Applied Surface Science 390 (2016) 591601

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Applied Surface Science

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

Synthesis and characterization of Ag doped TiO2 heterojunction lms

and their photocatalytic performances
Selim Demirci a, , Tuncay Dikici b , Metin Yurddaskal c,e , Serdar Gultekin d,f ,
Mustafa Toparli c,d,e , Erdal Celik c,d,e
a

Marmara University, Department of Metallurgical and Materials Engineering, Kadiky, 34722 Istanbul, Turkey
Izmir Katip Celebi University, Department of Materials Science and Engineering, Cigli, 35620 Izmir, Turkey
c
Department of Metallurgical and Materials Engineering, Dokuz Eylul University, 35390 Izmir, Turkey
d
Department of Nanoscience and Nanoengineering, Dokuz Eylul University, 35390 I zmir, Turkey
e
Center for Fabrication and Application of Electronic Materials, Dokuz Eylul University, 35390 Izmir, Turkey
f
Experimental Science Applications and Research Center, Celal Bayar University, 45140 Manisa, Turkey
b

a r t i c l e

i n f o

Article history:
Received 28 February 2016
Received in revised form 14 July 2016
Accepted 28 August 2016
Available online 31 August 2016
Keywords:
Titanium dioxide
Silver
Photocatalytic activity
Methylene blue (MB)
Hydrophilicity

a b s t r a c t
In this study, undoped and silver (Ag) doped titanium dioxide (TiO2 ) lms were successfully synthesized
by sol-gel spin coating technique on the Si substrates. Photocatalytic activities of the TiO2 lms with
different Ag content were investigated for the degradation of methylene blue (MB) under UV light irradiation. The crystal phase structure, surface morphology, chemical and optical properties of Ag-doped
TiO2 lms were characterized using an X-ray diffractometer (XRD), scanning electron microscopy (SEM),
X-ray photoelectron spectroscopy (XPS), UVvis spectrophotometer, and FTIR spectrophotometer. The
results showed that the Ag-doped TiO2 lms calcined at 500 C had the crystalline anatase phases and the
surface morphologies with some cracks. Ag substitution into TiO2 matrix enhanced the photocatalytic
activity of TiO2 lms under UV light irradiation as compared to the undoped TiO2 lm. Furthermore, the
results indicated that the 0.7% Ag doped TiO2 lm exhibited a superior photocatalytic activity than that
of undoped and other Ag-doped TiO2 lms. This study demonstrated the potential of an application of
Ag doped lms to efciently treat dissolved organic contaminants in water.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Semiconducting metal oxides are considerable category of functional materials which are promising a broad range of new and
different technological application elds [16]. One of the important and common used semiconducting metal oxides is titanium
dioxide (TiO2 ). TiO2 is characteristically chemically stable and nontoxic, which has exceptional physical, electronic, photoactive, and
electrochemical properties [710]. Lots of works have focused on
this material, because of its huge technological and commercial
potential [11,12]. Studies show us, TiO2 could be employed many
different application area such as air and water purications, selfcleaning window glasses, lithium batteries, gas sensing, dielectric
layer, solar cell etc. [1319]. Different attempts have been made to
increase applicability and efciency of TiO2 . Some of these works
were based on doping various transition metal or rare earth ions

Corresponding author.
E-mail address: selim.demirci@marmara.edu.tr (S. Demirci).
http://dx.doi.org/10.1016/j.apsusc.2016.08.145
0169-4332/ 2016 Elsevier B.V. All rights reserved.

into the TiO2 crystal lattice. For example according to studies of T.

Umebayashi and his friends, the S doping caused the absorption
edge of TiO2 to be shifted into the lower energy region [20]. Similar
studies were carried out by many researchers. S. Sakthivel and his
team compared the photonic efciency of Pt, Au and Pd doped TiO2
with pristine TiO2 . They revealed that absorption of light in the visible region by TiO2 increases with metal content [21]. One of the
most remarkable dopant elements for TiO2 is silver. Ag doped TiO2
is more efcient than undoped TiO2 at photocatalytic degradation
of AR88 (Acid Red 88) [22]. Temperature depended photodegradation properties of Ag doped TiO2 nanoparticle and nanobers
were reviewed by Nasser A.M. Barakat. K. Ubonchonlakate research
shows that under UV irradiation antibacterial disinfection efciency of pure TiO2 and Ag doped TiO2 is 57% in 15 min and 100%
in 10 min respectively [23]. Analogous study was performed by
Xuemin Wang. He determined molar ratio Ag as 5% for best antibacterial ability [24]. Furthermore, when TiO2 produced as thin lm,
it is possible that performance of this material can be considerably
improved [25]. TiO2 and Ag have long been known photodegrading, antimicrobial and antibacterial materials and used in different

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Table 1
The comparison of our study to the some published studies.
Material

Synthesis Method

Type of Nanostructure

Application

Substrate

References

Ag doped TiO2

Sol-gel spin coating

Sol-gel dip coating

Film
Film

Silicon
Glass

Sol-gel

Powder

Degradation of methylene blue

Degradation of Rhodamine B (RhB)
Degradation of methylene blue
Degradation of methylene blue
Disinfestation of P. aeruginosa bacteria
Degradation of Rhodamine B (RhB)
Reduction efciency of Cr(VI)

This work
[34]
[35]
[36]
[37]
[38]
[39]

Table 2
The amounts of the titanium (IV) isopropoxide and silver nitrate precursors.
Composition

Titanium (IV) isopropoxide (ml)

Silver Nitrate (g)

Undoped
0.1% Ag
0.3% Ag
0.5% Ag
0.7% Ag
0.9% Ag

3.052
3.021
2.931
2.7844
2.5895
2.3564

0
0.0170
0.0510
0.0850
0.1190
0.1530

technological elds [26,27]. For this reason, numerous researchers

have focused on growth of TiO2 thin lms on various substrates,
such as glasses, polycarbonate, copper [2830], using various different technique including magnetron sputtering, chemical vapor
deposition, thermal oxidation [3133]. Table 1 summarizes the
comparison of our study with some of the other published articles with Ag doped TiO2 lm materials [3439]. To the best of our
knowledge very few study about producing of photodegrading Ag
doped TiO2 lm especially on Si substrate using spin coating technique is available. In our study, silicon wafers were employed as
substrate material and wettability properties of undoped and Ag
doped TiO2 solutions on this substrate were examined by measuring contact angles. TiO2 lms including with various molar ratio of
Ag which is 0.1%, 0.3%, 0.5%, 0.7% and 0.9% were then manufactured
on the Silicon substrate. Structural, morphological, optical and photocatalytic degradation of methylene blue were then examined in
detail.

