Electrochimica Acta 193 (2016) 24–31

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Characterization and application of a new pH sensor based on

magnetron sputtered porous WO3 thin films deposited at oblique
angles
Pedro Salazar* , Francisco J. Garcia-Garcia, Francisco Yubero, Jorge Gil-Rostra,
Agustín R. González-Elipe*
Laboratory of Nanotechnology on Surfaces, Institute of Materials Science of Seville (CSIC-Univ. Sevilla), Calle Américo Vespucio 49, 41092 Sevilla, Spain

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

Article history: In this communication we report about an outstanding solid-state pH sensor based on amorphous
Received 17 November 2015 nanocolumnar porous thin film electrodes. Transparent WO3 thin films were deposited by reactive
Received in revised form 5 February 2016 magnetron sputtering in an oblique angle configuration to enhance their porosity onto indium tin oxide
Accepted 8 February 2016
(ITO) and screen printed electrodes (SPE). The potentiometric pH response of the nanoporous WO3-
Available online 9 February 2016
modified ITO electrode revealed a quasi-Nernstian behaviour, i.e. a linear working range from pH 1 to
12 with a slope of about
57.7 mV/pH. pH detection with this electrode was quite reproducible, displayed
Keywords:
excellent anti-interference properties and a high stable response that remained unaltered over at least
WO3
pH
3 months. Finally, a pH sensor was developed using nanoporous WO3-modified screen printed electrode
Magnetron Sputtering (SPE) using a polypyrrole-modified Ag/AgCl electrode as internal reference electrode. This full solid state
GLAD pH sensor presented a Nernstian behaviour with a slope of about
59 mV/pH and offered important
oblique angle deposition analytical and operation advantages for decentralized pH measurements in different applications.
screen printed electrode ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction because they are less sensitive to interferences, mechanically more

With ca. one and a half century of history, ion-selective
electrodes (ISEs) have become an important tool in application
areas such as clinical diagnostics [1], industrial and pharmaceuti-
cal process control [2,3], physiology [4] or environmental
monitoring [5] among others. For example, in clinical trials,
potentiometric sensors replaced the technology of flame photom-
etry, offering rapid, low-cost and accurate analysis at lower prices
[6,7]. Conventional ISEs consist of membrane-based devices where
a perm-selective ion-conducting material separates the sample
from the inside of the electrode containing an ion solution at
constant activity of the target analyte [8]. Although thanks to their
high selectivity, reliance and wide operational pH range, glass
electrodes are widely used, some problems such as a high
impedance, acid and alkaline errors, mechanical fragility and high
temperature instability may limit their use for certain applications
[5,8–11]. Recently, easily miniaturized solid-contact electrodes
based on metals oxides have deserved considerable attention
* Corresponding authors.
E-mail addresses: psalazar@icmse.csic.es (P. Salazar), arge@icmse.csic.es
(A.R. González-Elipe).
robust, less expensive and present a higher thermal stability. These
characteristics make likely a widespread incorporation of this kind
of electrodes in the next generations of ISEs [7]. Metal oxides of, for
example, ruthenium, platinum, iridium, palladium, lead, tin,
tantalum, zirconium, cobalt, rhodium, osmium, titanium or
tungsten have been essayed as pH sensors [12–17]. WO3 is one
of the most promising oxides for this application due to its high
stability, reasonable conductivity and high catalytic activity. In
addition, it also presents very interesting electrochromic proper-
ties [18–20] that make it the material of choice for applications in
fenestration and related industries. The pH sensing capability of
WO3 was already reported in the early twenties [21] and since then
several research studies have utilized this type of electrodes for pH
monitoring. However, the dependence of potential on pH for this
kind of solid-state pH sensor generally presents a non-Nernstian
behaviour with sensitivities ranging from
41 to
53 mV/pH [21–
25], i.e., considerably lower than the theoretical value (
59.1 mV/
pH). An exception to that are the recently works reported by
Fenster et al. [26], Wen et and Wang [27], Lale et al. [28] and Santos
et al. [29] where a sensitivity close to this ideal behaviour is
reported and where it was clear the great interest for optimize the
sensor response in solid state pH sensors.

