materials

Article
SAW Hydrogen Sensors with Pd/SnO2 Layers
Izabela Constantinoiu 1,2 , Dana Miu 1 and Cristian Viespe 1, *

1 Laser Department, National Institute for Laser, Plasma and Radiation Physics, Atomistilor 409,
RO-077125 Magurele, Romania
2 Faculty of Chemical Engineering and Biotechnologies, University Politehnica of Bucharest,
RO-011061 Bucharest, Romania
* Correspondence: cristian.viespe@inflpr.ro

Abstract: Pd/SnO2 bilayers for surface acoustic wave (SAW) sensors were obtained using pulsed laser
deposition (PLD). Bilayers were made at several deposition pressures in order to observe the influence
of the morphology of the sensitive films on the response of the sensors. The morphological properties
were analyzed by scanning electron microscopy (SEM). The SnO2 monolayers were initially deposited
on quartz substrates at 100, 400 and 700 mTorr, to observe their morphology at these pressures. The
Pd/SnO2 bilayer depositions were made at 100 and 700 mTorr. The sensors realized with these
sensitive films were tested at different hydrogen concentrations, in the range of 0.2–2%, at room
temperature. In order to establish selectivity, tests for hydrogen, nitrogen, oxygen and carbon dioxide
were carried out with SnO2 -700, Pd-100/SnO2 -700 and Pd-700/SnO2 -700 sensors. The sensor with
the most porous sensitive film (both films deposited at 700 mTorr) had the best results: a sensitivity of
0.21 Hz/ppm and a limit of detection (LOD) of 142 ppm. The morphology of the SnO2 film is the one
that has the major influence on the sensor results, to the detriment of the Pd morphology. The use of
Pd as a catalyst for hydrogen improved the sensitivity of the film considerably and the selectivity of
the sensors for hydrogen.

Keywords: pulsed laser deposition (PLD); surface acoustic wave (SAW); Pd; SnO2 ; bilayer; hydrogen;
Citation: Constantinoiu, I.; Miu, D.; thin film; gas sensor; porous morphology
Viespe, C. SAW Hydrogen Sensors
with Pd/SnO2 Layers. Materials 2022,
15, 8012. https://doi.org/10.3390/
ma15228012 1. Introduction
Academic Editor: Marina Hydrogen is considered a viable alternative for replacing fossil fuels, which have harm-
N. Rumyantseva ful effects on the environment [1]. However, for hydrogen applications in the automotive
field and beyond, it is necessary to take safety measures, since at concentrations over 4% it
Received: 12 October 2022
becomes flammable and explosive [1,2]. Hydrogen is an odorless and colorless gas, which
Accepted: 11 November 2022
makes it difficult to detect [2–4]. Also, hydrogen gas leaks easily, its inflammability being
Published: 13 November 2022
explained by its ultra-small molecule size and high chemical activity [3]. Consequently, the
Publisher’s Note: MDPI stays neutral control of hydrogen concentration in the installations that use it, as well as in surrounding
with regard to jurisdictional claims in areas, is an important aspect for its integration as a fuel. There is a need for devices such as
published maps and institutional affil- sensors, which can monitor the concentration of hydrogen where it is likely to accumulate,
iations. keeping its concentration as low as possible and thus avoiding dangerous incidents [5].
A wide range of sensors for hydrogen detection have been developed to date: resistive,
conductometric, chemoresistive, metal-oxide semiconductor, surface acoustic wave (SAW)
sensors, etc. [6–10]. Each of these types of sensor has advantages and disadvantages that
Copyright: © 2022 by the authors.
influence important parameters such as sensitivity, limit of detection (LOD) and response
Licensee MDPI, Basel, Switzerland.
This article is an open access article
time, as well as costs of production and consumption.
distributed under the terms and
Surface acoustic wave sensors stand out due to their good sensitivity, satisfactory
conditions of the Creative Commons stability, possibility of wireless operation, ease of manufacture and small size [3,11,12]. They
Attribution (CC BY) license (https:// were developed both for hydrogen and for other gases such as volatile organic compounds,
creativecommons.org/licenses/by/ ammonia and other toxic and explosive substances [11,13,14]. A SAW sensor consists in
4.0/). a piezoelectric substrate, two pairs of interdigital transducers, and a sensitive film placed

Materials 2022, 15, 8012. https://doi.org/10.3390/ma15228012 https://www.mdpi.com/journal/materials

