Received: 13 October 2019 Revised: 12 February 2020 Accepted: 14 February 2020

DOI: 10.1002/er.5313

REVIEW PAPER

Inorganic thermoelectric materials: A review

Md. Nazibul Hasan1 | Herman Wahid1 | Nafarizal Nayan2 |

Mohamed Sultan Mohamed Ali1

1
School of Electrical Engineering,
Universiti Teknologi Malaysia, Johor
Bahru, Johor, Malaysia
2
Department of Electronic Engineering,
Faculty of Electrical and Electronic
Engineering, Universiti Tun Hussein Onn
Malaysia, Johor, Malaysia
Correspondence
Mohamed Sultan Mohamed Ali, School of
Electrical Engineering, Universiti
Teknologi Malaysia, 81310 UTM Johor
Bahru, Johor, Malaysia.
Email: sultan_ali@fke.utm.my
Funding information
Fundamental Research Grant Scheme
(FRGS), Grant/Award Number:
R.J130000.7851.5F081; Collaborative
Research, Grant/Award Number: CRG
Q.J130000.2451.04G94
Summary
Thermoelectric generator, which converts heat into electrical energy, has great
potential to power portable devices. Nevertheless, the efficiency of a thermo-
electric generator suffers due to inefficient thermoelectric material perfor-
mance. In the last two decades, the performance of inorganic thermoelectric
materials has been significantly advanced through rigorous efforts and novel
techniques. In this review, major issues and recent advancements that are
associated with the efficiency of inorganic thermoelectric materials are encap-
sulated. In addition, miscellaneous optimization strategies, such as band engi-
neering, energy filtering, modulation doping, and low dimensional materials
to improve the performance of inorganic thermoelectric materials are reported.
The methodological reviews and analyses showed that all these techniques
have significantly enhanced the Seebeck coefficient, electrical conductivity,
and reduced the thermal conductivity, consequently, improved ZT value to
2.42, 2.6, and 1.85 for near-room, medium, and high temperature inorganic
thermoelectric material, respectively. Moreover, this review also focuses on the
performance of silicon nanowires and their common fabrication techniques,
which have the potential for thermoelectric power generation. Finally, the key
outcomes along with future directions from this review are discussed at the
end of this article.

KEYWORDS
thermoelectric generator, Seebeck coefficient, thermal conductivity, electrical conductivity, band
engineering, energy filtering, modulation doping, low dimensional materials

1 | INTRODUCTION power these devices, various micro-energy harvesters

The use of wearable electronics and implantable devices
such as cardiac pacemakers,1 sensory and neurological
implantable devices,2 pulse oximetry sensors,3 wearable
pressure sensor,4 biometrics monitoring,5 and electrocar-
diography monitoring sensor6 are increasing exponen-
tially in the biomedical field. Most of these devices use a
battery as their main power source, which is an exhaust-
ible source that limits the longevity of these devices and
needs replacement after a finite period time.7 In order to
such as thermo-photovoltaic, piezoelectric devices, tribo-
electric generators, and thermoelectric generators (TEGs)
have been developed and reported.8 These micro-energy
harvesters usually convert environmental energy sources
such as sunlight, mechanical vibrations, and human body
heat into electrical energy. Micro-energy harvesters could
prolong the lifespan of these biomedical devices as well
as maintain a green energy environment. For example,
by using micro-energy harvesters it is possible to deploy
wireless sensor networks in remote areas without

Int J Energy Res. 2020;1–53. wileyonlinelibrary.com/journal/er © 2020 John Wiley & Sons Ltd 1
2 HASAN ET AL.
depending upon batteries, resulting in self-powered and
perpetual system operations.9
Among all the energy scavenging devices, TEG is get-
ting more attention due to its promising features such as
its high reliability and durability at low cost, no mainte-
nance required, direct conversion with no intermediate
energy conversion process, and its eco-friendliness.10-13
TEG is a solid-state device that converts heat into elec-
tricity by using the Seebeck effect. It is made of p-and n-
type legs (it could be semiconductor legs or metal legs),
which are placed in series, electrically, and in parallel,
thermally. When a temperature gradient, ΔT, is applied
in between the two legs, charge carriers in the thermo-
electric (TE) material will diffuse from the hot side, TH,
to the cold side, TC, and a potential difference, ΔV = SΔT,
will be formed across the material, where, S is the
Seebeck coefficient, which is positive for p-type and nega-
tive for n-type conduction.14,15 A schematic of a TEG is
depicted in Figure 1, where both the heat and charge flux
(ie, electrons and holes) have the same direction, that is,
TH to TC, and an electrical current, I, flows from the n- to
the p-type material due to ΔT. The overall efficiency of a
TEG could be determined by a dimensionless figure of
merit, ZT, of TE materials, which is defined as16:


S2 σ
ZT = T ð1Þ
κt
where σ and κ t defines the electrical and thermal conduc-
tivity of the material, respectively. To generate high volt-
age, a material with a large S is required. According to
the Boltzmann transport theory, S and σ, for a metal and
a degenerate semiconductor with single parabolic band
model and energy-independent scattering approximation,
could be defined as17-19:
8π 2 k 2B *  π 2=3
s= m :T ð2Þ
3eh2 3n
where kB, e, h, n, and m* defines the Boltzmann constant,
electrical charge carrier, Planck's constant, carrier con-
centration (/cm3), and effective mass of the carrier,
respectively.19 Concurrently, the thermocouple, a build-
ing block of TEG, will be used to generate electricity,
hence, the thermocouple must be made of materials with
high σ, could be defined as:


eτ ne2 τ
σ = neμ = ne = ð3Þ
mb mb
where μ, τ, and mb defines the mobility of charge car-
riers, carrier relaxation time, and band mass, respectively.
For a two carrier transport system, total electrical con-
ductivity, σtotal, and Seebeck coefficient, Stotal, could be
defined as20,21:
 
σtotal = σn + σp ð4Þ


σ n Sn + σ p Sp
Stotal = ð5Þ
σtotal
where σn, σp, Sn, and Sp defines σ for n-and p-type mate-
rial, and S for n-type material, p-type material,
respectively.
Since the discovery of the thermoelectric effect, by
Thomas Johann Seebeck in the year 1821, numerous
materials have been explored, to find the most suitable
for the TE power generation, starting from inorganic
(inorganic material includes both metals and semicon-
ductors) to organic materials. Although the beginning of
the research on TE materials was ponderous, neverthe-
less, since the mid-20th century, the basic science of TE
effect was clearly understood and the classic inorganic
TE materials, such as Bi2Te3, PbTe, and SiGe alloys, were
acknowledged as magnificent TE materials which offered
ZT values close to 1.22,23 Since then, the field of thermo-
electrics has quickly expanded, especially due to the pro-
digious development of novel techniques such as using
low-dimensional structure,24,25 nanocomposites, 23,26
band engineering,27-30 and carrier filtering.31
Recently, a number of reviews on TE materials have
been published that, in summary, mainly focused on bulk
TE materials,32 both inorganic and organic TE
materials,33 progress and emerging TE materials,13,34,35
design of advanced TE materials,36 and high efficiency
TE materials.17 Nonetheless, to the best of the authors’
knowledge, there is no systematic review highlighting the
major problems, as well as the optimization techniques
of fundamental properties, which are directly related to
the efficiency of inorganic TE materials at different tem-
perature range. Therefore, in this review, for the first
time, a comprehensive overview of the most prominent
inorganic TE materials and their major advancements in
the TE industry in recent years are surveyed and ana-
lyzed at divergent temperature ranges. In addition, this
review also addresses the major issues, various tuning
methods, synthesis processes, and performance analyses
that are associated with the efficiency of inorganic TE
materials. Moreover, all the recent optimization tech-
niques to tune κ t without deteriorating the σ value, and
to tune σ without affecting the S value too much, are also
stated. Finally, the summary of this review, along with
future directions associated with TE materials efficiency
optimization techniques are discussed.
HASAN ET AL.
2 | PROBLEMS ASSOCIATED
WITH THE EFFICIENCY OF TE
MATERIALS
Numerous TE materials have been studied and
reviewed, so far, since the first observation of the
Seebeck effect in 1821.37 The ZT of TE materials, mainly
depends on three parameters, S, σ, and κt. A good TE
material, should constitute a high S (high density of
charge carrier or high μ is beneficial to maximize S38) to
enhance the conversion of heat into electrical power, a
high σ to reduce Joule heating (typical value of σ is
about 105 Sm−1 for good TE materials38), high power
factor (PF = S2σ), low κt to hinder thermal shorting39
and it should maintain a large ΔT in between the hot
and cold sides.15,40 The term κ t is basically defined as the
ability of a material to conduct heat. In solids and semi-
conductors, it comes from two sources: (a) electron-hole
transportation (κe), and (b) phonons travelling through
the lattice (κ lat), where, κ e is related to σ via the
Wiedemann-Franz law41:
κt = ðκ e + κ lat Þ ð6Þ
and
κ e = σLT = neμLT ð7Þ
where L is the Lorenz number of free electrons.16 In a
metal, the value of σ is very high, whereas S is
very low.
As can be seen from the Equations (1), (2), (3), (6),
and (7), all the necessary parameters that are associated
with ZT are functions of n. The σ and κ e values
enhance with the enhancement of value n, whereas S is
reduced.15 In a metal, κ e is much higher in the thermal
transport process, whereas in the case of a semiconduc-
tor or an insulator, κ lat is dominant. Thus, in metals,
the ratio of κ e to σ is specified, as the electron is domi-
nant. Nonetheless, in the case of semiconductor κlat
needs to be minimized, but retain σ as high as possible
and it should maintain a low ratio of κlat/κ e for good
TE efficiency.
Although metals have very high σ, they have a low
value of S and a high κt due to high n that makes them
less efficient TE materials. However, compared to
metals, semiconductors have a relatively high S and
low κ t. Besides, the band structure of semiconductors
also shows better TE effects than the band structure of
metals. n in terms of the fermi distribution function, f0
(E), is defined as23,37:
3
ð/
n= f 0 ðE Þ gðE Þ:dE ð8Þ
0
and

 −1
E −E F
f 0 ðE Þ = exp +1 ð9Þ
kT
Where g (E). dE is the number of permitted electron
states in the energy range between (E + dE) and EF is the
fermi energy level, which is defined as the maximum
electron energy at absolute 0 K.
The energy gaps (Eg) for metal, intrinsic semiconduc-
tor, and p-type semiconductor is shown in Figure 2. It
manifestly depicts that Eg is lowest for metal (Eg ~ 0;
Figure 2A), followed by semiconductors (Eg ~ 0.2-3 eV;
Figure 2B). Therefore, σ is much higher in metal than in
the semiconductors as it requires less energy to break its
atomic bond for electrical conduction.42 Besides,
quations (8) and (9) suggested that EF is proportional to
n. It lies in the conduction band for metals due to a
higher n, whereas, for undoped intrinsic semiconductors,
it lies in the middle of the conduction band and valence
band. For a p-type semiconductor around room tempera-
ture, EF lies near to the valence band (Figure 2C),
whereas, at high temperature, EF lies in the middle of the
conduction and valence bands, as EF changes with
increased temperature (Figure 2D). Thus, both Eg and EF
play a crucial role in determining the value of S. Any
metal that has a small Eg and high σ exhibits a low S,
while for semiconductors, the Eg is higher than metals,
so it is possible to enhanced S by tuning its electronic
properties using various optimization techniques that are
discussed in the following section.
3 | OPTIMIZATION TECHNIQUES
TO ENHANC E THE Z T OF TE
MATER IALS
To enhance the ZT of TE materials by optimizing S, σ,
and κt in a single TE material is a challenging task as all
these properties are related to each other. For instance,
the enhancement of S results in a decreased σ, and κ t is
related to σ via the Wiedemann-Franz law, where κ t is
proportional to σ, that is, the higher the σ of materials,
the higher κt becomes as mentioned in the above
Equation (7). Therefore, it is necessary to optimize these
properties in order to enhance the ZT of TE materials.
Miscellaneous strategies to maximize the properties of TE
4 HASAN ET AL.

materials in order to enhance the ZT are discussed in the ZT, optimization of n is necessary. The single band model
following subsections. suggests that the optimal carrier concentration (n*) is
related to m*dos as48,49:

 1:5
3.1 | Strategies to enhance the Seebeck n* = m*dos :T ð11Þ
coefficient

S could be enhanced by initiating distortion at the energy
level, into the conduction and valence band, or by
enhancing the density of states (DOS).43,44 According to
Cutler and Motto, S for degenerate semiconductors or
metals could be written as38,45-47:
where T signifies the temperature. From quations (2),
(10), and (11), it can be seen that S ∞ m*dos. In addition,
μ depends on the effective mass of a carrier within its
respective band (NV), where,
2

 m*dos = N 3V :m*band ð12Þ

π 2 k 2B T dlnfσ ðEÞg
s=
3e dE E = EF
 Therefore, quations (2), (11), and (12) suggest that
π 2 k2B T 1 dfnðE Þg 1 dfμðEÞg
= +
3e n dE μ dE E = EF
where σ(E) = n(E) e μ(E), which signifies the energy
dependent σ at EF and n(E) is the n at energy level
E which is equal to g(E) f(E). Equation (10) suggests that
S could be enhanced by varying both the n(E) and μ(E) at
EF, where n(E) and μ(E) could be realized by initiating a
high DOS effective mass (m*dos), and band engineering,
respectively.
3.1.1 | Tuning of DOS effective mass
(m*dos) And carrier effective mass (m*band)
in a band
In thermoelectricity, electronic transportation happens in
such a way that a large n leads to an increase in S with
decreases in σ and vice versa. In order to achieve high
S could be enhanced by enhancing the m*dos via
ð10Þ
increased NV as well as m*band. Typically, m*band could be
enhanced via band flattening38,50 and resonant levels
through doping,51 alloying, and high temperature.48 In
TE materials, doping not only supplies the carriers to
optimize the PF but also minimize the point-defect scat-
tering of phonons to suppressing κ lat by modifying their
electronic band structure.33 As a result, the number of
states per energy level is increased with the addition of
the dopant atoms and hence net DOS is modified. For
instance, recently, Tan et al used CdTe alloying and Sb
doping to enhance the m*dos and the S, of PbTe. CdTe
alloying widened the band gap of PbTe by 50% and
enhanced S of −195 μVK−1 while Sb doping helped to
increase n. They reported ZT of 1.2 at 750 K for Sb-doped
Pb0.97Cd0.03Te alloy.52 Besides, Hong et al used Sb and In
dopants in GeTe to optimized n and S. The addition of
both the dopants into GeTe enhanced its S value up to
190 μVK−1 while reducing σ at the same time. Dopants