2. Experimental details
2.1. Preparation of solutions
Titanium (IV) isopropoxide (C12 H20 O4 Ti, 97%, Aldrich Chemistry) and silver nitrate (AgNO3 , 99.9%, Aldrich Chemistry)
precursors were utilized as initial materials in order to synthesize
undoped and Ag doped TiO2 solutions. All solvents and chemicals
were of analytical grade and were used without further purication.
Precursors were weighed in appropriate amounts in the dened
molar ratio to prepare all Ti-based solutions. Firstly, 3.052 ml of
titanium (IV) isopropoxide was hydrolyzed in the 10 ml of absolute
ethanol under magnetic stirring in order to get undoped TiO2 solution at room temperature. After stirring of the solution for 30 min,
1 ml glacial acetic acid was added into the solution. In the case of
the Ag doped TiO2 solutions, the calculated quantities of titanium
(IV) isopropoxide and silver nitrate precursors were distinctively
dissolved in 10 and 5 ml of ethanol. Then, the both titanium and
silver solutions were mixed together under magnetic stirring so as
to achieve desired dopant concentration of Ag in the TiO2 . The quantities of Ag ions in the TiO2 were adjusted to be 0.1%, 0.3%, 0.5%, 0.7%
and 0.9% mol respectively. After the stirring of the solution vigorously, 1 ml glacial acetic acid was again added into all the Ag doped
TiO2 solutions. The amounts of the titanium (IV) isopropoxide and
silver nitrate precursors were listed in Table 2.

Glass bre roving

2.2. Deposition of TiO2 based lms on substrates

A simple and cost-effective solgel spin coating method was
used for the deposition of the solution of the undoped and Ag doped
TiO2 lms onto the Si wafers (15 mm 15 mm). Before the deposition of the solutions onto the silicon wafers, the silicon wafers
were cleaned by an ultrasonic bath in isopropyl alcohol and acetone, respectively, for each 30 min, followed by rinsing with well
distilled water and drying in air in order to remove any surface contamination existing on the silicon surfaces. Subsequently, oxygen
plasma treatment has been applied for 10 min as a last step in the
cleaning process. After the cleaning process, the prepared Ti based
solutions were deposited onto the silicon wafers by spin-coater
(POLOS-SPIN150i) at 3000 rpm for 60 s. The deposited lms were
dried at 100 C for 10 min. The process was repeated ve times.
Then, the deposited lms were thermally treated at 500 C for 2 h
in air and cooled to ambient temperature. The fabrication steps of
the preparation of the undoped and Ag doped TiO2 lms were given
in Fig. 1 in detail.
2.3. Materials characterization
Fourier transform infrared spectroscopy (FTIR) studies were
carried out using (Thermo scientic Nicolet I10) device. Phase identication and crystal structures of the lms were performed by
X-ray diffractometer (XRD, Rigaku D/MAX-2200/PC). The surface
morphology of the lms was characterized by scanning electron
microscope (SEM, JEOL 6060). UV spectrophotometer with diffused
reectance apparatus (Thermo Scientic Evolution 600) was used
for optical measurements in the wavelength range of 300700 nm.
Surface analyses of the lms were characterized by photoelectron
spectroscopy (XPS, Thermo Scientic K-Alpha X-ray). The surface
wettabilities of the undoped and Ag doped TiO2 lms were determined by measuring the contact angles with one drop (5 l) of
pure water using a contact angle meter (Theta Lite, Biolin Scientic,
Sweden).
2.4. Photocatalytic activity measurements
The methylene blue (MB) molecule was selected as a target pollutant in order to assess photocatalytic performance of undoped
and Ag doped TiO2 lms. The photodegradation of MB experiments were exploited in a homemade reactor as given in Fig. 2,
which was surrounded with a cooling system to keep the photocatalytic reaction system at room temperature. All tests were
performed using a light source (Osram, UltraVitalux E27, 300W)
which emits both UV light and visible light. The light intensity of
the source was measured to be about 1.9 W/cm2 (at wavelength
of 365 nm) by a sun checker (visible-irradiance meter). The lms
were placed into beakers containing 30 ml of MB aqueous solution.
The initial concentration of MB is 3 mg/L corresponding to 105 M
(pH = 8). The distance between the lamp and the beakers was kept
at 20 cm for all specimens. Before irradiation, the lamp was preheated for 5 min, and the samples were soaked in the solution for
10 min in order to achieve an adsorption/desorption equilibrium.

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593

Fig. 1. The ow chart for undoped and Ag doped TiO2 lms using sol-gel spin coating method.

Afterwards, the lamp was switched on to initiate the photocatalytic

reaction. During the whole reaction, 3 ml of the MB aqueous solution from each beaker was extracted at an interval of 30 min in
order to measure the absorption spectra of MB. The absorption of
the MB solutions was conducted and analyzed by a UV-1240 Shimadzu spectrophotometer based on the characteristic absorption
of MB peak at 664 nm [40]. After collecting of the absorbance of MB,
the absorbance values were converted to concentration values. The
Beer-Lambert law (or Beers law) has linear correlation between
absorbance and concentration of transparent solutions at low concentration of MB. Their photocatalytic degradation efciency was
dened as [(C0 C)/C0 ] 100, in which C0 is the initial concentration of MB and C is the concentration of MB after photocatalytic
reaction [40]. The rate of a photocatalytic reaction is an important
issue for determination of any catalyst to be transferred into device
or industrial applications.

and 2878 cm1 are assigned to the asymmetric and symmetric C H

stretching mode of the CH2 group that derived from the presence of the ethanol and acetic acid. The intensity of these peaks
decreased with the increasing of heat-treated temperature because
of the vaporization and removing of ethanol and acetic acid in the
solution. In the case of the high-treated temperature, one can be
observed that a peak at around 1626 cm1 which also belongs to
hydroxyl ( OH) group appeared. The bands appeared at 1378 cm1
is related to the vibration mode of carboxylic group ( COO) because
of the acetic acid and ethanol [42]. The characteristic stretching
vibrations of C O of the ethanol are positioned at 1089 cm1 and
1046 cm1 . The presence of the strong bands at 880 cm1 correspond to antisymmetric stretching and antisymmetric in-plane
bending of NO3 in the nitrate groups [42]. The peaks beneath
810 cm1 are attributed to the stretching vibrations corresponding
to the Me O bonds such as Ti O or O Ti O [43].

