Materials Today Communications 33 (2022) 104196

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Materials Today Communications

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A study of structural, morphological, optical and humidity sensing

properties of CaCu3Ti4O12 powders synthesized by combustion method
Anamitra Chattopadhyay, Biswajyoti Mohanty, Jhasaketan Nayak *
Oxide semiconductor Laboratory, Department of Physics, IIT(ISM) Dhanbad, Jharkhand 826004, India

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

Keywords: Calcium Copper Titanate (CCTO) powder was synthesized via a low-cost facile combustion method at various
CCTO powder calcination temperatures and times. The structural properties of the prepared CCTO powder were investigated
Crystal Structure from an X-ray diffraction (XRD) study, which confirmed the formation of the cubic phase with space group Im3.
Microstructure
Further, Rietveld refinement of the XRD data was performed for the detailed structural analysis of the samples.
Bandgap
Humidity sensor
The surface morphology of the CCTO powder was studied by Field Emission Scanning Electron Microscopy
(FESEM), which showed an increase in particle size with an increase in the calcination temperature. The optical
properties of the powders were examined by UV–vis Diffuse Reflectance Spectroscopy (DRS) and Photo­
luminescence Spectroscopy. The optical bandgap values, estimated from Tauc’s plot, increase with the increase
in calcination temperature due to the elimination of structural defects or localized states inside the bandgap. The
porous single-phase CCTO ceramic was subjected to a homemade experimental set-up combined with an LCR
meter to investigate its room temperature humidity sensing characteristics in capacitive mode at various oper­
ating frequencies. At 100 Hz, the obtained humidity response curve for the CCTO-based sensor showed a 560 %
increment in capacitance as the Relative Humidity (RH) changed from 40 % to 90 %.

1. Introduction
Over the last few decades, inorganic perovskite nanostructured ma­
terials have received substantial research attention due to their
impressive utilization in diverse fields [1–5]. Many cubic perovskite
structured compounds with the chemical formula ABO3 are found in the
environment. The coordination numbers for the B and A cations are six
and twelve, respectively, although significant deviation from the ideal
structure and stoichiometry can be frequently observed [6]. A common
orthorhombic distortion is noticed in ideal perovskite, where the octa­
hedral structure of BO6 tilted to create square planar coordination for
three-quarters of the A cations. This structure is commonly known as
ACu3M4O12. CaCu3Ti4O12 (CCTO) is such a body-centered cubic
perovskite structured material that belongs to the centrosymmetric Im3
space group (No. 204) [7]. Mismatch of atomic sizes and the nature of
the A cation causes an octahedral tilt distortion in the CCTO structure.
This tilting of TiO6 octahedron derives a complex perovskite structure
where three-quarters of the A site is occupied by Jahn-Teller Cu2+
cation. The remaining sites are occupied by calcium atoms [8]. In CCTO,
the Ti–O–Ti angles are reduced to 141º from the ideal angle of 180 º by
the TiO6 octahedral tilt. Interestingly, the tilt/rotations of the octahedra
do not affect the connectivity of corner cations. However, various
fundamental physical properties of perovskite titanates (ACu3Ti4O12)
depend on this octahedral tilt distortion.
Some of the important characteristics of CCTO are its temperature-
independent high dielectric permittivity (~105 for single crystal and
104 for bulk) over a wide range of temperatures (100–400 K), high
melting point, high chemical and mechanical stability [9]. These prop­
erties make CCTO an eligible candidate for various technological ap­
plications such as antenna, switches, microwave devices, capacitors, and
sensors [10–13]. The polycrystalline porous nanostructure makes it
eligible to fabricate reliable and affordable sensors. To date, several
synthesis processes of CCTO have been reported. High purity CCTO has
been synthesized by the solid-state method, sol-gel synthesis method,
wet-chemistry method, sonochemical method, and chemical precipita­
tion method [14–19]. These conventional synthesis methods generally
require a high temperature and long reaction time for the formation of
single-phase CCTO crystals. Therefore, this work has investigated the
properties of the CCTO nanopowder, synthesized via combustion
method that requires a shorter reaction time and yields greater

