polymers
Article
Conductive PEDOT:PSS-Based Organic/Inorganic Flexible
Thermoelectric Films and Power Generators
Dabin Park, Minsu Kim and Jooheon Kim *






Citation: Park, D.; Kim, M.; Kim, J.
Conductive PEDOT:PSS-Based
Organic/Inorganic Flexible
Thermoelectric Films and Power
Generators. Polymers 2021, 13, 210.
https://doi.org/10.3390/polym
13020210
Received: 3 January 2021
Accepted: 6 January 2021
Published: 8 January 2021
Publisher’s Note: MDPI stays neu-
tral with regard to jurisdictional clai-
ms in published maps and institutio-
nal affiliations.
Copyright: © 2021 by the authors. Li-
censee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and con-
ditions of the Creative Commons At-
tribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Polymers 2021, 13, 210. https://doi.org/10.3390/polym13020210
School of Chemical Engineering & Materials Science, Chung-Ang University, Seoul 06974, Korea;
dragoo@naver.com (D.P.); alstn275@gmail.com (M.K.)
* Correspondence: jooheonkim@cau.ac.kr; Tel.: +82-2-820-5763; Fax: +82-2-812-3495
Abstract: We present a simple thermoelectric device that consists of a conductive poly(3,4-ethylene-
dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-based inorganic/organic thermoelectric film
with high thermoelectric performance. The PEDOT:PSS-coated Se NWs were first chemically syn-
thesized in situ, and then mixed with an Ag precursor solution to produce the PEDOT:PSS-coated
Ag2 Se NWs. The PEDOT:PSS matrix was then treated with dimethyl sulfoxide (DMSO) prior to
the production of flexible PEDOT:PSS-coated Ag2 Se NW/PEDOT:PSS composite films with various
weight fractions of Ag2 Se via a simple drop-casting method. The thermoelectric properties (Seebeck
coefficient, electrical conductivity, and power factor) of the composite films were then analyzed.
The composite film with 50 wt.% NWs exhibited the highest power factor of 327.15 µW/m·K2 at
room temperature. The excellent flexibility of this composite film was verified by bending tests,
in which the thermoelectric properties were reduced by only ~5.9% after 1000 bending cycles. Finally,
a simple thermoelectric device consisting of five strips of the proposed composite film was con-
structed and was shown to generate a voltage of 7.6 mV when the temperature difference was 20 K.
Thus, the present study demonstrates that that the combination of a chalcogenide and a conductive
composite film can produce a high-performance flexible thermoelectric composite film.
Keywords: thermoelectric; silver selenide; nanowire; poly(3,4-ethylenedioxythiopene)-poly(4-styre-
nesulfonate)
1. Introduction
Due to continuing global concerns about environmental pollution and the sustainabil-
ity of energy generation, the identification and exploitation of new clean energy resources
is vital. In this respect, thermoelectric (TE) devices have demonstrated significant potential
for use in energy harvesting based on their conversion of thermal energy to electrical en-
ergy via the movement of charge carriers and internal phonons [1–6]. In the development
of these devices, the TE performance of a prospective material is calculated using the
dimensionless figure of merit (ZT), given by the formula in Equation (1):
ZT = S2 · σ · T/κ (1)
where S, σ, T, and κ are the Seebeck coefficient, electrical conductivity, absolute temperature,
and thermal conductivity of the materials, respectively. A high figure of merit can be
achieved by producing a high power factor (PF = S2 · σ) and a low thermal conductivity.
The recent research on high-performance TE devices has focused primarily on inorganic
materials such as oxides (e.g., NaCo2 O4 , SrTiO3 , and CaMnO3 ) [7–10], in particular bulk
materials (e.g., lead antimony silver telluride) [11,12], and Te-based semiconductors (e.g.,
Bi2 Te3 , Sb2 Te3 , and PbTe) [13–19]. However, conductive polymers such as polypyrrole
(PPy) [20,21], polythiophene (PTh) [22,23], and polyaniline (PANI) [24,25] have been used
as alternatives to the aforementioned inorganic TE materials due to their environmentally
friendly nature, ease of processing, and low raw material costs. In addition, because
https://www.mdpi.com/journal/polymers
Polymers 2021, 13, 210 2 of 12

polymers have high flexibility, high electrical conductivity, and low thermal conductivity,
they have been explored for use in the fabrication of flexible TE devices. For instance,
Wang et al. [26] fabricated PPy/graphene/PANI ternary nanocomposites and achieved an
outstanding power factor of ~52.5 µW/m·K2 , which is much larger than that of the pristine
PPy and PANI. Other researchers have prepared single-walled carbon nanotube (SWCNT)-
poly(aniline-co-pyrrole) copolymers with advantageous TE properties using traditional
oxidative polymerization without mechanical agitation [27]. In particular, the conductive
polymer poly(3,4-ethylenedioxythiopene):poly(4-styrenesulfonate) (PEDOT:PSS) has been
extensively studied and has been shown to exhibit an outstanding electrical conductivity
after doping or adjustment of its oxidation levels. For example, Luo et al. [28] studied the
dimethyl sulfoxide (DMSO) post-treatment of a PEDOT:PSS thin film and reported a high
electrical conductivity of ~930 S/cm. Similarly, Kim et al. achieved an improvement in
electrical conductivity (~620 S/cm) and a high power factor (~33 µW/m·K2 ) by treating
PEDOT:PSS with DMSO. However, conductive PEDOT:PSS has a lower power factor
than that of inorganic TE materials due to its low Seebeck coefficient. This is because
the improved technology mentioned above generally reduces the Seebeck coefficient by
moving the Fermi level to the edge of the conductor [29]. For this reason, numerous
studies have been conducted to improve the TE properties of polymer-based materials
by introducing inorganic TE materials with a high Seebeck coefficient (e.g., Bi2 Te3 , SnSe,
and Cu2 SnSe3 ) [30–32]. For instance, Ge et al. [32] produced a Cu2 SnSe3 /PEDOT:PSS
composite via spark plasma sintering to improve the TE properties. In addition, Zhang
et al. [33] added Bi2 Te3 to the PEDOT:PSS matrix to enhance the Seebeck coefficient and
obtain a much larger power factor than that of the pure conductive polymers.
Silver selenide (Ag2 Se) is a narrow bandgap N-type semiconductor material that has
low thermal conductivity and high electrical conductivity at room temperature. Ag2 Se has
two phases, α-and β-Ag2 Se, with β-Ag2 Se acting as a cubic superionic conductor at ~408 K.
Several studies have reported the outstanding TE properties of Ag2 Se [34]. For example,
Perez-Taborda et al. [35] used pulsed hybrid reactive magnetron sputtering to prepare
an N-type Ag2 Se film that exhibited a high figure of merit (i.e., 1.2) at room temperature.
However, although Ag2 Se has been proven to have advantageous TE properties at room
temperature, pristine Ag2 Se has not yet been widely used in the development of flexible
TE devices.
Recently, our group developed a facile method for preparing an Ag2 Se-based flexible
film with a PEDOT:PSS matrix [36]. The composite film was shown to exhibit an enhanced
power factor of 178.59 µW/m·K2 at room temperature. However, this value remained
much lower than that of the bulk Ag2 Se. This relatively low power factor is related to the
density of the previously-reported composite film, which is only ~70% of the theoretical
density due to the presence of voids between the polymer matrix and inorganic fillers.
In the present study, a polymer-coated NW type filler was first synthesized in order
to improve the power factor of the composite film. The change in the morphology of the
filler was shown to result in a compact film (~85% relative density) after drop casting.
The PEDOT:PSS-coated Ag2 Se NWs were fabricated by first coating Se nanoparticles with
the PEDOT:PSS and then allowing these to grow to produce PEDOT:PSS coated Se NWs.
The NWs were then reacted with the Ag precursor to form the PEDOT:PSS-coated Ag2 Se
NWs. The proposed inorganic/organic composite film was then generated by drop-casting
and the PEDOT:PSS-coated Ag2 Se NW/PEDOT:PSS composite film with 50 wt.% Ag2 Se
was shown to exhibit a maximum power factor of 327.15 µW/m·K2 at room temperature.
In addition, a simple thermoelectric generator was manufactured using the synthe-
sized composite film and was shown to provide an output voltage of 7.6 mV when the
temperature difference was 20 K. These results demonstrate the potential of the composite
material for application in flexible electronic devices.
Polymers 2021, 13, 210 3 of 12

