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Radiation Effects and Defects in Solids:

Incorporating Plasma Science and
Plasma Technology
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Effects of γ rays irradiation on

structure and property of TiO2 thin
films
ab ab ab ab
Liu Gui-ang , Li Da , Zou Chang-wei , Xie Wei & Cao Lian-
a
quan
a
School of Physical Science and Technology, Zhanjiang Normal
University, Zhanjiang 524048, People's Republic of China
b
Development Center for New Materials Engineering & Technology
in Universities of Guangdong, Zhanjiang 524048, People's Republic
of China
Published online: 15 Jan 2014.

To cite this article: Liu Gui-ang, Li Da, Zou Chang-wei, Xie Wei & Cao Lian-quan , Radiation Effects
and Defects in Solids (2014): Effects of γ rays irradiation on structure and property of TiO2 thin
films, Radiation Effects and Defects in Solids: Incorporating Plasma Science and Plasma Technology,
DOI: 10.1080/10420150.2013.860971

To link to this article: http://dx.doi.org/10.1080/10420150.2013.860971

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 Radiation Effects & Defects in Solids, 2014
http://dx.doi.org/10.1080/10420150.2013.860971

Effects of γ rays irradiation on structure and property of TiO2

thin films
Liu Gui-anga,b∗ , Li Daa,b , Zou Chang-weia,b , Xie Weia,b and CAO Lian-quana
Downloaded by [Moskow State Univ Bibliote] at 14:11 13 February 2014

a School of Physical Science and Technology, Zhanjiang Normal University, Zhanjiang 524048,
People’s Republic of China; b Development Center for New Materials Engineering & Technology in
Universities of Guangdong, Zhanjiang 524048, People’s Republic of China

(Received 12 June 2012; final version received 10 October 2013)

TiO2 thin films were deposited on a glass substrate by the radio frequency magnetron sputtering method,
and annealed for 2 h at temperatures of 550◦ C. Then, 60 Co γ rays with different doses were used to irradiate
the resulting TiO2 thin films. The surface features of films before and after irradiation were observed by
scanning electron microscope (SEM). Simultaneously, the crystal structure and optical properties of films
before and after irradiation were studied by X-ray diffraction (XRD), UV–VIS transmission spectrum and
Photoluminescence (PL) spectrum, respectively. The SEM analysis shows that the film is smooth with
tiny particles on the film surface, and non-crystallization trend was clear after irradiated with γ rays. The
XRD results indicated that the structure of the film at the room temperature mainly exists in the form of
amorphous and mixed crystal at a sputtering power of 200 W, and non-crystallinity was more obvious after
irradiation. Obvious difference can be found for the transmissibility of the irradiated and pre irradiation
TiO2 films by the UV-VIS spectra. The color becomes light yellow, and the new absorption edge also
appeared at about 430 nm. PL spectra and photocatalysis experiments indicate that the photocatalysis
degradation rate of the TiO2 films on methylthionine chloride solution irradiated with the maximum dose
can be increased to 90%.

Keywords: TiO2 thin films; γ rays; irradiation; non-crystallization

1. Introduction

There has been a tremendous amount of scientific interest on the nano-TiO2 thin film due to its
potential application in photocatalytic degradation of contaminant in water and air, photoelectro-
chemical solar cells, and hydrogen production on photocatalysts. In spite of the low utilization
ratio for TiO2 thin-film solar cell (1), it exhibits favorable prospects in thin-film solar cell and
especially in aeronautics and space field since the enhancement of the utilization ratio of TiO2
cell by using dye sensitization, chemical treatment and ion doping (2–5).
However, in outer space, solar cells made of nano-TiO2 thin films, photocatalytic setup and
window material will unavoidably suffer from irradiation of γ rays, high energy proton, cosmic
rays and so on. Irradiation from space will not only destroy human DNA, mutate cells, and also
harm inorganics parts (6).
With the development of science and technology, man-made γ rays source has been used
to simulate space environment on the earth and allows the object to be irradiated with different

