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Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, POB 162, Arhimedova 3, 1000 Skopje, Republic of Macedonia
Research Center for Environment and Materials, Macedonian Academy of Sciences and Arts, Krste Misirkov 2, 1000 Skopje, Republic of Macedonia
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, G. Bonchev Str. Bldg. 11, 1113 Soa, Bulgaria
a r t i c l e
i n f o
Article history:
Received 26 February 2015
Revised 20 July 2015
Accepted in revised form 21 July 2015
Available online 29 July 2015
Keywords:
Thin lms
Vanadium(V) oxide xerogels
Chemical synthesis
Electrochromism
Optical properties
Electrochemical properties
a b s t r a c t
An optimized chemical bath method is applied to obtain well-structured thin lms with composition
Na0.33V2O5nH2O (n = 1 and 1.3). The method is based on a controlled precipitation reaction that takes place
in the system of sodium metavanadate and diethyl sulfate at 85 C. The lm structure, morphology and the
changes occurring during prolonged aging are examined by XRD, IR spectroscopy, TG-DTA, SEM and AFM. The
electrochemical and electrochromic properties are studied by cyclic voltammetry and UVvis spectroscopy.
The as-deposited thin lms are characterized with high optical transmittance varying between 40 and 70% at
the 500 nm visible region in dependence on lm thickness. The Na0.33V2O5nH2O thin lms exhibit stable electrochemical cycling combined with relatively high electrochromic activity. The reproducibility of the transmittance variance of 55% after 500 cycles in the electrochromic cell is a promising result for the potential
application of Na0.33V2O5nH2O thin lms in electrochromic devices.
2015 Published by Elsevier B.V.
1. Introduction
Vanadium(V) oxide and derived compounds have been extensively
studied due to valuable chemical and physical properties which determine a wide range of applications in catalysis, high-energy lithium batteries and a variety of electric and optical devices. The synthetic procedures
at ambient conditions usually produce hydrated vanadium(V) oxides,
V2O5nH2O, known as xerogels which adopt layered structures with
V2O5 layers and interstitial water molecules [13]. Vanadium(V) oxide
xerogels like crystalline V2O5 are typical intercalation compounds with
multiple valence state of vanadium which enables redox-dependent
properties [46]. Due to the high intercalation capacity (for instance, a
lithium intercalation capacity about 1.4 times larger than that of crystalline V2O5) [7] they have a great potential for applications like reversible
cathodes for lithium batteries [8,9], micro-batteries [6], supercapacitors
[10], electrodes [11] and humidity sensors [12]. The reversible cation
intercalation/deintercalation within the xerogel framework is concomitant with reversible reduction/oxidation of V(V) to V(IV) or to a lower
Corresponding author at: Institute of Chemistry, Faculty of Natural Sciences and
Mathematics, Ss. Cyril and Methodius University, POB 162, Arhimedova 3, 1000 Skopje,
Republic of Macedonia.
E-mail addresses: metonajd@pmf.ukim.mk (M. Najdoski), vkoleva@svr.igic.bas.bg
(V. Koleva), sashostojkovikj@gmail.com (S. Stojkovikj), toni.todorovski@irbbarcelona.org
(T. Todorovski).
1
Present address: Institute for Research in Biomedicine, Parc Cientc de Barcelona,
08028 Barcelona, Spain.
http://dx.doi.org/10.1016/j.surfcoat.2015.07.041
0257-8972/ 2015 Published by Elsevier B.V.
However, the use of the same simple synthetic procedure in the case
of initial NaVO3, i.e. acidication of NaVO3 solution with acetic acid at
75 C (pH = 3), leads to the formation of unstructured amorphous
thin lms as we have previously established [23]. In that case a further
thermal treatment at 400 C was needed in order to obtain crystalline
lms which represent a two-phase mixture of sodium vanadium oxides
such as NaV6O15 and Na1.1V3O7.9. Thus prepared thin lms exhibited insufciently high T values of about 20% in the voltage range of 2 V.