* Corresponding author.
E-mail address: nayakj@iitism.ac.in (J. Nayak).

https://doi.org/10.1016/j.mtcomm.2022.104196
Received 3 August 2021; Received in revised form 28 July 2022; Accepted 5 August 2022
Available online 7 August 2022
2352-4928/© 2022 Elsevier Ltd. All rights reserved.
A. Chattopadhyay et al. Materials Today Communications 33 (2022) 104196

Table 1 their variation with calcination temperature have also been studied. The
Synthesis parameters for CCTO powders. crystalline CCTO powders were pressed into cylindrical pellets and
Sample Calcination Calcination sintered at 1000 ºC and 1100 ºC for 4 h in the atmosphere separately. A
temperature (◦ C) Time (h) detailed study has been done on the microstructure and the variation of
S1 600 0.5 microstructure with sintering conditions of the pellets. In addition, the
S2 700 0.5 porous CCTO pellet has been employed for the humidity sensing mea­
S3 800 0.5 surements, and the sensing mechanism has also been discussed in detail.
S4 600 2
S5 700 2
S6 800 2
2. Experimental

Pure CCTO powders were synthesized by a wet-chemistry method

Fig. 1. XRD pattern for (a) precursor (S0), CCTO powder calcined at 600 ºC for
30 min (S1), 2 h (S4), and (b) CCTO powder calcined at 700 ºC for 30 min (S2),
2 h (S5) and at 800 ºC for 30 min (S3), 2 h (S6) respectively.
known as the combustion method. Calcium nitrate tetrahydrate (Ca
(NO)3, 4H2O) (≥99 %), Titanium (IV) isopropoxide (Ti[OCH(CH3)2]4)
(≥97 %), Copper (II) nitrate hemi-pentahydrate (Cu(NO)3, 2.5H2O) (98
%), Acetylacetone, Citric acid (≥99.5 %) and Ammonium hydroxide
(≥99 %) were purchased from Sigma Aldrich India and were used
without further purification.
In the synthesis process, 1.92 g of citric acid was first dissolved in
100 ml of deionized water. Then, 0.01 mol of titanium (IV) isopropoxide
and 0.01 mol of acetylacetone were mixed under constant stirring for
5 min using a magnetic stirrer. This titanium solution was added to the
aqueous citric acid solution. In the next step, 1.74 g of copper (II) nitrate
hemi-pentahydrate and 0.59 g of calcium nitrate tetrahydrate were
added to 20 ml of deionized water and were poured dropwise into the
titanium-citric acid solution under constant stirring. This resulted in a
light green solution. The addition of a few drops of ammonium hy­
droxide to control the rate of hydrolysis via pH adjustment made this
solution bluish green. This bluish green solution was heat-treated at
80 ◦ C for several hours until the water evaporated completely and
formed a highly viscous blue gel. Subsequently, the gel was calcined at
450 ◦ C for 15 min to burn out the organic component, resulting in
porous black powder. This black powder was named precursor S0.
Precursor S0 was first ground into a fine powder and divided into 6
parts, and each part was separately calcined at different temperatures
and times. The calcination temperature was 600–800 ◦ C, and the time
was 30 min to 2 h. The synthesis parameters for CCTO powders are
shown in Table 1.
The crystallinity and the phase of the prepared powders were
examined by Xpert Pro MPD X-ray diffractometer equipped with Cu-Kα
radiation (λ = 1.5406 Å). The 2θ range was from 20◦ to 80◦ with a
scanning rate of 0.02◦ min− 1. Detailed structural analysis was per­
formed by Rietveld refinement using Fullproof software. Morphology of
powders was studied by Supra 55 (Carl Zeiss, Germany) field emission
scanning electron microscope (FESEM) set at 5 kV. The UV-Vis DRS
spectra in the 200–800 nm range were recorded by Agilent Cary 5000
spectrophotometer. Hitachi F 2500 FL spectrophotometer, equipped
with a xenon lamp, was used to study the Photoluminescence spectra.
For humidity sensing measurements, the porous CCTO powder was
pressed into an 11 mm diameter pellet using a hydraulic press under the
pressure of 5 tons. The humidity sensing measurements were done by a
homemade set-up using an aquarium pump, humidity clock, and two air-
tight plastic boxes, as mentioned by Sahoo et al. [23].
3. Results and discussions

