coatings

Review
Thin Film Thermoelectric Materials: Classification,
Characterization, and Potential for
Wearable Applications
Xinqi Chen 1,2 , Wei Dai 1 , Tian Wu 1 , Wei Luo 2, *, Jianping Yang 2 ID
, Wan Jiang 2,3
and Lianjun Wang 2, *
1 School of Physics and Mechanical & Electrical Engineering, Hubei University of Education,
Wuhan 430205, China; chenxinqi@hue.edu.cn (X.C.); daiwei@hue.edu.cn (W.D.); twu@whu.edu.cn (T.W.)
2 State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai 201620, China; jianpingyang@dhu.edu.cn (J.Y.);
wanjiang@dhu.edu.cn (W.J.)
3 School of Materials Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333001, China
* Correspondence: wluo@dhu.edu.cn (W.L.); wanglj@dhu.edu.cn (L.W.); Tel.: +86-21-6787-4091 (W.L.)




Received: 22 May 2018; Accepted: 9 July 2018; Published: 10 July 2018


Abstract: Thermoelectric technology has the ability to convert heat directly into electricity and
vice versa. With the rapid growth of portable and wearable electronics and miniature devices,
the self-powered and maintenance of free thermoelectric energy harvester is highly desired as
a potential power supply. Thin film thermoelectric materials are lightweight, mechanically flexible,
and they can be synthesized from abundant resources and processed with a low-cost procedure,
which offers the potential to develop the novel thermoelectric devices and hold unique promise for
future electronics and miniature accessories. Here, a general classification for thin film thermoelectric
materials varied by material compositions, and thermoelectric properties depended on different
measurement technique. Several new flexible thermoelectric strategies are summarized with the hope
that they can inspire further development of novel thermoelectric applications.

Keywords: thermoelectric materials; thin film; organic materials; composite materials; energy
conversion; thermoelectric devices

1. Introduction
Thermoelectric (TE) technology, converting heat into electricity directly and vice versa,
is significant facing recent energy crisis [1–7]. When the heat flow passes through the TE device,
the temperature difference between the hot end and the cold end generates the current, and the
motion of the current makes the device heat or cool. This practical application attracts a lot of
research interests, however, TE conversion technology is not for typical use in daily life due to the
low conversion efficiency. The efficiency of TE device, as determined by electrons passing from
p-type materials to n-type materials, can be improved via optimizing the property of TE materials [8].
The efficiency of TE materials is expressed by the dimensionless TE figure of merit (ZT). ZT = S2 σT/κ,
where S is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, and T
is the absolute temperature [9,10]. The higher ZT value demonstrated, the better TE performance of
the semiconductor materials [11–13].
Conventional bulk TE materials have a long research history, dating back to Seebeck discovered the
phenomenon of “thermomagnetism” in 1821 [14–16]. These materials are mainly based on elements,
like Bi, Te, Sb, Pb, etc., including typical inorganic materials of Bi2 Te3 , PbTe, SiGe, skutterudite,
and half-Heusler alloys [17–19]. To this date, the highest reported ZT value is still below 3, which limits

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Coatings 2018, 8, 244 2 of 16

the usage of thermoelectric energy conversion to niche applications. Reaching higher ZT value can
realize the efficient conversion for widespread commercial TE device applications [20–24]. Furthermore,
bulk TE materials encountered a bottleneck in practical application, such as limitation of shape and
stagnancy of performance, which restricted the development of intelligent TE devices. In contrast,
thin film TE materials are lightweight and low cost and are easily synthesized on different kinds of
substrates, which offer possibility in the development of novel TE devices meeting bendable and
miniature requirements [25–28].
In this review, we discuss the general classification, typical synthesis approaches, and TE
measurement technique of thin film TE materials. Three kinds of thin film TE materials, inorganic
based, organic based, and inorganic-organic composite thin film TE materials, are introduced with
their common synthetic methods. Some novel TE measurement technique for electrical conductivity,
Seebeck coefficient, and thermal conductivity of thin film TE materials are mentioned. Finally, several
new perspectives for the further development of novel TE devices are outlined.

2. Classification of Thin-Film TE Materials

2.1. Inorganic-Based Thin Film TE Materials

Inorganic bulk TE materials are limited in their application by their low efficiency and high
cost. It has been shown recently that the low-dimensional material design improves TE efficiency
through more effective phonon scattering, thus contributing strongly to a reduced lattice thermal
conductivity [29]. Some theories explain that quantum well effect and superlattice structure of thin
films determine these better TE properties [18]. The following section is the fabricated thin films of
typical inorganic TE materials system and their TE performance.

2.1.1. Bi-Te Based Superlattices

In the last two decades, Bi-Te based bulk materials have improved their TE performance by doping.
When compared with single-phase Bi2 Te3 , the samples dispersed with Ag nanoparticles exhibited the
much lower thermal conductivity and higher power factor. A maximum ZT value of 0.77 obtained at
475 K from the bulk Bi2 Te3 dispersed with 2.0 vol % Ag nanoparticles, approximately three times higher
than that of the pristine bulk Bi2 Te3 [30]. Similarly, Bi-Te based superlattices have been studied with
doping and their ZT values were measured in thin film TE devices, which showed a great performance
(Figure 1a) [31,32]. For example, low-temperature growth process in metal-organic chemical vapor
deposition has been used for Bi2 Te3 system thin film for preparation of the individual layer as small
as 10 Å [31,33]. In this work, p-type Bi2 Te3 /Sb2 Te3 superlattices and n-type Bi2 Te3 /Bi2 Te2.83 Se0.17
superlattices thin films showed ZT value ~2.4 and ~1.4 at 300 K, separately. Besides, regarding the
reduction of production cost of this material system, p-type Bi0.4 Te3.0 Sb1.6 and n-type Bi2.0 Te2.7 Se0.3
thin films were fabricated by a flash evaporation method (Figure 1b,c) [32]. This deposition method
depends on a simple equipment that has three parts, including a vacuum chamber with particle holder,
tungsten heater, and a substrate holder. The p-type and n-type spherical powders of TE thin films
with average size 200 µm on glass substrates result in the good electrical performance, which reach
15.9 µW cm−1 K−2 in power factor of p-type thin film and 21.5 µW cm−1 K−2 in power factor of the
n-type thin film. However, when comparing to the Bi-Te system thin film TE devices, less cost Zn
based thin films and Cu based thin films have been studied recently [27,28,34,35].
Coatings 2018, 8, 244 3 of 16
Coatings 2018, 8, x FOR PEER REVIEW 3 of 16