2. Materials and Methods

2.1. Materials
Selenium(IV) oxide (SeO2 , 99%), β-cyclodextrin (C42 H70 O35 , 98%), ethylene glycol
(EG, C2 H6 O2 , 99.5%), silver(I) nitrate (AgNO3 , 99%), and L(+)-ascorbic acid (C6 H8 O6 , 99%)
were purchased from Daejung Chemical & Materials Co. (Seoul, Korea). The PEDOT:PSS
(Clevious PH 1000) was purchased from Heraeus Clevios GmbH (Leverkusen, Germany).
The dimethyl sulfoxide (DMSO; (CH3 )2 SO, 99%), and ethanol (C2 H5 OH, 98%) were pur-
chased from Sigma Aldrich (St. Louis, USA). All materials were used without further
purification.

2.2. Synthesis of PEDOT:PSS-Coated Ag2 Se NWs

Solution I was produced by adding SeO2 (0.5 g), β-cyclodextrin (5 g), and PEDOT:PSS
(2 mL) were to deionized (DI) water (100 mL) in a round-bottomed flask under stirring.
Solution II was produced by adding ascorbic acid (2.5 g) to DI water (100 mL) in another
beaker. After each solution was completely dissolved, solution II was poured into solution
I and the reaction maintained for 4 h. The composite was then centrifuged and washed
separately with DI water and ethanol. The synthesized product was stored in ethanol
(100 mL). Subsequently, ammonium hydroxide (10 µL) was added to the solution, which
was then left to stand for 48 h at room temperature, allowing time for a flocculant precipitate
of PEDOT:PSS-coated Se NWs to form. The precipitate was collected using centrifugation
and redispersed in ethylene glycol (200 mL).
An Ag precursor solution was produced with a certain amount of AgNO3 and ascorbic
acid in DI water (5 mL). The molar ratio of the ascorbic acid and AgNO3 was 1:3. This Ag
precursor solution was then poured into the as-prepared Se NW solution. After vigorous
stirring for 4 h at room temperature to allow complete reaction, the product was centrifuged
and washed with DI water and ethanol several times. Finally, the synthesized PEDOT:PSS-
coated Ag2 Se NWs were dried in a vacuum oven at 333 K for 24 h.

2.3. Fabrication of the PEDOT:PSS-Coated Ag2 Se NW/PEDOT:PSS Composite Film

First, an appropriate amount of DMSO was mixed with the PEDOT:PSS solution and
sonicated for 1 h to form a 5 vol.% DMSO/PEDOT:PSS mixture. After that, various amount
of PEDOT:PSS-coated Ag2 Se NWs (10 wt.%, 20 wt.%, 30 wt.%, 50 wt.% and 70 wt.%) were
dispersed in the DMSO-treated PEDOT:PSS solution, and the mixtures were ultrasonicated
for 3 h. The final solutions were drop-cast onto a glass substrate to produce the composite
film and then dried in a vacuum oven at 333 K for 24 h.

2.4. Device Preparation

The synthesized composite film was cut into strips (18 mm × 6 mm). The 8 strips
were then pasted onto a polyimide film at intervals of ~5 mm. The strips were then
connected with copper wire, and an Ag adhesive was applied to connect the legs in series.
An automatic temperature control system was used to vary the temperature at the ends
of the device. The temperature at the two ends was measured using thermocouples.
A multimeter (SENIT, A830L) was used to measure the output current and voltage.

2.5. Characterization
Field-emission transmission microscopy (FE-TEM, JEM-2100F, ZEISS, Oberkochen,
Germany) and field-emission scanning electron microscopy (FE-SEM, SIGMA) were used
to determine the microstructure and morphology of the composites. In addition, X-ray
spectroscopy (EDS, NORAN system 7, Thermo Scientific, Seoul, Korea) was employed to
determine the elemental mapping of the samples. The crystal structure of the material was
characterized via X-ray diffraction (XRD, New D8-Advance/Bruker-AXS, Massachysetts,
USA) at 40 kV and 40 mA with a scan rate of 1◦ /s and a 2θ range of 5◦ to 70◦ under Cu
Kα radiation (0.154056 nm). The binding energy of the materials was investigated using
X-ray photoelectron spectroscopy (XPS, Thermo, U.K. alpha) with a monochromatic Al Kα
Polymers 2021, 13, 210 4 of 12
Polymers 2021, 13, x FOR PEER REVIEW 4 of 12

X-ray source (1486.6

ray photoelectron eV). Thermogravimetric
spectroscopy (XPS, Thermo,analysis (TGA,
U.K. alpha) TGA-2050,
with TA Instruments,
a monochromatic Al Kα
X-ray source (1486.6 eV). Thermogravimetric analysis (TGA, TGA-2050, TAthe
New Castle, USA) was used to investigate the thermal degradation of sample in
Instruments,
an N2Castle,
New atmosphere at aused
USA) was heating rate of 10 the
to investigate K/min. A degradation
thermal homemade device consisting
of the sample in anofNa2
pair of voltmeters and thermocouples was used to measure the Seebeck coefficient
atmosphere at a heating rate of 10 K/min. A homemade device consisting of a pair of volt- (S),
which was determined based on the linear relationship between the thermal electromotive
meters and thermocouples was used to measure the Seebeck coefficient (S), which was
force (∆V) and the temperature difference (∆T) of the composite (S = ∆V/∆T). A four-
determined based on the linear relationship between the thermal electromotive force (ΔV)
point probe method was used to measure the electrical conductivity (σ) of the composite,
and the temperature difference (ΔT) of the composite (S = ΔV/ΔT). A four-point probe
and a digital micrometer was used to measure its thickness. The charge carrier mobility
method was used to measure the electrical conductivity (σ) of the composite, and a digital
(µ) and concentration (n) were investigated using Van der Pauw technique-based Hall-
micrometer was used to measure its thickness. The charge carrier mobility (μ) and con-
effect measurements (HMS-3000, Ecopia, AZ, USA). The density of the prepared film was
centration (n) were investigated using Van der Pauw technique-based Hall-effect meas-
determined by measuring the mass and geometrical dimensions of the film. Five replicates
urements (HMS-3000, Ecopia, AZ, USA). The density of the prepared film was determined
of the composite samples were used for each test to verify the reproducibility of the
by measuring the mass and geometrical dimensions of the film. Five replicates of the com-
experiments.
posite samples were used for each test to verify the reproducibility of the experiments.
3. Results and Discussion
3. Results and Discussion
The process for the synthesis of the proposed PEDOT:PSS-Ag2 Se NW composite film
The process
is shown for the synthesis
schematically in Figureof 1.the
The proposed PEDOT:PSS-Ag
fabrication of the Se NWs 2Se NW composite film
followed the same
is shownasschematically
process that described in Figure 1. Thestudies
in previous fabrication
[37].ofTo
theproduce
Se NWs thefollowed the same pro-
PEDOT:PSS-Ag 2 Se
cess
NWs,asfirst
thatSeO
described
2 , in previous
PEDOT:PSS, and studies [37].
β-cyclodextrin To produce
were the
dispersed PEDOT:PSS-Ag
in (deionized) Se
2DI NWs,
water.
first resulting
The SeO2, PEDOT:PSS,
solution was andthen
β-cyclodextrin
slowly poured were
intodispersed in (deionized)
an L-ascorbic acid solutionDI water.
and mixedThe
resulting solution was then slowly poured into an L-ascorbic acid solution
for four hours to synthesize PEDOT:PSS-coated Se nanoparticles (NPs). The reaction at thisand mixed for
four hours to synthesize PEDOT:PSS-coated
stage can be described by Equation (2): Se nanoparticles (NPs). The reaction at this
stage can be described by Equation (2):
SeO2 + 2C6 H8 O6 → Se + 2C6 H6 O6 + 2H2 O (2)
SeO2 + 2C6H8O6 → Se + 2C6H6O6 + 2H2O (2)

