International Journal of Nanoscience

Vol. 11, No. 5 (2012) 1250035 (7 pages)

#
.c World Scientic Publishing Company
DOI: 10.1142/S0219581X12500354

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PRESSURE INDUCED PHASE TRANSITION

AND ELECTRONIC PROPERTIES OF 1D ZnO
NANOCRYSTAL: AN AB INITIO STUDY
ANURAG SRIVASTAVA* and NEHA TYAGI
Advanced Material Research Group
Computational Nanoscience & Technology Laboratory
ABV-Indian Institute of Information
Technology and Management
Gwalior, M.P. 474015, India
*profanurag@gmail.com
Received 13 April 2012
Accepted 19 September 2012
Published 19 November 2012
We have analyzed the one-dimensional (1D) ZnO nanocrystals in its wurtzite (B4); zinc-blende
(B3) and rocksalt (B1) type phases, by means of density functional theory (DFT) calculations. The energetic stability of nanocrystal has been analyzed using Revised Perdew

Burke
Ernzerhof (revPBE) type parameterized GGA potential. The B3 type phase is most
stable amongst other phases of nanocrystals. The computation of ground state properties for all
the phases of ZnO nanocrystals nds that the bulk modulus are smaller than their bulk
counterpart, in turn softening the material at reduced dimensions. The electronic band structure analysis conrms the semiconducting nature of B4 type phase whereas other two are
metallic.
Keywords: ZnO; nanocrystals; ab initio; electronic structure; bulk modulus; phase transition.

1. Introduction
Oxides have been a subject of intensive research for
the scientists and the industry for decades and
specially ZnO. Its pigments and protective coatings
on metals have been used for a long time, but recent
interest is because of its structural and electronic
properties. ZnO is known to be a wide band-gap
semiconductor of about (3.37 eV) with a high exciton binding energy.1 ZnO nanostructures have
a great potential for applications in solar cells,2
gas sensors,3 chemical absorbent,4 electrical and
optical devices,5
7 electrostatic dissipative coatings8
and catalysts for photo-catalytic degradation.9,10 A

number of experimental studies have been performed using dierent physical methods such
as pulse laser deposition,11 vapor phase transport
deposition,12 chemical vapor deposition13 and
sol
gel14 for the preparation of ZnO nanostructures. Recently, Wang et al.15 have synthesized
high quality indium-doped zinc oxide (in-doped
ZnO) nanocrystals using a one-step ester elimination reaction based on alcoholysis of metal carboxylate salts. In another experimental study by
Viswanatha et al.16 ZnO nanocrystal has been synthesized using poly vinyl pyrollidone (PVP) as a
capping agent and analyzed the eect of complex

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A. Srivastava & N. Tyagi

and unexpected dependencies of nanocrystal size

on various reaction parameters. Variety of novel
nanostructures, such as nanocandle arrays, winebottle-shaped rod arrays, nanorivet arrays, periodic
diamond-string and needle arrays, nanofern and
needle arrays, toothshaped belt, spinal-shaped
nanostructures and bamboo-shaped nanorod of
ZnO have also been fabricated via an atmosphere
pressure physical vapor deposition method.17 ZnO
nanocrystalline particles of size ranging from 10 nm
to 30 nm has been prepared using alcoholic solutions
of zinc acetate dihydrate through a colloidal process
and the photoluminescence spectra showed highintensity in UV emission and very low intensity in
the visible emission, indicates a good surface morphology of the these nanoparticles with little surface
defects.18 Mechanical and electromechanical properties of 1D ZnO nanostructures have also been
subject of interest because ZnO nanostructures
forms the fundamental components of nanopiezotronics,19 a current area in nanotechnology where
piezoelectric nanostructures are employed for harvesting energy in self-powered wireless nanodevices.
Several high pressure experiments on semiconductor
nanocrystals have also been carried out rstly by
Tolbert and Alivisatos.20,21 The elevated transition
pressure of the nanocrystals as compared to that of
bulk has been attributed to surface energy eects
with its coherently changing shape by undergoing
uniform deformation during the transformations.
A wurtzite to rocksalt type phase transformation
has been observed in ZnO nanowires and nanocrystals
using X-ray diraction technique at 13.7 GPa and
10.5 GPa respectively which is larger than its bulk
counterpart, however the bulk modulus of ZnO nanowire is signicantly higher than those of bulk ZnO.22
Besides these experimental works several theoretical studies have also been made using variety of
methods such as ab initio with dierent exchange
correlation functionals LDA, GGA23 and HartreeFock24 for predicting various properties of ZnO. The
rst principles density-functional theory approach
has been used to investigate innitely long (0001)
ZnO nanowires with hexagonal cross section are
found to be semiconducting, with band gaps larger
than its bulk counterpart.25 Using similar approach
the structural phase transition in ZnO nanowires
from wurtzite to rocksalt type phase has been analyzed and observes the eect of size and doping
on nanowires of dierent diameters. It has been
found that the critical pressure of structural phase
transition for nanowires is generally lower than that

