Article

The Work Function of TiO2

Shun Kashiwaya 1,2, Jan Morasch 1, Verena Streibel 1,†, Thierry Toupance 2 ,
Wolfram Jaegermann 1 and Andreas Klein 1,*
1 Department of Materials and Earth Sciences, Surface Science Division, Technische Universität
Darmstadt, Otto-Berndt-Straße 3, 64287 Darmstadt, Germany; skashi@surface.tu-darmstadt.de (S.K.);
j.morasch@web.de (J.M.); streibel@stanford.edu (V.S.); jaegerw@surface.tu-darmstadt.de (W.J.)
2 Institute of Molecular Sciences, University of Bordeaux, CNRS UMR 5255, Bâtiment A12,
351 Cours de la Liberation, 33405 Talence CEDEX, France; thierry.toupance@u-bordeaux.fr
* Correspondence: aklein@surface.tu-darmstadt.de; Tel.: +49-6151-16-20772
† Current address: SUNCAT Center for Interface Science and Catalysis,
SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025, USA.
CHECK EOJ
Received: 13 July 2018; Accepted: 1 September 2018; Published: 7 September 2018 updates

Abstract: Polycrystalline anatase thin films, (001)- and (101)-oriented anatase TiO2 single crystals
and (001)- and (110)-oriented rutile TiO2 single crystals with various surface treatments were
studied by photoelectron spectroscopy to obtain their surface potentials. Regardless of orientations
and polymorph, a huge variation of the Fermi level and work function was achieved by varying
the surface condition. The most strongly oxidized surfaces are obtained after oxygen plasma
treatment with a Fermi level ∼2.6 eV above the valence band maximum and ionization potentials
of up to 9.5 eV (work function 7.9 eV). All other treated anatase surfaces exhibit an ionization
potential independent of surface condition of 7.96 ± 0.15 eV. The Fermi level positions and the
work functions vary by up to 1 eV. The ionization potential of rutile is ∼0.56 eV lower than that of
anatase in good agreement with recent band alignment studies.

Keywords: TiO2; anatase; rutile; work function; electron spectroscopy; photocatalysis

1. Introduction
Titanium dioxide (TiO2) is widely applied in photocatalysis [1] and as electrode in solar cells
[2], and has been considered to be a promising material owing to its physical and chemical
properties. Among the different polymorphs of TiO 2, mostly fundamental properties of rutile have
been studied experimentally and theoretically despite a superior photocatalytic activity of anatase as
compared to rutile, which is associated with its longer charge carrier life time and higher carrier
mobility [3]. Oriented rutile substrates, of which the rutile (110) is the most stable and can be easily
prepared, have been thoroughly investigated as model surfaces for fundamental surface phenomena
[4]. In contrast, information about oriented anatase is sparse because of their difficult preparation
[5]. Only recently novel techniques to prepare oriented anatase substrates have been developed [6].
In 2008 Yang et al. [7] synthesized anatase single crystals with 47% of the minority (001) facet via a
hydrothermal route employing fluoric acid. This successful synthesis has surged further
fundamental investigations of both anatase (101) and (001) facets [8–11]. However, although the
electronic structure of anatase bulk and surfaces including band gaps and surface states are well
known due a wide range of experimental and theoretical studies using complementary techniques,
particularly using electron spectroscopy (see e.g., [11–21]), the surface potentials—Fermi level
position, work function and ionization potential—have not yet been studied systematically.
The work function ϕ of materials is especially relevant for photocatalysis and solar cells as it
governs the band alignments of interfaces such as TiO2/metal contacts forming Schottky barriers,

Surfaces 2018, 1, 73–89; doi:10.3390/surfaces1010007 www.mdpi.com/journal/surfaces

Surfaces 2018, 1 7

TiO2/p-type semiconductor interfaces forming p-n junctions, and TiO 2/liquid junctions related to
redox potentials. Despite its importance for TiO 2, only few work function data have been reported
[22–24]. The work function is affected by the Fermi energy EF and by the vacuum energy Evac, which
can be manipulated separately by doping, surface space charge layers, or the surface dipole,
respectively [25]. The latter depends on surface polarity and termination [26]. Changes in the
surface dipole directly affect the ionization potential IP, which is the difference between vacuum
energy and valence band maximum EVB and which does not depend on the Fermi energy.
The ionization potential of metal oxide surfaces depends on surface orientation and surface
termination, where the latter can vary with the oxygen activity during preparation [25,27–31]. Due
to a strong electronegativity of oxygen, less oxygen results in a lower negative surface charge and
thus in a lower IP and ϕ. The oxygen activity also affects the Fermi energy in oxides. A lower oxygen
activity, i.e., more reducing conditions, generally results in a higher Fermi energy and thereby in a
lower ϕ = Evac − EF. Detailed data on the interplay between the surface potentials and oxygen
activity for most TiO2 surfaces are still lacking.
Figure 1 displays a ball-and-stick model of bulk-terminated surfaces of rutile (110) and (001),
and anatase (101) and (001) without structural relaxations. At the rutile (110) surface bridging
oxygen atoms missing one bond to Ti can be easily removed by thermal annealing, whereas at
the rutile
(001) surface, oxygen vacancies VO are believed to easily form at a twofold-coordinated surface O
atom [4,32]. It was theoretically predicted and experimentally shown that the point defect is located
at the bridging oxygen row on the rutile (110) surface whereas for the anatase (101) surface V O are
favored to be situated in the subsurface rather than on the surface [18,33–35]. At anatase (101) and
(001) surfaces, the VO has a lower formation energy in the subsurface than on the surface while the
rutile
(110) surface exhibits an inverse trend. Thus, at anatase (101) and (001) surfaces, V O are energetically
stable in the subsurface or even in the bulk whereas at rutile (110) and (001) surfaces, the VO form
most likely at the bridging oxygen site on the top surface. This difference in oxygen vacancy
distribution is expected to lead to different electronic properties.

Figure 1. Bulk-terminated surfaces of (a) anatase (101), (b) anatase (001), (c) rutile (110) and (d) rutile
(001), illustrated using VESTA.

Many applications of TiO2 such as water splitting, water purification and self-cleaning,
undergo an interaction with water [36–39]. Thus, the investigation of water adsorption on the
surface is important. Water adsorption has therefore been investigated intensively by many groups
with different techniques (see e.g., [4,40–50] and references therein). Studies of water adsorption on
TiO2 are usually performed at liquid nitrogen or lower temperature, where multilayers of molecular
water can be adsorbed in a vacuum system [51]. Many studies have focused on the initial state of
adsorption: molecular, dissociative, or multilayer adsorption. Most calculations have predicted that
on rutile (110) surfaces dissociative adsorption of water is energetically preferred over molecular
adsorption [4]. However,
there is a consensus established by several experiments that water dissociates only at the vacancy
sites of so-called bridging oxygen rows while only molecular adsorption takes place on the
stoichiometric defect-free rutile (110) surface [4,40,41]. For anatase, it was found that water adsorbs
dissociatively on the surface in the presence of subsurface VO, although it has also been reported
that water would adsorb only molecularly on the anatase surfaces [42–46]. Based on these reports,
we assume that the distribution of VO influences the interface of TiO2 and water, which affects
photocatalytic redox reactions. Despite the wealth of studies on this subject, it remains largely
unknown how water adsorption affects the work function of different surfaces.
In this work, (001)- and (101)-oriented and polycrystalline anatase surfaces in different
oxidation conditions were studied. The same treatments were applied to rutile (110)- and (001)-
oriented surfaces. Polycrystalline anatase thin films prepared by spray pyrolysis are also included in
this study. The chemical and electronic surface properties were accessed using X-ray und UV
photoelectron spectroscopy (XPS and UPS). The reported results provide the variation of the surface
potentials of TiO2, i.e., the Fermi level position (EF) with respect to the valence band maximum (EVB)
and the work function ϕ, with surface condition. For anatase, we have also studied the variation of
surface properties after exposure to water vapor at room temperature without breaking vacuum.
Furthermore, we compare anatase and rutile surfaces and discuss differences in their electronic
properties. Overall, the work provides guidance towards manipulating the work function of TiO2
surfaces.

