Recent Progress of Two Dimensional Thermoelectric Materials: Review

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ISSN 2311-6706

e-ISSN 2150-5551
CN 31-2103/TB

REVIEW https://doi.org/10.1007/s40820-020-0374-x

Recent Progress of Two‑Dimensional Thermoelectric


Materials
Cite as
Nano-Micro Lett.
(2020) 12:36 Delong Li1, Youning Gong1, Yuexing Chen2, Jiamei Lin1, Qasim Khan3,
Yupeng Zhang1 *, Yu Li4 *, Han Zhang1 *, Heping Xie5
Received: 26 October 2019
Accepted: 24 December 2019 * Yupeng Zhang, ypzhang@szu.edu.cn; Yu Li, liyu@szu.edu.cn; Han Zhang, hzhang@szu.edu.cn
Published online: 23 January 2020 1
Collaborative Innovation Centre for Optoelectronic Science & Technology, and Key Laboratory
© The Author(s) 2020
of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, Institute
of Microscale Optoelectronics, College of Chemistry and Environmental Engineering, Shenzhen University,
Shenzhen 518060, Guangdong, People’s Republic of China
2
Shenzhen Key Laboratory of Advanced Thin Films and Applications, College of Physics and Optoelectronic
Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
3
Department of Mechanical and Mechatronics Engineering, University of Waterloo, Waterloo, ON, Canada
4
Shenzhen Key Laboratory of Special Functional Materials, Shenzhen Engineering Laboratory for Advanced
Technology of Ceramics, Guangdong Research Center for Interfacial Engineering of Functional Materials,
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, Guangdong,
People’s Republic of China
5
Shenzhen Clean Energy Research Institute, Shenzhen University, Shenzhen 518060, Guangdong,
People’s Republic of China

HIGHLIGHTS

• A comprehensive review on the recent development of two-dimensional (2D) nanomaterials for bulk or thin-film thermoelectric
materials, as well as composite filler, has been extensively presented.

• Development of micro-device platform and its application to study the inherent thermoelectric properties of individual single- and
few-layer 2D nanomaterials.

ABSTRACT Thermoelectric generators have attracted a wide research interest


owing to their ability to directly convert heat into electrical power. Moreover, the Sintering
Bulk
thermoelectric properties of traditional inorganic and organic materials have been
significantly improved over the past few decades. Among these compounds, layered
two-dimensional (2D) materials, such as graphene, black phosphorus, transition s Gr
ap
ne he
metal dichalcogenides, IVA–VIA compounds, and MXenes, have generated a large Composite Xe ne Restack
M
filler Thin Film
research attention as a group of potentially high-performance thermoelectric materi-
s

2D-Materials for
Pho

als. Due to their unique electronic, mechanical, thermal, and optoelectronic proper-
enid

Thermoelectric
Blac orus

Cha IV-VI
sph

lcog

ties, thermoelectric devices based on such materials can be applied in a variety of


k

applications. Herein, a comprehensive review on the development of 2D materials TMDs

for thermoelectric applications, as well as theoretical simulations and experimental


Nano-Micro Self-Power
preparation, is presented. In addition, nanodevice and new applications of 2D ther- Devices Devices
moelectric materials are also introduced. At last, current challenges are discussed
and several prospects in this field are proposed.

KEYWORDS Two-dimensional thermoelectric materials; Black phosphorus analogue; Tin selenide; Transition metal dichalcogenides;
Photothermoelectric effect

Vol.:(0123456789)
13
36 Page 2 of 40 Nano-Micro Lett. (2020) 12:36

1 Introduction ­ i4N3), and Xenes (e.g., black phosphorene, arsenene, bis-


T
muthine, and antimonene) [21, 23–34] These 2D materials
Due to the increasing demand in high-efficiency clean exhibit different allotropes with outstanding electronic and
energy, it is essential to develop renewable energy devices optical properties. For this reason, they have been widely
to resolve the energy issues and avoid further environ- used in electronics, optoelectronics, topological spintronic,
mental deterioration [1, 2]. In the past several decades, bio-application energy storage (e.g., battery and supercapaci-
thermoelectric device, solar cells, wind-driven generators tors) and energy conversion devices (e.g., thermoelectric and
and fuel cells have attracted a large attention and shown a solar cells) [35–38].
reliable quality in power generation. Among these kinds Due to their outstanding advantages in electronic and
of energy conversion technologies, thermoelectric devices mechanical properties, 2D materials with a layered struc-
show a high potential in their application in many areas ture have attracted a considerable attention as efficient ther-
including power generators, cooling devices, and sen- moelectric materials [8, 39]. In the past several decades,
sors [3–6]. Thermoelectric materials can directly convert the thermoelectric performance of a series of 2D materials,
thermal energy (such as waste heat and solar energy) into such as SnSe, B ­ i2Te3, and M­ oS2, has been theoretically
electrical energy; this property makes them important predicted and the samples have been experimentally fabri-
compounds for the development of sustainable energy cated [33, 34, 40]. These 2D materials exhibit fascinating
efficient technologies [7–9]. When compared with other properties exhibit such as a large potential when they are
energy conversion devices, thermoelectric device show used in the fabrication of high-performance thermoelectric
unique advantages including stability, long service life, devices.
and noiseless [10–12]. The thermoelectric performance Currently, although interesting research results in both
of the materials at a certain temperature is evaluated by theoretical predictions and experimental analyses have been
the dimensionless figure of merit (ZT), ZT= σS 2T/κ. In achieved, a comprehensive review about 2D thermoelectric
this expression, σ, T, and κ correspond to the electrical materials is still missing. To promote their development, it
conductivity, the Seebeck coefficient, and the absolute is pivotal to focus on the research progress in this field. In
temperature, respectively. Moreover, κL refers to the lattice this review, the theoretical and experimental advances in the
thermal conductivity κ(L) and κ(e) to the electronic ther- 2D thermoelectric materials field are summarized. Initially,
mal conductivity [13, 14]. These parameters are strongly their unique electrical and thermal properties are illustrated.
coupled and dependent on the material’s band and crystal Then, the application of 2D nanomaterials to fabricate bulk
structure. Due to the complex inter-relation among these thermoelectric compounds, thin-film thermoelectric materi-
three parameters, it is almost impossible to optimize them als, and composite fillers is discussed in detail. Moreover,
independently [15]. However, several records for the high- the thermoelectric properties of single- or multilayer 2D
est ZT values have been continuously broken in the last materials studied by using nano–micro-devices are intro-
few years due to the development of novel materials, new duced. Finally, thermoelectric compounds combined with
processing techniques, and new concept/mechanisms photodetection devices are discussed. A perspective and
[16–20]. an outlook on 2D thermoelectric materials conclude this
Since the initial discovery of graphene in 2004, the review.
research interest in these materials has been growing explo-
sively in the last decades [21, 22]. With the development of 2 Properties of 2D Thermoelectric Materials
novel theoretical simulation methods and materials synthesis
technics, a variety of 2D materials have been theoretically 2.1 Graphene
predicted and successfully fabricated. Typical 2D materi-
als are graphene, black phosphorus (BP), transition metal As a typical 2D material, graphene has become a popu-
dichalcogenides (TMDCs) (e.g., M ­ oS2, ­WS2, ­MoSe2, and lar topic in scientific research due to its distinctive physi-
­MoTe2), Group IVA–VA compounds (e.g., SnSe, GeSe, and cal and chemical properties since it can be exfoliated from
SnS), nitrides (e.g., boron nitride), MXenes (e.g., ­Ti3C2, and bulk graphite [41, 42]. Due to its unique electrical, optical,

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 3 of 40 36

catalytic, and mechanical features, graphene has attracted a deviation increases with the temperature [49]. Figure 1e, f
broad attention in recent years in many fields. For instance, shows the simulation of the electron and phonon transport
graphene shows an ultrahigh electrical conductivity through an edge-disordered zigzag graphene layer [50].
­(106 S cm−1) at room temperature due to its high electron The simulation results on the graphene nanoribbons with
mobility [43]. Its maximum Seebeck coefficient value was different sample lengths and number of zigzag chains (Nz)
reported to be about 80 mV K−1 [27, 44, 45]. The thermal were studied. Sevincli et al. found that the edge disorder
conductivity of graphene is in the 4840–5300 W mK−1 range in zigzag graphene nanoribbons (ZGNRs) can significantly
at room temperature [46]. A large theoretical and experimen- reduce the phonon thermal conductance, whereas the elec-
tal effort has been done to study the thermoelectric perfor- tronic conduction remains almost intact at the first conduct-
mance of graphene [44, 45, 47–69]. ance plateau [50]. Sevincli predicted that the edge disorder
Nam et al. investigated the in-plane thermoelectric prop- suppresses the thermal conductivity by few orders of mag-
erties of bilayer graphene by using a micro-device, and nitude in the zigzag edges graphene nanoribbons. Moreover,
their results were simulated by using the Mott formula it gives rise to a ZT value of 4 at 300 K [50].
with a hyperbolic dispersion relation [49]. The gate-volt- These results indicate that graphene can be optimized
age dependence of the thermoelectric properties of bilayer to achieve high-performance thermoelectric properties.
graphene has been carried out for various temperatures and However, for practical applications, both the Seebeck coef-
charge-carrier densities. Figure 1a–d shows the measured ficient and the power factor of graphene should be improved,
Seebeck coefficient of bilayer graphene, which follows the whereas its thermal conductivity should be decreased. To
semiclassical Mott formula at low temperature (T = 30 K achieve large ZT values in graphene-based thermoelec-
and T = 50 K). However, at high temperature (T = 140 K and tric materials, two major barriers need to be overcome:
T = 250 K), the Seebeck coefficient measured by using the (1) the graphene thermal conductivity is too high, and
micro-device reveals a deviation from the simulated See- (2) the Seebeck coefficient is too small due to its gapless
beck coefficient near the charge neutrality point, and this band structure. Although graphene exhibits advantage as a

ZGNR(10)
30 (e) 5
(a) (b) 200
Conductance (2e2 h−1)

Experiment 40 Experiment
lel (nm)

15
Mott Mott 4 100
20
Sxx (µV K−1)

Sxx (µV K−1)

3 0
0 0 −2 0 2
2
−20
−15 1
T = 30 K −40 T = 50 K 0
−30 −2 −1 0 1 2
−60 −30 0 30 60 −60 −30 0 30 60 Energy (eV)
VBG (V) VBG (V)
ZGNR(20)
80
(c) 140 (d) (f) 6
Conductance (2e2 h−1)

Experiment Experiment 3000


Mott Mott
lel (nm)

40 70 1500
Sxx (µV K−1)

Sxx (µV K−1)

4
0
0 0 −2 0 2

−40
2
−70

−80 T = 140 K −140


T = 250 K
0
−60 −30 0 30 60 −60 −30 0 30 60
−2 −1 0 1 2
VBG (V) VBG (V) Energy (eV)

Fig. 1  The in-plane Seebeck coefficient of bilayer graphene as a function of the backgate voltage (VBG) at different temperatures: a T = 30 K,
b T = 50 K, c T = 140 K and, d T = 250 K. Reproduced with permission from Ref. [49]. Copyright 2010, American Physical Society. Electron
transport through the edge-disordered zigzag edges graphene nanoribbons: sample lengths e Nz = 10 and f Nz = 20. Reproduced with permission
from Ref. [50]. Copyright 2010, American Physical Society

