Aligned Grid Shaped NiO Nanowires for Humidity

Sensing at Room Temperature

Masoumeh Mohammadi
University of Kashan
Mohammad Almasi-Kashi
University of Kashan
Somayeh Fardindoost
Sharif University of Technology
Azam Iraji zad (  [email protected] )
Sharif University of Technology

Research Article

Keywords: Aligned NiO nanowires, Electrodeposition, Humidity sensor, Impedance spectroscopy, Ionic
conduction

Posted Date: December 30th, 2020

DOI: https://doi.org/10.21203/rs.3.rs-135179/v1

License:   This work is licensed under a Creative Commons Attribution 4.0 International License.
Read Full License
 Aligned Grid-shaped NiO Nanowires for Humidity Sensing at Room
Temperature

Masoumeh Mohammadi a, Mohammad Almasi-Kashi a,b*, Somayeh Fardindoost c and Azam Iraji zad c&d*
a
Institute of Nanoscience and Nanotechnology, University of Kashan, 8731753153, Kashan, Iran
b
Department of Physics, University of Kashan, 8731753153, Kashan, Iran
c
Department of Physics, Sharif University of Technology, Azadi Street, 11365-9161, Tehran, Iran
d
Institute for Nanoscience and Nanotechnology, Sharif University of Technology, Azadi Street,
11155-8639, Tehran, Iran
*
E-mail: [email protected] and [email protected]

Abstract
A grid configuration based on the aligned nickel oxide nanowire (NiO NW) for humidity
sensing were fabricated through the oxidation of ferromagnetic nickel NWs prepared by a
template-assisted electrodeposition process. Their structure and elemental compositions
were characterized by field emission scanning electron microscopy (FESEM), X-ray
diffraction (XRD), and energy-dispersive X-ray analyses (EDAX). The room-temperature
humidity sensing behavior of the NiO NWs was investigated successfully based on DC and
AC impedance spectroscopy (IS) method in frequencies range 10 Hz to 2 MHz. The sensors
showed excellent humidity sensing characteristics such as a high response of about 66 with
rather rapid response-recovery times about 9 and 2 s for 90%RH, and good stability. The
equivalent circuits were simulated for impedance responses to humidity in the range of
40% to 90% RH. According to the results, ionic conduction via NW-NW junctions as well
as NW-electrode interfaces in the grid configuration is responsible for sensing behavior.

Keywords: Aligned NiO nanowires, Electrodeposition, Humidity sensor, Impedance

spectroscopy, Ionic conduction.

1
 1. Introduction
Sensing and control of humidity are important in a broad spectrum of applications such
as agricultural activities, industrial production processes, medical fields, and living
environment [1-4]. Therefore, the necessity of microclimate control in different
environmental conditions has led to the design and development of various types of
humidity sensors [5-7]. The advancements in sensing materials are expected to produce
sensors with high sensitivity, fast response-recovery times, low operating temperatures,
and good chemical and thermal stability [8-9]. Various kinds of materials such as polymers
[10], ceramics [11], graphene [12], carbon nanotubes [13], silica [14], photonic crystals
[15], and metal oxides [16] have been studied for humidity sensors. Among them, metal
oxides have attracted considerable attention because of their excellent sensing properties,
low cost, simple manufacturing process, and obvious operating mechanism [17-18].

The common method to determine environmental relative humidity (RH) is the

measurement of changes in conductance or capacitance of these moisture-sensitive
materials, originating from the interaction between water molecules and the sample surface
[19]. The water molecules in contact with the metal oxide humidity sensor give rise to a
change in charge carrier concentrations and alter the resistance and capacitance of the
material [19]. Large surface area can significantly improve the response to humidity [20-
21]. So, we expect that the one-dimensional (1D) nanowires can provide a much higher
surface area, as compared to thin film or bulk materials. As reported for the 1D nanowire
arrays, the number of surface active sites for the absorption of water molecules increases,
resulting in the overall change of the sensing conduction and increase of the humidity-
sensitive characteristic of the sensor [22-25].
Herein, we introduce a humidity sensor based on the grid-shaped arrays of NiO NWs.
These sensors were fabricated through oxidation of ferromagnetic Ni NWs prepared by an
electrodeposition technique using the anodized aluminum oxide (AAO) template. The
template-assisted electrodeposition is a relatively simple and cost-effective technique that
can be used for mass production of metal NWs with defined geometry and size [26]. Ni