crystallinity. Recently few works have been published on humidity

3.1. Structural analyzation
sensing characteristics of CaCu3Ti4O12 thin films [20–22]. However, the
humidity response of porous CCTO powder synthesized by the com­
XRD patterns of S0 (precursor), S1, and S4, as shown in Fig. 1(a),
bustion method has not been investigated yet. Furthermore, a detailed
contains two intense peaks at 35.7º and 38.9º corresponding to (− 111)
study of structure, temperature-dependent morphology, and optical
and (111) planes of monoclinic CuO (Tenorite). Standard JCPDS data
properties are also important for its application in advanced technology.
(JCPDS No- 00–001–1117) has been plotted for reference. Fig. 1(b)
In this work, CCTO powders have been synthesized by varying the
shows the evolution of the XRD pattern for CCTO powder calcined at
calcination temperature (600 ºC - 800 ºC) and calcination time (30 min -
700–800 ◦ C for 30 min (S2-S3) and 2 h (S5-S6) respectively. The main
2 h), respectively. This report also investigates the change in the crystal
diffraction peaks for the powder calcined at 600 ◦ C (S1 and S4) are for
structure, morphology, and, porosity with the variation in synthesis
CuO (Tenorite). As the calcination temperature increases to 700 ◦ C the
parameters. Furthermore, the optical behavior of the nanopowders and
principal diffraction peaks are attributable to CCTO. The X-ray

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A. Chattopadhyay et al. Materials Today Communications 33 (2022) 104196

Fig. 2. Rietveld refinement for CCTO powder calcined at 700 ºC for (a) 30 min (S2), (b) 2 h (S5), and at 800 ºC for (c) 30 min (S3), and (d) 2 h (S6) respectively.

Table 2
Rietveld parameters for CCTO powders.
Sample S2 S3 S5 S6

Crystal system; BCC; Im-3 BCC; Im-3 BCC; Im-3 BCC; Im-3
space group (No.204) (No.204) (No.204) (No.204)
Lattice 7.39126 7.39214 7.3922 7.39264
parameters
a =b =c
(Å)
Background linearly interpolated between linearly interpolated between linearly interpolated between linearly interpolated between
background selected points background selected points background selected points background selected points
Density (g/cm3) 5.049 5.048 5.051 5.051
Angle (in 90 90 90 90
degree)
V (Å3) 403.790 403.809 403.941 404.016
Rp 5.87 5.95 5.33 6.45
Rwp 7.64 7.61 7.61 8.25
Re 6.30 6.03 6.12 6.41
S=Rwp/Re 1.21 1.26 1.24 1.28

diffraction peak positions at 29.5 º, 34.2 º, 38.4 º, 42.3 º, 45.9 º, 49.2 º,
61.4 º and 72.2 º match well with that of the standard JCPDS file 01–075-
2188. This corresponds to the body-centered cubic perovskite structure
of CCTO. The presence of CuO is no longer apparent here. However,
under 30 min heat treatment, samples (S2 and S3) show three diffraction
peaks at 27.50 º, 36.04 º, and 54.23º, which arise due to the presence of
rutile TiO2 as an impurity. But for the samples calcined at 700–800 ◦ C
for 2 h (S5 and S6), the principal diffraction peaks are only due to CCTO.
Any other detectable impurity phase is not observed here within the
limits of the instruments. As calcination temperature rises, the intensity
of the XRD peaks increases, indicating higher crystallinity of CCTO
nanopowders. The XRD patterns for S0, S1 and, S4 exhibit copper oxide
peaks and, S2-S3 contain three TiO2 (rutile) peaks. This denotes that the
titanium isopropoxide and copper nitrates formed oxides in the first step
of the heat treatment and, thereafter, CCTO in crystalline form resulted
from polyesterification reaction between copper oxide and other crys­
talline or amorphous metal phases.
Crystal structures of the prepared CCTO powders have also been
examined by Rietveld refinement. The Rietveld refinement has been
performed by Fullproof software, and, the pictorial representation of the
crystal structure has been shown by using VESTA software. Fig. 2(a-d)
shows the experimental, calculated, difference between expt. and cal.

