Copyright 2013 American Scientic Publishers Journal of

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RESEARCH ARTICLE

Electronic Properties of GaN Nanotube: Ab Initio Study

Kavita Rao Khaddeo1 2 , Anurag Srivastava1 , and Rajnish Kurchania2
1
Advanced Materials Research Group, Computational Nanoscience and Technology Lab,
ABV-Indian Institute of Information Technology and Management,
Gwalior (M. P.) 474010, India
2
Department of Physics, Maulana Azad National Institute of Technology (MANIT),
Bhopal (M. P.) 462051, India

The electronic properties of single wall (graphitic) zigzag GaN nanotubes (GaNNTs) n 0 (n =
315) with tube diameter (dt  ranging from 3.225 to 16.126 have been analyzed using
ab-initio approach. The Density Functional Theory (DFT), with LDA-PZ and GGA-PBE as exchange-
correlation functional, is employed to optimize the conguration and to evaluate the band structure of
GaNNT with specied tube diameter dt  and chirality . The computation nds that at dt = 323 ,
LDA and GGA shows almost same bandgap, whereas at dt = 1397 LDA shows metallic behavior
and with GGA semiconducting. Noticeable, buckling has also been seen at dt = 11825 , which
increases as radius of nanotube increases. In another nding, GaNNT of single atomic layer shows
smaller band gap in comparison to that of multi atomic layer and this variation has been explained in
terms of presence or absences of inter layer interactions. Interestingly, the GaNNT of single atomic
layer does not show monotonic, semiconducting or metallic behavior within diameter ranging from
3.225 to 16.126 .
Keywords:
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Electronic Properties,Technology to: Chinese
Band Structure, University
Zigzag GaNNT, Ab-Initio.
of Hong
Buckling, Kong
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1. INTRODUCTION
GaN single crystal is technologically the most interest-
ing compound (III group nitride) and has attracted much
attention due to its optoelectronic application in short
wavelength range, applicability to high temperature, high
power and high frequency electronic devices. It has great
potential as a wide band gap ( 34 eV) semiconducting
material.1 It is very hard, mechanically stable semicon-
ductor with high heat capacity and thermal conductivity.2
In response to high voltages and large stresses this material
behaves as highly piezoelectric material.3 Wurtzite lattice
type of GaN is naturally occurring most stable phase.4 5
Similar to Si, the honeycomb structures of AlP, GaAs and
GaN are found to be stable, but less energetic relative to
their bulk crystal arrangement.6 The binding energy of the
graphitic phase of GaN is smaller than that of the wurtzite
phase thus the synthesis of graphitic GaN is challenging
than wurtzite phase, however they can exist as metastable
phase.7 There are several techniques for the synthesis of
bulk high quality gallium nitride powder like solid state
metathesis reactions, high temperature owing ammonia
techniques8 and low temperature deposited buffer layer
Author to whom correspondence should be addressed.
technology.9 Both p and n type of GaN can be tuned for its
use in various molecular electronic devices. P -type GaN
can be used in blue/UV-LEDs10 and room-temperature
stimulated emission.11 High crystalline quality GaN based
hetero structures with two-dimensional electron gas are
used in Hall effect magnetic eld sensors, operable at
high temperatures ( 400  C). IIIV compound semi-
conductor Hall effect magnetic eld sensors are widely
used in the electronic industry for monitoring rotation
in various scientic equipments such as optical memory
disks and for banknote authentication in vending machines
etc. In the past two decades, nanostructured materials
have received much attention due to their interesting size-
dependent chemical and physical properties. As a result
one-dimensional (1D) nanostructures such as nanowires,
nanobelts, nanorods, and nanotubes have become the focus
of intensive research.12 The theoretical research on 1D
GaN nanomaterial involves the analysis of different prop-
erties like mechanical, structural, optical, vibrational and
so on.1 Nanotubes of compound such as BN13 and GaN1 14
have increased the interest in the theoretical analysis of
compound nanotubes.15 16 Lee et al.17 have showed that the
extra strain energy is required for nanotube wrapping from
graphitic sheet and this strain energy in forming GaNNT
comparable to that of CNTs, proving the existence of the

2066 J. Comput. Theor. Nanosci. 2013, Vol. 10, No. 9 1546-1955/2013/10/2066/005 doi:10.1166/jctn.2013.3169
Khaddeo et al. Electronic Properties of GaN Nanotube: Ab Initio Study

GaN in the form of nanotubes. However, experimentally, to be relaxed. We found that the relaxed conguration of
the prime goal is to focus on the efcient method of fab- the GaNNT shows buckling. The energy of the congura-
rication of GaN nanomaterial.1819 GaNNTs and wires can