http://dx.doi.org/10.1016/j.electacta.2016.02.040
0013-4686/ ã 2016 Elsevier Ltd. All rights reserved.
 P. Salazar et al. / Electrochimica Acta 193 (2016) 24–31 25

Herein, we present a novel WO3 nanostructured sensor also referred as glancing angle deposition (GLAD), are known to
consisting of a thin film deposited by magnetron sputtering yield highly porous films formed by separated nanocolumns tilted
(MS) at oblique angles (oblique angle deposition, OAD) onto the with respect to the surface [30]. Besides describing the synthesis
surface of an Indium Tin Oxide (ITO) substrate. OAD conditions, procedure and the characterization of the obtained thin films by a

Fig. 1. High-resolution XPS spectra of W 4f7/2 and W 4f5/2 core-level lines of the tungsten films obtained in the present work: (a) WO3-O and (b) WO3-N.
26 P. Salazar et al. / Electrochimica Acta 193 (2016) 24–31
large variety of thin film techniques, their electrochemical
properties have been studied in detail and results compared with
those obtained with compact thin films obtained by MS in a normal
geometry. In addition, to assess the application possibilities of this
type of sensors, they have been used to determine the pH of real
beverages and samples and their performance compared with that
of a commercial sensor. Finally, nanostructurated WO3 solid
contact pH sensor is also introduced in this work. It was integrated
onto a commercial screen printed electrode, where the Ag
pseudoreference electrode was conveniently modified to give a
stable reference potential during the electrochemical measure-
ments.
2. Experimental
2.1. Thin film preparation
WO3 thin films were prepared by reactive pulsed DC MS using a
50 mm diameter tungsten target. The magnetron was operated
with a power of 100 W and a pulsed voltage of about 550–600 V at a
frequency of 80 kHz. The base pressure of the system was
3  10
6 mbar and the pressure during deposition was fixed at
5  10
3 mbar. The process gas consisted of an O2/Ar mixture dosed
into the chamber in a mass flow ratio of 0.1. Silicon plates and ITO
electrodes (electrode area 2 cm2) were used as substrates to carry
out different characterization studies as indicated in the text. The
angle between the target, in a horizontal and upper position, and
the substrate was 80 (i.e., OAD conditions) and the distance
between the centre of the target and the substrates was 10 cm. A
more detailed description of the deposition procedure can be
found in [18,20]. These samples will be designated in the text as
WO3-O. For comparison, compact WO3 thin films were also
prepared by placing the substrate parallel to the MS target. These
samples will be designated as WO3-N.
WO3 thin films were deposited onto gold screen printed
electrode (SPE) (C220AT, DropSens) using a similar deposition
protocol. To avoid the deposition of the WO3 film onto the Ag
pseudoreference electrode and connexions, a mask consisting of a
soft tape, was placed over the entire electrode except the working
area.
2.2. Thin film characterization
The microstructure of the films was examined by scanning
electron microscopy using a Hitachi S4800 field emission
microscope. X-ray photoelectron spectroscopy measurements
were carried out with a Phoibos 100 spectrometer using the pass
energy constant mode and the Mg Ka as excitation source. The
binding energy (BE) scale of the spectra was referenced to the C1s
line of adventitious carbon at 284.6 eV. X-ray diffraction spectra in
a grazing angle configuration were acquired using a Panalytical
X'PERT PRO diffractometer. A rough estimation of the density of the
porous WO3-O layers was done by calculating their refraction
index by UV–vis absorption spectroscopy and comparing this value
with that determined for the compact WO3 film [31].
2.3. Electrochemical tests
All chemicals employed in this study were of analytical grade