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A. Chattopadhyay et al.
Fig. 3. Cubic perovskite crystal structure for CCTO powder calcined at 700 ºC for 2 h (S5) using VESTA software.
diffraction peaks for Rietveld refinement. Rietveld refinement was not
performed for S1, and S4 powders as CCTO phase formation occurs after
700 ℃ (confirmed by the XRD data). The percentages of rutile TiO2
present in S2 and S3 are 12.63 % and 7.44 % respectively as estimated
from Rietveld refinement: however, this percentage in S5 and S6 are
insignificant. The analytical function pseudo-Voigt (pV) was used for
experimental profile fitting as it considers both strain broadening and
particle size individually [24]. The related refinement parameters for
the CCTO powders (S2, S3, S5, S6) after stimulation are shown in Table 2
and are in good agreement with previous literatures [25–27]. Fig. 3 is
the pictorial representation of the CCTO (S5) crystal structure. The
approximate bond lengths between Ca-O, Cu-O and Ti-O are 2.6353 Å,
1.9452 Å, and 1.9667 Å respectively, while the respective bond angles
between O-Ti-O and Ti-O-Ti are 90.7835 º and 140.071º as estimated
from the crystal structure using VESTA software. This reduction of
Ti-O-Ti angle to 140.071º from the ideal angle of 180 º is due to the TiO6
octahedral tilt distortion.
3.2. Morphology
As shown in Fig. 4(a) and (d), powders calcined at 600 ◦ C (S1 and S4)
contain irregular-shaped particles and flakes with large size distribu­
tions. As the calcination temperature increases to 700 ◦ C for S2 and S5
(Fig. 4(b) and (e)), further agglomerations of particles occur. When the
calcination temperature is increased to 800 ◦ C for S3 and S6 (Fig. 4(c)
and (f)), a series of connected CCTO crystallites with sharp boundaries
are formed. These particles possess relatively larger diameters compared
to low-temperature calcined powders. When the temperature rose, pri­
mary particles continued to aggregate, and as the agglomeration came to
an end, isolated particles began to develop quickly. The thermally pro­
moted crystals growth during calcination results in nanoparticles with
larger sizes [28]. A change in morphology due to a change in calcination
time of the powders can also be observed. For 2 h heat treatment, the
formation of distinct, large particles (S5) occurred at a calcination
temperature of 700 ◦ C. Similarly, looking at the images of S3 and S6, it
can be concluded that an increase in the calcination time improves the
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Materials Today Communications 33 (2022) 104196
granularity of the CCTO powder. The distribution of particle diameters
is shown in Fig. 5(a)-(f), and the mean lateral dimensions of the particles
of all the powder samples (S1-S6) are given in Table 3.
3.3. UV–vis reflectance spectra
As shown in Fig. 6(a), the UV-Vis diffused reflectance spectra (DRS)
of S1 is similar to that of S4 and showed 55 % reflectance at around
800 nm. A broad reflectance peak at about 615 nm is observed for S2-S3
and S5-S6, and at around 800 nm, the samples showed 62–70 %
reflectance. From this UV–vis DRS data, Urbach energy can be deter­
mined, which provides information about the crystallinity of the mate­
rial [29]. Urbach energy can be estimated by the following equation
hν
α = α0 exp (1)
Eu
Here, α0 is a constant, α is the absorption coefficient, Eu is the Urbach
energy of the material, and hν is the photon energy. DRS spectracan be
converted to the Kubelka-Munk function [30] using the following
equation
(1 − R)2
F(R∞ ) = (2)
2R
Replacing absorption coefficient (α), by Kubelka-Munk function [
F(R∞ )], Eq. (1) becomes,
F(R∞ ) = α0 exp
hν
(3)
Eu
hν
⟹lnF(R∞ ) = lnα0 + (4)
Eu
If we plot lnF(R∞ ) along the y-axis, and photon energy hν along the
x-axis, as shown in Fig. 6(b), then the slope of the graph will provide us
the Urbach energy Eu . Therefore, the estimated values of Urbach energy
for S1, S2, S3, S4, S5, and S6 are 1639 meV, 469 meV, 456 meV,
1515 meV, 460 meV, and 460 meV. It is observed that the Urbach en­
ergy decreases with increasing the calcination temperature and
A. Chattopadhyay et al.
Fig. 4. FESEM images for CCTO powder (a) S1 (b) S2 (c) S3 (d) S4 (e) S5 and (f) S6 respectively.
synthesis time of the materials. The lower the value of Urbach energy,
the higher will be the crystallinity. Hence, CCTO samples achieve
crystallinity with increasing synthesis temperature and time, as also
observed by the XRD pattern.
Optical band gap Eg of the powders have been determined by using
the following equation
αhν = ∁(hν − Eg)n (4)
Here, α is the absorption coefficient of the material, h is the Planck
constant, ν is the frequency of the and photon, ∁ is a constant denoting
the band edge parameter.
As absorption coefficient α is proportional to Kubelka-Munk function
F(R∞ ) then expression (4) can be changed as follows
[hνF(R∞ )]1/n = ∁(hν − Eg) (5)
This expression is known as Tauc’s equation [31]. By extrapolating
the linear portion of the [hνF(R∞ )] 1/n Vs E graph to the energy (E) axis,
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Materials Today Communications 33 (2022) 104196
the optical bandgap of the material can be estimated. The value of n
depends upon the nature of transition i.e., n = 2 for indirect allowed
transition and n = ½ for direct allowed transition. Similar to the report
by Clark et al. [32] both n = 2 and ½ values exhibit good linear fit in the
Tauc plot. Hence, we get band gap energy in between 1.9 and 2.3 eV (for
direct transition Fig. 7(a)) and 1.3–2.1 eV (for indirect transition Fig. 7
(b)). Table 4 summarizes the direct and indirect bandgap values of the
CCTO samples (S1-S6). The insignificant difference between the direct
and indirect band gap transitions represents the conductive nature of the
powder [33]. Therefore, the UV-DRS data depicts that the CCTO powder
possesses two bandgaps of different nature and both are in the visible
region. The bandgap increases with increasing calcination temperature.
This increment of optical band gap with increasing temperature is
associated with the elimination of structural defects or localized states
inside the bandgap [34]. The reduction of oxygen vacancies in the
BO6 − octahedra is the possible reason for this reduction in intermediate
energy states. A rise in calcination temperature causes distortion in the
A. Chattopadhyay et al. Materials Today Communications 33 (2022) 104196

