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Improving photocatalytic properties of SrTiO3

through (Sb, N) codoping: a hybrid density
Cite this: RSC Adv., 2014, 4, 45703
functional study
Brindaban Modak, K. Srinivasu and Swapan K. Ghosh*

A systematic study using hybrid density functional theory has been carried out to investigate the synergistic
effect of Sb and N doping on the photocatalytic properties of SrTiO3 under visible light. The calculated band
gap (3.19 eV) for SrTiO3 with the Heyd, Scuseria, and Ernzerhof hybrid functional is found to be very close to
the experimentally observed value of 3.2 eV. Although doping with N is able to enhance the visible light
activity by reducing the effective band gap to 2.31 eV, the localized occupied and unoccupied states in
the forbidden region may affect the photocatalytic activity. However, the presence of Sb not only
passivates those unoccupied states completely, but also shifts the localized occupied states near the
valence band to form a continuum band structure. The introduction of N into the SrTiO3 crystal
structure is favored by the presence of Sb. In the codoped system charge compensation is established,
thereby unwanted vacancy formation will be minimized. The absorption curve for the (Sb, N)-codoped
SrTiO3 is found to shift towards the visible region due to reduction in band gap to 2.66 eV. Moreover, the
Received 18th July 2014
Accepted 10th September 2014
band alignment shows that the (Sb, N)-codoping makes SrTiO3 thermodynamically more suitable for
hydrogen production as compared to the undoped system. Based on the present study, we can propose
DOI: 10.1039/c4ra07289h
(Sb, N)-codoping as one of the effective approaches to improve the photocatalytic activity of SrTiO3 for
www.rsc.org/advances water splitting under visible light irradiation.

stable in hexavalent state (Cr6+).8 Hence keeping chromium in

1. Introduction trivalent state is a challenge as it has tendency to be converted in
Photo splitting of water under sunlight is one of the most the hexavalent state. Secondly, localized mid gap states intro-
promising ways to generate hydrogen which has been widely duced due to Cr doping not only hinder the mobility of the charge
accepted as an alternative energy carrier.1 The biggest challenge carriers, but also bring signicant changes in the band edge
is to nd a suitable catalyst for this purpose. To date numerous positions, thus affect overall water splitting property.11 Owing to
efforts have been made towards developing semiconductor attractive visible light activity Rh-doped SrTiO3 has been found to
based photocatalysts.2–4 Among the perovskites, SrTiO3 has been be studied by several groups.12–16 However, photoactivity of Rh-
extensively studied for its potential applications in this eld. doped SrTiO3 is limited by the presence of Rh4+ species, which
Since the band gap of SrTiO3 is 3.2 eV, its photoactivity is limited plays signicant role in the electron–hole recombination.16
to the UV region of the solar spectrum.5 There have been made Doping with non-metal elements are also extensively studied for
several experimental as well as theoretical attempts by doping the band gap engineering of the oxide based semiconductor
with foreign element/elements to improve the visible light photocatalysts. Among them N-doping has attracted immense
activity of SrTiO3. These include cationic doping either at the Sr interest for extending the absorption curve to the desirable
lattice site6 or at the Ti lattice site7–16 as well as anionic doping at range. Wang et al. observed that the photocatalytic activity under
the oxygen lattice site.17–23 Among the transition metal doped visible light is signicantly improved due to N doping and the
systems, Cr-doped SrTiO3 has been extensively studied due to its visible light absorption increases with increasing amount of N
potential application to split water and organic compounds into the SrTiO3 crystal structure.21 However, this is due to the
under visible light.7–11 However, there exists some major issues presence of localized N 2p states which appear above the valence
that limit the photocatalytic efficiency of Cr-doped SrTiO3. band (VB) reducing the effective band gap.22 Another major
Improved photocatalytic activity has been observed only when challenge in case of monodoping is to avoid charge compen-
chromium is in trivalent state (Cr3+), although chromium is more sating defects, which are well known to diminish photocatalytic
efficiency. There have been shown many efforts using codoping
approach to overcome the undesirable consequences associated
Theoretical Chemistry Section, Bhabha Atomic Research Centre, Homi Bhabha
National Institute, Mumbai – 400 085, India. E-mail: [email protected]; Tel:
with those localized states and the additional charge introduced
+91-22-25595092 due to N-doping. Miyauchi et al.24 and Wang et al.25 successfully

