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 Nanotechnology

Nanotechnology 32 (2021) 335705 (12pp) https://doi.org/10.1088/1361-6528/abeeb7

PANI coupled hierarchical Bi2S3 nanoflowers

based hybrid nanocomposite for enhanced
thermoelectric performance
Surbhi Sharma, Huidrom Hemojit Singh, Sunil Kumar and Neeraj Khare
Department of Physics, Indian Institute of Technology Delhi, New Delhi-110016, India

E-mail: nkhare@physics.iitd.ernet.in

Received 24 January 2021, revised 10 March 2021

Accepted for publication 15 March 2021
Published 26 May 2021

Abstract
Bismuth sulfide (Bi2S3) is a promising material for thermoelectric applications owing to its non-
toxicity and high abundance of bismuth (Bi) and sulfur (S) elements on earth. However, its low
electrical conductivity drastically reduces the value of the figure of merit (ZT). In this work, we
have synthesized three-dimensional (3D) hierarchical Bi2S3 nanoflowers (NFs) by the
hydrothermal route and further incorporated them with conducting polymer polyaniline (PANI)
by simple chemisorption method. We have investigated the thermoelectric properties of the as-
prepared Bi2S3 NFs and PANI/Bi2S3 nanocomposite samples and it is demonstrated that the
incorporation of the PANI matrix with the 3D hierarchical Bi2S3 NFs provides a conducting
substrate for the easy transport of the electrons and reduces the barrier height at the interface,
resulting in ∼62% increment in the electrical conductivity as compared to Bi2S3 NFs. Moreover,
a decrement in the thermal conductivity of the PANI/Bi2S3 nanocomposite is observed as
compared to pristine Bi2S3 NFs due to the increased phonon scattering at the interfaces
facilitated by the hierarchical morphology of the NFs. Furthermore, an increment in the electrical
conductivity and simultaneous decrement in the thermal conductivity results in an overall ∼20%
increment in the figure of merit (ZT) for PANI/Bi2S3 nanocomposite as compared to pristine
Bi2S3 NFs. The work highlights an effective strategy of coupling 3D hierarchical metal
chalcogenide with conducting polymer for optimizing their thermoelectric properties.
Keywords: Bi2S3 nanoflowers, conducting polymer, nanocomposite, electrical conductivity,
thermal conductivity, figure of merit
(Some figures may appear in colour only in the online journal)

1. Introduction the following dimensionless figure of merit (ZT) value [2]:

The high consumption rate and limited stock of conventional
energy sources demand the development of new energy
sources to fulfill the rising global energy demand. The pro-
duction of electricity through thermoelectric devices by uti-
lizing waste heat energy in day to day life is an effective
approach. Therefore, the design and exploration of sustain-
able and eco-friendly materials for the fabrication of ther-
moelectric devices and thermal energy storage systems have
attracted worldwide attention due to their capability of har-
vesting waste heat energy and power generation [1–4]. The
efficiency of the thermoelectric materials can be estimated by
S 2sT
ZT = , (1 )
k
where S, s, T , and k is the Seebeck coefficient, electrical
conductivity, absolute temperature, and thermal conductivity,
respectively. Typically, the thermal conductivity (k ) is
defined as the sum of electronic thermal conductivity
(kelectronic ) and lattice thermal conductivity (klattice ). It is
noteworthy that for achieving a high ZT value, the thermo-
electric material with a high value of power factor (S 2s ), and
simultaneously a low value of thermal conductivity is
required. However, for attaining the maximum ZT value of

