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Single material TiO2 double layers

antireflection coating with photocatalytic
property prepared by magnetron sputtering
Impact Factor: 1.86 DOI: 10.1016/j.vacuum.2014.05.009




Zhaoyong Wang

Xing hu

Henan University of Urban Construction

Zhengzhou University




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Available from: Zhaoyong Wang

Retrieved on: 12 February 2016

Vacuum 108 (2014) 20e26

Contents lists available at ScienceDirect

journal homepage: www.elsevier.com/locate/vacuum

Single material TiO2 double layers antireection coating with

photocatalytic property prepared by magnetron sputtering technique
Zhaoyong Wang a, b, Ning Yao a, *, Xing Hu a

School of Physical Engineering and Laboratory of Material Physics, Zhengzhou University, Zhengzhou 450052, People's Republic of China
School of Mathematics and Physics, Henan Urban Construction University, Pingdingshan 467036, People's Republic of China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 24 March 2014
Received in revised form
12 May 2014
Accepted 13 May 2014
Available online 23 May 2014

Single material TiO2 was used to fabricate the double layers antireection coating with photocatalytic
property. TiO2 layers with low and high refractive indices were prepared by the direct reactive magnetron
sputtering technique and energy ltrating magnetron sputtering technique, respectively. The structure,
surface morphology and optical property were tested by X-ray diffraction, eld emission scanning electron
microscope and spectroscopic ellipsometer. The photocatalytic property of the coating was evaluated by
UVevis spectrophotometer. Results suggested that the coating had both antireective and photocatalytic
performances. The refractive indices of the top and bottom TiO2 layers were 2.10 and 2.47 (at 600 nm),
respectively. The average and max transmissivities were obtained of 88.4% and 98.9% in the wavelength
range of 400e800 nm and the degradation rate on Rhodamine B was obtained of 0.0034 min1.
2014 Elsevier Ltd. All rights reserved.

EFMS technique

1. Introduction
TiO2 has been studied comprehensively because it is non-toxic,
convenient to be obtained and easy to be doped by other materials.
It has many excellent performances such as high energy gap, high
refractive index, high electric inductivity and good chemical stability
[1e3]. There are three kinds of TiO2 including anatase, rutile and
brookite [4], while the anatase and rutile TiO2 are more widely
studied and utilized for their better optical and structural properties.
Anatase TiO2 is commonly used as the photocatalytic materials for
the high band gap. Also some researchers reported that the hybrid of
anatase and rutile TiO2 had better photocatalytic performance [5].
Since the discovery of photo stimulated water splitting on the TiO2
electrodes in 1972 [9], the application of TiO2 in the photocatalytic
technology and method have been investigated [6e8]. However, TiO2
coating with high transmissivity should also be provided in circumstances such as the application in architectural glass and glass
cover for solar cells. Therefore double functional coating with both of
self-cleaning and antireective properties is required. Anatase TiO2
was not usually used as the surface layer for the large scattering
losing due to the high refractive index (n 2.52) [10]. Some researchers have managed to fabricate the double functional coating
* Corresponding author. Tel.: 86 371 67767832.
E-mail address: yaoning@zzu.edu.cn (N. Yao).
0042-207X/ 2014 Elsevier Ltd. All rights reserved.

[11e16]. The antireective and self-cleaning properties were realized

by the low refractive index material and anatase TiO2. But two disadvantages exist in the fabricating process. The rst one is that lattice
distortion for the different material will be induced during the
annealing. And the second one is that the surface modication process is complicated. TiO2 lm can be prepared by several methods
such as chemical vapor deposition (CVD), dealloying and anodic
oxidation, Sol-Gel, radio fraction magnetron sputtering (RFMS) and
direct current reactive magnetron sputtering (DMS) [17e21].
Compared with other methods, DMS technique was used to prepare
TiO2 lms in our experiment for its special advantages that the
deposition parameters are stable, easy to control and high quality
lm with uniform distributions can be deposited in fast speed.
Double layers antireection coating is commonly selected over
single layer because two maximum can be achieved in the transmission spectrum. Furthermore the optical performance of the
coating is less sensitive to the variations of the refractive index and
layer thickness [22].
In this paper, single material double layers coating was fabricated by the well-matched individual TiO2 layers with low and high
refractive indices. Anatase TiO2 with low refractive was fabricated
by the DMS technique. TiO2 with high refractive index was prepared by the energy ltrated magnetron sputtering (EFMS) technique. Both the double functional properties of antireection and
photocatalysis were investigated.

