Materials Chemistry and Physics 258 (2021) 123966

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Materials Chemistry and Physics

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

Plasma sprayed copper oxide sensor for selective sensing of

carbon monoxide
V. Ambardekar a, P.P. Bandyopadhyay a, *, S.B. Majumder b
a
Department of Mechanical Engineering, Indian Institute of Technology, Kharagpur, 721302, India
b
Materials Science Centre, Indian Institute of Technology, Kharagpur, 721302, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Plasma sprayed CuO coating shows

maximum CO response (~110 %) at
150◦ C.
• Coating showed repeatability of
response % with good stability of base­
line resistance.
• At 150 ◦ C, selectivity ratio of 20 ppm CO
with respect to 5 ppm NO2, 500 ppm
CH4, 250 ppm i-C4H10 were 38, 12.67
and 7.6.
• Coating is suitable for selective CO
sensing for automobile cabin air
quality..

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

Keywords: This investigation deals with a carbon monoxide (CO) sensing of copper oxide (CuO) coating obtained using
Atmospheric plasma spray plasma spraying of CuO powder. CO sensing measurements were undertaken using a dynamic flow gas sensing
CuO coating set up that operated in the temperature range of 100–350 ◦ C. The coating showed a maximum sensor response at
CO sensing
150 ◦ C. Therefore, effect of variation of CO gas concentration (500-5 ppm) on the sensor response was studied at
Stability
Selectivity
150 ◦ C. Coating exhibited reproducible CO sensing characteristics along with good stability of baseline resis­
tance. To understand the stability aspect, time dependent sensor response at various concentrations were ana­
lysed using a reversible sensing model following the Langmuir-Hinshelwood mechanism. To ascertain the
selectivity of response towards CO, sensing measurements were performed at 150 ◦ C in the presence of other
gases like nitrogen dioxide (NO2), iso-butane (i-C4H10), and methane (CH4) in addition to CO. The plausible
reasons for selective CO sensing are also discussed. To the best of authors’ knowledge, this is the first report
presenting the CO sensing capability of plasma sprayed CuO coating.

1. Introduction commonly present in industrial environments such as boiler rooms,

petroleum refineries, coke ovens, blast furnaces, automobile garages,
Carbon monoxide (CO), being a colourless, tasteless and odourless etc. [3]. Internal combustion engines are the major source of CO emis­
poisonous gas, generated owing to the incomplete combustion in urban, sion in urban environment [4] whereas the wooden stove used for
industrial and domestic applications [1,2]. Harmful CO levels are cooking in rural areas, natural gas heater in a small room, domestic

* Corresponding author.
E-mail address: ppb@mech.iitkgp.ac.in (P.P. Bandyopadhyay).