0957-4484/21/335705+12$33.00 1 © 2021 IOP Publishing Ltd Printed in the UK

Nanotechnology 32 (2021) 335705
any material, it is very difficult to control these parameters
independently due to their strong interdependency.
Semiconductor chalcogenides with chemical formula
A2B3 (where A=Bi, Sb, Pb, and B=S, Se, Te) are proven
as the most promising materials for thermoelectric applica-
tions [5–8]. Until now, chalcogenide materials such as Bi2Te3
[9, 10], PbTe [11], SnTe [12], Cu7Te4 [13], and PbTe-SrTe
doped Na2Te [14] have exhibited excellent thermoelectric
performance at the room as well at moderate temperatures,
however, telluride and lead-based elements are rare and toxic
which hinders their use in practical applications. Therefore,
the development of some assuring alternative thermoelectric
materials is required. Among metal chalcogenides, bismuth
sulfide (Bi2S3) is a layered semiconductor with a band gap of
∼1.3 eV that crystallizes in pbnm orthorhombic space group
and non-toxic in nature. Owing to its unique physical, che-
mical, and electrical properties, it has been widely used in
different research areas for example photocatalysis [15],
photoelectrochemical water splitting [16], resistive switching
[17], solar cells [18], photodetectors [19], and supercapacitors
[20]. Recently, it has received tremendous research interest as
an alternative to mostly used tellurium and lead-based mate-
rials for thermoelectric applications due to its high Seebeck
coefficient and low thermal conductivity [21–28]. Never-
theless, its low electrical conductivity is a major obstacle for
obtaining a high ZT value [24, 29]. Most of the enduring
efforts for improving the thermoelectric properties of Bi2S3
are focussed on elemental doping [21–23], microstructuring
[24], nanostructuring [25–27], and texturing [28]. It is note-
worthy that the electrical conductivity of Bi2S3 can be
enhanced by increasing the charge carrier concentration but it
will adversely affect the value of the Seebeck coefficient and
thermal conductivity. For example, Wong et al [30] have
synthesized Bi2S3 composite materials via percolation
approach through mixing Bi-rich Bi2S3 (Bi2+xS3) with com-
mercially available Bi2S3 in different weight ratios to enhance
the electrical conductivity. Although, the incorporation of
Bi2+xS3 led to the increment in the electrical conductivity as
compared to the pristine Bi2S3 sample but it caused the
reduction in the Seebeck coefficient and simultaneously a
slight increment in the thermal conductivity in the 40 wt%
Bi2+xS3 composite. The observed decrement in the Seebeck
coefficient is due to the increment in the charge carrier con-
centration in the composite system. In another report, Wu
et al [31] have adopted the doping technique for optimizing
the thermoelectric properties of Bi2S3 material and synthe-
sized the Bi2S3 bulk samples by doping with different mol%
of LaCl3 via solid state reaction and spark plasma sintering
method. It is observed that for doped Bi2S3 bulk material, the
electrical conductivity initially increases and then gradually
decreases with increasing temperature due to competition
between increased carrier concentration near room temper-
ature (RT) and decreased carrier mobility at high temperature.
Whereas, a reduction in the Seebeck coefficient due to the
enhancement in the charge carrier concentration as well as
decrement in thermal conductivity owing to multi-scale
phonon scattering is observed for 2 mol% LaCl3 doped Bi2S3
material. Therefore, the electrical conductivity should be
2
S Sharma et al
increased, simultaneously maintaining the high Seebeck
coefficient and low thermal conductivity. In this perspective,
the design of conducting polymer-based nanocomposite,
which integrates the advantages of low thermal conductivity
of conducting polymer and high power factor of inorganic
material for maximizing the ZT value would be beneficial.
Among the various conducting fillers, polyaniline
(PANI), a p-type conducting polymer has emerged as a
potential organic thermoelectric material due to its unique
properties such as intrinsically low thermal conductivity, high
