Article

pubs.acs.org/JPCC

Searching for the Formation of Ti−B Bonds in B‑Doped TiO2−Rutile

Luca Artiglia, Davide Lazzari, Stefano Agnoli, Gian Andrea Rizzi, and Gaetano Granozzi*
Department of Chemical Sciences, Università di Padova, Via Marzolo 1, I-35131 Padova, Italy

ABSTRACT: Surface B-doped TiO2−rutile (110) single crystals obtained through

different approaches have been characterized by X-ray photoelectron spectroscopy
(XPS), and their thermal stability investigated. The thermal decomposition of
dimethylaminoborane on the clean TiO2(110) surface, both stoichiometric and
understoichiometric (Ar+ sputtered), leads to a complete B oxidation to B2O3, which
segregates from the TiO2. B-ion implantation (using B2H6 as a source) has allowed us to
obtain both B2O3 and interstitial B doping, which is stable at high temperature. Two
further methods were developed to deposit B in a titanium-rich surface, either by reactive
Ti evaporation in B2H6 or by dosing B2H6 on a thin Ti overlayer. In both cases, Ti−B
bonds were formed, due to the creation of substitutional B and boride-like compounds,
but after a thermal treatment, they converted into B−O bonds, demonstrating that, in all
cases, the system tends to evolve to the most stable species (B2O3). The reported XPS
data represent useful benchmarks to characterize B-doped titania materials.

1. INTRODUCTION positions, or replace Ti, resulting in different geometries with

Because of its low cost, green character, long-term stability, and
high oxidative power, titania (TiO2) is a leading material in the
field of photocatalysis.1,2 It finds application in the photo-
decomposition of water,3 in dye-sensitized solar cells,4−6 in the
photocatalytic degradation of pollutants, and photoelectro-
chemical conversion of solar energy.7,8 However, the relatively
wide band gap of this material (3.2 eV for anatase and 3.0 eV
for rutile) limits its potential photocatalytic applications to the
UV range (λ < 387 nm), which corresponds to about 5% of the
total solar spectrum power.
To increase the light harvesting, many strategies have been
adopted based on doping the oxide with either a transition
metal9 or nonmetal heteroatoms.10,11 The addition of d group
elements in the TiO2 lattice can shift the absorption edge in the
visible region, and many attempts have been carried on using
Cr, Co, or Fe.12−15 However, the observed increase in the
photocatalytic activity is often offset by thermal instability and
high charge carrier recombination rates.13,16,17
On the contrary, the use of nonmetal anionic dopants, such
as N,8,18−24 C,25−27 S,28 F,29,30 Br,31 and I,32 has attracted a
great amount of interest for two main reasons:
(i) They can introduce localized states in the TiO2 band gap,
thus allowing visible light absorption.8,11,33,34
(ii) They maintain the conduction band minimum as high as
that of the pure oxide and, in any case, higher than the
H2O/H2 reduction potential (to ensure the photo-
reduction activity).8
To obtain a narrower TiO2 band gap and an enhancement of
the electron−hole pair lifetime, some studies have recently
focused on boron-doped TiO2 (B-TiO2),35−38 including also B
codoping with other nonmetal elements (e.g., codopant with
N).36,39 However, these studies are not abundant and their
results somewhat contradictory.10 As recently shown by Geng
et al.,40 B atoms can either substitute oxygen, sit in interstitial
specific electronic structures. The conflicting results might
reflect diverse structural situations that are associated with the
sample preparation procedure. In fact, while theoretical analysis
investigate single TiO2 polymorphs, powder samples, used to
perform photocatalysis experiments, are often composed of a
mixture of polymorphs. The modeling of experimental data can
be, therefore, biased by the difficulties in excluding the
coexistence of small amounts of a second TiO2 phase/
polymorphs. This highlights the importance of preparing and
characterizing well-defined systems adopting a rigorous surface
science based approach.