Z. Wang et al. / Vacuum 108 (2014) 20e26


2. Experiments
2.1. Material preparation
The glass substrates were primarily cleaned before deposition.
Sequentially they were soaked in the KMnO4 solution (40 g/l) for
4 h, and then were ultrasonic cleaned in proper order with the
detergent solution, de-ionized water, acetone, de-ionized water,
isopropyl alcohol and de-ionized water. Finally the substrates were
dried in the oven.
Home made CS-300 DMS system was used to fabricate the
TiO2 lms on the substrates. Ti target (180  60  6 mm3, purity
99.99%) and the substrate with 70 mm-distance between them
were set as the cathode and anode. The base pressure of below
5.0  104 Pa was realized by the mechanical pump and molecular pump. As the substrates were heated to the given temperature, high-purity gas Ar (purity 99.999%) was introduced into
the chamber. Ar plasma was generated by the electric eld
applied between the target and substrate. After the surface of the
target was puried by the bombardment of Ar for 5 min, reactive gas of O2 (purity 99.5%) was introduced in to deposit TiO2
In order to prepare lms with better performances, EFMS
technique was designed on the base of the DMS technique [23].

Fig. 2. Structure of single material TiO2 double layers antireective coating.

cos dL

inL sin dL

i=nL sin dL
cos dL

cos dH
inH sin dH

i=nH sin dH
cos dH


where n0, nL and nH represent the refractive indices of the air, low
refractive index and high refractive index of the TiO2 lms,
respectively. d is the phase thickness and can be described by
d (2p/l)nd for the normal incidence. Y given by Eq. (2) represents
the admittance of the lm-substrate assembly.

ng cos dL cos dH  nL ng sin dL sin dH nH inL sin dL cos dH nH cos dL sin dH

B cos dL cos dH  nH sin dL sin dH nL i ng sin dL cos dH nH ng cos dL sin dH nL


The schematic diagram is illustrated in Fig. 1. The stainless metal

ltrating electrode in 0.1 mm thickness with square grid was
connected with the anode (ground) in front of the substrate.

For the normal incidence and equal phase thickness layers

(nHdH nLdL l0/4), the reectance (R) at the wavelength l0 turns
into Eq. (3).

2.2. Preparation of double layers coating

The structure of the coating is illustrated in Fig. 2. TiO2 lms

with high and low refractive indices are marked as TiO2eH and
TiO2-L. TiO2eH layer was rst deposited by the EFMS technique and
then TiO2-L layer was prepared by the DMS technique on it.
Based on the matrix theory [24], the characteristic matrix for the
construction of the lm-substrate is given by Eq. (1).

n0  Y
n0 Y


n0  n2L nH

n0 n2L nH


Provided that there is no light absorption or scattering occurring

in the optical process, the relation of transmission (T) and R can be
described as Eq. (4).

T 1R


In order to obtain the maximum T (R minimum), the low and

high refractive indices should satisfy the following relation.

nH nL


ng n0


W-shipped (l0/4l0/2) antireection coating is designed to

smooth the transmission property of the coating [22]. The parameters of the optical layers are optimized by TFCalc thin lm design
software so that the highest calculation transmission curve can
2.3. Material characterization

Fig. 1. Schematic diagram of the EFMS technique.

