J Mater Sci (2020) 55:3774–3794

Ceramics
CERAMICS

Contamination of TiO2 thin films spin coated

on borosilicate and rutile substrates
I. I. Kabir1,* , L. R. Sheppard2 , R. Shamiri1 , P. Koshy1 , R. Liu3 , W. Joe1 ,
A. Le1 , X. Lu1 , W.-F. Chen1 , and C. C. Sorrell1

1
School of Materials Science and Engineering, UNSW Sydney, Sydney, NSW 2052, Australia
2
School of Computing, Engineering and Mathematics, Western Sydney University, Penrith, NSW 2751, Australia
3
Office of the Deputy Vice Chancellor, Research and Development, Western Sydney University, Penrith, NSW 2751, Australia

Received: 28 August 2019 ABSTRACT

Accepted: 6 December 2019
Published online:
16 December 2019
 Springer Science+Business
Media, LLC, part of Springer
Nature 2019
The present work reports data for TiO2 thin films on borosilicate glass and (001)
single-crystal TiO2, annealed at 200–550 C for 8 h. Characterization included
GAXRD, laser Raman microspectroscopy, AFM, UV–Vis, XPS, SIMS, TEM,
ellipsometry, and methylene blue (MB) dye degradation. The substrate deter-
mined the TiO2 polymorph that formed, while the annealing temperature and
boron contamination from the substrate determined most of the associated
properties. The films on glass substrates were amorphous following annealing
at 200 C but were anatase at higher temperatures. The films on rutile exhibited
epitaxial growth at all annealing temperatures. Annealing caused diffusion of
glass component elements into the films and counterdiffusion of Ti into the glass
substrates. Since aqueous MB testing caused decreased glass ion concentrations,
the diffusion mechanism is via the grain boundaries. Volatilization of boron
occurred during annealing at 550 C. The morphological features dominated the
optical properties; the anatase films exhibited high transmissions and low
reflectances, while the rutile films exhibited the converse. The band gap
decreased slightly with increasing annealing temperatures, reflecting increasing
crystallinity. The refractive indices showed an anomalous trend of decrease with
increasing annealing temperature and associated crystallinity; this is attributed
to the effects of boron volatilization and associated air-filled pore formation.
Although the anatase films outperformed the rutile films, the effect of annealing
temperature is likely to have been dominant in that it determined the relative
extents of crystallinity, grain size, RMS roughness, optical indirect band gap,
and oxygen vacancy concentration.