https://doi.org/10.1016/j.matchemphys.2020.123966
Received 12 June 2020; Received in revised form 28 September 2020; Accepted 20 October 2020
Available online 23 October 2020
0254-0584/© 2020 Elsevier B.V. All rights reserved.
V. Ambardekar et al.
water heater in poorly ventilated bathrooms are typical CO emission
sources in domestic applications. People may get exposed to ~400–500
ppm CO from a cigarette smoke [5,6]. CO reacts with haemoglobin to
form carboxyhaemoglobin that in turn reduces oxygen carrying capacity
of the blood [7]. The large amounts of CO exposure can result in loss of
consciousness, vomiting, suffocation, confusion, tightness across the
chaste, headache, dizziness, fatigue, nausea, etc. [8]. A gasoline engine
exhaust is mainly composed of carbon monoxide (CO), hydrocarbons
(HCs) and oxides of nitrogen (NOx) [9]. In practice, the exact concen­
tration of said pollutants varies with engine design and operating con­
ditions. The typical concentration range of four stroke gasoline engine
for CO, HC and NOx gases is 0.1–6%, 500–5000 ppm and 100–4000 ppm
[10]. These concentration levels are subsequently reduced by catalytic
converter to 1/5th of the initial concentration. After interaction with
ambient air, these tailpipe emissions are eventually diluted so that the
concentration ranges of CO, HC and NO2 are 10–100 ppm and 0.5–5
ppm, respectively [9,11]. In order to monitor the air quality of trailing
automobile cabin or on the streets, a gas sensor is required to generate
an alarm to circumvent ill effects of residual amount of the said gases.
For detection of toxic and harmful gases, gas sensors based on
resistive, catalytic, electrochemical, and infrared absorption have been
reported in the literature [12]. Though the sensing performance of such
sensors is satisfactory in terms of sensitivity, these sensors suffer from
various drawbacks such as longer response time, higher initial and
maintenance cost, poor suitability for portable instrumentation, etc.
Usually resistive type sensors are preferred to the sensors mentioned
above, owing to their excellent sensitivity, lower cost, quick response
time, and suitability for integration to portable set ups. Stand-alone
polymer [13] and polymer-metal oxide composite [14–16] type semi­
conducting gas sensors are reportedly useful for room temperature gas
detection. However, oxidizing gases such as ozone (O3) and oxides of
nitrogen (NOx) may cause photochemical destruction of polymer sen­
sors. On the other hand, high temperature of flue gases may degrade the
polymer sensor. Owing to these factors, sensing properties of polymer
based gas sensors change irreversibly over a short duration [12]. Also,
the average lifespan of a metal oxide sensor is higher than that of a
polymer sensor.
Copper oxide (CuO) is a p-type semiconductor metal oxide having
superior catalytic oxidation towards CO gas [17]. The working principle
of chemi-resistive gas sensor involves adsorption/desorption and surface
reaction of test gas with surface adsorbed oxygen species [18,19].
Accordingly, various researchers demonstrated CO sensing ability of
CuO nanostructures, namely, nanowires [11,20], microcubes [21],
urchin-like, fiber-like, and nanorods [22], and thin film [23], nanotubes,
nanocubes [24], nanoleaves [25] devices. Kim et al. [11] prepared CuO
nanowire sensing element by thermal oxidation of Cu foil and demon­
strated CO and NO2 sensing in the range of 300–370 ◦ C. Liao et al. [20]
developed a gas sensor using CuO nanowires drop coated over Si sub­
strate and reported superior CO sensor response over H2S, C2H5OH,
NO2, and H2 gases at 200 ◦ C. Zhang et al. [21] developed Cu2O micro­
cubes, CuO microcubes and Cu2O/CuO micro-frame sensor by spin
coating method. Using Cu2O/CuO micro-frame sensor, a higher CO
sensor response (Rg/Ra ~1.8) was obtained over stand-alone Cu2O
microcubes (Rg/Ra ~1.3), and CuO microcubes (Rg/Ra ~1.05) operated
at 240 ◦ C. Superior CO sensor response using Cu2O/CuO micro-frame
sensor was attributed to formation of p-p heterojunctions between
Cu2O and CuO. Volanti et al. [22] fabricated CuO element sensor with
three different surface morphologies, namely, urchin, fiber and nanorod.
Three different sensing layers were drop coated over alumina substrate
having gold electrodes. Gas sensing measurements were carried out for
H2 (500 ppm), CO (500 ppm) and NO2 (50 ppm) gases by varying the
operating temperature. CuO urchin type sensor was found suitable for
H2 and NO2 gases whereas CuO fiber type sensor was suitable for CO gas.
Such behaviour was attributed to the possible effect of surface
morphology on gas diffusion, and associated surface reaction effects.
Ghosh et al. [23] deposited CuO thin film using spin coating over glass
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Materials Chemistry and Physics 258 (2021) 123966
substrate and achieved selective CO sensing performance over i-C4H10
and NO2 gases at an operating temperature of 275 ◦ C. Hou et al. [24]
prepared CuO nanocube and CuO nanotube sensing elements and
compared their sensing characteristics in the presence of 1000 ppm CO
gas. In this report, CuO nanotube sensor exhibited superior sensor
response (Rg/Ra ~3.27 at 175 ◦ C) over CuO nanocube sensor (Rg/Ra ~2
at 250 ◦ C). The difference in the sensor response was attributed to sur­
face morphology and crystallographic plane orientation. Molavi et al.
[25] synthesized CuO and Al doped CuO nanoleaves using
co-precipitation method. Sensing element was fabricated by drop
coating the said compositions over glass substrate having DC-sputtered
gold electrodes. Al doped CuO sensor showed higher sensor response
(Rg/Ra ~3) over stand-alone CuO sensor (Rg/Ra ~2.42) in the presence
of 800 ppm CO gas at 150 ◦ C.
Gas sensing films are deposited using various techniques such as
physical vapour deposition (PVD), and spin coating using chemical so­
lution deposition (CSD). These techniques have a lower yield as
compared to atmospheric plasma spraying (APS) technique. APS can be
automated with three-dimensional robotics and further scaled-up for
mass production of functional coatings [26]. Therefore, it is worth
investigating plasma sprayed CuO coating as a CO sensing device.
Conventionally, APS technique was widely applied by various re­
searchers to deposit various functional coatings for thermal barrier,
wear and decorative and others [27,28]. APS uses plasma plume as a
heat source to melt the feedstock powder. The powder particles undergo
partial or full melting and accelerated towards the substrate by the
plasma forming gas [29]. These particles impact upon a substrate, un­
dergo flattening, and produce deformed particles known as splats [30,
31]. These splats are joined together to produce lamellar structure of the
coating [32,33]. Therefore, a thin layer is produced on the substrate [34,
35]. The next layer is subsequently coated on the first layer and
layer-wise formation constitutes the final coating [36].
Recently, APS was reported to be a useful deposition technique to
develop various useful devices such as catalytic coatings [37,38], pho­
tocatalytic coatings [39], heat flux sensor [40], thermocouple [41],
strain gauges [42], electrode for the battery [43], etc. APS was suc­
cessfully implemented to develop gas sensors in the past decades
[44–47]. APS can be used to deposit functional coatings over external
[48] as well as internal surfaces. For CuO particulate sensing element,
temperature pertaining to maximum sensor response was found lower
than that for maximum catalytic conversion [49]. Therefore APS can be
implemented to produce a functional surface that will not only detect
but also catalytically convert poisonous gas into benign gas [50,51].
Though the CO sensing capability of CuO sensor was investigated by
a number of researchers, CO sensing performance of plasma sprayed
CuO coating was hardly reported in the literature. In two of prior pub­
lications, promising CO sensing capability of plasma sprayed SnO2
coatings was reported by present group of authors. However, highest CO
response was realized beyond 200 ◦ C in the temperature range of
250–275 ◦ C [52,53]. Therefore, the presents work was undertaken to
obtain effective CO sensing performance <200 ◦ C using atmospheric
plasma sprayed CuO coating.
The present work deals with CO sensing characteristics of atmo­
spheric plasma sprayed CuO sensor. Resistance transients for the CO
sensing measurement were obtained using a dynamic gas sensing
chamber in 500 ppm concentration by varying the operating tempera­
ture (100–350 ◦ C). Resistance transients were also recorded by varying
the CO concentration in the range of 500–5 ppm. Further, repeatability
of response % and stability of baseline resistance of CuO coating was
verified in the presence of 500 ppm CO gas. Finally, selectivity of CO gas
was also tested in the presence of NO2, CH4, and i-C4H10 gases.
V. Ambardekar et al. Materials Chemistry and Physics 258 (2021) 123966