electrical conductivity, air stability, and ease of synthesis
[32, 33]. Owing to its good electrical, mechanical and thermal
properties, various PANI based nanocomposites such as
PANI/Ag [34], PANI/CdS [35], PANI/ZnSe [36], PANI/
PbTe [37], PANI/Bi2Te3 [38], PANI/Bi0.5Sb1.5Te3 [39],
SWCNT/PANI [40], PANI/Ag2Te [41], PANI/RGO [42],
and PANI/CNT/Ag [43] have been widely reported for the
demonstration of improved thermoelectric performance.
Therefore, the strategy of combining organic conducting
polymer PANI with metal chalcogenide would be advanta-
geous for improving the thermoelectric performance of the
pristine Bi2S3.
In this paper, we have synthesized Bi2S3 nanoflowers
(NFs) and PANI/Bi2S3 nanocomposite via facile chemical
route and investigated their thermoelectric properties. The
addition of the PANI matrix in the 3D hierarchical Bi2S3 NFs
provides a conducting substrate for the easy transport of the
electrons and reduces the barrier height at the interface
resulting in ∼62% increment in the electrical conductivity as
compared to Bi2S3 NFs. Moreover, a decrement in the ther-
mal conductivity of the PANI/Bi2S3 nanocomposite is
observed as compared to Bi2S3 due to the increased phonon
scattering at the interfaces facilitated by the hierarchical
morphology of the NFs. The as-prepared PANI/Bi2S3 nano-
composite has demonstrated an overall ∼20% improvement
in the figure of merit (ZT) as compared to the Bi2S3 NFs
owing to an increment in the electrical conductivity and
simultaneous reduction in the thermal conductivity.
2. Experimental
2.1. Synthesis of PANI
Polyaniline (PANI) was synthesized by chemical oxidative
polymerization method according to our previous reports
[44–47]. Aniline, ammonium peroxydisulfate ((NH4)2S2O8),
and hydrochloric acid (HCl) were used as the precursors. A
0.1 M of aniline and 1 M of HCl were prepared by adding into
1 l of deionized (DI) water and the mixture was stirred at
500 rpm maintained at a low temperature of 1 °C for 6 h.
Subsequently, 1 M of (NH4)2S2O8 was added into the pre-
viously prepared mixture. After continuous stirring for 7 h,
the resultant precipitates were extracted by filtering and the
residual was maintained at 70 °C for 20 h. Eventually, the
conducting PANI (emeraldine salt form) is acquired.
Nanotechnology 32 (2021) 335705
Figure 1. Synthesis process of PANI, Bi2S3 NFs, and PANI/Bi2S3 nanocomposite.
2.2. Synthesis of Bi2S3 NFs
Bismuth sulfide (Bi2S3) NFs were prepared by hydrothermal
route [48–50]. For the synthesis, 20 mM of bismuth nitrate
(Bi(NO3).5H2O) was dissolved in deionized water and poly-
ethylene glycol (PEG) solution (80 ml, molar ratio of 1:3) by
stirring for 15 min to form a homogenous solution. Subse-
quently, 80 mM of thiourea (CH4N2S) was gradually mixed in
the above aqueous solution with continuous stirring at
450 rpm for 1 h. Next, the resulting yellow solution was filled
in a Teflon beaker which was inserted inside stainless steel
autoclave and kept at 150 °C for 24 h. The obtained black
precipitates of Bi2S3 were filtered and washed with deionized
water and ethanol and dried at 70 °C for 20 h.
2.3. Synthesis of PANI/Bi2S3 nanocomposite
Polyaniline (PANI) incorporated Bi2S3 nanocomposite was
synthesized via facile chemisorption route. PANI was used as
a conducting substrate for the preparation of PANI/Bi2S3
nanocomposite. Initially, a solution containing PANI and
tetrahydrofuran (THF) was prepared by adding 0.05 g of
PANI in 100 ml of THF followed by ultrasonication for
30 min. Subsequently, the Bi2S3 nanostructured sample was
mixed in the PANI (THF) solution and vigorously stirred at
3
S Sharma et al
450 rpm for 24 h at RT. Finally, the obtained precipitates
were filtered and properly dried at 80 °C for 20 h. The
synthesis process of PANI, Bi2S3 NFs, and PANI/Bi2S3
nanocomposite is illustrated in figure 1.
2.4. Characterization techniques
The structural analysis of the samples was performed
employing a x-ray diffraction (XRD) system (Rigaku Ultima
VI) having a CuKα radiation source of wavelength 1.54 Å
[51, 52]. The morphology of the samples was analyzed by
scanning electron microscopy (SEM) characterization tech-