Fig. 5. Distribution of lateral dimensions of the particles obtained from FESEM image of the prepared CCTO powders S1-S6.

observed throughout the photon energy range for low temperature

Table 3 (600 ◦ C) calcined powder. This is due to a higher number of secondary
Lateral diameters of CCTO particles obtained from FESEM image analysis. phases, as can be confirmed by XRD analysis. Therefore, it is concluded
Sample Diameter Mean that the structural rearrangement is a function of calcination tempera­
Range (nm) Diameter (nm) ture. Different values of the band gaps can be assigned to the ordered
S1 30–130 61 and disordered phases of CCTO powders.
S2 25–180 68
S3 80–300 154
S4 40–160 85 3.4. X-ray photoelectron spectra
S5 60–260 110
S6 80–340 166 Fig. 8(a)-(c) depict the O 1 s core-level XPS spectrum of the CCTO
powders calcined at 600 ℃ − 800 ℃ for 2 h (S4-S6). The O 1s spectra of
TiO6 octahedra group. The change in lattice or local atomic structure is all the three CCTO samples exhibit a broad asymmetric peak, indicating
also confirmed by XRD analysis. The higher bandgap value for the CCTO the existence of multiple oxygen species in the near-surface region.
powder calcined at 700–800 ◦ C indicates an ordered structure of CCTO Using the Gaussian fit function, these asymmetric peaks were decon­
with no such intermediate energy states. A higher absorption value is voluted into three distinct peaks with respective positions ~ 528.3 eV,
529.5 eV, and 530.3 eV and are designated as Oa, Ob, and Oc,