Figure
Figure 1.1. (a)
(a) Temperature
Temperature dependence
dependence ofof figure
figureofofmerit
merit(ZT)
(ZT)ofof1010Å/50Å /50ÅÅp-type
p-typeBiBi2 Te 3 /Sb
2Te 3/Sb22Te
Te33
superlattice
superlattice compared to those of several recently reported materials. Reproduced from [31] with
compared to those of several recently reported materials. Reproduced from [31] with
permission; Copyright Nature
permission; Copyright NaturePublishing
PublishingGroup
Group2001;
2001;Schematic
Schematic illustration
illustration (b)(b)
and and photograph
photograph (c)
(c) of the bismuth-telluride-based alloy thin film thermoelectric (TE) generator.
of the bismuth-telluride-based alloy thin film thermoelectric (TE) generator. Reproduced [32] with Reproduced [32]
with permission;
permission; Copyright
Copyright ElsevierElsevier 2007; Schematic
2007; Schematic illustration
illustration of the Znofbasedthe Znthinbased thingenerator
film TE film TE
generator (TFTEG): (d) A p-n couple was formed through connecting the n-type
(TFTEG): (d) A p-n couple was formed through connecting the n-type Al-doped ZnO and p-type and Al-doped ZnO Zn-
p-type
Sb based thin films by metal layer bonding with Cu films deposited on both sides of the substrate;the
Zn-Sb based thin films by metal layer bonding with Cu films deposited on both sides of (e)
substrate; (e) Structure of the whole TFTEG; (f) and (g) are pictures of real Zn based TFTEG products.
Structure of the whole TFTEG; (f) and (g) are pictures of real Zn based TFTEG products. Reproduced
Reproduced [35] with permission; Copyright AIP Publishing 2015; (h) Cross-section scanning electron
[35] with permission; Copyright AIP Publishing 2015; (h) Cross-section scanning electron
microscopic (SEM) image of the Cu2 Se thin film on Al2 O3 substrate; (i) Photograph of the Cu2 Se thin
microscopic (SEM) image of the Cu2Se thin film on Al2O3 substrate; (i) Photograph of the Cu2Se thin
film on the polyimide substrate. Reproduced [27] with permission; Copyright John Wiley & Sons,
film on the polyimide substrate. Reproduced [27] with permission; Copyright John Wiley & Sons, Inc.
Inc. 2017; (j) The photograph of a CuI thin film sample deposited on polyethylene terephthalate
2017; (j) The photograph of a CuI thin film sample deposited on polyethylene terephthalate (PET)
(PET) substrate with a bending angle; (k) Schematic illustration for the power output measurement
substrate with a bending angle; (k) Schematic illustration for the power output measurement of the
of the CuI/PET single-leg TE device; and, (l) The example infrared image taken during one of the
CuI/PET single-leg TE device; and, (l) The example infrared image taken during one of the
measurements. Reproduced from [28] with permission; Copyright Nature Publishing Group 2017.
measurements. Reproduced from [28] with permission; Copyright Nature Publishing Group 2017.

2.1.2. Zn Based Thin Films

2.1.2. Zn Based Thin Films
ZnO thin film has numerous applications in an energy-related area, including various metal-doped
ZnO thin film has numerous applications in an energy-related area, including various metal-
ZnO thin film in TE application [36,37]. Among them, Al-doped ZnO thin film can serve as
doped ZnO thin film in TE application [36,37]. Among them, Al-doped ZnO thin film can serve as
high-temperature TE modules for practical applications. At the preparation step, the direct current
high-temperature TE modules for practical applications. At the preparation step, the direct current
(DC) magnetic sputtering method was selected in the deposition of the metal-based film due to its
(DC) magnetic sputtering method was selected in the deposition of the metal-based film due to its
high purity, large-scale, and low cost. Based on this method, n-type Al-doped ZnO thin film that
high purity, large-scale, and low cost. Based on this method, n-type Al-doped ZnO thin film that was
was deposited on glass substrates at room temperature. After measurement, the ZnO with 3 wt %
deposited on glass substrates at room temperature. After measurement, the2 ZnO with 3 wt % Al-doped
Al-doped thin film reaches the maximum power factor of 1.54 µW/cm K [34]. The maximum power
thin film reaches the maximum power factor of 1.54 µ W/cm K2 [34]. The maximum power output of
Al-doped ZnO film is 2.3 nW for a temperature gradient of 20 K near room temperature, which is
more practical for TE devices [38]. Beyond the hard substrates, n-type Al-doped ZnO and p-type Zn-
Coatings 2018, 8, 244 4 of 16

output of Al-doped ZnO film is 2.3 nW for a temperature gradient of 20 K near room temperature,
which is more practical for TE devices [38]. Beyond the hard substrates, n-type Al-doped ZnO and
p-type Zn-Sb based thin film were deposited on the flexible substrate with the thickness of 0.15 mm.
The final assembled TE devices with ten couples showed maximum output power 246.3 µW in a 180 K
temperature difference (Figure 1d–g) [35].

