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 Page 1 of 10 Physical Chemistry Chemical Physics
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Band Alignment and Charge Transfer Predictions of
Published on 19 January 2018. Downloaded by University of Florida Libraries on 19/01/2018 14:16:35.

ZnO/ZnX (X = S, Se, Te) Interfaces Applied to Solar

Cells: A PBE+U Theoretical Study†
Efracio Mamani Flores,∗a Rogério Almeida Gouvea,∗a Maurício Jeomar Piotrowskia and
Mário Lucio Moreiraa

The engineering of semiconductor materials for the development of solar cells is of great impor-
tance today. Two topics are considered of critical relevance for the efficiency of the Grätzel-type
solar cells, the efficiency of charges separation and charge carrier transfer. Thus, one of the
focuses is the combination of semiconductor materials with the aim of reducing charge recombi-
nation, which occurs by the spatial charge separation. From the experimental point of view the
combination of the materials can be achieved by decorating a core with another material shell
resulting in a core-shell system, which allows to control the desired photoelectronic properties. In
this context, the computational simulation is mandatory for the atomistic understanding of possi-
ble semiconductor combinations and for the properties prediction. Considering the construction
of the ZnO/ZnX (X = S, Se, Te) interfaces, we seek to find the electronic influence of the shell
(ZnX) on the core (ZnO) and, consequently, find out which of the interfaces would present the
appropriate properties for the (Grätzel-type) solar cell applications. To perform this study, we have
employed density functional theory (DFT) calculations, considering the Perdew-Burke-Ernzerhof
(PBE) functional. However, it is well-known that the plain DFT fails to describe strong electronic
correlated materials, where in general, the band gap underestimation is obtained. Thus, to the
correct description of the electronic properties was employed a Hubbard correction, i.e., PBE+U
calculations. The PBE+U methodology has provided the correct electronic structure properties for
bulk ZnO in good agreement with the experimental values (99.4%). The ZnO/ZnX interfaces were
build considering six ZnO layers and two ZnX layers, which represents the decoration process.
The core-shell band gap was of 2.2 eV for ZnO/ZnS, ∼1.71 eV for ZnO/ZnSe, and ∼0.95 eV for
ZnO/ZnTe, which also exhibited a type-II band alignment. The Bader charge analysis showed an
accumulation of charges in the 6th layer of ZnO for the three interfaces ZnO/ZnX. On the basis of
these results, we have proposed that ZnO/ZnS and ZnO/ZnSe core-shell can be applied as good
candidates (better efficiency) for photovoltaic devices.

1 Introduction
There are two main features that have the merit figures for the
semiconductors become ideal materials for the solar cell applica-
tions. The efficiency for separation and transference of the charge
carriers, both are of critical importance for solar cell efficiency 1 .
Today, it is still hard to achieve a good efficiency considering a
single semiconductor II-VI, due to the high recombination rates
for the charge carriers and also because of the photocorrosion 2 .
a
Department of Physics, Federal University of Pelotas, P.O. Box 354, 96010-900,
Pelotas, RS, Brazil; E-mail: mlucio3001@gmail.com
∗
Contributed equally to this work
† Electronic Supplementary Information (ESI) available: [Convergence tests and
extra analysis.]. See DOI: 10.1039/b000000x/
Therefore, the combination of semiconductors receives a strong
attention due to the tunability of their electronic properties, lead-
ing to many relevant nanotechnology and optoelectronic appli-
cations 3,4 . Among various semiconductors, wide band gap zinc
oxide (ZnO), especially with highly ordered one-dimensional ar-
rays, has attracted tremendous attention because of its remark-
able physicochemical properties, such as tunable alignment and
morphology, high aspect ratio, deep-level defects, and a relatively
large excitation binding energy of 60 meV 5–7 . These merits spon-
taneously transform ZnO into a promising candidate for the con-
stitution of solar cells 8,9 . However, the practical application of
ZnO is severely hindered by its wide band gap (∼3.2 eV) 2 , which
restricts its use to the ultraviolet light region, and the high recom-
bination rate of charge carriers relentlessly causes poor utilization