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A. Chattopadhyay et al. Materials Today Communications 33 (2022) 104196

Fig. 6. (a) UV–vis diffused reflectance spectra in the range 200–800 nm and (b)
Urbach energy of CCTO powder (S1-S6).
Fig. 7. Tauc’s plot for CCTO powder S1-S6 for (a) direct band gap and (b)
indirect band gap respectively.
respectively. The peak with the low binding energy (Oa) corresponds to
the oxygen in the CCTO lattice. The peak of the highest binding energy
(Oc) is associated with the loosely bound oxygen on the CCTO surface
Table 4
and is attributed to H2O and OH groups integrated into the materials
Optical bandgap values of the CCTO samples (S1-S6) as estimated from Tauc’s
[35]. Finally, the peak with medium binding energy (Ob) is attributed to plot.
the number of oxygen ions present in the oxygen deficit region and ul­
Sample Direct bandgap Indirect bandgap
timately provides information about the oxygen vacancy concentration (eV) (eV)
[36]. The area of Ob/Oa was estimated to be 1.11, 0.94 and 0.96 for S4,
S1 1.96 1.30
S5 and S6 respectively. Therefore, this finding indicates that an overall
S2 2.31 1.97
decrease in oxygen vacancy is observed as the calcination temperature S3 2.26 1.96
increases from 600 ℃ to 800 ℃ i.e., as the CCTO powder transforms S4 2.01 1.97
from disorder phase to ordered phase. S5 2.31 2.10
S6 2.35 1.97

3.5. Photoluminescence
all the samples, S2 shows the maximum PL intensity. The PL intensity is
a function of the heat treatment conditions [37,38]. PL emission peak
Fig. 9(a) shows the photoluminescence spectra of the synthesized
intensity can be lowered due to the disordered lattice structure of CCTO,
CCTO powders. Four prominent PL peaks were observed in the spectra
indicating that high temperature causes a reduction in disorder or de­
under 488 nm excitation wavelength. The emission peaks were detected
fects in the material. The disordered materials (S2 and S4) are initially
in the range of 550 nm̶ 800 nm for all the CCTO samples. The peaks
composed of polymeric precursors and metal oxides, which show some
were spotted at 590 nm (2.1 eV), 697 nm (1.7 eV), 722 nm (1.7 eV), and
PL intensity. As the temperature increased, the organic matter and metal
746 nm (1.6 eV) on the emission spectrum. A similar trend is observed in
oxides were eliminated from the material, and PL intensity increased.
the PL spectra for all the samples calcined for 30 min and 2 h. The CCTO
The charge transfer mechanism occurring between the titanium, cal­
powder calcined at 700 ºC (S2 and S5) shows higher PL intensity than
cium, and copper ions and structure organization levels are the likely
the powders calcined at 600 ºC and 800 ºC (S1, S3, and S4, S6). Among

