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Electronic and magnetic properties of an AlN

monolayer doped with first-row elements: a first-
Cite this: RSC Adv., 2015, 5, 18352
principles study
Yujie Bai,ab Kaiming Deng*a and Erjun Kan*a

Received 31st October 2014
Accepted 3rd February 2015
DOI: 10.1039/c4ra13522a
www.rsc.org/advances
Two-dimensional (2D) magnetic materials are the focus of one of the most active areas of nano-materials
research. However, most of them contain d electrons in the hosts or dopants which may lead to extrinsic
magnetic behavior. Here we report a density functional study on the structural, electronic, and magnetic
properties of an AlN monolayer (ML) doped with first-row atoms of X (X ¼ Be, B, and C), which are free
of d electrons. The calculations reveal that Be and C dopants, which substitute Al and N atoms
respectively, can induce local spin moments, while B (for N) cannot lead to spin polarization in the AlN
ML. More importantly, for Be doped AlN ML, a half-metallic ferromagnetism is observed, and the
estimated Curie temperature is higher than room temperature. The long-range ferromagnetic coupling
between doped Be atoms can be explained by a hole-mediated p–p interaction. Thus, our results
provide a promising way toward 2D magnetic materials.

optics and photoelectronics.21,22 Compared with bulks, 2D

I. Introduction
Since the discovery of the exotic properties of the two-dimensional
(2D) layered material graphene,1 developing spintronics with one-
atom-thick materials has attracted wide research attention to meet
the goal of miniaturization of electronic devices.2,3 However, most
of these pristine 2D materials are intrinsically nonmagnetic
semiconductors or metals. In order to achieve their applications in
spintronics, numerous efforts have been made in recent years to
introduce magnetic structures into these 2D materials.4–11 For
example, Schmidt et al. demonstrated that a Co doped graphene-
like ZnO monolayer (ML) presented ferromagnetic (FM)
coupling,12 and recently, a pulsed laser deposition technique has
been used to dope graphene with transition metals (TM) to
generate ferromagnetism.13 On other hand, different to the tradi-
tional way of introducing a magnetic structure in 2D materials,
C-doped ZnO ML and CdS ML have revealed the existence of long-
range ferromagnetism,14,15 which can survive at room temperature.
Similarly, other researchers found that cationic substitutions can
also lead to ferromagnetism.16,17 When compared with conven-
tional TM dopants, the main advantage of non-magnetic dopants
is that they can induce high-temperature magnetism, which may
benet the rapid development of today's spintronics.
Among the III–V compounds, AlN-based semiconductors
have been a focus of research18–20 due to their applications in
hexagonal-AlN ML recently has been become a focus of
research, and its stability is conrmed by structure optimiza-
tion and phonon-mode calculations.23 AlN ML exhibits some
peculiar properties which are different from their bulk-phase
counterparts. For example, the band gap of AlN ML can be
changed from indirect to direct gap under different kinds of
strains,24 which shows different structural-property relationship
with that of bulk. Zhang investigated the magnetic properties of
the intrinsic defects of AlN ML and found N-defective systems
demonstrated a FM property with Curie temperatures above
room temperature,25 while Almeida Junior et al. explored the
most typical defects in AlN ML, including vacancies, antisite
defects and impurities.26 It is well known that the chemical
modication is also an effective way to control the electronic
and magnetic properties of nanostructures. Therefore, hydro-
genated, uorinated and chlorinated AlN ML have been well
studied,27–29 and the results indicated that their electronic and
magnetic properties might be efficiently tuned by modifying
different Al and N sites. Although the magnetism in AlN ML has
been broadly studied, the research of doping the rst-row-
elements is still not performed. Actually, because of the
similar ion radius, it is practically possibly to dope AlN ML with
such atoms. Consequently, it is quite interesting and impor-
tantly to study the electronic and magnetic properties of rst-
row-elements X ¼ (Be, B, and C) doped AlN ML.

a
Department of Applied Physics, Nanjing University of Science and Technology,
Nanjing, Jiangsu 210094, P. R. China. E-mail: kmdeng@njust.edu.cn; ekan@njust. II. Computational details
edu.cn
b
Physics Department, Yancheng Institute of Technology, Yancheng, Jiangsu 224051, The spin-polarized calculations are performed using the
P. R. China projector augmented wave (PAW) pseudopotential method as