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synthesized (La, N)-codoped SrTiO3, which shows improved pho- 12.5% and N concentration of 4.17%. The exchange and corre-
tocatalytic activity under visible light. However, this photoactivity lation energy density functionals were dened by generalized
has been found to be limited to the decomposition of organic gradient approximation (GGA) with Perdew–Burke–Ernzerhof
compounds. Although, it has been shown in the theoretical study (PBE) scheme41 during geometry optimization. K-point mesh of 8
of Wei et al. that codoping of either nonmetal (H, F, Cl, Br, I) or  8  8 was found to be sufficient to attain convergence. The
metal (V, Nb, Ta, Sc, Y, La) is able to passivates the N-induced total energy convergence tolerance was set to 106 eV per atom
Published on 10 September 2014. Downloaded by Christian Albrechts Universitat zu Kiel on 23/10/2014 22:40:24.

discrete states, their applicability for the photo-splitting of water for the self consistent iteration. Electronic structure calculations
is still to be explored.26 Recently, Yu et al. synthesized (Cr, N)- have been carried out by employing the HSE hybrid functional,
codoped SrTiO3, which has been shown to generate only H2 where the short-range interactions are calculated with exact
during water splitting under visible light.27 In the present study, we exchange mixing in both HF and DFT. The exchange-correlation
employ Sb as codopant to improve the photoactivity of N- energy is expressed as
doped SrTiO3 under visible light. The advantages for choosing Sb
as codopant are: (a) being very similarity in ionic radius (Sb5+: Ref ¼ EHSE
XC ¼ aEX (m) + (1  a)EX
SR PBE,SR
(m) + EPBE,LR
X (m) + EPBE
C (1)
0.60 Å; Ti4+: Ref ¼ 0.605 Å),28 Sb can be easily tted at the Ti lattice
site without causing major lattice distortion in the host crystal where, ‘a’ stands for the mixing coefficient. The screening
structure; (b) introduction of Sb into the N-doped system is parameter m denes the short ranged (SR) and long ranged (LR)
expected to maintain charge balance in the codoped SrTiO3 (Ti4+ + part of the interaction. In the present study, we use the mixing
O2 ¼ Sb5+ + N3); (c) use of a non transition metal (Sb) may be exchange parameter of 28% and standard screening parameter
more preferable over transition metal to avoid localized ‘d’- of 0.2 Å1 to reproduce the experimental band gap of SrTiO3.11
states in the forbidden region. It has been successfully shown in K-point mesh of 3  3  3 was set for the hybrid functional
the earlier reports that introduction of Sb as a codopant calculations. The valence states considered during the calcula-
signicantly increases the photocatalytic property of the mon- tions are: Sr (4s24p65s2), Ti (4s23d2), Sb (5s25p3), O (2s22p4), and
odoped entity.16,29–36 As for example, codoping of Sb into the Rh- N (2s22p3). The energy cutoff of 600 eV has been chosen for the
doped SrTiO3 effectively reduces the electron–hole recombi- plane wave basis sets. To investigate the absorption behavior
nation rate by xing Rh oxidation state to +3 forming a charge frequency-dependent dielectric function calculation has been
compensated system.16 Similarly, codoping of Sb into the Cr- carried out for the codoped and undoped SrTiO3.
doped SrTiO3 has been found to enhance the photoactivity for
H2 evolution by suppressing the formation of hexavalent 3. Results and discussion
chromium (Cr6+) as well as vacancy, which are known to
diminish the photoactivity of SrTiO3.29 However, detailed Salient features of the electronic structure of undoped SrTiO3,
theoretical studies exploring the effect of Sb on the electronic monodoped SrTiO3 using N and Sb as dopants, and (Sb, N)-