2. Experimental

2.1. Materials and methods

Gas sensor coating was sprayed using commercially available CuO

powder (Nano Lab, India). As-received CuO powder was heat treated at
600 ◦ C for 60 min followed by sieving to have − 44 + 11 μm agglomerate
size that is suitable for plasma spraying. Alumina substrate of di­
mensions 19 mm × 9.5 mm × 0.65 mm was acquired from Ants Lab,
Mumbai, India. For electrical resistance measurement of the sensing
film, a pair of planar silver electrodes was painted on the top surface of
alumina plate [52]. These electrodes were fired at 150 ◦ C for 5 min using
a hot plate and subsequently annealed at 800 ◦ C for 5 min. Finally, CuO
sensing layer is deposited over alumina plate having pair of planar silver
paste electrodes using a 9 MB plasmatron (Sulzer Metco, Westburry,
New York) using set of plasma spraying parameters listed in Table 1.
Any possible overheating of substrate was restricted using a com­
pressed air as cooling media [54]. Phase constitution of CuO coating was
identified in the 2θ range of 20–90◦ using X-ray diffraction apparatus
(Empyrean, Panalytical, Netherlands) equipped with a CuKα source (λ
= 1.54 Å). Top surface morphology was observed using a field emission
scanning electron microscope (Gemini, Zeiss, Germany). For thickness
measurement, fractograph of the coating produced over alumina sub­
strate and its element profile plot were obtained using a scanning elec­
tron microscope (Evo 18, Zeiss, Germany).
Gas sensing experiments were carried out in the presence of CO gas
in 500 ppm concentration using a dynamic gas sensing unit equipped
with a temperature controller, mass flow controllers and a LABVIEW
based data acquisition system [52,55]. The details of this chamber are
reported elsewhere [56]. Resistance transients were recorded by varying
the operating temperature and gas concentration. Known values of
sensor resistances in the presence of air (Ra) and test gas (Rg) were used
to estimate the response % as per the following expression [55]:
⃒ ⃒
⃒Rg − Ra ⃒*100
Response% = (1)
Ra
3. Results
3.1. Phase identification and microstructural characterization
Fig. 1 shows X-ray diffraction pattern for (a) Al2O3 substrate, (b) CuO
powder, (c) CuO coating. Inset shows the details of CuO peaks present in
the plasma sprayed coating. CuO peaks are indexed to monoclinic phase
(Space group: C2/c and JCPDS-PDF 01-089-5895). Strong Al2O3 and Ag
peaks were observed that can be attributed to the small thickness of the
CuO layer. Crystallite size of powder and coating (D) was determined
using well known Debye-Scherer’s formula [57]:
0.9 × λ
D= (2)
B × cosθ
where λ is the wavelength of X-ray radiation used (1.54 Å), θ is the Bragg
diffraction angle of the XRD peak (in degree), B represents broadening of
the diffraction peak at half maxima (in radian).
Two prominent peaks, namely, (− 111) and (111) were considered
for the estimation of average crystallize size. The estimated value of
average crystallite size for powder and coating is 12.56 nm and 21.63
Table 1
Plasma spraying parameters.
Stand-off Gun Gun Plasma N2 flow H2 Powder
distance current voltage power rate flow flow rate
(mm) (A) (V) (kW) (slpm) rate (g/min)
(slpm)
100 325 68 22.1 50 0 50
Fig. 1. X-ray diffraction pattern (a) Al2O3 substrate, (b) CuO powder, (c) CuO
coating. Inset shows the details of CuO peaks present in the coating.
nm, respectively.
Fig. 2 (a) shows the surface microphotograph for CuO coating. Based
on the SEM image, average pore size is in the range of 50–100 nm. By
inspecting the surface morphology, larger pores (>50 nm) forming
macroporous regions and smaller pores (2–50 nm) forming mesoporous
regions are detected. The gas sensor response of the coating reportedly
enhanced in the presence of these pores [52–54]. Mesoporous regions
facilitate efficient oxygen adsorption. Test gas reacts with adsorbed
oxygen to form reaction product and electrons are transported back to
the conduction band of the sensor. If reaction product is not completely
removed, sensor resistance recovers partially. After prolonged use of
such sensor, sensor may stop functioning. Macroporous regions may
expedite easy desorption of reaction product produced owing to the test
gas interaction with the adsorbed oxygen ions. Owing to the removal of
reaction product, sensor resistance reflects back to the initial value in
the presence of air [58,59]. In line with this discussion, superior
response % along with complete recovery of baseline resistance is ex­
pected in case of plasma sprayed copper oxide coating utilized in the
present investigation.
The thickness of the CuO layer was 5 μm as estimated from the
fractograph of the cross section as shown in Fig. 2 (b). Fig. 2 (c) shows
element profile plot recorded from the fractograph of the cross section
that confirms presence of Cu in the coating.
3.2. Gas sensing performance
Fig. 3 shows the schematic representation of the sensing mechanism.
At room temperature, ambient oxygen is physi-adsorbed on the sensor
surface as shown Fig. 3 (i). When the sensor is heated to an elevated
temperatures (above room temperature-350 ◦ C), physi-adsorbed oxygen
(O2) takes out electrons to form chemi-adsorbed oxygen species (O−2 ,
O− ). This effect, in turn, produces an increase in hole concentration in
the CuO bulk. Hence, there is a formation of hole accumulation region
(green color) as represented in Fig. 3 (ii). For p-type CuO sensor, holes
are the majority charge carriers. Therefore, sensor resistance first de­
creases and then saturates in the presence of air (Ra in Fig. 3 (v)). After
getting stable baseline resistance in the presence of air (Ra in Fig. 3 (v)),
sensor surface was exposed to CO gas. CO gas reacts with O−2 (<150 ◦ C)
or O− species (150–350 ◦ C) to form CO2 as an oxidized reaction product
and thus, releases electrons back to the conduction band of CuO [25]. As
a result of this electron transfer, recombination of holes and electrons for
CuO sensor takes place (shown by red color in Fig. 3 (iii)) [60]. Owing to
the decrease in the hole carrier concentration (Fig. 3 (iii)), sensor
resistance first increases and then saturates in the presence of CO gas as