13
36 Page 4 of 40 Nano-Micro Lett. (2020) 12:36

high-performance thermoelectric material, more efforts in the layer thickness, as shown in Fig. 2b. The significantly
simulations and experiments need to be done to optimize its increased electrical conductivity as well as the PF/τ is
thermoelectric performance. mainly caused by the valley degeneracy at the valence band
edge [73]. The ZT values of TMDCs (­ MoSe2, ­WS2, and
­WSe2) along the in-plane direction have been predicted. As
2.2 TMDC shown in Fig. 2d–f, the few layers’ structure shows large
increase in the values of their ZT compared to those of
As a novel class of layered materials, 2D TMDCs, such as the bulk. Besides the theory prediction, the thermoelec-
­MX2 (M = Mo, W, Ti, and X = S, Se, Te), have attracted a tric properties of 2D TMDCs have also been measured and
large attention in last decades due to their semiconducting the experimental results have proven that their thermo-
characteristics, outstanding chemical stability, and mechani- electric properties can be enhanced by applying external
cal and physical properties. Moreover, they have been widely electric field and pressure. Buscema et al. [71] reported a
studied in various fields including optoelectronic, energy large Seebeck coefficient with a large tunability between
harvests and conversion, and cancer therapy. These types of − 4 × 102 and − 1 × 105 μV K−1 for the M ­ oS2 monolayer
material have been widely studied in many fields, such as in the presence of an external electric field. However, in a
photodetector, thermoelectric, and gas-sensing applications. highly positive gate range, the Seebeck coefficient varies
Their relatively high electrical conductivity and relatively from −2 × 102 to − 1.5 × 103 μV K−1 and in a highly nega-
low thermal conductivity make the TMDCs emerge as prom- tive gate range, it varies from − 3 × 104 to − 3 × 105 μV K−1,
ising materials for high-performance thermoelectric devices, showing an increases of about two orders of magnitude. Wu
especially for the fabrication of wearable heating/cooling et al. observed a large Seebeck coefficient of 30 mV K−1
devices and power generators. by adjusting the backgate voltage [74]. The thermoelectric
The thermoelectric properties of 2D TMDCs with dif- properties of an exfoliated 2D ­MoS2 flake with different
ferent thickness have been investigated both experimen- thickness were studied by Hippalgaonkar. Due to the high
tally and theoretically. The most common TMDCs, such as electron concentration of n = 1.06 × 1013 cm−2, the bilayer
­MoS2, ­MoSe2, ­WS2, and ­WSe2, exhibit very similar elec- ­MoS2 exhibits the highest power factor (8.5 mW mK−2) as
tronic properties. For instance, the ­MoS2 monolayer is a the gate voltage is 104 V [72]. Due to the high electron con-
direct semiconductor with a band gap of 1.9 eV, whereas centration of n = 1.06 × 1013 cm−2, the M
­ oS2 bilayer exhibits
−2
bulk ­MoS2 is an indirect semiconductor with a band gap of the highest power factor (8.5 mW mK ) as the gate voltage
1.2 eV [70]. The band structures of the 2D TMDCs share reaches 104 V.
a similar transition from the direct band gap to the indirect The 2D TMDCs exhibit a relatively lower thermal
band gap, as the atomic layer increases from a monolayer conductivity when compared to graphene, which make
to a bilayer [8]. them a promising material for various applications in
As previously mentioned, the ZT value depends on three thermoelectric devices. The low thermal conductivity of
inherent physical quantities: the thermal conductivity, the the 2D TMDCs has been widely studied in experimental
electrical conductivity, and the Seebeck coefficient. These and theoretical works [75–89]. For instance, Sahoo et al.
quantities have been widely studied in the case of 2D mate- measured the thermal conductivity of a suspended few-
rials. Owing to their characteristic quasi-two- dimensional layer ­MoS2 film by using a laser-power-dependent Raman
crystal structures, TMDCs exhibit high Seebeck coefficient scattering experiment method. As a result, the thermal
[71–73]. By considering ­MoS2 as a reference compound, conductivity at room temperature for few-layer M ­ oS 2
−1
a brief introduction about the thermoelectric properties of was found to be 52 W mK [80]. Yan et al. [79] care-
2D TMDCs is presented below. As shown in Fig. 2a–c, the fully measured and analyzed the temperature-dependent
thermoelectric properties of ­MoS2 multilayers at 300 K are Raman spectra of the exfoliated M ­ oS2 monolayer at room
calculated along the in-plane direction. According to the temperature, and the measured thermal conductivity is
calculation results, the Seebeck coefficients are not affected 34.5 W mK −1. Taube et al. measured the temperature-
so much by the change of the layer numbers. However, the dependent thermal conductivity of the ­MoS2 monolayer
electric conductivity shows clear changes depending on on a ­S iO 2 /Si substrate via Raman spectroscopy. The

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 5 of 40 36

(a) 1200 (b) 2.0 (c) 5


−0.026 eV
1-layer 9 300K

PF/τ (1011 WK−2 m−1 s−1)


1000 2-layers
500K
6 700K

σ/τ (1018 Ω−1 cm−1 s−1)


4
4-layers 1.5 3
800 bulk 0
3
S (µV K)

Bulk 4 2 1
600 1.0
2
400
0.5
1
200

0 0.0 0
−0.2 0.0 0.2 0.4 −0.2 0.0 0.2 0.4 −0.2 0.0 0.2 0.4
E-VBM (eV) E-VBM (eV) E-VBM (eV)
3 3 3
(d) MoSe2 (e) WS2 (f) WSe2
1L 1L 1L
2L 2L 2L
3L 3L 3L
2 4L 2 4L 2 4L
Bulk Bulk Bulk
ZT

ZT

ZT
1 1 1

0 0 0
−10 −5 0 5 10 −10 −5 0 5 10 −10 −5 0 5 10
ηF ηF ηF

Fig. 2  a In-plane Seebeck coefficient, b electrical conductivity, and c power factor of p-type ­MoS2 at 300 K depending on their thickness and
chemical potential. Reproduced with permission from Ref. [73]. Copyright 2016, American Physical Society. ZT at 300 K for d ­MoSe2, e ­WS2,
and f ­WSe2 for bulk (black), 1 layer (blue), 2 layers (red), 3 layers (green), and 4 layers (purple) structures as a function of the reduced Fermi
energy, ηF. The n-type ZT is plotted with a solid line and p-type ZT with a broken line. Reproduced with permission from Ref. [90] Copyright
2014, AIP Publishing. (Color figure online)

results show that the thermal conductivity decreases from decades. These materials, such as Sn(S, Se, T(e), Ge(S, Se,
62.2 to 7.45 W mK −1 as the temperature increases from Te), Pb(S, Se, Te), Sn(Se, S)2, and their alloys, have been
300 to 450 K [78]. widely studied in the thermoelectric field. Moreover, they
In addition, the wide tunability of inherent thermo- have been used to fabricate high-performance thermoelec-
electric parameters of a ­M oS 2 monolayer or a few lay- tric power generators, thermoelectric sensors, and cooling
ers makes this material an ideal candidate for applica- devices [91, 92]. Among them, Sn(S, Se) and Ge(S, Se),
tions as a conventional thermoelectric generator or a which belong to the space group Pnma, exhibit a typical lay-
cooler. Although the calculation predictions show that ered 2D structure feature along the c direction. The reduction
the TMDCs should exhibit an outstanding thermoelec- in the dimensionality of these materials has been proved as
tric performance, these results have not been proven yet. one of the most efficient methods to enhance their ZT values
The measured Seebeck coefficient is much lower than the since the Seebeck coefficient increases due to the increased
calculations suggest data, and the thermal conductivity is density of the states near the Fermi level [93, 94]. In 1993,
much higher than in the case of conventional thermoelec- by carefully studying the properties and the structure of a
tric materials but much lower than graphene. low-dimensional ­Bi2Te3 material, a theory to explain the
relation between its structure and its thermoelectric proper-
2.3 Group IVA–VIA Compounds ties was presented by Dresselhaus and Hicks [95]. According
to their results, the numerous grain boundary and interfaces
As the most efficient kinds of thermoelectric materials, the in the material would generate a strong phonon scatter-
compounds that belong to group IVA–VIA have became the ing, which leads to a reduction in its thermal conductivity.
hot research field of thermoelectric science during the past Because of this reduced thermal conductivity and almost

13
36 Page 6 of 40 Nano-Micro Lett. (2020) 12:36

unchanged electrical properties, an enhanced ZT value could properties of polycrystalline SnSe have been improved con-
be obtained in the case of such low-dimensional materials tinuously and their ZT value have been improved from 0.5 to
[95]. Several years later, Sofo and Mahan [96] proposed a nearly 1.7 via optimization of the carrier concentration [109,
modified theory. They suggested that the well-quantum mix- 110]. The thermoelectric performance of polycrystalline
ing and the changing density of state from a 2D into a 3D SnSe can further improved since its ZT value is still much
lead to a higher thermoelectric performance. Subsequently, lower than that of a single-crystal SnSe. For polycrystal-
by converting them into the well-quantum, the highest ZT line SnSe, the thermal conductivity remains higher than its
value of bulk B ­ i2Te3 was improved 13 times. This result theoretical calculation value and its electrical conductivity
confirms the validity of the theory that the reduction in the is lower than a single-crystal SnSe due to the existing grain
dimensionality is helpful to enhance the energy conversion boundaries [111]. Achieving an ultrahigh ZT value for the
efficiency of these materials [97]. Fei and Cheng [98, 99] polycrystalline comparable to its single-crystal counterpart
reported a bismuth monolayer showing very promising ther- is still a challenge, and more experimental and theoretical
moelectric properties. work needs to be done in the next years.
As a typical compound belonging to the group IVA–VIA,
tin selenide (SnSe) has been widely studied due to its out-
standing electronic and photonic properties. SnSe exhibits 2.4 Black Phosphorus
potential applications in many fields such as in energy stor-
age and conversion devices and novel optoelectronic devices A monolayer phosphorene and a few-layer phosphorene
[92, 100–102] SnSe exhibits a layered orthorhombic struc- have been successfully exfoliated from bulk BP in 2014 and
ture and belongs to the Pnma space group at room tempera- have attracted a tremendous research interest in the past few
ture. Its structure can be derived from a three-dimensional years [28, 112, 113]. As a novel elementary 2D material, the
distortion of a rock-salt structure. Normally, the Sn and Se few-layer BP has gained tremendous attention in theoreti-
atoms are arranged in double layers with two planes consist- cal and experimental investigations [114–119]. Due to its
ing of zigzag Sn–Se chains along the a-axis. unique crystal structure and in-plane anisotropic properties,
As a thermoelectric material, the thermoelectric proper- BP has been widely studied in various fields including in
ties of SnSe are limited by its poor electrical conductivity at the development of photodetectors [116, 120, 121], cancer
room temperature. However, Zhao et al. reported a remark- therapies [115, 122, 123], supercapacitors [124], field-effect
ably high ZT value of 2.6 (at 923 K) and of 2.2 (at 773 K) transistors (FETs) [125, 126], batteries [127, 128], and ther-
in p-type and n-type single-crystal SnSe, respectively [33, moelectric devices [39, 98, 129–133].
103]. These results triggered the researchers in performing Moreover, BP has also been reported as a prospective
further studies on the thermoelectric properties of SnSe and materials for the production of thermoelectric devices
its alloys. According to Zhao’s study, such excellent thermo- due to its large Seebeck coefficient (335 μV K−1 at room
electric performances originate from the ultralow thermal temperature) [130], high carrier mobility (1000 cm 2
conductivity when the SnSe transfers into a high-temper- (Vs)−1 at room temperature) [28], and moderate band gap
ature phase at T >973 K. Inspired by the ultralow thermal (0.3–2.0 eV) [28, 112, 130]. According to the experimen-
conductivity and by the excellent electrical properties, SnSe tal results, bulk BP displays a high Seebeck coefficient
and its alloys have attracted a significant attention in recent of 335 μV K −1 and the few-layer BP show an increased
years [104]. Despite the excellent thermoelectric properties Seebeck coefficient up to 510 μV K−1 [130, 134]. Due
obtained for the SnSe single crystals, their complex crys- to its puckered structure, the electrical conductivity, the
tal growth conditions and high production costs limit their Seebeck coefficient, and the thermal conductivity of BP
practical applications [105]. Therefore, scientists focused on exhibit a strongly in-plane anisotropic behavior. This char-
the development of high-performance polycrystalline SnSe. acteristic has been proved theoretically and experimentally
Via systematic optimization methods, such as texturing, dop- in various kinds of BP materials including few-layer BP,
ing, and alloying, a significant enhancement of the ZT value thin-film BP, and bulk BP [135–140]. Recently, a number
of polycrystalline SnSe materials was achieved during the of theoretical simulation results have been published and
last several years [106–108]. Recently, the thermoelectric predicted that the few-layer BP is an appealing materials