structure of SrTiO3 are rare. Here, we present a systematic study codoped SrTiO3 are discussed below.
to investigate the synergistic effect of both N (as a substituent of
O) and Sb (as a substituent of Ti) as codopants, and compare the 3.1. SrTiO3
results with that of the N-doped, Sb-doped and undoped
Cubic SrTiO3 is described by a framework of TiO6 perfect
SrTiO3, using density functional theory as a tool. Since the use
octahedron, where the center position is occupied by Ti.
of Heyd, Scuseria, and Ernzerhof (HSE)37 functional is known to
Fig. 1a shows the band structure plot for the undoped SrTiO3
successfully reproduce the experimental band gap for undoped
along high symmetric k-path of the Brillouin zone (the hori-
SrTiO3, we employ the same functional in our calculations.
zontal dashed line represents the Fermi level). The calculated
Conclusions have been drawn by analyzing the band structure,
band gap (3.19 eV) shows excellent agreement with the
partial density of states (PDOS), optical spectrum, and band
experimental value (3.2 eV).5 Analysis of the projected density
alignment with respect to the water redox levels.
of states (Fig. 2) indicates that the valence band maximum
(VBM) is dominated by O 2p states while conduction band
2. Computational methods minimum (CBM) is composed of Ti 3d states. We will now
discuss the effect of doping and codoping on the electronic
Spin-polarized DFT calculations have been carried out using
structure of SrTiO3.
Vienna ab initio simulation package (VASP)38 electronic structure
code. The electron-ion interaction has been treated by projector
augmented wave (PAW) potential,39 which is widely used for the 3.2. N-doped SrTiO3
studies of electronic structure of semiconductor materials. For Since, doping of nitrogen in the oxide based material mainly
the Brillouin zone integration we employ Monkhorst and Pack involves replacement of oxygen by nitrogen, we consider only
scheme to generate gamma-centered k-point sets.40 The mono- substitutional doping. From the optimized cell structure,
doped system is modeled by replacing either one of the Ti or O obtained in our calculation, it is found that N doping does not
atoms by Sb or N, respectively from a 2  2  2 supercell (40 make any signicant change in the SrTiO3 crystal structure. The
atoms) of the cubic (space group: Pm3m) SrTiO3 crystal structure. Ti–N bond length (1.976 Å) in N-doped SrTiO3 is slightly higher
In the case of codoping, we simultaneously introduce both Sb than the Ti–O bond length (1.974 Å) in undoped crystal. This
and N into SrTiO3. This corresponds to Sb concentration of leads to increase in lattice parameter by only a small extent.

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contribution from Ti 3d state. Consequently, the band gap

(energy difference between the occupied impurity states and
the conduction band) is reduced to 2.31 eV, which is respon-
sible for the visible light absorption of N-doped SrTiO3.
However, these localized states are highly undesirable for the
photocatalytic purpose as they may hinder the mobility of the
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charge carriers. Therefore one needs to introduce a codopant

to passivate these discrete states for better photocatalytic
property. Since the CBM of SrTiO3 (prominent Ti 3d character),
is located just 0.8 eV above the water reduction level (H+/H2),
we carefully choose Sb as the codopant, which is expected not
to perturb the conduction band (CB) level largely. Before dis-
cussing the results of the codoped system, it will be instructive
to rst discuss the monodoped system with Sb as the dopant.