FIGURE 1 Schematic diagram of a TEG incorporating with n- and p-type TE legs [Colour figure can be viewed at wileyonlinelibrary.com]
HASAN ET AL. 5

F I G U R E 2 The differences
in Eg for (A) metal, (B) intrinsic
semiconductor, (C) p-type
semiconductor at room
temperature, and (D) p-type
semiconductor at high
temperature [Colour figure can
be viewed at
wileyonlinelibrary.com]

distorted the DOS near the fermi level, consequently,
enhanced the m*band of the valence band. They obtained
ZT value of ~2.3 for Ge0.89Sb0.1In0.01Te at ~650-780 K.53
Therefore, it is essential to tune m*dos or m*band to
enhance the S in compromise with μ of TE materials.
3.1.2 | Energy filtering
Typically, low-energy carriers negatively contribute to
S while higher-energy carriers contribute more towards
high S.48 An energy filtering technique is typically used
in nanocomposites to enhance S. This technique allows
the passing of only the higher-energy carriers and
restricts the low-energy carriers by utilizing nanoscale
barriers and nano-inclusions, as depicted in Figure 3.54
As quation (5) and (6) suggested that Stotal consists of
both Se and Sh, that have opposite signs to each other,
consequently Stotal is always less than the majority S. In
this regard, if a nanoscale energy barrier acts as an
energy filter at the grain boundaries, then without an
energy filter, both the high and low energy carriers pass
through the components, consequently, this has no effect
on the Stotal. However, with an energy filter, this allows
6 HASAN ET AL.

F I G U R E 3 Schematic diagram depicting (A) energy filtering through the nanoscale barrier. (B) Transmission electron microscopy
(TEM) image of p-type BiSbTe/Y2O3 nanocomposite bulk showing the uniformly distributed Y2O3 particles throughout the matrix and the
effect of carrier filtering on the enhancement of S, reduction of κ t, and enhancement of ZT. Source: Reference 56 Copyright 2017,
Reproduced with permission from Elsevier [Colour figure can be viewed at wileyonlinelibrary.com]

only the high-energy carriers to pass and restricts the added Y2O3 nanoparticles (NPs) into BiSbTe and formed
low-energy carriers from Stotal and σ total, hence, Stotal will a nanocomposite via ball milling and spark plasma
be enhanced without much change in the σtotal, as sintering technique, as depicted in Figure 3B.56 They dis-
depicted in Figure 3A.21,55 For instance, Madavali et al pensed the Y2O3 nanoparticles uniformly throughout the
HASAN ET AL. 7

F I G U R E 4 Schematic diagram depicting the carrier transport for (A) undoped semiconductor, modulation doped semiconductor, and
uniformly doped semiconductor (black line defined as carriers). Fermi level energy (EF) positions in undoped, modulation doped, and
uniformly doped semiconductors for (B) n-type doping and (C) p-type doping [Colour figure can be viewed at wileyonlinelibrary.com]

BiSbTe matrix to scatter the carriers through energy fil- Nonetheless, S of the nanocomposite decreased with ele-
tering effect, and as a consequence, the value of S was vated temperature due to minority carrier excitations.
enhanced while both the σ and κt were reduced. They reported a maximum ZT value of 1.24 for 2%wt
8 HASAN ET AL.

F I G U R E 5 Crystal structure of
Bi2Te3 depicting the quintuple layer
and van der Waals gaps. Source:
Reference 94 Copyright 2015,
Reproduced with permission from
AIP Publishing [Colour figure can be
viewed at wileyonlinelibrary.com]

FIGURE 6 Emerging Bi2Te3 alloys highlighting (A) ultra-low κt and (B) enhanced ZT value at different temperature range96,99,106,108-125
[Colour figure can be viewed at wileyonlinelibrary.com]
HASAN ET AL. 9

F I G U R E 7 (A) Schematic representation of dislocation arrays at grain boundaries of Bi0.5Sb1.5Te3, (B) Inverse fast Fourier transform
image of the boxed region showing grain boundary of Bi0.5Sb1.5Te3, (C) effect of various scattering mechanisms to κlat across a diverse range
of frequency, and (D) reduced κ lat value of Bi0.5Sb1.5Te3 due to dislocation arrays. Source: Reference 48 Copyright 2018, Reproduced with
permission from Wiley-VCH [Colour figure can be viewed at wileyonlinelibrary.com]

Y2O3 at room temperature. Besides, Zhang et al also
introduced nanoprecipitates via mechanical alloying and
a spark plasma sintering technique and dispersed SiC
nanoparticles into p-type Bi0.46Sb1.54Te3. The nan-
oprecipitates acted as an energy filter that filtered the low
n. As a result, there was a decrease in the n while the SiC
nanoparticles enhanced the mean carrier energy, so alter-
ing the DOS and enhancing S up to 255 μVK−1 at room
temperature. They reported a high ZT of 1.45 at 325 K
and a reduced κt of about 0.33 Wm−1 K−1 for 0.2 wt% SiC
nanoparticles.57
3.2 | Strategy to enhance electrical
conductivity
σ is defined as the ability of a material to conduct cur-
rent, which is directly proportional to n and μ as
mentioned in the above Equation (3). To enhance σ,
n and μ should be kept as high as possible. Typically, in
most of the cases, enhancement of n is done by introduc-
ing the doping technique. Nevertheless, a heavily doped
material enhances n between 1019-1021 cm−3, while it
reduces μ of charge carriers due to enhanced ionized
impurity scattering.58 In order for a trade-off between
n and μ, modulation doping has been recently used to
discretize the charge carriers from ionized dopants to
reduce ionized impurity scattering for high μ, while
enhanced n in TE materials.59-61 Figure 4 shows the mod-
ulation doping of semiconductors and their energy dia-
gram for n- and p-type doping. Modulation doping
consists of two dissimilar phases of composites made of
undoped (where n is low, but μ is high) and uniformly
doped (where n is high but μ is low) nanograins
(Figure 4A). The EF for undoped material lies in the mid-
dle of Eg, whereas EF moves to the conduction band
10 HASAN ET AL.

FIGURE 8 (A) Schematic diagram illustrating the formation of vertically aligned SiNWs in the presence of a conductive back
substrate. (B) Scanning electron microscope (SEM) images of SiNWs grown on the silicon wafer. Source: Reference 157 Copyright 2002,
Reproduced with permission from Wiley-VCH [Colour figure can be viewed at wileyonlinelibrary.com]

(CB) and valence band (VB) for n- and p-type doping,
respectively, as shown in Figure 4B and Figure 4C. Due
to the EF variance between the undoped and uniformly
doped, the carriers in the modulation doped material
overflow from the uniformly doped region to the
undoped region, as a result of enhanced μ due to eluding
of ionized impurity scattering.32 Recently, Feng et al used
a modulation doping technique in BiCuSeO and obtained
higher PF and ZT values of 5.4 μW cm−1 K−2 and 0.99 at
873 K, respectively, than for uniformly and heavily doped
BiCuSeO.62 Besides, this technique has been widely used
in PbTe quantum wells,63 MnSi1.7 film,64 bulk SrTiO3,65
and PbS66 to enhanced n without much deterioration of μ
of charge carriers.
3.3 | Strategies to reduce thermal
conductivity
For solids and semiconductors, κt rises mainly due to κe
and κ lat as mentioned in the above Equation (6).
Equations (3), (7), and (10) suggest that if S is enhanced,
then both σ and κt are reduced, which adversely affects
the ZT. Although various promising techniques such as
doping, alloying, nanostructures, nanocomposites are
used to reduce κ t and phonon scattering, nonetheless, to
trade-off between S, σ, and κ t; low-dimensional materials
and phonon scattering techniques are widely used.
Both these techniques are discussed in the following
subsections.
HASAN ET AL. 11

F I G U R E 9 Schematic diagram illustrating the growth process of vertically aligned SiNWs by VLS method [Colour figure can be viewed
at wileyonlinelibrary.com]

F I G U R E 1 0 Schematic diagram of a (A) crystal structure of PbTe and (B) movement of energy band convergence in PbTe with
enhanced temperature [Colour figure can be viewed at wileyonlinelibrary.com]

3.3.1 | Low-dimensional (D) materials Typically, nanodots are introduced in a TE material to

Dimensionality plays an elementary role to control the
fundamental properties of TE materials. Low-
dimensional materials modify the energy level at Eg
which causes changes in the DOS.24,67,68 For the past two
decades, research has been focused on various
nanostructures such as 0D (nanodots), 1D (nanowires),
and 2D (quantum wells and superlattices) to enhance
S and reduced κ t without affecting σ too much.67,69
reduce κlat instead of enhancing PF. For instance, Te-
nanodots in ZnO/BTS interfaces, enhanced σ and S due
to the quantum confinement effect,70 Ge-nanodots in Si-
based material reduced κ t to ~1.2 Wm−1 K−1,71 Au-
nanodots in Bi2Te3 nanocomposites reduced κ lat to
~0.47 Wm−1 K−1,72 and Sn-nanodots in Ge reduced κt to
2.305 Wm−1 K−1.73 Likewise, nanowires with small elec-
tron effective mass and a diameter greater than 5 nm
could attain low κ t as well as high PF,69 whereas,
12 HASAN ET AL.

F I G U R E 1 1 (A) Miscellaneous PbTe alloys with its ultra-low κlat value at divergent temperature range. (B) Enhanced ZT values of
best performing PbTe alloys using miscellaneous optimization techniques33,173,174,181-196 [Colour figure can be viewed at
wileyonlinelibrary.com]

superlattices enhance the performance of TE materials by Subramanian et al showed that the multiple-quantum-
reducing the κt by controlling the transport of phonons well of Bi2Te3-Sb2Te3 superlattices provide a high ZT
and electrons without any effect on PF.33 For instance, value of ~2.4 by reducing κ t.74
HASAN ET AL. 13

FIGURE 12 Crystal structure of SnSe with space group (A) Pnma and (B) Cmcm. Source: Reference 209 Copyright 2018, Reproduced
with permission from Elsevier. (C) Field Emission SEM image of Sn0.97Ge0.03Se nanoplates. Source: Reference 215 Copyright 2019,
Reproduced with permission from American Chemical Society. (D) SEM and optical image of synthesized flower-like Sn0.948Cd0.023Se
microplates. Source: Reference 216 Copyright 2019, Reproduced with permission from Wiley-VCH. Structure of Cu2Se at (E) α-phase and
(F) β-phase. Source: Reference 218 Copyright 2013, Reproduced with permission from Wiley-VCH [Colour figure can be viewed at
wileyonlinelibrary.com]
 14

TABLE 1 The effect of various dopants, alloying, nanostructures, and nanocomposites on the TE performance of promising PbTe alloys over the last decade

Materials Synthesis process Operating Seebeck Electrical Thermal PF (S2σ; ZT References

Temperature (K) coefficient conductivity conductivity μWcm−1 K−2)
(μVK−1) (Scm−1) (Wm−1 K−1)
Tl0.02Pb0.98Te Hot-pressed 300 130 520 1.8 8.78 0.146 Heremans
et al44
Tl0.02Pb0.98Te Hot-pressed 800 325 172 1 18.2 1.5 Heremans
et al44
PbTe N/A 300 −225 333 1.45 16.9 0.34 Li et al197
PbTe N/A 673 −310 105 1.1 10 0.65 Li et al197
Pb0.95Ce0.05Te Induction melting, ball milling, 300 −150 357 1 8 0.24 Li et al197
and spark plasma sintering
Pb0.95Ce0.05Te Induction melting, ball milling, 673 −220 208 0.8 10 0.88 Li et al197
and spark plasma sintering
PbTe:Na(2%) Melting, quenching, annealing, 700 225 543 1.5 27 1.28 Pei et al198
grinding, and hot-pressing
PbTe0.85Se0.15 with Na- Melting, quenching, annealing, 700 202 590 1.3 24 1.3 Pei et al198
doped grinding, and hot-pressing
Na0.02Mg0.03Pb0.95Te (2% Melting, quenching, annealing, 700 294 232 1.3 20 1.07 Pei et al199
Na-doped) grinding, and hot-pressing
Pb0.91Cr0.009Te with co- Melt growth process 550 275 625 1.2 47.3 ~2.2 Paul et al200
doped and Iodine
Pb0.96Mn0.04Te: Na Melting, quenching, annealing and 700 263 333 1 23 1.6 Pei et al201
hot-pressing
PbTe-SrTe (2%) N/A 800 285 250 0.95 20 1.7 Kanatzidis
et al202
PbTe-PbSnS2 (3%) N/A 700 −240 320 0.9 18.4 1.43 Kanatzidis
+ 0.055 mol% PbI2 et al202
PbTe-5 mol% CaTe (Na- N/A 800 265 350 1.15 24.6 1.7 Kanatzidis
doped) et al202
Na2Te-Sr0.01PbTe1.01 N/A 700 275 270 1.15 20.4 1.24 Kanatzidis
et al202
Na2Te-Sr0.02PbTe1.01 N/A 700 280 250 1.16 19.6 1.2 Kanatzidis
et al202
Na2Te-Sr0.03PbTe1.01 N/A 700 282 260 1.16 20.7 1.24 Kanatzidis
et al202
(Continues)
HASAN ET AL.
HASAN ET AL. 15