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 7 of 40 36

with outstanding thermoelectric properties. As shown investigated the thermoelectric properties of the Sb-doped
in Fig. 3a, b, the Seebeck coefficient and the electrical few-layer BP, and their calculation indicates that the high-
conductivity were calculated by using the first-principles est ZT value measures almost 6.0 for P ­ 0.75Sb0.25. As shown
calculations and the Boltzmann transport theory. These in Fig. 3, the anisotropy of the electrical conductivity cor-
results are presented as a function of the carrier concen- responds to the opposite of its thermal conductivity, which
tration at 300 K [132]. As predicted, a peak ZT value makes the study of BP for thermoelectric more challenging
of 1.1 was obtained with an electron concentration of [39]. Although the theoretical results have predicted that
1.5 × 10 20 cm−3. The electrical conductivity of the few- BP, the few-layer BP, and bulk BP exhibit a huge potential
layer BP along the zigzag direction is much lower than as excellent thermoelectric materials, only a few experi-
along the armchair direction. The Seebeck coefficient mental results were reported. A larger experimental efforts
almost maintains an identical level along all the direc- need to be done to promote layered BP as a potential can-
tions. The thermal conductivities of the few-layer BP with didate for the production of thermoelectric devices.
different thicknesses are shown in Fig. 3c, d. It can be
concluded that the thermal conductivity along the zigzag 2.5 MXene
direction is higher than that along the armchair direction.
Moreover, the ZT value can be further enhanced by doping As a newly developed group of 2D materials consisting
the few-layer BP with a proper element. Zhang et al. [132] of transition metal carbides and nitrides, MXenes exhibit

(a) (b) 20
200 300K-x 300K-x
300K-y 300K-y
300K-z 15 300K-z
100
σ (106 S m−1)
S (µV K−1)

0 10

−100
5

−200
0
−1.0×1021 −0.5×1021 0.5×1021 1.0×1021 −1.0×1021 −0.5×1021 0.5×1021 1.0×1021
Carrier concentration (cm−3) Carrier concentration (cm−3)
(c) 104 (d) 104
Bulk Bulk Monolayer
Monolayer 274 nm 39.2 nm
55.6 nm 274 nm 39.2 nm
55.6 nm 274 nm 39.2 nm
55.6 nm 145 nm 170 nm
103 170 nm 103 145 nm 170 nm (Lee)
κ (W m−1 K−1)

κ (W m−1 K−1)

170 nm (Lee) 145 nm

102 102

101 101
0 100 200 300 0 100 200 300
T (K) T (K)

Fig. 3  a Calculated Seebeck coefficient and b electrical conductivity of a few-layer black phosphorus at T = 300 K. Reproduced with permission
from Ref. [132]. Copyright 2016, Royal Society of Chemistry. Measured thermal conductivity of black phosphorus depending on their thickness
and temperature along different directions: c zigzag direction, d armchair direction. The dashed lines and the solid lines correspond to the calcu-
lation results for the defect-free black phosphorus and the black phosphorus with additional vacancy point defects, respectively. Reproduced with
permission from Ref. [135]. Copyright 2017, Wiley–VCH

13
36 Page 8 of 40 Nano-Micro Lett. (2020) 12:36

either metallic or semiconducting properties depending their thermoelectric properties [147]. For instance, the
on its surface functionalization [141]. MXenes can be pre- ­Mo2TiC2Tx film exhibits the highest power factor (about
pared by exfoliating the MAX phases into 2D nanosheets 309 μW mK−2 at 800 K) among these samples. Although
via selective etching of “A” layers by using appropriate a high thermoelectric performance for MXene has been
hydrofluoric acids [29, 141–145]. These materials are theoretically predicted [141, 146–148], more experimental
defined as M ­ n+1AXn, where n = 1, 2, or 3, “M” corresponds results have to be performed.
to an early transition metal (Sc, Ti, V, Cr, Zr, Nb, Mo, Hf,
Ta), “A” is an element from groups 13–16 in the periodic
3 Thermoelectric Materials Based on 2D
table (Al, Si, P, S, Ga, Ge, As, In, Sn, Tl, Pb), and “X” is
Materials
carbon and/or nitrogen. Due to its excellent thermal stabil-
ity in air, MXene has been studied as a high-temperature
Layered 2D materials have been widely employed as effi-
thermoelectric material. Moreover, Kumar et al. have pre-
cient thermoelectric materials in the last decades. In this
dicted that the functionalization of MXene by O, F, and
section, the 2D layer structure materials based on the ele-
OH groups can significantly affect its structural properties
ments belonging to the groups IV–VI and on TMDCs are
and electronic band structure, further enhancing its ther-
investigated. The previously reported results proved that
moelectric performance [146]. For instance, when S ­ cC2
bulk and monolayer materials exhibit extremely different
is functionalized with C, O, or OH, its band gap measures
thermoelectric properties [149]. In this section, the ther-
1.84 (indirect), 1.03 (indirect), and 0.44 eV (indirect),
moelectric properties of bulk and thin films based on 2D
respectively [146]. Such varied band gap structure leads
materials are discussed.
to different thermoelectric properties of the materials. The
calculation results show that the Seebeck coefficient of
­Sc2C(OH)2 measures only 372 μV K−1, while the Seebeck 3.1 Bulk Thermoelectric Materials
coefficient of ­Sc2CO2 and ­Sc2CF2 is above 1000 μV K−1
at room temperature [146]. Furthermore, the calculation Due to the limitations in materials synthesis techniques,
results show that these materials exhibit different thermal bulk thermoelectric materials are usually fabricated via a
conductivity. The lattice thermal conductivity of S ­ c2CO2, simple melting process or a ball milling process followed by
­Sc2CF2, and S ­ c2C(OH)2 is 59, 36, and 10 W mK−1, respec- a post-sintering process (such as spark plasma sintering or
tively. By using the Boltzmann transport theory and the hot press process). Although the materials exhibit a layer-by-
first-principles electronic structure calculations, Khazaei layer structure, the synthesis of these compounds via these
et al. [141] predicted the thermoelectric properties of more methods is not discussed in this review. With the devel-
than 35 kinds of different functionalized MXene monolay- opment of nanotechniques, a series of new methods have
ers and multilayers of the type ­M2C, where M=Sc, Ti, V, been developed to fabricate nanomaterials with a variety of
Zr, Nb, Mo, Hf, and Ta, and M ­ 2N, M=Ti, Zr, and Hf. The microstructures. Currently, it is possible to synthesize 2D
calculation results prove that the monolayer and multilayer compounds in large amounts to fabricate bulk thermoelectric
­Mo2C nanosheets exhibit a higher power factor than other materials. Since the grain boundary can scatter the phonons
functionalized MXenes samples. However, several positive and can lead to low a thermal conductivity, it may be useful
results show that MXene can achieve a higher thermoelec- to fabricate high-performance thermoelectric materials by
tric performance. According to the calculations, almost all decreasing the particle size of the nanostructure thermoelec-
the semiconducting MXene shows a Seebeck coefficient tric material. Recently, 2D metal chalcogenides (including
larger than 100 μV K−1 at 400 K and some of them (such the group IV–VI compounds and the TMDCs) have trig-
as ­M o 2CF 2, ­M o 2C(OH) 2, and ­M o 2CCl 2) exhibit a high gered a considerable attention in the field of thermoelectrics
electrical conductivity [141]. as they exhibit a high ZT value. Due to their anisotropic
The outstanding thermoelectric performance of MXenes crystal and electronic structures, these materials exhibit an
has also been proved by a series of experiments. Kim intrinsically low thermal conductivity, which makes them
et al. fabricated two kinds of Mo-based MXene ­(Mo2CTx, promising thermoelectric materials [17, 150].
­Mo2TiC2Tx, and M ­ o2Ti2C3Tx) flexible thin films and studied

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 9 of 40 36

Among the 2D metal chalcogenides thermoelectric lower than those of single-crystal ones. During the last
materials, SnSe seems to be promising commercially several years, numerous efforts have been done to fabri-
available thermoelectric material. Until now, the highest cate high-performance SnSe polycrystalline bulk thermo-
ZT value for both the p-type (2.6 at 923 K) and n-type electric materials. 2D SnSe samples with different mor-
(2.8 at 923 K) compounds was obtained from SnSe single phologies can be synthesized by using different methods.
crystals. This may be due to their layered structure, soft Figure 4a–c shows typical 2D SnSe nanosheet and nano-
chemical bonding, and lattice anharmonicity. However, plate morphologies [150–152]. For instance, Han et al.
the ZT value of polycrystalline SnSe bulk materials is developed a surfactant-free solution-based method for the

(a) (001) (b) (c)


3° (011)
13

(011)
100 nm

(011)
94°
(001)
(011)
(011)
20 nm 5 µm 5 µm

(d) (e) (f)

50 nm 50 nm
353K 423K

500 nm
100 nm 50 nm 10 nm
503K

(g)
Phonon

Scattering
site

Sn Se S
Phonon scattering Nanoscale Isoelectric atoms Introduction
boundaries as dopants of pores

Fig. 4  a TEM image of a SnSe nanoplate. Reproduced with permission from Ref. [151]. Copyright 2016, Wiley–VCH. b SEM image of the
SnSe nanomaterials. Reproduced with permission from Ref. [152]. Copyright 2019, Wiley–VCH. c SEM image of the S ­ nSe0.9Te0.1 nanoplates.
The inset shows the layer thickness. Reproduced with permission from Ref. [154]. Copyright 2017, Royal Society of Chemistry. d TEM image
of the SnSe nanosheets. e SEM image of the S ­ n0.94Bi0.06Se nanosheets. Reproduced with permission from Ref. [150]. Copyright 2018, Ameri-
can Chemical Society. f Low-magnification FE-TEM images of the porous S ­ nSe0.8S0.2 NSs treated at the reaction temperatures of 353, 423,
and 503 K and high-magnification FE-TEM image of the sample in the panel. g Schematic diagram of the phonon scattering mechanism of the
­SnSe0.8S0.2 NSs. Reproduced with permission from Ref. [153]. Copyright 2017, American Chemical Society

