J Mater Sci: Mater Electron (2024) 35:600

Effect of A‑site and B‑site ion substitution

on the electrical and thermoelectric properties
of nanostructured perovskite ­CaMnO3
S. Berbeth Mary1,*, K. S. Mohan2, and M. Muthu Krishnan3

1
Department of Physics, K. Ramakrishnan College of Engineering (Autonomous), Tiruchirappalli, Tamil Nadu 621 112, India
2
Department of Physics, Nandha Engineering College (Autonomous), Erode, Tamil Nadu 638 052, India
3
Department of Physics, Sona College of Technology (Autonomous), Salem, Tamil Nadu 636 005, India

Received: 27 June 2023 ABSTRACT

Accepted: 5 March 2024 The impact of A-site and B-site ion substitution (A-site: Sr and B-site: Co) on
Published online: the electrical and thermoelectric properties of the perovskite ­CaMnO3 nanopar-
19 March 2024 ticles has been investigated. The perovskite nanoparticles have been prepared
by sol–gel hydrothermal method at 200 °C followed by annealing at optimum
© The Author(s), under temperature. Thermal, structural, morphological, elemental, functional, optical,
exclusive licence to Springer electrical, and thermoelectric properties of the samples have been performed
Science+Business Media, LLC, using TG-DTA analysis, powder X-ray Diffraction, Raman analysis, Scanning
part of Springer Nature, 2024 Electron Microscopy with Energy Dispersive X-ray Analysis, Fourier Transform
Infrared Spectroscopy, UV–Vis spectroscopy, and thermoelectric measurement.
Powder XRD analysis reveals the perovskite structure and the optimized anneal-
ing temperature. Surfactants reduced the average particle size which improves
the thermopower. The decrease in substitution ionic size causes an increase in
lattice parameters and unit cell volume. Oxygen-deficient nanoparticles were
observed with symmetric Raman lines and the mesoporous structured nanopar-
ticles enhanced the surface area leading to higher electrical conductivity. The
temperature dependence thermoelectric measurement was performed between
ambient temperature and 673 K. The electrical resistivity depends on the nature of
substituent ions. The absolute Seebeck coefficient values for pure ­CaMnO3, A-site,
and B-site substituted were − 312, − 287, and 98µVK−1, respectively. The system-
atic analysis revealed that ion substitution at the A-site and B-site influenced
significant changes in the crystal structure and the type of carrier concentration.

Address correspondence to E-mail: [email protected]

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600 Page 2 of 14 J Mater Sci: Mater Electron (2024) 35:600