2. Materials and Methods

Natural anatase crystals were employed for both (101) and (001) surfaces (SurfaceNet GmbH,
Rheine, Germany). Polycrystalline anatase substrates were prepared by spray pyrolysis. Epitaxially
polished rutile (110) and (001) substrates were purchased from CrysTec GmbH (Berlin, Germany).
The size of the substrates is 5 × 5 × 1 mm3. A surface roughness less than a lattice constant was
achieved after epi-polishing the single crystal substrates. For anatase, in addition to the ex-situ
surfaces (ex-a(001), ex-a(101), and ex-a-poly) with contamination from air and polishing,
unreconstructed (101) and (001), and polycrystalline surfaces were in situ prepared inside an
integrated vacuum system to expose different well-defined stoichiometries: sputtered (sp-a(001), sp-
a(101), and sp-a-poly), annealed (an-a(001), an-a(101), and an-a-poly), oxidized (ox-a(001), ox-a(101),
and ox-a-poly), and stoichiometric (st-a(001), st-a(101), and st-a-poly). For rutile, annealed (an-r(110)
and an-r(001)) and oxidized (ox-r(110) and ox-r(001)) were prepared.
Sample preparations and measurements were carried out in the Darmstadt integrated system
for materials research (Daisy-Mat) [52] equipped with a multitechnique surface analysis system
Physical Electronics PHI 5700, which is connected to different sample preparation chambers via a
sample transfer system. The sputtered surfaces were prepared by repeated cycles of Ar + ion
sputtering with an energy of 1 keV for 15 min and annealing under ultrahigh vacuum (UHV)
conditions at 873 K for 30 min until no remaining emissions from contaminations were observed by
X-ray photoelectron spectroscopy (XPS). Although this procedure has been conventionally accepted
to prepare clean surfaces of single crystal TiO 2, Ar sputtering not only results in a highly reduced
surface and thus leads to the formation of oxygen vacancies and Ti3+ surface states, but also
partially destroys the crystallinity of the surface and introduces an amorphous phase [4,6,53].
After Ar ion etching, the sputtered surfaces were oxidized in an Oxygen plasma at room
−
temperature in an atmosphere of 7.5 × 10 5 mbar O2 for 15 min to re-oxidize the surface, followed
by annealing at 873 K in UHV to re-crystallize the surface. Here the O plasma was selected to
replenish the lattice O instead of annealing in O2 atmosphere, which has been frequently used for
oxidation,
as annealing in O2 could form additional incomplete reconstructions [54]. Furthermore, annealing
in O2 may lead to iron oxide layer formation since elevated temperatures may trigger the surface
segregation of Fe, which is a typical contamination of natural anatase crystals [6]. In addition,
atomic O in the O plasma is more oxidative than molecular O 2 during annealing in O2 atmosphere,
which leads to partially remaining VO [18,55].
 The surfaces, which are in this work referred to as annealed, (The term annealing might be used
differently in literature) were prepared by an oxygen plasma treatment and a subsequent reduction
by annealing in vacuum at 873 K. Low energy electron diffraction (LEED) patterns recorded for
these surfaces are shown in Figure A1. They show unreconstructed 1 × 1 patterns with low
background intensity, indicating well-ordered surfaces. Finally, the stoichiometric surfaces were
prepared by removing O adatoms by annealing the oxidized (plasma treated) surfaces in UHV at
473 K for 20 min [56,57]. An overview of the preparation procedures for the above described
different surfaces is given in Figure 2. It is noted that the color of rutile substrates, which are less
conductive than anatase, changed from transparent into dark blue after the reduction procedure,
making the surfaces sufficiently conductive to avoid charging during photoemission measurements.

Figure 2. Scheme of the preparation procedure for ex-situ (ex), sputtered (sp), annealed (an), oxidized
(ox), and stoichiometric (st) surfaces of the TiO 2 surfaces.

To further understand the electronic structures of different surfaces in a practical situation for
photocatalytic reactions, water was dosed through a diaphragm valve for atomic layer deposition
in a vacuum chamber [58] onto the annealed, oxidized, and stoichiometric surfaces for the anatase
(001) and (101), and polycrystalline anatase. The water exposure at room temperature was
completed using 15 water pulses of 0.5 s duration followed by evacuation for 60 s. The amount of
exposed water molecules in this process depends on the pumping speed and the chamber geometry.
We estimate the exposure to 106–108 Langmuir. The resulting TiO2 substrates were transferred to the
XPS chamber and investigated immediately after this adsorption procedure. XPS analysis revealed
a small C 1s emission after water exposure.
X-ray photoelectron spectra were recorded with monochromatic Al Kα radiation at an
◦
emission angle of 45 and a pass energy of 5.85 eV, which gives a total energy resolution of 0.4 eV,
as determined from the Gaussian broadening of the Fermi edge of a sputter-cleaned Ag sample.
Binding energies
of core levels and the valence band maximum EVB can be determined with an accuracy of 50 meV,
and 100 meV, respectively. For the determination of work function ϕ and ionization potentials IP,
ultraviolet photoelectron spectra were recorded in normal emission with He I radiation (hν = 21.2
eV) from a He discharge lamp and a negative sample bias of 4.0 V. The total energy resolution is 0.2
eV. No charging problems were observed during the XPS and UPS measurements. Obtained binding
energies for XPS and UPS were calibrated by the Fermi level energy of a sputter-cleaned Ag sample.
Hence, all binding energies are given with respect to the calibrated Fermi level at 0 eV. More details
of the experimental setup and approach in performing the experiments may be found elsewhere
[52,59].

3. Results and Discussion

The Ti 2p3/2 and O 1s core level spectra of the differently treated surfaces are shown in Figure 3.
The Ti 2p3/2 emission of the sputtered anatase (101) surface shows a strong low binding energy
emission associated with Ti3+ and Ti2+ shifted relative to the main emission line of Ti4+ by ∼1.7 and
∼3.5 eV, respectively [45,60,61]. All other samples, including the sputtered anatase (001), exhibit
sharp
and symmetric lines consisting of a single Ti4+ oxidation state. Evidently, the anatase (101) surface
is much easier reduced than the (001) surface. The low binding energy Ti 2p3/2 emissions related to
surface reduction of anatase (101) are neither observed after re-oxidation by O plasma treatment nor
after re-crystallization by annealing in vacuum.