3.3. Sb-doped SrTiO3

Previous experimental reports show that, Sb occupies exclusively
Ti lattice site in the Sb-doped SrTiO3 as the ionic size of Sb5+ (Ref
¼ 0.60 Å) is closer to the ionic size of Ti4+ (Ref ¼ 0.605 Å) than that
of Sr (Ref ¼ 1.44 Å).16,29,35,36,42 The optimized structure shows that
the introduction of Sb into the Ti lattice site does not lead to
much change in the lattice structure. As the stable oxidation state
for Sb is the pentavalent state (Sb5+), it leaves one extra electron to
the system. This is manifested in the band structure plot (Fig. 1c),
with the Fermi level located in the conduction band. Analysis of
PDOS plot (Fig. 3b) clearly indicates that the defects states are
contributed by Ti 3d state. This is due to localization of the extra
unpaired electron in the Ti 3d orbital. One more thing we should
point out is that the respective band edges are still dominated by
Fig. 1 Electronic band structure along the high symmetry k-path of the O 2p and Ti 3d states, as observed in the case of undoped
the Brillouin zone for (a) undoped SrTiO3 (b) N-doped SrTiO3 (c) Sb-
SrTiO3. The contribution of the Sb 5s and 5p states to the band
doped SrTiO3 (d) (Sb, N)-codoped SrTiO3. The horizontal dashed lines
represent the Fermi level. edges is found to be less signicant. This may be due to more
ionic character of the Sb–O bond as indicated in the study of
Wang et al.42 This is again supported by the analysis of Bader
charge density.43 In the case of undoped SrTiO3, the calculated

Fig. 2 DOS and PDOS plots for undoped SrTiO3. The vertical dashed
lines indicate the Fermi level.

Introduction of N (2s22p3) in place of O (2s22p4) is found to

bring signicant changes in the electronic structure of SrTiO3.
The N-doped SrTiO3 is decient by one electron. Comparison
of band structure plot of the N-doped SrTiO3 (Fig. 1b) with that
of the undoped SrTiO3 (Fig. 1a) shows that, some occupied and
unoccupied states are introduced above the VB. Analysis of
PDOS plot (Fig. 3a) indicates that these states are formed due Fig. 3 DOS and PDOS plots for (a) N-doped SrTiO3 (b) Sb-doped
to mixing of N 2p state with O 2p state along with small SrTiO3. The vertical dashed lines indicate the Fermi level.

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Bader charges on Ti and O centers are 2.04|e| and 1.23|e|, formation energy in each case.45,46 The defect formation energy
respectively, while, for Sb-doped SrTiO3, the values on the Sb and relates chemical potential of the elements as
O centers are 2.80|e| and 1.29|e|, respectively.
DHf ¼ Edoped + nOmO + nTimTi  ESrTiO3  nNmN  nSbmSb (3)

3.4. (Sb, N)-codoped SrTiO3 where, Edoped represents total energy for the doped/codoped
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SrTiO3 supercell. m stands for chemical potential of the

Before going to the discussion on the electronic structure of (Sb,
element. n is the number of elements inserted or removed for
N)-codoped SrTiO3, we calculate the defect pair binding energy
the construction of doped/codoped structure. At the equilib-
(Eb) using the relation44
rium condition between the reservoir of Sr, Ti and O and SrTiO3
Eb ¼ ESb-SrTiO3 + EN-SrTiO3  E(Sb,N-SrTiO3)  ESrTiO3 (2) eqn (4) must be satised