1 Introduction limited for low-temperature applications. These

problems can be conquered by oxide thermoelec-
Nowadays, environmentally friendly, clean and cost- tric materials owing to their stability thermally and
effective production, management, conservation, and chemically at elevated temperatures. The invention
implementation of energy sources are not effective. of layered sodium cobalt oxide ­(NaxCoO2) by Tera-
Universally, energy loss due to chemical reactions, saki et al. in 1997 with low electrical resistivity (0.2
nuclear reactions, and combustion processes from mΩ at 300 K) and high Seebeck coefficient (100mV/K
industries in the form of heat is 60% [1]. To convert the at 300 K) proved that there are layered oxide ther-
irrecoverable waste heat into electricity is possible by moelectric materials with low electrical resistivity
thermoelectric power generation method. The major [3]. It is one of the most significant perovskite metal
advantages of this technology are no greenhouse gas oxides because of its enhanced properties like elec-
emission, no moving parts, and cost-effective main- trical, electrochemical, magnetic, superconducting,
tenance hence it is used especially in the aerospace and thermoelectric properties for various energy
sector as autonomous electric power generation [2]. storage applications like supercapacitors, solid oxide
The electrical energy power conversion efficiency is fuel cells, batteries, thermoelectric modules, and so
measured by the dimensionless figure of merit on [4–6].According to the current Scenario, increas-
ing the effective mass is one of the possible methods
ZT =
S2 𝜎
, (1) to increase the Seebeck coefficient via drag effects.
𝜅T Recently Ran Ang et al. and Matsuura.H et al. stud-
where Z, S, 𝜎 , κ, T are dimensionless figure of merit, ied and reported the increased Seebeck coefficient
Seebeck coefficient, electrical conductivity, ther- in ­CuFeS2chalcopyrite, ­Fe2VAl Heuslers by magnon
mal conductivity, and absolute temperature, respec- dragging effect [7, 8]. Especially transition metal
tively. Good thermoelectric materials should have a oxides are used for various energy storage devices
large Seebeck coefficient that confirms a conversion of like supercapacitors, thermoelectric devices, batter-
heat directly into electricity, low electrical resistivity ies, and so on [9]. Recently, wearable thermoelectric
to cover ohmic losses, and a Joule heat as a result of generators may become a very viable power source
high electrical conductivity and high thermal resistiv- for low-power wearable electronic devices. There is
ity to avoid heat losses and to maintain the thermal a great deal of interest in lightweight, durable, and
gradient between source and sink of the thermoelectric on-board power supplies due to the advancements in
device. The power factor ­S2𝜎 describes the simulta- wearable technologies such as activity trackers and
neous generation of large voltage and large current portable health monitors like pacemakers, wrist-
in a perovskite thermoelectric oxide material. ­S2𝜎can watches [10, 11]. It has thus become a promising pos-
be maximized by optimizing the properties of exist- sibility to harvest the energy available in our daily
ing materials and introducing a state of art materi- environments. Active and passive energy scavenging
als. Nanomaterials and band-engineered materials are two ways to use irrecoverable energy for wear-
will progress the absolute Seebeck coefficient value able electronics. Around 100 to 525 W power is gen-
whereas inclusions and imperfections will decrease erated from the human body as irrecoverable heat
the thermal conductivity by reducing the phonon energy. From this dissipated heat energy, 1 to 5.25
mean free path. Thermal conductivity is an intrinsic W electrical power can be generated. This amount
property of any material and is temperature-depend- of energy is enough to power the thermoelectric
ent concerning the concentration of imperfections. sensor, and thermoelectric materials, maintain the
Highly concentrated lattice imperfections produce temperature gradient between source and sink, ther-
significant thermal conductivity reduction in Umklapp mal conditions of wearers, and so on. In particular,
phonon scattering which is the dominant mechanism thermoelectric materials and the influencing factors
in perovskite oxides at elevated temperature. Hence, of the environment play a vital role in wearable ther-
the materials should be engineered to have a high moelectric devices.
power factor and high thermal resistivity. Several perovskite-type oxides are well-known
High ZT intermetallic materials like ­Bi2Te3, ­Bi2Se3, as highly conductive ceramics whereas undoped
and ­CoSb3 are toxic, low abundant, degradable, and ­CaMnO3 has poor thermoelectric properties owing
to its low electrical conductivity. A-site and B-site
J Mater Sci: Mater Electron (2024) 35:600 Page 3 of 14 600

