88 Recent Patents on Materials Science 2009, 2, 88-111

Recent Progress on Development of TiO2 Thin Film Photocatalysts for

Pollutant Removal
Radhiyah A. Aziz and Iis Sopyan*

Department of Manufacturing and Materials Engineering, Faculty of Engineering, International Islamic University
Malaysia (IIUM), PO Box 10, 50728 Kuala Lumpur, Malaysia

Received: December 5, 2008; Accepted: December 18, 2008; Revised: January 5, 2009
Abstract: This review paper is to give an overview of the recent progress on the development of TiO2 thin film
photocatalysts for pollutant removal. Photocatalysis process involves the photoinduced oxidation and reduction reactions
in the photocatalyst that has the ability in degrading most organic compounds into carbon dioxide, water and any harmless
substances. Upon the exposure of ultraviolet light of wavelength
< 390nm, the photocatalyst plays its role in degrading
any kind of pollutants either in liquid or gaseous phase. One of the most outstanding photocatalysts that has received
particular attention in application is titanium dioxide due to its high chemical stability and photocatalytic activity. The
development of the photocatalyst in the form of a thin film is due to the impractical use of conventional powder
photocatalyst in certain environmental applications. Recent patents of the thin film photocatalyst as well as some
environmental applications have also been reviewed. Also included are techniques for modifying thin film characteristics,
film deposition methods and variation in types of substrates used for improved photocatalytic properties of the TiO2 thin
film.
Keywords: Thin film, TiO2, photocatalysis, pollutant removal, patent, review.

INTRODUCTION higher photocatalytic activity compared to CdS for the

Nowadays, the most severe problem is environmental
pollution either water or air pollution due to uncontrollable
industry development and inadequate pollution prevention/
treatment techniques. For last two decades, researchers have
paid much attention on another alternative method to settle
environmental problems namely photocatalysis. A photo-
catalytic process is a surface reaction on a photocatalyst
semiconductor which basically takes places under UV light
irradiation to produce radical oxidizing and reducing agents.
Photocatalyst creates a strong oxidation agent to break-
down any organic matter to carbon dioxide and water in the
presence of photocatalyst and light. A catalyst does not
change itself or be consumed in the chemical reaction and
the possibility of using solar energy as the light source
makes the process of photocatalysis suitable for developing
nations. Furthermore, this reaction only occurs under
ambient temperatures and does not produce any harmful
substance after the process has completely finished. The
most valuable aspect of this photocatalysis is the reusability
of photocatalyst that make this process inexpensive and cost
effective.
Titanium dioxide (TiO2) has been recognized as an
excellent photocatalyst since it has chemical stability and
high photocatalytic activity. Many researchers found that
TiO2 has greater photocatalytic activity than ZrO2, WO3,
SnO2, and CdS. For example, TiO2 photocatalyst showed
*Address corresponding to this author at the Department of Manufacturing
and Materials Engineering, Faculty of Engineering, International Islamic
University Malaysia (IIUM), PO Box 10, 50728 Kuala Lumpur, Malaysia;
Tel: +603-61964592; Fax: +603-61964477; E-mail: sopyan@iiu.edu.my
decomposition of phenol as the target organic species [1].
Even though ZnO shows higher photocatalytic activity than
TiO2, the photochemically stable TiO2 in aqueous media
makes it more favorable for environmental applications [1].
There are 3 kinds crystal structure of TiO2; anatase, rutile
and brookite. TiO2 that is used as the photocatalyst is mainly
the anatase-type crystal structure since it has a higher band
gap energy compared to the rutile crystal structure. This
character of anatase can reduce the electron-hole recom-
bination process and leads to the higher degree of surface
hydroxylation that will produce more hydroxyl radical on the
surface upon illumination. Definitely, this would lead to the
higher photocatalytic activity. The rutile type structure can
absorb the rays that are slightly closer to the visible region. It
is assumed that the rutile type is more preferable photo-
catalyst for photocatalysis applications. However, the energy
structure of rutile type cannot give better photocatalytic
performance since its conduction band is positioned near the
oxidation-reduction potential of the hydrogen, leading to its
weak reducing power.
The position of oxygen ions on the exposed crystal
surface of anatase shows a triangular arrangement, allowing
effective absorption of organics [1]. Moreover, the position
of titanium ions creates a favorable reaction condition with
the absorbed organics that are not available for the rutile
structure [1]. This unique character of anatase would lead to
the high photocatalytic activity. However, some researchers
stated that pure anatase TiO2 would not necessarily lead to
such better photocatalytic performance [1]. The presence of
several percent of rutile phase introduces mesoporosity
structure and a wider pore distribution that may be
responsible for the improved photocatalytic activity. One of

1874-4648/09 $100.00+.00 © 2009 Bentham Science Publishers Ltd.