Address correspondence to E-mail: i.kabir@unsw.edu.au

https://doi.org/10.1007/s10853-019-04282-1
J Mater Sci (2020) 55:3774–3794
Introduction
Although the principal application of titanium diox-
ide (TiO2) is as a pigment [1], it also has gained
considerable attention as a photocatalyst [1–3], par-
ticularly for photoelectrodes [4], gas sensors [5], and
self-cleaning materials [6]. It also has applications as
surface coatings because TiO2 films exhibit good UV-
induced hydrophilicity owing to chemisorption of
water molecules from the ambient air at the Ti?3
surface sites, which are generated by UV light irra-
diation [7]. Its wide band gap limits its light
absorption largely to the UV range [8], so its appli-
cations in energy have remained limited. TiO2 has the
advantages that it is abundant, inexpensive, chemi-
cally stable, and nontoxic.
However, the use of semiconducting materials in
the form of thin films raises the often-overlooked
issue of contamination of the films by the substrate,
which would alter the semiconducting properties if
these ionic contaminants create defects resulting from
substitutional or interstitial solid solubility. Since the
most commonly used substrates are of inexpensive
vitreous materials, the present work reports TiO2 film
contamination by a low-expansion borosilicate glass.
Titania occurs in nature in three different forms:
anatase, rutile, and brookite. The properties of these
three common polymorphs are summarized in
Table 1 in the supplementary information. Although
rutile is the more thermodynamically stable poly-
morph [2, 3], metastable anatase usually is consid-
ered to be the more promising photocatalyst because,
while rutile has a narrower band gap, anatase has a
lower electron–hole recombination rate, which
enhances its performance [4]. Brookite is not studied
commonly because it is difficult to prepare owing to
its metastability.
Of the different forms of TiO2 for investigation,
thin films generally are considered the most advan-
tageous owing to the simplicity of process and broad
scope of characterization. Many methods have been
applied to this end, including inter alia, sputtering
[11], pulsed laser deposition (PLD) [12], and metal
organic chemical vapor deposition (MOCVD) [13].
While these methods have the advantage that the
films have the capacity to remain relatively pure, they
usually require the use of a vacuum chamber and
heating of the substrates during deposition can cause
contamination. Convenient alternatives are wet
3775
chemical methods, which generally are easy,
uncomplicated, rapid, and economical. While they
can be done in air, they require heating to modest
temperatures, which also establishes the risk of
chemical contamination from the substrate. These
methods include, inter alia, spin coating [14], chemical
bath deposition [15], electrodeposition [16], spray
pyrolysis [17], and sol–gel [18]. Spin coating is par-
ticularly attractive because it allows the rapid and
reproducible production of films of uniform and
controlled thickness.
The intention of the present work was to synthesize
TiO2 thin films on low-expansion borosilicate glass
(BS) substrates using spin coating, to determine the
resultant contamination of the films by the substrates,
and to assess the effects on the resultant properties
(chemical, mineralogical, structural, microstructural,
morphological, topographical, and optical). While
effectively all titania thin films can be considered to
be contaminated to some extent by impurities, even
at annealing temperatures as low as 200 C [16–18],
those deposited on TiO2 would be the exception to
this rule. Hence, (001) single-crystal rutile substrates
also were examined for comparison. Contamination
of TiO2 thin films often is not examined by
researchers because it typically requires advanced
analytical facilities in the form of X-ray photoelectron
spectroscopy (XPS) or secondary ion mass spec-
trometry (SIMS). Such contamination is known to
have a significant impact on the performance of films
[4].
Since the anatase ? rutile phase transformation
occurs irreversibly over a reported temperature range
of * 400–1200 C, with 600 C being considered
typical [4], and the melting point of TiO2 is 1858 C,
single-crystal TiO2 substrates are by necessity com-
prised of rutile. In contrast, the annealing tempera-
tures of 200–550 C applied to the spin-coated sol–gel
films used in the present work resulted in the
recrystallization of anatase. This temperature was
selected in order to examine the effects of substrate
contamination of amorphous TiO2, incompletely
recrystallized anatase, and fully recrystallized ana-
tase, but not rutile. These films were applied to
borosilicate glass substrates, which contain the prin-
cipal oxides Na2O, B2O3, and SiO2, of which the latter
two are glass former, although B2O3 also is a pow-
erful flux. This amorphous material has been used by
numerous other investigators as substrate for the
fabrication of pure and doped TiO2 thin films, and
3776
the resultant contamination has been examined; these
data are summarized in Table 2 in the supplementary
information.
Unfortunately, boron is a light element that cannot
be detected by XPS or conventional energy dispersive
spectroscopy (EDS). Although boron can be detected
by electron probe microanalysis (EPMA) and X-ray
fluorescence (XRF) with the use of specific spec-
trometers, none of these techniques would be suit-
able since the instrumental beams would penetrate
the films (* 330–340 nm thickness) and so analyze
the substrates simultaneously. However, the use of
SIMS is suitable because it detects boron and it
probes both surfaces and volumes.
Experimental methods
The method used to fabricate the TiO2 thin films by
spin coating is described in detail elsewhere [29].
Consequently, Table 3 in the supplementary infor-
mation summarizes the relevant particulars.
Results and discussion
Mineralogy
Figure 1a shows GAXRD patterns for TiO2 films on
borosilicate glass substrates annealed at 200, 350,
450, and 550 C for 8 h. At 200 C, the film appears
Figure 1 Glancing angle X-ray diffraction patterns of TiO2 thin films on a borosilicate glass and b rutile substrates annealed at 200 C or
550 C for 8 h.
J Mater Sci (2020) 55:3774–3794
to be amorphous. The other films reveal only anatase,
with the peak intensities increasing with increasing
temperature owing to increasing crystallinity.
Although the anatase ? rutile phase transformation
is known to take place in the range * 400–1200 C
[4], it can occur at as low as 350 C [37]. However,
impurities play a significant role in the transforma-
tion and Si is known to inhibit the transformation
[4, 38, 39]. No peaks corresponding to brookite or
rutile are observed in any of the samples.
The degree of crystallinity was not determined as
the established methods [40, 41] are for powder
containing internal standards. The crystalline/amor-
phous ratio was not determined owing to the impact
of the amorphous substrate.
Figure 1b shows that for the films on rutile (un-
smoothed baseline), the peak intensities increase
slightly with increasing annealing temperature; they
also indicate that well-crystallized rutile in (001) ori-
entation formed owing to epitaxial growth on the
single-crystal rutile substrates. Since film and sub-
strate consist of rutile, the trend in intensities is not a
result of increasing amount of rutile. This may be an
effect of increasing crystallinity, but the absence of an
ex situ standard [42] prevents confirmation of this. It
is not possible using these data alone to determine
the relative contributions to the peak intensities from
the film and substrates.
Figure 2a, b shows the laser Raman microspectra
for the same films. Although these data are in
J Mater Sci (2020) 55:3774–3794
Figure 2 Laser Raman microspectra of TiO2 thin films on a borosilicate glass substrates and b rutile substrates annealed for 8 h at
different temperatures.
agreement with the GAXRD results, they also sup-
port the speculative comment concerning increasing
crystallinity of the films deposited on rutile
substrates.
Surface chemistry
XPS
The XPS spectra for the Ti 2p and O 1s regions for the
TiO2 films on borosilicate glass and rutile substrates
annealed at 200 C or 550 C for 8 h are shown in
Fig. 3. The reported XPS binding energy peak posi-
tions are given in Tables 4 and 5 in the supplemen-
tary information. The latter data suggest that
differentiation between the three valences of Ti is, in
principle, possible owing to sufficient differences in
peak positions [44].
However, the commonly observed absence of
peaks attributed to Ti3? indicates that this is not the
case. A second indication of the presence of Ti3? lies
in peak shifts toward lower binding energies (of Ti3?)
[30]. However, these also are absent. Consequently, it
is concluded that the 2p1/2 and 2p3/2 Ti3? peak
intensities (XPS sensitivity * 0.1 at% [42]) and/or
the 2p1/2 and 2p3/2 Ti4? peak shifts toward lower
binding energies (of Ti3?) [30] are not detectable.
Although the 2p1/2 and 2p3/2 Ti3? and Ti4? data
register only Ti4?, other work has shown that
annealing at 800 C in air can generate Ti3? [37]. Since
there were no consistent shifts in XPS peak positions,
3777
the proportion of Ti3? either was small or the effect of
solubility on the lattice stability [45] was minimal.
Alternatively, the O1s and/or O2s Ti3?-O and
4?
Ti -O peaks can be analyzed, although these often
are not considered. The relevant data in Fig. 3
demonstrate that deconvolution is capable of both
identifying and quantifying the level of Ti3?.
Table 1 summarizes the XPS data following nor-
malization to remove the adventitious carbon and
OH- peaks [45], the latter of which forms from dis-
sociative adsorption of H2O [47–49]. In semiconduc-
tors, oxygen vacancies (VO ) are considered to be
intrinsic defects [49, 50]. They are associated through
0000
charge compensation with Ti vacancies (VTi ) or, more
4? 3?
likely, Ti ? Ti reduction, giving the well-known
stoichiometry of TiO2-x [51, 52]. Consequently, in the
0000
absence of VTi to compensate the charge of the oxy-
gen vacancies, the maximal oxygen vacancy concen-
tration ([VO ]), based on theoretical considerations, is
one-half the Ti3? concentration. Further, these defects
and redox effects can be associated with intentional
doping or contamination from the substrate. Con-
cerning the data in Table 1, the following points are
made:
• Column C: XPS data were obtained before and
after MB testing for the films on borosilicate glass
because it has been shown that immersion in
water can result in leaching from the grain
boundaries of the contaminants from the substrate
[29, 45].
3778 J Mater Sci (2020) 55:3774–3794