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 Physical Chemistry Chemical Physics
of sunlight, limiting its photocatalytic efficiency 10 . Therefore, it
is still a challenging task to exploit new approaches for improving
the visible light absorption ability and energy-harvesting 11 .
Recently, zinc chalcogenides, ZnX (X = S, Se, Te), belonging to
II-VI semiconductors, have attracted extensive interest toward ap-
plications in photovoltaic or photocatalytic systems 12 with great
emphasis on solar cells 13 , due to its narrow band gap (∼2.2
eV), which matches well with the solar visible spectrum. More-
over, as one of the few direct-type band gap semiconductors, ZnS
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has attracted interest as a promising candidate with great appli-
cation potential in the construction of ZnO/ZnS core-shell sys-
tems, with the proposal to serve as an efficient light absorber
and photoinduced electron provider 5 . Furthermore, many ZnX-
based heterostructures, such as ZnO/ZnS 9 , ZnO/ZnSe 14–16 , and
ZnO/ZnTe 17–19 have been extensively characterized from exper-
imental points of view. These core-shell structures not only pro-
mote the generation of charge carriers but also considerably sup-
press the recombination rate of charge carriers. Since it is well-
known that interfacial charge recombination is a serious prob-
lem for photovoltaic based devices, inasmuch as this phenomenon
causes a loss of photo-generated electrons 20 .
From the first-principles calculations point of view, a large num-
ber of studies have been addressed to the understanding of the
ZnX (X = O, S, Se, Te) properties. The vast majority of studies
have employed the plain density functional theory (DFT) calcula-
tions 21,22 . However, it is widely known that the standard DFT cal-
culations using, for example, the Perdew-Burke-Ernzerhof (PBE)
functional 23 typically suffers from a bad band gap description,
i.e., an underestimation of the band gap values. This problem
occurs especially for strongly correlated materials 24 . Thus, an
inadequate methodology could lead to inaccurate estimations of
the ZnX electronic properties, especially because of the bad de-
scription of the d and f orbitals 8,25 .
The band gap underestimation by DFT-PBE calculations can be
corrected, for example, using the GW approximation, in which
a self-energy of a many-body system of electrons is taken into
account 26,27 . Zhang et al. 28 estimated the wurtzite ZnO band
gap to be between 2.82 eV and 4.54 eV, using GW approxima-
tion. An additional way to improve the band gap description is
to employ the hybrid exchange correlation functionals, in combi-
nation with DFT-PBE calculations, e.g., Heyd, Scuseria, and Ernz-
erhof (HSE06) functional 29 . Using the HSE06 functional, Bo-
Tao et al. 30 predicted the band gap of wurtzite ZnO to be 2.79
eV. While both GW approximation and hybrid functional have
proved to be effective in mitigating the band gap from plain DFT-
PBE calculations, a major downside is the larger computational
requirement in comparison with standard DFT calculations. Al-
ternatively, DFT+U (e.g., PBE+U) calculations have emerged as
a means to improve the electronic properties predictions, with a
computational cost similar to the plain DFT-PBE calculations 31,32 .
In a DFT+U calculation, an additional Hubbard-like term is con-
sidered through the Hubbard parameters, U and J 33,34 . The
method more frequently employed to estimate the Hubbard pa-
rameter values was provided by Cococcioni et al. 32 , by the linear
response approach.
Thus, in the present work, we performed the first-principles
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calculations within PBE and PBE+U approximations to study the
ZnO and ZnX bulk systems and ZnO/ZnX interfaces (X = S, Se,
Te). Firstly, the bulk materials were investigated by plain DFT-
PBE, considering the structural and electronic properties. After,
PBE+U calculations were performed to study their sensitivity to
Physical Chemistry Chemical Physics Accepted Manuscript
on-site Coulomb correlations. The on-site Coulomb interaction
correction has usually been restricted to the d shell electrons 35 ,
however, in the current study, it was extend to both the O-2p and
the Zn-3d shell for ZnO bulk and similarly for p and d orbitals of
the ZnX (X = S, Se, Te). The predicted band gap, as well as, the
lattice parameters are strongly depend on the Hubbard-like term,
thus, it is possible to achieve the experimental band gaps and good
lattice parameters carefully selecting the adequate values for the
Hubbard U term. Based on such approach, the structural opti-
mizations for the ZnO/ZnX interfaces were performed, with the
posterior study of the interface properties. Subsequently were
analyzed and discussed the electronic properties of ZnO/ZnX, in
which the results are compared with the literature. Finally, we
have also examined the Bader charge analysis for the ZnO/ZnX
interfaces.
2 Theoretical Approach and Computational
Details
We carried out spin-polarized DFT calculations within the gen-
eralized gradient approximation formulated by Perdew-Burke-
Ernzerhof 23 (PBE) to the exchange-correlation functional. To
improve the description of the on-site Coulomb interactions in
the ZnO and ZnX systems, which is crucial to obtain a correct
description of the electronic structure of the strongly correlated
systems, 32 we employed the rotationally invariant approach pro-
posed by Dudarev et al. 33 The Hubbard U term corresponds to
the mean-field approximation of the on-site Coulomb interaction,
which is added to the exchange-correlation functional. We used
an effective Hubbard parameter, i.e., the difference between the
Coulomb U and exchange J parameters is taken into account,
Ue f f = U − J. Among the Ue f f combinations that could yield the
correct description of the itinerant or localized behavior, we have
also properly described the relative orbital positions with respect
to the Fermi level. Thus, we have considered Ue f f values from
a self-consistent linear response procedure, 32 which describe the
correct band gap value for ZnO (3.3 eV) and attend simultane-
ously the correct position of the d- and p-states in the valence
band (VB). In this work, we find good correspondence using Ud,Zn
= 8.5 eV and U p,O = 7.25 eV for ZnO. The correction Ud,Zn = 8.5
eV, defined for ZnO, was kept for ZnS, ZnSe, and ZnTe. The val-