substitution with various rare earth elements improves ­CaMnO3(CMO), A-site substituted ­SrMnO3(SMO) and
the carrier mobility sequentially and a significant B-site substituted ­Ca3Co4O9(CCO) nanoparticles were
change is observed in its electrical conductivity [12]. characterized and the results were studied [22, 23].
Engineering perovskite-type oxides by doping at dif-
ferent positions, band modulating, and nanostructur- 2.2 C
 haracterization of pure and substituted
ing enhances the dimensionless figure of merit [13]. ­CaMnO3 nanoparticles
­Ca1 − xRexMnO3 can be successfully synthesized by var-
ious techniques like chemical combustion, sputtering, A powder X-ray diffractometer equipped with Bruker
sol-gel, co-precipitation, solvothermal, hydrothermal D8 advanced diffractometer (λ = 1.5406Å) was used to
and so many others [14–16]. Here sol-gel hydrother- determine purity, crystallinity, and phase of samples
mal method has been adopted to acquire the homo- from 10° to 80°. Thermo gravimetric (TG) analysis in
geneous fine nanoparticles with controlled grain size an oxygen atmosphere is performed by SDT Q600
[17–20]. ­CaMnO3-based thermoelectric material shows TA using an alumina crucible under air atmosphere
a significant absolute Seebeck coefficient value but less between room temperature and 1000 °C at a heating
dimensionless figure of merit due to high electrical rate of 10 °C/min with the rate of 20 ml/ min for all the
and thermal resistivity [21]. To improve the thermo- samples to find the oxygen stoichiometry. Jobin Yvon
electric property of ­CaMnO3 nanoparticles, substitu- Horibra LABRAM – HR visible spectrometer was used
tion at A-site (Sr) and B-site (Co) has been done. In to measure the vibrational spectra in a micro-Raman
this research article, A-site (Sr) and B-site (Co) ion- spectrometer using a He –Ne laser as an excitation
substituted ­CaMnO3samplesare prepared, systemati- source at room temperature. A JEOL JSM 5600 SEM
cally characterized and the results are investigated, and an EDAX were adopted for the analysis of the
analyzed, and reported. surface morphology and elemental composition of the
samples. To conduct thermoelectric experiments, par-
affin wax was compressed with the annealed powders
2 Materials and methods at 50 MPa and sintered under conventional sintering
conditions after being heated at 10 °C/minute for 4
2.1 S
 ynthesis of pure and substituted ­CaMnO3 h. To investigate the thermoelectric properties like
nanoparticles electrical resistivity (ρ), Seebeck coefficient (S), activa-
tion energy, and the power factor ­(S2σ) of the samples
Analytical Reagent graded calcium nitrate Ca(NO3)2. from ambient temperature to 600 °C where 50 °C is
­4 H 2 O (Sigma–Aldrich, 99%), strontium nitrate the temperature gradient(∆T) at the atmosphere of
Sr(NO 3 ) 2 , manganese nitrate Mn(NO 3 ) 2 . ­H 2 O pure helium by employing LSR-3, Seebeck, Linseis,
(Sigma–Aldrich, 99%), cobalt nitrate, and ­NH3 in H ­ 2O Germany model.
were used for the preparation of metal oxide nanopar-
ticles without any further purification. Capping agent
Polyvinyl Pyrrolidone (PVP) and chelating agent Cit- 3 Results and discussion
ric acid were used for controlling the grain size of
nanoparticles. To obtain a metal ion solution, stoi- 3.1 Analysis of oxygen deficiency
chiometric amounts of metal nitrates were weighed
and dissolved in distilled water in the ratio 1:1 (citric Oxygenation is an efficient and feasible method to
acid: metal ion) along with the optimum value (2 g) find the oxygen deficiency of metal oxide nanopar-
of PVP. The solution was added to the ammonium ticles by thermogravimetric analysis (TGA) under
hydroxide solution and stirred for 30 min. Hence, the an oxygen atmosphere and is represented in Fig. 1
standardized solution is heated until it reaches the pH for the samples. Oxygen insertion in the samples in
value of 9.2, then it changes to half its volume. For observed between room temperature and 1000 °C
the acquisition of the particles, inorganic and organic during annealing. The effective oxygen content after
solvents were used to remove the byproducts from annealing at high temperatures formed the oxygen
the sol before placing it in an autoclave lined with Tef- vacant sites. The concentration of oxygen vacancy
lon and placing it at 200 °C for 20 h. After drying and increased due to annealing at elevated temperatures.
annealing at optimum temperature, the obtained pure An apparent weight loss is transpired by the removal
600 Page 4 of 14 J Mater Sci: Mater Electron (2024) 35:600

