Control of the optical and crystalline properties of TiO2 in visible-light active

TiO2/TiN bi-layer thin-film stacks

Wilson Smith, Houssam Fakhouri, Jérôme Pulpytel, and Farzaneh Arefi-Khonsari

Citation: J. Appl. Phys. 111, 024301 (2012); doi: 10.1063/1.3671428

View online: http://dx.doi.org/10.1063/1.3671428
View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v111/i2
Published by the American Institute of Physics.

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 JOURNAL OF APPLIED PHYSICS 111, 024301 (2012)

Control of the optical and crystalline properties of TiO2 in visible-light active

TiO2/TiN bi-layer thin-film stacks
Wilson Smith,a) Houssam Fakhouri, Jérôme Pulpytel, and Farzaneh Arefi-Khonsari
Laboratoire de Génie des Procédés Plasma et Traitement de Surface, Université Pierre et Marie Curie,
11 Rue Pierre et Marie Curie, Paris 75231, France
(Received 27 April 2011; accepted 17 November 2011; published online 18 January 2012)
Multi-layered thin films of TiO2 and TiN were created by rf reactive magnetron sputtering, and their
crystalline, optical, and photoelectrochemical properties were measured. The overall composition of
the films (TiO2-to-TiN ratio) was kept constant with the height of each film. The number of layers
and thickness of each layer was controlled to create bi-layer thin films that were composed of: 9 bi-
layers, 18 bi-layers, 27 bi-layers, 36 bi-layers, and 45 bi-layers. XRD patterns were observed for each
film after annealing to measure the grain size and composition of anatase and rutile as a function of
temperature. It was found that the phase-transition temperature is able to be substantially controlled
(between 550  C and 850  C) for the anatase to rutile transition by varying the number of layers/
thickness of each layer. In addition, bi-layer stacking significantly affected the film’s optical proper-
ties by lowering the bandgap into the visible-light region, and also showed up to three times the
improvement in photoelectrochemical performance under uv and visible irradiation. Overall, bi-layer
stacking of TiO2/TiN films has shown a unique and highly desirable control over several important
physical characteristics that can be beneficial for many applications, such as high-temperature sensors
and optoelectronic devices. V C 2012 American Institute of Physics. [doi:10.1063/1.3671428]

I. INTRODUCTION Several methods have been developed to improve the

overall efficiency of TiO2 by adjusting the structural and
The ability to obtain and use clean water is a paramount
morphological properties of the material. For instance, the
goal of every developing nation. Many countries have access
crystal structure of TiO2 plays an important role in its optoe-
to polluted and contaminated water and are in desperate need
lectronic performance. When TiO2 is prepared in the amor-
of a solution to quickly, cheaply, and effectively clean their
phous phase, it has very poor photocatalytic efficiency under
water supply. One of the most promising materials to combat
uv irradiation.11 However, when TiO2 is in the anatase crys-
this problem is TiO2, which has been used for many decades
tal phase, it has shown a significant increase in the photoca-
as a photocatalyst with strong applications in water purifica-
talytic performance.11 Furthermore, many groups have
tion, because of its ability to absorb uv light and break down
shown that preparing TiO2 with a predominant anatase phase
many organic compounds dissolved in water.1–4 Recently, its
(75%), and having a relatively small amount of the rutile
applications have become more versatile, including coatings
phase (25%), allows for optimized photocatalytic effi-
for self-cleaning windows,5,6 water electrolysis for hydrogen
ciency under uv irradiation.12,14–16 In fact, the TiO2 indus-
production,7,8 and gas-sensing devices.9,10 However, for sev-
trial powder standard, Degussa P25, is prepared to this
eral photoactive applications, TiO2 by itself has several defi-
approximate ratio of anatase to rutile.17 However, at high
ciencies that will not allow it to be a commercially viable
temperatures (>550  C), TiO2 has generally shown rutile-
option for large-scale integration. For example, the bandgap
dominated crystal-phase characteristics.18,19 Wiggins et al.20
energy for anatase TiO2 is Eg ¼ 3.2 eV, which corresponds
have shown the ability to prepare rutile directly from amor-
to an absorption wavelength of k ¼ 388 nm. Whereas this
phous TiO2,20 whereas many other groups have made the
makes TiO2 a suitable candidate for uv-based photoactive
transition from amorphous to anatase, and then anatase to ru-
systems, a practical long-term solution requires the use of
tile. Yang et al.21 reported that the anatase-to-rutile phase
visible light, and thus the ability to use the sun’s solar spec-
change in crystallinity can occur anywhere from 450  C to
trum to initiate photoreactions. In addition, the relatively
1100  C.21 The discrepancy in the observed phase-transition
short electron–hole pair lifetime in TiO2 obstructs the
temperatures can be attributed to the differences in deposition
advancement of its applications. The electrons and holes are
parameters (pressure, relative gas flow rates of argon and ox-
used in separate reduction and oxidation reactions at the
ygen, target to substrate distance, and substrate temperature),
TiO2 surface, so extending the lifetime of each charge carrier
as well as the different thicknesses of the films studied. Thus,
is vitally important to improving the efficiency of TiO2 as a
there are many factors that can affect the crystallization of
functional photocatalyst.
TiO2, and each is important to understand to compare the dif-
ferences between films. Whereas the pure rutile phase of
TiO2 has a smaller bandgap (Eg ¼ 3.0 eV) than the anatase
a)
Author to whom correspondence should be addressed. Electronic mail: phase (Eg ¼ 3.2 eV), it has generally shown significantly
wilsonasmith@gmail.com. worse photoactive properties, such as reduced photocatalytic

0021-8979/2012/111(2)/024301/10/$30.00 111, 024301-1 C 2012 American Institute of Physics