ues found for the remaining X species were U p,S = 3.5 eV, U p,Te
= 3.9 eV, and U p,Se = 3.5 eV.
The calculations are performed using the plane-wave pseu-
dopotential method as implemented in the Quantum ESPRESSO
package 36 . Electron-ion interactions were described using the
projector-augmented wave (PAW) method 37 . A cutoff energy of
140 Ry and 1140 Ry were used for the plane-waves expansion
and for the electronic density, respectively. For the Brillouin-zone
integration, we have applied the Monkhorst-Pack method 38 , with
a k-mesh of 6×6×6 and 6×1×6 k-points for the bulk and surface
 Page 3 of 10 Physical Chemistry Chemical Physics
(vertical direction was taken along of the y-axis) calculations, re-
spectively. The convergence criteria for the energy and force were
10−4 Ryd and 10−3 Ryd/Bohr, respectively. In addition, we per-
form convergence tests for ZnX bulk systems as detailed in the
Supporting Information Material. We have tested the total en-
ergy values with respect to the cutoff energy (Fig. S1) and k-point
mesh sizes (Fig. S2).
The ZnO(11̄00) surface was modeled using 6 layers with sym-
metric slab and a repeated slab geometry, with a vacuum size of 7
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Å to avoid interactions among the periodic images of the surface
(Fig. 1A). Similarly, the ZnO/ZnX interfaces was modeled using a
slab asymmetric of 6 layers of ZnO and 2 layers of ZnX, as showed
in (Fig. 1B).
Fig. 1 Illustration for the relaxed ZnO surfaces with 6 layers and ZnX (X
= S, Se, Te) 2 layers.
3 Results and Discussion
3.1 Geometry and Structural Optimization
In Table 1 are reported the lattice constant parameters, with both
PBE and PBE+U approximations, for the ZnO hexagonal wurtzite
(w-ZnO) and ZnX (X = S, Se, Te) cubic zincblend bulk systems,
which are compared with experimental 39,40 and theoretical 41,42
values reported in the literature. It is shown that for all stud-
ied compounds the theoretical description, using PBE functional,
overestimates the lattice parameters for wurtzite and underesti-
mates the lattice parameters for zincblend in different percent-
ages in comparison with the experimental data 39,40 . The w-
ZnO lattice parameter is overestimated by 1.54% compared to
the experimental date 39 , which is well-known from literature,
i.e., the PBE calculations overestimate (underestimate) the lat-
tice constants of wurtzite (zincblend) solids 43 . The larger error
has occurred for ZnTe lattice constant, it is equal to 5.07% in
comparison with the experimental value 9 . It is followed by the
ZnS lattice constant error, 4.98% in comparison with the experi-
mental values. Considering PBE+U (inclusion of Ud and U p pa-
rameters), we have obtained a significative decrease in the error
for the structural parameters, i.e., the error change from 0.18 to
0.52% for bulk systems, in good agreement with other theoretical
results 41,42 .
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DOI: 10.1039/C7CP08177D
3.2 Electronic Structure
It is well-known from the literature that DFT-PBE fails in the de-
scription of the electronic structure of semiconductors, for ex-
ample, type II-VI, causing a large underestimation of the band
gap 46,47 . This underestimation is generated by an incorrect po-
Physical Chemistry Chemical Physics Accepted Manuscript
sitioning of the semi-core d states from Zn, yielding an excessive
hybridization with the valence p states from the anion. This arti-
ficial coupling between the p − d orbitals pushes the VB to higher
values, reducing the gap 24,48 . The density of states (DOS) for
the ZnO system, obtained from DFT-PBE calculations, is shown
in Fig. 2A. It is possible to observe that the p − d hybridization
reduces the gap to only 1.3 eV, which is much smaller than the
experimental value of 3.32 eV 39 .
The addition of a correction, considering the Ue f f term, can
solve this problem, although, previous reports 49 have showed
that applying Ue f f only at the d orbitals is not enough to ac-
curately describe the electronic structure of transition metal ox-
ides with strong Coulomb interactions. Recently, some theoretical
studies have been successfully to describe these semiconductors,
including ZnO, applying the Hubbard correction in both orbitals
d of the cation and p of the anion 50,51 . Some remarkable works
which proof the reliability of this approach for ZnO are those of
Ma et al. 24 that correctly describes electronic structure for differ-
ent crystalographic phases, using Ud = 10 eV e U p = 7 eV for
the orbitals d and p, respectively. The work of Calzolari et al. 52
accurately have described the electronic structure, the dielectric
properties, and the Raman spectrum applying Ud = 12.0 eV and
U p = 6.5 eV.
In the present work, following the literature, we have simulta-
neously determined the values for the Hubbard correction to the
orbitals 3d of zinc (Ud ) and 2p of oxygen (U p ) in the case of ZnO,
or 3p of sulphur in the case of ZnS, as well as 5p for both cases
selenium and tellurium. Although, this bilateral correction has
not been found yet for ZnS, a few works 46,52,53 have suggested
that similar to ZnO, the same kind of localization can be applied
to all semiconductors in the group II-VI. Several Ud and U p values
were tested for ZnO, many combinations could yield the correct
band gap value for ZnO, however, only one could attend simul-
taneously the correct position of the d-states in the VB and the
band gap of 3.3 eV. We have found good correspondence for these
values using Ud = 8.5 eV and U p = 7.25 eV for ZnO as shown
in Fig. 2B.
To further understand the effect of Hubbard-term correction
on w-ZnO band gap, we have studied the band structure, as seen
in Fig. 2C and Fig. 2D (the band gap values are given in Table 2).
In the Fig. 2C the band structure is obtained with DFT-PBE ap-
proach, while in Fig. 2D the band structures are calculated using
Hubbard corrections for Zn-3d and O-2p atoms, with PBE+U ap-
proach. As seen in Fig. 2D, the highest energy value was observed
for point L − L and the lowest energy value for the point Γ − Γ.
Additionally, the energies at these points are sensitive to Hub-
bard corrections. It was observed an electron excitation, from the
lowest conduction band (CB) to the highest VB, which is at the
lowest energy band gap. Therefore, in our case, the point Γ − Γ
was observed to be the point where the electron excitation most
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DOI: 10.1039/C7CP08177D