The study of structural aspects has been tackled recently
using density functional theory (DFT) calculations, both in the
case of anatase11 and rutile41 polymorphs. In bulk anatase,11
both a paramagnetic species, [BTi3]•, and a diamagnetic
species, BO3, corresponding to substitutional and interstitial
boron, respectively, have been described. The possibility to
have B interstitial and/or substitutional, preferentially located
on the surface or homogeneously distributed in the bulk,
strongly depends on the preparation methodology. As an
example, segregation of large amounts of photocatalytically
inactive bulk B2O3 is favored at high B loadings (see ref 10 and
paper therein cited). The [BTi3]• center, resulting from O
substitution, introduces new states positioned quite high in the
gap, leading to a red shift in the absorption of the material. On
the other hand, interstitial boron can easily transfer three
valence electrons to the 3d states of the lattice Ti ions.11 In the
case of rutile B-TiO2, DFT calculations have been carried out in
both oxygen-rich42 and titanium-rich43 conditions.41
According to these results:
Received: May 7, 2013
Revised: June 2, 2013
Published: June 6, 2013

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(i) Interstitial B is the most stable species. In this
configuration, B atoms adopt an sp3 hybridization,
forming a tetrahedral structure, with four oxygen atoms
at the edges, and is fully oxidized (calculated charge of
+0.6), in good agreement with other calculations made
on anatase.11
(ii) Under titanium-rich conditions, the formation of substitu-
tional B is favored (negative defect formation energy).
(iii) Interstitial B could be responsible for the calculated blue
shift of the absorption spectra in B-TiO2 samples.44
In this paper, adopting a rigorous surface science based
approach, that is, using a rutile TiO2 single crystal and ultra-
high-vacuum (UHV) preparative strategies, we report the
results of a comprehensive search of the conditions for the
formation of direct Ti−B or interstitial B bonds (see Figure 1).
Figure 1. Schematic representation of the B-doped TiO2−rutile (110)
crystal: (a) substitutional B, (b) interstitial B, in a tetrahedral
configuration.
Methods under either thermodynamic (i.e., thermal decom-
position of B-containing precursors) or kinetic control (i.e., B-
ion implantation and sputtering) were adopted, and the
achievement of interstitial or substitutional B doping was
monitored by using X-ray photoelectron spectroscopy (XPS).
We used a TiO2−rutile single crystal exposing the (110)
surface, that is, the most stable and well-characterized crystal
face of rutile.45 Our aim is to verify experimentally the results of
the literature DFT calculations, in order to understand what are
the chemical species formed after different treatments and
whether it is possible to influence the type of defect formed by
changing the sample preparation procedure and/or the boron
deposition strategy.
2. EXPERIMENTAL SECTION
All the experiments have been carried out in a multitechnique
ultra-high-vacuum facility consisting of two separate chambers:
a preparation and an analysis chamber. The former is equipped
with a four-grid rear-view LEED (Omicron), a hot cathode ion
gun (VG), a water-cooled e-beam evaporator (Ti evaporation
from rod), a residual gas analyzer (RGA − Pfeiffer PRISMA),
and gas lines connected with leak valves. The analysis chamber
is equipped with a twin (Mg/Al) anode X-ray source (VG
MKII) and a hemispherical electrostatic analyzer with a five
channeltron detector (VG-ESCALAB). All the displayed XPS
spectra have been acquired using a Mg anode (1253.6 eV). The
sample was mounted on a manipulator with five degrees of
freedom. Heating was performed by means of a pyrolytic boron
nitride (PBN) stage, and the temperature was measured with a
K-type thermocouple in direct contact with the sample surface.
The TiO2−rutile (110) single crystal (Mateck) was cleaned by
several cycles of Ar+ sputtering, followed by annealing in UHV
at 950 K until no C 1s signal was detectable by XPS and a clear
(1 × 1) surface reconstruction was observed by LEED.
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Dimethylaminoborane (DMAB) (97%, Aldrich) was dosed
from a CF flanged glass test tube connected to a gas line, after
several freeze pumping cycles for purification. The presence
and purity of the precursor were checked by means of the RGA.