3.3.2 | Phonon scattering

References

Tan et al205

Sun et al206
Sie et al175
Li et al203

et al204
Heat conduction in the crystal lattice of solids is due to μ

Ding
of charge carriers and lattice vibration, which is carried
out by phonon waves. κ lat in the case of bulk TE materials
could be defined as75,76:

~0.41
~1.4
0.81
ZT

1.5

1.5
1
μWcm−1 K−2)

κlat = CV2g τ ð13Þ

3
PF (S2σ;

where C, Vg, and τ defines specific heat capacity, group

N/A
40.9

0.67

29.7
108

velocity, phonon relaxation time, respectively. Among all

the parameters that are defined in quation (13), τ has been
the main focus for TE materials, being strongly dependent
on frequency. To suppress κ lat of a TE material, τ needs to
conductivity
(Wm−1 K−1)

be minimized by scattering the phonons. So far, miscella-

Thermal

neous strategies have been used to scatter the phonons

~0.55

N/A

N/A
~0.5

~2.2

such as point defects, dislocation arrays, grain boundary,

stalking faults, and twin boundary. Among all phonon
scattering techniques, point defect scattering is the most
efficacious technique to reduce κ lat. These defects perturb
conductivity

the crystal lattice at an extent of interatomic distance or at

Electrical

(Scm−1)

most a unit cell that targets the high frequency pho-

~1428.3

~2000

nons.38,77,78 The mechanism of reducing κlat by point

53.52
N/A

625

defects mainly comes from the large mass and strain fluc-
tuations between the guest and the host atoms. These fluc-
tuations could be enhanced by using interstitial atoms,78,
Temperature (K) coefficient

79 creating vacancies80-83 or by substitution of atoms in

(μVK−1)
Seebeck

TE materials.84-87 Besides, dislocation arrays are usually

−143

−112

−218
~275

N/A

used to scatter mid-range frequency phonons. Dislocations

scatter the phonons via dislocation lines and dislocation
cores. The crystal structure close to a dislocation line is
finitely strained, as a consequence, scattering of phonons
Operating

will occur once they move near to the dislocation line.

Moreover, κlat has been reduced via interfacial defects
723

Melt spinning and rapid induction 773

Melting and spark plasma sintering 900

700

300

through grain boundaries, stacking faults, and twin

boundaries.88-90 Typically, melting, spinning, or high-
Cold pressing and spark plasma
Melting, quenching, and hot-

energy ball milling, integrated with spark plasma sintering

Ball milling and hot-pressed

or direct-current hot pressing, are used to fabricate nano-

structured materials with a high density of grain bound-
Synthesis process

aries. It should be noted that all these techniques are

autonomous with each other, and that reduces κlat of the
hot pressing

sintering

sintering

TE materials, and as a result, enhances ZT.

pressing

4 | H IG H P E R F O R M A N C E
(Continued)

I NO R GA NI C TE M A T E R I A L S
n-type PbTe doped-
(Pb0.96Na0.04Te)1-x

Pb0.9875Sb0.0125

Inorganic TE materials are the classic and most widely

(Sm2Se3)x
PbTeCd0.02

used materials in the TE industry. The aim herein is to

Zn0.02PbTe
Materials
TABLE 1

Na2Te

provide an overview and the most current progress of

prominent inorganic TE materials according to their tem-
perature range. The most conventional and recent
16
inorganic TE materials are discussed in the following
subsections.
4.1 | Near-room temperature inorganic
TE material
High performance materials, like bismuth telluride, and
more recently, silicon, have been studied for TE applica-
tions in the near-room temperature range. These mate-
rials are extensively used to harvest the human body and
on-chip energy. The material properties, crystal structure,
and recent techniques to elevate the ZT of both bismuth
telluride and silicon are discussed under this section.
4.1.1 | Bismuth telluride (Bi2Te3)
Bi2Te3 based alloys are the most notable and widely used
material in the TE industry and have been studied exten-
sively since the 1960s.91-93 They crystallize in the rhombo-
hedral space group and are made of five, atomic thick,
lamellae, Te1-Bi-Te2-Bi-Te1, each of which is called a quin-
tuple layer (QL). These QL layers are stacked by van der
Waals (vdW) interactions along the c-axis in the unit cell,
where the Te2 atoms are covalently bonded to the sur-
rounding six Bi-atoms by sp3d2 hybrids, as depicted in
Figure 5.93,94 The values of its unit cell parameters are
a = 4.345 Å and c = 30.483 Å at room temperature.95 Fur-
thermore, it is a narrow gap semiconductor with an Eg of
~0.13 eV at room temperature, which is detrimental for TE
applications since the charge carriers of this material get
easily excited into CB, with increased temperature, and as a
consequence, the same number of holes remain in
VB. These remaining electron-hole pairs, thus contribute to
the total heat conduction and as a result, S decreases.96,97
HASAN ET AL.
Therefore, to use this material in cases of high temperature
applications, it must have an enhanced Eg.
Figure 6A,B shows the best performing Bi2Te3 alloys
that exhibit ultra-low κ t and provide high ZT values. Typ-
ically, p-type Bi2Te3 alloys, provide very higher ZT values
rather than n-type Bi2Te3 alloys, due to a low κ t. For
instance, Sharma et al obtained a highest ZT value of
2.42 at 700 K for p- type Bi2Te3 alloys, while n-type Bi2Te3
alloys have a high κ t due to low Eg and minority n.98 Sig-
nificant research has been already done in order to
enhance Eg and to reduce κ t, of n-type Bi2Te3 via diver-
gent techniques. Among all techniques, doping,99,100
alloying,96 nano-structuring,101, 102 nanocomposites,103
nanoplates,104 quantum dots,105 and twin boundary engi-
neering106 are the most conventionally used techniques.
Recently, Rashad et al obtained an Eg of 4.8 eV for n-type
Bi2Te3 nanoparticles in the presence of Sodium hydroxide
(NaOH), which is much higher than the Eg of ~0.13 eV
for pure Bi2Te3.107 Besides, using dislocation arrays at
grain boundaries of n-type Bi2Te3 is an effective and non-
invasive way to reduce κt by preventing the contribution
of minority carriers to electronic transport properties.21
For instance, Kim et al used liquid-phase compaction to
form dislocation arrays at low-energy grain boundaries,
via melt-spun and liquid-phase sintering process, as
depicted in Figure 7A,B.126 The main function of the
liquid-phase compaction is to scatter the mid-range fre-
quency phonons to reduce κ lat (Figure 7C). They reported
a reduced κlat of 0.33 Wm−1 K−1 (Figure 7D) and an
enhanced ZT value around 1.86 at 320 K. Besides, Yang
et al synthesized n-type Bi2Te3 nanostructures and
showed an ultra-low κlat of ~0.2 Wm−1 K−1 due to high
density grain boundaries via dislocations.101 Moreover,
Shin et al reported a low κ lat of 0.63 Wm−1 K−1 for
reduced graphene oxide (RGO) incorporated
Bi0.36Sb1.64Te3 composites.127
F I G U R E 1 3 Schematic diagram
of (A) Binary Skutterudites with
metal atoms (M) that construct a
cubic sub-lattice and pnictogen atoms
(X) that form six rings along (010),
(001), and (100) direction, and
(B) filled Skutterudites with the
general structure of EPyT4X12. Source:
Reference 227 Copyright 2019,
Reproduced with permission from
Elsevier [Colour figure can be viewed
at wileyonlinelibrary.com]
HASAN ET AL. 17

F I G U R E 1 4 (A) Miscellaneous Skutterudites with its lowest κt value at divergent temperature range. (B) Miscellaneous optimization
techniques for the enhancement of ZT values of high performance skutterudites226,228,238-256 [Colour figure can be viewed at wileyonlinelibrary.com]

4.1.2 | Silicon nanowire structure, is a recently studied material in the TE indus-

try. Nonetheless, the use of bulk Si is incompetent in the
Silicon (Si), a tetravalent metalloid and a semiconductor TE industry as it has moderate S, low σ, and very high κ t
that consists of a face-centered diamond-cubic crystal of 148 μVK−1, 111 Scm−1 and 150 Wm−1 K−1 at room
 18

TABLE 2 Effect of dopants, nanocomposites, and filler atoms on the performance of n-type and p-type Skutterudites at divergent temperature range over the last decade

Materials Synthesis process Operating Seebeck Electrical Thermal conductivity PF (S2σ; ZT References
Temperature (K) coefficient conductivity (Wm−1 K−1) μWcm−1 K−2)
(μVK−1) (Scm−1)
In0.2Ce0.1Co4Sb12 N/A 573 340 230 1 26.5 1.6 Subramanian
et al257
In0.2Ce0.2Co4Sb12 N/A 573 295 330 1 28.7 1.7 Subramanian
et al257
In0.25Ce0.1Co4Sb12 N/A 573 325 500 2.2 52.8 1.4 Subramanian
et al257
In0.25Ce0.2Co4Sb12 N/A 573 300 450 1.6 40.5 1.5 Subramanian
et al257
In0.2Ce0.1Yb0.1Co4Sb12 N/A 573 325 320 1.65 33.8 1.2 Subramanian
et al257
In0.2Ce0.1Sm0.1Co4Sb12 N/A 573 305 280 1.15 26 1.3 Subramanian
et al257
In0.2Ce0.1Tb0.1Co4Sb12 N/A 573 348 280 1.4 33.6 1.4 Subramanian
et al257
In0.2Ce0.1Ho0.1Co4Sb12 N/A 573 310 230 1 2.21 1.3 Subramanian
et al257
Ba0.1Yb0.2Co4Sb12 Melting, annealing, and spark 800 −213 960 4.03 43.5 0.85 Ballikaya
plasma sintering et al258
Ba0.1Yb0.2In0.1Co4Sb12 Melting, annealing, and spark 300 −137 1779 3.76 22.1 0.26 Ballikaya
plasma sintering et al258
Ba0.1Yb0.2In0.1Co4Sb12 Melting, annealing, and spark 800 −205 1040 3.5 437 0.99 Ballikaya
plasma sintering et al258
Ba0.1Yb0.2In0.2Co4Sb12 Melting, annealing, and spark 300 −126 1950 3.60 31 0.25 Ballikaya
plasma sintering et al258
Ba0.1Yb0.2In0.2Co4Sb12 Melting, annealing, and spark 800 −178 1200 3.5 38 0.87 Ballikaya
plasma sintering et al258
Ba0.1Yb0.2In0.25Co4Sb12 Melting, annealing, and spark 300 −123 2065 3.55 31.2 0.26 Ballikaya
plasma sintering et al258
Ba0.1Yb0.2In0.25Co4Sb12 Melting, annealing, and spark 800 −209 1280 3.38 56 1.32 Ballikaya
plasma sintering et al258
Ba0.15Yb0.2In0.2Co4Sb12 Melting, annealing, and spark 300 −117 2345 3.55 32.1 0.27 Ballikaya
plasma sintering et al258
Ba0.15Yb0.2In0.2Co4Sb12 800 185 1410 3.32 48.3 1.16
(Continues)
HASAN ET AL.
TABLE 2 (Continued)

Materials Synthesis process Operating Seebeck Electrical Thermal conductivity PF (S2σ; ZT References
Temperature (K) coefficient conductivity (Wm−1 K−1) μWcm−1 K−2)
HASAN ET AL.