2
NWs obtained by this method has a specific diameter and high surface-to-volume ratio
with a good crystal structure. On the other hand, the NW grid-shaped arrays is easily
accomplished by exerting a uniform magnetic field in two perpendicular directions. To
investigate the successful formation of NWs, they were characterized by X-ray diffraction
(XRD), optical microscope, field emission scanning electron microscopy (FESEM), and
energy-dispersive X-ray (EDX) analyses. The electrical characteristics of NWs in a humid
atmosphere such as response and response-recovery times is provided by DC analysis.
Impedance spectroscopy is also employed to develop the equivalent circuit model. The
proposed circuit is utilized to explain the sensor response mechanism, indicating whether
it has resulted from the body of the NWs, junctions, or the electrode-NWs interfaces [27].
In general, the sensor based on the aligned grid-shaped NiO nanowires shows excellent
humidity sensing characteristics such as high sensitivity, rapid response-recovery times,
and stability.

2. Experimental details

2.1. Preparation of the sensors based on aligned NiO NWs

NiO NWs were prepared by calcination of Ni NWs fabricated by a template-assisted
electrodeposition process. In this method, a hard-AAO template was used to fabricate metal
NWs [28]. For electrodepositing Ni NWs into nanopores of the template, an aqueous
electrolytic bath containing NiSO4·6H2O (0.3 M) and boric acid (40 g.l-1) was used, and
the temperature was kept at 30°C. The electrodeposition process of NWs was performed
with a constant reduction voltage of 12 V, an initial oxidation voltage of 10 V, a
reduction/oxidation time of 2.4/4.8 ms, and an off-time of 48 ms. During the process, the
maximum reduction current density was kept constant at 50 mA cm-2. By chemical etching
with NaOH solution (2 M) at room temperature for 2 h, the porous alumina membrane was
completely removed to finally release the Ni NWs.

The obtained NWs were dispersed in deionized (DI) water to prepare slurry by
sonication, followed by distributing it to a glass substrate located in a uniform magnetic

3
field. The presence of the magnet assisted in the preferential orientation of NWs along the
field lines. Accordingly, a grid-shaped structure of NWs was created by placing the glass
substrate in two directions perpendicular to the field. The aligned Ni NWs were then
converted into the oxide state by calcinating them at a temperature of 500°C for 1 h. The
calcination process resulted in better adherence of the NWs onto the substrate while also
improving their interfacial contacts and eliminating any organics left by the solvent.
Finally, Ag was sputtered on the array of NiO NWs using a delicately-designed shadow
mask with inter-digitized comb-like electrodes (Yar Nikan Saleh Co., Iran). The respective
width and length of each finger were about 0.25 and 4 mm. Moreover, the electrode inter-
spacing was 0.27 mm. This architecture has hundreds to many thousands of NWs well
oriented with many NW–NW junctions and NW–electrode interfaces.

2.2. Characterization and measurement techniques

The wide-angle XRD analysis was performed by an X-ray diffractometer (Panalytical
X'Pert Pro) using Cu Kα radiation (λ=1.5418 Å) operating at 40 kV and 30 mA in the range
of 35°–80°. The optical image of the sample was obtained from an Optika B-383PLi
microscope. FE-SEM images and EDX pattern were recorded using a MIRA3TESCAN-
XMU microscope with an accelerating voltage of 15 kV.
The resistive humidity sensing of the grid-shaped NiO NWs was measured by applying
a DC voltage of less than 1 V via a Sanwa Electronic Instrument Co., Ltd. The relative
humidity with different percentages ranging from 25% to 90% was generated by the well-
controlled flow of dry air into a bowl containing DI water (18 MOhm-cm). The sensor was
placed on top of the bowl close to a hygrometer. The impedance spectroscopy sensing
performance was tested using an impedance analyzer (Model SI 1260) in a two-point
configuration, and a voltage of 50 mV AC signal which overlapped on a constant voltage
of less than 1 V DC was applied. The variation in the impedance while the sensor was
exposed to humidity was collected in 10 Hz to 2 MHz frequency range. Then the obtained
IS data analyzed to figure out the equivalent circuit elements versus RH using a software

4
package (IS spectrum analyzer software) [29]. All of the sensing measurements were
performed at room temperature.

3. Results and discussion

3.1. Structure of the aligned NiO nanowires

Crystal structure and purity of the as-fabricated and calcined Ni NWs were analyzed using
the XRD characterization technique. According to the XRD peaks depicted in Fig. 1a, the
as-fabricated Ni NWs show three diffraction peaks at 44.5°, 51.8°, and 76.4° corresponding
to (111), (200), and (220) crystal planes, respectively. In Fig. 1b, four diffraction peaks at
2θ°= 37.4°, 43.3°, 62.8°, and 75.44° are observed, which correspond to (111), (200), (220),
and (311) planes of NiO, respectively. These results indicate that Ni NWs are completely
converted into crystalline NiO NWs after the calcination process.

