JOURNAL OF RARE EARTHS

Vol. 2 5 , Suppl. , Jun. 2007, p . 64

Ce02-Ti02N O z Anti- Reflecting and UV-Shielding Double-Functional

Films Coated on Glass Substrates Using Sol-Gel Method
Zhao Qingna (&.*I&) * , Dong Yuhong ( 3 3 i $ X ) , Wang Peng (3- @), Zhao Xiujian (&@&)
( kky Laboratory o f Silicate Materials Science and Engineering o f Ministry o f Education, W h n Universityo f Technology ,
Wuhan 430070, China )

Abstract: Ce02-Ti02/Si02double-layered films were coated on glass substrates using sol-gel method. The films, formed
using spin-coating process, had two optical properties at the same time, anti-reflection in visible region and ultraviolet rays
( UV ) shielding. The films could be used as museum windows, commercial high-resolution displays and so on. These films
were composed of Ce02 and Ti02 with molar ratio of 50 to 50 in the first layer and silica matrix in the 2nd layer. Further-
more, the 2nd layer was composed of porous silica films, which showed a lower refractive index, reducing the reflectance
significantly in visible wavelength region. The reflectance of the films in visible region between 400 700 nm was lower -
than 2 % , and almost 100% UV was shielded. The surface roughness of the films was observed through an atomic force
microscope, a depth composition profile of the double layered film was measured with an X-ray photoelectmn spectrometer
(XPS).
Key words : anti-reflection and UV shielding; Ce02-Ti02/Si02 double-layered functional films ; porous silica films ;
sol-gel process; rare earths
CLC number: 0614.33 Document code: A Article ID: 1002 - 0721(2007) - 0064 - 04

The ultraviolet rays (UV) can transmit into room
through the soda-lime silicate glass (float glass)"'.
Some materials, e .g . , paper, furniture and plastics,
irradiated by UV, will be colored and deteriorated.
And UV also causes harmful damage to the human
body and eyes. It is necessary to prevent the interior
materials from damaging by UV. Along with the
change to high-resolution display terminals in recent
years, the surface treatment of the display has changed
from anti-glare treatment that lowers the resolution to
anti-reflection treatment. The anti-reflection treatment
on displays can prevent operators from getting eye-
strain. Anti-reflection in visible region or shielding
from UV irradiation can be achieved through coating
films on the glassL2'3 1 .
The films can be deposited using either a sputter-
ing ( dry type) or by a sol-gel method ( wet type).
Ce02-Ti02 films on glass substrates for UV shielding
had been deposited by radio-frequency magnetron
sputtering, using Ce02-TiOz targets with different mo-
lar ratio of Ce02 to Ti02[41. The composition of the
Ce02-Ti02films is different from that of the target. In
general, it has been recognized that the sol-gel coating
formed multi-layered film has the advantage of higher
chemical uniformity when many kinds of ions are
mixed.
In this study, therefore, sol-gel process was used
for forming double-layered functional films, Ce02-Ti02
UV shielding and silica matrix anti-reflection films.
The structure and properties of the films were investi-
gated, especially, a depth composition profile of the
double layered film was measured with an X-ray pho-
toelectron spectrometer (XPS) . The results were dis-
cussed.
1 Experimental
1.1 Preparation of coating solutions
In the 1st layer sol-gel solution, Ti [ 0
(CH2 )3CH3 1 4 and CeC13* 7H20 were dispersed in alco-
hol ( C . P. ) and water (deionized water) in moderate
amounts, respectively, and then the obtained two so-
lutions were mixed with the molar ratio of Ce/Ti = l ,
which were used as the first layer solutions. The 2nd
layer sol-gel solutions were prepared by acid hydrolysis
of silicon alkoxides , namely tetraethoxysilane
(TEOS) , to obtain the silica oligomer, which were

