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Density Functional Study of Manganese Atom Adsorption on Hydrogen-

Terminated Armchair Boron Nitride Nanoribbons

Article in Physica B Condensed Matter · August 2014

DOI: 10.1016/j.physb.2014.04.043

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 Physica B 447 (2014) 65–69

Contents lists available at ScienceDirect

Physica B
journal homepage: www.elsevier.com/locate/physb

Density functional study of manganese atom adsorption

on hydrogen-terminated armchair boron nitride nanoribbons
Yusuf Zuntu Abdullahi a,b, Md. Mahmudur Rahman a,n, Alhassan Shuaibu a,f,
Shamsu Abubakar a,c, Hishamuddin Zainuddin a,g, Rifki Muhida d, Henry Setiyanto e
a
Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
b
Department of Physics, Faculty of Science, Kaduna State University, P.M.B. 2339, Kaduna State, Nigeria
c
Department of Physics, Faculty of Science, Yobe State University, P.M.B. 1144, Yobe State, Nigeria
d
Department of Physics-Energy Engineering, Surya University, Gedung 01 Scientia Business Park, Jl. Boulevard Gading Serpong Blok O/1, Summarecon
Serpong, Tangerang 15810, Banten, Indonesia
e
Analytical Chemistry Research Group, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha no. 10,
Bandung 40132, Indonesia
f
Department of Physics, Faculty of Science, Nigerian Defence Academy, P.M.B 2109 Kaduna, Nigeria
g
Institute for Mathematical Research, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

art ic l e i nf o a b s t r a c t

Article history: In this paper, we have investigated stable structural, electric and magnetic properties of manganese (Mn)
Received 20 January 2014 atom adsorption on armchair hydrogen edge-terminated boron nitride nanoribbon (A-BNNRs) using first
Accepted 13 April 2014 principles method based on density-functional theory with the generalized gradient approximation.
Available online 4 May 2014
Calculation shows that Mn atom situated on the ribbons of A-BNNRs is the most stable configuration,
Keywords: where the bonding is more pronounced. The projected density of states (PDOS) of the favored
Boron nitride nanoribbons configuration has also been computed. It has been found that the covalent bonding of boron (B),
Density functional theory nitrogen (N) and Mn is mainly contributed by s, d like-orbitals of Mn and partially occupied by the 2p
Structural like-orbital of N. The difference in energy between the inner and the edge adsorption sites of A-BNNRs
Electric and magnetic properties
shows that Mn atoms prefer to concentrate at the edge sites. The electronic structures of the various
configurations are wide, narrow-gap semiconducting and half-metallic, and the magnetic moment of Mn
atoms are well preserved in all considered configurations. This has shown that the boron nitride (BN)
sheet covered with Mn atoms demonstrates additional information on its usefulness in future
spintronics, molecular magnet and nanoelectronics devices.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction Alternatively, half-metallic behavior of BNNRs can be achieved

Recent experimental synthesis of boron nitride nanoribbons
(BNNRs) [1] has triggered great research interests because of its
noble chemical and thermal stabilities [2,3]. However, there are
some challenges that need to be addressed before it can be used
for various fields of applications. The main challenge is the
insulating nature of this material. This problem needs to be
overcome before BNNRs can be proposed for nanoscale applica-
tions ranging from spintronics to nanophotonics. Finding the right
methods and mechanism of modifying the electronic properties
has motivated further studies [4–12]. One of the methods of
tuning band gap of BNNRs involves application of transverse
electric field [13].
n
Corresponding author.
E-mail address: mahmudur@upm.edu.my (Md.M. Rahman).
by the charge injection and fluorination of edges [14,15]. More-
over, density functional theory (DFT) calculations have shown that
hydrogen terminated BNNRs with different edge orientations such
as armchair and zigzag edges boron nitride nanoribbons (A-BNNRs
and Z-BNNRs) are non-magnetic with wide energy gap [13,16].
The induced magnetism based on substitutions (or adsorption) of
carbon atom on B or N vacancies of the BN sheet has been
confirmed and also carefully explained [2,5,8].
In spite of numerous studies on BNNRs edge-termination with
different nanostructures [14,17,18], theoretical investigations of
adsorption of metallic nanostructures on the surface and the edges
of BNNRs have received less attention. It has been reported that
Z-BNNRs with a doped carbon atom chain can exhibit significant
magnetic moment and tunable band gap [19]. More recently,
attention has now been shifted to study the effects of transition
metals (TM) atoms adsorption on boron nitride (BN) and its
ribbons because of their tendencies to induce noble changes in
electric and magnetic properties such as half-metallicity and