Figure 3 XPS spectra showing a–d Ti2p and e–h O1s peaks for and (d, h) rutile substrates annealed at 550 C for 8 h (shaded
TiO2 thin films on a, e borosilicate glass substrates annealed at regions are from National Institute of Standards XPS Database
200 C for 8 h, (b, f) borosilicate glass substrates annealed at [39]).
550 C for 8 h, (c, g) rutile substrates annealed at 200 C for 8 h,
Table 1 Ionic species and oxygen vacancy concentrations (at%) in TiO2 thin films spin coated on borosilicate glass and single-crystal (001) rutile substrates annealed for 8 h at
200 C and 550 C

Parameters Normalized to remove C and OH levels Calculated [VO ]
J Mater Sci (2020) 55:3774–3794

TiO2 matrix [Ti] and [O] Contaminants [M] Normalizedc

[Ti4?] and [Ti3?]

A B C D E F G H I J K L M N O
Substrate TAnneal MB Ti4?/ O2- O2- Na? Ca2? Mg2? Si4? F- O O O (Ti3?) O2- O2-
3?
(C) testing (Exp.)a (Calc.)b (Ti4?) (Ti3?) (Max.)d (Max.)e (Calc.)f

Borosilicate 200 Before 29.25 61.82 57.23 7.67 0.15 0.38 0.61 0.12 89.32 10.68 5.34 5.33 1.96
glass After 30.44 62.43 60.45 6.28 0.14 0.33 0.28 0.10 89.36 10.64 5.32 5.31 1.98
550 Before 34.25 58.65 56.58 3.96 1.21 0.66 1.10 0.17 85.66 14.34 7.17 7.16 1.75
After 37.71 56.10 53.53 3.60 1.18 0.33 0.92 0.16 87.94 12.06 6.03 5.98 1.42
Rutile 200 Before 35.51 64.49 64.49 0 0 0 0 0 91.89 8.11 4.06 4.10 18.50
550 Before 33.95 66.05 66.05 0 0 0 0 0 87.63 12.37 6.19 6.20 5.50
a
Experimental O2-
b
O2- (Exp.) - (0.5Na? ? Ca2? ? Mg2? ? 2Si4?)
c
Experimental O (Ti4?) ? O (Ti3?) normalized to 100%
d
Maximal value calculated on the basis that charge balance requires two Ti3? per O vacancy
e
 
 

100 2:0 2:0 O Ti4þ þ 1:5 O Ti3þ
f
Step 1: titanium concentration = Ti4?/3?; Step 2: oxygen concentration = O2- (Calc.); Step 3: determine TiO2-x by normalizing Ti4?/3? to 1.0; Step 4: 100 [2.0 - (2 - x)]
3779
3780
• Column F: The experimental oxygen content
(Column E) includes contributions from the con-
taminants, so these have been removed. These
data (Column F) are considered to be more
representative.
• Columns K and L: The Ti3? and Ti4? concentra-
tions were obtained from the respective O Ti3?
and O Ti4? data normalized to 100%.
• Column M: There are several methods that can be
used to calculate the [VO ]. The maximal value is
0.5 (Ti3?–O).
• Column N: A second method to calculate the [VO ]
is based solely on the Ti3?–O and Ti4?–O data.
• Column O: A third method to calculate the [VO ] is
based on the oxygen deriving from both Ti4?/3?
([Ti]) and O2- (Calc.) ([O]).
The preceding allow the following conclusions to
be made. First, it is clear that the oxygen content from
the impurities should be removed from considera-
tion, so Column F provides the best estimate. Second,
the [VO ] based on [Ti3?] (Column M) and the [VO ]
based on [Ti4?] ? [Ti3?] are in close agreement, while
the [VO ] based on the Ti4?/3? and O2- (Calc.) (Col-
umn O) gives anomalous results. Hence, it is con-
cluded that the [V 3?
O ] based on [Ti ] provides a
representative estimate and so the theoretical con-
sideration is justified. This conclusion also contra-
dicts the potential for charge compensation by Ti
vacancies.
For the borosilicate glass substrates, MB testing
revealed the following before-and-after effects:
 
• Decreasing Ti3þ and associated maximal [V O ].
 4þ 
• Elimination of Si owing to leaching from the
grain boundaries in the form of silanol, Si–OH
groups [36] (i.e., grain boundary diffusion
[40, 53]).
   
• Slightly decreasing ½Naþ , Ca2þ , Mg2þ , and
[F-], also suggesting leaching from contaminants
located on the grain boundaries, in contrast to the
suggestion of bulk diffusion ([54]).
The principal effect on the band gap of these phe-
nomena potentially derives from (1) alteration of the
defect chemistry from the presence of the lattice
solutes [55], (2) role of creation of oxygen vacancies
[56], (3) counterdiffusion of ions (and creation of Ti
vacancies and their associated midgap stages [57]),
(4) partial amorphization arising from lattice strain
J Mater Sci (2020) 55:3774–3794
[58], and (5) blockage of the active sites by the grain
boundary phases [54].
 