Table 1 Lattice constant parameters for ZnO hexagonal wurtzite (a and c) and cubic zincblend ZnX (X = S, Se, Te) a (in Å), obtained with DFT-PBE and
DFT-PBE+U approximations compared with theoretical (Theo.), and experimental (Exp.) studies.

PBE Error1 (%) PBE+U Error2 (%) Exp. Theo.

ZnO a = 3.29 Å 1.54 a = 3.25 Å 0.30 a = 3.24 Å a = 3.35 Å
c = 5.29 Å 1.92 c = 5.21 Å 0.38 c = 5.19 Å 39 c = 5.36 Å 41

Physical Chemistry Chemical Physics Accepted Manuscript

ZnS a = 5.15 Å -4.98 a = 5.41 Å -0.18 a = 5.42 Å 40 a = 5.54 Å 44
ZnSe a = 5.45 Å -3.88 a = 5.70 Å 0.52 a = 5.67 Å 21 a = 5.75 Å 42
ZnTe a = 5.80 Å -5.07 a = 6.13 Å 0.32 a = 6.11 Å 9 a = 6.19 Å 45
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1 Relative error between PBE results and experimental data.

2 Relative error between PBE+U results and experimental data.

12 C D
12
8 O2p
8 O2p
Zn3s
4
4
Energy (eV)

Energy (eV)

Zn3s
0 Ef
Ef
O2p 0 O2p
-4 Zn3d
Zn3d
-4
-8 Zn3s
Zn3d
-8 O2p
-12
ZnO - PBE ZnO - PBE+U
-12
-16 O2s O2s
-16
W Γ X W L Γ W Γ X W L Γ
Wave Vector Wave Vector

Fig. 2 Total and partial density of states for bulk ZnO: A without Hubbard-term correction and B with Hubbard-term correction. Band structure for bulk
ZnO along with the high-symmetry points of the Brillouin zone: C without Hubbard-term correction, D with Hubbard-term correction.

