Article

Cite This: ACS Appl. Energy Mater. 2019, 2, 2680−2691 www.acsaem.org

Band Engineered I/III/V−VI Binary Metal Selenide/MWCNT/PANI

Nanocomposites for Potential Room Temperature Thermoelectric
Applications
Anuraj S. Kshirsagar,† Chaitanya Hiragond,† Abhijit Dey,‡ Priyesh V. More,†
and Pawan K. Khanna*,†
†
Nano Chemistry and Quantum Dots R & D Lab, Department of Applied Chemistry Defence Institute of Advanced Technology
(DIAT), Ministry of Defence, Government of India, Girinagar, Pune 411 025, India
‡
Energetic Materials Research Division, High Energy Materials Research Laboratory, Defence Research & Development
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Organization, Pune 411 021, India

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*
S Supporting Information

ABSTRACT: Room temperature thermoelectric studies are reported

herein of ternary hybrids fabricated by ex situ processing involving
polyaniline (PANI), multiwalled carbon nanotubes (MWCNTs), and
binary metal selenide nanoparticles (MSe NPs) such as CuSe, Ag2Se,
In2Se3, and Sb2Se3 synthesized by using cyclohexeno-1,2,3-selenadiazole
(SDZ) as selenium precursor. The presence of phase pure MSe NPs in
ternary hybrids was confirmed by XRD analysis. FTIR analysis suggested
a strong π−π interaction between PANI and MWCNTs. Electrical
conductivities, Seebeck coefficients, and power factors of these band
engineered ternary nanocomposites were investigated at room temper-
ature. Ag2Se NPs/MWCNT/PANI (ASCP) showed p-type behavior with figure of merit (zT) of 0.012 at room temperature,
while other hybrids exhibited n-type behavior. All of the ternary hybrids showed high electrical conductivities, and among n-
type hybrids, CuSe NPs/MWCNT/PANI showed the best thermoelectric performance. The present work opens up an efficient
approach to enhance the utility of metal chalcogenides as sensitizers in thermoelectric applications. The possible mechanism for
charge transport is also discussed.
KEYWORDS: thermoelectric, conducting polymer, polyaniline, MWCNT, ternary hybrid

■ INTRODUCTION
Ever increasing clean energy demand can be met through
alternative environmentally benign, sustainable, and renewable
energy sources.1 The current energy requirement is being
satisfied by combustion of fossil fuels which are rapidly
depleting. Moreover, their use as an energy source is known to
exhibit adverse effect on the environment due to release of
greenhouse gases.2 Therefore, high efficiency sustainable
energy generation and conversion technologies based on
clean energy sources are of great importance and attracting
attention globally.3 Thermoelectric energy conversion is one of
the important and promising technologies which works on the
principle of conversion of thermal energy to electricity. Heat
released from heat sources, such as sun, car exhaust, power
plants, and other sources, is considered as waste and is
estimated to be in huge amount.4 Energy harvesting from such
waste leads to generation of electricity and can be considered
as an alternative solution as global sustainable energy.
Thermoelectric materials are promising candidates and have
been widely studied for their application in solid state cooling/
heating and power generation.5 However, low energy
conversion efficiency is a major concern which limits their
use in widespread applications, and therefore, enhancement of
energy conversion efficiency of such materials is a great
challenge.6
The performance of the thermoelectric materials (TEs) is
evaluated by dimensionless figure of merit (zT), which is given
by the equation zT = S2σT/(kL+ ke), where S is the Seebeck
coefficient, σ is electrical conductivity, T is average absolute
temperature, kL is lattice/phonon thermal conductivity, and ke
is electronic thermal conductivity. The figure of merit consists
of two distinct contributors such as (a) power factor expressed
as S2σ and (b) heat conductivity represented as k = (kL + ke),
which emphasizes the fact that the total thermal conductivity is
dependent on both lattice and electronic thermal conductivity
of a material.1,7 Therefore, to enhance TE performance, it is
essential to increase the power factor (S2σ) and minimize the
total thermal conductivity (k), which is a difficult task owing to
their interdependency. Elaborately this can be well-explained
by considering the relation between carrier concentration,
Seebeck coefficient, and electronic thermal conductivity.
Generally, an increase in carrier concentration enhances
Received: January 3, 2019
Accepted: March 4, 2019
Published: March 4, 2019

© 2019 American Chemical Society 2680 DOI: 10.1021/acsaem.9b00013

ACS Appl. Energy Mater. 2019, 2, 2680−2691
ACS Applied Energy Materials
electrical conductivity (σ) which adversely affects the Seebeck
coefficient and eventually the power factor. On the other hand,
Wiedemann−Franz law demonstrates that ke is proportional to
σ and hence increased electrical conductivity eventually
increases electronic thermal conductivity, which leads to a
negative impact on figure of merit. Therefore, it is a
challenging and difficult job to optimize all these parameters
in a single material to draw high TE performance.1,8
One of the most important and possible ways to enhance zT
of the thermoelectric materials is to reduce the thermal
conductivity of the material without altering electronic
transport properties. Alloying, doping, and nanocomposite
formation are the main possible options available to enhance
the power factor. Among these, band engineering via
nanocomposite formation has attracted recent attention. To
date, many materials have been explored and tested to generate
thermoelectricity, among them BiSbTe, SiGe alloys, PbTe,
Bi2Te3, and SnSe, etc., are reported to have great potential in
TE devices.9−11 However, brittleness, high cost, and poor
processability of semiconductors restricted the realization of
practical thermoelectric devices.12,13 With the current techno-
logical advancement in nanotechnology, processability can be
addressed effectively as the disc and the flexible film formation
become easier and likely improve conversion efficiency. The
approach of combining two or more nanomaterials irrespective
of their nature can show a synergetic effect.14−19 Recently,
composites of organic conducting polymers with graphene,
carbon nanotubes (CNTs), and hybrids containing semi-
conducting NPs as sensitizers have been explored to improve
the thermoelectric power factor and figure of merit as well as to
fabricate flexible thermoelectric devices and therefore are
considered as promising candidates.20−24 However, conducting
polymers possess relatively low electrical conductivity which is
eventually unsuitable for TE devices, and therefore, incorpo-
ration of a 1D conductive template (CNT) can help to
improve the performance.25,26 CNTs are known to exhibit zero
band gap, excellent electrical conductivity, good mechanical
properties, and facile processability and are suitable for
thermoelectrics.27,28 Therefore, combination of CNT and
conducting polymers such as poly(3,4-ethylenedioxythio-
phene) (PEDOT),29 polypyrole (PPy),30 polythiophene,31
and polyaniline (PANI)32,33 have gained recent popularity.
