Review Article

https://doi.org/10.1038/s41563-021-01109-w

High-performance thermoelectrics and challenges

for practical devices
Qingyu Yan 1
and Mercouri G. Kanatzidis 2 ✉

Thermoelectric materials can be potentially employed in solid-state devices that harvest waste heat and convert it to electri-
cal power, thereby improving the efficiency of fuel utilization. The spectacular increases in the efficiencies of these materials
achieved over the past decade have raised expectations regarding the use of thermoelectric generators in various energy saving
and energy management applications, especially at mid to high temperature (400–900 °C). However, several important issues
that prevent successful thermoelectric generator commercialization remain unresolved, in good part because of the lack of a
research roadmap.

T
he efficiency of a thermoelectric (TE) material is defined
by the dimensionless figure of merit ZT = S2σT/κ, where S
is the Seebeck coefficient, σ is the electrical conductivity, T
is the operational temperature and κ is the thermal conductivity,
composed of the electronic contribution (κel) and lattice contribu-
tion (κlat). However, the power conversion efficiency (PCE) of a TE
device (η) depends not on the ZT maximum at a given tempera-
ture, but on the average ZT (ZTave) over a wide temperature range as
well as the temperature difference between the hot (Th) and the cold
source (Tc) as follows:
√ that there is considerable progress on development of organic
T − Tc 1 + ZT − 1
η= h .
Tc
√
1 + ZT + Tc /Th
Because these material properties (S, σ and κ) are interconnected
through both the carrier concentration and electronic structure,
the optimization of any particular property is generally performed
at the expense of another property, which makes the achievement
of high ZT values very challenging1. Effective routes to increasing
ZT include electronic structure modifications such as electronic
band structure engineering and the generation of extrinsic defects
through alloying and nanostructuring to lower the lattice thermal
conductivity.
A small but important commercial area where first-generation
TE devices and modules have already been successfully employed
was the long-term space exploration conducted by NASA (US
National Aeronautics and Space Administration) and the Soviet
Union. Similar to the original Voyager 1 and Voyager 2 missions,
the recent Mars 2011 (rover Curiosity, November 2011) and 2020
missions (rover Perseverance, July 2020) are equipped with a
radioisotope TE power system, and future Mars missions will also
rely on the same system of electrical power generation. Using heat
from the radioactive decay of plutonium oxide, this system pro-
duces dependable electricity that charges the rover’s two primary
batteries, and its TE modules are composed of the first-generation
PbTe/tellurium–antimony–germanium–silver (TAGS) materi-
als manufactured by Teledyne. The long-term reliability possible
with TE generators (TEGs) was proven by these and other NASA
missions, where none have ever failed because of failure in the TE
power generation system. After a long dormant period in research
activity caused by the frustration over unsuccessful attempts to
further enhance performance, TE materials have again attracted
serious attention from researchers during the past two decades.
As a result, tremendous progress has been made in increasing
the figure of merit. The field has bloomed with an outburst of
new concepts and ideas that were subsequently implemented to
break the four-decade-old ZT records established in the 1950s
and 1960s. The result was a new generation of materials devel-
oped since the early 2000s that significantly exceeded expecta-
tions (the timeline of these advances is shown in Box 1). We note
and hybrid organic–inorganic materials and devices relevant to
room-temperature energy harvesting2–4, which will not be dis-
cussed here because their ZT values are not yet on a comparable
level to the inorganic counterparts at higher temperatures. The
new figures of merit achieved by the new materials exceeded the
old values by more than a factor of two and are widely considered
to be adequate for their implementation in modern TE devices
with efficiencies greater than those of the state-of-the-art devices
by more than 100%. However, the development of correspond-
ing TE devices and modules that can transform heat to electricity
using high-temperature sources operated between 400 and 900 °C
has proceeded very slowly5. The question is why.
Key developments in TE materials over past 15 years
The first-generation materials employed in TE devices decades ago
had PCEs of 3–6% in the temperature range of 300–1,000 °C. The
new materials could easily achieve PCEs of between 12% and 15%,
which would be a remarkable breakthrough in the conversion of
low-quality energy (heat) to high-quality energy (electricity). It is
reasonable to expect that such large PCEs would be commercially
viable for a variety of applications. Practical TEGs can be divided
into stationary and mobile ones. In the stationary generators, the
hot-side temperatures tend to be stable, and some parameters that
may affect the device performance (such the overall weight and sen-
sitivity to vibration) are typically relaxed. However, in mobile appli-
cations (such as those harvesting exhaust waste heat in vehicles),
additional challenges include temperature fluctuations of the hot
source and mechanical vibrations negatively affecting the device
integrity and stability.

School of Materials Science and Engineering, Nanyang Technological University, Singapore, Singapore. 2Northwestern University, Evanston, IL, USA.
1

✉e-mail: m-kanatzidis@northwestern.edu

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Review Article Nature Materials

Box 1 | Timeline of progress in TEs and some methods of improving TE properties

Multiband convergence is when the electronic conduction band
(CB) or valence band (VB) extrema in the electronic structure
of a TE material occur multiple times and fall within a small
energy range. For example, when an electronic structure has
only one extremum, it generally is considered to be inferior from
the TE performance point of view to a corresponding structure
that has multiple extrema. The presence of many such band
extrema can enable the achievement of very high power factors.
When electron or hole pockets are created through doping in
each individual band extremum of the CB or VB, each pocket
contributes to the power factor in roughly an additive manner
(see ref. 11 for a more extensive discussion).
In situ inclusion of nanostructures is of great importance
for improving TE performance. Nanoprecipitates of a second
phase are caused to grow in the TE material, which acts as the
host matrix. These dispersed nanosized objects act as efficient
phonon scattering centres, strongly impeding heat flow. During
the nucleation and growth, the interface created between the host
matrix and the precipitates should be as coherent as possible,
which is referred to as endotaxy. Electronic band alignment
between the two phases is necessary to easily transmit charge
carriers, especially in an endotaxial interface. This arrangement
can effectively scatter phonons and at the same time allow charge
carriers to pass through with ease, but the strategy requires the
creation of specially spatially heterogeneous materials with
electronic bands in the different phases that have suitably aligned
energy levels for good carrier transmission (referred to as electronic
band alignment). When the heterogeneity scale extends beyond
the nanosize regime (for example, 5–50 nm) and into what we
call the mesoscale (50–1,000 nm), then additional heat-carrying
phonons can be scattered whose mean free paths are comparable
to the scale. In that case, we have an all-scale architecture that can
scatter a broad spectrum of phonons. The all-scale architecture is
the most effective composite structure for many TE systems.

Pb(Se, Te) Cu2(Se, S) CB

3 AgPbmSbTe2 + m SnSe
Multiband convergence
Bi2Te3 SnTe
Half-Heusler VB
SiGe
BiCuSeO
CoSb3
GeTe
2 Mg3Sb2
CB Minimal valence
ZTmax

band offset
Eg E′g
VB ΔE
Matrix
Second
phases
1 Band alignment
Vacancy

ate
Dislocation

cipit
Interstitial Pre
0
1960 1980 2000 2020
Substitution
Year
Nanostructuring

Decadal timeline and progress in raising the efficiency of TE materials through successive innovations since around 2000. The red line is drawn as
a guide to the eye. On the right-hand side, some of the key innovations in materials design concepts that have enabled these advances are shown
schematically. The bottom right inset shows the nature of nanostructuring in an advanced thermoelectric material composed of two elements (the blue
and yellow spheres). It contains atomic-scale defects (all shown in the magnified section) such as vacancies (marked with a red square), foreign atom
substitutions (marked with a purple sphere), interstitials (marked with the red sphere), and dislocations caused by excess atoms of an element, as well
as nanoscale precipitates (marked by the brown ellipse throughout the image) and mesoscale grains (with grain boundaries shown as white lines),
all of which scatter heat-carrying phonons, resulting in very low thermal conductivity.