In contrast, for the rutile substrates, the Ti3þ and
associated maximal [VO ] increased upon MB testing.
However, these values are similar for both substrates.
This is different from the case of fused silica sub-
strates [29], which revealed significantly lower values
for the films on rutile. While this was explained by
differences in stability of the two substrates [4], the
similar values in the present work preclude this
explanation. The principal difference between TiO2
films on the fused silica substrates and borosilicate
glass substrates is the multiple contaminants of the
latter. It is possible that the extensive presence of
grain boundary oxides of B, Na, Ca, Mg, and Si
suppressed the tendency to reduce the Ti4? valence
state in TiO2.
SIMS
Figure 4a shows the SIMS data for the TiO2 films on
borosilicate glass and rutile substrates annealed at
200 C for 8 h.
Rutile substrates
• The data trend for titanium is horizontal, as
expected from the identical compositions of film
and substrate.
Borosilicate glass substrates
• The constant compositions of all species in the
film demonstrate that saturation levels were
achieved for all species.
• Considering beam mixing effects [59–61] for the Si
and B profiles and the large inflections in the Ti,
Na, Ca, and Mg profiles, the data suggest that the
interface occurs at * 310 nm, which is similar to
the film thickness of * 338 nm observed in TEM
(discussed subsequently). The small inflections
consistently present at * 390 nm suggest that
there may be a corrosion layer sandwiched
between film and substrate.
• The horizontal trends of the data in the film
suggest that boron volatilization from the sub-
strate does not occur.
• The decreasing approximately linear profile for
[Ti] in the substrate demonstrates (zeroth-order
kinetics) diffusion into the substrate. This would
require the generation of VTi 0000
(and charge-
J Mater Sci (2020) 55:3774–3794 3781

Figure 4 SIMS spectra of TiO2 thin films on borosilicate glass and rutile substrates annealed at a 200 C or b 550 C for 8 h.

compensating oxygen vacancies) in the film, Rutile substrates

which would result in lattice strain.
• The data trend is horizontal, as expected from the
• The Si profile is as expected, revealing (first-order
identical compositions of film and substrate.
kinetics) diffusion into and contamination of the
substrate. The [Si] reaches matrix level Borosilicate glass substrates
at * 380 nm.
• The profiles for most of the species are not
• It is likely that the B profile is nearly identical to
horizontal, indicating more complex behavior.
that of the Si profile since both oxides are glass
• The major inflections at * 340 nm suggest that
formers and so are intimately associated. These
the interface is at this location. This is somewhat
data indicate that they derive from substrate
greater than the variable range of thickness
contamination rather than from an instrumental
of * 200–300 nm observed in TEM (discussed
source.
subsequently). The locations of the inflections and
• The Ca and Mg profiles in the substrate are
the natures of the profiles do not support the
opposite to those expected. The apparent maxi-
presence of a corrosion layer.
mum at the interface occurs because the increase
• The absence of indication of a corrosion layer
in [Ti] into the substrate is relatively large, so the
probably is due to the recrystallization of the film
minor species in the glass appear to decrease (the
precursor, which occurred more readily at 550 C
XPS data confirm very low [Ca] and [Mg]).
than 200 C.
• The Na profile is more complex (the XPS data
• The decrease in [Ti] in the film commencing
confirm high [Na]). The [Na] at the interface
at * 80 nm depth again demonstrates diffusion
would be expected to increase with increasing
into the substrate.
depth into the substrate, but it decreases initially.
• The apparent decreases in [B], [Na], [Ca], [Mg],
This results from the dominant effect of the
and [Si] commencing at the film surface also
increase in [Ti]. The [Na] then increases, which
suggest significant diffusion of these species into
reflects the dominant effect of the decrease in [Si].
the substrate.
Finally, it decreases again, which reflects the
• The approximate leveling of [Ti] and the increas-
dominant effect of the [Ti], which increases, while
ing trends in [Na], [Ca], [Mg], and [Si] commenc-
[Si] remains constant.
ing at * 160 nm are contradictory but can be
Figure 4b shows the SIMS data for the TiO2 films explained by volatilization of boron from the
on borosilicate glass and rutile substrates annealed at film/substrate interface. This also explains the
550 C for 8 h. trend in [B].
3782
• In other words, with increasing depth into the
film, the [Ti] actually decreases, but its (not quite)
linearity is a result of the competing effects of Ti
diffusion into the substrate and B loss. The [Na],
[Ca], [Mg], and [Si] initially decrease owing to
diffusion into the substrate, but their trends
reverse owing to the competing effects of Ti and
B loss.
• Approaching the film/substrate interface from the
substrate side, the concentration profiles of all
species from the substrate are as expected.
Figure 5 AFM topographical
(a)
images of TiO2 thin films on
borosilicate glass substrates
annealed at a 200 C,
b 350 C, c 450 C, d 550 C
or on rutile substrates annealed
at e 200 C, f 550 C for 8 h.
(c)
(e)
J Mater Sci (2020) 55:3774–3794
Microstructural characteristics
AFM
Figure 5 shows AFM images, and Table 2 provides
corresponding quantitative data for the films
annealed at different temperatures. For the films
deposited on borosilicate glass and annealed at
200 C, the GAXRD and Raman data show that the
TiO2 is amorphous. This suggests that the grains
visible in the AFM images are nuclei (* 5 nm). At
(b)
100 nm
(d)
100 nm
(f)
100 nm
J Mater Sci (2020) 55:3774–3794 3783

Table 2 AFM and XRD data for TiO2 thin films on borosilicate glass and rutile substrates annealed at different temperatures for 8 h

Substrate Annealing Visual estimation of grain size (nm) Apparent RMS surface XRD crystallite
temperature (C) porosity (%) roughness (nm) size (nm)
Average Standard deviation