Materials 2022, 15, 8012 2 of 12

between the interdigital transducers [5,15]. Their operating principle is based on converting
an electrical input into mechanical waves, which propagate over the sensitive film surface,
and are subsequently converted back into an electrical signal. In the presence of the analyte
at the surface of the sensitive film, a shift in the frequency of the waves occurs, due mainly
to mass accumulations or acoustoelectric interactions. Thus, the nature and the type of
sensitive film are very important aspects in the design of a SAW sensor for a certain type of
gas [5,15].
Semiconductor metal oxides are widely used in sensors, including hydrogen sensors.
Among the advantages they present in this domain are high sensitivity due to the wide
bandgap, the possibility of miniaturization, reliability and ease of processing into sensor
devices [16]. ZnO, TiO2 , SnO2 , WO3 , In2 O3 , are some of the semiconductor oxides with
very good sensing properties [16–18].
SnO2 is well known for its sensing properties, making it one of the most used oxides
in this field [19]. This results from the fact that it is an n-type wide band-gap semiconductor
(Eg = 3.6 eV at 300 K), with excellent electrical properties and chemical stability [17,20].
Some of the disadvantages of SnO2 are the difficulty of room-temperature detection, and
the lack of selectivity, since it has very good sensitivity to a wide range of materials [2,19].
One of the methods used to obtain results with a SnO2 sensor at the lowest possible
concentrations is to heat the sensor and use the temperature as an energy source to increase
the interaction between the film and the analyte [21]. However, this method requires a heat
source. In addition, detecting hydrogen at high temperatures becomes dangerous, since it
can trigger an explosion at high hydrogen concentrations. Considering previous experience
in the development of sensitive materials for hydrogen detection and other results from
the literature, we found that optimizing the morphology of sensitive films for sensors (in
this case, SAW sensors), leads to obtaining sensors capable of detecting hydrogen at room
temperature [20,22,23]. This method is based on the principle of increasing the interaction
surface between the analyte and the sensitive layer [19,20]. The larger the interaction
surface, the lower the LOD and the shorter the response time [2,24].
The very low selectivity of SnO2 can be compensated by combining it with a selective
material [2]. In the case of hydrogen detection, it is known that metals such as Pd or Pt have
catalytic properties for hydrogen [25–29]. Thus, in their presence, the hydrogen molecule is
dissociated and its subsequent penetration into the volume of the film is favored [16,30].
One morphology suitable for obtaining good sensitivity is the porous one [2,31,32].
Pulsed laser ablation (PLD) is a deposition method allowing good control of the mor-
phology of the deposited film [22,33]. Pulsed laser ablation permits the control of many
deposition parameters: deposition pressure, laser wavelength and power, pulse repetition
rate, substrate temperature, target-substrate distance, etc. [33,34]. Among the other advan-
tages of this method are maintaining the target stoichiometry in the deposited film, the
possibility of making deposits from a large category of materials and at low temperatures,
ensuring purity and good film adhesion [35–37]. Taking these considerations into account,
PLD becomes a suitable method for developing hydrogen SAW sensors with optimal
porous morphology.
In previous work, we developed SAW sensors for hydrogen using PLD with different
types of sensitive materials: ZnO, TiO2 , WO3 , Pd [18,22,23]. All these sensors were tested
with good results at room temperature. It could be observed that in order to obtain
sensibility for hydrogen, Pd/oxide (ZnO, TiO2 , WO3 ) bilayer sensors have much better
sensitivity and detection limits than sensors with monolayer oxide film. This improvement
comes from the use of Pd as a catalyst layer for hydrogen molecules. We also observed
that the porous morphology of the sensitive film improves the response of the sensors,
offering better sensitivity and a shorter response time, based on the previously discussed
principle [18,22,23]. Based on the above-mentioned results, and on the very good sensor
properties of SnO2 presented in the literature, we proposed to develop SAW sensors for
hydrogen with a bilayer structure of Pd and SnO2 .
Materials 2022, 15, 8012 3 of 12

The present paper presents research on the behavior of SnO2 and Pd in different
PLD deposition conditions, and the influence of these conditions on SAW sensor results
in hydrogen detection. The contribution of Pd to the improvement of the sensibility and
selectivity of the SAW sensors at different gas concentrations was also investigated.

2. Materials and Methods

2.1. Film Deposition and Characterization
The sensitive films were deposited using the PLD method. A Nd-YVO4 laser was
used, at stable parameters of 10 ps pulse duration, 0.2 W laser power and a repetition rate
of 10 kHz.
In order to study the effect of various parameters on the morphology of the sensitive
film, the depositions were initially made onto quartz substrates (without interdigital trans-
ducers). Commercial SnO2 and Pd targets were used (Goodfellow, Huntingdon, UK), which
were placed on computer-controlled x-y tables whose movement avoided target erosion.
The substrates were placed parallel to the target, at a distance of 4 cm; the depositions
were made at room temperature. The sensor substrate was positioned in a special mask,
in order to limit the film deposition to the area between the interdigital transducers, and
protect them from the deposition process. The depositions were carried out in two types
of gas: oxygen for SnO2 , and argon for Pd. Their pressure and flow were controlled by
means of a system attached to the PLD deposition chamber. A throttle valve (MKS 253B)
controlled by a pressure controller (MKS 600) mounted on a preliminary vacuum pump
(Agilent Varian—DS602, Leini, Italy) adjusts the deposition pressure, and a mass-flow
control system (MKS multigas 647, Munchen, Germany) controls the flow from the gas
cylinders. The sensors and the deposition conditions are given in Table 1. The morphology
of the films was analyzed by scanning electron microscopy (SEM) using a FEI QUANTA
microscope (Hillsboro, OR, USA).

Table 1. The sensors and the thin film deposition characteristics.

Composition of the Deposition Pressure (mTorr)

Sensor
Sensitive Layer O2 Ar
SnO2 -100 100 -
SnO2
SnO2 -700 700 -
Pd-100/SnO2 -100 100 100
Pd-100/SnO2 -700 700 100
Pd/SnO2
Pd-700/SnO2 -100 100 700
Pd-700/SnO2 -700 700 700

