (TM) doped AlN bulk or nanosheet possesses room temperature magnetic ordering [10–13]. Shi
et al. reported room temperature ferromagnetism in Cr-doped AlN via first-principle calculations [12].
Ko et al. studied the structural and magnetic properties of V-doped AlN thin films deposited on c-plane
sapphire by reactive cosputtering and found that the films exhibited ferromagnetism at room temper-
ature [10]. In our previous paper, the influence of in-plane biaxial strains on structural transforma-
tions and electronic structure modulations has been investigated by the first-principles calculations
[14]. Gil et al. considered the strain effects on the optical properties of AlN epilayers grown on various
substrates, which accounted for the excitonic splitting of AlN [15]. These relevant experimental and
theoretical researches stimulate us to investigate the strain effects on the magnetic interactions in
the V-doped AlN nanosheet.
In this work, we perform a comprehensive first-principles study of the electronic and magnetic
properties of V-doped 2D AlN nanosheet under in-plane biaxial strains. By analyzing the strain effects
on the mechanism of magnetic coupling, we aim to provide a theoretical foundation for the fabrication
of 2D AlN heterostructure based DMS. The work is organized as follows. The theoretical methods and
details are described in Section 2. Section 3 presents our results and discussions. Finally, a brief sum-
mary is given in Section 4.

2. Methods and details

The calculations are performed by using the Vienna ab initio simulation package (VASP) [16] based
on density functional theory (DFT) [17]. The generalized gradient approximation (GGA) [18] in the
form of Perdew–Wang 91 (PW91) [19] is used for the exchange–correlation function. The cut-off
energy for the plane-wave expansion is 450 eV to ensure a good convergence of the geometric optimi-
zation. Pseudopotentials with 2s22p3, 3s23p1 and 3d34s2 valence electron configurations for N, Al and V
are used, respectively. A Monkhorst–Pack of 8  8  1 k-point mesh is used for the self-consistent
Brillouin zone integration. The structural optimization is allowed to relaxed until the maximum force
on each atom become less than 0.01 eV/Å and maximum energy change between two steps is smaller
than 105 eV.

3. Results and discussions

3.1. Pure AlN nanosheet

At ambient temperature and pressure, the stable AlN phase is hexagonal wurtzite (WZ) structure
with P63mc space group. The primitive structure of 2D AlN nanosheet is cut from a bulk WZ AlN with
[0 0 0 1] polar surface as can be seen in Fig. 1(a). It contains 16 Al and 16 N atoms. To reduce the inter-
action between neighboring layers, a vacuum of 15 Å along the z-axis is applied. The lattice constants
of pure AlN nanosheet after structural optimization are a = b = 3.115 Å, consistent with experimental
and theoretical values of 3.112 Å and 3.121 Å, respectively [20,21]. Furthermore, the optimized struc-
ture of pure 2D AlN nanosheet transfers from typical WZ to a flat graphene-like structure in Fig. 1(b).
H. Cao et al. / Superlattices and Microstructures 73 (2014) 113–120 115

Fig. 1. Top and side view of pure 2D AlN nanosheet (a) without and (b) with relaxation (The blue spheres are N atoms and the
pink spheres are Al atoms). N, Al and H stand for the doping at N, Al and hollow sites, respectively. The numbers 1–4 indicate the
positions of Al substituted by V in the system. (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)

The relaxed AlN bond length decreases from 1.890 Å in bulk AlN to 1.810 Å, which agrees well with
previous theoretical results of 1.808 Å [21].
As can be seen in Fig. 2(a), the AlN nanosheet is a semiconductor with an indirect band gap of
2.37 eV. Although GGA has the limitation in producing well the unoccupied electronic states leading
to lower band gap energy compared to experimental values, our results are close to previous calcula-
tions [6]. Also in Fig. 2(b), the partial density of states (DOS) of Al and N atoms are displayed. The
upper valence band around Fermi level is mainly consist of N 2p and Al 3p states, while the conduction
band around 6 eV is dominated by Al 3p states.

3.2. Magnetic properties

To investigate the structural stability of V-doped AlN nanosheet and find the preferred substitution
sites, we firstly calculated the formation energy of an isolated V atom on different doping sites (N, Al
and hollow sites in Fig. 1) using the following definition:
Ef ¼ EðV : AlNÞ  EðAlNÞ þ nAl lðAlÞ þ nN lðNÞ  nV lðVÞ

where E(V:AlN) and E(AlN) are the total energy of AlN nanosheet with and without Al dopant. nk is the
number of ions (Al, N or V) exchanged from a perfect AlN nanosheet and l is the chemical potential of

Fig. 2. (a) The energy band structure and (b) partial DOS (PDOS) of intrinsic 2D AlN nanosheet.
116 H. Cao et al. / Superlattices and Microstructures 73 (2014) 113–120

