Journal of the Korean Ceramic Society

https://doi.org/10.1007/s43207-020-00088-z

ORIGINAL ARTICLE

Gas sensing behavior of ­Cu2O and CuO/Cu2O composite nanowires

synthesized by template‑assisted electrodeposition
Moein Hadiyan1 · Alireza Salehi1 · Hamid Mirzanejad1

Received: 1 August 2020 / Revised: 22 September 2020 / Accepted: 29 September 2020

© The Korean Ceramic Society 2020

Abstract
Metal oxide-based conductometric gas sensors are one of the promising candidates for highly sensitive, harsh environment
resilient, low cost and nontoxic sensors for industrial applications. Here we present conductometric gas sensors based on
­Cu2O and CuO/Cu2O composite nanowires investigated towards few VOCs and CO gases. The C ­ u2O nanowires with an
average length of 8 µm and diameter of 180 nm were synthesized through template-assisted electrodeposition of C ­ u2O into
a polycarbonate membrane pores, from an aqueous solution. The CuO/Cu2O composite nanowires were obtained by anneal-
ing the synthesized C­ u2O nanowires in an oxygen environment. The morphology, dimension, and crystallography of the
synthesized nanowires are studied using scanning electron microscopy and X-ray diffraction measurements before and after
annealing process. Our proposed sensor based on C ­ u2O nanowires showed a fast response in sensing ethanol gas at 250 °C
response values of 178 and 15% towards 50 and 1 ppm of ethanol, respectively. CuO/Cu2O nanowires behaved selective and
sensitive at 150 °C with a response value of 55% towards 500 ppm of CO.

Keywords Template-assisted · Copper oxide · Gas sensor · Nanowire · Ethanol

1 Introduction in gas sensing for reducing gases such as ethanol, CO [10],

­CH4 [12] and oxidizing gases such as H
­ 2S [11] and N
­ O2 [9].
Conductometric gas sensors based on metal oxides nano- CuO with a narrow in-direct bandgap of 1.2 eV is mostly
structures have been widely investigated in different indus- investigated for photodetector [13], catalytic applications
tries thanks to their interesting properties such as low cost, [14–16] and gas sensing properties [17–20]. For gas sensing
stability in harsh environments, non-toxicity and high sen- applications, CuO nanostructures sensing properties have
sitivity. Despite decades of commercial and industrial use, been investigated for target gases such as CO [19, 21, 22],
researches for enhancement of gas sensing properties of ethanol [23–25], formaldehyde [26], ­H2S [27, 28], and ­NO2
metal oxide nanostructures are still a subject of interest [1–4] [29, 30].
and has remained a challenge to address. Various CuO nanostructures can be achieved by thermal
Cu2O and CuO are two stable forms of copper oxide annealing of ­Cu2O nanostructures at the ambient atmos-
which both are p-type metal-oxide semiconductors. ­Cu2O is phere and temperatures higher than 300 °C [31–35]. How-
a semiconductor with a wide direct band gap of 1.9–2.17 eV ever, it has been shown that depending on the annealing
which makes it an appealing candidate for photovoltaic [5, temperature and time, partial conversion of C ­ u2O to CuO
6] and photocatalysts applications [7]. ­Cu2O based nano- can occur resulting in CuO/Cu2O composite nanostructures
structures such as nano-cubes [8], nano-octahedral [8], [31, 36–38]. CuO/Cu2O nanostructures such as nanocubes
nano-sphere [9], and nanorod [10, 11] are widely studied [38], micro [36] and nanospheres [31] and nanotubes [39]
have been reported in literature for sensing ethanol [23],
acetone [38], ­H2S [37], and ­NO2 [40].
Being one of the most studied copper oxide nanostructure
* Moein Hadiyan
[email protected] for gas sensing, CuO nanowires can be synthesized using
various methods such as thermal oxidation of Cu film [19,
1
Semiconductor Device Laboratory, Electrical Engineering 28, 30], Hydrothermal growth [41–43], PVD [24, 44], and
Department, K.N. Toosi University of Technology, electrochemical deposition [45, 46]. One of the synthesize
Seyed‑Khandan Bridge, Tehran, Iran