RESEARCH ARTICLE
tion is minimized without any symmetry constraint using
be synthesized by the reaction of Ga with ammonia20 and the conjugate-gradient algorithm, until maximum resid-
by an epitaxial casting method where ZnO nanowires are ual forces between atoms becomes less than 0.05 eV/.
initially used as templates. GaNNT synthesized from these Monkhorst Pack grid of special k-points 2 2 12 is used
methods with a diameter of 300 and a minimum wall corresponding to the simple Brillouin zone (  Z) sum-
thickness of 50 .1 21 The effective electron mass has been mation. The plane wave mesh cutoff energy is nalized
investigated in different nanostructures (quantum wells, on the basis of convergence; the total energy converges
quantum wires, inversion layers, quantum conned effec- at 36.75 Ry, which is used in further calculation and the
tive mass superlattices and superlattices) with graded inter- whole calculation is done self consistently.
faces in the presence of strong external photo excitation The Fermi level EF is determined by equation as
on the basis of newly formulated electron dispersion laws reported elsewhere34
by using k.p. formalism.22 Structural and electronic prop-
erties of unusual carbon nanorods have been investigated 
2 Wki EF En k i  = z (1)
by quantum chemical methods.23 The two rst-principles
k i n
computational schemes for investigating electron-transport
properties of nanostructures attached between semi-innite
where z is the number of electrons per primitive cell. Wki
electrodes have been proposed by Ono et al.24 The GaN-
NTs are electronically and optically active and exception- is the weight for each special point k i ,35 and  is the
ally durable and their conductive properties are indepen- Heaviside step function. The valence charge density is cal-
dent of chirality and radius unlike CNTs. culated from34
 

r = 2 n  
k
r  n k 
r  (2)
2. THEORETICAL APPROACHES

k BZ

n
En  k EF
Electronic band structure calculation of zigzag GaNNTs
n 0 (n = 315) have been performed
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by Publishing
The nanotube can be uniquely dened by a roll-up vec-
calculating to: Chinese University of Hong Kong
wave functions of the valenceIP:band On: Sun, 06known
states and large
72.248.197.155 tor as chiral
Dec 2015 vector Ch which is expressed in terms
06:31:34
number of conduction band states using DensityAmerican
Copyright: of the primitive
Func- Scientific unit vectors a 1 and a 2 of lattice36
Publishers
2526
tional Theory approach. Local Density Approxima-
tion parameterized with Perdew Zunger (LDA-PZ)27 and Cn = na 1 + ma 2 n m
z (3)
Generalized Gradient Approximations (GGA) parameter-
ized with Perdew Burke Ernzerhof (GGA-PBE) are used where n and m are integers, that are specic to a n m
as exchange-correlation functionals2829 within ATK-VNL (tube index).3637 The magnitude of Ch corresponds to the
30
tool. This simulation tool uses nonlocal norm-conserving circumference around the nanotube. The diameter (dt  and
pseudo potentials31 to describe the potential of the core chiral angle ) both depend on n and m.  is dened as
electrons and linear combination of nite-range numerical the angle between Ch and a 1 and calculated through the
atomic orbitals to describe the valence states. The elec- relation given38 as
tronic structure of the valence electrons is expanded in a
basis set and Double Zeta Polarized (DZP) orbitals are  
1 3
used to improve its quality.3233 Geometry optimization has  = tan n (4)
been performed by allowing all atoms in the super cell 2m + n

Fig. 1. Buckling as a function of diameter of GaN nanotube.

J. Comput. Theor. Nanosci. 10, 20662070, 2013 2067

 Electronic Properties of GaN Nanotube: Ab Initio Study Khaddeo et al.

Table I. Calculated Energy gap of GaNNTs n 0 (n = 315) suing The diameter dt  of the nanotube can be written in
LDA as well as GGA , tube diameter and the amount of charge trans-
form of following relation reported in Ref. [36]-
ferred from Ga to N atoms with GGA.

RESEARCH ARTICLE

Charge 

ch  ch

ch a n2 + m2 + nm
transferred dt = = = (5)
Tube (e) from Ga   
index to N atoms a is the nearest neighbor distance (1.905 ).
n m Diameter () Eg (eV) (LDA) Eg (eV) (GGA) with GGA