V

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024301-2 Smith et al.
activity, reduced photocurrent generation, and diminished
charge transport.12,14–20 For these reasons, the ability to tailor
and control the crystal phase and composition of TiO2 is criti-
cal in improving its optoelectronic performance.
Other ways to improve the photoactive properties of TiO2
include coupling it with other semiconductors or metals,20–23
and doping.24–28 When TiO2 is in contact with other semicon-
ductors that have similar conduction and valence-band posi-
tions, a type-II electronic heterostructure is formed, which can
localize electrons and holes in the conduction and valence
bands, extending the lifetime of the photogenerated charge
carriers. This can allow uv-generated electrons in the TiO2
conduction band to travel to the secondary semiconductor, or
allow visible-light-generated holes to transfer to the TiO2 va-
lence band. When TiO2 is in contact with metals, a Schottky
barrier is formed that is proportional to the difference between
the Fermi energy level of TiO2 and the metal. This barrier is
an electric field that can affect charge carriers in a nearby
region, the space-charge layer, which can further increase the
effective lifetime of the photogenerated electron–hole pairs.
The increased lifetime of the charge carriers caused by TiO2–
semiconductor/metal coupling has shown the ability to signifi-
cantly increase the photocatalytic and photoelectrochemical
properties of these structures.
Doped TiO2 has also seen much attention in recent years.
Typically, the two most common doping elements include
using 3D transition metals, such as Cr, V, and Nb, or non-
metals, such as C, S, and, most commonly, nitrogen.26–28
When doped, the transition metals can add stable energy lev-
els just below the conduction band, whereas the non-metals
can add energy levels just above the valence band. In both
cases, the bandgap can be decreased, which can allow for the
onset of visible-light absorption and photoactivity. Asahi
et al.28 first explored N-doped TiO2 in 2001, and through the-
oretical and experimental results, they were able to determine
that nitrogen is the best-suited element to improve TiO2
photo-functionality in the visible-light region.26 Since then,
many studies have shown the viability and success of N-
doped TiO2 as a visible-light photoactive material.
In addition to being used primarily as a photocatalyst,
TiO2 has found increased use as an anti-reflective coating for
heat mirrors when it is coupled with TiN. TiO2/TiN/TiO2
multi-layer thin films were first used by Georgson et al.31 in
1991 as solar control films. They compared single-layer TiO2
and TiN films with TiO2/TiN/TiO2 thin films, and found that
the triple-layer structure had the best-overall optical properties
for heat-mirror performance, relating to the ratio between the
maximum transmission and reflectance at 2 lm. Tazawa
et al.32 expanded on this work recently by utilizing the photo-
catalytic properties of the TiO2/TiN/TiO2 thin-film heat mir-
rors. They used a combination of rf and dc sputtering of a Ti
metal target to deposit the TiO2/TiN/TiO2 films to determine
the optical morphological parameters that allowed both heat-
mirror and photocatalytic applications. The thickness for this
optimized film was found to be TiO2 (377.5 nm)/TiN (20
nm)/TiO2 (43 nm). Jung et al. also studied the optical proper-
ties of pulsed dc sputtered TiO2, TiN, and TiO2/TiN/TiO2
films from a metallic Ti target. They found that these films
showed high reflectance in the ir region, but that the reflection
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J. Appl. Phys. 111, 024301 (2012)
and transmission spectra were highly dependent on the thick-
ness of the TiO2 and TiN layers. For example, they found
optimal optical properties for a thin film with TiO2 (370 nm)/
TiN (22 nm)/TiO2 (450 nm).33 Kawasaki et al. further studied
TiO2/TiN/TiO2 films deposited by pulsed laser deposition
from a TiN target. They also found beneficial optical proper-
ties of these mutli-layered films that suggested their use as
heat mirrors. In addition to the ir reflective properties, Kawa-
saki et al. also used the photocatalytic properties of the top
layer of TiO2 to photodegrade methylene blue. They used a
film with size TiO2 (60 nm)/TiN (14 nm)/TiO2 (60 nm) to
decompose methylene blue under uv irradiation.34 These
results were quantitative, and no empirical data was given with
regard to the efficiency of this reaction. Whereas these studies
show how stacking three-layer TiO2/TiN/TiO2 thin films can
improve photocatalysis and the optical properties of TiO2,
nobody has scaled this process up to more than three layers
and created a large series of heterojunctions that could further
enhance the film’s structural and optoelectronic properties.
In this study, we present a novel organization of TiO2/
TiN bi-layer thin films created by rf reactive magnetron sput-
tering. Films were deposited with 9 bi-layers, 18 bi-layers, 27
bi-layers, 36 bi-layers, and 45 bi-layers, all with the same
total height (500 nm) and composition of TiO2 and TiN. By
designing each film with the particular amount of bi-layers,
we were able to create 17, 35, 53, 71, and 89 TiO2/TiN heter-
ojunctions in each respective sample. These are by far the
largest amount of heterojunctions attempted with these mate-
rials, and for these applications.29–32 The only structural pa-
rameters that were changed were the number of layers, and
the thickness of each layer, allowing the ratio of TiO2 to TiN
to remain at a constant 5:1 ratio throughout each film. The
films were then annealed from TA ¼ 450  C to 950  C for 2 h
in 100  C intervals, and their crystalline structure was meas-
ured to examine the phase-transition temperatures for TiO2
from amorphous to anatase, and from anatase to rutile. It was
observed that the phase-change temperature from anatase to
rutile varied significantly (6150  C) depending on the thick-
ness/number of the TiO2 layers. In addition, the photoelectro-
chemical properties were measured for these films, which
displayed a distinct response in photocurrent generation under
uv and visible-light irradiation, dependent on the thickness/
number of layers. These results demonstrate a unique and
simple way to control the structural and photoactive proper-
ties of TiO2, with room for further optimization in the future.
II. EXPERIMENTAL
TiO2 films and TiN films were fabricated in the same rf
magnetron sputtering deposition chamber (SPT 120, Plas-
mionique). The depositions for the bi-layer films were car-
ried out in succession without opening the chamber between
depositions, and thus have the same base pressure for both
depositions, p  3 to 7  106 Torr, whereas the total work-
ing pressure was kept constant at 3 mTorr. Both films were
deposited using a metallic Ti target (50 mm diameter) having
a purity of 99.95%. The target was sputtered in a reactive
gas atmosphere containing Ar þ O2 for TiO2 films, and
Ar þ N2 for TiN films. The argon gas flow rate was fixed at
024301-3 Smith et al. J. Appl. Phys. 111, 024301 (2012)