2.1.3. Cu Based Thin Films

Copper-based composites, no matter in bulk form or thin film, have attracted much attention
in TE application [21,22,39–41]. The Cu2 Se bulk has been reported reaching the highest ZT value of
2.4 at 1000 K [42]. The excellent TE performance of copper selenide crystals is related to their lower
lattice thermal conductivity [21,22]. Nevertheless, the research on Cu2 Se thin films exhibits lower TE
performance than that in bulk form. A method for thin flexible films deposition using high-performance
Cu2 Se powders has found recently. In this approach, the Cu2 Se powder was dissolved in the organic
solution making an ink solution. Then, through the wet-deposition method, this ink solution was
covered on flexible substrates evenly (Figure 1h,i). The Cu2 Se thin film fabricated by this route exhibits
a power factor of 0.62 mW cm−1 K−2 at 684 K [27]. Furthermore, the TE generators working in room
temperature range will be a significant breakthrough in the development of wearable and portable
devices. CuI in its γ-phase or low temperature is a p-type conductor [28]. Recent research explored
that γ-CuI thin film has a large Seebeck coefficient and hole conductivity, as well as low thermal
conductivity. These polycrystalline CuI thin films were deposited on glass by reactive sputtering at
room temperature (Figure 1j). A high purity copper target was used for sputtering and iodine vapor
was injected by a needle valve from gasified iodine source. The measured hole conduction of these
p-type undoped CuI thin film is 156 S/cm and I-doped CuI thin film is 283 S/cm (Figure 1k,l) [43].
The total figure of merit ZT of CuI thin film is 0.21 at 300 K. These CuI thin films, the thickness of
200–300 nm, were able to assemble as transparent and flexible TE modules opening a path for future
flexible TE devices [28].

2.1.4. Cobalt Oxide-Based Thin Films

Cobalt oxide-based thin films, like NaCoOx with two-dimensional layered structure, exhibit
high power factor in the in-plane direction [44,45]. An example of NaCo2 O4 single crystal thin
film showed the TE power of 100 µV K−1 at 300 K [46]. Besides these research, Ca3 Co4 O9 were
found with good performance in thermopower at room temperature recently. The single crystal of
Ca3 Co4 O9 presented resistivity of 10–40 mΩ cm, thermopower of 125 µV K−1 , and power factor
of 0.04–0.16 mW m−1 K−2 , respectively [47]. The nanostructured Ca3 Co4 O9 thin films can reach the
high power factor above 1 × 10−4 W m−1 K−2 in a wide temperature range. These films are flexible
and bendable without any deterioration of the TE performance [48]. When introducing nanoporous
structures into Ca3 Co4 O9 thin films, the TE performance improved due to the selectively scattering
phonons. The porosity of Ca3 Co4 O9 structures can be controlled, which determined the TE properties
of the nanoporous Ca3 Co4 O9 thin films. The lowest electrical resistivity is around 7 mΩ cm, yielding
a power factor of 2.32 × 10−4 W m−1 K−2 near room temperature [49]. Furthermore, these films are
transferable from the primary substrates to other arbitrary polymer platforms by simple dry transfer,
which opens an opportunity for wearable applications. Additionally, layered calcium cobalt oxides and
strontium cobalt oxides, synthesizing from sodium cobalt oxide precursors by ion-exchange reactions,
displayed an increased power factor [50–52]. The maximum power factor of layered Ca0.33 CoO2 is
9 × 10−4 W m−1 K−2 at 300 K, which is about 25% higher than that of Ca3 Co4 O9 [52]. The power
factor of layered Sr0.29 CoO2 is 3.5 × 10−4 W m−1 K−2 at 300 K [51]. Power factor is more important
than the thermal conductivity for TE power generation for a given ZT value, which is due to tuning
power factor does not influence thermo-mechanical stability while lowering thermal conductivity
leads to severe thermo–mechanical issues [53]. Thus, for low power applications, achieving high
power factor is more practical than reducing thermal conductivity in wearable applications.
Coatings 2018, 8, 244 5 of 16

2.2. Organic-Based Thin Film TE Materials

Apart from inorganic semiconductors discussed above in TE application, organic polymers,
or called semi-metallic polymers, inherently possess a low thermal conductivity, which gives them
a significant advantage over conventional TE materials [54–57]. After all, semiconducting polymers
are potentially abundant, light-weight, flexible, solution-processable, and low-cost [58]. However,
most of the polymers suffer poor efficiency, which requires a suitable doping agent to improve their
TE performance. Numerous doped p-type semiconducting polymers, such as typical polyacetylene,
polyaniline, polypyrrole, polythiophene, and poly(3,4-ethylenedioxythiophene), and some typical
n-type conductive polymers have been researched for their TE applications [59–63].

2.2.1. Polyacetylene and Polyaniline

Iodine-doped polyacetylene film showed the highest value of electrical conductivity of
1 × 105 S/cm, which was better than that in non-doped polyacetylene film (3 × 103 S/cm) [64].
Other metal chlorides, for example, FeCl3 , MoCl5 , NbCl5 , and ZrCl4 , have been doped with
polyacetylene. The electrical conductivity and TE power of these doped polyacetylene films have been
measured at different temperatures. The results demonstrated that FeCl3 -doped polyacetylene film
exhibited the highest value of electrical conductivity of 3 × 105 S/cm at 220 K [65]. Besides, Bi0.5 Sb1.5 Te3
nanoplates embedded polyaniline composites presented highly increased Seebeck coefficient and thus
an enhanced power factor from 16.5 × 10−8 to 84.4 × 10−8 W m−1 K−2 at 400 K [66]. However,
the obvious disadvantage of polyacetylene is unstable in the atmosphere.
Searching for more stable conducting polymers, the electrically conductive emeraldine salt form
of polyaniline is air stable, which is able to produce in large scale in low-cost [67,68]. The combination
film of polyaniline with camphorsulfonic acid (CSA) showed good electrical conductivity between
10 K and 300 K. These thin films exhibit metallic conductivity due to the doping level. Among the
different doping level, the 60% doped thin films have the electrical conductivity of 300 S/cm [69].
The multilayered polyaniline film (electrically insulating emeraldine based layers and electrically
conducting CSA-doped emeraldine salt layers) even presented the higher ZT at 300 K than that of
a bulk film of CSA-doped polyaniline [70].