Various economic factors, such as the long-term uncertainty
in the price of fossil fuels, are also stifling the development of TE
devices on a commercial scale. For example, to recover waste heat
in automobiles, the accrued energy savings can be used as electrical
power to extend the vehicle mileage6. These savings must be sub-
stantial and significantly exceed the TEG cost. Over the past decade,
crude-oil price fluctuations have resembled a rollercoaster, and
their long-term average values have exhibited a decreasing trend.
Although it is difficult to accurately predict the price of crude oil,
its value should sustainably be well above current prices to stimu-
late utilization of TEGs in automobiles. Because taxation strongly
affects the fuel price, certain countries with high petrol taxes may
reach this level sooner than others.
Stationary applications of TEGs can involve large units
installed in industrial facilities7 that are utilized for various manu-
facturing processes emitting large amounts of waste heat. To date,
the number of commercially available TEGs is very small and
affects only very few niche applications. These generators still use
first-generation materials, specifically bismuth telluride alloys
and lead telluride.
Vehicles that can be considered viable candidates for the imple-
mentation of TEGs include articulated lorries, which run more than
100,000 miles per year at a fuel economy of approximately 6 miles
per gallon. Therefore, even at the 5% minimum energy savings
achieved by TEG utilization, approximately US$6,000 yr−1 can be
saved, which translates into US$90,000 over the vehicle lifetime of

504 Nature Materials | VOL 21 | May 2022 | 503–513 | www.nature.com/naturematerials

Nature Materials
10–15 yr. For personal vehicles, the savings would be considerably
smaller.
What is holding back the development of high-efficiency TEGs
containing the new high-performance materials? The key technical
obstacles are related to the thermal stability of the electrical contacts
attached to the hot generator side: the mechanical stability and the
long-term chemical stability of TE materials, which must be main-
tained for at least ten years, under the hot side.
It is interesting to compare the current development stage of TE
technology, and the little progress made in creating commercially
viable energy converters, with the robust advances in the photo-
voltaics field. In the latter, the past two or three decades have also
been transformational in the development of photovoltaic semi-
conductors with increased efficiency. This process has resulted in a
flourishing and rapidly growing solar photovoltaic technology with
falling costs and an industry with a market size of billions of dol-
lars. What is particularly striking is the speed at which the recent
emergence of perovskite halides as materials for solar cells has led
to a budding industry currently on the cusp of commercializa-
tion. The field of TEs has analogous advances in new materials but
there is a striking lag to the development of devices, as mentioned
above, and very few researchers have the capability to fabricate TE
power-generating devices.
Owing to the advances and breakthroughs in TE materials, this
Review discusses their potential for implementation in devices and
modules with a focus on TE power generation. After classifying
the materials in terms of operating temperature, those most likely
to be used in future devices are briefly discussed. We also discuss
the key challenges and possible future strategies that can promote
the further development of TE power generation technology; how-
ever, more extensive and comprehensive reviews can be found else-
where5,6,8–10. This perspective does not discuss TE cooling devices, as
they have existed for decades, and no corresponding enhancements
in material performance have been achieved.
The powerful general design concepts devised more than a
decade ago that have remarkably enhanced the performance of
bulk TE materials are the following11: endotaxial nanostructur-
ing involving the nucleation, growth and spinodal decomposition
processes that reduce the thermal conductivity of a material; elec-
tronic band alignment, electronic band convergence, resonance
states and electronic structure modification that enhance the
power factor (S2σ); and panoscopic all-scale architecturing that
combines all beneficial effects into a single material system. In
particular, proper band alignment is very important for achieving
high power factors for two-phase nanostructured composites12,13.
In this case, a designed composition contains two separate phases
with energy-aligned conduction or valence bands to facilitate
carrier transport while actively scattering heat-carrying phonons.
Electronic band convergence has been critical for tuning the elec-
tronic structure to achieve the maximum power factor. It involves
the modification of separate electronic bands of the same car-
rier type aiming to converge their energies and so substantially
increase their contributions to carrier transport13,14. Because each
band makes its own contribution to the Seebeck coefficient on a
weighted basis, strong enhancement can be achieved while main-
taining high electrical conductivity. Some of the performance
optimization process in first-generation ternary TE materials,
(Bi0.2Sb0.8)2Te3 for example, is related to the band convergence, but
has not been referred to specifically as such15. The Pb-based chal-
cogenides (PbTe, PbSe and PbS), filled skutterudites (REM4Sb12:
RE = rare earth, M = Fe, Co or Ni) and half-Heusler (HH) alloys
are the key systems in which the above concepts led to superior
performance characteristics. In terms of their ZTmax and ZTave val-
ues achieved during operation in the mid-temperature range, lead
tellurides are the most promising materials, followed by complex
filled skutterudites. However, in terms of mechanical strength
Nature Materials | VOL 21 | May 2022 | 503–513 | www.nature.com/naturematerials
Review Article
(a key feature for the actual electronic devices), skutterudites
and HH alloys are the most promising materials, followed by tel-
lurides. In addition to these concepts, there were discoveries of
compounds with unprecedented ZT performance, such as SnSe,
MgAgSb, Mg3Sb2, Yb14MnSb11 and La3−xTe4.
This Review is organized as follows. First, it discusses recent
advances in the development of high-performance TE materials,
especially those with high stability, low manufacturing costs and
high scalability. Second, it describes the demand for novel TE
device fabrication technologies based on these materials and the
current state. Third, it considers the key challenges and possible
strategies for transitioning to high-efficiency devices and mod-
ules that will open the path to broader use and commercializa-
tion. Fourth, it concludes that the main reasons for the absence
of available TE devices and modules based on the materials are
knowledge gaps in how to develop stable high-temperature elec-
trical and thermal interfaces.
The most important breakthroughs in new TE materials
occurred in the mid-temperature range from 300 °C to approxi-
mately 650 °C, which matches the majority of heat sources suitable
for energy harvesting, and thus is where TE devices will produce
the strongest impact. Above 650 °C, their implementation is con-
siderably more challenging because the stability requirements
become even more severe, not only for the TE materials, but also
for many other components of the devices and modules, includ-
ing heat exchangers. Therefore, the prospects for harvesting the
energy of high-temperature heat sources via solid-state TE technol-
ogy are more remote than for mid-temperature sources. Leading
materials systems for applications above 650 °C include the HH
alloys Nb1−xTixFeSb and Nb1−xHfxFeSb with a ZT of ~1.5 at 1,200 K
(refs. 16,17) and a promising ZTave of ~1 (500–1,200 K) (ref. 16), La3−xTe4
with a ZT of ~1.2 at 1,200 K (ref. 18) and Yb14MnSb11 with a ZT of 1.3
at 1,223 K through suitable doping19.
TE modules from high-performance materials
General requirements for practical modules. To fabricate reli-
able TE power generation modules, it is important to realize very
stable low-resistance electrical contacts (especially on the hot gen-
erator side) between the connecting electrodes and TE materials. A
TE module is exposed to high temperatures, which can result in a
chemical reaction and/or atomic diffusion at the electrode–material
interface, leading to its instability and degradation. This extreme
environment sets in motion several complex phenomena that pro-
mote the development of detrimental secondary phases, which
reduce module conversion efficiency. Therefore, efficient and very
stable diffusion barriers between the connecting electrodes and TE
materials are required to prevent the chemical reactions and/or
atomic diffusion. This is a non-trivial challenge because such barri-
ers must also have low electrical contact resistance (of the order of a
few μΩ cm2) and be tailored to the specific TE materials. It requires
a clearer fundamental understanding of these parasitic processes
and more basic research on this subject. The coefficients of thermal
expansion of TE materials, electrodes and barrier materials should
match well to reduce thermomechanical stresses, which degrade
stability. One reason for the sparse basic research conducted in this
area has been the broad perception that this essentially is an easily
tractable device engineering problem that can be solved empirically.
TE materials with good mechanical properties are critical for device
modules with long service lifetimes. Vickers hardness and fracture
toughness are often used to gauge the mechanical performance of
TE materials. Some published works on TE devices, TE materials
and module efficiency tests have reported Vickers hardness >1 GPa
and fracture toughness >1 MPa m1/2, which can serve as a rough
guide for the required mechanical properties for practical device
applications; however, these may vary for different applications
(for example, stationary, mobile and so on).
505
Review Article Nature Materials

a b c
2.5
873

Ge 800 2.0
Na 6
873 K
700
4 1.5

P (W)
T (K)
600
2 773 K
500 0 1.0
Ge 15 673 K
Na 400
10 15 0.5 573 K
Te
303 10
5 z
5 y 0.0
x 0 1 2 3 4 5
00
I (A)

d 10 e f
12 Th = 12
873 K 673 K
8 773 K 573 K 10
873 K 10

6 ηmax (%) 8 8
η (%)