30 sccm for both depositions, whereas the O2 flow rate was
1.5 sccm for the TiO2 films, and the N2 flow rate was fixed at
3 sccm for the TiN films. The rf cathode power was 200 W
for all the depositions to minimize the target poisoning
effect. In addition, prior to each deposition the target was
pre-sputtered in Argon atmosphere for 10 min to remove any
contaminations or “poisoned film” from the target surface.
The films were deposited on several substrates including
electro-polished stainless steel, Si (100) and (101) wafers,
and ordinary microscope glass slides. Prior to deposition, the
non-metallic substrates were ultrasonically cleaned with ace-
tone and ethyl alcohol, and then in de-ionized water for 20
min each. The substrate holder was maintained at 300  C
and no bias was applied. The distance between the substrate
holder and the target was fixed at 10 cm.
The crystalline properties of the films were character-
ized by x-ray diffraction (XRD) (X’Pert Pro PW3040-Pro,
PANalytical Inc.) using a Cu Ka (k ¼ 1.5418 Å) x-ray radia-
tion source. All XRD measurements were performed in the
Bragg configuration, allowing sufficient depth analysis of the
film’s crystal structure throughout the height of the films
down to the substrate. With the Bragg configuration, we can
accurately measure the crystal properties throughout the
thickness of the films, and, therefore, the crystallinity
and grain size calculated will reflect the average crystal
size throughout the film, even if it is not uniform within the
entire structure because of the effects of the initial crystal
growth, substrate orientation, and interfacial effects from the
two layers. Optical measurements were carried out by a uv-
vis spectrophotometer (Varian 6000). Photoelectrochemical
measurements were studied by linear sweep voltammetry
with a voltage controlled potentiostat (BioLogic EC-Lab
V9.00). Reference and counter electrodes during the PEC
measurements were an Ag/AgCl electrode (CHI Instruments/
saturated KCl) and a mesh Pt electrode, respectively.
III. RESULTS AND DISCUSSION
A. Morphological and crystal structure of TiO2/TiN
bi-layer thin films
The thickness of each film was measured by profilome-
try. The total thickness was measured by depositing a thin
film with a mask on top to conceal a small portion of the
substrate, to compare the height of the uncoated portion of
the substrate with the coated part. Profile scans were meas-
ured moving from the non-deposited area to the area with the
thin films to measure the total thickness of the films. In addi-
tion to the bi-layer films, thin films of pure TiO2 and TiN
were deposited for a fixed period of time, and their thick-
nesses were measured. This allowed us to estimate the aver-
age deposition rate for each material. The average height for
all of the thin films was found to be h ¼ 500 6 50 nm. Based
on the deposition rate, and the time of deposition for each
layer, we were able to estimate the thickness of each layer in
the multi-layered films. For instance, in the 9-bi-layer films,
the height of each TiO2 layer was h ¼ 46.3 6 2.0 nm,
whereas the height of the TiN layer was estimated to be
h ¼ 9.3 6 0.8 nm. For the 45-bi-layer films, the height of
each TiO2 layer was h ¼ 9.3 6 1.2 nm, whereas the height of
the TiN layer was estimated to be h ¼ 1.9 6 0.4 nm. The esti-
mated height for each layer is listed in the top row of Table
I. When the oxygen gas is turned off and the nitrogen gas is
turned on, there is a possibility that residual oxygen is still
inside the deposition chamber. At the deposition pressure of
106 Torr, approximately one mono-layer of oxygen may
be deposited before the nitrogen-based plasma reaches equi-
librium. Therefore, there may be roughly one atomic layer of
oxygen-rich TiOx, which separated the TiO2 and TiN layers.
This discontinuity may add to the unique properties of these
highly ordered thin-film stacks.
The crystal properties of the as-deposited and annealed
bi-layer samples (at Ta ¼ 450  C, 550  C, 650  C, 750  C,
850  C, and 950  C) were determined by X-ray diffraction
(XRD). Each sample was annealed for 2 h at the respective
temperatures in a closed furnace with no additional gases
introduced, and kept at atmospheric pressure. To most effec-
tively demonstrate the differences in the TiO2 crystallinity as
a function of temperature for the bi-layer films, the films
with the fewest (9 bi-layers) and the most (45 bi-layers), are
discussed in detail here. In the higher annealing tempera-
tures, it is important to note the crystal phase transformation
in TiO2, but we must also pay attention to the oxidation
kinetics of the TiN layers. Whereas there is a possibility that
the TiN layers can become oxidized at the higher annealing
temperatures, it is unlikely that all or even most of the TiN
layers will change to TiO2. The morphology of the films
requires that oxygen and heat would need to diffuse through
a top layer of TiO2, which is roughly 20  25 nm, and then

TABLE I. The calculated grain size of the anatase and rutile crystals in each bi-layer and single-layer TiO2 thin film at various post-deposition annealing tem-
peratures. The thicknesses of the TiO2 and TiN layers in each bi-layer films are respectively listed in parentheses below the label for each sample.

