Materials Science in Semiconductor Processing 100 (2019) 185–191

Contents lists available at ScienceDirect

Materials Science in Semiconductor Processing

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

Synthesis of stable and highly oxygen deficient V2O5 thin films for physical T
functionalization of nanofiltration membranes
S.R. Indhumathia, M. Manoj Cristophera, P. Karthicka, M. Dhivya Pushpaa, B. Poornimaa,
C. Gopalakrishnanb, K. Jeyadheepana,∗
a
ASK – 2107, Multifunctional Materials & Devices Lab, School of Electrical & Electronics Engineering, SASTRA Deemed to be University, Tirumalaisamudram, Thanjavur,
613401, India
b
Nanotechnology Research Centre, SRM Institute of Science and Technology, Kattankulathur, 603203, India

A R T I C LE I N FO A B S T R A C T

Keywords: Functionalization of nanofiltration membranes by physical modification of the membrane surface is the chal-
V2O5 lenging field of research to enhance the stability of the membrane by reducing the membrane fouling. Herein,
Films stable vanadium pentoxide (V2O5) thin films, deposited by using the nebulizer spray pyrolysis technique by
Interfaces varying the precursor concentration, were reported for the application of the surface modification of nanofil-
Defects
tration membranes. The films were characterized to study their physical properties and hence to predict the
XPS
optimized deposition conditions. The orthorhombic crystal phase and 2D nanorod-like morphology were ob-
served for the optimized films which were inferred from the structural and surface morphological studies.
Optical transparency of 78% and the optical band gap of 2.4 eV were determined from the optical studies. The
highly oxygen deficient V2O5 thin films deposited with the perfected precursor concentration of 0.15 M show the
super-hydrophilic nature of the film (contact angle, θ < 20°) which is suitable for the functionalization of
nanofiltration membranes.

1. Introduction advantageous not only regarding efficiency and also due to the high
selectivity, greater permeability, and less fouling by free oil and con-
Most of the ceramic and polymeric membranes used in nanofiltra- centrated oily emulsions [10]. The bio-fouling, adhesion of macro-
tion process have excellent physical and chemical properties; however molecules and various organisms on the surface of membranes are
fail to posses the suitable surface related characteristics such as the mostly constrained by the deposition of hydrophilic coatings over the
hydrophobicity, hydrophilicity, anti-static, anti-fouling, surface rough- ceramic or polymeric membranes [11].
ness and also the conductivity [1]. Hence, the functionalization of the Graphene oxide based hydrophilic coating materials have shown
membranes, either by deposition of hydrophilic/hydrophobic materials greater potential in the nanofiltration field [12], recently. However, it
on the surface or by physical/chemical modification of the surface, has has been proved that the graphene-based materials are usually unstable
gained greater interest to the material researchers [2] for membrane- in the water environment [13]. Titanium dioxide (TiO2) is also a pre-
based separation and desalination [3] applications. Amongst, the hy- ferred candidate for the hydrophilic applications for the past two dec-
drophilic surfaces have a wide range of applications as nanomem- ades, since from the first report on the hydrophilicity of TiO2 surfaces.
branes, nanoscaffolds and nanofilters due to the properties of self- However, the TiO2 exhibits the hydrophilic nature upon the ultra-violet
cleaning, anti-corrosion, anti-fogging, etc [4]. Also, the surface mod- (UV) light irradiation only [14], which limits the applications of TiO2
ified materials play a significant role in enhancing the efficiency in thin films in nanofiltration processes. To overcome the problems of UV-
larger margin in solar cells [5], gas sensors [6], optoelectronic devices induced hydrophilicity [15], doped metal oxides [16,17] and inorganic
[7], automobiles [8] and to improve the cell adhesion for dental im- mixed-metal oxides (such as ZnO-TiO2 [18], V2O5-TiO2 [19], SiO2-TiO2
plants [9]. Also, the nanofiltration process is used for the separation of [20], SiO2/Bi2O3/TiO2 [21] etc), which are highly stable in mostly all
water from the fuel of automobiles which helps increase the engine wet environments, have been employed recently as the hydrophilic
efficiency and life. Albeit the presently used ultrafiltration process is coatings in the field of membrane-based separation technology [22].
efficient, the superhydrophilic nanofiltration process is more The porosity-driven hydrophilicity is also reported for the pure, doped

∗
Corresponding author.
E-mail address: [email protected] (K. Jeyadheepan).