Figure 3. X-ray photoelectron spectra of the Ti 2p3/2 (top) and the O 1s (bottom) core level emissions
of (left) anatase (001), (middle) anatase (101), and (right) polycrystalline anatase substrates with
sputtered, annealed, stoichiometric, and oxidized surfaces. Solid and dash lines represent spectra
before and after water exposure, respectively.

Exposing an-a(001) and an-a(101) to an O plasma results in a shoulder in the O 1s emission at 3

eV higher binding energy compared to the O 1s emission related to TiO2 (see bottom row of Figure
2−
3). This shoulder is likely attributed to peroxo
2 (O ) surface species, like for example in bridging
oxygen dimers [62]. The stoichiometric anatase (001) and (101) surfaces show no shoulder in the O
1s emission
after annealing in vacuum at 473 K. The surface peroxo species observed after oxygen plasma
treatment at ox-a(001) and ox-a(101) is therefore effectively removed by annealing.
X-ray and ultraviolet valence band spectra are shown in Figure 4. UP spectra are usually more
sensitive to surface defects than XP spectra, which is mostly due to the higher surface sensitivity of
UPS and the higher intensities. It is accepted that the so-called band gap surface states would form
due to occupied Ti 3d states (Ti3+) near the O vacancy sites on the surface, but also due to Ti3+
interstitials in the subsurface region [4,11,18,63,64]. It is clear from Figure 4 that all sputtered TiO2
surfaces show the well-known Ti 3d1 emission lines in the band gap region.

Figure 4. X-ray (top) and ultraviolet (bottom) valence band spectra of sputtered, annealed,
stoichiometric, and oxidized surfaces for (left) anatase (001), (middle) anatase (101), and (right)
polycrystalline anatase substrates before and after water exposure.

The emission of the gap states is different for the (001) and (101) surface orientation of anatase.
The state energically closer to the Fermi energy at a binding energy of ∼0.5 eV is more pronounced
for
 the (101) surface. As this emission is clearly observed only for the sputtered (101) surface, this
shallow gap state is likely related to the observation of the reduced Ti species.
The intensity of the band gap states is generally reduced with surface oxidation for both
orientations and all treatments. However, the deep gap state, which is closer to the onset of the
valence band maximum at 1.5–2.0 eV binding energy, is still observed in the XP and the UP valence
spectra for the (001) surface even after O plasma treatment. In contrast, the deep gap state is
completely attenuated for the oxidized and the stoichiometric (101) surface.
The valence band maximum binding energies EF − EVB are determined by a linear extrapolation
of the low binding energy valence band emission edge. Only XPS data are used here as they are less
affected by the gap state emissions. The extracted values are summarized in Table 1 together with
the core level binding energies, which are determined from the spectra shown in Figure 3.

Table 1. Binding energies (Ti 2p and O 1s), Fermi level position EF − EVB, work function ϕ, and ionization
potential IP for anatase (001), anatase (101), and polycrystalline anatase, as well as for rutile (001) and rutile
(110) with different surface stoichiometries: sputtered, annealed, stoichiometric, oxidized and ex-situ
prepared surfaces. Number in brackets are obtained after in situ exposure to water
vapor at room temperature.

Sputtered Annealed Stoichiometric Oxidized Ex-Situ

Ti 2p3/2 (eV)
a-(001) 459.08 459.07 (459.36) 458.70 (459.20) 458.64 (459.06) 459.27
a-(101) 459.21 459.17 (459.31) 458.73 (458.93) 458.69 (458.91) 459.28
a-poly 459.25 459.28 (459.44) 459.06 (459.37) 458.95 (459.09)
r-(001) 459.38 458.78
r-(110) 459.35 458.95
O 1s (eV)
a-(001) 530.35 530.33 (530.62) 529.95 (530.47) 529.93 (530.32) 530.60
a-(101) 530.81 530.52 (530.68) 530.07 (530.27) 529.93 (530.19) 530.62
a-poly 530.57 530.56 (530.71) 530.35 (530.64) 530.20 (530.44)
r-(001) 530.69 530.04
r-(110) 530.62 530.21
EF − EVB (eV)
2.64 (3.06)
a-(001) 3.10 3.06 (3.39) 2.53 (2.87) 3.44
a-(101) 3.55 3.23 (3.40) 2.84 (3.08) 2.69 (2.91) 3.35
a-poly 3.23 3.09 (3.37) 3.12 (3.31) 2.94 (3.16)
r-(001) 3.07 2.57
r-(110) 3.12 2.68
ϕ in (eV)
a-(001) 4.70 4.72 (4.36) 5.35 (4.34) 6.44 (4.97) 3.61
a-(101) 4.62 4.72 (4.36) 5.23 (4.40) 6.76 (5.03) 3.65
a-poly 4.51 4.23 (4.22) 5.16 (4.38) 5.62 (4.94)
r-(001) 4.29 6.08
r-(110) 4.31 5.96
a-(001) 7.80 7.78 (7.75) IP (eV)
7.99 (7.40) 8.97 (7.84) 7.05
a-(101) 8.17 7.95 (7.76) 8.07 (7.48) 9.45 (7.94) 7.00
a-poly 7.74 7.32 (7.59) 8.28 (7.69) 8.56 (8.10)
r-(001) 7.36 8.65
r-(110) 7.43 8.64

Independent of surface orientations, the valence band maximum binding energy decreases in
the order sputtered, annealed, stoichiometric, and oxidized treatment. The valence band maximum
and the core levels show comparable binding energy shifts. In particular, the binding energy
difference between the O 1s and the Ti 2p core level is 71.29 ± 0.04 eV, with the only exception of the
sputtered anatase surface, where the binding energy of the Ti 2p core level is more uncertain due to
the strong
reduction of the surface. The binding energy differences between the core levels and valence band
maxima also remain within ±0.15 eV, which can also be considered to be constant considering the
changes of the valence bands in dependence on treatment. The binding energy shifts can therefore
be attributed to different Fermi energies. These are likely caused by different concentrations of
oxygen vacancies at the surface or in the bulk. The former would cause binding energy shifts due to
surface electron accumulation, the latter due to enhanced doping.
The overall variation of the Fermi energy is 0.46 eV for the (001) and 0.71 eV for the (101)
surface orientation, respectively. It is noteworthy that EF − EVB of the (101) surface is always higher
than that of the (001) surface. This difference of EF − EVB results in a variation of surface potential
with orientation, which will drive photogenerated electrons and holes towards the (101) and (001)
surfaces,
respectively. This charge separation mechanism agrees with literature reports [65,66].
The secondary electron edges of the UP spectra of anatase are shown in Figure 5. Their
energetic position is determined at the middle of the steep rise of the edge. (Most authors use the
intersection of the secondary electron edge with the baseline to determine the work function. We
take the middle of the steep rise instead as we assume that the onset is broadened by the resolution
of the spectrometer system. We use this procedure when the width of the steep part of the edge is
≤0.2 eV, which is the case for all spectra in this manuscript. In this case, the difference between the
two approaches is less than 0.1 eV.) The extracted work functions ϕ and ionization potentials IP are
summarized in Table 1 and the work function is plotted as a function of the Fermi energy in Figure
6. More extended data including polycrystalline and water exposed samples are provided in the
appendix in Figure A2 and Table A1. The work functions are decreasing in the order oxidized >
stoichiometric > annealed > sputtered for both single crystal anatase surface orientations. It
therefore decreases monotonically with the increase of the Fermi level to valence band maximum
distance, EF − EVB. This is to be expected as both depend on the oxidation state of the surface and
subsurface. Similar dependencies have been reported for ZnO, In2O3 and SnO2 [25].