nique using a scanning electron microscope (Carl Zeiss EVO–
50) and TEM and high resolution TEM (HRTEM) employing
transmission electron microscope (FEI Tecnai G2). The ele-
mental mapping analysis was done using an energy dispersive
x-ray spectroscopy (EDX) using a spectrophotometer (SWIFT
ED–3000 series). A spectrometer (Thermo Fisher iS50 Sci-
entific Nicolet) was utilized to record the Fourier transform
infrared (FTIR) spectra in the mid-IR spectral region of
400–3500 cm−1. The Kelvin probe force microscopy (KPFM)
measurements were performed by using a Pt–Ir coated Sb
doped Si cantilever (Bruker Dimension Icon). In order to
Nanotechnology 32 (2021) 335705
Figure 2. XRD patterns of PANI, Bi2S3 NFs, and PANI/Bi2S3
nanocomposite.
obtain the surface potential images of the prepared samples, a
lift height of 100 nm was used.
2.5. Thermoelectric measurements
For performing the thermoelectric measurements, pellets of
the powered samples were made using a cold-pressing tech-
nique employing a hydraulic press (pressure ∼3000 lbs/sq.)
and electrical contact pads (∼2 mm2) were made using the
electron-beam evaporation method. The values of the Seebeck
coefficient were estimated through a differential technique
employing a home-made thermoelectric setup kept under
vacuum condition (∼10−3 Torr). During the measurement,
the temperature difference between the hot and cold side was
kept at ∼5 K, and obtained Seebeck voltage was calculated by
nano voltmeter (Keithley 2182 A). For performing the elec-
trical conductivity measurements of the samples in the pellet
form, we have used the same home-made measurement set up
under vacuum condition in a four-probe configuration. The
four probes were arranged linearly in a straight line at equal
distance from each other and a constant current (I) was
allowed to pass through the two end probes while the
potential drop (V ) was measured across two middle probes. In
order to study the behavior of the samples with increasing
temperature, a copper block was installed with a heater for
heating the sample during the measurements. The temperature
dependent thermal conductivity measurements were per-
formed employing a hot disc thermal constant analyzer (Hot
Disc TPS 2200) by transient plane source (TPS) method.
3. Results and discussion
To probe the phase purity and crystal structure of the nano-
materials, XRD measurement has been performed. Figure 2
depicts the XRD patterns of the PANI, Bi2S3 NFs, and
PANI/Bi2S3 nanocomposite. The XRD patterns of PANI
exhibited three peaks at 14.98°, 20.84°, and 25.02°
4
S Sharma et al
corresponding to (010), (100), and (110) crystal planes sug-
gesting that most of the polymer chains are oriented in these
diffraction planes. The appearance of these PANI peak
positions confirms its semi-crystalline nature and its forma-
tion in emeraldine salt (doped) form which is found in good
agreement with the earlier published reports [53, 54]. For
Bi2S3, the sharp peak positions at different diffraction angles
corresponding to particular diffraction planes of the Bi2S3
(well correlated with JCPDS no. 06-0333) confirmed its
synthesis in the pure orthorhombic phase. No extra XRD
peaks were detected. The intense and sharp XRD peaks of the
Bi2S3 signify the high crystallinity of the nanostructured
sample. The observed XRD peaks for PANI/Bi2S3 nano-
composite is similar to the Bi2S3 material showing only the
characteristic peaks of Bi2S3 nanostructure as the XRD peaks
of PANI (emeraldine salt form) in the nanocomposite might
get suppressed due to the low loading percentage of PANI
which is found in agreement with previously reported studies
[55, 56]. However, no diffraction peaks of PANI are observed
due to its low loading amount. It can be inferred that the
crystal phase of Bi2S3 NFs is not altered even after incor-
poration with PANI.
Furthermore, to analyze the surface morphology and
structure of the as-prepared samples SEM, transmission
electron microscopy (TEM), and HRTEM measurements
have been performed. The SEM and TEM images of the as-
prepared Bi2S3 and PANI/Bi2S3 nanocomposite are shown in
figure 3. The SEM images of Bi2S3 demonstrate the hier-