X-ray diffraction (XRD, PANational X'Pert Pro) was used to

determine the structure of the TiO2 lms. The eld emission
scanning electron microscope (FESEM, JSM 6700F) was used to
observe the surface morphologies.
V-Vase spectroscopic ellipsometer (Vase 32) was used to
examine the optical property (incident angles 55 , spectral range


Z. Wang et al. / Vacuum 108 (2014) 20e26

350e1000 nm). The arguments J and D measured by the spectroscopic ellipsometer rely tightly on the parameters of the lm
that can be described as follows.

r n0 ; nf ; ns ; f0 ; d; l tanJeiD


where n0 is the refractive index of the air, nf and ns are the refractive
indices of the lm and the substrate. F0 is the incidence angle, l is
the wavelength and d is the physical thickness.
The surface roughness, thickness and optical property of the
lm can be obtained by inverting the experimental data with the
basis on the established optical model. The model is composed of
a Bruggeman effective medium approximation (EMA) layer, a
dense TiO2 layer and the glass substrate. The EMA layer containing 50% TiO2 and 50% void is used to model the surface
roughness. Cauchy model [25] described in Eq. (7) is used to t
the experimental data.

1 1

nl A 2 4 ; kl b exp g
l L

Fig. 3. XRD patterns of TiO2 lms deposited at different temperature.


where n is the refractive index, k is the extinction coefcient. A, B, C,

b, g and L are the model parameters.
The UVevis spectrophotometer (UV-300, Shimadzu Japan)
equipped with an ultraviolet analyzer (ZF-1, HangZhou China) was
used to examine the photocatalytic performance of the coating by
determining the changing of the solution concentration represented by the maximum absorbance at 550 nm 10 ml RhB solution
(20 mg/L, pH 6) was breathed into the beaker with the coating
(20  20 mm2) in the bottom. After the adsorption/desorption
equilibrium in the dark for 2 h, the coating was irradiated by the
ultraviolet lamp (12 w, 365 nm) with a distance of 150 mm away
from the coating surface.
The degradation of RhB under the illuminant by the TiO2 lm
obeys pseudo-rst order kinetics [26]. The degradation rate K is
obtained by plotting the relationship of ln(c/c0) versus t, which
represents the photocatalytic performance of the coating. c and c0
are the concentrations of RhB solution after being irritated for t and
at the initial state.
3. Results and discussion
3.1. Structural and optical properties of TiO2 lms deposited by the
DMS technique
Fig. 3 shows the XRD patterns of the TiO2 lms prepared at
different temperature. The lms were deposited for 90 min. The
deposition pressure was 0.75 Pa and the deposition current was
maintained at 1 A. The ows of O2 and Ar were regulated at 6 sccm
and 36 sccm. It is observed that the lms exhibit standard anatase
diffraction curves [27] except the lm deposited at room
TiO2 lms prepared at the temperature of above 100  C present
polycrystalline anatase phase (described as A) with several crystal
orientations and the priority growth orientation of the lms is A
(101). It can be observed that the sequence of the crystallinity follows d > c > e > b. The crystallinity of the lm deposited at 300  C is
the best. As is known, the crystallinity is closely correlated with the
deposition particles kinetic energy and the substrate temperature.
Particles with similar kinetic energy are generated at the same
deposition parameters. And the migrate ability of the particles increase with the rising of the substrate temperature. Films deposited
at lower substrate temperature such as 100  C and 200  C have
worse crystallinities for the weaker migration energy. At the higher
temperature (400  C), poor crystallinity is induced for the faster

gathered speed for the deposition particles. The crystal sizes of

lms deposited at 100  C, 200  C, 300  C and 400  C are calculated
of 15.5 nm, 16.4 nm, 14.3 nm and 17.6 nm from Scherrer equation
D Kl/Bcosq, in which D is the crystal size, K is a constant (0.89)
and l is the wavelength of CuKa (1.54 ), B is the full-width at halfmaximum (FWHM) and q is the diffraction angle.
The thicknesses of the lms are obtained by the tted spectroscopic ellipsometry data. The depositing rates and thicknesses are
presented in Table 1. It can be observed that the lm deposited at
100  C presents the lowest depositing rate. With the increasing of
the temperature, the depositing rate increases to the highest
(4.8 nm min1) at 300  C and decreases at 400  C.
Fig. 4 shows the refraction indices of the lms deposited at
different temperature. The highest refractive index obtained at
400  C ranges from 2.97 to 2.34 in the wavelength range of
350e1000 nm. And the lowest refractive index acquired at 100  C
varies from 2.77 to 2.24 (within 350e1000 nm). The refractive index of the TiO2 lm increases with the rising of the substrate
temperature. A substantial increase is presented at the temperature
of below 300  C. While smaller amplication of the refractive
indices is illustrated at the substrate temperature of between
300  C and 400  C. The relationship of the refractive index with the
density (r) can be described as follows [28].