η (%)
773 K 6 6
4
673 K 4
4
2 573 K
2 2
Tc = 283 K
0 0
0 1 2 3 4 5 0
0 4 8 12 16 20 24 0.0 0.5 1.0 1.5 2.0 2.5 3.0
I (A) Time (h) I (A)

Fig. 1 | The power and conversion efficiency of PbTe-based modules. a, Schematic diagram shows the nanoprecipitates and disk-like nanostructures in
Pb0.953Na0.040Ge0.007Te. b, Typical results of numerical simulations for the nanostructured PbTe-based module (PbTe–2% MgTe doped with 4% Na (p type)
and PbTe doped with 0.2% PbI2 (n type)) for the hot side at 873 K, the cold side at 303 K and a load conductivity of 4.5 × 102 S cm−1. Dimensions of the
module are in millimetres. c,d, Electrical power output (P) (c) and η (d) of the nanostructured PbTe-based module as functions of I. Th was changed from
873 K to 573 K, while Tc was maintained at 283 K. e, ηmax as a function of time for 24 h testing of a nanostructured PbTe-based module with Th = 873, 773,
673 and 573 K and Tc = 283 K. f, η as a function of I of the nanostructured Pb0.953Na0.040Ge0.007Te module cascaded with a Bi2Te3 module (inset). Th and Tc
were at 873 K and 283 K, respectively. The measurements were performed at various currents (2.0−4.0 A) (refs. 22,23). Reproduced from ref. 23, Cell Press
(a,e); adapted from ref. 23, Cell Press (c,d,f); reproduced from ref. 22, The Royal Society of Chemistry (b).

PbTe-based modules. The so-called legacy (first-generation)
PbTe-based modules developed in the 1960s and 1970s exhibited
a PCE of 5.1% at Th = 783 K and Tc = 366 K (refs. 20,21). The efficien-
cies of the second-generation modules containing nanostructured
PbTe-based materials (Fig. 1a) exceeded these by more than 100%.
A low contact resistivity of below 10 mΩ cm was important for the
minimization of thermal losses. For example, modules constructed
from p-type PbTe–MgTe (second-generation, ZT ≈ 1.9) and n-type
PbTe (first-generation) materials demonstrated PCE ≈ 8.5% at
Th = 873 K and Tc = 283 K (refs. 22,23). On the basis of a simulated
temperature distribution, a subsequent segmented module was
designed utilizing legacy Bi2 −xSbxTe3−ySey alloys on the cold side of
the TE legs to increase the PCE at lower temperatures to 12% (Fig.
1b). The key to this successful demonstration was the fabrication
process, which employed the pressure-assisted sintering of TE mate-
rials with diffusion barriers such as Fe and 80% Co–20% Fe-based
alloys23. The theoretically predicted efficiency for this cascaded
module was 15.6%, which included 23% losses experienced by an
early experimental module due to the high resistance of electrode
contacts. These losses pointed to the necessity of design improve-
ments and were ultimately minimized to approximately 5–10%
of the theoretical efficiency. Thermal cycling stability is another
critical aspect of commercial applications. Generally, PbTe-based
TE modules demonstrate good thermal stability at T < 793 K.
In the PbTe–MgTe-based module, a slight decrease in PCE was
observed during operation at Th = 873 K for 24 h, while no appar-
ent changes were detected at Th ≤ 773 K (ref. 23). The correspond-
ing module comprising the nanostructured Pb0.953Na0.040Ge0.007Te
p-type leg (Fig. 1a) with Th and Tc maintained at 873 K and 283 K,
respectively, produced 2 W with promising stability and ~12% PCE
(Fig. 1c–f). In addition, the n-type (PbSn0.05Te)0.92(PbS)0.08 TE mate-
rial (ZT ≈ 1.5) was used to build a unicoupled module24 by cou-
pling with p-type Ge0.87Pb0.13Te (ZT ≈ 2.2). A high PCE of 12% was
achieved at Th = 773 K, and Tc = 323 K with maximum power output
Pmax = 0.145 W, close to the theoretically predicted PCE of 13.6% and
Pmax = 0.16 W.
Tellurium is a rare metal with an abundance of ~0.001 ppm in
the Earth’s crust, and is mainly obtained as a by-product of the
electrolytic refining of Cu25. The annual production of Te is diffi-
cult to assess but is estimated to be ~1,000 t, which could become
a scale-up bottleneck for TE devices using PbTe. Thus, the use
of PbSe or PbS instead of PbTe in TE devices has been consid-
ered by researchers26–29. Not only would the implementation
of Pb(S, Se) materials lower the costs, but also because of their
higher melting points they could increase the operational tem-
perature for higher efficiency and higher Vickers hardness than
PbTe. A recent report described a demonstration in a TE device
with ZTmax in the range 1.5–1.9 at around 700–900 K (ref. 30)
using a heavily alloyed composition Pb0.99−ySb0.012SnySe1−2xTexSx
segmented with n-type Se-doped Bi2Te3 as the n-type leg and cou-
pled with a typical p Na-doped PbTe segmented with Bi2−xSbxTe3
as the p-type leg. An eight-couple module produced 3.1 W of
power, corresponding to a maximum conversion efficiency of
12.3% with ΔT = 507 K and current I = 3.7 A. The simulated high-
est conversion efficiency of the segmented module was 13.9% at a
temperature difference ΔT = 513 K. The slightly lower efficiency
compared with the theoretical value was attributed to subopti-
mal electrical contact resistance. Here too, Te may be problematic
for broad-basedapplications of Bi–Sb–Te compounds as the most
used segmented modules for low temperature. Thus, alternative

506 Nature Materials | VOL 21 | May 2022 | 503–513 | www.nature.com/naturematerials

Nature Materials Review Article
a b Module no. 1 c
10

Percentage of ideal Voc at 450 °C

Th = 200 °C 100
Tc = 50 °C Th = 300 °C 90
8
Th = 400 °C 80
Th = 500 °C 70
6
Th = 600 °C

η (%)
60
Th = 650 °C
4 50
40 P-1
2 P-4
30 P-6
20 N-3
0
0 10 20 30 0 20 40 60 80 100 120
I (A) Cycle no.

d e f 16
10 15
80
Theoretical prediction
70 Ta0.74V0.1Ti0.16FeSb
8 12 ZrCoBi0.65Sb0.15Sn0.2
60
Zr joint @ 873 K Nb0.8Ti0.2FeSb
10
R (µΩ cm2)

50
6
Pmax (W)

η (%)
40

η (%)
8
Zr joint @ 823 K
30
4
20 5
Nb joint @ 873 K 4
10 2
0 Nb joint @ 848 K
Tc = 336 K
Tc: ~287–317 K
0 20 40 60 80 100 0 0 0
600 700 800 900 1,000 400 500 600 700 800 900 1,000
Time (d)
Th (K) Th (K)