and solutions were prepared using ultrapure water (Millipore
Direct-Q system, >18 MV cm). Commercial buffer solutions such as
borax/sodium hydroxide (pH 10), phosphate (pH 7) and acetate
buffer solutions (pH 5.12) were obtained from Sigma. Other
commercial buffer solutions (pH: 4 and 9) were obtained from
Crison. In order to obtain different pH values commercial buffer
solutions were adjusted to the desired pH value by adding either
sodium hydroxide (NaOH) or hydrochloric acid (HCl) solutions.
Prior to each electrochemical measurement, the pH of each
solution was tested using a pH-meter (CRISON GLP 21).
Cyclic voltammetry (CV) was performed in a three-electrode
glass cell, with a commercial Ag/AgCl (3 M) reference electrode, a
platinum counter electrode and ITO deposited specimens of
1.5 cm2 working area. Open-circuit potential (OCP) measurements
were made by room temperature immersion of specimens in
buffer solutions. All electrochemical measurements were moni-
tored and controlled by a mStat400 potentiostat (DropSens, Spain).
2.4. Electrochemical modification of the Ag pseudoreference electrode
under screen printed approach
In order to obtain a stable reference potential in OCP
measurements the Ag pseudoreference electrode, supported on
the SPE, was conveniently modified according to the next protocol.
Thus and after the deposition of the WO3 layer, a Ag/AgCl layer was
deposited onto the Ag pseudoelectrode using CV. The final
prodecure for the fabrication of the home-made Ag/AgCl/PPy
reference electrode is described below:
First step, chlorination of the Ag reference electrode: a
conventional electrochemical cell was used were the Ag pseu-
doelectrode was used as the working electrode and a commercial
Ag/AgCl (3 M KCl) and a Pt wire were used as reference and counter
electrodes respectively. The full electrochemical cell was im-
mersed in 0.1 M HCl and cycled 20 times to deposit the Ag/AgCl
layer (scan rate: 50 mV s
1, range: 0–1 V) on the Ag pseudorefer-
ence electrode.
Second step, deposition of the polypyrrole film (under CV
approach): the three electrodes (similar than in the previous step)
were connected to the potentiostat and immersed in a 0.1 M
pyrrole solution implemented with 0.1 M KCl, while sweeping the
potential from
0.6 to 1.2 V at a 50 mV s
1 during 25 cycles. During
this step the commercial Ag/AgCl (3 M) reference electrode was
bridged with a saline bridge (1 M KCl).
3. Results and discussions
3.1. Chemistry and microstructure of thin film electrodes
Both WO3 thin films (WO3-O and WO3-N) were amorphous
when examined by X-ray diffraction (not shown). The films were
colorless, as expected taking into account the conditions chosen for
the deposition of the films. In other words, tungsten atoms in the
films were fully oxidized [18,20]. This is further confirmed by XPS.
The corresponding W 4f XPS spectra for both films are shown in
Fig. 1. The spectra are characterized by two pronounced spin-orbit
split peaks at 35.85 eV (W 4f7/2) and 38.0 eV (W 4f5/2) typical of the
W6+ state [18].
The microstructure of sample WO3-O depicted in Fig. 2a and
consisting of a porous layer formed by 25 tilted nanocolumns with
large pores among them was typical of OAD thin films [32–36] and
a layer thickness of ca. 700 nm. An estimation by optical methods
of the pore volume of these films yields an approximate value of
36% [20,33]. Meanwhile, SEM images obtained for the WO3-N
electrodes show a highly compact microstructure (Fig. 2b) and a
lower surface roughness (Fig. 2b, inset) than for the WO3-O thin
films.
3.2. Electrochemical behavior of WO3-O-modified ITO electrodes and
potentiometric pH detection
The amorphous character of the WO3-O and WO3-N thin films
prepared by MS accounts well for the shape of the voltammogram
(Fig. 3a) and are very similar to equivalent voltammograms
 P. Salazar et al. / Electrochimica Acta 193 (2016) 24–31 27