https://doi.org/10.1016/j.mssp.2019.04.048
Received 11 April 2019; Received in revised form 29 April 2019; Accepted 30 April 2019
Available online 20 May 2019
1369-8001/ © 2019 Elsevier Ltd. All rights reserved.
S.R. Indhumathi, et al. Materials Science in Semiconductor Processing 100 (2019) 185–191

and composite TiO2 thin films [23]. However, the preparation of porous
films and the composite metal oxides is complex, which impacts the
cost-effectiveness of the hydrophilic surfaces. Apart from pure, doped
and composite TiO2 films, Fe2O3 [24], WO3 [25] and V2O5 are the
prescribed alternatives for hydrophilic applications, again on UV-irra-
diation. Amongst, V2O5 has attracted a lot of attention for its me-
chanical, thermal and chemical stability [26]; the must required
properties for nanofiltration applications. Also recently, Zhang et al.
[27] have reported that the as-prepared V2O5 films are hydrophilic in
nature, which paved the way of preparing V2O5 thin films for hydro-
philic applications, without UV-irradiation.
V2O5 thin films can be prepared by both chemical and physical
vapor routes that include but not limited to the hydrothermal method
[28], chemical vapor deposition technique [29], spray pyrolysis [30],
electron beam evaporation [31] and sputtering [32]. Amongst, the
spray pyrolysis method is known for its preparation of cost-effective,
device quality thin films for various applications. Recently, among the
variants of spray pyrolysis method, nebulizer spray pyrolysis method is
considered for its proven quality (of thin films) that is comparable to
the quality of chemical vapor deposition method, as discussed in the
earlier reports [33,34].
Hence, on considering the complexities of mixed metal oxides and
the various sophisticated preparation methods, herein, the preparation
and characterization of simple, stable, and super-hydrophilic V2O5
surfaces are reported, which could be used for nanofiltration applica-
tions.

2. Experimental details

The V2O5 thin films were deposited by using nebulizer spray pyr-
Fig. 1. XRD patterns of spray deposited V2O5 thin films with different precursor
olysis [33], onto the dried glass substrates that were ultrasonically
concentration of (a) 0.05 M, (b) 0.10 M, (c) 0.15 M, (d) 0.20 M, and (e) 0.25 M.
cleaned using the concentrated sulphuric acid, ethanol and acetone to
remove the impurities on the surface. The source of vanadium, am-
monium meta-vanadate was added to 80 ml of de-ionized water, and concentrations (0.05 and 0.10 M) are amorphous. The films deposited
the solution was continuously stirred and heated at constant tempera- with higher precursor concentrations (0.15, 0.20 and 0.25 M) are phase
ture of 60 °C until the precursor solution get converted into transparent pure, polycrystalline in nature, and the peaks are well matched with the
pale yellow and then concentrated HCl was added to the solution drop ICDD card no. 00-041-1426 which corresponds to the orthorhombic
by drop to maintain its pH level near to 2, which turns the solution into V2O5. The XRD patterns also indicate a preferred growth along (011)
deep orange color. The precursor was sprayed onto the cleaned glass plane for the films deposited with higher concentration and the in-
substrates retained at 300 °C of the substrate temperature. For the tensity of the (011) peak is decreasing with the increase in precursor
present work, the samples were deposited by varying the precursor concentration, though the thickness of the films (values not given) are
concentration (in molarity) as 0.05, 0.10, 0.15, 0.20 and 0.25 M and by increasing in the present study. It is obvious that increasing precursor
keeping all other deposition parameters like substrate to nozzle dis- concentration leads to the increasing growth rate [35,36]. The de-
tance (5.5 cm), carrier gas pressure (1.6 kg cm−2) as constant. The de- creased peak intensity with the increasing precursor concentration may
posited thin film samples were characterized for structural properties be attributed to the restricted growth of the grains. These confined
using PANalytical Xpert Pro MP X-ray diffractometer (operated at the grain growth may be due to the less available duration associated with
parameters of 30 kV & 40 mA tube settings, 0.02° of step width, 20s of the increased growth rate [37,38]. Moutinho et al. [39] reported that
integration time/step for X'celerator detector)and JEOL JSM 2100 HR- the decrease of preferential orientation is also due to the increase in
TEM microscope (source accelerated at 200 kV). Surface morphology film thickness, which is favored by the increased growth rate. To vali-
was observed by using FEG Quanta-250 FESEM with the working date the limited growth of grains with the increased growth rate/pre-
parameters of 30 kV of acceleration voltage, 3 mm of spot size, 11 mm cursor concentration, the average crystallite sizes (D) were calculated
of working distance). Surface compositional analysis was performed by using the Scherrer's formula,
using Thermo Fisher Scientific Inc., K-Alpha X-ray photoelectron 0.9λ
spectrometer and the optical studies were done using Thermo Scientific D=
βcosθ (1)
Evolution Bio 260 UV–Vis–NIR Spectrophotometer by recording the
transmittance of the film with respect to the glass substrate from where λ is the wavelength of Cu-Kα radiation (1.54 Å), β is the full
200 nm to 1100 nm. Also the samples were subjected to water contact width at half maximum (in radians) θ is the Bragg position of the dif-
angle measurements (using Rame-Hart contact angle measurement fraction peak. The crystallite sizes of the films deposited with higher
station, USA). precursor concentrations are 112.2 nm, 102.4 nm, and 90.9 nm, re-
spectively for 0.15, 0.20 and 0.25 M. These decreasing crystallite size
3. Results and discussions with increasing precursor concentration confirm that the decrease of
preferential orientation is favored by the increased growth rate.
The structural properties of the V2O5 thin films revealed through the The vanadium oxide is crystallizing in different structure with the
X-ray diffraction (XRD) patterns shown in Fig. 1. XRD patterns of V2O5 slight variation in oxidation states of vanadium which may lead to the
thin films deposited with precursor concentrations varying from 0.05 to mismatched pattern indexing, the structural properties of the films;
0.25 M show that the films deposited with lower precursor crystal class and the lattice orientation are further confirmed by the