Figure 1. Schematic diagrams showing the preparation of the PEDOT:PSS-coated Ag2 Se NWs.
Figure 1. Schematic diagrams showing the preparation of the PEDOT:PSS-coated Ag2Se NWs.
To confirm the successful synthesis and surface morphology of the PEDOT:PSS-coated
Se NWs, XRD, FE-SEM
To confirm and FE-TEM
the successful wereand
synthesis conducted and the results
surface morphology are presented
of the PEDOT:PSS- in
Figure S1. Thus, all of the XRD peaks for Se (Figure S1a) can be indexed as
coated Se NWs, XRD, FE-SEM and FE-TEM were conducted and the results are presented orthorhombic
SeFigure
in (JCPDS S1.no. 86-2246),
Thus, while
all of the XRDthe FE-SEM
peaks for Seimage (Figure
(Figure S1b)
S1a) can be confirms
indexed asthe presence of
orthorhombic
wire-like
Se (JCPDSSe,no.and the high-magnification
86-2246), while the FE-SEM FE-TEM
image image
(Figure(Figure S1c) clearly
S1b) confirms reveals the
the presence of
coating layer.
wire-like Se, and the high-magnification FE-TEM image (Figure S1c) clearly reveals the
coating layer.
 Polymers 2021, 13, 210 5 of 12
rs 2021, 13, x FOR PEER REVIEW 5 of 12

The resulting product was stored in ethanol with ammonium hydroxide to allow
The resulting productofwas
the growth NWsstored
within ethanol withorientation
a preferential ammonium ofhydroxide
(100). Thistosolution-based
allow the template-
growth of NWs with a preferential orientation of (100). This solution-based template-ori-
oriented fabrication approach is a simple strategy for 1D Se generation. At this stage,
ented fabrication approach is a simple
the PEDOT:PSS-coated Sestrategy
NPs were fortransformed
1D Se generation.
into NWs.At this
The stage, the PEDOT:PSS-
fabricated
PEDOT:PSS-coated Se NPs were transformed into NWs. The fabricated PEDOT:PSS-
coated Se NWs and Ag precursor solution were then poured into ethylene glycol (EG)
coated Se NWs toand Ag precursor
produce solution
Ag2 Se NWs. were
The then poured
reaction processinto
for ethylene glycol (EG)
the fabrication of Agto2 Se NWs is as
produce Ag2Sesummarized
NWs. The reaction process for the
by Equations (3) and (4): fabrication of Ag 2Se NWs is as summa-

rized by Equations (3) and (4):

2Ag+ + C6 H8 O6 → 2Ag + C+6 H6 O6 + 2H+ (3)
2Ag+ + C6H8O6 → 2Ag + C6H6O6 + 2H (3)
2Ag + Se → 2Ag + Se → Ag2 Se
Ag2Se (4) (4)
Here, Ag +is reduced byand
ascorbic acid and the newly formed
Here, Ag+ is reduced by ascorbic acid the newly formed Ag reacts withAgthereacts
Se to with the Se to
produce
produce the Ag2Se NWs. the Ag 2 Se NWs.
The successfulThe successful
synthesis of thesynthesis of the PEDOT:PSS-coated
PEDOT:PSS-coated Ag2Se NWs was Agdemonstrated
2 Se NWs was demonstrated
by by
XPS. The wide-range XPS spectrum is presented in Figure
XPS. The wide-range XPS spectrum is presented in Figure S2a, and the high-resolution S2a, and the high-resolution
core-level
core-level signals of S 2p,signals
Ag 3dofand S 2p,
Se Ag 3d and
3d are Se 3d are
presented presented
in Figure S2b–d,in Figure S2b–d, respectively.
respectively.
Here, the Ag 3dHere, the Ag 3d binding
5/2 and Ag 3d3/25/2
and Ag 3d3/2 binding
energies energies
are observed are observed
at ~367.9 and 374.1 at eV,
~367.9
re- and 374.1 eV,
spectively, and the peaks for Se 3d5/2 and Se 3d3/2 are visible at ~53.6 and 54.3 eV, respec- and 54.3 eV,
respectively, and the peaks for Se 3d 5/2 and Se 3d 3/2 are visible at ~53.6
respectively.
tively. These results These
are in good results are
agreement in good
with agreement
the previously with the
reported datapreviously reported data for
for the bind-
the binding energies of Ag and Se in nanostructured Ag
ing energies of Ag and Se in nanostructured Ag2Se [38]. For the PEDOT:PSS, the binding 2 Se [38]. For the PEDOT:PSS,
energies of 166-168 eV in the S 2p peaks are attributed to the PSS unit, while the PEDOTunit, while the
the binding energies of 166-168 eV in the S 2p peaks are attributed to the PSS
PEDOT
units are indicated units
by the are indicated
binding energiesbyofthe binding
163–166 eV.energies of 163–166
The observed bindingeV. energies
The observed binding
energies agree with the previously reported values for S 2p, thus confirming the presence
agree with the previously reported values for S 2p, thus confirming the presence of PE-
of PEDOT:PSS.
DOT:PSS.
The crystalline phases of the synthesized Ag Se NWs, PEDOT:PSS-coated Ag2 Se NWs,
The crystalline phases of the synthesized Ag2Se NWs, 2PEDOT:PSS-coated Ag2Se
and pristine PEDOT:PSS were determined via XRD analysis, as shown in Figure 2a. Here,
NWs, and pristine PEDOT:PSS were determined via XRD analysis, as shown in Figure 2a.
the XRD patterns of the Ag2 Se NWs and PEDOT:PSS-coated Ag2 Se NWs can be attributed
Here, the XRD patterns of the Ag2Se NWs and PEDOT:PSS-coated Ag2Se NWs can be at-
to the orthorhombic crystalline phase of Ag2 Se (JCPDS no. 24-1411), thus verifying the
tributed to the orthorhombic crystalline phase of Ag2Se (JCPDS no. 24-1411), thus verify-
formation of well-defined Ag Se (a = 0.705 nm, b = 0.782 nm, and c = 0.434 nm) [39].
ing the formation of well-defined Ag2Se (a =20.705 nm, b = 0.782 nm, and c = 0.434 nm) [39].

Figure 2. The characterization

Figure of the PEDOT:PSS-coated
2. The characterization Ag2Se NWs and
of the PEDOT:PSS-coated theirNWs
Ag2Se synthetic intermediates:
and their (a) the XRD patterns;
synthetic interme-
(b) the TGA diates:
results.(a) the XRD patterns; (b) the TGA results.