13
36 Page 10 of 40 Nano-Micro Lett. (2020) 12:36

synthesis of single-phase SnSe nanoplates. Their power range are ­Bi2Te3-based alloys, which are also layered materi-
factor measured perpendicularly to the hot-pressing direc- als. Until now, the optimized ZT value of these compounds
tion reaches 0.4 mW mK−2 at 550 K [151]. Rongione et al. measure around 1.0. The highest ZT value for the p-type and
[152] fabricated a series of SnSe nanosheets and obtained n-type ­Bi2Te3 alloys is obtained in the case of B ­ i0.5Te1.5Se3
an ultralow thermal conductivity of 0.09 W m−1 K−1. Such ­(ZTmax = 1.2) and ­Bi2Te2.7Se0.3 ­(ZTmax = 0.9) [17, 160]. Both
value mainly originates from the large thermal boundary these samples are bulk materials. Recently, ­Bi2Te3-based
resistance of the materials due to the strong phonon scat- nanosheets have been widely reported in the fabrication of
tering near the interfaces between two SnSe nanosheets. bulk ­Bi2Te3-based thermoelectric materials. As shown in
In order to further improve the ZT value of SnSe bulk, Fig. 5a, Son et al. synthesized an ultrathin ­Bi2Te3 nanoplate
Bi-, Te-, and S- doped SnSe nanosheets were synthesized with a thickness of about 1 nm via a simple solution process
by using a large variety of methods [150, 153–155]. The [161]. The ­Bi2Te3 bulk was prepared by sintering ­Bi2Te3
SEM morphology of the doped SnSe samples is shown in nanoplates via spark plasma sintering, and the maximum
Fig. 4d–f. Chandra et al. synthesized a 2D ultrathin n-type ZT value obtained was 0.62 at 400 K. Figure 5b, c shows
Bi-doped SnSe nanosheet via a simple low-temperature the TEM images of the B ­ i2Se3@Bi2Te3 heterostructure
solvothermal method [150]. The thickness of the SnSe nanoplates and of the ­Bi2Se3@Bi2Te3@Bi2Se3@Bi2Te3
nanosheet measures about 1–3 nm. Due to the presence multishell nanoplates, which were scalable synthesized via
of the nanoscale grain boundaries and the layered aniso- a solution epitaxial growth process [162]. The thickness of
tropic structure, the heat-carrying phonons strongly scat- the nanoplate is in the 5–20 nm range. Via the simultaneous
ter. This leads to an ultralow lattice thermal conductivity modulation of the electronic and thermal transport in the
of 0.3 W mK−1 in the range of 300–720 K. Ju et al. fab- presence of highly dense grain and phase boundaries, the
ricated a porous S ­ nSe1−xSx nanosheet, and the details of peak ZT value measures 0.71 and it was obtained at 450 K
this structure are shown in Fig. 4g [153]. A reduction in for via the bulk sintering of the B­ i2Se3@Bi2Te3 nanoplates.
the thermal conductivity and an improved ZT value were Hong et al. synthesized a n-type ­Bi2Te3−xSex nanoplate by
obtained. Such enhanced ZT value is mostly due to the using the microwave-assisted surfactant-free solvothermal
substitution of the S atoms into SnSe, which induces the method. The TEM images of the nanoplate are shown in
scattering of the phonons and several atomic disorders and Fig. 5d, e [163]. The schematic diagram of the phonon scat-
nanosized boundaries. The mechanism of phonon scat- tering is shown in Fig. 5f, g. The grain boundaries, the point
tering in porous ­SnSe0.8S0.2-based materials is illustrated defects, and the dislocations may lead to the reduction in the
by the simple schematic diagram in Fig. 4g. As a result, lattice thermal conductivity. The experimental results prove
the high ZT value of the bulk based on porous ­SnSe0.8S0.2 these predictions. In this case, a relatively high ZT value of
nanosheets reaches 0.12 at 310 K. The substitution of the S 1.23 at 480 K for the n-type ­Bi2Te2.7Se0.3 nanostructures was
atoms into SnSe and the fabrication of the ­SnSe1−xSx NSs obtained from the sintered pellets. Since the nanostructure
reduce the thermal conductivity by introducing phonon was employed as a raw material to obtain the sinter pellets,
scattering in the atomic disorders and nanoscale bounda- a high amount of grain boundaries was maintained and sub-
ries, leading to a higher ZT. stantially reduced the thermal conductivity of the sample
Similarly to SnSe, S­ nSe2 is also a layered structure ther- [163].
moelectric material and exhibits promising thermoelectric In the case of the bulk layered thermoelectric materials,
performance [156–159]. Saha et al. fabricated ultrathin the layered structure induces strong anisotropic thermo-
Cl-doped ­SnSe2 nanosheets with the thickness of 3–5 nm electric properties along three different directions. More
via a simple low-temperature solvothermal process [159]. importantly, the grain boundaries, which were introduced
Similarly to SnSe, the hot-pressed ­SnSe2 pellet achieves by the nanostructuring, can substantially reduce the ther-
an ultralow thermal conductivity of 0.67 W/mK due to its mal conductivity when compared to the pellet structure.
effective phonon scattering at the grain boundary, which These samples were, in fact, synthesized by using ball
is induced by its anisotropic layered structure. milling and other melting methods. The 2D nanostruc-
During the last decades, the most efficient single-phase ture materials employed to fabricate bulk thermoelectric
thermoelectric materials used in the near room temperature materials further enhance their ZT value.

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 11 of 40 36

(a) (b) (c)

50 nm 200 nm 500 nm

(d) (e)

0.22 nm

500 nm 1 nm

(f) Reduction in κl
(g) (h)
due to grain boudndaries Phonons 1.2
0.05 This study
(II) Reduction in κl
(I) due to point defects
κs (pW sm−1 K−1)

0.04
Heat flow

(III) 1.0
ZT

0.03
Reduction in κl
due to dislocations 0.8
0.02
U+E Reported ZT for
0.01 U+E+B
U+E+B+PD 0.6 Bi2Te3 systems
Lattice disorder Dislocation
U+E+B+PD+DC+DS
0.00 Grain boundary
300 350 400 450 500 550
0.0 0.2 0.4 0.6 0.8 1.0 T (K)
ω/ωD

Fig. 5  a TEM image of the B ­ i2Te3 nanoplate, the inset shows the lateral view of the stacked plates). Reproduced with permission from Ref.
[161]. Copyright 2012, American Chemical Society. b Bright-field TEM image of the B ­ i2Se3@Bi2Te3@Bi2Se3 double shell nanoplates. c TEM
image of the ­Bi2Se3@Bi2Te3@Bi2Se3@Bi2Te3 multishell nanoplates. Reproduced with permission from Ref. [162]. Copyright 2015, American
Chemical Society. d TEM image, and e HRTEM image of the B ­ i2Te2.7Se0.3 nanoplate. f Calculated room-temperature κs value for the phonons
­ i2Te2.7Se0.3 pellet. g Schematic diagram illustrating the scattering of wide-frequency phonons by various sources. h Carriers
scattering of the B
mobility and ZT value of the B ­ i2Te2.7Se0.3 pellet. Reproduced with permission from Ref. [163]. Copyright 2016, American Chemical Society

3.2 Thin‑Film Thermoelectric Materials polymer-based thin-film thermoelectric materials, the more


recent research efforts have been focused on thin-film ther-
Thin-film thermoelectric materials have attracted a moelectric materials fabricated by using nanostructures.
large attention due to their potential application as flex- Such newly developed 2D materials, such as graphene,
ible and wearable devices. Besides the investigations on BP, TMDCs, and group IV–VI compounds, can be easily

13
36 Page 12 of 40 Nano-Micro Lett. (2020) 12:36

synthesized and manufactured into thin films via various exhibits an outstanding stability. However, the thermoelectric
methods. As previously mentioned, the quantum size effect performance of ­MoS2 can be further enhanced by introduc-
induced in the 2D nanostructure materials can increase the ing several modifications. For instance, when the material is
Seebeck coefficient. Moreover, the phonon scattering at the decorated with Au nanoparticles, the power factor of ­MoS2
interfaces may lead to the a decrease in the thermal con- increases to about 166.3 μW mK−2 [182].
ductivity. The methods used to fabricate thin-film thermo- TiS 2 is another widely studied 2D thermoelectric
electric materials include vacuum evaporation, pulsed laser materials [13, 183–186]. As shown in Fig. 8a, Wan
deposition, molecular beam epitaxy, magnetron sputtering, et al. [186] introduced a novel electrochemical intercala-
drop casting, spin coating, and inkjet printing [164–166]. tion and solvent exchange process to synthesize a n-type
Due to its unique electronic and optical properties, 2D ­TiS2[(hexylammonium) x(H2O)y(DMSO)z] hybrid super-
BP has been widely studied in many research fields [114, lattice. The organic cations were distributed onto the two
120, 122–124, 167–174]. Furthermore, it has been reported sides of each T
­ iS2 layer. As shown in Fig. 8c–f, an electrical
that it exhibits an ultrahigh Seebeck coefficient in the order conductivity of 790 S cm−1 and a very high power factor
of 10 mV K−1, which makes it a promising thermoelectric of 0.45 mW mK−1 were obtained in the case of the hybrid
materials. Flores et al. studied the thermoelectric properties superlattice of T­ iS2/[(hexylammonium)x(H2O)y(DMSO)z].
of bulk BP and found that its Seebeck coefficient measures Moreover, its in-plane lattice thermal conductivity measures
about 335 μV K−1 at room temperature [130]. These results about 0.12 W mK−1. This value is two orders of magnitude
are lower than the theoretical predict data. Due to the poor lower than that of single-layer and bulk ­TiS2. A high ZT
stability of 2D BP, it is difficult to fabricate thermoelectric value of 0.28 at 373 K was reported due to the high power
devices based on pristine BP. An et al. [129] decorated the factor and low thermal conductivity of the superlattice. This
BP surface with Au nanoparticles to enhance its thermo- material exhibits an enormous potential for its application
electric properties and stability. The characterization of such in wearable electronics devices. Tian et al. [184] fabricated
structure is shown in Fig. 6a–c and its thermoelectric prop- a ­TiS2/organic superlattice and tried to manufacture a P–N
erties in Fig. 6d, e. The highest value of the Seebeck coef- prototype device. The devices with 5 P–N legs can gener-
ficient of this sample reaches 498 μV K−1 and the highest ate an output voltage of 33 mV with a maximum power
power factor is 68.5 μW mK−2, which is about 2740 times density of 2.5 W m−2. The thermoelectric performance of
higher than that of pristine BP. ­TiS2 can also be enhanced via a chemical welding process.
Recently, 2D TMDCs have collected a wide attention due As shown in Fig. 8g, i, when the T ­ iS2 nanosheets bridge
to their special properties and are considered to be the next with the multivalent cationic metal, ­Al3+, during the film
generation of high-performance thermoelectric materials [70, deposition process, the Seebeck coefficient and the electrical
74, 90, 175–180]. The measured Seebeck coefficient of sin- conductivity can be improved simultaneously, thus leading
gle-layer ­MoS2 can measure over 30 mV K−1, providing an to an enhanced power factor [183].
ideal candidate material for high-performance thermoelectric
devices. Huang et al. studied the thermoelectric properties of
metallic 1T-phase ­MoS2 nanosheets. These ­MoS2 nanosheets 4 2D Materials as Composite Filler
were synthesized via a chemically exfoliated process, and
the thin films were fabricated via a simple vacuum-assisted Composite engineering has been considered the simplest and
filtration process, as shown in Fig. 7a–d [181]. The schematic most efficient way to enhance the performance of thermo-
diagram of the crystal structure and the band structure of electric materials since the formative crystallite boundaries
the ­MoS2 monolayer were calculated. By studying the band scatter phonons effectively and decrease the thermal con-
structure of the 2H and of the 1T M ­ oS2 monolayers, the high ductivity of the material. Moreover, the transport properties
thermoelectric performance of the ­MoS2 film can be attrib- can be optimized if the filler is distributed in the matrix with
uted to the metallic characteristic and to the conductivity a proper amount. In addition, it is possible to decouple the
nature of the 1T phase M ­ oS2. As shown in Fig. 7e, g, the three parameters and to enhance the thermoelectric perfor-
power factor of the M ­ oS2 film reaches 73.1 μW m ­ K−2 and mance of the materials.