Fig. 1  TGA spectra of ­

CaMnO3−δ, ­SrMnO3−δ and ­
Ca3Co4O9
nanoparticles

of organic by-products and stable, single-phased sam-

ples formed. The stoichiometries of the perovskite
samples were confirmed to be ­CaMnO2.5, ­SrMnO2.3,
and ­Ca3Co4O9 respectively at optimum temperatures
Fig. 2  XRD Pattern of C
­ aMnO3-δ, ­SrMnO3-δ and C
­ a3Co4O9 nan-
that are represented in Fig. 1. It is confirmed from the
oparticles
XRD results that secondary peaks are observed in the
oxygen-deficient samples CMO and SMO that is due
to the removal of one oxygen per pair along (101) axis along the a-axis is obtained (5.45Å) than the reported
which is concurrent with the previously reported data. one (5.424Å), representing that the observed phase is
They have revealed that annealing at air atmosphere oxygen-deficient i.e., ­CaMnO3−δ nanoparticles. This
­La0.5Sr0.5MnO3 sample showed oxygen deficiency and oxygen vacancy of the Mn-O1 site in the ­CaMnO3 sam-
it can be recovered while annealing at oxygen atmos- ple leads to high electrical resistivity [17, 28]. Figure 2b
phere [24, 25]. This significant oxygen deficiency intro- demonstrates the powder XRD pattern of perovskite
duces the local structural distortions and non-homoge- ­SrMnO3samples that are indexed and matched with
neous nature of electrical properties which affects the the JCPDS card no 24-1213. A pure hexagonal phase
transport properties in materials. Non-stoichiometric with secondary peaks is obtained for the annealed
samples show a significant leap in electrical resistivity sample at 950℃which is due to the presence of oxy-
which leads to low thermopower hence this issue can gen vacancies in the sample. This substituted cation
be overcome by annealing and sintering the samples vacancy generates oxygen deficiency in the samples
in an oxygen atmosphere [26, 27]. and this oxygen deficiency in turn reduces the thermo-
electric performance of these samples and is ascribed
result of reduced electrical conductivity [29]. These
3.2 Analysis of structural properties secondary peaks might vanish while preparing stoi-
chiometric samples and the calculated lattice param-
Figure 2 represents a powder XRD pattern of pure eters are listed that are in good agreement with the
­C aMnO3−δ, A-site substituted ­S rMnO 3−δand B-site previously reported data.
substituted ­C a 3 Co 4 O 9 nanoparticles. Figure 2a Figure 2c signifies the powder XRD pattern of
represents the diffraction spectrum of annealed annealed ­C a 3Co 4O 9nanopowder at optimum tem-
­C aMnO 3nanoparticles at 950 °C in an air atmos- perature. The diffraction peaks are matching with the
phere. It reveals that the ­C aMnO 3−δnanoparticles standard JCPDS card 23–0110. The crystal structure
have orthorhombic perovskite structure with the is a monoclinic sub-system and the lattice parameter
space group Pbam. Calculated cell parameters and values are calculated and tabulated [30].These pow-
are listed in Table 1, where a larger lattice parameter der XRD results show that the crystal structure is not
J Mater Sci: Mater Electron (2024) 35:600 Page 5 of 14 600

Table 1  Lattice parameters

Sample name JCPDS card no Crystal structure Lattice parameters (Å) Average
and average particle size
particle size
of the CMO, SMO & CCO A b C
(nm)
samples
CaMnO3-δ 46-1009 Orthorhombic 5.452 10.233 3.741 26
SrMnO3-δ 24-1213 Hexagonal 5.508 5.508 9.114 67
Ca3Co4O9 23–0110 Monoclinic 4.842 b1 = 4.576 1.087 61
b2 = 2.823

affected by annealing time and atmosphere but the

peak intensity varies. As a result, stoichiometric nano-
particles with high thermopower can be obtained by
nullifying the oxygen vacancies which can be done by
annealing the samples in an oxygen atmosphere [31].
Scherrer formula is applied to estimate the average
particle size of the nanoparticles.
K𝜆
D= , (2)
𝛽 cos 𝜃