2.2.2. Polypyrrole and Polythiophene

Polypyrrole, distinguished from above two conductive polymers, shows comparatively higher
conductivity (>300 S/cm) at very low temperatures (T ~0 K). A series of polypyrrole samples
from different synthesized methods measured the TE power and conductivity as a function of
temperature, including chemically synthesized soluble polypyrrole films, wrinkled polypyrrole films
on indium-tin-oxide electrodes, films were grown on nonconducting substrates, and polypyrrole gas
sensors with different dopants. It turns out that the highest conductivity of 340 S/cm was obtained for
polypyrrole that was doped with PF6 [71].
High-quality free-standing polythiophene and poly(3-methylthiophene) nanofilms with high
tensile strength were investigated. They show a decent TE performance of ZT value of 0.03 at 250 K,
which is higher than that of many other conducting polymers [72]. Sun et al. initially claimed that
high conducting polymers tend to exhibit conductivity from carriers that are close to the Fermi level
(Figure 2c). They fabricated poly(3-hexylthiophene) thin film on Si substrate and characterized the
thickness of 100 nm (Figure 2d) [73]. Although the TE performance of this thin film was not particularly
high, this work demonstrated a theoretical route for reaching a high Seebeck coefficient.

2.2.3. Poly(3,4-ethylenedioxythiophene)
Poly(3,4-ethylenedioxythiophene) is another extensively studied polymer, especially the combination
of poly(3,4-ethylenedioxythiophene) and polystyrenesulfonate (PEDOT:PSS). The mixtures show high
electrical conductivity along the casting plane [74]. For example, of 20 µm drop-cast films, the thermal
Coatings 2018, 8, 244 6 of 16

Coatings 2018, 8, x FOR PEER REVIEW

and electrical in-plane conductivities are, respectively, 1.0 W m−1 K−1 and 500 S cm−1 . The6 high of 16

electrical conductivity leads to a highly anisotropic thermal conductivity of drop-cast dimethylsulfoxide

cast dimethylsulfoxide (DMSO)-mixed PEDOT: PSS films. When using DMSO post-treatment instead
(DMSO)-mixed PEDOT: PSS films. When using DMSO post-treatment instead of DMSO addition in the
of DMSO addition in the PEDOT: PSS films, the power factor of the film is 65% increased. The
PEDOT: PSS films, the power factor of the film is 65% increased. The electrical conductivity-improving
electrical conductivity-improving contributes to this increase while the Seebeck coefficient is in minor
contributes to this increase while the Seebeck coefficient is in minor change [75]. Besides, there is
change [75]. Besides, there is a significant enhancement of the electrical conductivity of PEDOT: PSS
a significant enhancement of the electrical conductivity of PEDOT: PSS (from 787.99 to 4839.92 S cm−1 )
(from 787.99 to 4839.92 S cm−1) and Te-PEDOT:PSS hybrid − 1 (from 11.01 to 334.68 S cm−1) by chemical
and Te-PEDOT:PSS hybrid (from 11.01 to 334.68 S cm ) by chemical treatment with H2 SO4 [76].
treatment with H2SO4 [76].
2.2.4. Other n-type Polymers
2.2.4. Other n-type Polymers
For n-type organic TE materials, poly(nickel-ethylenetetrathiolate) (poly(Ni-ett)) reaches the
ForZT
highest n-type
valueorganic
of 0.3 atTE materials,
room poly(nickel-ethylenetetrathiolate)
temperature [77]. An example shows that the (poly(Ni-ett)) reaches
optical power factorthe
of
highest ZT value of 0.3 at room temperature [77].
− 1 An
− 2 example shows that the optical
poly(Ni-ett) synthesized at 0.6 V (131.6 µW m K at 360 K) is higher than that of at 1 or 1.6 V via power factor of
poly(Ni-ett)
potentiostatic synthesized
depositionat 0.6 Poly(benzobisimidazobenzophenanthroline)
[78]. V (131.6 μW m−1 K−2 at 360 K) is higher than (BBL) that ofhas
at demonstrated
1 or 1.6 V via
potentiostatic deposition [78]. Poly(benzobisimidazobenzophenanthroline) (BBL) has demonstrated
the electron mobility as high as 0.1 cm2 V−1 s−1 with the field-effect [79]. It can achieve 2.4 S cm−1 in
the
the electron
electricalmobility as high
conductivity as 0.1
[80]. As cm
2 V−1 s−1 with the field-effect [79]. It can achieve 2.4 S cm−1 in the
a new class of promising n-type organic TE materials, self-doping
electrical conductivity
perylene diimide (PDI) [80]. As a new
derivatives has class of promising
been reported with n-type organic
the power factorTEofmaterials,
1.4 µW m−self-doping
1 K−2 [81].
perylene diimide (PDI) derivatives has been reported with the power factor of 1.4 μW m−1 K−2 [81].

Figure 2. (a)
Figure (a) Chemical
Chemical structures
structures ofof polyacetylene,
polyacetylene, polyaniline,
polyaniline, polypyrrole,
polypyrrole, andand polythiophene.
polythiophene.
Reproduced from [61]
Reproduced [61] with
withpermission;
permission;Copyright
CopyrightJohn JohnWiley
Wiley && Sons, Inc.
Sons, 2014;
Inc. (b)(b)
2014; SEMSEMimage of the
image of
surface
the of aofpolypyrrole
surface a polypyrrolefilm (doped
film (doped with PFPF
with 6 )6that
) thatwas
wasfacing
facingthe
theITO
ITO (indium tin oxide)
oxide)electrode.
electrode.
Reproduced from
Reproduced from[71] withwith
[71] permission; Copyright
permission; John Wiley
Copyright John& Sons,
Wiley Inc.& 1999;
Sons,(c)Inc.
Schematic
1999;
(c) Schematic illustration of proposed organic TE composite, consisting of an additive that sets and
illustration of proposed organic TE composite, consisting of an additive that sets the Fermi level the
a bulk in
Fermi which
level andcharge
a bulkcarriers at higher
in which energy
charge levels are
carriers transported;
at higher energyandlevels
(d) Atomic force microscope
are transported; and
(AFM)
(d) image
Atomic of drop-cast
force microscopeblend poly(3-hexylthiophene)
(AFM) image of drop-castthin blendfilm on Si substrate. Reproduced
poly(3-hexylthiophene) fromon[73]
thin film Si
with permission; Copyright American Chemical Society 2010.
substrate. Reproduced from [73] with permission; Copyright American Chemical Society 2010.