n rns 1  rnv


where ns and nv are the refractive indices of the solid and the void
part of the lm. It can be concluded that n increases with r. The
migration energy of the deposition particles is determined by the
substrate temperature. More particles connect together at higher
temperature, which induces higher density with fewer voids. The
refractive index increases greatly with the rising of the substrate
temperature up to 300  C for the incremental migration energy
while there is little difference in the migrate ability at higher
temperature. The near result was reported by Y.Q. Hou et al. [29].
As is observed in Figs. 3 and 4, anatase TiO2 lm with the lowest
refractive index is deposited at 100  C. Fig. 5 illustrates the
dispersive relations of the lms deposited at 100  C at different
deposition pressure. The refractive index decreases with the
increasing of the deposition pressure. The highest refractive index
appears at 0.3 Pa with the variation range of 3.02e2.33
(350e1000 nm). The lowest refractive index emerges at 3.0 Pa with
the variation range of 2.48e1.96. The refractive index reduces
greatly at the pressure of over 0.75 Pa while little alteration presents at the pressure from 0.3 Pa to 0.75 Pa. The regular pattern of

Z. Wang et al. / Vacuum 108 (2014) 20e26


Table 1
Depositing rates and thicknesses of the TiO2 lms.
DMS technique (90 min)

Rate (nm min1)

Thickness (nm)

EFMS technique

Temperature ( C) (0.75 Pa, 0 mesh)

Pressure (Pa) (100  C, 0 mesh)



























the refractive index can be explained by the deposition process in

the DMS technique. As the deposition pressure increases, many
particles are introduced into the chamber and the mean free path
decreases for the increased collisions frequency. The kinetic energy
of deposition particles also decreases due to the increased collisions, which induce a worse combining ability. On the other hand,
the discharge current is a function of electron with its density and
average electron temperature that can be described as
I ne1.71(kTe)1/2. According to the quasi-neutrality condition, ne is
approximately equal with nAr which is proportional to the density
of neutral Ar. So ne is proportional to the deposition pressure. In our
experiment the current was maintained at 1 A, and ne increases
with the decline of Te. As a result, the energy being transported to
the substrate decreases and the migration ability becomes poor. So
the refractive index decreases for the weaker crystallization as the
deposition pressure increased. But the refractive index changes
little at low pressure of below 0.75 Pa. This is due to the mean free
path that is comparable to the target-substance distance [30].
It is discovered from Table 1 that the depositing rate decreases
as the deposition pressure increases. The highest depositing rate
(3.8 nm min1) is obtained at 0.3 Pa and the lowest depositing of
3.0 nm min1 is generated at 3.0 Pa. According to the above analysis, the declination of the depositing rate is mainly due to the
shortened free path of the deposition particles.
According to the structural and optical properties of the TiO2
lms deposited at different deposition parameters, anatase TiO2
lm with the lowest refractive index is deposited at 100  C and
3.0 Pa.
3.2. Structural and optical properties of TiO2 lms deposited by the
EFMS technique
In order to avoid mis-match of the crystal lattice in the preparation of the double layers coating, TiO2 lm with high refractive index
was deposited at the same substrate temperature by the EFMS

Grid number (mesh) (100  C, 0.75 Pa)