Borosilicate Glass Substrate – – – 0.25 –

200 * 5 0.31 0.23 0.36 –
350 * 11 0.18 0.19 0.91 12.2
450 * 24 0.27 0.15 1.18 23.1
550 * 26 0.36 0.12 1.25 25.4
Rutile Substrate – – – 4.11 –
200 * 7 0.90 1.04 4.23 10.4
550 * 29 0.88 0.56 5.27 28.6

higher annealing temperatures, grain outlines TEM

become clear, showing increasing grain size,
increasing roughness, and decreasing apparent
porosity with increasing annealing temperature, all of
which derive from increasing recrystallization. For
the films deposited on rutile, annealing at 200 C also
resulted in the formation of nuclei (* 7 nm),
although the GAXRD and Raman data indicated
crystallinity. Consequently, the respective peaks in
the data were generated by penetrations of the beams
into the rutile substrate. Again, the higher tempera-
ture (550 C) results in the same nanostructural
characteristics as films on the other substrate. Fur-
ther, it can be seen that the increased grain growth
resulted in interparticle necking and agglomeration
as part of the sintering process. It is possible that the
epitaxial growth of rutile was associated with the
grain coarsening that typically accompanies the
anatase ? rutile phase transformation [4]. Since the
roughness changed only to a minor extent at the
lowest annealing temperatures (20 C and 200 C),
this indicates that the unpolished substrate topogra-
phy dominates the roughness of the nuclei, which
will be discussed subsequently in conjunction with
the TEM data. The increasing roughness of the films
annealed at higher temperatures derives from the
recrystallization and grain growth of the rutile grains.
For both films, the similarities of the grain and
crystallite sizes show that the grains are single crys-
tal. Also, the grain growth with increasing tempera-
ture is consistent with the decreasing apparent
porosity as both are associated with densification.
Figure 6 shows TEM images of the cross sections of
the thin films annealed at 200 C and 550 C, and
Table 3 estimates the nuclei (200 C) and grain sizes
(550 C) and the range of film thickness. These data
show that the particle sizes of the films estimated
from the AFM data (Table 2) and TEM data (Table 3)
are relatively close. The morphologies of the two
polymorphs after annealing at 550 C are different in
that the anatase is equiaxed, but the rutile is both
equiaxed and elongated, owing to necking, particu-
larly within layers formed by the dropwise deposi-
tion process.
While the thickness and planarities of the anatase
films appeared to be consistent, those of the rutile
films were highly variable. The profilometry data
(Table 3 in the supplementary information) indicate
coarse-scale roughness (i.e., unevenness) of 16 nm for
the borosilicate glass and 539 nm for rutile substrates.
The AFM data (Table 2) for the RMS roughness give
fine-scale values of 0.25 nm for borosilicate glass and
4.11 nm for the rutile substrates. It is clear that the
large variations in thickness of the rutile films derive
from the coarse-scale unevenness of the rutile
substrates.
The greater thickness of the anatase films is con-
sistent with the greater atomic volume of anatase
(0.1363 nm3) compared to that of rutile (0.0624 nm3).
However, a converse relation was observed for the
thickness of films deposited on fused silica and rutile
using identical experimental conditions [29]. In that
case, it was observed that different separations
between grains were responsible. The main differ-
ence between that work and the present is that nature
3784 J Mater Sci (2020) 55:3774–3794

Figure 6 TEM images of

cross sections of TiO2 films
(a) (b)
deposited on a borosilicate
glass annealed at 200 C,
b borosilicate glass annealed
at 550 C, c rutile annealed
200 C, d rutile annealed at
550 C for 8 h. 338 nm 333 nm

100 nm Substrate 100 nm Substrate

(c) (d)
290 nm

242 nm

206 nm
237 nm

100 nm
Substrate 100 nm Substrate

Table 3 TEM data for TiO2 thin films on borosilicate glass and rutile substrates annealed at different temperatures for 8 h

Substrate Annealing temperature (C) Measurement of grain size (nm) Film thickness (nm)