TiO2 9 bi-layer 18 bi-layer 27 bi-layer 36 bi-layer 45 bi-layer

(500 nm) (46.3/9.3 nm) (23.1/4.7 nm) (15.4/3.1 nm) (11.6/2.3 nm) (9.3/1.9 nm)

Sample A (nm) R (nm) A (nm) R (nm) A (nm) R (nm) A (nm) R (nm) A (nm) R (nm) A (nm) R (nm)

As-deposited 22.0 … 13.0 … 9.3 … … … … … … …

450  C 42.9 … 21.9 … 15.8 … 35.0 … 37.4 … 45.3 …
550  C 48.1 54.9 29.4 47.6 32.2 45.9 37.2 44.5 41.4 39.2 51.4 36.8
650  C 62.9 68.9 42.3 66.2 42.9 60.7 50.7 58.7 52.1 54.2 60.7 44.5
750  C 63.2 71.8 … 69.5 … 70.1 … 60.7 61.2 63.4 62.1 49.7
850  C 63.2 77.9 … 74.8 … 74.5 … 65.4 61.7 65.6 62.4 59.5
950  C … 87.3 … 84.2 … 82.9 … 73.3 … 67.4 … 65.2

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024301-4 Smith et al.
each pair of successive bi-layers. Although the oxidation of
TiN is possible, it would be very difficult for heat and oxy-
gen to diffuse from the surface of the films throughout the
bulk, and affect all of the TiN layers within the films. Fur-
thermore, the possibility for TiN oxidation is more likely at
higher temperatures, for which only XRD experiments were
carried out. The optical and photoactive properties were
measured using samples annealed at a maximum of 450  C,
therefore it is highly unlikely that these films have any
appreciable oxidation in the TiN layers, and this phenom-
enon should not be observed.
The XRD patterns for the as-deposited and annealed
9-bi-layer films are shown in Fig. 1(a). The as-deposited film
showed a very small and wide bump centered on 2h ¼ 25.4 ,
corresponding to the (101) orientation of the anatase crystal
phase. This peak is very weak, and shows very poor crystal-
linity in the as-deposited sample. After annealing at Ta
¼ 450  C, the film showed a stronger peak at 2h ¼ 25.4 , in
addition to new small peaks at 2h ¼ 35.3 , and 54.5 , corre-
sponding to the (004), and (200) orientations of the anatase
phase of TiO2. When the film was annealed at Ta ¼ 550  C,
the (101) anatase peak became much taller and thinner,
showing a drastic increase in the anatase crystallinity. The
secondary anatase peaks at 2h ¼ 35.3 , and 54.5 also
increased their peak intensity. In addition to the growth of
the anatase peak heights at this temperature, a small peak
can be seen at 2h ¼ 27.5 , corresponding to the (100) orienta-
tion of the rutile phase of TiO2, showing that there is a mixed
anatase/rutile phase composition of the film at this tempera-
ture. When this film is further annealed at Ta ¼ 650  C, the
original anatase peaks are indistinguishable. The peak that
was previously at 2h ¼ 25.4 has become a barely noticeable
bump in the pattern, and the other peaks are not present at
all. Furthermore, at this temperature, the diffraction peak at
2h ¼ 27.5 for the rutile phase had become dominant,
increasing its peak height several hundred times over the pre-
vious temperature. The peak is much narrower compared to
the previous peak, because of an increase in the crystal size.
After annealing at Ta ¼ 750  C, 850  C, and 950  C, the
overall shape of the pattern remains the same, only showing
the rutile phase diffraction peaks. The only change in the pat-
tern is that the (100) rutile peak becomes taller and thinner
as the temperature increases, again corresponding to an
increase in crystal size. No diffraction peaks for TiN are
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J. Appl. Phys. 111, 024301 (2012)
present at any annealing temperature, perhaps because of the
thinness of the layers.
The XRD patterns for the 45-bi-layer film annealed at
the same temperatures are shown in Fig. 1(b). The as-
deposited pattern shows no discernable peaks, corresponding
to the amorphous phase for TiO2, and again no peaks are
seen for TiN because of the thinness of the layers. After
annealing at Ta ¼ 450  C, the film revealed relatively strong
peaks at 2h ¼ 25.4 , 35.3 , 48.2 , and 54.1 , corresponding
to the (101), (004), (200), and (211) orientations of the ana-
tase phase of TiO2. After annealing at Ta ¼ 550  C, all of the
anatase peaks present at Ta ¼ 450  C become more pro-
nounced, increasing their peak height. In addition, three new
peaks arise at 2h ¼ 27.5 , 44.4 , and 54.4 , corresponding to
the (110), (210), and (211) orientations of the rutile phase of
TiO2. This phase transition is identical to the 9-bi-layer film
when annealing from Ta ¼ 450  C to Ta ¼ 550  C, which also
changes from the pure anatase phase to an anatase-
dominated phase with a small amount of rutile. However, the
45-bi-layer film shows a different trend for the phase transi-
tion at higher temperatures. When the 45-bi-layer film is
annealed at Ta ¼ 650  C, the XRD pattern reveals a pattern
that is very similar to the previous one, which is dominated
by anatase and showing only a small amount of rutile. Fur-
thermore, when annealing at Ta ¼ 750  C, an identical trend
is seen with a large amount of anatase remaining, and still
only a small amount of rutile is visible. After annealing at
Ta ¼ 850  C, the (101) anatase peak begins to shrink, and the
(100) rutile peak begins to grow. In fact, at this temperature,
the peak height for the (101) anatase peak and the (100) ru-
tile peak are almost identical, revealing an almost uniformly
equal composition of the two crystal phases. When this film
is annealed at Ta ¼ 950  C, the anatase peaks completely dis-
appear, and the XRD pattern is dominated by the rutile
peaks, specifically the (100) peak, which becomes very tall
and very thin (see Figure 1(b)). The other bi-layer samples
were analyzed similar to the above films, with the crystalline
peaks and phase composition being observed accordingly.
From the XRD patterns, it is also possible to determine
the grain size of the anatase crystals and rutile crystals using
the Scherrer formula,
Kk
D¼ ; (1)
b cosðhÞ
FIG. 1. (Color online) XRD patterns of
the (a) 9-bi-layer film, and (b) the 45-bi-
layer thin film sample. The patterns were
taken of the as-deposited sample (bot-
tom), and after annealing for 2 h from
Ta ¼ 450  C to Ta ¼ 950  C, in 100  C
intervals. The patterns at the bottom of
the graph represent the lower tempera-
tures, with successive patterns increasing
in post-deposition annealing temperature
toward the top of the graph.
024301-5 Smith et al.
where D is the grain size, K is a constant (0.9), k is the x-ray
wavelength (1.54 Å), b is the full width of the peak at half