where K is Scherrer constant, since the exact value for

K is not known, a default value of K = 0.9 was used
and all the D calculations are estimates, λ is incident
radiation wavelength (λ = 1.5406Å), β is the full width
at half maximum of the diffraction peaks, and θ is the
Bragg’s angle [32]. The average particle size of the
CMO, SMO, and CCO samples are listed in Table 1.
This reduced average particle size is due to the addi-
tion of capping and chelating agents. Lattice param-
eter values and unit cell volume get reduced when the
average particle size is reduced. Hence lattice thermal
conductivity reduces and subsequently thermopower
of the material gets enhanced [33].
Raman spectroscopy determines the structural
Fig. 3  Raman Spectra of ­CaMnO3−δ, ­SrMnO3−δ and ­Ca3Co4O9
distortions, crystal symmetry, and possible sec- nanoparticles
ondary phases of nanoparticles. It can also reveal
the oxidation state and doping level. Raman meas-
urements are skilled in backscattering geometry 559, 472, 435, 393, 330, 266, 223, and 176 ­c m −1 and
using a micro-Raman spectrometer and the excita- these sharp and stronger peaks are examined due
tion wavelength is 632 nm with a charge-coupled to one phonon scattering. The fingerprint of Mn–O
device CCD detector. To eliminate the scattered vibrations in the ­MnO6 layer of the birnessite-type
light notch filters are used and the Raman spectra structure is observed at 579 ­cm−1. The Ag modes are
of the samples are documented between 100 and 800 obtained at 266, 223, and 489 ­cm−1, and B2g mode at
­cm−1 at ambient temperature. Figure 3a–c represents 635 ­cm−1. Annealed CMO sample shows suppressed
the Raman spectra of ­C aMnO 3−δ , ­S rMnO 3−δ, and peaks at 485 and 618 ­cm−1 because of low Jahn-Teller
­Ca3Co4O9 nanoparticles with highly intensified mul- distortion [35]. For 4 H hexagonal SrMnO3, Eight
tiple peaks. The obtained Raman modes confirm the Raman active phonons (2A1g, 2E1g, and 4E2g) are
orthorhombic phase in the ­CaMnO3−δsample, which envisaged with the space groupofP63/mmc [36].
is in good agreement with the previously reported At low frequencies, some displacements are due
data [34]. Raman peaks of CMO are at 669, 635, 579, to manganese ions and oxygen ions. Displacement
600 Page 6 of 14 J Mater Sci: Mater Electron (2024) 35:600

of octahedral stretching modes is associated with 3.3 A

 nalysis of morphological
strong frequency peaks whereas lower frequency and compositional properties
peaks are associated with Mn ions. Figure 3c depicts
the Raman spectra of ­Ca3Co4O9 nanoparticles where Figure 4a–f shows the morphological scanning elec-
four peaks are observed at 286, 516, 635, and 704 tron microscopic images and EDAX spectrum of
­cm−1 which coexist with the literature reports. These ­CaMnO3−δ, ­SrMnO3−δ, and ­Ca3Co4O9 nanoparticles
low-frequency phonon modes are due to the heavier annealed at optimum temperature. Pores are devel-
atoms like Ca and Co whereas high-frequency pho- oped in the samples during preparation which may
non modes are due to the lighter atoms such as oxy- be due to the discharge of large volumes of gases. At
gen [37]. A lack of oxygen, however, will result in a the optimum annealing temperature nanoparticles
widening of certain spectral bands and large shifts arrange themselves in homogeneously dispersed
in the Raman spectrum of transition metal oxides. spherical shapes with a high number of connected
Oxygen-deficient ­CaMnO3 and ­SrMnO3 nanoparti- pores. A mesoporous structure with a connected net-
cles show broadened spectral lines, while oxygen- work improves the surface area of the nanoparticles
stoichiometric ­Ca3Co4O9 nanoparticles show intensi- which will result in high electrical conductivity as a
fied peaks [38, 39]. result enhanced thermopower is observed. Since the
pores are smaller and closer together than the phonon
mean free path, they act as phonon scattering centers,

Fig. 4  a–f SEM images and EDAX pattern of ­CaMnO3−δ, ­SrMnO3−δ and ­Ca3Co4O9 nanoparticles
J Mater Sci: Mater Electron (2024) 35:600 Page 7 of 14 600

resulting in a drastic decrease in thermal conductivity.