2.2. Sensor Structure and Testing

A ST-X quartz substrate was used for the SAW sensor, with a parallelogram geometry,
in order to reduce unwanted reflections. There are several types of piezoelectric materials
used for SAW sensors, but one advantage of the quartz substrate is its relatively low
temperature coefficient in comparison to other piezoelectric materials [15]. The dimensions
of the piezoelectric quartz are: 38 mm long, 10 mm wide and 0.5 mm thick. The SAW sensor
is a delay-line type with the gold interdigital transducers in a double-comb configuration
fabricated by photolithography. The oscillation frequency of the SAW sensors is about
69 MHz. The entire test system is presented in Figure 1. The oscillating system consists
in a DHPVA amplifier (MessTechnik GmbH, Berlin, Germany) connected to a CNT-91
Pendulum frequency counter (Spectracom Corp, Rochester, NY, USA). The SAW sensors
were tested at gas concentrations between 0.2% and 2%. For testing, we used a system
consisting of gas cylinders, one with 100% artificial air, and the others with carbon dioxide
(CO2 ), nitrogen (N2 ), oxygen (O2 ) and 2% H2 in synthetic air. The gas concentration in
the test chamber was controlled with two mass flow meters connected to a mass flow
controller. Throughout the experiments, the gas flow from the cylinders was maintained
Materials 2022, 15, x FOR PEER REVIEW 4 of 12

used a system consisting of gas cylinders, one with 100% artificial air, and the others with
Materials 2022, 15, 8012
carbon dioxide (CO2), nitrogen (N2), oxygen (O2) and 2% H2 in synthetic air. The4 of 12
gas
concentration in the test chamber was controlled with two mass flow meters connected to
a mass flow controller. Throughout the experiments, the gas flow from the cylinders was
at a value ofat0.5
maintained L/min.
a value ofThe tests were
0.5 L/min. Theinitially carried
tests were out at
initially room out
carried temperature, but tests
at room tempera-
were but
ture, also tests
carried
wereoutalso
at different
carried temperatures of the
out at different sensors. Theoftemperature
temperatures the sensors.was Thevaried
tem-
in the range
perature 20–60 ◦inC.the
wasofvaried Therange
test system consisted
of 20–60 °C. Theintest
a Peltier
system element (70 W),
consisted in abidirectional
Peltier ele-
thermoelectric
ment controller (TEC-1089-SV),
(70 W), bidirectional thermoelectric temperature
controller sensor for support
(TEC-1089-SV), (Pt100), computer,
temperature sensor
software interface, voltage source. This assembly allows the sensor temperature
for support (Pt100), computer, software interface, voltage source. This assembly allows to be
controlled with a precision greater than 0.01 ◦ C.
the sensor temperature to be controlled with a precision greater than 0.01 °C.

Figure 1.
Figure Experimental setup
1. Experimental setup for
for SAW
SAW sensor measurements.

3. Results
3. Results and
and Discussion
Discussion
3.1. Film
3.1. Film Morphology
Morphology
Initially, the
Initially, the SnO2
SnO2 and
and Pd
Pd monolayer
monolayer films
films were
were analyzed
analyzed through
through SEM
SEM images.
images. The
The
variation of
variation of the
the gas
gas pressure
pressure (100,
(100, 400
400 and
and 700
700 mTorr)
mTorr) during
during the
the PLD
PLD deposition
deposition of
of the
the
SnO2 thin films for 2 h led to different film morphologies. The SEM images in Figure 22
SnO 2 thin films for 2 h led to different film morphologies. The SEM images in Figure
show the
show the results
resultsofofthe
thevariation
variationofof
deposition
depositiongasgas
pressure on the
pressure on SnO 2 layer.
the SnO The increase
2 layer. The in-
in the degree of porosity with the increase in the deposition pressure can be observed. At
crease in the degree of porosity with the increase in the deposition pressure can be ob-
the pressure of 100 mTorr (Figure 2a,b), the film is denser and presents granules of different
served. At the pressure of 100 mTorr (Figure 2a,b), the film is denser and presents gran-
shapes and sizes on the surface; however, these can induce a high level of noise in the
ules of different shapes and sizes on the surface; however, these can induce a high level of
sensors. Increasing the pressure to 400 mTorr (Figure 2c,d), the granules become smaller
noise in the sensors. Increasing the pressure to 400 mTorr (Figure 2c,d), the granules be-
and are more numerous. When the gas pressure is higher, the interactions between the
come smaller and are more numerous. When the gas pressure is higher, the interactions
species in the plasma and the gas molecules are more pronounced. In these conditions,
between the species in the plasma and the gas molecules are more pronounced. In these
increased gas-phase nucleation occurs in the region between the target and the substrate.
conditions, increased gas-phase nucleation occurs in the region between the target and
Increasing the pressure up to 700 mTorr, the morphology becomes much more porous,
the substrate. Increasing the pressure up to 700 mTorr, the morphology becomes much
which is visible even at low magnifications of the SEM images (Figure 2e). It consists
of spherical granules with dimensions of tens to hundreds of nm. A sensor with such
morphology is expected to have the best results. The explanation is related to the fact
that the more porous morphology implies a larger specific surface, therefore a larger
surface of interaction between the analyte molecules and the sensitive film [2–24]. Thus,
 Materials 2022, 15, x FOR PEER REVIEW
more porous, which is visible even at low magnifications of the SEM images 5 of(Figure
12 2e
It consists of spherical granules with dimensions of tens to hundreds of nm. A senso
with such morphology is expected to have the best results. The explanation is related t
morefact
the porous,
that which is visible
the more evenmorphology
porous at low magnifications
implies of the SEM
a larger images surface,
specific (Figure 2e).
therefore
It consists of spherical granules with dimensions of tens to hundreds of nm. A sensor
Materials 2022, 15, 8012 larger surface of interaction between the analyte molecules and the sensitive 5 offilm
12 [2–24
with such morphology is expected to have the best results. The explanation is related to
Thus, detection can be performed at lower concentrations, with a shorter response tim
the fact that the more porous morphology implies a larger specific surface, therefore a
and
largeratsurface
room temperature.
of interaction between the analyte molecules and the sensitive film [2–24].
detection can be can
Thus, detection performed at lower
be performed atconcentrations, with a with
lower concentrations, shorter response
a shorter time and
response at
time
room temperature.
and at room temperature.