maximum (FWHM), and h is the diffraction angle of the
peak. For the anatase crystal, the (101) peak located at
2h ¼ 25.4 was used, whereas for the rutile crystal, the (100)
peak located at 2h ¼ 27.4 was used. The crystal size for the
anatase and rutile phases at each annealing temperature were
calculated for each of the bi-layer films, as well as the pure
TiO2 film using Eq. (1), and the values are shown in Table I.
There are several trends that are apparent for all the samples,
as well as several trends that can be seen that differ for the
number of layers. To further highlight these changes, the an-
atase and rutile grain sizes were plotted in three dimensions
with respect to the post-deposition annealing temperature
and number of bi-layers in Figs. 2(a) and 2(b), respectively.
For every sample, as the post-deposition annealing tem-
perature increases, so does the size of each crystal (without
taking into account the emergence or disappearance of each
crystal phase). This trend is consistent with previous litera-
ture regarding the crystal size of TiO2 at high temperatures.
It is interesting to note that as the number of layers increases,
FIG. 3. (Color online) The percentage of anatase for the bi-layer films as
the post-deposition annealing temperature is increased from Ta ¼ 450  C to
Ta ¼ 950  C in 100  C increments. The plots represent the 9-bi-layer film
(bottom line), the 18-bi-layer film, 27-bi-layer film, 36-bi-layer film, 45-bi-
layer film, and the TiO2 film (top line). It can be seen that as the number of
bi-layers increases, the change in the percentage anatase shifts out to higher
temperatures becoming closer to the trend of pure TiO2.
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J. Appl. Phys. 111, 024301 (2012)
FIG. 2. (Color online) The grain size as
calculated by XRD as a function of the
number of bi-layers and annealing tem-
peratures for (a) the anatase crystals, and
(b) the rutile crystals.
the average size of the crystals also increases. This is an un-
usual trend because as the number of layers increases, the
thickness of each layer decreases, giving less vertical room
for the crystals to form. This pattern suggests that as the
TiO2 layer thickness decreases, either the anatase and rutile
crystal orientations grow along the horizontal axis as
opposed to the vertical axis, which is preferred in the thicker
films, or the crystals span several layers. This possibility
would be very interesting, because it would effectively place
the thin TiN layers in the middle of a larger TiO2 crystal,
which could then act as a nitrogen-doped TiO2 crystal. This
should thus have a significant impact on the optical proper-
ties of the films. In addition, the natural anatase formation
versus the crystallization of the anatase phase seems to be
dependent on the thickness of the layers as well. For exam-
ple, the as-deposited thin film of TiO2 shows an anatase crys-
tal size of d ¼ 22.0 nm. The only other films that show an
as-deposited anatase crystal structure are the 9-bi-layer, and
18-bi-layer, which have TiO2 layer thicknesses of 47 nm and
23 nm, respectively. This suggests that the anatase formation
during deposition requires at least 23 nm within the TiO2
layer to form, which is consistent with the average crystal
size of the TiO2 film (22 nm). In turn, this crystal size is very
close to the thickness of the 18-bi-layer film (23 nm), and
therefore the anatase formation should be greater in this film
and the film with a thicker TiO2 layer (9 bi-layers) because
of the larger area for crystal growth in the TiO2 layers of
these films.
Whereas the trend for the anatase crystal size increases
with the number of layers, a reverse trend is seen for the ru-
tile crystal size. This could be explained by the preferred ori-
entation of the rutile crystal, as well as the effect of the
interfacial area between the TiO2 and TiN layers. It appears
that as the TiO2 layer decreases in thickness, the anatase
crystals are able to incorporate the nitrogen from the TiN
intermediary layers, and form larger crystals that span the
thickness of more than one TiO2 layer. This is seen through
the optical properties, which show a bandgap within the visi-
ble light range, indicative of nitrogen doping in TiO2. How-
ever, the rutile crystallites show the opposite trend, and
appear to be confined strongly within the TiO2 layer. In this
case, as the layer thickness decreases, the rutile crystal size
also decreases, showing a direct relationship between the
024301-6 Smith et al.
TiO2 layer thickness and the size of the rutile crystal. In
addition, the rutile TiO2 layers appear to not incorporate the
nitrogen from the intermediary layers very well, nor extend
the crystal size beyond one layer. The optical properties of
these films show strong reflection in the visible light range,
which is not indicative of nitrogen-doped TiO2. Thus, it
appears that the anatase crystal structure is able to extend its
crystal size beyond one TiO2 layer by incorporating nitrogen,
whereas the rutile crystal is unable to perform this act in this
situation.
To calculate the phase content of each sample, the peak
intensities for the rutile peak (100) and anatase peak (101)
can be compared. The fraction of anatase in each sample, fA,
can be calculated using the following equation:12,13
1 A possible explanation for the large variance in the
fA ¼ ; (2)
1 IR
1þ
K IA
where K is a constant (K ¼ 0.79 for fA > 0.2, and K ¼ 0.68 for
fA  0.2), IR is the height of the (100) rutile peak, and IA is
the height of the (101) anatase peak. It is straightforward to
calculate the fraction of rutile, fR, in each sample,
fR ¼ 1  fA :
Because this system of numerous bi-layers is very compli-
cated and unique, a standard method to determine the exact
uniform crystallinity is not straightforward. It is especially
hard to determine the impact and concentration of the
amorphous phase by x-ray diffraction.35 Therefore, we have
utilized the method of Yan et al.,12 shown in Figure 3 to
determine the relative fraction of anatase and rutile in each
film. For a comparison, the method of DeLoach et al.36 was
also utilized, and the results that compare the two methods
are shown in the Supplementary section.37 Overall, the
trends of these two methods are comparable, and show simi-
lar results.