The present work is focused on the examination of well-structured
hydrated sodium vanadium oxide thin lms with electrochromic properties. Such thin lms are prepared by an optimized chemical bath
method that ensures one-step deposition of the thin lms at low
temperature. For the purpose we have applied a different synthetic approach: instead of a direct acidication, we have used here an indirect
acidication through the hydrolysis of diethyl sulfate present in the
chemical bath. This controlled precipitation reaction gives rise to the deposition of thin lms of vanadium(V) oxide xerogel with composition of
Na0.33V2O5H2O having well-organized layered structure in the nanoscale region. These lm characteristics are advantageous to achieving
electrochemical stability and high T value of 55% which is reproducible
for 500 cycles. The changes during the lm aging are studied in respect
to the lm structure, V(V) reduction and electrochromic effect.
It is worth emphasizing that the as-prepared well-structured
Na0.33V2O5H2O composition (solid or lm) is highly benecial for
further obtaining a variety of chemical compositions. Thus, once obtained it can be used to produce either lower hydrated xerogels
Na0.33V2O5nH2O (0.3 b n b 1) or a single phase of NaV6O15 by thermal
treatment at an appropriate temperature. All these compositions having
a layered or tunnel structure can serve as host matrices for intercalation
processes which open opportunities for different applications. From this
point of view the difference with the previously studied (NH4)xV2O5
1.3H2O compositions is obvious: their thermal treatment produces the
well studied V2O5.
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Fig. 1. XRD patterns of (a) as-deposited lm, (b) brown precipitate and (c) greenish
precipitate.
Fig. 2. IR spectra of (a) NaVO3, (b) as-deposited scraped lm obtained for 30 min, (c) lm
aged 20 months, (d) fresh brown precipitate and (e) brown-greenish precipitate aged
more than 3 years.
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Fig. 3. TG-DTA curves for Na0.33V2O5H2O xerogel precipitates: (a) fresh and (b) aged
20 days.
process, however, does not appear to modify the XRD pattern of greenish precipitate (Fig. 1c) which is very similar to that of the fresh one and
only differences in the relative intensity of some peaks such as at 25.44
and 32.74 (2) are observed (Fig. 1b). Since the IR spectroscopy can
give valuable information on the change in the valence state of vanadium [41,42] we have further examined the IR spectra of the precipitate
and lm, both aged at different times, 20 days, 20 months and 3 years,
and some of them are included in Fig. 2. The inspection of the IR spectra
showed that the spectra of the precipitates aged 3 years and lm aged
20 months match closely those of the corresponding samples aged
20 days, as well as the spectra of the lms that are practically the
same with the spectra of the precipitates. So that, as an illustration in
Fig. 2 the IR spectra of a lm aged 20 months (Fig. 2c) and a precipitate
aged 3 years (Fig. 2e) are compared with the spectra of the corresponding fresh samples (Fig. 2b,d).
By IR spectroscopy it was established that the electrochemical reduction of V(V) from V2O5 to V(IV) causes a considerable modication
of the spectra as both the terminal V_O and bridging V\\O\\V
stretching vibrations are mainly affected [41,42]. Therefore, in the presence of more V(IV) species we should expect a red shift of the band at
1012 cm1 as well as a decrease in the intensity and frequency of the
band at 761 cm1 [41,42]. The close examination of the IR spectra in
Fig. 2 reveals that even prolonged aging does not result in any signicant difference in the band positions and intensities in comparison
with the fresh samples. Only a very small frequency variation between
2 and 4 cm1 is observed in some spectra, but these variations are not
consistent and, particularly the former one is within the limit of the experimental resolution (Fig. 2). These spectral features provide evidence
for the low degree of reduction of V(V) to V(IV) that takes place during
the aging, so the amount of the newly obtained V(IV) is not high enough
to affect the internal V\\O framework of the initial xerogel. We could
also suppose that the reduction process occurs mainly on the surface
of the particles, and thus the vibrational characteristics of the bulk
material appear to be unchanged.
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From the above data it follows that the vanadium reduction during
aging of our Na0.33V2O5H2O is accompanied by an increase in the
water content to Na0.33V2O51.3H2O. Such phenomenon has been previously reported for reduced xerogels [44]. Babonneau et al. [44] have
found that the reduced gels having V(IV)/V(V) of 16% contain 2.5 H2O
per V2O5 instead of 1.61.8 H2O for gels with usual V(IV)/V(V) about 1
to 4%.