3. Result and discussion

3.2. Crystalline structure

3.1. FTIR analysis

Fig. 4 depicts the XRD patterns of the undoped and Ag doped

TiO2 lms with different Ag content onto the silicon wafers at 500 C
for 2 h. The sharp and intense peaks in spectra are indication of the
presence of highly crystalline lms. The all main diffraction peaks
at 25.38 (101), 37.96 (004), 48.04 (200), 53.94 (105) and 54.20 (211)
coincide with the JCPDS values (PDF Card No: 00-021-1272) which
correspond to crystal structure of anatase [44]. It is clear that the
XRD peaks do not contain any characteristic peak regarding to Ag
or its oxides for all lms because of the small amount of Ag into
titanium oxide matrix [45]. The crystallite size of the lms was

Fig. 3 presents the FTIR spectra of the 0.1% Ag doped TiO2 solution heat-treated at different temperatures. The large bands in
the region of 36003100 cm1 is attributed to stretching vibrations of the metal-attached hydroxyl group ( OH), which indicates
the product hydrolyzed [41]. The peak became weaker with the
increasing of heat-treated temperature. The sharp peak at approximately 2971 cm1 is ascribed to the asymmetric C H stretching
mode of CH3 groups, whereas these peaks at around 2926 cm1

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Table 3
Micro structural parameters for undoped and Ag doped TiO2 lms.
Composition

Undoped
0.1% Ag
0.3% Ag
0.5% Ag
0.7% Ag
0.9% Ag

Cell Units

Microstructure

a ()

c ()

3.788
3.786
3.777
3.787
3.787
4.042

9.499
9.487
9.466
9.507
9.494
9.700

Unit Volume ()3

136.3
135.98
135.04
136.34
136.16
158.48

Grain Size (nm)

20.36
22.62
19.39
20.35
20.36
21.43

2 of (101) plane

1014 lines/m2

Strain (1000)
3.246
1.178
4.747
2.193
1.971
5.893

25.38
25.36
25.38
25.34
25.36
25.40

24.12
19.54
26.59
24.14
24.12
21.77

Fig. 4. XRD patterns of the undoped and Ag doped TiO2 lms.

Fig. 2. The homemade reactor for evaluation of photocatalytic performance of catalysts.

Fig. 3. The FTIR spectra of the 0.1% Ag doped TiO2 solution.

determined from the intensities of the strongest peaks at 2 = 25.38

using the well-known the Scherrer relation [40] following with
D = k/cos , where k = 0.94, = 1.5407 , = Full Width Half Maximum (FWHM) and = Diffracting angle. The crystallite size of the
lms was given in Table 3. It is reported that Ag doping enhances
the crystallization of TiO2 in some cases, whereas hinders or does
not affect the crystallization in other cases [46]. Within this framework, it can be observed that the intensities of lm peaks showed
the decreasing tendency with increasing the Ag content. In spite of
fact that there is a big difference between ionic radius of Ag+ (129
pm) and Ti4+ (74.5 pm), the existence of Ag content did not cause
apparent varieties in both crystalline size and lattice parameters.
There is no remarkable neither reduction nor increase in crystalline
size observed with the increase of silver amount in our study. This
can be explained by precipitation and dispersion of Ag particles
on the surface of the TiO2 lm owing to differences between ionic
radii. Therefore, Ag+ ions can migrate to the TiO2 surface during
crystallization. These ndings are in good agreement with both literature [47,48] and SEM images. Dislocation density () of the TiO2
lms was calculating using the = 1/D2 equation [49], in which D
and are dened as crystalline size and the length of dislocation
lines per unit volume of the crystal, respectively. Dislocations are
imperfection in a crystal associated with the mis-match of the lattice in one part of the crystal with respect to another part. The
dislocation density of the lms was given in Table 3. It was noticeable that the dislocation density of the undoped, 0.5% Ag doped and
0.7% Ag doped TiO2 lms were almost same, whereas that of 0.1%
Ag doped and 0.9% Ag doped TiO2 lms decreased. Kondalkar et al.
[50] reported that the decreasing of defects and dislocations is an
indication for the better crystallinity of the lms which means the
increase in crystalline size. Our results are coherent with literature
[49,50].

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595

Fig. 5. SEM images of (a) undoped TiO2 lm (b) 0.1% Ag doped TiO2 lm (c) 0.3% Ag doped TiO2 lm (d) 0.5% Ag doped TiO2 lm (e) 0.7% Ag doped TiO2 lm and (f) 0.9% Ag
doped TiO2 lm.

3.3. Morphological structure of TiO2 based lms

Fig. 5 shows the SEM images of the undoped and Ag doped
TiO2 lms formed on the Si substrates by sol-gel process. The
microstructure of the TiO2 lms consisted of many mud-crackshaped layers/dry river bed-like layers at annealing temperature
of 500 C. It can be attributed to the heat treatment regime of the
TiO2 lms including thermal shock which might cause mud cracks
on the surface. For the undoped TiO2 lm (Fig. 5a), mud-crackshaped layers are more intense and smaller than others (Fig. 5bf).
It is noticeable that when the Ag concentration was increased, the
larger Ag particles were observed on the mud-crack-shaped layers.
We could also observe the presence of Ag particles in the 0.9% Ag
doped lm (Fig. 5f). Fig. 6 demonstrates the EDS results obtained

at 0.7% Ag doped TiO2 lm surface. Ag particles were detected in

different points. The EDS analysis provided a semiquantitative elemental analysis of the surface indicating that Ti and Ag were present
on the surface.