DMAB was dosed (5.0·10−6 mbar) on the TiO2 single crystal
surface at room temperature (RT), and its adsorption was
confirmed by the presence of B 1s, N 1s, and C 1s
photoemission peaks. The decomposition of the precursor
was studied by XPS after sample heating at increasing
temperature in the RT−870 K range. Already at 720 K, no
traces of C or N were detected, whereas the only peak was B 1s,
indicating a complete decomposition of the DMAB precursor.
Diborane (B2H6, 1% in He, Voltaix gas) was dosed at RT from
a gas line in direct connection with the preparation chamber.
The Ti evaporator (e-beam, Tectra) was calibrated by angle
resolved (AR)-XPS, after Ti deposition on a clean Cu foil
substrate, using the overlayer calibration function procedure,46
that allowed an estimate of the equivalent monolayer (ML) by
dividing the total measured thickness by the interlayer spacing
(2.94 Å) of Ti.
3. RESULTS AND DISCUSSION
All the experimental reports about B-TiO2 adopt XPS as the
main tool to identify, through the B 1s core level peak position
and shape, the boron oxidation states.35,39,47−49 We will follow
a similar procedure, and the literature data reported in the
following will be taken as a reference. B 1s BE for boron oxide
(B2O3) is in the 192.8−194 eV range, whereas, for titanium
boride (TiB2), it is in the 187.5−188.0 eV range, a BE similar to
that of elemental B.36 It is to be outlined that TiB2 has a
peculiar layered structure,50 whereas, in B2O3, interconnected
BO3 triangles are present, where B is at the center of a trigonal
coordination. When B occupies an interstitial site in titania (see
Figure 1b), a BE in the 191.5−192.0 eV range has been
documented.39,47−49 Substitutional B (i.e., BTi3 bonds; see
Figure 1a) has been reported in one case (anatase) and
associated with a BE value of 190.6 eV.36 On the other hand,
DFT calculations predict that, when B substitutes O in the
titania anatase lattice, the B 1s peak position should be
negatively shifted by about 4.8 eV with respect to B in its
highest oxidation state, thus in the 188.0−189.2 eV range.51
In the following, we will describe the XPS results obtained on
B-TiO2 samples obtained by different preparation procedures in
UHV starting from TiO2(110).
3.1. In Situ Decomposition of Dimethylaminoborane
(DMAB). DMAB has been chosen due to its relatively high
vapor pressure, which allowed us to easily dose it on the titania
single crystal by a gas line connected to the preparation
chamber. Moreover, as already reported in the Experimental
Section, its decomposition guarantees a clean doping of the
TiO2 surface, since neither C nor N are present above 700 K
(as gathered from XPS). Several attempts have been carried
out, changing both the deposition time and the temperature of
the sample, but we will report herein only the data of a 30 min
dosing of DMAB (5.0·10−6 mbar), corresponding to a total
amount of about 6900 Langmuir (L), performed at a
temperature of 720 K. An elemental analysis based on the
photoemission peaks intensities reveals a 8 at % of deposited
boron.
XPS data reported in Figure 2a show that the Ti 2p peak
corresponding to the clean (as-prepared) surface is single and
centered at 459.0 eV (2p3/2), a typical Ti4+ BE value.45 The data
collected after DMAB dosing (black) show a low BE shoulder,
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Figure 2. Photoemission spectra (hν = 1253.6 eV) of theTiO2(110) single crystal collected before (clean) and after the decomposition of DMAB on
a crystal held at 720 K and after thermal treatments at 920 K: (a) Ti 2p, (b) difference spectra between the Ti 2p signals normalized areas, (c) B 1s
and (d) O 1s regions.
which corresponds to Ti in a reduced oxidation state (hereafter
TiOx). The area of this component is 4% of the overall peak
intensity. It is important to point out that the same thermal
treatment (30 min at 720 K) performed on a clean sample,
without dosing DMAB, does not lead to the formation of TiOx.