where E is the measured potential, E is the standard potential

(potential when a(H+) = 1), R is the gas constant (8.314 J K
1 mol
1),
T is the temperature (K), z is the signed ionic charge and F is the
Faraday constant (96487.34C mol
1). At room temperature
(T = 298 K) eq. (2) would read:
E = E
59.1 pH (3)
Meaning that the pH variation of the measured potential for an
ideal WO3 electrode should be characterized by a lineal depen-
dence and a slope equal to
59.1 mV/pH units (Eq. (3)).
Fig. 3b shows the potential dependence on pH of the WO3-O-
modified ITO electrode registered under OCP conditions for the pH
varying from 1 to 12. The obtained pH response presents a linear
dependence over the full range of studied pH showing a quasi-
Nernstian behaviour with a slope of about
57.7 mV/pH, i.e.,
almost identical to the theoretical value expected from eq. (3). For
a comparative assessment of the two electrodes, the WO3-N
sample displayed a sensitivity of
56.8 mV/pH. To our knowledge,
these sensitivities are considerably higher than the majority of
values previously reported for other WO3 electrode systems
[21–25].
In general, these deviations from the theoretical values have
been attributed to the distinct morphologies, composition and
structures of the respective oxide films [25]. In this regard,
Drensler et al. reported that in crystalline and compact tungsten
oxide materials the local structure at the surface determines the

Fig. 2. (a); SEM cross-section and top-view (inset) images of a tungsten oxide thin
film grown on a silicon wafer for (a) WO3-O and (b) WO3-N samples.

recorded for amorphous WO3 films evaporated onto unheated

substrates as previously reported in the literature [37]. The
monitored changes in the oxidationstate of tungsten during cycling
can be described by the reversible reaction [20]:
WO3 + xH+ + xe
, HxWO3 (0 < x < 1) (1)
According to it, the pH dependence on voltage in WO3 electrodes
is linked to the intercalation and deintercalation of H+ ions into the
oxide layer [26]. A reaction similar to that schematized in Eq. (1) is
responsible for the electrochromism of tungsten oxide [18,20]. The
easy intercalation of protons within the lattice of a WO3 structure
agrees with the existence of stoichiometric and crystalline phases of
this oxide with protons intercalated in their structure. For example,
the HWO3 compound, corresponding to x = 1, is a crystalline material
characterized by a perovskite structure. Meanwhile, defective
perovskites characterized by an open structure and high proton
conductivity appear when x < 1, while a distorted ReO3-type
structure [21,26] occurs for x = 0.
According to eq. 1 for x = 1 and the model proposed by Fog and
Buck [13] for a single phase interaction [25], the electrode potential
can be described according to the following modified Nernst
equation (Eq. (2)):
RT aðHWO3 Þ RT aðHWO3 Þ RT 1
E ¼ E
In
¼ E
In
In