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Paper
implemented in the Vienna ab initio Simulation Package
(VASP).30,31 The generalized gradient approximation (GGA) with
the Perdew–Burke–Ernzerhof (PBE) functional32 is selected to
describe the electron–electron exchange and correlation ener-
gies in the DFT calculations. A plane-wave energy cutoff of
400 eV is used throughout the calculations. Geometry structures
are relaxed until the force on each atom is less than 0.01 eV Å1,
and the convergence criteria for energy of 1  105 eV is met. To
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explore the magnetism of single and double X doped AlN ML,
the (4  4  1) and (6  6  1) supercells containing 16 and
36 unit cells are modeled, respectively, as shown in Fig. 1(a) and
(b). The gamma-centered k points are sampled for the 2D Bril-
louin zone according to the Monkhorst–Pack method.33 The
k-points are set to 9  9  1 and 5  5  1 meshes for the
structural relaxations and physical properties, respectively. The
vacuum size is set as 12 Å to avoid interactions between two
neighboring layers.
III. Results and discussion
A. The pristine AlN monolayer
We rstly construct a 2D 4  4  1 supercell from bulk wurt-
zite structure (0001) plane. Aer fully relaxation, AlN ML
transforms from a rippled surface to a planar graphene-like
structure, where the relaxed lattice parameter of 3.100 Å and
Al–N bond length of 1.790 Å are in good agreement with
Fig. 1 (a) and (b) Schematic view of geometric structure for 4  4  1 and 6  6  1 AlN ML supercells. The substituted positions of X dopants are
denoted by 1–5 and I–V, respectively. (c) and (d) The TDOS and band structure of AlN ML after structural relaxation. The Fermi level is indicated by
the dotted line.
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previous theoretical work.7,23 The spin-polarized density of
states for the pristine AlN ML is calculated aer structural
optimization, as shown in Fig. 1(c). Clearly, the majority spin
and minority spin are totally symmetric, which indicates that
AlN ML is intrinsic nonmagnetic materials. On the other hand,
as plotted in Fig. 1(d), the calculated band structure exhibits
an indirect band gap with an energy of 2.97 eV. All above
results are in good agreement with previous theoretical
results.7,25,27,28
B. Single X doped AlN monolayer
Now, we begin to consider the effect of single X doped AlN ML
as shown in Fig. 1(a). Since the radius of Be atom is close to that
of Al atom, and the radii of B and C atoms are similar to that of
N atom, the Be atoms will be introduced at the cationic Al sites,
while B and C atoms will be at the anionic N sites in our
calculation.
The optimized structural and energy results for different
doped systems are listed in Table 1. Aer structural relaxation,
the relaxed X–N/Al (X ¼ Be, B, and C) bond lengths are 1.671,
2.018, and 1.899 Å, respectively. The Be–N bond length is
shorter than Al–N bond length which is 1.790 Å. While Al–B and
Al–C bond lengths are larger than the Al–N bond length. The
possible reasons are attributable to the differences in atom
radius between the X dopants and the replaced atoms.14 Since
RSC Adv., 2015, 5, 18352–18358 | 18353

