Materials Today: Proceedings 62 (2022) 4254–4259

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Materials Today: Proceedings

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Synthesis of visible spectrum-active TiO2 thin film induced by RF

magnetron sputtering
Divyeshkumar P. Dave ⇑, Kamlesh V. Chauhan
CHAMOS Matrusanstha Department of Mechanical Engineering, Chandubhai S. Patel Institute of Technology (CSPIT), Charotar University of Science and Technology
(CHARUSAT), Changa 388421, Gujarat, India

a r t i c l e i n f o a b s t r a c t

Article history: TiO2 anatase phase has a key role in environmental and photocatalysis research. But, the TiO2 anatase
Available online 6 May 2022 phase is not able to give photocatalytic activity in the visible spectrum as it has a large bandgap, i.e.,
3.2 eV which is the main drawback of it. Thus, if some method could decrease the bandgap of anatase,
Keywords: TiO2 - able to photocatalysis in the visible light irradiation. Hence, visible spectrum-active TiO2 (visi-
RF magnetron sputtering TiO2) thin films on corning glass were deposited using RF magnetron sputtering in the present study.
Visible spectrum working TiO2 thin films The visi- TiO2 was deposited at various RF powers (60, 120, 180, 200, and 300 W) and characterized using
Optical properties
X-ray diffraction (XRD), UV–vis spectroscopy, and dye degradation under visible light. The XRD spectrum
Photocatalytic activity
confirmed that an increase in RF power was generated phase transformation from rutile to anatase. The
bandgap energy was calculated by the Tauc method, and the direct optical band gap of the visi- TiO2 film
was observed to decrease from 3.15 to 2.87 eV as an increase in RF power. The visible light absorption
edge in all Visi- TiO2 thin films is due to surface morphology. Photocatalytic activity of Visi-TiO2 film
has been explored by degradation of direct blue 14 azo dye in aqueous solution as a contaminant of water
in presence of visible spectrum irradiation. The photocatalytic degradation potential of Visi-TiO2 film was
found to be 99% after 210 min. The newly discovered low bandgap anatase phase can be achieved by
changing the sputtering parameters. The synthesis of a TiO2 anatase phase with a bandgap belongs to
the visible and more chemical reactivity has implications for its use as a photocatalyst and artificial
photosynthesis.
Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Confer-
ence on Materials, Processing & Characterization.

1. Introduction [7], optical waveguides [8], thin-film MOS capacitors [9], solar cells
[10,11], gas sensors [12], and photochromic devices [13].
Semiconductors have received a lot of attention in recent years, The broad bandgap of semiconductors like TiO2, has a high
particularly for their application as photocatalysts in environmen- degree of stability, although charge separation requires stimula-
tal remediation via photocatalytic degradation of water contami- tion with wavelengths of less than 380 nm. Photocatalysts that
nants. Because of its physiochemical stability, water-insoluble can respond efficiently in visible light regions are in high demand
nature, chemical inertness, cheap, excellent photosensitivity, great as attention in a hydrogen economy grows [14,15]. Many innova-
oxidizing power, nontoxic, corrosion resistance, and biocompati- tive ways to expand TiO2 responsiveness into the visible range
bility, TiO2 has been widely explored as a semiconductor photocat- have been investigated throughout the last decade. During chemi-
alyst [1,2]. Because of its great photocatalytic activity, titanium cal synthesis, intrinsic doping and transition metal ions were some
dioxide has been extensively studied as a potential material for a of the most effective. But, chemically doped transition metal ions,
variety of environmental applications, including self-cleaning, on the other hand, were shown to increase charge recombination
self-sterilizing surfaces, and de-polluting, [3–5]. Moreover, other rate and reduce overall catalytic performance [16]. However, the
applications that benefit from its electrical and optical features physical doping of transition metal ions like Cr, V, and Ag into
include anti-reflective coatings[6], organic light-emitting diodes TiO2 using improved ion-implantation methods has been proven
to allow TiO2 photocatalysts to operate under visible light irradia-
tion. [17,18]. Another potential technique is positively charged ion
⇑ Corresponding author.

