Applied Surface Science 324 (2015) 705–709

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Band offsets of novel CoTiO3 /Ag3 VO4 heterojunction measured

by X-ray photoelectron spectroscopy
Kanlayawat Wangkawong a , Doldet Tantraviwat b , Sukon Phanichphant c ,
Burapat Inceesungvorn a,∗
a
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
b
Thai Microelectronics Center (TMEC), National Electronics and Computer Technology Center (NECTEC), Chachoengsao 24000, Thailand
c
Materials Science Research Centre, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: The energy band diagram and band offsets of the novel CoTiO3 /Ag3 VO4 heterojunction photocatalyst
Received 2 September 2014 are investigated by X-ray photoelectron spectroscopy for the first time. Excluding the strain effect, the
Received in revised form 2 November 2014 valence-band and conduction-band offsets are determined to be 0.2 ± 0.3 eV and −0.6 ± 0.3 eV, respec-
Accepted 4 November 2014
tively. The CoTiO3 /Ag3 VO4 composite forms a type-II heterojunction, for which the photogenerated
Available online 11 November 2014
charge carriers could be effectively separated. The results suggest that determination of the energy band
structure is crucial for understanding the photogenerated charge transfer mechanism at the interfaces,
Keywords:
hence the corresponding photocatalytic activity and would also be beneficial to the design of new and
Band offset
Heterojunction
efficient heterostructure-based photocatalysts.
XPS © 2014 Elsevier B.V. All rights reserved.
Ag3 VO4
CoTiO3
Photocatalyst

1. Introduction electron–hole separation of the heterostructure as supported by

Ag3 VO4 has gained substantial interests from the viewpoints
of photocatalytic degradation of contaminants and water splitting
[1,2]. However, the photoactivity of Ag3 VO4 is still low due to its
high electron–hole recombination rate [3]. As one of the effective
methods to suppress the photogenerated charge recombination
process, heterojunction formation is of increasing interest. The
heterostructure photocatalysts with suitable matching conduction
band (CB) and valence band (VB) potentials can offer the driving
force to transfer and separate the electron–hole pairs via close
interface, therefore an enhanced photocatalytic activity could
be attained due to the abundance of photogenerated charge
carriers participating in the photocatalytic process. Several studies
have shown that the photoactivity of Ag3 VO4 is remarkably
improved upon heterojunction formation such as g-C3 N4 /Ag3 VO4
[4], ZnFe2 O4 /Ag3 VO4 [5] and NiTiO3 /Ag3 VO4 [6]. Our previous
investigation on CoTiO3 /Ag3 VO4 composite [7] also indicated that
this heterostructure exhibited notably enhanced photocatalytic
activity compared with its corresponding individual materials.
Such increased activity was partially ascribed to an efficient
∗ Corresponding author. Tel.: +66 81 9930337; fax: +66 53 892277.
E-mail address: binceesungvorn@gmail.com (B. Inceesungvorn).
a significant decrease in photoluminescence (PL) intensity of the
hybrid catalyst. However, to understand the improved charge sepa-
ration efficiency at the interface, determination of the energy band
lineup and the band offsets of this novel composite is of importance.
X-ray photoelectron spectroscopy (XPS) has widely been
employed to determine the band discontinuities and the band
lineup of many heterojunctions [8–13]. The obtained energy band
structures are found to correspond well with their PL studies which
help suggest the possible electron–hole transfer mechanism at
interfaces [10,11]. Two methods based on the XPS study, namely
direct and semidirect techniques, can be used for this purpose
[12]. Although the direct technique is simple, this method can-
not be applied to all interfaces because it requires a continuous
measurement of VB XPS spectra as increasing layer thickness of
the interfaces [12,13]. Therefore, the semidirect method based on
the measurements of the core level (CL) and valence band maxi-
mum (VBM) of the two constituent materials, has generally been
employed [8–13].
In this present work, the energy band structure and the band
offsets of the novel CoTiO3 /Ag3 VO4 heterojunction are firstly inves-
tigated by XPS. The results indicate that the hybrid catalyst is
a type-II heterojunction which could benefit from an effective
photogenerated charge separation. The obtained band lineup also
corresponds well with the PL results in our previous study [7]. This

http://dx.doi.org/10.1016/j.apsusc.2014.11.020
0169-4332/© 2014 Elsevier B.V. All rights reserved.
706 K. Wangkawong et al. / Applied Surface Science 324 (2015) 705–709