Binary composites of PANI with CNT or graphene or reduced
graphene oxide have been widely studied to improve power
factor values. The presence of inorganic semiconductor in such
hybrid composites acts as energy filters and further improves
thermoelectric performance.23,25,27,34 The combination of
semiconductors with CNT and PANI helps to form extra
heterojunctions with energy barriers at interfaces that help to
filter out low energy carriers and allow high energy carriers to
cross an energy barrier leading to enhancement in the TE
performance.35,36 There are several reports in the literature
demonstrating the utility of ternary composites in thermo-
electricity. A ternary nanocomposite of polypyrrole/graphene/
PANI demonstrated a power factor up to 52.5 μW/mK2, which
was reported to be more than their binary and individual
counterparts.37 Similarly, Choi et al.38 have documented a
ternary hybrid of reduced graphene oxide (RGO)/PE-
DOT:PSS/Te nanowires exhibiting a power factor of 143
μW/mK2. Wang et al.39 have investigated the ternary
composite of PANI/SWCNT/Te for thermoelectric perform-
ance which showed a power factor of 101 μW/mK2. Recently,
Erden et al.40 have reported the highest power factor value
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(114 μW/mK2) for TiO2/a-CNT/PANI among PANI based
ternary composites. We recently reported thermoelectric
performance of p-type RGO/CdS/PANI and PDOT:PSS or
PVAc/graphene/titanium dioxide nanocomposites with sig-
nificant enhancement in the Seebeck coefficient24,41 due to
filtering of the low energy carriers at junction. The thermo-
electric study of RGO/CdS/PANI composite showed
enhancement in electrical conductivity and thermopower by
increasing CdS QDs and RGO concentration. The literature
thus highlights that the enhancement in TE performance is
possible by incorporation of semiconducting NPs as
sensitizers, which helps to adjust band positions leading to
formation of heterojunctions. Such band engineering is
considered to be helpful for better TE performance via
effective charge transportation as well as filtering of the low
energy carriers.38 Recently, the highest power factor of 2.2
mW/mK2 has been reported using ytterbium silicide as
thermoelectric material at room temperature.42 Layered
compound Yb2−xEuxCdSb2 has been studied for its room
temperature TE performance and exhibited high Seebeck
coefficient and low thermal conductivity.43 Ohta et al.44 have
reported ∼9 mW/mK2 power factor of high mobility 2D
electron gas. There are some other reports describing
promising materials for the room temperature thermoelectric
devices.45
The performance of the thermoelectric materials is depend-
ent on several factors such as phase purity, stoichiometry, and
morphology, etc., and therefore, chemical or physical tailoring
of nanomaterials is often required. Various methods are
available in literature for the synthesis of binary metal selenide
NPs, such as chemical vapor deposition (CVD), chemical bath
deposition (CBD), hot injection, sol−gel, solvothermal, and
thermal decomposition of single molecular precursors,
etc.46−48 Many reports are highlighting these advantages, and
some of them are briefly discussed here. Choi et al.49 have
reported synthesis of high quality nanodiscs of copper selenide
using imidazoline-2-selenone as novel selenium precursor.
Pyridine selenolate copper and indium complexes were
employed as single molecular precursors for the synthesis of
CuSex as well as In2Se3 NPs by Cheng et al.,50 wherein they
have described decomposition of copper complex for
formation of α-CuSe at low temperature and Cu2−xSe at
higher temperature, while In complex decomposed to form
In2Se3. Similarly, indium(III) (3-methyl-2-pyridyl) selenolate
complex has been shown to be an excellent precursor by
Sharma et al.51 for the formation of In2Se3 nanocrystals. In a
recent report coordination polymers of the indium and copper
selenolates have been described for the formation of In2Se3,
Cu1.8Se, and CuInSe2 NPs.52 Silver benzoate and cyclo-
hepteno-1,2,3-selenadiazole have also been documented for
the facile synthesis of Ag2Se NPs.53,54 In the case of antimony
selenide, diselenophosphate complex Sb[Se2P(OiPr)2]3 has
been utilized as molecular precursor for synthesis of NPs of
Sb2Se3.55 There are several other reports describing the use of
different organoselenium compounds as selenium precursor for
the synthesis of binary metal selenide NPs.56 Chemical
synthesis involving use of organoselenium compounds as
selenium precursor offers advantages such as formation of less
toxic byproducts, lower reaction temperature, use of nontoxic
reagents, easy extrusion of active selenium, and its reaction
with metal ions to maintain stoichiometry and phase purity
during synthesis of MSe NPs.