Figure 5. UP spectra of SEE of sputtered, annealed, stoichiometric, and oxidized surfaces for anatase
(001), anatase (101), and polycrystalline anatase substrates before and after water exposure.

The overall variation of the work function is 1.74, 2.14 and 1.39 eV for anatase (001), anatase
(101) and polycrystalline anatase, respectively. The change of ϕ between stoichiometric, annealed,
and sputtered single crystal surfaces is caused mainly by a change of EF − EVB as the ionization
potential is almost constant for these surface conditions with IP = 7.96 ± 0.15 eV. Such a behavior
has also been
reported by Henrich et al. for rutile (110) surfaces [22]. The ionization potential of the polycrystalline
surfaces varies more with preparation conditions than at the single crystalline surfaces. This is likely
attributed to a less pure surface condition, as the surfaces typically show residual carbon
contamination. Considerably higher ionization potentials of up to 9.45 eV are observed for the
oxygen plasma treated surfaces. This matches with the assumed peroxo or bridging oxygen species
on the surface, which are induced by radical oxygen atoms of the oxygen plasma. Electronegative
oxygen accumulates with a negative charge, leading to high work functions and ionization
potentials of oxidized surfaces due to an increase of the surface dipole [31,67].

Figure 6. Work function versus Fermi level to valence band maximum distance, EF − EVB, of
sputtered, annealed, stoichiometric, and oxidized surfaces for anatase (001), anatase (101), and
polycrystalline anatase substrates before and after water exposure. Values for annealed and oxidized
rutile (001) and
(110) surfaces are added for comparison.

Water vapor was exposed to the surfaces at room temperature and the resulting electronic
properties were investigated by XPS and UPS. Obtained core level binding energies and surface
potentials of the surfaces exposed to water are included in brackets in Table 1. The chemical
modification of the surface resulting from water exposure is not clear. During low temperature
adsorption, a mixture of molecular and dissociative adsorption is reported [4,40–46]. The
adsorption of water molecules is not expected at room temperature in ultra-high vacuum but
formation of hydroxides is likely. However, we do not have a clear confirmation for this. The O 1s
peaks do not show the high binding energy shoulder typical for hydroxides. Nevertheless, the O 1s
spectra do exclude a low OH coverage. Further studies, which are beyond the scope of the present
work, are required to resolve the interaction of water vapor with TiO2 surfaces.
Irrespective of the uncertainty of the chemical state of the surface, water exposure reproducibly
induces shifts of the Ti 2p and O 1s core levels and the valence band edge towards higher binding
energies. The shifts can therefore be attributed to a downward band bending at the TiO2 surface,
resulting in an accumulation of electrons at the surface. This observation emphasizes the importance
of adsorbates for the frequently reported electron accumulation layers at oxide surfaces [68–70]. The
final Fermi level positions, which are extracted from the valence band maximum and the core level
binding
energies do not depend on surface orientation and are ∼3.4, ∼3.1 and ∼2.9 eV for the annealed,
stoichiometric and oxidized (001) and (101) surfaces, respectively. The original difference in EF −
EVB
between the anatase (101) and (001), which was present for all surface conditions, thus disappeared
after water exposure.
The work function after water exposure is ∼4.4 eV for the annealed and stoichiometric
surfaces, while it is significantly higher (∼5.0 eV) for the oxidized surface. Apparently, the adsorbed
peroxo or
bridging oxygen species, which cause the increased ionization potential, are not completely
removed by water exposure. These species are therefore strongly enough bound to the surface to
withstand the reduction of the sample by water exposure. The latter is indicated by the rise of the
Fermi energy.
XP spectra of the valence band region, the Ti 2p3/2, and the O 1s core levels of annealed and
oxidized rutile (001) and (110) surfaces are shown in Figure 7. Corresponding core level binding
energies and surface potentials are included in Table 1. Obtained work functions and ionization
potentials are plotted together with the anatase data in Figure 6. A large difference of EF − EVB and
ϕ between the two treatments but no significant dependence on surface orientation are observed.
The ionization potential of the annealed surfaces amounts to 7.40 ± 0.04 eV, which is 0.56 eV lower
than that of the corresponding anatase surfaces.

Figure 7. XP spectra of Ti 2p, O 1s, and valence band emission lines, and UP spectra of secondary
electron edge and valence band region for rutile (001) and (110) substrates with reduced and
oxidized surfaces.

The ionization potentials of the anatase and rutile surfaces (except for the ones treated in the O
plasma), which are 7.96 and 7.40 eV, respectively, are comparable to those of ZnO surfaces exposed
to oxidizing conditions (∼7.6 eV) [25,29]. Similar ionization potentials are also found for surfaces
of Sn-doped In2O3 (∼7.7 eV) and reduced SnO 2 surfaces [25,29,71,72]. The latter are characterized
by a Sn2+ oxidation state [28,73–75]. Except for the sputtered anatase (101) surfaces, which exhibits
substantial reduction of Ti, most of the Ti adopts a +IV oxidation state. One might therefore expect
that the ionization potential is comparable to that of the stoichiometric SnO 2 surface, which amounts
to ∼8.9 eV [25,29,71,72]. The deviation is quite substantial, even for rutile, which has the same
crystal structure as SnO 2. The ionization potential of TiO2 is therefore substantially lower than that
of SnO2. TiO2 surfaces do also not show the variation of cation oxidation state and the associate
change of IP, which is characteristic for SnO2. The origin of these remarkable differences remains to
be resolved. Due to the similar ionization potentials and work functions of TiO2, ZnO and In2O3,
the superior
photocatalytic and solar cell properties of TiO 2 are probably not caused by an advantageous energy
band alignment.
The difference in ionization potential between anatase and rutile amounts to ∼0.5 eV. Aligning
the vacuum energies of the two polytypes does therefore result in a valence band maximum of
anatase being ∼0.5 eV lower in energy than that of rutile. This is the same direction and of the same
magnitude as the energy band alignment established recently by different experimental and
theoretical approaches [19,76,77], supporting the conclusion that the energy bands of rutile are
higher than those of anatase.