Received date: 2006 - 10 - 18; revised date: 2007 - 04 - 12

Foundation item: Project supported by the Program for Changiiang Scholars and Innovative Research Team in University (PCSIRT , IRT0.547)
Biography: Zhao Qingnan (1963 - ), Male, Doctor, Professor; Research interest: Processing glass, optical and electronic film materials
* Corresponding author (E-mail : zhaoqingnan @ tom. corn)
 Zhuo Q N et a1 . Double-FunctionalFilms Coated on Glass Substrates Using Sol-Gel Method 65

dispersed in water and alcohol in approximately 1% 2.2 Properties of double-layered Ce02-

concentration. In addition, porous silica (mean diam-
TiO,/SiO, anti-reflection and W
-
eter of approximately 20 50 nm) was suspended in
shielding films
alcohol and added into the second silica matrix layer
-
solution in approximately 10% 15% . The thickness of the silica matrix 2nd layer on the
above mentioned 1st layer was approx. 95 nm. The
1.2 Coating procedures reflectance of the double-layered film is demonstrated
The UV shielding and anti-reflection double- in Fig . 3 . It is apparent that the film reflectance was
layered films were formed on the 2 mm thickness float
glass substrates in the following process : ( 1 ) The sub-
strates were cleaned out by water and alcohol. ( 2 )
The substrates were heated to approximately 50 *
5 c . The 1st layer solution was spin-coated at the ro-
tation speed of approximately 120 rev per minite and
dried for approximately 3 min. ( 3 ) In the same meth-
od as the 1st layer, the 2nd layer was spin-coated onto
the previous 1st layer and dried at approximately 120
T for 30 min. (4) Finally, the spin-coated double
layer was heat-treated at approximately 500 c for 30
min in the air to obtain a double-layered UV shielding
and anti-reflection film.
Fig. 1 Typical AFM image of a single CeOz-TiOZ layer spin-
1.3 Characterization coated on glass substrate
The reflectance and transmittance of the double-
layered coating films was measured using a spectrome-
ter (Cary 500). The surface roughness of the films
was observed through an atomic force microscope
(AFM , SPM-9500J3) . A depth composition profile of
the double layered film was measured with an X-ray
photoelectron spectrometer ( XPS, V . G . ESCALAB
MK 11). The film thickness was measured using a
spectrometer (nkd-7000WRev, Cauchy model) .
2 3 4 5 6 7 8 9 1 0 1 1
2 Results and Discussion WavelengtNl 0 nm