∗ Corresponding author. Email: liuga888@sohu.com

© 2014 Taylor & Francis

 2 L. Gui-ang et al.

doses. By referring relevant literature, the irradiation dose was set at 2 × 103 − 8 × 104 Gy in this
experiment. Methyl methacrylate has been successfully inarched on the surface of nanocrystalline
TiO2 with anatase and rutile structure by Zu et al.(7) with electron irradiation dose of 3 × 103 Gy.
In addition, Jin et al.(8) reported the irradiation stability of TiO2 and TiO2 –SiO2 composite films
toward uranium. TiO2 –SiO2 and corresponding hydration oxide showed good irradiation ability
under total irradiation absorption dose of 480 and 1150 kGy, respectively (8).
In this paper, TiO2 thin films were deposited on the glass substrate by the radio frequency (RF)
magnetron sputtering method, and annealed for 2 h at temperatures of 550◦ C. Then, 60 Co γ rays
with different doses (2 × 103 − 8 × 104 Gy) were used to irradiate the resulting TiO2 thin films.
XRD, scanning electron microscope (SEM), UV–VIS and Photoluminescence (PL) experiments
were used to study the phase microstructure and photoelectricity characteristics of the TiO2 thin
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films before and after irradiation. This research will provide a science basis for using TiO2 thin
films in space with irradiation environment, e.g. solar cell, photocatalyst.

2. Experimental details

2.1. Deposition of TiO2 thin films

TiO2 thin films were deposited using a RF magnetron sputtering system operating at 13.6 MHz
(FJL560). Soda-lime glass substrates with thickness of 1.1 mm were ultrasonically cleaned with
acetone, ethanol and rinsed in de-ionized water before mounting onto the substrate holder. The
TiO2 ceramic target with a purity of 99.99% was used in the experiments and the distance between
the target and the substrate was set at 65 mm. The base pressure of the vacuum system was
6.5 × 10−4 Pa and the substrate was glow discharge cleaned for 10 min in Ar atmosphere at 4 Pa.
During a standard deposition, the substrate temperature was set at 25◦ C and other parameters were
set at 2.0 Pa total gas pressure, 1/3 O2 / Ar ratio, 30 min sputtering time. The glass substrate was
cut into five pieces after deposition and placed on a vacuum tube sintering furnace (OTF/GSL)
for annealing. The annealing temperature and time were kept at 550◦ C and 2 h, respectively.

2.2. γ rays irradiation on TiO2 thin films

Irradiation was performed used 60 Co irradiation with cobalt bomb activity of 4.5 × 105 Curie.
The four pieces of samples irradiated with different dose were named S1, S2, S3, and S4, while
the sample without irradiation was named S0. The irradiation doses for S1, S2, S3, and S4 were
2 × 103 , 2 × 104 , 4 × 104 , and 8 × 104 Gy while the irradiation times were 2.5, 48, 96, and 192 h,
respectively. For convenience, the conditions of the sputtering power, irradiation dose, annealing
temperature, and time are shown in Table 1.

Table 1. Conditions of the sputtering power, irradiation dose, anneal-

ing temperature, and time for samples.

Sample Power Annealing Annealing Irradiation

number (W) temperaturte (◦ C) time (h) dose (Gy)

S0 200 550 2 0
S1 200 550 2 2 × 103
S2 200 550 2 2 × 104
S3 200 550 2 4 × 104
S4 200 550 2 8 × 104
 Radiation Effects & Defects in Solids 3

2.3. Characterization of TiO2 thin films

The structure of the deposited TiO2 films before and after irradiation was characterized by X-ray
diffraction (XRD, Bruker axs Focus) with Cu Kα radiation. The UV–VIS transmission spectra
of the as-prepared films were recorded in the wavelength range of 300–800 nm by a UV–VIS
Spectrophotometer (Type: UV-2300) at room temperature. The surface topography was studied
using an SEM (FEI SIRION TMP). PL measurements were performed to study the emission
properties of the irradiated TiO2 thin films using a 254 nm excitation source.
The photocatalytic activity of the as-prepared samples was evaluated by the photodegradation
of methylene blue solution (2 mg/L) under UV illumination. The transmittance of methylene blue
solution at a wavelength of 664 nm was measured by a UV-2300 scanning spectrophotometer. UV
illumination was done with a 15 W UV lamp that emits with a peak at 265 nm. The methyl orange
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solution (10 mL) containing the as-prepared sample was well stirred in an evaporating dish. The
experiment was started when when the lamp was set about 10 cm above the evaporating dish.
Every 30 min interval, the transmittance of methylene blue solution in the evaporating dish was
analyzed using the UV–VIS spectrophotometer. For comparison, the same experiment was also
performed in the absence of sample.