3
V. Ambardekar et al. Materials Chemistry and Physics 258 (2021) 123966

Fig. 2. (a) Surface microphotograph of CuO coating, (b) fractograph of the cross section of the CuO coating, (c) element profile plot.

Fig. 3. Schematic of the sensing mechanism.

represented schematically (Rg in Fig. 3 (vi)). Upon removal of CO gas,
the reaction product, i.e. CO2 desorbs from the sensor surface. This al­
lows re-adsorption of oxygen species (O−2 , O− ) that in turn, increases the
hole carrier concentration, and sensor resistance decreases eventually to
Ra as shown schematically in Fig. 3 (vii).
Fig. 4 (a) shows the temperature dependent response % variation for
500 ppm CO sensing. The trend of variation of response % matches well
with typical p-type semiconductor gas sensors reported in the literature
[61]. CO sensing mechanism for CuO sensor was illustrated earlier [25].
The temperature dependent sensor response % is determined by the type
of oxygen species, adsorption/desorption of test gas and reaction
product owing to gas-solid interaction during response and recovery

4
V. Ambardekar et al.
Fig. 4. (a) Variation of response % with temperature. CO gas concentration was kept fixed at 500 ppm, (b) typical resistance versus time plot in the presence of 500
ppm CO measured at 150 ◦ C.
processes, respectively [62]. Thus, at low operating temperatures
(<150 ◦ C), CO gas species have low thermal energy to interact with
chemi-adsorbed oxygen (O−2 ). It is also reported that sensor response %
is grossly enhanced by O− species as compared to O−2 [59]. At elevated
temperatures, CO gas species have enough thermal energy to interact
with O− . This effect, in turn, results in higher response %. However, with
an increase in the operating temperature, CO gas species tends to desorb
from the sensor surface. Therefore, the advantage of having O− is grossly
reduced to obtain enhanced response %. In such situation, rate of
oxidation (CO to CO2 that is a catalytic reaction) is higher than the rate
of test gas adsorption as reported by Kocemba et al. [63]. Therefore,
response % decreases systematically with an increase in the operating
temperature as noted from Fig. 4 (a).
Fig. 4 (b) shows the resistance versus time plot for 500 ppm CO
sensing measured at 150 ◦ C. The time taken for 63% change in resistance
after exposure to target gas and air are defined as the response time (τres)
and recovery time (τrec), respectively [64]. It is realized that both τres
and τrec are <1 min (Fig. 4 (b)). Since the maximum response % was
obtained at 150 ◦ C, resistance transients were also recorded by varying
CO gas concentration (500-5 ppm) at 150 ◦ C as shown in Fig. 5 (a). It is
clear that CuO coating is useful to detect CO gas in a wide range of
concentrations. After successive response and recovery cycles at various
concentrations, baseline resistance in air (Ra) is almost completely
recovered (Fig. 5 (a)). Therefore, coating showed reversible type gas
sensing that is a favorable aspect for commercial adaptability of sensing
Fig. 5. (a) resistance transients measured at 150 ◦ C in the range of 500–5 ppm, (b) response versus time plot for 500 ppm CO sensing measured at 150 ◦ C. Symbols
represent experimental data and the solid line was obtained using Eq. (13). Inset shows variation of τrev (s) with concentration (ppm).
5
Materials Chemistry and Physics 258 (2021) 123966
element. Sensitivity index (ñ0.55) was estimated from the slope of the ln
(S) versus ln (C) plot (Inset of Fig. 5 (a)) as per the following expression
[65]:
S = a.Cn (3)
where S is the sensor response ((Rg-Ra)/Ra), and a is a constant.
A reversible type gas sensing is characterized by complete recovery
of baseline resistance whereas irreversible type gas sensing is charac­
terized by partial recovery of baseline resistance after successive
response and recovery cycles. In the present work, coating showed
reversible type gas sensing as pointed out earlier.
4. Discussion
In general, the gas sensing process can be well explained on the basis
of Langmuir-Hinshelwood mechanism. As per Langmuir-Hinshelwood
mechanism, two adsorbates, namely oxygen (O2) and reducing test gas
‘R’ (i.e. CO) first adsorb on the solid adsorbent surface (i.e. sensor) and
subsequently collide with each other to form an activated complex, i.e.,
reaction product ‘RO’. The liberated electrons are given back to the
conduction band that changes the sensor resistance form Ra to Rg as
discussed in the earlier section 3.2. Based on the CO sensing mechanism
as outlined earlier, one can represent the gas sensing process as follows:
V. Ambardekar et al.
1 sensing can be expressed using the following relation:
O2 + Sensorsurface ↔ Oadsorbed (physi − adsorption) (4)
2 /
Oadsorbed + e ↔ Oadsorbed− (chemi − adsorbed) (5)
Fig. 6 schematically represents the energy diagram based on the
Langmuir-Hinshelwood mechanism. ‘A’ represents presence of physi-
adsorption of reducing test gas ‘R’ and chemi-adsorbed oxygen (Oad­
sorbed-) on the sensor surface.
In order to produce an activated complex or reaction product
‘ROadsorbed’ (denoted by B), both reactants R and Oadsorbed-should cross
the energy barrier represented by transition state (TS) in Fig. 6. In simple
words, it can be stated that the physi-adsorbed test gas ‘R’ of concen­
tration (C) can react with Oadsorbed-to form ROadsorbed after surpassing
transition state (TS) only. In this illustration, total surface coverage on
the sensor surface can be expressed as ‘Fθ’. It is assumed that the site