http://dx.doi.org/10.1016/j.physb.2014.04.043
0921-4526/& 2014 Elsevier B.V. All rights reserved.
66 Y.Z. Abdullahi et al. / Physica B 447 (2014) 65–69

narrow band-gap semiconducting behaviors which are needed for

spintronics and related field of application [20,21].
A current study in this perspectives reported spin gapless
semiconducting behavior for the majority of stable Fe adsorption
on hydrogen-terminated BNNRs systems [22]. This recent
approach has provided a platform for the possible future fabrica-
tion of spintronics devices particularly for the preservation of
magnetic moment of the Fe atom, which is found to be almost the
same as the value of an isolated Fe atom. Therefore, it is quite
interesting to theoretically extend the study to the rest of mag-
netic TM atoms so that a clear mechanism can be found on the
possible future utilization. We have considered Mn atom in this
study because of its high local spin magnetic moment compared to
rest of the members in the group. It has also been reported based Fig. 1. The top view of the various adsorption positions of Mn atom indicated
on first-principles investigation that armchair edge BN nanorib- by the red star.
bons are more energetically stable than the zigzag ones [23].
In this work, we have investigated the structural, electric and
magnetic properties of A-BNNRs system with adsorbed Mn atom Table 1
based on first-principles method. The results are discussed based Details of the optimized properties for Mn/A-BNNRs systems. The optimized
on the available literatures and a clear statement will be estab- properties of the favored configuration are highlighted in bold. The binding
lished on the electronic structures of all the considered energies Eb, the average bond length between Mn adatom and B, N and H denoted
as dMn–B, and dMn–N, and dMn–H, resprectively. The charge transferred into the
configurations. A-BNNR based on Lö wdin's charge analysis, magnetic moment per unit cell,
electronic character of the Mn/A-BNNRs system and the approximate band gap
are denoted by Q, M, EC and BG, respectively.
2. Calculation method
Site Eb dMn–B dMn–N dMn–H Q M EC BG
(eV) (Å) (Å) (Å) (electrons) (mB) (eV)
Our calculations have been performed based on first-principles
[24] density functional theory implemented in the QUANTUM H 0.59 4.15 4.15 – 0.02 5.00 SC 3.48
ESPRESSO simulation package [25]. The electron–electron interac- Bri 0.59 4.05 3.90 – 0.02 5.00 HM –
TN 0.59 – 3.94 – 0.02 5.00 SC 3.50
tion has been considered within generalized gradient approxima-
TB 0.59 3.92 – – 0.02 5.00 SC 3.50
tion (GGA) and spin polarized GGA as parameterized by Perdew– EBN 0.84 2.22 2.37 – 0.25 5.00 SC 0.70
Burkew–Enzerhof (PBE) [26] exchange correlation scheme. Elec- EBH 0.61 3.67 – 3.63 0.01 5.00 SC 1.75
tron–ion core interaction has been treated by ultrasoft pseudopo- ETB 0.77 2.21 – – 0.25 5.00 SC 1.29
tentials for B, N and H (2s, 2p, and 1s valence orbitals as in the EBri 0.76 2.22 2.26 2.79 0.25 5.00 SC 0.77

pseudopotential file, respectively), and Mn (3s23p64s23d54p0) [27].