Review on TiO2 Film Photocatalyst
the examples is the commercially available Degussa P25
TiO2, that contains 70% anatase and 30% rutile.
Another factor that affects the photocatalytic activity is
the surface area of photocatalyst used. Theoretically, a
smaller particle size gives larger surface area and directly
leads to higher expected photocatalytic activity. It is due to
the increase in the number of active sites per square meter
which leads to the greater ability of pollutants absorption on
the photocatalyst surface [1].
Many studies have been published on the use of TiO2 as a
photocatalyst for the decomposition of organic compounds.
There is no harmful by-products produced and process has
been proven effective in removing trace amounts of organic
compounds from either the liquid or gaseous phase. For
example; organic dyes [2-10], aldehyde gas [11-15], alcohol
[16, 17], oxide gaseous [18-21], organic acid [22, 23] have
been degraded by TiO2 photocatalytic action. There are also
many reports on the use of photocatalysis for the destruction
of microorganism like bacteria, fungi and algae [24-26].
Most of the photocatalysts used for removing pollutants
are in the form of fine powders, due to the strong oxidation
power of photo-generated holes on the surface of the fine
powder. However, in certain applications, the use of fine
powder could create several problems: (1) Difficulties in
separation of the photocatalyst from suspension [27-30], (2)
Aggregation of suspended particles especially at high
concentrations [30], (3) Only small amount of powder can be
applied [30], and (4) Even when photocatalyst powder is
used in a coated form, its weak adherence could not avoid
from easy detachment from the supports [30]. Therefore,
development of supported or film type photocatalyst
becomes essential for environmental applications. Various
Reduction
mechanism O2 -
Free electron
O2
e-
e- e-
H2 O
Oxidation Hole(+)
mechanism OH
Fig. (1). Photocatalysis mechanism.
Recent Patents on Materials Science 2009, Vol. 2, No. 2 89
materials have been used as the supports for TiO2 powder
photocatalyst. Polymers, clays, cements, silica are in the list
of materials tried. In this review TiO2 film photocatalyst will
be discussed involving techniques for the enhancement of
photocatalytic properties, deposition methods, and its
application for pollutants removal. Several recent patents of
TiO2 thin film photocatalyst development will be also
discussed.
PHOTOCATALYSIS PROCESS
Since the discovery of the photocatalytic splitting of
water on TiO2 electrodes in the early 1980s by Fujishima and
Honda, TiO2 photocatalysts have generated great attention as
alternative semiconductor materials for its application in
solar energy conversion and environmental purification [31].
In the field of photocatalysis, they are highly suitable due to
a favorable combination of electronic structure, light
absorption properties, charge transport characteristics, and
excited-state lifetimes. In their electronic structure, which is
characterized by a filled valence band and an empty
conduction band, semiconductors like metal oxide or sulfides
(ZnO, CdS, TiO2, Fe2O3 and ZnS) can act as sensitizers for
light-induced redox process. The energy difference between
the lowest energy level of the conduction band and the
highest level of the valence band is known as the band gap
energy, Ebg. It corresponds to the minimum energy of light
required to make the material electrically conductive. When
a semiconductor photocatalyst surface absorbs impinging
light with energies equal to or higher than its band gap or
threshold, it excites the electrons in the valence band to the
conduction band, resulting in the formation of positive hole
(p+) in the valence band and an electron (e-) in the
conduction band Fig. (1).
Sun
UV Irradiation
<< 380 nm
Band Gap Energy
(TiO2 = 3.2eV)
e- e- e- e- e- e-
Electron (-)
90 Recent Patents on Materials Science 2009, Vol. 2, No. 2
The positive hole oxidizes either pollutants directly or
water to produce OH. radicals, whereas the electron in the
conduction band reduces adsorbed oxygen. This is illustrated
in Fig. (1). The mechanism can be expressed by Eqs. (1)- (5)
below;
Photocatalyst (TiO2) + hv (> Ebg) e- + p+ (1)
- -2
e + O2 O (2)
p+ + organic CO2 (3)
p+ + H2O OH• + H + (4)
OH• + organic CO2 (5)
The degradation process of the pollutants, the reduction
process of oxygen and oxidation process of pollutants do not
proceed simultaneously, since these charge carriers may take
different paths. Beydoun et al. [32] explained that they can
get trapped, either in shallow traps or in deep traps.
Secondly, they can recombine, non-radiatively or radiatively,
dissipating the input energy as heat if large particles of
semiconductors are used. As such, favorable nanoscale of
TiO2 particles was widely utilized in most of photocatalyst
application. Theoretically, nanosized particles of photo-
catalyst would increase the band gap energy, and directly
decrease the charge carrier recombination problem. In
addition, it is easier for excited charge carriers to reach the
surface active sites and react with adsorbed pollutants (See
Fig. (2)). However, the nanosized particles of photocatalyst
would also lead to charge carrier recombination but at a
different situation and different location, which is known as
surface recombination. This happens due to the higher
surface recombination rate than interfacial charge carrier
transfer processes and most of the charge carriers produced
UV
Large scale TiO2 particle
CB
Lower band gap
VB
Slower photocatalytic
activity
Fig. (2). Effect of nanoparticles photocatalyst on photocatalysis.
Aziz and Sopyan
in nanosized particles are close to the surface. This is the
reason why there exists an optimum particle size of photo-
catalyst for maximum photocatalytic efficiency [32]. How-
ever, the nanosized particles of photocatalyst would lead to
other serious problems when applying it in the environment.
DEVELOPMENT OF PHOTOCATALYST THIN
FILMS
Nanocrystalline semiconductor films constitute a
network, wherein electronic conduction can occur [32]. Thin
film photocatalyst has certain potential properties that can
make it more favorable for applications in environmental
purification. It is proved that TiO2 thin films are widely used
in many fields such as functional materials, adsorbent
catalysts, and gas and humidity sensors as well as in ecology
for wastewater treatment and air purification [33, 34]. Thin
film photocatalyst could prevent from respirable particle
problems that exist in mobile photocatalyst powder which is
not good for human health [18]. Besides, it is more practical
for the immobilization technique since the thin film can be
applied on certain materials in buildings such as stainless
steel that has high mechanical strength and relatively high
resistance to chemical corrosion. Indirectly, this building
material can become self-cleaning and air-purifying with a
layer of thin film photocatalyst [18]. Thin film photocatalyst
can also overcome the problems of using powder or slurries
photocatalyst [4, 8, 23, 31, 35]. The penetration of light is
also one of the problems in the photocatalysis process when
using powder or slurry of fine particles. However, by coating
the photocatalyst on support materials this problem can be
eliminated. Unlike the powder form, the thin film form can
prevent the scattering of light and enhance the transmittance
of light, therefore resulting in higher photoreaction effi-
ciency [36]. Another advantage of the thin film photocatalyst
application is that the layer may be connected to an external
UV
Nanoscale TiO2 particle
CB
Higher band gap
VB
Higher photocatalytic
activity
Review on TiO2 Film Photocatalyst
power source to reduce the recombination of UV-activated
electrons and holes and thus, the efficiency of the catalyst
could be increased [37]. Zhou et al. [38] mentioned that if a
conductive material is used as the substrate, the catalyst film
can be connected to an external potential to remove excited
electrons to reduce electron-hole recombination, thereby
significantly improving the process efficiency.
However, there are several problems of film immobi-
lization technique. Zhou et al. [38] revealed two obvious
problems arising from this method; the accessibility of the
catalytic surface to the photons and the reactants, and a
significant influence of the external mass transfer parti-
cularly at the low fluid flow rate. If the thickness of thin film
increases, the internal mass transfer may play its negative
role by limiting the utilization of the catalyst near the
substrate surface. Therefore, a lower overall degradation rate
is found in the immobilized system compared to that of the
suspended system.
It is well known that the photocatalytic activity of TiO2
thin film depends strongly on doping method [18], the
amount of doping [18], structure [33], morphology, grain
size, specific surface area, surface hydroxyl content, film
thickness and substrate used. All of these factors can be
modified by varying certain preparation condition and
properties of the thin film photocatalyst. All these topics will
be discussed in the next section.
THIN FILM PHOTOCATALYST PROPERTIES
REQUIREMENT
Thickness of Thin Film
Even though the thin film photocatalyst application could
overcome the problem of the use of conventional powder
photocatalyst in environmental purification, the fabrication
of desirable character of thin film photocatalyst would be a
critical aspect that a researcher needs to consider. For
instance, the fabrication of TiO2 thin film coated on window
glasses, light bulbs, ceramic tiles, or walls face many
practical problems since it has to be fitted with industrial
application. Among the problems are transparency of TiO 2
thin films, adhesion to glass substrate, blocking of impurity
migration from the substrate and determination of optimum
film thickness.
Photocatalysis is a surface reaction [16, 23]. Since the
surface area of thin film is not appreciably affected by the
change of thickness, it is logical to assume that photo-
catalytic activity is irrelevant to the thickness of the TiO 2
thin film [16]. In fact photocatalytic activity is strongly
dependent on film thickness. Thicker films tend to show
higher photocatalytic activity due to some reasons such as;
(1) larger surface area associated with increased roughness,
(2) more difficult diffusion of impurities from substrate to
film surface during calcinations for thicker film, so the effect
of impurities on photocatalytic activity is reduced, (3) TiO2
underneath the surface can be excited by irradiation light if
the thin film is transparent enough, and the photogenerated
electron-hole pair may be transferred to the surface of TiO2.
However, these possible factors must be reconsidered with
the condition of thin film fabrication technique such as the
sol-gel method which would not produce a rough surface of
Recent Patents on Materials Science 2009, Vol. 2, No. 2 91
TiO2 thin film, and the diffusion of impurities would not
occur for pure silica substrate. The number of active sites
increase with the increasing thickness film since the
electron-hole pairs can be transferred easily once they have
moved to the grain boundary and continue to be transferred
to the surface of film along the grain boundary Fig. (3).
Fig. (3). Suggested possible pathways for the transfer of electron-
hole pairs generated in the bulk to the surface of TiO2 [16].
Fallet et al. [22] also found that the photocatalytic
activity gradually increases with film thickness. In the
degradation of malic acid, they observed the participation of
the inner part of the film to the photocatalytic activity, whose
mechanism can be explained as follows; (1) the ability of
adsorbed liquid or gaseous reactant on the film surface to
diffuse through the pores which induced a greater quantity of
TiO2 particles involved in the photocatalytic reaction and (2)
the ability of charge carriers transfer and migration through
intergranular towards the surface in contact with the reactant.
This activity increases, however, more slowly than the film
thickness. They explained that the photocatalytic activity is
expected to be directly proportional to the mass of catalyst
for a true heterogeneous catalytic system. According to their
observation, densification of TiO2 particles on the surface
affects the photocatalytic activity. For the same thickness,
denser films are richer in TiO2 particles than porous ones
[22].
Bernardi et al. [39] proposed that the crystalline substrate
favors a better packing, leading to a minor density and
consequently, a smaller thickness obtained. The author found
that the thickness of thin film deposited on Si (100) were
thinner than those deposited on the glass substrate under the
same conditions. There are several ways to synthesize the
thicker thin film whether by repeating the cycle time of
deposition or by using a template in producing the precursor
solution. Some types of templates are available in the market
such as ionic and neutral surfactant, and non-surfactant, for
example, polyoxyethylene (10) cetyl ether [40], polyethylene
glycol [41, 42], hydroxypropyl cellulose, diolates and
cyclodextrines, Pluronic F-127 [40, 43], Pluronic P123,
Cetyltrimethylammonium Bromide [44], polyvinyl alcohol
[45], which have been used as a thickener and pore formers.
Block copolymers have also been utilized to direct the
formation of mesoporous TiO2. For instance, Truijen et al.
92 Recent Patents on Materials Science 2009, Vol. 2, No. 2
[45] utilized poly(vinyl alcohol) (PVA) in the precursor
solution, which acts as a thickener and pore-forming agent.
Cernigoj et al. [40] developed thin film with two different
surfactant; Pluronic F-127 and polyoxyethylene (10) cetyl
ether (Brij 56). The difference between these surfactants is
their molecular weight. The molecular weight of Pluronic F-
127 and polyoxyethylene (10) cetyl ether (Brij 56) is
12600g/mol and 363 g/mol, respectively. Higher molecular
weight surfactant is expected to give more viscous sol,
resulting in thicker and crack-free films.
Another approach to getting thicker film of photocatalyst
is by controlling the hydrolysis of metal alkoxide and
polymerization sol [46]. However, it is difficult to control
the solution viscosity in the sol-gel route because the
solution viscosity depends on temperature, humidity,
reaction time, mixing ratio of reagents, etc. Negishi and
Takeuchi [46] suggested a new approach to control the
solution viscosity, which is by adding a highly viscous
solvent. They used
-terpineol as a solvent since it success-
fully gives a fine and transparent thin film photocatalyst. It
does not react with metal alkoxide and has good affinity to
glass substrate, which is suitable for dip coating to be
applied in depositing the thin film. The results show that the
dipping cycle was reduced as the
-terpineol was used.
Surface Morphology
The efficiency of photocatalytic activity for semicon-
ductor is affected by several surface morphology charac-
teristics. Several researchers have come out with different
procedures to produce the suitable surface morphology for
remarkable photoactivity of thin film photocatalyst.
Ge et al. [47] produced TiO2 thin film photocatalyst with
a large strip-like crystal particles using peroxo titanic acid
(PTA) sol precursor solution without adding the PEG
template. The compact and homogeneous TiO2 thin film was
obtained after heating at 500˚C. The addition of PEG
templates greatly changed the surface structure of the TiO2
thin film. Small particles and uniform pores structure
appeared. The function of the PEG template is to suppress
the agglomeration of the TiO2 particles and induce the
formation of pore structure during the calcinations process.
The pore structure formation is strongly depending on the
amount of PEG addition. Large amounts of PEG
concentration will produce more amounts of gas during
heating, which enlarges pore size and at the same time
decrease particle size. Furthermore, the PEG templates also
act as a binder to avoid any crack formation and produce
high mechanical stability of the TiO2 thin film photocatalyst.
The porous structure of the thin film attributed to the large
specific area and the thin film easily adsorbs water vapor in
air, which leads to the formation of many hydroxyl groups.
This would lead to high photocatalytic activity of the thin
film. Falaras et al. [48] developed silver modified thin film
TiO2 photocatalyst that consisted of porous, sponge like
network of high roughness and complexity TiO2 thin film.
This lead to the high surface area TiO2 thin film which has
been proved to be highly efficient for the photocatalysis
applications. Andrew et al. [49] supported that porous film
allows the photocatalytic process to occur unhindered since
its porosity is expected to provide channels through which
Aziz and Sopyan
the essential co-reactant, oxygen, can diffuse to the surfaces
of the TiO2. In contrast, TiO2 film with dense, compact and
non-porous structure will have fewer channels, so that the
rate of diffusion to the active sites will be less [49]. The
porous structure can be collapsed when an excessive addition
of a second metal oxide in the TiO2 photocatalyst is made,
due to the decreasing homogeneity as proved by Smirnova et
al. [50] for TiO2/ZrO2 films.
US20046803077B2 [51] describes the method for
preparing mesoporous TiO2 thin film with high photo-
catalytic and antibacterial activities. The TiO2 sol-gel was
prepared from hydrolysis and condensation of titanium
alkoxide in the presence of a stabilizer and the thin film was
heat treated at temperatures ranging from 400°C to 900°C.
The stabilizer acts as a complexing agent to react with
titanium alkoxide and ensures that the TiO2 sol-gel solutions
can effectively be used to produce thin film on the substrate
even after being stored for more than two months. The
mesoporous structure of thin film was formed by adding a
template during the preparation of the TiO2 sol-gel. It has
been found that the porous size and size distribution can be
controlled by adjusting the molecular weight and the amount
of the used template. The patent discloses that the meso-
porous TiO2 thin film exhibits higher photocatalytic and
antibacterial activities than ordinary TiO2 thin film.
Defects of thin film surface can also give significant
changes in photocatalytic activity. Sheng et al. [23] produced
Pt-anatase film by magnetron sputtering at low temperatures.
They proved that the surface defects such as oxygen vacancy
can serve as active sites for the absorption of gases. Since the
photocatalytic reaction is surface reaction and only the
substance absorbed on the surface can react with the
photogenerated active seeds (e.g., h+, OH- and O), defects
may contributed to the photocatalysis reaction by providing
active sites for chemisorption and/or decomposition of the
molecules. In contrast, Quan et al. [52] mentioned that a lot
of Ti-O atomic arrangement defects would act as a center for
the recombination of photoinduced electron-hole pairs.
Therefore, regular crystal structure is the prerequisite for
TiO2 thin film photocatalyst.
Addamo et al. [53] reported that high roughness film
would lead to the high photocatalytic activity. The presence
of important mountains and valleys in the rough surface of
thin film allows a good ability to capture the incident photon
energy and directly enlarges real surface. This surface not
only enables the adsorption of a greater number of pollutant
molecules but also creates a rough environment where
multiple light reflections occur and leads to increasing the
amount of absorbed photons. This was supported by Zhou et
al. [3] who suggested that with a rougher surface more
photocatalytic reactions will take place due to larger surface
area. They also mentioned that the fractal surfaces absorb
light more efficiently and produce more photocurrent than
smooth surfaces. In their work, they produced binary
semiconductor of TiO2/SiO2 thin film which composed of
1:1 ratio. They found that TiO2/SiO2 = 1:1 has a rough
surface and highest intensity of absorbed water, which was
dependent on the surface microstructure.
It was also reported that the surface topology of a thin
film of titanium dioxide particles has an effect on the
Review on TiO2 Film Photocatalyst
photocatalytic activity. Kon et al. [54] mentioned that
increased surface roughness leads to a higher surface area as
well as allowing better diffusion of reactants. They
developed polymer honeycomb templated microporous TiO2
films and measured its photocatalytic activity on cyanide dye
degradation. They found that the honeycomb film showed
the highest photocatalytic activity due to the increased
surface area, enhanced diffusion of the dye through the
hierarchic structure and increased photon scattering leading
to an increase in quantum yield.
Characteristic of Substrate and Adhesion Property of
Thin Film on Substrate
The application of the immobilization technique on
certain substrates would lead to a wider utilization of thin
film application in solving environmental problems.
However, its sustainability to photocatalytic reaction can be
a major problem. For instance, substrates comprising of
organic materials can be decomposed and deteriorated due to
photocatalytic reaction whereas, substrates composed of
inorganic materials lead to problems of durability. Although
it can be solved by adding certain organic polymer resin
which acts as an adhesive agent, its photocatalytic perfor-
mance may be reduced due to surface coverage of photo-
catalyst particles with such resin. Therefore, the appropriate
substrate needs to be chosen according to its application.
There are several types of substrates that have been used
to support the TiO2 thin film such as; stainless steel [18],
soda lime glass [19, 28, 31], silica glass [30], borosilicate
glass [55, 56], foam nickel [57], PET [3] , Si substrate [58,
59], polyamide sheet [23], Ti metal substrate [35], porous
Vycor glass (PVG) [21] etc.
Zhou et al. [3] developed TiO2 thin film photocatalyst on
the PET substrate. Physical and chemical characterization on
the substrate showed that it has low surface energy and
thermal sensitivity, limiting the application of polymer type
substrate. To solve this problem, many methods have been
designed to prepare high photocatalytic activity TiO2 thin
film at a low temperature. A group of researchers has used
magnetron sputtering to produce TiO2 thin film on Pt-
buffered polyamide substrate [3] whereas, another group of
researchers has used the sol gel method followed by the
treatment of the films in boiling water to prepare the
crystallized TiO2 thin films. However, the treatment would
affect the adhesion of the films to the substrates. Another
technique is liquid phase deposition (LPD) which can
prepare the TiO2 thin film at low temperatures. However, the
application technique is due its low depositing rate and poor
transmittance. Zhou et al. [3] prepared the TiO2-SiO2 thin
film on the modified PET substrate by the advanced sol-gel
method. The cleaned PET substrate was immersed 5 min into
the treatment solution which was prepared by KH550
((aminopropyl) triethoxysilane) dissolved in acetone and
aged for 240h. The modified PET substrate with the silane
coupling agent would increase the adhesion between TiO2 -
SiO2 film and substrate.
Tomaszewski et al. [60] proposed that the chemical
composition of the glass support used as the substrate does
influence the activity of annealed films. The authors reported
that when the soda lime glass is used as a substrate, the
Recent Patents on Materials Science 2009, Vol. 2, No. 2 93
sodium ion diffuses into the thin film upon annealing,
suppressing the anatase crystallization and thus decreasing
its photocatalytic activity. This was due to sodium ions
acting as the recombination centre or disordering the
crystallinity of TiO2. The sodium ion in the film affects the
photocatalytic activity of theTiO2 thin films through
changing the particle size of anatase. This was supported by
Cernigoj et al. [40] who gave the following explanation. The
diffusion of Na+ ions from the bare sodium glass support led
to the formation of mixed oxide phase and larger anatase
grains. The negative influence of sodium diffusion could be
observed in the light absorption property of the thin film.
Thin films supported on the sodium glass absorbed much
less UV light than the films deposited on the glass support
which layered with SiO2. Larger anatase grains would also
bring a rougher surface as reported by Kim et al. [61]. They
revealed that surface roughness increased by abnormal grain
growth probably due to sodium or calcium diffusion near the
interface between the film and soda-lime-silica glass (SLSG)
substrate, resulting in higher root mean square (RMS)
roughness. They observed that there was difficulty in finding
a three-dimensional abnormal grain growth for the TiO2 thin
film on the silica glass (SG) substrate, while, at 600˚C, the
TiO2 thin film deposited on the SLSG substrate contained
needle-shaped abnormal grains owing to nonstoichiometry of
the TiO2 thin film. Therefore, SG substrate is more prefer-
able than SLSG substrate in obtaining highly transparent and