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 13 of 40 36

(a) (b)

ZZ AC

AC

ZZ 2 nm

(c)

50 nm
2 nm
2.3 Å

(d) (e)
80 800 100
Electrical conductivity (S cm−1)

Seebeck coefficient (µV K−1)

Power factor (µW m−1 K−2)

600 80
60

60
400
40
Pristine BP

40
200
20
20
0
0 0
−200
0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08 0.10
Content of Au NP (molar ratio) Content of Au NP (molar ratio)

Fig. 6  a Low-magnitude TEM image of the black phosphorus nanosheet decorated with Au nanoparticles. b Lattice image of the exfoliated
black phosphorus nanosheet (inset illustration showing the corresponding crystal structure). c High magnitude HRTEM image of the black phos-
phorus nanosheet decorated with Au nanoparticles. d In-plane Seebeck coefficient, electrical conductivity, and e their corresponding in-plane
power factor of the black phosphorus decorated with Au nanoparticles. Reproduced with permission from Ref. [129]. Copyright 2018, Wiley–
VCH

13
36 Page 14 of 40 Nano-Micro Lett. (2020) 12:36

(a) (b) (c) (d)

300 nm

500 nm 500 nm

(e) (f) (g)


90 80

Electrical conductivity (S m−1)


10×103

Power factor [µW (mK2)−1]


70
80
60
Seebeck (µV K−1)

9×103
70 50
8×103
40
60 30
7×103 Nitrogen
Oxygen 20
50 6×103 40% RH
10
40 5×103 0
0 100 200 300 400 0 100 200 300 400 0 100 200 300 400
Time (min) Time (min) Time (min)

Fig. 7  MoS2 nanosheets restacked film a on a cellulose ester membrane and b on a PET substrate. c TEM image of a single exfoliated ­MoS2
nanosheet and d cross-sectional SEM image of the M ­ oS2 nanosheets restacked film. e Dynamic Seebeck coefficient, f electrical conductivity, and
g power factor of the ­MoS2 nanosheets restacked film in a nitrogen, oxygen and 40% relative humidity atmosphere. Reproduced with permission
from Ref. [181]. Copyright 2016, Elsevier

4.1 2D Materials in Inorganic Bulk Thermoelectric the carrier and the phonon-transport characteristics can be
Materials modulated. Besides, the addition of a 2D material introduces
a heterojunction interface, which can scatter the carrier and
The fabrication of hybrid composites is one of the most decrease its carrier mobility, thus leading to an enhancement
important methods to improve the thermoelectric per- in the thermoelectric performance of the compound.
formance of bulk thermoelectric materials, in which the Graphene has been widely investigated in many fields due
nanomaterials are either located at the grain boundary or to its excellent properties. Its high Seebeck coefficient (about
homogeneously dispersed in the matrix. The matrix materi- 30 mV K−1), ultrahigh electrical conductivity (> 14 S c­ m−1),
als form a continuous conductive network to maintain the large charge-carrier mobility (> 2 × 105 cm2 (Vs) −1), and
same electrical conductivity within the matrix. Moreover, extraordinary electronic transport properties make it an ideal
the dispersed second phase present in the matrix can scat- candidate for the fabrication of high-performance thermo-
ter the phonons. The addition of a 2D material introduces electric materials. In the past years, graphene was chosen
a heterojunction interface, which can scatter the carrier and as a composite filler to fabricate high-performance bulk
decrease its mobility, thus leading to a further enhancement thermoelectric composites. In 2015, Lin et al. fabricated a
of the thermoelectric performance. By adding a nanofiller graphene/lanthanum strontium titanium oxide (LSTO) com-
added into the matrix, the relation among the electrical posite [187]. Upon the addition of a small amount of gra-
conductivity, the Seebeck coefficient, and the thermal con- phene, the thermal operation window of LSTO decreases to
ductivity can be decoupled by modulating the electron and room temperature. As shown in Fig. 9, the highest ZT value
phonon-transport characteristics. is about 0.42 at room temperature and 0.36 at 750 °C was
In order to further enhance the thermoelectric properties obtained when a quantity of 0.6% of graphene was added
of conventional thermoelectric materials, several kinds of into the samples. Chen et al. successfully modulated the
2D materials have been added into the bulk to fabricate dif- carrier concentrations, the electrical conductivity, and the
ferent composites. Upon the addition of 2D materials filler, thermal conductivity by adding reduced graphene oxide

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 15 of 40 36

(a) (b) (c)

Electrical conductivity (S cm−1)


800
TiS 2 700

600

500 TiS2 single crystal


TiS2[(HA)0.08(H2O)0.22(DMSO)0.03]
400

300

5 nm 1 nm 200
300 320 340 360 380
Temperature (K)
Seebeck coefficient (µV K−1)

−200 10
(d) (e) 0.30 (f)
−180
Thermal conductivity

Figure of merit ZT
0.25
−160
(W m−1 K−1)
0.20
−140
TiS2 single crystal TiS2 single crystal 0.15 TiS2 single crystal
−120 TiS2[(HA)0.08(H2O)0.22(DMSO)0.03] TiS2[(HA)0.08(H2O)0.22(DMSO)0.03]
TiS2[(HA)0.08(H2O)0.22(DMSO)0.03] 0.10
−100 1
0.05
−80
0.00
300 320 340 360 380 300 320 340 360 380 300 320 340 360 380
Temperature (K) Temperature (K) Temperature (K)
0 20×104 300
(g) (h) (i)
−10 18×104
250
16×104

α2σ [µW (mK2)−1]


−20
200
14×104
α (µV K−1)

σ (S m−1)

−30
12×104 150
−40
10×104
100
−50 8×104
−60 50
6×104
−70 4×104 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300 0 50 100 150 200 250 300
Temperature (K) Temperature (K) Temperature (K)

Fig. 8  a, b HAADF-STEM image of the T ­ iS2[(HA)x(H2O)y(DMSO)z] hybrid superlattice, c electrical conductivity, d Seebeck coefficient, e
thermal conductivity, and f ZT of the ­TiS2[(HA)x(H2O)y(DMSO)z] hybrid superlattice. Reproduced with permission from Ref. [186]. Copyright
2015, Springer Nature. g Seebeck coefficient, h electrical conductivity, and i power factor of the ­TiS2 nanosheet assembled thin film. Repro-
duced with permission from Ref. [183]. Copyright 2017, American Chemical Society

into the Al-doped ZnO [188]. Since the carrier concentra- the ­Bi2Te3 density at the interface increases. Moreover, the
tion and the electrical conductivity of graphene oxide are high density of the heterojunction interface may enhance
much larger than those of ZnO, the nanocomposite exhibits carrier scattering and decrease its mobility, thus leading to
an enhanced electrical conductivity when compared to pris- a decrease in the electrical conductivity and in the thermal
tine Al-doped ZnO. More importantly, although the thermal conductivity of the compound. In addition, the size of the
conductivity of graphene oxide is much higher than that of dopant shows a pronounced effect on the carrier and pho-
ZnO and Al-doped ZnO, the total thermal conductivity and non-transport characteristics. For example, as reported in
the lattice thermal conductivity show an obvious decrease, ­ i2Te3/graphene composite exhibits a high-
Li’s paper, the B
upon the addition of graphene. These results are shown in est ZT value (~ 0.55) at 425 K as the size of the graphene
Fig. 9d. Li et al. [189] found that by adjusting the density reaches 20 nm, as shown in Fig. 9e [189]. The same result
and the dispersion manner of graphene in the bulk matrix, was also reported for other bulk thermoelectric material sys-
the thermoelectric performance of the composite could be tems, such as PbTe/graphene composite [190], ­Cu2SnSe3/
further enhanced. Upon an increase in the graphene amount, graphene [191], ­CuInTe2/graphene [192], ­CoSb3/graphene

13
36 Page 16 of 40 Nano-Micro Lett. (2020) 12:36

(c) 0.4
(a) (b)
0.3

ZT@750 °C
0.2

0.1

0.0
0.0 0.2 0.4 0.6 0.8 1.0
Concentration (wt%)
0.4
0.3

ZT@RT
0.2
0.1
20 µm 10 µm 0.0
0.0 0.2 0.4 0.6 0.8 1.0
Concentration (wt%)
20 (d) 20 0.5
(e)
Lattic thermal conductivity (W mK−1)

18 16
κ (W mK−1)

16
12 0.4
14
8
12
4
10 0.3
8 0 200 400 600 800 ZT
Temperature (°C)
6
0.2
4
2
0 0.1
0 200 400 600 800 300 325 350 375 400 425 450 475
Temperature (°C) Temperature (K)

Fig. 9  EBSD analysis of lanthanum strontium titanium oxide sample, and graphene/lanthanum strontium titanium oxide. a Band contrast image
of a pure lanthanum strontium titanium oxide sample; b band contrast image of 0.1 wt % graphene/lanthanum strontium titanium oxide. c ZT
at room temperature and at 750 °C as a function of the graphene concentration. Reproduced with permission from Ref. [187]. Copyright 2015,
American Chemical Society. d Lattice thermal conductivity and (inset) total thermal conductivity of the Al-doped ZnO and AZO/rGO samples.
Reproduced with permission from Ref. [188]. Copyright 2015, American Chemical Society. e Thermoelectric properties of the ­Bi2Te3/GQDs
samples with different GQD contents. Reproduced with permission from Ref. [189]. Copyright 2017, American Chemical Society

[193], SnSe/MoS2/graphene [194], and ­Bi0.5Sb1.5Te3/gra- d. For the ­MoSe2/SnSe composite, the carrier concentration is
phene [195]. about one order of magnitude higher than that of pure SnSe.
Besides graphene, TMDCs have also been widely used as Moreover, the carrier mobility of the composite shows an
efficient composite fillers. In 2017, Li et al. [196] partially impressive enhancement. This phenomenon may be related to
decoupled the electrical conductivity, the Seebeck coefficient, the carrier scattering, due to the energy barrier introduced at the
and the thermal conductivity by adding 2D ­SnS2 nanosheets heterojunction interface.
into a ­Bi2Te2.7Se0.3 matrix. As shown in Fig. 10a, the S ­ nS2
nanosheets homogenously assemble onto ­Bi2Te2.7Se0.3 grain
boundaries and formed a nanoscale heterojunction interface. 4.2 2D Materials in Polymer Thermoelectric Materials
A ZT of 0.93 at 450 K was measured. Such high value was
attributed to the optimized carrier and phonon-transport char- As a potential high-performance thermoelectric material,
acteristics induced by the ­SnS2/Bi2Te2.7Se0.3 interface. Huang conductive polymers exhibit unique advantages such as
et al. [197] reported a high ZT value for a polycrystalline SnSe a low thermal conductivity, flexibility, lightweight, and
sample via the fabrication of a M­ oSe2/SnSe composite. Upon efficient solution processability [9, 198–202]. However,
the addition of 2D ­MoSe2 into the SnSe matrix, both the carrier more work needs to be done to further improve their ther-
concentration and the carrier mobility are significantly improved moelectric performance to use them in flexible and wear-
when compared to pure polycrystal SnSe, as shown in Fig. 10c, able thermoelectric devices. The power factor for typical

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 17 of 40 36

(a) (b)
electrons

BTS/SS interface
phonons

~4 nm
10 nm BTS/SnS2 interface

1000 70
4 (c) SnSe+x%MoSe2 (d) SnSe+x%MoSe2
2 4 60
100 x=0
10 2 x = 1.5
300K 50

μH [cm−1 (V·s)−1]
100

μH [cm2 (V·s)−1]
nH (1017 cm−3)

nH (1017 cm−3)
4 10
2
40
4

1 x=0
2 1 30
x = 1.5
4
10
20
2 4 0.1
10
0.1 2

1 0.01 0
0.0 0.5 1.0 1.5 2.0 2.5 300 400 500 600 700 800
x (%) Temperature (K)

Fig. 10  a HRTEM image of the B ­ i2Te2.7Se0.3/SnS2 bulk; b mechanisms that contribute to the high ZT value of the B­ i2Te2.7Se0.3/SnS2 nano-
composites. Reproduced with permission from Ref. [196]. Copyright 2017, Elsevier. c Carrier concentration and mobility of the SnSe/MoSe2
­ oSe2 content. d Temperature dependence of carrier concentration and of the carrier mobility of SnSe/
composites at 300 K as a function of the M
MoSe2. Reproduced with permission from Ref. [197]. Copyright 2017, IOP Publishing

conductive polymer thermoelectric materials is in the 1­ 0−4 206]. The simulation results indicate that the Seebeck coef-
to ­102 μW mK−2 range at room temperature. This value is ficient and the electrical conductivity cannot exceed those
about 3 orders of magnitude lower than those of traditional of their individual components [207, 208]. However, recent
inorganic thermoelectric materials [199, 203, 204]. Accord- advances in the theory have proven that the introduction of
ing to the theoretical and experimental achievement, the fab- an energy filtering effect at the interface can overcome this
rication of composite blends is an efficient way to improve limitation and can be experimentally proven [206, 207, 209].
the thermoelectric performance of conductive polymers. 2D materials with a high Seebeck coefficient have been
In the last decade, a number of investigations have been widely employed as efficient fillers to enhance the ther-
reported to improve the thermoelectric performance of con- moelectric performance of polymer blends. 2D materi-
ductive polymers by adding a nanostructure filler. Polymer als were added into the polymer blends to increase their
blends fabricated by employing highly electrical conduc- Seebeck coefficient. For instance, the group IV metal
tive constituents and high-Seebeck-coefficient constituents chalcogenides (e.g., SnSe, SnS) can be exfoliated into 2D
show an improvement in both their Seebeck coefficient and materials. The crystal structures of SnSe along different
electrical conductivity. As previously discussed, 2D materi- directions at 300 K are shown in Fig. 11a. The strong
als possess excellent electrical and mechanical properties, Sn–Se bonds along the b–c planes are connected with the
which are suitable to fabricate high-performance composite weak Sn–Se bonds along the a-axis of SnSe, indicating
thermoelectric materials. In a simple 2D materials/polymer that bulk SnSe can be easily exfoliated into 2D ultrathin
composite system, its thermoelectric performance of the materials along the a-direction. Ju et al. [205] prepared
composite can be evaluated based on either a serially or par- SnSe nanosheets via hydrothermal lithium-intercalation,
allel connected model, if the interfaces are neglected [205, which was then followed by an exfoliation process from