fraction ‘θ’ on the sensor surface is occupied by Oadsorbed-whereas R is
adsorbed on the remaining vacant sites.
Interaction of R with sensor and Oadsorbed-can be written as:
R + Sensorsurface ↔ Radsorbed (physi − adsorption) (6)
R + Oadsorbed− ↔ ROadsorbed + e (7)
ROadsorbed ↔ ↑ROgas + ↑sensorsurface (8)
In this reaction sequence, rate of physi-adsorption of oxygen (Eq. (4))
and test gas (Eq. (6)) is faster as compared to that of rate of reaction of
test gas with adsorbed oxygen (Eq. (7)). For generation of an electrical
signal, there must be formation of ROadsorbed along with transfer of
electrons back to the conduction band. Thus, Eq. (7) represents the rate
determining step for the sensor response process. For recovery of sensor
resistance from Rg to Ra, reaction product (ROadsorbed) must be
completely desorbed from the sensor surface. Therefore, Eq. (8) repre­
sents the rate determining step for the sensor recovery process.
The detailed description of this model can be found elsewhere [66,
67]. The gas sensor response process is related to Eq. (7). The equilib­
rium constant of Eq. (7) can be expressed as K whereas the forward and
reverse rate constants are expressed by k and k/K, respectively. It is
assumed that at a particular operating temperature, the total number of
available sites on the sensor surface (Fθ) is conserved. Thus, one can
write,
θ(occupied by Oadsorbed− ) + ROadsorbed (occuipied by R) = Fθ (9)
It was tacitly presumed that the reaction product ROadsorbed occupies
the same sites where the reducing gas species are adsorbed initially. The
rate of sensor response S related to test gas concentration C for reversible
Fig. 6. Schematic representation of Langmuir-Hinshelwood Mechanism.
6
Materials Chemistry and Physics 258 (2021) 123966
d[RO]
= k[Oadsorbed− ]C − k K[ROadsorbed ] (10)
dt
Eq. (10) can be expressed in terms of site occupancies. Thus one can
write,
d[RO]
/
= k[Fθ − ROadsorbed ]C − k K[ROadsorbed ] (11)
dt
Simplification of Eq. (11) leads to following form
[ROadsorbed ](t) = Fθ[C.K / (1 + C.K)][1 − exp − {(1 + C.K) / K}kt] (12)
The sensor response attains maxima when all the active sites (Fθ) are
occupied by the ROadsorbed. Thus, the sensor response ‘S’ at a time ‘t’ (i.e.
S(t)) can be written as follows [52]:
Assuming 1 + C.K ≈ C.K and τrev = (1 /k) × [k /[1 + C.K]]; simplifi­
cation of Eq. (12) leads to:
[ ( )]
− t
S(t) = Smax 1 − exp (13)
τrev
where Smax is the maximum sensor response and τrev is the characteristic
response time (s) for reversible type gas sensing.
Fig. 5 (b) shows the response versus time plot obtained in the pres­
ence of 500 ppm CO gas. Experimental points are shown by symbols and
the solid line was obtained using reversible sensing model in accordance
with Eq. (13). Similar analyses were also carried out for different con­
centrations in the range of 500–5 ppm to estimate τrev for reversible
sensing. In the lower concentration regime (5–20 ppm in the present
work), the value of τrev was 120 s whereas in the higher concentration
regime (50–500 ppm in the present work), the value of τrev was 86 s. This
can be attributed to the gas-solid interaction [59]. An efficient sensing
reaction requires sufficient number of adsorbed oxygen species together
with sufficient amount of test gas species. Therefore, higher value of τrev
at low concentration can be attributed to the slow sensor response ki­
netics [66]. Similar reversible trend was also reported for CO sensing
characteristics for plasma sprayed SnO2 coating [52]. From the inset of
Fig. 5 (b), it is perceived that coating showed reversible sensing behavior
in both lower and higher concentration regimes that can be attributed to
the porous surface morphology (Fig. 2 (a)). Such reversible type sensing
simplifies the electronic circuitry associated with gas sensing element. In
the case of irreversible type gas sensing, a separate compensation circuit
is required to rectify the drift in the baseline resistance. Chemi-resistive
gas sensors require heat energy for efficient operation. In practice, the
heater is powered by the battery. In the present work, superior CO
response characteristics were achieved at 150 ◦ C. Hence this sensor
could be used to minimize the power consumption associated with the
battery.
Fig. 7 (a) shows the five response and recovery cycles in the presence
of 500 ppm CO gas measured at 150 ◦ C. It is interesting to note that both
response time (τres) and recovery time (τrec) was almost same in all cy­
cles. Thus, coating showed repeatable behavior [21]. In addition, sensor
baseline resistance in air was recovered completely after successive
repetitions that indicates good stability of sensing element [68].
In addition to repeatability, reversibility, baseline stability and lower
operating temperature; selective detection of CO is a prime requirement
for air quality monitoring applications. Fig. 7 (b) compares response %
recorded for various gases such as CO, CH4, i-C4H10 and NO2. Selectivity
(Kgas1_gas2) ratio is defined as the relative response % of gas 1 to gas 2.
The selectivity ratio can be obtained from following relation [55]:
Sgas1
kgas1 gas2 = (14)
Sgas2
The estimated selectivity of 20 ppm CO with respect to 5 ppm NO2,
250 ppm i-C4H10, and 500 ppm CH4 were 38, 7.6 and 12.67, respectively
at 150 ◦ C. Such coating can be used as a potential candidate to avoid
V. Ambardekar et al.
Fig. 7. (a) five response and recovery cycles measured at 150 ◦ C showing repeatability of response % and stability of baseline resistance, (d) response % recorded for
various test gases.