Due weakness
Due to the relative to the relative
of theweakness
PEDOT:PSSof the PEDOT:PSS
diffraction peaks,diffraction
these werepeaks,
not ob-these were not
observed in XRD the pattern of the PEDOT:PSS-coated Ag2 Se NWs. However, the presence of
served in XRD the pattern of the PEDOT:PSS-coated Ag2Se NWs. However, the presence
PEDOT:PSS in the composite material was confirmed via TGA, as shown in Figure 2b. Here,
of PEDOT:PSS in the composite material was confirmed via TGA, as shown in Figure 2b.
the pure Ag2 Se NWs is seen to exhibit an outstanding thermal stability in an N2 atmosphere
Here, the pure Ag2Se NWs is seen to exhibit an outstanding thermal stability in an N2
atmosphere of up to ~1000 K, whereas the PEDOT:PSS suffers extensive thermal degrada-
tion at ~500 K, with a weight ratio of ~10 wt.%.
Polymers 2021, 13, 210 6 of 12

Polymers 2021, 13, x FOR PEER REVIEW 6 of 12

of up to ~1000 K, whereas the PEDOT:PSS suffers extensive thermal degradation at ~500 K,

with a weight ratio of ~10 wt.%.
The successful
successfulcoating
coatingofofPEDOT:PSS
PEDOT:PSSononthe AgAg
the 2 Se NWs
2Se NWs was
wasfurther demonstrated
further demonstratedvia
FE-SEM and FE-TEM imaging, as shown in Figure 3. The wire-like structure
via FE-SEM and FE-TEM imaging, as shown in Figure 3. The wire-like structure of the of the PEDOT:PSS-
coated Ag2 Se NWs is
PEDOT:PSS-coated clearly
Ag 2Se NWs visible in the visible
is clearly FE-SEM inimage in Figure
the FE-SEM 3a, while
image the coating
in Figure 3a, whileis
confirmed
the coatingbyis the low- andby
confirmed high-magnification FE-TEM images in
the low- and high-magnification Figure images
FE-TEM 3b,c. In in
addition,
Figure
the FE-TEM
3b,c. imagesthe
In addition, of FE-TEM
the pristine Ag2 SeofNWs
images providedAg
the pristine in2Figure
Se NWs S3provided
reveal their
in crystalline
Figure S3
structure and
reveal their the two indexed
crystalline structurelattice planes
and the at (200) and
two indexed (002)
lattice withatinterplanar
planes spacings
(200) and (002) with
of 0.35 nm and 0.25 nm, respectively [40]. Furthermore, uniform distributions
interplanar spacings of 0.35 nm and 0.25 nm, respectively [40]. Furthermore, uniform dis- of Ag, Se,
and S atoms are observed in the FE-SEM images and the corresponding
tributions of Ag, Se, and S atoms are observed in the FE-SEM images and the correspond- EDS maps of the
PEDOT:PSS-coated
ing EDS maps of theAg 2 Se NWs in FigureAg
PEDOT:PSS-coated S4.2Se NWs in Figure S4.

Figure 3.
Figure Imaging of
3. Imaging of the
the PEDOT:PSS-coated
PEDOT:PSS-coated Ag high-magnification FE-TEM.
Ag22Se NWs: (a) FE-SEM; (b,c) low- and high-magnification FE-TEM.

The temperature-dependent
The temperature-dependent thermoelectric
thermoelectric properties
properties (Seebeck
(Seebeck coefficient,
coefficient, electrical
electrical
conductivity, and
conductivity, and power
power factor)
factor) of
of the
the PEDOT:PSS-coated
PEDOT:PSS-coated Ag Se NWs
Ag22Se NWs areare indicated
indicated inin
Figure 4. Here, the Seebeck coefficient is seen to decrease moderately with
Figure 4. Here, the Seebeck coefficient is seen to decrease moderately with increasing tem- increasing
temperature
perature in Figure
in Figure 4a, 4a, while
while in in Figure
Figure 4b4bwewesee
seethat
thatthe
theelectrical
electricalconductivity
conductivity initially
initially
increases with increasing temperature up to ~400 K, and subsequently
increases with increasing temperature up to ~400 K, and subsequently decreases. The decreases. The latter
lat-
result is similar to the previously reported behavior of Ag Se-based semiconducting
ter result is similar to the previously reported behavior of2 Ag2Se-based semiconducting ma-
terials [40].[40].
materials These trends
These trendsin the
in Seebeck coefficient
the Seebeck and and
coefficient electrical conductivity
electrical reveal
conductivity that
reveal
the PEDOT:PSS-coated
that the PEDOT:PSS-coated Ag2 Se Ag
NWs exhibits a maximum power factor of 434.13 µW/m·K2
2Se NWs exhibits a maximum power factor of 434.13
at 400 K.2 at 400 K.
μW/m·K

Figure 4. The
Figure Thetemperature-dependent
temperature-dependent thermoelectric properties
thermoelectric of the
properties PEDOT:PSS-coated
of the Ag2Se
PEDOT:PSS-coated AgNWs: (a) Seebeck
2 Se NWs: coeffi-
(a) Seebeck
cient, (b) electrical
coefficient, conductivity,
(b) electrical (c) power
conductivity, factor.
(c) power factor.

The temperature-dependence of the Seebeck coefficient (S) and the electrical conduc-
tivity (σ) within the composite can be understood by analyzing the Hall measurement
results in Figure S5 due to the relationships in Equations (5) and (6):
σ=n·e·μ (5)
Polymers 2021, 13, 210 7 of 12

Polymers 2021, 13, x FOR PEER REVIEW The temperature-dependence of the Seebeck coefficient (S) and the electrical conduc-
7 of 12
tivity (σ) within the composite can be understood by analyzing the Hall measurement
Polymers 2021, 13, x FOR PEER REVIEW 7 of 12
results in Figure S5 due to the relationships in Equations (5) and (6):

8 ∙ σ ∙= n · e · µ∗ (5)
S 8∙ ∙ ∙ ∙ ∙ (6)
S 3∙ 2∙ 2 ∙ ∗
∙ ∙ 3 2 ∙ (6)
3 ∙ ·∙k B ·m∗ · T · π 33 ∙
8· π  
S =
where n, e, μ, kB, h, and m* are the3·ecarrier concentration, electron charge, carrier (6)
· h2 3· n
where
mobility,n, e, μ, k B, h, and m* are the carrier concentration, electron charge, carrier
where n, e,Boltzmann
µ, kB , h, andconstant, Planck
m* are the constant,
carrier and effective
concentration, masscharge,
electron of the carrier,
carrierrespec-
mobil-
mobility,
tively. TheBoltzmann constant,
Ag2Se undergoes Planck
a phase constant,
transition andthe
from effective mass of the
semiconducting carrier, respec-
orthorhombic to
ity, Boltzmann constant, Planck constant, and effective mass of the carrier, respectively.
the Se undergoes
tively. The Ag2cubic a phase
408 Ktransition
Thefrom the changes
semiconducting TEorthorhombic to
Thesuperionic
Ag2 Se undergoes phase near
a phase [41].from
transition sudden
the semiconducting in the properties
orthorhombic to and
the
the superionic
Hall measurementcubicresults
phasebetween
near 408 K [41]. The sudden changes in the TE properties and
superionic cubic phase near 408 K 390 [41].and
The 420 K are due
sudden to this
changes in phase
the TEtransition.
propertiesThus,
and
Hall
the measurement results between 390 and 420 K are due to this phase transition. Thus,
Hallcarrier mobilityresults
measurement initiallybetween
increases390asand
the 420
temperature
K are dueistoincreased
this phase from 300 to 360
transition. K,
Thus,
the carrier
and mobility
subsequently initially (first
decreases increases as theand
gradually temperature
then more is increased
rapidly) from
as the 300transition
phase to 360 K,
the carrier mobility initially increases as the temperature is increased from 300 to 360 K,
and subsequently
temperature decreases (first gradually and then more rapidly) as the phase transition
is approached.
and subsequently decreases (first gradually and then more rapidly) as the phase transition
temperature
As shownis approached.
schematically in Figure 5, the PEDOT:PSS-coated Ag2Se NWs were subse-
temperature is approached.
As shown
quently added schematically
to a solution of in PEDOT:PSS
Figure 5, the PEDOT:PSS-coated Ag2Se NWs were subse-
As shown schematically in Figure 5, thein 5 vol.% DMSO, followed
PEDOT:PSS-coated Ag2 Se NWsby drop-casting
were subse-
quently
and added
drying
quently to a
to produce
added solution of PEDOT:PSS
the composite
to a solution of PEDOT:PSS in 5 vol.% DMSO, followed by drop-casting
film.in 5 vol.% DMSO, followed by drop-casting and
and drying
drying to produce
to produce the composite
the composite film.film.