All pseudopotentials can be found from the plane-wave self-
consistent field (PWSCF) pseudopotentials online references [28].
To expand the wave functions, we have used plain wave basis set
with kinetic energy cut-off of 500 eV. For integrals, smearing has
been employed to aid convergences and to be specific, Marzari–
Vanderbilt method with small Gaussian spreading of 0.03 eV has
been used [29]. For Brillouin zone (BZ) integrations, we have
sampled 1
1
22 set of k-points with the Mankhorst–Pack
scheme [30]. In modeling pristine A-BNNR, we have used two
periodic units along the ribbons growth directions and a width of
nine dimer lines (2
9 periodicity) comprising of 44 atoms per
unit cell. The pristine BNNRs have been constructed with experi-
mental lattice constant of 2.51 Å [31]. To minimize the interaction
between the adatom in the BNNRs and its neighboring image, a
vacuum space of 14 Å perpendicular to the ribbons has been
considered in all configurations.
It is important to note that all calculation parameters have
been tested for convergences. The convergence has been consid-
ered to be achieved when there are two consecutive iterative
steps with energy difference less than 1 meV. In the case of Mn
adsorption on BNNRs, eight possible initial adsorption sites as
shown in Fig. 1 have been considered which can be classified into
two namely, the inner and edge adsorption sites. The inner sites
comprise the adsorption sites in which the Mn atom are located
above N atom, B atom, B–N bond and the center of the hexagonal
BN namely TN, TB, Bri and H sites, respectively. The edge sites
consist of the following adsorption sites, the Mn atom situated
above B atom, B–N ribbons side, above the bay site of B–N and
above B–H bond namely ETB, EBN, EBri and EBH, respectively. The
relaxations for each configuration are performed along all the
atomic coordinates by keeping the cell dimension fixed. We have
used Broyden–Fletcher–Goldfarb–Shanno (BFGS) algorithm for the
forces and energy minimization process during structural
relaxation.
3. Results and discussions
In this work, we have considered Mn atom adsorption on the
A-BNNRs system at various adsorption sites. Table 1 summarizes
the detail structural stabilities parameters and magnetic moment
per unit cell for the obtained various A-BNNR with adsorbed
Mn atom, i.e., the binding energy, bond lengths between Mn and
the atoms in the A-BNNRs, the electronic character of the
Mn/A-BNNRs system and the approximate band gap. The charge
transfer into the A-BNNR is based on Löwdin's charge analysis
[32]. The stability for Mn adatom is measured by the binding
energy Eb defined as
Eb ¼ Etotal  ðEBN þ EMn Þ; ð1Þ
in unit of eV/atom, where Etotal represents the spin-polarized total
energy of the Mn A-BNNRs system, EMn stands for the total energy
of an isolated Mn atom and EBN is the total energy of pristine
ABNNRs. Detailed discussions are presented in the following
paragraphs.
Among the eight initial structural configurations for A-BNNR
with adsorbed manganese atom, the favored binding site for Mn is
located on the edge site of the B–N ribbons named EBN as shown
in Fig. 1. It is interesting to know that the binding energies listed in
Table 1 are virtually the same within the various adsorption sites
in the central part of the A-BNNRs, which is in agreement to the
 Y.Z. Abdullahi et al. / Physica B 447 (2014) 65–69
results in Ref. [22]. In addition, the binding energy indicates that
the Mn adatom can barrierlessly migrate within the various
adsorption sites in the central region. Moreover, the Mn atom
situated at the edge sites shows the most negative binding energy
with values of almost  0.3 eV, which is more than the binding
energy values in the inner region adsorption sites indicating more
covalent bonding between the adatom and the atoms of the
A-BNNRs. It is also known that after full relaxation, the adatom
may slightly deviate from their original high symmetric locations,
and the new position shows the nearest possible configurations.
For the favored configuration shown in the charge density dis-
tribution of Fig. 2, the Mn adatom is closer to B than the N.
Consequently, the bond lengths between the Mn adatom and the
nearest B, N atoms are 2.221 Å and 2.366 Å, respectively which are
as well far less than the obtained values in the inner region.
The self-consistent total energy computations reveal that
A-BNNRs with adsorbed Mn system for all considered configura-
tions are magnetic with total magnetic moment of approximately
5.0μB per unit cell. This value shows that magnetic moment per
unit cell is the same as the value for an isolated manganese atom,