https://doi.org/10.1016/j.matpr.2022.04.755
2214-7853/Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Materials, Processing & Characterization.
D.P. Dave and K.V. Chauhan Materials Today: Proceedings 62 (2022) 4254–4259

doping on TiO2 films and nanostructures. Doping with nitrogen for 15 min, then applying methanol, and dried at room tempera-
[19], sulfur [20], and carbon [21] has also been used to decrease ture before deposition started. Before starting the actual experi-
the bandgap. The valence band is shifted to a less negative poten- ment, the target was pre-sputtered for 15 min along with a
tial, resulting in a smaller bandgap. Asahi et al. [22], have exhibited shutter located amid the target and the substrate. Afterward,
photocatalytic activity for the decomposition of methylene blue high-purity argon and oxygen gas (99.999%) were inserted into
and gaseous acetaldehyde under visible spectrum irradiation. the deposition chamber. The flow rate of argon inert gas was kept
It is widely known that the PVD deposition process has a signif- constant and maintained by the Mass Flow controller (MFC), (ALI-
icant impact on the physical characteristics of TiO2 thin films. Dif- CAT instruments, USA). The deposition was carried out at constant,
ferent approaches, such as sputtering [23], electron-beam i.e., 10 sccm flow rates of Argon and oxygen each for 60 min and a
evaporation [24], sol–gel spin coating [25], a hydrothermal method sputtering pressure of  2.0 Pa. Visi- TiO2 coatings were deposited
[26], spray pyrolysis [27], chemical vapor deposition [28], and at different RF powers of 60 W, 120 W, 180 W, 200 W, and 300 W,
pulsed laser deposition [29], are some of the processes used to indicated by the sample names P_60, P_120, P_180, P_200, and
form TiO2 thin films. In the current work, the radio-frequency mag- P_300, respectively (Table 1).Fig. 1.
netron sputtering deposition (RF-MS) technique was used to
develop a novel visible spectrum working TiO2 thin film (Visi- 2.2. Characterization
TiO2) as a photocatalyst on a corning glass substrate. The photocat-
alytic activities of Visi-TiO2 thin films for toxic direct blue 14 azo The structural characteristics and phase identification of the
dye degradation have been investigated in the visible light spec- films were determined using an X-ray diffractometer (Model: Bru-
trum. The surface morphology, crystalline structure, optical char- ker D8 Advance X-ray diffractometer) with CuK radiation (=1.5406)
acteristics, and photocatalytic dye degradation ability of RF (Bruker D8 Advance X-ray diffractometer) from 20 to 80
Celsius at
magnetron sputtered TiO2 thin films were examined in this work. room temperature. The optical properties of TiO2 thin film have
Our main aim is to deposit a TiO2 thin film that has the ability to been investigated by a UV–Vis-NIR spectrophotometer (Varian
give the best response under visible light using the improved depo- Cary 5000).
sition parameter and its effective photocatalytic activities in visible
spectrum irradiation. 2.3. Evaluation of photocatalytic activity

2. Methods: The photocatalytic activity was assessed by the degradation of

direct blue 14 azo dye under visible spectrum irradiation with a
2.1. Visible spectrum working TiO2 thin film synthesis 200 W tungsten filament bulb. The standard solution of direct blue
14 azo dye with a concentration of 10 ppm was used as a model
The RF magnetron sputtering was used to deposit titanium pollutant organic dye to explore the photocatalytic potential of
oxide thin films in a conventionally -designed cylindrical chamber the prepared visi-TiO2 thin film. Photodegradation testing was per-
(Excel Instruments, India). For the sputtering procedure, a 200 diam- formed for various exposition time intervals, and the distance
eter Ti target (99.99% purity, 50.8 mm  6.5 mm) was taken and between the visible light source and the dye solution was static
mechanically clamped to the cathode side magnetron of the sput- at 30 cm. Prior to exposing to visible light, the dye solution was
tering system. Initially, the deposition chamber was evacuated to stirred in the dark for 1 h with a magnetic stirrer, which helped
approximately 1  10-3 Pa through a turbo molecular pump achieve an adsorption–desorption equilibrium between the visi-
assisted by a rotary pump. The titanium oxide thin films were TiO2 thin film and dye. The direct blue 14 dye (15 ml) was filled
deposited using an RF magnetron sputtering setup (Excel Instru- into the beaker at room temperature. Afterward, the visi-TiO2 thin
ments, India) (Fig. 1). The substrates were cleaned ultrasonically film was immersed in the glass beaker, and the visible light bulb

Fig. 1. An RF magnetron sputtering deposition set up.