Figure 5. A
Aschematic
schematic diagram
diagram of
of the
the preparation
preparation process for the PEDOT:PSS-coated Ag22Se NW/PEDOT:PSS composite films.
PEDOT:PSS-coated Ag
Figure 5. A schematic diagram of the preparation process for the PEDOT:PSS-coated Ag2Se NW/PEDOT:PSS composite films.
characteristicsof
The characteristics ofthe
theresulting
resultingPEDOT:PSS-coated
PEDOT:PSS-coatedAg Ag2Se2 Se NW/PEDOT:PSS
NW/PEDOT:PSS com-
compo-
posite
site The
film characteristics
film
are are
shownshown ofFigure
in
in Figurethe6.resulting
Here, thePEDOT:PSS-coated
6. Here, theisfilm
film seenistoseen Agbe
to
be black 2Se NW/PEDOT:PSS
inblack
color in color
and and
square incompo-
square
shape,
siteshape,
in
with film are
a length shown
with of a~18 inmm
Figure
length 6. Here,
of ~18
(inset, mmthe
Figure film
(inset,
6a), andis highly
seen to
Figure be and
6a), blackhighly
flexible in color
(main and square
flexible
image, (main
Figure in shape,
image,
6a), thus
with a length of ~18 mm (inset, Figure 6a), and highly flexible (main image,
indicating its suitability for use in flexible TE modules. Further, the cross-sectionalcross-
Figure 6a), thus indicating its suitability for use in flexible TE modules. Figure
Further, 6a),
the thus
and
indicating
sectional andits suitability
surface for
FE-SEM use in
image flexible
in TE
Figure modules.
6b,c revealFurther,
the the
uniform
surface FE-SEM image in Figure 6b,c reveal the uniform distribution of the PEDOT:PSS- cross-sectional
distribution of and
the
surfaceAg
coated FE-SEM
PEDOT:PSS-coated
2Se NWs imageAg2in
Se Figure
within NWs
the 6b,c reveal
within
PEDOT:PSS the uniform
the matrix.
PEDOT:PSS distribution of the PEDOT:PSS-
matrix.
coated Ag2Se NWs within the PEDOT:PSS matrix.

Figure 6. Imaging
Figure 6. Imaging of
of the
the PEDOT:PSS-coated
PEDOT:PSS-coated Ag
Ag22Se
Se NW/PEDOT:PSS composite films:
NW/PEDOT:PSS composite films: (a)
(a) digital
digital photograph
photograph showing
showing the
the
Figure 6. property;
bendable Imaging of the
(b,c) PEDOT:PSS-coated
FE-SEM images.
property; (b,c) FE-SEM images. Ag 2 Se NW/PEDOT:PSS composite films: (a) digital photograph showing the
bendable property; (b,c) FE-SEM images.
To investigate the potential of the composite film for use in TE devices, the TE prop-
ertiesTo
of investigate the potential
films containing variousof the composite
weight fractions film for use
of NWs (10 in TE devices,
wt.%, 20 wt.%,the
30 TE prop-
wt.%, 50
erties and
wt.% of films containing
70 wt.%) various weight
were analyzed fractions
at room of NWsThe
temperature. (10 Seebeck
wt.%, 20coefficient
wt.%, 30 wt.%, 50
(S) and
wt.% and 70 wt.%) were analyzed at room temperature. The Seebeck coefficient
electrical conductivity (σ) of complex organic/inorganic systems can be predicted using a(S) and
electrical conductivity
parallel-connected (σ) of
model, as complex organic/inorganic
summarized systems
by Equations (7) can be predicted using a
and (8):
parallel-connected model, as summarized by Equations (7) and (8):
Polymers 2021, 13, 210 8 of 12

To investigate the potential of the composite film for use in TE devices, the TE prop-
erties of films containing various weight fractions of NWs (10 wt.%, 20 wt.%, 30 wt.%,
50 wt.% and 70 wt.%) were analyzed at room temperature. The Seebeck coefficient (S)
Polymers 2021, 13, x FOR PEER REVIEW and
8 of 12
electrical conductivity (σ) of complex organic/inorganic systems can be predicted using a
parallel-connected model, as summarized by Equations (7) and (8):

Sc,p =
1 xs )σp S p
xs σs Ss + (1 −
(7)
, xs σs + (1 − (7)
1 xs )σp
, 1 xs )σp
σc,p = xs σs + (1 − (8)
(8)
where SSc,p
where c,p, ,SS s , and Sp are the Seebeck coefficients of the parallel-connected model, the
s, and Sp are the Seebeck coefficients of the parallel-connected model, the PE-

DOT:PSS-coated Ag2Ag
PEDOT:PSS-coated Se NWs,
Se 2NWs, and and the PEDOT:PSS
the PEDOT:PSS film,film, respectively,
respectively, σc,p, σσ c,p , σs , and σp
s, and σp are the
are the electrical conductivities of the parallel-connected model, the PEDOT:PSS-coated
electrical conductivities of the parallel-connected model, the PEDOT:PSS-coated Ag2Se
Ag2 Se NWs, and the PEDOT:PSS film, respectively, and xs is the volume fraction of the
NWs, and the PEDOT:PSS film, respectively, and xs is the volume fraction of the PE-
PEDOT:PSS-coated Ag Se NWs. The curves obtained from Equations (7) and (8) are plotted
DOT:PSS-coated Ag2Se2 NWs. The curves obtained from Equations (7) and (8) are plotted
in Figure 7a,b, and the input values are listed in Table S1.
in Figure 7a,b, and the input values are listed in Table S1.

Figure
Figure 7. Analyses of
7. Analyses of the
the TE
TE properties
properties of
of the
the PEDOT:PSS-coated
PEDOT:PSS-coated AgAg22Se
Se NW/PEDOT:PSS composite films
NW/PEDOT:PSS composite films with
with various
various NW
NW
contents according to the parallel connected model (a) Seebeck coefficient, (b) electrical
according to the parallel connected model (a) Seebeck coefficient, (b) electrical conductivity (c) power factor values.