Fig. 2 | The conversion efficiency and stability of skutterudite and half-Heusler-based modules. a, An 8 × 8-leg device made from n-type CoSb3 (filled
with Yb, Ca, Al, Ga, ZT ≈ 1.2) and p-type CoSb3 (filled with Pr, Ti, Ga, Ba, Fe, ZT ≈ 0.85). b, Energy conversion efficiency with different Th values. The
cold-side temperature is kept at 50 °C (323 K) (ref. 40). c, Change of Voc of four skutterudite legs upon thermal cycling. The hot sides are cycled between
150 °C (423 K) and 500 °C (773 K), and the cold sides are cycled between 25 °C (298 K) and 50 °C (323 K) (ref. 42). P-1, P-4 and P-6 are three skutterudite
legs of p-type; N-1 is a skutterudite leg of n-type. d, Interfacial resistivity R for skutterudite/Nb and skutterudite/Zr joints after ageing at 823, 848
and 873 K for 100 days. Dots are experimental data, and lines are numerical curve fitting43. e, Pmax and η as a function of Th for a TE device made from
FeNb0.88Hf0.12Sb and ZrNiSn. The dashed line represents the theoretical conversion efficiency assuming no electrical or thermal contact resistances16.
The inset images show consolidated thermoelectric material processed into thermocouple pellets (bottom right) for the fabrication of thermoelectric
modules (bottom left) and a typical thermoelectric module composed of eight n- and p-type thermocouples (top). f, Measured heat-to-electricity PCE
of Ta0.74V0.1Ti0.16FeSb and ZrCoBi0.65Sb0.15Sn0.2 as a function of hot-side temperature48. Reproduced from ref. 40, Science Direct (a,b); reproduced from ref. 42,
Springer Nature Ltd (c); reproduced from ref. 43, Springer Nature Ltd (d); reproduced from ref. 16, Springer Nature Ltd (e); reproduced from ref. 48, Springer
Nature Ltd (f).

Te-free compounds are highly desirable. Recently, high efficien-
cies of 6.5–7.3% have been achieved at low temperatures (<593 K)
for devices with Mg–Sb-based compounds (for example, Mg3Sb331
or Mg3(Sb, Bi)232), which is promising for scalable applications.
High mechanical strength is rare in the top-performing TE
materials but is necessary for viable module fabrication. PbTe
single crystals exhibit a low Vickers hardness of approximately
0.3 GPa, which can be increased to 0.8 GPa through Na doping33.
Hot-pressed polycrystalline PbTe pellets containing 5–10 mol% PbS
possess higher Vickers hardness values up to 1.2 GPa, which is still
lower than those of skutterudite and HH alloys (3–4 GPa) (ref. 34).
Further enhancements of the material mechanical strength are
desirable to increase the resistance to mechanical fracture during
operation. In this regard, replacing Te with S or Se in PbTe, as in
Pb0.93Sb0.05S0.5Se0.5, which exhibits a Vickers hardness above 2.0 GPa,
is another advantage23.
A study on PbTe evaporation revealed that for the device
operated at Th = 793 K and Tc = 333 K, some reduction in the
cross-sectional area was observed due to material sublimation
occurring at distances of 0.5 and 1.1 mm from the hot generator side
after 456 h (ref. 35). This suggests that high thermal stability of TE
devices can be achieved if a proper threshold is maintained for the
high-temperature side. Recent studies on this topic are promising,
such as those on Ga-doped PbTe–GeTe with ZTave = 1.27 between
400 and 773 K (ref. 36).
Skutterudite-based modules. Skutterudite-based TE materi-
als have been favourites for TEGs because of attractive mechani-
cal properties (corresponding to a Vickers hardness of 4 GPa and
flexural strength up to 180 MPa for Yb-filled CoSb3)37 and suffi-
ciently high ZT values38. A 4 × 4-leg device built using YbyCo4Sb12
(ZT ≈ 1.5) as the n-type component and CeyFe3CoSb12 as the p-type
component achieved an η of 8.4% with ΔT = 577 K and Th = 873 K
(ref. 39). An 8 × 8-leg device (Fig. 2a) using CoSb3 as both the n-type
(doped with Yb, Ca, Al and Ga; ZT ≈ 1.2) and p-type (doped with
Pr, Ti, Ga, Ba and Fe; ZT ≈ 0.85) components has been fabricated
as well40. The PCE and Pmax were ~9.1% and ~42 W at a current of
~15 A and ΔT of 600 K (Fig. 2b). In segmented TE modules com-
posed of Bi2Te3/skutterudite41, PCE reached ~12% with ΔT of 540 K.
The above-mentioned tests were performed in controlled gas
environments (such as Ar or N2). The results of a durability test con-
ducted on skutterudite legs during thermal cycling in an open atmo-
sphere revealed that their failure mainly resulted from oxidation and
interlayer diffusion processes42. If crack generation occurs typically
on the hot side of the TE legs, it increases the internal resistance and
decreases the open circuit voltage (Voc) (Fig. 2c). Mitigation efforts
include an interfacial barrier layer and packaging protective against
oxidation. A recent study on the screening of barrier layers involv-
ing density functional theory modelling revealed that an Nb elec-
trode could be used to effectively inhibit the interfacial reaction43. A
subsequent experimental study on such a skutterudite/Nb junction