smooth surface of TiO2 thin film.
Tomaszewski et al. [60] have also developed a method to
decrease the influence of sodium ions by coating soda lime
glass with the e-beam evaporated SiO2 barrier layer. For the
thickness of the SiO2 layer more than 300nm, diffusion of
sodium was prevented and anatase crystallization was
observed. Watanabe et al. [12] suggested another way to
prevent the negative effect of sodium ions on the photo-
catalytic activity which is by dipping the TiO2 thin film in
HCl solution or H2SO4 solution that can reduce the
concentration of sodium and other impurities on the surface
of the TiO2 thin films.
Another kind of substrate that was recently developed by
a group of researchers from Wenfeng Shangguan is foam
nickel substrate.Hu et al. [57] developed TiO2/Al2O3 com-
posite thin film on the foam nickel substrate through the sol-
gel route and evaluated the photocatalytic activity on the
photodegradation of acetaldehyde gas. The foam nickel,
shown in Fig. (4), is a potential substrate material in practical
applications because of its excellent hydrodynamic pro-
perties for gas passing. The foam metal materials have been
used due to the uniform open-porous and reticulate structure
of foam metal materials which offers the catalytic system
excellent gas-dynamic properties and sufficient contact of
the gaseous reactants with the surface of the catalyst. It has
been proved that applications of this type of substrate are
more favorable in the liquid and gas phase photocatalytic
reactions. Thus, they are expected to be a potential substrate
in the remediation of indoor air pollution.
Adhesion of thin film on the substrate is one of the major
problems that have to be solved since most of the thin film
applications are exposed to the unpredictable conditions of
the environment. It is due to different physical and chemical
94 Recent Patents on Materials Science 2009, Vol. 2, No. 2
(a)
Acc V Macn WD 200mm
500kV 125x 179
Fig. (4). FESEM image of bare foam nickel (a) and TiO2 coated foam nickel (b) [57].
properties of the substrate which can influence the thin film
adhesion such as thermal sensitivity, surface energy, chemi-
cal stability and etc.
EP1785457A1 [62] discloses a method to provide a
coating composition that has excellent transparency and
adhesion to organic substrates and has excellent storage
stability and is also related to a layered product that has a
coating film obtained from this coating composition. A
coating composition for undercoating composition for a
photocatalytic layer which has similar properties as
mentioned before is also provided in this patent. This coating
composition is capable in forming a coating film that has
high resistance to photocatalytically generated radicals,
enhances adhesion between an organic substrate and a
photocatalytic layer and there is no decrease in photo-
catalytic performance of the photocatalytic layer. The inven-
tors found a coating composition that contains a specific
organic-inorganic hybrid polymer and polysiloxane and has
a specific molecular weight. As mentioned in this patent,
organic-inorganic hybrid polymer is prepared by adding a
catalyst to accelerate hydrolysis and condensation and water
to a mixture of at least one silane compound and a specific
silyl group-containing polymer at a specific ratio. Another
coating composition containing polysiloxane was used in
this invention. The weight-average molecular weight of
polysiloxane which are preferable in this invention were
ranged from 800-50000, 1000-40000, 2000-40000 and 3000-
30000 in terms of polystyrene. A coating composition
containing a polysiloxane with a range as mentioned above
produced a coating film with excellent adhesion to organic
substrate and durability.
Limitation of light irradiation on the photocatalyst leads
to the design of immobilized photocatalyst on a certain
substrate. Examples of substrates that have been disclosed in
some patents are; cellulose nitrate, glass, poly(vinyl
chloride), plastics, nylon, methacrylic resin, polypropylene,
ceramics, acryl and polyester resins. However, organic
materials can be decomposed and deteriorated due to
catalytic reaction caused by a photocatalyst. Even though an
inorganic material can be applied as a substrate, there are
Aziz and Sopyan
(b)
Accv Spot Macn Det WD 200mm
5.00kV 3.0 250x 2.7
problems in terms of the durability of the substrate. If an
organic polymer resin is used as an adhesive agent for
immobilizing photocatalyst on the substrate, it may lower the
photocatalytic activity due to the coverage of photocatalyst
particles with such resin. One example is fluororesin that has
been disclosed by JP06315614 [63]. However, the cost of
fluororesin is high as it needs to cover most of the surface of
the photocatalyst particles.
EP0633064A1 [64] discloses a process for obtaining a
firm adhesion of photocatalyst particles onto any substrate
over an extended period of time without lowering the
photocatalytic function of the particles. In this invention, a
photocatalyst composite consists of a substrate provided with
a first layer of less degradative adhesive without any
photocatalytic particles and a second layer of less
degradative adhesive and 5-98% by volume TiO2 having
photocatalytic function. The less degradative adhesive is one
or more polymers selected from the group consisting of a
fluorinated polymer and a silicone based polymer or
inorganic adhesive. These less degradative adhesives result
in most reduced decomposition and degradation of the
adhesives owing to the photocatalytic reaction of the
photocatalyst particles. Therefore, the photocatalyst particles
can be strongly adhered for a long period. The most
preferable less degradative adhesive comprises primarily of a
copolymer of vinylethers and/or vinylesters and fluoroo-
lefins. This patent also discloses a process for adhering
photocatalyst particles which is comprised the steps of
disposing photocatalyst particles and less degradative
adhesive by coating or spraying a coating composition
containing the photocatalyst particles, the adhesive and a
solvent on the surfaces of a substrate and then fixing the
adhesive.
EP1955768A1 [65] discloses a silicon-modified resin
such as acryl-silica resin or epoxy-silicon resin containing 2-
60% by weight of silicon, a resin containing 5-40% by
weight of colloidal silica and a resin containing 3-60% by
weight of polysiloxane, can strongly glue a photocatalyst and
protect the substrate from photocatalytic action derived from
the photocatalyst. It has been found that the binding force
Review on TiO2 Film Photocatalyst
between the adhesive layer and photocatalyst layer is
degraded and the adhesive layer is deteriorated due to the
action of photocatalyst when a silicon-modified resin
containing silicon in an amount of less than 2% by weight
and a resin containing polysiloxane in an amount of less than
3% by weight and a resin containing colloidal silica in an
amount of less than 5% by weight is used. If a resin
containing polysiloxane in an amount of more than 60% by
weight or a resin containing colloidal silica in an amount of
more than 40% by weight is used, the adhesive layer
becomes a porous and binding condition between the
substrate and adhesive layer degrades. As a resin in which
silicon is to be introduced, acryl resins and epoxy resins are
the most suitable in terms of film-forming properties,
toughness and adhesion properties to the substrate. A resin
suitable to be introduced with a polysiloxane is such as
acryl-silicon resins and epoxy-silicon resins due to its dura-
bility property. A resin which contains colloidal silica should
have a specific colloidal silica particle of 10nm or less. If the
diameter exceeds 10nm, the resin in the adhesive layer
further deteriorates due to the influence of a photocatalyst
and the binding condition between the photocatalyst layer
and adhesive layer deteriorates as well. The application of
photostabilizing and/or ultraviolet absorbent into the resin
can prevent the deterioration of a resin. In this invention,
applying a metal oxide gel or a metal hydroxide gel in a
photocatalyst layer gives strong adhesion between the
photocatalyst and adhesive layer. It also discloses that the
metal oxide gel and metal hydroxide gel have a porous
structure and are adsorbent, which further enhance the photo-
catalytic activity.
US20036649561B2 [66] describes a titania-coated
honeycomb catalyst matrix for the ultraviolet-photocatalytic
oxidation of organic pollutants. This invention uses a
honeycomb-shaped skeletal structure that has a thin,
lightweight substrate of metal or ceramic, typically an
aluminum alloy which is covered by a surface coating of
photocatalyst instead of using the polymer honeycomb as
applied by Kon et al. [50]. The honeycomb-shaped skeletal
structure is formed from a plurality of metal sheets, each
having an alternating series of crests and troughs and the
sheets are stacked such that the crests and troughs form the
respective cells. The photocatalyst is bonded to the substrate
via a thin oxide layer on the substrate. The photocatalyst
coating is made by mixing titania powder in a TiO2 sol-gel to
form a titania slurry and coated on the substrate then heat
treated. The objective of this invention is to provide a
structural support for a photocatalyst, which is relatively low
cost, light weight, has a high structural integrity, possesses
good flow characteristics and can be illuminated effectively
by an external ultraviolet source. This structural support is
also provided with the photocatalyst coating which is
adherent, durable and possesses good photocatalytic
properties.
FACTORS AFFECTING THE EFFICIENCY OF
PHOTOCATALYTIC PROCESS ON THIN FILM
Doping Materials
The photocatalytic activity of a particular semiconductor
is evaluated by several factors including the stability of the
Recent Patents on Materials Science 2009, Vol. 2, No. 2 95
semiconductor under illumination, the efficiency of the
photocatalytic process, the selectivity of the products, and
the wavelength response. For example, CdS semiconductor
is able to receive excitation in the visible region of the solar
spectrum since it has small band gap. However, it is usually
unstable and photodegraded with time [31], whereas, TiO2 is
quite stable photocatalyst, but it is only active in the
ultraviolet region since the band gap is quite large (Ebg = 3.2
eV) compared to CdS.
TiO2 photocatalyst does not allow the absorption of
visible light in the photocatalytic reaction and it only makes
use of 3-5% of the solar light that reaches the earth,
demanding the use of an ultraviolet light source such as a
high pressure Hg lamp or a black lamp [29]. To enhance
light sensitivity of TiO2 several approaches have been
investigated. Development of visible light sensitive TiO2 is
crucial to efficiently utilize the solar energy or rays from
artificial sources in photocatalytic reactions. A visible light
sensitized photocatalyst eliminates the need for UV lamp and
peripheral equipment in some particular applications and
opens up a whole realm of possibilities [41]. This happens
when the band gap energy decreases to a certain level. One
of the approaches is by doping TiO2 with transition metals or
non-metallic elements. Several new developments on doped
TiO2 photocatalyst have been made such as transition metals
doping (Sc/TiO2 [56], Ag/TiO2 [48], Ag/InVO4 -TiO2 (co-
doped) [8], Fe/TiO2 [18], Pt/TiO2 [23], V/TiO2 [7], Mn/TiO 2
[59], Pb/TiO2 [31], Ni/TiO2 [67]), non-metal atom doping
(S/TiO2 [68], N/TiO2 [41], N-C/TiO2 [69], C/TiO2 [70],
Fe3+/TiO2 [71] etc.
The doping process can be defined as depositing or
incorporating metal ion dopants into the TiO2 particles that
can influence the performance of the photocatalysts. The
addition of foreign metal ions such as Fe3+, Cu2+, Ag+, and
Pt4+ affect the TiO2 phase formation, structure, and photo-
catalytic activity [56]. Yu et al. [31] investigated Pb-doped
TiO2 thin films on a soda lime glass by using the sol-gel
method and dip coating technique. They found that the Pb
dopant reduced the band gap of the photocatalyst, thus
extending the wavelength response a little bit more towards
the visible range, as shown in Fig. (5). The number of
photogenerated electrons and holes participating in the
photocatalytic reaction also increased, resulting in an
enhancement in photocatalytic activity. It is clear from Fig.
(5), the absorption edge shifted towards the longer wave-
length range for Pb-doped TiO2 thin film and clearly
indicated a decrease in the band gap of TiO2.
Qiu et al. [72] have developed zirconium doped TiO2
films via atomic layer deposition method. The doped film
with 9:1 Ti/Zr pulse ratio showed 50% more stearic acid
decomposed than the undoped film under visible light
irradiation. The doped film has greater visible light
absorption than undoped film resulting in high photocatalytic
activity, due to the increase of oxygen vacancy concen-
tration. The size difference between titanium and zirconium
caused the increase of lattice parameters and cell volume
thus leading to structure defects. High concentration of
doped zirconium led to the flat and low roughness of film
surface compared to the film surface of the low zirconium
concentration. However, it has low crystallinity due to the
96 Recent Patents on Materials Science 2009, Vol. 2, No. 2
100
3
80
Transmittance %
60
40
20
0
200 300
Fig. (5). UV-VIS spectra of the Pb-doped (1), un-doped (2) TiO2 thin films and soda lime glass (3) [31].
presence of amorphous mixed oxide. Therefore, the film
with the low concentration of doped zirconium is more
preferable since it showed crystalline phase at the same time
has smoother surface than pure TiO2 films.
Vanadium is another metallic material that has been used
as doping material. An et al. [73] developed vanadium doped
TiO2 thin film via sol-gel method and used metal
naphthenate as a precursor. Doping with vanadium metal
cations can shift the threshold for photonic excitation of the
TiO2 towards the visible range. All metal dopants are
conveniently substituted into the lattice if their ionic radii are
identical or nearly identical to that of the Ti4+ ion. It is
believed that vanadium can increase the charge carrier
lifetime and apparently also extend the absorption range of
TiO2. In the work, they also studied the effect of doped
vanadium concentration on thin film surface morphology.
They found that the TiO2 thin film with low concentration of
doped vanadium exhibited relatively smooth. Surface
roughness has increased with the increasing concentration of
doped vanadium. Besides, a relatively high transmittance in
the visible range and a clear absorption edge of the thin film
with low concentration of vanadium doping were observed,
attributed to the small particle size which eliminates light
scattering.
Ge et al. [8] developed silver and indium vanadate co-
doped TiO2 thin films and concluded that the system with
two semiconductors having different redox energy levels can
prolong the lifetime of separated electrons and holes,
improve the charge separations, and enhance the efficiency
of the interfacial charge transfer to the adsorbed substrate.
The conduction band of TiO2 must be anodic than the
corresponding band of semiconductor that act as the sensi-
tizer to produce efficient interparticle electron transfer
between them. Once the sensitizer is excited under visible
light irradiation and electrons generated to their conduction
band are injected into the inactivated TiO2 conduction band.
From Fig. (6), it is clear that the conduction band of
InVO4 is more cathodic than the conduction band of TiO2.
Aziz and Sopyan
2
1
400 500 600 700 800
Wavelength nm
The difference between the conduction bands of the two
semiconductors is the driving forces of electron injection.
When visible light is irradiated, the semiconductor of InVO 4
(sensitizer) can excite electrons which is generated in the
conduction band of InVO4,and the electrons quickly transfer
to a TiO2 particle from the InVO4 particle since the
conduction band of InVO4 is more negative than the TiO2.
The anatase of TiO2 is coupled by the interparticle electron
transfer from InVO4 particles. The electrons are scavenged
by oxygen molecules and produce superoxide radical anion.
The holes that remain in the valence band of InVO4 after
electron excitation can also react with the hydroxyl groups (-
OH) and form .OH radicals, whereas, the metallic Ag can act
as electron traps facilitating the electron-hole separation and
transfer the trapped electron to the adsorbed O2 acting as an
electron acceptor. Thus, the charge transfer can enhance the
photocatalytic activity.
The photocatalytic activity of this thin film was evaluated
on methyl orange degradation and it was demonstrated that
Ag doping can effectively enhance the photocatalytic activity
of InVO4-TiO2 thin film under visible light irradiation.
Yu et al. [18] developed a study on Fe doped TiO2 thin
film and found that Fe-O species at the interface of TiO 2
crystallites inhibit the formation of the rutile phase by
preventing the nucleation that was necessary for the phase
transformation to rutile. They found that the phase transfor-
mation temperature of anatase to rutile was ca. 900˚C for the
Fe doped TiO2 thin film. It was necessary to provide greater
heat to promote the phase transformation of anatase to rutile.
Theoretically, increasing the calcination temperature will
increase the performance of photocatalytic activity.
However, they found that the Fe-doped TiO2 thin film only
exhibits maximum photocatalytic activity for the thin film
heat treated at 500˚C compared to the thin film obtained at
900˚C although the sample has a better crystallization
property. This is due to the excees amount of Fe3+ dopant
concentration in the TiO2 thin film. The increase in photo-
catalytic activity of the thin film heat treated for 400 and
500˚C is due to the enhancement of crystallization of anatase
Review on TiO2 Film Photocatalyst
O2
O2
O2 O2
Ag* CB
CB
T iO2
VB
hv
Ag
VB
h+
Fig. (6). Redox process of the valence and conduction bands of Ag/InVO4-TiO2 thin films samples under visible light irradiation [8].
and increase of the Fe3+ concentration. However, if the
concentration of Fe3+ exceeds the optimum value, it would
lead to the increase in the recombination rate of photo-
generated charge carriers and thus a decrease in photo-
catalytic performance.
The charge trapping sites can also be formed by
impregnation of three different metals (platinum (Pt), iron
(Fe), copper (Cu)) as doping material into the TiO2 matrix
films. Lee et al. [74] investigated the photocatalytic activity
of Pt doped TiO2 thin film. Pt doped TiO2 thin film showed
higher photocatalytic activity than that of Degussa P-25
commercial photocatalyst. Rapid increase in initial reaction
rate observed because the Pt doping functioned as a trap of
excited electron and consequently retards the recombination
step in photocatalytic reaction cycle. However, other doping
metals only showed similar activity performance at initial
step but then changed worse than Degussa P-25 as reaction
proceeded. Likely, those metals function as trap at initial
stage as similar to Pt but it changed to be the center for
recombination as reaction further proceeded.
Ho et al. [75] reported that the non-metal atom doping of
sulfur would shift the absorption edge of TiO2 to a lower
energy, thereby showing photocatalytic activity under visible
light irradiation. According to their work, sulfur dopant acts
as an anion and replaces the lattice oxygen in TiO2.The work
carried out by Ho et al. [75] found that the crystallite size of
the S/TiO2 photocatalyst increased and noticed the shifted
absorption edge towards the visible region. This result
confirmed that the sulfur dopants are incorporated into the
lattice of TiO2 and changing its crystal and electronic
properties. The sulfur content in the doped TiO2 greatly
influences the visible light absorption of TiO2, hence the
visible light photocatalytic activity.
US2008017502A1 [76] discloses a method to produce
TiO2 film which has visible light-responsive photocatalytic
activity. The sputtering method with at least one gas selected
from the group consisting of rare gas (nitrogen or oxygen
gas) within a chamber by means of a sputtering target
Recent Patents on Materials Science 2009, Vol. 2, No. 2 97
visible light irradiation
e
Ag
EBG hv
InVO 4
h+ OH
OH
composed of TiOx (1<x<2) wherein the total content of
titanium and oxygen is at least 99% in mass. Then, the film
thermally is treated in the presence of oxygen at a tempe-
rature ranging from 400°C to 750°C within 1 to 28 minutes.
Its hydrophilicity and anti-fogging property is initiated by
visible light irradiation and it has an excellent transparency
property.
US2007066053A1 [77] describes a method for producing
a carbon doped TiO2 layer on the substrate, which is
excellent in its durability (high hardness, scratch resistance,
wear resistance, chemical resistance, heat resistance). This
visible light-responding type of photocatalyst is produced by
heating in a combustion gas atmosphere of a gas consisting
essentially of a hydrocarbon or in a gas atmosphere consis-
ting of hydrocarbon at 900°C to 1500°C. Another method
that is used in this invention by heating in a combustion
flame of a gas composing essentially of a hydrocarbon, is
directly struck against the surface of the substrate for heat
treatment such that the surface temperature of the substrate is
900°C to 1500°C. This inventor also discloses a multi-
functional material that has a carbon doped titanium oxide
layer in US20070040278A1 [78].
US20060247125A1 [79] discloses a titanium oxide-based
photocatalyst that are prepared by substituting O of pure
TiO2 with C and N. The method used is reactive sputtering
by using gases such as Ar, N2, CO2, CO and O followed by a
process of heat treating at around 500°C to provide
crystallizing. Its general formula is TiO2-x-
CxN
. This
invention has a smaller optical band gap compared to pure
TiO2 which makes it possible to activate the photocatalysis
under the visible light range. Due to its small particle size,
the efficiency and self-cleaning effect of the photocatalysts
are very high.
Binary Metal Oxide Semiconductor Systems
Doping the thin film photocatalyst with another
semiconductor material is an alternative approach in order to
modify the surface of semiconductor colloids which can be
98 Recent Patents on Materials Science 2009, Vol. 2, No. 2
directly improve charge separation and minimize or inhibit
charge-carrier recombination [32]. Several studies have
found that these dual semiconductor systems can result in an
excited electron injection into the lower lying conduction
band of the second semiconductor. There are several
research groups which have developed this dual semicon-
ductor systems or composite thin film photocatalyst such as;
TiO2/V2O5 [6], TiO2/SiO2 [4,16, 34], TiO2/ZrO2 [50],
TiO2/Al2O3 [57], WO3/TiO2 [80], TiO2/SnO2 [81] etc.
Recently, Hu et al. [57] developed TiO2/Al2O3 composite
film on the glass substrate through the sol-gel route. Their
work proved that TiO2/Al2O3 composite films show much
higher photocatalytic activity and stability for degradation of
gaseous acetaldehyde than the single TiO2 films. It is due to
the addition of Al2O3 as a transition layer, which
concentrates the target substances around TiO2 particles and
increases the specific surface area of the substrate to provide
more sites for TiO2 loading. Since the photocatalytic reaction
occurs on the surface of photocatalysts, and the photo-
generated electrons and holes recombine very fast, it is
necessary for the separation of interfacial charge carrier. The
Al2O3 transition layer acts as an absorbent to form a
relatively higher concentration of gaseous acetaldehyde on
TiO2 and afterwards transfers the acetaldehyde molecules
rapidly to TiO2 films thus increasing the photocatalytic
activity.
Another approach that has been used to increase the
photocatalytic activity is via doping materials that can
increase the concentration of organic pollutants at the
semiconductor surface. Baiju et al. [82] reported that the
TiO2 with doping material of lanthanides showed high
photocatalytic activity of p-chlorophenoxy acetic acid than
the undoped one. It is due to the interaction of the orbital of
lanthanide ions with the functional groups of organic
pollutants, which causes the increase in photocatalytic
activity.
A hybrid photocatalyst thin film system has been studied
by Higashimoto [80] and his co-workers. They used tungsten
oxide (WO3) coupled with TiO2 photocatalyst and found that
the hybrid WO3/TiO2 films photocatalyst show less photo-
catalytic activity under only UV-irradiation. However, this
hybrid photocatalyst shows high photocatalytic activity
under potential bias than either TiO2 or WO3 by themselves.
According to their theory, an amorphous phase of WO3 film
plays a significant role in the enhancement of electro-
chemically assisted photocatalysis than the polycrystalline
WO3 film due to the enhancement of charge separation. They
reported that the amorphous WO3 showed larger band gap
energy (3.35eV) than the polycrystalline WO3 (2.5-2.8eV).
