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3 AUTHORS, INCLUDING:
Zhaoyong Wang
Xing hu
Zhengzhou University
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Vacuum
journal homepage: www.elsevier.com/locate/vacuum
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.
Keywords:
Antireection
Photocatalysis
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).
http://dx.doi.org/10.1016/j.vacuum.2014.05.009
0042-207X/ 2014 Elsevier Ltd. All rights reserved.
21
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
lm.
In order to prepare lms with better performances, EFMS
technique was designed on the base of the DMS technique [23].
B
cos dL
C
inL sin dL
i=nL sin dL
cos dL
cos dH
inH sin dH
i=nH sin dH
cos dH
1
ng
(1)
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
C
Y
B cos dL cos dH nH sin dL sin dH nL i ng sin dL cos dH nH ng cos dL sin dH nL
(2)
n0 Y
n0 Y
2
!2
n0 n2L nH
n0 n2L nH
(3)
T 1R
(4)
nH nL
q
ng n0
(5)
22
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
(6)
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
l
l
B
(7)
n rns 1 rnv
(8)
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
23
Table 1
Depositing rates and thicknesses of the TiO2 lms.
DMS technique (90 min)
EFMS technique
100
200
300
400
0.3
0.75
1.5
3.0
60
120
280
340
460
3.6
324
3.8
342
4.8
432
4.0
360
3.8
342
3.6
324
3.4
306
3.0
270
2.3
121
1.6
117
1.2
120
0.8
118
0.7
120
3.0
0.3 Pa
0.75Pa
1.5 Pa
3.0 Pa
Refractive index
2.8
2.6
2.4
2.2
2.0
400
500
600
700
800
900
1000
Wavelength/nm
Fig. 4. Dispersive relations for the refractive indices of TiO2 lms deposited at different
substrate temperature.
24
100
90
Transmittance/%
Fig. 6. Properties of TiO2 lms deposited with various grids by the EFMS technique.
80
70
Glass substrate
Experiment
Theory
60
50
40
30
20
400
500
600
700
800
900
1000
Wavelength/nm
Fig. 8. Transmissivity curves of the glass substrate, experiment and theory of the
coating.
25
Table 2
Fitted parameters of TiO2 double layers coating.
Layers
Thickness (nm)
MSE
TiO2-L
TiO2eH
2.10
2.47
52.5
102.9
16.5
(a)
Absorbance
2.5
Absorbance
3.0
2.0
0.0
Time/h
1.5
1.0
0.5
0.0
450
500
550
600
Wavelength/nm
(b)
3.0
0 h
0.5h
1.0h
1.5h
2.0h
2.5h
0.0
-0.1
Absorbance
2.0
ln(c/c )
2.5
-0.2
-0.3
-0.4
-0.5
1.5
0.0
0.5
1.0
1.5
2.0
2.5
Time/h
1.0
4. Conclusions
0.5
0.0
450
500
550
600
Wavelength/nm
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.
26
Acknowledgment
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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