(3, 0) 3225 1607 16 1.202

(4, 0) 4301 175 19 1.098
3. RESULTS AND DISCUSSION
(5, 0) 5375 1967 1967 0.926
(6, 0) 6451 2 2
The present ab-initio based computation of GaNNT
0.925
(7, 0) 7525 1667 18 observes the buckling in relaxed conguration of GaNNT.
0.858
(8, 0) 86 1214 15 The atoms of surface layer undergoes a bond-length con-
0.779
(metallic) traction, where the electronegative N atoms get relaxed
(9, 0) 9675 1333 1406 0.758 only parallel to the surface, whereas the electropositive
(10, 0) 10751 1433 133 0.672
Ga atoms get relaxed both parallel as well as perpendicu-
(11, 0) 11825 0967 1235 0.753
(12, 0) 12901 0867 1143 0.729 lar to the surface, moving radically inward and leading to
(13, 0) 1397 1071 1235 0.819 the buckling of the GaNNT. This buckilng might be due
(metallic) the atoms on the surface, having dangling bonds and in
(14, 0) 15051 1 0821 0.847 order to stabilize the geometry they have to readjust the
(metallic)
conguration by reducing the surface energy. Such type
(15, 0) 16126 0749 0749 0.905
of buckling has also been observed in experimentally by
Wang et al.38 Noticeable buckling is seen at dt = 11825 ,
which increases as radius of nanotube increases, shown
Nanotubes of tube index (n, 0) (zigzag nanotube) has a in Figure 1. The relaxed Ga N bond length is about
chiral angle 0 and n n (armchair nanotube) has a chiral 1.901 , which is contracted by 4.9% compared to the
angle of 30 , while n m (chiral nanotube) has a chiral ideal bond length of 1.95 in the bulk. The optimized
angle between 0 andDelivered
30 (n by
m).Publishing Technology to:average
Chinese nearest distance
University between
of Hong Ga Ga and N N are
Kong
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Copyright: American Scientific Publishers

Fig. 2. Band structure of GaNNTs (8, 0), (10, 0), (13, 0) and (14, 0) using GGA.

2068 J. Comput. Theor. Nanosci. 10, 20662070, 2013

Khaddeo et al. Electronic Properties of GaN Nanotube: Ab Initio Study

3.292 , 3.453 respectively, are in good agreement with observed a band gap of 235 eV, where they analysed
the observations made by Rezouali et al.39 According to the GaNNT with interlayer spacing of 4.5 and reported
the Mulliken population analysis,40 a considerable amount

of electron charge is transferred from Ga to N atoms,
resulting in an ionic nature of bond as shown in Table I.
Nitrogen (N) loses few s electrons and gains more p
electrons, whereas Gallium (Ga) loses more p than s
electrons. Remarkably, It was observed that there is no
effect of change in length on band structure of GaNNT7 so
we took the length constant and varied the diameter to see
its effect on the band structure. It shows a direct band gap,
which is in good agreement with the earlier rst princi-
ple calculation report.41 Lee et al.7 and Xu et al.42 studied
the band structure of GaNNT of multi atomic layer and
RESEARCH ARTICLE
a monotonic variation of Eg with dt i.e., Eg decreases
with decreasing dt .7 In case GaNNTs of single atomic
layer, due to the absence of inter layer interaction, overall
decrease in Eg ( 19 eV) has been observed. Figure 2
shows the band structures of GaNNT with tube indexes
(6, 0) (8, 0) (10, 0) and (13, 0). For deep understand-
ing of the features at the band edges, we computed the
total density of states (DOS) and partial density of states
(PDOS) too, as shown in Figure 3 for the representative
atoms in each nanotube. PDOS shows that the edges of
the valence and conduction bands (VB and CB) near the
band gap characterize a hybridization of atomic orbitals

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Fig. 3. (a)(d) showing the total DOS and PDOS of Ga and N atoms of GaNNT (8, 0), (10, 0), (13, 0), (14, 0) respectively.

J. Comput. Theor. Nanosci. 10, 20662070, 2013 2069

 Electronic Properties of GaN Nanotube: Ab Initio Study
from Ga and N atoms. Comparing of DOS and PDOS we
observes the major contribution of valence electrons are
RESEARCH ARTICLE
due to N atoms (s and p orbitals), which is in consistent to
a similar observation reported by Xu et al.42 and Durgun
et al.43 and most of the conduction electrons (from s and
p orbital) are from Ga atoms. The computed band gaps Eg
corresponding to dt with both LDA and GGA have been
reported in Table I. In zigzag GaNNT shift of eigen states
of conduction electrons (CE) away from Fermi level (EF 
has been observed with increase in radius of nanotube. We
found that there is no introduction of new states until it
reaches the maximum distance from EF (at dt = 7525 ).
Further increase in radius causes down shift of CE states
near the EF and new states can be seen in both CB and VB,
close to EF . These observations show that the band gap of
GaNNT can be tuned by varying its radius (curvature) and
hence their exploitation in variety of optoelectronic device
developments.
4. CONCLUSIONS AND PERSPECTIVES
DFT formalism was used to analyse the stability and elec-
tronic properties of zigzag shaped GaN nanotube. The
simulated GaNNTs of single atomic layer shows smaller
bandgap in comparison to that of silicon hence can be used
as an alternative to silicon. Besides this the study con-
cludes that the band gap engineering of these nanotubes
is possible by varying Delivered by Publishing
its diameter and henceTechnology
variety of to: Chinese
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applications.
Copyright: American Scientific
Acknowledgment: Kavita Rao Khaddeo is thankful to
Ministry of Human Resource and Development, Govern-
ment of India for GATE scholarship and also to Advanced
Materials Research Group, ABV-IIITM, Gwalior for pro-
viding infrastructural support.
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Received: 2 June 2012. Accepted: 29 June 2012.
J. Comput. Theor. Nanosci. 10, 20662070, 2013