To test the stability of TiOx, we have performed two
consecutive thermal treatments at 920 K: 5 and 15 (a total of
20) min. The respective Ti 2p lines (blue and green) show that
the first thermal treatment does not substantially modify the
peak shape, whereas the second restores almost completely the
pristine stoichiometry. Figure 2b is useful to put better in
evidence the discussed XPS data: we have normalized the Ti 2p
spectra areas and then calculated a difference spectrum by
subtracting the curve corresponding to the clean TiO2 from the
other spectra. The results show that, immediately after the
DMAB decomposition, a reduction of TiO2 occurs (Ti4+ at
459.0 eV) and substoichiometric TiOx (457.0 eV) is formed.
The first annealing results in a small decrease of the 457.0 eV
area, and it is necessary to heat the sample for 20 min to
reoxidize almost all the defects (migration of O2− ions through
the crystal lattice).
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The analysis of the B and O 1s signals (Figure 2c,d) is
necessary to understand how B interacts with the substrate and
whether it is responsible for the TiOx defect creation. The B 1s
signal (Figure 2c) presents a single peak centered at 192.8 eV, a
BE value in agreement with the formation of oxidized boron
(B2O3).39,47−49 No peak asymmetry is evident, so we can
exclude the presence of both interstitial and substitutional B
atoms. Thermal treatments do not change either the peak shape
or its intensity, in good agreement with the full oxidation of
boron (to form B2O3). The O 1s line-shape analysis (Figure
2d) provides important information: after DMAB decom-
position, the peak clearly broadens and can be separated into
three components, 530.2, 531.6, and 532.7 eV (labeled as 1, 2,
and 3, respectively, in Figure 2d). The first corresponds to the
TiO2 crystal lattice oxygen (comparison with the spectrum of
the clean rutile), the second to surface −OH groups (formed
during DMAB decomposition), and the latter to B−O bonds.49
It is noteworthy that, as observed for B 1s, the peak shape does
not change after a thermal treatment, suggesting a high stability
of the system.
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Figure 3. Photoemission spectra (hν = 1253.6 eV) of the TiO2(110) single crystal collected on the clean surface, after 5 min of Ar+ sputtering at 1.0
keV, after the decomposition of DMAB on a crystal held at 720 K and after thermal treatment at 920 K (20 min): (a) Ti 2p, (b) B 1s regions.
Therefore, summarizing all the experimental results, when
DMAB is decomposed on the clean TiO2−rutile (110) surface
held at 720 K, a reaction takes place between DMAB and the
substrate, so that boron is oxidized by TiO2 to form B2O3
(probably segregated), TiOx, and Ti−OH. Both B−O and Ti−
OH bonds are very stable, whereas TiOx defects disappear after
prolonged thermal treatment at 920 K (20 min). This behavior
suggests that a temperature mediated migration of oxygen from
the crystal bulk is the responsible for the defects healing.
Another important point emerging from our results is that, by
simply decomposing a boron-containing precursor on the
stoichiometric (1 × 1) surface of TiO2(110), neither interstitial
nor substitutional boron is formed. This is in agreement with
DFT calculations, which predict the instability of a substitu-
tional dopant (either to O or to Ti) on an oxygen-rich surface.41
We can conclude that, even though DMAB does not contain
oxygen and no oxygen is dosed during its decomposition, the
energy gain deriving from the formation of three BO bonds
(enthalpy of formation 536 kJ/mol) drives the reaction, leading
to the unique formation of B2O3 patches.