3. Results and discussion

3.1. Crystal structure analysis of the films

Figure 1 shows the XRD spectra of TiO2 thin films before and after irradiation. As can be seen
from Figure 1, the XRD results indicated that the structure of the film before irradiation (S0)
mainly exists in the form of amorphous and mixed crystal at a sputtering power of 200 W. As
compared with samples before irradiation, TiO2 films irradiated with small dose show a slight
decrease in diffraction intensity and increase in full-width at half-maximum values which indicate
the trend of noncrystallization.
With increase in irradiation dose, amorphous width of wave packet appeared in samples S2, S3,
and S4. The wave packet became mild and the XRD peak intensity, position, and shape slightly
changed. The origin of the changes can be attributed to noncrystalization which is caused by

Figure 1. XRD spectra of TiO2 thin films before and after irradiation.
 4 L. Gui-ang et al.

Figure 2. SEM images of TiO2 thin films before (a) and after (b) irradiation.
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γ rays irradiation, and is contradictory with the literature completely (9). For γ rays irradiation
with a dose of 8 × 104 Gy, as shown in Figure 1 for sample S4, the wave packet completely
disappeared which indicates that the crystallinity phase of TiO2 film has been largely effected.
The amorphous width of XRD diffraction peaks indicates that the samples become noncrystalline
after irradiation (10).

3.2. The surface morphology of the films

Figure 2 shows the SEM images of samples S0 and S3 before (a) and after (b) irradiation. No
obvious microparticles are observed. As can be seen from Figure 2, the surface of the TiO2 films
is smoother and similar with Ga-doped TiO2 films deposited by the magnetron sputtering method
(3). However, combination of the crystalline grain appears after irradiation which coincided with
the XRD results shown in Figure 1.

3.3. UV–VIS spectroscopy analysis

As observed by the naked eye, the color of the TiO2 films was changed after irradiation. There was
no color for samples before irradiation and the color became brunet with increase in irradiation
dose.
The transmittance spectra of the TiO2 samples before and after irradiation are shown in Figure 3.
The transmittance ratio decreased with the increase in irradiation ratio which is the same as the
color changes. The decrease in transmittance ratio can be attributed to increase in amorphization
and defects in TiO2 films. At the same time, the corresponding absorption ratio increased which
gave rise to the deep color of the films and the decrease in heights of the curves. In addition, a
new absorption edge appears at 430 nm when the irradiation dose reached 4 × 104 Gy.
The optical band gap Eg values are determined by plotting (αhv)1/2 versus hv, where h is
Planck’s constant, v is the frequency of the incoming radiation and α is the absorption coefficient
related to transmittance T by T = exp(−αd), where d is the film thickness, and fits a straight line
to the linear part of the plot. The band gap is obtained from the intercept of energy axis at α = 0
as shown in Figure 4. Compared with anatase TiO2 with a bandgap of 3.2 eV, the TiO2 films before
irradiation shows bandgap at 3.3 eV which has been reported by Liu et al. (3). The absorption edges
of the TiO2 films have a slight red shift with the increase in irradiation. The bandgap decreased to
2.92 eV when the irradiation dose reached 8 × 104 Gy. Partial origin of decrease in bandgap with
increase in irradiation dose may be attributed due to quantum size effects which were introduced
by irradiation. Consistent with the Davis–Mott energy band model (11), the amorphous material
always contains defects which can cause energy levels in the band gap and thus the decrease in
band gap of irradiated TiO2 films.
 Radiation Effects & Defects in Solids 5
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Figure 3. UV–VIS spectra of TiO2 thin films before and after irradiation.