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Scheme 1. Schematic Presentation of Conversion of Metal Selenide NPs, Polyaniline, and MWCNT to Ternary Hybrid
In the present article, we report the synthesis of a series of I/
III/V−VI Group (I-Cu, -Ag, III-In, V-Sb, and VI-Se) binary
metal selenide NPs (CuSe, Ag2Se, In2Se3, and Sb2Se3) using
cyclohexeno-1,2,3-selenadiazole and investigation of thermo-
electric performance of MSe NPs/MWCNT/PANI ternary
hybrids at room temperature. The present study is the first of
its kind, and per our knowledge, there is no report to date
explaining the utility of such ternary hybrids for thermoelectric
application. Separately synthesized series of binary metal
selenide nanoparticles (MSe NPs) were employed to construct
novel ternary hybrids with MWCNT and PANI. MSe NPs
were characterized by using advanced characterization tools.
As-formed hybrids were then employed for thermoelectric
studies by fabricating thick pellets. The Seebeck coefficient and
electrical conductivity of ternary nanohybrids were exper-
imentally measured, and power factor values were estimated.
Thermal conductivities of two representative samples were
measured, and zT values were estimated. The variation in
thermoelectric performance due to the change in semi-
conductor NPs in ternary hybrids is studied in detail and
comparatively discussed by considering a possible charge
transport mechanism.
■
EXPERIMENTAL SECTION
Materials and Methods. Silver nitrate (AgNO3), oleic acid,
diphenyl ether, ethanol, and methanol were purchased from Sigma-
Aldrich Pvt. Ltd. India, Indium(III) chloride (InCl3) and antimony-
(III) chloride (SbCl3) were procured from TCI chemicals Pvt. Ltd.
India. Copper chloride dihydrate (CuCl2·2H2O) was purchased from
Merck Pvt. Ltd. India, while aniline was procured from Spectrochem
Pvt. Ltd. India. Multiwalled carbon nanotubes (MWCNTs; Type 5;
o.d., 30−50 μm; length, 10−30 μm) were acquired from SRL Pvt.
Ltd. India. All chemicals were reagent or analytical grade and were
used without further purification. Cyclohexeno-1,2,3-selenadiazole
(SDZ) was synthesized by reported method.57,58 For powder X-ray
diffraction analysis a Mini Flex Rigaku X-ray diffractometer with Cu
Kα (λ = 1.5406 Å) was used. SEM and EDS analyses were performed
on a Carl Zeiss scanning electron microscope. Transmission electron
microscopy (TEM) images were taken on a FEI-Technai G2 (Czech
Republic) with a 300 kV instrument. ESCA+ (Oxford Instrument,
Germany) equipped with monochromator aluminum source (Al Kα,
radiation hν = 1486.7 eV) operated at 15 kV and 20 mA was used for
X-ray photoelectron spectroscopy (XPS). UV−visible absorption
spectra were recorded at room temperature using a SPECORD 210
PLUS (Analytikjena, Germany) UV spectrophotometer. Raman and
infrared (FTIR) spectra were recorded using an EZ Raman
spectrometer (USA; λEm = 780 nm) and FTIR PerkinElmer spectrum
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two (USA) in the range of 4000 cm−1 to 400 cm−1 at room
temperature. The Hall voltage measurement was carried out using an
Indosaw SK-006 measurement system with magnetic field sweeping
up to 2.2 T in both positive and negative directions. The carrier
concentration (n) and the Hall carrier mobility (μH) were calculated
by n = 1/RHe, where e is elementary charge
Synthesis of Binary Metal Selenide Nanoparticles. The
synthesis of binary metal selenide NPs involves reaction between
respective metal salt and previously synthesized SDZ as selenium
precursor.57,58 In a typical procedure, the mixture of copper(II)
chloride dihydrate (0.011 mol)/silver nitrate (0.011 mol)/antimony
chloride (0.0087 mol)/indium chloride (0.0090 mol), diphenyl ether
(10 mL), and oleic acid (8.0−10 mL) was heated to 85−90 °C under
nitrogen atmosphere for 10−15 min. Subsequently predissolved SDZ
(0.0058 mol for silver, 0.0117 mol for copper salt, and 0.0134 mol for
In and Sb salt) in 2.0 mL of oleic acid was injected into the above
reaction mixture. The reaction was then carried out at 180 °C for
about 3 h. n-Hexane was added after cooling the mixture and was
stirred for some time. The black precipitate was obtained after adding
ethanol followed by the centrifugation process. The precipitate of
MySez (M = Cu, Ag, In, Sb, y = 1 for Cu and 2 for Ag, In, and Sb, z =
1 for Cu and Ag and 3 for In and Sb) were the final products and
dried in an oven for 3−5 h.
Synthesis of Polyaniline. The chemical oxidative polymerization
of aniline was carried out as per the previous literature report.59 A two
neck round-bottom flask was filled with a mixture of aniline (3.06
mL) and 1 M HCl solution (50 mL) and continuously stirred at 0−5
°C. To this mixture, predissolved ammonium persulfate (7.49 g in 100
mL of water) was added dropwise by ensuring a stable reaction
temperature. The reaction was continued for about 4 h between 0 and
5 °C. The green suspension/solution was centrifuged at 5000 rpm
and repeatedly washed with water as well as with methanol to remove
traces of HCl. As-formed product was then dried in an oven for 24 h.
Dark green colored polyaniline powder is stored in an airtight
cylindrical vial for further use.
Preparation of Ternary Hybrid for Thermoelectric Study.
Separately synthesized and thoroughly characterized MSe NPs were
used as fillers or sensitizers along with commercially procured
MWCNT and freshly synthesized PANI for preparation of ternary
hybrids. Semiconductor MSe NPs (1.0 g) were homogeneously mixed
with MWCNT (0.25 g) and PANI (0.25 g) by using a mortar and
pestle. The hybrids obtained after proper grinding and mixing were
collected and used for the pellet preparation. The pellets of 12 mm
diameter were prepared by using a hydraulic KBr press and used
further for thermoelectric measurements.