(μVK−1) (Scm−1)
Melting, annealing, and spark Ballikaya
plasma sintering et al258

Ba0.06La0.05Yb0.02Co4Sb12 Induction melting, high 850 −21 1052 3 46.3 1.28 Shi et al259
temperature annealing, and spark
plasma sintering
Ba0.08La0.05Yb0.04Co4Sb12 Induction melting, high 300 −126 2398 2.7 38.1 0.42 Shi et al259
temperature annealing, and spark
plasma sintering
Ba0.08La0.05Yb0.04Co4Sb12 Induction melting, high 850 −192 1428 2.6 52.6 1.71 Shi et al259
temperature annealing, and spark
plasma sintering
Ba0.10La0.05Yb0.07Co4Sb12 Induction melting, high 300 −107 3003 3.1 34.4 0.33 Shi et al259
temperature annealing, and spark
plasma sintering
Ba0.10La0.05Yb0.07Co4Sb12 Induction melting, high 850 −185 1666 3.1 57 1.56 Shi et al259
temperature annealing, and spark
plasma sintering
Ba0.09La0.04Yb0.13Co4Sb12 Induction melting, high 300 −104 3058 3 33.1 0.33 Shi et al259
temperature annealing, and spark
plasma sintering
Ba0.09La0.04Yb0.13Co4Sb12 Induction melting, high 850 −174 1818 3.3 55 1.41 Shi et al259
temperature annealing, and spark
plasma sintering
Ba0.09La0.04Yb0.14Co4Sb12 Induction melting, high 300 −93 3367 3 29.1 0.29 Shi et al259
temperature annealing, and spark
plasma sintering
Ba0.09La0.04Yb0.14Co4Sb12 Induction melting, high 850 −161 2220 3.47 57.5 1.4 Shi et al259
temperature annealing, and spark
plasma sintering
In0.2Yb0.2Co4Sb12 Melting and spark plasma sintering 300 −141 1500 3.6 30 0.25 Graff et al260
In0.2Yb0.2Co4Sb12 Melting and spark plasma sintering 800 −216 1100 3.35 51.3 1.22 Graff et al260
Ce0.1In0.1Yb0.2Co4Sb12 Melting and spark plasma sintering 300 −174 1500 3.34 45.4 0.40 Graff et al260
Ce0.1In0.1Yb0.2Co4Sb12 Melting and spark plasma sintering 800 −225 1000 3.08 51 1.34 Graff et al260
(Continues)
19
 20

TABLE 2 (Continued)

Materials Synthesis process Operating Seebeck Electrical Thermal conductivity PF (S2σ; ZT References
Temperature (K) coefficient conductivity (Wm−1 K−1) μWcm−1 K−2)
(μVK−1) (Scm−1)
Ce0.1In0.15Yb0.15Co4Sb12 Melting and spark plasma sintering 300 −143 1500 3.47 30.7 0.26 Graff et al260
Ce0.1In0.15Yb0.15Co4Sb12 Melting and spark plasma sintering 800 −208 1200 3.04 52 1.4 Graff et al260
In0.27Co4Sb11.9 Melting and hot pressing 750 −227 8 × 102 2.7 41.2 1.2 Tang et al261
3
Ba0.14In0.23Co4Sb12 High pressure sintering/high 850 −208 0.98 × 10 ~6 42.3 1.8 Rogl et al262
pressure-high temperature
DD0.7Fe2.7Co1.3Sb11.8Sn0.2 Melting reaction technique and 850 N/A N/A N/A N/A 1.45 Rogl et al263
quenching
DD0.59Fe2.7Co1.3Sb11.8Sn0.2 Melting reaction technique and 780 182 8.93 0.185 32 (at 672 K) 1.3 Rogl et al263
quenching
Sm0.7Fe2.8Ni1.2Sb12.8 Melting, high temperature 560 196 4.6 × 102 N/A 17.6 0.55 Carlini
annealing et al264
Al0.3Yb0.25Co4Sb12 Ball milling and Sintering 850 212 N/A 2.7 43 (at 877 K) 1.36 Elsheikh
et al252
Co23.4Sb69.1Si1.5Te6.0 Melting and spark plasma sintering 773 190 8 × 102 1.5 29 1.6 Khan et al241
3
Ce0.8Fe3CoSb12 Ball-milling, melting-annealing and 773 140 1.1 × 10 2.5 21.6 0.68 Prado-Gonjal
hot pressing et al265
Ce0.5Yb0.5Fe3.25Co0.75Sb12 Ball milling, melting-annealing and 823 150 0.98 × 103 2.65 22 0.93 Prado-Gonjal
hot pressing et al265
CoSb2.875Te0.125 Hand milling and sintering 820 −210 9.3 × 102 3 41 1.1 Liang et al240
Mm0.6Co4Sb12 Melting and Spark Plasma Sintering 700 −150 N/A 4.2 N/A 0.25 Sekine
et al266
In0.2Ce0.15Co4Sb12/InSb Induction melting and spark plasma 800 −210 10.1 × 102 2.4 44.5 1.5 Li et al267
sintering
La0.5Co4Sb11.5Te0.5 Ball milling and spark plasma 792 −228 0.04 × 104 4.27 20 0.47 Said et al268
sintering
Ag 2 wt% -Ba0.5Co4Sb12 N/A N/A N/A N/A N/A N/A 1.4 Peng et al269
Ni0.15Co3.85Sb12 Advanced high pressure and high 600 −238 0.44 × 103 ~3 25 0.52 Kong et al270
temperature synthesis
n-type Melt solidification and spark 800 −200 15 × 102 3.15 60 1.48 ± Lee et al271
In0.12Yb0.20Co4.00Sb11.84 plasma sintering 0.17
750 170 13 × 102 2.4 37.6 Lee et al271
(Continues)
HASAN ET AL.
HASAN ET AL. 21

temperature, respectively. As a consequence, it exhibits

Bashir et al252
a very low PF of 2.43 μWcm−1 K−2 and a ZT of 0.0004.33

Kong et al273
References

Benyahia
et al272

et al247
The use of Si in TE applications in the form of nano-

1.096 Bouhafs
wires has been started after Boukai et al obtained a high
1.15 ± ZT value of ~1 at 200 K for silicon nanowires
0.13 (SiNWs).128 This research has brought aspiration for the
1.15

0.91
ZT

1.4
use of Si in the TE industry in the form of nanowires.
μWcm−1 K−2)

As compared to bulk Si, SiNWs have low κt and have a

great effect on phonon transportation by increasing the
Thermal conductivity PF (S2σ;

phonon-boundary scattering and changing the phonon

N/A

N/A
12.3

23 dispersion relation. Besides, they have a large mean free

path length, in between electrons and phonons, at room
temperature. For an electron, it is 110 nm in the case of
highly doped samples, and for phonons, it is about
(Wm−1 K−1)

300 nm.128-130 As a result, the structure of SiNWs, below

300 nm, has a reduced κ t without affecting S and σ
value.
N/A

N/A
~1.9
1.9

The surface roughness of SiNWs plays an imperative

role in phonon-boundary scattering. The Surface rough-
ness of SiNWs enhance the performance of TE by
conductivity

reducing the κ lat. NWs widths, less than 50 nm, are

~0.56 × 103

0.052 × 104
Electrical

found to very effective for TE operations.129 Moreover,

(Scm−1)

Zianni showed that reduction of κ t could be possible

N/A

N/A

without affecting S by using modulated SiNWs in the

presence of single constrictions on the electron trans-
port properties of SiNWs.131 She used the Monte-Carlo
Temperature (K) coefficient

simulation technique to study the effect of width-

(μVK−1)
Seebeck

modulation on the TE properties of SiNWs. Neverthe-

~ −210
N/A

N/A

less, the obtained simulation results show that the addi-

220

tion of second constrictions on the electron transport

properties of SiNWs decreased the σ.
SiNWs can be synthesized by using various method
Operating

such as reactive ion etching (RIE),132-135 laser

ablation,136-139 chemical vapor deposition (CVD),140-142
692

837

700

700

and thermal evaporation.143-145 Nonetheless, SiNWs

incorporated in a TEG should be grown perpendicularly
and uniform, on a substrate, and each nanowire should
Hand milling and hot pressing
Ball milling and spark plasma

melting, annealing, and spark

Melt solidification and spark

exhibit good TE properties. Based on this, the synthesis

High temperature and high

of the SiNWs is mostly done by metal-assisted chemical

etching (MACE)146-150 and vapor-liquid-solid (VLS) pro-
Synthesis process

Ce0.91Fe3.40Co0.59Sb12.14 plasma sintering

plasma sintering

cesses.151-153 Both these processes provide more control

over diameter, length, and the electronic properties of
sintering

pressure

SiNWs that are essential for this application. MACE is a

promising technique to fabricate SiNWs with high
aspect ratios. Besides, it does not require masking and
(Continued)

dry etching, which makes the process simple, fast and

low-cost.154 Generally, etching of Si occurs in the
Ba0.3Ni0.15Co3.85Sb12

n-type In0.25Co4Sb12
Co3.5Sb11.8Pd0.5Se0.2

<100> direction anisotropically to form vertically

In0.3La0.5Co4Sb12

aligned SiNWs. Nevertheless, researchers have devel-

oped diverse methods to form vertically aligned SiNWs,
Materials
TABLE 2

on non (100) substrates, or to form zig-zagged155,156

p-type

slanted or curve shaped NWs, or pores.150 For the first

time, Peng et al proposed a MACE technique for a large
22
area growth of SiNWs on Si wafers, in an aqueous HF
solution containing AgNO3, near room temperature
(Figure 8B).157 In this technique, noble metals such as
gold (Au) and silver (Ag) are used, on a Si substrate, to be
catalyzed, in the presence of HF and H2O2 as an aqueous
solution, and an oxidant, respectively. The formation of
vertically aligned SiNWs is depicted in Figure 8A. This
synthesis technique has been widely used in TE devices
to grow vertical SiNWs. For instance, Tahrim et al inves-
tigated the TE performance of SiNWs, using a MACE
process, at an etching rate of ~0.2303 μm/min for p-type
Si, which is slightly higher than that of the n-type Si,
which is about ~0.1861 μm/min. A diameter of SiNWs
around 70-100 nm was obtained and they reported maxi-
mum Seebeck voltages of ~35 and ~16 mV, for p-type and
n-type SiNWs, respectively, at ΔT = 278 K and S values
of ~8 and ~4 mVK−1, for p-type, and n-type SiNWs,
respectively.158 In addition, Lee et al fabricated a TEG
using n-type and p-type SiNWs using a dry etching pro-
cess. This process permitted an increase in the surface
roughness of the SiNWs, and as a consequence, a reduc-
tion in κt which was about 10.1 and 14.8 Wm−1 K−1, for
n- and p-type SiNWs, respectively. The fabricated device
generated an open circuit voltage of 216.8 mVcm−2 and a
maximum power of 3.74 μWcm−2 at ΔT of 180 K, which
is the highest reported value for a SiNW based TE mod-
ule to date.159
In the MACE process, the morphology and structure
of SiNWs depend on several parameters such as the metal
catalyst,160 concentrations of HF and H2O2,155,161 etching
time,162,163 and etching temperature.162 Recently, Chen
et al found that a conductive back-substrate incorporated
on p-type Si, with the assistance of MACE, could improve
the overall performance of SiNWs.164 The fabrication
HASAN ET AL.
steps of the back-substrate with MACE process are
depicted in Figure 8A. Conductive back-substrates extract
the electrons that are associated with Si and help in the
oxidation of Si during Si/Ag nucleation, and as a result,
increase the etching rate of the MACE process. Besides,
they found that the sidewalls and the length of the SiNWs
also increased and this hindered the formation of
nanopores from the catalytic etching reaction.
Additionally, SiNWs can be grown by another tech-
nique called a vapour-liquid-solid method (VLS). In this
process, metal particles such as Au, Ag, Cu, Al, and In
are used as a catalyst to initiate and define nucleation, as
well as to activate/decompose the molecular reactants,
while SiH4 and SiCl4 are used as gaseous Si precur-
sors.165 The overall VLS process is depicted in Figure 9,
where an Au-film is deposited on a Si wafer and heated
up above the eutectic temperature where an Au-Si liquid
alloy droplet forms upon the substrate from where the
SiNWs grow. Then Si, in the form of gaseous SiH4, enters
the chamber as a vapor and the Au catalyst decomposes
the SiH4 into Si and H2 near film is deposited on a Si
wafer and heated up above the eutectic temperature
where an Au-Si liquid alloy droplet forms upon the sub-
strate from where the SiNWs grow. Then Si, in the form
of gaseous SiH4, enters the chamber as a vapor and the
Au catalyst decomposes the SiH4 into Si and H2 near the
growth site. The Si atoms are then incorporated into Au
and form Au-Si droplets. The continuity of this process,
then leads to the growth of SiNWs with the alloy droplet
riding atop the growing wire. This method offers several
advantages such as its versatility of control over the
nanowire diameter, growth direction, periodic twining,
and crystal structure.166 Besides, it provides a high nano-
wire density with a uniform distribution over a large area
F I G U R E 1 5 Schematic
diagram depicting the polyanionic
framework of Type-I and Type-II
clathrates (dark blue color denotes
pentagonal dodecahedra, light blue
color denotes tetrakaidecahedra).
Source: Reference 252 Copyright
2018, Reproduced with permission
from Elsevier [Colour figure can be
viewed at wileyonlinelibrary.com]
TABLE 3 Effect of synthesis process, various dopants, and material composition on TE properties of clathrates

Seebeck Electrical
Operating coefficient conductivity Thermal conductivity PF (S2σ;
HASAN ET AL.