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Review Article
a b
Vickers hardness (GPa)
Heat sinks
TE device
Heater
Keithley
Fig. 3 | SnSe-based modules and summaries of mechanical and thermal properties of TE materials. a, Three-dimensional printed SnSe TE power
generator67. b, Plot of Vickers hardness and fracture toughness of bulk polycrystalline CoSb393,94,98,99, Bi2Te3113–116, SnSe65,66, Cu2Se76,110, PbTe33,89,117,118,
Mg3Sb2104,106 and MgAgSb99,119. The error bar in fracture toughness of Bi2Te3-based materials is due to different processing techniques such as zone
melting and mechanical alloying/spark plasma sintering methods. As shown in the legend, the data bars of each material are colour coded according to
the temperature range of their peak ZT values. c, Plot of thermal expansion coefficient data and peak ZT of bulk polycrystalline CoSb393–97, ZrNiSn102,120,
Bi2Te3115,116,121,122, SnSe65,108,109, Cu2Se71,76, PbTe87,88,117,118, Mg3Sb2104,105 and MgAgSb119,123,124. The thermal expansion coefficient is plotted using a logarithmic scale.
Reproduced from ref. 67, Wiley VCH (a).
showed stable hot-side interfacial resistance for up to 100 d at 848 K
with PCE of 10.2% and Pmax of 4.1 W at a ΔT of 574 K (Fig. 2d).
In addition to the above, Sb sublimation losses at T > 873 K caus-
ing composition changes represent a potential risk that degrades
the performance of CoSb3-based TE devices44. To minimize it, the
skutterudite-based materials can be chemically engineered to shift
the ZT peak to lower temperatures. This concept was tested on
two-leg devices45 containing n-type Yb0.25Fe0.25Co3.75Sb12 (ZT ≈ 1.3
at 740 K) and p-type La0.7Ti0.1Ga0.1Fe2.7Co1.3Sb12 (ZT ≈ 0.97 at 760 K),
which demonstrated an efficiency of 7.2% at a ΔT of only 366 K
(Th = 679 K).
HH modules. The HH compounds with the XYZ formula (X and Y,
transition or rare earth metals; Z, p-block elements) exhibit robust
mechanical strength, versatile composition, high thermal stability
and reasonably high ZT values. For these reasons, some of these
materials can potentially be used in practical applications. However,
their synthesis is a complex procedure due to the very high tem-
perature and activation energy. The recent development of p-type
HH materials with high ZT values considerably increased the effi-
ciencies of the corresponding modules16,46. A 4 × 4-leg TE device16
with FeNb0.88Hf0.12Sb (ZT ≈ 1.5 at 1,200 K) as the p-type leg and
ZrNiSn (ZT ≈ 1.0 at 950 K) as the n-type leg exhibits a PCE of 6.2%
at ΔT = 655 K with Th = 1,000 K (Fig. 2e). Here, Hf doping of the
p-type legs is used to decrease the lattice thermal conductivity; how-
ever, Hf is expensive, and its use may lead to unfavourable material
costs. To avoid Hf, Bi-doped ZrCoSn47 and Ti-doped TaFeSb48 have
been proposed for p-type HH materials with ZT values of 1.4–1.5
at 973 K. The single-leg modules based on these HH alloys dem-
onstrate PCEs of 9.0–11.4% with Th = 823–973 K and Tc = 300 K
(Fig. 2f).
The optimization of geometrical parameters is useful for mini-
mizing heat and electrical losses and predicting increases in η and
Pmax. This was done using finite-element analysis for a 4 × 4-leg
device consisting of n-type Hf0.5Zr0.5NiSn0.98Sb0.02 (ZT ≈ 1.03)
and p-type (Nb0.8Ta0.2)0.8Ti0.2FeSb (ZT ≈ 1.12) (refs. 49,50). At close
ZT values of the p-type and n-type legs in this example16, a PCE
of 8.3% and Pmax of 8.5 W were reported for the single-stage TE
device50. Segmented modules were prepared with n-type Zr0.5Hf0.5
NiSn0.985Sb0.015 and p-type Zr0.5Hf0.5CoSb0.8Sn0.2 HH compounds on
the hot side and Bi2Te3 on the cold side49. The obtained 4 × 4-leg
device exhibited a record high PCE of 12.4% with a maximum area
power density of 1.5 W cm−2. Adding nanoparticles as inclusions
508
Nature Materials
c
p-Cu2 – xSe
5 p-SnSe p-PbTe
300–600 K 3
p-CoSb3
CoSb3
4 600–900 K n-CoSb3
n-PbTe
900–1,200 K n-ZrNiSn
2
3 Mg3Sb2
ZT
p-Bi2Te3
2 1
Pb(Te,Se,S) MgAgSb n-Mg3Sb2 900
1 Bi2Te3 Cu2Se
0
p-MgAgSb 600
10 n-Bi2Te3
SnSe
)
(K
0 20 30 300
Therm
T
0.2 0.8 1.4 2.0 al exp 100
ansio
n (10 –6
Fracture toughness (MPa m1/2) K –1)
to HH alloys to form nanocomposites is a promising method for
reducing their thermal conductivity. A unicoupled TE device fabri-
cated from (Hf0.6Zr0.4)NiSn0.99Sb0.01/W nanocomposite (n type) and
Hf0.5Zr0.5CoSb0.8Sn0.2 (p type) possessed a PCE of 10.7% and area
power density of 13.9 W cm−2 with ΔT = 674 K (ref. 51). This device
exhibited no apparent performance degradation after 10 thermal
cycles conducted between 373 and 1,027 K. For successful commer-
cialization of HH-alloy-based TE devices, the manufacturing costs
must be kept low by avoiding expensive elemental components
and developing a synthetic approach with a lower energy input.
Although thermal cycling of HH-alloy-based devices has been per-
formed in the past51,52, these cycles were either too few (only 10 ther-
mal cycles were conducted for a (Hf0.6Zr0.4)NiSn0.99Sb0.01/W-based
TE device51) or performed at too low a temperature (up to 873 K
for a Zr0.5Hf0.5CoSb0.8Sn0.2-based device52). Therefore, longer tests
lasting thousands of hours at Th > 1,000 K and post mortem stud-
ies with a focus on the interfacial region close to the hot side are
required to further understand device reliability.
Mg2Sn1−xSix-based modules. Mg2Sn1−xSix-based TE devices have
been widely explored due to several attractive features, includ-
ing the absence of toxic elements. Encouraging results have been
reported for the Mg2Si TE devices with Ni electrodes prepared using
a plasma-activated sintering technique, which exhibited no perfor-
mance deterioration after ageing for 1,000 h (ref. 53). Unfortunately,
the effectiveness of the p-type counterpart of Mg2(Si,Sn) is very low
(ZT ≈ 0.7 at 750 K)54. The volatile nature of magnesium at moder-
ately high temperatures results in phase instability, compositional
changes and degradation of the TE properties. Despite enormous
efforts, these drawbacks have seriously limited commercial appli-
cations53,55–60. A single leg (3.6 mm × 3.6 mm × 4.35 mm) of poly-
crystalline n-type Mg3Sb2-based material, in which In52Sn48 and
Ag56Cu22Zn17Sn5 were used as brazes for the cold and hot sides,
respectively, demonstrated a PCE of 10.6% at a temperature gra-
dient of 400 K (Th = 773 K). This is among the highest efficiencies
obtained for this temperature difference61. However, the large-scale
application of Mg3Sb2-based generators is currently impeded by
challenges related to the material and device fabrication procedures.
Nascent SnSe modules. The recent discovery of SnSe single crystals
with ZT values above 2.6 in the temperature range of 600–700 °C
and their availability in both p-type and n-type forms have raised
expectations for SnSe-based TE devices in the near future62–65. This
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Nature Materials Review Article
Table 1 | Summary of properties and device conversion efficiency of discussed materials
Material Peak ZT Linear thermal expansion Vickers Fracture PCE (%) Melting/ Operation
(×10−6 K−1) hardness toughness decomposition temperature
(GPa) (MPa m1/2) point (K) range (K)
PbTe based 1.4 (n)24 α373−773 K = 19–20 0.3 0.59 (ref. 33,89) 14.0 (n)24 1,190–1,210 500–900
2.2 (p)24 (n & p)a87,88 (ref. 33,89) (Tc = 323 K,
Th = 773 K)
PbSe based 1.8 (n)30 α300 K = 19.4 (n & p)a91 0.18 (ref. 92) 0.67 (ref. 89) 12.3 (n)30 1,340–1,350 600–1,000
1.7(p)90 (Tc = 293 K,
Th = 800 K)
Skutterudite based 1.7 (n)93 α473−873 K = 10–12.2b95–97, 4.2 (ref. 98) 1.49 (ref. 99) 9.1 (n)40 1,137–1,147 (ref. 100) 500–900
1.45 (p)94 14.5c95 (Tc = 323 K,
Th = 923 K)
HH based 1.0 (n)101 α200−800 K = 8.6–12.1d50,102, 8.5–14.4 2.1 (ref. 102) 6.2 (p)101 — >900
1.5 (p)101 10.6–12.9e50,102 (ref. 102) (Tc = 336 K,
Th = 991 K)
Mg3Sb2 based 1.7 (n)103 α300−773 K = 22.3 (n & p)a105 1.1 (ref. 106) 1.4 (ref. 106) 10.6 (n)61 1,508–1,528 500–900
1.3 (p)104 (Tc = 373 K, (ref. 107)
Th = 773 K)
SnSe based 2.8 (n)64 α200−800 K = 13–14.9 (n & 0.67 (ref. 66) 0.62 (ref. 66) — 1,120–1,140 >900
2.6 (p)62 p)a108,109
Cu2Se based 2.7 (p)76 α773−1,000 K = 107 (ref. 71) 0.43 (ref. 110) 2 (ref. 110) 9.1 (p)111 1,376–1,396 >900
(Tc = 300 K,
Th = 973 K)
Yb14MnSb11 1.3 (p)78 — >3 (ref. 78) — — >1,200 (ref. 112) >900
a
Chemical composition and thermal expansion coefficient data are very similar for both n- and p-type variations. bFor n-type filled CoSb3-based skutterudites. cFor p-type filled FeSb3-based skutterudites.
d
For n-type (Ti, Zr, Hf)NiSn-based HH alloys. eFor p-type Ti(Fe, Co)Sb-based HH alloys.