3.4. XPS analyses of lms

The chemical states and composition of the all samples were
analyzed by XPS. Narrow XPS spectra of the three major peaks for
the Ag 3d, O 1s and Ti 2p are depicted in Fig. 7. The binding energy
values of all samples are present in Table 4. Fig. 7(a) shows the high
resolution XPS spectra of Ag 3d for the ranging from 0.1% to 0.9% Ag
doped TiO2 lms. The Ag 3d photoelectron peaks usually gives two
individual peaks, which was assigned to Ag 3d5/2 and Ag 3d3/2 tran-

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S. Demirci et al. / Applied Surface Science 390 (2016) 591601

Fig. 6. EDS results of the TiO2 lms.

Table 4
Binding energy values of undoped and Ag doped TiO2 lms from XPS analysis.
Samples

Undoped
0.1% Ag
0.3% Ag
0.5% Ag
0.7% Ag
0.9% Ag

Ag 3d

Ti 2p

3d5/2 (eV)

3d3/2 (eV)

368.28
368.08
367.78
367.98
367.88

374.28
374.08
373.78
373.98
373.88

O 1s

2p3/2 (eV)

sition. The 3d5/2 and Ag 3d3/2 peaks for metallic silver are centered
at 368.28 eV and 374.28 eV, respectively. This typical the splitting of
the 3d doublet (6 eV) proves that Ag certainly presents in the lms
in the form of metallic Ag. The shift in binding energy to the lower
level has been attributed to the strong interaction between the Ag
and the defective site on the surface of TiO2 , and the excited electrons in TiO2 transferred to Ag. This effective interfacial interaction
is helpful for the enhancing photocatalytic performance. Fig. 7(b)
shows the high resolution XPS spectra of O 1s for the undoped
and in the presence of different Ag doping concentrations ranging between 0.1% and 0.9% in TiO2 lms. The XPS spectra of O 1s
from 525 eV to 538 eV are asymmetric. The deconvulated XPS of
O 1s includes of two sub peaks at binding energy of 530.38 and
533.18 attributed to the Ti O bonds and dissociated oxygen or
hydroxyl-like group on the surface of the TiO2 , respectively [38].
The XPS results of Ti 2p are shown in Fig. 7(c). The peaks corresponding to the photo-splitting electrons Ti4+ 2p3/2 and Ti4+ 2p1/2
have been obtained 459.48 and 465.18 eV [51]. While it is observed
these result from undoped TiO2 lm, samples with Ag doped exhibited shift in binding energy. It could be attributed metallic silver to
the transition of electrons to the conduction band [52]. From the
XPS results, it can be concluded that the content of dissociated oxygen or hydroxyl-like group on the surface of Ag doped TiO2 lm is
increased remarkably in contrast to that of undoped TiO2 .

459.48
459.18
458.88
458.58
458.88
458.78

2p1/2 (eV)

O2 (eV)

OH (eV)

465.18
464.88
464.48
464.38
464.58
464.58

530.38
530.28
529.88
529.88
530.18
529.78

533.18
533.58
533.08
532.78
533.18
532.88

3.5. Contact angles of the lms

Surface wettability of the samples was investigated by contact
angle measurement. Contact angles of undoped and Ag doped TiO2
lms were given in Table 5. The highest contact angle was observed
on the undoped TiO2 lm. Contact angle test showed that surface
hydrophilicity of the TiO2 lms was increased with Ag doping until
0.07 mol of Ag content. There were no signicant differences in contact angles of the 0.1, 0.3, 0.5 and 0.9% Ag doped TiO2 lm surfaces.
The changes of contact angle may be related to the surface structure
of the TiO2 lms.
3.6. Optical properties of the lms
The synthesized undoped and Ag doped TiO2 thin lms were
rst analyzed by UVvis absorption spectroscopy. As seen Fig. 8(a)
the absorbance of the lms exhibits a sharp decrease in the visible
region (>350 nm). Doping of Ag can have signicantly inuence on
the absorption of light. With the doping amount increasing, it is
obvious that absorbing edge shifted in absorption spectra. Cut-off
wavelength has been enlarged to the visible regions by doping. The
cut-off wavelength can be determined by drawing a tangent along
the absorption edge. Intersection point with wavelength axis on the
absorbance spectra and tangent edge gives us cut-off wavelength.

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597

Table 5
Contact angles of the undoped and Ag doped TiO2 lms.
Undoped

0.1% Ag

0.3% Ag

0.5% Ag

0.7% Ag

0.9% Ag

74.3
1.06

60.4
1.51

54.4
0.36

51.8
1.64

39.1
0.13

51.6
0.36

Fig. 8. (a) Absorbance spectra of the TiO2 based lms, (b) Plot of (h)2 versus
photon energy (h) of TiO2 based lms.
Table 6
Band gap values of the undoped and Ag doped TiO2 lms.

Fig. 7. The XPS spectra of the three major peaks for the (a) Ag 3d, (b) O 1s, (c) Ti 2p.

Film

Cut off wavelength (nm)

Eg (eV)

Undoped
0.1% Ag
0.3% Ag
0.5% Ag
0.7% Ag
0.9% Ag

382
401
405
415
418
425

3.26
3.23
3.18
3.11
3.05
2.93

The cut-off wavelengths, which were exhibited in Table 6, regularly shifted from 382 to 425 by increasing with Ag content. These
results show that the ranges of light absorption of doped TiO2 are
wider than undoped TiO2 lms. Also optical band-gap measurements of the lms were carried out. For band-gap calculation well
known Tauc relation; h = A(h Eg )n was used [53]. Where is
the absorption coefcient, A is a constant and n = 1/2 for direct or

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Fig. 9. LambertBeer correlation curve for MB solutions.