13
36 Page 18 of 40 Nano-Micro Lett. (2020) 12:36

(a)

c
a a
a b c b
Sn b c
Se

(b) (c) (d)

1 µm 100 nm 2 µm

0.5 1.0 0.40


(e) (f) (g)
Thermal conductivity [W (m·K)−1]

0.35
Power factor [mW (m·k2)−1]

0.4 0.8
0.30
Figure of merit, ZT

0.3 0.6 0.25


0.20
0.2 0.4 0.15
0.10
0.1 0.2
0.05

0.0 0.0 0.00


0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.0 0.1 0.2 0.3 0.4 0.5 0.6
Weight fraction of SnSe Weight fraction of SnSe Weight fraction of SnSe

Fig. 11  a Crystal structures of SnSe along the a-, b-, and c- axial directions. b SEM morphology and c TEM image of SnSe nanosheets. d
SEM of the SnSe/PEDOT:PSS composites with SnSe a content of 50%. e Power factor, f thermal conductivity, and g ZT value of the SnSe/
PEDOT:PSS composites. Reproduced with permission from Ref. [205]. Copyright 2016, American Chemical Society

the SnSe powders. During the intercalation process, eth- SnSe. The increase in the power factor to 386 μW mK−2 is
ylene glycol acts as both the solvent and the reducing induced by the substantial increases in the Seebeck coef-
agent. The morphology of the exfoliated SnSe nanosheets ficient when compared to the reduction in the electrical
is shown in Fig. 11b–d. Their thickness is about 3.4 nm. conductivity of the material. Other 2D group IV metal
The Seebeck coefficient of pure SnSe at room temperature chalcogenides have also been fabricated and added as
is higher than 520 μV K −1, whereas for PEDOT:PSS is fillers to enhance the thermoelectric performance of the
about 30 μV K−1. As the SnSe nanosheets are dispersed composites [210–213]. Ju et al. [212] coated the SnSeS
into the PEDOT:PSS solution, the measured Seebeck coef- nanosheet by polyaniline (PANI) and then used it as a
ficient increases with the increase in the weight fraction of filler to fabricate the composite. The PANI-coated SnSeS

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 19 of 40 36

(a) (b) (c) 200

PANI

SnSeS
nanosheet
150

Power factor (µW m−1 K−2)


Composite film

5 nm 100 µm
100

50

30 nm 0
250 300 350 400 450 500 550
Temperature (K)
π-π stacking
(d)
(e)
Pyrrole 50

Power factor (µW m−1 K−2) 40


FeCl3
in situ PPy PANi/GNs
Graphene nanosheets polymerization
30 PANi PPy/GNs/PANi
PPy/GNs
20
PPy/GNs composite

π-π stacking
hydrogen bonding PANi 10

0
Solution mixing
PPy/GNs/PANi composite 20 30 40 50 60 70 80 90
Temperature (°C)

Fig. 12  a TEM image of the S ­ nSe0.8S0.2 nanosheets, b SEM image of the PANI-coated S
­ nSe0.8S0.2 film and c power factor of the PANI-SnSeS
nanosheet/PVDF composite film with a PANI-SnSeS nanosheet-to-PVDF ratio of 2:1 as a function of temperature. Reproduced with permission
from Ref. [212]. Copyright 2018, American Chemical Society. d Schematic process of the polypyrrole/graphene/polyaniline ternary nanocom-
posite and e its power factor. Reproduced with permission from Ref. [220]. Copyright 2017, American Chemical Society

nanosheet added into polyvinylidene fluoride (PVDF) as a potential thermoelectric material in recent years due to
exhibits a maximum power factor of 134 μW mK −2 at their low thermal conductivity (0.1–1 W mK−1) and their
400 K, as shown in Fig. 12a. SnS has also been chosen as a large in-plane mobility (200–500 cm (Vs) −1). Recently, sev-
filler to improve the properties of polymer thermoelectric eral theoretical and experimental studies on the thermoelec-
materials. Recently, Cheng et al. [214] have fabricated a tric performance of TMDCs have been reported. Although
SnS/PEDOT:PSS composite and showed that its Seebeck the thermoelectric performance of the TMDCs-based bulk
coefficient increases upon the increase in its SnS content. materials is limited due to their poor electrical conduc-
In 2019, Ju et al. fabricated PANI-coated porous SnS tivity, TMDCs with their large Seebeck coefficient are an
nanosheets and characterized its thermoelectric proper- ideal composite filler to fabricate high-performance poly-
ties [214]. An outstanding ZT value of 0.078 at 450 K was mer blends. In 2010, Zhang et al. [215] incorporated both
obtained by adjusting the PANI coating layer. a n-type and a p-type ­Bi2Te3 into a PEDOT:PSS solution
Besides the group IV metal chalcogenides, TMDCs have and successfully fabricated both p-type and n-type polymer
also been widely studied as high-performance thermoelec- composite materials. However, by adjusting the morphol-
tric materials. TMDCs have gained considerable attention ogy of the nanostructure, the thermoelectric performances

13
36 Page 20 of 40 Nano-Micro Lett. (2020) 12:36

of these composites were further enhanced. Du et al. [216] the thermoelectric performance of the films [205, 211, 212,
fabricated a ­Bi2Te3 nanosheet/PEDOT:PSS thin-film com- 215–219].
posite via a simple coating process. With the addition of Moreover, the addition of a high-Seebeck-coefficient
­Bi2Te3 nanosheets, the Seebeck coefficient and the electri- component, high-electrical-conductivity component was
cal conductivity of the composite increase simultaneously. also employed to enhance the electrical properties of the
Generally, in this kind of composite materials, a 2D mate- hybrid composite, leading to an enhanced power factor.
rial filler is chosen to improve the Seebeck coefficient, thus However, 2D materials with a high electrical conductivity,
leading to a high power factor. In 2016, Jiang et al. [217] such as graphene and reduced graphene oxide, have also
fabricated a high-performance M ­ oS2/PEDOT:PSS thin film been widely studied. Due to their relatively low electrical
via a vacuum filtration process. By the addition of a small resistivity, this group of 2D materials is usually employed
amount of liquid-phase exfoliated ­MoS2 nanosheets into a to enhance the electrical conductivity of the composite. As
PEDOT:PSS solution, the thermoelectric properties of the shown in Fig. 12c, Wang et al. [220] fabricated a polypyr-
PEDOT:PSS-based thin film were enhanced significantly. role/graphene/polyaniline ternary nanocomposite via a
Several 2D nanostructures including nanosheet, nanopar- simple in situ polymerization process. Due to the ultrahigh
ticles, nanowire, and nanobarbell were reported to enhance electrical conductivity of graphene, this ternary composite

(a) (b)

few layers rGO

10 mm

[001]
Te lattice direction

5 nm
30 µm

(c) Constituents (d) Ternary hybrid


Te PEDOT:PSS rGO Te PEDOT:PSS rGO
Evac Evac Evac Evac

ΦTe ΦPEDOT:PSS ΦrGO Φb = 0.24 eV


= 4.95 eV = 4.71 eV = 4.40 eV
Φb = 0.31 eV
Ef
VB
CB LUMO Ef
Ef COLD holes
HOMO
scattering
HOT holes
Ef
VB flowing
Low evergy holes
High evergy holes
VB or HOMO level
Energy filtering at two junctions

Fig. 13  a Photographs and cross-sectional SEM images of the flexible rGO/PEDOT:PSS/Te hybrid paper. b HRTEM images of the rGO/
PEDOT:PSS/Te hybrid composite. c Energy diagram of the rGO/PEDOT:PSS/Te heterojunctions. d Energy filtering effects at two junctions.
Reproduced with permission from Ref. [208]. Copyright 2016, Wiley–VCH

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 21 of 40 36

exhibits at least two magnitude higher Power factors than behind their thermoelectric effect. For example, Kumar et al.
that of PANI and PPy. As shown in Fig. 13, Choi et al. [208] [149] simulated the thermoelectric properties of bulk and
fabricated a novel Graphene/PEDOT:PSS/Te composite. The monolayer ­MoSe2 and W ­ Se2 by using the first-principles cal-
electrical conductivity of such composite is about 15 times culations and the semiclassical Boltzmann transport theory.
higher than that of PEDOT:PSS/Te although the Seebeck The calculation results proved that the electrical conductiv-
coefficient is almost identical. The significant increase in the ity, the Seebeck coefficient, and the thermal conductivity
electrical conductivity of the ternary composite is ascribed of the monolayer materials are extremely different from the
to the carrier scattering at the double interface, as shown bulk ones. These results allow one to optimize the thermo-
in Fig. 13c, d. This work shows that graphene may be an electric properties based on the unit materials.
ideal composite filler to optimize the thermoelectric perfor- Decoupling the Seebeck coefficient, the electrical con-
mance of polymers. Inspired by these pioneer works, several ductivity, and the thermal conductivity is a challenging
investigations, including graphene/P3HT, rGO/PEDOT:PSS, problem to solve. However, the different mean free paths of
PANI/graphene and graphene/CNT, have reported the use electrons and phonons provide the possibility to decouple
of graphene or reduced graphene oxide into a conductive the electrical properties and the thermal properties, which
polymer [43, 59, 221–226]. are governed by the Wiedemann–Franz law [228]. In detail,
Besides their use in the enhancement of either the See- several kinds of low-dimensional nanostructure material sys-
beck coefficient or the electrical conductivity, 2D material- tems may enable high-speed transmittance of electrons by
based composites can be employed as electrodes to fabri- impeding the propagation of acoustic phonons. As a result,
cated high-performance flexible devices. Jiang et al. [227] these compounds exhibit a suppressed thermal conductiv-
prepared a graphene/polyethyleneglycol composite, which ity, whereas their electrical conductivity remains almost
was used for heat collection and transport. The presence identical [93, 228, 229]. When the size of the material is
of highly conductive graphene in this composite introduces small enough to influence its band structure, the profile of
several conductive pathways for heat transfer and acts as a the density of states (DOS) can evolve into sharp shapes at
highly thermal conductive reservoir of phase-change mate- the band edges due to the quantum confinement effect of
rials for thermal energy collection, storage, and release. these nanomaterials [228]. This phenomenon may increase
Moreover, this work opens a new door to fabricate novel the Seebeck coefficient, since this is strongly related to the
thermoelectric materials and to realize high-performance change rate of the DOS near the Fermi energy [93, 230].
flexible thermoelectric devices. The typical structure of the micro–nanodevices, which are
used to measure the thermoelectric performance of a single-
or multilayer 2D material, is shown in Fig. 14. Two main
5 Thermoelectric Properties of Single‑ micro-devices are currently used: a typical micro-device
or Few‑layer 2D Materials for the Seebeck coefficient and the electrical conductivity
measurements and a suspended micro-device to determine
In the past years, a significant effort has been made to the ZT value. The thermoelectric properties of nanostructure
improve the thermoelectric efficiency of the 2D materials. materials with different morphologies, including nanowires,
The most efficient ways to enhance their thermoelectric per- nanosheets, nanoplates, and single- or multilayer 2D materi-
formance is developing novel materials and novel nanostruc- als, can be measured via these micro-devices.
tures. As previously mentioned, 2D layered materials have In a typical platform, the micro-device is usually patterned
been widely investigated either by fabricating bulk/thin film onto a silicon substrate which is coated with an insulating
or by manufacturing hybrid composites as fillers. Moreo- ­SiO2 layer. As shown in Fig. 14, one or two heaters are
ver, studying the thermoelectric properties of single- or few- employed to build a temperature gradient through the nanosa-
layer materials via the fabrication of micro–nanodevices is mple. The samples are usually placed onto the substrate via a
another important field in the thermoelectric research envi- simple drop-casting process from a solution, which contains
ronment. The thermoelectric properties of the bulk and of a suspension. Then, the metal electrodes are deposited onto
individual single-layer materials may differ and this may the sample via an electron beam lithography process. The
provide a deeper understanding of the physical mechanism Au/Cr metal contact with the sample is fabricated and serves