is particularly true in the light of new developments suggesting
that polycrystalline compactions can achieve efficiencies close to
those of single crystals. Currently, applications of SnSe in devices
are limited by the poor mechanical properties of single crystals66.
However, the mechanical properties of polycrystalline SnSe are bet-
ter (Vickers hardness 669 MPa, flexural strength 21 MPa, fracture
toughness 0.62 MPa m1/2). To date, very few SnSe-based TEGs have
been reported. A p-type polycrystalline SnSe-based power genera-
tor was built using a pseudo-three-dimensional printing method
with a small peak output power of 20 µW and Th = 772 K (Fig.
3a)67. A recent study showed that coupling n-type Sn1–xPbxSe legs
(ZT = 2.5) with p-type Bi2Te2.7Se0.3 delivered a conversion efficiency
of 4.4% with ΔT = 200 K (ref. 68). This efficiency is much lower than
the expected value because of suboptimal electrical contact between
the electrode and the legs. Therefore, finding effective metallization
layers is critical for SnSe-based devices. Initial results have high-
lighted how challenging this can be. For example, a single Ag metal-
lization layer was unable to inhibit the diffusion of Sn atoms into
the Ag layer, resulting in a high contact resistivity of 7.03 mΩ cm2.
Meanwhile, the application of a single Ni metallization layer gener-
ated surface cracks because of the different thermal expansion coef-
ficients of the various Ni-based compounds, such as Ni17Sn3, Ni3Sn
and Ni5.63SnSe269. An Ag/Co/Ti metallization multilayer achieved
a specific contact resistance of 1.53 mΩ cm2, lower than that of a
single Ag layer, but still much higher than the contact resistances of
commercial bismuth antimony telluride devices70.
Cu2Q (Q = S, Se, Te) modules. Cu2Q p-type materials are highly
promising TE materials with ZT = 1.5 at 1,000 K for Cu2Se and
ZT = 1.7 at 1,000 K for Cu2S71,72. These materials show good elec-
tronic transport properties and intrinsically low lattice thermal
conductivities of the phonon-liquid electron-crystal frameworks.
Unfortunately, the same liquid-like mobility also decreases stability
due to electromigration of Cu ions in the samples destroying the
TEG modules. This was deemed to be insurmountable and led to
the termination of decade-long research studies mainly by NASA’s
Jet Propulsion Laboratory73. Recent strategies, however, employing
electrically conductive but ion-blocking secondary phases or inter-
faces, show that the long-range Cu ion electromigration can be hin-
dered, potentially allowing stable devices to be studied74–76.
Potential Yb14MnSb11 modules. The Yb14MnSb11 compound is a
promising material for power generation in the temperature range
of 975–1,275 K with a peak ZT of 1.0 at 1,223 K (ref. 77). The ZT value
can be further increased to 1.3 at 1,223 K through suitable doping19.
Yb14MnSb11 shows good compatibility with other state-of-the-art
p-type TE materials, which can be used to prepare segmented
modules in various temperature ranges. A high PCE of 18.6% was
predicted for a segmented p-type leg composed of Yb14MnSb11/
CeFe4Sb12/TAGS/(Bi, Sb)2Te3, with ΔT = 975 K (Th = 1,275 K and
Tc = 300 K)77. Yb14MnSb11 exhibits good mechanical properties
(Vickers hardness >3 GPa)78 and high thermal stability (no vapour
losses up to 1,395 K with La doping)79, and can be produced by a
scalable ball-milling process under Ar atmosphere78. However, no
experimental testing of functional modules or single-leg devices
fabricated from Yb14MnSb11 has been reported. The material would
be almost exclusively used in space applications because of the
cost-prohibitive nature of its composition.
On the basis of the above discussion, a summary of the mate-
rials properties and device efficiency is shown in Table 1. For
mid–high-temperature operation, the thermal expansion match-
ing is essential for module reliability. Because of the heavy atoms
present in the top-performing TEs, they tend to have a ‘soft’ lattice
nature and thus high thermal expansion coefficients. In contrast,
the best metal electrodes have much lower values, by a factor of 2
to 4. How can such contacts achieve the very low resistivity that
must be maintained and survive the large temperature fluctuations?
It is known that doping or adding secondary phases can tune the