Borosilicate glass 200 *2 338

350 * 11 335
450 * 26 334
550 * 28 333
Rutile 200 *5 200–300
550 * 30 200–300

of the contaminating ions. Although the ionic radii
data in Table 1 in the supplementary information
suggest that lattice expansion would occur upon
dissolution and associated bulk diffusion, the con-
clusion of grain boundary diffusion suggests that the
greater thickness of the anatase films results from the
greater number and hence amount of contaminants
on the grain boundaries.
While the AFM data are consistent with densifica-
tion, the observation of voids in the TEM images is
not. This apparent discrepancy is explained by the
expectation that particle coarsening, which occurs
during sintering, is associated with the alteration of
the proximities of the particles [62].
While the rutile films became relatively smooth
owing to infilling of the uneven substrate profiles,
J Mater Sci (2020) 55:3774–3794
Figure 7 UV–Vis optical transmittance and reflectance spectra of TiO2 thin films deposited on a, b borosilicate glass substrates, c, d rutile
substrates: a, c optical transmittance spectra, b, d reflectance spectra annealed for 8 h at different annealing temperatures.
they were uneven owing to the blistering in the sur-
faces, which is consistent with gas escape from the
pyrolysis of the organic component of the precursor
(Table 3 in the supplementary information). Since
this occurred only with the rutile films, this suggests
that the recrystallization to form rutile was more
rapid than the recrystallization to form anatase.
Optical properties
Transmittance and reflectance
Figure 7 shows the UV–Vis spectra of the thin films
deposited on borosilicate glass annealed at
200–550 C and on rutile at 200 C and 550 C. The
estimated band gaps (Eg) are listed in Table 4.
3785
In Fig. 7a, the transmittance spectra for the anatase
films on borosilicate glass substrates reveal that the
films were highly transparent (85%) in the visible
region. The interference fringes indicate that the films
were relatively flat and microstructurally
homogeneous.
Figure 7c shows extremely low transmittances for
the rutile films owing to the unevenness and rough-
ness of the substrates. The trend between films is
consistent with the expectation of increasing trans-
mission with increasing crystallinity. Also, the rutile
transmittance spectra are rough owing to the surface
topographies of the rutile films, which contained
blisters. It is likely that the trends (slopes) in the
spectra in the visible region are not approximately
horizontal owing to the low transmittances; similar
3786
Table 4 Band gaps determined from UV–Vis spectra
Substrates Annealing
temperature (C)
Borosilicate glass 200
350
450
550
Rutile 200
550
trends for TiO2 [52, 63] and other materials [64, 65]
have been observed.
Figure 7b shows that the reflectance spectra for the
anatase films on borosilicate glass substrates are
considerably more complex than the transmittance
spectra. The minor variable amplitudes of the indi-
vidual curves are a reflection of the minor differences
in thickness of the films. The presence of interference
fringes confirms that the films are relatively flat. As
expected, the films exhibit greater reflectances than
the substrate since scattering occurs at two interfaces
(substrate–film, film–air) rather than one (substrate–
air).
Figure 7d shows that that the reflectance spectra
for the rutile films are more regular and in the order
(visible region): 200 C \ substrate \ 550 C. Exami-
nation of the TEM data (Fig. 6) reveals that the film
annealed at 550 C exhibits large grains and voids
generated by particle rearrangement and grain
growth, while the film annealed at 200 C exhibits
homogeneous and densely packed nuclei. The voids
represent a second phase that can be expected to
enhance scattering, which explains the high reflec-
tance for the film annealed at 550 C. In contrast, the
film annealed at 200 C consists of highly packed
rutile nuclei that serve to fill in the asperities present
in the rough substrates with a phase that is miner-
alogically identical to that of the substrate. Conse-
quently, it is likely that the decrease in surface
unevenness of the substrate to produce a flatter sur-
face is responsible for the lower reflectance of the film
annealed at 200 C.
Figure 8 and Table 4 show the Eg values from the
UV–Vis transmission and reflectance data. The Eg
values (Table 4) from transmission and reflection
differ by 0.54–0.57 eV for TiO2 thin films on the
borosilicate glass substrates and by 0.17–0.20 eV for
those on the rutile substrates. Further, the values
J Mater Sci (2020) 55:3774–3794
Transmission optical Reflectance optical
indirect band gap (eV) indirect band gap (eV)
3.77 3.33
3.71 3.31
3.68 3.29
3.63 3.16
2.87 2.67
2.88 2.71
obtained are not in agreement with those reported for
anatase (3.2 eV [64]) and rutile (3.0 eV [65]). It is clear
that the Eg of the anatase films deceases from that of
amorphous TiO2 (Eg [ 3.4 eV) [49]) with increasing
crystallinity due to increasing annealing temperature
[49]. The increase in Eg from the transmission data for
the anatase films may derive from the grain bound-
ary volumes in the bulk, which consist of voids
(smaller but more homogeneously distributed than in
the rutile films) that may act as photonic band gaps,
thereby increasing the total Eg [66–68]. Further, the
GAXRD data in Fig. 1 confirm that the anatase films
also are bulk-disordered from low crystallinity, and
the XPS data in Table 3 confirm that the anatase films
are surface-disordered from contamination, both of
which could increase the Eg. More to the point, the
SIMS data in Fig. 4 show boron contamination from
the borosilicate glass substrates at 550 C, which has
been reported to increase the Eg of the anatase films
[69, 70].
The epitaxial rutile films show a slight increase in
Eg, although this is likely a result of the imprecision
of the graphical technique used for determination
[49]. It is expected that the Eg would decrease with
increasing annealing temperature [11]. The low Eg
values probably result from increased absorption
owing to the roughness (Fig. 6) and increased resul-
tant increased absorption. Another factor may be
increased [VO ], which also would derive from the
roughness [49].
Although Table 2 shows that the differences in the
Eg for the rutile films are small, Fig. 8d is unam-
biguous in that it shows there is an apparent increase
in the Eg of the rutile films with increasing annealing
temperature. If real, it may be an artifact of the
nanostructure [38]. The TEM images in Fig. 6 show
that there are significant differences in the nanos-
tructures annealed at different temperatures. It is
J Mater Sci (2020) 55:3774–3794
Figure 8 UV–Vis optical transmittance and reflectance spectra based on a, b Tauc plots and c, d Kubelka–Munk plots for TiO2 thin films
deposited on a, c borosilicate glass (BS) substrates, b, d rutile (R) substrates.
probable that the apparent increase in Eg derives