Materials Synthesis process Temperature (K) (μVK−1) (Scm−1) (Wm−1 K−1) μWcm−1 K−2) ZT References
Ba8Ni0.31Zn0.52Ga13.06Ge32.2 Arc/induction melting and spark 1000 N/A N/A N/A 15 1.2 Shi et al288
plasma sintering
Ba8Au5.3Ge40.7 Melting and spark plasma 511 340 40 0.7 4.6 0.3 Zhang
sintering et al289
Ba8Au5.3Ge40.7 Melting and spark plasma 680 N/A N/A ~0.25 N/A 0.9 Zhang
sintering et al289
Ba8Ni0.22Zn7.22Ge37.12Sn1.44 Arc melting and hot pressing 830 ~ −180 N/A ~1.05 N/A 0.9 Falmbigl
et al290
Ba8Ga15.7In0.2Sn30.1 Self-flux 540 N/A N/A N/A N/A 1.05 Chen et al291
Ba8Ga16Ge30 alloys High-temperature and high- 773 176.2 ~870 (at 300 K) 0.71 11.62 1.14 Sun et al292
pressure
Cu-doped Ba24Cu6Ge94 Melting and spark plasma 873 ~ −79 N/A ~2.15 4.1 0.17 Fu et al293
sintering
Ag-doped Ba24Ag6Ge94 Melting and spark plasma 873 ~ −87 N/A ~2.1 7.8 0.31 Fu et al293
sintering
Ba8Cu14Ge6P26 Bridgman growth and solid-state 812 234 102.04 0.7 5.62 0.63 Wang
reaction et al294
Ba8Cu16P30 Bridgman growth and solid-state 812 46 526.32 1.4 11 0.07 Wang
reaction et al294
Sr7.92Ga15.04Sn0.35Ge30.69 Flux method 750 N/A N/A 0.8 N/A 1 Deng et al295
K9Ba15Al38Sn98 Direct melting and spark plasma 590 N/A N/A N/A N/A 0.57 Utsunomiya
sintering et al296
K9Ba15Al31Ga8Sn97 direct melting and spark plasma 640 ~−200 ~180 N/A 7.2 0.82 Utsunomiya
sintering et al296
K7.6Ga5.8Zn0.8Si39.6 Melting and spark plasma 320 −67.8 N/A 1.8 N/A 0.0096 Singh
sintering et al297
(Eu/Ba)8Ga16Sn30 Flux method 483 N/A N/A N/A 15.1 0.87 Deng et al298
(Eu/Ba)8Ga16Sn30 Flux method 550 ~−247 116 N/A 82 0.46 Cheng
et al299
Bi1.8Sb0.2Te2.7Se0.3 N/A 423 N/A N/A N/A N/A 0.89 Shin et al300
Ba8Cu6Si40 High temperature and high 720 62 N/A 1.26 N/A ~0.16 Liu et al301
pressure
(Continues)
23
 24 HASAN ET AL.

of the wafer.167 Calaza et al surveyed the TE properties

References
Yan et al302
of ordered dense arrays of p-type SiNWs grown by VLS

et al303
technique and reported an enhanced S and reduced κt

Bouyrie
value of ~128.73 μVK−1 and ~2.82 Wm−1 K−1, at room
temperature, respectively, while its PF was in the range
between 8.3 and 25.5 μWcm−1 K−2.168 Recently, Noyan
μWcm−1 K−2) ZT
0.9
0.7
et al designed and fabricated a planer μTEG with an
integrated heat exchanger, where, SiNWs, SiGe NWs,
and Si-microbeams were used as TE materials. These TE
Thermal conductivity PF (S2σ;

materials were fabricated with Chemical Vapor Deposi-

N/A
N/A

tion (CVD) and the VLS method. They obtained maxi-

mum power densities about 41.6, 45.2, and
34.5 μW cm−2 for SiNWs, SiGe NWs, and Si-micro
beams, respectively, with a hot plate temperature of
(Wm−1 K−1)

373 K.169
N/A
0.58

4.2 | Medium temperature inorganic

TE materials

The chalcogenides of lead, tin, copper, skutterudites,

conductivity
Electrical

and clathrates have been studied for medium range tem-

(Scm−1)

perature TE applications, that is, in the range in

N/A
N/A

between 450 and 850 K. Among these materials, lead

chalcogenides have been utilized in the radioisotope
thermoelectric generator used by NASA since the 1960s,
besides, skutterudites and clathrates have been used in
coefficient
Temperature (K) (μVK−1)

many commercial generators as well. The material prop-

Seebeck

erties, crystal structure, and recent techniques to

−208
N/A

enhance the ZT of lead telluride, skutterudites, and

clathrates are discussed under this section.
Operating

4.2.1 | Lead telluride (PbTe)

900
665

PbTe and its alloys have been used in TE power genera-

tion applications for almost 50 years. PbTe is one of the
most efficient inorganic TE materials for mid-range
Cu26Nb2Ge6TxS32 (T = Co, Melting and spark plasma

(600-800) K temperature applications.93 It consists of a

NaCl crystal structure with a lattice parameter
Synthesis process

a = 0.6464 nm,170 with Pb atoms occupying the cation

and Te forming the anionic lattice, as depicted in
sintering

Figure 10A. It is a narrow gap semiconductor with a

band gap of 0.25 and 0.32 eV at 0 and 300 K, respec-
N/A

tively. The valence band structure of PbTe consists of

(Continued)

two different valleys with divergent temperature, as

depicted in Figure 10B.171 In Figure 10B, the higher val-
Ba8Cu4.6Ga1.0Ge40.4

ley determines the energy gap at room temperature,

which is denoted by L, whereas the lower valley is
Ni; x ≤ 1)

defined by Σ. The dotted blue line indicates the move-

Materials
TABLE 3

ment of the L band as temperature increases, neverthe-

less, the lower valley does not change much. These two
valleys converge at a high temperature, which leads to
HASAN ET AL. 25

the optimization of n and further enhancement of the
PF.171,172
Although these alloys have been extensively studied
and used due to their high electrical transport properties,
their narrow energy gap and high κlat value make them
unsuitable for high efficiency TE applications. So far, var-
ious optimization techniques have been used to reduce
κ lat and enhance S, of PbTe, via using nanostructures,173
dislocations,81,170 band converging,171,172 dopants,174-176
alloying,177 and nanocomposites.178 Figure 11 depicts
recently synthesized best performing PbTe alloys with
ultra-low κlat (Figure 11A) and their enhanced ZT via
miscellaneous optimization techniques (Figure 11B). All
these optimization techniques not only reduced κ lat but
also enhanced the ZT value of PbTe alloys. For instance,
introducing both n-type and p-type doping, where Pb-
majority PbTe behaves as n-type semiconductor and Te-
majority PbTe behaves as p type semiconductor, the

F I G U R E 1 6 Crystal structure of promising zintl phases (A) BaGa2Sb2, (B) YbZn2Sb2, (C) Ca3AlSb3, (D) Yb14MnSb11. Source: Reference
234 Copyright 2018, Reproduced with permission from Elsevier. (E) Crystal structures of bulk Mg3Sb2 and its (F) mono layer. The red atoms
are Mg and the green atoms are Sb. The band structures of (G) bulk Mg3Sb2 and (H) mono layer (The Fermi energy is set to zero). Source:
Reference 310 Copyright 2019, Reproduced with permission from Elsevier [Colour figure can be viewed at wileyonlinelibrary.com]
 26

TABLE 4 The TE properties of emerging Zintl compounds with divergent temperature range

Electrical Thermal
Operating Seebeck conductivity conductivity PF (S2σ;
Materials Synthesis process Temperature (K) coefficient (μVK−1) (Scm−1) (Wm−1 K−1) μWcm−1 K−2) ZT References
Yb14Mn0.6Zn0.4Sb11 Sn-flux and hot-pressing 1275 190 ~238 0.95 8.6 1.1 Brown et al333
Yb14Mn0.2Al0.8Sb11 Sn-flux and hot-pressing 1223 250 100 0.5 6.25 1.3 Toberer et al334
Yb13.6La0.4MnSb11 Sn-flux and hot-pressing 1150 230 117.6 0.68 6.22 1.15 Toberer et al335
YbZn1.9Mn0.1Sb2 Melting and hot-pressing 726 150 666.7 1.6 15 0.65 Yu et al336
EuZn2Sb2 Melting and spark plasma 713 180 555.6 1.45 18 0.9 Zhang et al337
sintering
Zn2.98Nb0.02Sb3 Melting and hot-pressing 680 180 ~358 0.72 ~11.6 1.1 Li et al338
Zn4Sb2.92Te0.08 Melting and hot-pressing 673 170 2.8 × 103 0.75 81 1 Li et al339
Yb14MnSb11 Grinding, Sn-flux, and hot- 300 43 500 0.83 0.92 0.03 Snyder et al340
pressing
Yb14MnSb11 Grinding, Sn-flux and hot- 1200 190 185 0.72 6.7 1.1 Snyder et al340
pressing
Yb14Mn0.67Zn0.33Sb11 Grinding, Sn-flux and hot- 1200 240 212 0.83 12.2 1.7 Snyder et al340
pressing
Yb14Mn0.33Zn0.67Sb11 Grinding, Sn-flux and hot- 1200 190 222 0.65 8 1.47 Snyder et al324
pressing
Yb14Mn1Al0.00Sb11 Grinding, Sn-flux and hot- 1200 200 212 0.7 8.48 1.48 Snyder et al340
pressing
Yb14Mn0.8Al0.2Sb11 Grinding, Sn-flux and hot- 1200 230 208 0.74 11 1.76 Snyder et al340
pressing
Yb14Mn0.4Al0.6Sb11 Grinding, Sn-flux and hot- 1200 230 131 0.62 6.93 1.33 Snyder et al340
pressing
Yb13CaMnSb11 Flux growth 1175 200 181.8 0.8 7.3 0.9 Cox et al341
Ca4.75Na0.25Al2Sb6 Hot-pressing 1000 200 100 0.7 40 0.6 Toberer et al342
Yb0.6Ca0.4Cd2Sb2 Grinding and spark plasma 700 240 227.3 0.9 13 0.96 Cao et al343
sintering
Yb0.75Eu0.25Cd2Sb2 Heating and spark plasma 650 240 250 1 14.4 0.97 Zhang et al344
sintering
Zn4Sb3.94Bi0.06 Heating and hot pressed 673 160 0.42 × 103 0.7 10 1.09 Zhou et al345
Zn3.98Fe0.02Sb3 Melting and hot-pressing 300 140 N/A 0.95 N/A 0.12 Pan et al346
Zn4Sb3.985I0.015 Melting and hot-pressing 300 110.8 N/A 1.1 N/A 0.1 Pan et al347
(Continues)
HASAN ET AL.
TABLE 4 (Continued)

Electrical Thermal
Operating Seebeck conductivity conductivity PF (S2σ;
HASAN ET AL.

Materials Synthesis process Temperature (K) coefficient (μVK−1) (Scm−1) (Wm−1 K−1) μWcm−1 K−2) ZT References
Zn4Sb2.985Se0.015 Melting and hot-pressing 300 120 N/A 0.9 N/A 0.11 Pan et al348
Yb14MnSb11 N/A 1275 220 166.7 0.5 8 1.3 Paik et al349
Ca4.8Zn0.2Al1.8Sb6 Ball milling and hot-pressing 773 150 166.7 1 3.75 0.4 Zevalkink et al350
Ca2.94Na0.06AlSb3 Ball milling and hot-pressing 1050 260 55.6 0.7 3.76 0.78 Zevalkink et al351
YbCd1.85Mn0.15Sb2 direct solid-state reaction and 650 245 175.4 0.6 10.5 1.14 Guo et al352
spark plasma sintering
Zn3.96Cd0.04Sb3 Heating and sintering 600 200 3.2 × 102 0.65 12.8 1.3 Wang et al353
YbMg2Bi2 Melting, grinding, and annealing 650 180 N/A 1.8 N/A 0.44 May et al354
Ca5Al1.9Mn0.1Sb6 Ball milling and hot-pressing 900 21 95.2 0.85 4.2 0.4 Zevalkink et al355
Sr3Ga0.93Zn0.07Sb3 Ball milling and hot-pressing 1000 21 125 0.6 5.5 0.94 Zevalkink et al356
Zn3.99Ge0.01Sb3 Melting 680 203 ~3.48 0.72 0.143 1.35 Wang et al357
Zn3.98Pb0.02Sb3 Heating and spark plasma 660 18 ~377 0.75 12.2 1.2 Wang et al358
sintering
Ca5Ga1.9Zn0.1Sb6 Milling and pressing 773 150 24.3 1.1 0.546 0.35 Johnson et al359
Ca5In1.9Zn0.1Sb6 Ball milling and hot-pressing 973 180 166.7 0.8 5.4 0.7 Zevalkink et al360
Mg3Bi0.2Sb1.8 Mechanical milling and hot- 750 400 25 0.58 4 0.6 Bhardwaj et al361
pressing
Yb9Mn4.2Sb9 Ball milling and sintering 950 185 128.2 0.58 4.38 0.7 Bux et al362
Eu11Cd6Sb12 Flux growth 773 125 100 0.68 1.56 0.23 Kazem et al363
Ca5Al0.95In0.95Zn0.1Sb6 Ball milling and hot-pressing 900 200 125 0.7 5 0.7 Zevalkink et al364
Yb0.99Zn2Sb2 Ball milling and hot-pressing 800 160 769.2 1.7 19.6 0.85 Zevalkink et al365
Zn3.82In0.18Sb3 Grinding and sintering 700 222 N/A 0.62 12 1.41 Tang et al366
Zn3.96Al0.04Sb3 Heating and annealing 273 115 N/A 0.6 N/A 0.23 Carlini et al367
3
Yb5Al2Sb6 Ball milling and hot-pressing 900 48 2 × 10 2.6 4.6 0.13 Aydemir et al368 and
Hu et al306
Yb14Mn1.05Sb11 Melting and spark plasma 1000 220 166.7 0.75 8.06 1.2 Grebenkemper
sintering et al369
Yb13.82Pr0.18Mn1.01Sb10.99 powder metallurgy, ball milling, 1275 230 133.3 1 7 1.2 Hu et al370
and annealing
Yb13.80Sm0.19MnSb11.02 1275 200 166.7 0.97 6.7 1 Hu et al370
(Continues)
27
 28

TABLE 4 (Continued)

Electrical Thermal
Operating Seebeck conductivity conductivity PF (S2σ;
Materials Synthesis process Temperature (K) coefficient (μVK−1) (Scm−1) (Wm−1 K−1) μWcm−1 K−2) ZT References
powder metallurgy, ball milling,
and annealing