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Review Article
respective thermal expansion coefficients, and this could be a way
to mitigate these issues to a certain extent. It has been demonstrated,
by matching the thermal expansion of n- and p-type HH, that the
interfacial shear stresses can be reduced by 40% and the reliabil-
ity significantly improved80. For segmented modules with Bi2Te3,
both thermal expansion and dimension of the segment components
should be consistent between n- and p-type legs. Therefore, con-
tinued innovations in design are needed to reconcile the thermally
disparate materials.
Future research directions
Despite the tremendous progress in the field of TE materials for
power generation, commercialization and practical implementa-
tion of TEGs proceed very slowly. Currently, the fabrication of com-
mercial Bi2Te3 π-type modules is fully automated at each step and
is capable of mass production. However, module fabrication using
the newly developed high-ZT materials is not a trivial task and is
required for practical TE power generation. There is a long way yet
to go before addressing the critical issues, and before there is a via-
ble heat-to-electricity conversion industry for widespread TEG use
is achieved. Beyond sporadic activities, no systematic basic research
is being conducted to solve the problems blocking the full develop-
ment of modules based on the new TE materials. The basic ongoing
research focus needs to be expanded beyond only increasing ZT to
tackle all the other issues discussed above.
Therefore, future research will need to be aimed at addressing
simultaneously these key challenges, all of which have to do with
mechanical strength and interfaces. The mechanical and fracture
strength of most high-performance TE materials is poor, with a
few exceptions such as the HH alloys and perhaps the skutterudites
(Fig. 3b). Is it possible to raise the toughness and fracture strength
of the new high-ZT materials or to mitigate the risk of cracking
during operation via innovative device design? In general, most
high-performing TE materials tend to have high thermal expan-
sion coefficients, whereas those of the best metal electrodes are low
(Fig. 3c). The differences in thermal expansion coefficients across
the interfaces of the materials in any given module will inevitably
cause cracking at the interface and electrical discontinuities, and
will have to be reconciled. The development of metal electrodes
matching the thermal expansion coefficients of TE materials will
be required to create stable low-resistance electrical contacts for
high-temperature operation. This can be realized either by alloy-
ing metals with various thermal expansion coefficients or by clever
architecture design such as multiple layers. From Table 1, the ther-
mal expansion coefficient of TE materials (except Cu2Se) is usually
in the range of 10–20 × 10−6 K−1, while metals such as Cu, Ag, Ni, Co
and Ti have a thermal expansion coefficient between 1 × 10−6 K−1
and 20 × 10−6 K−1 (refs. 81,82), which makes the strategy possible.
Electrodes with low-resistance contacts must be achieved at both
the high-temperature and low-temperature ends of the TE leg.
This is more difficult to achieve at the high-temperature end of the
device. The understanding of effective diffusion barrier layers to the
electrode joints on the hot side is crucial. Obviously, there are other
factors that contribute to overall mechanical strength, such as yield
strength and fracture toughness. These are properties that we do not
know much about for most of the high-performance TE materials,
as even small compositional modifications typically made to opti-
mize ZT also change these.
What is the cutting-edge fundamental material science that
needs to be done to try to increase the mechanical strength, or at
least learn to live with low strength by ingenious design of devices
that are tolerant to this weakness? The interface stability as a func-
tion of temperature, temperature fluctuations and time will need to
be understood at a fundamental level and controlled. Specifically,
reactions between electrodes and TE materials and creation of new
detrimental phases are the most worrisome. A moderate diffusion
510
Nature Materials
rate at the interface is essential for the formation of a strong inter-
face, but a rather rapid or extensive one could lead to the unwanted
degradation of TE materials. For development of stable metalliza-
tion at high temperature, high-throughput methods should be a
useful strategy to identify viable electrode systems43. The potential
for chemical sublimation of TE materials during operation can be
a problem, and must be mitigated or suppressed by developing
low-cost protective media, including various epilayers, as well as
argon or helium gas (more conventional gases such as nitrogen or
carbon dioxide can be also applied for this purpose). Solid insu-
lation coatings containing silica, certain types of ceramic, phos-
phate glasses and lead oxide enamels may decrease the sublimation
rates of TE materials as well; however, the latter would require
proper engineering to prevent failure due to rupture. In view of
the above-mentioned key challenges for TE devising, a transverse
TE device83 is worth highlighting. In such devices, the electrical
contacts are made only on the cold sides, which avoids the con-
cerns about the instability of the interface and contact of the hot
sides as in conventional devices. A high device ZT of ~0.7 has been
achieved for an Re4Si7 single crystal in a transverse TE device83.
Such devices may not be applicable to all TE materials because
they have special requirements for anisotropic transport proper-
ties along different crystal axes for p- and n-type carriers requir-
ing single crystals. The subfield of transverse TEs is undeveloped
as a result. For TE materials with symmetric crystal structures or
polycrystalline nature, it may be necessary to construct multilayer
heterostructures, where, however, only very low ZT values (~10−2)
have been demonstrated. Although there are additional issues to
overcome, including optimal thermal interfaces to efficiently guide
the heat from the source through the devices and resist detach-
ment, the aforementioned challenges are make-or-break proposi-
tions. These are not necessarily just engineering issues. There has
to be considerable basic research focus to raise our fundamental
understanding, as tackling these challenges will define the lifetime
of the TE modules, which will have to be of the order of a decade
or two. A scientific and technological research roadmap is needed
to highlight necessary steps to transition from real advances in ZT
research into a viable TEG technology. The stability, reliability and
efficiency of TE devices and modules need to be measured reliably
and this is not trivial. The development of TE modules and TEGs is
in a similar state as the materials research was 20–30 years ago, but
the challenges are more severe. Therefore, such work currently is
only being done in very few laboratories with home-built systems.
Easy-to-use commercial device and module measurement systems
need to be available for use by non-specialists to produce reliable
data that can be compared across different laboratories. It may also
be useful to establish third-party agencies for standard evaluation
of TE device performance, similar to what currently is done in pho-
tovoltaic device research, for reliable comparison between differ-
ent materials and devices reported by different groups. In addition,
several new engineering approaches have been developed to fabri-
cate planar and vertical TE devices including laser direct sintering84,
tape casting85 and vacuum filtration86, where these methods still use
Bi–Te commercial powder in device fabrication. Similar processing
techniques could be adapted for the new TE materials. We are opti-
mistic that future research focusing on bridging the chasm between
the materials discovery and development on the one hand and the
device/module engineering communities on the other will achieve
meaningful advances in broad-based module development.
Received: 10 April 2021; Accepted: 19 August 2021;
Published online: 21 October 2021
References
1. Wood, C. Materials for thermoelectric energy conversion. Rep. Prog. Phys.
51, 459–539 (1988).
Nature Materials | VOL 21 | May 2022 | 503–513 | www.nature.com/naturematerials
Nature Materials
2. Nandihalli, N., Liu, C. J. & Mori, T. Polymer based thermoelectric
nanocomposite materials and devices: fabrication and characteristics.
Nano Energy 78, 105186 (2020).
3. Petsagkourakis, I. et al. Thermoelectric materials and applications for
energy harvesting power generation. Sci. Technol. Adv. Mater. 19,
836–862 (2018).
4. Tarancon, A. Powering the IoT revolution with heat. Nat. Electron. 2,
270–271 (2019).
5. Jaziri, N. et al. A comprehensive review of thermoelectric generators:
technologies and common applications. Energy Rep. 6, 264–287 (2020).
6. Kober, M. Holistic development of thermoelectric generators for automotive
applications. J. Electron. Mater. 49, 2910–2919 (2020).
7. Lan, S., Yang, Z. J., Stobart, R. & Chen, R. Prediction of the fuel economy
potential for a skutterudite thermoelectric generator in light-duty vehicle
applications. Appl. Energy 231, 68–79 (2018).
8. Zoui, M. A., Bentouba, S., Stocholm, J. G. & Bourouis, M. A review on
thermoelectric generators: progress and applications. Energies 13,
3606 (2020).
9. He, R., Schierning, G. & Nielsch, K. Thermoelectric devices: a review of
devices, architectures, and contact optimization. Adv. Mater. Technol. 3,
1700256 (2018).
10. Tan, G. J., Ohta, M. & Kanatzidis, M. G. Thermoelectric power generation:
from new materials to devices. Phil. Trans. R. Soc. A 377, 20180450 (2019).
11. Sootsman, J. R., Chung, D. Y. & Kanatzidis, M. G. New and old concepts in
thermoelectric materials. Angew. Chem. Int. Ed. 48, 8616–8639 (2009).
12. Tan, G. J., Zhao, L. D. & Kanatzidis, M. G. Rationally designing
high-performance bulk thermoelectric materials. Chem. Rev. 116,