Using Eq. (2) and Eq. (3), it is possible to examine how
the fraction of anatase and rutile change for each bi-layer
sample as a function of temperature. The constant, K, in
Eq. (2) is used as a scaling factor which can inherently
include a portion of amorphous content in the films at very
low levels of crystallization. For example, the value of K is
smaller when the anatase fraction is less than or equal to
20%. These initial growth phases from amorphous to anatase
may in fact have small amounts of amorphous crystal struc-
ture within the crystallizing lattices. This is why the value for
K changes for very small fractions of anatase, and can be con-
sidered the scaling factor that includes the amorphous phase.
The percentage of anatase for each of the bi-layer samples as
well as the pure TiO2 films is plotted in Fig. 3 as a function of
the annealing temperature. The general trend for each sample
is that the anatase phase emerges predominantly after anneal-
ing at TA ¼ 450  C, which is consistent with prior experiments
and literature. After annealing at TA ¼ 550  C, the rutile phase
emerges for each bi-layer sample, and thus the percentage of
anatase begins to decrease. The pure TiO2 film shows the
most stability in the anatase phase at high temperatures, and
is dominated by anatase up to TA ¼ 850  C. The 45-bi-layer
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J. Appl. Phys. 111, 024301 (2012)
film shows the closest trend to the pure TiO2 film, staying
predominantly anatase up to TA ¼ 750  C. The overall trend
for the bi-layer films is that as the number of layers decreases,
the anatase to rutile phase transition shifts to lower tempera-
tures. For instance, the 9-bi-layer film is only dominated by
the anatase phase up to TA ¼ 550  C, a significant change
from the pure TiO2 film and the other bi-layer films. The
phase-transition temperatures we found for the anatase to
rutile transition vary a great deal for each of the bi-layer
samples. The maximum and minimum phase-transition tem-
peratures we found for the 9-bi-layer and 45-bi-layer films
are within the limits that Yang et al.21 reported, compiling the
results from several studies, showing the unique control this
fabrication method has for controlling the anatase to rutile
phase transition.
phase change temperatures can be ascribed to the TiN films
that border the TiO2 layers. TiN is a hard ceramic material,
and can possibly make it harder for the TiO2 crystals to
change shape/form close to the TiO2/TiN boundaries. When
the film layers are very thin, this boundary effect may not be
large enough to affect the whole TiO2 layer, whereas in the
thicker films this boundary effect can be felt throughout the
(3) entire surrounding TiO2 layers. However, thin films of TiN
begin to oxidize to rutile TiO2 between TA ¼ 650  C and
750  C. After annealing at TA ¼ 850  C, all of the bi-layer
films become rutile, with no discernable peaks for TiN pres-
ent. For the bi-layer films with a thicker layer of TiN, i.e.,
the 9-layer film, the rutile phase arises and is dominant at
TA ¼ 650  C. At this temperature, the TiN layer is suppos-
edly not oxidized and should show no peaks for rutile TiO2,
meaning the origin of the rutile peaks can be attributed to the
phase change in the TiO2 layer, and not the TiN layer. For the
films with thinner TiN layers, i.e., the 45-layer film, a rutile
diffraction peak can be found beginning at TA ¼ 550  C, which
again is not consistent with the oxidation of TiN. In addition,
Arbiol et al.29 reported that Nb-doped TiO2 films showed dis-
tinct changes in their crystallography and phase-transition
temperatures because of the effects of doping, which are con-
sistent with our results. Because of this, it seems reasonable to
assert that the variance in the phase-transition temperature
found in the TiO2 layers is because of either the spatial con-
finement of the TiO2 layers, the thickness of these layers, and
possible boundary effects from TiN, or from a small amount
of nitrogen doping present at the boundary layers.
B. Optical properties
A predominant aspect of the bi-layer films was their
change in color and transparency that was a function of the
number of layers and TiN/TiO2 thickness. A photograph was
taken of each of the bi-layer films, as well as a pure TiO2
film deposited on glass substrates with the same thickness,
shown in the Fig. 4. The pure TiO2 film is almost completely
transparent compared to the films with different layers of
TiN. The films with thicker TiN (smaller number of layers)
appear to be the darkest, and the films get progressively
lighter as the TiN layers become thinner. This description of
the color change in the samples is only subjective, but it is
024301-7 Smith et al.
used to provide quantitative agreement with the optical prop-
erties measured by spectroscopy.
The optical properties for the TiO2 and bi-layer thin film
samples were measured before and after annealing at
Ta ¼ 450  C. The transmission and reflection spectra for each
sample were measured directly, and the spectra for the
annealed films are shown in Fig. 5. The TiO2 single-layer
film shows high transmission at longer wavelengths with dis-
tinct interference oscillations, then a sharp decrease begins
around k ¼ 380 nm toward smaller wavelengths. The trans-
mission spectra look very similar for the 45- and 36-bi-layer
thin films, with a very small increase in the transmission
onset, shifting further out to longer wavelengths by several
nanometers. However, the transmission spectra for the 9-,
18-, and 27-bi-layer films differ greatly from the previous
films. The 27-bi-layer film shows a similar trend to the previ-
ous samples, but the transmission onset at lower wavelengths
has shifted out to k ¼ 391 nm, and shows a slightly lower
overall transmission at higher wavelengths. The 9- and 18-
bi-layer films shows very small transmission at higher wave-
lengths, with the 9-layer films showing the lowest overall
transmission. The transmission for both films significantly
decreases at around k ¼ 466 nm, a marked shift out to the
visible range from the TiO2 film and bi-layer films with 36
or more layers.
The reflection spectra for all the samples show similar
trends, with only slight differences in the number and height
of oscillations, Fig. 5(b). Each film shows distinct oscilla-