186
S.R. Indhumathi, et al. Materials Science in Semiconductor Processing 100 (2019) 185–191

Fig. 2. (i) High-resolution TEM image, (ii) recorded SAED pattern, (iii) SAED pattern with the extracted intensity profile, and (iv) Indexed SAED pattern of V2O5 thin
films of 0.15 M precursor concentration.

high resolution transmission electron microscope (HRTEM) image and deposited over the amorphous glass substrates [41]. Also, at the lower
selected area electron diffraction (SAED) pattern, shown in Fig. 2(i), (ii) precursor concentrations, the sprayed droplets are as randomly pre-
& (iii), for the samples prepared with 0.15 M of precursor concentra- cipitated, high solubility precursor droplets, which could result in iso-
tion. The average lattice spacing was measured from the fringe pattern lated nanoparticles upon drying and decomposition of the droplets
of the HRTEM image (Fig. 2(i)), using the software ImageJ and the [42]. These fine, tiny nanoparticles cover the surface of the substrate to
average measured lattice spacing (0.28(3) nm) matches with the d- form the thin film, which is more compact and smooth. The films de-
spacing (2.764 Å) of the (011) plane of the ICDD card no. 00-041-1426. posited with 0.15 M (Fig. 3(iii)) show nano-rod like morphology dis-
Fig. 2(ii) shows the SAED of the films deposited with 0.15 M of pre- tributed randomly throughout the sample. The structural studies also
cursor concentration. The ring pattern obtained in the SAED pattern show that the films deposited with 0.15 M of precursor concentration
confirms the polycrystalline nature of the V2O5 films deposited using show high crystallinity. This formation of high crystalline nanos-
nebulizer spray pyrolysis with 0.15 M of vanadium precursor con- tructures indicates that the 0.15 M may be the optimized precursor
centration. The intensity profile pattern (shown as the inset of concentration, in which the enhanced surface precipitation (of droplet
Fig. 2(iii)) was extracted from the SAED image using the tool CrysTBox- evolution of spray pyrolysis) of the solute is favored. The enhanced
ringGUI [40], and the pattern was indexed using with the crystal- surface precipitation favors the evolution of droplets to form as the
lographic information file (cif) obtained from American Mineralogist micro-reactor shaped droplets in which the reaction rate is high and
Crystal Structure Database having the code no. 0013891. The indexing leads to the high crystalline quality thin films. Further, at very high
of the pattern shows the presence of (011) peak with the d-spacing precursor concentration, film morphology may be affected due to anti-
value of 2.81 Å, which are well matched with the XRD analysis. A coalescence of grain leads to the smooth surface [43,44] as inferred
slightly increased value (negligible too) of the d-spacing observed in from Fig. 3(iv & v). Also, at higher precursor concentration, due to the
HRTEM and SAED may be attributed to the strain induced on the film low solubility of the precursor, the solute is precipitated in bulk rather
during the sample preparation for TEM analysis. than the surface of the droplets, which leads to the decreased reaction
The FESEM images of V2O5 thin films deposited with different rate that affects the crystallinity and enhances the anti-coalescence of
precursor concentrations were presented in Fig. 3. The films deposited grains. This decreased crystallinity and increased anti-coalescence of
with lower precursor concentrations (Fig. 3(i and ii)) are qualitatively grains influence the morphology of the films [45] at higher precursor
smooth, which may be due to the amorphous nature of the films. The concentrations.
amorphous nature of the films deposited with lower precursor con- The optical transmission spectra of V2O5 thin films deposited with
centration might be attributed to the lower thickness of the samples varying precursor concentrations are depicted in Fig. 4(i). The figure

187
S.R. Indhumathi, et al. Materials Science in Semiconductor Processing 100 (2019) 185–191

Fig. 3. Field-emission SEM images of spray deposited V2O5 thinfilms with different precursor concentration of (i) 0.05 M, (ii) 0.10 M, (iii) 0.15 M, (iv) 0.20 M, and (v)
0.25 M.