2 for indirect allowed transitions, h is the photon energy and Eg

is the optical band gap. In our study we calculate direct band gap.
Extrapolation of the linear region of (h)2 versus h plot to x axis
which means = 0 gives the value of band gap. Fig. 8(b) shows the
band gap plot of the undoped and Ag doped TiO2 lms. Band gap
values were given in Table 5. As the Ag doping ratio is rising from
0% mol to 0.9% mol, the band gap values decreased. These band
gap and absorbance spectra supported each other. These results
prove that doping can reduce the wideness of forbidden band of
TiO2 thin lms. The range of values in the literature for the band
gaps of anatase are 3.203.56 eV [54]. In our study, while the band
gap of undoped TiO2 lm is 3.26 eV, it obviously decreased to 2.93
for 0.9% mol Ag doped TiO2 lm. One possible mechanism behind
the decreasing band gap of Ag-doped TiO2 lms could be that lattice distortion occurs with doped Ag ions in TiO2 and produce the
impurity level in the forbidden band of TiO2 . In addition, it can be
speculated that fermi level of TiO2 is higher than that of loaded
silver. Silver deposits behave as accumulation sites for photogenerated electrons transferred from TiO2 [55]. Better separation of
electrons and holes will be reached by rising of silver content up to
the optimum proportion.
3.7. Photocatalytic properties of the Ag doped TiO2 lms
As mentioned before, the MB dye was used to assess the photocatalytic performance of the prepared undoped and Ag doped
TiO2 lms. The photocatalytic performance of the lms was evaluated by photocatalytic decolorization of MB aqueous solution under
UV-light irradiation. The UVvis spectra of MB at = 664 nm is
concerning the color of methylene blue which is known as the
characteristic [40]. Prior to derivation of photocatalytic degradation
kinetics of TiO2 lms, LambertBeer correlation curve was plotted
as given in Fig. 9 to verify a linear relation between absorbance and
concentration.
The photocatalytic parameters of the lms were given in Fig. 10.
According to Fig. 10(a), the absorption spectra of MB for 0.7% Ag
doped TiO2 lm gradually decreased with increasing UV exposure
time. It can be clearly seen from Fig. 10(b) that all prepared catalysts showed good photocatalytic activity, but the addition of Ag
ions into the TiO2 lms enhanced the photocatalytic performance
of the lms when compared to undoped TiO2 lm. The degradation
efciency of the 0.7% Ag doped TiO2 lm was 54.13%, whereas that
of the undoped TiO2 lm was 36.32%. The degradation efciency
of the catalysts was given in Table 6. Further observation showed
that photocatalytic activity gradually increased with increasing
amount of Ag in the lms. The 0.7% Ag doped TiO2 catalyst exhibited the highest photocatalytic activity at 8 h. Furthermore, one can

Fig. 10. Photocatalytic performance of the TiO2 based lms (a) UV absorption spectra of the MB dye measured after the photocatalysis process for different exposure
times, (b) Photocatalytic degradation efciency of the TiO2 lms for different Ag
doping concentration and (c) Photocatalytical kinetics of the TiO2 lms for different
Ag doping concentration.

be found that when the amount of the Ag exceeds 0.7% mol, the
photocatalytic activity of the 0.9% mol Ag doped TiO2 lm began
to decrease. There could be couples of explanations for the behavior of the photocatalytic performance of the lms versus amount
of Ag content in the TiO2 catalysts. The enhancement behavior of
the photocatalytic performance of the lms when the amount of
Ag increased might be attributed to narrowing the band gap of
the lms, increasing of lm wettability and defects in the lms
[40,56]. Our results are in good agreement with photocatalytic
results. The appropriate amount of the Ag on the TiO2 lms captures the excited electrons and holes and then transfers the excited
electrons to the adsorbed O2 to generate the superoxide radical
anion (O2 ) on the surface of Ag [38,48]. The XPS results supported

S. Demirci et al. / Applied Surface Science 390 (2016) 591601

599

Fig. 11. Mechanism for the photocatalytic degradation.

Table 7
Photocatalytic parameters of the undoped and Ag doped TiO2 lms.
Sample

Undoped

0.1% Ag

0.3% Ag

0.5% Ag

0.7% Ag

0.9% Ag

Degradation efciency (%)

Kinetic rate constant (k) (103 h1 )
R2

36.32
56.2
0.9964

42.55
68.7
0.9990

47.61
80.6
0.9965

51.37
87.6
0.9975

54.13
96.4
0.9981

51.81
89.5
0.9985

these ndings. Also, the presence of the Ag on the TiO2 surface serve
as a Schottky barrier which prevents the recombination probability of holes and the excited electrons which results in increase in
the concentration of h+ , OH and O2 thus enhances photocatalytic
activity [5759]. It is well known that number of surface hydroxyls, superoxide radical onions and holes are responsible for the
oxidation decomposition of MB [40,56,60]. On the other hand, the
tendency of drop of the photocatalytic performance for 0,9% Ag
doped TiO2 lm could be ascribed to decreasing of the concentration of the photogenerated charge carriers such as holes and excited
electrons because of the covering TiO2 surface by Ag which limits
the amount of light [61,62]. Another explanation for reducing of
photocatalytic performance for 0,9% Ag doped TiO2 lm could be
that Ag becomes recombination centers which cause the reducing
of the amount of the holes and excited electrons [63,64]. Moreover, the photocatalysts were recycled up to ten times which could
slightly lead to deteriorating of their photocatalytic activity after
ten consecutive photocatalytic experiments, accompanied with the
decreased adsorption capacity [59]. The proposed mechanism for
the photocatalytic degradation of MB under visible light irradiation
undergoes the following reactions [59,61,65].
TiO2 + h e + h+

(1)

h+ + H2 O H + + OH

(2)

e + Ag Ag

Ag + O2 Ag + O2

(3)
(4)

O2 + e + H + H2 O2

(5)

H2 O2 OH

(6)

(7)

OH + organiccompond CO2 + H2 O

In addition to the mechanism for the photocatalytic degradation of MB, the schematic diagram of the mechanism was also
given Fig. 11. By using the converted molarity values photocatalytical degradation kinetics were calculated for whole cases using
following equation [40].

ln

C0
= kt
C

(8)

where C0 and C are the initial concentration of MB and the

corresponding concentration along with the exposure time (t),
respectively and k is the degradation rate constant. The degradation rate constant of the lms were given in Fig. 10(c). According to
Fig. 10(c) it is revealed that the corresponding kinetic studies of the
lms demonstrate that the photocatalytic degradation of MB for
lms belongs to the quasi-rst order kinetics. The resulting k values show that decomposition of MB increases signicantly with the
increasing of Ag concentration from 0 to 0.7% mol, reaches a maximum at 0.7% mol, and then decreases with the further increasing of
Ag concentration. The k values of the catalyst were given in Table 7.