detrimental effects of CO exposure in an automobile cabin as discussed
earlier in the introduction section.
Plausible sensing mechanism for NO2, i-C4H10, CH4 and CO gases is
discussed in following paragraphs: NOx is a generic term used to denote
nitrogen oxides, namely, NO and NO2. At ambient temperatures, oxygen
and nitrogen do not form nitrogen oxides. However, at higher temper­
atures such as an internal combustion engine exhaust, reaction between
oxygen and nitrogen is favored and nitrogen oxides are produced [69].
As per the occupational safety and health administration (OSHA), the
permissible exposure limit for NO2 gas is 5 ppm [70]. The concentration
level associated with immediate danger to health is 20 ppm. Even a low
ppm concentration (5 ppm) of NO2 gas anaesthetizes a nose. Owing to
this effect, there is a possibility that a higher concentration of NO2 in the
ambient remains unnoticed by the human olfactory system. This may
lead to potential health risks. A sensor that is activated in the presence of
NO2 in a low concentration can be utilized to protect people from pro­
longed exposure to this gas. Therefore, to test the efficacy of CuO coating
for NO2 sensing, NO2 concentration was kept low on purpose (5 ppm).
During gas sensing, NO2 should first decompose to NO and O2 as in­
termediate products. Next, NO reacts with chemi-adsorbed oxygen (O− )
to produce NO−3 as given by the following equations [71]:
NO + Oad →NO2− + h (15)
NO2− + Oad →NO3− (16)
These reactions are expedited at elevated temperatures (≥300 ◦ C).
Thus, as represented in Eq. (15), reaction of NO with adsorbed oxygen
leads to an increase in the hole carrier concentration in CuO sensor, and
the sensor resistance is expected to decrease during NO2 sensing. Since
the measurement is carried out at 150 ◦ C, decomposition of NO2 into NO
and O2 is not favored at such a low temperature [71]. Therefore, CuO
sensor was not found suitable for NO2 sensing at this temperature.
As per the American Conference of Government Industrial Hygien­
ists, threshold limit value (TLV) for hydrocarbons is 1000 ppm [72].
Since these hydrocarbons are highly flammable, low ppm sensing
(≤500 ppm) is indeed desirable to prevent danger of explosion at higher
concentrations (1000 ppm). In case of butane sensing, sensing process
involves several intermediate steps. The exact sensing mechanism for
butane sensing is not yet fully understood. However, the plausible
sensing reactions during butane sensing could be written as follows [73]:
Cn H2n+2 + 2O− →H2 O + Cn H2n : O + e− (17)
7
Materials Chemistry and Physics 258 (2021) 123966
Cn H2n : O + O− →CO2 + H2 O + e− (18)
For n = 4, CnH2n+2 represents butane whereas CnH2n: O represents
partially oxidized intermediate products over the sensor surface. Since
cracking of C–H and C–C bonds usually requires elevated temperature
(≥250 ◦ C), formation of intermediate products is severely limited at
150 ◦ C in the present work. It was reported that cracking of C–C bonds is
initiated at low operating temperatures in the case of an acidic sensor
surface. However, CuO sensor is reported to be a basic surface [74]. In
case of a basic surface, probability of cracking of C–C bonds is lower as
compared to that of an acidic surface. This, in turn, results in low
response % of CuO towards butane at 150 ◦ C. As mentioned earlier,
cracking of C–H bond also requires high operating temperature (≥275◦ )
[65]. Therefore, methane sensor response % was also negligible at
150 ◦ C in the present work. It is interesting to note that the CO response
% is superior over other gases. This can be attributed to favorable cat­
alytic activity of CuO towards CO oxidation. In contrast with n-type
semiconductor, p-type semiconductor usually possess large amount of
adsorbed oxygen species as reported in the literature [59]. It was also
reported that response % is greatly influenced by the amount of adsor­
bed oxygen species over sensor surface. Accordingly, higher CO
response % was obtained as low as 150 ◦ C in the present work. There­
fore, such CuO coating could be a potential candidate for selective CO
sensing applications. The permissible exposure limit (PEL) for CO gas is
50 parts per million averaged during 8-h time weighted average (TWA)
as per the norms of the occupational safety and health administration
(OSHA) [25]. The 8-h PELs for workers engaged in maritime and roll-on
roll-off operations during cargo loading-unloading are 50 ppm and 200
ppm, respectively. From Fig. 5 (a), it is perceived that CuO coating is
capable of detecting such low CO concentrations. Therefore, CuO
coating can be used for CO detection in the said applications. Table 2
presents comparison of CO sensing characteristics of plasma sprayed
CuO sensor and other sensing elements reported earlier.
In comparison with n-type sensing elements as listed in Table 2, p-
type CuO coating showed superior sensing performance in terms of
response % and operating temperature. The superior sensing perfor­
mance of p-type CuO can be understood from the following explana­
tions: for a p-type semiconductor, O− species are produced owing to the
transfer of electrons from the metallic ions and sensor surface is satu­
rated with adsorbed oxygen [75]. It was reported that the metal ions
could be quickly oxidized to higher oxidation state during oxidation
process [12]. This can be correlated to low stability of p-type oxides
associated with reduction–oxidation (redox) reactions promoted by
V. Ambardekar et al. Materials Chemistry and Physics 258 (2021) 123966