probably occurs, since it showed the lowest band gap value for all
the Hubbard correction parameters between the CB and the VB.
In order to better understand the electronic properties of semi-
conductors ZnS, ZnSe, and ZnTe in zinc blende phase, we have
studied qualitatively the band structures, the total DOS and the
partial DOS (PDOS) for the cation (Zn) and anion (X = S, Se,
Te). We have discussed below the main results comparing DFT-
PBE and DFT-PBE+U for the electronic structure of the bulk ZnS,
ZnSe, and ZnTe, the respective figures for the band structures and
DOS (Fig. S3, Fig. S4, Fig. S5) are reported in the Supporting in-
formation Material.
The Fig. S3 shows a direct band gap at Γ for bulk ZnS. From
Table 2, Fig. S3A, and Fig. S3C, we observe a band gap underesti-
mation for the PBE functional of 39.70% in comparison with the
experimental value. The underestimated value occurs because
of the inaccurate description of the PBE functional for both the
exchange-correlation energy and its charge derivative. However,
PBE+U improves the band gap in contrast to PBE functional. In
order to explain the overall profile of the DOS, the different peaks
of the DOS have been identified with their corresponding elec-
tronic states in Fig. S3B. In the lower part of the VB, the sharp
peaks around -11.87 eV arises from S-3s states while the peaks in
next higher energy region, just below EF , are predominantly due
to 3s and 3p states of Zn. The peaks found in the next further
higher region (in the CB above EF ) are mainly due to 3s states of
Zn, which hybridize with 3p and 3s states of S. The Zn-3d state is
treated as valence state, so the Zn-3d state, inside the upper VB,
has a minor dispersion, which together with S-3p give rise to the
p − d coupling. The bottom of the CB at Γ point is mainly due to
a mixture of Zn-3s and S-3p states (Fig. S3D).
In Fig. S4AB we have different contributions to the total
and partial DOS for ZnSe, calculated with PBE and PBE+U ap-
proaches, respectively. The total DOS for the zinc blend ZnSe has
the lower part of the VB clearly dominated by chalcogenide states