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techniques rarely studied, is template-assisted electrodeposi- uniformity for NWs dimension and morphology while
tion [39, 47] which is used widely for synthesizing nanow- showing superior gas sensing properties. Therefore, our
ires of various materials including metal [9, 48], metal work paves the way not only towards scalable, high sensi-
oxides [23, 37, 40] and organic materials [8] in applications tive and cost-efficient gas sensors but also lends its simple
such as nanomagnetism [39], photocatalysts [35] and gas and reproducible technique to the other applications that
sensors [33, 34, 39]. In the recent years, template-assisted demand nano-composite nanowire structures.
synthesize of nanowires for gas sensing applications has
become more attractive [32, 34, 49, 50] as it facilitates the
high throughput fabrication of high aspect ratio nanowires
with precisely controlled dimensions and compositions. 2 Experimental
In template-assisted synthesize of metal oxide nanowires,
the template is either an anodized alumina membrane or an In ordero fabricate a conductometric gas sensor based on
Ion-Track etched polycarbonate membrane [31]. To fabricate ­Cu2O/CuO nanowires, first C ­ u2O nanowires were synthe-
nanowires, the pores of the membrane should be filled with sized by electrodeposition into polycarbonate membrane
the desired materials that can be accomplished by different pores. Afterwards, the ­Cu2O nanowires were released from
methods such as electrochemical deposition [9, 23, 32, 34, the template into a solution which was subsequently used
39, 47, 51], solvothermal [37, 40], atomic layer deposition to transfer NWs onto a pair of Au interdigitated electrode
[34, 52] among which electrodeposition is more attractive (IDE) on a Si/SiO2 substrate. Then, the ­Cu2O nanowires
due to simplicity, low cost and robust reproducibility. on the IDE went through annealing process to obtain
In this work, the ­C u 2O/CuO nanowires were synthe- ­Cu2O/CuO composite nanowires. To study the gas sens-
sized by template-assisted electrodeposition of C ­ u 2O ing behavior of ­Cu2O and CuO/Cu2O nanowires.
nanowires followed by subsequent high-temperature Figure 1 shows the schematic of the fabrication process
annealing. Comparing to more studied approaches such to obtain the gas nanowire gas sensors.
as CuO NWs synthesize by thermal oxidation of Cu film
[23–25], our method offers higher reproducibility and

Fig. 1  Fabrication process of the conductometric sensor based on the Au residual (8) drop-casting the NWs on IDE (9) dispersing the
CuO Nws, (1) polycarbonate membrane (2) Au layer deposition (3) ­Cu2O NWs on IDE (10) converting C ­ u2O NW to CuO by thermal
template sealing (4) electrodeposition of ­ Cu2O (5) separating the annealing
filled template from sealing (6) dissolving the template (7) filtering

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2.1 Cu2O nanowires synthesize