Fig. 1: XRD patterns of: (a) as-fabricated Ni, and (b) the calcined Ni (NiO) NWs.

Fig. 2a shows the image taken by an optical microscope after the calcination process.
As can be seen, a grid-shaped structure of NiO NWs is created by placing them in two
perpendicular directions of a magnetic field. The surface morphology and microstructure
of the NiO NWs were also examined by using FESEM. As it is seen from Fig. 2(b–d), the
average diameter and length of the NiO NWs are about 270 nm and 25 μm, respectively.

5
 Fig. 2: (a) Optical microscope image, and (b-d) FESEM images of aligned NiO NWs.

The elemental compositions of NiO NWs were explored using EDX as shown in Fig.
3. The result shows that the sample contains nickel and oxygen elements.

6
 Fig. 3: EDX spectrum of the grid-shaped NiO NWs.

3.2. Humidity sensing

To investigate the sensor performance, stable responses of the aligned grid-shaped NiO
NWs to humidity ranging from 25% to 90% RH were obtained under a constant DC voltage
at room temperature. The resistance changes of the sensor to humidity is represented in
Fig. 4a. It is observed that the resistance of the sensor decreases with an increase in RH.
Variation of the responses (defined as Rair/ Rhumidity in which Rair and Rhumidity are the
sensor resistance in the absence and presence of the exposed humidity, respectively [17].)
against RH% is shown in Fig. 4b. The plot exhibits an increase in the response of the sensor
with the increment in RH. The fitting equation for the lower humidity range can be
represented by an exponential function as Response = 0.0129 e RH/9.5417 + 0.8208 with the
fit correlation R2 = 0.9963. In the above humidity range of 80%, it shows saturation
behavior.
Fig. 4c represents typical three consecutive response-recovery cycles for 90% RH
indicating fast response and recovery times. As an important characteristic parameter, the
response time is defined as the time taken to reach 90% variation in the sample resistance
with respect to equilibrium value following an injection of humidity. The recovery time
also is defined as the time required for the sample to return to 10 % variation in its

7
resistance in the air after the removal of the exposed humidity [30]. In our samples, the
response and recovery times were around 9 s and 2 s at RH of 90%. Generally, samples
presented good stability.

Fig. 4: (a) Resistance of the NiO NWs sample as a function of time for different RH, (b) sample response versus
relative humidity and (c) typical three consecutive cycles of sample current versus time.

To understand the transport mechanism and different behavior in the response as a

function of concentrations at high RH, we perform impedance measurements. The
measured signal of the sensor in exposure to humidity includes many components such as
the surface and bulk of the sensing material, the wire/wire junctions, and the
wires/electrode interfaces. The Nyquist plot of impedance spectroscopy can differentiate
the contributions of each of these components [27]. Generally, an equivalent electrical

8
circuit is used to explain these different processes, which is extremely useful in clarifying
the mechanism of the humidity sensor. The response of NiO NWs to humidity investigated
by complex impedance spectra [Z(ω) = Z′(ω) + j Z"(ω)] is shown in the Nyquist diagrams
(Fig. 5a for 40-60% and 5b for 80-90%). The plots show the imaginary part of impedance
(-Z") versus the real part (Z′) with the centers of semicircles depressed below the real axis
so that each point corresponds to a different angular frequency (ω=2πf). The equivalent
electrical circuits of each semicircle include a resistor (R) in parallel with a constant phase
element (CPE; Randle loop). The CPE usually refers to a non-ideal capacitor whose
impedance is given by equation (1) [31]:

1
ZCPE = 0 (1)
Q (jω)n

Where the constant Q0 determines the impedance modulus, and the exponent n is related
to the impedance angle which goes from 0 ◦ to 90◦. In the special case of n = 1 (90◦),
Q0 becomes C and the CPE acts as a pure capacitor. For n = 0, Q0 becomes 1/R and the
element behaves as a pure resistor. If the value of n is between 0 and 1, CPE would not
take the value of either the capacitance or the resistance. In this case, CPE takes a
combination of resistor and capacitor [32]. When CPE is in parallel with a resistance, true
capacitance values can be calculated from the following equation [31]:

1/n
(Q0 ×R)
C= (2)
R

For nanostructured material, we expect three resistor-capacitor (RC) elements in series,

each representing a physical entity of the device. The semicircle plot at lower frequencies
is attributed to the material-electrode interface, the middle semicircle to the junctions, and
the semicircles at higher frequencies are assigned to the bulk of the material. In practice,
the bulk capacitance is usually small compared to that of various interfaces [27]. However

9
for our samples as shown in Fig. 5(a, b), at low humidity (40–60%), the Nyquist plot shows
one semicircle in the whole frequency region, while at high humidity (80–90%), two arcs
have appeared (an incomplete depressed arc at low frequency and a nearly perfect
semicircle at high frequency). These can be referred to the circuit model in which two
frequency-independent resistances, R1 and R2, are in parallel with two constant phase
elements, CPE1, and CPE2, respectively. The fitting parameters for the different RHs are
summarized in Table 1. According to the observed range of capacitance values, it is
concluded that in the low humidity, the sensor electrical properties originate mainly from
NW-NW junctions (R1 resistance and C1 capacitance of junctions). Moreover, the
electrode-NW interfaces (R2 resistance and C2 capacitance of electrode interfaces) can play
an important role in the response to the high humidity range.

Fig. 5: The complex impedance spectra of aligned NiO NWs measured at the RH values of: (a) 40% and 60%, (b) 80% and
90%. For all complex impedance plots, the points and solid lines represent the experimental and fitted data, respectively.

Table 1 indicates that all the calculated resistances are reduced by increasing RH, which
can be attributed to the ionic conduction mechanism [33]. Depending on the RH value,
both chemisorption and physisorption of the water molecules happen on the NWs surface,
at the junctions and interfaces. At low RH, the water molecules chemisorb on the metal
cation sites present in the surface of the NWs to make hydroxyl ions by a dissociative
mechanism. This chemisorbed layer stays stable and forms the base for further
10
physisorption of water molecules by the increment of RH at room temperature. As the
sensor is exposed to higher RH, the water molecules are physisorbed by hydrogen bonding
on the hydroxide surface forming the first physisorbed water layer. By increasing the RH,
resistance damped indicates much more water molecules were physically adsorbed forming
continuous layer and results in proton hopping between neighboring water molecules. The
junctions and interfaces of the nanowires in this grid configuration present a strong
electrostatic field, which promotes the water dissociation into H3O+ and OH-. This
dissociation provides protons as charge carriers of the hopping transport. The charge
transport occurs when the H3O+ releases a proton to a nearby H2O water molecule, ionizing
it and forming another H3O+, resulting in the hopping of protons from one water molecule
to another and decreases the sensor resistance. This process is known as the Grotthuss chain
reaction, and it is assumed that it also represents the conduction mechanism in liquid water
in higher RHs [34]. In other words, with the increase of the RH, the Grotthuss proton-
transfer process takes place, leading to the participation of NW-NW junctions and
electrode-NW interfaces in the conduction.
From Table 1, it can also be drawn that the capacitances increase by forming adsorbed
layers in the junction and at electrode surfaces of the sensing material with increasing RH
to 90%. This means that singly bonded water molecules can form dipoles and reorient
freely under an externally applied electric field and thus enhance the electrode and water
molecular polarization effects. As seen, the C2 is far larger than C1. It verifies that the
electrode polarization effect is much stronger than the water molecular polarization effect.
The schematic diagram of NiO NWs sensor is shown in Fig. 6.

Table 1: Equivalent circuit model data fittings from aligned NiO NW measurements for different RH%.

Q01 C1 R2 Q02 C2
RH% R1 (MΩ) n1 n2
(10 ×Ω-1sn)
-12
(p F) (MΩ) (10 ×Ω-1sn)
-9
(n F)
40 48 5 0.91 2 – – – –
60 24 10.1 0.91 4 – – – –
80 5.9 38 0.91 17 5.1 25 0.45 2.02
90 3.15 83 0.91 37 1.01 15 0.93 10.94

11
 Fig. 6: The schematic diagram of NiO NWs sensor’s geometry.

Compared to some metal oxide nanostructure-based humidity sensors (see Table 2),
our sensor parameters indicate good sensing behavior at room-temperature. This is due to
the high surface-to-volume ratio of the nanowires as well as presence of many junctions in
an aligned grid-shaped configuration that provide high adsorption sites for water molecules
and the large interspaces between the aligned nanowires help water molecules pass quickly
through the materials, contribute to the rapid response behavior.