shows that the higher transmittance, nearly 78% was observed for the with different oxidation states [49]. The asymmetry of V2p3/2 peak was
samples deposited with 0.05 M and the transmittance is getting reduced deconvoluted and found that the de-convoluted V2p3/2 peak, with the
(except for the film deposited with the higher precursor concentration largest area, centered at 517.4 eV, belongs to the V5+ state and another
of 0.25 M) with the increased in precursor concentration. This may be peak centered at 515.87 eV belongs to the V4+ state [50]. The fraction
imputed to the increased film thickness [22]. The optical band gap for of vanadium oxidation states (RV) was estimated from the area
V2O5 thin films is determined from the Tauc's plot, which is shown in (AV 5 + &AV 4 + ) of the two deconvoluted peaks of V2p3/2 peak using the
Fig. 4(ii). The optical band gap for the V2O5 thin films ranges from 2.22 relation,
to 2.39 eV, which is similar to the literature values [46]. The film, de-
AV 5 +
posited with the higher precursor concentration of 0.25 M, have in- RV =
AV 4 + (2)
creased bandgap (2.44 eV), which may be due to the size confinement
effect [47], which is supported by the crystallite size determined The above relation is a simplified form of relations found in litera-
(90.9 nm) from the XRD analysis. ture [51], considering the ionization cross-sections of both V4+ and
The XPS survey spectrum of the V2O5 thin films deposited with V5+ ions are same. This reveals that the concentrations of V5+ and V4+
0.15 M is illustrated in Fig. 5(i). The survey spectrum confirms the states are 0.74 and 0.26, respectively. The peak with the largest area
composition purity of the films, and the peak present at 284.8 eV cor- corresponds to the 5 + oxidation state and the determined value of V5+
responds to C 1s which is due to the adventitious carbon present on the state confirm that the films consist the V2O5 phase largely.
surface of the films [48]. The chemical shift present in the spectrum was The asymmetric O1s peak (shown in Fig. 5(iii)) was also deconvo-
corrected using the carbon peak. Fig. 5(ii) & Fig. 5(iii) shows the core luted into three different symmetric peaks indicating the presence of
level spectrum corresponds to the V2p and O1s peaks. From Fig. 5(ii), it various oxygen species; the peak having the binding energy 529.86 eV
is inferred that the V2p3/2 and V2p1/2 peaks were centered at 517.33 eV can be attributed to the metal bonded oxygen atoms in V2O5 metal
and 524.65 eV respectively. The difference in binding energy of these oxide thin films. The peaks centered at 530.36 eV and 531.74 eV could
V2p peaks due to the doublet spin orbital interactions was determined be assigned to the oxygen deficiency sites (Ox−) [52] and hydroxyl
and is 7.32 eV (DS-2p), which suggests the stoichiometry of vanadium groups (O-H) [53]. The concentration ratio of vanadium to oxygen was

Fig. 4. (i) UV–vis–NIR transmittance spectra, and (ii) Tauc's plot of spray deposited V2O5 thin films (Inset: Plot of bandgap vs. precursor concentration). In Figure (a)
0.05 M, (b) 0.10 M, (c) 0.15 M, (d) 0.20 M, and (e) 0.25 M precursor concentration.

188
S.R. Indhumathi, et al. Materials Science in Semiconductor Processing 100 (2019) 185–191

Fig. 5. (i) XPS Survey scan spectra, (ii) & (iii) Spectra of V2p and O1s Core-levels, respectively for the V2O5 thin film deposited with 0.15 M precursor concentration.

obtained by following a relation [51], hence are hydrophilic. Also, the samples prepared with the 0.15 M of
precursor concentration have the contact angle ∼12°; the super-hy-
AV
IV
drophilic nature, as expected from the XPS analysis. The achieved
⎛ AV + AO ⎞ super-hydrophilicity may also be due to the increased surface free en-
CV
⎜ ⎟

= ⎝ IV IO ⎠
ergy (SFE) of nano-rod morphology of the films [59], which may have
AO
CO IO more surface roughness according to the Wenzel model [60]. Also, the
⎛ AV + AO ⎞ orientation of the grown V2O5 thin films along (011) plane (shown in
(3)
⎜ ⎟