Thermoelectric Measurements of Ternary Hybrids. a. See-
beck Coefficient Measurement. In order to measure thermopower,
pellets of ternary hybrid having dimensions of 12 mm × 6 mm × 1
mm60 were sliced and placed on a thermal insulating fiber glass. One
end of the film was connected by Peltier cooling module possessing
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ACS Applied Energy Materials
Figure 1. (a) XPS survey of CS, AS, IS, and SS and core level spectra of (b) copper (Cu 2p), (c) silver (Ag 3d), (d) indium (In 3d), (e) antimony
(Sb 3d), and (f) selenium (Se 3d).
thermally conductive and electrically insulating epoxy (2763 Stycast)
and a Peltier heater was placed at another end. The contact between
the Peltier cooler and heater was established by a piece of copper. The
voltage drops and temperature gradient were measured along the film
with thermocouples arranged in a series using two copper wires. Cu
films with thermally/electrically conducting silver epoxy (Dupont
4929N) were attached to the sample to ensure measurement of
thermal gradient and the voltage drop at the same place. The
connection was completed by attaching voltage wires and a
thermocouple to these Cu films. The Peltier cooling module was
used for alteration of temperature. The Keithley 2182A nano-
voltmeter was used to monitor the thermoelectric voltages with
respect to temperature.
b. Electrical Conductivity Measurements. The pellets of
dimensions 12 mm × 6 mm × 1 mm of ternary hybrids were
prepared to measure electrical conductivity. The heating of samples at
low temperature was avoided by applying the lowest possible current.
The electrical resistivity of the samples was measured by employing a
δ mode four probe method using a Keithley 6220 nanovoltmeter. Due
to high electrical conductivity, the 100 mA current source was applied
and voltage was recorded with a Keithley nanovoltmeter.
■ RESULTS AND DISCUSSIONS
The synthesis of MSe NPs was executed by employing SDZ as
selenium precursor. The synthesis of binary metal selenides
such as CuSe (CS), In2Se3 (IS), and Sb2Se3 (SS) has never
been reported by employing SDZ as Se source despite a report
on silver selenide a decade ago.61 The present article highlights
the first report on synthesis of copper, indium, and antimony
selenides employing SDZ. As-synthesized binary metal selenide
NPs were thoroughly characterized by UV−visible, FTIR,
Raman spectroscopy, XRD, SEM/EDS, TEM, XPS, particle
size analyzer, and employed for preparation of ternary hybrid
as depicted in Scheme 1.
Optical properties of as-prepared binary metal selenide NPs
were studied by the UV−visible spectroscopy. UV−visible
spectra revealed broad absorption profiles in the case of AS, IS,
and CS covering the entire visible region [Supporting
Information Figure S1a]. The absorption values of about 605
and 617 nm can be approximately predicted for CS and IS,
while it cannot be predicted for AS because of featureless
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profile tailing into the near-IR region. SS showed a well-defined
absorption profile with absorption maxima at 616 nm [Figure
S1a].
The band gaps were estimated by plotting (αhν)2= (1/
l) (Ahν)2 versus hν (Tauc’s plot), where α is the absorption
2
coefficient, hν is photon energy, l is the path length in
centimeters, A and h are absorbance and Planck constant,
respectively.62−64 The band gap energies were much higher as
the absorption profile was much blue-shifted for each metal
selenide nanoparticles. Typically, the band gaps of AS, SS, IS,
and CS were estimated to be 1.24 (bulk Eg, 0.15 eV), 2.92
(bulk Eg, 1.05 eV), 1.81 (bulk Eg, 1.45 eV), and 1.70 (bulk Eg
∼ 1.00 eV), respectively.65−68 The higher band gap values
obtained for all MSe NPs are correlated with a decrease in the
particle size, which indeed was confirmed by other
spectroscopic tools also. Normally, the effect of quantum
confinement is responsible for the increased energy gap
between conduction and valence bands of the MSe NPs.
X-ray photoelectron spectroscopy (XPS) was employed to
understand the oxidation state of various elements present in
the samples and to confirm the purity of MSe NPs. The XPS
survey of CS, AS, IS, and SS is presented in Figure 1a, which
confirms the presence of all elements with expected oxidation
states. HRXPS of CS, AS, IS, and SS are presented in Figure
1b−f. The core level spectrum of CS revealed the presence of
four different peaks due to Cu. The broad peaks obtained at
936.04 and 955.94 eV are due to Cu 2p3/2 and Cu 2p1/2 states,
confirming the presence of monovalent Cu. However, these
peaks also comprise two other peaks with slight humps at
933.78 and 957.45 eV due to Cu 2p3/2 and Cu 2p1/2, implying
the presence of Cu2+ in the sample. Additionally, two satellite
shakeup peaks were observed at binding energies of 944.28 and
964.11 eV, which also confirms the presence of Cu2+ in the
sample. A similar observation for Cu is reported by others.69
The possibility of slight oxidation of the sample upon exposure
to the environment cannot be ruled out during XPS analysis,
which may lead to observation of peaks for divalent copper
also. Based on the observations reported in the literature, it is
opined that the monovalent nature of the copper in the sample
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Figure 2. XRD patterns of (a) CS, (b) AS, (c) IS, and (d) SS NPs and their respective hybrids (CSCP), (ASCP), (ISCP), and (SSCP). Yellow
highlighted areas correspond to peaks due to MWCNT and PANI.
is due to conversion of Cu2+ to Cu+ during reaction.62 The
core level spectrum of Se 3d [Figure 1f CS] showed the peak at
56.68 eV, which is due to the presence of selenium in −2
oxidation state. Absence of a peak near 58 eV confirms that the
sample is free from the oxidized form of selenium.70 HRXPS of
Ag (Figure 1c) showed two peaks at binding energies of 368.31
and 374.32 eV due to 3d5/2 and 3d3/2 states. The peaks were
found to be separated with peak splitting binding energy of 6.0
eV, suggesting monovalent silver [Ag+] in the sample.