of the bulk, and it decreases as the diameter of the

nanowire decreases.26 Using ab initio method the
stabilities of AlN, GaN and ZnO nanowires/nanorods with dierent structures and sizes have been
investigated and observed the structural transformation from the graphite like phase to wurtzite
phase as the diameter and length of the nanowire
increases.27 Wen et al.28 have studied the pressure
induced phase transition in CdSe and ZnO nanocrystals and found that the transition pressure
increases as the crystal size decreases. Our group has
recently investigated the structural, electronic29,30
and high pressure31 behavior of various nanostructures using ab initio calculations. Theoretical
studies on the pressure-induced phase transitions in
ZnO nanomaterials are in the early stage and needs
more attention. In this paper, we have analyzed the
stability of 1D ZnO nanocrystals in its three dierent
phases, structural phase transition and electronic
band structure using ab initio approach.

2. Computational Details
The Atomistix toolkit-Virtual Nano Lab (ATKVNL)32 software has been used for the rst-principles calculation of structural phase transition and
electronic properties of 1D ZnO nanocrystals in its
wurtzite (B4), zinc-blende (B3) and rocksalt (B1)
type phases. ATK is a further development of
TranSIESTA-C33 which, in turn, is based on the
technology, models and algorithms developed in
the academic code TranSIESTA and, in part,
McDCal,34 employing localized basis sets as developed in SIESTA.35 For the computation of total
energy the Revised Perdew
Burke
Ernzerhof
(revPBE) type parametrized generalized gradient
approximation (GGA) exchange correlation functional36,37 has been employed. The study has been
made in self consistent manner using steepest descent geometric optimization technique with pulay
algorithm for iteration mixing. Double

double
polarized (DZDP) basis set are used as local combination of atomic orbital's (LCAOs) to describe
the valence electrons. A mesh cut-o of 100 Ryd
with 1  1  50 k-points has been taken for the
present work. To get better understanding of fundamental physics associated with dierent phases of
1D ZnO nanocrystal, the binding energies have also
been computed using GGA potential. Murnaghan's
equation of state38 has been implemented for the
computation of lattice parameter, bulk modulus
and pressure derivatives of ZnO nanocrystal. The

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Pressure Induced Phase Transition and Electronic Properties of 1D ZnO Nanocrystal

present calculation has been performed using sixteen atoms and the nanocrystals are assumed to be
roughly spherical whose diameter (d) can be calculated using the following relationship:
  1=3
3N
;
da
4
where a is the lattice parameter and N is the number of atoms present in the nanocrystals. For the
present study the diameter of nanocrystal ranges
from  0.6 nm to  0.8 nm.
Fig. 1. (Color online) Energy as a function of volume for 1D
ZnO nanocrystals.

3. Results and Discussions

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3.1.