which is consistent with the recent case of Mn adsorbed BN sheet
[21]. Furthermore, the observed magnetic moment is independent
of the adsorption sites indicating that BN covered with Mn atoms
has unique features for magnetic device applications. It is also
worth noting that pristine BNNRs have no magnetic ordering, and
these values of magnetic moments show that there is charge
transfer between BNNRs and manganese atom resulting in fine
tuning the magnetic properties of the system.
This charge transferred is clearly evidenced in Table 1 that
shows the Lö wdin charge analysis with not more than 0.3 electrons
transferred into the A-BNNRs. Besides charge transfer into
A-BNNRs upon Mn adatom adsorption, Lö wdin charge analysis
has further confirmed that the charge transfer between the
orbitals from 4s to 3d orbitals results in the increase in unpaired
electrons of the 3d orbital of Mn, and consequently the magnetic
Fig. 2. (a) The top view charge density plot of the favored Mn/A-BNNRs system
with colors scale n(r) indicating ranges of charge accumulation and depletion in a.u.
(b) The side view charge density plot of the favored Mn/A-BNNRs system with
colors scale n(r) indicating ranges of charge accumulation and depletion in a.u.
67
moment may be retained. It is worth noting that the charge
transfer into the A-BNNRs calculated in this work for the inner
adsorption sites is similar to the values computed in Ref. [30], even
though there may be some differences in the considered popula-
tions of the electrons in the valence orbitals.
To explore further insights into the charge transfer between
Mn/A-BNNRs system, Fig. 2(a) and (b) shows the top and side view
of the charge distributions of Mn atom and the nearest bonding B
and N atoms. It is observed that the height and bonding points of
the adsorption site are reflected in the figure showing charge
accumulation at the bonding points in the substrate and uniform
charge depletion between the points of the interaction. According
to the color scale of the charge distributions, the bonding charge
between the Mn adatom and nitrogen and boron of the A-BNNRs
system at the edge is not more than 3.0 e/Å3.
The electronic properties are discussed based total density of
states (TDOS) and projected density of states (PDOS) in this part.
To have a bench mark of accuracy, we have reproduced the result
of density of states (DOS) of pristine hydrogen edge-terminated
A-BNNRs with a width of nine dimer lines and two periodic units
along the ribbon growth direction. As can be seen in Fig. 3 the DOS
shows a direct band gap of  4.26 eV, and also the system is found
to be non-magnetic. This is in agreement with the result obtained
by Du et al. [16]. Shown in Fig. 4a–h are the various TDOS of all the
atomic configurations considered in the calculations. We have
found that in all the cases considered the electronic structures of
the Mn/A-BNNRs systems are mostly wide-gap or narrow-gap
semiconductor (SC) except the one that shows half-metallic
property. It is interesting to know that these semiconducting
electronic structures and the simultaneous magnetic behavior of
this material have been found to have great promise in spintronics
and related field of applications [33]. The spin-polarized TDOS and
PDOS for the favored A-BNNRs with adsorbed Mn system are
shown in Fig. 5a–e; we see that A-BNNRs system with adsorbed
Mn is a narrow-gap semiconductor with an energy gap of
approximately 0.70 eV. This is consistent with many studies
[6,7], that single atom adsorption on BNNRs can change the
insulating character of the system into different forms. The
asymmetric majority and minority spins states of the favored
configuration have further confirmed the presence of magnetic
moment in the system. We can see that the proportion of the
bonding orbitals in the PDOS analysis are mainly dominated by s, d
like orbitals of Mn majority spin and s, p orbitals of N for both
majority and minority spins. At approximately  1.0 eV there is a
strong hybridization in the majority spin states between the s, p
orbitals of Mn, B and N atoms, and is responsible for the covalent
bonding. We can further infer from the spin states that the
magnetic moment per unit cell is contributed by the unpaired s
and d electrons of Mn and the p electrons of N atoms. Moreover,
the states occupation of p in majority state of N atom provides
further evidence for the electron transfer into the A-BNNRs
system.
Fig. 3. Density of states of pristine armchair boron nitride nanoribbon showing a
direct band-gap at Fermi level.
68 Y.Z. Abdullahi et al. / Physica B 447 (2014) 65–69