zF aðWO3 Þa Hþ zF aðWO3 Þ zF a Hþ
Fig. 3. (a) Cyclic voltammogram obtained for the WO3-O/ITO electrode in 0.1 M
2:303RT HClO4 at 0.1 V s
1 (b) pH response curve of the WO3-O-modified ITO electrode in the
¼ E0
pH ð2Þ
zF 1–12 pH range.
28 P. Salazar et al. / Electrochimica Acta 193 (2016) 24–31
operational pH-range and the actual sensitivity of the system [21].
This phase dependence is related with lattice space constrains,
especially in the monoclinic phase of WO3 where, unlike the
perovskite type phases mentioned above, H+ can hardly be
intercalated [21]. It is likely that the amorphous character of
WO3-O electrodes prepared by MS imposes lower lattice limi-
tations to proton intercalation, thus rendering a better pH response
and higher operational ranges than using crystalline materials.
This agrees with data for amorphous tungsten oxide electrodes
characterized by much larger diffusion constants (DHþ Þ than those
typical in crystalline bulk materials [38,39].
3.2.1. Performance of WO3-O-modified ITO electrodes as pH sensors
Beyond their electrochemical response under well controlled
conditions, practical electrodes should depict additional character-
istics to be considered reliable pH sensors. This encompasses a
good repeatability and reproducibility, a minimum hysteresis,
constancy in the measurement, absence of interferences and
stability over long periods of time. All these characteristics have
been investigated here to prove the reliability as pH sensor of WO3
thin films prepare by MS.
To assess the repeatability and reproducibility of results with
the WO3 electrodes each sensor measurement was carried out five
times with three different sensors prepared and tested under
similar conditions. In all cases we found similar results for all
studied pH, while relative standard deviation (RSD) values for
repeatability and reproducibility of about 2.2% and 3.8%, respec-
tively, were determined from these series of tests. No significant
Fig. 4. Hysteresis width of the WO3-O-modified electrode when the pH-value
changes for several times in the range, 7–10 (a), 4–7 (b) and 4–10 (c).
differences were found when comparing WO3-O and WO3-N
electrodes.
According to some authors memory effect phenomena in
potentiometric electrodes renders a delay of the pH sensor
response [17,40]. To check this point in our electrodes, the
hysteresis behavior of the WO3-O sensors was evaluated by
alternating the measurement of the potential under OCP con-
ditions using different commercial buffers (pH = 4, 7 and 10). For
this study, pH sensors were dipped in different buffer solutions
following the sequence shown in Fig. 4 and the OCP potential
measured after ca. 100 s, when the sensor response reached the
steady state.
The hysteresis values for the WO3-O sensor deduced from the
curves in Fig. 4 in the 7–10 and 4–7 pH ranges were 2.4 and 3.5 mV,
respectively (Fig. 4a and 4b), while a higher hysteresis of ca.
10.5 mV was obtained in the 4–10 range (Fig. 4c). All these values
assure the reliability of the measurement procedure according to
the literature on the subject [17,25].
The sensor stability during continuous pH monitoring was
determined during a time window of 2 hours. Fig. 5 shows that the
OCP response at pH 5.12 and 10 had total small changes of 6 and
4 mV, respectively, that is, a drift of ca. 2.5 mV/h or 0.04 pH units/h.
The selectivity (Kij) of the WO3-O-modified ITO electrode
prepared by OAD was established by studying the effect of some
common ions (Li+, Na+, K+ and NH4+) on the potentiometric
response. For this analysis we used the Two Separated Method
(TSM) recommended by IUPAC [17,25], whereby the OCP of a cell
comprising an ion-selective electrode and a reference electrode is
measured for two separated solutions, one containing the ion i of
the activity ai (but no j), and the other one containing the ion j at
the same activity, ai = aj, (but no i). Therefore the selectivity was
determinate according to equation (4):