archical NFs-like morphology which consists of many inter-
connected nanorods having an average diameter of about
35 nm and length of few μm (figures 3(a) and (c)). For PANI/
Bi2S3 nanostructure, it is revealed that the surface of Bi2S3
NFs has been covered by polymer matrix (figures 3(b) and
(d)). Furthermore, the TEM image of Bi2S3 also evidences the
structure of NFs as illustrated in figure 3(e). It can be
observed from the TEM image of PANI/Bi2S3 nanocompo-
site that the conducting PANI polymer fills in the gaps of the
interconnected nanorods and on their surface also thus,
facilitating the formation of many interfacial contacts between
PANI and hierarchical Bi2S3 NFs (figure 3(f)). The inter-
planar spacing of the crystallographic planes is estimated as
∼0.394 nm correlating to the (220) plane of the orthorhombic
Bi2S3 NFs. The HRTEM image of the PANI/Bi2S3 nano-
composite signified the appearance of the two overlapping
crystal lattices with the covering of PANI over Bi2S3 NFs due
to successful loading of PANI on its surface (figure 4(h)). In
the PANI/Bi2S3 nanocomposite, the interplanar spacing
remains similar as observed for pristine Bi2S3 NFs however;
the lattice fringes are less distinguishable due to the covering
of PANI over the Bi2S3 surface.
Moreover, EDX analysis of the as-prepared nano-
composite sample has been done to probe the chemical
composition and elemental distribution. Figure 4 depicts the
low magnification SEM image, corresponding elemental
maps, and the EDX spectrum of the PANI/Bi2S3 nanos-
tructured sample. The EDX spectrum of the PANI/Bi2S3
nanocomposite depicts different peaks correlating to the ele-
ments, bismuth (Bi), sulfur (S), carbon (C), and nitrogen (N).
Nanotechnology 32 (2021) 335705
Figure 3. SEM images of (a), (c) Bi2S3 NFs, (b), (d) PANI/Bi2S3
nanocomposite, TEM images of (e) Bi2S3 NFs, and (f) PANI/Bi2S3
nanocomposite, and HRTEM images of (g) Bi2S3 NFs, and (h)
PANI/Bi2S3 nanocomposite.
No other peaks are detected indicating the high purity of the
nanocomposite sample. Figures 4(b)–(e) illustrate the ele-
mental mapping images of bismuth (red), sulfur (green),
carbon (blue), and nitrogen (N) of selected SEM image of the
PANI/Bi2S3 nanocomposite (figure 3(a)) and color overlay
image of bismuth (red), sulfur (green) and carbon (blue)
elements are presented in figure 3(f). The successful loading
of PANI over Bi2S3 NFs is confirmed from the coexistence of
the distinct elements in the elemental maps.
In addition, to classify the associated functional groups
and chemical bonds related to the vibrational transitions in
PANI and Bi2S3 NFs and to explore the possible chemical
bonding and interactions between them, the FTIR measure-
ments have been conducted. Figure 5 depicts the FTIR spectra
of PANI, Bi2S3 NFs, and PANI/Bi2S3 nanocomposite. The
characteristic peak of Bi2S3 at 1019 cm−1 is attributed to the
5
S Sharma et al
stretching vibrations of C–O bond [57, 58]; whereas the peak
at 1423 and 1639 cm−1 correspond to the bending vibration of
C–H bond and stretching vibration of C=C bonds in oleyl
amine hydrocarbon chain [59]. The peak positions of PANI at
505 cm−1 is attributed to C–Cl aromatic out of plane band
[60]. The peak of PANI at 573 and 692 cm−1 correspond to
C–C ring deformation, whereas the peak at 798 cm−1 is
ascribed to the out of plane C–H bending [61]. The peak at
1032 cm−1 is attributed to the C–N stretching vibration [54].
The peak at 1125 cm−1 is related to the vibration mode of
bipolaron (−C=NH+) or polaron (−C–NH+•) structure
which also signifies the redistribution of electrons over
polymer chains [54, 60, 62], and the appearance of FTIR peak
at 1170 cm−1 is related to the degree of delocalization on
polymer chains, which is a characteristic peak of the elec-
trically conductive form of doped PANI (emeraldine salt
form) [54]. The peaks at 1287 cm−1, 1489 cm−1, and
1575 cm−1 in the FTIR spectrum are attributed to the C–N
stretching vibration mode of benzenoid ring or displacement
of the π electrons on the polymer chains [60–62], C–C
stretching vibration of benzenoid (B) rings (=N=B=N)