A commercially available ion-track etched polycarbonate

circular membrane (Whatman Nuclepore) 19 mm in diam-
eter, with an average pore diameter of 100 nm was used as
the template. To obtain an electrode for subsequent electro-
deposition a 200 nm Au film was deposited on one side of
the membrane by thermal evaporation using a shadow mask.
The Au layer also serves as a conductive cap layer to seal the
bottom side of the membrane pores. Afterwards, the tem-
plates were mounted on a glass slide with the Au deposited
side completely sealed using silicone-based adhesive and
Kapton tape. The complete sealing of the Au side is critical
to ensure that ­Cu2O is electrodeposited into the pores.
The prepared template was used as the working electrode
in a standard three-electrode cell with an Ag/AgCl (in 3 M Fig. 3  Cyclic voltammetry of Au-backed polycarbonate membrane
KCL) and a graphite rod served as the reference and counter in the solution containing 0.2 M CuSO4 and 3 M lactic acid with an
adjusted PH of 12
electrodes, respectively. The electrodeposition was carried
out using a Keithly 238 Source Measurement Unit (SMU)
wired and programmed to operate as a potentiostate (Fig. 2). CuLac2 + OH− + e− → CuOH + 2Lac− , (1)
Cu2O nanowires were electrodeposited in the template
at −300 mV (vs Ag/AgCl) in a solution of 3 M lactic acid
with 0.2 M copper sulfate ­(CuSO4⋅5H2O) aqueous solu-
2CuOH → Cu2 O + H2 O. (2)
tion at 65 °C under vigorous stirring. Concentrated Sodium
hydroxide solution was added dropwise to adjust the solution
PH value to 12–12.5 while stirring. 2.2 Releasing the ­Cu2O nanowires
According to the cyclic voltammetry measurement of the from the template
Au-back template in the prepared solution (Fig. 3), the elec-
trodeposition process performed at the potential of −350 mV After the electrochemically filling up the template to
with respect to the Ag/AgCl electrode for 1 h. obtain nanowires, the polycarbonate template was dis-
The electrodeposition mechanism of C ­ u2O in the elec- solved in dichloromethane. The Au thin film residuals
trolyte solution can be explained by the formation of copper were separated from the nanowires solution by letting
lactate complex and subsequent reduction to Cu(OH) (Eq. 1) them to sediment at the bottom of the microtube. Due to
followed by dehydration to ­Cu2O (Eq. 2) [53]: larger dimensions of Au particles and their higher density,

Fig. 2  Three electrode electro-

chemical cell wired to a Keithly
SMU as a potentiostate with
sealed polycarbonate membrane
as the working electrode

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the Au residual particles would precipitate in consider- longer durations, using Cr/Au electrodes, annealing at higher
able shorter time than C­ u2O nanowires which then can be temperatures or for longer durations would cause consider-
separated from the solution. able degradation of the Cr/Au electrodes.
The dissolved polycarbonate can be removed from the
nanowires solution by letting the nanowires to sediment (for
approximately 1 h), removing the polycarbonate-dichlo- 2.4 Characterization
romethane solution and replace it with fresh dichlorometh-
ane. By repeating the washing process for three times, a sus- The nanowires dimensions and their surface morphology
pension of nanowires in clean dichloromethane was achieved were characterized using a Philips KL30 Scanning Electron
for further drop-casting on the IDE. Microscope (SEM) and a Hitachi S-4800 Field Emission
Scanning Electron Microscope (FE-SEM) before and after
2.3 Gas sensor fabrication annealing. The IDE and the distribution of nanowires on the
IDE were examined by an optical microscope. The grazing
A pair of IDEs were defined by depositing Cr (10 nm)/ incident X-ray diffraction (GIXRD) patterns of the nanow-
Au(100 nm) (the Cr layer serves as adhesion layer) on Si/ ires were obtained using a panalytical xpert PRO MPD X-ray
SiO2 substrate followed by optical lithography to obtain IDE diffractometer with the fixed incident angle of 1°.
with 3 µm gap between fingers. Gas sensing tests were accomplished using an air-tight
Cu2O nanowires were placed on the IDE by drop-casting test chamber through a static approach as illustrated in
from the prepared suspension. After evaporating the dichlo- Fig. 5. The sensor response was measured by a Keithly 238
romethane by heating at 150 °C for 10 min, the IDE was source-measurement-unit (SMU) connected to adjustable
examined using an optical microscope to make sure that probes in the testing chamber. To achieve a desired con-
enough number of nanowires were placed between elec- centration of target VOC gas, a specific amount of the VOC
trode fingers (Fig. 4). As it can be seen in Fig. 4, bundles of liquid was evaporated in a 1.5 L glass container to obtain a
nanowires were dispersed randomly between electrode fin- high-ppm source. Afterwards, a measured volume of high-
gers with different densities. To address the bundling issue, ppm container atmosphere was sampled and injected into the
the dispersion of nanowires could be enhanced by applying air-tight testing chamber. Regarding the CO sensing tests,
dielectrophoresis methods to align nanowires between the desired concentrations can be generated by inserting a meas-
electrodes as proposed in Refs. [13, 52, 54]. ured volume of CO gas into the chamber using an ALICAT
To compare the gas sensing behaviors of C ­ u2O and CuO MC-100SCCM MFC connected to a lab-grade CO cylinder.
nanowires, the prepared sensor was annealed at 400 °C for All the tests were conducted in ambient atmosphere with an
30 min to oxidize the ­Cu2O nanowires and convert them average relative humidity of 30% RH monitored by a HIH-
to CuO [54–56]. However, as we discuss later in Sect. 3.1, 4000 humidity sensor. The response value was calculated as
further crystallography characterization showed partial con- [((Rg − Ra )∕Ra ) × 100] where Ra and Rg are the resistances
version of C­ u2O to CuO resulting in CuO/Cu2O compos- measured from the sensor in the clean and contaminated
ite nanowires. Although the complete conversion of C ­ u 2O atmospheres, respectively.
nanowires could be achieved at higher temperatures and