In close
In closeagreement
agreementwith withthethe previous
previous research
research [42],
[42], the the Seebeck
Seebeck coefficient
coefficient of theofpris-
the
pristine PEDOT:PSS (0 wt.% NWs) is seen to be ~12.85 µV/K
tine PEDOT:PSS (0 wt.% NWs) is seen to be ~12.85 μV/K in Figure 7a, with the positive in Figure 7a, with the
positive value indicating
value indicating P-type conduction.
P-type conduction. However,However, with
with a filler a fillerof
content content of more
more than than
10 wt.%,
10 wt.%, the Seebeck coefficient becomes negative, thus indicating N-type
the Seebeck coefficient becomes negative, thus indicating N-type semiconducting behav- semiconducting
behavior
ior of the of the composite
composite film. Further,
film. Further, as theas the contents
contents of theofPEDOT:PSS-coated
the PEDOT:PSS-coated Ag2SeAg 2 Se
NWs
NWs increased, the absolute value of the Seebeck coefficient tends to
increased, the absolute value of the Seebeck coefficient tends to increase, reaching a max- increase, reaching
a maximum of −78.29 µV/K at 70 wt.%. Meanwhile, the room temperature electrical
imum of −78.29 μV/K at 70 wt.%. Meanwhile, the room temperature electrical conductivity
conductivity of the composite film is seen to decrease with increasing PEDOT:PSS-coated
of the composite film is seen to decrease with increasing PEDOT:PSS-coated Ag2Se NW
Ag2 Se NW contents in Figure 7b. This is because the electrical conductivity of the DMSO
contents in Figure 7b. This is because the electrical conductivity of the DMSO that was
that was added to the PEDOT:PSS is higher than that of the PEDOT:PSS-coated Ag Se
added to the PEDOT:PSS is higher than that of the PEDOT:PSS-coated Ag2Se NWs.2Fi-
NWs. Finally, due to the changes in the Seebeck coefficient and electrical conductivity of
nally, due to the changes in the Seebeck coefficient and electrical conductivity of the com-
the composite films, the room temperature power factor is the highest (~327.15 µW/m·K2 )
posite films, the room temperature power factor is the highest (~327.15 μW/m·K2) with a
with a PEDOT:PSS-coated Ag2 Se NWs content of 50 wt.%, see Figure 7c.
PEDOT:PSS-coated
The variations in 2Se NWs content of 50 wt.%, see Figure 7c.
Agthe TE properties of the PEDOT:PSS-coated Ag2 Se NW/PEDOT:PSS
The variations
composite films within50 the TE properties
wt.% and 70 wt.% of NWs
the PEDOT:PSS-coated
according to the numberAg2Se of NW/PEDOT:PSS
bending cycles
composite films with 50 wt.% and 70 wt.% NWs according to the number
are presented in Figure S6. Thus, although both films exhibit a reduction in durability of bendingwith cy-
cles are presented in Figure S6. Thus, although both films exhibit a reduction
an increasing number of bending cycles, this is relatively minor. Hence, the composite film in durability
with
can be anconsidered
increasingto number of bending durability.
have outstanding cycles, this is relatively minor. Hence, the compo-
site film can be considered to have outstanding
To verify the high TE performance of the proposed durability.
composite film in practical applica-
tion, To verify the
a flexible TE high TE performance
prototype device wasof the proposed
assembled. Thecomposite film in of
device consisted practical appli-
five strips of
cation, a flexible TE prototype device was assembled. The device consisted
the composite film, as shown in Figure 8a. The open-circuit voltage and output power were of five strips
of the composite
measured film,
using the as shown in
homemade Figure
device 8a. The
shown open-circuit
in Figure S7. Atvoltage and output
a temperature power
difference
were measured using the homemade device shown in Figure S7. At a temperature differ-
ence (∆T) of 20 K, the prototype’s open-circuit voltage reached 7.6 mV (Figure S7b), which
is similar to the theoretical value of 71.59 mV calculated according to Equation (9): [43]
Voc = N·│ S│ ·∆T (9)
Polymers 2021, 13, 210 9 of 12

(∆T) of 20 K, the prototype’s open-circuit voltage reached 7.6 mV (Figure S7b), which is
similar to the theoretical value of 71.59 mV calculated according to Equation (9): [43]

Voc = N · |S| · ∆T (9)

Polymers 2021, 13, x FOR PEER REVIEW 9 of 12
where N is the number of TE legs.

Figure Thestructure
Figure 8. The structureand
andperformance
performance ofof
thethe flexible
flexible TE TE prototype
prototype device:
device: (a) schematic
(a) schematic diagram
diagram of theofTEthe TE device
device struc-
ture; (b) the
structure; (b) open-circuit voltage
the open-circuit at various
voltage temperature
at various temperaturedifferences; (c)(c)the
differences; theoutput
outputvoltage
voltageand
andpower
power versus
versus current atat
temperature differences of 20 and 30
temperature differences of 20 and 30 K. K.

measure the device’s output properties, a simple circuit was built using thermo-
To measure
couples and
andaavoltage
voltagemeasurement
measurementdevice.
device. A plot
A plot of the
of the open open circuit
circuit voltage
voltage against
against tem-
temperature difference is presented in Figure 8b. In addition, plots of the output
perature difference is presented in Figure 8b. In addition, plots of the output voltage and voltage
and
powerpower
versusversus current
current at temperature
at temperature differences
differences of 20 K ofand
20 K30and 30 presented
K are K are presented in
in Figure
Figure 8c.the
8c. Here, Here, the voltage
output output and
voltage andcurrent
output output are
current
seen are seen
to be to be inversely
inversely related.
related. The out-
The outputPpower
put power P was calculated
was calculated using Equation
using Equation (10): [43](10): [43]
 2
2 V0c (10)
P = I Rload = Rload (10)
Rin + Rload
where I, Rload, and Rin are the output current, load resistance, and internal resistance of the
where I, Rload
TE device, , and Rin areThe
respectively. themaximum
output current, load
output resistance,
power and internal
is obtained when Rinresistance of .the
equals Rload At
TE device, respectively. The maximum output power is obtained when Rin equals
a ∆T of 20 K (44.5 ◦°C and 20.6 ◦°C), the maximum output power Pmax was approximately Rload . At
a ∆T ofNW,
157.29 20 Kcorresponding
(44.5 C and 20.6 C), the
to a load maximum
resistance output
of 91.8 Ω. Inpower Pmaxfor
addition, was approximately
a ∆T of 30 K, Pmax
157.29 NW, corresponding to a load resistance of 91.8 Ω. In addition, for a ∆T of 30 K, Pmax
reached 353.92 NW, and Rload was 91.6 Ω.
reached 353.92 NW, and Rload was 91.6 Ω.
Finally, the voltage was measured by applying different temperatures to both sides
Finally, the voltage was measured by applying different temperatures to both sides of
of the device. As shown in Figure S7, when the temperature difference was 20 K, the out-
the device. As shown in Figure S7, when the temperature difference was 20 K, the output
put voltage was 7.6.
voltage was 7.6.
4. Conclusions
4. Conclusions
In this
In this report,
report, PEDOT:PSS-coated
PEDOT:PSS-coatedAg AgSe2Se NW/PEDOT:PSS inorganic/organic compo-
NW/PEDOT:PSS inorganic/organic compos-
2
site films with various NW contents were
ite films with various NW contents were synthesized synthesized andand their
their TETE properties
properties analyzed.
analyzed.
The PEDOT:PSS-coated Ag 2Se NWs were prepared with an Se template using in situ so-
The PEDOT:PSS-coated Ag2 Se NWs were prepared with an Se template using in situ
lution-phase synthesis.
solution-phase synthesis.The
Thesynthesized
synthesizedNWs NWswerewerethen
thenadded
addedto to aa PEDOT:PSS solution
PEDOT:PSS solution
and drop-cast to form the flexible inorganic/organic composite film.
and drop-cast to form the flexible inorganic/organic composite film. The morphology of The morphology of
the composite film was analyzed using FE-SEM, FE-TEM, EDS, XPS,
the composite film was analyzed using FE-SEM, FE-TEM, EDS, XPS, and XRD. The dra- and XRD. The dra-
matically enhanced
matically enhancedTE TEpower
powerfactor
factorofofthe
the proposed
proposed composite
composite filmfilm is primarily
is primarily duedue to
to the
the higher Seebeck coefficient and lower electrical conductivity. The
higher Seebeck coefficient and lower electrical conductivity. The addition of PEDOT:PSS- addition of PE-
DOT:PSS-coated
coated Ag2 Se NWs Ag2to
SeDMSO-treated
NWs to DMSO-treated
PEDOT:PSS PEDOT:PSS
film alsofilmled also
to a led to a higher
higher power power
factor.
factor. However,
However, when thewhen
NWs thecontent
NWs content
was higherwas higher
than 70than 70 awt.%,
wt.%, viable a viable composite
composite film
film could
could
not benot be fabricated.
fabricated. Nevertheless,
Nevertheless, the the composite
composite films
films with
with 5050 wt.%and
wt.% and7070wt.%
wt.% NWs
NWs
exhibited outstanding durability after 1000 bending cycles. Finally, Finally, a simple flexible ther-
moelectric device was fabricated with five composite legs and was shown to generate generate a
voltage of 7.6 mV at a temperature difference of 20 K. In summary, an efficient strategy
was presented for designing and synthesizing high-performance inorganic/organic TE
composite films by combining the high power factor of an inorganic filler with the high
flexibility of a polymer.
Polymers 2021, 13, 210 10 of 12

voltage of 7.6 mV at a temperature difference of 20 K. In summary, an efficient strategy

was presented for designing and synthesizing high-performance inorganic/organic TE
composite films by combining the high power factor of an inorganic filler with the high
flexibility of a polymer.