13
36 Page 22 of 40 Nano-Micro Lett. (2020) 12:36

(a) (b)
C1 Th1

H1 Th2

C2

Si NWs H2

5 µm

Fig. 14  SEM images of a non-suspended thermoelectric micro-device platform and b suspended thermoelectric micro-device platform. Repro-
duced with permission from Ref. [235]. Copyright 2008, Springer Nature

simultaneously as both an electrode and a thermometer [231]. reduction of diameter of the sample. By using these micro-
However, for such micro-devices, since the electrodes and structure measurement platforms, the thermoelectric proper-
the sample are directly in contact with the substrate, only ties of many individual nanowires, nanosheets, quantum dot
the Seebeck coefficient and the electrical conductivity can superlattices, and thin films were investigated [227, 231, 233,
be measured. In order to evaluate the ZT value of the nano- 234, 236, 238–245]. Recently, the thermoelectric properties
structure 2D materials, a modification of this micro-device of single-layer and multilayer 2D materials have been studied
has been developed. As shown in Fig. 14b, the electrode and via these microstructure measurement platforms.
the micro-heaters are supported by five slender S ­ iNx beams As previously mentioned, graphene and BP are consid-
which support the platform in vacuum onto the substrate. ered potential high-performance thermoelectric materials and
This micro-device platform allows one to measure the ther- have been widely employed as composite fillers to enhance
mal conductivity of the nanomaterials and to calculate their the thermoelectric properties of the composites. However,
ZT value [49, 232–235]. Under high vacuum, the heat loss the thermoelectric properties of individual sample of gra-
of the sample via convection and radiation is negligible. phene and BP have also been studied via these microstructure
Moreover, the monolithic silicon device minimizes the ther- measurement platforms. Choi et al. [131] measured the ther-
mal contact resistances. When a micro-heater is applied to moelectric performance at various temperatures and at gate
the system, the suspended micro-device in vacuum forces electrical fields of BP and then studied its transport character-
a heat flow across the samples. By carefully measuring the istics in samples with a thickness of 10–30 nm. The structure
temperature at both sides of the sample and calculating the of this device is shown in Fig. 15a. The test results prove that
total amount of heat delivered to the micro-heater, the ther- the 2D Mott’s variable rang hopping is a dominant mecha-
mal conductance of the nanostructure 2D materials can be nism in the thermal and electrical transport in thin BP sam-
calculated. When combined with the dimensional data of the ples. Saito et al. [134] investigated the gate-tuned thermo-
2D materials, the thermal conductivity of each 2D material electric performance of BP at low temperature (210 K). By
can be obtained based on such well-established thermometric using the electric-double-layer transistor configuration, the
technique [227, 231, 236]. Seebeck coefficient of ion-gated BP reached + 510 μV K−1
A number of researchers have investigated the thermo- at 210 K. This value is about 1.5 times higher than the value
electric properties of individual 2D nanostructure materials (+ 340 μV K−1 at 300 K) of a bulk single crystal.
for several years. In 2008, two remarkably high ZT values of Several computational simulation results have shown
0.6 and 1.2 for two samples of highly doped silicon single- that an ultrahigh thermoelectric performance can be
crystalline nanowires at near room temperature have been achieved in various graphene nanostructures, including
reported independently by Heath and Yang’s group [235, zigzag and armchair graphene nanoribbons, graphene
237]. According to their studies, a suppression of the thermal nanomeshes, and graphene superlattices [48–50, 52–55,
conductivity was observed due to the rough surface and the 64, 246, 247]. These simulation results show that the ZT

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 23 of 40 36

(a) (b)
0.4

S (mV K−1)
0.2
Vg (V)
−60
−40
TH2 −25
0.0
TH1 0 100 200 300
T(K)

(c) SGNM16 (d) SGNM12 (e) SGNM8

20 nm 20 nm 20 nm

Fig. 15  a Optical microscope images of the measurement devices prepared onto a 300-nm-thick S­ iO2/Si substrates. b Seebeck coefficient of
few-layer black phosphorus depending on temperature and gate voltage. Reproduced with permission from Ref. [131]. Copyright 2016, Ameri-
can Chemical Society. c TEM image of single-layer graphene nanomeshes with neck width of 16 nm. TEM image of bilayer graphene nano-
meshes with neck width of d 14 nm and e 8 nm. Reproduced with permission from Ref. [249]. Copyright 2017, Elsevier

value can be enhanced by controlling the nanostructure or neck widths exhibit an ultralow thermal conductivity and
by employing a proper post-treatment. By controlling the an enhanced ZT value. Anno et al. achieved a ZT value of
microstructure and the layers of graphene, its thermoelec- graphene, which is about 3 times higher than in the case of
tric efficiency can be greatly improved. Furthermore, by pristine graphene via defect engineering [66].
tuning the band structures, a high thermopower and a lower Besides graphene and BP, the thermoelectric properties
thermal conductivity can be achieved simultaneously due of other 2D materials including 2D tellurium, TMDCs, and
to the dominant effect of the phonon-edge scattering. In group IV–VI compounds were measured via these micro-
addition, these theoretic predictions have been proved via structure measurement platforms. Moreover, the nanopat-
experimental measurements. Xiao et al. [248] found that tern effect and the pattern geometry effect on the thermal
the Seebeck coefficient of a few-layer graphene sample can and the thermoelectric phenomena of nanopatterned 2D
be greatly enhanced (> 700 μV K−1) after oxygen plasma materials were characterized [249]. For example, Qiu
treatment. Since a graphene monolayer is easy to damage et al. [228] investigated the thermoelectric properties of
during the plasma treatment process, the oxygen plasma 2D tellurium for the first time and reported a ZT value of
treatment is not suitable. Oh et al. [249] fabricated single- 0.63 at room temperature. The Seebeck coefficient and the
and bilayer graphene nanomeshes with various neck widths electrical conductivity of 2D Tellurium were measured by
via block copolymer self-assembly on graphene, as shown using the microstructure measurement platforms as shown
in Fig. 15c–e. Since the patterned graphene nanostructure in Fig. 14a. The thermal conductivity was measured via
can induce a dominant phonon-edge scattering and quan- the micro-Raman method. Pettes et al. [234] investigated
tum confinements to control the electron and phonon-trans- the thermoelectric properties of a ­Bi2Te3 nanoplate with
port behavior, the bilayer graphene nanomeshes with 8 nm the thickness in the 9–25 nm range by using a suspended

13
36 Page 24 of 40 Nano-Micro Lett. (2020) 12:36

micro-device. When the thickness increases, the ­Bi2Te3 nan- fabricated cross-plane thermoelectric devices to investigate
oplate exhibits a suppressed Seebeck coefficient, whereas the cross-plane thermoelectric properties of 2D materials.
both the electrical conductivity and the thermal conductiv- Figure 16a, b shows an optical image of a completed device
ity are decreased. However, this result is mostly related to and the schematic diagram of its fabrication process. To man-
the surface band bending and the diffuse surface scattering ufacture such cross-plane device, a bottom/top metal 4-probe
of the electrons and the phonons in the nanoplates. The resistance temperature detector and a serpentine metal heater
thermoelectric signature of 2D materials, such as the W ­ Se2 are patterned onto the silicon oxide/silicon substrate via
single crystal, the single-layer SnSe, the SnTe nanoplate, electron beam lithography. This process is then followed by
and the C­ d3As2 superlattice, was also studied by using the metal deposition of a metal electrode. Before the top resist-
microstructure measurement platform [243, 244, 250, 251]. ance temperature detector is deposited, the sample should
As previously shown, the thermoelectric properties of indi- be capped with an insulating film of ­Al2O3. By using such
vidual 2D materials were investigated along the plane direc- microstructure measure platform, the Cronin’s group studied
tion. As is well known, 2D materials usually exhibit a high the thermoelectric properties of ­SnSe2 and (SnS(e)n(TiS(e)n
anisotropy along the perpendicular direction and in-plane (n = 1, 3, 4, 5) thin-film layer materials along cross-plane
direction. However, it is difficult to measure the thermal con- direction [252, 253]. The Seebeck coefficient and the thermal
ductivity, the Seebeck coefficient, and the electrical conduc- conductivity of the layered structure materials are strongly
tivity of single-layer and multilayer 2D materials along the dependent on the number of layers. Moreover, several
perpendicular direction. Recently, several researchers have researchers found that the Seebeck coefficient, the electrical

(b)
Bottom RTD (SnSe)n(TiSe2)n
deposition and
lift-off (SnSe)(TiSe2)
sample
Silicon Oxide Silicon Oxide
Silicon Silicon

Top RTD
(a) fabrication

Heater (SnSe)(TiSe2)
Bottom Top sample
ALD deposition RTD RTD
Aluminum and heater
oxide fabrication

20 µm

(c)
(d) 0
Ti
0.35
Se
Sn −10
Seebeck (μV K−1)

0.30
κ (W K−1 m−1)

−20 0.25

0.20
−30

3 nm n=1 0.15
Layer configuration (n)

Fig. 16  a Schematic diagram of the device fabrication process, and b its optical microscope image. c STEM images of the (SnSe)n(TiSe2)n thin
film (n = 1). d Cross-plane Seebeck coefficient and thermal conductivity of the (SnSe)n(TiSe2)n thin film with different layer configurations.
Reproduced with permission from Ref. [252]. Copyright 2017, American Chemical Society