They assumed that the wider band gap was due to the
structural fluctuation of amorphous WO3 and high
dispersibility of WO3 particles on the TiO2 surface. In their
proposed system, the electrons go through the outer electric
circuit towards the counter electrode under potential bias,
probably causing the reduction of oxygen. The generated
charge carriers are effectively transferred to the conduction
band of WO3, and to the valence band of TiO2 respectively,
by accumulating the charge carriers in two different
semiconductor mixture layers.
Aziz and Sopyan
Further studies of the binary metal oxide semiconductor
system of TiO2/SiO2 thin film photocatalyst have been done
by some research group. It is due to the effect of the SiO 2
addition on the crystalline phase, grain size, surface hydroxyl
content, and transmittance, which would lead to the better
photocatalytic activity. Yu et al. [4] investigated the effect of
the SiO2 addition on the grain size and photocatalytic activity
of TiO2 thin films. They prepared a different coating cycle
and characterized the transmittance of the thin film and
found that the absorption edge of a less coating cycle shifted
towards the shorter wavelength rather than the more coating
cycle. This shifting phenomenon is attributed to the
difference in crystallite size. They concluded that the
addition of SiO2 gives a suppressive effect on the grain
growth of TiO2 crystal. This finding was also supported by
Zhou et al. [3] who developed TiO2-SiO2 thin film on the
PET substrate. They mentioned that SiO2 limits the
aggregation of TiO2 particles and most of TiO2 and SiO2
exist independently if there is only small amount of Ti-O-Si
bonds are formed. However, they also mentioned that the
SiO2 can act as the “neck” and connect TiO2 particles to
form larger second particles if there is an excessive addition
of SiO2. Their work also explained the other function of
adding SiO2 into the TiO2 photocatalyst system. SiO2 can act
as an absorbent and TiO2 as a photocatalytic center. The
formation of Ti-O-Si gives more surface acidity sites that
would take the form of stronger surface hydroxyl groups and
to absorb more water molecules. They proposed that this
generation of new strong acid sites is attributed to the
imbalance positive charge caused by chemically mixing
tetrahedrally coordinated silica and non-tetrahedral titania at
a molecular level. Permpoon et al. [58] also supported the
theory to describe acidity of TiO2/SiO2 surface. They
mentioned that the enhanced the acidity of Si-O-Ti bonds at
the SiO2/TiO2 interfaces which would induce a greater
amount of hydroxyl groups at the film surface.
EP1153658A1 [83] relates to a visible light response type
photocatalyst. It involves the invention of a film for forming
a visible light response type photocatalyst layer onto a base
material surface. It has been found that the visible light
response type photocatalyst can be obtained by providing a
mixed layer of a TiO2 and SiO2 on a TiO2 layer in which a
light absorption region for TiO2 was extended to include
visible light. This lamination of mixed layer onto the TiO2
layer leads to the formation of an interface between the
mixed layer and TiO2 layer. A potential gradient (Schottky
barrier) is generated on this interface and forms the
interfacial level. A trap level is formed that can be excited by
visible light. Therefore, TiO2 absorbs the light in the visible
light region and produces a positive hole. It is diffused in the
SiO2 layer, reacts with water on the uppermost surface and
forms the hydroxyl radical. As such, the SiO2 layer in the top
is possible to contribute to the photocatalytic activity.
Another function of this SiO2 layer is to create a resistance to
abrasion, contamination, water and chemical instead of using
TiO2 itself as outer layer.
THIN FILM PHOTOCATALYST DEPOSITION
METHODS
There are several methods that have been used to coat the
photocatalyst thin film on certain substrate. Among the
Review on TiO2 Film Photocatalyst
examples are liquid phase deposition (LPD) [3, 7, 18], sol-
gel [57], vapor phase deposition (CVD [2], MOCVD,
MOCVD [2]),physical vapor deposition (PVD)), pulsed laser
deposition (PLD) [35], reactive evaporation [35], reactive
magnetron sputtering [17, 23], electrophoretic deposition
[84], ionized cluster beam (ICB) [29], RF reactive ion
plating [11], hydrothermal treatment [35], and atomic layer
deposition (ALD) [41].
Each method has its own advantages and disadvantages.
For example, the sol-gel method that is classified as the wet
preparation process of thin film needs high temperature
calcinations post-treatment to obtain the desired mechanical
strengths or stabilities when supported on various substrates
[29]. The high temperature calcination can possibly cause
potential damages to some porous support. Furthermore, it
causes a limitation in the use of non-refractory substrate
[23]. Some consensus mentioned that the properties of the
TiO2 films depend not only on the preparation techniques but
also on the deposition conditions [85]. All these methods
have been modified by researchers in order to obtain and
produce nano-sized particles with exactly defined physical
properties including crystalline structure, surface area,
porosity, size and shape, according to their application
requirements. The most common processes used are
discussed below:
Sol-Gel Method
The sol-gel process is one of the most appropriate
technologies for the preparation of thin oxide films [19]. The
microstructure of the gels (e.g. pore volume, pore size, and
surface area) can be easily controlled by changing the
reaction parameters such as the H2O to alkoxide ratio,
hyrolysis procedure, etc [19]. The particle sizes can be
controlled by changing the composition of the precursor
solutions [19]. However, for certain applications need to
control the pore size of porous materials. There are several
methods to produce the porous TiO2 thin films such as;
solvent exchange, processes using polymer additives and
using surfactant templating. The microstructure of the thin
films, including the size and shape of the pores and grains,
can be controlled by changing the species and concentration
of surfactants [19].
Cavalheiro et al. [56] reported that the sol-gel method is
one of the suitable methods for preparing TiO2 films since
the dopant can be easily inserted and no high temperature
required in preparing the precursor solution. Habibi et al.
[86] recognized that this method is an efficient way for
fabricating homogeneous porous films by incorporating
organic polymer with precursor solution. However, they
found that the porous films are not thick enough to satisfy
the need for practical applications. Therefore, the deposition
method of spin or dip needs to be repeated for a number of
times or the viscosity of the precursor solution needs to be
increased in order to increase the thickness of the films.
However, thicker films may induce a cracking problem since
the tensile stress stimulates the shrinkage of the films during
heat treatment. Another factor that induces crack formation
is the calcinations temperature. As mentioned by Wen et al.
[87], as the temperature and time increase, the size of crystal
enlarged and crystal dispersed very disorderly. Cavalheiro et
Recent Patents on Materials Science 2009, Vol. 2, No. 2 99
al. [56] suggested a solution to this problem by using
methylcellulose as a dispersant to reduce the problem of
inhomogenity and defects in the films.
An additional advantage of the sol-gel route is the
insensitivity of the reagents to air and humidity. It has been
reported by Truijen et al. [45] that low cost uncomplicated
equipment is used and no special precautions are needed to
be taken in order to protect the starting products and
precursor solutions since insensitivity of the reagents to air
and humidity.
However, Quan et al. [52] stated the disadvantageous of
using the sol-gel route in synthesizing the TiO2. They
reported that the sol- gel process needs relatively expensive
titanium alkoxides as raw materials, such as tetra-n-butyl
titanate etc and a lot of organic solvents such as methanol
and ethanol. The authors used the coprecipitation method
and compared it with the sol-gel route in order to synthesize
the lanthanum-doped TiO2 photocatalysts. Compared to the
sol-gel process, the coprecipitation process uses relatively
cheap organic raw materials and a simple process without
organic solvents. In addition this type of process provides a
potential alternative in realizing large scale production [52].
Besides, they found that the inhibition effect of lanthanum
doping is related to the doping process and that the inhibition
effects are greater by using the coprecipitation process rather
than the sol-gel process. It is due to the precursor prepared in
the coprecipitation method composed of the hydroxides of
titanium and lanthanums which are similar in chemical
structure and will produce much more Ti-O-La bonds much
more than in the sol-gel process. The more Ti-O-La bonds in
the coprecipitation are prepared, the precursor increases the
inhibition effect of phase transformation from anatase to
rutile.
If the metal ion is doped into the TiO2 thin film
photocatalyst by the chemical method such as sol-gel and
impregnation, the doped ions form a small metal oxide island
in the bulk of TiO2 which act as the photoinduced charge
carriers recombination centers and result in a dramatic
decrease in the photocatalytic performance under the band
gap irradiation. As demonstrated by Zhou et al. [29],
physical doping causes a completely different modification
of the electronic properties of the TiO2 photocatalyst from
the previous doping method. In their work, they used the
ionized cluster beam (ICB) deposition method to develop the
TiO2 thin film photocatalyst and applied the metal-ion
implantation method to produce V-ion-implanted TiO2 thin
film. This physical doping method allows the doping of V
ions with a high dispersion state.
Generally, the sol-gel route involves metal-organic
compounds as the precursor. These types of precursor are
much more expensive and intractable because of their rapid
hydrolysis with water in the air. Therefore, Ge et al. [28]
suggested the peroxo route to prepare the TiO2 thin film
precursor solution. In their work, they used TiCl4 and
H2TiO3 to prepare the peroxo titanic acid (PTA) sol.
Theoretically, this method starts from an aqueous solution of
metal peroxo complex. Thus, there are no organic residues
left in the precursor film. Compared to the common sol-gel
method, this method can be utilized even at a low processing
temperature without sacrificing the quality of the deposited
100 Recent Patents on Materials Science 2009, Vol. 2, No. 2
layers. However, only a dense and low surface area TiO2 thin
film could be obtained via this method, which restricts the
improvement of photocatalytic performance of the TiO2 thin
film. Similar work is carried out by Yuan et al. [5], with this
group being involved in the use of peroxo titanic acid to
prepare TiO2 thin film via the sol-gel method Fig. (7). They
mentioned that the product from this type of method is much
more neutral and stable for a long period of time to be coated
on various materials including metals. In addition, the
preparation is easy and low cost. Previous studies mentioned
that the flexibility of low processing temperature. In contrast,
Yuan et al. [5] declared that this method is difficult to fit into
the industrial process since its operation is limited to a lower
temperature such as 0-5˚C in an ice-water bath.
Ethanol solution
TiCl4
TiCl4 Ethanol solution
Ammonia solution
Titanic acid gel
H2 O2 solution
PTA solution
Leaving in the air
PTA gel
Dip coating on the substrate Heating treatment
TiO 2 nanoparticle
Fig. (7). A flow diagram for preparation of TiO2 from peroxo
titanic acid [5].
Liquid Phase Deposition (LPD)
This process involves the deposition of metal oxide thin
film or hydroxide thin films on a substrate that is placed in
aqueous solution containing a corresponding metal-fluoro
complex iron. The films are formed through the hydrolysis
reaction of metal-fluoro complex ions. Since the formation
Aziz and Sopyan
of oxide films occurs in aqueous solution of metal-fluoro
complex, which are typical homogeneous mixing system,
homogeneous thin film can be obtained [7]. The mixed oxide
thin films can also be produced by the addition of selected
objective ions into the precursor solution. This kind of
process is slightly easier because neither vacuum nor high
temperature is required and any substrates with large areas
can also be used [33]. In addition, the low temperature that is
used in the process make it more practical in order to use low
heat resistant materials such as organic polymer [33] and
allows for greater flexibility in material combinations that
could lead to devices with greater and more varied
functionality [88]. This gives a quality improvement, lower
costs and environmental-friendly processing [89].
Chemical Vapor Deposition (CVD)
Thin film photocatalyst can be deposited using wet or dry
process [30]. The use of wet process is limited for certain
applications as the films need to be heated at ca. 500˚C,
which makes it difficult to deposit them on the large area
glasses or polymer substrate. Compared to dry processes, the
processes are considered to be more appropriate techniques
for large area uniform coatings with high packing densities
and strong adhesion. One of the dry process techniques is the
chemical vapor deposition method. There are several kinds
of vapor deposition methods such as; plasma enhanced
chemical vapor deposition (PECVD) [41], metal organic
chemical vapor deposition (MOCVD) [39], and low pressure
metal organic chemical vapor deposition (LPMOCVD) [2].
Theoretically, in a typical CVD process, the substrate is
exposed to one or more volatile precursors, which react
and/or decompose on the substrate surface to produce the
desired deposit. It is considered as a chemical process which
produce high-purity, high performance solid materials and is
usually used in the semiconductor industry to produce thin
films.
For instance, MOCVD consists of heating an
organometallic solution, which is evaporated and deposited
on a heated substrate [39]. Generally, this kind of method
requires expensive, sophisticated apparatus but it is capable
of producing homogeneous thin films which are crucial
attributes for the study of optical properties.
US007211513B2 [90] describes a process for forming a
TiO2 coating on glass and more particularly, a process for
preparing a TiO2 coating doped with nitrogen and depositing
by similar a chemical vapor deposition on a hot glass
substrate. This nitrogen doped TiO2 coatings are prepared by
providing a uniform vaporized reactant mixture containing a
titanium compound, a nitrogen compound and an oxygen-
containing compound, delivering the reactant mixture to the
surface of a ribbon of hot glass under essentially atmospheric
pressure and reacting the mixture at a temperature ranging
from 1100°F-1280°F. Then the reactant mixture reacts to
deposit a coating of nitrogen doped TiO2 on the major
surface of the hot glass substrate and followed by cooling the
coated glass substrate to an ambient temperature. In this
invention, the vaporized reactant mixture comprising
titanium tetrachloride (TiCl4), ethyl acetate and ammonia
was used. This nitrogen doped TiO2 coating absorbed at least
Review on TiO2 Film Photocatalyst
20% more light in the wavelength range of 400-800nm than
the undoped TiO2 coating.
US20070054044A1 [91] relates to a method of CVD to
produce a photocatalytic composite material having a
photocatalytic TiO2 film on the surface of a substrate. In this
invention, TiCl4 vapor is reacted with water vapors. The
TiCl4 and water vapor are injected into a vapor deposition
chamber with two nozzles respectively such that the
resulting two injected vapor streams meet before reaching
the substrate, thereby mixing the two vapors. Within 3
seconds after this mixing, the mixed vapors are brought into
contact with a substrate which is moving in one direction.
TiCl4 vapors are injected in a reverse direction with respect
to the direction of the movement of the substrate.
Cathodic Electrodeposition Method
This technique appears to be a simple and low cost
method to get porous as well as compact TiO2 thin films.
The easy control of film thickness, morphology, composition
etc. through electrical quantities such as current deposition
and potentialapplied is the main advantage of this technique.
Previously, Lokhande et al. [92] prepared thin film TiO 2
depositing on an ITO substrate by galvanostatic deposition
from an aqueous alkaline solution containing complexed
titanium with ethylene-diamine-tetra acetic acid (EDTA).
The process is conducted at room temperature and results to
form an amorphous, compact, non-porous and uniform TiO 2
film on the ITO substrate.
Ion Chamber Accelerator
lon at low speed lon at middle speed lon at high speed
(Low Energy) (Middle Energy) (High Energy)
Formation of thin layer Sputtering
Fig. (8). Schematic diagram of an advanced metal ion implantation method.
Recent Patents on Materials Science 2009, Vol. 2, No. 2 101
Ionized Cluster Beam
This technique of deposition can produce free-conta-
minant thin films since the thin films are prepared in a high
vacuum chamber as a dry process. It involves the heating
process of the Ti metal in a crucible up to about 2000˚C to
generate Ti vapor which is introduced into a high vacuum
chamber with a low pressure O2 atmosphere to produce small
TiO2 clusters. These TiO2 clusters are ionized by the electron
beam irradiation, and then these ionized TiO2 clusters are
accelerated by a high electric field and bombarded onto a
substrate to form TiO2 thin film on it. When the electronic
properties of thin film need to be modified, the metal-ion-
implantation method can be used after the thin film
deposition. Takeuchi et al. [21] applied the metal-ion-
implantation method after depositing the thin film using the
ICB technique. They developed Cr-ion-implanted TiO2 thin
film for photocatalysis application. The acceleration energy
that is applied in this method can be adjusted to control the
depth of the metal ions implanted. An appropriate depth
profile of the metal ion implanted causes an electronic
modification of the TiO2 thin film photocatalysts due to the
interaction between the implanted Cr ions and TiO2 [21].
Anpo and Takeuchi [93] designed and developed second
generation titanium dioxide photocatalysts which absorb
UV-visible light and operate effectively under visible and/or
solar beam irradiation by applying an advanced metal ion
implantation method Fig. (8).
Sample
lon implantation
102 Recent Patents on Materials Science 2009, Vol. 2, No. 2
Hydrothermal Method
The advantage of this method is to produce a coating at
room temperature, although a higher temperature is required
to crystallize titanium dioxide [94]. It has been known as a
powerful method for the preparation of high-purity, highly
crystalline, ultrafine and homogeneous powders of various
single and multicomponent oxide powders [95]. It can be
modified to prepare polymorphs of titania with a different
morphology.
One example of the hydrothermal route for the pre-
paration of the TiO2 thin film is briefly stated below. TiO 2
thin films were prepared on a Ti metal substrate by calcining
a Ti metal foil of 0.25mm thickness at 873K for 5h in air.
Then, the thin films were subjected to reactions with 10M
NaOH aqueous solution in an autoclave and kept for 12-72h
at 393K. After cooling to room temperature, then thin films
were washed in 0.1M HCl solution and finally TiO2 thin
films were obtained.
Electrophoretic Deposition Method
This method is a promising technique for the fabrication
of novel nanostructured and nanoscaled materials, including
the use of nanoparticles, nanosheets, nanotube and related
nanomaterials [96]. The equipment used in this technique is
simple and inexpensive. Moreover, the time required to
finish the deposition is short and even coatings can be
obtained since the uniform electric field is applied. Basically,
the process involves electrodes that are made from two
identical substrates (e.g. stainless steel). The substrate to be
coated is placed onto the cathode, to which a negative
potential of 40V is applied for certain duration of time,
which would control the catalyst loading. During the coating
process, the TiO2 powder in the suspension moves to the
anode and deposited onto the substrate following the parallel
electric field between the electrodes.
Matsuda et al. [96] designed the improvement of
electrophoretic deposition by combining the method with the
sol-gel method. The authors developed the electrophoretic
sol-gel deposition combining particle preparation through the
sol-gel method and film formation by the electrophoretic
deposition method.
Magnetron Sputtering Method
There are some limitations of certain processes in
depositing the thin film photocatalyst such as spray coating
needs a high temperature for the heating process to
decompose metallorganics causing a limitation in the use of
non-refractory substrate. Sheng et al. [23] attempted to
prepare photocatalytic Pt-TiO2 thin films with special
attention to the formation of anatase at temperatures as low
as 200˚C and to the use of flexible substrate (e.g., poly-
amide) to widen the application of film photocatalysts.
Briefly, Sheng and his co-workers used the tripole
magnetron sputtering system to prepare the thin films. They
used two different methods of deposition. First, the Pt-TiO 2
thin film prepared by alternately sputtering co-axially placed
platinum and titanium targets. The deposition time of
platinum was kept at 2s whereas that of titanium was varied
from 20s to 140s in each cycle in order to obtain different
Aziz and Sopyan
composition. The platinum particles are dispersed in the
TiO2 layer. Another method, the Pt-TiO2 film was prepared
by depositing at first with pure TiO2 film on polyamide
sheet, followed by coating a small amount of platinum
particles on the surface. These platinum particles were
coated on the TiO2 thin film. This method did not only give
the bonding strength of film/polyamide interface but also
made it possible to deposit anatase film at temperatures as
low as 200˚C. Tomaszewski et al. [60] used the dc mag-
netron sputtering from ceramic targets to prepare transparent
nanostructured TiO2 thin films.
Spray Pyrolysis Deposition Method
This spray pyrolysis deposition method has advantages of
being capable of forming a film even at a low heating
temperature of the substrate, a high rate of film formation
and less frequency of maintenance due to the simple
construction of the apparatus. However, there are several
disadvantages of this method since it is difficult to control
the size or the velocity of sprayed droplets due to the
temperature changes of a glass substrate, changes in the
concentration of a material solution and changes in the
atmosphere of a glass substrate. In addition, there is a need
to remove the parts that do not form a film, such as an
unreacted component and a reaction side product of the raw
material solution to the outside of the system. Therefore, an
unfavorable non-uniform thickness of thin film is obtained.
This method comprises steps of spraying a material
solution containing a thin film forming material on one
surface portion of a heated substrate to form a thin film. A
material solution is prepared by dissolving a thin film
material in an organic solvent. This material solution is
mixed with a compressed gas and a jet of the mixture is then
emitted to a heated substrate. The emitted mixtures of
material solution in the form of misty liquid droplets are
supplied to a surface of a substrate.
EP1536036B1 [97] relates to a method of spray pyrolysis
deposition method to form a thin film photocatalyst. In this
invention, a thin film forming apparatus composing of a
housing body that has housing space to place a substrate. Its
process composes of heating the substrate in the housing
space at prescribed temperature. Then, a prescribed solution
containing a thin film material is sprayed on the surface of
the substrate; the thin film forming material decomposes
thermally because the substrate has been heated. This
apparatus is equipped with thickness information generating
means that has prescribed information on the thickness of a
thin film to be formed, which is controlled by spraying. An
atomized solution floats around the substrate inside the
housing space, but the atomized solution can be eliminated
by removing means to prevent the atomized solution around
the substrate that is not necessary, to obtain a desired
thickness of the thin film with higher accuracy. In the
invention, it also has the means of control to adjust the
spraying to obtain the desired thickness of the thin film. The
inventor stated that the thickness information generated
means that it generates color shading information. This color
shading information gives the thickness thin film changes
through a change of component of light reflected by the thin
film.
Review on TiO2 Film Photocatalyst Recent Patents on Materials Science 2009, Vol. 2, No. 2 103