Table 2
Comparison of CO sensing characteristics of plasma sprayed CuO sensor and other metal oxide sensing elements reported earlier.
Sensing element (type of charge carrier) Operating temperature (◦ C) and concentration of test gas (ppm) Sensor response Response time Recovery time Reference

CuO urchin like morphology (p-type) 200 (500) ~3.8* ~2.25 min – [22]
CuO nanowires (p-type) 300 (10) ~200** ~8 s ~13 s [80]
CuO nanowires (p-type) 350 (100) ~1.05* ~300 s ~600 s [81]
CuO nano-cubes (p-type) 175 (1000) ~1.75* ~11 s ~18 s [24]
Al doped CuO nanoleaves (p type) 150 (800) ~200** – – [25]
Cu2O/CuO microframe sensor (p type) 240 (200) ~1.8 ~21 s – [21]
SnO2/CuO bilayer 180 (500) ~13** ~12 s ~105 s [82]
CuO thin film (p-type) 275 (500) ~48** ~178 s ~190 s [23]
ZnO thin film (n-type) 300 (500) ~40** ~55 s ~78 s [23]
CuO–ZnO composite thin film (n type) 325 (500) ~65** ~66 s ~331 s [23]
WO3 thin film (n-type) 300 (500) ~40** – – [83]
Co doped ZnO thin film (n-type) 325 (500) ~68** – – [84]
Plasma sprayed SnO2 coating (n-type) 250 (500) ~73** ~60 s ~192 s [52]
Plasma sprayed SnO2 coating (n-type) 275 (500) ~74** ~33 s ~118 s [53]
Plasma sprayed CuO coating (p-type) 150 (500) ~110** ~280 s ~665 s (This work)
⃒ ⃒
Rg ⃒Rg − Ra ⃒*100
* , ** ; where Ra and Rg are the sensor resistance values in the presence of air and test gas, respectively.
Ra Ra