Figure
Figure2.2.2. SEMimages
SEM images of
ofSnOSnO
SnO 2 films
2 films deposited
deposited at different
at different gas pressures.
gas pressures.
Figure SEM images of 2 films deposited at different gas pressures.

Thehigh
The
The high
high porosity
porosity
porosity of
the the
of film
of the filmfilm deposited
deposited
deposited at at 700at
700 mTorr 700 mTorr
mTorr is by
is confirmed is cross-section
confirmed
the confirmed
by the by th
cross-section
cross-section
SEM SEM
SEMimage
image in Figure 3.image
From inthe
Figure
in Figure3. From the
3. From
measurements mademeasurements
the made
on measurements
several SEM on several
made
cross-section on SEM
several SEM
images,
cross-section
cross-section images,
images,the average
the averagethickness of
thicknessthe
ofSnO
the2 film deposited at 700 mTorr ox-
SnO film deposited
the average thickness of the SnO2 film deposited at 700 mTorr oxygen was approximately
2 at 700 mTorr ox
ygen
ygen
1400 was approximately 1400
was approximately 1400 nm.
nm. nm.

Figure 3. Cross-section SEM image of the SnO2 film deposited at 700 mTorr.

Figure3.3.Cross-section
Figure Cross-section SEM
SEM image
image ofSnO
of the the2SnO film deposited
film2deposited at 700 mTorr.
at 700 mTorr.
The role of Pd in the bilayer structure of the sensitive film is as a catalyst for hy-
drogen molecules, thus improving both the sensitivity and the selectivity of the sensor. It
wasThe Therole
found role of
of Pd
that Pdthe
in
with inbilayer
the the bilayer
increase in thestructure
structure of
of the
of the sensitive
thickness sensitive
the film
Pd is as its
film, film
a catalyst is for
catalytic asactivity
a catalyst
hydrogenon for hy
molecules,
drogen thus
molecules,improving both the sensitivity and the selectivity of the sensor. It was
hydrogen molecules thus improving
is decreased [3]. both the sensitivity
Therefore, the Pd layer andmust
the selectivity
have a veryofsmall the sensor. I
found
was that with
found thewith
that increase
the inincrease
the thickness
in theof thickness
the Pd film,ofitsthe
catalytic
Pd activity
film, its on hydrogen
catalytic activity o
thickness, compared to the sensitive base layer. Thus, in the present case, PLD deposi-
molecules
hydrogen is decreased [3]. Therefore, the Pd layer must have a very small thickness, com-
tions of 2′23″molecules
were carried is out,
decreased
at 100 and [3].700
Therefore, the Pd the
mTorr, to observe layer must of
influence have a very sma
pressure
pared to the sensitive base layer. Thus, in the present case, PLD depositions of 20 2300 were
thickness,
on Pd morphology.compared BothtoSEM the images
sensitive base layer.
in Figure 4 of PdThus,
layers,indescribed
the present above, case, PLD deposi
indicate
carried out, at 100 and 700 mTorr, to observe the influence of pressure on Pd morphology.
the formation
tionsSEM of 2′23″ of continuous
were Pd layers with spherical formations of different sizes on the pressur
Both images in carried
Figure 4out, of Pd at layers,
100 anddescribed
700 mTorr, to observe
above, indicate the the influence
formation of of
surface. No
on Pd morphology. major difference
Both can be
SEM images identified between
in Figure 100
4 of Pd and 700
layers, mTorr deposition
continuous Pd layers with spherical formations of different sizes on thedescribed
surface. Noabove,major indicat
pressure, considering the very small amount of deposited material. Therefore, regarding
the formation
difference can beof continuous
identified betweenPd layers
100 and with
700 spherical formations
mTorr deposition pressure,of different
consideringsizes on th
the performance of the sensors depending on the Pd deposition pressure, we did not
surface.
the very smallNo amount
major difference
of deposited can be identified
material. Therefore,between
regarding 100theand 700 mTorr
performance depositio
of the
expect that the Pd deposition pressure would have a significant influence.
sensors depending on the Pd deposition pressure, we did not expect
pressure, considering the very small amount of deposited material. Therefore, regardin that the Pd deposition
pressure would haveofa significant
the performance the sensors influence.
depending on the Pd deposition pressure, we did no
expect that the Pd deposition pressure would have a significant influence.
Materials 2022, 15, x FOR PEER REVIEW 6 of 12
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12

Figure 4. SEM images of Pd films at different gas pressures.