2.1 Properties of CeOz-TiOzsingle-layer Fig. 2 Typical UV-vis transmittance curve of glass substrate
(1 ) and single CeOZ-TiOz layer ( 2 ) spin-coated on
coating films glass substrate
In order to optimize the reflectance forming in the
double-layered films, the optical thickness of the 1st
layer was about h 14, where h is the observed wave-
length. According to the refractive index of the UV
c
shielding single-layer composed of CeO2-TiOz, the 1st
layer thicknesses was to be approximately 75 nm .
AFM image showed that the surface roughness for the
1st layer was about rt 4.15/2 nm, which means that
the film surface was extremely homogeneous and po-
rous (Fig. l ) .
Fig. 2 shows the UV-vis transmittance curve of
the single Ce02-Ti02 layer spin-coated on glass sub-
strate (2) and the glass substrate ( 1) . From Fig. 2 , it
can be seen that, compared with the substrate, the
single Ce02-Ti02layer can shield almost 100% UV .
66
lower than that of the non-coated substrate (approx.
7.8%) in the visible wavelength region. The rnini-
mum values of the reflectance curve for the double-
layered films were approximately 1 .0% .
Fig.4 shows the XPS depth analysis of the dou-
ble-layered film. From Fig. 4 it can be shown that the
distribution profiles of Ce and Si were overlapped in
the 1st layer. It was assumed that the Ce ions in the
1st layer were diffused into the 2nd silica layer to form
an inclining refractive index structure by generating
the mixture layer for optical effect. The reflectance of
the double-layered film shows an extremely wide re-
flection curve (Fig. 3 ) , which proves the inclining re-
fractive index structure.
2.3 Effects of porous silica incorporated
in 2nd layer film on double-layered
anti-reflection and UV shielding
In order to investigate the refractive index of po-
rous silica particles qualitatively, the refractive indices
of single layer silica films with different porous silica
contents were measured using an ellipsometer as shown
in Fig. 5 . It was obvious that the refractive indices de-
creased with an increase of the porous silica content
incorporated into the silica matrix films. This is be-
cause the refractive index of porous silica is lower than
Silica 2nd layer CeO,-TiO, layer Substrate
0 20 25 30 35 40 45 50 55 60
Sputtering timehin
Fig. 4 Typical depth composition profiles of double-layered film
composed of CeO,-Ti@ 1st layer and silica matrix 2nd layer
400 500 600 700
Wavelengthhm
Fig.6 Reflectance ( a ) and transmittance (b) of double-layered films, the silica matrix 2nd layer containing 10% porous silica
JOURNAL OF RARE EARTHS, Vol. 2 5 , Suppl. , Jun 2007 .
that of the ordinary pore-free silica film"'.
Fig. 6 is the reflectance and transmittance curve
of the double-layered film, in which the 2nd layers
with 10% porous silica contents were formed on the
1st layer of Ce02-Ti02films by the spin-coat method.
From Fig. 6( a ) it can be seen that the minimum value
of the reflectance is lower than 1% , and the shape of
the reflection valley is similar to that of the silica ma-
trix with no incorporation of the porous silica content
(Fig. 3 ) . From Fig. 6 ( b ) it can be seen that the trans-
mittance of the double-layered film in the visible re-
-
gion of 480 650 nrn is higher than 98%, and almost
100% UV is shielded. So, the prepared double-
layered film shows two optical properties at the same
time, i .e . , anti-reflection in visible region and ultra-
violet rays (UV) shielding.
3 Conclusions
1 . A double-layered anti-reflection in the visible
wavelength region and almost 100% UV shielding
films was successfully obtained, by sol-gel method to
spin-coat 1st layer Ce02-Ti02films on glass substrates
using Ti[O( CH2)3CH3]4and CeC13* 7 H 2 0with molar
ratio of Ce/Ti = 1 , and the 2nd layer silica matrix film
coated on the 1st layer.
Concentration of porous silica/(%, mass fraction)
Fig. 5 Refractive index of silica matrix vs concentration of porous
silica incorporated into the silica matrix films
"1 i
01 J ' 1 I I
800 300 400 500 600 700 800
Transmittance/%
 Zhuo Q N et a1 . Double-Functional Films Coated on GIass Substrates Using Sol-Gel Method
2. There was inter-diffusion between the two
films, forming a microstructure of a mixture layer,
which might result in refractive indices distributing in
an inclining structure.
3. An extremely low reflection curve (reflectance
< 2%) of the double-layered films were obtained by
incorporating porous silica to the 2nd silica matrix
layer, because porous silica had a lower refractive in-
dex .
References :
[ 1] Jiang Guodong et a l . Handbook of Glass [ M 1 . Beijing:
P .R .China, China Publishing House of Building Materi-
67
als, 1983. 654.
[2] Tang Jinfa, Zheng Quan. Application of Optical thin
Films [ M ] . Shanghai China, Shanghai Publishing House
of Science and Technology, 1984. 115.
31 Takeshi Morimoto, Hiroyuki Tomonaga, Akemi Mitani .
Ultraviolet ray absorbing coatings on glass for automobiles
[ J ] . Thin. Solid. Films., 1999, 351: 61.
41 Zhao Qingnan, Ni Jiamiao, Zhang Naizhi, Zhao Xiujian,
et a1 . Structure and properties of Ti02-Ce02films depos-
ited on soda-lime glass substrates by R .F Magnetron sput-
tering [J]. 1. Rare Earths, 2004, 22: 151.
[ 51 Stober W , Fink A , Bohn E . Controlled growth of mono-
.
disperse silica spheres in the micro size range [J] 1Col-
loid Interface Sci . , 1968, 26: 62.