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A. Chattopadhyay et al.
Fig. 8. High-resolution XPS spectra of the O1s region for the CCTO powder (a) S4, (b) S5, and (c) S6, respectively.
reasons for this change in peak intensity. However, it is also important to
note that the electronic levels in the crystalline bandgap are introduced
by disordered structure, evidencing a charge transfer between the two
centers of TiO5 and TiO6. In this case, two octahedra are formed, one
with TiO6 complex and the other with TiO5 complex. This TiO5 octa­
hedra possesses one oxygen vacancy. The coexistence of the two octa­
hedral structures (TiO6 and TiO5) compensates for the oxygen vacancy
by the positive charge of two holes [39]. This indicates that disordered
CCTO structure formation can introduce energy levels in the forbidden
bandgap and eventually decreases the optical bandgap. This was also
observed in the Tau’s plot (Fig. 7) by UV–vis DRS data of CCTO. The
highest PL intensity is recorded for the CCTO powder that is not fully
disordered (600 ºC) and not highly crystalline (800 ºC). When the
structure is fully crystalline, only the TiO6 complex exists, and the PL
intensity diminishes. Before the crystallization is achieved fully, the
structure is a mixture of octahedra TiOx (x = 5 and 6) intercalated by Cu
and Ca atoms. As the heat treatment time increases, the more frequently
the conformation of TiO6 occurs, and the structure gets more crystal­
lized. This is also proved by XRD data analysis. The comparison of PL
peak intensity for various samples are shown in Fig. 9(b).
3.6. Brunauer-Emmett-Teller (BET) surface area
The porosity and surface areas of the CCTO powders synthesized via
combustion method at various calcination times and temperatures were
investigated by Brunauer–Emmett–Teller (BET) method. For ceramic
particles, the specific surface area is a crucial microstructural charac­
teristic that depends on the porosity and geometrical shape of the
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Materials Today Communications 33 (2022) 104196
material. The N2 adsorption-desorption isotherms for the CCTO samples
(S2-S3, S5-S6) are depicted in Fig. 10. The hysteresis loops of the curves
are attributed to a type IV isotherm which indicates the mesoporous
nature of the substance. Table 5 lists the average pore diameter, pore
volume, and BET surface areas of the CCTO samples. The interaction
between the sensing material and water molecules is more prominent in
CCTO materials with larger pores and greater surface area [40]. The
capacitance of the ceramic changes significantly as a result of this
interaction, producing a high sensing response.
3.7. Morphology of the sintered CCTO pellets
Sintering of CCTO pellets at high temperatures is a method that in­
volves heating the CCTO electroceramic at different temperatures below
its melting point for various applications. Fig. 9(a)-(d) show the FESEM
images of S5 and S6 pellets, each sintered at 1000 ºC and 1100 ºC for 4 h,
respectively. The remarkable change in microstructure with sintering
temperature can clearly be observed. The obtained surface morphology
of the sintered pellets can be classified into two groups: Group A_
bimodal distribution of grain sizes and Group B_ large and non-uniform
grain sizes. As shown in Fig. 9(a) and (c), the surface morphologies of the
S5 pellet exhibit bimodal distribution of grains. The smaller ones with a
mean diameter of 197 nm are surrounding the larger ones. For the S5
pellet sintered at 1000 ºC and 1100 ºC, the mean diameters of the grains
are 1170 nm and 1677 nm, respectively. As the sintering temperature
increases from 1000 ºC to 1100 ºC, the number of small grains starts
decreasing, and also the diameter of the large particles starts increasing.
This implies that the smaller grains get swallowed by larger ones. Here,
A. Chattopadhyay et al.
Fig. 9. (a) Photoluminescence spectra for CCTO powder S1-S6 and (b) comparison between the intensities of the four PL peaks for the six CCTO samples.
the larger grains are of angular shape while the smaller grains are
preferentially of spheroidal shape. These CCTO pellets are very porous
as larger grain sizes need a higher sintering time to be densified. Simi­
larly, S6 pellet surface morphology analysis shows that grain size in­
creases with increasing the sintering temperature from 1000 ºC to
1100 ºC. The grain sizes are 738 nm and 1190 nm for Fig. 9(b) and (d),
respectively. The sintering process causes materials from separate par­
ticles in the neighborhood to diffuse into each other. The driving force
here is the reduction of the surface energies of the particles. This
decrease in energy is achieved by the process of atomic diffusion [41].
This process transports matter from grain inside into the pores between
the pore surfaces leading to densification of the body. This will even­
tually result in a low amount of pore volume inside the pellets.
3.8. Humidity response of S5 pellet
Fig. 10(a) shows the humidity response curve of the S5 pellet sin­
tered at 1100 ºC for 4 h. The key points of the curve are a) At low relative
humidity (RH), the capacitance is almost constant like an ideal capacitor
b) Capacitance and the increment of capacitance both increase with an
increase in RH, indicating greater humidity response in high relative
humidity regime and c) capacitance decreases with an increase in fre­
quency. At a higher frequency, the capacitance of S5 is almost constant,
and a slight increase is observed when the RH value is nearly 90 %. As
RH changes from 40 % to 90 %, capacitance changes approximately by
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Materials Today Communications 33 (2022) 104196
560 %, 525 %, 185 %, and 92 % at 100 Hz, 120 Hz, 1 kHz, and 10 kHz,
respectively.
The response of the CCTO pellet to atmospheric humidity mainly
depends on the physical and chemical adsorption of water molecules. At
low RH, a small amount of water molecules are chemisorbed onto the
CCTO surface. As RH increases, the surface hydroxyl layer gets
completed, and physisorption of water molecule comes into play [42,
43]. At high RH, physisorbed water molecules get dissociate and forms
H3O+. A proton is released in this process and is accepted by neighboring
molecules while releasing another proton and so on (Grotthuss’s chain
reaction) [43]. These protons have a free movement similar to bulk
liquid water along with the physisorbed water molecules. A schematic
diagram showing this water adsorption mechanism is shown in Fig. 10
(b). Furthermore, when an electric field is applied, these protons accu­
mulate at the grain boundaries, and space charge polarization occurs.
This increases the overall capacitance of the CCTO pellet. Adsorbed
water molecules get polarized at a low frequency when placed in an
external electric field. Nevertheless, as the frequency increases, the
electric field direction changes very rapidly and, polarization speed
cannot catch up with it. This leads to a small frequency-independent
capacitance in the higher frequency region.
4. Conclusion
Single-phase CCTO powder was successfully synthesized at 700 ºC
A. Chattopadhyay et al. Materials Today Communications 33 (2022) 104196