from the differences in the grain boundary volumes,
which would contain both contaminants and amor-
phous TiO2, the Eg of the latter of which ([ 3.4 eV) is
higher than that of rutile [49]. Further, there do not
appear to be any reports of the recrystallization of
epitaxially grown sol–gel rutile films, which would
be subject to constraint from shrinkage by the
substrates.
Also, since both the transmittance and reflectance
of the less crystalline film are lower than those of the
more crystalline film, the absorbance of the former is
higher, which equates to a decrease in the Eg. At the
higher annealing temperature, the apposition of a
smooth film of crystalline TiO2 on a rough crystalline
TiO2 substrate would be expected to result in lower
reflectance, which is the case. However, at the higher
annealing temperature, the greater optical density of
3787
crystalline TiO2 compared to that of amorphous TiO2
would be expected to decrease the transmission,
which is not the case. Since there is a contradiction in
these intrinsic parameters, it is concluded that the
anomalous Eg data derive from extrinsic parameters
associated with the unevenness of the substrate and
the nature of the Tauc and Kubelka–Munk [31, 68]
methods, which assume a planar film.
Finally, Fig. 8c, d shows similar trends but differ-
ent Eg values from the UV–Vis reflectance data. The
different values are not unexpected since the trans-
mission data are largely for the bulk, while reflec-
tance data are for the surface. As mentioned, the
GAXRD data in Fig. 1 confirm that relative to the
rutile films, the anatase films are bulk-disordered
from low crystallinity and the XPS data in Table 1
confirm that the anatase films are surface-disordered
from contamination.
3788
Figure 9 Refractive index data for TiO2 thin films on borosilicate
glass annealed for 8 h at different temperatures.
Refractive index
Figure 9 shows the refractive indices n as a function
of wavelength for the TiO2 thin films deposited at
200–550 C. (The n of the borosilicate glass substrate
was determined to be 1.5086.) Although these
asymptotic data are typical of anatase [34, 71], the
ranges of values are significantly lower than those
reported for single-crystal values for anatase (2.561
nx and 2.488 ne) [72] and for other for sol–gel
[34, 73, 74] and sputtered [71, 75] anatase. As will be
discussed, this is likely to have resulted from the
effect of boron contamination of the thin films.
However, it is more significant that the trend in n
as a function of annealing temperature is reverse that
typically observed for anatase thin films [76]. That is,
the optical density of an amorphous material
increases with increasing recrystallization, so the n
should increase. Figure 1 confirms that the crys-
tallinity increases with increasing temperature.
Therefore, another mechanism must dominate these
data. The SIMS data in Fig. 4 show that there is sig-
nificant diffusion of the small and mobile ion boron
into the films. Previous work has suggested tenta-
tively that boron dissolves in the anatase lattice at
low temperatures [70, 77–79], although other work
has indicated that significant levels (14.5 at% [79]) of
boric oxide (B2O3) undergo grain boundary diffusion.
Although there are various scenarios for the
microstructural effects that can be considered to
J Mater Sci (2020) 55:3774–3794
interpret the trend in n as a function of annealing
temperature, that most consistent with the data is
based on the saturation of the TiO2 grain boundaries
with B2O3. Its presence lowers the refractive index of
what can be viewed as a B2O3–TiO2 composite. (The n
of amorphous B2O3 is in the range 1.4470-1.4881 [80].)
B2O3 is well known to volatilize in the presence of
water vapor at low temperatures, particularly above
its melting point of 450 C [81], forming boric acid
(H3BO3) and (HBO2)3, as shown in Fig. 1 in the sup-
plementary information. As it volatilizes, it leaves
behind pores filled with air, which has a refractive
index of * 1 [82]. Thus, the composite with three
components would exhibit a decrease in n owing to
the increasing amount of the phase of the lowest n
with increasing annealing temperature.
The SIMS data in Fig. 4 are significant in that they
confirm that the B concentration in the thin film
annealed at 200 C exhibited a constant saturation
level, while that in the film annealed at 550 C did
not, which supports the preceding scenario.
The data in Table 1 provide relevant data for the
other ionic species for which SIMS data in Fig. 4 were
obtained. While the SIMS data for B and Si are vir-
tually identical, Si exhibited complete removal by
leaching in water during the 24-h soak prior to MB
testing. (XPS is not capable of detecting B.) This
supports reported phase equilibria data to the effect
that that the solid solubility of Si in anatase is effec-
tively nil [83–86], causing all of the Si contamination
to exhibit grain boundary diffusion, the diffusion
coefficients of which (at 200 C and 550 C) have been
reported by the authors [29]. In contrast, while the
effect of water vapor on the formation of Si–OH gases
is well known [87], these species form only at rela-
tively high temperatures. So, the observed concen-
tration gradient at 550 C derives from (unsaturated)
grain boundary diffusion of the larger and less
mobile Si ion.
The SIMS data in Fig. 4 for the other ions (Na, Ca,
Mg) show that saturation levels were not achieved
and that concentration gradients were present. The
XPS data in Table 1 suggest that only a small amount
of leaching occurred, which can be explained by
unsaturated solid solubility (bulk diffusion), low
grain boundary diffusion coefficients, or low solu-
bility in water. The former is unlikely owing to what
appear to be low solid solubility limits of these cor-
responding oxides in anatase [85, 88–90]. The latter is
highly unlikely as the high solubility of Na2O in H2O
J Mater Sci (2020) 55:3774–3794
Figure 10 Extinction coefficient data for TiO2 thin films on
borosilicate glass annealed for 8 h at different temperatures.
is very well known. Thus, the SIMS and XPS data are
interpreted in terms of low grain boundary diffusion
coefficients.
Figure 10 shows that the trend in extinction coef-
ficient k of the TiO2 films as a function of wavelength
parallels that of the n, which is in accordance with the
Kramers–Kronig relation [71, 91]. The relatively low
values over 400–800 nm probably resulted from the
presence of B. It may be noted that these low values
also are consistent with the films’ low mass absorp-
tion owing to the thinness of the TiO2 films
(* 335 nm, Table 3), associated high transmittance
(* 85%, Fig. 7a), low balance reflectance (* 15%,
Fig. 7b), and presence of apparent porosity (Fig. 5).
Further, the low values also are indicative of topo-
graphical quality [90, 92], which confirms the
smoothness over a large area, as suggested by the
AFM and TEM data, the fields of view of which are
limited to B 1 lm. At the lower wavelength range of