RSC Advances
each X atom forms three equivalent X–N/Al bonds, the local
structure maintains the D3h symmetry.
To investigate the stability of these doped systems, the
formation energy Eform are calculated according to the following
formula Eform ¼ EAlN(X)  EAlN + E(Al or N)  E(X),34 where
EAlN(X) and EAlN are the total energy of the AlN supercell with
and without the X dopants. E(Al or N) and E(X) are the total
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energy of an isolated Al, N and X atoms, respectively. As
summarized in Table 1, the calculated formation energies are
2.21, 4.63, and 1.35 eV, for Be, B, and C atoms, respectively. In
order to compare with the AlN ML with a defect site (a missing
Al or N atom), the formation energy of vacancy defects are also
calculated. The formation energies are 13.02 and 9.94 eV for Al
and N vacancy defect, respectively. As we know, when the
formation energy is smaller, the dopants are much easier to be
incorporated into the lattice sites of AlN ML. Therefore, our
calculated results suggest that Be and C atoms can be doped
into AlN ML in experiments.
Now, we explore whether the X-doping could induce local
magnetic moments in AlN ML. For Be-, and C-doped AlN
systems, we nd that total energies of the spin-polarized state
are lower by about 90 and 346 meV than that of the spin-
unpolarized states, indicating that the spin-polarized states
are energetically more favorable. In contrast, B doping does not
lead to spin polarization in B-doped AlN ML. Fig. 2 shows the
calculated DOS of single X-doped AlN ML and partial density of
states (PDOS) of X dopants and one of the nearest neighboring
Al and N atoms. For all X dopants, the substitution results in
deep acceptor levels in the band gaps of AlN ML host. Therefore,
the band gap of doped-AlN ML is obviously decreased, which
signicantly affects the optical and magnetic properties. As
stated previously, pristine AlN ML is a nonmagnetic semi-
conductor, it will become magnetic for the single Be or C doping
but remains nonmagnetic for single B doping. Interestingly,
both Be and C dopants induce a total magnetic moments of
1.00mB per supercell. Different with the case of C-doped AlN ML,
the spin-polarized states around Fermi level is dominated by
the nitrogen p orbitals for Be-doped AlN ML. Moreover, for Be
substitution, the majority spin levels are all located below the
EF, while the EF goes into valance band in the minority spin
channel, indicating that the system belongs to a half-metallic
ferromagnetism, which maybe a good candidate for spin-
tronic applications.
In order to further understand the distribution of magnetic
moments in the Be-, and C-doped systems, the isosurface of
Table 1 Optimized X–N/Al (X ¼ Be, B, and C) bond lengths. Total
energy difference between spin-polarized (Esp) and spin-unpolarized
(Espun) states (DE ¼ Espun  Esp). Formation energy (Eform). Total
magnetic moments of the supercell, Mtot
Models X–N/Al (Å) DE (meV) Eform (eV) Mtot (mB)
Be@AlN 1.671 90 2.21 1
B@AlN 2.018 0 4.63 0 electron transferring from Be atom to the nearest neighboring
C@AlN 1.899 346 1.35 1 three N atoms averagely by means of Bader analysis. We would
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spin density is shown in Fig. 3. As shown in Fig. 3(a), the
C-doped system, the induced spin moments mainly arise from
unsaturated C atom, and the nearest neighboring N atom only
have small contribution to the local moments, which agrees
well with the plotted PDOS in Fig. 2(f). For the Be-doped system,
the total magnetic moments (1.00mB) mainly arise from the
nearest neighboring N atoms (0.149mB per N atom). Different
with the case of C-doped AlN, we found that all the nitrogen
atoms in the lattice grids have the some spin density. It's
important to note that the orbitals of Be-doped AlN ML show a
duality: one is the localized nature with most of the spin density
is on the nearest neighboring N atoms; the other is the extended
nature with some of the spin density spreading over almost the
whole supercell as shown in Fig. 3(b). The strongly localized
nature favors a spin-polarized ground state and the formation
of local magnetic moments, while the extended tail of the
impurity wave functions can facilitate the long-range magnetic
coupling between impurity-induced local magnetic moments,35
which is discussed below.
One can note that, in AlN ML, each Al atom can nominally
transfer three electrons to the N atom, and therefore the N3
anion has six p electrons ([[[YYY) without unpaired elec-
trons. Since B, and C have one and two electrons in their six
p orbitals, the substitution of N atoms induces two and one
holes in B-, and C-doped AlN ML. Similarly, Be substitution of Al
atom also induces one hole. For Be- and C-doped AlN ML, the
total magnetic moments exactly correspond to the number of
holes induced by impurities. However, for B-doped AlN ML, the
magnetic moment is zero. As we know, the bulk AlN has a
wurtzite structure with local structure Td symmetry. Under the
Td symmetry, the 2p orbitals form the triply degenerate (px, py,
and pz) states. Therefore, according to Hund's rule, the four
electrons in B 2p orbitals tend to form a high spin state and the
resulting magnetic moments equal to unpaired electrons
([[[Y) of 2p orbitals. This electron conguration is respon-
sible for the magnetic moments of 2mB in B-doped AlN bulk. As
mentioned above, the local structure of each X atom doped in
AlN ML maintains the D3h symmetry. Under D3h symmetry, the
triply degenerate 2p orbitals split into two-fold degenerate
(px and py) and a nondegenerate (pz), and pz orbital has a higher
energy.36,37 The B3 anion has four electrons in their six p
orbitals. There are two possible electron congurations: one is
high spin state px([Y)py([)pz([), the other is low spin state
px([Y)py([Y). The rst conguration is impermissible because
of three electrons occupying the px, py degenerate orbital pair,
which would cause Jahn–Teller structural distortion to li the
degeneracy. However, we have not observed any structural
distortion. Therefore, B3 anion adopts low spin state congu-
ration: px([Y)py([Y), which is consistent with the PDOS of
B-doped AlN ML in Fig. 2(e) and is responsible for the zero
magnetic moment of B-doped AlN ML. Similarly, for C-doped
system it has ve electrons in their p orbitals and adopts the
conguration only: ([[[YY), so it has 1.00mB magnetic
moments. In the case of Be-doped system, we nd valance
expect Be2+ and the nearest neighboring three N atoms
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Fig. 2 DOS of AlN ML with single X substitution: total DOS for (a) Be-, (b) B-, (c) C-doped systems, respectively; PDOS for dopant atoms (d) Be-,
(e) B-, and (f) C-doped systems and one of the nearest neighboring Al and N atoms. The Fermi level is indicated by the dotted line.