tions beginning at longer wavelengths, and they continue to
shorter wavelengths. The only noticeable difference in all
the samples is that the 9- and 18-bi-layer films have a
slightly decreased reflection throughout the spectra, but the
overall shapes of the spectra remain very similar.
To obtain the effective optical bandgap of the single
layer and bi-layer films, we have calculated the absorption
spectra using the following equation:38,39
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J. Appl. Phys. 111, 024301 (2012)
FIG. 4. (Color online) Photograph of the
as-deposited films on glass showing the
range of colors produced for the differ-
ent samples with (a) pure TiO2, (b) 9 bi-
layers, (c) 18 bi-layers, (d) 27 bi-layers,
(e) 36 bi-layers, and (f) 45 bi-layers.
0 !1=2 1
ð1  RÞ2 ð1  RÞ4
A ¼ ad ¼ ln@ þ A; (4)
2T 4T 2
where A is the absorbance, a is the absorption coefficient, d
is the thickness of the sample, and R and T are the reflection
and transmission spectra. This equation is useful for obtain-
ing a useful absorption spectra from composite transmission
and reflection spectra, which have very high levels of inter-
ference oscillations, as seen in our spectra (Fig. 5). The cal-
culated absorbance spectra for the annealed samples are
shown in Fig. 6(a). The TiO2 film shows very low absorb-
ance at higher wavelengths, and the absorption increases
drastically at around k ¼ 360 nm. Similarly, the 45- and 36-
bi-layer films show very low absorbance at higher wave-
lengths, and their absorption onset shifts out to k ¼ 365 nm
and k ¼ 376 nm, respectively. The 27-bi-layer film shows a
drastic change in the shape of its absorption spectra. The
absorption is very low at higher wavelengths, but begins to
increase steadily at around k ¼ 500 nm, then dramatically at
around k ¼ 369 nm. The 9- and 18-bi-layer samples both
show significantly higher absorption at higher wavelengths,
with the 9-bi-layer sample showing the highest absorption.
In addition, the absorption onset for the 18- and 9-bi-layer
samples shifts out to around k ¼ 550 nm for both samples.
The shift in the absorption spectra for the samples with 9-,
18-, and 27-bi-layer samples can be because of the effect of
the TiN layer on the TiO2. There is a possibility that the
interface between the TiO2 and TiN layers can allow for a
small amount of nitrogen diffusion into the TiO2, creating a
layer of nitrogen-doped TiO2, as well as the thin TiN layers
becoming encapsulated within the larger TiO2 crystals, as
mentioned above. This effect could be pronounced in the
aforementioned samples because of the thickness of the TiN
layers, whereas this phenomenon is not seen in the samples
with 36 and 45 bi-layers because the TiN layer is too thin.
FIG. 5. (Color online) Transmission (a),
and reflection (b) spectra for the pure
TiO2 (top most curve), 9-bi-layer (bottom
most curve), 18-bi-layer, 27-bi-layer, 36-
bi-layer, and 45-bi-layer films.
024301-8 Smith et al.
FIG. 6. (Color online) Calculated absorbance spectra for the pure TiO2 (bot-
tom curve), 9-bi-layer (top curve), 18-bi-layer, 27-bi-layer, 36-bi-layer, and
45-bi-layer films. The inset shows a zoomed-in view of the absorption onset
region, between k ¼ 300 nm and k ¼ 550 nm.
N-doped TiO2 has shown the ability to effectively absorb
visible light, which could explain the shift in the observed
absorption spectra.
The effective optical bandgaps were also calculated for
each sample. To obtain the bandgap for the thin films, we
plotted (ah)1/2 versus h, shown for the annealed samples
in Fig. 7. The bandgap energy can be obtained by following
the linear portion of this plot through the x axis, at which
point we determine the bandgap. The effective bandgaps for
the TiO2 film and bi-layer samples were determined by this
method, and the calculated values were placed into Table II
for comparison. There are several interesting trends that can
be seen from this table. The pure TiO2 films show a bandgap
very close to that of bulk TiO2, EG ¼ 3.2 eV, as reported in
literature. The samples with 45 and 36 bi-layers show a
bandgap energy closest to the pure TiO2 before and after
annealing. This can be because of the thinness of the TiN
layers in these films. It is possible that the TiN layers are so
thin that they have a very small or negligible effect on the
optical properties of TiO2, similar to how these samples
were the closest to the pure TiO2 in crystallinity found in
the XRD patterns. However, as the thickness of the TiN
layers (and TiO2 layers) increase, the bandgap appreciably
decreases. A minimum bandgap energy is achieved in the
9-bi-layer sample, showing an energy close to EG ¼ 2.93 eV,
which corresponds to a wavelength of k ¼ 421 nm. In addi-
tion, secondary bang gap energies can also be estimated for
the 9-, 18-, and 27-bi-layer samples, because they exhibit an
extra shoulder of absorbance, with a second linear portion
that can also be extracted to the zero-point. If these areas are
extracted, the bandgap energies correspond to EG ¼ 2.37 eV,
2.27 eV, and 2.06 eV for the 27-, 18-, and 9-bi-layer sam-
TABLE II. The calculated bandgap energy for each bi-layer and single layer TiO2 thin film before (as-deposited/A.D.) and after (450  C) annealing.
TiO2 9 Layer
Sample A.D. 450  C A.D. 450  C A.D.
EG (eV) 3.38 3.29 3.08 2.99 3.16
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J. Appl. Phys. 111, 024301 (2012)
FIG. 7. (Color online) Tauc plot used to extract the banggap energy for the
pure TiO2 (bottom curve), 9-bi-layer (top curve), 18-bi-layer, 27-bi-layer,
36-bi-layer, and 45-bi-layer films.
ples, respectively. These energies correspond to visible light
absorption at k ¼ 523 nm, 546 nm, and 602 nm, which
directly correlate to the initial absorption edges seen in the
absorbance spectra for these samples. The reduced bandgap
may be from the interface between the film layers that can
create an N-doped TiO2 layer, which has shown the ability to
shift the absorption of TiO2 from the uv range to the visible,
described above.
C. Linear sweep voltammetry
Linear sweep voltammograms of the bi-layers films and
TiO2 were measured in an ambient dark condition, as well as
under uv and visible light irradiation. For simplicity, the
dark, uv, and visible light linear sweeps are shown for the
9-bi-layer (Fig. 8(a)) and 45-bi-layer films only (Fig. 8(b)).