Stability and phase transition

The structural stability, phase transition and electronic band structure of 1D ZnO nanocrystal in
its B4, B3 and B1 type phases have been investigated using ab initio approach. The total energy
calculations have been performed in self consistent
manner to get the minimum energy conguration
for dierent phases of 1D ZnO nanocrystal. The
energy as a function of volume has been plotted for
1D ZnO nanocrystal in its three probable phases to
realize their stability as shown in Fig. 1. For analyzing the stability we have also calculated the
binding energy per atom for all the nanocrystals.
The binding energy per basis is calculated by

determining the nanocrystal energy per basis of the

unit cell and subtracted it from the energy of its
bulk counterpart. B3 type phase of nanocrystal, can
be considered as the most stable structure as it
posses the lowest total energy and highest binding
energy. The lattice parameter of nanocrystals in B4,
B3 and B1 type phases are relatively larger than its
bulk counterpart. The calculated lattice parameters
for the bulk ZnO in B4, B3 and B1 type phases are
in close match with its experimental/theoretical
counterpart.39,40 These parameters have been
computed for nanocrystals too and summarized
in Table 1 along with their bulk counterpart.

Table 1. Lattice parameter (a), bulk modulus (B0 ) and pressure

derivatives (B 00 ) for B4 (wurtzite), B3 (zinc blende) and B1 (rocksalt)
type phases of bulk and nanocrystal of ZnO.
ZnO

Nanocrystal

Bulk

B4
a ()
c/a
B0 (GPa)
B 00
Eg (eV)

3.858*
1.353*
36.06*
4.54*
0.26*

3.288*, 3.2496 a
1.603*, 1.6138 b , 1.6076 b
154.16*, 183 a , 162.3 b , 133.7 b
7.885*, 4 a , 4.05 b , 3.83 b
1.02*, 0.83 c , 0.68e, 0.75e, 0.76e, 0.73e, 0.55e

B3
a ()
B0 (GPa)
B 00
Eg (eV)

5.127*
92.62*
2.33*
M

4.732*
133.56*, 161.7 b , 135.3 b
3.153*, 3.95 b , 3.72 b
0.96*, 0.71 c , 0.55 e , 0.6 e , 0.65 e , 0.58 e , 1.4 e

B1
a ()
B0 (GPa)
B 00
Eg (eV)

4.636*
117.26*
6.66*
M

4.431*, 4.271 a
126.27*, 228 a , 205.7 b , 172.7 b , 132 d
3.598*, 4 a , 3.9 b , 3.68 b , 3.8 d
1.62*, 2.62 c , 0.97 e , 0.98 e , 0.95 e , 0.94 e , 1.62 e

Note: M Metallic, *Present work, a Reference 39,

c Reference 41, d Reference 42 and e Reference 43.
1250035-3

b Reference

40,

A. Srivastava & N. Tyagi

Comparative analysis shows that the bulk modulus

in all the three stable phases of nanocrystals is
comparatively smaller than its bulk counterpart. As
a eect of compression, the B4 ! B1 type structural
phase transformation has been observed in ZnO
nanocrystal at around 3.39 GPa which is signicantly lower than that observed at 8.91 GPa in bulk
ZnO and our bulk result is in good agreement with
the data reported by Gao et al.26 Gao and his
coworkers have also observed the B4 ! B1 structural transition in dierent size ZnO nanowires at
5.64 GPa and 6.35 GPa, which is also lower than its
bulk counterpart, which supports our ndings.
Besides B4 ! B1 transition we have also observed
the B3 ! B1 transition in bulk ZnO at around
10.07 GPa however such transition is missing in the

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Fig. 2. Relative volume as a function of pressure for 1D ZnO

nanocrystals.

(a)

(b)

(c)
Fig. 3.

(a)
(c) Electronic band structures of ZnO nanocrystals in three phases.

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Pressure Induced Phase Transition and Electronic Properties of 1D ZnO Nanocrystal

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(a)

(b)

(c)
Fig. 4.