Eu11Cd4.5Zn1.5Sb12 Sn-flux growth 800 185 142.9 0.65 4.9 0.5 Kazem et al371
Sr5In1.9Zn0.1Sb6 Ball milling and hot pressing 750 270 50 0.8 3.64 0.4 Chanakian et al372
Eu5In1.9Zn0.1Sb6 Heating and annealing 660 180 100 0.9 3.24 0.4 Chanakian et al373
Eu9Cd3.75Ag1.42Sb9 Sn-flux growth and spark plasma 750 850 500 1 3.61 0.32 Kazem et al374
sintering
Mg2.9875Na0.0125Sb2 Ball milling and hot-pressing 773 200 185.2 0.95 7.4 0.6 Shuai et al375
Zn3.75In0.05Sb3 Melting and Bridgman method 700 220 2.7 × 102 0.62 130.6 1.4 Wei et al376
Yb13.6Y0.4MnSb11 Melting and flux growth 1200 220 142.9 0.9 6.9 1.05 Grebenkemper
et al377
Yb13.6Sc0.4MnSb11 Melting and flux growth 1200 230 166.7 1 8.81 1.05 Grebenkemper
et al377
Ca9Zn4.35Cu0.15Sb9 Melting and spark plasma 873 140 333.3 0.72 6.53 0.72 Wu et al378
sintering
YbCd1.9Mg0.1Sb2 Melting and spark plasma 650 230 ~303 1.02 ~16 1.08 Cao et al379
sintering
Ca0.5Yb0.5Mg2Bi2 Ball milling and hot-pressing 873 187 357.14 1.08 12.4 1 Shuai et al380
Ca0.995Na0.005Mg2Bi1.98 Ball milling and hot-pressing 873 200 333.3 1.25 13.3 0.9 Shuai et al380
Eu0.2Yb0.2Ca0.6Mg2Bi2 N/A 875 215 285.7 0.92 13.2 1.3 Shuai et al381
Mg3.2Sb1.5Bi0.49Te0.01 Ball milling and sintering 716 −280 166.7 0.8 13 1.5 Tamaki et al323
Ca9Zn4.6Sb9 Ball milling and hot-pressing 873 270 90.9 0.48 6.6 1.1 Ohno et al382
Mg2.985Ag0.015Sb2 N/A 725 −280 111.1 0.65 8.71 0.51 Shuai et al304
Mg3Sb1.48Bi0.48Te0.04 Arc melting and spark plasma 750 −205 100 0.73 4.2 1.6 Zhang et al313
sintering
Mg3.05Nb0.15Sb1.5Bi0.49Te0.01 Ball milling and hot-pressing 700 −277 222.2 0.84 17 1.57 Shuai et al383
Eu5In2-xCdxSb6 Heating, annealing, and sintering 709 170 ~125 0.68 3.61 ~0.5 Lv et al384
n-type KSnSb N/A 800 −276 352 0.95 26.8 2.2 Huang et al385
n-type KSnSb N/A 300 −212 934 2.04 42 0.6 Huang et al385
Eu0.9Yb0.1Zn2Sb2 Ball milling and spark plasma 773 165 ~510 ~1.6 13.9 0.68 Takagiwa et al386
sintering
(Continues)
HASAN ET AL.
TABLE 4 (Continued)

Electrical Thermal
Operating Seebeck conductivity conductivity PF (S2σ;
HASAN ET AL.

Materials Synthesis process Temperature (K) coefficient (μVK−1) (Scm−1) (Wm−1 K−1) μWcm−1 K−2) ZT References
n-type Mg2Ge Ball milling and spark plasma 750 N/A N/A N/A 10.8 0.32 Santos et al387
sintering
Sb doped Mg2Ge Ball milling and spark plasma 750 N/A N/A N/A N/A 0.2 Santos et al387
sintering
Bi-doped Mg2Si0.6Sn0.4 Ball milling and sintering 775 N/A N/A N/A N/A 1.36 Fan et al388
La0.99Yb0.99Zn2Sb2 Direct reaction, melting, 680 125 12.3 2.2 0.192 0.4 Zhang et al389
annealing, and spark plasma
sintering
Te-doped n-type Zr3Ni3Sb4 Ball milling and direct-current 773 −194 N/A 2.26 17.2 ~0.6 Liu et al390
press
Yb1.6Eu0.4CdSb2 Mechanical milling and spark 523 N/A N/A N/A N/A 0.67 Cooley et al391
plasma sintering
Ca.99Na.01MgZnSb2 Ball milling and pressing 850 N/A N/A N/A N/A 0.87 Wood et al392
2
Li2ZnGe N/A 1200 150 5.6 × 10 ~4.7 12.6 0.4 Yousuf et al393
Ba(Zn0.996Ag0.004)2Sb2 Melting and hot-pressing 760 160 N/A 1.05 9.45 (at 567 K) 0.63 Yan et al394
Mg2.4875Zn0.5Na0.0125Sb2 Ball milling and hot-pressing 773 197 N/A 0.84 ~8.5 0.8 Ren et al329
29
30
electronic state of PbTe optimizes S by distorting the
DOS and increasing n.33 Sie et al used Na2Te dopant in
PbTe and obtained a high S, σ, and ZT of −112 μVK−1,
53.52 Scm−1, and 0.81 respectively.175 Besides, Jood et al
combined both dopant and nanostructures for PbTe and
reported a high ZT value of ~1.9 for
Pb0.953Na0.040Ge0.007Te (p-type leg) and PbTe0.9964I0.0036
(n-type leg) at ~805 K.179 Moreover, Xiao et al combined
both Se and Sn alloying in PbTe, where Se reduced the κ t
from ~3 to ~1.21 Wm−1 K−1 and Sn increased both n and
μ of PbTe. They reported a high ZT of 1.2 at 673 K and a
high PF of ~14.6 μWcm−1 K−1 at 300 K.180 Thus, to get
high ZT of PbTe alloys, it is imperative to enhance DOS
to get a high S and there is a need to reduce κ lat without
having much effect on their electronic transport proper-
ties. Table 1 summarizes the effect of dopants, alloying,
nanostructures, and nanocomposites on the reduction of
kt and the enhancement of ZT for PbTe alloys. Among
them, incorporation of proper dopants into PbTe alloys to
enhance the ZT ≥ 2 and reduce κ t ≤ 1.
4.2.2 | Tin selenide (SnSe) and copper
selenide (Cu2Se)
SnSe has emerged as a new sort of high performance TE
material for medium temperature range. It exhibits excel-
lent features such as its great stability and simple com-
pound comprises of earth-abundant elements, shows an
intrinsically ultralow κ t, and less toxicity.207 The crystal
structure of SnSe consist of a layered orthorhombic struc-
ture with space group Pnma (Figure 12A) and lattice
parameters of a = 11.501 Å, b = 4.153 Å, and c = 4.445 Å
at room temperature. The structure is composed of
strongly bound double layers and can be derived from a
3D distortion of the NaCl structure.208,209 Moreover, it
has an indirect Eg of 0.86 eV and behaves as a p-type
material with a hole concentration and very high ρ of
~1017-1018 cm−3 and ~101-105 Ωcm at room temperature,
respectively. Thus, the polycrystalline form of this mate-
rial at room temperature is not suitable for TE applica-
tions owing to its very high ρ.45 However, upon
increasing the temperature to around ~750-800 K, the
material notably changes its phase to Cmcm space group,
causes further changes to Eg ~ 0.39 eV and lattice param-
eters (a = 4.31 Å, b = 11.70 Å, and c = 4.31 Å) as shown
in Figure 12B.209
Polycrystalline SnSe typically exhibits low μ and thus
provides low ZT value.210 To improve its performance,
doping and nanostructuring are widely adopted. For
instance, Chandra et al used Ge dopants to enhance
n and reduce κ t. The morphology of the Sn0.97Ge0.03Se
nanoplates is shown in Figure 12C. They reported
HASAN ET AL.
ultralow κt and very high ZT of 0.18 Wm−1 K−1 and
2.1 at 873 K, respectively.211 Likewise, using similar tech-
nique Shi et al presented ZT value of ~1.7 for
Sn0.948Cd0.023Se microplates (Figure 12D).212 Moreover,
Liu et al used both doping and nanostructuring tech-
niques to enhanced PF and reduced κ lat of
5.43μWcm−1 K−2 and 0.13 Wm−1 K−1, respectively, at a
time. In this work, they used Pb and Zn dopants to poly-
crystalline SnSe and formed Sn0.98Pb0.01Zn0.01Se and
reported high ZT of 2.2 at 873 K.213 Owing to the hugely
anisotropic transport properties of SnSe, single crystal
SnSe presented the best TE performance at mid-range
temperatures.214 For instance, a very high ZT of 2.6
(at 923 K) with ultralow κt and κlat of ~0.35 and 0.23
Wm−1 K−1, respectively, at 973 K was obtained by Zhao
et al along the b-axis of orthorhombic unit cell in single
crystal SnSe.215 While employing dopants, high ZT can
be achieved at a relatively low temperature. For example,
Peng et al used Na dopant in SnSe to enhance its n which
further optimized PF of 2.8 mW/mK2, as a consequence,
obtained a high ZT of 2 at 800 K.216 Besides, Chang et al
achieved an outstanding ZT value of 2 at 800 K by
enhancing μ and S using Br dopant in SnSe (a-axis).217
Even though the single crystals SnSe exhibits excellent
TE properties due to its ultralow κt along b and c-axis,
nevertheless, the poor mechanical property, rigid crystal
growth environment, and high production cost could
make it adverse for large-scale TE applications.
Similar to SnSe, Cu2Se is a promising TE material due
to its environmental friendliness and earth abundance,
which can exhibit remarkable TE performance when
optimized.210 The crystal structure of this alloy consists of
two phases, namely, α-phase and β-phase.218 The α-phase
of Cu2Se consists of a monoclinic crystal structure with
comparatively low symmetry at low temperature
(Figure 12E).218 When the temperature increased to
400 K, it undergoes a structural transition to a cubic
structure β-phase with the space group Fm3m, where, Se
atoms and Cu ions in a simple face-centered cubic struc-
ture and distributed on the different interstitial sites,
respectively (Figure 12F).218 The TE properties of β-phase
of Cu2Se provides higher ZT value than α-phase due to
enhancement of S, σ, overall PF, and reduction of κt. For
instance, in spite of the fact that the enhancement of
n elevated σ, reduced S, and vice versa, which has an
adverse effect on PF for TE materials; β-phase of metallic
Cu2Se exhibits an excellent PF as well as ultra-high ZT
value of 2.3Wm−1 K−2 and 400, respectively.219
To enhance the TE performance of Cu2Se, doping and
nanostructuring techniques are widely used. For
instance, Liu et al used iodine dopant to tune the phase
transition temperature of Cu2Se, as a result, high ZT
value of 2.3 at 400 K obtained,220 while, Hu et al doped
HASAN ET AL.
Cu2Se with alkaline metal Li to enhance S. They reported
ZT of 2.14 at 973 K for Cu1.98Li0.02Se.221 In addition, Yang
et al used nanostructuring technique that reduced κ lat up
to ~0.2 Wm−1 K−1, as a result obtained high ZT value of
1.82 at 850 K.222 Recently, carbon-based materials have
been exploited in Cu2Se materials to elevated S and
reduced κt for better TE performance. For example, Hu
et al used carbon nanodots into Cu2Se that enhanced
S and reduced κ t to ~290 μVK−1 and 0.45 Wm−1 K−1,
respectively, and consequently obtained ZT value of
1.98 at 973 K.223 In addition, Li et al used carbon-coated-
boron nanoparticles in Cu2Se and reported ZT value of
~2.23 at 1000 K.224 Similarly, Li et al integrated graphene
nanoplates into a Cu2Se matrix that reduce κt to ~0.4
Wm−1 K−1 and as a result obtained ZT of ~2.44 at
873 K.225 All these substantial improvements indicate
that both SnSe and Cu2Se are a robust candidate for TE
applications.
4.2.3 | Skutterudites
The term “Skutterudites” came from a small mining
town in Norway called “Skutterud”, where, CoAs3 based
minerals were mined in large quantities. The compounds
that have a homogeneous crystal structure similar to
CoAs3 are called Skutterudites. The structure of
Skutterudites, with a general formula of MX3, was first
determined by Oftedal in 1928, where, M denotes transi-
tion metals such as Co, Rh, or Ir, and X signify pnictogen
atoms such as P, As, or Sb.226 Binary Skutterudites have
an open frame structure and consist of a body-centered-
cubic structure in the space group Im3, Where the void is
created by eight surrounding octahedral atoms, as shown
in Figure 13A, where, the unit cell is relocated by (1/4)
distance across the body diagonally.227 Skutterudites
structure consists of two voids in every unit cell which
are typically filled with electropositive filler-atoms
(EP) such as Yb.228,229 In,230 and Ti.231 These filler atoms
are surrounded by an icosahedral cage structure formed
by pnicogen octahedral atoms (X) and each atom are cen-
tered by a transition metal atom (T) such as Co, Rh, Ir,
Ni, and Pd that form the general structure of EPyT4X12, as
depicted in Figure 13B.227,232 This type of “filled
Skutterudite” was first synthesized by Prof. Jeitschko
et al in 1977.233
Typically, most binary skutterudite TE materials that
have been studied so far exhibit high μ and n.234 For
instance, CoSb3 has a very high μ of 3445 cm2V−1 second−1
and with high n of 4 × 1017 cm−3.235 Nevertheless, the
main drawback of this material is its high κ t, about 8.9
around room temperature, which is highly detrimental
for TE applications.236 Alternatively, filled Skutterudites
31
exhibit low κt with the introduction of filler atoms. These
loosely bonded filler atoms in filled Skutterudites inco-
herently rattles the crystal structure and reduce the κ t by
scattering phonons in an arbitrary way.234,237 Figure 14
depicts the effects of filler atoms, low dimensional mate-
rials, and doping, on recently synthesized prominent
Skutterudite materials with low κt (Figure 14A) and their
enhanced ZT (Figure 14B). Although the addition of filler
atoms enhances the ZT, they have very less effect on the
reduction of κt. Recently, Hu et al suggested that
the reduction of κ lat in filled Skutterudites is possible by
the quasi-harmonic interaction between the host lattice
and the filler atoms.225 For instance, Khovaylo et al
obtained an ultra-low κt value of ~1.25 and a high ZT
value of ~1.5 at 725 K by using indium filler atoms in
Co4Sb12, which is the record value of single-filled
skutterudite compounds.228 Table 2 Summarizes the
effects of proper dopants, micro-nano pores, carrier filter-
ing, and boundary scattering of phonons to reduce κ t and
the enhancement of ZT for emerging Skutterudites.
Although the Skutterudites exhibit high κ t, nonetheless,
most of the Skutterudites provide high ZT ≥ 1 and thus
shows great potential for high efficiency TE applications.
4.2.4 | Clathrates
The word “Clathrates” in material science is typically
defined as a class of single phase solids that are composed
of cage-like crystal structures which are encapsulated by
loosely bound guest atoms in the crystal lattice.23 The
word “Clathrates” was first proposed in the year 1948 by
Palin and Powell.274,275 Like skutterudites, the crystal
structure of clathrates is composed of tetrahedrally coor-
dinated atoms, such as Al, Si, Ga, Ge, and Sn that forms
an open framework with voids. The compounds of this
material pose a complex structure with more than one
phase present, nevertheless, only the semiconductor
phase is desirable for TE applications.276
Depending on the shape and the number of voids,
clathrates are classified into various types. Among all the
classes of clathrates, type I and type II clathrates are
widely used in TE applications. Type I and type II clath-
rates are represented by the general formulae X2Y6E46
and X8Y16E136, respectively, where X and Y are guest
atoms on two different sites and E represents the tetrahe-
drally coordinated atoms. The unit cell of type-I has a
space Pm3n group and is composed of two dodecahedral
(512) water cages and six big tetrakaidecahedral (51262)
cages, whereas, type- II has a space fd3 m group and is
composed of 16 512 cages and eight large hexadecahedral
(51264) cages, as demonstrated in Figure 15.277,278 The
main function of these guest atoms is to rattle in the host
32
FIGURE 17 The highest ZT values of (A) n-type and (B) p-type Mg3Sb2 based compounds307,312-322,324-332 [Colour figure can be viewed
at wileyonlinelibrary.com]
matrix and scatter the lattice phonons to reduce the τ of
heat carrying phonons which further reduces κ t.279
Several experiments suggested that these guest atoms
also have an impact on group velocity. Christensen et al
investigated a type I clathrate, Ba8Ga16Ge30, and claimed
that the main influence of the rattling atoms is to reduce
the group velocity rather than reducing τ.280 Neverthe-
less, Tadano et al evaluated that rattling atoms have
more impact on reducing τ but have less significance on
the group velocity. Dopants have a huge impact on the
tuning of the PF as well as the ZT of clathrates.281 For
instance, Chen et al obtained a ZT value of 0.91 at 900 K
for Yb doped Ba7.79Yb0.21Ni0.07Zn0.38Ga14.02Ge30.25.282
Shen et al reported ZT value of 0.63 at 537 K for Zn-
doped Ba8Ga16Sn30,283 and ZT value of 0.52 was
obtained in Ge doped Ba8Ga16InxGe30-x by Liu et al.284
Moreover, material synthesis processes also play a signif-
icant role in enhancing the overall performance of these
materials. For instance, Wang et al prepared p-type
Ba8Ga16Ge30 from the melt by the vertical Bridgman
method, where the melt was controlled, to prepare
Ba8Ga16Ge30 poly-crystals with varying Ga/Ge atomic
ratios. They reported a high ZT of 1.10 at 823 K.285 Hou
et al used the same technique with p-type Ba8Ga16Ge30
by varying Ga/Ge ratios between 0.567 and 0.579. They
reported ZT of 1.0 at 773 K.286 Yet another example,
where Sun et al used high-pressure and high-
temperature sintering for n-type polycrystalline
Yb0.5Ba7.5Ga16Ge30 bulks. Samples obtained under high
pressure provided a great number of nanograins and lat-
tice structural disorders that helped to reduce κ t. They
HASAN ET AL.
reported a low κ t of 0.86 Wm−1 K−1 and maximum ZT
value of 1.13 at 773 K for the Yb0.5Ba7.5Ga16Ge30 sample
fabricated at 5 GPa.287 An overview of the effect of vari-
ous dopants, material composition, and synthesis pro-
cesses, on TE properties of clathrates, are summarized in
Table 3. From the summarized Table 3 and the recent
survey on clathrates, it is suggested that although most
of these materials have low κ t values, that is, less than
1.5, nevertheless, the overall ZT values of these materials
are still low, that is, in the range of (0.5-1.3). Thus, these
materials need further improvement for practical use in
TE applications.
4.3 | High temperature inorganic TE
materials
The Zintl phases, oxides, and silicon-germanium (SiGe)
alloys have been recently studied for high temperature
TE applications, that is, above 850 K. Among these mate-
rials, in 2013 SiGe alloys have been utilized in the radio-
isotope thermoelectric generator used by NASA due to its
very high operating temperature, that is, in between 1073
and 1273 K. Recently, in Zintl phases, magnesium anti-
monide has shown promise for TE applications with a ZT
value exceeding 1.8 at high temperature. Moreover, a
new class of oxide-based materials is being extensively
studied for TE applications due to their extremely low κt
value. Hence, the material properties and recent tech-
niques to reinforce the ZT of these materials are dis-
cussed in this section.
HASAN ET AL. 33