Supplementary Materials: The following are available online at https://www.mdpi.com/2073-4

360/13/2/210/s1, Figure S1: Characterization of the PEDOT:PSS-coated Se: (a) XRD pattern; (b)
FE-SEM image; (c) FE-TEM image, Figure S2: XPS characterization of the PEDOT:PSS-coated Ag2 Se
NWs: (a) survey spectrum, and (b–d) high-resolution S 3p, (b) Ag 3d (c) Se 3d (d) spectra, Figure S3:
FE-TEM images of the pristine Ag2 Se NWs: (a) low magnification; (b) high magnification, Figure S4:
Elemental characterization of the PEDOT:PSS-coated Ag2Se NWs: (a) FE-SEM image; (b–d) the
corresponding EDS mappings of Ag (b), Se (c), and s (d) atoms, Figure S5: (a) Temperature dependent
carrier concentration and (b) carrier mobility of PEDOT:PSS-coated Ag2 Se NWs, Figure S6: The TE
properties of PEDOT:PSS-coated Ag2 Se NWs/PEDOT:PSS composites films with 50 and 70 wt.%
of NWs as a function of bending cycles: (a) the Seebeck coefficient; (b) the electrical conductivity;
(c) the power factor, Figure S7. The fabricated device: (a) schematic diagram of the electrical circuit;
(b) measuring voltage difference due to the temperature difference between the two ends of the
device; (c) an infrared thermal image showing a temperature difference of ~ 25 K, Table S1: Measured
electrical conductivity, and Seebeck coefficient for the calculation of parallel-connected models.
Author Contributions: Conceptualization, investigation, writing—original draft, D.P.; data curation,
M.K.; supervision, project administration, funding acquisition, J.K. All authors have read and agreed
to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: This research was funded and conducted under the Competency Development
Program for Industry Specialists of the Korean Ministry of Trade, Industry and Energy (MOTIE),
operated by Korea Institute for Advancement of Technology (KIAT). (No. P0012453, Next-generation
Display Expert Training Project for Innovation Process and Equipment, Materials Engineers).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Snyder, G.J.; Toberer, E.S. Complex thermoelectric materials. Nat. Mater. 2008, 7, 105–114. [CrossRef]
2. Zebarjadi, M.; Esfarjani, K.; Dresselhaus, M.; Ren, Z.; Chen, G. Perspectives on thermoelectrics: From fundamentals to device
applications. Energy Environ. Sci. 2012, 5, 5147–5162. [CrossRef]
3. Zhang, Q.; Sun, Y.; Xu, W.; Zhu, D. Organic thermoelectric materials: Emerging green energy materials converting heat to
electricity directly and efficiently. Adv. Mater. 2014, 26, 6829–6851. [CrossRef]
4. Biswas, K.; He, J.; Blum, I.D.; Wu, C.I.; Hogan, T.P.; Seidman, D.N.; Dravid, V.P.; Kanatzidis, M.G. High-performance bulk
thermoelectrics with all-scale hierarchical architectures. Nature 2012, 489, 414–418. [CrossRef]
5. Kim, K.; Wie, J.; Kim, J. Syneristic interaction of P and N co-doping EDTA with controllable active EDTA-cobalt sites as efficient
electrocatalyst for oxygen reduction reaction. J. Ind. Eng. Chem. 2020, 83, 252–259. [CrossRef]
6. Zhou, W.; Fan, Q.; Zhang, Q.; Cai, L.; Li, K.; Gu, X.; Yang, F.; Zhang, N.; Wang, Y.; Liu, H. High-performance and compact-designed
flexible thermoelectric modules enabled by a reticulate carbon nanotube architecture. Nat. Commun. 2017, 8, 1–9.
7. Sotelo, A.; Depriester, M.; Torres, M.; Sahraoui, A.; Madre, M.; Diez, J. Effect of simultaneous K, and Yb substitution for Ca on the
microstructural and thermoelectric characteristics of CaMnO3 ceramics. Ceram. Int. 2018, 44, 12697–12701. [CrossRef]
8. Tiu, T.; Wang, C.; Hou, J.; Zhang, C.; Chen, H.; He, H.; Wang, N.; Wu, H.; Cao, G. Enhanced electron collection in perovskite solar
cells employing thermoelectric NaCo2 O4 /TiO2 coaxial nanofibers. Small 2016, 12, 5146–5152.
9. Park, D.; Ju, H.; Kim, J. One-pot fabrication of Ag–SrTiO3 nanocomposite and its enhanced thermoelectric properties. Ceram. Int.
2019, 45, 16969–16975. [CrossRef]
10. Park, D.; Ju, H.; Kim, J. Effect of SrTiO3 Nanoparticles in Conductive Polymer on the Thermoelectric Performance for Efficient
Thermoelectrics. Polymers 2020, 12, 777. [CrossRef]
Polymers 2021, 13, 210 11 of 12