[54, 60, 61], and C=C stretching vibration of quinoid (Q)
rings (N=Q=N) [54, 60, 61], respectively.
For PANI/Bi2S3 sample, FTIR peaks corresponding to
both Bi2S3 and PANI are observed which signified the for-
mation of the nanocomposite. It is observed that the peaks of
PANI at 573 cm−1, 798 cm−1, 879 cm−1, 1170 cm−1,
1287 cm−1, 1489 cm−1, and 1575 cm−1 are shifted to higher
wavenumbers of 613 cm−1, 800 cm−1, 881 cm−1, 1173 cm−1,
1288 cm−1, 1495 cm−1, and 1578 cm−1, respectively. How-
ever, the peak position of Bi2S3 at 1019 cm−1 is shifted to the
lower wavenumber of 1015 cm−1 in the PANI/Bi2S3 nano-
composite. In the FTIR spectra of the PANI/Bi2S3 nano-
composite, we observed the shifting of the FTIR peaks related
to the PANI and Bi2S3 samples. The shifting of the peak
positions is attributed to the effective transfer of charges and
strong chemical interaction between them which is found in
agreement with previously reported PANI-based nano-
composites [46, 63]. The change in the FTIR spectra of
PANI/Bi2S3 nanocomposite clearly showed that the extent of
charge delocalization on the polymeric PANI chains is
increased due to the synergistic interaction between PANI and
Bi2S3. Thus, it can be concluded that PANI gets adhered to
the surface of Bi2S3 NFs to form nanocomposite.
KPFM is a useful technique for the estimation of the
local surface potential distribution of various nanomaterials.
Since the value of the surface potential depends on the dif-
ference in the work function of the tip and the sample,
materials with different work functions will have different
surface potential. As a result, we can obtain information of the
potential interface barrier from the surface measurement
analysis. We have performed the surface potential measure-
ment of PANI, Bi2S3, and PANI/Bi2S3 samples using KPFM.
The measurements have been carried out using a Pt/Ir coated
AFM tip in which the potential was measured at a lift height
of 100 nm. Figure 6 illustrates the surface height, potential
surface profile, and potential distribution of PANI, Bi2S3 NFs,
and PANI/Bi2S3 nanocomposite samples. From the surface
Nanotechnology 32 (2021) 335705
Figure 4. SEM image (a) PANI/Bi2S3 nanocomposite, corresponding elemental maps of (b) bismuth (Bi), (c) sulfur (S), (d) carbon (C), (e)
nitrogen (N) and (f) color overlay of bimusth (Bi), (c) sulfur (S) and carbon (C) elements and (g) EDX spectrum of the PANI/Bi2S3
nanocomposite.
Figure 5. FTIR spectra of PANI, Bi2S3 NFs, and PANI/Bi2S3
nanocomposite.
potential profile, using the NanoScope Analysis software, the
statistical distribution of the potential is extracted, and it is
found that for PANI, the maximum surface potential dis-
tribution is obtained at −200 mV and for Bi2S3 it is observed
6
S Sharma et al
at −137 mV. It is to note that the appearance of single peaks
of the potential distribution for PANI and Bi2S3 samples
confirmed that there exist no secondary phases in the nano-
materials. However, in the potential distribution graph of the
PANI/Bi2S3 nanocomposite, two different peaks appeared at
−170 and −220 mV, which confirms the presence of two
phases, one corresponding to Bi2S3 NFs and the other to
PANI, respectively. The difference in the potential barrier
between PANI and Bi2S3 NFs in the nanocomposite sample is
estimated as ∼50 mV only, which indicates that the charge
carriers can easily transport across the interface in the nano-
composite sample.
In order to investigate the effect of temperature on the
figure of merit (ZT) of Bi2S3 NFs and PANI/Bi2S3 nano-
composite various thermoelectric measurements have been
conducted in the temperature range of 313–353 K. Figure 7(a)
depicts the temperature dependent electrical conductivity of
the Bi2S3 NFs and PANI/Bi2S3 nanocomposite. The value of
the electrical conductivity for both Bi2S3 NFs and
PANI/Bi2S3 nanocomposite exhibits an increasing trend with
the increase of temperature which confirms the semi-
conducting nature of the as-prepared samples. After incor-
poration of PANI with Bi2S3 NFs, its electrical conductivity is
observed to increase from ∼13 to ∼21 S cm−1 at 353 K. This
Nanotechnology 32 (2021) 335705 S Sharma et al