suggests that determination of the band alignment of the hetero-
junction is necessary for better understanding the electron-hole
transfer process and hence its corresponding photocatalytic activ-
ity.
2. Experimental details
To determine the energy band diagram of the novel
CoTiO3 /Ag3 VO4 system, pure Ag3 VO4 , pure CoTiO3 and
CoTiO3 /Ag3 VO4 heterojunction were used in this study. Syn-
thesis methods of the three samples can be found elsewhere [7].
XPS measurements were performed on Kratos Axis ULTRADLD using
a 1486.6 eV Al K␣ source, which has been carefully calibrated for
CL energy positions using polycrystalline gold, silver and copper
foils (>99.8% purity). For the XPS analysis, the powder sample
was pressed into a disc of 1.0 cm in diameter and 0.2 cm thick.
To reduce the contamination effect, the disc was subjected to Ar+
bombardment for 2 s at 500 eV. After the cleaning process, no
new peaks were introduced and peaks related to impurities were
greatly reduced. Since only the relative energy position in each
sample is used in the calculation, the absolute energy calibration
for the samples is not necessary [8]. Charge neutralization was
performed by using an electron flood gun and all XPS spectra were
calibrated by the C 1s at 285 eV to compensate the charge effect.
Field emission scanning electron microscopy (FESEM) and energy
dispersive X-ray (EDX) spectroscopy were also performed using

Fig. 1. FESEM images of (a) CoTiO3 , (b) Ag3 VO4 , (c) CoTiO3 /Ag3 VO4 heterostructure and (d) the corresponding EDX spectrum of (c).

Fig. 2. TEM investigation on CoTiO3 , Ag3 VO4 and CoTiO3 /Ag3 VO4 composite.
 K. Wangkawong et al. / Applied Surface Science 324 (2015) 705–709 707

Hitachi S4700. Transmission electron microscopy was carried out However, one should be aware that the Ag3 VO4 is very sensitive to
on FEI, TECNAI G2 F20. electron beam and can be quickly damaged as stated in our previous
report [7], therefore the TEM analysis has to be quickly performed.
3. Results and discussion In our study, several attempts were made to obtain high resolu-
tion image of the Ag3 VO4 . Unfortunately, sample decomposition
As shown in Fig. 1a and b, the CoTiO3 and Ag3 VO4 are found resulting in small fragments around the Ag3 VO4 specimen is clearly
as 1D rods and irregular agglomerates, respectively. The FESEM observed (Fig. S1), making it impossible for HRTEM analysis.
image of CoTiO3 /Ag3 VO4 heterostructure in Fig. 1c presents both Herein, XPS has been employed to determine the valence-band
the Ag3 VO4 agglomerates and CoTiO3 rods. EDX spectrum in Fig. 1d offset (VBO, Ev ) at the CoTiO3 /Ag3 VO4 interfaces. The semidirect
also confirms the presence of Ag, V, Co, Ti and O elements in the method used to estimate the energy band lineup is based on the
heterostructure material. measurement of CL at the heterostructure interface and the sep-
The heterojunction formation between CoTiO3 and Ag3 VO4 can arate measurement of the VB positions relative to the CL for each
be confirmed by HRTEM images showing a close interfacial contact constituent material [12,13]. The Ev can be calculated using the
at the heterostructure interfaces as presented in Fig. 2. It can be formulation of Kraut et al. [14] as follows:
seen from the figure that smooth CoTiO3 surfaces are covered with CoTiO3
 CoTiO3 Ag3VO4
 
Ag3 VO4

Ev = ETi2p − EVBM − EAg3d − EVBM + ECL (1)
small Ag3 VO4 particles, indicating the presence of heterojunctions.

3d5/2 Ag3VO4: Ag 3d 3d5/2 CoTiO3/Ag3VO4: Ag 3d

a b
3d3/2 3d3/2
Intensity (a.u.)

Intensity (a.u.)

366 368 370 372 374 376 378 366 368 370 372 374 376 378
Binding energy (eV) Binding energy (eV)

2p3/2 2p3/2
c CoTiO3: Ti 2p d CoTiO3/Ag3VO4: Ti 2p
Intensity (a.u.)
Intensity (a.u.)

2p1/2 2p1/2

456 458 460 462 464 466 468 456 458 460 462 464 466 468
Binding energy (eV) Binding energy (eV)
Ag3VO4
e
CoTiO3
Normalized intensity

1.4 1.6
-2 0 2 4 6 8 10
Binding energy (eV)

Fig. 3. CL spectra of Ag 3d recorded on (a) Ag3 VO4 and (b) CoTiO3 /Ag3 VO4 heterojunction, CL spectra of Ti 2p recorded on (c) CoTiO3 and (d) CoTiO3 /Ag3 VO4 heterojunction
and (e) VB spectra recorded on Ag3 VO4 and CoTiO3 .
708 K. Wangkawong et al. / Applied Surface Science 324 (2015) 705–709

Table 1
XPS CL peaks and VBM positions used to calculate the VBO of CoTiO3 /Ag3 VO4
heterojunction.