The counterion of AS (i.e., selenide) showed peaks at 53.88
and 54.58 eV due to 3d5/2 and 3d3/2 states of selenium
confirming the −2 oxidation state (Figure 1f AS).64 The
change in the peak position of the selenide is attributed to the
change in counterion. Another sample IS showed two peaks
due to 3d5/2 and 3d3/2 states at binding energies of 446.34 and
453.90 eV. These peaks were observed to be separated by
binding energy difference of 7.56 eV, which implies the
trivalent nature (In3+) of indium in IS. Selenium showed a
single broad peak at 55.90 eV, confirming the presence of the
3d state due to Se2−.62,63
Two different peaks were observed in the case of Sb at
531.44 and 540.82 eV with peak splitting binding energy of
9.38 eV. These peaks are indicative of 3d5/2 and 3d3/2 states of
Sb and suggest trivalent antimony in SS.69 Core level spectrum
of selenium showed a peak at 55.93 eV similar to that in the
case of IS, indicating 3d valence with −2 oxidation state. This
study highlights the purity of all synthesized binary metal
selenides. The analysis of XPS data is presented in Table S1 in
the Supporting Information. The phase purity of as-formed
MSe NPs and their presence in hybrids along with MWCNT
and PANI were evaluated by considering XRD results.
Figure 2 shows the XRD pattern for all MSe NPs and their
hybrids. The presence of diffraction peaks due to (100), (101),
(103), (006), (106), (110), (108), (202), (116), and (208) in
the case of copper selenide confirms the formation of
hexagonal α-CuSe (Klockmannite).71 The absence of
diffraction peaks between 35° and 37° rules out the presence
of CuO or Cu2O in the sample and thus highlights the purity.72
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The diffraction peaks present in CuSe were all found in its
hybrid along with the presence of a broad peak at 25° (Figure
2a), which confirms the presence of MWCNT and PANI in
the sample.73
In the case of samples AS and ASCP (Figure 2b) all
diffraction peaks are matched well with the orthorhombic
crystal phase of Ag2Se (naumannite) and observed to be
crystalline, while the presence of MWCNT and PANI was
confirmed due to the presence of a broad peak at 25° similar to
that of CSCP. Major intense peaks obtained at 33.4° and 34.7°
for (112) and (121) crystal planes indicate formation of phase
pure Ag2Se. Synthesis of IS showed formation of hexagonal γ-
In2Se3 as it is evident from well-matching the XRD profile
(Figure 2c) with literature. The possibility of the presence of
InSe, In4Se3, and In6Se7 was eliminated due to the absence of
intense peaks at 2θ 22° and 35.5°.74 Another binary metal
selenide, i.e., Sb2Se3, was also well-indexed to an orthorhombic
crystal structure and 2θ values were found to be matching with
literature reports.75−77 In both cases the XRD of the hybrid
showed a merging of peaks near 25° due to broadening caused
by the presence of MWCNT and PANI.
Morphological analysis of as-prepared samples was carried
out by TEM and SEM analysis. Figure S2 shows TEM images
of all binary metal selenide NPs. The TEM images of CS
(Figure S2a) and IS (Figure S2c) revealed NPs of varied shape
and size, while AS (Figure S2b) and SS (Figure S2d) showed
spherical shape with smaller sized particles. From TEM images
the particle size range can be estimated to be about 10−20 nm
in all samples. SAED patterns of IS and SS are shown in the
inset of Figure S2c,d, respectively. The presence of circular
bright spots due to selected area electronic diffraction reveals
crystallinity of both samples. These spots are considered due to
the diffractions from the respective crystal planes. In the case
of IS the diffractions from (110), (200), (201), and (116)
crystal planes are responsible for the bright circular spots in the
SAED, while in case of SS (130), (230), (211), (221), and
(301) crystal planes are involved. This further confirms the
crystallinity of these samples.
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The particle size distribution profile of as-synthesized MSe
NPs was obtained from particle size analyzer working on the
principle of dynamic light scattering (DLS). The results
revealed formation of MSe particles in the nanoregime with
reasonably narrow size distribution (Figure 3). CS, AS, and SS
Figure 3. Particle size distribution of the as-synthesized MSe NPs.
showed nearly similar distribution in the range of 2−25 nm
which is in good agreement with the FESEM and TEM results,
while IS showed excellent size distribution with average
particle size of 5−8 nm. The result obtained from the particle
size analyzer closely matches with the TEM result indicating
the formation of NPs with different size distributions.
The SEM image of sample CS showed formation of mostly
pyramidal to oval shaped NPs along with some spherical NPs.
The formation of agglomerates of CuSe NPs can be observed
leading to generation of large flake-like structures with
inhomogeneous size distribution (Figure 4a). Formation of
large globules with a rough and uneven surface due to
agglomeration of small Ag2Se NPs can be observed from SEM
image b in Figure 4. In the case of sample IS, mixed
morphology was observed. It is evident from Figure 4c that the
growth of IS NPs was nondirectional and led to form uneven
and polydispersed NPs with different shapes such as, rods,
flakes, and spheres, etc. However, IS NPs are observed to be
less agglomerated as compared to other samples. Smooth, large
globules due to agglomeration of SS NPs are visible from
Figure 4d. The agglomerated spherical NPs showed formation
of larger structures of varied morphology. Almost similar
observations have been made from the TEM images. Overall,
results obtained from SEM and TEM images of MSe NPs are
closely correlated and found to be well-matching. Ternary
hybrids prepared by ex situ method using MWCNT, PANI,
and binary metal chalcogenides as sensitizer have been
characterized by FESEM to understand their morphological
changes. The FESEM images are presented in Figure 4,
suggesting formation of a giant network leading to mesh-like
appearance of as-prepared hybrids. Since PANI and MWCNT
contain a number of π-bonds, their interaction within hybrid is
well-known to exhibit temporary π−π stacking.59 Therefore,
combination of all three materials was expected to show
formation of a homogeneous hybrid along the surface of
MWCNT. As expected FESEM images of hybrids revealed a
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Figure 4. FESEM images of (a−d) CS, AS, IS, and SS NPs and (e−h)
ternary hybrids of CSCP ASCP, ISCP, and SSCP, respectively.