⎝ IV IO ⎠
Supplementary as Fig. S1) has the highest density of oxygen sites on the
surface of the layer-structured orthorhombic V2O5 (4 numbers in its
where, AV and AO are the areas of V2p3/2 and O1s peaks respectively. IV
unit cell). These high-density oxygen sites may be the oxygen defect
(2460.14) and IO (1608.60) are the ionization cross-section of vana-
sites that may adsorb the hydroxyl groups to favor the super-hydro-
dium and oxygen to the Al Kα radiation (1.4866 keV). The calculated
philicity. Further, the minimum water contact angle of 12° may also be
ratio of vanadium to oxygen is 0.478, and the value suggests that the
attributed to the increased work of adhesion of energy between the
films are near stoichiometry to VO2 phase. However, the substantial
water and thin film interfaces.
amount of V5+ state (determined from equation (2)) and the shift of
Hence, to attest the hydrophilicity of the prepared V2O5 thin films,
vanadium peaks to higher binding energy confirm that the film is V2O5
the work of adhesion (Wad), a measure of the strength of contact be-
phase having a large amount of oxygen deficiency. These increased
tween two different phases, was obtained by Young-Dupré relation
surface oxygen deficiency may favor the adsorption of hydroxyl groups
[61],
from the ambient atmosphere [54]. The presence of these surface ad-
sorbed hydroxyl groups, which were also confirmed from the decon- Wad (1 + cosθ) σ (4)
voluted oxygen peak (at 531.74 eV that corresponds to the hydroxyl
groups) are the most required parameter for the hydrophilicity of the where, σ is the surface tension of water on the solid surface 72.8 mJ/
oxide thin film surfaces [55]. The quantity of hydroxyl group content m2, and θ is the water contact angle. The calculated values of work of
was determined from the ratio of peak area of O-H peak centered at adhesion along with the water contact angle are represented in
531.74 eV to the total peak-sum area of O1s peak [56]. In the present Fig. 6(ii). It is inferred from the non-near-zero values of work of ad-
work, the sample deposited with 0.15 M have the hydroxyl content to hesion of the V2O5 thin film samples that all the films are hydrophilic
the maximum of 24.7%, which may lead to the chemisorption of the and the film deposited with 0.15 M is in the state of nearly perfect
hydroxyl groups in addition to the physical adsorption. These chemi- wetting since the work of adhesion value is approaching twice of the
sorbed, stable hydroxyl groups are beneficial for the super-hydro- value of the surface tension of water [62]. The greater value of work of
philicity of the surfaces [57] since the chemisorbed hydroxyl layer can adhesion reveals that the interfacial attraction between water and the
further adsorb layers of water more quickly by van der Waals forces film surface is huge since the reversible thermodynamic work required
[58]. to separate the phases to an infinite distance from the equilibrium state
The images of the water contact angle measurement to study the of two phases is high when the water contact angle is too low [63]. The
hydrophilic/hydrophobic nature of the films are given in Fig. 6(i). The results obtained were compared with the contact angle values for the
images show that all the samples have the contact angle less than 90°, samples without UV-irradiation, reported in literature. Comparison of

Fig. 6. (i) Contact angle measurement, and (ii) Plot of contact angle and work of adhesion with the precursor concentration of the spray deposited V2O5 thin films. In
Figure (a) 0.05 M, (b) 0.10 M, (c) 0.15 M, (d) 0.20 M, and (e) 0.25 M precursor concentration.