Fig. 4  Images of nanowires dis-

persed on Au IDE at X400 (1)
and X600 (2, 3) magnifications

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Fig. 5  Gas sensing test system

3 Results and discussion

3.1 Nanowires morphology and crystallography

Figure 6 shows SEM images of as-fabricated ­Cu2O nanow-

ires released from the template with an average diameter
and length of 180 nm and 8 µm, respectively. As shown
in Fig. 7, after thermal annealing the nanowires show an
increase in the surface roughness which could be attrib-
uted to the density difference and relief of stress caused
by oxidation and recrystallization [39].
Previous literature on thermal oxidation of ­C u 2O to
CuO have shown that at temperatures above 350 °C, ­Cu2O
changes to CuO [54–56]. Figure 8 compares the XRD pat-
terns for nanowires before and after annealing. Comparing
the obtained patterns to standard reference JCPDS cards
(No. 78-2076 for ­C u 2O and No. 80-1917 for CuO), the
CuO formation after annealing can be clearly observed.
Well-defined diffraction reflections indexed at 35.7°, 38.7°
and 49° are observed in post-annealing
−
XRD correspond-
ing to CuO lattice planes (1 11 − 002) , (111–200), and
(020), respectively. The weaker peaks at 36.6° and 42.5°
represent (111) and (002) ­Cu2O lattice planes.
By conducting Rietveld analysis of XRD pattern using
HighScore Plus software the volume ratio of CuO to ­Cu2O
for the annealed nanowires were calculated to be about
85:15. As reported by other groups in Refs. [55, 57], the
CuO/Cu2O nanowires synthesized by thermal annealing of Fig. 6  SEM images of synthesized C
­ u2O nanowires

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­Cu2O form a core–shell structure. Considering the average

diameter of 180 nm for the CuO/Cu2O nanowires with 85%
content of CuO, the CuO shell thickness is estimated to be
about 80 nm.