nominally carry 17 p-electrons in total. The resulting magnetic
moments of Be-doped system is 1.00mB with one unpaired
electron of 2p orbitals. Due to the local symmetry, these elec-
trons will be equably assigned to the px, py, or pz orbitals of the
nearest neighboring three N atoms, Thus each of the nearest
neighboring N atom has the same magnetic moments, which is
consistent with the spin-density distribution of Be-doped AlN
ML in Fig. 3(b).
C. The magnetic coupling of double X doped AlN monolayer
To investigate the magnetic coupling between the doped atoms,
we adopt a larger 6  6  1 supercell, and consider four inde-
pendent congurations of the two dopant atoms as shown in
Fig. 1(b). We use (1,i) and (I, j) to denote C–C and Be–Be pairs,
respectively (i ¼ 2–5, j ¼ II–V). The energy difference between
ferromagnetic (FM) and antiferromagnetic (AFM) states
[DE ¼ E(FM)  E(AFM)], band gap Eg and the relative energy ERS
with respect to the ground state of conguration for two doped
systems are summarized in Table 2.
We nd that for Be-doped AlN ML, the FM states are always
energetically favorable for all those congurations with the
band gap of about 3.0 eV in the spin-up channel. When the
distance between two Be atoms increases, the Be-doped AlN ML
turns into a half-metallic ferromagnetism. Such large energy
differences between FM and AFM states for the four congu-
rations (301, 94, 80, and 209 meV, respectively) suggest that
ferromagnetism with Curie temperatures above room temper-
ature is quite feasible. Using mean-eld theory and the energy
difference between FM and AFM states, we can estimate the
Curie temperature of by the formula gkBTc/2 ¼ E(AFM)  E(FM),
where g is the dimension of the system and kB is Boltzmann

Fig. 3 The spin-density distribution of (a) C-doped, and (b) Be-doped AlN ML. The yellow isosurfaces represent the charge density of spin up.
The isosurface value of spin charge is 0.003 e Å3.

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Table 2 The calculated X–X distance (dX–X), relative stability energy (ERS), the difference between FM and AFM [DE ¼ E(FM)  E(AFM)], band gap
(Eg), total magnetic moments (Mtot), and magnetic state for each (1,i)/(I,j) structure of the two-X-doped AlN ML

Models (1,i)/(I,j) dX–X (Å) ERS (eV) DE (eV) Eg (up, down, eV) Mtot (mB) Coupling

Be (I, II) 3.053 0.000 0.301 3.006 0.2 2 FM

(I, III) 5.356 0.138 0.094 3.013 0.1 2 FM
(I, IV) 8.194 0.240 0.080 3.021 0 2 FM
(I, V) 10.738 0.257 0.209 3.024 0 2 FM
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C (1, 2) 3.211 0.059 0.066 0.999 0.999 0 AFM

(1, 3) 5.377 0.000 0.012 1.373 1.282 0 AFM
(1, 4) 8.205 0.014 0.001 1.337 1.253 0 AFM
(1, 5) 10.737 0.016 0.001 1.368 1.258 0 AFM