189
S.R. Indhumathi, et al. Materials Science in Semiconductor Processing 100 (2019) 185–191

Table 1 [6] H. Graphenes, S. Some, Y. Xu, Y. Kim, Y. Yoon, H. Qin, A. Kulkarni, T. Kim, H. Lee,
Comparison of contact angle measurements of V2O5 thin films with different Sci. Rep. 3 (2013) 1868.
deposition methods reported in literature. [7] N. Chen, D.H. Kim, P. Kovacik, H. Sojoudi, M. Wang, K.K. Gleason, Annu. Rev.
Chem. Biomol. Eng. 7 (2016) 373–393.
Materials Method of preparation Contact angle (o) References [8] H.J. Kim, S.J. Park, C.S. Park, T.H. Le, S. Hun Lee, T.H. Ha, H. il Kim, J. Kim,
C.S. Lee, H. Yoon, O.S. Kwon, Chem. Eng. J. 339 (2018) 204–213.
V2O5 Sol-gel 19 [64] [9] C.M. Stanford, Oral Maxillofac. Surg. Clin. 14 (2002) 39–51.
V2O5/ITO Spin coating 31.68 [65] [10] J.E. Zhou, Q. Chang, Y. Wang, J. Wang, G. Meng, Separ. Purif. Technol. 75 (2010)
243–248.
Brush painted 36.13
[11] C. Zilio, L. Sola, F. Damin, L. Faggioni, M. Chiari, Biomed. Microdevices 16 (2014)
Pd/V2O5 DC Magnetron reactive sputtering 98 [66]
107–114.
V2O5 Spray Pyrolysis 51 [67]
[12] R. Hu, Y. He, C. Zhang, R. Zhang, J. Li, H. Zhu, J. Mater. Chem. 5 (2017)
V2O5 Nebulizer spray pyrolysis 12 Present work 25632–25640.
[13] L. Huang, Y. Li, Q. Zhou, W. Yuan, G. Shi, Adv. Mater. 27 (2015) 3797–3802.
[14] R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A. Kitamura,
water contact angle measurements of V2O5 thin films with various de- M. Shimohigoshi, T. Watanabe, Light-induced amphiphilic surfaces, Nature (1997),
https://doi.org/10.1038/41233.
position methods were reported with the literature in Table .1 [64–67]. [15] Z. Xu, Z. Ao, D. Chu, A. Younis, C.M. Li, S. Li, Reversible hydrophobic to hydrophilic
Hence, the results suggest that the V2O5 thin films prepared, with transition in graphene via water splitting induced by UV irradiation, Sci. Rep.
the 0.15 M of precursor concentration using nebulizer spray pyrolysis, (2014), https://doi.org/10.1038/srep06450.
[16] H. Irie, S. Washizuka, K. Hashimoto, Hydrophilicity on carbon-doped TiO2 thin
can successfully be used in as-prepared condition for super-hydrophilic films under visible light, Thin Solid Films (2006), https://doi.org/10.1016/j.tsf.
applications such as physical functionalization of nanofiltration mem- 2005.08.374.
branes. Also, these super-hydrophilic and stable oxide thin films of [17] Y.C. Lee, Y.P. Hong, H.Y. Lee, H. Kim, Y.J. Jung, K.H. Ko, H.S. Jung, K.S. Hong,
Photocatalysis and hydrophilicity of doped TiO2 thin films, J. Colloid Interface Sci.
vanadium can be utilized in self-cleaning applications [58].
(2003), https://doi.org/10.1016/S0021-9797(03)00603-9.
[18] Y. Chen, C. Zhang, W. Huang, C. Yang, T. Huang, Y. Situ, H. Huang, Synthesis of
4. Conclusion porous ZnO/TiO2 thin films with superhydrophilicity and photocatalytic activity
via a template-free sol-gel method, Surf. Coating. Technol. (2014), https://doi.org/
10.1016/j.surfcoat.2014.08.042.
The stable and highly oxygen deficient V2O5 thin films were de- [19] X. Jiang, X. Chen, Crystallization behavior and hydrophilic performances of V2O5-
posited successfully onto the glass substrate using an automated TiO2 films prepared by sol-gel dip-coating, J. Cryst. Growth (2004), https://doi.
nebulizer spray pyrolysis technique with different precursor con- org/10.1016/j.jcrysgro.2004.07.048.
[20] B. Jin, J. He, L. Yao, Y. Zhang, J. Li, Rational design and construction of well-
centration. XRD analysis show the polycrystalline nature of the stable organized macro-mesoporous SiO2/TiO2 nanostructure toward robust high-perfor-
V2O5 thin films having orthorhombic crystal structure for the films mance self-cleaning antireflective thin films, ACS Appl. Mater. Interfaces (2017),
deposited at higher precursor concentrations. The decreasing values of https://doi.org/10.1021/acsami.7b04140.
[21] Z. Bai, Y. Hu, S. Yan, W. Shan, C. Wei, Preparation of mesoporous SiO2/Bi2O3/TiO2
crystallite sizes confirm the limited growth of grains with the increased superhydrophilic thin films and their surface self-cleaning properties, RSC Adv.
growth rate favored by the increasing precursor concentration. Surface (2017), https://doi.org/10.1039/c6ra26078k.
analysis indicates the formation of nano-rod like structures on the [22] S.N. Ariffin, H.N. Lim, F.A. Jumeri, M. Zobir, A.H. Abdullah, M. Ahmad,
N.A. Ibrahim, N.M. Huang, P.S. Teo, K. Muthoosamy, I. Harrison, Ceram. Int. 40