2.3. Inorganic-Organic
2.3. Inorganic-Organic Composite Thin Film TE Materials
Although conducting
Although conducting polymer
polymer thin
thinfilms
filmsare
are low
low density,
density, low
low cost,
cost, low
low thermal
thermal conductivity,
conductivity,
and easy
and easy synthesis,
synthesis, it has not
not been
been feasible
feasible to
to apply
apply these
these materials
materials along
along inin TE
TE generators
generators due
due to
to the
the
limitations of electrical
limitations electrical conductivity and ZT value. When combining inorganic materials
and ZT value. When combining inorganic materials and organicand organic
conducting polymers, both advantages
conducting advantages from
from these
these two
two types
types of
of materials
materials present
present significant
significant potential
potential
for producing relatively low-cost and high-performance TE materials [82]. Recently, an increasing
number of studies have reported on inorganic-organic thin film TE nanocomposite materials [83].
Coatings 2018, 8, 244 7 of 16

for producing relatively low-cost and high-performance TE materials [82]. Recently, an increasing
number of studies have reported on inorganic-organic thin film TE nanocomposite materials [83].
Coatings 2018, 8, x FOR PEER REVIEW 7 of 16

2.3.1. Metal-Organic Frameworks

2.3.1. Metal-Organic Frameworks
Metal-organic frameworks (MOFs) start to be researched in TE application since its electrical
Metal-organic frameworks (MOFs) start to be researched in TE application since its electrical
conductivity has been reported [84,85]. Recently, the composite of tetracyanoquinodimethane (TCNQ)
conductivity has been reported [84,85]. Recently, the composite of tetracyanoquinodimethane (TCNQ)
and Cu (BTC) (BTC = benzene tricarboxylate) thin films that are deposited by a solution-based
and Cu33(BTC)22 (BTC = benzene tricarboxylate) thin films that are deposited by a solution-based
method at room temperature (Figure 3a). The TE properties of these TCNQ@Cu (BTC) films were
method at room temperature (Figure 3a). The TE properties of these TCNQ@Cu33(BTC)22 films were
measured under the controlled temperature gradient, which shows the Seebeck coefficient of 375 µV/K
measured under the controlled temperature gradient, which shows the Seebeck coefficient of 375
at room temperature (Figure 3b,c). This value exceeds some organic thin films and even Bi2 Te3 bulk
µ V/K at room temperature (Figure 3b,c). This value exceeds some organic thin films and even Bi 2Te3
materials [86]. However, the electrical performance of TCNQ@Cu3 (BTC)2 film was lower than the
bulk materials [86]. However, the electrical performance of TCNQ@Cu3(BTC)2 film was lower than
above-mentioned TE materials. Although this work presents a new type of TE materials, the TE
the above-mentioned TE materials. Although this work presents a new type of TE materials, the TE
properties of MOFs films still need to improve.
properties of MOFs films still need to improve.

(a) Cross-section
Figure 3. 3. SEM image
(a) Cross-section SEMof animage
infiltrated
of tetracyanoquinodimethane (TCNQ)@Cu3 (BTC)2
an infiltrated tetracyanoquinodimethane
thin film; (b) Schematic illustration of the TE measurement
(TCNQ)@Cu3(BTC)2 thin film; (b) Schematic illustration of the TE measurement for metal-organic frameworks (MOF)
for metal-organic
thin film. An(MOF)
frameworks infrared (IR)
thin camera
film. is used(IR)
An infrared to measure
camera is theused
temperature
to measure difference betweendifference
the temperature heat side
and cool heat
between sideside
of the
andsubstrate
cool sideand a multimeter
of the substrate and is adetected
multimeter for the voltagefor
is detected generated between
the voltage two
generated
of the metal
between two contacts; (c) Example
of the metal contacts;IR (c)image
Example takenIR during one ofduring
image taken the measurements. Reproduced
one of the measurements.
from [86] with
Reproduced permission;
from [86] withCopyright
permission; John Wiley &John
Copyright Sons, Inc. 2015;
Wiley & Sons, (d)Inc.
Method
2015;for
(d)the preparation
Method for the
and assembly of the single-walled carbon nanotubes (SWCNTs)-polyaniline
preparation and assembly of the single-walled carbon nanotubes (SWCNTs)-polyaniline composite composite thin film TE
module;
thin film(e,f)
TE Photograph
module; (e,f) of fabricated
Photograph flexible TE module;
of fabricated (g,h) Thermal
flexible TE module; voltage generation
(g,h) Thermalfrom the
voltage
TE module before and after touching at one side of the module; Reproduced
generation from the TE module before and after touching at one side of the module; Reproduced fromfrom [87] with permission;
Copyright
[87] John Wiley Copyright
with permission; & Sons, Inc. 2016;
John (i) Schematic
Wiley & Sons, Inc. illustration of the layer-by-layer
2016; (i) Schematic illustrationself-assembly
of the layer-
procedure of polyaniline/CNT/graphene multilayer film; and
by-layer self-assembly procedure of polyaniline/CNT/graphene multilayer film; (j) carrier transport in these
and multilayer
(j) carrier
film. Reproduced
transport in these from [88] with
multilayer permission;
film. Reproduced Copyright
from [88] John Wiley
with & Sons, Inc.
permission; 2015. John Wiley &
Copyright
Sons, Inc. 2015.

2.3.2. Carbon Nanotube-Polymer Composites

Carbon nanotubes (CNTs), which are a new star of carbon materials, are increasingly used in TE
composites or other energy storage materials due to their remarkable electrical property and low cost
[89–94]. A good example is that an excellent flexible n-type and p-type single-walled CNTs (SWCNTs)
networks film showed good power factor of 1.5 × 103 and 1.84 × 103 µ W m−1 K−2, respectively, with a
Coatings 2018, 8, 244 8 of 16