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Table 2 The band gap Eg (eV) for ZnO hexagonal wurtzite and cubic zincblend ZnX (X = S, Se, Te), within the DFT-PBE and DFT-PBE+U approximations,
compared with theoretical (Theo.) and experimental (Exp.) data.
PBE Error1 (%) PBE+U
ZnO 1.30 eV -60.84 3.30 eV
ZnS 2.30 eV -39.79 3.50 eV
ZnSe 2.00 eV -25.53 2.60 eV
ZnTe 1.70 eV -28.87 2.25 eV
1 Relative error between PBE results and experimental data.
2 Relative error between PBE+U results and experimental data.
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(Se-5s). It emerges from the partial DOS, that the highest peak
in the VB comes from the contributions of Zn-3d states, situated
at ∼-10 eV. It may also be noted that the chalcogenide 5p states
are dominant at the level close to the Fermi energy in the VB. Ad-
ditionally, the contributions of 5s and 5p states of the anion (Se)
and 3s states of the cation (Zn) predominate in the CB. Accord-
ing to our decomposition of the total and partial DOS, it is shown
that the main mechanism of the chemical bond is the hybridiza-
tion between 5p of Se and 3d and 3s states of Zn at the top of the
VB. Thus, the chemical bond for ZnSe, in the zinc blend phase,
has a covalent and ionic character simultaneously, as expected.
Fig. S4CD show the electronic band structures calculated using
the PBE and PBE+U approximations, respectively. The band gap
calculated by PBE is underestimated compared with experimental
and theoretical results, shown in Table 2. This band gap under-
estimation occurs mainly due to the bad description for the self-
quasiparticle energy 61 , which is not flexible enough to accurately
reproduce both the energy exchange-correlation and its derivative
charge. Thus, the direct comparison between DFT-PBE and ex-
perimental results for the electronic structure is limited 34 , conse-
quently, the electronic properties are better estimated by PBE+U,
since that the band gap is corrected to 2.6 eV.
The DOS for the bulk ZnTe are shown in Fig. S5AB within PBE
and PBE+U, respectively. From the partial DOS we observe that
the peaks from the Fermi level to -6 eV are due to Te-5p states and
3s states of Zn. The peaks around -10 eV occur because of the 3d
states of Zn and a small contribution of 5s state of Te, these peaks
constitute the VB. The small peaks from 2.2 eV to 6 eV are con-
tributions from the Zn-3s and Te-5p orbitals and constitute the
CB. The electronic band structures are shown in Fig. S5CD, for
PBE and PBE+U approximations. The direct band gap, giving by
the energy difference between the VB maximum and CB mini-
mum at Γ point, is 1.7 eV, which is smaller than the experimental
value, shown in Table 2. However, PBE+U improves the band gap
in contrast to PBE, and hence, the value of 2.25 eV is reached,
which is closer to experimental value (Table 2) and is in fairly
good agreement with previous theoretical results 55,56 .
To prove that our ZnO and ZnX electronic results are well-
described using DFT-PBE+U approximation, we have performed
additional calculations using the screened hybrid functional of
Heyd, Scuseria, and Ernzerhof (HSE06) 29 functional. The to-
tal and partial DOS are presented in the Supporting Information
Fig. S6. These calculations are based on DFT-HSE06, within the
PAW potentials 37 as implemented in the VASP code 62,63 . Basi-
cally, we have tested several different percentages of the exact
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DOI: 10.1039/C7CP08177D
Error2 (%) Exp. Theo.
-0.60 3.32 eV 39 3.32 eV 54–56
-10.99 3.82 eV 57,58 3.90 eV 56
Physical Chemistry Chemical Physics Accepted Manuscript
-5.31 2.82 eV 59 2.60 eV 60
-5.85 2.39 eV 58,59 2.20 eV 55,56
exchange energy, and hence, in Fig. S6 we show the best results
obtained for the 75% of the PBE exchange combined with 25% of
the nonlocal Hartree-Fock exchange, and the screening parameter
that separates the exchange potential into short- and long-range
parts was set at 0.2 64 . We can observe an excellent agreement for
the band gap values with PBE+U calculations and, consequently,
with experimental data (Table 2), thus, the results obtained by
a description with PBE+U can be compared with the expensive
hybrid (HSE06) calculations.
3.3 Surface (11̄00) of ZnO and ZnO/ZnX interfaces
A prerequisite to build a decorated system consists of the correct
choice of the surface to be exposed to the vacuum region. In this
sense, the preferential growth direction of w-ZnO is parallel to the
c axis, i.e., the direction [0001], as reported experimentally 65 .
Consequently, the most exposed surfaces are generally those that
constitute the lateral faces of the hexagonal crystal. In agreement
with experimental 66,67 and theoretical studies 68–74 , the most fre-
quently exposed surfaces are (11̄00) and (112̄0). First principles
calculations show that the surface (11̄00) is the most stable by a
small surface energy difference of only 0.2 J/m2 in comparison
with (112̄0) 69 . Thus, the most common surface (11̄00) was used
in this work to build ZnO/ZnX heterostructures. This approach
is suitable due to the fact that the (11̄00) surface is also the low-
est energy surface, beyond that, it is the most homogeneous and
promising to uniform charge accumulation along of the interface.
To prevent interactions between periodic images of the surface,
we have considered a vacuum region with 7 Å. A total of 6 ZnO
layers were enough to ensure the convergence of the total energy
in a symmetric slab. The relaxed ZnO surface used in the calcula-
tions is shown in Fig. 1. After the optimization, the variable cell
presented the lattice parameters a = 6.40 Å, b = 39.54 Å, and c
= 5.42 Å, with all force components smaller than 10−4 Ry/Bohr.
We have calculated the total and partial (for O and Zn atoms)
DOS for the ZnO (11̄00) surface, which are shown in Fig. 3A. We
observe a reduction to the band gap (3 eV) of the surface in re-
lation to the bulk band gap (3.3 eV). This reduction is associated
with the process of construction of the surface from the bulk, and
it agrees with previous work, 69 using hybrid B3LYP functional,
which demonstrates the success of PBE+U correction extended to
the surfaces. The decrease in the band gap of 0.3 eV with respect
to the bulk structure occurs due to an elongation of the O-2p and
Zn-3s states from the VB and CB, respectively. A broadening of
the Zn-3d semi-core states can also be seen. Analyzing the contri-
bution to the total DOS by layer in the Fig. 3A (the partial DOS
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 Physical Chemistry Chemical Physics