Thermal conductivity is reduced as a result thermoe-
lectric performance is increased which is the reason for
this mesoporous structure with a connected network
structure [40, 41].
Increased electrical resistivity is observed in oxy-
gen-deficient samples which are the result of the
porosity of the sample that will condense the thermo-
power of the samples. Increased grain size is due to
the annealing process and it can be rectified by intro-
ducing surfactant. Polyvinyl Pyrrolidone (PVP) is used
as a capping agent that reduces the growth of grain
size during the synthesis process by forming a layer
around the nanoparticle and also this layer is removed
while annealing [16]. Annealing the oxygen-deficient
samples in the atmosphere of oxygen lessens the oxy-
gen insufficiency by recuperating the oxygen atoms at
elevated temperatures and hence connected network
structure is observed with homogeneously dispersed
nanoparticles for the stoichiometric nanoparticles. The Fig. 5  FTIR spectrum of C
­ aMnO3−δ, ­SrMnO3−δ and ­Ca3Co4O9
synthesis methods influence the microstructure and nanoparticles
grain size of the nanoparticles in the presence of sur-
factant and capping agents. Surfactants such as PVP,
and citric acid augment the surface area of the nano- c­ m−1 for all the samples which is the fingerprint peak
particles and it condenses the grain size without any of MnO where elongation of Mn-O bond length for
agglomeration. ­SrMnO3−δis due to the reduction in the intensity of
Citric acid and polyvinyl pyrrolidone are used as peak. Dislocations are due to the interaction between
chelating and capping agents that enhance the porous the oxygen and ion molecules [44, 45]. Out-of-plane
nature of the sample and hence surface area increases bending mode of the C–O bond was obtained at 877
subsequently improving the thermopower [42]. EDAX ­cm−1indicating the vibration of ­NO3 ions [46]. The
pattern of ­CaMnO3−δ, ­SrMnO3−δ, and ­Ca3Co4O9 nano- addition of surfactants increases the peak inten-
particles annealed at optimum temperature is shown sity when there is a high percentage of carbon. The
in Fig. It shows that the cationic composition is 1:1 intensive absorption peak of asymmetric stretching
for all the samples. During the sintering process grain vibrations of C = C bond was observed at 1412 ­cm−1
boundaries start connecting and as a result network which is due to the synthesis process. The broad
structure formed gradually within cations. The sinter- peak at 3421 ­cm−1is stretching vibrations of absorbed
ing process changes the morphology of the sample and water molecules during the synthesis process [47]. All
the evaporation of organic compounds decreased the bending and stretching modes suggest the formation
density of the nanoparticles. The above results imply of perovskite-structuredCaMnO 3−δ, ­SrMnO3−δ, and
that sol-gel hydrothermal routed perovskite oxide ­Ca3Co4O9 nanoparticles which are concurrent with
nanoparticles are pure [43]. the reported XRD results.

3.4 Analysis of functional group

3.5 Analysis of optical properties
FTIR is used to find the lattice vibration, purity, and
phase composition of the given systems. Figure 5a–c An optical band gap of the ­CaMnO3−δ, ­SrMnO3−δ, and
illustrates the FTIR spectrum of ­CaMnO3−δ, ­SrMnO3−δ, ­ a3Co4O9 nanoparticles was measured by Ultravio-
C
and ­Ca3Co4O9 nanoparticles. Several strong charac- let-visible (UV-Vis) absorption spectroscopy from 200
teristic peaks were observed in the Infrared region to 800nm and is illustrated in Fig. 6a&b. The band gap
and the stretching mode of Mn-O is observed at 595 Eg was determined from the Tauc’s equation
600 Page 8 of 14 J Mater Sci: Mater Electron (2024) 35:600