3.2. In situ Decomposition of DMAB on a Sputtered
TiO2 Surface. In Figure 3a, we report the effect of a 5 min Ar+
sputtering at an energy of 1.0 keV on the clean (1 × 1) surface
of rutile (110). The Ti 2p peaks broaden, so that a shoulder in
the 454−457 eV range is observed. The higher sputtering yield
of oxygen allows us to obtain a set of understoichiometric states
of TiO2 (TiOx), thus providing titanium-rich conditions. In
these conditions, according to DFT calculations,41 the
formation of both substitutional and interstitial boron should
be favored. After DMAB decomposition, performed with the
same procedure described above, a clear decrease in the
shoulder corresponding to TiOx is visible. This healing effect is
due to the O2− ion migration from the crystal bulk during the
DMAB decomposition, performed at 720 K. B 1s (Figure 3b)
shows a symmetric, single component peak centered at 192.8
eV, just like the spectrum acquired after DMAB decomposition
performed on the oxygen-rich surface. A 20 min thermal
treatment at 920 K restores the TiO2 stoichiometry and does
not have any effect on the B 1s peak. Thus, the XPS data show
that, although the sputtering treatment removes the TiO2
lattice oxygen, creating understoichiometric TiOx, this is not
enough to prevent a complete boron oxidation during DMAB
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decomposition; that is, TiO2 is a reducible oxide with high
oxygen mobility that ensures a good oxygen reservoir for B to
be oxidized. In other words, thermodynamics seems to govern
all processes also in this case.
3.3. Ion Implantation of the TiO2 Surface with B2H6.
We then checked the outcome of a preparative route that is
surely far from thermodynamic equilibrium. Ion implantation
has been performed using a 1% B2H6 in He gas mixture at an
ion energy of 1.0 keV for 30 min with the crystal at RT. The
aim of the experiment was to partially reduce the crystal surface
by sputtering (even if He+ leads to a lower oxygen sputtering
yield) and, at the same time, to implant B ions in an oxygen-
depleted environment.52 An elemental analysis based on the
XPS peaks intensities reveals a total of 4 at % of deposited
boron using this strategy. After ion implantation, the loss of
surface reconstruction is confirmed by the absence of the
pristine (1 × 1) LEED pattern.
The XPS analysis (Figure 4a, black) shows that TiO2 is
partially reduced as a consequence of ion sputtering (mainly
due to He+), as demonstrated by the appearance of a low BE
shoulder due to TiOx in the Ti 2p spectrum. As expected, its
intensity is lower if compared to the Ti 2p spectrum shown in
Figure 3a (black), where the peaks are broader and more
intense due to the higher sputtering yield due to Ar+ ions. The
B 1s line shows a broad peak, centered at about 192.4 eV, which
can be separated into two components, labeled 1 and 2 (Figure
4c, red). Peak 1, centered at 192.8 eV, is due to BO3 bonds of
the oxide (B2O3), whereas peak 2, centered at 191.5 eV, after a
comparison with the literature data, can be ascribed to
interstitial boron.
The relative intensity of the peak 2 component is ca. 20% of
the overall B 1s signal. If we compare the position and shape of
the peak obtained after DMAB decomposition at 720 K
(oxygen-rich conditions, Figure 4c, blue) and after B2H6
sputtering (Figure 4c, red),53 it is possible to observe a shift
of the peak by ca. 0.4 eV and a larger fwhm, due to the presence
of multiple components.
After a 20 min thermal treatment at 920 K, the Ti 2p line
shape is comparable to that of the clean, stoichiometric
TiO2(110) (Figure 4a, blue). Moreover, LEED reveals the
presence of a (1 × 1) pattern, due to the TiO2 surface
reconstruction.
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Figure 4. Photoemission spectra (hν = 1253.6 eV) of the TiO2(110) single crystal collected on the clean surface, after 30 min of B2H6 (1% in He)
ion implantation and after thermal treatment at 920 K (20 min): (a) Ti 2p, (b) B 1s, (c) B 1s signal separated into two components compared with
the DMAB decomposition procedure, (d) O 1s.
Surprisingly, the B 1s spectrum shows a further peak
broadening toward lower BE: the peak deconvolution into
components 1 and 2 results in a slight increase of the interstitial
B area from 20% to 25%. The O 1s XPS spectra (Figure 4d) are
in tune with the B 1s behavior: immediately after ion
implantation, the peak broadens (Figure 4d, black) and its
shape is similar to that shown in Figure 2d (after DMAB
decomposition). Nevertheless, after an annealing at 920 K, the
high BE shoulder intensity decreases, even though the peak
does not overlap with that of the clean TiO2 due to the
presence of residual −OH and B−O bonds.