THIN FILM PHOTOCATALYST APPLICATIONS
Photocatalysis process has been proven to be beneficial
for environmental purification (air purification, water
treatment) and destruction of many organic compounds and
microorganism (bacteria, viruses, cancer cells). The appli-
cation of photocatalyst is also widely used as a self cleaning
material since it has hydrophilicity property. Here some
common applications will be discussed.
etc.) at different sites, leading to oxidation and reduction
processes and produces O2•- and •OH. Under weak UV
illumination intensity, most of acetaldehyde molecules is
oxidized to acetic acid (intermediate product), and then the
acetic acid is further oxidized into CO2 and water [57]. The
oxidative decomposition process of acetaldehyde on TiO2 in
principle is described as follows:
O2 + e-CB O2•- (6)

Air Purification Application H2O + h+ •OH + H+ (7)

The most common semiconductor used in this application
of photocatalytic oxidation is titanium dioxide because of its
stability under most reaction conditions. Numerous studies
have indicated that illuminating the anatase form of TiO2
with near UV radiation has been successful in eliminating
organic and gas phase compounds such as; alkanes, aliphatic
alcohols, aliphatic carboxylic acids, alkenes, phenols,
aromatic carboxylic acids, halogenated alkanes and alkenes,
SOx, NOx, aldehyde etc. Referring to the illustration Fig. (9),
TiO2 photocatalyst can be applied on the structure of
buildings such as; on the glass window as thin film and on
the cement as a layer of paint etc. For outdoor applications,
UV irradiation that originated from the solar system would
be a main source of light for generating the charge carriers
that are involved in the pollutant degradation.
The decomposition of organic gas compound such as
acetaldehyde can be explained through some equations.
Basically, when TiO2 thin film is illuminated by the UV
light, excitation of electron from valence band to the
conduction band occurred. Then, holes are created at valence
band. The electron-hole pairs, after migrating to the surface,
can in turn trapped by surface-adsorbed molecules (O2, H2O,
CH3CHO + 2•OH CH3COOH + H2O (8)
2CH3CHO + O2•- 2CH3COOH + e- (9)
CH3COOH + 2H2O + 8h+ 2CO2 + 8H+ (10)
CH3COOH + 2O2 2CO2 + 2H2O (11)
Sopyan et al. [14] have also studied the decomposition of
acetaldehyde gas using TiO2 film. In their work, the
calculated quantum yield obtained exceeds 100%, indicate
that the photocatalysis did not proceed only via the simple
initiation steps as described above. They suggested one of
the possible pathways is the direct oxidation of intermediate
species by oxygen that produced carbonyl radical. This
carbonyl radical is considered to play main role in
propagation of chain reaction. An additional possibility is
that the superoxide ion which is created by the excited
electron takes part in the oxidation reactions to produce
hydrogen peroxide, H2O2. Then, this H2O2 is subsequently
followed by hydroxyl radical forming reactions. The H2O2
also can produce hydroxyl radical via direct photolysis.

Indoor Outdoor

Sun

UV

Air purification, self-

Photocatalytic Photocatalytic cleaning, soil proof,
decomposition decomposition deodorization,
sterilization

TiO2 thin film on substrate

(glass or tile)

Fig. (9). Schematic diagram of TiO2 thin film photocatalyst applications.