Sample Region Binding energy (eV)

Ag3 VO4 Ag 3d5/2 368.0 ± 0.1

VBM 1.6 ± 0.1

CoTiO3 Ti 2p3/2 458.1 ± 0.1

VBM 1.4 ± 0.1

CoTiO3 /Ag3 VO4 Ag 3d5/2 368.1 ± 0.1

Ti 2p3/2 458.2 ± 0.1


CoTiO3 − E CoTiO3

where ETi2p is the energy difference between Ti 2p
VBM  
Ag3 VO4 − E Ag3 VO4
and VBM in pure CoTiO3 , EAg3d VBM
is the energy dif-
 CoTiO /Ag VO
ference between Ag 3d and 
VBM in pure Ag3 VO4 and ECL =
CoTiO3 /Ag3 VO4 is the energy difference between
EAg3d 3 3 4 − ETi2p
Ag 3d and Ti 2p CL peaks in CoTiO3 /Ag3 VO4 heterojunction. All
CL spectra are fitted to Voigt (mixed Lorentzian–Gaussian) line
shape using Shirley background. The VBM energy is determined
by extrapolating the linear portion of the leading edge of the VB
spectrum to the spectral baseline. The accuracy of the XPS peak
position in this study is ±0.1 eV as evaluated by numerous fittings.
Therefore, the uncertainty of the band offset is ±0.3 eV.
Fig. 3 shows CL and VB edge XPS spectra for Ag3 VO4 , CoTiO3
and CoTiO3 /Ag3 VO4 composite. The CL spectrum of Ag 3d recorded
on pure Ag3 VO4 (Fig. 3a) shows two main peaks contributing
to Ag 3d5/2 and Ag 3d3/2 . The Ag 3d5/2 peak at 368.0 ± 0.1 eV
can be deconvoluted into two components at 367.9 ± 0.1 eV
and 368.5 ± 0.1 eV that correspond to Ag+ and Ag0 , respectively
[2,15–17]. The presence of metallic silver in this work might be
due to the reduction by light of the photosensitive Ag+ species
during catalyst handling. A positive shift of ∼0.1 eV to the bind-
ing energy of 368.1 ± 0.1 eV is found for the Ag 3d5/2 in the
CoTiO3 /Ag3 VO4 heterojunction (Fig. 3b) and the two components
appear at 368.0 ± 0.1 and 368.6 ± 0.1 eV. The CL spectrum of Ti 2p
for pure CoTiO3 is shown in Fig. 3c. The Ti 2p3/2 state at the bind-
ing energy of 458.1 ± 0.1 eV consists of three components located
at 458.1 ± 0.1 eV and 458.9 ± 0.1 eV for Ti4+ in Cox Ti1−x O2 and at
459.7 ± 0.1 eV for Ti4+ in bulk TiO2 [18–20]. The three Ti 2p3/2 sub-
peaks also concomitantly shift to 458.2 ± 0.1 eV, 459.0 ± 0.1 eV and
459.9 ± 0.1 eV, respectively. Since the CL shifts of both Ag 3d5/2 and
Ti 2p3/2 (∼0.1 eV) are within the error of measurement, these shifts
may or may not be significant.
The VBM values of Ag3 VO4 and CoTiO3 deduced from the VB
spectra in Fig. 3e are 1.6 ± 0.1 eV and 1.4 ± 0.1 eV, respectively. A
summary of CL peak positions and VBM energies used for the cal-
culation is presented in Table 1. In this study, charge neutralization
from an electron flood gun and charge correction using the C 1s
line from adventitious hydrocarbon were employed to reduce the
charging effect [21]. In addition, the photoelectrons emitted from
the sample were neutralized by the electrons provided through the
grounded sample holder. Therefore, the BE shift due to charging in
this study is considered as minimized. Also, if the charging actually
exists, both CL and VBM will shift by the same amount and since
we are interested only in the position of the CL relative to VBM
for the calculation of band offsets, the difference between binding
energy values would have a less significant effect on the obtained
band offsets [8,22–24]. A small difference in VBM position (0.2 eV)
of Ag3 VO4 from the one reported previously (1.8 eV) [6] may be
ascribed to the differences in various physical factors such as local
electronic state, defect and strain, which are known to affect the
XPS spectra [13,25,26].
Since the CL emissions of Ag 3d and Ti 2p for the CoTiO3 /Ag3 VO4
heterojunction are measured on the same surface, the effect of
band bending at the interface can be canceled out for the ECL