similar pattern. In all samples MWCNT is easily identified
along with decoration of NPs and PANI over its surface
(Figure 4e−h). Globular agglomerates around MWCNT are
considered due to PANI, while careful observation of images
has revealed the presence of smaller spherical NPs within the
hybrid particularly in the cases of CSCP, ASCP, and SSCP,
while ISCP showed large agglomeration which could be due to
PANI. Because of mixed morphology of IS, their presence in
hybrid is difficult to identify. The decoration of NPs and PANI
over MWCNT are clearly seen in the case of ASCP and SSCP
(Figure 4f,h), which are suggesting the formation of a
homogeneous hybrid. Therefore, FESEM images suggest that
metal selenide NPs are firmly seized over the surface of
MWCNT by PANI leading to formation of uniform hybrid.
Elemental composition of as-prepared binary metal selenide
NPs was estimated using EDS analysis (Figure S3).
All samples showed stoichiometric elemental composition.
In the case of CS, atomic percentage values revealed nearly
equal amounts of Cu and Se (Figure S3a), confirming the
purity of CS. AS represents 2:1 silver to selenium ratio,
confirming stoichiometric formation (Figure S3b). Two other
samples are also found to be stoichiometric (Figure S3c,d).
The EDS analysis of the ternary hybrids showed the presence
of all expected elements with nearly stoichiometric ratio as it is
evident from Figure S3e−h. The presence of a higher
percentage of carbon in all samples of hybrid is due to PANI
and MWCNT.
The FTIR analysis of MSe NPs and their hybrids have been
carried out in order to understand the presence of different
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Figure 5. (a) Electrical conductivities, (b) Seebeck coefficients, and (c) power factors of CSCP, ISCP, SSCP, and ASCP; (d) charge transfer
mechanism in p- and n-type hybrids.
functional groups due to a capping agent and the presence of
PANI as well as vibrational modes of NPs. During the
synthesis oleic acid was employed as a capping agent, and
therefore, peaks due to different functional groups such as,
CC, CO, and -O−H, etc., are expected in FTIR spectra of
MSe NPs. The FTIR spectra of MSe and their hybrids are
shown in Figure S4a,b. The presence of low intensity peaks
around 3300 cm−1 is considered due to O−H vibrations.
Symmetric and asymmetric C−H vibrations lead to peaks in
the range of 2800−3000 cm−1. Low intensity peaks between
1540 and 1627 cm−1 are due to stretching vibrations of CC.
The C−H rocking vibrational mode of oleic acid showed a
strong to medium intensity peak between 1370 and 1445 cm−1.
Other low intensity vibrational peaks near 1100 cm−1 are
considered due to C−O stretching. All these peaks observed in
MSe NPs are due to capping of NPs by oleic acid.
In ternary hybrids it is expected that NPs will get deposited
over the surface of MWCNT and N−H group in the PANI will
hold them firmly by loose/temporary bond since nitrogen
atom contains a lone pair of electrons. The composites of
MWCNT and PANI are known to possess π−π stacking due to
the presence of a number of π-bonds,59 and therefore, addition
of MSe NPs in such hybrids may lead to their insertion
between MWCNT and PANI resulting in a firm network.
Therefore, it is essential to understand the different
functionalities in the hybrids by FTIR. The presence of
broad vibrational stretching near 3450 and 3100 cm−1 are
confirming the presence of -N−H and -C−H symmetric and
asymmetric groups from PANI. The most important features
for confirmation of PANI in the hybrid are the presence of
CC stretching peaks due to quinonoid and benzenoid
structures. The high intensity peak at about 1620 cm−1 is
associated with the quinonoid ring, while the peak near 1390
cm−1 originated from benzenoid.78 The noticeable high
intensity peak in ternary hybrid is due to delocalization of
electrons in PANI as well as π−π interaction between PANI
and MWCNT. The low intensity peaks observed between 990
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and 1100 cm−1 are indicative of C−O stretching arising due to
presence of oleic acid as a capping agent (Figure S4b). Raman
spectroscopy of as-synthesized binary metal selenide reveals
the presence of all expected peaks. In the case of AS
characteristic peaks for Ag−Se, bond vibrations appeared as
low intensity peaks at 137 and 157 cm−1.79,80 A broad peak at
269 cm−1 in the case of CS is attributed to the vibrational
frequency of Cu−Se bond.