variable oxidation states as compared to n-type oxides [61]. Also, p-type
oxides usually possess larger amount of adsorbed oxygen as compared to
n-type oxides [61]. It is well known that hole concentration is higher in
the case of p-type oxides as compared to that of n-type oxides. Thus, each
hole may provide a vacancy for oxygen adsorption that leads to higher
amount of adsorbed oxygen ions for p-type oxides. In tune with this
discussion, p-type oxides are reported to possess full monolayer of ox­
ygen ions [76]. It is well known that the hole concentration for n-type
oxides is lower than that of p-type oxides. In case of stoichiometric
n-type oxides having non-oxidizable metal ions, oxygen adsorption is
limited. However, in case of an oxygen deficiency, n-type oxides adsorb
oxygen as much as required to restore their stoichiometry. In line with
this discussion, it was reported that the concentration of oxygen ions is
less than 1% of monolayer for n-type oxides [77].
Iwamoto et al. conducted an experiment using temperature pro­
grammed desorption (TPD) technique on different metal oxides powder
samples, namely, CuO, Co3O4, NiO, Fe2O3, SnO2, ZnO, TiO2, MnO2,
Cr2O3 [78]. The aim of this experiment was to determine the amount of
oxygen adsorbed on these oxide samples by measuring the total amount
of oxygen desorbed below 560 ◦ C (termed as V560 in this report). It was
found that the V560 values for p-type oxides namely, CuO, Co3O4, NiO,
MnO2 and Cr2O3 were considerably higher as compared to n-type ox­
ides, namely, Fe2O3, SnO2, ZnO, and TiO2. This finding revealed that
p-type oxides possess large amount of adsorbed oxygen as compared to
n-type oxides as mentioned earlier. Lee et al. reported that the larger
amount of adsorbed oxygen in case of p-type oxides can be correlated to
low stability of p-type oxides associated with reduction–oxidation
(redox) reactions promoted by variable oxidation states as compared to
n-type oxides [61].
Gas sensor response % is determined by the amount of oxygen spe­
cies present over the sensor surface [78]. Maximum sensor response %
can be attributed to the efficient active test gas species as well as
availability of enough adsorbed oxygen species at a particular operating
temperature [79]. Since more amount of active oxygen species exist in
the case of a p-type oxide, gas sensing performance could be improved as
compared to n-type oxides using more than one method: (a) either
reduction in the operating temperature pertaining to the maximum
response % (Topt), (b) or enhanced response % at a particular temper­
ature. Accordingly, few authors have reported enhanced sensor response
using p-type CuO in the form of thin film [23], nanocubes [24], nano­
wires [80,81] as listed in Table 2. Few reports are based on hetero­
junctions sensor using CuO–ZnO composite thin film [23], Cu2O/CuO
composite micro-frame [21], and SnO2/CuO bilayer thin film [82] as
listed in Table 2. However, the Topt in these reports was in the range of
175–350 ◦ C. Topt for the plasma sprayed CuO coating (without any
dopant or bilayer) is 150 ◦ C which is comparable with Al doped CuO
(150 ◦ C) [25].
Previously, the present group of authors investigated the sensing
performances of plasma sprayed SnO2 coatings in the presence of 500
ppm CO gas. The maximum response % (73–75%) for SnO2 coatings was
obtained in the temperature range of 250–275 ◦ C. As listed in Table 2,
the CO response % and Topt for n-type WO3 [83], n-type ZnO [23],
n-type Co-doped ZnO thin film [84] sensing elements were in the range
of (40–68%) and (300–325 ◦ C), respectively.
In comparison with these reports based on n-type oxides, plasma
sprayed p-type CuO coating exposed to 500 ppm CO gases exhibited
maximum response % (110%) at 150 ◦ C. Thus, results obtained in the
present work clearly demonstrate the improvement in the CO sensing
performance in terms of reduction in Topt and enhanced response %. In
spite of all these findings, response time and recovery time of CuO
coating need to be reduced further. Since both τres and τrec are less than
1 min, CuO coating is useful to detect CO gas at 150 ◦ C for various
practical applications such as smoke from the wooden stove, tobacco,
cigarettes, water heater in poorly ventilated bathrooms, automobile
exhaust pipe, etc.
5. Conclusions
Plasma spray technique was used to produce CuO sensing layer with
porous surface morphology. Gas sensing process including sensor
response and sensor recovery is thought to be enhanced owing to the
presence of pores (50–100 nm size). CO sensing characteristics of plasma
sprayed CuO sensor was investigated in the presence of 500 ppm CO gas
using a dynamic gas sensing chamber in the temperature range of
100–350 ◦ C. Since the CuO coating showed maximum response %
(~110%) at 150 ◦ C, resistance transients were further measured by
varying the CO gas concentration in the range of 500–5 ppm. Coating
also exhibited repeatability of response %. Stability of baseline resis­
tance after successive cycles was ascertained by analyzing time depen­
dent sensor response at different concentrations to estimate τrev. Since
τrev does not changed greatly with an increase in CO concentration in the
lower (5-20 ppm) and higher (50-500 ppm) concentration regimes,
coating showed reversible type sensing that can be attributed to the
porous surface morphology. Selectivity of coating was further tested
towards various gases such as CH4, i-C4H10 and NO2. Coating showed
superior response % in the presence of CO as compared to that for other
gases. In practice, such coating can be utilized for selective CO sensing at
150 ◦ C for various applications such as exhaust gas emitted by the
wooden stove in rural areas, poorly ventilated water heater in a bath­
room, petrol engine exhaust pipe, automobile cabin air quality, etc.
Data availability statement
The raw and processed data required to reproduce these findings

8
V. Ambardekar et al.
cannot be shared at this time as the data also forms part of an on-going
study.
CRediT authorship contribution statement
V. Ambardekar: Investigation, Data curation, Formal analysis,
Writing - original draft, Writing - review & editing. P.P. Bandyo­
padhyay: Conceptualization, Methodology, Supervision, Writing -
original draft, Writing - review & editing. S.B. Majumder: Conceptu­
alization, Methodology, Supervision, Writing - original draft, Writing -
review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The above research work was partially supported by the research
grant obtained from MeiTY, Government of India; vide sanction letter
Nos. 5(1)/2017-NANO dated March 28, 2018 and DST/NM/NNETRA/
2018(G)-IITKGP dated March 21, 2018. One of the authors (Mr. Vibhav
Ambardekar) wishes to acknowledge the “FESEM Lab (DST FIST Facil­
ity) at Materials Science Centre, IIT Kharagpur” for characterization of
coating.
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