Fig. 4. Schematic diagram of type-II CoTiO3 /Ag3 VO4 heterojunction with a possible
electron–hole transfer process under visible light irradiation.
determination [27]. According to Eq. (1), the Ev of the
CoTiO3 /Ag3 VO4 heterojunction is calculated to be 0.2 ± 0.3 eV. The
conduction-band offset (CBO, Ec ) of the CoTiO3 /Ag3 VO4 het-
erostructure can be estimated by the following formula [14]:
Ec = EgAg3 VO4 − EgCoTiO3 − Ev (2)
By substituting the band gap values at room temperature
(EgAg3 VO4 ≈ 2.2 eV and EgCoTiO3 ≈ 2.6 eV [7]), Ec is calculated to be
−0.6 ± 0.3 eV. The negative value means that the conduction band
minimum (CBM) of Ag3 VO4 is below that of CoTiO3 . Accordingly, a
type-II band alignment is formed at the CoTiO3 /Ag3 VO4 interface,
as schematically shown in Fig. 4. The type-II band lineup has pre-
viously been reported to reduce the electron–hole recombination
rate at the interfaces, thus increasing the photoactivity of the hybrid
materials [6,9–11]. In this work, the obtained band alignment cor-
responds well with our previous PL and photocatalytic studies [7],
where a decreased PL intensity and an enhanced photoactivity
were found for the CoTiO3 /Ag3 VO4 heterostructure, implying an
improved charge separation efficiency. This suggests that determi-
nation of the band structure has shed some light on the possible
photogenerated charge transfer at the heterostructure interface.
Upon considering our synthesis method where the preformed
CoTiO3 was suspended in the silver vanadate precursor and then
the suspension was subjected to hydrothermal treatment, the
thickness of Ag3 VO4 overlayer could not be precisely and homoge-
neously controlled. There is a possibility that some CoTiO3 rods are
completely or partially covered with Ag3 VO4 particles/layers of dif-
ferent sizes/thicknesses, so both relaxed Ag3 VO4 layer with misfit
dislocations at the CoTiO3 /Ag3 VO4 interfaces and strained Ag3 VO4
layer could exist in the heterostructure. Since the strains and dislo-
cations can modify the atomic positions as well as the interatomic
distances at the interfaces, a shift in VB-XPS spectrum and the varia-
tion in Ev as a consequence are also possible [9,28,29]. In addition,
the TEM images of CoTiO3 /Ag3 VO4 heterostructure (Fig. 2) also
indicate the presence of nano-heterostructures (small Ag3 VO4 par-
ticles on smooth CoTiO3 surfaces) which are theoretically assumed
as fully strained [13]. Therefore, the strained layer may also exist
in the heterojunction being studied. Note that only an approxi-
mate band lineup of the CoTiO3 /Ag3 VO4 heterostructure can be
constructed in this work as the strain-induced piezoelectric field
originated from lattice mismatch and the possibility of gap emis-
sion existing between the VBM and the Fermi level (EF ) due to
 K. Wangkawong et al. / Applied Surface Science 324 (2015) 705–709
compositional disorder, which make it difficult to determine the
exact leading edge of VBM position [13,29], are not included.
4. Conclusions
In the present study, the energy band diagram of novel
CoTiO3 /Ag3 VO4 heterojunction has firstly been studied by semidi-
rect XPS technique. A type-II band alignment with a VBO of
0.2 ± 0.3 eV and a CBO of −0.6 ± 0.3 eV is found. The obtained band
lineup very well supports the improved electron–hole separation
efficiency of this heterostructure in our previous report [7]. The
determination of energy band structure as in this work provides
a better understanding in the charge transfer mechanism at the
interfaces, and is expected to be useful in the design of new het-
erojunction photocatalysts.