104 Recent Patents on Materials Science 2009, Vol. 2, No. 2
More hydroxyl radicals are produced via carbonyl-radical-
mediated chain reaction mechanism. Therefore, they pro-
posed that photodegradation of acetaldehyde is not wholly
mediated by photogenerated holes but also by adsorbed
oxygen, superoxide radicals and/or hydrogen peroxide.
The limited source of UV light from solar system is one
of the major problems in applying the photocatalysis for
environmental purification. However, this photocatalyst can
also be applied in an indoor environment although without
applying the UV light source, since the TiO2 photocatalyst
can be electronically modified to operate under visible light
up to wavelength of 400-600nm such as via doping with
other metal oxides, metal ions and etc. Therefore, the TiO 2
photocatalyst can easily be applied in removing pollutant
compounds in whatever conditions of the polluted area.
The odor problems encountered in such environment are
connected with the presence of Volatile Organic Compounds
(VOCs). Photocatalysis-based techniques are promising
approaches for remediating VOC and odor problems. On the
deodorizing application, the VOCs will be broken down by
destroying its molecular bonds using hydroxyl radicals.
Organic gases will form a single molecule that is harmless to
humans and will directly improve the air. There are several
kinds of odor molecules that contribute to the odor problem
especially in a confined area; tobacco odor, aldehyde,
nitrogen dioxide, urine and fecal odor, gasoline and many
other hydrocarbon molecules in the environment. Therefore,
by applying the TiO2 thin film photocatalyst in the confined
area, most of the odor molecules will be degraded and
eliminate the source of the odor problem.
US20080131311A1 [98] discloses the invention of a
fluorescent lamp device that is capable for cleaning air. A
design of a fluorescent lamp coated with photocatalysis
materials was revealed in this patent. The nanocrystalline
TiO2 anatase was made by sol-gel techniques on a glass fiber
cloth or glass fiber sleeve to be acted upon under visible
light, and then wrapping the cloth or placing the sleeve on a
fluorescent lamp. The application of this invented
fluorescent lamp is not limited for illumination, but is also
used to the clean air as fluorescence radiates on the surface
of the photocatalysis materials to generate charge carriers for
the decomposition of air pollutants.
The most common problem of the exterior walls of
buildings is that they become soiled from automotive
exhaust fumes, which contain oily components. Since the
surface has high hydrophilicity character when the TiO2 is
activated by UV light this makes it suitable to be a self-
cleaning material. The water layer is attracted between the
dirt and the surface resulting in the washing off of the dirt
particles especially when it is applied on the smooth surface
like glass and ceramic tiles. Horakova et al. [99] reported
that the TiO2 thin film deposited at a higher deposition
temperature using PECVD would increase its hydrophility
property. In the architectural concrete, the use of white
cement with TiO2 at the surface of buildings and cons-
truction attributes to the durability of the visual aspect of the
building. The whiteness of the building will remain and dirt
will be washed away more easily due to the hydrophilic
characteristics or it will be decomposed after the photo-
catalytic reaction is completed. However, there is a difficulty
Aziz and Sopyan
in this application if the material applied is on the concrete
surface due to the physical anchoring of the dirt in the larger
pores.
US20080241550A1 [100] relates to the application of
thin film in the structural layer, which is most widely utilized
in construction surfaces like roofing (e.g. tiles and shingles).
This patent discloses the structure that comprises a structural
layer that has an external surface and a coating on the
external surface of the structural layer. In the invention, the
coating is composed of polyurethane binder and
photocatalytic particles within the polyurethane binder. This
type of structure equipped with photocatalytic particles was
invented in order to combat the discoloration of roofing
substrate and other building materials due to algae
infestation and airborne contaminants such as soot and
grease. Polyurethane binder systems provide the preferred
level of photostability.
Water Purification Application
Another application of thin film photocatalyst is in water
treatment. Generally, water treatment is the process of
eliminating pollutants either organic or inorganic from
surface water or groundwater to ensure it is harmless and
palatable for human consumption. The conventional method
that has been applied such as adsorption by activated carbon
or oxidation by chlorine or iodine is not a totally efficient
way to treat the polluted water since it has side effects and
need further treatment. For instance, adsorbed pollutants on
the activated carbon need to be removed after completing the
treatment process, so that, the application of TiO2 thin film
photocatalyst is more favorable used especially in the
industry. In addition, the TiO2 thin film photocatalyst is more
preferable rather than TiO2 powder in the photocatalytic
system for water purification. It is due to the disadvantages
of conventional powder that requires stirring during the
reaction and separation after the reaction. Abundant amounts
of studies on photocatalytic performance of TiO2 thin film
photocatalyst on the degradation of several organic and
inorganic pollutants were done by researchers that proved
the capability of TiO2 thin film photocatalyst. The
applications of the thin film photocatalyst have been
summarized in the Tables 1 and 2.
The mechanism of organic compound degradation via
photocatalyst has been discussed by Zainal et al. [101]. They
have developed glass coated TiO2 thin film and used various
dyes in aqueous solution such as methylene blue (MB),
methyl orange (MO), indigo carmine (IC), chicago sky blue
6B (CSB) as a representative of pollutant compound. Detail
mechanism of dye degradation under visible light irradiation
is described by Eq. (12)-(17):
Dye + hv Dye* (12)
Dye* + TiO2 Dye•+ + TiO2 (13)
TiO2 + O2 TiO2 + O2•- (14)
O2•- + TiO2 + 2H + H2O2 (15)
H2O2 + TiO2 •OH + OH- (16)
Review on TiO2 Film Photocatalyst Recent Patents on Materials Science 2009, Vol. 2, No. 2 105

Table 1. A Variety of Methods to Prepare TiO2 Thin Film Photocatalysts Along with their Substrates Used and Compounds
Degraded

No Deposition Method Substrate Used Compound Degraded Reference

1 Sol gel Soda lime glass Acetaldehyde [12]

2 Sol gel Glass slide Dyes (Diazo dye, Light yellow X6G) [113]

3 Sol gel Glass plate - [55]

4 Sol gel Glass plate Trichloroethylene gas [114]

5 Sol gel Si wafer Stearic acid [115]

6 Sol gel Borosilicate glass Ketones [116]

7 Sol gel Quartz glass Methyl orange [5]

8 Sol gel Glass slide Acetaldehyde gas [14]

9 Sol gel Glass slide Fatty stains [117]

10 Sol gel Soda lime glass Methylene blue [10]

11 Sol gel Glass and n-type Si (100) - [118]

12 Sol gel Glass slide Dyes [9]

13 Sol gel Glass slide Methyl orange [28]

14 Sol gel Glass slide NOx [19]

15 Sol gel Glass slide 2-propanol [53]

16 Sol gel Borosilicate glass - [119]

17 Sol gel Silica glass 2-propanol [16]

18 Sol gel Glass slide Acetaldehyde, H2S, NH3 [13]

19 Sol gel Glass slide MO,MB, IC,CSB, MD [120]

20 Sol gel Silica glass - [121]

21 Sol gel Borosilicate Creatine [111]

22 Chemical vapor deposition Graphite - [122]

23 Spin coating-pyrolysis Silica glass - [30]

24 Magnetron sputtering Si wafer Phenol, E.coli [17]

25 Chemical vapor deposition Alumina balls MB [2]

26 Electrophoretic deposition Stainless steel TOC removal [84]

27 Commercial powder Pyrex glass Trichloroethylene gas [123]

28 Liquid phase Glass fiber NO [124]

Dye•+ + O2 (or O2•- or •OH)
peroxylated or hydroxylated intermediates
degraded or mineralized products
Antibacterial Application
Numerous studies have utilized a strong oxidation power
of TiO2 photocatalysts to purify environmentally toxic
substances of water and air. However, poor condition of
water and air are still consumed by human being since it still
has some unhealthy microorganisms. Therefore, TiO2
photocatalyst has been designed with the sterilizing ability
(17) and well-suited to be applied in whatever condition. It is
necessary to remove or kill microorganisms which are found
in the water, air or surfaces. For example, available disinfec-
tion techniques are used to deactivate the pathogenic bacteria
(e.g., Pseudomonas aeruginosa [102], Staphylococcus
aureus [102], and Escherichia coli [102, 103]), fungi (e.g.,
Candida albicans), protozoa, and viruses (e.g., Phage MS-2)
106 Recent Patents on Materials Science 2009, Vol. 2, No. 2 Aziz and Sopyan

Table 2. Modified TiO2 Thin Film Photocatalysts Along with its Deposition Method, Substrate Used and Compounds Degraded

Modified TiO 2 Thin Deposition Method Substrate Used Compound Degraded Reference
Film Photocatalyst

V doped TiO2 Liquid phase deposition Soda lime glass Methyl orange [7]

Pt doped TiO2 Magnetron sputtering Glass slide Acetic acid [23]

Mn doped TiO2 Sol gel - - [59]

Pb doped TiO2 Sol gel Soda lime glass Dimethyl-2-2 dicholorovinyl phosphate [31]

Cr ion implanted TiO2 Ionized cluster beam Porous Vycor glass NO [21]

Fe doped TiO2 Liquid phase deposition Stainless steel NO [18]

Ag/InVO4 doped TiO2 Sol gel Glass slide Methyl Orange [8]

V doped TiO2 Spin coating-pyrolyis Soda lime glass - [125]

Cu2+ doped TiO2 Liquid flame sprayed Stainless steel Acetaldehyde gas [126]

N-C doped TiO2 Sol gel Glass slide Methyl Orange [69]

N doped TiO2 Sol gel Glass slide Stearic acid and PEG [41]

Sc doped TiO2 Sol gel Borosilicate glass Diclofenac potassium solution [56]

S doped TiO2 Commercial powder Silica coated soda lime glass Acetaldehyde gas [68]

TiO2/V 2O5 Commercial powder Glass slide Methylene blue [6]

V ion implanted TiO2 Ionized cluster beam Quartz slide Formic acid [29]

TiO2 and TiO2-SiO2 One step soft solution Indium doped SnO2 (ITO) - [57]

TiO2/SiO 2 Commercial powder Tiles - [34]

TiO2/ SiO2 Sol gel PET substrate Rhodamine B [3]

TiO2/ SiO2 Sol gel Soda lime glass Methyl Orange [4]

TiO2/ZrO2 Sol gel Glass slide 2-4-dinitroaniline [50]

TiO2/Al2O 3 Sol gel Foam nickel Acetaldehyde [57]

TiO2/ SiO2 Liquid Phase deposition Glass slide Methylene blue [33]

F doped TiO2 Commercial powder Ti plate AO7, phenol, DCA, TCA,NaF [127]