ai exp zj F DRET
1
K i;j ¼ ð4Þ
ðaj Þzi =zj
this expression utilizes the single potential measurement for the
primary ion (i) and for various interference ions (j) taken
individually. Therefore ai and aj are the activities for the primary
and the interference ions respectively, and zi and zj correspond to
the associated ionic charges for the primary and interference
species.
In this study for primary (H+) and interference (Li+, Na+, K+ and
NH4+) ions the concentration selected was 0.1 mol L
1, in agree-
ment with previous studies on similar systems [17,25]. The values
Fig. 5. OCP potential measured in acetate (pH 5.12) and borax/NaOH (pH 10) buffer
during 2 hours under unstirred condition and at room temperature.
 P. Salazar et al. / Electrochimica Acta 193 (2016) 24–31
Table 1
Ion selective coefficients of the WO3-O-modified ITO electrode.
Interfering ion Concentration (mol L
1)
Li+ 0.1
Na+ 0.1
K+ 0.1
NH4+ 0.1
of log Kij determined for the interferences essayed in this study
presented a value close to 10, thus proving that interference effects
on pH by the most common ions (Li+, Na+, K+ and NH4+) is negligible
(Table 1).
The sensors stability was determined over a long period
(3 months) of time, during which they were stored in dry
conditions at room temperature. After this period of time, the
WO3-O sensor showed a sensitivity of
56.81 1.55 mV/pH
(mean  SD, n = 4), a result clearly sustaining an excellent stability
over this period of time. Unlike this optimum behavior, the WO3-N
electrode presented a sensitivity value of
28.87  2.37 mV/pH
after its storage under similar conditions. This means that although
the compact and porous electrodes investigated here present a
similar pH dependence, the WO3-O electrode was superior when
intended for long lasting applications because it maintained an
unaltered performance even after three months, a period after
which the WO3-N electrode experienced a significant decrease in
sensitivity.
3.2.2. Measurements with real samples
Various real samples such as mineral and tap water, apple juice
and a Cola drink were used to test our WO3-O-modified ITO
electrodes in comparison with the values determined with a pH-
meter equipped with a commercial glass electrode. The good
agreement obtained with the two systems (Table 2) sustained the
good prospects of the nanostructured tungsten oxide electrodes
prepared by OAD for real test applications.
3.2.3. Development of a pH sensor integrated on a screen printed
electrode
In this section we introduce, as a proof of concept, a full solid
state pH sensor. Future works will have to be carried oyt to prove
the reliability and utility of our tungsten film in this kind of sensors
for automatic measurements in industrial and environmental
applications.
A full solid state pH sensor requires that both, the pH-sensitive
sensor and the reference electrode are integrated in a full
electrochemical cell. To this end, herein we introduce a new
configuration where the two electrodes are integrated in a single
chip. In previous sections we studied and discussed the pH-
response of the WO3-O film obtained under GLAD/OAD approach a
commercial Ag/AgCl (3 M) reference electrode during OCP
measurements. In the present section wedevelop the other
electrochemical component needed in potentiometry, the reference
electrode (RE). During recent decades much effort has been made to
miniaturize the RE to facilitate its coupling with solid-state sensors
lab-on-a-chip applications. Among different references electrodes,
Table 2
Determined pH of various real samples [mean (SD)] n = 3 with the WO3-O-modified ITO electrode.
Sample
Tap water
Commercial water
Apple juice
Cola soda
Commercial buffer (pH = 10)
29
Ag/AgCl is so far the most common type of RE used, mainly due to
the simplicity of construction, great stability and security.
Log Kij Therefore, the ideal reference electrode provides a stable and

