Vacuum 187 (2021) 110097

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Vacuum
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Short communication

Highly crystalline V2O5 and V6O13 thin films by PLD and a study on
morphology transition of V2O5 by post annealing
V. Shobin Vijay, Rojin Varghese, A. Sakunthala **, S. Rajesh *, B. Vidhya
Solid State Ionics and Thin Film Batteries Lab, Department of Physics, Karunya Institute of Technology and Sciences, Coimbatore, Tamil Nadu, 641 114, India

A R T I C L E I N F O A B S T R A C T

Keywords: Vanadium oxide thin films were deposited on stainless steel substrates at different temperatures using the Pulsed
Vanadium oxides laser deposition technique. Post annealing effect on the better crystalline V2O5 film was studied and found that
PLD the annealing had a positive impact on the crystallization. The structural and morphological properties were
Morphology transition
investigated by XRD, Raman, and SEM analysis. The presented work opens up the changes that occur in phase
Phase orientation
orientations and the tunable morphological growth in the Vanadium oxide thin films. The prepared thin films
have potential applications in energy storage devices.

The Vanadium oxides V2O5 and V6O13 are considered as the potential
cathode materials for lithium microbatteries, for their ability to
accommodate more Li ions [1,2]. Since the research on thin films of
V2O5 and V6O13 is highly demanded for the development of micro­
batteries, the lack of a good understanding on the growth of different
phases of above materials is to be addressed. Due to their multivalent
nature, it is incredibly challenging to grow the Vanadium oxide phases
in thin film form of desired properties. As for the microbatteries are
considered, utilizing Vanadium oxides grown on the flexible stainless
steel (SS) substrates would be economical. Recently, many successful
efforts have been made to deposit V2O5 thin film using various deposi­
tion techniques such as Chemical Vapor Deposition [3], Magnetron
Sputtering [4], Spray Pyrolysis [5], Pulsed laser deposition (PLD) [6],
etc. Among the above techniques, PLD has been preferred to grow high
quality and epitaxial layered thin films, which will also have the same
stoichiometry as the target used. Scarce reports are seen on the growth
of V2O5 on SS substrates by Pulsed laser deposition method. Petnicota
et al. [7] reported on the V2O5 amorphous thin film grown on SS sub­
strates by PLD. Yan-Qiu Chu et al. [8] prepared V2O5 polycrystalline thin
film on SS substrates, but the peaks in the XRD patterns were not intense.
In contrast, Hai-Rong Liu et al. [9] reported on the crystalline V2O5 thin
film with a dendrite grain structure deposited on SS substrates by PLD.
But, no reports are seen on the growth of V6O13 on SS substrate in any of
the techniques. V6O13 was an outstanding cathode material for batteries
and attracted much interest because of its high theoretical capacity of
420 mAh/g and good electrical conductivity. The structure of V6O13 is
built up with alternating single and double layers made up of VO6
octahedra [10], which are connected by corner-sharing oxygen atoms.
These alternating single and double layers could provide much more
sites for lithium intercalation. Theoretically, the maximum lithium up­
take was eight Li atoms per formula unit and the insertion process is fully
reversible. Previously, Mutta et al. [11] developed V6O13
nano-architectures, including rods and flowers by hydrothermal method
and rod-like structures were prepared by Jinyun et al. [12] using sol­
vothermal method. But there were only scarce reports on pulsed laser
deposited V6O13 thin films. Shibuya et al. [13] prepared V6O13 thin films
on Si substrates by PLD technique and obtained a close-packed structure
with irregular grains. Wang et al. [14] reported a mixed phase of V6O13
along with V3O7 and V2O5 deposited on Si substrates using PLD. Hence a
good understanding of the growth of V2O5 and V6O13 thin films on SS
substrate by PLD is the need of the hour for the most promising field of
microbatteries. In the present work, highly crystalline phases of V2O5
and V6O13 was systematically grown on flexible SS substrates of desired
properties with a single target.
The Vanadium Oxide powder purchased from Sigma Aldrich, of
purity 99.9% was used in making the target with thickness and diameter
of 2 and 25 mm, respectively using a hydraulic pelletizer. Subsequently,
the target was sintered at 500 ◦ C for 5 h. Stainless Steel substrate (SS
304) of thickness 0.1 mm was well polished and cleaned in an ultra-sonic
bath for 2 h. After loading the target and the substrate in the respective
holders, the vacuum chamber was steadied to a base pressure of 13 ×
10− 6 mbar using Turbo molecular pump. A 355 nm pulsed Nd-YAG laser