such as; chlorination and ozonation. According to Srivinasan
et al. [103], these available disinfection technique involved
chemical or photochemical induced damage or physical
removal by filtration. Ozonation is also not effective for the
inactivation of some pathogens like Cytospordium [103].For
example, irradiation from germicidal lamps (254 nm) results
in cross-linking of thymine groups in DNA. Free radicals
such as chlorine atom or hydroxyl radical, OH·, can result in
DNA strand breakage or initiate autoxidation of lipids or
other cell components. However, they mentioned that these
microorganisms show a challenge in terms of structure and
defence mechanism that must be overcome by the
disinfection technique. Their defence and repair system
allows them to live in an aerobic environment and to deal
with the low levels of UV radiation found in sunlight.
Therefore, application of TiO2 photo-catalyst as a sterilizing
material is one of alternative ways to destroy microorganism
in the environment. TiO2 itself has no toxicity to microbe
and cell. However, it can perform sterilization function only
after the irradiation of UV light. The very strong oxidizing
power of TiO2 can destroy bacteria’s cell wall and
membrane. There are two different biochemical mechanism
of sterilization process using TiO2 photocatalyst; (1) charge
carriers can directly react with the cell wall, cell membrane
and cell component. In the sterilizing process of microzyme
and bacilli, CoA (molecule in cell to be used in power
generator) inside cell oxidized to CoA dimer loses its
activity, which causes the respiration of the cell to stop and
finally results in death and (2) the active hydroxyl radical,
super oxide anion, peroxide hydroxyl radical and hydrogen
peroxide can react with biomacro-molecule such as protein
enzyme and lipid which will destroy the cell structure and
react with the cell wall and its component. These free
radicals also have a powerful bonding ability with bacteria
and fungi. Then, the bacteria and fungi will be suppressed
with DNA damaged by superoxide and hydroxyl free
radicals.
Review on TiO2 Film Photocatalyst
Ditta et al. [24] studied the photocatalytic antimicrobial
activity of thin surface films of TiO2, CuO and TiO2/CuO
dual layers on Escherichia coli and bacteriophage T4. They
used atmospheric Chemical Vapor Deposition (Ap-CVD)
and the sol-gel method to prepare the thin film photocatalyst.
They found that the combination of photocatalysis and
toxicity of copper acted synergistically to inactivate the
bacteriophage T4 and retained some self-cleaning activity.
Their works show that TiO2/CuO coated surfaces are highly
antiviral and can be applied in the food and healthcare
industries.
A similar work was carried out by Sunada et al. [26],
with this group being involved in the development of the
copper deposited TiO2 thin film that can be applied under
weak UV light irradiation. They used the dip coating method
to deposit the TiO2 thin film on the silica-coated soda lime
glass plates. The photocatalytic performance of the copper
deposited TiO2 thin film evaluation is based on the
bactericidal activity (E. coli). They observed that Cu/TiO 2
thin film exhibits bactericidal activity even for copper-
resistant E. coli under very weak UV illumination. They
have suggested that the mechanism by which titania is able
to kill bacteria involves the disruption of outer membrane
followed by the cytoplamic membrane and that these
processes then allowed the complete degradation of the cells.
Sheel et al. [104] developed biocidal silver and
silver/titania composite films by chemical vapor deposition
method which active to a range of organisms such as Gram-
negative and Gram-positive bacteria and viruses. The
presence of silver on titania films gives high biocidal
activity. The antimicrobial properties of silver were well
known to the ancient Egyptians and Greeks, for example,
Hippocrates mentions silver as a treatment for ulcers [104].
The silver ions can strongly interact with electron donors,
and the antimicrobial activity of Ag involves interactions
with sulphydryl groups in proteins. The silver can inhibits
energy production by inhibition of the respiratory chain of
Escherichia coli. Another way of antimicrobial activity is by
increasing the toxicity indirectly. The indirect toxicity arises
from salt formation with silver ions that result in a chloride
or anion limitation within the cell.
A similar study carried out by Sun et al. [105] who have
developed Ag-TiO2 composite film by liquid phase
deposition method on ceramic tiles. Its antibacterial activity
was evaluated on S.aureus and E. coli. They suggested two
different theories to explain the antibacterial mechanism; (1)
silver ions which is formed by reaction between silver and
water combine with sulphydryl in bacteria, resulting in the
blocking of breathing and till the death of the bacteria and
(2) silver can react with the oxygen dissolved in water and
generate activated oxygen O• which can decompose the
bacteria. They mentioned that Ag reacts with proteins by
combining the -SH groups of enzymes, which leads to the
inactivation of the proteins. Silver ions make DNA
molecules to lose their replication abilities.
Xu et al. [106] found that the antibacterial activity
efficiency depends on the characteristics of the films. They
developed nanostructure of N-TiO2 films via sol-gel method
and evaluated its antibacterial activity efficiency on the
Pseudomonas aeruginosa strain (AS1.50) and Bacillus
Recent Patents on Materials Science 2009, Vol. 2, No. 2 107
subtilis strain (AS1.439). They suggested that the
antibacterial efficiency of the N-TiO2 films was affected by
the morphology and thickness of the film, the grain size of
nanoparticles, surface area, mass anatase composition of N-
TiO2. Wong et al. [107] also developed nitrogen doped TiO 2
thin film via ion-assisted electron beam evaporation system.
They evaluated the antibacterial activity on human pathogens
(e.g., Shigella flexineri, Listeria monocytogenes, Vibrio
parahaemolyticus, Staphylococcus aureus, Streptococcus
pyogenes and Acinetobacter baumannii). This nitrogen
doped TiO2 thin film exhibited the antibacterial activity even
under visible light illumination.
US20080081758A1 [108] discloses a photocatalytic
titanium oxide sol which exhibits antibacterial properties in a
dark place. Generally, most of antibacterial activity only
happens by illumination of sunlight or UV light source to the
photocatalyst. This invention reveals a method to produce
titanium oxide sol which is coated on the surface of the
substrate. In order to activate the antibacterial activity under
a dark place, antibacterial agents have been added together to
the photocatalyst. The antibacterial agents that have been
used in this patent are made from an inorganic substance
because the photocatalyst can decompose organic matters.
The antibacterial component included a metal such as silver,
copper and zinc, in which the inorganic antibacterial
component existed on the surface of a substrate to exhibit the
antibacterial properties. In this patent, the photocatalytic
titanium oxide sol composed of silver, copper and a
quaternary ammonium hydroxide (tetramethylammonium
hydroxide).
CURRENT & FUTURE DEVELOPMENTS
Recently, most of the researchers and inventors direct
their interest and invention towards the porous structure of
thin film photocatalyst since this type of physical character is
believed to have high surface area and remarkable
photocatalytic activity. In addition, almost all porous thin
film available today is synthesized via the sol-gel method by
adding certain amount of pore creating agents during the
process, since this type of method is easily modified to get
the desired physical and chemical properties of thin film
photocatalyst. Carreon et al. [109] reported that the photo-
catalytic efficiency of periodic mesoporous nanocrystalline
anatase thin films depends on the pore architecture. They
mentioned that the ability to alter the pore architecture and
scale of meso-TiO2 is of vital importance since the pore size,
shape and dimensionality can exert a profound effect not
only on the accessibility, adsorption and diffusion behavior
of quest molecules within the pore network but also on the
material’s mechanical, optical and electrical properties. In
their research, they designed two types of mesoporous
nanocrystalline anatase thin films; 2D hexagonal and 3D
cubic. They found that the 3D cubic mesoporous nano-
crystalline TiO2 has a larger accessible surface area but a
lower adsorption surface affinity compared to the 2D
hexagonal mesoporous nanocrystalline TiO2. In the degra-
dation of methylene blue in solution, the 3D cubic
mesoporous nanocrystalline TiO2 showed optimum photo-
catalytic activity compared to the other type of pore design.
It is believed that the more open cubic framework of the 3D
cubic mesoporous nanocrystalline TiO2 gives higher
108 Recent Patents on Materials Science 2009, Vol. 2, No. 2
photocatalytic activity. The geometrical advantages such as a
larger surface area and less obstructed 3D diffusion paths of
quest molecules also contributed to the higher photocatalytic
activity.
Similar studies on the porous structure of the TiO2 thin
film have been done by Chen et al. [110]. They produced
mesoporous TiO2 films with ultrafine anatase nanocrystallite
on borosilicate glass using the non-acidic sol-gel preparation
route. They used nonionic surfactant Tween 20 as the pore
directing agent since it is not only environmentally friendly
but also highly viscous, which is beneficial to increase the
film thickness per coating. From their result, it proved that
the addition of Tween 20 in the sol will produce the
mesoporous structure of the TiO2 thin film and directly
increase the photocatalytic activity. It is due to the enhanced
active surface area/pore volume and increased amount of
anatase nanocrystalline materials that are immobilized on the
substrate. Gan et al. [111] also reported the formation of the
mesoporous structure in the thin film of TiO2 by using the
tri-block polymer as structure directing agent.
Another area of recent research on the thin film
photocatalyst development is to vary the available substrate
that can be used in immobilizing the photocatalyst. Nume-
rous studies that have been discussed previously is always
subjected to the use of glass (borosilicate, silica, soda lime).
Only a few studies focused on the use of other types of
substrates such as; stainless steel, Ti plate, Si wafer, tiles and
etc. Recently, some of researchers started to use other types
of substrates which is more applicable and can influence the
photocatalytic activity of the thin film photocatalyst. One of
the new types of substrate that is used in order to immobilize
the thin film photocatalyst is hydrophobic clay. Meng et al.
[112] designed the SiO2/TiO2 photocatalyst on hydrophobic
clay via the sol-gel method and evaluated the photocatalytic
performance on removing methyl orange from water. They
used an organoclay (Na-montmorillonite) layer to
immobilize the photocatalyst. This type of organoclay has
high adsorption capability to enrich the organic compounds
around the photoactive centers. The use of polymer materials
as a substrate should be examined further by researchers to
ensure the extension application of thin film photocatalyst.
However, this type of substrate has low surface energy and
thermal sensitivity. As such, designing a method to prepare
high photocatalytic activity TiO2 thin film at a low tempe-
rature is highly required. The work carried out by Zhou et al.
[3] shed a new light on the design of a modified sol-gel
method which is been done at a low temperature. They
developed the TiO2/SiO2 film on PET substrate via modified
sol-gel method at 100˚C. As such, the use of various types of
substrates which has high commercial potent application
should be developed to fit with important applications such
as self-cleaning, anti-bacterial and waste purification. Other
types of new substrate that has been studied is polymer
honeycomb [54] and foam nickel substrate [57].
A problem in the solar system that could not supply
enough UV light source (3-4%) to activate the photocatalyst
is one of the major recent research in this photocatalysis
field. Therefore, an abundant amount of recent researches
have been done on modifying the electronic properties of the
photocatalyst. It is important to ensure the activation of the
Aziz and Sopyan
photocatalysis process in the presence of visible light. There
are many ways that have been applied by researchers such
as; doping with other metals or non-metal dopants, coupled
with second semiconductor. This kind of method is an
alternative way to change the absorption edge from the UV
light range (<380nm) to the visible light range (400-650nm).
Directly, it is beneficial for the photocatalyst to be efficient
under visible light since its application can be more widely
used in any condition. Referring to Table 1 and Table 2 this
shows the list of TiO2 and modified TiO2 thin film photo-
catalyst along with their deposition method and substrate
used, compounds that have been degraded and its reference
[113-127].
ACKNOWLEDGEMENT
The authors thank Research Management Center,
International Islamic University Malaysia (IIUM) for the
partial financial support provided through an IIUM research
project No. EDW B0802-71.
CONFLICT OF INTEREST
The paper bring no conflict of interest.
REFERENCES
[1] Thiruvenkatachari R, Vigneswaran S, Moon IS. A review on
UV/TiO2 photocatalytic oxidation process. Korean J Chem Eng
2008; 25(1): 64-72.
[2] Jung SC, Imaishi N. Preparation, crystal structure, and
photocatalytic activity of TiO2 films by chemical vapor deposition.
Korean J Chem Eng 2001; 18(6): 867-872.
[3] Zhou L, Yan S, Tian B, Zhang J, Anpo M. Preparation of TiO 2-
SiO2 film with high photocatalytic activity on PET substrate. Mater
Lett 2006; 60: 396-399.
[4] Yu JG, Yu JC, Zhao XJ. The effect of SiO2 addition on the grain
size and photocatalytic activity of TiO2 thin films. J Sol-Gel Sci
Technol 2002; 24: 95-103.
[5] Yuan ZF, Li B, Zhang JL, Xu C. Synthesis of TiO2 thin film by a
modified sol-gel method and properties of the prepared films for
photocatalyst. J Sol-Gel Sci Technol 2006; 39: 249-253.
[6] Stoyanov S, Mladenova D, Dushkin C. Photocatalytic properties of
mixed TiO2/V2O5 films in water purification at varying pH. React
Kinet Catal Lett 2006; 88(2): 277-283.
[7] Gu DE, Yang BC, Hu YD. A novel method for preparing V-doped
titanium dioxide thin film photocatalysts with high photocatalytic
activity under visible light irradiation. Catal Lett 2007; 118: 254-
259.
[8] Ge L, Xu M, Fang H. Preparation and characterization of silver and
indium vandate co-doped TiO2 thin films as visible-light-activated
photocatalyst. J Sol-Gel Sci Technol 2006; 40: 65-73.
[9] Bouras P, Lianos P. Photodegradation of dyes in aqueous solutions
catalyzed by highly efficient nanaocrystaliine titania films. J Appl
Electrochem 2005; 35: 831-836.
[10] Funakoshi K, Nonami T. Photocatalytic treatments on dental mirror
surfaces using hydrolysis of titanium alkoxide. J Coat Technol Res
2007; 4(3): 327-333.
[11] Chiba Y, Kokai H, Kashiwagi K. Effect of the plasma treatment on
an anatase TiO2 film. J Mater Sci Mater Electr 2005; 16: 645-648.
[12] Watanabe T, Fukayama S, Miyauchi M, Fujishima A, Hashimoto
K. Photocatalytic activity and photo-induced wettability conversion
of TiO2 thin film prepared by sol-gel process on a soda-lime glass.
J Sol-Gel Sci Technol 2000; 19: 71-76.
[13] Sopyan I. Kinetic analysis on photocatalytic degradation of gaseous
acetaldehyde, ammonia and hydrogen sulfide on nanosized porous
TiO2 films. Sci Technol Adv Mater 2007; 8: 33-39.
[14] Sopyan I, Watanabe M, Murasawa S, Hashimoto K, Fukishima A.
An efficient TiO 2 thin-film photocatalyst: photocatalytic properties
in gas-phase acetaldehyde degradation. J Photochem Photobiol Part
A Chem 1996; 98: 79-86.
Review on TiO2 Film Photocatalyst
[15] Noguchi T, Fujishima A, Sawunyama P, Hashimoto K.
Photocatalytic degradation of gaseous formaldehyde using TiO2
films. Environ Sci Technol 1998; 32(23): 3831-3833.
[16] Xianyu WX, Park MK, Lee WI. Thickness effect in the
photocatalytic activity of TiO2 thin films derived from sol-gel
process. Korean J Chem Eng 2001; 18(6): 903-907.
[17] Choi YL, Kim SH, Song YS, Lee DY. Photodecomposition and
bactericidal effects of TiO2 thin films prepared by a magnetron
sputtering. J Mater Sci 2004; 39: 5695-5699.
[18] Yu JG, Yu HG, Ao CH, et al. Preparation, characterization and
photocatalytic activity of in-situ Fe-doped TiO2 thin films. Thin
Solid Films 2006; 496: 273-280.
[19] Yusuf MM, Imai H, Hirashima H. Preparation of porous titania
film by modified sol-gel method and its application to
photocatalyst. J Sol-Gel Sci Technol 2002; 25: 65-74.
[20] Takeuchi M, Yamashita H, Matsuoka M, et al. Photocatalytic
decomposition of NO on titanium oxide thin film photocatalysts
prepared by an ionized cluster beam technique. Catal Lett 2000; 66:
185-187.
[21] Takeuchi M, Yamashita H, Matsuoka M, et al. Photocatalytic
decomposition of NO under visible light irradiation on the Cr-ion-
implanted TiO2 thin film photocatalyst. Catal Lett 2000; 67: 135-
137.
[22] Fallet M, Permpoon S, Deschanvres JL, Langlet M. Influence of