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Table 1
A Summary of Experimental Parameters for Studying the Effect of RF Power.

Substrate Material Base Pressure (Pa) Sputtering Pressure (Pa) Oxygen Flow rate (sccm) Temperature (°C) Time (min) Sample Power variation (W)
ID
Corning Glass 1  10-3 2 10 600 °C 60 P_60 60
P_120 120
P_180 180
P_200 200
P_300 300

(200 W) was turned on. The absorbance of residual direct blue 14 h = Bragg diffraction angle.
azo dye was detected every 30 min. The concentration of the direct b = full width at half maximum (FWHM) of the most dominant
blue 14 dye in the supernatant was measured by obtaining the peak.
absorbance at 590 nm using UV– Visible spectroscopy. The effi- The crystal size was raised with the increasing RF power. The
ciency of adsorption was calculated by the following formula, per- crystallite size calculated from the XRD peak (1 0 1) with 2h = 25.
cent efficiency of dye degradation [25], 3
at an RF power of 300 W was found to be 79.31 nm. In addition,
the grain sizes increase with the applied power according to the
Dð%Þ ¼ ½ðA0  ATÞ=A0  100
calculation from XRD patterns listed in Table 1. Subsequently,
Where Ao denotes the initial absorbance, and AT expresses the the crystal growth is predominantly based on the deposition of
changing absorbance of the direct blue 14 dye after degradation. TiO2 thin films, which is synthesized in the plasma. Hence, high
RF power will generate larger TiO2 clusters. Furthermore, because
the primitive cell volume (136.29 Å) is greater than the rutile phase
3. Results and discussion
(62.05 A), larger anatase grains are found in the thin film.
3.1. Surface morphology and structural properties
3.2. Optical characteristics
The XRD pattern of TiO2 thin films deposited with various sput-
The transmittance spectra of the visi-TiO2 thin film on corning
tering powers is shown in Fig. 2. The results show that all the film
glass deposited at various RF power levels are shown in Fig. 3(a).
characteristic peaks are mixed anatase/rutile and anatase struc-
From the optical transmission spectrum, it was observed that
tures, suggesting. The films deposited at the power of 60–200 W
transmission decreased as RF power was raised from 60 to
have a mixed phase of polycrystalline anatase (1 0 1) and rutile
300 W. The absorbance spectrum of the visi-TiO2 thin film depos-
(1 1 0) structures, whose diffractive angles (2h) were 25.3 and
ited at various RF power levels is depicted in Fig. 3(b). It’s seen that
27.5
, respectively. The pure anatase crystal phase (1 0 1) was found
the visible light spectrum is absorbed by the visi-TiO2 thin film as
at 25.3 diffractive angles (2), with a sputtering power of 300 W.
increasing RF power. This reveals that the grain size was increased
The content of rutile is about twice as much as anatase under 60,
with the increase of RF power at 300 W. The optical bandgap of the
120, 180, and 200 W. It was discovered that the applied RF power
visi- TiO2 thin film was measured by using Tauc’s plot. The absorp-
provided the necessary driving force, which aided in the formation
tion coefficient (a) and optical energy gap (Eg) are related by the
of anatase phase TiO2. As adequate energy is applied, the TiO2 thin
equation [31].
film growth pattern of anatase is comparable to that of rutile. Thus,
greater RF power will be deposited in larger TiO2 crystal clusters. ahv ¼ Aðhv  Eg Þn
Scherrer formula was used to calculate the average crystallite
size (D) of the samples as represented in equation [30].

0:9k
D¼
b cos h
Where,
k = the X-ray wavelength (1.54056 Å),

Fig. 2. The XRD spectrum of TiO2 thin film at various RF Power. Fig. 3a. % transmission spectra.