* Corresponding author.
** Corresponding author.
E-mail addresses: sakunthala@karunya.edu (A. Sakunthala), drsrajesh@karunya.edu (S. Rajesh).

https://doi.org/10.1016/j.vacuum.2021.110097
Received 7 December 2020; Received in revised form 13 January 2021; Accepted 24 January 2021
Available online 29 January 2021
0042-207X/© 2021 Elsevier Ltd. All rights reserved.
V.S. Vijay et al. Vacuum 187 (2021) 110097

Fig. 1. XRD patterns of the films deposited at (a) 200 ◦ C to 500 ◦ C substrate temperature (b) 600 ◦ C and 700 ◦ C substrate temperature (c) 300 ◦ C substrate tem­
perature which is annealed at 600 ◦ C for 1 and 2 h.

Table 1
Lattice constants of sample deposited at 300 ◦ C substrate temperature, samples annealed at 600 ◦ C for 1 h and 2 h, and V6O13 film deposited at 700 ◦ C substrate
temperature.
a(Å) b(Å) c(Å) Cell volume (Å)3 Crystallite size,D (nm) Microstrain (10− 3) Dislocation density (nm)− 2

Sample

V2O5 film deposited at 300 ◦ C 11.55 3.59 4.40 182.86 23 8.7 1.8 × 103
Annealed at 600 ◦ C for 1 hour 11.51 3.57 4.36 180.09 19 1.3 2.7 × 103
Annealed at 600 ◦ C for 2 hour 11.47 3.55 4.46 182.20 20 9.7 2.5 × 103
V6O13 film deposited at 700 ◦ C 11.99 3.71 10.11 443.55 31 4.6 1.0 × 103

(Quantel QSmart 450, France) having 10 ns pulse width, a repetition
rate of 10 Hz and with energy of 155 mJ was used as a laser source. The
background gas used was oxygen, and the depositing pressure (PO2) was
maintained at 5.8 10− 2 mbar throughout the deposition process. The
target carousel was rotated with a motor at a speed of 10 rpm to avoid
the depletion of material at one spot. The distance between the target
and the substrate was fixed at 3 cm, and the substrate was maintained at
different temperatures ranging from 200 ◦ C to 700 ◦ C. All the PLD
process parameters were optimized carefully to obtain homogeneous
films. The structural properties and the crystallinity of thin films were
analyzed using X-ray Diffraction (XRD-6000 SHIMADZU, JAPAN) with
Cu Kα standard wavelength of 1.5406 Å in the 2θ range from 5⁰ to 80⁰.
The morphology of the film was studied using a Scanning Electron Mi­
croscope (JEOL, JAPAN), and the Raman spectrum was recorded using
Laser Raman Spectrometer (Lab RAM HR Evolution HORIBA).
The XRD patterns of thin films are shown in Fig. 1(a-c), and the
structural data is given in Table 1. The film deposited at 200 ◦ C was
found to be amorphous. Among the films deposited at 300, 400, and
500 ◦ C (Fig. 1a), the one deposited at 300 ◦ C has diffraction peaks at
15.2⁰, 19.8⁰, 31⁰ and 50.6⁰ of 2θ value corresponding to the (200), (001),
(301) and (020) planes of V2O5, respectively (JCPDS No: 41–1426).
Further, to increase the crystallinity of the film deposited at 300 ◦ C, it
was annealed at 600 ◦ C for different time intervals of 1 and 2 hours in an
air atmosphere. As seen in Fig. 1c, the film annealed for 1 h shows an
increase in the intensity of the diffraction peaks, and the orientation of
the dominant peak was along (200) plane [15]. Whereas the sample
annealed at 600 ◦ C for 2 h leads to a further increase in the intensity of
the peaks, and the dominant peak was along the (001) plane/c-axis,
which will favor the energy applications [16]. The increase in the in­
tensity of the peaks was due to the phenomenon of recrystallization
when the film was annealed at higher temperatures, also the annealing
had a positive effect on the crystallization.
When the substrate temperature was increased to 600 ◦ C (Fig. 1b) it
was observed that a phase belonging to the V6O13 starts to rise as seen by
the growth of the peak at 26.88⁰, whereas when the temperature was
increased to 700 ◦ C, a highly crystalline form of V6O13 phase was ob­
tained with a minor phase of V2O5 at 2θ=20.26⁰ (Fig. 1b). The diffrac­
tion peaks of V6O13 were found to be at 2θ=8.97⁰, 14.98⁰, 17.83⁰,

2
V.S. Vijay et al. Vacuum 187 (2021) 110097

Fig. 2. Raman spectra of (a) V2O5 thin film deposited at 300 ◦ C substrate temperature and the films annealed at 600 ◦ C for 1 and 2 h (b) V6O13 thin film deposited at
700 ◦ C substrate temperature.