600

S. Demirci et al. / Applied Surface Science 390 (2016) 591601

4. Conclusion
In summary, undoped and Ag doped TiO2 lms were prepared on
Si wafers by sol-gel spin coating method, and then calcined at 500 C
for 2 h. It is a low-cost and efcient means to produce lm materials
with unique structural features. It was observed that the dopant
affects the crystal size, chemical composition, surface morphology
and contact angle of TiO2 lms. XRD measurements had revealed
that all diffraction patterns were typical of the anatase structure.
SEM micrographs indicated that TiO2 thin lms had some cracks
and non-uniform morphology. The result showed that Ag-doped
TiO2 lms had better photocatalytic activity than undoped TiO2
lm. It was observed that the photocatalytic activity of TiO2 lm
increased after Ag doping, and the optimal Agdoped content was
0.7%. The occurrence of optimal dopant concentration exhibiting
maximum photocatalytic activity is explained on the basis of space
charge creation, rate of charge carrier recombination because of
the presence of Ag and defects such as dislocation, narrowing the
band gap, increase of hydrophibility behaviour of the TiO2 lm.
This study may open a versatile route to achieving high efciency
of photocatalytic activity of TiO2 .
Acknowlegements
The authors are indebted to State Planning Foundation (DPT) and
Dokuz Eylul University for nancial and infra- structural support for
establishment of Dokuz Eylul University, Center for Production and
Applications of Electronic Materials (EMUM) where this research
was carried out.
References
[1] N. Pinna, G. Neri, M. Antonietti, M. Niederberger, Nonaqueous synthesis of
nanocrystalline semiconducting metal oxides for gas sensing, Angew. Chem.
Int. Ed. 43 (2004) 43454349.
[2] K. Wetchakun, T. Samerjai, N. Tamaekong, C. Liewhiran, C. Siriwong, V.
Kruefu, A. Wisitsoraat, A. Tuantranont, S. Phanichphant, Semiconducting
metal oxides as sensors for environmentally hazardous gases, Sens. Actuators
B: Chem. 160 (2011) 580591.
[3] M.S. Wrighton, P.T. Wolczanski, A.B. Ellis, Photoelectrolysis of water by
irradiation of platinized n-type semiconducting metal oxides, J. Solid State
Chem. 22 (1977) 1729.
[4] S. Huang, L. Kavan, I. Exnar, M. Grtzel, Rocking chair lithium battery based on
nanocrystalline TiO2 (anatase), J. Electrochem. Soc. 142 (1995) L142L144.
[5] M. Katayama, S. Ikesaka, J. Kuwano, Y. Yamamoto, H. Koinuma, Y. Matsumoto,
Field-effect transistor based on atomically at rutile TiO2, Appl. Phys. Lett. 89
(2006) 2103.
[6] C.-H. Chang, Y.-L. Lee, Chemical bath deposition of CdS quantum dots onto
mesoscopic TiO2 lms for application in quantum-dot-sensitized solar cells
(2007).
[7] L.A. Majewski, R. Schroeder, M. Grell, Low-voltage, high-performance organic
eld-effect transistors with an ultra-thin TiO2 layer as gate insulator, Adv.
Funct. Mater. 15 (2005) 10171022.
[8] M. Matsui, M. Akaogi, Molecular dynamics simulation of the structural and
physical properties of the four polymorphs of TiO2, Mol. Simul. 6 (1991)
239244.
[9] F. Labat, P. Baranek, C. Domain, C. Minot, C. Adamo, Density functional theory
analysis of the structural and electronic properties of TiO2 rutile and anatase
polytypes: performances of different exchange-correlation functionals, J.
Chem. Phys. 126 (2007) 154703.
[10] H. Wang, J.P. Lewis, Effects of dopant states on photoactivity in carbon-doped
TiO2, J. Phys.: Condens. Matter 17 (2005) L209.
[11] T. Kamegawa, N. Suzuki, H. Yamashita, Design of macroporous TiO 2 thin lm
photocatalysts with enhanced photofunctional properties, Energy Environ.
Sci. 4 (2011) 14111416.
[12] M. Takahashi, M. Inoue, R. Ihara, T. Yoko, T. Nemoto, S. Isoda, L. Malfatti, S.
Costacurta, P. Innocenzi, Photo-fabrication of titania hybrid lms with
tunable hierarchical structures and stimuli-responsive properties, Adv. Mater.
22 (2010) 33033306.
[13] Y. Xie, X. Zhao, Y. Chen, Q. Zhao, Q. Yuan, Preparation and characterization of
porous C-modied anatase titania lms with visible light catalytic activity, J.
Solid State Chem. 180 (2007) 35763582.
[14] D. Li, H. Haneda, S. Hishita, N. Ohashi, Visible-light-driven NF-codoped TiO2
photocatalysts. 2. Optical characterization, photocatalysis, and potential
application to air purication, Chem. Mater. 17 (2005) 25962602.