constant.38 Our estimated result is 900 K at least, when the AlN
monolayer is treated as a 2D system. It is worth noting that
mean-eld theory oen gives an overestimation of the actual
ordering temperature39 owing to that it neglects the effect of
uctuation of the spins from their average values. Aer all, our
results could provide a theoretical basis for further experi-
mental studies in the future. However, that of the C-doped AlN
ML are all AFM states semiconductor with the band gap of
about 1.0 to 1.3 eV. The small energy difference between the FM
and AFM states [except conguration (1,2)] suggest that an
antiferromagnetic-to-paramagnetic transition is observed at
room temperature. The nearest distance for (I, II) case exhibits
the lowest energy than other congurations, indicating that Be
atoms have a clear clustering tendency. On the other hand, the
(1,3) conguration is the lowest energy conguration, indi-
cating that the clustering effect is not obvious in C-doped AlN
ML. However, two neighboring Be atoms in (I, II) conguration
will not form a dimer pair but occupy the original lattice-site
positions of substituted Al atoms with the Be–Be distance
being 3.053 Å. This would suggest that Be-doped AlN ML
displays a good potential ferromagnetic behavior.
At this point, it is instructive to investigate the magnetic
coupling between the two dopant atoms. Magnetic coupling is
found to exist even if the separation distance is 10.738 Å for
Be-doped AlN ML [(I, V) conguration], indicating slowly
decaying extended tail of the impurity wave functions mediate
the long-range magnetic coupling between local moments, as
shown in Fig. 4(a). A long-range magnetic coupling is critical for
achieving high temperature magnetism at low impurity
concentrations.40 However, C-doped AlN ML is short-range
magnetic coupling with the distance of 5.377 Å.
The origin of the long-range FM coupling between the
magnetic moments induced by Be-doping can be understood
based on the analysis of the calculated PDOS and spin density
distribution. As can be seen from in Fig. 4(b), the Be-s and Al-p
states are almost symmetric and do not occur spin splitting. But
the 2p states of the N atoms occur spin polarization and overlap
signicantly, suggesting a strong p–p hybridization interaction
between them.41 Fig. 4(a) shows magnetic coupling between the
two Be atoms separated by 10.738 Å. As can be seen, the nearest-
neighbor anions between two impurity Be atoms mediate the
magnetic coupling. Obviously, the charge carriers localized
around the anions between two Be atoms are polarized and have
the same spin orientation with each other. Consequently, these
polarized charge carriers mediate the long-range ferromagnetic
coupling between the Be atoms. When replacement of Al by Be,
N anion has ve valence electrons and introduces one hole in 2p
orbital. Therefore, based on the above analysis, we propose the
hole-mediated p–p coupling interactions may be responsible for
indirect long-range ferromagnetic coupling in Be-doped AlN
ML. Our further calculations show that by doping one hole, the
magnetic moment is increased by 1.00mB per supercell, further
conrming hole-mediated ferromagnetism. Sufficiently large
spin-polarized carriers are able to effectively mediate indirect
long-range ferromagnetic coupling between the Be dopants.
Such a coupling mechanism has been reported in the alkali
metal-doping induced magnetism in AlN,20 and light elements-
doping induced magnetism in ZnS and ZnO.41,42 It is obvious

Fig. 4 The spin-density distribution of two Be-doped AlN ML is shown in (a) FM state of configuration (I, V). The yellow isosurfaces represent the
charge density of spin up. The isosurface value of spin charge is 0.001 e Å3. (b) The partial density of states (PDOS) for Be-s, Al-p, 1N-, 2N-, and
3N-p, respectively.

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that the spatially extended wavefunctions of the host and the
impurity are very useful to facilitate long-range magnetic
coupling between the impurities. The extended of wave-
functions have also been proposed to mediate long-range
magnetic interactions between defect-induced magnetic
moments in GaN and BN.35
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IV. Conclusion
We have studied Be, B, and C doped AlN ML by means of density
functional theory calculations. It has been shown that for single
X doped AlN ML, Be, and C impurities induce local spin states,
leading to a magnetic moment of 1.00mB, which is equal to the
number of holes introduced by the dopants. While the B-doped
AlN ML displays no magnetic behavior. Double X doped AlN ML
shows two different magnetic behaviors: the Be-doped AlN ML
has a stable FM states, independenting on the distance between
two impurities, but the C-doped system demonstrates AFM
states, and nally it exhibits paramagnetic behavior at room
temperature with increasing distance. The long-range ferro-
magnetic coupling of Be-doped AlN ML can be understood by
hole-mediated p–p coupling interactions. The predicted strong
room-temperature ferromagnetism suggests that Be-doped AlN
ML might have important potential application in spintronics.
On the other hand, magnetism in X-doped AlN ML which is free
of d electrons will start a new concept in the search for poten-
tially useful magnetic semiconductors.
Acknowledgements
This work was supported by the NSFC (21203096, 11374160,
11404278), by NSF of Jiangsu Province (BK20130031,
BK2012392), by the Fundamental Research Funds for the
Central Universities (no. 30920130111016), by New Century
Excellent Talents in University (NCET-12-0628), by the Qinglan
Project of Jiangsu Province, and by NUST Research Funding
(AB41374). We also acknowledge the support from the Shanghai
Supercomputer Center.
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