Figure 6. Surface topography, surface potential, and potential distribution of (a)–(c) PANI, (d)–(f) Bi2S3 NFs, and (g)–(i) PANI/Bi2S3
nanocomposite.

Figure 7. Temperature dependent (a) electrical conductivity and (b) Seebeck coefficient of the Bi2S3 NFs and PANI/Bi2S3 nanocomposite.

7
Nanotechnology 32 (2021) 335705
Figure 8. Temperature dependent total thermal conductivity of the
Bi2S3 NFs, and PANI/Bi2S3 nanocomposite.
∼62% enhancement in the electrical conductivity of the Bi2S3
NFs after the addition of conducting PANI matrix is ascribed
to the formed conducting interfaces between PANI and Bi2S3
NFs, which facilitates easy passage for the conduction of the
charge carriers across Bi2S3 NFs, resulting in lowering the
energy barrier at the interface. Figure 7(b) illustrates the
temperature dependent Seebeck coefficient of the Bi2S3 NFs
and PANI/Bi2S3 nanocomposite. The Seebeck coefficient (S)
of semiconducting material can be expressed as per
the following Mott formula using a simple parabolic band
structure [2]:
8p 2k 2
⎛p⎞ ,
2/3
S= m*T (2 )
3eh2 ⎝ 3n ⎠
where k is the Boltzmann constant, m* is the effective mass of
the charge carrier, T is the temperature, e is the electronic
charge of the carrier, h is the Planck’s constant, and n is the
carrier concentration. Typically, the n and p-type conductivity
of semiconducting material is confirmed from the negative
and positive values of the Seebeck coefficient (S ), respec-
tively [2, 5]. It is noted that a negative value of the Seebeck
coefficient is observed for both Bi2S3 NFs and PANI/Bi2S3
samples in the entire temperature range signifying their n-type
semiconducting behavior having electrons as the majority
carriers. The Seebeck coefficient of both Bi2S3 NFs and
PANI/Bi2S3 samples is found to increase with increasing
temperature. The abrupt increase in the Seebeck coefficient
(S ) of Bi2S3 NFs at 353 K is due to the bipolar diffusion
effect. Such behavior for Bi2S3 material has been reported
earlier also [27]. However, the incorporation of PANI leads to
reduce the Seebeck coefficient of the nanocomposite system.
The value of S for PANI/Bi2S3 nanocomposite is −219
μV K−1 which is found to be lower as compared to the value
of S, −267 μV K−1 for pristine Bi2S3 NFs.
Figure 8 illustrates the variation of the thermal con-
ductivity with increasing temperature for Bi2S3 NFs and
PANI/Bi2S3 nanocomposite. It is observed that the value of
thermal conductivity for both Bi2S3 NFs and PANI/Bi2S3
samples increases with the increase of temperature. Typically,
8
S Sharma et al
the thermal conductivity reduces with increasing temperature
owing to strong phonon scattering caused by lattice thermal
vibrations, following a linear dependency between thermal
conductivity and reciprocal of temperature (T−1) [24, 31]. In
the present case the total thermal conductivity (k total ) deviates
from T−1 dependency and increases with increasing temper-
ature as shown in figure 8, which can be attributed to the
bipolar diffusion effect in Bi2S3 [27, 64–66]. Generally, the
bipolar effect occurs in narrow band gap materials under
which the electrons are thermally excited at a finite temper-
ature from the valence band to the conduction band leaving
holes behind, and both the charge carriers contribute to the
thermal conductivity [65]. In the literature, Ma et al also
demonstrated the behavior of gradual increment of thermal
conductivity with increasing temperature due to bipolar dif-
fusion in free-standing single crystal Bi2S3 nanowire [66].
However, after the addition of PANI, the value of the total
thermal conductivity of the Bi2S3 sample is reduced from
0.65 to 0.62 W mK−1 at 353 K in the nanocomposite system.
In general, the total thermal conductivity is a sum of
electronic thermal conductivity (κelectronic) which arises from
the contribution of charge carriers and lattice thermal con-
ductivity (κlattice) which originates from the contribution of
lattice vibrations [9, 40]:
k total = kelectronic + klattice. (3 )
The electronic thermal conductivity can be estimated
using the Weidmann–Franz law [9, 40]:
kelectronic = sTL, (4 )
where s is the electrical conductivity, T is the absolute
temperature, and L is the Lorentz number (2.44 ´ 10-8
WΩ K−2 at 323 K) in the degenerate limit [9, 40]. The lattice
thermal conductivity can be determined by substituting the
value of kelectronic in equation (3) using the following relation:
klattice = k total - kelectronic. (5 )
Figure 9(a) depicts the variation of electronic thermal
conductivity with the temperature for Bi2S3 NFs and
PANI/Bi2S3 nanocomposite. It is found that the electronic
thermal conductivity (kelectronic ) increases for both the samples
with the increasing temperature. Importantly, the 50% incre-
ment in the electronic thermal conductivity for PANI/Bi2S3
nanocomposite (1.77×10−2 W mK−1 at 353 K) than that of
Bi2S3 NFs (1.18×10−2 W mK−1 at 353 K) is attributed to
the comparatively much increased electrical conductivity in
the nanocomposite system. Figure 9(b) depicts the variation
of lattice thermal conductivity with the temperature for Bi2S3
NFs and PANI/Bi2S3 nanocomposite. The lattice thermal
conductivity (klattice ) of the PANI/Bi2S3 nanostructured
sample (0.60 W mK−1 at 353 K) is observed to be lower than
that of Bi2S3 NFs (0.64 W mK−1 at 353 K) owing to the
possibly increased phonon scattering at the interfaces. The
incorporation of conducting polymer with metal chalcogenide
facilitated conducting channels for the transportation of high
energy charge carriers across the interfaces at the interfacial
barrier. Besides, the hierarchical nanostructures of the ther-
moelectric material in the nanocomposite system are
Nanotechnology 32 (2021) 335705 S Sharma et al

Figure 9. Temperature dependent (a) electronic thermal conductivity (κelectronic) and (b) lattice thermal conductivity (κlattice) of the Bi2S3 NFs,
and PANI/Bi2S3 nanocomposite.