[15] V. Romeas, P. Pichat, C. Guillard, T. Chopin, C. Lehaut, Testing the efcacy and
the potential effect on indoor air quality of a transparent self-cleaning
TiO2-coated glass through the degradation of a uoranthene layer, Ind. Eng.
Chem. Res. 38 (1999) 38783885.
[16] J.S. Chen, Y.L. Tan, C.M. Li, Y.L. Cheah, D. Luan, S. Madhavi, F.Y.C. Boey, L.A.
Archer, X.W. Lou, Constructing hierarchical spheres from large ultrathin
anatase TiO2 nanosheets with nearly 100% exposed (001) facets for fast
reversible lithium storage, J. Am. Chem. Soc. 132 (2010) 61246130.
[17] M. Kumar, A.K. Gupta, D. Kumar, Mg-doped TiO2 thin lms deposited by low
cost technique for CO gas monitoring, Ceram. Int. 42 (2016) 405410.
[18] S.K. Kim, W.-D. Kim, K.-M. Kim, C.S. Hwang, J. Jeong, High dielectric constant
TiO2 thin lms on a Ru electrode grown at 250 C by atomic-layer deposition,
Appl. Phys. Lett. 85 (2004) 41124114.
[19] N.-G. Park, J. Van de Lagemaat, A. Frank, Comparison of dye-sensitized
rutile-and anatase-based TiO2 solar cells, J. Phys. Chem. B 104 (2000)
89898994.
[20] T. Umebayashi, T. Yamaki, S. Tanaka, K. Asai, Visible light-induced degradation
of methylene blue on S-doped TiO2, Chem. Lett. 32 (2003) 330331.
[21] S. Sakthivel, M.V. Shankar, M. Palanichamy, B. Arabindoo, D.W. Bahnemann, V.
Murugesan, Enhancement of photocatalytic activity by metal deposition:
characterisation and photonic efciency of Pt, Au and Pd deposited on TiO2
catalyst, Water Res. 38 (2004) 30013008.
[22] M. Behnajady, N. Modirshahla, M. Shokri, B. Rad, Enhancement of
photocatalytic activity of TiO2 nanoparticles by silver doping:
photodeposition versus liquid impregnation methods, Global Nest J. 10
(2008) 17.
[23] K. Ubonchonlakate, L. Sikong, F. Saito, Photocatalytic disinfection of
P.aeruginosa bacterial Ag-doped TiO2 lm, Procedia Eng. 32 (2012) 656662.
[24] X. Wang, X. Hou, W. Luan, D. Li, K. Yao, The antibacterial and hydrophilic
properties of silver-doped TiO2 thin lms using solgel method, Appl. Surf.
Sci. 258 (2012) 82418246.
[25] B. Xi, L.K. Verma, J. Li, C.S. Bhatia, A.J. Danner, H. Yang, H.C. Zeng, TiO2 thin
lms prepared via adsorptive self-assembly for self-cleaning applications,
ACS Appl. Mater. Interfaces 4 (2012) 10931102.
[26] C. Sahoo, A. Gupta, A. Pal, Photocatalytic degradation of methyl red dye in
aqueous solutions under UV irradiation using Ag+ doped TiO 2, Desalination
181 (2005) 91100.
[27] K. Gupta, R. Singh, A. Pandey, A. Pandey, Photocatalytic antibacterial
performance of TiO2 and Ag-doped TiO2 against S. aureus. P. aeruginosa and
E. coli, Beilstein J. Nanotechnol. 4 (2013) 345351.
[28] S. Takeda, S. Suzuki, H. Odaka, H. Hosono, Photocatalytic TiO 2 thin lm
deposited onto glass by DC magnetron sputtering, Thin Solid Films 392 (2001)
338344.
[29] H. Yaghoubi, N. Taghavinia, E.K. Alamdari, Self cleaning TiO2 coating on
polycarbonate: surface treatment, photocatalytic and nanomechanical
properties, Surf. Coat. Technol. 204 (2010) 15621568.
[30] J. Li, J. Jiang, H. He, Y. Sun, Synthesis, microstructure, and mechanical
properties of TiO 2/Ni nanocomposite coatings, J. Mater. Sci. Lett. 21 (2002)
939941.
[31] M. Kitano, K. Funatsu, M. Matsuoka, M. Ueshima, M. Anpo, Preparation of
nitrogen-substituted TiO2 thin lm photocatalysts by the radio frequency
magnetron sputtering deposition method and their photocatalytic reactivity
under visible light irradiation, J. Phys. Chem. B 110 (2006) 2526625272.
[32] D.H. Lee, Y.S. Cho, W.I. Yi, T.S. Kim, J.K. Lee, H.J. Jung, Metalorganic chemical
vapor deposition of TiO2: N anatase thin lm on Si substrate, Appl. Phys. Lett.
66 (1995) 815816.
[33] C.-C. Ting, S.-Y. Chen, D.-M. Liu, Structural evolution and optical properties of
TiO2 thin lms prepared by thermal oxidation of sputtered Ti lms, J. Appl.
Phys. 88 (2000) 46284633.
[34] F. Bensouici, T. Souier, A.A. Dakhel, A. Iratni, R. Tala-Ighil, M. Bououdina,
Synthesis, characterization and photocatalytic behavior of Ag doped TiO2 thin
lm, Superlattices Microstruct. 85 (2015) 255265.
[35] A. Guilln-Santiago, S.A. Mayn, G. Torres-Delgado, R. Castanedo-Prez, A.
Maldonado, M.d.l.L. Olvera, Photocatalytic degradation of methylene blue
using undoped and Ag-doped TiO2 thin lms deposited by a solgel process:
effect of the ageing time of the starting solution and the lm thickness, Mater.
Sci. Eng.: B 174 (2010) 8487.
[36] C. He, Y. Yu, X. Hu, A. Larbot, Inuence of silver doping on the photocatalytic
activity of titania lms, Appl. Surf. Sci. 200 (2002) 239247.
[37] J. Kaewkhao, P. Limsuwan, P.P.Y.P. Yupapin, S.J. JanJai, K. Ubonchonlakate, L.
Sikong, F. Saito, ISEECPhotocatalytic disinfection of P.aeruginosa bacterial
Ag-doped TiO2 lm, Procedia Eng. 32 (2012) 656662.
[38] B. Xin, L. Jing, Z. Ren, B. Wang, H. Fu, Effects of simultaneously doped and
deposited Ag on the photocatalytic activity and surface states of TiO2, J. Phys.
Chem. B 109 (2005) 28052809.
[39] X.F. Lei, X.X. Xue, H. Yang, Preparation and characterization of Ag-doped TiO2
nanomaterials and their photocatalytic reduction of Cr(VI) under visible light,
Appl. Surf. Sci. 321 (2014) 396403.
[40] S. Demirci, B. ztrk, S. Yildirim, F. Bakal, M. Erol, O. Sancakoglu, R. Yigit, E.
Celik, T. Batar, Synthesis and comparison of the photocatalytic activities of
ame spray pyrolysis and solgel derived magnesium oxide nano-scale
particles, Mater. Sci. Semicond. Process. 34 (2015) 154161.
[41] A. Maira, J. Coronado, V. Augugliaro, K.L. Yeung, J. Conesa, J. Soria, Fourier
transform infrared study of the performance of nanostructured TiO 2 particles
for the photocatalytic oxidation of gaseous toluene, J. Catal. 202 (2001)
413420.