The peak broadening in Raman scattering is due to the
smaller particle size and amorphous nature of the CS.81 Sample
IS showed different peaks at 142, 225, 266, 335, 424, and 552
cm−1, confirming the formation of In2Se3. The low intensity
peak at 142 cm−1 is due to In−In bond vibrations, generally
illustrated as transverse and longitudinal optical modes (TO-
LO states), while the broad peak at 225 cm−1 is due to Se
chain vibrations. The peak at 254 cm−1 may be assigned to Se8
ring vibrations, and strong peaks at 424 and 552 cm−1 are due
to second order Raman scattering in In2Se3 NPs.82 Similarly,
SS also showed peaks due to Se chain vibrations and Se8 at 260
and 550 cm−1. Other characteristic peaks of Sb−Se and Sb−Sb
bond vibrations appeared at 199 and 142 cm−1.83−85
Hybrids have showed a different nature of spectra in
thelower frequency region which could be due to dominance
of MWCNT and PANI stretching vibrations. In order to
confirm the different modes due to MWCNT and PANI,
Raman spectra were recorded in the range of 1000−2000
cm−1. Spectra of all hybrids revealed an almost similar pattern
with different peaks at 1069, 1258, 1344, 1548, 1674, 1693,
1781, and 1877 cm−1. The CC quinonoid and benzenoid
forms of PANI have also been identified in Raman spectra
similar to that of FTIR. Peaks at 1548 and 1674 cm−1 were due
to quinonoid and benzenoid forms of the PANI. The
quinonoid form also showed a peak due to C−N+ at 1344
cm−1.86−88 However, another contributor of the hybrid is
MWCNT, which is known to exhibit peaks at 1340 and 1611
cm−1 and corresponding to the D and G band,89 but these
peaks are found to be merged with the peaks due to quinonoid
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ACS Applied Energy Materials
and benzenoid forms of PANI. The merging of the peaks leads
to peak broadening as it is evident from Figure S4e. It is also
observed that all peaks were matched well with the hybrids of
MWCNT and PANI, which confirms their presence in all
other samples also (Figure S4e CP). The broadness of the
peaks for all these samples hints toward scattering of phonons
which may help in lowering the thermal conductivity in them.
The low thermal conductivity would be beneficial to obtain
higher thermopower from these samples.
Thermoelectric Performance of Ternary Hybrid.
Thermoelectric properties of the materials can be well-
explained by three different components such as, electrical
conductivity (σ), Seebeck coefficient (S), and power factor (PF
= S2σ). Since power factor values are good enough to evaluate
thermoelectric performance, its estimation is essential and
hence measurement of the first two factors was carried out at
room temperature (RT). Electrical conductivities of CSCP and
SSCP were found to be higher (4570 and 4975 S/m,
respectively) than those of ASCP and ISCP; this could be
due to higher charge carrier mobility within the hybrid
possessing a giant network possibly comprised of strong
connectivity between PANI, metal selenide NPs, and
MWCNT (Figure 5a).
FESEM images of the hybrids (Figure 4) are clearly
indicative of giant network formation with connections
between these three materials which probably helps for easy
movement of the charge carriers. PANI comprises benzene and
quinoid rings as it is already confirmed from FTIR study in the
present case. These rings are linked with each other by an
amine nitrogen atom. This linkage leads to active π−π
conjugated interactions and forms a channel for carrier
transport. Similarly, carbon nanotubes also possess a π-bonded
surface and may exhibit strong π−π interaction with
conjugated PANI. Such interactions can favor charge transport
leading to enhanced electrical conductivity.27 Moreover,
incorporation of the MSe NPs in such a system may further
help in energy filtering. Nevertheless, all ternary hybrids
contain the same quantity of MWCNT and PANI therefore;
the difference observed in electrical conductivities is
considered due to change in binary metal selenide NPs in
hybrid.
Generally, combination of two materials with a huge
difference in their electrical conductivities obeys the
percolation law which helps to enhance electrical conductivity,
and therefore, this possibility also cannot be ruled out in the
present case since PANI has lower electrical conductivity than
MWCNT. Thus, good electrical conductivity of CuSe/
MWCNT/PANI and Sb2Se3/MWCNT/PANI is expected to
show a negative impact on the Seebeck coefficient along with
increased electronic thermal conductivity (ke), This therefore
can be claimed as the main reason for decreased power factor
in totality. The thermal conductivity of CSCP was obtained to
be 0.54 W/mK at room temperature which affected the power
factor and thus the zT value (0.002). In view of the above it
can be concluded that lower Seebeck coefficient values of
CSCP, ISCP, and SSCP as compared to ASCP are due to their
increased charge carrier concentration as it is evident from
electrical conductivity values (Figure 5b) and high thermal
conductivity. To the contrary, ASCP exhibited a moderate σ
value (2962 S/m), which is justified by its higher Seebeck
coefficient (65 μV/K), and thus power factor (12.5
μWm−1K−2) at room temperature (Figure 5c). The positive
value of the Seebeck coefficient for ASCP suggests p-type
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semiconducting behavior, while other hybrids are observed to
be n-type owing to their negative S. The thermal conductivity
of ASCP was found to be lower (0.31 W/mK) as compared to
that of CSCP, and therefore, zT of ASCP at room temperature
is 0.012 and higher than CSCP.
Among n-type hybrids, CSCP showed higher S (−28 μV/K)
and PF (3.6 μWm−1K−2), and therefore, it is compared with
the p-type ASCP by measuring thermal conductivity at room
temperature. The higher power factor and zT obtained in the
case of ASCP could be due to scattering of the charge carriers
via energy filtering.90,91 The presence of AS in the hybrid could
be responsible for decoupling of electrical and thermal
conductivities resulting in enhanced performance. The present
investigation therefore revealed formation of various hybrids
with electrical conductivity in order of 103 with p- and n-type
behaviors which can become valuable materials in thermo-
electric field for better energy conversion. Such p- and n-type
hybrids can be compiled for efficient flexible thermoelectric
devices by further improvement in their performance.
Possible Charge Transport Mechanism in Ternary
Hybrid. As per the literature reports, nanostructured material
possesses more interfaces and grain boundaries in comparison
to their bulk materials.92 The formation of hybrids with two or
more materials containing NPs leads to further increase in
grain boundaries and interfaces. Such increased interfaces and
grain boundaries help to scatter electrons resulting in reduction
in electrical conductivity as compared to bulk materials.