11. Ni, J.E.; Ren, F.; Case, E.D.; Timm, E.J. Porosity dependence of elastic moduli in LAST (lead–antimony–silver–tellurium)
thermoelectric materials. Mater. Chem. Phys. 2009, 118, 459–466. [CrossRef]
12. Ren, F.; Case, E.; Timm, E.; Schock, H. Young’s modulus as a function of composition for an n-type lead–antimony–silver–telluride
(LAST) thermoelectric material. Philos. Mag. 2007, 87, 4907–4934. [CrossRef]
13. Ju, H.; Kim, J. Preparation and structure dependent thermoelectric properties of nanostructured bulk bismuth telluride with
graphen. J. Alloys Compd. 2016, 664, 639–647. [CrossRef]
14. Ju, H.; Kim, M.; Kim, J. A facile fabrication of n-type Bi2 Te3 nanowire/graphene layer-by-layer hybrid structures and their
improved thermoelectric performance. Chem. Eng. J. 2015, 275, 102–112. [CrossRef]
15. Ju, H.; Kim, J. The effect of temperature on thermoelectric properties of n-type Bi2 Te3 nanowire/graphene layer-by-layer hybrid
composites. Dalton Trans. 2015, 44, 11755–11762. [CrossRef]
16. Li, Z.; Miao, N.; Zhou, J.; Sun, Z.; Liu, Z.; Xu, H. High thermoelectric performance of few-quintuple Sb2 Te3 nanofilms. Nano
Energy 2018, 43, 285–290. [CrossRef]
17. Vieira, E.M.; Figueira, J.; Pires, A.L.; Grilo, J.; Silva, M.F.; Pereira, A.M.; Goncalves, L.M. Enhanced thermoelectric properties of
Sb2 Te3 and Bi2 Te3 films for flexible thermal sensors. J. Alloys Compd. 2019, 774, 1102–1116. [CrossRef]
18. Li, W.; Zheng, L.; Ge, B.; Lin, S.; Zhang, X.; Chen, Z.; Chang, Y.; Pei, Y. Promoting SnTe as an eco-friendly solution for p-PbTe
thermoelectric via band convergence and interstitial defects. Adv. Mater. 2017, 29, 1605887. [CrossRef]
19. Xiao, Y.; Zhao, L.D. Charge and phonon transport in PbTe-based thermoelectric materials. NPJ Quantum Mater. 2018, 3, 1–12.
[CrossRef]
20. Wu, J.; Sun, Y.; Pei, W.B.; Huang, L.; Xu, W.; Zhang, Q. Polypyrrole nanotube film for flexible thermoelectric application. Synth.
Met. 2014, 196, 173–177. [CrossRef]
21. Liang, L.; Chen, G.; Guo, C.Y. Polypyrrole nanostructures and their thermoelectric performance. Mater. Chem. Front. 2017, 1,
380–386. [CrossRef]
22. Wang, L.; Jia, X.; Wang, D.; Zhu, G.; Li, J. Preparation and thermoelectric properties of polythiophene/multiwalled carbon
nanotube composites. Synth. Met. 2013, 181, 79–85. [CrossRef]
23. Shi, H.; Liu, C.; Xu, J.; Song, H.; Lu, B.; Jiang, F.; Zhou, W.; Zhang, G.; Jiang, Q. Facile fabrication of PEDOT:PSS/polythiophenes
bilayered nanofilms on pure organic electrodes and their thermoelectric performance. ACS Appl. Mater. Interfaces 2013, 5,
12811–12819. [CrossRef] [PubMed]
24. Ju, H.; Park, D.; Kim, J. Conductive polymer based high-performance hybrid thermoelectrics: Polyaniline/tin (II) sulfide
nanosheet composites. Polymer 2019, 160, 24–29. [CrossRef]
25. Ju, H.; Park, D.; Kim, J. Solution-processable flexible thermoelectric composite films based on conductive polymer/SnSe0.8 S0.2
nanosheets/carbon nanotubes for wearable electronic applications. J. Mater. Chem. A 2018, 6, 5627–5634. [CrossRef]
26. Wang, Y.; Yang, J.; Wang, L.; Du, K.; Yin, Q.; Yin, Q. Polypyrrole/graphene/polyaniline ternary nanocomposite with high
thermoelectric power factor. ACS Appl. Mater. Interfaces 2017, 9, 20124–20131. [CrossRef]
27. Yao, Q.; Wang, Q.; Wang, L.; Chen, L. Abnormally enhanced thermoelectric transport properties of SWNT/PANI hybrid films by
the strengthened PANI molecular ordering. Energ. Environ. Sci. 2014, 7, 3801–3807. [CrossRef]
28. Luo, J.; Billep, D.; Waechtler, T.; Otto, T.; Toader, M.; Gordan, O.; Sheremet, E.; Martin, J.; Hietschold, M.; Zahn, D.R. Enhancement
of the thermoelectric properties of PEDOT:PSS thin films by post-treatment. J. Mater. Chem. A 2013, 1, 7576–7583. [CrossRef]
29. Kim, G.H.; Shao, L.; Zhang, K.; Pipe, K.P. Engineered doping of organic semiconductors for enhanced thermoelectric efficiency.
Nat. Mater. 2013, 12, 719–723. [CrossRef]
30. Du, Y.; Cai, K.; Chen, S.; Cizek, P.; Lin, T. Facile preparation and thermoelectric properties of Bi2 Te3 based alloy
nanosheet/PEDOT:PSS composite films. ACS Appl. Mater. Interfaces 2014, 6, 5735–5743. [CrossRef]
31. Gainza, J.; Serrano, S.F.; Rodrigues, J.E.; Huttel, Y.; Dura, O.J.; Koza, M.M.; Fernández, D.M.T.; Meléndez, J.J.; Márkus, B.G.;
Simon, F. High-Performance n-type SnSe Thermoelectric Polycrystal Prepared by Arc-Melting. Cell Rep. Phys. Sci. 2020, 1, 100263.
[CrossRef]
32. Ge, Z.H.; Chang, Y.; Li, F.; Luo, J.; Fan, P. Improved thermoelectric properties of PEDOT:PSS polymer bulk prepared using spark
plasma sintering. Chem. Commun. 2018, 54, 2429–2431. [CrossRef] [PubMed]
33. Zhang, B.; Sun, J.; Katz, H.; Fang, F.; Opila, R. Promising thermoelectric properties of commercial PEDOT:PSS materials and their
Bi2 Te3 powder composites. ACS Appl. Mater. Interfaces 2010, 2, 3170–3178. [CrossRef] [PubMed]
34. Ding, Y.; Qiu, Y.; Cai, K.; Yao, Q.; Chen, S.; Chen, L.; He, J. High performance n-type Ag2 Se film on nylon membrane for flexible
thermoelectric power generator. Nat. Commun. 2019, 10, 1–7.
35. Perez, T.J.A.; Caballero, C.O.; Vera, L.L.; Briones, F.; Martin, G.M. High Thermoelectric zT in n-Type Silver Selenide films at Room
Temperature. Adv. Energy Mater. 2018, 8, 1702024. [CrossRef]
36. Park, D.; Kim, M.; Kim, J. Fabrication of PEDOT:PSS/Ag2 Se Nanowires for Polymer-Based Thermoelectric Applications. Polymers
2020, 12, 2932. [CrossRef]
37. Lu, Y.; Qiu, Y.; Cai, K.; Ding, Y.; Wang, M.; Jiang, C.; Yao, Q.; Huang, C.; Chen, L.; He, J. Ultrahigh power factor and flexible silver
selenide-based composite film for thermoelectric devices. Energ. Environ. Sci. 2020, 13, 1240–1249. [CrossRef]
38. Qu, J.; Goubet, N.; Livache, C.; Martinez, B.; Amelot, D.; Gréboval, C.; Chu, A.; Ramade, J.; Cruguel, H.; Ithurria, S. Intraband
mid-infrared transitions in Ag2 Se nanocrystals: Potential and limitations for Hg-free low-cost photodetection. J. Phys. Chem. C
2018, 122, 18161–18167. [CrossRef]
Polymers 2021, 13, 210 12 of 12

39. Pei, J.; Chen, G.; Jia, D.; Jin, R.; Xu, H.; Chen, D. Rapid synthesis of Ag2 Se dendrites with enhanced electrical performance by
microwave-assisted solution method. New J. Chem. 2013, 37, 323–328. [CrossRef]
40. Tan, L.; Fu, J.; Liu, S. Growth of photoluminescent Ag2 Se nanowires from a simple precursor solution. Cryst. Eng. Comm. 2014,
16, 10534–10538. [CrossRef]
41. Jiang, C.; Ding, Y.; Cai, K.; Tong, L.; Lu, Y.; Zhao, W.; Wei, P. Ultrahigh Performance of n-Type Ag2 Se Films for Flexible
Thermoelectric Power Generators. ACS Appl. Mater. Interfaces 2020, 12, 9646–9655. [CrossRef]
42. Ju, H.; Kim, J. Chemically exfoliated SnSe nanosheets and their SnSe/poly(3, 4-ethylenedioxythiophene): Poly(styrenesulfonate)
composite films for polymer based thermoelectric applications. ACS Nano 2016, 10, 5730–5739. [CrossRef]
43. Lu, Y.; Qiu, Y.; Cai, K.; Li, X.; Gao, M.; He, J. Ultrahigh Performance PEDOT/Ag2 Se/CuAgSe Composite Film for Wearable
Thermoelectric Power Generators. Mater. Today Phys. 2020, 14, 100223. [CrossRef]