4. Summary and Conclusions

Chemical and electronic properties of anatase (001), anatase (101), polycrystalline anatase, rutile
(110) and rutile (001) with different surface treatments were studied using XPS and UPS. The Fermi
energy and work function depend drastically on surface conditions, which are characterized by
different oxygen vacancy concentrations and surface adsorbates. We have shown how the surface
Fermi energy, work function and ionization potentials are affected and can therefore be adjusted by
different surface treatments.
For anatase, the Fermi level can be manipulated between EF − EVB = 2.53–3.10, 2.69–3.55, and
2.94–3.23 eV for the (001), (101) and polycrystalline surfaces, respectively. Along with the different
Fermi energies goes a variation of work function between ϕ = 4.70–6.44, 4.62–6.76, and 4.51–5.62 eV
for the (001), (101) and polycrystalline surfaces, respectively. Apart from the plasma treated
samples, which have exceptionally high work functions likely due to the presence of peroxo species,
the ionization potential is rather insensitive to the surface treatments and exhibits a value of IP =
7.96 ± 0.15 eV. This is approximately 0.5 eV higher than of rutile, which agrees with the band
alignment obtained from other techniques. For the anatase samples, the Fermi energy at the (101)
surface is furthermore higher than at the (001) surface for all surface treatments.
Exposure of the samples to water vapor at room temperature reproducibly causes a downward
band bending on all surfaces (rise of the Fermi energy). For the anatase surfaces, the dependence
of Fermi energy on surface orientation is removed by water exposure. Water exposure also affects
the ionization potential. Together, both effects result in a lowering of the work function down to
4.34 ± 0.06 eV (IP = 7.61 ± 0.15 eV) for the annealed and the stoichimetric surfaces. The ionization
potential of the plasma treated surfaces remains rather high (7.96 ± 0.13 eV), resulting in work
functions of 4.98 ± 0.05 eV after water exposure.

Author Contributions: Single and polycrystalline surfaces were prepared and analyzed by S.K. and J.M.,
supervised by A.K., W.J. and T.T.; Discussion and interpretation of results was conducted by S.K., A.K. and
W.J.; The original draft has been composed by S.K., edited by A.K. and revised by all authors; Funding has been
acquired by W.J. and T.T.
Funding: This work was partly supported by the European Commission within the Erasmus Mundus Joint
Doctoral program International Doctoral School in Functional Materials for Energy, Information Technology,
and Health (ids-funmat), the French-German University (UFA Doctoral College in Functional Materials for
Energy and Information Technology) and was carried out within the framework of EMMI (European
Multifunctional Material Institute). Further support was received from the European Commission under the
FP7 project “Novel Composite Oxides by Combinatorial Material Synthesis for Next Generation All-Oxide-
Photovoltaics,” project number 309018.
Acknowledgments: Receipt of polycrystalline samples from Arie Zaban’s group at Bar Ilan University, Israel,
is also gratefully acknowledged.
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the
design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and
in the decision to publish the results.
Abbreviations
The following abbreviations are used in this manuscript:

XPS X-ray photoelectron spectroscopy

UPS ultraviolet photoelectron spectroscopy
UHV ultra-high vacuum
LEED low-energy electron diffraction

Appendix A. LEED Pattern for Annealed Anatase Surfaces

Figure A1. LEED pattern of the annealed anatase (001) (a) and (101) (b) surfaces. The unit cells are
indicated.

Appendix B. Further Work Function Data

Figure A2. Extended set of work function and Fermi energy data. The description of the sample
numbers are given in Table A1.
Table A1. Sample descriptions and surface potentials for Figure A2. All values are in eV with a
typical uncertainty of ±0.1 eV.