F I G U R E 1 8 Crystal structures of promising oxide-based materials (A) ZnO that crystallizes in hexagonal wurtzite structure with space
group P63mc (The unit cell contains 2 × Zn and 2 × O atoms where each Zn atom is tetrahedrally coordinated with O), (B) SrTiO3
crystallizes in cubic Pm3m perovskite structure where the Ti atoms placed at the cube centres, Sr atom at the corners, and the O atom at the
face centres, (C) BiCuSeO crystallizes in a ZrCuSiAs type structure with the space group P4/nmm. Besides, the structure consists of Bi-O
layers that are alternately stacked with the isostructural Cu-Se layer along the c axis, and (D) NaCo2O4 consisting of an orthorhombic unit
cell with Pmmn symmetry and the Co-O layer and the Na-layer stacked alternately along the c-axis. Source: Reference400 Copyright 2018,
Reproduced with permission from Elsevier [Colour figure can be viewed at wileyonlinelibrary.com]

4.3.1 | Zintl phases
The term “Zintl phases” refers to a subclass of intermetal-
lic compounds that are composed of electropositive cat-
ions, typically, group 1 (alkali metal), group 2 alkaline
earth metals and post-transition metals or metalloids
from groups 13, 14, 15, or 16. Although the use of Zintl
phases is comparatively new in thermoelectrics, nonethe-
less, the study of their structure and chemical bonding
was started in the 1920s. The Zintl phases were first dis-
covered by a German chemist Eduard Zintl, and the
name “Zintl phases” was coined by Laves in the year
1941.304 Zintl phases exhibit several advantages as TE
materials such as a high S. For instance, Yb2-xEuxCdSb2
has the highest S value of 269 μVK−1,305 besides, S value
of ~280 μVK−1 has been shown by both Mg3Pb0.2Sb1.8
and Yb14MgSb11.306,307 Moreover, one of the most impor-
tant features of these materials is their adaptability to a
divergent temperature range. For example, from low-to-
middle temperature ranges, the Zintl 1-2-2 compounds
display the best properties among p-type and n-type Zintl
phases, while for high-temperature range, typically, in-
between (975-1275) K, the Zintl 14-1-11 compounds per-
form better than other p-type Zintl families.308
Among all the Zintl phases, Yb14MnSb11 have
emerged as promising TE materials, especially for high-
temperature applications, where the compounds belong
to A14MPn11 compounds, where A, M, Pn defines
alkaline-earth or rare-earth metal, transition or main-
group metal, and a pnictogen, respectively.309 Besides,
34 HASAN ET AL.

various promising Zintl compounds such as KSnSb,
Zn4Sb3, BaGa2Sb2 (Figure 16A), Eu5In2Sb6, YbZn2Sb2
(Figure 16B), CaZnSb, Ca3AlSb3 (Figure 16C), Yb14AlSb11
(Figure 16D), EuZn2Sb2, and ZnInSb provide high ZT
values and are widely used for high-temperature applica-
tions, are listed in Table 4. Recently, Mg3Sb2 based Zintl
compounds have been found to be very attractive for TE
applications owing to its features such as environmental
amiability, nontoxicity, and earth-abundance. It has an
inverse α-La2O3-type crystal structure (P3m1 ) having a
[Mg2Sb2]2− framework and Mg2+ cation layer sheets sta-
cked along the c-direction. Theoretically, the layered
structure can be generated into a single thin film layer by
splitting the ionic bonds between the Mg2+ cationic layer
and Mg2Sb22− anionic layer. Even though the 2D-Mg3Sb2
can be realized theoretically, nevertheless, there is no
significant experimental study on the mono layer at the
moment. Figure 16E,F shows atomic and band structures
of bulk Mg3Sb2 and mono layer, where, lattice constants
a ═ 4.59 Å and c ═ 7.26 Å are for bulk Mg3Sb2 and a ═
4.72 Å for mono layer, which is slightly higher.307
Figure 16G, H depicts the band structures of single crys-
tal and mono layer Mg3Sb2, respectively. Meanwhile,
both the structures are indirect band gap semiconductors
and show a band gap of bulk 0.47 and 0.41 eV,
respectively.
Besides, Mg3Sb2 compounds, inherently have p-type
transport properties due to intrinsic Mg vacancies and
provide low ZT values. Surprisingly, various studies have
suggested that it is possible to transform p-type Mg3Sb2
compounds into n-type compounds to achieve high per-
formance Mg3Sb2 by terminating Mg vacancies and

F I G U R E 1 9 Best performing oxide-based materials highlighting (A) highest σ, (B) low κ t and (C) ZT value via miscellaneous
optimization techniques65,391,393,403-415 [Colour figure can be viewed at wileyonlinelibrary.com]
TABLE 5 TE properties of promising oxide-based materials with the effects of various dopants in the enhancement of σ and ZT

Operating Seebeck Electrical Thermal

Temperature coefficient conductivity conductivity PF (S2σ;
HASAN ET AL.

Materials Synthesis process (K) (μVK−1) (Scm−1) (Wm−1 K−1) μWcm−1 K−2) ZT References
−3
Nb-doped SrTiO3 Solid-state reaction and pressure- 900 −140 0.431 1.7 8.45×10 0.34 Wang et al416
less sintering
Bulk Nb-doped SrTiO3 Solid-state reaction and normal 900 −155 0.38 3.1 9.129 ×10−3 0.165 Wang et al417
pressure sintering
Sr0.92La0.08TiO3 Ball milling and spark plasma 1045 −23 N/A ~3.2 N/A 0.37 Kikuchi
sintering et al418
La0.08Sr0.92TiO3 Sol-gel process and spark plasma 679 −184 N/A ~2 N/A 0.08 Shang et al419
sintering
Zn0.97Ni0.03O Liquid route synthesis 1000 −419 N/A 6.5 N/A 0.09 Colder et al420
Al-doped ZnO Solid-state reaction and sintering 1073 −140 319 7.9 6.25 0.126 Yamaguchi
et al421
Indium-doped ZnO Sonication and cold-pressed 1000 N/A N/A 3 N/A 0.45 Jood et al422
Bi0.925Ca0.075CuSeO Solid-state reaction and cold- 923 248 N/A 5.1 N/A 0.9 Pei et al423
pressed
(Ga0.002,In0.002)Zn0.996O N/A 773 140 N/A 3.9 N/A 0.19 Takemoto
et al424
TiO2-x Plasma spray 750 −230 5.48 × 103 1.5 to 2 289 0.132 Lee et al425
Polycrystalline BiCuSeO High pressure sintering 800 N/A N/A 0.42 2.1 0.4 Zhu et al426
La-Bi co-doped SrTiO3 Solid-state reaction and sintering 1073 −250 ~90 2.3 5.6 0.269 Gong et al427
La0.1Dy0.1Sr0.75TiO3 Sol-gel method, cold isostatic 773 −292 ~88 1.9 7.5 0.29 Han et al428
pressing, and sintering
Vanadium-SrTiO3 Ball-milling and hot-pressing 673 −380 33 ~3.7 4.76 0.084 Khan et al429
Y-doped SrTiO3 Ball-milling, and hot-pressing 773 −290 ~79 2.9 6.64 0.18 Khan et al430
ZnO/Bi2Te2.7Se0.3 Ball milling and spark plasma N/A N/A N/A N/A 22 ~1.3 Jiang et al431
sintering
Bi2O2Se0.985Cl0.015 Ball-milling and spark plasma 823 −110 ~205 0.88 24.8 0.23 Tan et al432
sintering
CaMn0.98Re0.02O3 Ball milling and sintering 947 −230 N/A ~3 ~4.22 0.16 Shin et al433
Ca0.97Bi0.03MnO3 Ball milling and hot pressing 473 −217 ~107.5 0.12 5 0.065 Paengson
et al434
Ca0.96Gd0.04MnO3-δ Ball milling, calcination, and 973 −180 110 2.68 3.56 0.14 Löhnert
sintering et al435
(Continues)
35
 36

TABLE 5 (Continued)