2.3.2. Carbon Nanotube-Polymer Composites

Carbon nanotubes (CNTs), which are a new star of carbon materials, are increasingly used in
TE composites or other energy storage materials due to their remarkable electrical property and low
cost [89–94]. A good example is that an excellent flexible n-type and p-type single-walled CNTs
(SWCNTs) networks film showed good power factor of 1.5 × 103 and 1.84 × 103 µW m−1 K−2 ,
respectively, with a long working lifespan up to three months [25]. A novel technology for decreasing
internal resistivity to assemble a flexible TE module based on these CNT films is initially demonstrated,
which is different from previous works. Large-area thick p-type CNT films were fabricated firstly and
then cut into stripes sticking on the substrate. Then, the CNT film stripe was covered alternately for
remaining as p-type and converted uncovered part into n-type. In this technique, the p-n couples were
creatively built in one stripe. Before measuring performance, pasting two metal electrodes for each edge.
It is an improving inspiration for the design of flexible TE devices. The SWCNTs-polyaniline composite
films were attempted in TE measurement, which presented the power factor was 217 µW m−1 K−2 .
In addition, 65 wt % SWCNTs-polyaniline composite segments that were prepared and assembled as
a TE module, which can generate 10.4 µW m−1 K−2 of power efficiency with good stability in the air
(Figure 3d–h) [87]. Further research reported that polyaniline/CNT/graphene multilayer film has
a comparable power factor of 1.825 × 103 µW m−1 K−2 at room temperature (Figure 3i,j) [88].
In conclusion, inorganic-based, organic-based, or inorganic-organic composites thin film TE
materials present some obvious advantages, including improved power factor, better performance
at room temperature, facile synthesis approaches, and low cost of production. Thus, they have great
potential in the further development of flexible and portable TE devices.

3. Measurement Technique of Thin Film TE Materials

Different from TE measurements for bulk materials, the accurate characterization of TE
performance in thin films is challenging. In 1958, T.C. Harman first published a measurement method,
which is called the Harman method, utilized for measuring the ZT value in many works [95]. However,
this method is not accurate for applying to thin films due to the slow thermal response of thin films
and insensitive of small transient Seebeck voltage [96]. In much research, TE data of thin films
were obtained using homemade apparatus for matching samples at different characteristics [97,98].
Thus, there is no uniform measurement method for all kinds of thin film TE materials. Because of
that, some novel measurement techniques for electrical conductivity (σ), Seebeck coefficient (S),
and thermal conductivity (κ), which will discuss as following, are developed for simple and more
accurate characterization for thin films.

3.1. Electrical Conductivity

The electrical conductivity (σ) for thin films was measured with a four-point probe device.
Although two-point measurement is generally used for bulk TE materials, the four-point method can
eliminate any contact resistance during the measurement when considering the very thin thickness of
the films (Figure 4a). Electrical conductivity can be calculated by the following equation:

σ = 1/ρ (1)

ρ = (V/l)/[I/(wt)] (2)

in which ρ is electrical resistivity, V and I are measured voltage and current, l is the length of electrons
travel, and w and t are the width and thickness of a sample. The length (l) is the spacing of the probe
tips and the width (w) is estimated by the software. The thickness (t) of each sample was measured
with surface profilometry using a KLA Tencor P–16+ [99]. Firstly, three lines were scratched onto the
Coatings 2018, 8, 244 9 of 16

sample without destroying the surface of the substrate (Figure 4b). Then, the step height was measured
at each of these scratches. The thickness of the samples is estimated by the following equation:

t = {[(t1 + t3 )/2] + t2 }/2 (3)

For more accuracy, several electrical conductivity measurements will be taken near the center of
the sample and8,calculate
Coatings 2018, x FOR PEERthe average (Figure 4c).
REVIEW 9 of 16
Coatings 2018, 8, x FOR PEER REVIEW 9 of 16

Figure 4. (a) Four-point electrical conductivity circuit. Current is supplied between pin 1 to pin 4,
Figure 4. (a) Four-point electrical conductivity circuit. Current is supplied between pin 1 to pin 4,
while voltage is measured between pin 2 to pin 3; (b) The process and between
locationspin
of 1thickness
whileFigure 4. (a)
voltage is Four-point
measuredelectrical
betweenconductivity
pin 2 to pin circuit.
3; Current
(b) Theisprocess
supplied and locations to
of pin 4,
thickness
measurements
while voltage using the profilometer;
is measured and 2(c)toThe
between pin pinelectrical conductivity
3; (b) The measurement
process and locations ofarea of the
thickness
measurements using the profilometer; and (c) The electrical conductivity measurement area of the
sample. Reproduced
measurements usingfrom [99] with permission;
the profilometer; and (c) The Copyright
electricalMassachusetts Institute of Technology
conductivity measurement area of the
sample. Reproduced from [99] with permission; Copyright Massachusetts Institute of Technology 2013.
2013.
sample. Reproduced from [99] with permission; Copyright Massachusetts Institute of Technology
2013.
3.2. Seebeck Coefficient
3.2. Seebeck Coefficient
3.2. Seebeck Coefficient
In Snyder’s work, a scanningapparatus
apparatus is
In Snyder’s work, a scanning is reported
reportedtotodirectly
directly detect
detectlocal variations
local of Seebeck
variations of Seebeck
coefficient on thin film samples. This scanning Seebeck coefficient measurement system is idealfor
coefficient
In on
Snyder’s thin film
work, samples.
a scanning This scanning
apparatus is Seebeck
reported coefficient
to directly measurement
detect local system
variations is
ofideal
Seebeck
for thin
thin film samples,
coefficient on thinespecially
film since it can
samples. measure films directly without separation from substrates
film samples, especially since it canThis scanning
measure films Seebeck
directlycoefficient
without measurement
separation system is ideal for[100].
from substrates
[100]. A typical
thin film samples, scanning
especiallySeebeck
sincecoefficient
it can measuremeasurement
films directlysystem has a separation
without ‘‘hot probe’’fromandsubstrates
a “cold
A typical scanning Seebeck coefficient measurement system has a “hot probe” and a “cold probe”,
probe”,
[100]. Aintypical
which scanning
they create the temperature
Seebeck coefficient gradient
measurement for the Seebeck
system hascoefficient measurement.
a ‘‘hot probe’’ and a “cold In
in which
this they create
setup, theistemperature gradient for theside,
Seebeck coefficient measurement.scanning In this setup,
probe”, inthe heater
which they located
create theon the sample holder
temperature gradient for and thethe cold (room-temperature)
Seebeck coefficient measurement. In
the heater
probe is
acts
this setup, located
as on finger.
theaheater
cold the sample onholder
In Figure
is located the 5a, side, and the
one holder
sample probe keepscold
side, the(room-temperature)
and same
the temperature
cold scanning
and
(room-temperature) probe acts
is electrically
scanning
as a connected
cold
probefinger. In
actstoasthe Figure
bottom
a cold 5a,the
of
finger. one
In probe
sample
Figure keeps
surface
5a, andthethe
one probe same
other
keeps temperature
probe
the samewith aand is electrically
thermocouple
temperature and isjunction connected
at
electrically
to the
the bottom
tip contact
connected of the
with
to the sample
the film
bottom of surface
sample
the sample andsurface
surface the other
moving
and the probe
under
otherthewith a with
thermocouple
motorized
probe stage. junction
A simulated
a thermocouple at the
sample
junction at tip
test
contact process
thewith theis film
tip contact shown in Figure
withsample
the 5b. The
filmsurface
sample unique
moving
surface merit
underof
moving thismotorized
the
under Seebeck coefficient
the motorized stage.
stage. measurement
simulatedsystem
AAsimulated sample
sample test
istest
process no requirement
isprocess
shown isinshown forinsubstrate
Figure Figure
5b. removal,
The5b. The unique
unique which
merit ofmeans
merit that
of Seebeck
this this thecoefficient
Seebeck homogeneity
coefficient of the film system
measurement
measurement sample
systemis no
deposited on
is no requirement
requirement an insulating
for substrate substrate
forremoval,
substratewhich (or
removal, multilayer
means which film
that means insulated from
that the homogeneity
the homogeneity a conducting substrate)
of the film
of the film sample can on an
sample
deposited
be directly
deposited evaluated.
on an(or This
insulating merit simplifies
substrate the measurement
(or multilayer steps and eliminates the possibility of
insulating substrate multilayer film insulated fromfilm insulated from
a conducting a conducting
substrate) substrate)
can be directly can
evaluated.
sample degradation. Thus, the thermocouple junction is located onto
be directly evaluated. This merit simplifies the measurement steps and eliminates the possibility ofthe same surface where the
This merit simplifies the measurement steps and eliminates the possibility of sample degradation. Thus,
scanning probe contacts,
sample degradation. but the
Thus, at athermocouple
different temperature
junctiondetermined
is located onto by the thesubstrate temperature,
same surface where theas
the thermocouple
shown in Figure junction
5c,d. is located onto the same surface where the scanning probe contacts, but at
scanning probe contacts, but at a different temperature determined by the substrate temperature, as
a different
showntemperature
in Figure 5c,d. determined by the substrate temperature, as shown in Figure 5c,d.