(a)
(c) Density of states for ZnO nanocrystals in three phases.

nanocrystal of this material. Besides the bulk

modulus, the amount of volume collapse at transition pressure also helps us in making a basic
comprehension about the hardness of these nanocrystals, the calculated volume collapse at B4 ! B1
transition is about 21.62% as shown in Fig. 2.

3.2.

Electronic band structure and

density of states

To understand the electronic behavior of the stable

phases of 1D ZnO nanocrystals, electronic band
structures and density of states (DOS) analysis
have been performed. The band structures of all the
stable phases of nanocrystals are illustrated in
Figs. 3(a)
3(c). In order to have a comparative
analysis we have also analyzed the band structure of
bulk ZnO in B4, B3 and B1 type phases and

observed a band gap of about 1.02 eV, 0.96 eV and

1.62 eV, respectively at the
point. In the band
structure of B4 nanocrystals there are six energy
bands in the valence band region and two bands
in the conduction band region, having a small
band gap of around 0.26 eV at the
point shown in
Fig. 3(a). Figure 3(b) represents the band structure
of B3 type phase of nanocrystal, where one conduction band is crossing the Fermi level shows the
semi-metallic behavior of this phase. The electronic
band structure of B1 type phase of nanocrystal as
shown in Fig. 3(c), have metallic nature as here too
one conduction band is crossing the Fermi level. In
comparison to their bulk counterparts a semiconducting to metallic transition can be seen as a
function of size. Our calculated band gap of the ZnO
1D nanocrystals is much smaller than that of bulk
ZnO. In contrast, the quantum size eect generally

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A. Srivastava & N. Tyagi

enhances the band gaps. This abnormality in band

gap can be explained by surface eects, where surface states associated with the individual atoms at
side surface in nanocrystals generate new energy
levels at both valence and conduction band edges,
which narrow the band gaps considerably relative to
bul. The Zn
O bond length in case of nanocrystal is
around 1.92 which is comparatively less than its
bulk counterpart, responsible for their band structures far away from bulk ZnO. A similar report has
been given by Zhou et al.44 where they have also
observed the shortening of bond length and a
smaller band gap in AlN nanowires as compare to
bulk AlN.
For the basic comprehension of electronic behavior near the Fermi level we have also plotted the
DOS prole for all the stable phases of ZnO nanocrystals as shown in Figs. 4(a)
4(c). In the DOS
prole of B4 type phase of nanocrystal, the highest
magnitude peak appears in the valence band region
at around
3.2 eV with two small peaks and
absence of peaks in the conduction band region;
clearly suggest very less localization of states near
the Fermi level. In case of B3 type phase of nanocrystal, two highest magnitude peaks are present,
one near the Fermi level at around
0.3 eV and
other at
2.8 eV, whereas there are two small distorted peaks appear in the conduction band region,
suggests that allowed states are near the Fermi
level. In the DOS prole of B1 type phase of
nanocrystals, one small distorted peak appear in the
conduction band region whereas the highest magnitude peak appear in the valence band region along
with few small peaks, shows localization of states
near the Fermi level. The overall conclusion is that
few sharp peaks that appears in the valence band
region are mainly due to the eect of Zn and O s and
p-orbital electrons however the few prominent peaks
that appears in the conduction band region is the
combine eect of Zn and O p-orbital electrons.

4. Conclusion
Ab initio based structural stability analysis of 1D
ZnO nanocrystals in B4, B3 and B1 type phases
have been performed with B3 type phase as most
stable one. The calculated bulk moduli of all the
phases of nanocrystal are relatively smaller than its
bulk counterpart, suggests the softening of material
at reduced dimensions. B4 ! B1 type structural
phase transformation has also been observed in the

nanocrystal at comparatively lower pressure than

its bulk counterpart. The electronic band structure
analysis conrms the B4 type phase as semiconducting whereas B3 and B1 type phases are
semi-metallic in nature, however, all these phases
are semiconducting in its bulk form.

Acknowledgments
Authors gratefully acknowledge the ABV-Indian
Institute of Information Technology and Management, Gwalior for the infrastructural support provided to the research work.

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