To summarize this section, ion implantation of B2H6 (1% in
He) promotes the formation of interstitial B, which is still
present after recovering the TiO2 stoichiometry and the (1 × 1)
surface reconstruction.54 A possible reason to explain this could
be that the energy given to B2H6 ions impinging on the surface
is enough to form stable interstitial dopant sites, which are still
present after the surface reconstruction. The slight increase in
the interstitial B percentage could be due both to the reaction
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of B2O3 aggregates with TiOx during the thermal treatment and
to a B2O3 migration toward the TiO2 substrate bulk.
3.4. Reactive Deposition of 2.0 ML of Ti on TiO2(110)
in a B2H6 Background. We developed a further strategy to
realize a titanium-rich surface in the attempt to create Ti−B
bonds: 2.0 ML of metallic Ti was deposited at RT on
TiO2(110) from an e-beam evaporator in a B2H6 background
(3.0·10−6 mbar), so testing a kind of reactive deposition.
Although it is well-known that, when Ti is evaporated on a
stoichiometric TiO2 surface, a reaction takes place between the
metal and the oxide, leading to the growth of a TiOx buffer
layer,55 our aim was to dose our precursor (B2H6) in a
reducing, titanium-rich, environment. Figure 5a (black) shows
that, after the reactive deposition, the Ti 2p peaks broaden, as a
consequence of the creation of understoichiometric TiOx on
the substrate surface. The B 1s signal (Figure 5b, black) has a
complex line shape due to the presence of multiple
components. In particular, two peaks are distinguished, at
192.4 and 188.5 eV.
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Figure 5. Photoemission spectra (hν = 1253.6 eV) of the TiO2(110) single crystal collected on the clean surface, after the reactive deposition at RT
of 2.0 ML of Ti in a B2H6 background and after thermal treatments at 470 and 770 K: (a) Ti 2p, (b) B 1s with peak deconvolution, (c) B 1s peak
components analysis vs temperature.
The whole curve can be actually fitted with four components,
numerically labeled from 1 to 4. Components 1 and 2, centered
at 192.8 and 191.5 eV, can be ascribed to oxidized (B2O3) and
interstitial boron, in agreement with the results reported in the
previous paragraph. Component 3, centered at 188.7 eV, can be
assigned to substitutional B, and component 4, centered at
187.5 eV, is probably due to the formation of Ti−B bonds
reminiscent of TiB2 (hereafter TiB2-like).56 It is to be outlined
that our XPS data for a supposed substitutional B are
positioned to a lower BE value than the ones reported in the
literature,36 but in good agreement with theoretical predic-
tions.51
To test the stability of the reduced B 1s components, we
treated the sample at increasing temperatures. During a first
heating step, the temperature was increased to 470 K for 5 min.
The Ti 2p spectrum (Figure 5a, blue) shows that the peaks
become narrower, presumably due to a small oxidation of the
substoichiometric Ti ions. At the same time, also the shape of
the B 1s peak changes (Figure 5b, blue): a clear reduction of
the 188.5 eV peak takes place, while the 192.4 eV intensity
increases. A further temperature increase to 770 K (5 min)
causes the disappearance of the low BE peak (Figure 5b, green)
while a single peak remains at 192.4 eV, in analogy with those
observed previously.