Figure 5. (a) Photograph of the scanning Seebeck coefficient measurement system and (b) schematic
illustration of Photograph
Figure 5. (a) the scanningoftip routes;
the Schematic
scanning illustration
Seebeck coefficientofmeasurement
the setup for (c) bulk and
system and (b)
(d) schematic
thin-film
Figure 5. (a) Photograph
samples. Reproduced of the
from scanning
[100] Seebeck coefficient
with Schematic
permission; measurement
CopyrightofSpringer 2012. system and (b) schematic
illustration of the scanning tip routes; illustration the setup for (c) bulk and (d) thin-film
illustration of the scanning tip routes; Schematic illustration of the setup for (c) bulk and (d) thin-film
samples. Reproduced from [100] with permission; Copyright Springer 2012.
samples.
3.3. Reproduced
Thermal from [100] with permission; Copyright Springer 2012.
Conductivity
3.3. Thermal Conductivity
The experimental measurement of thermal conductivity (κ) for thin films, to some extent, results
in a manifest error (~±10%)
The experimental [101]. Some
measurement developed
of thermal novel solutions
conductivity canfilms,
(κ) for thin calibrate the experimental
to some extent, results
error and present
in a manifest fast
error measurement
(~±10%) approaches.
[101]. Some For novel
developed instance, “steady-state
solutions isothermal
can calibrate technique”
the experimental
improves
error and accuracy
present fastby measurement
collecting data under conditions
approaches. where
For instance, thermal losses
“steady-state and errors
isothermal are
technique”
unimportant. Analysisbyofcollecting
improves accuracy this technique
data while
underusing a Peltierwhere
conditions coolerthermal
demonstrates
losses theanderror of less
errors are
 Coatings 2018, 8, 244 10 of 16

3.3. Thermal Conductivity

The experimental measurement of thermal conductivity (κ) for thin films, to some extent, results
in a manifest error (~±10%) [101]. Some developed novel solutions can calibrate the experimental error
and present fast measurement approaches. For instance, “steady-state isothermal technique” improves
accuracy by collecting data under conditions where thermal losses and errors are unimportant.
Coatings 2018, 8, x FOR PEER REVIEW 10 of 16
Analysis of this technique while using a Peltier cooler demonstrates the error of less than 1% [102].
When considering real TE generators, including qualitative demonstration, experimental uncertainty
than 1% [102]. When considering real TE generators, including qualitative demonstration,
is reduced by this technique by more than a factor of 2. “Scanning hot-probe” and “lock-in transient
experimental uncertainty is reduced by this technique by more than a factor of 2. “Scanning hot-
Harman” methods reduce error by highly detailed treatment of interfacial contact effects, including
probe” and “lock-in transient Harman” methods reduce error by highly detailed treatment of
electrical contact resistance and thermal contact effects. In scanning hot-probe technique, average probe
interfacial contact effects, including electrical contact resistance and thermal contact effects. In
temperature is also measured far from the sample to avoid the amount of heat loss. The heat transfer
scanning hot-probe technique, average probe temperature is also measured far from the sample to
coefficient of “lock-in transient Harman” method was determined to be about 2%. Its uncertainty
avoid the amount of heat loss. The heat transfer coefficient of “lock-in transient Harman” method
was assumed to be closer to 10% [103]. In addition, the thermal conductivity along the cross-plane
was determined to be about 2%. Its uncertainty was assumed to be closer to 10% [103]. In addition,
and in-plane direction have been measured and reported by the 3ω methods and time-domain
the thermal conductivity along the cross-plane and in-plane direction have been measured and
thermoreflectance measurements (TDTR) [26,55,74]. However, these two methods still need to
reported by the 3ω methods and time-domain thermoreflectance measurements (TDTR) [26,55,74].
be improved for the measurement of thin films with a relatively large surface roughness [62].
However, these two methods still need to be improved for the measurement of thin films with a
A self-heating 3ω method was used for solve the problem for the in-plane measurement where
relatively large surface roughness [62]. A self-heating 3ω method was used for solve the problem for
a gold wire with width should be thinner or comparable to the film thickness. In this method,
the in-plane measurement where a gold wire with width should be thinner or comparable to the film
the self-supported thin film with substrate acted both as a heater to create a temperature fluctuation
thickness. In this method, the self-supported thin film with substrate acted both as a heater to create
and a sensor to measure the thermal response under a four-probe resistance measurement configuration
a temperature fluctuation and a sensor to measure the thermal response under a four-probe resistance
(Figure 6a,b) [104].
measurement configuration (Figure 6a,b) [104].