Figure 4. Energy band-gap changement of TiO2 thin films before and after irradiation.

3.4. PL spectra of TiO2 films

As shown in Figure 5, samples before irradiation (S0) show a typical PL spectrum, revealing the
dominant luminescence peaks at 387.5 nm and a weak emission at 421 nm. The PL spectra have
almost an identical shape after irradiation as compared with S0 which have strong emission mainly
located 380–390 nm and a weak located at 421 nm.At the same time, S2 has the most weak intensity
which indicates the low electron–hole recombination rate and therefore the high photocatalysis
activity (12, 13). So, it is likely that the low irradiation dose is related to high photocatalysis
activity. There will be a certain number of crystal defects after a low dose irradiation of γ rays.
These defects may become a trapped center for electrons or holes which will restrain recombination
and lead to the weakening of intensity of spectral line. However, too large radiation will result in
excessive defects. Some of these defects will act as a recombination center for photo-generated
electrons or holes. At this time, the intensity of spectral lines will increase. Recently, it was found
that there is a PL quenching if there is a defect present in the system. Singh et al. (14) have studied
the energy transfer rate and PL quantum efficiency between donor and acceptor quantum dots
 6 L. Gui-ang et al.
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Figure 5. PL spectra of TiO2 thin films before and after irradiation.

Figure 6. Degradation of TiO2 thin films as a function of UV irradiation time.

(QDs) embedded in a nonlinear photonic crystal. They found that as the concentration of donor
QDs increases, the PL efficiency decreases.

3.5. Photocatalytic activity

The original methylene blue solution with a concentration of 2 mg/L has a transmittance ratio of
20.2% at wavelength of 664 nm before photocatalytic degradation. Samples S0–S4 were placed
in the original methylene blue solution for photocatalytic degradation and the original methylene
blue solution without any sample was marked as S00. The photocatalytic degradation properties
 Radiation Effects & Defects in Solids 7

of various samples in methylene blue solution at different stages under ultraviolet light irradiation
are shown in Figure 6.
As shown in Figure 6, the photocatalytic degradation ratio of TiO2 film evidently increases with
increase in irradiation time. Samples S2 and S4 exhibit the highest degradation efficiency when
the irradiation time is lower than 1 h which is confirmed with the PL spectra shown in Figure 4.
However, when the photocatalytic time is higher than 1.5 h, the photocatalytic efficiency and
irradiation time have preferable consistency. Sample S4 exhibits a better photocatalytic ability
with a degradation ratio of 90% when the irradiation time is long as 3 h. Therefore, higher γ
ray irradiation dose improves the photocatalytic ratio of the TiO2 thin films. The reasons will be
researched further.
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4. Conclusions

(1) TiO2 thin films were deposited on soda-lime glass substrates using a RF magnetron sputtering
system operating at 13.6 MHz. Irradiation was performed used 60 Co irradiation with cobalt
bomb activity of 4.5 × 105 Curie. There was no color for samples before irradiation and
the color became brunet with increase in irradiation dose. In addition, new absorption edge
appears at 430 nm when the irradiation dose reached 4 × 104 Gy.
(2) The XRD results indicated that the structure of the film before irradiation (S0) mainly exists
in the form of amorphous and mixed crystal at a sputtering power of 200 W. With the increase
in the irradiation dose, the amorphous width of wave packet appeared in samples S2, S3,
and S4. The wave packet became mild and the XRD peak intensity, position, and shape had
slightly changed.
(3) PL spectra indicate that TiO2 films with an irradiation dose of 2 × 104 Gy have the most
weak intensity which indicates the low electron–hole recombination rate and therefore the
high photocatalysis activity.
(4) Samples S4 exhibit the highest degradation efficiency when the irradiation time is lower than
1 h which is confirmed with the PL spectra. Therefore, higher γ ray irradiation dose improves
the photocatalytic ratio of the nano-TiO2 thin films.

Acknowledgements
This work was supported by the foundation on science research of Oceanic and Fisheries administrator of Guangdong
Provincial.

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