300–350 nm, the k values of * 0.1–0.5 are in general
agreement with other previously reported values for
anatase [34, 71, 93].
Equations 1 and 2 give alternative forms used to
utilize the n to determine other relevant values, par-
ticularly the Eg [94, 95]:
1 E0 ðhvÞ2
¼  ð1Þ
n2  1 Ed E0 Ed
3789
Figure 11 Plot of (n2 - 1)-1 against (hm)2 (eV2) for TiO2 thin
films on borosilicate glass annealed for 8 h at different
temperatures.
E 0 ED
n2 ðmÞ ¼ 1 þ ð2Þ
E20  ðhmÞ2
where n = refractive index; E0 = oscillator energy
(* 1.5 Eg); Ed = oscillator strength (dispersion
energy); h = Planck’s constant; m = frequency;
hm = photon energy.
By plotting (n2 - 1)-1 versus (hm)2, as shown in
Fig. 11, the linear relationship reveals a slope of
(E0Ed)-1 and an ordinate intercept of E0/Ed, which
effectively allow another approach to the determi-
nation of the Eg. The determined ranges with
increasing annealing temperature for E0
(6.02–5.74 eV) and Ed (14.7–12.6 eV) can be compared
with reported values for single-crystal anatase of
5.24 eV and 25.7 eV, respectively [71]. Since these
data were determined using transmission data, the Eg
range determined from transmission by the Tauc
method (Table 4), which is 3.87–3.72 eV with
increasing annealing temperature, can be contrasted
with approximate values determined using the pre-
ceding plot, which are 4.01–3.82 eV (E0 7 1.5). These
ranges may be compared with the literature values
for the optical indirect Eg of crystalline anatase,
which are in the range of 3.13–3.27 eV, and of
amorphous TiO2, which are [ 3.40 eV [96–101].
These data indicate that the high Eg values are
indicative of the disruption of recrystallization by B,
which promoted the amorphization indicated in
3790
Figs. 1 and 2. Although it is known that the n and Eg
of semiconductors are inversely proportional [102],
the direct proportionality of the present work sug-
gests that this relation is overshadowed by the effect
of annealing temperature on the extent of recrystal-
lization but not B contamination.
Figure 11 also reveals that the data for the thin film
annealed at 550 C are parallel to the data for the
other annealing temperatures, only over the range
7 eV \ hm \ 9 eV. The divergent data at lower values
suggest that as stated above, significant volatilization
of B commences above the melting point of B2O3 at
450 C. The linear part of these data was used to
determine E0 and Ed, which is consistent with the
previous comment about B contamination.
Photocatalytic activity
Figure 12 shows the photocatalytic degradation of
methylene blue solution at exposure times up to 24 h
in terms of the residual concentration of dye (C/C0)
versus time (t). The fact that the films do not exhibit
the first-order kinetics may have resulted from low
extents of recrystallization, although contamination
of the anatase films from the borosilicate glass sub-
strate also is a potential cause, all of which could act
to block the photocatalytically active sites.
For the data for the rutile films, the contribution
from the exposed surface of the rutile substrate has
Figure 12 Methylene blue dye degradation data for TiO2 thin
films on borosilicate glass and rutile substrates annealed at
different temperatures for 8 h (rutile substrate contribution
subtracted from test data).
J Mater Sci (2020) 55:3774–3794
been subtracted from both curves. Since there is no
contamination of the rutile films, despite the sharp
XRD peaks (Fig. 1), the absence of the first-order
kinetics suggests that the rutile films may not be fully
recrystallized despite their epitaxial growth.
These data, which are at both low (200 C) and
high (550 C) temperatures, are more suggestive of
the expected first-order kinetics than those of the
anatase films. This supports the conclusion that the
rutile film epitaxially deposited at the lower tem-
perature may be relatively well recrystallized.
The order of performance at the 24-h time point is
as follows:
550  CAnatase [ 450  CAnatase [ 350  CAnatase
[ 550  CRutile [ 200  CRutile [ 200  CAnatase
[ Rutile Substrate
These data make clear that the performance of
anatase is superior to that of rutile, which is as
expected [49]. While the effect of crystallinity (posi-
tive) dominates that of contamination (negative),
examination of the individual temperature-depen-
dent data for anatase and rutile reveals that the grain
sizes (Table 2), RMS roughness (Table 2), optical
indirect Eg (Table 4), and [VO ] (Table 1) correlate
with the performance. Between the data for the two
TiO2 polymorphs, the electron–hole recombination
time also may be significant since this is shorter for
anatase than for rutile [11, 13, 103, 104]. In effect, it is
not possible to decouple these influences on the
performance in order to identify the principal effect,
although previous work [4, 29, 38–42, 44] tends to
support the conclusion of the critical role of
crystallinity.
Conclusions
Anatase and rutile thin films annealed at different
temperatures were deposited on borosilicate glass
and rutile substrates, respectively. Analyses of the
microstructural, mineralogical, optical, chemical, and
photocatalytic characteristics were assessed using a
range of analytical techniques.
The key observations of the present work are as
follows: First, both the anatase films deposited on
borosilicate glass and the rutile films deposited on
(001) rutile substrates, annealed at 200–550 C for 8 h,
were not fully recrystallized. Second, the XPS data
J Mater Sci (2020) 55:3774–3794
before and after MB testing revealed that the Si was
completely leached and the other contaminating ions
from the substrate decreased slightly. Third, the SIMS
data indicate that the grain boundaries were satu-
rated by the contaminants from the substrate, with B
probably at very significant levels; Ti counterdiffu-
sion from the film to the substrate also occurred. The
SIMS data also indicate that B volatilization took
place at 550 C. Fourth, the Eg data derived from the
UV–Vis spectra indicated that the values for anatase
were low owing to bulk disorder from low crys-
tallinity and surface disorder from contamination.
The Eg values for rutile were low owing to surface
roughness of the unpolished substrates. Fifth, con-
verse to expectation, the n decreased with increasing
annealing temperature. This was attributed to the
alteration with increasing annealing temperature of
what is effectively a B2O3–TiO2 composite to a B2O3–
TiO2–air composite, where volatilization of B2O3,
with an n lower than that of TiO2, caused the for-
mation of pores filled with air, with an n lower than
that of B2O3.
Funding
This project was not funded through a formalized
research funding agency.
Compliance with ethical standards
Conflict of interest The authors declare that they
have no conflicts of interest.
Electronic supplementary material: The online
version of this article (https://doi.org/10.1007/s108
53-019-04282-1) contains supplementary material,
which is available to authorized users.
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