where, EN-SrTiO3, ESb-SrTiO3, E(Sb,N)-SrTiO3 and ESrTiO3 represent the mSr + mTi + 3mO ¼ mSrTiO3(bulk) (4)
energy of the N-doped, Sb-doped, (Sb, N)-codoped, and undo-
The chemical potential of the element cannot exceed that of
ped SrTiO3 supercell, respectively. The positive value of the
the respect bulk (Sr/Ti) or gaseous (O) state, i.e. mSr # mSr(bulk),
defect pair binding energy (1.58 eV per supercell) indicates that
mTi # mTi(bulk) and mO # mO(gas).
the codoped system is sufficiently stable.
The expression for the heat of formation SrTiO3 is given by
Let us discuss the synergistic effect of both N and Sb on the
electronic structure of SrTiO3. The band structure plot (Fig. 1d)
D ¼ mSrTiO3(bulk)  mSr(bulk)  mTi(bulk)  3mO(gas) (5)
for the codoped SrTiO3 shows that the Fermi level resides above
the VBM, similar to that of an intrinsic semiconductor. It is Since the heat of formation for SrTiO3 is a negative quantity
interesting to observe that the band gap reduces signicantly to we can write
2.66 eV, which ensures the absorption of visible light. This is the
consequence of elevation of VB edge associated with the mSr(bulk) + D # mSr # mSr(bulk) (6a)
formation of (N 2p, O 2p) hybridized state (Fig. 4). The discrete
acceptor states as appearing in the case of N-doped SrTiO3 are mTi(bulk) + D # mTi # mTi(bulk) (6b)
completely passivated, resulting into a continuum band struc-
ture. This is due to the presence of Sb which compensates for 3mO(gas) + D # 3mO # 3mO(gas) (6c)
the electron deciency introduced through N-doping. It has
The chemical potential, mSr(bulk), mTi(bulk), and mSb have been
been quantied by Bader charge analysis, which indicates a
calculated from the energy of an atom in the respective bulk
higher electronic charge on the N centre in the (Sb, N)-codoped
structure. On the other hand, mO(gas) and mN have been calcu-
SrTiO3 (1.36|e|) as compared to that in N-doped SrTiO3
lated from the energy of an oxygen atom (1/2EO2) and nitrogen
(1.15|e|). On the other hand, the Ti 3d defect states arising in
atom (1/2EN2) in the corresponding gaseous molecule conned
the case of Sb-doped SrTiO3 is no longer present in the (Sb, N)-
at the centre of a 20  20  20 Å3 cubic box.
codoped SrTiO3. Presence of both Sb and N leads to formation
The calculation of the formation energy (Fig. 5a and b) indi-
of charge compensated system, which will minimize formation
cates that in both the cases substitutional doping is energetically
of undesired defects and thus reduce charge carrier loss.
more favored in comparison to the interstitial doping. Fig. 5a
shows the variation of formation energy for N-doped SrTiO3 as a
3.5. Defect formation energy function of oxygen chemical potential (mO  mO(gas)). Under O-
rich condition the formation energy has a large positive value,
In order to nd favorable growth condition for doping of the
which shows a decreasing trend as we proceed towards O-poor
individual element as well as both, we calculate defect
condition. As shown in Fig. 5b, that the formation energy for
Sb-doping is highly positive under Ti-rich condition. This indi-
cates that the doping with individual element is highly unfa-
vorable under host rich condition, may be due to requirement of
large energy for vacancy formation in the substitution process.
However, this is found to be feasible in presence of both the
dopant elements as shown in Fig. 5c. The calculation indicates
that the O-rich condition is more suitable than the Ti-rich
condition for the growth of the (Sb, N)-codoped SrTiO3.

3.6. Optical property

To investigate the absorption property we calculate the
frequency dependent dielectric function, 3(u) ¼ 31(u) + i32(u).
Fig. 4 DOS and PDOS plots for (Sb, N)-codoped SrTiO3. The vertical The real part (31) and imaginary part (32) of the dielectric tensor
dashed lines indicate the Fermi level. are obtained from Kramers–Kronig transformation, and using

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Fig. 5 The variation of defect formation energy with the chemical potential of O (mO  mO-gas) and Ti (mTi  mTi-bulk) for (a) N-doped SrTiO3 (b) Sb-
doped SrTiO3 (c) (Sb, N)-codoped SrTiO3. The color lines (5c) corresponds to different formation energies for the (Sb, N)-codoped SrTiO3. The
codoped system cannot be formed in the lower half of the diagonal axis (large white region) in the case of 5c because the chemical potential of Sr
(mSr) is exceeded (eqn (6a)).

summation over the empty states, respectively, as implemented

in VASP. The absorption coefficient a(u) has been evaluated
using the formula47
 1=2
pffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
aðuÞ ¼ 2u 31 ðuÞ2 þ 32 ðuÞ2  31 ðuÞ (7)

Fig. 6 shows that the absorption curve for the undoped

SrTiO3 is limited to the UV region, while it is shied towards the
visible region in presence of both Sb and N dopants. This
observation supports the band gap reduction of SrTiO3 due to
codoping with Sb and N as discussed in the earlier section. Fig. 6The calculated optical absorption curves for the undoped and
codoped SrTiO3.