was increased for easier visualization) it is clear that the band
gap reduction and the broadening of Zn-3d states is mainly due
to the atoms composing the first layer of the structure. This fact
can be attributed to the smaller bond distance between Zn and O
atoms in the first layer, as can be seen in Fig. 1, which occurs to
compensate the smaller coordination number in the surface.
For ZnO/ZnS interface there is a strong tendency to epitaxy,
which means that although the ZnS is in another phase (zinc
blend), it tries to imitate the substrate structure, in this case,
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hexagonal ZnO. The DOS and PDOS curves calculated for the ZnO
(11̄00) surface with ZnS monolayer are shown in Fig. 3B, where
the top shows the total DOS and subsequently are showed the
partial DOS contributions per atom separated in its orbitals for S
and Zn (ZnS layer) and for O and Zn specifically for the first two
ZnO layers. The S-3p states cause a decrease in the electronic gap
of 0.8 eV in comparison to the individual ZnO surface, resulting
in a band gap of 2.2 eV. This decrease in the band gap agrees with
the experimental results of Lahiri et al. 75 which performed ad-
sorption of a monolayer of ZnS on ZnO(0001). This effect also
induces a red-shift in the photoluminescence spectrum of ZnO,
which is often observed when these materials are combined 5,76 .
Analyzing the partial DOS curves Fig. 3B, it is clear that the re-
duction of the total band gap from bulk value (3.3 eV) to only 2.2
eV for ZnO/ZnS interface is due to a synergetic effect between
the O atoms of the top layer (ZnO) and the S atoms in the ad-
sorbed ZnS. From Fig. 3B, the contribution of ZnS layer evinces
that this transition is associated with the first layer of ZnS (the
interfacial layer). Thus, the interface facilitates the introduction
of charge carriers coming from the ZnS into the ZnO layer, as
demonstrate in Fig. 4A. Beyond that, the interface also acts as
a depletion zone with charge gradient to separate spatially elec-
trons and holes, i.e., hindering the recombination (from Fig. 4A).
This mechanism explains the better efficiency achieved by core-
shell ZnO/ZnS structures in Grätzel-type solar cells.
From the total and partial DOS for ZnO/ZnSe (Fig. 3C) we can
suggest a mechanism for the band gap narrowing, as follow. In
the ZnO/ZnSe, the highest occupied Se-4p state in the interface
is always higher in energy than the highest occupied O-2p state,
thus, the band gap is essentially determined by the energetic dif-
ference between the highest occupied Se-4p state and the lowest
unoccupied Zn-4s state. From Fig. 3C, we observe that the highest
occupied Se-4p state shifts to higher energies, whereas the low-
est unoccupied Zn-4s state drifts slightly toward lower energies.
The net result of these opposite trends is a narrowing of the total
band gap value for ∼1.71 eV for the ZnO/ZnSe interface. This de-
crease in the band gap agrees with the experimental results that
performed adsorption of a ZnSe layer on ZnO(11̄00) 14,16 . The
observed shifts in the Se-4p and Zn-4s states can be related to the
Bader 77 atomic charges on all atoms in the ZnO/ZnSe interfaces.
The charges on the Zn and Se atoms for ZnSe layer decreased
in magnitude relative tobulk ZnSe by 0.7067e, on average. Also,
the charges on the Zn and O atoms of the ZnO layers, were less
affected, just only by 0.0487e, on average. In addition, the distri-
bution of the accumulated charges is confined in layer 6 (6th L) of
ZnO side (Fig. 4B), which serves as an electron sink, facilitating
the charge separation and retarding charge recombination.
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DOI: 10.1039/C7CP08177D
Similarly, the electronic structure for ZnO/ZnTe interface can
be elucidated by considering the partial DOS reported in Fig. 3D.
The Zn-3d and O-2p orbitals associated to the Te-5p orbitals con-
tribute mostly to the top of VB, while the Zn-4s and O-2s orbitals
dominate the bottom of CB. The significant overlap of the Te px ,
Physical Chemistry Chemical Physics Accepted Manuscript
py , and pz orbitals observed in the partial DOS close to the top of
VB is coming from the sp3 hybridization. Thus, the redistribution
of the accumulated charges occurs mainly between the 6th layer
of ZnO and 1st layer of ZnTe in the interface as can be observed
in Fig. 4C. However, this charge accumulation does not favor the
reduction of the electron-hole recombination rate as observed in
the case of ZnO/ZnS and ZnO/ZnSe. The sp3 hybridization al-
lows a high spatial charge delocalization, which can be a reason
for the charge transfer reduction between ZnTe and ZnO. It is
very important to pay attention on the interface in Fig. 4C, where
is possible to identify a depletion zone, which in both sides shows
an accumulation of negative charges (e). This result can be de-
scribed better by the diagram of Schottky barrier as a function of
depletion zone charge density, which is schematically presented
in Fig. S7. In this case, both interface sides have approximately
the same height, avoiding the charge flux through the interface.
Thus, this interface avoids the charge recombination and also
avoids the charge transfer. Finally, the 2nd layer of ZnTe presents
a decrease of -0.4 ∆e, if compared to the corresponding atomic
charges in isolated bulk ZnTe.
Fig. 5 Band alignment modification upon the formation of a ZnO/ZnX
heterostructure and the corresponding charge transfer process.
Based on the charge diagram, Fig. 4, is appropriate to propose
that the accumulated charges at the VB top is now able to be
photoexcited by solar radiation in visible region. However for
ZnO/ZnTe the depletion zone avoids its application in solar cells.
The VB top (VBM) and CB bottom (CBM) for ZnO/ZnX (X= S,
Se, Te) interfaces are shown in Fig. 5, in which the band align-
ments are highlighted and its absorption edge is attributed to the
band alignment type-II. The carriers are spatially separated under
indirect transition from the VBM of ZnX (X = S or Se) to the CBM
of ZnO at interface. Gu et al. 78 observed a type-II alignment for
the ZnO/ZnS interfaces, which suggest that ZnS is suitable for us-
ing as the barrier layer of ZnO for charge separation and transfer
efficiently. Besides, Guo et al. 79 showed a type-II band alignment
for ZnS/ZnO heterojunction to reduce the energy barrier height
at the interface and enhance the separation of photo-generated
 Page 7 of 10 Physical Chemistry Chemical Physics
View Article Online
DOI: 10.1039/C7CP08177D