Figure 6. (a) Schematic illustration of the four-probe configuration for measuring the specific heat and
Figure 6. (a) Schematic illustration of the four-probe configuration for measuring the specific heat
thermal conductivity
and thermal of a of
conductivity filament-like specimen;
a filament-like specimen;andand
(b) (b)
The four-probe
The four-probeconfiguration
configurationononthe
the
specimen
specimen holder for measuring the in-plane thermal conductivity of the film. Reproducedfrom
holder for measuring the in-plane thermal conductivity of the film. Reproduced from[62]
[62]
with
withpermission;
permission;Copyright
CopyrightJohn
JohnWiley
Wiley&&Sons,
Sons,Inc.
Inc.2016.
2016.

4. Conclusions and Outlooks

4. Conclusions and Outlooks
In summary, traditional inorganic TE semi-conductive materials have been restricted, to some
In summary, traditional inorganic TE semi-conductive materials have been restricted, to some
extent, in their stagnancy of performance and high cost. Although low-dimensional inorganic TE
extent, in their stagnancy of performance and high cost. Although low-dimensional inorganic TE
materials, such as superlattices and thin films, have been proved in decreasing thermal conductivity
materials, such as superlattices and thin films, have been proved in decreasing thermal conductivity in
in many researches, the overall TE performance is insufficient to investigate TE devices. Furthermore,
many researches, the overall TE performance is insufficient to investigate TE devices. Furthermore,
the TE working temperature of inorganic materials is usually above 500 K, which is the fatal weakness
the TE working temperature of inorganic materials is usually above 500 K, which is the fatal weakness
of these kind materials in the development of portable and wearable devices. The ideal TE devices
of these kind materials in the development of portable and wearable devices. The ideal TE devices
are best served at room temperature or low temperature, which makes it easier to meet working
are best served at room temperature or low temperature, which makes it easier to meet working
temperature requirement.
temperature requirement.
When compared to inorganic materials, organic conducting polymer thin films have many
When compared to inorganic materials, organic conducting polymer thin films have many
features, including low cost, facile synthesis, lower working temperature, and low thermal
features, including low cost, facile synthesis, lower working temperature, and low thermal conductivity,
conductivity, and they attract increasing attention. However, these organic polymer TE thin films still
and they attract increasing attention. However, these organic polymer TE thin films still need to
need to improve electrical conductivity and Seebeck coefficient in TE measurements.
improve electrical conductivity and Seebeck coefficient in TE measurements.
Recently, the study of the combination of inorganic-organic composite TE materials is a possible
Recently, the study of the combination of inorganic-organic composite TE materials is a possible
strategy to meet breakthrough in intelligent TE devices, especially introducing high-performance
strategy to meet breakthrough in intelligent TE devices, especially introducing high-performance
inorganic TE materials into polymer thin films. The hybridization of CNTs or graphene and polymer
thin films have been displayed amazing TE performance in many reports. As a recently developed
strategy, inorganic-organic composite TE thin films is a promising direction for portable and
wearable TE devices in the future, because they can achieve high TE performance, benefiting from
both high electrical conductivity of inorganic materials and poor thermal conductivity of organic
conducting polymers.
Coatings 2018, 8, 244 11 of 16

inorganic TE materials into polymer thin films. The hybridization of CNTs or graphene and
polymer thin films have been displayed amazing TE performance in many reports. As a recently
developed strategy, inorganic-organic composite TE thin films is a promising direction for portable
and wearable TE devices in the future, because they can achieve high TE performance, benefiting
from both high electrical conductivity of inorganic materials and poor thermal conductivity of organic
conducting polymers.
TE measurement technique, especially for thin films, is another hurdle to be conquered in the
development of devices. Although it is sufficient that the theoretical fundamentals and experimental
techniques of TE measurements in bulk materials, the measurement of thin films cannot rely solely on
above theories and experimental techniques. In this case, a series of measurements of TE thin films
are using a homemade apparatus for matching characteristics of samples. The accuracy of measured
results is the priority of these research. Meantime, the improvement of measurement techniques is an
auxiliary means to achieve the better performance of TE devices.
The interest in the development of portable and wearable TE devices will never terminate. As the
inspiration of thin film TE materials, a prototype with liquid TE legs is under exploration, which can
solve potential damage easily in the usage of TE devices. When compared with solid materials,
liquid materials possess attractive advantages consisting of excellent deformability, ease of doping,
and self–healing abilities, which could afford great promise for intelligent TE devices.

Funding: This project was funded by the National Natural Science Foundation of China (51702091, 51702046,
51772050, and 51432004), the Natural Science Foundation of Hubei Province, China (2017CFB192), the Innovation
Program of Shanghai Municipal Education Commission (2017–01–07–00–03–E00025), the Shanghai Committee
of Science and Technology, China (17ZR1401000, 18JC1411200 and 16JC1401800), China Postdoctoral Science
Foundation (2017M621320), the Fundamental Research Funds for the Central Universities, the Programme of
Introducing Talents of Discipline to Universities (111–2–04), DHU Distinguished Young Professor Program,
Shanghai Pujiang Program (17PJ1400100), and State Key Laboratory for Modification of Chemical Fibers and
Polymer Materials, Donghua University.
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the
decision to publish the results.

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