Fig. 7  Temperature dependence electrical resistivity of

­CaMnO3−δ, ­SrMnO3−δ and ­Ca3Co4O9 nanoparticles

hν axis provide the optical band gaps of ­CaMnO3−δ,

­SrMnO3−δ,and ­Ca3Co4O9 nanoparticles were deter-
mined. The linear nature of the plot confirms the direct
transition of the samples and it was extrapolated to the
energy axis α = 0. It was found to be 3.52 eV, 3.34 eV,
and 3.31 eV, respectively [49]. The higher band gap
value is ascribed to the direct quantum confinement
effect of the samples at the nanoscale. From the above
results, it was found that the prepared samples are
indirect wideband gap semiconductors and suitable
for energy storage applications.
Fig. 6  a UV-Visible spectra of C ­aMnO3-δ, ­SrMnO3-δand
­Ca3Co4O9 nanoparticles. b Bandgap of C
­ aMnO3-δ , ­SrMnO3-δ 3.6 Analysis of electrical properties
and ­Ca3Co4O9 nanoparticles
Electrical resistivity is one of the temperature-depend-
( ) ent intrinsic properties of perovskites. Moreover elec-
(𝛼h𝜈)n = B h𝜈 − Eg , (3) trical resistivity depends on carrier concentration and
charge carriers mean free path. Electrical resistivity
where α is the absorption coefficient, hν is the pho- and Seebeck coefficient were measured using Seebeck
ton energy, B is the dimensional constant, and n is coefficient and electrical resistance measurement,
the index representing the transmission order, where between room temperature to 650° in a Helium atmos-
n = 2 and 1/2 for direct and indirect band gap, respec- phere [50]. Figure 7 shows the electrical resistivity
tively [48].Lower cutoff frequency and transparency ρ(T) of ­CMO−δ, ­SMO−δ and CCO nanoparticles from
throughout the visible region of the samples prove ambient temperature to 600 °C. The electrical resis-
that these are efficient candidates for optoelectronic tivity of ­CMO−δ, A-site substituted ­SMO−δ and B-site
devices. For a wide range,(αhν)2 and hν values were substituted CCO are 7.4, 15.3, and11.5 mΩ cm, respec-
in linearity signifying a direct transition process in tively, which is concurrent with the reported data [51,
all the samples. The intercepts of these plots on the 52]. Large electrical resistivity is due to the highly
J Mater Sci: Mater Electron (2024) 35:600 Page 9 of 14 600

induced single polarons. Perovskite manganite with

lower average grain size nanoparticles shows higher
electrical resistivity due to improved width and height
of the tunneling barrier [53].
High electrical resistivity in nanostructured
­SrMnO3−δ is owing to changes in crystal symmetry
attributed to the formation of oxygen vacancies, dis-
sociation of cations, and hopping between ­Mn4+ and
­Mn3+ ions [54, 55]. The Seebeck coefficient value for
­Ca3Co4O9 nanoparticles is positive, revealing that
the holes are majority charge carriers and its value
at ambient temperature is 98 µV/K. The S (T) value
increases with increasing temperature due to the
metallic behavior of the sample. Maximum resistivity
at 100 °C is attributed to the metallic-insulator transi-
tion. Electrical resistivity decreases while increasing
the temperature indicating that samples are semicon- Fig. 8  Absolute Seebeck coefficient value of ­
CaMnO3−δ,
ductors with higher carrier concentration. The nega- ­SrMnO3−δ and ­Ca3Co4O9 nanoparticles
tive temperature coefficient in Mn-based samples is
because of the small hopping conduction mechanism researchers that depend on parameters like synthesis
and doping or substituting the rare earth elements at process, annealing time and temperature, sintering
the A- or B-site significantly lowers the resistivity [56]. time, cycle and temperature, capping agent, and so on.
The positive Seebeck value of ­Ca3Co4O9 implies that
3.7 Analysis of thermoelectric properties holes are major charge carriers. The absolute Seebeck
values for ­CaMnO3−δ, ­SrMnO3−δ, and ­Ca3Co4O9 are
Arrhenius plots of ln (σT) versus 1000/T gives the − 312µVK−1, − 287µVK−1and 98µVK−1at ambient tem-
value of activation energy of samples. Because of non- peratures, respectively [27]. The product of Seebeck
linearity in the temperature range, the linear fitting coefficient value and electrical conductivity is called
method is adopted to find the activation energy. Acti- as temperature-dependent power factor of nanostruc-
vation energy is directly proportional to the electri- tured perovskite thermoelectric metal oxides and is
cal resistivity of the samples [57, 58]. Figure 8 shows shown in Fig. 9. The Power factor value of the sam-
the temperature dependence Seebeck coefficient S(T) ples increases with increasing temperature whereas
value of the samples from ambient temperature to the values are low when compared with stimulated
600 °C. The previously reported results are compared values that are due to the presence of oxygen defi-
and listed in Table 2 [13, 21, 59–63]. Electrons are the ciency [65, 66].
primary charge carriers of the samples which is deter-
mined from the negative values of Seebeck value for
­CaMnO3−δ ­andSrMnO3−δ. Seebeck coefficient depends
on charge carriers and sample nature. A Seebeck coef- 4 Conclusion
ficient’s absolute value depends mainly on the con-
centration of carriers, whereas electrical conductivity Nanocrystalline ­CaMnO3−δ, A-site substituted ­SrMnO3−δ
depends on the mobility of carriers. As fine-grained and B-site substituted ­Ca3Co4O9 nanoparticles were
nanoparticles have more grain boundaries, they scatter synthesized by sol-gel hydrothermal method at 200
carriers and as a result, the materials with nanoparti- °C followed by annealing. Based on TGA results, the
cles without grain boundaries have improved thermo- samples are stable at higher temperatures and exhibit
electric properties [64]. oxygen deficiency caused by removal of one oxygen
The absolute Seebeck coefficient value S(T) value per pair along (101) axis. In the XRD results, the sec-
decreases while increasing the temperature in the ondary peak formation is caused by oxygen deficiency,
complete temperature range. Different S values for which is caused by higher amounts of ­Mn3+ ions than
the same range of temperatures are observed for the ­Mn4+ ions, which can be corrected by annealing under
600 Page 10 of 14 J Mater Sci: Mater Electron (2024) 35:600