3.7. Photocatalytic activity

H2) and VB should be located below the water oxidation level
As we know, reduction in the band gap is necessary to improve
(H2O/O2). To check this criterion for our proposed system we
the visible light activity, but not sufficient to achieve high
align the positions of the band edges with respect to that of the
photocatalytic activity for water splitting. The band edges must
undoped SrTiO3. For undoped SrTiO3 the CBM is located 0.8
be in proper position with respect to the water redox levels for
eV above the water reduction (H+/H2) level and the VBM is 1.17
spontaneous release of hydrogen as well as oxygen from water
eV below the water oxidation level (H2O/O2).48 The VBM and
splitting. The conduction band potential should be more
CBM for the (Sb, N)-codoped SrTiO3 is now placed by consid-
positive than the H+/H2 potential and the valence band
ering the relative shis of the corresponding electronic energy
potential should be more negative than the H2O/O2 potential,
levels with respect to that of the undoped SrTiO3. As can be
i.e. CB should be located above the water redox potential (H+/

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seen from Fig. 7, that the VBM of (Sb, N)-codoped SrTiO3 is 2  2  2 (Fig. 5c) and 2  2  3 supercell (Fig. 8) has been
located 0.20 eV below the water oxidation level and the CBM found to be almost similar. This justies the choice of supercell
position is 1.23 eV above the water reduction level. Hence, size used in the calculation.
overall water splitting is thermodynamically feasible in the
(Sb, N)-codoped SrTiO3. Interestingly, the CBM of the (Sb, N)-
SrTiO3 is located even 0.43 eV above the CBM of the undoped 4. Conclusion
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SrTiO3. This implies that the modied system should be more The hybrid DFT calculations reported here reveal the signi-
feasible for H2 evolution due to enhancement of reducing cance of codoping of Sb and N into SrTiO3 for improving the
power with respect to the undoped SrTiO3. photocatalytic activity under visible light. The positive defect
pair binding energy indicates that the (Sb, N)-codoped SrTiO3 is
3.8. Effect of supercell size sufficiently stable. The band gap is reduced signicantly
without introducing any isolated midgap states. As the codoped
To investigate the effect of supercell size, we have also consid- system is charge compensated, it is expected to reduce unde-
ered larger supercell (2  2  3). The formation energy has been sirable vacancy formation, and consequently defect assisted
calculated following the same procedure as discussed in the carrier loss can be avoided. Presence of Sb also facilitates the
case of 2  2  2 supercell. Fig. 8 shows the formation energy introduction of N into the SrTiO3 crystal structure by reducing
variation as a function of chemical potential of Ti and O. The formation energy. The band alignment for the codoped SrTiO3
calculated formation energy for (Sb, N)-codoped SrTiO3 using is such that both the photo-oxidation and photo-reduction
processes associated with water splitting are thermodynami-
cally feasible. Moreover, the reducing power of the modied
SrTiO3 is higher than that of the undoped material, making it
more suitable for H2 generation. Hence we can propose that the
codoping of Sb and N into the SrTiO3 crystal is one of the
promising approaches to enhance the efficiency for photo-
splitting of water using visible light.

Acknowledgements
We thank the BARC computer centre for providing the high
performance parallel computing facility. The authors like to
acknowledge Dr A. K. Samanta, Dr C. Majumder and Dr D.
Karmakar for valuable discussions. We also thank Dr B. N.
Jagatap for his encouragement and support. The work of Prof.
Swapan K. Ghosh is supported through Sir J. C. Bose Fellowship
Fig. 7 The band alignment of the undoped, and codoped SrTiO3 with from the Department of Science and Technology, India.
respect to the water redox levels.

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