Acknowledgements
This research was supported by the Development and Promo-
tion of Science and Technology talents project (DPST 020/2013);
the Center of Excellence in Materials Science and Technology and
the Graduate School, Chiang Mai University; the National Research
University Project under Thailand’s Office of the Higher Education
Commission, Materials Science Research Center. The authors also
thank Sarunya Suntalelat for FESEM measurement.
Appendix A. Supplementary data
Supplementary material related to this article can be found
in the online version at http://dx.doi.org/10.1016/j.apsusc.
2014.11.020.
References
[1] R. Konta, H. Kato, H. Kobayashi, A. Kudo, Phys. Chem. Chem. Phys. 5 (2003)
3065.
[2] H. Xu, H. Li, L. Xu, C. Wu, G. Sun, Y. Xu, J. Chu, Ind. Eng. Chem. Res. 48 (2009)
10771.
709
[3] C. Shifu, Z. Wei, L. Wei, Z. Huaye, Y. Xiaoling, C. Yinghao, J. Hazard. Mater. 172
(2009) 1415.
[4] S. Wang, D. Li, C. Sun, S. Yang, Y. Guan, H. He, Appl. Catal., B: Environ. 144 (2014)
885.
[5] L. Zhang, Y. He, P. Ye, Y. Wu, T. Wu, J. Alloys Compd. 549 (2013) 105.
[6] B. Inceesungvorn, T. Teeranunpong, J. Nunkaew, S. Suntalelat, D. Tantraviwat,
Catal. Commun. 54 (2014) 35.
[7] K. Wangkawong, S. Suntalelat, D. Tantraviwat, B. Inceesungvorn, Mater. Lett.
133 (2014) 119.
[8] D.O. Scanlon, C.W. Dunnill, J. Buckeridge, S.A. Shevlin, A.J. Logsdail, S.M. Wood-
ley, C.R.A. Catlow, M.J. Powell, R.G. Palgrave, I.P. Parkin, G.W. Watson, T.W. Keal,
P. Sherwood, A. Walsh, A.A. Sokol, Nat. Mater. 12 (2013) 798.
[9] P. Guo, J. Jiang, S. Shen, L. Guo, Int. J. Hydrogen Energy 38 (2013) 13097.
[10] Z. Zhang, J. Zu, S. Li, Y. Mao, J. Solid State Chem. 211 (2014) 120.
[11] J. Chen, S. Shen, P. Guo, P. Wu, L. Guo, J. Mater. Chem. A 2 (2014) 4605.
[12] A.M. Abdel Haleem, M. Ichimura, J. Appl. Phys. 107 (2010) 034507.
[13] N.N. Halder, P. Biswas, B. Nagabhushan, S. Kundu, D. Biswas, P. Banerji, J. Appl.
Phys. 115 (2014) 203719.
[14] E.A. Kraut, R.W. Grant, J.R. Waldrop, S.P. Kowalczyk, Phys. Rev. A: At. Mol. Opt.
Phys. 44 (1980) 1620.
[15] C. Belver, C. Adán, S. García-Rodríguez, M. Fernández-García, Chem. Eng. J. 224
(2013) 24.
[16] L.H. Tjeng, M.B. meinders, J. Elp, J. Ghijsen, G.A. Sawatzky, Phys. Rev. B: Condens.
Matter 41 (1990) 3190.
[17] G.B. Hoflund, Z.F. Hazos, Phys. Rev. B: Condens. Matter 62 (2000) 11126.
[18] S.H. Lim, C. Ferraris, M. Schreyer, K. Shih, J.O. Leckie, T.J. White, J. Solid State
Chem. 180 (2007) 2905.
[19] S. Sharma, N. Thakur, R.K. Kotnala, K.C. Verma, J. Cryst. Growth 321 (2011) 19.
[20] X. Xia, Z. Zeng, X. Li, Y. Zhang, J. Tu, N.C. Fan, H. Zhang, H.J. Fan, Nanoscale 5
(2013) 6040.
[21] J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, Handbook of X-ray Photo-
electron Spectroscopy: A Reference Book of Standard Spectra for Identification
and Interpretation of XPS Data, Perkin-Elmer Corporation, Minnesota, 1992 (p.
22).
[22] M.K. Hudait, Y. Zhu, N. Jain, D. Maurya, Y. Zhou, S. Piya, J. Appl. Phys. 114 (2013)
024303.
[23] S.W. King, M. French, C. Xu, B. French, M. jaehnig, J. Bielefeld, J. Brockman, M.
Kuhn, Appl. Surf. Sci. 285P (2013) 545.
[24] Z. Li, B. Zhang, J. Wang, J. Liu, X. Liu, S. Yang, Q. Zhu, Z. Wang, Nanoscale Res.
Lett. 6 (2011) 193.
[25] W.A. Harrison, E.A. Kraut, J.R. Waldrop, R.W. Gran, Phys. Rev. B: Condens. Matter
18 (1978) 4402.
[26] K. Okada, A. Kotani, B.T. Thole, J. Electron Spectrosc. Relat. Phenom. 58 (1992)
325.
[27] C. Jia, Y. Chen, Y. Guo, X. Liu, S. Yang, W. Zhang, Z. Wang, Nanoscale Res. Lett. 6
(2011) 316.
[28] H.L. Ju, K.M. Krishnan, D. Lederman, J. Appl. Phys. 83 (1998) 7073.
[29] A. Ashrafi, Surf. Sci. 604 (2010) L63.