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smaller crystalline size will increase the band gap of the visi-
TiO2 thin film.
Swanepoel’s envelope approach was used to measure optical
constants, i.e. refractive index. With an increase in RF power, the
refractive index was also rising. With increased RF power, sput-
tered ions receive more energy and may therefore disperse more
energy to the target, leading to a higher sputtering rate at the tar-
get [33].
The extinction coefficient (k) was calculated using the following
formula: [34].

ak
k¼
4p
The extinction coefficient for the visi- TiO2 thin film is repre-
sented in Table 2. The extinction coefficient k was calculated via
the total optical losses due to both scattering waves and
Fig. 3b. Absorbance spectra. absorption.

3.3. Photocatalytic activity

where a represents the absorption coefficient, A is based on the
transition probability and it can be considered as a constant within
The photocatalytic activity of the corning glass supported TiO2
the range of optical frequency, h is the Planck’s constant, and v
thin films synthesized in the present work was explored by the
expresses.
photodegradation of direct blue 14 azo dye in liquid solutions
photon frequency, thus hv is known as the incident photons
using anatase and anatase/rutile phase films prepared at various
energy, and Eg represents the bandgap corresponding to transitions
RF powers. An uncoated corning glass substrate was taken to cre-
which is dependent on the value n that denotes the type of the
ate a baseline for photocatalytic dye degradation that had a prelim-
optical transition process. The calculated band gaps of the visi-
inary concentration of 10 ppm, without a photocatalyst. The
TiO2 thin film deposited under different RF powers were repre-
decline in direct blue 14 azo dye concentrations (relating to the ini-
sented in Fig.3(c). The bandgap of visi- TiO2 thin film were
tial concentration) at every time interval throughout the photo-
decreased with increased applied RF power, as shown in Fig. 3(c).
catalysis experiment is expressed in Fig. 4. It was seen that the
As the deposition RF powers are increased, the visi-TiO2 thin film
absorbance intensity of direct blue 14 azo dye decreases noticeably
was phase transformed from rutile to anatase phases. However,
under visible light irradiation, which indicates that direct blue 14
the presence of anatase decreases the bandgap, although anatase
azo dye has been photodegraded. The obtained results revealed
is of the greater bandgap. It revealed that the energy gaps can also
that as RF power increases from 60 to 300 W, time required for
be modified by the control of the deposition conditions. An
direct blue dye degradation is also decreasing. At a power of
increase in deposition RF power has the potential to accelerate
300w, the anatase phase TiO2 thin film required a very short time
anatase grain growth and close energy gaps [32]. It was observed
span, 210 min, to degrade 99% of the dye (Fig. 4). This elucidation
that the decrease in optical bandgap was from 3.15 to 2.87 eV with
has also been extended to clarify surface morphology dependent
an increase in RF power (Table 2). The sputtering power was
activities.
increased, the visi-TiO2 thin films grew thicker and smoother.
And also, as the thin film thickness is increases, the % transmit-
tance of the light beam generally decreases and moves towards 4. Conclusions
the higher wavelengths, whereby the optical absorption edge
moves towards the higher wavelengths, and as a consequence, An investigation of the photocatalytic activity of visi-TiO2 thin
the optical gap energy of visi- TiO2 decreases. It indicates that film under visible spectrum irradiation was explored. A visi-TiO2

Fig. 3c. (aht)2 vs photon energy (ht) of TiO2 thin film deposited at different temperatures.

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Table 2
The optical properties of TiO2 thin film at various RF Power.

Sr. No RF Power (W) Crystal size (nm) Absorbance coefficient (a (cm-1)) Extinction coefficient (k = ak/4p) Refractive Index (n) Band Gap (eV)
1 60 43.9 18192.2 0.05 1.05 3.15
2 120 50.3 19990.9 0.06 1.06 3.04
3 180 59.7 31371.5 0.11 1.10 3.06
4 200 65.2 33029.7 0.12 1.11 2.99
5 300 79.31 35,761 0.13 1.12 2.87

Fig 4. Photocatalytic degradation of direct blue 14 dye using TiO2 film.

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