physico-structural properties on the photocatalytic activity of sol-
gel derived TiO2 thin films. J Mater Sci 2006; 41: 2915-2927.
[23] Sheng J, Shivalingapa L, Karasawa J, Fukami T. Low-temperature
formation of photocatalytic Pt-anatase film by magnetron
sputtering. J Mater Sci 1999; 34: 6201-6206.
[24] Ditta IB, Steele A, Liptrot C, et al. Photocatalytic antimicrobial
activity of thin surface films of TiO2, CuO and TiO2/CuO dual
layers on Escherichia coli and bacteriophage T4. Appl Micrbiol
Biotechnol 2008; 79(1): 127-133.
[25] Sunada K, Kikuchi Y, Hashimoto K, Fujishima A. Bactericidal and
detoxification effects of TiO2 thin film photocatalysts. Environ Sci
Technol 1998; 32(5): 726-728.
[26] Sunada K, Watanabe T, Hashimoto K. Bactericidal activity of
copper-deposited TiO2 thin film under weak UV light illumination.
Environ Sci Technol 2003; 37(20): 4785-4789.
[27] Begum NS, Ahmed HMF. Synthesis of nanocrystalline TiO2 thin
films by liquid phase deposition technique and its application for
photocatalytic degradation studies. Bull Mater Sci 2008; 31(1): 43-
48.
[28] Ge L, Xu M. Fabrication and characterization of TiO2
photocatalytic thin film prepared from peroxo titanic acid sol. J
Sol-Gel Sci Technol 2007; 43: 1-7.
[29] Zhou J, Takeuchi M, Zhao XS, Ray AK, Anpo M. Photocatalytic
decomposition of formic acid under visible light irradiation over V-
ion-implanted TiO2 thin film photocatalysts prepared on quartz
substrate by ionized cluster beam (ICB) deposition method. Catal
Lett 2006; 16(1-2): 67-70.
[30] Cho DL, Min H, Kim JH, et al. Photocatalytic characteristics of
TiO2 thin films deposited by PECVD. J Ind Eng Chem 2007; 13(3):
434-437.
[31] Yu JG, Yu JC, Cheng B, Zhao XJ. Photocatalytic activity and
characterization of the sol-gel derived Pb-doped TiO2 thin films. J
Sol-Gel Sci Technol 2002; 24: 39-48.
[32] Beydoun D, Amal R, Low G, McEvoy S. Role of nanoparticles in
photocatalysis. J Nanoparticle Res 1999; 1: 439- 458.
[33] Mei F, Liu C, Zhang L, et al. Microstructural study of binary
TiO2:SiO 2 nanocrystalline thin films. J Cryst Growth 2006; 292:
87-91.
[34] Machida M, Norimoto K, Watanabe T. The effect of SiO2 addition
in super-hydrophilic property of TiO2 photocatalyst. J Mater Sci
1999; 34: 2569-2574.
[35] Kitano M, Mitsui R, Eddy DR, et al. Synthesis of nanowire TiO2
thin films by hydrothermal treatment and their
photoelectrochemical properties. Catal Lett 2007; 119: 217-221.
[36] Otsuka E, Kurumada K, Suzuki A, Matsuzawa S, Takeuchi K. An
application of transparent mesoporous bulk silica to a titanium
dioxide photocatalyst with adsorption and decomposition functions.
J Sol-Gel Sci Technol 2008; 46: 71-78.
[37] Besserguenev VG, Pereira RJF, Mateus MC, et al. TiO2 thin film
synthesis from complex precursors by CVD, its physical and
photocatalytic properties. Int J Photoener 2003; 5:99-105.
Recent Patents on Materials Science 2009, Vol. 2, No. 2 109
[38] Zhou S, Ray AK. Kinetic studies for photocatalytic degradation of
Eosin B on a thin film of titanium dioxide. Ind Eng Chem Res
2003; 42: 6020-6033.
[39] Bernardi MIB, Lee EJH, Lisboa-Filho PN, et al. TiO2 thin film
growth using the MOCVD method. Mater Res 2001; 4(3): 223-226.
[40] Cernigoj U, Lavrencic Stangar U, Trebse P, Ribic PR. Comparison
of different characteristics of TiO2 films and their photocatalytic
properties. Acta Chim Slov 2006; 53: 29-35.
[41] Clouser S, Samia ACS, Navok E, Alred J, Burda C. Visible-light
photodegradation of higher molecular weight organics on N-doped
TiO2 nanostructured thin films. Top Catal 2008; 47: 42-48.
[42] Negishi N, Takuechi K, Ibusuki T. Surface structure of the TiO 2
thin film photocatalyst. J Mater Sci 1998; 33: 5789-5794.
[43] Zhang Y, Wang J, Li J. Mesophase configurations and optical
properties of mesoporous TiO2 thin films. J Electroceram 2006; 16:
499-502.
[44] Liu GQ, Jin ZG, Liu XX, Wang T, Liu ZF. Anatase TiO2 porous
thin films prepared by sol-gel method using CTAB surfactant. J
Sol-Gel Sci Technol 2007; 41: 49-55.
[45] Truijen I, Van Bael MK, Van den Rul H, D’Haen J, Mullens J.
Preparation of nanocrystalline titania films with different porosity
by water-based chemical solution deposition. J Sol-Gel Sci Technol
2007; 43: 291-297.
[46] Negishi N, Takeuchi K. Preparation of TiO2 thin film
photocatalysts by dip coating using a highly viscous solvent. J Sol-
Gel Sci Technol 2001; 22: 23-31.
[47] Ge L, Xu M, Sun M, Fang H. Low-temperature synthesis of
photocatalytic thin film from aqueous anatase precursor sols. J Sol-
Gel Sci Technol 2006; 38: 47-53.
[48] Falaras P, Arabatzis IM, Stergiopoulos T, Bernard MC. Enhanced
activity of silver modified thin film TiO2 photocatalysts. Int J
Photoener 2003; 5: 123-130.
[49] Mills A, Hill G, Crow M, Hodgen S. Thick titania films for
semiconductor photocatalysis. J Appl Electrochem 2005; 35: 641-
653.
[50] Smirnova N, Gnatyuk Y, Eremenko A, et al. Photoelectrochemical
characterization and photocatalytic properties of mesoporous
TiO2/ZrO2 films. Int J Photoener 2006; Article ID 85469: 6.
doi:10.1155/IJP/2006/85469
[51] Yu, C.J.:US20046803077B2 (2004).
[52] Quan X, Tan H, Zhao Q, Sang X. Preparation of lanthanum-doped
TiO2 photocatalysts by coprecipitation. J Mater Sci 2007; 42: 6287-
6296.
[53] Addamo M, Augugliaro V, Di Paola A, et al. Photocatalytic thin
films of TiO 2 formed by a sol-gel process using titanium
tetraisopropoxide as the precursor. Thin Solid Films 2007; 516(12):
3802-3807.
[54] Kon K, Nakajima K, Karthaus O. Polymer honeycomb templated
microporous TiO2 films with enhanced photocatalytic activity. J
Surf Sci Nanotechnol 2008; 6: 161-163.
[55] Bockmeyer M, Lobmann P. Formation, densification and properties
of sol-gel TiO2 films prepared from triethanolamine-chelated
soluble precursor powders. J Sol-Gel Sci Technol 2008; 45: 251-
259.
[56] Cavalheiro AA, Bruno JC, Saeki MJ, Valente JPS, Florentino AO.
Effect of scandium on the structural and photocatalytic properties
of titanium dioxide thin films. J Mater Sci 2008; 43: 602-608.
[57] Hu H, Xiao W, Yuan J, et al. High photocatalytic activity and
stability for decomposition of gaseous acetaldehyde on TiO2/Al2O 3
composite films coated on foam nickel substrate by sol-gel
processes. J Sol-Gel Sci Technol 2008; 45: 1-8.
[58] Permpoon S, Houmard M, Riassetto D, et al. Natural persistent
superhydrophilicity of SiO2/ TiO 2 and TiO2/SiO 2 bi-layer films.
Thin Solid Films 2008; 516: 957-966.
[59] Zhang S, Zhao Z, Liu C, et al. Study on the optical properties of
Mn-doped TiO2 thin films. J Mater Sci 2004; 39: 2909-2910.
[60] Tomaszewski H, Eufinger K, Poelman H, et al. Effect of substrate
sodium content on crystallization and photocatalytic activity of
TiO2 films prepared by DC magnetron sputtering. Int J Photoener
2007; Article ID 95213: 5.
doi:10.1155/2007/95213
[61] Kim BH, Ahn JH, Jeong JH, et al. Preparation of TiO2 thin film on
SiO2 glass by a spin coating-pyrolysis process. Ceram Int 2006; 32:
223-225.
[62] Kanamori,T., Yajima, K., Nishikawa, A.: EP1785457A1 (2006).
110 Recent Patents on Materials Science 2009, Vol. 2, No. 2
[63] Ibusuki, A., Takeuchi, H., Aragai, K., Nishikata, S., Miyamoto, M.,
Noguchi, K., Takahashi, T.: JP06315614 (1994).
[64] Murasawa, S., Murakami, H., Fukui, Y., Watanabe, M., Fujishima,
A., Hashimoto, K.: EP0633064 (1994).
[65] Kimura, N., Abe, S., Yoshimoto, T., Fukayama, S.: EP1955768A1
(1996).
[66] Sangiovanni, J.J., Dardas, Z.A., Ioneva M.A., Li, L.:
US006649561B2 (2003).
[67] Lim YM, Jeong JH, An JH, et al. Nickel-doped titanium oxide
films prepared by chemical solution deposition. J Ceram Process
Res 2005; 6(4): 302-304.
[68] Nishijima K, Naitoh H, Tsubota T, Ohno T. Visible-light-induced
hydrophilic conversion of an S-doped TiO2 thin film and its
photocatalytic activity for decomposition of acetaldehyde in gas
phase. J Ceram Soc Jpn 2007; 115(5): 310-314.
[69] Yang J, Bai H, Jiang Q, Lian J. Visible-light photocatalysis in
nitrogen-carbon-doped TiO2 films obtained by heating TiO2 gel-
film in an ionized N2 gas. Thin Solid Films 2008; 516(8): 1736-
1742.
[70] Choi Y, Umebayashi T, Yoshikawa M. Fabrication and
characterization of C-doped anatase TiO2 photocatalysts. J Mater
Sci 2004; 39: 1837-1839.
[71] Smirnova N, Eremenko A, Rusina O, Hopp W, Spanhel L.
Synthesis and characterization of photocatalytic porous Fe3+/ TiO 2
layers on glass. J Sol-Gel Sci Technol 2001; 21: 109-113.
[72] Qiu S, Starr TL. Zirconium doping in titanium oxide photocatalytic
films prepared by atomic layer deposition. J Electroceram Soc
2007; 154(6): 472-475.
[73] An JH, Kim BH, Jeong JH, et al. Preparation of vanadium-doped
TiO2 thin films on glass substrates. J Ceram Process Res 2005;
6(2): 163-166.
[74] Lee BY, Kim SW, Lee SC, Lee HH, Choung SJ. Photocatalytic
decomposition of gaseous formaldehyde using TiO2, SiO 2-TiO 2 and
Pt-TiO2. Int J Photoener 2003; 5: 21-25.
[75] Ho WK, Yu JC, Lee S. Low-temperature hydrothermal synthesis of
S-doped TiO2 with visible light photocatalytic activity. J Solid
State Chem 2006; 179: 1171-1176.
[76] Fukawa, M., Odaka, H., Oyama, T., Mitsui, A.: US200817502A1
(2008).
[77] Furuya, M.: US2007066053A1 (2007).
[78] Furuya, M.: US20070040278A1 (2007).
[79] Choi, W.K., Jung, Y.S., Kang, D.H., Lee, K.J.: US20060247125A1
(2006).
[80] Higashimoto S, Ushiroda Y, Azuma M. Electrochemically assisted
photocatalysis of hybrid WO3/TiO 2 films: effect of the WO3
structures on charge separation behavior. Top Catal 2008; 47: 148-
154.
[81] Hattori A, Tokihisa Y, Tada H, et al. Patterning effect of a sol-gel
TiO2 overlayer on the photocatalytic activity of a TiO2/SnO2
bilayer-type photocatalyst. J Sol-Gel Sci Technol 2001; 22: 53-61.
[82] Baiju KV, Periyat P, Wunderlich W, et al. Enhanced photoactivity
of neodymium doped mesoporous titania synthesized through
aqueous sol-gel method. J Sol-Gel Sci Technol 2007; 43: 283-290.
[83] Miyashita, K., Kuroda, S., Ubukata, T., Enomoto, M.:
EP1153658A1 (2001).
[84] Chan AHC, Porter JF, Barford JP, Chan CK. Effect of thermal
treatment on the photocatalytic activity of TiO2 coatings for
photocatalytic oxidation of benzoic acid. J Mater Res 2002; 17(7):
1758-1765.
[85] Hasan MM, Haseeb ASMA, Saidur R, Masjuki HH. Effects of
annealing treatment on optical properties of anatase TiO2 thin
films. Proceedings of World Academy of Science, Engineering and
Technology 2008; 30: 221-225.
[86] Habibi MH, Sardashti MK. Preparation of glass-supported
nanostructure ZnO thin film deposited by sol-gel spin coating
technique and its photocatalytic degradation to monoazo textile
dye. J Nanomater 2008; Article ID 356765: 5.
doi:10.1155/ 2008/356765
[87] Wen T, Gao J, Shen J, Zhou Z. Preparation and characterization of
TiO2 thin films by the sol-gel process. J Mater Sci 2001; 36: 5923-
5926.
[88] Ma B, Goh GKL, Ma J. Crystallinity and photocatalytic activity of
liquid phase deposited TiO2 films. J Electroceram 2006; 16: 441-
445.
Aziz and Sopyan
[89] Tao HY, Qing SS, Ying XZ, Yan DC, Yan M. TiO 2 thin films
prepared from aqueous solution and their sterilizing capability. J
Ceram Process Res 2006; 7(1): 49-52.
[90] Remington, Jr. M.R., Varanasi, S., Strickler, D.A.:
US2007211513B2 (2007).
[91] Shimosaki, S., Ogasawara, T., Nagaoka, S., Masaki, Y.:
US20070054044A1 (2007).
[92] Lokhande CD, Min SK, Jung KD, Joo OS. Cathodic electro-
deposition of amorphous titanium oxide films from an alkoxide
solution bath. J Mater Sci 2005; 40: 491-494.
[93] Anpo M, Takeuchi M. Design and development of second-
generation titanium oxide photocatalysts to better our environment-
approaches in realizing the use of visible light. Int J Photoener
2001; 3: 89-94.
[94] Ohba Y, Baba Y, Sakai E, et al. Porous anatase layer formed on
titanium substrate through hydrothermal processes. J Mater Sci
2008; 43: 2163-2170.
[95] Madhusudan Reddy K, Guin D, Manorama SK, Ramachandra
Reddy A. Selective synthesis of nanosized TiO2 by hydrothermal
route: Characterization, structure property relation, and
photochemical application. J Mater Res 2004; 19(9): 2567-2575.
[96] Matsuda A, Higashi Y, Tadanaga K, Tatsumisago M. Hot-water
treatment of sol-gel derived SiO2-TiO2 microparticles and
application to electrophoretic deposition for thick films. J Mater Sci
2006; 41: 8101-8108.
[97] Okada, H., Imanaka, T.: EP1536036B1 (2007).
[98] Wang, W.H.: US2008131311A1 (2008).
[99] Horakova M, Kolouch A, Spatenka P. UV induced hydrophility of
TiO2 thin films. Vacuum Plasma Surf Eng 2006; 24.
[100] Jacobs, J.L., Anderson, M.T., Carlson, J.G., Spawn, C.L., Gould,
R.A.T.: US20080241550A1 (2008).
[101] Zainal Z, Hui LK, Hussein MZ. Removal of dyes using
immobilized titanium dioxide illuminated by fluorescent lamps. J
Hazardous Mater 2005; B125: 113-120.
[102] Miron C, Roca A, Hoisie S, Cozorici P, Sirghi L. Photoinduced
Bactericidal activity of TiO 2 thin films obtained by radiofrequency
magnetron sputtering deposition. J Optoelec Adv Mater 2004; 7(2):
915-919.
[103] Srivinasan C, Somasundaram N. Bactericidal and detoxification
effects of irradiated semiconductor catalyst, TiO2. Curr Sci 2003;
85(10): 1431-1438.
[104] Sheel DW, Brook LA, Ditta IB, et al. Biocidal silver and
silver/titania composite films grown by chemical vapour
deposition. Int J Photoener 2008; Article ID 168185: 11.
doi:10.1155/2008/168185.
[105] Sun SQ, Sun B, Zhang W, Wang D. Preparation and antibacterial
activity of Ag-TiO2 composite film by liquid deposition (LPD)
method. Bull Mater Sci 2008; 31(1): 61-66.
[106] Xu MF, Lin S, Chen XM, Peng YZ. Studies on characteristics of
nanostructure of N-TiO2 thin films and photo-bactericidal activity.
J Zhejiang Univ Sci B 2006; 7(7): 586-590.
[107] Wong MS, Chu WC, Sun DS, et al. Visible-light-induced
bactericidal activity of a nitrogen-doped titanium photocatalyst
against human pathogens. Appl Environ Microbiol 2006; 72(9):
6111-6116.
[108] Kuroda, T., Izutsu, H., Yamaguchi, I., Nakanishi, Y.:
US2008081758 (2008).
[109] Carreon MA, Choi SY, Mamak M, Chopra N, Ozin GA. Pore
architecture affects photocatalytic activity of periodic mesoporous
nanocrystalline anatase thin films. J Mater Chem 2007; 17: 82-89.
[110] Chen Y, Stathatos E, Dionysiou DD. Microstructure
characterization and photocatalytic activity of mesoporous TiO2
films with ultrafine anatase nanocrystallites. Surf Coat Technol
2008; 202: 1944-1950.
[111] Gan WY, Lee MW, Amal R, Zhao H, Chiang K.
Photoelectrocatalytic activity of mesoporous TiO2 films prepared
using the sol-gel method with tri-block copolymer as structure
directing agent. J Appl Electrochem 2008; 38: 703-712.
[112] Meng X, Qian Z, Wang H, et al. Sol-gel immobilization of SiO2 /
TiO2 on hydrophobic clay and its removal of methyl orange from
water. J Sol-Gel Sci Technol 2008; 46: 195-200.
[113] Habibi MH, Esfahani MN, Egerton TA. Photochemical
characterization and photocatalytic properties of a nanostructure
composite TiO2 film. Int J Photoener 2007; Article ID 13653: 8.
doi:10.1155/2007/13653.
Review on TiO2 Film Photocatalyst
[114] Kim JS, Lee TK. Effect of humidity on the photocatalytic
degradation of trichloroethylene in gas phase over TiO2 thin films
treated by different conditions. Korean J Chem Eng 2001; 18(6):
935-940.
[115] Surca Vuk A, Jese R, Orel B, Drazic G. The effect of surface
hydroxyl groups on the adsorption properties of nanocrystalline
TiO2 films. Int J Photoener 2005; 7:163-168.
[116] Coronado JM, Zorn ME, Tejedor-Tejedor I, Anderson MA.
Photocatalytic oxidation of ketones in the gas phase over TiO2 thin
films: A kinetic study on the influence of water vapor. Appl Catal
B Environ 2003; 43: 329-344.
[117] Vicente JP, Gacion T, Barboux P, et al. Photocatalytic
decomposition of fatty stains by TiO2 thin films. Int J Photoener
2003; 5: 95-98.
[118] Sabtaityte J, Oja I, Lenzmann F, Volobujeva O, Krunks M.
Characterization of nanoprous TiO2 films prepared by sol-gel
method. C R Chimie 2006; 9: 708-712.
[119] Bockmeyer M, Lobmann P. Crack formation in TiO2 films
prepared by sol-gel processing: Quantification and characterization.
Thin Solid Films 2007; 515: 5212-5219.
[120] Zainal Z, Hui LK, Hussein MZ, et al. Removal of dyes using
immobilized titanium dioxide illuminated by fluorescent lamps. J
Hazardous Mater 2005; B125: 113-120.
Recent Patents on Materials Science 2009, Vol. 2, No. 2 111
[121] Imao T, Hazama D, Noma N, Ito S. Photopatterning of titanium
oxide gel films prepared from titanium alkoxide modified with
hydroxyl-substituted aromatic ketones. J Ceram Soc Jpn 2006;
114(3): 238-240.
[122] Parthangal PM, Zachariah MR. Inorganic-filler chemical vapor
deposition: A new approach to grow nanoporous thin films. Chem
Mater 2005; 17: 3830-3836.
[123] Kim SB, Kim GS, Hong SC. Degradation of gaseous
trichloroethylene over a thin-film TiO2 photocatalyst. J Ind Eng
Chem 2006; 12(5): 749-756.
[124] Yu H, Lee SC, Yu J, Ao CH. Photocatalytic activity of dispersed
TiO2 particles deposited on glass fibers. J Mol Catal A Chem 2006;
246: 206-211.
[125] Hwang KS, Ahn JH, Kim BH. Vanadium-doped nanocrystalline
TiO2 layer prepared by spin coating pyrolysis. J Mater Sci 2006;
41: 3151-3153.
[126] Yang GJ, Li CJ, Li CX, Wang YY, Huang XC. Effect of Cu2+
doping on photocatalytic performance of liquid flame sprayed TiO2
coatings. J Thermal Spray Technol 2006; 15(4): 582-586.
[127] Park H, Choi W. Effects of TiO 2 surface fluorination on
photocatalytic reactions and photoelectrochemical behaviors. J
Phys Chem B 2004; 108: 4086-4093.