No. Sample Description EF ϕ IP

1 rutile (110) (i) same as #2; (ii) O2 plasma, RT, 15 min 2.68 5.96 8.64
◦ ◦
2 rutile (110) (i) 500 C, 0.5 Pa O2, 2h; (ii) 600 C, 3.24 4.43 7.67
−6
10 Pa, 1 h
3 rutile (110) same as #2 3.12 4.31 7.43
4 rutile (001) same as #1 2.57 6.08 8.65
5 rutile (001) same as #2 3.26 4.31 7.57
6 rutile (001) same as #2 3.07 4.29 7.36
7 anatase (101) same as #2 2.93 4.26 7.19
8 anatase (101) same as #2 + air exposure 3.35 3.65 7.00
9 anatase (101) O2 plasma, RT, 15 min 2.83 5.55 8.38
10 anatase (101) same as #9 + air exposure 2.90 3.90 6.80
11 anatase (101) (i) same as #12; (ii) O2 plasma, RT, 3.25 5.05 8.30
−
15 min; (iii) annealing in 10 6 Pa, 200
◦ C, 20 min
◦
12 anatase (101) cycles of sputtering + annealing 600 C, 3.55 4.62 8.17
−6
10 Pa, 1 h
13 anatase (101) (i) same as #12; (ii) O2 plasma, RT, 2.80 5.91 8.71
15 min
14 anatase (101) stoichiometric as in manuscript 2.84 5.23 8.07
15 anatase (101) (i) same as #14; (ii) H2O adsorption 3.08 4.40 7.48
16 anatase (101) reduced as in manuscript 3.23 4.72 7.95
17 anatase (101) (i) same #16; (ii) H2O adsorption 3.4 4.36 7.76
18 anatase (101) oxidized as in manuscript 2.69 6.76 9.45
19 anatase (101) (i) same as #18; (ii) H2O adsorption 2.91 5.03 7.94
20 anatase (001) same as #7 3.05 4.36 7.41
21 anatase (001) same as #8 3.44 3.61 7.05
22 anatase (001) same as #9 2.83 5.55 8.38
23 anatase (001) same as #10 2.90 3.90 6.80
24 anatase (001) same as #11 3.25 5.05 8.30
25 anatase (001) same as #12 3.55 4.62 8.17
26 anatase (001) same as #13 2.80 5.91 8.71
27 anatase (001) same as #14 2.84 5.23 8.07
28 anatase (001) same as #15 3.08 4.4 7.48
29 anatase (001) same as #16 3.23 4.72 7.95
30 anatase (001) same as #17 3.40 4.36 7.76
31 anatase (001) same as #18 2.69 6.76 9.45
32 anatase (001) same as #19 2.91 5.03 7.94
33 powder sol-gel, as prepared 3.18 3.94 7.12
34 powder hydrothermal, as prepared 3.44 3.87 7.31
35 nanocrystals (101) facetted 3.41 4.32 7.73
◦
36 sprayed film 0.5 Pa O2, 400 C, 12 h 3.21 5.25 8.46
◦
37 sprayed film 0.5 Pa Ar, 400 C, 12 h 3.24 5.14 8.38
38–42 sprayed film same as #36 2.98–3.45 4.85–5.25 7.88–8.62
43–50 sprayed film as received 3.47–3.60 3.75–3.96 7.29–7.46
51 thin film (i) in situ magnetron sputtering at RT; 2.98 5.53 8.51
◦
(ii) 0.5 Pa O2, 600 C, 1 h
52 thin film (i) in situ magnetron sputtering at RT; 3.09 5.37 8.46
◦
(ii) 0.5 Pa O2, 400 C, 1 h
53 sprayed film same as #11 3.24 4.82 8.06
54 sprayed film same as #12 3.23 4.51 7.74
55 sprayed film same as #13 2.85 5.70 8.55
56 sprayed film stoichiometric as in manuscript 3.12 5.16 8.28
57 sprayed film (i) same as #58; (ii) H2O adsorption 3.31 4.23 7.32
58 sprayed film reduced as in manuscript 3.09 4.23 7.32
59 sprayed film (i) same as #60; (ii) H2O adsorption 3.37 4.22 7.59
60 sprayed film stoichiometric as in manuscript 3.12 5.16 8.28
61 sprayed film (i) same as #62; (ii) H2O adsorption 3.16 4.94 8.10
62 sprayed film oxidized as in manuscript 2.94 5.62 8.56
References
1. Linsebigler, A.L.; Lu, G.; Yates, J.T. Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected
Results. Chem. Rev. 1995, 95, 735–758. [CrossRef]
2. Grätzel, M. Solar Energy Conversion by Dye-Sensitized Photovoltaic Cells. Inorg. Chem. 2005, 44, 6841–
6851. [CrossRef] [PubMed]
3. Selcuk, S.; Selloni, A. Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces
and aqueous interfaces. Nat. Mater. 2016, 15, 1107. [CrossRef] [PubMed]
4. Diebold, U. The surface science of titanium dioxide. Surf. Sci. Rep. 2003, 48, 53–229. [CrossRef]
5. Herman, G.S.; Gao, Y. Growth of epitaxial anatase (001) and (101) films. Thin Solid Films 2001, 397, 157–
161. [CrossRef]
6. Setvin, M.; Daniel, B.; Mansfeldova, V.; Kavan, L.; Scheiber, P.; Fidler, M.; Schmid, M.; Diebold, U. Surface
preparation of TiO2 anatase (101): Pitfalls and how to avoid them. Surf. Sci. 2014, 626, 61–67. [CrossRef]
7. Yang, H.G.; Sun, C.H.; Qiao, S.Z.; Zou, J.; Liu, G.; Smith, S.C.; Cheng, H.M.; Lu, G.Q. Anatase TiO2 single
crystals with a large percentage of reactive facets. Nature 2008, 453, 638. [CrossRef] [PubMed]
8. Chen, W.; Kuang, Q.; Wang, Q.; Xie, Z. Engineering a high energy surface of anatase TiO2 crystals
towards enhanced performance for energy conversion and environmental applications. RSC Adv. 2015,
5, 20396–20409. [CrossRef]
9. Liu, G.; Yu, J.C.; Lu, G.Q.M.; Cheng, H.M. Crystal facet engineering of semiconductor photocatalysts:
motivations, advances and unique properties. Chem. Commun. 2011, 47, 6763–6783. [CrossRef] [PubMed]
10. Scheiber, P.; Fidler, M.; Dulub, O.; Schmid, M.; Diebold, U.; Hou, W.; Aschauer, U.; Selloni, A.
(Sub)Surface Mobility of Oxygen Vacancies at the TiO2 Anatase (101) Surface. Phys. Rev. Lett. 2012, 109,
136103. [CrossRef] [PubMed]
11. Reckers, P.; Dimamay, M.; Klett, J.; Trost, S.; Zilberberg, K.; Riedl, T.; Parkinson, B.A.; Brötz, J.;
Jaegermann, W.; Mayer, T. Deep and Shallow TiO2 Gap States on Cleaved Anatase Single Crystal (101)
Surfaces, Nanocrystalline Anatase Films, and ALD Titania Ante and Post Annealing. J. Phys. Chem. C
2015, 119, 9890–9898. [CrossRef]
12. Baldini, E.; Chiodo, L.; Dominguez, A.; Palummo, M.; Moser, S.; Yazdi-Rizi, M.; Auböck, G.; Mallett,
B.P.; Berger, H.; Magrez, A. Strongly bound excitons in anatase TiO2 single crystals and nanoparticles.
Nat. Commun. 2017, 8, 13. [CrossRef] [PubMed]
13. Moser, S.; Moreschini, L.; Jac´imovic´, J.; Barišic´, O.S.; Berger, H.; Magrez, A.; Chang, Y.J.; Kim,
K.S.; Bostwick, A.; Rotenberg, E.; et al. Tunable Polaronic Conduction in Anatase TiO 2. Phys. Rev. Lett.
2013, 110, 196403. [CrossRef] [PubMed]
14. Emori, M.; Sakino, A.; Ozawa, K.; Sakama, H. Polarization-dependent ARPES measurement for valence
band of anatase TiO2. Solid State Commun. 2014, 188, 15–18. [CrossRef]
15. Sandell, A.; Sanyal, B.; Walle, L.; Richter, J.; Plogmaker, S.; Karlsson, P.; Borg, A.; Uvdal, P. Probing and
modifying the empty-state threshold of anatase TiO2: Experiments and ab initio theory. Phys. Rev. B 2008,
78, 075113. [CrossRef]
16. Tuan, A.C.; Kaspar, T.C.; Droubay, T.; Rogers , J.W., Jr.; Chambers, S.A. Band offsets for the epitaxial
TiO2/SrTiO3/Si(001) system. Appl. Phys. Lett. 2003, 83, 3734–3736. [CrossRef]
17. Thomas, A.G.; Flavell, W.R.; Kumarasinghe, A.R.; Mallick, A.K.; Tsoutsou, D.; Smith, G.C.; Stockbauer, R.;