technique. The pressure of 0.75 Pa was chosen as the deposition

pressure for the consideration of the results being illustrated by Fig. 5.
Fig. 6 illustrates the structure and refraction indices of TiO2 lms
deposited by the EFMS technique in which ve kinds of grids with
different mesh (the numbers of holes per inch) are used. All the lms
were deposited at almost 120 nm by controlling the deposition time.
From Fig. 6(a) we can discover that all the lms are well fabricated of
anatase phase with the same preferred growth orientation at A (101)
and there are no obvious difference in the curves, which indicates
that the crystallinities are similar. It is observed from Fig. 6(b) that
the refractive index increases with the increasing of the mesh
number. TiO2 lm deposited at 460 mesh has the highest refractive
index ranging from 3.11 to 2.37 (350e1000 nm). The energy ltrating
electrode plays the key role in inuencing the structural and optical
properties of the fabricated lm. Being connected with the anode,
the energy ltrating electrode absorb high energy ions including O
anions and secondary electrons, which forms the results that both
the overall ux of particles and the bombardment on the substrate
reduce. The deposition particles with uniform kenotic energy in
smaller incident angle can be produced by colliding with the ltrating electrode. Mean while, the energy ux from positive argon
ions reaching the substrate can be reduced for the reduced or
eliminated anode sheath in front of the substrate by the ltrating
electrode. All the reasons mentioned above provide more time and
lower migrating energy for the deposition particles diffusing and
gathering on the substrate surface. Thus lm containing smaller
particles is fabricated in higher density with higher refractive index
for the ltrating electrode. Our previous work reported that ITO lm
deposited by the EFMS technique had smoother surface with
compact structure [23]. Filtrating electrode with larger mesh number causes deeper inuence on properties of the deposited lm.
It is observed in Table 1 that the depositing rates drop dramatically with the increasing of the mesh number. The depositing rate
ranges from 2.3 nm min1 to 0.7 nm min1 with the increasing of
the mesh number.


0.3 Pa
1.5 Pa
3.0 Pa

Refractive index








Fig. 4. Dispersive relations for the refractive indices of TiO2 lms deposited at different
substrate temperature.

Fig. 5. Dispersive relations of the TiO2 lms deposited at different pressure.


Z. Wang et al. / Vacuum 108 (2014) 20e26

Fig. 7. SEM image of the double layers coating.

3.3. TiO2 double layers antireective coating

TiO2 lms with low refractive index can be prepared by the DMS
technique and TiO2 lms with wide range high refractive indices
are achievable by using different mesh numbers in the EFMS
technique. This leads to the feasibility of fabricating double layers
coating with single material. To obtain the maximum transmission
at 600 nm, the high refractive index is calculated by Eq. (5), in
which ng and n0 are the refractive indices of the glass (1.52) and air
(1.0). nL being extracted from curve 3.0 Pa in Fig. 5 is 2.0. nH is then
calculated at 2.50. Compared with the results displayed in Fig. 6,
460 mesh is the best choice for the refractive index (2.49 at
600 nm). W-shaped (l0/4l0/2) layers are fabricated according to
the optimized results by TFCcalc thin lm design software
(dL 59.9 nm, dH 102.0 nm).
Fig. 7 shows the SEM images of the double layers antireection
coating. It can be observed that clear TiO2 particles with some gaps
distribute in the surface. It shows that the smaller TiO2 particles are
clearly agglomerated. The cluster and gaps are the result of the
TiO2-L layer deposited on the denser TiO2eH layer containing
smaller particles.
Fig. 8 presents the transmissivity curves of the glass substrate,
experimental value and theoretical value of the coating. It can be
found that the antireection coating change the distribution of the
transmissivity curves. There are two maximum values appearing at
the wavelength of about 426 nm and 680 nm. From the experimental curve the highest transmissivity of 98.9% is observed at
423 nm. The transmissivity of the coating is higher than the glass



Fig. 6. Properties of TiO2 lms deposited with various grids by the EFMS technique.

substrate in the wavelength range of 405e456 nm and

630e930 nm. However the transmissivity of the coating is lower in
the wavelength rang of 456e630 nm. According to the antireection theory, the low transmissivity scope may be adjusted by
altering the thicknesses of the layers [31]. The average transmissivities are obtained of 88.0%, 88.4% and 89.1% respectively for
the glass substrate, experimental and theoretical values of the
antireection coating at 400e800 nm. The experimental curve
agrees with the theory. However, there are distinctions in some
wavelength. The reason may be that the optical property of the
layers such as the thickness and refractive index do not exactly
match with the calculated values.
Fig. 9 shows the experimental and tted data of the spectroscopic ellipsometer. The curve of experimental data coincides with
the tted data well. Table 2 presents the parameters of the TiO2
lms including low and high refractive indices. It can be observed
that the refractive index of TiO2-L (2.10) is higher than the theoretical value (2.03). The refractive index of TiO2eH (2.47) is lower
than the calculated value (2.50). The experimental thickness is
smaller and this may be caused by the different deposition substrate. The similar result was reported by M. M. Hasan et al. [4].
Mean squared error (MSE) is used to assess the quality the tted
data. The MES of the coating is 16.5 (in the credible range, <30) that