Figure4.4.SEM
Figure SEMimages
imagesof
ofPd
Pdfilms
filmsat
atdifferent
differentgas
gaspressures.
pressures.
The bilayer films were deposited at 100 and 700 mTorr, both for SnO2 and Pd (Table
Thebilayer
The bilayerfilms filmswere
weredeposited
depositedatat100 100and
and 700700 mTorr,
mTorr, bothbothfor for
SnOSnO 2 and Pd (Table
1). These pressures were chosen because they form considerably 2 and
different Pd (Table 1).
morphologies,
1).
TheseThese pressures were chosen because they form considerably different morphologies,
so thatpressures
the influence wereof chosen because they
the morphology onform considerably
the sensor resultsdifferent morphologies,
can be highlighted. Com-so
so that
that the influence
thethe
influence ofmorphology
of the the morphology onsensor
the sensor results becan be highlighted. Com-
paring SEM images from Figureon2 the (images results
with onlycanSnO 2highlighted.
films), withComparing
the corre-
paring
the SEMtheimagesSEMfrom images
Figurefrom Figure with
2 (images with only SnOwith2thatfilms), with the corre-
sponding ones from Figure 52 (only
(images only SnO
with bilayer 2 films),
films), we notice the corresponding
the morphology onesis
sponding
from Figure ones
5 from
(only Figure
with 5 (only
bilayer with
films), we bilayer
notice films),
that the we notice thatisthe
morphology morphology
similar. Thus, theis
similar. Thus, the presence of Pd is not decisive for a change in the morphology of the
similar. Thus,
presence isthe
of Pdneither notpresence
decisive of
forPd is not decisive
a change in the for a change
morphology in bilayer
of the the morphology
films, of the
neither at
bilayer films, at 100 mTorr nor at 700 mTorr. This is due to the small amount of Pd
bilayer
100 mTorrfilms,
nor neither
at 700 at 100 This
mTorr. mTorr is nor at
due to 700
the mTorr.
small This is of
amount duePd todeposited
the smallon amount
the of Pd
surface
deposited on the surface of the SnO2 films, as explained previously. In conclusion, we
deposited
of the SnO on the as
2 films,
surface
explainedof the SnO2 films, as explained previously. Inthe
conclusion, we
observe that the morphology ofpreviously. In conclusion,
Pd/SnO2 bilayer thin films weisobserve
dictatedthatby the morphology
morphology
observe
of that the morphology of Pd/SnO bilayer thin films is dictated by the morphology
of Pd/SnO 2 bilayer thin films is dictated by the morphology of SnO2 films.
2
SnO2 films.
of SnO2 films.

Figure 5. SEM images of Pd/SnO2 films at different gas pressures.

Figure5.5.SEM
Figure SEMimages
imagesof
ofPd/SnO films at
Pd/SnO22 films at different
different gas
gas pressures.
pressures.

3.2. Sensor Properties

3.2.
3.2. Sensor
Sensor Properties
Properties
Following the tests carried out at different hydrogen concentrations, all the sensors
Following
Following the the tests
tests carried
carried outout at
atdifferent
differenthydrogen
hydrogenconcentrations,
concentrations, all allthe
thesensors
sensors
responded at
responded at room
room temperature.
temperature. The The tests
tests were
were carried out
carried out atat hydrogen
hydrogen concentrations
concentrations
responded at room temperature. The tests were carried out at hydrogen concentrations
between 0.2
between 0.2 and2%. 2%. Taking into account that over a concentration ofhydrogen
4% hydrogen be-
between 0.2and and 2%.TakingTaking into account
into accountthat over
that a concentration
over a concentration of 4% of 4% hydrogen becomes be-
comes
flammable flammable and
and explosive, explosive, the
the sensors sensors must
must bemust able tobe able to detect lower concentrations.
comes flammable and explosive, the sensors be detect
able tolower
detectconcentrations.
lower concentrations.
Figure 66 shows
Figure shows the frequency shifts of the SAW sensors tested
tested at different
different hydrogen
Figure 6 showsthe thefrequency
frequencyshiftsshiftsof
ofthe
the SAW
SAWsensors sensors testedat at differenthydrogen
hydrogen
concentrations.
concentrations. It can be observed that there is a clear delimitation between the sensor
concentrations. It can be observed that there is a clear delimitation between the sensor
It can be observed that there is a clear delimitation between the sensor
results
results for SnO 2 films deposited at different pressures. The sensors with the SnO2 films
results forforSnO
SnO22 films
films deposited
deposited at at different
differentpressures.
pressures. The The sensors
sensors with
withthe theSnO
SnO22 films
films
deposited at
deposited 700 mTorr (more porous)
porous) recorded frequency
frequency shifts approximately
approximately six times times
depositedat at700
700 mTorr
mTorr(more (more porous)recorded
recorded frequencyshifts shifts approximatelysix six times
higher than
higher than thosewith with SnO2 2deposited
deposited at100 100mTorr
mTorr forfor
thethe same hydrogen concentra-
higher thanthose those withSnO SnO2 depositedatat 100 mTorr for same
the hydrogen
same hydrogen concentration.
concentra-
tion. confirms
This This confirmsthat thethatmorphology
the morphology of SnOof 2SnO 2 ismajor
is the the major influence
influence on theon sensor
the sensor re-
results.
tion. This confirms that the morphology of SnO 2 is the major influence on the sensor re-
sults. However,
However, the the presence
presence of Pd ofalso
Pd also makes
makes a a difference
difference in in
the the sensor
sensor results.ItIt can
results. can bebe
sults. However, the presence of Pd also makes a difference in the sensor results. It can be
observed that both bilayer films with SnO films
observed that both bilayer films with SnO2 films deposited at 700 mTorr (Pd-100/SnO2 -700
2 deposited at 700 mTorr
observed that both bilayer films with SnO2 films deposited at 700 mTorr
(Pd-100/SnO
and Pd-700/SnO 2-700 -700)and ledPd-700/SnO
to better2-700)
resultsledthan to the
better results
single layer than
SnO -700the single
sensor.layerThe
(Pd-100/SnO2-7002 and Pd-700/SnO2-700) led to better results than2 the single layer
SnO
same observation is true for sensors with SnO2 deposited at 100 mTorr. However,atthere
2 -700 sensor. The same observation is true for sensors with SnO 2 deposited 100
SnO2-700 sensor. The same observation is true for sensors with SnO2 deposited at 100
mTorr.
is However,
a relatively small there is a relatively
difference between small difference
the sensors with between
different thedeposition
sensors with different
pressures of
mTorr. However, there is a relatively small difference between the sensors with different
deposition
the Pd films,pressures
those with ofPd thedeposited
Pd films,at those
700 mTorrwith having
Pd deposited
a slightly athigher
700 mTorr having
frequency shifta
deposition pressures of the Pd films, those with Pd deposited at 700 mTorr having a
slightly
than higher
those frequency
deposited at 100 shift than those deposited at 100 mTorr.
mTorr.
slightly higher frequency shift than those deposited at 100 mTorr.
 Materials 2022,15,
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12