Fig. 3. SEM images of V2O5 thin films (a–b) deposited at 300 ◦ C substrate temperature (c–d) annealed at 600 ◦ C for 1 h (e–f) annealed at 600 ◦ C for 2 h and (g–h)
FESEM images of V6O13 film deposited at 700 ◦ C substrate temperature (different scales and magnification).

26.88⁰, 30⁰, 36.2⁰, 45.47⁰ and 55.25⁰ with corresponding miller indices
(001), (200), (002), (003), (− 401), (− 113), (005) and (006) with a
monoclinic structure and crystallised in P21/a space group. The 2θ
values match well with the JCPDS card No: 25–1251 [17].
As seen from Raman Spectra (Fig. 2a), it was clearly observed that
the increase in the intensity of the peaks when the film was annealed,
which agrees with the results obtained from XRD analysis. The peaks at
wavenumbers 144 and 196 cm− 1 corresponds to the relative motion of
V2O5 layers [18]. The peaks observed at 283, 405, 527, 481, and 994
cm− 1 were in good agreement with the previous reports [19]. From the
(Fig. 2b), the high intense peak at 142 cm− 1 corresponds to the Bg
symmetry of the V6O13 thin film [20]. The peak at 191 cm− 1 was due to
the rigid layer modes. The wavenumbers 283 and 406 cm− 1 are assigned
to the bending vibrations of two different V–
– O bonds [21], whereas the

3
V.S. Vijay et al.
peak at 297 cm− 1 belongs to the bending of the bonds near the triply
coordinated oxygen atom [21]. The peaks at 537 and 686 cm− 1 indicate
the triply coordinated V3O groups. The band at 837 cm− 1 corresponds to
infrared-active mode, which was usually Raman-inactive because of the
V6O13 symmetry. However, it will be activated when a structural dis­
order is present [22] and confirms the formation of the V6O13 structure.
The weak intensity peaks at 1030, 162, 506 cm− 1 are also in good
agreement with the literatures [22,23]. The strong peak at 993 cm− 1 is
assigned to the stretching mode of vanadyl oxygen.
SEM analysis were carried out for the films at the scale of 1 μm and
0.5 μm (Fig. 3Fig. 3(a-f)). It was observed clearly that the morphology
changes when the film was subjected to annealing. Fig. 3(a-b) shows
typical SEM images of V2O5 grain-like structure when it was deposited at
300 ◦ C substrate temperature. In contrast, Fig. 3(c-d) indicates the
morphology transition of the film from grains to Nanorods when the film
deposited at 300 ◦ C was subjected to annealing at 600 ◦ C for 1 h. Fig. 3
(e-f) shows the image of the sample annealed at 600 ◦ C for 2 h and
observed further increase in the length of the rods with decrease in
width when compared to Fig. 3(c-d). The average length of nanorods
was in the range of 0.59–1.18 μm. The average width of nanorods was in
the range of 32–55 nm for 1 h annealing and in the range of 66–190 nm
for 2 h. This indicates a stable morphology wherein the results were
reproducible. The nanorod formation was because of the oxygen
adsorption when the film was annealed in an air atmosphere. This
nanorod growth directly influenced the crystalline quality of the films
and agrees with the results obtained from XRD analysis. In all the cases,
the SEM images in 1 μm range shows the even distribution of
morphology throughout the film. The V2O5 grown on the Si substrate by
PLD method with a mixture of nanorods and nanoflakes morphology
was reported by Sinha [24]. It was noticed that morphology and crys­
tallization is highly dependant on the annealing temperature. Fig. 3(g-h)
reveals the morphology of the thin film deposited at 700 ◦ C substrate
temperature on stainless substrates at a scale of 100 and 200 nm range. A
dense micrometer-sized slate-like structure was observed, and it is
randomly oriented throughout the film.
Conclusion
A systematical approach in pulsed laser deposition method,
controlled growth of polycrystalline V2O5 thin film in the desired
orientation with aligned nanorod morphology on flexible SS substrate
has been prepared. The highly crystalline phase of V6O13 slate-like thin
film structures were developed during the deposition at a higher tem­
perature with the same target. These preferable vanadium oxides thin
films with tunable structures can play a vital role in energy storage
devices.
Vacuum 187 (2021) 110097
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
The authors thank the Department of Science and Technology, Sci­
ence and Engineering Research Board (EMR/2017/003227 dated July
16, 2018) Government of India, for the funding.
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