Fig. 10. N2 adsorption-desorption isotherms of CCTO powders (a) S2, (b) S3, (c) S5, and (d) S6 prepared via combustion method. (Inset: The BJH pore size dis­
tribution of the samples).

10
A. Chattopadhyay et al. Materials Today Communications 33 (2022) 104196

Fig. 11. FESEM image for CCTO pellets (a) S5, (b) S6 sintered at 1000 ºC for 4 h and (c) S5, (d) S6 sintered at 1100 ºC for 4 h respectively.

11
A. Chattopadhyay et al. Materials Today Communications 33 (2022) 104196

Fig. 12. (a) Humidity sensing characteristics of CCTO (S5) pellet sintered at 1100 ºC for 4 h and (b) schematic diagram for humidity sensing mechanism.

Declaration of Competing Interest

Table 5
Specific surface area, pore diameter, and pore volume of the samples synthesized
The authors declare that they have no known competing financial
at various calcination times and temperatures.
interests or personal relationships that could have appeared to influence
Sample BET surface BJH average Pore volume the work reported in this paper.
area (m2/g) pore diameter (Å) (cm3/g)

S2 11.8034 122.258 0.004438 Data availability

S3 7.3918 129.609 0.002572
S5 8.9767 127.722 0.003041
S6 6.6408 102.273 0.002375 No data was used for the research described in the article.

via combustion method as confirmed by XRD. The average particle size
from the FESEM study ranges from 60 nm to − 160 nm. An increase in
the calcination temperature leads to an increase in particle size. The
optical band gap values, as estimated from the UV–vis DRS study were
found as (1.9–2.3 eV) and (1.3–2.1 eV) for direct and indirect transitions
respectively. The optical band gap value in both cases increases with the
increase in calcination temperature due to decrease in the impurity
content of the powder. Furthermore, the oxygen vacancy concentration
also decreases as the CCTO powder transformed from disordered to
crystalline state as confirmed by XPS analysis. The PL spectra revealed
that the intense photoluminescence peak was obtained from the CCTO
structure which is neither fully disordered not crystalline. The humidity
response curve for the CCTO pellet sintered at 1100 ºC for 4 h showed a
560 % variation in its capacitance when RH changes from 40 % to 90 %.
Therefore, the low-cost fabrication, porous structure and high perfor­
mance over a wide range of relative humidity (RH) could make the re­
ported material a promising candidate for humidity sensing application.
Acknowledgements
We would like to thank the Department of Physics and Central
Research Facility IIT(ISM) Dhanbad for the measurement facilities. Also,
we would like to thank TIFR Mumbai, India for the XRD facility.
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