Figure6.
Figure 6. Frequency
Frequency shift
shift of
of the
the SnO
SnO22 and
and Pd/SnO
Pd/SnO22sensors
sensorsat
atdifferent
differenthydrogen
hydrogen concentrations.
concentrations.

Animportant
An importantaspect
aspectininthe the characterization
characterization of sensors
of sensors is selectivity.
is selectivity. When When the sen-
the sensitive
sitive material of the sensor has sensitive properties for several types
material of the sensor has sensitive properties for several types of gases, it is necessary of gases, it is nec-
to
essary
use to use aelement
a selective selectiveforelement
the gas of forinterest.
the gasSemiconductor
of interest. Semiconductor
metal oxides,metal oxides,
especially SnOes-
2,
pecially
are good SnO 2, arematerials
sensing good sensing materials
for a wide range forofagases.
wide range of gases.
In order
In ordertotodetermine
determinethe the degree
degree of of selectivity,
selectivity, the the
threethree sensors
sensors that that
obtainedobtained the
the best
best hydrogen
hydrogen sensitivity
sensitivity (SnO(SnO2 -7002 -700 sensor,
sensor, Pd-100/SnO
Pd-100/SnO 2 -700
2 -700 sensor
sensor and
and SnO
SnO 2 -700/Pd-700
-700/Pd-700
2

sensor) were
sensor) werechosen
chosenfor fortests
testson onseveral
severalgases:
gases:hydrogen
hydrogen(H (H22),),nitrogen
nitrogen(N(N22),), oxygen
oxygen (O(O2
x FOR PEER REVIEW 8 of 12 2 )
and carbon
and carbondioxide
dioxide(CO(CO 2).The
2 ). Thefrequency
frequencyshiftsshiftsrecorded
recorded byby these
these sensors
sensors areare presented
presented in
the graphs
in the graphsin Figure
in Figure7. All
7. Allsensors
sensorshad results
had resultsin the gasgas
in the concentration
concentration range
range of 0.2–2%.
of 0.2–2%.
The tests showed that the best result of the SnO2-700 sensor was for CO2 gas. The
Pd-100-SnO2-700 sensor and Pd-700/SnO2-700 sensor, on the other hand, had the best
results for hydrogen. The major difference between the mentioned sensors is given by the
presence of Pd. Thus, we can state that the use of Pd represents an important point for
obtaining sensors with an important degree of hydrogen selectivity. The mechanism of
action of Pd was explained previously, and through these tests it was confirmed.
For a wide category of sensors, the use of thermal energy during detection improves
sensor properties. The tests were carried out after the sensors reached the set tempera-
ture, which was kept constant with a Peltier controller. According to the graph in Figure
8, as the sensor temperature increases, the frequency shift is greater. In addition, consid-
ering the pronounced danger of explosion that hydrogen presents at an accumulation of
only 4% in the environment, the temperature factor coming from the sensor can be the
catalyst of the explosion reaction in an emergency situation, because the reactivity in-
creases with temperature.

Figure 7. FrequencyFigure
shifts7. of: (a) SnO
Frequency 2 sensor,
shifts (b) 2Pd-100/SnO
of: (a) SnO 2-700 sensor
sensor, (b) Pd-100/SnO and (c) Pd-700/SnO2-700
2 -700 sensor and (c) Pd-700/SnO2 -700
sensor, at different sensor,
concentrations
at differentof H2, N2, O2 and
concentrations of H2CO
, N22,.O2 and CO2 .

The tests showed that the best result of the SnO2 -700 sensor was for CO2 gas. The
Pd-100-SnO2 -700 sensor and Pd-700/SnO2 -700 sensor, on the other hand, had the best
results for hydrogen. The major difference between the mentioned sensors is given by the
presence of Pd. Thus, we can state that the use of Pd represents an important point for
Materials 2022, 15, 8012 8 of 12

obtaining sensors with an important degree of hydrogen selectivity. The mechanism of

action of Pd was explained previously, and through these tests it was confirmed.
For a wide category of sensors, the use of thermal energy during detection improves
sensor properties. The tests were carried out after the sensors reached the set temperature,
which was kept constant with a Peltier controller. According to the graph in Figure 8,
as the sensor temperature increases, the frequency shift is greater. In addition, consid-
ering the pronounced danger of explosion that hydrogen presents at an accumulation
of only 4% in the environment, the temperature factor coming from the sensor can be
the catalyst of the explosion reaction in an emergency situation, because the reactivity
Figure 7. Frequency shifts of: (a) SnO2 sensor, (b) Pd-100/SnO2-700 sensor and (c) Pd-700/SnO2-700
increases with temperature.
sensor, at different concentrations of H2, N2, O2 and CO2.