Fig. 4. The spin-polarized total density of states for the various Mn/A-BNNRs configurations considered showing their electronic structures ranging from wide-gap, narrow-
gap semiconducting to half-metallic system. (a) Total density of states for the A-BNNRs with Mn adsorbed on the B–N bond site named Bri, (b) total density of states for the
A-BNNRs with Mn adsorbed on the center of the hexagonal BN site named H, (c) total density of states for the A-BNNRs with Mn adsorbed on the B atom site named TB,
(d) total density of states for the A-BNNRs with Mn adsorbed on the N atom site named TN, (e) total density of states for the A-BNNRs with Mn adsorbed on above B–H bond
site at the edge named EBH, (f) total density of states for the A-BNNRs with Mn adsorbed on the bay site of B–N site at the edge named EBri, (g) total density of states for the
A-BNNRs with Mn adsorbed on B atom at the edge site named ETB and (h) total density of states for the A-BNNRs with Mn adsorbed on B–N ribbons at the edge site
named EBN.

4. Conclusions A-BNNRs system shows that Mn atoms will prefer to concentrate

In summary, the stable structure, electronic and magnetic
properties of armchair hydrogen-terminated boron nitride nanor-
ibbons with adsorbed Mn atoms have been studied using first-
principles calculations. For various Mn/A-BNRRs system consid-
ered, the binding energy of Mn in the inner adsorption sites
has been found to be the same indicating that the Mn atom can
easily migrate within the various adsorption sites. The difference
in energy between the inner and the edge adsorption sites of
at the edge sites. The electronic structures of the various config-
urations considered are wide-gap, narrow-gap semiconducting
and half-metallic and the magnetic moment of the atom is well
preserved in all the adsorption sites. This has shown that the BN
sheet covered with Mn atoms has unique promise in future
spintronics, molecular magnet and nanoelectronics devices. The
favored adsorption site is preferentially located at the edge where
Mn atom is situated on the B and N bridge. The orbital contribu-
tions for the favored Mn/A-BNNRs configuration are mainly
 Y.Z. Abdullahi et al. / Physica B 447 (2014) 65–69 69

Fig. 5. (a) The spin-polarized total density of states for the favored Mn/A-BNNRs system, (b) the spin-polarized projected density of states for d like-orbital of Mn atom in the
adsorbed A-BNNRs system, (c) the spin-polarized projected density of states for sp like-orbital of Mn atom in the adsorbed A-BNNRs system, (d) the spin-polarized projected
density of states for sp like-orbital of B atom in the A-BNNRs system after Mn atom adsorption and (e) the spin-polarized projected density of states for sp like-orbital of N
atom in the A-BNNRs system after Mn atom adsorption.

dominated by s, d like orbitals of Mn with some contributions
from p like orbitals of N.
Acknowledgments
This work is supported by Universiti Putra Malaysia and
Kaduna State University Nigeria and the Ministry of Higher
Education, Malaysia (MOHE), through Fundamental Research
Grant Scheme (FRGS) (Project code: FRGS/1/11/ST/UPM/02/11).
Figures showing electronic configurations and charge density are
generated using the XCRYSDEN program Ref. [34].
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