Patel, S.; Grätzel, M.; Hengerer, R. Resonant photoemission of anatase TiO2 (101) and (001) single crystals.
Phys. Rev. B 2003, 67, 035110. [CrossRef]
18. Thomas, A.G.; Flavell, W.R.; Mallick, A.K.; Kumarasinghe, A.R.; Tsoutsou, D.; Khan, N.; Chatwin, C.;
Rayner, S.; Smith, G.C.; Stockbauer, R.L.; et al. Comparison of the electronic structure of anatase and rutile
TiO2 single-crystal surfaces using resonant photoemission and X-ray absorption spectroscopy. Phys. Rev.
B 2007, 75, 035105. [CrossRef]
19. Pfeifer, V.; Erhart, P.; Li, S.; Rachut, K.; Morasch, J.; Brötz, J.; Reckers, P.; Mayer, T.; Rühle, S.; Zaban, A.;
et al. Energy Band Alignment Between Anatase and Rutile TiO 2. J. Phys. Chem. Lett. 2013, 4, 4182–4187.
[CrossRef]
20. Schwanitz, K.; Weiler, U.; Hunger, R.; Mayer, T.; Jaegermann, W. Synchrotron-induced photoelectron
spectroscopy of the dye-sensitized nanocrystalline TiO2/electrolyte interface: Band gap states and their
interaction with dye and solvent molecules. J. Phys. Chem. C 2007, 111, 849–854. [CrossRef]
21. Liu, G.; Schulmeyer, T.; Thissen, A.; Klein, A.; Jaegermann, W. In situ preparation and interface
characterization of TiO2/Cu2S heterointerface. Appl. Phys. Lett. 2003, 82, 2269–2271. [CrossRef]
22. Henrich, V.E.; Dresselhaus, G.; Zeiger, H.J. Observation of Two-Dimensional Phases Associated with Defect
States on the Surface of TiO2. Phys. Rev. Lett. 1976, 36, 1335–1339. [CrossRef]
23. Thompson, T.L.; Diwald, O.; Yates, J.T. CO2 as a Probe for Monitoring the Surface Defects on
TiO2(110)Temperature-Programmed Desorption. J. Phys. Chem. B 2003, 107, 11700–11704. [CrossRef]
24. Borodin, A.; Reichling, M. Characterizing TiO2(110) surface states by their work function. Phys. Chem. Chem.
Phys. 2011, 13, 15442–15447. [CrossRef] [PubMed]
25. Klein, A.; Körber, C.; Wachau, A.; Säuberlich, F.; Gassenbauer, Y.; Schafranek, R.; Harvey, S.P.; Mason, T.O.
Surface Potentials of Magnetron Sputtered Transparent Conducting Oxides. Thin Solid Films 2009,
518, 1197–1203. [CrossRef]
26. Goniakowski, J.; Finocchi, F.; Noguera, C. Polarity of oxide surfaces and nanostructures. Rep. Prog. Phys.
2008, 71, 016501. [CrossRef]
27. Ishii, H.; Sugiyama, K.; Ito, E.; Seki, K. Energy Level Alignment and Interfacial Electronic Structures at
Organic/Metal and Organic/Organic Interfaces. Adv. Mater. 1999, 11, 605–625. [CrossRef]
28. Batzill, M.; Diebold, U. The surface and materials science of tin oxide. Prog. Surf. Sci. 2005, 79, 47–154.
[CrossRef]
29. Klein, A.; Körber, C.; Wachau, A.; Säuberlich, F.; Gassenbauer, Y.; Harvey, S.P.; Proffit, D.E.; Mason, T.O.
Transparent Conducting Oxides for Photovoltaics: Manipulation of Fermi Level, Work Function, and
Energy Band Alignment. Materials 2010, 3, 4892–4914. [CrossRef] [PubMed]
30. Hohmann, M.V.; Ágoston, P.; Wachau, A.; Bayer, T.J.M.; Brötz, J.; Albe, K.; Klein, A. Orientation
Dependent Ionization Potential of In 2O3: A Natural Source for Inhomogeneous Barrier Formation at
Electrode Interfaces in Organic Electronics. J. Phys. Condens. Matter 2011, 23, 334203. [CrossRef] [PubMed]
31. Wardenga, H.; Klein, A. Surface Potentials of (111), (110) and (100) oriented CeO2−x thin films. Appl. Surf.
Sci.
2016, 377, 1–8. [CrossRef]
32. Morgan, B.J.; Watson, G.W. A Density Functional Theory + U Study of Oxygen Vacancy Formation at the
(110), (100), (101), and (001) Surfaces of Rutile TiO2. J. Phys. Chem. C 2009, 113, 7322–7328. [CrossRef]
33. Cheng, H.; Selloni, A. Surface and subsurface oxygen vacancies in anatase TiO2 and differences with rutile.
Phys. Rev. B 2009, 79, 092101. [CrossRef]
34. Li, H.; Guo, Y.; Robertson, J. Calculation of TiO2 Surface and Subsurface Oxygen Vacancy by the Screened
Exchange Functional. J. Phys. Chem. C 2015, 119, 18160–18166. [CrossRef]
35. He, Y.; Dulub, O.; Cheng, H.; Selloni, A.; Diebold, U. Evidence for the Predominance of Subsurface
Defects on Reduced Anatase TiO2(101). Phys. Rev. Lett. 2009, 102, 106105. [CrossRef] [PubMed]
36. Bahnemann, D. Photocatalytic water treatment: solar energy applications. Solar Energy 2004, 77, 445–459.
[CrossRef]
37. Fujishima, A.; Zhang, X.; Tryk, D.A. TiO2 photocatalysis and related surface phenomena. Surf. Sci. Rep.
2008, 63, 515–582. [CrossRef]
38. De Angelis, F.; Valentin, C.D.; Fantacci, S.; Vittadini, A.; Selloni, A. Theoretical Studies on Anatase and
Less Common TiO2 Phases: Bulk, Surfaces, and Nanomaterials. Chem. Rev. 2014, 114, 9708–9753.
[CrossRef] [PubMed]
39. Bourikas, K.; Kordulis, C.; Lycourghiotis, A. Titanium Dioxide (Anatase and Rutile): Surface Chemistry,
Liquid-Solid Interface Chemistry, and Scientific Synthesis of Supported Catalysts. Chem. Rev. 2014,
114, 9754–9823. [CrossRef] [PubMed]
40. Pang, C.L.; Lindsay, R.; Thornton, G. Chemical reactions on rutile TiO2(110). Chem. Soc. Rev. 2008,
37, 2328–2353. [CrossRef] [PubMed]
41. Hussain, H.; Tocci, G.; Woolcot, T.; Torrelles, X.; Pang, C.L.; Humphrey, D.S.; Yim, C.M.; Grinter, D.C.;
Cabailh, G.; Bikondoa, O.; et al. Structure of a model TiO2 photocatalytic interface. Nat. Mater. 2017, 16,
461. [CrossRef] [PubMed]
42. Vittadini, A.; Selloni, A.; Rotzinger, F.P.; Grätzel, M. Structure and Energetics of Water Adsorbed at TiO2
Anatase (101) and (001) Surfaces. Phys. Rev. Lett. 1998, 81, 2954–2957. [CrossRef]
43. Aschauer, U.; He, Y.; Cheng, H.; Li, S.C.; Diebold, U.; Selloni, A. Influence of Subsurface Defects on the
Surface Reactivity of TiO2: Water on Anatase (101). J. Phys. Chem. C 2010, 114, 1278–1284. [CrossRef]
44. Li, Y.; Gao, Y. Interplay between Water and TiO2 Anatase (101) Surface with Subsurface Oxygen Vacancy.
Phys. Rev. Lett. 2014, 112, 206101. [CrossRef]
45. Jackman, M.J.; Thomas, A.G.; Muryn, C. Photoelectron Spectroscopy Study of Stoichiometric and
Reduced Anatase TiO2(101) Surfaces: The Effect of Subsurface Defects on Water Adsorption at Near-
Ambient Pressures. J. Phys. Chem. C 2015, 119, 13682–13690. [CrossRef]
46. Liu, L.; Zhao, H.; Andino, J.M.; Li, Y. Photocatalytic CO2 Reduction with H2O on TiO2 Nanocrystals:
Comparison of Anatase, Rutile, and Brookite Polymorphs and Exploration of Surface Chemistry. ACS
Catal. 2012, 2, 1817–1828. [CrossRef]
47. Duncan, D.; Allegretti, F.; Woodruff, D. Water does partially dissociate on the perfect TiO2 (110) surface:
A quantitative structure determination. Phys. Rev. B 2012, 86, 045411. [CrossRef]
48. Walle, L.E.; Borg, A.; Uvdal, P.; Sandell, A. Experimental evidence for mixed dissociative and molecular
adsorption of water on a rutile TiO2 (110) surface without oxygen vacancies. Phys. Rev. B 2009, 80, 235436.
[CrossRef]
49. Mu, R.; Zhao, Z.J.; Dohnálek, Z.; Gong, J. Structural motifs of water on metal oxide surfaces. Chem. Soc. Rev.
2017, 46, 1785–1806. [CrossRef] [PubMed]
50. Patrick, C.E.; Giustino, F. Structure of a water monolayer on the anatase TiO2 (101) surface. Phys. Rev. Appl.
2014, 2, 014001. [CrossRef]
51. Henrion, O.; Klein, A.; Pettenkofer, C.; Jaegermann, W. Low temperature adsorption of water on cleaved
GaAs(110) surfaces. Surf. Sci. Lett. 1996, 366, L685. [CrossRef]
52. Klein, A. Interface Properties of Dielectric Oxides. J. Am. Ceram. Soc. 2016, 99, 369–387. [CrossRef]
53. Wendt, S.; Sprunger, P.T.; Lira, E.; Madsen, G.K.H.; Li, Z.; Hansen, J.O.; Matthiesen, J.; Blekinge-
Rasmussen, A.; Lægsgaard, E.; Hammer, B.; et al. The Role of Interstitial Sites in the Ti3d Defect State in
the Band Gap of Titania. Science 2008, 320, 1755–1759. [CrossRef] [PubMed]
54. Li, M.; Hebenstreit, W.; Gross, L.; Diebold, U.; Henderson, M.A.; Jennison, D.R.; Schultz, P.A.; Sears, M.P.
Oxygen-induced restructuring of the TiO2(110) surface: A comprehensive study. Surf. Sci. 1999, 437, 173–
190. [CrossRef]
55. Wu, C.C.; Wu, C.I.; Sturm, J.C.; Kahn, A. Surface modification of indium tin oxide by plasma treatment:
An effective method to improve the efficiency, brightness, and reliability of organic light emitting devices.
Appl. Phys. Lett. 1997, 70, 1348. [CrossRef]
56. Klissurski, D.; Hadjiivanov, K.; Kantcheva, M.; Gyurova, L. Study of peroxide-modified titanium dioxide
(anatase). J. Chem. Soc. Faraday Trans. 1990, 86, 385–388. [CrossRef]
57. Iwamoto, M.; Yoda, Y.; Yamazoe, N.; Seiyama, T. Study of metal oxide catalysts by temperature
programmed desorption. 4. Oxygen adsorption on various metal oxides. J. Phys. Chem. 1978, 82, 2564–
2570. [CrossRef]
58. Bayer, T.J.M.; Wachau, A.; Fuchs, A.; Deuermeier, J.; Klein, A. Atomic layer deposition of Al 2O3 onto Sn-
doped In2O3: Absence of self-limited adsorption during initial growth by oxygen diffusion from the
substrate and band offset modification by Fermi level pinning in Al2O3. Chem. Mater. 2012, 24, 4503–4510.
[CrossRef]
59. Klein, A. Transparent Conducting Oxides: Electronic Structure - Property Relationship from
Photoelectron Spectroscopy with in-situ Sample Preparation. J. Am. Ceram. Soc. 2013, 96, 331–345.
[CrossRef]
60. Idriss, H.; Barteau, M.A. Characterization of TiO2 surfaces active for novel organic syntheses. Catal. Lett.
1994, 26, 123–139. [CrossRef]
61. Moulder, J.F.; Stickle, W.F.; Sobol, P.E.; Bomben, K.D. Handbook of X-ray Photoelectron Spectroscopy; Physical
Electronics, Inc.: Eden Prairie, MN, USA, 1995.
62. Yesodharan, E.; Grätzel, M. Photodecomposition of Liquid Water with TiO2? Supported Noble Metal
Clusters. Helv. Chim. Acta 1983, 66, 2145–2153. [CrossRef]
63. Kodaira, S.; Sakisaka, Y.; Maruyama, T.; Haruyama, Y.; Aiura, Y.; Kato, H. Angle-resolved photoemission
study of an in-gap state in TiO2. Solid State Commun. 1994, 89, 9–12. [CrossRef]
64. Finazzi, E.; Valentin, C.D.; Pacchioni, G.; Selloni, A. Excess electron states in reduced bulk anatase TiO2:
Comparison of standard GGA, GGA+U, and hybrid DFT calculations. J. Chem. Phys. 2008, 129, 154113.
[CrossRef] [PubMed]
65. Ohno, T.; Sarukawa, K.; Matsumura, M. Crystal faces of rutile and anatase TiO2 particles and their roles in
photocatalytic reactions. New J. Chem. 2002, 26, 1167–1170. [CrossRef]
66. Yu, J.; Low, J.; Xiao, W.; Zhou, P.; Jaroniec, M. Enhanced Photocatalytic CO2-Reduction Activity of Anatase
TiO2 by Coexposed 001 and 101 Facets. J. Am. Chem. Soc. 2014, 136, 8839–8842. [CrossRef] [PubMed]
67. Dette, C.; Pérez-Osorio, M.A.; Kley, C.S.; Punke, P.; Patrick, C.E.; Jacobson, P.; Giustino, F.; Jung, S.J.; Kern,
K. TiO2 Anatase with a Bandgap in the Visible Region. Nano Lett. 2014, 14, 6533–6538. [CrossRef]
[PubMed]
68. King, P.D.C.; Veal, T.D.; Fuchs, F.; Wang, C.Y.; Payne, D.J.; Bourlange, A.; Zhang, H.; Bell, G.R.; Cimalla, V.;
Ambacher, O.; et al. Band gap, electronic structure, and surface electron accumulation of cubic and
rhombohedral In2O3. Phys. Rev. B 2009, 79, 205211. [CrossRef]
69. Berthold, T.; Rombach, J.; Stauden, T.; Polyakov, V.; Cimalla, V.; Krischok, S.; Bierwagen, O.; Himmerlich,
M.
Consequences of plasma oxidation and vacuum annealing on the chemical properties and electron
accumulation of In2O3 surfaces. J. Appl. Phys. 2016, 120, 245301. [CrossRef]
70. Vasheghani Farahani, S.K.; Veal, T.D.; Mudd, J.J.; Scanlon, D.O.; Watson, G.W.; Bierwagen, O.; White, M.E.;
Speck, J.S.; McConville, C.F. Valence-band density of states and surface electron accumulation in epitaxial
SnO2 films. Phys. Rev. B 2014, 90, 155413. [CrossRef]
71. Körber, C.; Ágoston, P.; Klein, A. Surface and Bulk Properties of Sputter Deposited Intrinsic and Doped
SnO2 Thin Films. Sens. Actuators B 2009, 139, 665–672. [CrossRef]
72. Rachut, K.; Körber, C.; Brötz, J.; Klein, A. Growth and Surface Properties of Epitaxial SnO2. Phys. Stat. Sol.
(A) 2014, 211, 1997–2004. [CrossRef]
73. Batzill, M.; Katsiev, K.; Burst, J.M.; Diebold, U.; Chaka, A.M.; Delley, B. Gas-phase-dependent properties
of SnO2 (110), (100), and (101) single-crystal surfaces: Structure, composition, and electronic properties.
Phys. Rev. B 2005, 72, 165414. [CrossRef]
74. Cox, D.F.; Fryberger, T.B.; Semancik, S. Oxygen vacancies and defect electronic states on the SnO2(110)-1×1
surface. Phys. Rev. B 1988, 38, 2072–2083. [CrossRef]
75. Ágoston, P.; Albe, K. Disordered reconstructions of the reduced SnO 2-(110) surface . Surf. Sci. 2011,
605, 714–722. [CrossRef]
76. Deák, P.; Aradi, B.; Frauenheim, T. Band Lineup and Charge Carrier Separation in Mixed Rutile-Anatase
Systems. J. Phys. Chem. C 2011, 115, 3443–3446. [CrossRef]
77. Scanlon, D.O.; Dunnill, C.W.; Buckeridge, J.; Shevlin, S.A.; Logsdail, A.J.; Woodley, S.M.; Catlow, C.R.A.;
Powell, M.J.; Palgrave, R.G.; Parkin, I.P.; et al. Band alignment of rutile and anatase TiO 2. Nat. Mater. 2013,
12, 798. [CrossRef] [PubMed]

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