surface of the films deposited with 0.15 M precursor concentration. The (2014) 6927–6936.
V2O5 thin films deposited at optimized precursor concentration of [23] W. Huang, M. Lei, H. Huang, J. Chen, H. Chen, Effect of polyethylene glycol on
0.15 M was having a lesser contact angle of ∼12° which may be due to hydrophilic TiO2 films: Porosity-driven superhydrophilicity, Surf. Coating. Technol.
(2010), https://doi.org/10.1016/j.surfcoat.2010.03.030.
the increased amount oxygen vacancies present on the surface and the
[24] B. Yan, J. Tao, C. Pang, Z. Zheng, Z. Shen, C.H.A. Huan, T. Yu, Reversible UV-light-
nanostructured morphology having increased surface free energy. induced ultrahydrophobic-to-ultrahydrophilic transition in an α-Fe2O3 nanoflakes
Based on the analyzed results, it is suggested that the V2O5 thin films film, Langmuir (2008), https://doi.org/10.1021/la801900r.
[25] S. Wang, X. Feng, J. Yao, L. Jiang, Controlling wettability and photochromism in a
deposited with the optimized precursor concentration of 0.15 M are
dual-responsive tungsten oxide film, Angew. Chem. Int. Ed. (2006), https://doi.org/
favorable for super-hydrophilic applications like functionalization of 10.1002/anie.200502061.
nanofiltration membranes. [26] A.L.S. Eh, A.W.M. Tan, X. Cheng, S. Magdassi, P.S. Lee, Recent advances in flexible
electrochromic devices: Prerequisites, challenges, and prospects, Energy Technol.
(2018), https://doi.org/10.1002/ente.201700705.
Conflicts of interest [27] C. Zhang, Z. Peng, X. Cui, E. Neil, Y. Li, S. Kasap, Q. Yang, Reversible super-
hydrophilicity and hydrophobicity switching of V2O5 thin films deposited by
There are no conflicts of interest to disclose. magnetron sputtering, Appl. Surf. Sci. (2018), https://doi.org/10.1016/j.apsusc.
2017.10.146.
[28] D. Vernardou, M. Apostolopoulou, D. Louloudakis, N. Katsarakis, E. Koudoumas,
Acknowledgements Hydrothermally grown β-V2O5 electrode at 95°C, J. Colloid Interface Sci. (2014),
https://doi.org/10.1016/j.jcis.2014.03.004.
[29] D. Vernardou, I. Marathianou, N. Katsarakis, E. Koudoumas, I.I. Kazadojev,
This work has been partly supported by a project numbered “SB/ S. O'Brien, M.E. Pemble, I.M. Povey, Capacitive behavior of Ag doped V2O5 grown
FTP/PS-038/2013” funded by DST-SERB, India and SASTRA - TRR in- by aerosol assisted chemical vapour deposition, Electrochim. Acta (2016), https://
tramural research projects numbered “SASTRA/SEEE/KJ/TRR-2”. doi.org/10.1016/j.electacta.2016.02.186.
[30] M.M. Margoni, S. Mathuri, K. Ramamurthi, R.R. Babu, K. Sethuraman, Investigation
Author C.G thanks to DBT - India for the project numbered “BT/
on the Pure and Fluorine Doped Vanadium Oxide Thin Films Deposited by Spray
PR8910/NNT/28/684/2013”. Pyrolysis Method, Thin Solid Films (2016), https://doi.org/10.1016/j.tsf.2016.03.
035.
[31] S. Thiagarajan, M. Thaiyan, R. Ganesan, Physical property exploration of highly
Appendix A. Supplementary data
oriented V2O5 thin films prepared by electron beam evaporation, New J. Chem.
(2015), https://doi.org/10.1039/c5nj01582k.
Supplementary data to this article can be found online at https:// [32] M. Panagopoulou, D. Vernardou, E. Koudoumas, N. Katsarakis, D. Tsoukalas,
doi.org/10.1016/j.mssp.2019.04.048. Y.S. Raptis, Tunable properties of Mg-doped V2O5 thin films for energy applications:
Li-ion batteries and electrochromics, J. Phys. Chem. C (2017), https://doi.org/10.
1021/acs.jpcc.6b09018.
References [33] P. Karthick, D. Vijayanarayanan, M. Sridharan, A.K. Ananth, C. Sanjeeviraja,
K. Jeyadheepan, Thin Solid Films 631 (2017) 1–11.
[34] K. Jeyadheepan, P. Karthick, C. Sanjeeviraja, Development of automated spray
[1] Z. Xu, L. Wan, X. Huang, Surf. Eng. Polym. Membr. (2009) 80–149.
pyrolysis setup for chemical vapour deposition like growth of thin solid films, J.
[2] H. Irie, K.I. Tsuji, K. Hashimoto, Phys. Chem. Chem. Phys. 10 (2008) 3072–3076.
Instrum. 14 (2019) P04002.
[3] M.M. Ling, T.S. Chung, Desalination 278 (2011) 194–202. [35] R. Irani, S.M. Rozati, S. Beke, Appl. Phys. Mater. Sci. Process 124 (2018).
[4] E. Ueda, P.A. Levkin, Adv. Mater. 25 (2013) 1234–1247.
[36] G. Amin, M.H. Asif, A. Zainelabdin, S. Zaman, O. Nur, M. Willander, J. Nanomater.
[5] N.K. Subbaiyan, C.A. Wijesinghe, F. D'Souza, J. Am. Chem. Soc. 131 (2009)
2011 (2011).
14645–14647.
[37] N. Anitha, M. Anitha, J. Raj Mohamed, S. Valanarasu, L. Amalraj, J. Asian Ceram.