4.3. Morphology of Na0.33V2O5H2O thin lms
As described in the literature [6,31] vanadium(V) oxide xerogels
normally exist in the form of long ribbons. SEM images of two thin
lms prepared for the 15 and 30 min deposition times are depicted in
Fig. 4.
Among the studied lms these are the lms exhibiting the best optical properties (see Section 4.5) and their thickness determined by the
prolometer is about ~150 and ~300 nm (for the 15 and 30 min deposition times, respectively). The cross-sectional SEM image of the lm for
the 30 min deposition time (Fig. 4d) gives a thickness of about 250 nm.
The chemical bath deposition method produces thin lms which
surface is completely covered with the deposited material (Fig. 4a, b
and c). Both lms are dense and without any porosity. The SEM image
of the thinner lm recorded at a higher magnication (Fig. 4b) clearly
shows the granular structure of the lm. It is composed of nanograins,
spherical and elongated, with sizes between 50 and 200 nm. Besides
well separated nanograins, randomly oriented ribbon-like units (about
200 nm wide and 11.5 m long) are also visible (Fig. 4a).
The observations by SEM are supported by AFM data for the same
Na0.33V2O5H2O thin lms (Fig. 5). The 2D surface topography of the
thinner lm (Fig. 5a) shows nanograins with sizes in the range of
50150 nm. In addition, there are elongated ribbon-like units with the
following dimensions: width from 150 to 300 nm and length from 0.7
to 2 m. The longer deposition time ensures the growth of the grains
and, expectedly, the thicker lm (Fig. 5b) exhibits larger grains with
sizes from 250 to 700 nm as well as larger ribbons reaching to 1 m
Fig. 4. SEM images of Na0.33V2O5H2O thin lms with different thickness: (a) and (b) ~150 nm, (c) ~300 nm and (d) cross-section view of the thin lm with ~300 nm thickness.
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Fig. 5. AFM images of Na0.33V2O5H2O thin lms: (a) and (b) are 2D images with proles of lms with 150 and 300 nm thickness, respectively; (c) and (d) are 3D images of lms with 150
and 300 nm thickness, respectively.
wide and 3 m long. Moreover, AFM data reveal that the lms exhibit
comparatively high surface roughness with amplitude of the grain
height at around 600 nm for the thinner lm and 250500 nm for the
thicker one, i.e. the thickness is not uniform throughout the whole
lm area. The 3D images, and especially those for the thinner lm
(Fig. 5c), clearly illustrate the way for the formation of the ribbons.
We can see that the ribbons arise as a result of the coalescence of
nanograins in a preferred direction. We suppose that only the grains
having the most suitable orientation and that are situated closely to
each other are able to coalesce and thus to form long ribbon-like units.
Moreover, we can also speculate, that a possible growth mechanism of
Na0.33V2O5H2O thin lms is the island mechanism (Fig. 5d) in which
the coalescence of the islands generates ribbon-like units and the latter,
at a certain point, will form the compact lm layer.
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Fig. 6. Five cyclic voltammograms of Na0.33V2O5H2O thin lms with thickness: (a) 150 nm
and (b) 300 nm at a scanning rate of 10 mV/s.
intensive A2/C2 redox pair as well as the voltage ranges for the anodic
(from 0.23 to 0.64 V) and cathodic (from 0.8 to 0.3 V) peaks are
very similar to our data.
The calculation of the exchanged charge showed that the values
for the extracted charge for the thin lm with 150 nm thickness is
65.5 mC/cm2 and for the lm with 300 nm thickness is 75.5 mC/cm2.
The inserted charge values are much lower, 19.9 mC/cm2 and
22.3 mC/cm2 respectively. The higher values for the exchanged charge
for thicker lms are expected due to their higher capacity.
The electrochemical reversibility for 200 cycles was monitored at
scanning rate of 50 mV/s for the lm with 300 nm thickness (Fig. 7).
In conformity with the higher scanning rate all CV curves in Fig. 7
display one broad pair of oxidation/reduction peak instead of the
three pairs well-separated at the lower scanning rate (Fig. 6b). The
oxidation/reduction pair remains stable during the cycling with a slight
shift of the peak maximum to lower potentials: from 0.48 V/0.44 V for
the 5th scan to 0.43 V/ 0.41 V for the 200th scan. Moreover, the peak
maxima move to higher potentials than those of the most intensive
A2/C2 pair at the lower rate. It is also observed that the peak area
(exchanged charges) decreases during the cycling and this process is
Fig. 7. Cyclic voltammograms to 200 scans of thin lm with 300 nm thickness at a scanning
rate of 50 mV/s.