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The B 1s components area evolution is shown in Figure 5c,
to put in evidence how the overall peak area modifies after each
temperature increase. It is possible to observe that, after heating
at 470 K, the intensity decrease of components 3 and 4
corresponds to an increase in both components 1 and 2. This
means that a mild thermal treatment is enough to allow the
conversion of part of the substitutional and TiB2-like boron to
interstitial and oxidized B, in agreement with DFT
calculation.41
After the following thermal treatment at 770 K, both
components 3 and 4 go to zero, component 2 decreases, and
component 1 shows a steep increase. This is in tune with the
conversion of all the reduced B components (3 and 4) to
oxidized ones. The overall behavior shown by this graph
indicates that, although, by depositing Ti in a reducing B2H6
background, it is possible to obtain both substitutional and
TiB2-like boron, these arrangements are not stable. Their
tendency is to evolve to more oxidized species: a mild thermal
treatment promotes the formation of both interstitial B and
B2O3, whereas an increase in the temperature is enough to drive
the reaction to the most stable product, the oxide (B2O3). This
clearly indicates that B substitutional doping of a TiO2 surface
is not favored for the following reasons:
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Figure 6. Photoemission spectra (hν = 1253.6 eV) of the TiO2(110) single crystal collected on the clean surface, after the dosing of B2H6 on a 5.0
ML Ti film and after thermal treatments in the RT−870 K range: (a) Ti 2p, (b) B 1s with peak deconvolution, (c) B 1s peak components analysis vs
temperature.
(i) It is hard to realize titanium-rich conditions on a
reducible oxide like TiO2.
(ii) The system tendency is to evolve in each situation to the
formation of boron oxide, which is the most stable
product.
3.5. Dosing of B2H6 on a 5 ML Ti Film Deposited on
TiO2(110). The last procedure we adopted to induce titanium-
rich conditions was the following: we deposited 5 ML of Ti on
TiO2(110) and then dosed B2H6 (p = 5·10−6 mbar) for 15 min
(about 3450 L) at RT. An amount of 5 ML was necessary to
obtain metallic Ti on the surface, as shown in Figure 6a by the
presence of a peak at 453.6 eV in the Ti 2p spectrum. The B 1s
signal (Figure 6b) shows two distinct peaks, in agreement with
the results discussed in the previous paragraph. Also, in this
case, it is possible to separate four components: 187.5 eV, due
to TiB2-like boron (component 4), 188.7 eV to substitutional B
(component 3), 191.5 eV to interstitial B (component 2), and
192.8 eV, to B2O3 patches (component 1).
A thermal treatment in the 320−870 K range was performed,
keeping the sample at each intermediate temperature for 5 min,
to observe the evolution of the B 1s components. A progressive
reduction of the low BE peak (187.5 eV), together with a shift
to higher BE (ca. 188 eV), is present, whereas the 191.5 eV
peak intensity increases and shifts to ca. 192.0 eV.
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This behavior is in tune with the temperature-driven
disappearance of the reduced components, which can be
converted into either interstitial or oxidized boron. A plot
reporting the evolution of each component as a function of the
temperature is reported in Figure 6c. Both peak 3 and 4 areas
gradually decrease, so that, after the last annealing (870 K),
they completely disappear. The component 2 area increases in
the 320−470 K range and then remains almost constant,
whereas component 1, whose intensity is the lowest at 320 K,
shows a steep increase and becomes the main after thermal
treatment at 870 K. It is important to point out that the overall
B 1s peak area does not substantially change in the whole
(320−870 K) temperature range, thus confirming that there is
no B migration inside the crystal bulk. As also pointed out in
the previous paragraph, even after the last annealing cycle, the
Ti 2p peak does not recover its pristine shape, showing a
reduced shoulder that suggests the presence of under-
stoichiometric TiOx.
The presented data can be rationalized as follows: in
agreement with the literature data,55 after 5 ML Ti deposition,
the TiO2(110) surface is covered by a buffer layer of TiOx,
resulting from the reaction between evaporated Ti and the
surface O ions, and a topmost metallic film. Therefore, dosed
B2H6 can interact directly with metallic Ti on the sample
surface. This is the main difference between this procedure and
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the reactive deposition described above: in the previous case,
we created a homogeneous doped layer, whereas, in this case,
just a doped surface. This is the reason why only a minor B2O3
component is observed immediately after B2H6 dosing. It is also
interesting to note that the interstitial B (component 2) area is
higher than that of component 1, demonstrating that, in
extreme titanium-rich conditions, the formation of B−O−Ti
bonds is favored over the B−O ones. TiB2-like bonds
(component 4), formed after the chemisorption of B2H6 on
the metal, is the main component, whereas substitutional B
(component 3) is a minority component, and this could be due
to the small amount of TiOx available on the surface.