Operating Seebeck Electrical Thermal

Temperature coefficient conductivity conductivity PF (S2σ;
Materials Synthesis process (K) (μVK−1) (Scm−1) (Wm−1 K−1) μWcm−1 K−2) ZT References
Ca0.8Dy0.2MnO3 − δ Grinding and hot-pressed 1073 −120 212 1.86 3.05 0.18 Seo et al436
lanthanide doped-Sr0.7Ba0.3Nb2O6 Grinding, and sintering N/A −140 ~260 1.55 5.09 ~0.35 Li et al437
Ca0.96Er0.02Yb0.02MnO3 Sol-gel and cold pressing 973 −234 N/A N/A N/A 0.12 Yang et al438
Sn doped-BiCuSeO Melting and hot-pressing 773 188 ~244 0.83 10.1 1.09 Das et al439
Bi0.96Pb0.04CuSe0.95Te0.05O Self-propagating high- 873 250 ~113 N/A 7 1.2 Ren et al440
temperature, hand grinding,
and cold pressed
BiCu1-xAgxSeO Ball-milling and spark plasma 923 290 N/A N/A N/A 0.64 Farooq et al441
sintering
BiCu0.95Ag0.05SeO Melting and hot-pressing 750 350 32.4 0.38 39.6 0.72 Sun et al442
Bi0.9Sn0.1CuSeO Hand grinding, ball-milling, and 773 ~230 ~27.5 0.62 1.45 0.3 Yang et al443
spark plasma sintering
Bi0.875Ba0.125Cu0.85Ni0.15SeO Ball-milling and spark plasma 923 360 ~39 0.56 5 0.97 Wen et al444
sintering
Ba0.125Bi0.875Cu0.85Co0.15SeO Ball-milling and spark plasma 350 ~280 0.3 × 102 0.88 2.35 0.082 Wen et al444
sintering
Bi0.85Na0.15CuSeO Ball-milling and spark plasma 873 242 85 ~0.6 3.39 0.7 Lan et al445
sintering
Bi0.95Sb0.05CuSeO Mechanical alloying and 873 ~330 N/A 0.51 N/A 0.73 Feng et al446
resistance pressing sintering
TiO1.72 Cold-pressed and high-pressure 873 −97 ~385 2.67 3.6 0.13 Liu et al447
high temperature (HPHT)
reactive sintering
La-doped SrTiO3 Planetary mill and cold isostatic 300 N/A N/A N/A N/A ~0.06 Liu et al448
pressing
Sr0.8La0.067Ti0.8Nb0.2O3-δ Incipient wetness technique, 1000 −170 N/A 3.1 8 (at 700 K) 0.38 Kanas et al448
milling, and pressed
Ca3Co4-xO9 + δ (CCO) Uniaxial pressing, grinding, cold- 1073 152 63 0.89 1.46 0.11 Srivastava
isostatic pressing and spark et al449
plasma sintering
BiCuSeO (Biaxial strain) N/A 900 N/A N/A N/A 1.9 1.7 Li et al450
(Continues)
HASAN ET AL.
HASAN ET AL. 37

enhancing n. For instance, Li et al theoretically investi-

1.01 Feng et al452

gated the band structure of n-type Mg3Sb2 using first-

References
0.68 Ma et al451
principles density functional theory (DFT) and obtained

et al453
Ishizawa
a very high ZT value of 3.1 at 725 K.311 Yet another exam-
ple, where they obtained a high ZT value of 2.75 at 725 K
using DFT.312 Nevertheless, no experimental results have
ZT

0.6
exceeded the ZT value of more than 2. Figure 17A,B
depicts the contrast in the performance of the best per-
μWcm−1 K−2)

forming n-type and p-type Mg3Sb2 based compounds,

PF (S2σ;

with the highest ZT values, where p-type Mg3Sb2 based

compounds have transformed into n-type Mg3Sb2
N/A
4.94

6.8

based compounds. It is clearly shown that n-type Mg3Sb2

based compounds are more efficient than the p-type
conductivity
(Wm−1 K−1)

Mg3Sb2 based compounds.

Thermal

~6.2
0.62

0.64

4.3.2 | Oxide-based materials

conductivity

Previously, oxide-based materials have been neglected in

Electrical

thermoelectricity for a long time since most of these

(Scm−1)

materials were considered as deficient conductors due to

~170

N/A

low μ and high κ t.93 Nonetheless, this outlook had chan-

64

ged after 1997 when Terasaki et al claimed a low ρ of

200 μΩcm and a moderate PF of 100 μVK−1 for a single
coefficient

crystal of NaCo2O4.395 Although the PF of NaCo2O4 is

(μVK−1)
Seebeck

not that sufficient, as required for TE applications, none-

~200

~420
278

theless, it opened the door to explore oxide-based mate-

rials as feasible TE materials. The study on oxide-based
Temperature

materials has been growing rapidly owing to their attrac-

Operating

tive features such as high chemical and thermal stability,

earth's abundance, relatively inexpensive, nontoxicity,
(K)

chemically inert, and robust properties that make them

873

873

773

suitable for the TE power generation, particularly for

high-temperature applications.22,248
resistance pressing sintering
temperature synthesis and

Grinding, cold-pressed, and

The crystal structures of promising oxide based TE

spark plasma sintering

spark plasma sintering

Mechanical alloying and

materials are depicted in Figure 18. Among all the stud-

Self-propagating high
Synthesis process

ied oxide-based materials, narrow bandgap materials

such as Ca3Co4O9, CaMnO3, SrTiO3 (Figure 18B),
BiCuSeO (Figure 18C), NaCo2O4 (Figure 18D), and
Sr2TiO4 are promising TE material. All these narrow
bandgap materials, in their polycrystalline form, exhibit
relatively high S, low κ t, and low σ, which is detrimental
to TE applications. For example, BiCuSeO exhibits high
S and low κ t of 200 μVK−1 and ~0.5Wm−1 K−1, respec-
tively, while it has low σ of ~40 Scm−1 that leads to a low
Polycrystalline Bi1-xCuSeO

ZT of ~0.7 at 773 K396; polycrystalline Ca3Co4O9 shows

(Continued)

Bi0.88Ba0.06Pb0.06CuSeO

moderate S, low σ, and PF of 150 μVK−1, 80 Scm−1, and

1.5 × 10−4 Wm−1 K−2, respectively, at 300 K397; polycrys-
(0 ≤ x ≤ 0.05)

talline CaMnO3 shows high S of approximately −350

Bi0.975CuSeO

μVK−1 and low κ t of 3 Wm−1 K−1 while σ is very low, that

Materials
TABLE 5

is, in the range of 0.1 to 1 S cm−1 at a temperature

range of (300-1000) K398; and polycrystalline SrTiO3
exhibits the S < 100 μVK−1.399 Likewise, wide bandgap
38
oxide-based materials such as ZnO (Figure 18A), TiO2,
SnO2, In2O3, and V2O5 are promising TE materials.418
For instance, ZnO offered high S value of 481 μVK−1 and
PF of 0.65 × 10−4 Wm−1 K−2 at n of 10−23 m−3 401; crystal-
line TiO2 showed high κ t value of ~5.8 Wm−1 K−1 and PF
of 360 μWm−1 K−2.402 Table 5, summarized the effect of
various dopants in the enhancement of σ, PF, and ZT of
high efficient oxide-based TE materials for the last
decade. Among all the materials BiCuSeO has been
proven as promising TE material and has shown ZT in
the range of 0.7 to 1.7 and the rest are under 1, conse-
quently, BiCuSeO has the potential to use in TE applica-
tions and the rest of the materials still needed much
improvement to get ZT ≥ 1. For most of the polycrystal-
line oxide-based materials it is difficult to reach high PF
and high ZT due to their low n, thus, it is necessary to
tune their electronic properties to make them from the
insulator behavior to metallic behavior materials by alter-
ing their crystal orientations, doping and by changing
their chemical composition. Figure 19A-C depicts the
enhancement of σ, reduction of κ t, and enhanced ZT for
high performance oxide-based TE materials via various
dopants, composites, and low-dimensional materials.
Although for most of the oxide-based materials, dopants
have been the best option to enhance their σ and ZT, none-
theless, it has a great effect to accelerate the κ t as well.
4.3.3 | SiGe alloys
The potential of SiGe alloys in thermoelectrics for high
temperature applications was first explored in the late
1950s.454,455 However, the breakthrough achievement
F I G U R E 2 0 High performance SiGe alloys depicting (A) its reduced κ t and (B) enhanced ZT via miscellaneous optimization
techniques at different temperature range450,458,460-473 [Colour figure can be viewed at wileyonlinelibrary.com]
HASAN ET AL.
was done by Dismukes et al in the year 1964 when they
doped SiGe heavily and obtained a ZT value close to 1 for
n-type and 0.8 for p-type SiGe alloys, respectively.456 Ini-
tially, the research was started by the US military, but
later it was used by NASA for radioisotope TEG (RTGs)
applications. It has a diamond crystal structure that crys-
tallizes in the Fd3m space group and belongs to the face
centred cubic Bravais lattice. It has two prominent fea-
tures such as its melting point is very high ~1300 K and it
has magnificent stability at high temperatures, which is
why this material has been used in RTGs by NASA, for
the Mars mission in 2013, and other high temperature
applications. Nevertheless, the main challenges associ-
ated with this material are its high κ lat due to the low
mass of SiGe, and their strong chemical bonds, which
further minimize the ZT.22,33,457 Thus, the optimization
of SiGe alloys is mainly based on the reduction of its κlat.
Typically, the ZT value of n-type SiGe alloys is higher
than p-type SiGe due to its high κt and higher n. For
instance, the ZT value of n-type SiGe alloys is 1.3 and its
κt is about 2.8 Wm−1 K−1 at 1173 K, while for p-type SiGe,
the maximum ZT value is about ~0.5.458 Thus, current
efforts have endeavoured to reduce κ t and optimize ZT of
SiGe alloys via doping,459 nanostructuring, and compos-
ites, as shown in Figure 20. Dopants have enhanced the
ZT value as well as its κ t. Alternatively, nanostructuring
has a great impact in SiGe alloys as it reduces the κt,
while it enhances the ZT. Due to interfacial phonon scat-
tering and nanoscale size effects, SiGe superlattice nano-
wires provide a low κ t.474 For example, Usenko et al
prepared the n-type nanostructured SiGe bulk sample
using the ball-milling and spark plasma sintering process.
The sample provided a low κt of 2.47 Wm−1 K−1 at room
HASAN ET AL.
temperature and provided ZT of ~1.1 at 1073 K.466 Alter-
natively, p-type nanostructured SiGe has a low κt but the
main problem associated with this material is its low ZT
value. Usenko et al prepared boron-doped nanostruc-
tured bulk Si80Ge20 via a spark plasma technique and
reported a low κt and high ZT value around ~2.9
Wm−1 K−1 and 0.72 at 1073 K, respectively.472 Yet
another example, where Peng et al demonstrated a
boron-doped SiGe thin film and they reported an
improved S of 850 μVK−1 at 473 K but their ρ decreased
to 1.3 × 10−5 Ω.m and the PF increased to 5.6 × 10−2
Wm−1 K−2.475
Another interesting approach to reduce κlat of SiGe
alloy is via different composites. For example, Kikuchi
et al embedded SiNWs with a diameter of 10 nm into
SiGe0.3, where SiNWs were fabricated by the bio-template
mask and neutral beam etching techniques, and then
deposited by a thermal chemical vapor deposition tech-
nique. They reported κ t of 3.5 ± 0.3 Wm−1 K−1 for the
SiNW-SiGe0.3 composite film with a thickness of 100 nm
at 300 to 350 K.476 Besides, they reported an S and σ
value of 4.8 × 103 μVK−1 and 4.4 × 103 Sm−1, respec-
tively, at 873 K. Yet another example, where Usenko et al
obtained reduced κ lat value of 1.4 Wm−1 K−1 and an aver-
age ZT of ~0.8 at 1073 K for n-type Si0.9Ge0.1-Mg2Si.471
5 | C ONCLUSION AND O UTLOOK
In the past two decades, research on inorganic TE materials
has grown exponentially. New techniques and ideas have
evolved to optimize the basic TE properties such as S, σ,
and κt that are interconnected with each other to ensure a
high ZT by inducing n via doping, band engineering, con-
trolling the phonon transport, and lattice vibrations.
Among all the recent optimization techniques, band engi-
neering and energy filtering, to optimize S, modulation
doping to enhance σ, and low dimensional structures and
phonon scattering to reduce κt are conspicuously applaud-
able. All these techniques have made remarkable progress
in the reduction of κ t, to <1, and enhanced ZT, from <1 to
>2, of inorganic TE materials in recent years. Among them,
clathrates and Zintl phases possess ultra low κt values, but
exhibits very poor σ as well. Conversely, SiGe, SiNWs, and
PbTe alloys have very high σ while exhibiting a very low S,
and as a consequence, provide a low PF. Moreover, a new
class of materials such as SnSe, Cu2Se, and Mg3Sb2 provides
a high ZT with low κ t.
Although the performance of TE materials has
enhanced dramatically in recent years, the future of ther-
moelectricity depends on two major aspects. First, most
of the recent strategies are trying to optimize only one TE
property whilst keeping other properties unaffected,
39
rather than optimizing two or more properties which are
correlated via the Wiedemann-Franz law. Hence,
researchers should try to find out a novel technique that
could resolve the compromise between TE properties
such as S, σ, and κ t in a single step. Second, it is impera-
tive to design more high performance inorganic TE mate-
rials to meet the actual TE application demands, ranging
from room temperature to very high temperature, rather
than just be limited to laboratory research. In conclusion,
the performance of most of the inorganic TE materials is
not good enough to generate power to drive portable
devices. However, with the advancement and progress in
materials science, through microfabrication and nano-
technology, most research could be in the area of low-
dimensional inorganic TE materials, employing
nanostructures and nanocomposites, in the near future.
ACKNOWLEDGEMENTS
This work was supported in part by Universiti Teknologi
Malaysia and Universiti Tun Hussien Onn Malaysia
through Collaborative Research Grant (CRG Q.J130000.
2451.04G94) and the Ministry of Education Malaysia
through Fundamental Research under Grant (FRGS
R.J130000.7851.5F081).
ORCID
Mohamed Sultan Mohamed Ali https://orcid.org/0000-
0002-4692-2954
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