3.2 Gas sensing measurements

The sensing properties of the ­Cu2O and ­Cu2O/CuO nanow-

ires based gas sensors were characterized upon exposure to
ethanol, acetone, methanol and CO at different temperatures
and concentrations. Before initiating the gas sensing tests,
the sensors were kept at 200 °C for 24 h to enhance response
stability. The sensors were examined towards 50 ppm of
VOC gases and 500 ppm of CO at 250, 200, 150 and 100
°C which are below the transition temperature of C ­ u2O to
CuO [33, 35]. For all target gases, a consistent increase in
the ­Cu2O NWs response vs. temperature is shown Fig. 9a.
Regarding the CuO/Cu2O NWs, 150 and 200 °C were meas-
ured as the optimum temperatures for CO and ethanol sens-
ing, respectively (Fig. 9b). Comparing the results of the two
gas sensors, it can be inferred that C ­ u2O NWs were consid-
erably more responsive to VOC gases, especially ethanol,
while CuO/Cu2O NWs could be investigated as a CO gas
sensor at lower temperatures.
Figure 10a shows the sensitivity of C ­ u2O NWs towards
ethanol concentrations ranged from 50 ppm down to 1 ppm
at 250 °C. The response value reaches to 180% for 50 ppm
concentration, and declines to 17.5% at 1 ppm ethanol con-
centration. Figure 10b shows the normalized resistance of
the sensor vs. time to illustrate the dynamic behavior of etha-
nol sensing. Figure 11-a features a remarkable response time
of 17 s and recovery time of 35 s when exposing to 50 ppm
Fig. 7  FE-SEM images of annealed nanowires surface morphology
of ethanol which are outperforming the some of the similar
­Cu2O ethanol sensors compared in Table 1. To compare the
sensing dynamic behavior of ­Cu2O and CuO/Cu2O nanow-
ires, the response of CuO/Cu2O sensor towards for 50 ppm
of ethanol is presented in Fig. 11b. Comparing Fig. 11a, b
shows that the ­Cu2O sensor is almost 6 times faster than
CuO/Cu2O which show response and recovery times of 118
and 210 s.
When exposing to CO gas, it can be seen in Fig. 12 that
the CuO/Cu2O sensor operating at 150˚C showed response
values of 55 and 16% towards 500 and 60 ppm of CO gas,
respectively, while ­Cu2O sensor showed a response value of
25% towards 500 ppm of CO even at a higher temperature
of 250 °C.
The results for CO sensing show a significant performance
boost for our CuO/Cu2O sensor when compared to previous
reports [19, 21, 30, 57]. Therefore, the CuO/Cu2O based sen-
sors hold a great potential for sensor applications when low
Fig. 8  GIXRD patterns of nanowires before (a) and after (b) thermal operating temperature and selective CO sensing are required.
annealing Moreover, as it can be seen in Fig. 12c, response time of 90 s

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Fig. 9  Responses of a ­Cu2O nanowires, b CuO/Cu2O nanowires; towards 50 ppm of ethanol, acetone, methanol and 500 ppm of CO at different
temperatures

Fig. 10  Gas sensing of ­Cu2O NWs sensor towards ethanol at 250 °C. (a) Response values versus concentrations. b Normalized resistance of the
sensor versus time

Fig. 11  Comparing response and recovery times of the response towards 50 ppm of ethanol for a ­Cu2O NWs at 250 °C, b CuO/Cu2O NWs at
200 °C

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Table 1  The Comparison of Nanostructure Concentration Working The Response Recovery References
ethanol sensing performance of (ppm) temperature response time (s) time (s)
­Cu2O nanostructures (°C) value (%)

Nanocage 50 250 190 112 137 [49]

hollow polyhedral 50 210 850 24 36 [58]
NanoCube 50 250 150 27 30 [51]
Nanowire 50 250 180 17 35 Present work

and recovery time of 330 s were obtained for CO sensing of 2 × 1017 cm−3 [59] and dielectric constant of 10.2 [60] at
which are comparable values to reported values when it comes 200 °C, the Deby length would be approximately 10 nm:
to low sensing temperatures like 150 °C. (gas)
The ­Cu2O and CuO/CU2O nanowire sensors gas sensing O2 ⟷ O−(ads)
2
+ h+ , (3)
behavior towards ethanol and CO gases are summarized in
Table 2. It is worth mentioning that the recovery process in the O−(ads) ⟷ 2O−(ads) + h+ , (4)
test was accomplished by simply opening the air-tight cham- 2

