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Institut f
ur Physik & IMN MacroNanoV (ZIK), Technische Universit
at Ilmenau, Prof. Schmidt-Str. 26,
Ilmenau 98693, Germany
2
Department of Physics, GC University Faisalabad, Allama Iqbal Road, Faisalabad 38000, Pakistan
3
Department of Physics, University of Sargodha, 40100 Sargodha, Pakistan
(Received 11 November 2012; accepted 29 November 2012; published online 3 January 2013)
In this paper, all electron full-potential linearized augmented plane wave plus local orbitals method
has been used to investigate the structural and electronic properties of polar (0001) and non-polar
(10
10) surfaces of ZnO in terms of the defect formation energy (DFE), charge density, and
electronic band structure with the supercell-slab (SS) models. Our calculations support the sizedependent structural phase transformation of wurzite lattice to graphite-like structure which is a
result of the termination of hexagonal ZnO at the (0001) basal plane, when the stacking of ZnO
primitive cell along the hexagonal principle c-axis is less than 16 atomic layers of Zn and O atoms.
This structural phase transformation has been studied in terms of Coulomb energy, nature of the
bond, energy due to macroscopic electric field in the [0001] direction, and the surface to volume
ratio for the smaller SS. We show that the size-dependent phase transformation is completely
absent for surfaces with a non-basal plane termination, and the resulting structure is less stable.
Similarly, elimination of this size-dependent graphite-like structural phase transformation also
occurs on the creation of O-vacancy which is investigated in terms of Coulomb attraction at the
surface. Furthermore, the DFE at the (1010)/(1010) and (0001)/(0001) surfaces is correlated with
the slab-like structures elongation in the hexagonal a- and c-axis. Electronic structure of the neutral
O-vacancy at the (0001)/(0001) surfaces has been calculated and the effect of charge transfer
between the two sides of the polar surfaces (0001)/(0001) on the mixing of conduction band
through the 4s orbitals of the surface Zn atoms is elaborated. An insulating band structure profile
for the non-polar (1010)/(1010) surfaces and for the smaller polar (0001)/(0001) SS without
O-vacancy is also discussed. The results in this paper will be useful for the tuning of the structural
C 2013
and electronic properties of the (0001) and (1010) ZnO nanosheets by varying their size. V
American Institute of Physics. [http://dx.doi.org/10.1063/1.4772647]
I. INTRODUCTION
a)
Growth of the ZnO nanosheets along the [0001] direction9,10 or where the nanosheets are enclosed entirely by the
(0001) facets11 have been achieved by a number of different
techniques such as the pulsed laser deposition method10 or
by a thermal decomposition and reduction process of the initial ZnS powder followed by a simple oxidation process.11 It
is also well known that the ZnO polar surfaces (0001)/(0001)
formed by repeating the wurtzite primitive unit cell along the
c-axis leads to a macroscopic electric field perpendicular to
the (0001) surface due to the non-zero dipole moment, thus,
resulting in electrostatic instability.12 In spite of this, the low
Miller indexed surfaces (1010) and (0001) of ZnO are especially important as they usually appear as the dominate surfaces in the synthesized two-dimensional (2D) nanosheets and
one-dimensional (1D) nanostructures.13 For example, the
growth of highly crystalline ZnO nanorods with the microwave assisted hydrothermal method result in a predominately hexagonal phase along the (1010) plane.14 In
addition, synthesis of uniform hexagonal prismatic ZnO
whiskers, highly crystalline hexagonal ZnO quantum dots or
particles, as well as some of the sides of the hexagonal columns of the ZnO powder particles are also primarily made
up of these (1010) facets and surfaces.1517 Conversely,
113, 014304-1
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Wong et al.
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Wong et al.
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Wong et al.
(1)
TABLE I. Structural data for the type-A and type-B 1 1 N SS along with the heat of formation (eV) computed using the PBEsol functional. The interlayer
distances depicted in Figs. 1(a) and 1(b) and the surface ZnO bond lengths are presented.
1 1 N SS
1 1 2 Type-A
1 1 3 Type-A
1 1 4 Type-A
1 1 5 Type-A
1 1 2 Type-B
1 1 3 Type-B
1 1 4 Type-B
1 1 5 Type-B
% Volume
collapse
Interlayer
)
distance d1 (A
Interlayer
)
distance d2 (A
Interlayer
)
distance d3 (A
0.534
0.429
0.449
0.646
14.487
12.272
3.853
3.551
1.960
1.972
1.985
1.992
0.066
0.070
0.269
0.3112
0.662
0.644
0.632
0.620
2.423
2.416
2.162
2.125
1.937
1.949
1.956
1.964
0.024
0.010
0.466
0.504
)
Surface ZnO bond lengths (A
Zn-term
O-term
Hf (eV)
1.960
1.972
1.985
1.992
1.882
1.882
1.900
1.907
1.831
1.833
1.830
1.830
1.882
1.882
1.904
1.906
1.321
1.829
2.085
2.239
2.584
2.595
2.623
2.668
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After confirming that type-B SSs are the correct representatives for simulating the effects of shallow O-vacancy at
the (0001) surface on the electronic properties of ZnO, we
have computed the DFE, charge density and electronic band
structures. It is very well known that the O-vacancy in ZnO
can exist either in the neutral state (Vo ) or the two charge
states (Vo or Vo 2 ).34 In this paper, the formation energy of
neutral O-vacancy have only been considered as some studies suggest that Vo is the major component in the defect
structure of ZnO and Vo is more stable as compared to
Vo .35,36 The DFE have been estimated using32
EVo Edt Ept RDno lo qEF ;
(2)
where Edt and Ept are the minimum total energies of the O deficient and the perfect ZnO type-B 1 1 N SS, respectively. EF and q are the Fermi energy and charge state of the
defect, respectively. Dno is the difference in the number of O
atoms in the perfect and defective SS, while lo is the chemical potential of oxygen which in two extreme cases of the
growth conditions (i.e., O-rich and O-poor condition) is
given by Eqs. (3) and (4), respectively
lopoor EO Hf ;
(3)
lorich EO:
(4)
Vo (lo-poor)
Vo (lo-rich)
Vo (lo-poor)
Vo (lo-rich)
1.053
1.111
0.864
0.801
3.636
3.705
3.487
3.468
1.052
0.572
0.232
0.143
3.635
3.166
2.854
2.810
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FIG. 4. The charge density plots of the relaxed type-B 1 1 N SSs along
the (1120) plane (top panel) without an O-vacancy (perfect) and (bottom
panel) with a shallow O-vacancy. (a) 1 1 2, (b) 1 1 3, (c) 1 1 4,
and (d) 1 1 5 SS.