Al, N and V, which depends on the reservoir in different system. There are two chemical extremes
considered in this work. The total energy of metallic Al and gaseous N2 are chosen as the upper limits
for lAl (Al-rich condition) and lN (N-rich condition). According to the thermodynamic equilibrium
lAl + lN = lAlN, the chemical potentials of Al under N-rich condition and N under Al-rich condition
are obtained. As we all know, a system with smaller formation energy is more likely to be fabricated
in experiments. The calculated formation energy of a single V dopant at N (Al16N15V), Al (Al15N16V)
and hollow (Al16N16V) sites are summarized in Table 1. It is noted that configuration Al15N16V has
the lowest formation energy of 0.875 eV under N-rich condition, indicating V atoms favors to substi-
tute at the Al site in V-doped AlN nanosheet.
Next, we investigate the electronic and magnetic properties of two V dopants in AlN nanosheet,
where two Al atoms are substituted by two V atoms corresponding to a doping concentration of
12.5%. Three possible configurations are calculated, as shown in Fig. 1(a). For configuration I (0, 1),
two V atoms are paired via intermediate N atom; while in configuration II (0, 2) and III (0, 3), two
V atoms are separated by N–Al–N. In Table 2, the calculated V–N bond length is 1.812 Å, 1.817 Å
and 1.816 Å which are larger than Al–N bond length of 1.794 Å, 1.796 Å and 1.799 Å. It is mainly
due to that the ionic radius of V is larger than that of Al. With reference to Zheng et al. [22], the bond-
ing characteristic of neighboring atoms also has an important effect on the bond length. In order to
further understanding the attractive force between Al and N as well as V and N elements, the charge
density of V-doped AlN nanosheet (Taking configuration I as an example) is plotted in Fig. 3. It is noted
that there exists a clear covalent bond between Al and N atoms which can be explained by the sp-
hybridization displayed in Fig. 2(b) in the energy range from 5 to 1 eV. The charge density at the
position of Al is larger than V leading to a weaker V–N covalent bond. So the V–N bond length is larger
than the Al–N bond length.
The energy difference DE (DE = EAFM  EFM) for each configuration between ferromagnetic (FM) and
antiferromagnetic (AFM) states is also listed in Table 2. It is a good indicator to obtain the magnetic
coupling of V-doped AlN nanosheet. Positive DE means that FM coupling is more favorable, while neg-
ative DE indicates AFM coupling is more energetic. It is obvious that the magnetic states of configu-
ration I and III are FM coupling. Furthermore, the DE of configuration I (175 meV) is larger than the
heat energy KBT (30 meV) [8] signifying stable ferromagnetism at room temperature could be obtained
in V-doped AlN nanosheet. Our calculations give theoretical verification to the previous experimental
reports [10,23]. It is also noted that DE shows a rapid decline with the V–V distances increasing from
3.185 to 5.419 Å and degenerates in energy in the range of 5.419–6.246 Å. So the magnetic coupling of
V-doped AlN nanosheet is short-ranged.
In the previous experimental reports [10], nanosized clusters and the exchange interaction are
taken as the possible occurrence of ferromagnetism in V-doped AlN films. To clarify the origin of
FM coupling in V-doped AlN nanosheet, the total DOS and partial DOS of configuration I are plotted
in Fig. 4. Some localized gap states exist in the spin-up channel around Fermi level in Fig. 4(a) and
there are no contributions from the spin-down channel. So the V-doped AlN nanosheet of configura-
tion I in FM ordering possesses a half-metal characteristic. Meantime, it is clearly noted in Fig. 4(b)
that the localized states around Fermi level are consisted of V 3d and N 2p states in the spin-up
channel. The p-d hybridization between V 3d and N 2p is responsible for the ferromagnetism. To gain
further insight of the FM ordering of configuration I, the spin charge density which is the difference
between spin-up and spin-down electron densities is presented. As can be seen in Fig. 4(c), the

Table 1
Formation energy of Al16N15V, Al15N16V and Al16N16V under both Al-rich
and N-rich conditions.

Configurations Formation energy (eV)


Al-rich N-rich
Al16N15V (N site) 2.861 5.518
Al15N16V (Al site) 2.151 0.875
Al16N16V (hollow site) 3.532 3.532
H. Cao et al. / Superlattices and Microstructures 73 (2014) 113–120 117

Table 2
The calculated results for all the three configurations of V-doped AlN nanosheet (Al14N16V2).

Configurations dAl-N dV-N dV-V DE Coupling lV1 lV2 lN


I(0,1) 1.794 1.812 3.185 175 FM 2.033 2.031 0.067
II(0,2) 1.796 1.817 5.419 3 AFM 2.021 2.066 0.135
III(0,3) 1.799 1.816 6.246 5 FM 2.014 2.011 0.033

dAl-N, dV-N and dV-V (in Å) are the optimized bond length of Al–N, V–N and distances between two V atoms, respectively. DE (in
meV) is the energy difference of FM and AFM states for each configuration. lV1, lV2 and lN are the magnetic moments (in lB) of
two V and the nearest neighboring N atoms.