Fig. 8. Cyclic voltammograms of thin lms with 300 nm thickness: (a) fresh lm, 1st to 4th
and 16th and 20th scans, (b) aged lm, 5th, 7th, 10th, 15th and 20th scans (10 mV/s).
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triggered by the oxidation/reduction cycles [2] or to changes in morphology and microstructure of the lm leading to the formation of a
more homogeneous lm [48].
The observed redox peaks in the potential range 1 V for
Na0.33V2O5H2O thin lms are related to step-wise reduction of V(V) to
V(IV) concomitant with formation of different crystalline states LixV2O5
and, accordingly reversible V(IV) oxidation and Li-deintercalation
[46,49,50].
4.5. Optical properties
Optical transmittance spectra in the 350900 nm spectral range of
the as-deposited thin lms are given in Fig. 9. It is important that the
four lms exhibit very similar dependence of the optical transmittance
on the wavelength, but the overall transmittance decreases with the
lm thickness. This is expected since more states in the thicker lm
are available for the photons to be absorbed. The thin lms have relatively high transmittance (low absorbance) at wavelengths longer
than 550 nm as the thinner lms (obtained for 5, 10 and 15 min deposition time) exhibit transmittance between 70 and 90%, while the thick
lm (30 min deposition time) exhibits a lower transmittance between
55 and 70%. The marked reduction in the transmittance at wavelengths
shorter than 550 nm is associated with the fundamental absorption. It is
essential that the absorption edge for the four lms appears in a narrow
interval of wavelengths (365385 nm). This means that the lms with
different thicknesses should have very close values of the optical band
gap which implies the same or very close stoichiometry regarding the
different vanadium sites. In this regard we have also compared the IR
spectra of the scraped lms obtained for the 5, 15 and 30 min deposition
and we have not found any variation in the positions and intensity of the
vibrational bands in comparison with the IR spectrum presented in
Fig. 2b. Considering these data we believe that the change of the lm
color with the time of deposition from yellow to yellow-brown shade
is mainly related to the lm thickness and grain growth evidenced by
AFM analysis (Fig. 5a, b) rather than the same changes in the vanadium
oxidation state during the deposition.
The optical transmittance of Na0.33V2O5H2O thin lms in the
350900 nm range is recorded in a two-electrode electrochromic cell
using LiClO4/PC electrolyte. Our previous studies on (NH4)xV2O5
1.3H2O thin lms in the voltage range between 1 and 2.5 V have
shown that the increased voltage results in increasing transmittance
variance (T) and shorter bleaching and coloration response times [30].
It is important to notice that the current densities achieved in the
used two-electrode electrochromic cell are around 0.27 mA/cm2 at
+2.5 V (at the highest voltage), but these values are still much lower
than those achieved in the three-electrode cell (CV measurements):
around 1.5 mA/cm2 at a signicantly lower voltage of 0.3 V. This fact explains the longer response time (Fig. 10) observed in the two-electrode
electrochromic cell.
Fig. 9. Optical transmittance spectra of as-deposited thin lms with time of deposition.
Fig. 10. Response time of Na0.33V2O5H2O thin lm with 300 nm thickness at 900 nm at
2.5 V.
The response time () is calculated as the time required for the thin
lm to change its color from yellow/brown to obtain 90% [51] of the blue
color (c,90% coloration response time) or vice versa, to obtain 90% of
the yellow/brown color (b,90% bleaching response time). It is seen
in Fig. 10 that the bleaching response time b,90% is 10 min, while the coloration response time c,90% is 17.5 min i.e. the reduction process followed with Li+-intercalation is almost two times slower than the oxidation
process followed with Li+-deintercalation.