ber lid and exposing the sensor to fresh room air without any
pumping or air flow, therefore, it would represent more real-
√
𝜀kB T
istic recovery results. Moreover, as mentioned before, all gas 𝜆D = . (5)
Na q2e
sensing tests were measured in an average 30% RH.
In the presence of a reducing gas, the chemisorbed oxy-
3.3 Gas sensing mechanism gen ion reacts with the reducing gas and trapped electrons
by oxygen ions turn back to the metal-oxide surface which
Conduction of p-type metal oxides can be explained by accep- means a decrease in hole accumulation layer thickness and
tor levels in the bandgap which for CuO and C ­ u2O cases are subsequent decrease in sensor conduction (Fig. 13d).
copper vacancies. The copper vacancies determine the appear- Regarding CO sensing mechanism, the adsorbed oxy-
ance of holes in the valence band. In an oxygen-rich atmos- gen reacts with CO gas molecule to form C ­ O2 (Eq. 4). In
phere, adsorption of atmospheric oxygen on the surface of the case of ethanol sensing, ethanol molecules react with
copper oxides results in chemisorbed oxygen species and the adsorbed oxygen ions by consuming the holes so that it
creation of extra holes in the valance band [12]. The adsorbed breaks into ­CO2 and ­H2O molecules (Eq. 5):
oxygen can be in molecular form (O−2 ) for temperatures below
(gas)
150 °C or atomic (O−, O2−) for higher temperatures (Eqs. 3, CO(gas) + O−(ads) + h+ → CO2 , (6)
4) [24]. These reactions generate a hole accumulation on the
surface of nanowires which in turn increases the conductivity (gas)
of the nanowires (Fig. 13b). C2 H5 OH(gas) + 3O−(ads)
2
+ 3h+ → 2CO2 . (7)
The thickness of the hole accumulation layer can be
While the structure of the CuO/Cu2O nanowires can
approximated by Debye length which is calculated using
be considered as core–shell, by considering the CuO shell
Eq. (5) where 𝜀 and Na are dielectric constant and acceptor
thickness of 80 nm and comparing it to the Debye length of
density of the p-type metal oxide and kB , qe and T represent
less than 15 nm it can be inferred that the core–shell struc-
Boltzman constant, electron charge and operating tempera-
ture can be ignored in explaining the gas sensing mechanism.
ture, respectively. For instance, for CuO with acceptor density

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Response and recovery times are determined by the speed

of the reactions defined by the concentration of majority
carriers and mobility of the metal oxide ions. According
to literature, the CuO hole mobility is about 0.2 ­cm2/V s
[34] while a hole mobility of 4.7 c­ m2/V s is reported for
electrodeposited ­Cu2O [50]. Considering the similarity and
uniformity in nanowires dimensions of both sensors due
to template-assisted approach, the very low hole mobility
might explain the slow gas sensing behavior of the CuO/
Cu2O nanowires that can be the subject of future studies.

4 Conclusion

High aspect ratio C­ u2O nanowires with an average diameter

of 180 nm and length of 8 µm were synthesized by electro-
deposition into a polycarbonate template from an aqueous
solution. Subsequent annealing resulted in CuO/Cu2O com-
posite nanowires. Two conductometric gas sensors based on
­Cu2O and CuO/Cu2O composite nanowires were fabricated
and tested towards few VOCs and CO gases. The results
showed that ­Cu2O nanowires can be employed as a sensi-
tive and fast ethanol gas sensor at the temperature of 250 °C
while CuO/Cu2O nanowires show good and selective CO
sensing behavior at a lower temperature of 150 °C. Accord-
ing to the results, ­Cu2O nanowires gas sensor is nearly 6
times faster than the sensor based on CuO/Cu2O nanowires.
The fast response and high sensitivity of our ­Cu2O nanowire
sensors towards ethanol and low temperature and selective
CO sensing of CuO/Cu2O nanowires make them a promis-
ing candidate for future industrial applications where low
cost, low operating temperature and high sensitivity are
demanded.

Fig. 12  a CuO/Cu2O Sensor response towards different concentra-

tions of CO at 150 °C, b dynamic behavior of the sensor towards dif-
ferent concentrations of CO at 150 °C, c sensor response and recov-
ery times of the sensor towards 50 ppm of CO at 150 °C

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Table 2  The fabricated sensor Sensor type Target gas Optimum tem- Response Response time Recovery time
gas sensing test results toward perature (°C)
ethanol and CO gases
Cu2O NWs Ethanol 250 178% (50 ppm) ~ 17 s ~ 35 s
15%(1 ppm) ~ 15 s ~ 29 s
CuO/CU2O NWs CO 150 54% (500 ppm) ~ 90 s ~ 330 s
16% (60 ppm) ~ 110 ~ 108

Fig. 13  CO Gas sensing mechanism of CuO/Cu2O nanowire illustration. a, b Oxygen adsorption and hole accumulation layer formation, c
adsorbed oxygen ion reaction with CO, d reduction of HAL layer depth and resistance increase

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