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FIG. 6. The electronic band structure of the type-B 1 1 N SS (top panel) without, (middle panel) with an O-vacancy at the (0001) surface, respectively.
(Bottom panel) With an O-vacancy at the (000
1) surface. (a) 1 1 2, (b) 1 1 3, (c) 1 1 4, and (d) 1 1 5 SS.
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Wong et al.
TABLE III. The volume collapse and Hf of the relaxed N 1 1 SS after running the minimization program. The bond lengths and the bond angles at the
(1010) and (1010) surfaces.
At the (10
10) surface
N 1 1 SS
611
811
10 1 1
At the (
1010) surface
% Volume collapse
)
b.l1 (A
)
b.l2 (A
)
b.l3 (A
U1 (deg)
)
b.l1 (A
)
b.l2 (A
)
b.l3 (A
U2 (deg)
Hf (eV)
1.744
1.681
1.651
1.846
1.849
1.852
1.913
1.912
1.912
1.913
1.912
1.912
118.751
118.563
118.654
1.845
1.847
1.844
1.913
1.913
1.911
1.912
1.912
1.911
118.782
118.631
118.778
2.688
2.732
2.758
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SS defect formation
energy (eV) at the (
1010)
surface
Vo (O-poor)
Vo (O-rich)
Vo (O-poor)
Vo (O-rich)
0.546
0.261
0.208
3.233
2.991
2.965
0.546
0.487
0.467
3.233
3.217
3.224
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FIG. 8. The electronic band structure of the N 1 1 SS (top panel) without, (bottom panel) with O-vacancy at the (10
10) surface. (a) 6 1 1, (b) 8 1 1,
and (c) 10 1 1 SS.
In this study, the polar (0001) and non-polar (1010)
surfaces of ZnO have been modelled as supercell-slabs to
investigate the effects of O-vacancy at these surfaces. For
the two perfect polar (0001) SSs, type-A and -B 1 1 N
SS with a non-basal and basal plane termination, respectively, a wurtzite to graphite-like phase transformation is
observed only for the more stable type-B SS. Our results
show a clear evidence that the competition between the
bonding nature, the Coulomb energy, energy originating
from the macroscopic electric field of the dipole and the
larger surface to volume ratio for the type-B 1 1 2 and
1 1 3 SS triggers a structural phase transformation from
the wurtzite structure to graphite-like structure below a
which is longer and shorter
certain threshold length (<16 A
than the length of the type-B 1 1 3 SS and 1 1 4 SS,
respectively). This phase transformation results in an insulating band structure profile at the C point for the smaller
1 1 N type-B SS. However, the creation of surface
O-vacancy results in the removal of the stronger Coulombs
attraction at the surface and thus eliminates the graphite-like
structure for defective type-B SS even when they are smaller
.
than 16 A
In the case of perfect type-B 1 1 4, 1 1 5 SS and
all defective type B 1 1 N SS, a mixing of conduction
and valence band states at the C point leads to surface
metallization which is caused by the charge transfer to the
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Zn-terminated surface from the O-terminated surface. Importantly, a good correlation is observed in the type-B SS
between the longer bond lengths which is associated with a
smaller/larger Coulomb/bond energy that yields smaller values of the defect formation energy for the larger structures.
The higher values of DFE at the polar (0001) surfaces as
compared to the non-polar surface are a consequence of the
extra energy originating from the macroscopic electric field
along the [0001] direction in the polar SS.
On the contrary, for the non-polar (1010) and (1010)
surfaces, the computed DFE values for O-vacancy of the
N 1 1 SS reduce with increasing length of the SS along
the hexagonal a-axis and appears to be dependent on the
ionic and covalent nature of the surface ZnO bonds. However, the bond lengths and the bond angles for the surface O
atoms show no particular trends on going from the smaller
SS to larger ones. Therefore, the competition between the
bond energy and the Coulomb energy that controls the DFE
values of the neutral surface O-vacancy are a complex interplay of the ZnO bond lengths and the OZnO bond angles.
Importantly, the O-vacancy DFE values, the tilt angle, and
the interlayer spacing obtained using the SS model and the
PBEsol functional in this work are in good agreement with
the computationally more demanding calculations reported
in earlier studies. Importantly, our findings open up the possibility of tuning the structural and electronic properties of
ZnO polar and non-polar surfaces by controlling their size
which is essential for technological application.
ACKNOWLEDGMENTS
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