9.53 known potential, so that any change in OCP can be attributed to the

9.46 effect of proton activity on the potential of the pH-sensitive

9.33 electrode. Nevertheless, to obtain theses basics requirements the

9.40
Ag pseudoreference electrode supported on the commercial SPE
needs to be modified according experimental section (Section 2.4).
Due to the new design of the experimental setup (deposition of
the WO3-O film on a gold transducer), the pH response of the pH
sensor was evaluated again. Fig. 6a displays the OCP measurement
of the tungsten-modified SPE against a commercial Ag/AgCl (3 M)
reference electrode. Sensitivity presented a Nernstian behavior
with a sensitivity of ca. 59 mV/pH and confirmed the excellent
properties of the film. The better sensitivity obtained under the
present approach may be justified due to the better electrochemi-
cal properties of the gold transducer against the ITO electrode.
After checking the sensor response the need of modiying the
internal Ag reference electrode were evaluated. To this end two
different approaches was used, first the Ag pseudoreference
electrode was chlorinated, and then it was stabilize with a
polypyrrole (PPY) film (see Section 2.4). The formation of the Ag/
AgCl layer was obtained using CV. After this step a black deposit
was cleary observed on the surface of the electrode confirming the
successful deposition of the AgCl layer. Then, a PPY layer was
electrodeposited using CV to improve the performance of the
reference electrode.
Fig. 6b displays the OCP measurements for the different
reference electrodes proposed here against a commercial Ag/AgCl
(3 M) reference electrode in different buffer solutions. These
results showed that the Ag pseudoreference electrode presented a
high response against pH (ca.
35 mV/pH) and that this sensitivity
substantially decreased to 2 mV/pH in the final configuration (Ag/
AgCl/PPY). This value is lower than previously reported values in
literature for similar configurations (5 mV/pH)[41].
Fig. 6c displays the pH response of the WO3-O-modified SPE
using different reference electrodes. Our data reveal that pH
sensitivity is significantly improvedthrough the different RE
modifications to reach a Nernstian behavior in the final configura-
tion (Ag/AgCl/PPY). The pH response of the proposed full-solid
state pH sensor was evaluated in a wider pH range (Fig. 6d) and an
excellent sensitivity of about
58.42 mV/pH was then obtained.
These results are the consequence of the excellent pH sensing
properties of the WO3-O layer and the excellent bahavior of the
modified pseudoreference electrode, both of them integrated in a
solid-state electrode capable of robust pH measurements. Addi-
tionally, the sensor stability showed a drift of ca. 3 mV/h, quite
similar to the value reported above for a commercial Ag/AgCl (3 M)
reference electrode and those previously reported in literature for
similar approaches [41].
It should be mentioned that measurement interferences due to
chloride might be appear because the Ag/AgCl electrodes can be
sensitive to Cl
ions. Our analysis showed that in all configurations
this effect was neligible at low chloride concentrations, although it
was slightly greater in the 10–100 mmol L
1 range when it reached
pH WO3-modified ITO electrode pH glass electrode
7.55 (0.03) 7.53 (0.04)
7.68(0.05) 7.72 (0.03)
3.51 (0.04) 3.54 (0.02)
2.52 (0.06) 2.53 (0.02)
9.96 (0.03) 9.98(0.01)
30 P. Salazar et al. / Electrochimica Acta 193 (2016) 24–31

Fig. 6. (a) OCP potential for WO3-O-modified screen printed electrode (SPE) at different pH using a commercial Ag/AgCl (3 M) reference electrode. (b) OCP potential for
different internal Reference Electrodes (RE) using a commercial Ag/AgCl (3 M) reference electrode at different pH values. (c) OCP potential for WO3-O-modified SPE using
different internal reference electrodes (RE). (d) OCP potential for WO3-O-modified SPE measured using Ag/AgCl/PPY as internal reference electrodes.

a value ca. 25 mV/pCl for the Ag/AgCl/PPY configuration. Additional
improvements are planned to get rid of these interference at high
chloride concentrations.
4. Conclusions
In the present work we have developed a novel nanostruc-
tured tungsten oxide electrode deposited by reactive magnetron
sputtering at oblique angles. The sensor, with a thickness ca.
700 nm, presented a quasi-Nernstian response with a sensitivity
of ca.
57.7 mV/pH over a pH range comprised between 1 and 12.
This sensitivity is higher than the value reported by other
authors for similar electrodes. We argued that the amorphous
structure and high porosity of the films contribute to this
enhancement in sensitivity in contrast with previous works with
crystalline electrodes where H+ may be intercalated only to a
limited extension. The high reproducibility and repeatability of
the measurements and the short response times support the use
of the synthesized WO3 thin films as pH electrodes. The
satisfactory good response against some common interference
ions and the feasibility of application for real samples proved the
high potential of these materials as a robust and reliable
electrode for many applications. Finally, and as a proof of concept,
a full-solid state pH sensor based on commercial SPEs has been
developed modifying a Ag pseudoreference electrode that was
conveniently adapted for the special requirement needed in
potentiometry measurements. This sensor presented an excellent
results with a pH response of ca. 59 mV/pH.
Acknowledgement
The funds for the development of the present work have been
provided by the MINECO(projects RECUPERA 2020 together with
the “Fondo social Europeo”, MAT2013-40852-R and MAT2013-
42900-P) and the Junta de Andalucía(TEP 8067 and FQM 6900).
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