S. Demirci et al. / Applied Surface Science 390 (2016) 591601

[42] K.M. Vojisavljevic, P. Chevreux, J. Jouin, B. Malic, Characterization of the
alkoxide-based sol-gel derived La 9.33 Si 6 O 26 powder and ceramic, Acta
Chim. Slov. 61 (2014) 530541.
[43] F. Abbas, R. Bensaha, H. Taror, Hg-doped TiO 2 nanostructures thin lm
prepared by solgel method for gas sensing applications: correlation between
the structural and electrical properties, Opt.-Int. J. Light Electron Opt. 126
(2015) 671675.
[44] G. Kenanakis, D. Vernardou, A. Dalamagkas, N. Katsarakis, Photocatalytic and
electrooxidation properties of TiO2 thin lms deposited by solgel, Catal.
Today 240 (2015) 146152.
[45] F. Bensouici, T. Souier, A. Dakhel, A. Iratni, R. Tala-Ighil, M. Bououdina,
Synthesis, characterization and photocatalytic behavior of Ag doped TiO2 thin
lm, Superlattices Microstruct. 85 (2015) 255265.
[46] B.A. Akgun, C. Durucan, N.P. Mellott, Effect of silver incorporation on
crystallization and microstructural properties of solgel derived titania thin
lms on glass, J. Sol-Gel Sci. Technol. 58 (2011) 277289.
[47] B. Yu, K.M. Leung, Q. Guo, W.M. Lau, J. Yang, Synthesis of AgTiO2 composite
nano thin lm for antimicrobial application, Nanotechnology 22 (2011)
115603.
[48] A.A. Ismail, Facile synthesis of mesoporous Ag-loaded TiO 2 thin lm and its
photocatalytic properties, Microporous Mesoporous Mater. 149 (2012)
6975.
[49] P. Malliga, J. Pandiarajan, N. Prithivikumaran, K. Neyvasagam, Inuence of
lm thickness on structural and optical properties of solgel spin coated TiO2
thin lm, J. Appl. Phys. 6 (2014) 2228.
[50] V. Kondalkar, S. Mali, N. Pawar, R. Mane, S. Choudhury, C. Hong, P. Patil, S.
Patil, P. Bhosale, J. Kim, Microwave-assisted rapid synthesis of highly porous
TiO 2 thin lms with nanocrystalline framework for efcient
photoelectrochemical conversion, Electrochim. Acta 143 (2014) 8997.
[51] X. Lei, X. Xue, H. Yang, Preparation and characterization of Ag-doped TiO 2
nanomaterials and their photocatalytic reduction of Cr (VI) under visible light,
Appl. Surf. Sci. 321 (2014) 396403.
[52] A. Sowmya, S. Meenakshi, Photocatalytic reduction of nitrate over AgTiO2 in
the presence of oxalic acid, J. Water Process Eng. 8 (2014) e23e30.
[53] J. Tauc, Amorphous and liquid semiconductors, Springer Science & Business
Media, 2012.

601

[54] A. Nakaruk, D. Ragazzon, C. Sorrell, Anataserutile transformation through

high-temperature annealing of titania lms produced by ultrasonic spray
pyrolysis, Thin Solid Films 518 (2010) 37353742.
[55] Y. Cao, H. Tan, T. Shi, T. Tang, J. Li, Preparation of Ag-doped TiO2 nanoparticles
for photocatalytic degradation of acetamiprid in water, J. Chem. Technol.
Biotechnol. 83 (2008) 546552.
[56] M. Yurddaskal, T. Dikici, S. Yildirim, M. Yurddaskal, M. Toparli, E. Celik,
Fabrication and characterization of nanostructured anatase TiO2 lms
prepared by electrochemical anodization and their photocatalytic properties,
J. Alloys Compd. 651 (2015) 5971.
[57] H. Zhang, C. Liang, J. Liu, Z. Tian, G. Wang, W. Cai, Defect-mediated formation
of Ag cluster-doped TiO2 nanoparticles for efcient photodegradation of
pentachlorophenol, Langmuir 28 (2012) 39383944.
[58] N. Zhao, M.-m. Yao, F. Li, F.-p. Lou, Microstructures and photocatalytic
properties of Ag+ and La 3+ surface codoped TiO 2 lms prepared by solgel
method, J. Solid State Chem. 184 (2011) 27702775.
[59] Y. Wen, H. Ding, Y. Shan, Preparation and visible light photocatalytic activity
of Ag/TiO 2/graphene nanocomposite, Nanoscale 3 (2011) 44114417.
[60] J. Yu, J. Xiong, B. Cheng, S. Liu, Fabrication and characterization of AgTiO 2
multiphase nanocomposite thin lms with enhanced photocatalytic activity,
Appl. Catal. B: Environ. 60 (2005) 211221.
[61] T.-D. Pham, B.-K. Lee, Effects of Ag doping on the photocatalytic disinfection
of E. coli in bioaerosol by AgTiO2/GF under visible light, J. Colloid Interface
Sci. 428 (2014) 2431.
[62] H. Yan, Y. Chunwei, Low-temperature preparation of photocatalytic TiO2 thin
lms on polymer substrates by direct deposition from anatase sol, J. Mater.
Sci. Technol. 22 (2006) 239244.
[63] D. Yang, Y. Sun, Z. Tong, Y. Tian, Y. Li, Z. Jiang, Synthesis of Ag/TiO2 nanotube
heterojunction with improved visible-light photocatalytic performance
inspired by bioadhesion, J. Phys. Chem. C 119 (2015) 58275835.
[64] X. Hou, H. Ma, F. Liu, J. Deng, Y. Ai, X. Zhao, D. Mao, D. Li, B. Liao, Synthesis of
Ag ion-implanted TiO2 thin lms for antibacterial application and
photocatalytic performance, J. Hazard. Mater. 299 (2015) 5966.
[65] J. Schneider, M. Matsuoka, M. Takeuchi, J. Zhang, Y. Horiuchi, M. Anpo, D.W.
Bahnemann, Understanding TiO2 photocatalysis: mechanisms and materials,
Chem. Rev. 114 (2014) 99199986.