advantageous for the formation of many interfaces to effec-

tively enhance the phonon scattering. In a crystalline lattice (
i.e. free from cracks, impurities, and strains) the scattering
will be mainly caused by collisions between phonons via
Umklapp (U) processes in which the lattice will transfer
momentum between itself and the phonons owing to the
occurrence of interference effects between lattice and pho-
nons [66, 67]. As the temperature increases, the Umklapp
phonon–phonon scattering plays a dominating role in thermal
transport, due to the activation of high frequency phonons.
Thus, as compared to the pristine Bi2S3, the phonon scattering
becomes stronger at comparatively larger available interfacial
sites in the nanocomposite, which would hinder the thermal
transport causing the reduction in the thermal conductivity.
It is to note that the lattice part (klattice ) in the total
thermal conductivity dominates over the electronic part
(kelectronic ). Therefore, for PANI/Bi2S3 nanocomposite a Figure 10. Temperature dependent figure of merit (ZT) of the Bi2S3
NFs, and PANI/Bi2S3 nanocomposite.
decrement in the total thermal conductivity is observed in
comparison to Bi2S3 which is attributed to the dominant lat-
tice thermal contribution (klattice ) in the nanocomposite system 4. Conclusions
as a result of strong phonon scattering at the PANI/Bi2S3
interfaces. Herein, we have synthesized 3D hierarchical Bi2S3 NFs and
Figure 10 shows the variation of the figure of merit (ZT) PANI/Bi2S3 nanocomposite by low-cost hydrothermal and
with increasing temperature for Bi2S3 NFs and PANI/Bi2S3 facile chemisorption technique, respectively for the demon-
nanocomposite. From combining the deduced electronic stration of enhanced thermoelectric performance. The
transport and total thermal conductivity, ZT is represented as a PANI/Bi2S3 nanocomposite exhibited higher electrical con-
function of temperature. The value of ZT for PANI/Bi2S3 ductivity and lower thermal conductivity which accounts for
nanocomposite (0.06 at 353 K) is observed to increase in the enhancement in the value of figure of merit (ZT) in
comparison to Bi2S3 NFs (0.05 at 353 K). The incorporation comparison to Bi2S3 NFs. After incorporation with the PANI
of the PANI matrix with the Bi2S3 provides a conducting path matrix, the enhancement in the electrical conductivity of the
for the easy transport of the electrons and reduces the barrier PANI/Bi2S3 nanocomposite is ascribed to the formed con-
height at the interface. Therefore, ∼20% enhancement in the ducting interfaces between PANI and hierarchical Bi2S3 NFs,
ZT value of the PANI/Bi2S3 nanocomposite is ascribed to the which facilitates easy passage for the conduction of electrons,
increment in the electrical conductivity and decrement in the thereby lowering the energy barrier at the interface. More-
total thermal conductivity. The observed ZT value for the over, the reduction in the thermal conductivity is attributed to
PANI/Bi2S3 nanocomposite is found to be higher in com- the contribution of the dominant lattice thermal conductivity
parison to previously reported ZT value of 5.73×10−5 for owing to strong phonon scattering at the interfaces. The
PANI/Ag [34], 4.3×10−3 for PANI/Bi2Te3 [38], present study opens up an efficient and cost-effective para-
8.6×10−4 for PANI/Bi0.5Sb1.5Te3 [39], 2.0×10−4 for digm towards the utilization of other conducting polymer-
PANI/SWNT [40], 2.0×10−3 for PANI/Ag2Te [41], and based hybrid systems for low-grade energy conversion device
10−6 for PANI/RGO [42] nanocomposites. applications in the future.

9
Nanotechnology 32 (2021) 335705
Acknowledgments
The authors are grateful to the Department of Science and
Technology, DST (NNeTRA project with project no.
MI01756), and the Ministry of Electronics and Information
Technology, MeiTy (project no. RP03530) for the financial
assistance. We are thankful to NRF and CRF, IIT Delhi, India
for providing the characterization facilities. The authors are
also thankful to A Kaushal, CRF IIT Delhi for performing the
TEM and HRTEM measurements. Surbhi Sharma (SS)
acknowledges IRD, IIT Delhi, India for the award of the Early
Doc Fellowship.
Data availability statement
All data that support the findings of this study are included
within the article (and any supplementary files).
Conflict of interest
The authors declare no conflict of interest.
ORCID iDs
Neeraj Khare https://orcid.org/0000-0003-3702-2257
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