A) ZnO B) ZnO/ZnS C) ZnO/ZnSe D) ZnO/ZnTe

60.0

Physical Chemistry Chemical Physics Accepted Manuscript

40.0 Total
20.0
3 eV 2.2 eV 1.71 eV 0.95 eV
0.0
12.0

8.0
Zn 3d
4.0
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0.0
PDOS (eV−1)

6.0

4.0
Zn 4s
2.0

0.0
60.0

40.0
O 2p
20.0

0.0
1.5
1.0 O 2s
0.5
0.0
9.0
6.0 S 3p Se 4p Te 5p
3.0
0.0
−4 −2 0 2 4 6 −4 −2 0 2 4 6 −4 −2 0 2 4 6 −4 −2 0 2 4 6
E−Ef (eV) E−Ef (eV) E−Ef (eV) E−Ef (eV)

Fig. 3 Total and partial density of states (DOS) of A) ZnO (11̄00) surface, B) ZnO/ZnS interface, C) ZnO/ZnSe interface, and D) ZnO/ZnTe interface.
The Fermi level is always at 0 eV.

Fig. 4 The ZnO/ZnX interfaces and the increase (accumulation) and decrease of charges at the interfaces. The values have been subtracted from the
background of bulk values. The solid line are guides for the eyes.

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 Physical Chemistry Chemical Physics
carriers.
Our results for ZnO/ZnTe interface are in a good agreement
with experimental results reported by Luo et al. 18 . Thus, in both
cases the photon absorption across the interface is favored due
to the type-II band alignment. Then, both systems ZnO/ZnX (X
= S, Se) are interesting candidates to photo-electrodes applied in
solar cells of third generation. On the other hand, Liu et al. 80
have showed that the UV emission of ZnO/ZnSe heterostructures
was greatly suppressed by the ZnSe shells, which indicated an
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efficient suppression of electron-hole recombination rate due to
the forming of a staggered type-II band alignment.
4 Conclusions
In this work we have performed PBE and PBE+U calculations to
investigate the electronic structure of four bulk ZnX (X = O, S,
Se, Te) and three ZnO/ZnX (X = S, Se, Te) interfaces. Firstly,
it was found good correspondence for Hubbard parameter value
using Ud,Zn = 8.5 eV and U p,O = 7.25 eV for ZnO bulk, the value
of Ud,Zn = 8.5 eV was kept for ZnX, beyond the values U p,S =
3.5 eV, U p,Te = 3.9 eV and U p,Se = 3.5 eV for the bulk systems,
respectively. Then, the Hubbard-term corrections were success-
fully extended to the interfaces of ZnO/ZnX, resulting in a good
approximations to experimental values of band gap. From the in-
terface ZnO/ZnX study, the structural changes that arise with the
interface could be determined when ZnX zinc blend is adsorbed
on ZnO (11̄00) surface. The total and partial DOS for the interfa-
cial structure showed that the interface created by ZnS and ZnSe
reports the better configuration to the charge separation effect
among this interfacial systems. Additionally, the charge transfer,
by Bader analysis, indicates that ZnO/ZnSe should lead to a bet-
ter performance for modified Grätzel-type solar cells, due to the
recombination rate being minimized. This process also induces a
red shift by the electronic structure in the interface, reducing the
luminescent activity once the recombination is also diminished.
On the other hand, for ZnO/ZnTe was observed a conductive be-
havior, due to overlap of Te-5p states closer to the top of VB,
evidencing the sp3 hybridization. Then, our findings indicate that
it is possible to control the ZnO electronic properties such as the
band gap by forming ZnO/ZnX interfaces.
Conflict of interest
There are no conflicts of interest to declare about our manuscript.
Acknowledgement
Authors thank the Rio Grande do Sul Research Foundation
(FAPERGS, Grant Number 16/2551-0000525-7), National Coun-
cil for Scientific and Technological Development (CNPq, Grant
Number 305161/2015-6), and the Coordination for Improvement
of Higher Level Education (CAPES) for financial support. Au-
thors also thank the Physics Department from Federal University
of Pelotas for the cluster facilities and hosting.
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