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 25 of 40 36

conductivity, and the thermal conductivity along cross-plane wearable self-powered electronics devices. As a group
direction are very different from the properties along the in- of developing materials, 2D materials have been widely
plane direction. This is in agreement with the properties of employed as optoelectronic devices, including in the
bulk thermoelectric materials based on 2D materials (such manufacturing of photodetectors and photovoltaic
as SnSe, ­Bi2Te3, and ­Sb2Te3). For example, Li et al. found devices. When irradiated by light, these devices convert
that when the number of layers decreases from 5 to 1, the photons into electric current due to separation of the
cross-plane Seebeck coefficient decreases from − 31 to excited electron–hole pair via a built-in electric field.
− 2.5 μV K−1, whereas the cross-plane thermal conductiv- The development of low-cost and high-performance
ity decreases from 0.35 to 0.15 W ­mK−1 (Fig. 16c, d), due broadband photodetectors is the key to fulfill differ-
to an increased interfacial phonon scattering [252]. Juang ent application requirements. The photothermoelectric
et al. [254] proposed a cross-plane micro-device onto a sili- effect, which is based on the Seebeck effect, enables the
con substrate to measure the thermoelectric properties of the device to generate a photocurrent due to the temperature
vertical graphene/gold nanoparticles heterostructure along gradient induced by the absorbed light on an electric
the perpendicular direction. Since the Au nanoparticles can voltage. Moreover, this temperature gradient would be
further inhibit the phonon transport and enhance the electri- generated across the materials due to light irradiation
cal conductivity along the perpendicular direction, a high ZT and the photocurrent is generated by the photothermo-
value larger than 1.0 (at room temperature) can be achieved electric effect. Self-power photodetectors are promising
for a single-layer graphene. Chen et al. [255] fabricated a devices, which can be employed in a large variety of
graphene/hexagonal boron nitride/graphene heterostructure application including sensing, environmental monitor-
device and measured its thermoelectric transport properties. ing, night vision, and astronomy.
The top and bottom graphene surfaces in this device work 2D materials, such as graphene and BP, have been widely
as both an electrode and a micro-heater to induce a tempera- used as photothermal agents due to their efficient photother-
ture gradient. The measured thermoelectric properties are mal conversion efficient [122, 256–259]. Gabor found that
useful to understand the thermoelectric component in the upon heating a junction consisting of a single graphene sheet
cross-plane behavior of emerging 2D heterostructure devices. by shining laser onto it, a thermoelectric voltage is generated
The development of micro–nanoprocessing techniques across the junction [260]. However, this kind of photothermo-
enables us to fabricate micro-devices to investigate the electric effect was found in other 2D materials system, as well
thermoelectric properties of individual 2D nanostructure [51, 71, 126, 261–264]. As predicted by Basko, this effect can
materials. The study of the thermoelectric transport char- be potentially exploited in novel optoelectronic devices [70].
acteristics of individual 2D materials is pivotal to under- In 2011, Kraemer et al. [265] reported a novel solar ther-
stand its physical mechanism. The massive proliferation of mal flat panel, which converts thermal energy into electric
2D materials, such as TMDCs, BP, MXenes, graphene, and power based on the Seebeck effect and on the high thermal
Xene, offers new opportunities to engineer such compounds concentration. The peak efficiency of such solar thermoelec-
and to fabricate high-performance thermoelectric devices. tric generator is close to that of a common solar cell (4.6%).
The device structures reviewed in this section serve as a gen- However, the total power conversion efficiency of this device
eral approach to characterize the in-plane and cross-plane is limited by the photothermal and thermoelectric efficiency
transport properties of 2D materials. [56, 265].
Besides their use as solar energy converters, 2D thermo-
electric materials also can be employed in the fabrication of
6 Thermoelectric Materials Combined high-performance self-power photodetectors. When com-
with Photodetection pared to other photodetection mechanisms, such as photo-
conduction, photovoltage, and bolometry, the photothermo-
Thermoelectric materials have been widely used electric effect achieves a broadband detection without an
as power generators, cooling devices, and sensors. external bias at room temperature. A photodetector based on
Recently, they have been found to work as power sup- the photothermoelectric effect mechanism exhibits a respon-
plies and can be used to develop highly efficient and sivity, which is related to the light-induced temperature

13
36 Page 26 of 40 Nano-Micro Lett. (2020) 12:36

gradient and to its Seebeck coefficient. The temperature (20 pW Hz −1/2), referenced to the incident (absorbed)
gradient is determined by the absorption, heat capacity, and power. The performance of such graphene-based thermo-
the photothermal conversion efficiency of the material. electric terahertz photodetectors can compete with the best
Graphene and BP are the most widely studied 2D room-temperature terahertz detectors to develop optimally
materials and have attracted a large attention. In 2010, coupled devices. Echtermeyer et al. [61] investigated the
Xu et al. [51] found that the photothermoelectric effect influence of the wavelength on the performance of metal-
has a pronounced effect into the photocurrent generation graphene-metal photodetectors via polarization-dependent
process at the graphene interface in field-effect transis- measurements. The device that used in this study is shown
tors. This phenomenon has several positive benefits in in Fig. 17b. As shown in Fig. 17c, Muench et al. report
the design of high-performance optoelectronics devices a compact, photothermoelectric-based, waveguide- inte-
based on graphene. As shown in Fig. 17a, Cai et al. [266] grated, plasmonic enhanced graphene photodetector for
fabricated a simple thermoelectric terahertz photodetector telecom wavelengths operating at zero dark current. Owing
based on graphene, which exhibits an excellent sensitivity to the voltage generated by the photothermoelectric, the
exceeding 10 V W−1 (700 V W−1) at room temperature graphene photodetector exhibits an external responsiv-
and noise-equivalent power less than 1100 pW Hz −1/2 ity ~ 12.2 V W−1 and a 3 dB bandwidth ~ 42 GHz [267].

(a) x (b)
100 µm

y Graphene

Au Cr Au Cr

Metal

Graphene

3 µm 5 µm
SiO2

(c) (d)
1575 nm

Source
Photovoltage (µV)

1000
Gate 2

Gate 1

Drain

100

SLG SiN
0.01 0.1
channel Waveguide Power at device (mW)

Fig. 17  a Optical micrograph and atomic force microscopy of graphene photodetector with asymmetric metal electrodes. Reproduced with per-
mission from Ref. [266]. Copyright 2014, Springer Nature. b Optical micrograph of the graphene-based photodetector devices. Reproduced with
permission from Ref. [61]. Copyright 2014, American Chemical Society. c Scheme of the single-layer graphene photodetector SiN waveguide.
The green arrow indicates the light propagation direction. d The photovoltage Vph dependence of optical power. Reproduced with permission
from Ref. [267]. Copyright 2019, American Chemical Society

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 27 of 40 36

The photovoltage (Vph) generated by the thermoelectric 2D material-based devices. In addition, the photothermo-
current as for the Seebeck effect dependence on power is electric effect plays a significant role in such devices and
shown in Fig. 17d. The linear response indicates a power- can be used to develop high-performance self-power opto-
independent external voltage responsivities in the tested electronic devices.
optical power range [267]. Photothermoelectric photodetectors have exhibited their
As graphene, BP has also been studied as a high-per- advantages in developing low-cost, uncooled ultrafast and
formance photothermoelectric photodetector. Hong et al. ultrabroadband photodetectors, and their performance has
[126] investigated the electrical transport and optoelectronic been significantly enhanced owing to the development of
properties of FETs manufactured from a few-layer BP sam- low- dimensional materials and the micro–nanofabrication
ple. Their results reveal that the photocurrent signals at the technology. However, due to the limited effective active sur-
BP–electrode junctions can be mainly attributed to the pho- face area, the saturation effect and relatively low practical
tovoltaic effect in its the off-state, whereas the photothermo- Seebeck coefficient at room temperature limit the tempera-
electric effect occurs during its on-state. Leong et al. [268] ture gradient in the case of exfoliated or single-crystal 2D
fabricated a device based on exfoliated BP nanoflakes with a materials. For this reason, no high voltage can be gener-
responsivity of 1 mV W−1 for a 2.5-THz beam with a diam- ated. Although tremendous progress has been made in recent
eter of 200 μm. In this case, the photothermoelectric effect years, more work needs to be done to further optimize the
was found to be the primary source of the THz photosignal. performance of 2D material-based photothermoelectric
The photothermoelectric effect of several 2D TMDC photodetectors.
materials, such as M ­ oS2, ­WSe2, and B ­ i2Se3, has also been
widely investigated [71, 261, 262, 264]. Buscema et al. [71]
studied the photoresponse of ­MoS2 monolayer FETs via 7 Conclusions and Outlook
scanning photocurrent microscopy. The device and results
are shown in Fig. 18. To summarize, the photocurrent gen- During the last decades, a significant progress has been
eration in a M
­ oS2 monolayer is dominated by the photother- achieved in the development of thermoelectric materials.
moelectric effect. The separation of the photoexcited elec- As new members of the thermoelectric material family, 2D
tron–hole pairs across the Schottky barriers at the ­MoS2/ materials have attracted a large attention and many milestone
electrode interfaces only plays a marginal role. As shown in investigations have been reported. Due to their unique elec-
Fig. 18h, a large and controllable Seebeck coefficient in the tronic, thermal, and mechanic properties, 2D thermoelectric
− 1 × 105 to −4 × 102 μV K−1 range was observed in the case materials are expected to be the next-generation high-per-
of ­MoS2 monolayer. However, the mechanism behind the formance thermoelectric materials.
generation of the photocurrent is different when compared In this review, the thermoelectric properties of various 2D
to other 2D TMDC materials. In order to deeply understand materials, such as TMDCs, graphene, BP, group IVA–VA
such physical mechanism, Groenendijk et al. [262] studied compounds, MXene, and their nanocomposites, were illus-
the photocurrent in a ­WSe2 sample by fabricating a double- trated in detail. Moreover, the state-of-the-art of theoretical
gated ­WSe2 device and by applying varied gate voltages and experimental data were presented to elucidate the rela-
and illumination power. The results show that the photo- tion among various factors which determine the thermoelec-
current of the ­WSe2-based devices (for both the PN and tric properties of these materials. Although a tremendous
NP configurations) is mainly generated by the photovoltaic progress has been achieved in the past few years, these prop-
effect. Moreover, a maximum responsivity of 0.7 mA W−1 erties still need to be improved for their practical application
at 532-nm illumination was obtained. In the PP configura- as thermoelectric devices. Here, some major outlooks are
tions devices, the photocurrent mainly is generated by the presented to address this issue:
photothermoelectric effect and the intensity is about 2 times
larger than that generated by the photovoltaic effect. Due to 1. The thermoelectric performance of 2D materials is still
the strong optical absorption caused by an asymmetry in much lower then for conventional bulk thermoelectric
flake thickness or by the optical absorption of the electrodes, materials. A precise chemical doping during the fabrica-
a sizable temperature gradient can be generated across the tion and the functionalization of these composites must

13
36 Page 28 of 40 Nano-Micro Lett. (2020) 12:36

(a) (b) −8 nm 77 nm (c)


Laser excitation
2
Sample A

5
4
1
X mirror

2 µm 1 µm
3
Y mirror
Objective

(d) −40 0 40 2 (e)


MoS2 Current (pA)

4 5
SiO2 X
1
Si Au
Y

Vg
A 6

1 µm 1 µm
3

(f)109 (g)10−1 (h) 106


MoS2 MoS2
Bulk (n-doped)
Dark
10−2 105 ΔT = 0.13 K (0.04, 0.4)
108
−S (µV K−1)

λ = 750 nm
R (Ohms)

VPTE (V)

λ = 532 nm
104
107 10−3

103
10−4
106
102
−20 0 20 −20 0 20 −20 0 20
Vg (V) Vg (V) Vg (V)

Fig. 18  a Schematic of the scanning photocurrent microscopy setup. b AFM image of the micro-devices with a M ­ oS2 flake. c Spatial map of
the intensity of the reflected light from the device. d Photocurrent image of the M
­ oS2 FET. e Superposition of the photocurrent map and the con-
tours of the electrodes, which were obtained from the light reflection map. f Resistance and g photothermoelectric voltage of the ­MoS2 device as
a function of the gate voltage in its dark state and with the laser spot placed on the ­MoS2/electrode interface. Estimated Seebeck coefficient as a
function of the gate voltage. Reproduced with permission from Ref. [71]. Copyright 2013, American Chemical Society

be performed to achieve a high value of ZT value. This nism on the thermoelectric performance is still limited.
remains a challenging issue. Their deeper understanding should guide the design of
2. The electronic and phonon-transport mechanisms of 2D novel thermoelectric composite and further improve
materials are still obscure. Although the power factors their thermoelectric properties.
of individual single- and few-layer 2D materials have 3. The thermal conductivity of 2D materials is too high,
been investigated and a series of possible mechanisms and this limits their thermoelectric performance. The
have been proposed, it is still impossible to decouple inherent thermal conductivity of the most common 2D
these factors. The current knowledge of the effects of the materials, including graphene, TMDCs, and BP, is much
interfacial electronic and the phonon-transport mecha- higher than for the traditional semiconductor thermo-

© The authors https://doi.org/10.1007/s40820-020-0374-x


Nano-Micro Lett. (2020) 12:36 Page 29 of 40 36

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