Figure8.8.Frequency
Figure Frequencyshifts
shiftsofofPd-700/SnO
Pd-700/SnO2-700
-700 sensor,
sensor, at
at different
differenttemperatures,
temperatures,for
foraaconcentration
concentration
2
of 0.8% hydrogen.
of 0.8% hydrogen.

One of the important advantages of SAW sensors is repeatability. This is ensured by

One of the important advantages of SAW sensors is repeatability. This is ensured by
using a sensitive film that does not irreversibly interact with the gas molecules, allowing
using a sensitive film that does not irreversibly interact with the gas molecules, allowing
their desorption. The sensitive films obtained in this work present this property, the re-
their desorption. The sensitive films obtained in this work present this property, the
versibility being
reversibility beingproven
provenbybythethedynamic
dynamic response of of
response thethe
Pd-700/SnO
Pd-700/SnO 2-700 sensor in Fig-
2 -700 sensor in
ure 9, at 0.4% hydrogen concentration. Ten consecutive measurements
Figure 9, at 0.4% hydrogen concentration. Ten consecutive measurements were were made
madeforfor
Pd-700/SnO2-700-700 and
andPd-100/SnO
Pd-100/SnO2-700 sensors. After the tests, a relative error of ±4% was
Pd-700/SnO 2 2 -700 sensors. After the tests, a relative error of ±4% was
determined. From the same graph, the
determined. From the same graph, the response response and recovery
and recovery timescalculated,
times were were calculated,
which
were approximately 24 s and 30 s, respectively. The intervals of these times fortimes
which were approximately 24 s and 30 s, respectively. The intervals of these for all
all sensors
sensors were 20–30 s for the response time and 25–40 s for
were 20–30 s for the response time and 25–40 s for the recovery time.the recovery time.
The sensitivity is defined as the frequency shift in Hz per unit analyte concentration in
ppm; it was determined from an average sensitivity value of the determinations at each
gas concentration [15]. The LOD is defined as three times the noise level divided by the
sensitivity [15]. The noise level was estimated at 10 Hz. Table 2 shows the results of the
calculations for sensitivity and LOD for all sensors. It can be observed that the best results
were obtained by the sensors with sensitive films deposited at 700 mTorr (more porous),
both for SnO2 and Pd (Pd-700/SnO2 -700). These results are comparable or better than
other results from the literature and from our previous experiments [18,22,23,38,39]. In
our previous work [22], we developed Pd/TiO2 sensors for hydrogen detection. The best
sensitivity obtained in that case was of 0.10 Hz/ppm, with the sensor with the highest
porosity in those experiments, which was two times less than the best sensitivity obtained in
this work (0.21 Hz/ppm). The LOD for this best Pd/TiO2 sensor was 1210 ppm, eight times
higher than the one obtained in the present work for Pd/SnO2 (142 ppm). An important
factor for this result is the much lower level of noise recorded in the present work (10 Hz,
compared to 40 Hz in [22]).
Materials 2022,15,
Materials2022, 15,8012
x FOR PEER REVIEW 99 of 12
12

Figure9.9. Dynamic
Figure Dynamic response
responseof
ofsensor
sensorPd-700/SnO
Pd-700/SnO22-700
-700 at
at 0.4%
0.4% hydrogen
hydrogen concentration.
concentration.

Table The sensitivity

2. Sensitivity andislimit
defined as the frequency
of detection shift
(LOD) of the in Hz(∆f-frequency
sensors per unit analyte concentration
change; c-hydrogen
in ppm; it was
concentration, determined
n-noise level). from an average sensitivity value of the determinations at
each gas concentration [15]. The LOD is defined as three times the noise level divided by
the sensitivity [15]. The noise level was Sensitivity (∆f/c)at 10 Hz. TableLOD
estimated (3 × n)/(∆f/c)
2 shows the results of
Sensor
(Hz/ppm) (ppm)
the calculations for sensitivity and LOD for all sensors. It can be observed that the best
SnOobtained
results were 2 -100 by the sensors with0.02 sensitive films deposited at 1349 700 mTorr (more
SnO 2 -700 0.12
porous), both for SnO2 and Pd (Pd-700/SnO2-700). These results are comparable 251 or better
Pd-100/SnO2 -100 0.03 963
than other results from
Pd-100/SnO2 -700
the literature and from
0.16
our previous experiments [18,22,23,38,39].
189
In ourPd-700/SnO
previous work
2 -100
[22], we developed0.04 Pd/TiO2 sensors for hydrogen 818detection. The
best sensitivity obtained
Pd-700/SnO2 -700 in that case was of 0.10
0.21 Hz/ppm, with the sensor142with the high-
est porosity in those experiments, which was two times less than the best sensitivity ob-
tained in this work (0.21 Hz/ppm). The LOD for this best Pd/TiO2 sensor was 1210 ppm,
These results are a consequence of the mechanism of interactions between the sensitive
eight times higher than the one obtained in the present work for Pd/SnO2 (142 ppm). An
film and the hydrogen molecules. The mechanism consists in several stages, as shown in
important factor for this result is the much lower level of noise recorded in the present
the equations below (R1–R8) [3]. First of all, when the sensor is exposed to air, oxygen
work (10 Hz,
molecules compared
accumulate to 40
at the Hz of
level in the
[22]).
sensitive film. Upon their interaction with Pd, they
are dissociated into oxygen atoms, which will capture electrons from the SnO2 layer and
Table 2. Sensitivity and limit of detection (LOD) of the sensors (Δf-frequency change; c-hydrogen
become species such as O− , O2− , O2− . They spill over to the SnO2 film and accumulate at
concentration, n-noise level).
the intergranular boundaries.
Sensitivity (Δf/c) LOD (3xn)/(Δf/c)
Sensor O2(g) + Pd → 2O(Pd) (dissociation) (1)
(Hz/ppm) (ppm)
SnO2-100 O2(g) + O(Pd) → O(surf) (0.02
SnO2 ) + 2O(Pd) (spillover) 1349 (2)
SnO2-700 0.12 251
When hydrogen molecules appear at the level of the sensitive film, some of them
Pd-100/SnO2-100 0.03 963
react with the oxygen species accumulated at the level of the sensitive film, forming
Pd-100/SnO2-700 0.16 189
water molecules in vapor state. The rest of the hydrogen molecules are dissociated upon
Pd-700/SnO2-100 0.04 818
interaction with Pd into atomic hydrogen and spill over to the SnO2 . At this point, hydrogen
Pd-700/SnO 2-700 0.21
atoms and oxygen species adsorbed at the SnO layer interact, forming water 142 vapor.
2