Fig. 3. Total valence charge density of V-doped AlN nanosheet (Configuration I).

magnetic properties of V-dope AlN nanosheet are mainly contributed by two V and their intermedi-
ated N atoms which agree well with above results in Fig. 4(b). The local magnetic moments on two
V and the intermediated N atoms are 2.033, 2.031 and 0.067 lB, respectively. Thus, the carries induced
by V dopants play a dominant role, and the N atom bridging two V mediates the FM coupling in con-
figuration I since N 2p states hybridize with V 3d states. Based on the above analysis, the FM coupling
of V-doped AlN nanosheet is mediated by double-exchange mechanism [11].

3.3. Strain effects on magnetic properties

The magnetic properties of DMS can be affected in the presence of strains [24]. To figure out the
strain effects on the magnetism of V-doped AlN nanosheet on different substrate materials, the AlN
systems are subjected to in-plane biaxial strains given in the following procedures: the in-plane biax-
ial strains between V-doped AlN nanosheet and the underlying substrate e = e11 = e22 = (a1  a)/a,
where a is the lattice constant of AlN nanosheet and a1 is the corresponding lattice constant in the
strained system. e > 0 (a1 > a) represents the tensile strains, while e < 0 (a1 < a) stands for the compres-
sive strains. The magnitude of e ranges from 8% to 8% to avoid the formation of secondary phase
induced by strains. The calculated total energy of FM and AFM states and their relative energy DE
for configuration I under in-plane biaxial strains are shown in Fig. 5. The magnitude of strain e can lead
to the modification of the total energy. In Fig. 5(a), the strain-free states for both FM and AFM
118 H. Cao et al. / Superlattices and Microstructures 73 (2014) 113–120

Fig. 4. Spin polarized (a) total and (b) partial DOS of V-doped AlN nanosheet for configuration I in FM ordering (The yellow dash
dot line indicates the Fermi level). (c) The 3D iso-surface of the spin charge density of configuration I (The red and yellow
spheres indicate spin-up and spin-down directions, respectively). The iso-value of spin charge is 0.01 e/A3. (For interpretation of
the references to color in this figure legend, the reader is referred to the web version of this article.)

conditions have the lowest total energy and it increases with the increase of the biaxial strains e. As
can be seen in Fig. 5(b), the variations of DE are also diverse with respect to the compressive and ten-
sile strains indicating the magnetic properties of V-doped AlN nanosheet can be affected by in-plane
biaxial strains e. Under compressive strains e, DE monotonously decreases with the increase of e and
approximates to zero. So the magnetic coupling is nonmagnetic when the compression is large
enough. For tensile strains e, DE initially increases to the maximum, then it drop to a constant
value of about 311 meV. Compared to compressive strains, room temperature ferromagnetism is
stable during the application of tensile strains.
To further understand the magnetic interactions induced by strains, the PDOS of V 3d orbitals
under different strains are presented in Fig. 6. Compared to strain-free condition, the localized V 3d
states around Fermi level are broadened upon 4% tensile strains. As a result, the electron density
around Fermi level is increased leading to the enhancement of the FM coupling [24,25]. In the condi-
tion of -8% strains, the spin-up and spin-down curves of V 3d orbitals around Fermi level are symmet-
ric, namely the magnetic coupling is nonmagnetic. So the magnetic properties of V-doped AlN
nanosheet can be modulated by introducing the tunable in-plane biaxial strains.

4. Conclusion

In summary, we have investigated the electronic and magnetic properties of V-doped AlN nano-
sheet under in-plane biaxial strains using first-principles density functional theory. We find that V
atom prefers to substitute at the Al site in the V-doped AlN nanosheet. In order to simulate the mag-
netic coupling between two V atoms, three different configurations are considered. The spin-polarized
results indicate that configuration I behaves as stable FM coupling. The p-d hybridization between V
H. Cao et al. / Superlattices and Microstructures 73 (2014) 113–120 119

Fig. 5. (a) The total energy as a function of strain e for configuration I in FM and AFM states. (b) The energy difference
DE (DE = EAFM  EFM) as a function of strain e.

Fig. 6. PDOS of V 3d orbitals under strain-free, 8% and 4% states.

3d and N 2p is responsible for the ferromagnetism and can be explained by double exchange mecha-
nism. Finally, we find that the in-plane biaxial strains on the magnetic coupling of V-doped AlN are
diverse with respect to tensile and compressive strains. For the tensile strains applied in this work,
the system exhibits stable room temperature FM coupling. While for the compressive strains, the
FM interaction monotonously decreases, and then disappears when the compression is large enough.
It is possible to design and control the magnetic properties of V-doped AlN nanosheet by applying
appropriate in-plane biaxial strains. Our results indicate V-dope AlN nanosheet is a good candidate
for AlN based spintronic devices.

Acknowledgments

This work was supported by the National Basic Research Program of China (973 Program) under
Grant No. 2014CB643900, the National Natural Science Foundation of China (No. 61102024), and
the Fundamental Research Funds for the Central Universities (No. 2012RC0401).
120 H. Cao et al. / Superlattices and Microstructures 73 (2014) 113–120

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