Table 2: Humidity sensor performance of this study compared to that of some previous reports.
Sensitivity
Sensing material RH% Response tresponse (s) trecovery (s) Reference
(%)
ZnO NWs 53.6. - - 35.3 32.6 [25]
NiO–SnO2 nanofibers 83 7.45* - 18.4 37.2 [35]
ZnO-SnO2 thin film 92 - 24 21 32 [36]
TiO2 thin film 90 - 80.85 77.5 3 [37]
SnO2 thin film 93 55.5* - 17 2 [38]
Aligned grid-shaped NiO
90 65 98.5 9 2 This work
NWs
*we calculated from their data

12
4. Conclusion
Aligned grid-shaped NiO NWs were fabricated via the electrodeposition technique,
followed by a calcination process. The effect of RH on the electrical response of the sensing
element was studied based on DC and AC methods. The modeling of impedance
spectroscopy results in equivalent circuit and the role of NW-NW junctions and NW-
electrode interfaces in response behavior in different RH%. In general, rather good
humidity sensing of the sensor described based on sample grid configuration which has
many junctions and high surface to volume ratio, providing more active sites and connected
media for ion transport and results in short response and recovery times. The high
performance NiO nanowires can be used in researches into semiconductor sensors to early
detection systems for humidity.

Author contributions
Azam Iraji zad (A.I.) devised the main conceptual idea. Somayeh Fardindoost (S.F.) and
Masoumeh Mohammadi (M.M.) planned and carried out the experiments. M.M.
fabricated the samples. S.F. and M.M. did the measurements and analyzed the spectra.
A.I., Mohammad Almasi-Kashi (M.A.K.), and S.F. helped supervise the findings of this
work. M.M. wrote the manuscript with input from all authors. M.M. prepared all figures
and tables in the manuscript. All authors discussed the results and contributed to the final
manuscript.

Competing interests
The authors declare no competing interests.

Fig. 1: XRD patterns of: (a) as-fabricated Ni, and (b) the calcined Ni (NiO) NWs.
Fig. 2: (a) Optical microscope image, and (b-d) FESEM images of aligned NiO NWs.
Fig. 3: EDX spectrum of the grid-shaped NiO NWs.
Fig. 4: (a) Resistance of the NiO NWs sample as a function of time for different RH, (b)
sample response versus relative humidity and (c) typical three consecutive cycles of sample
current versus time.

13
Fig. 5: The complex impedance spectra of aligned NiO NWs measured at the RH values
of: (a) 40% and 60%, (b) 80% and 90%. For all complex impedance plots, the points and
solid lines represent the experimental and fitted data, respectively.
Fig. 6: The schematic diagram of NiO NWs sensor’s geometry.

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Table 1: Equivalent circuit model data fittings from aligned NiO NW measurements for different RH%.

Q01 C1 R2 Q02 C2
RH% R1 (MΩ) n1 n2
(10-12 ×Ω-1sn) (p F) (MΩ) (10-9 ×Ω-1sn) (n F)
40 48 5 0.91 2 – – – –
60 24 10.1 0.91 4 – – – –
80 5.9 38 0.91 17 5.1 25 0.45 2.02
90 3.15 83 0.91 37 1.01 15 0.93 10.94

Table 2: Humidity sensor performance of this study compared to that of some previous reports.
Sensitivity
Sensing material RH% Response tresponse (s) trecovery (s) Reference
(%)
ZnO NWs 53.6. - - 35.3 32.6 [25]
NiO–SnO2 nanofibers 83 7.45* - 18.4 37.2 [35]
ZnO-SnO2 thin film 92 - 24 21 32 [36]
TiO2 thin film 90 - 80.85 77.5 3 [37]
SnO2 thin film 93 55.5* - 17 2 [38]
Aligned grid-shaped NiO
90 65 98.5 9 2 This work
NWs
*we calculated from their data

16
Figures

Figure 1

XRD patterns of: (a) as-fabricated Ni, and (b) the calcined Ni (NiO) NWs.
Figure 2

(a) Optical microscope image, and (b-d) FESEM images of aligned NiO NWs.
Figure 3

EDX spectrum of the grid-shaped NiO NWs.

Figure 4

(a) Resistance of the NiO NWs sample as a function of time for different RH, (b) sample response versus
relative humidity and (c) typical three consecutive cycles of sample current versus time.
Figure 5

The complex impedance spectra of aligned NiO NWs measured at the RH values of: (a) 40% and 60%, (b)
80% and 90%. For all complex impedance plots, the points and solid lines represent the experimental and
tted data, respectively.

Figure 6
The schematic diagram of NiO NWs sensor’s geometry.