These results are a consequence

H2(g) + O(ofPdthe
) →mechanism
H2 Og ↑ +(ofPdinteractions
) between the sen-
(3)
sitive film and the hydrogen molecules. The mechanism consists in several stages, as
shown in the equations below 2(g) → H[3].
H(R1–R8) + HFirst
(dissociation
of all, when (4)
) the sensor is exposed to air,
oxygen molecules accumulate at the level of the sensitive
H + SnO2 → Had (SnO2 ) (spillover) film. Upon their interaction
(5)
with Pd, they are dissociated into oxygen atoms, which will capture electrons from the
SnO2 layer and becomeHspecies −O , O , O . They − spill over to the SnO2 film and
ad (SnOsuch asad
2) + O (SnO2 ) → OHad (SnO2 ) (6)
accumulate at the intergranular boundaries.
−
OHad (SnO2 ) + Had (SnO2 ) → H2 O(g) ↑ +(SnO2 ) + e− (7)
O ( ) + Pd → 2O(Pd) (dissociation) (1)
2Had (SnO2 ) + O2ad− (SnO2 ) → H2 O(g) ↑ +(SnO2 ) + 2e− (8)
Materials 2022, 15, 8012 10 of 12

According to the reactions above, this whole process leads to the release of electrons in
the conduction band of SnO2 , thus increasing its conductivity. This increase in conductivity
slows the speed of the SAW waves and reduces the central frequency of the gas sensor.
Although the interaction that causes the change of SnO2 conductivity takes place at the
SnO2 film, the presence of the Pd layer plays a role as well. The SnO2 -modified layer with
Pd leads to an improvement of its sensitivity, by facilitating the interaction of hydrogen
with oxygen species, resulting in changes in the conductivity of the film. It is very important
to monitor the uniformity of the Pd film and, of course, its thickness, to allow the complete
dissociation reaction.

4. Summary and Conclusions

Thin films of SnO2 and Pd/SnO2 were deposited by PLD onto quartz substrates.
Different pressures of oxygen and argon were used for depositing SnO2 and Pd, respectively,
and their influence on the morphology of the film was discussed based on SEM images.
It was observed that as pressure increases, the degree of porosity of the films increases.
Surface acoustic wave sensors were realized with single layer SnO2 and bilayer Pd/SnO2
sensitive films with different morphologies, deposited at 100 and 700 mTorr. The sensors
were tested at different hydrogen concentrations (0.2–2%) at room temperature. The best
results were obtained for the sensor with a bilayer sensitive film, when the depositions were
made at 700 mTorr, both in the case of SnO2 and in the case of Pd. The sensitivity of this
sensor (Pd-700/SnO2 -700) was 0.21 Hz/ppm, with a LOD of 142 ppm. The weakest result
was of the sensor with only SnO2 film, deposited at 100 mTorr. Thus, we see the importance
of both the morphology and the presence of Pd in order to obtain sensors with the best
possible results. The importance of Pd in the detection of hydrogen was also highlighted
after the tests on several gases, when the best result of the sensor without Pd was for CO2
and the best results for the sensors with Pd were for hydrogen. Tests at temperatures in the
20–60 °C range showed an increase in the frequency shift with the increase in temperature,
but not with a considerable value.
These results were better than previous results obtained for sensors with Pd/TiO2
layers (LOD for this best Pd/TiO2 sensor was 1210 ppm, eight times higher than the one
obtained in the present work for Pd/SnO2 (142 ppm)) [22] and represent a good and
important direction of study for the development of SAW sensors with better performances.
Also, the importance of Pd and its influence depending on the thickness for such structures
represents a subject of interest for study.

Author Contributions: Conceptualization, I.C. and C.V.; methodology, I.C. and D.M.; formal analysis,
I.C. and C.V.; investigation, I.C., D.M. and C.V.; writing—original draft preparation, I.C.; writing—
review and editing, I.C., D.M. and C.V.; funding acquisition, C.V. All authors have read and agreed to
the published version of the manuscript.
Funding: This research was supported by the National Authority for Research and Innovation in the
framework of the Nucleus Programme—LAPLAS VI (grant 16N/08.02.2019).
Conflicts of Interest: The authors declare no conflict of interest.

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