190
S.R. Indhumathi, et al. Materials Science in Semiconductor Processing 100 (2019) 185–191

Soc. 6 (2018) 121–131. 46624–46630.

[38] M. Baneto, A. Enesca, Y. Lare, K. Jondo, K. Napo, A. Duta, Ceram. Int. 40 (2014) [54] H.-L. Chen, H.-T. Chen, Chem. Phys. Lett. 493 (2010).
8397–8404. [55] Y. Hao, D.M. Soolaman, H.Z. Yu, J. Phys. Chem. C 117 (2013) 7736–7743.
[39] H.R. Moutinho, F.S. Hasoon, F. Abulfotuh, L.L. Kazmerski, J. Vac. Sci. Technol. A [56] A. Eshaghi Eshaghi, Bull. Mater. Sci. 35 (2012) 137–142.
Vac., Surf., Film. 13 (1995) 2877–2883. [57] K. Guan, B. Lu, Y. Yin, Surf. Coating. Technol. 173 (2003) 219–223.
[40] M. Klinger, A. Jäger, J. Appl. Crystallogr. 48 (2015) 2012–2018. [58] K. Guan, Surf. Coating. Technol. 191 (2005) 155–160.
[41] M. Dhivya Pushpa, Mateo Sanclemente Crespo, M. Manoj Cristopher, P. Karthick, [59] J. Xu, Z. Guo, J. Colloid Interface Sci. 406 (2013) 1–17.
M. Sridharan, C. Sanjeeviraja, K. Jeyadheepan, Vacuum 161 (2019) 81–91. [60] T.H. Yen, C.Y. Soong, Phys. Rev. E. 93 (2016).
[42] Sreekumar Rajappan Achary, Said Agouram, Juan F. Sánchez-Royo, M. [61] S. Mohamed Sali, S. Joy, N. Meenakshisundaram, R.K. Karn, C. Gopalakrishnan,
Carmen Martínez-Tomás, Vicente Muñoz-Sanjosé, RSC Adv. 4 (2014) P. Karthick, K. Jeyadheepan, K. Sankaranarayanan, RSC Adv. 7 (2017)
23137–23144. 37720–37728.
[43] S.K. Tong, P.W. Chi, S.H. Kung, D.H. Wei, Sci. Rep. 8 (2018). [62] N.A. Mortensen, Symp. A Q. J. Mod. Foreign Lit. 1 (1998) 1–5.
[44] A. Kocjan, M. Logar, Z. Shen, Sci. Rep. 7 (2017). [63] S. Ebnesajjad, C.F. Ebnesajjad, Surface Treatment of Materials for Adhesion
[45] A. González-González, G.M. Alonzo-Medina, A.I. Oliva, C. Polop, J.L. Sacedón, Bonding, 2nd ed, Elsevier, 2006, https://doi.org/10.1016/B978-081551523-4.
E. Vasco, Morphology evolution of thermally annealed polycrystalline thin films, 50006-7.
Phys. Rev. B Condens. Matter (2011), https://doi.org/10.1103/PhysRevB.84. [64] B. Ahmad Bhat, G.R. Khan, K. Asokan, Role of substrate effects on the morpholo-
155450. gical, structural, electrical and thermoelectrical properties of V2O5 thin films, RSC
[46] D.L. Ferreira, J.C.L. Sousa, R.N. Maronesi, J. Bettini, M.A. Schiavon, Adv. (2015), https://doi.org/10.1039/c5ra07542d.
A.V.N.C. Teixeira, A.G. Silva, J. Chem. Phys. 147 (2017). [65] S.P. Cho, J.S. Yeo, D.Y. Kim, S.I. Na, S.S. Kim, Brush painted V2O5 hole transport
[47] S. Thiagarajan, M. Thaiyan, R. Ganesan, RSC Adv. 6 (2016) 82581–82590. layer for efficient and air-stable polymer solar cells, Sol. Energy Mater. Sol. Cells
[48] G. Greczynski, L. Hultman, ChemPhysChem 18 (2017) 1507–1512. (2015), https://doi.org/10.1016/j.solmat.2014.08.019.
[49] Z. Xu, L. Wan, X. Huang, Surf. Eng. Polym. Membr. (2009) 80–149. [66] A. Sanger, A. Kumar, A. Kumar, J. Jaiswal, R. Chandra, A fast response/recovery of
[50] C.V. Ramana, M. Massot, C.M. Julien, Surf. Interface Anal. (2005) 412–416. hydrophobic Pd/V2O5 thin films for hydrogen gas sensing, Sensor. Actuator. B
[51] K. Jeyadheepan, M. Thamilselvan, K. Kim, J. Yi, C. Sanjeeviraja, J. Alloy. Comp. Chem. (2016), https://doi.org/10.1016/j.snb.2016.05.141.
620 (2015) 185–191. [67] M.S. Pawar, M.A. Sutar, K.I. Maddani, S.G. Kandalkar, Improvement in electro-
[52] Manoj Cristopher, P. Karthick, R. Sivakumar, C. Gopalakrishnan, C. Sanjeeviraja, chemical performance of spray deposited V2O5 thin film electrode by anodization,
K. Jeyadheepan, Vacuum 160 (2019) 238–245. Materials Today Proceedings, 2017, https://doi.org/10.1016/j.matpr.2017.02.246.
[53] Z. Li, Q. Zhu, S. Huang, S. Jiang, S. Lu, W. Chen, G.S. Zakharova, RSC Adv. 4 (2014)

191