Glass substrate









Fig. 8. Transmissivity curves of the glass substrate, experiment and theory of the

Z. Wang et al. / Vacuum 108 (2014) 20e26


Fig. 9. Experimental and tted data of the coating (a): J (b): D.

Table 2
Fitted parameters of TiO2 double layers coating.

Refractive index (at 600 nm)

Thickness (nm)





















0 h




ln(c/c )










veries the credibility of the parameters obtained from the proper

Fig. 10(a) shows the concentration of the solution irradiated by
the UV illumination without the coating. Fig. 10(b) shows the
variation of RhB solution absorption spectra under the UV illumination. It is found from Fig. 10(a) that the concentration changes
little, which represents that the photocatalytic degradation process
is induced by the TiO2 coating. So Fig. 10(b) reveals the photocatalytic degradation process by the UV irradiation. The solution
concentration reduces gradually with the increasing of the irritation time. By calculating ln(c/c0), the relation between ln(c/c0) and t
is obtained and shown in Fig. 10(b). The slash being obtained by
tting the data suggests the degradation ability of the TiO2 coating
on RhB. The photocatalytic degradation rate can be characterized
by the gradient of the tted line and the absolute value is obtained
of 0.0034 min1. The photocatalytic property of TiO2 and TiO2 based
materials have been studied by many researchers [32,33]. The
photocatalytic property lies in two probable ways including the
photocatalytic and super-hydrophilic property [34]. Electron-hole
pairs are generated by the photons. Photo-generated holes in the
valence band of TiO2 have high oxidation ability and organic
pollution will be oxidized by the holes directly or by the active
oxygen species in the oxidation product such as hydroxyl radicals
(,OH). Photo-generated electronics can decompose the organic
pollution by the reduction reaction products with high redox ability
such as carboxyl (,OOH), super oxide anions (,O2), hydrogen
peroxide (H2O2), hydroxide ion (,OH orOH-) and singlet oxygen
(1 O2 ). The super-hydrophilic property presented by the TiO2 lm
also plays an important role in the degradation process. The
carboxyl generated by oxidizing reaction between the holes and
Kesmez et al.
adsorbent water takes part in the degradation. O.
reported the bilayer antireection coating with self-cleaning
property [35]. Although the transmissivity of the coating was
higher, we calculated that the degradation rate was just about
0.000891 min1 by extracting the solution condensation illustrated
in the paper, which was much lower.



4. Conclusions


In this paper, single material TiO2 double layers coating was

prepared based on the optical theory. By controlling the deposition
parameters of temperature and pressure (at 100  C, 3.0 Pa), anatase
TiO2 lm with low refractive index was prepared by the traditional
DMS technique. By using the EFMS technique at the same deposition temperature, TiO2 lm with high refractive index was deposited. Anatase TiO2 lms with high refractive were achieved at low
temperature. The refractive index was adjusted by changing the
mesh number of the ltrating electrode to match the low refractive
index. Results indicated that the coating had two functional





Fig. 10. (a). Concentration of the solution without TiO2 under the UV illumination.
Insert: Concentration of the solution at different reaction time. (b). Photocatalytic
degradation of the coating on RhB under the UV illumination. Insert: Relation of ln(c/
c0) versus reaction time.


Z. Wang et al. / Vacuum 108 (2014) 20e26

properties of both antireection and photocatalysis. The average

transmissivity of the antireection coating was 88.4%
(400e800 nm) with the high degradation rate of 0.0034 min1.
Using the same deposition method, single material of TiO2 double
layers coating with both antireective and photocatalytic performances would be a new structure that could be applied in the
particular application.

This work is supported in partial by Natural Science Foundation
of China (61076041) and Science and Technology Projects of Henan
Province (122102210099, 12B14007).

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