The evolution of the system as a function of the temperature
follows the behavior observed in the case of Ti reactive growth
in a B2H6 background. It is clear that a temperature increase
promotes the migration of O2− ions from the TiO2 crystal bulk,
thus allowing the oxidation of Ti and TiOx to TiO2. Also, the
reduced B 1s components are metastable and gradually convert
to B−O bonds. In these titanium-rich conditions, interstitial B is
particularly stable; in fact, its area remains stable even after the
last thermal treatment. The presence of a thick TiOx buffer
layer could hinder the oxidation of Ti−O−B bonds by reacting
with the O ions migrating from the bulk.
4. CONCLUSION
In the present study, we adopted different doping strategies to
investigate the B doping of TiO2−rutile (110), monitored by X-
ray photoemission spectroscopy.
The thermal decomposition of dimethylaminoborane pre-
cursor on the clean TiO2(110) surface, both stoichiometric and
understoichiometric (Ar+-sputtered), leads to a complete B
oxidation to B2O3, most probably as segregated patches. When
a stoichiometric surface is used, after the precursor decom-
position, TiO2 is left partially reduced, so that Ti 3d states are
displayed in the spectra as a lower BE shoulder (TiOx).
Therefore, these defects could contribute to the photocatalytic
enhancement reported in many experimental works, where an
increase in the light absorption intensity is observed.47−49
Ion implantation, a far from equilibrium technique, using a
gas mixture of He and B2H6, leads to the formation of
interstitial B, which remains stable also after thermal treatments
that restore the substrate surface reconstruction and
stoichiometry. This deposition strategy has been successfully
used to obtain N-doped TiO2 nanotubes with good photo-
catalytic activity.57 We are planning to test such a procedure for
B-TiO2 in mild conditions to test the role of interstitial B in the
B-TiO2 photocatalytic activity.
The reactive deposition of Ti in a B2H6 background and the
dosing of B2H6 on a 5 ML thick Ti film deposited on
TiO2(110) were the only preparation procedures that allowed
us to obtain Ti−B bonds. In both cases, a B 1s reduced
component has been found in the 188.5−188.7 eV range, a BE
value that is in tune with theoretical calculations for
substitutional B-TiO2 in anatase.51 To the best of our
knowledge, this is the first XPS experimental determination
of substitutional B in rutile and can be considered as a reference
for this local structure, although tentative assignments of
substitutional B in anatase have been reported in the past by
Fittipaldi et al. through EPR experiments.38 However, an
analysis of the stability of this structural arrangement as a
function of temperature has revealed that, even after a mild
treatment, the relative XPS peak intensity decreases, so that
Ti−B bonds are converted into either Ti−O−B (interstitial
13170
Article
dopant) or B−O (B2O3). A further increase in the temperature
is enough to convert all the B−Ti bonds into B2O3, in good
agreement with the results of DFT calculations.41 Therefore,
Ti−B bonds can be formed only in extreme titanium-rich
conditions and are metastable, since they convert into B−O in
mild conditions, as a consequence of O2− migration from the
TiO2 bulk. Another interesting result is that, in the case of the
reactive deposition, interstitial B tends to convert to B2O3, once
again demonstrating that the oxide is the most stable formed
species. The only situation where interstitial B is stable at high
temperature is in the case of B2H6 dosing on 5 ML of Ti. The
presence of a TiOx buffer layer separating the bulk from the
doped surface could slow down the O migration and thus the
complete B oxidation.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: gaetano.granozzi@unipd.it.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work has been funded by the Italian Ministry of
Instruction, University and Research (MIUR) through the
FIRB Project RBAP115AYN “Oxides at the nanoscale:
multifunctionality and applications”, and through the fund
“Programs of national relevance” (PRIN-2009). We thank Prof.
E. Selli (University of Milano) for useful discussions.
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