Table 2  Thermoelectric properties of metal oxide nanoparticles

Sample Name Method of Preparation Electrical Resistivity (ρ) Absolute See- Power Factor (­ S2σ)
mΩ cm beck Coefficient Mw/m/K2
(S)
µV/K

Ca3Co4O9 Solid State Route 8.3 at 373 K 130 at 373 K 0.08 at 373 K
Ca3Co4O9 Thermal hydro-decomposition method 22 at 960 K 170 at 960 K 1.35 at 960 K
Ca3Co4O9 Solid State Reaction Method 11 at 300 K 135 at 300 K 0.17 at 300 K
CaMnO3 Solution Combustion Method 10,000 at 373 K − 460 at 373 K 0.9 at 373 K
CaMnO3 Solid State Reaction Method Electrical Conductivity is 1000 S/m − 475 at 300 K 0.1 at 300 K
at 300 K
CaMnO3 Solid State Reaction Method Electrical Conductivity is 0.4 S/m at − 545 at 400 K 0.1 at 400 K
400 K
Sr3Co4O9 Ball Milling 8000 at 650 K 234 at 650 K 0.15 at 650 K
Ca3Co4O9 Ball Milling 8200 at 650 K 151 at 650 K 0.0019 at 650 K
La0.7Sr0.3MnO3 Solid State Reaction Method 5280 at 523 K − 13 at 523 K 0.89 at 523 K
Sm0.6Sr0.4MnO3 Solid State Reaction Method 92 at 300 K 147 at 300 K 0.1 at 300 K

oxygen. Increases in annealing time and temperature due to their enhanced electrical conductivity and sus-
result in larger average particle size of the nanoparti- tained Seebeck coefficient.
cles. Physical properties of the samples, such as absolute
Seebeck coefficient, electrical conductivity, and power
factor, are improved by optimizing annealing time and Acknowledgements
temperature. The synthesis of mesoporous materials
with nanosized pores can result in materials with low One of the authors (Dr. S. Berbeth Mary) would like to
thermal conductivity. A decrease in the absolute See- thank UGC-DAE Consortium for Scientific Research,
beck coefficient value and a decrease in thermoelectric Indore for providing the opportunity to use the
power factor occur due to the expansion of the unit cell research facilities at this Centre.
due to oxygen deficiency. These materials are efficient
in thermoelectric applications at elevated temperatures
Author contributions

All authors contributed to the conceptual study of this

research article. Material preparation, data collection
and analysis were performed by Dr. S. Berbeth Mary,
Dr. K.S. Mohan. The first draft of the manuscript was
written by Dr. S. Berbeth Mary and all authors com-
mented on previous versions of the manuscript. All
authors read and approved the final manuscript.Dr.
M. MuthuKrishnan contributed to finding the oxygen
stoichiometry and also to answering the queries of
reviewers.

Funding

The authors declare that no funds, grants, or other

Fig. 9  Power factor value of ­
CaMnO3−δ, ­SrMnO3−δ and
support were received during the preparation of this
­Ca3Co4O9 nanoparticles manuscript.
J Mater Sci: Mater Electron (2024) 35:600 Page 11 of 14 600

Data availability Application to thin-film heusler alloy. Phys. Rev. B 104,

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