However, the presence of conducting constituents such as
MWCNT and PANI with strong π−π interactions nullifies this
possibility via electron transport from percolated network
resulting in enhancement in electrical conductivity.55 It is well-
understood from the literature93 that in the case of
nanocomposite systems interfacial scattering is more viable
than that of resonant levels (RLs) mechanism, and therefore, it
is apparent to consider interfacial scattering in the present case
also. Decoration of MSe NPs over the surfaces of MWCNT
and PANI can favor interfacial scattering of phonons and
transfer of electrons/holes leading to decreased thermal
conductivity and enhancement in electrical conductivity,
respectively. Since the lowest unoccupied molecular orbital
(LUMO) of PANI is assumed to be at higher energy than the
conduction band of MSe NPs (for better understanding
examples of Ag2Se (p-type) and CuSe (n-type) are considered
and discussed henceforth), while highest occupied molecular
orbital (HOMO) of PANI is considered slightly higher in
energy than that of the valence band of Ag2Se and CuSe NPs.
Such type-II heterojunction formation between these two
materials with band alignments as presented in Figure 5d helps
to favor electron transfer from PANI to Ag2Se NPs and holes
in reverse order for that of MWCNT, while in the case of CuSe
NPs exactly the opposite charge transfer can be considered
wherein electrons travel from CuSe NPs to MWCNT under
the influence of thermal or light energy. In the case of n-type
hybrids, we believe that MSe NPs, MWCNT, and PANI are
not connected together as seen above in the ASCP
nanocomposite. Here, the dense MWCNT network was locally
covered with either PANI or MSe but not together. Thus, we
obtain two separate active interfaces of MWCNT/PANI and
MWCNT/MSe, where MWCNT may act as a charge carrier
throughout the nanocomposite system Figure S5. This
arrangement may result in influx of electrons in MWCNT
from MSe while transfer of holes in MWCNT from PANI. The
end result may be n-type behavior of these hybrids due to
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ACS Applied Energy Materials
increased density of electrons in MWCNT decreasing the
density of holes in PANI.
MWCNT possesses an energy level higher than the HOMO
of PANI,41 and therefore, transfer of holes from PANI to
MWCNT are expected in p-type hybrid with transfer of
electrons from CuSe to MWCNT in n-type hybrid. This clearly
illustrates the charge carriers transport mechanism within the
ternary hybrid, responsible for good electrical conductivity as it
is evident from Figure 5a. The presence of MWCNT, PANI,
and binary metal selenide NPs altogether result in formation of
two interfaces, such as MWCNT/PANI and PANI/MSe or
MWCNT/MSe NPs, which are favoring charge transfer as well
as energy filtering. Filtering of the low energy charge carriers
allows high energy carriers to cross an energy barrier leading to
an increase in the electrical conductivity and Seebeck
coefficient. The higher Seebeck coefficient obtained in the
case of ASCP is attributed to the synergetic effect of the
interfacial electron and phonon scattering, while the other
three ternary hybrids containing CS, IS, and SS showed the
dominance of electronic scattering and lower phonon
scattering resulting in an overall decreased Seebeck coefficient.
Overall, such ternary hybrids show high electrical conductivity
and both n- and p-type semiconducting behavior depending on
the presence of binary metal selenide NPs.
■ CONCLUSION
A novel ternary hybrid comprising binary metal selenide
nanoparticles, MWCNT, and PANI have been synthesized and
investigated toward their thermoelectric performance. The
characterization of initially synthesized MSe NPs revealed their
phase pure formation with varied sized nanoparticles.
Decoration of MSe NPs between MWCNT and PANI have
clearly been identified from FESEM images. π−π stacking
between MWCNT and PANI could be responsible for
formation of channels for charge transport leading to electrical
conductivity in the order of 10 K. The room temperature
thermoelectric performance of the all hybrids suggests n- and
p-type behavior. Higher zT of 0.012 and power factor of 12.5
μW/mK2 were estimated in the case of Ag2Se/MWCNT/
PANI exhibiting p-type behavior, while zT of 0.002 and power
factor of 3.6 μW/mK2 were obtained in the case of Cu2Se/
MWCNT/PANI showing n-type behavior. The performance
of such hybrid composites can be further enhanced by
employing highly conductive filler such as reduced graphene
oxide (RGO) and/or doping of the binary selenides. Because
of the fact that these binary selenides and PANI show
photovoltaic effect, their thermoelectric efficiency may further
increase in the presence of visible to near-IR light. Such studies
to enhance the thermoelectric performance will be performed
in the next phase of the work.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsaem.9b00013.
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: pawankhanna2002@yahoo.co.in.
ORCID
Anuraj S. Kshirsagar: 0000-0002-5627-7450
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Abhijit Dey: 0000-0002-8996-3211
Priyesh V. More: 0000-0002-7570-4630
Pawan K. Khanna: 0000-0001-5112-4431
Author Contributions
The designing of schemes, planning of work, and draft
correction with overall guidance were executed by P.K.K.
The experimental work was carried out by A.S.K. and C.H.
Characterization, interpretation, and draft preparation were
done by A.S.K. P.V.M. was involved in the designing of
thermoelectric work, its interpretation, and draft correction.
The thermoelectric work was carried out by A.D. at HEMRL,
Pune.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank Vice-Chancellor, Defence Institute of Advanced
Technology (DIAT), Girinagar, Pune for encouragement and
permission. A.S.K. acknowledges DIAT for a Senior Research
Fellowship (SRF). We are thankful to Dr. A. Abhyankar, DIAT
(DU), Pune and Dr. Sreenu Bhanoth for their help in SEM
analysis, and Department of Applied Physics, DIAT, Pune for
providing Hall Effect measurement facility.
■ ABBREVIATIONS
AS = silver selenide
ASCP = Ag2Se/MWCNT/PANI
CS = copper selenide
CSCP = CuSe/MWCNT/PANI
IS = indium selenide
ISCP = In2Se3/MWCNT/PANI
MSe = binary metal selenides
MWCNT = multiwalled carbon nanotubes
NPs = nanoparticles
PANI = polyaniline
SS = antimony selenide
SSCP = Sb2Se3/MWCNT/PANI.
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2691 DOI: 10.1021/acsaem.9b00013

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