For the 9-bi-layer film, the dark current is approximately
5 lA/cm2 at 0.8 V, and there is a shift to a positive cur-
rent at about 0.5 V, reaching a maximum of about 1.5 lA/
cm2 at 0.3 V. As the applied potential increases to 1.0 V,
the dark current stays almost steady at around 1.5 lA/cm2.
At a cathodic potential greater than 1.0 V, there is a sharp
increase in the dark current because of water splitting. The
photocurrent deviates from the dark current under both uv
and visible excitation, although the difference is much
greater for uv light. Under these conditions, a maximum pho-
tocurrent of about 12 lA/cm2 is generated as the potential
sweep from 0.3 V to 0.4 V. However, under visible light
irradiation, a maximum photocurrent of approximately 3.5
lA/cm2 is generated in a similar potential sweep. This dis-
parity is understandable, because the absorption spectrum for
this film shows significantly larger absorbance at uv wave-
lengths than at visible wavelengths.
18 Layer 27 Layer 36 Layer 45 Layer
450  C A.D. 450  C A.D. 450  C A.D. 450  C
2.99 3.17 3.08 3.18 3.15 3.28 3.27
024301-9 Smith et al.
The linear sweep voltammograms show a similar trend
for the other bi-layer films. The 45-bi-layer film, however,
shows a distinct peak in the photocurrent at potential near
0.0V. The dark current shows a peak at around 0.1V,
whereas the visible and uv- induced currents show peaks at
0.0V and 0.1V, respectively. This peak may be because of
the intercalcination of Naþ and Hþ ions into the TiO2 layer
followed by their deintercalcination at higher potentials. The
peak is greater for the visible and uv light scans because of
the addition of photoexcited charge carriers to the overall
current. The uv light scan again shows the highest photocur-
rent, with a maximum 18.2 lA/cm2 at the height of the inter-
calcination peak, and an average maximum photocurrent
increasing from 12.2 lA/cm2 to 17.1 lA/cm2 as the potential
increases from 0.2 V to 1.0 V. The visible light scan shows a
similar trend, with a maximum photocurrent of 9.8 lA/cm2
at the height of the intercalcination peak, and an average
maximum photocurrent increasing from 4.2 lA/cm2 to 4.7
lA/cm2 as the potential increases from 0.1 V to 1.0 V.
To compare the photocurrent generation performance of
the bi-layers films, the maximum uv photocurrent is plotted
in Fig. 9. Two maxima are seen for photocurrent generation,
which can be attributed to two different effects. Initially, as
the number of layers increases from 9 to 18, the photocurrent
increases. This can be because of the increase in the
number of heterojunctions that promote effective charge sep-
aration. The 18-bi-layer films has almost double the amount
of TiO2/TiN junctions as the 9-bi-layer films, so it is straight-
forward to assume that the increase in junctions is directly
FIG. 9. (Color online) Photocurrent generated under uv light irradiation for
each of the bi-layer films. Films were annealed at 450  C.
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J. Appl. Phys. 111, 024301 (2012)
FIG. 8. (Color online) Linear sweep
voltammograms for (a) the 9-bi-layer
film, and (b) the 45-bi-layer film. Films
were annealed at 450  C.
related to an increase in charge separation. However, the 27-
bi-layer films show a sharp decrease in photocurrent genera-
tion as compared to the 18-bi-layer films. Whereas the 27-
layer film has more heterojunctions than the 9- and 18-bi-
layer films, it produces significantly less photocurrent. This
can be the result of overlapping charge separation regions,
which can have a destructive effect on the charge separation.
If photogenerated charges are free to move within the TiO2
layer after excitation, they can feel an equal and opposite
pull toward the opposing TiN layers. When two such regions
overlap, the result is that the charge will not separate effi-
ciently, have a decreased lifetime, and will be more likely to
recombine with a hole. As this effect was seen in the transi-
tion from the 18- to 27-bi-layer films, we can assume that the
critical effective charge separation region is a distance in
between the thickness of the TiO2 layers for these two films.
Furthermore, because the effective space charge region is
close to the TiO2/TiN interface, and there are two of these
interfaces on each TiO2 layer, we can assume that the effec-
tive charge separation is half of the thickness of these TiO2
layers. Using this, we can assume that the effective charge
separation region is between 7.5 nm and 11.5 nm for our
films. However, the thickness of the TiN layer may also be a
factor in the depth of the space charge region, so further
experiments keeping the TiO2 thickness constant and varying
the TiN thickness need to be carried out. Whereas the 9- and
18-bi-layers films show strongly improved photocurrent
because of enhanced charge separation, it is also important
to note the strong increase in photocurrent generation for the
36- and 46-bi-layer films. Although these films have smaller
TiN layers, and thus have a reduced charge separation com-
pared to the films with thicker TiN layers, the anatase crystal
size for these films is much larger than the other films (see
Table I). We therefore believe that the increase in the photo-
current measured for these films is because of an increased
anatase crystal size, which leads to improved charge mobil-
ity and produces more current.
Comparing the visible light photocurrent generation for
each sample reveals a similar trend, with a maximum
achieved at 18 bi-layers, then a sharp decrease because of
the diminishing space charge region, and then a gradual
increase as the layers increase. It is interesting to note that
the pure TiO2 film showed no visible light photocurrent, so
the addition of thin TiN layers has shown a remarkable abil-
ity to absorb visible light and create mobile electronhole
024301-10 Smith et al. J. Appl. Phys. 111, 024301 (2012)

10
pairs. This supports the uv-vis data, which showed that the O. K. Varghese, D. W. Gong, M. Paulose, K. G. Ong, and C. A. Grimes,
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ACKNOWLEDGMENTS 32
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6
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7
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8
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