The optical transmittance spectra recorded at 2.5 V with a
switching time of 20 min of four Na0.33V2O5H2O thin lms prepared
for different deposition times are shown in Fig. 11. It is seen that the dependence of the transmittance of the reduced forms on wavelength
passes through a maximum at 530 nm (Fig. 11a) and 560 nm
(Fig. 11b, c, d). The oxidized forms exhibit a steep increase in the transmittance up to 600 nm with further gradual increases up to 900 nm. It is
important that the fundamental absorption edge for both reduced and
oxidized lms exhibits a red shift (to lower energy) with the increase
in the lm thickness. The red shift of the absorption edge reects a decrease in the optical band gap and this effect has been attributed to
the increase in the grain size and effective decrease in the imperfections
at the grain-boundary regions [52].
Transmittance variance (T) dened as: T = T(bleached) T(colored)
is used to quantify the electrochromic effect of the prepared thin lms.
For all thin lms the maximum T value is obtained at 900 nm
(Fig. 11). The three thinner lms exhibit close T values of 3237%,
while for the thicker lm having 300 nm thickness T reaches 55%.
For the latter lm the optical response during a prolonged cycling up
to 500 cycles was also examined and the corresponding optical transmittance spectra are included in Fig. 11d. As seen the oxidized state is
completely recovered during the cycling and the transmittance curve
after 500 cycles well matches the initial curve. Some changes occur in
the reduced states between the 5th and 100th cycles resulting in an increase in the transmittance between 400 and 500 nm and shift of the absorption edge to lower wavelengths (high energy) as well as a slight
decrease in the transmittance between 500 and 700 nm. The observed
blue shift of the absorption edge reects a blue shift of the optical
band gap and this shift could be related to the change of the lm microstructure and increase in the imperfections during the lithium intercalation process [53]. Further changes between 100th and 500th cycles are
not observed, so that the reduced state is stabilized which is evident
from the overlap of the corresponding transmittance curves.
Therefore, the data for the optical stability of the thin lm after the
100th cycle in the electrochromic cell are in line with the data for its
electrochemical stability. Between 700 and 900 nm the transmittance
of the reduced forms in all cycles shows the same trend as the initial
scan. It is very important that the T value after 500 cycles is 53% at
900 nm i.e. it retains practically unchanged which is a demonstration
of the good optical stability of as-deposited lms. The comparison
with the literature data for electrochromic vanadium(V) oxide xerogels
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Fig. 11. In-situ optical transmittance spectra of Na0.33V2O5H2O thin lms prepared for different deposition times: (a) 5 min, (b) 10 min, (c) 15 min and (d) 30 min; after 5 cycles in
(a, b, c) and up to 500 cycles in (d).
[47,51,54,55] shows that the obtained results are promising and can
serve as a base for further design of electrochromic devices.
As was mentioned before, the as-deposited yellow/yellow-brown
lms turn greenish tint over time. Fig. 12 shows the change in the optical transmittance over time (up to 20 months) of the best lm with
300 nm thickness. The optical transmittance spectra evidence that
aging does not affect the transmittance in the 350550 nm spectral region. As expected from the greenish shade of the aged lm, however, a
gradual decrease of the lm transmittance at wavelengths longer than
550 nm (i.e. an increased absorption of the red light) is observed as
the transmittance reduction in 20 days aging is about 10% at 900 nm.
It is also seen that the transmittance reduction is most signicant up
to 10th day while the lm structure still stabilizes (about 8%) and after
that it is only about 2%. Further decrease of the transmittance is not recorded even for a prolonged aging of 20 months (Fig. 12). It is very important, however, that when such a lm aged 20 days is placed in the
electrochromic cell (Fig. 12b) it is completely recovered in its oxidized
state and thus T retains its high value (56%).
5. Conclusions
Well-structured nano-sized thin lms with compositions Na0.33V2O5
nH2O (n = 1 and 1.3) are successfully deposited by an optimized chemical bath method where the acidication of NaVO3 solution occurs
through the hydrolysis of diethyl sulfate. The thin lms demonstrate appreciable optical transmittance varying between 40 and 70% at 500 nm in
dependence on the lm thickness. The lm structure and morphology,
electrochemical behavior and electrochromic activity of fresh and aged
thin lms are studied. It is established that the long-term aging of the
lms does not affect their electrochromic properties. The thin lms exhibit maximum transmittance variance (T) at 900 nm which varies between 32 and 55% depending on the lm thickness. The electrochemical
Fig. 12. Optical transmittance spectra of as-deposited thin lm with 300 nm thickness:
(a) over time and (b) brown-greenish lm aged 20 days placed in the electrochromic cell.
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