12123–12149 (2016).
13. Pei, Y. Z. et al. Convergence of electronic bands for high performance bulk
thermoelectrics. Nature 473, 66–69 (2011).
14. Zhao, L. D., Dravid, V. P. & Kanatzidis, M. G. The panoscopic approach to
high performance thermoelectrics. Energy Environ. Sci. 7, 251–268 (2014).
15. Stordeur, M., Stolzer, M., Sobotta, H. & Riede, V. Investigation of the
valence band structure of thermoelectric (Bi1-xSbx)2Te3 single crystals. Phys.
Status Solidi b 150, 165–176 (1988).
16. Fu, C. et al. Realizing high figure of merit in heavy-band p-type
half-Heusler thermoelectric materials. Nat. Commun. 6, 8144 (2015).
17. Zou, M., Li, J.-F. & Kita, T. Thermoelectric properties of fine-grained FeVSb
half-Heusler alloys tuned to p-type by substituting vanadium with titanium.
J. Solid State Chem. 198, 125–130 (2013).
18. May, A. F., Fleurial, J. P. & Snyder, G. J. Thermoelectric performance of
lanthanum telluride produced via mechanical alloying. Phys. Rev. B 78,
125205 (2008).
19. Toberer, E. S. et al. Traversing the metal-insulator transition in a Zintl
phase: rational enhancement of thermoelectric efficiency in
Yb14Mn1-xAlxSb11. Adv. Funct. Mater. 18, 2795–2800 (2008).
20. LaLonde, A. D., Pei, Y., Wang, H. & Jeffrey Snyder, G. Lead telluride alloy
thermoelectrics. Mater. Today 14, 526–532 (2011).
21. Rowe, D. M. Thermoelectrics Handbook: Macro to Nano (CRC, 2005).
22. Hu, X. K. et al. Power generation from nanostructured PbTe-based
thermoelectrics: comprehensive development from materials to modules.
Energy Environ. Sci. 9, 517–529 (2016).
23. Jood, P., Ohta, M., Yamamoto, A. & Kanatzidis, M. G. Excessively doped
PbTe with Ge-induced nanostructures enables high-efficiency
thermoelectric modules. Joule 2, 1339–1355 (2018).
24. Hazan, E., Ben-Yehuda, O., Madar, N. & Gelbstein, Y. Functional graded
germanium–lead chalcogenide-based thermoelectric module for renewable
energy applications. Adv. Energy Mater. 5, 1500272 (2015).
25. Green, M. A. Rare materials for photovoltaics: recent tellurium price
fluctuations and availability from copper refining. Sol. Energy Mater. Sol.
Cells 119, 256–260 (2013).
26. Luo, Z. Z. et al. Soft phonon modes from off-center Ge atoms lead to
ultralow thermal conductivity and superior thermoelectric performance in
n-type PbSe–GeSe. Energy Environ. Sci. 11, 3220–3230 (2018).
27. Luo, Z. Z. et al. Strong valence band convergence to enhance thermoelectric
performance in PbSe with two chemically independent controls. Angew.
Chem. Int. Ed. 60, 268–273 (2021).
28. Lee, Y. et al. Contrasting role of antimony and bismuth dopants on the
thermoelectric performance of lead selenide. Nat. Commun. 5, 3640 (2014).
29. Hodges, J. M. et al. Chemical insights into PbSe–x%HgSe: high power
factor and improved thermoelectric performance by alloying with
discordant atoms. J. Am. Chem. Soc. 140, 18115–18123 (2018).
30. Jiang, B. et al. High-entropy-stabilized chalcogenides with high
thermoelectric performance. Science 371, 830–834 (2021).
31. Zihang, L. et al. Demonstration of ultrahigh thermoelectric efficiency of
∼7.3% in Mg3Sb2/MgAgSb module for low-temperature energy harvesting.
Joule 5, 1196–1208 (2021).
32. Ying, P. J. et al. Towards tellurium-free thermoelectric modules for power
generation from low-grade heat. Nat. Commun. 12, 1121 (2021).
Nature Materials | VOL 21 | May 2022 | 503–513 | www.nature.com/naturematerials
Review Article
33. Gelbstein, Y., Gotesman, G., Lishzinker, Y., Dashevsky, Z. & Dariel, M. P.
Mechanical properties of PbTe-based thermoelectric semiconductors.
Scr. Mater. 58, 251–254 (2008).
34. Ni, J. E. et al. Room temperature Young’s modulus, shear modulus, Poisson’s
ratio and hardness of PbTe–PbS thermoelectric materials. J. Mater. Sci. Eng.
B 170, 58–66 (2010).
35. Sadia, Y., Ben-Ayoun, D. & Gelbstein, Y. Evaporation–condensation effects
on the thermoelectric performance of PbTe-based couples. Phys. Chem.
Chem. Phys. 19, 19326–19333 (2017).
36. Luo, Z. Z. et al. High figure of merit in gallium-doped nanostructured
n-type PbTe–xGeTe with midgap states. J. Am. Chem. Soc. 141,
16169–16177 (2019).
37. Zhou, Z. X. et al. Uniform dispersion of SiC in Yb-filled skutterudite
nanocomposites with high thermoelectric and mechanical performance.
Scr. Mater. 162, 166–171 (2019).
38. Li, W. J. et al. Enhanced thermoelectric performance of Yb-single-filled
skutterudite by ultralow thermal conductivity. Chem. Mater. 31,
862–872 (2019).
39. Zong, P. A. et al. Skutterudite with graphene-modified grain-boundary
complexion enhances zT enabling high-efficiency thermoelectric device.
Energy Environ. Sci. 10, 183–191 (2017).
40. Nie, G. et al. High performance thermoelectric module through isotype
bulk heterojunction engineering of skutterudite materials. Nano Energy 66,
104193 (2019).
41. Zhang, Q. H. et al. Realizing a thermoelectric conversion efficiency of
12% in bismuth telluride/skutterudite segmented modules through
full-parameter optimization and energy-loss minimized integration. Energy
Environ. Sci. 10, 956–963 (2017).
42. Skomedal, G., Kristiansen, N. R., Sottong, R. & Middleton, H. Evaluation of
thermoelectric performance and durability of functionalized skutterudite
legs. J. Electron. Mater. 46, 2438–2450 (2017).
43. Chu, J. et al. Electrode interface optimization advances conversion efficiency
and stability of thermoelectric devices. Nat. Commun. 11, 2723 (2020).
44. Daniel, M. V., Friedemann, M., Franke, J. & Albrecht, M. Thermal stability
of thermoelectric CoSb3 skutterudite thin films. Thin Solid Films 589,
203–208 (2015).
45. Li, W. J. et al. High-efficiency skutterudite modules at a low temperature
gradient. Energies 12, 4292 (2019).
46. Fu, C. G., Zhu, T. J., Liu, Y. T., Xie, H. H. & Zhao, X. B. Band engineering
of high performance p-type FeNbSb based half-Heusler thermoelectric
materials for figure of merit zT > 1. Energy Environ. Sci. 8, 216–220 (2015).
47. Zhu, H. T. et al. Discovery of ZrCoBi based half Heuslers with high
thermoelectric conversion efficiency. Nat. Commun. 9, 2497 (2018).
48. Zhu, H. T. et al. Discovery of TaFeSb-based half-Heuslers with high
thermoelectric performance. Nat. Commun. 10, 270 (2019).
49. Xing, Y. F. et al. High-efficiency half-Heusler thermoelectric modules
enabled by self-propagating synthesis and topologic structure optimization.
Energy Environ. Sci. 12, 3390–3399 (2019).
50. Yu, J. J. et al. Half-Heusler thermoelectric module with high conversion
efficiency and high power density. Adv. Energy Mater. 10, 2000888 (2020).
51. Kang, H. B. et al. Decoupled phononic–electronic transport in multi-phase
n-type half-Heusler nanocomposites enabling efficient high temperature
power generation. Mater. Today 36, 63–72 (2020).
52. Bartholome, K. et al. Thermoelectric modules based on half-Heusler
materials produced in large quantities. J. Electron. Mater. 43, 1775–1781
(2014).
53. Sakamoto, T. et al. Thermoelectric behavior of Sb- and Al-doped n-type
Mg2Si device under large temperature differences. J. Electron. Mater. 40,
629–634 (2011).
54. Gao, P., Davis, J. D., Poltavets, V. V. & Hogan, T. P. The p-type
Mg2LixSi0.4Sn0.6 thermoelectric materials synthesized by a B2O3 encapsulation
method using Li2CO3 as the doping agent. J. Mater. Chem. C 4, 929–934
(2016).
55. Bux, S. K. et al. Mechanochemical synthesis and thermoelectric properties
of high quality magnesium silicide. J. Mater. Chem. 21, 12259–12266
(2011).
56. Kato, D., Iwasaki, K., Yoshino, M., Yamada, T. & Nagasaki, T. Control of
Mg content and carrier concentration via post annealing under different
Mg partial pressures for Sb-doped Mg2Si thermoelectric material. J. Solid
State Chem. 258, 93–98 (2018).
57. Inoue, H., Yoneda, S., Kato, M., Ohsugi, I. J. & Kobayashi, T. Examination
of oxidation resistance of Mg2Si thermoelectric modules at practical
operating temperature. J. Alloys Compd. 735, 828–832 (2018).
58. de Boor, J. et al. Fabrication and characterization of nickel contacts for
magnesium silicide based thermoelectric generators. J. Alloys Compd. 632,
348–353 (2015).
59. Thimont, Y., Lognoné, Q., Goupil, C., Gascoin, F. & Guilmeau, E. Design of
apparatus for Ni/Mg2Si and Ni/MnSi1.75 contact resistance determination for
thermoelectric legs. J. Electron. Mater. 43, 2023–2028 (2014).
511
Review Article
60. Park, S. H., Kim, Y. & Yoo, C.-Y. Oxidation suppression characteristics of
the YSZ coating on Mg2Si thermoelectric legs. Ceram. Int. 42, 10279–10288
(2016).
61. Zhu, Q., Song, S., Zhu, H. & Ren, Z. Realizing high conversion efficiency of
Mg3Sb2-based thermoelectric materials. J. Power Sources 414, 393–400
(2019).
62. Zhao, L.-D. et al. Ultralow thermal conductivity and high thermoelectric
figure of merit in SnSe crystals. Nature 508, 373–377 (2014).
63. Zhao, L.-D. et al. Ultrahigh power factor and thermoelectric performance
in hole-doped single-crystal SnSe. Science 351, 141–144 (2016).
64. Chang, C. et al. 3D charge and 2D phonon transports leading to high
out-of-plane ZT in n-type SnSe crystals. Science 360, 778–783 (2018).
65. Lee, Y. K., Luo, Z., Cho, S. P., Kanatzidis, M. G. & Chung, I. Surface oxide
removal for polycrystalline SnSe reveals near-single-crystal thermoelectric
performance. Joule 3, 719–731 (2019).
66. Li, J. et al. Substantial enhancement of mechanical properties for SnSe
based composites with potassium titanate whiskers. J. Mater. Sci. Mater.
Electron. 30, 8502–8507 (2019).
67. Burton, M. R. et al. 3D printed SnSe thermoelectric generators with high
figure of merit. Adv. Energy Mater. 9, 1900201 (2019).
68. Qin B. et al. Momentum and energy multiband alignment enable power
generation and thermoelectric cooling. Science 373, 556–561 (2021).
69. Park, S. H., Jin, Y., Ahn, K., Chung, I. & Yoo, C.-Y. Ag/Ni metallization
bilayer: a functional layer for highly efficient polycrystalline SnSe
thermoelectric modules. J. Electron. Mater. 46, 848–855 (2017).
70. Kim, Y., Yoon, G., Cho, B. J. & Park, S. H. Multi-layer metallization
structure development for highly efficient polycrystalline SnSe
thermoelectric devices. Appl. Sci. 7, 1116 (2017).
71. Liu, H. et al. Copper ion liquid-like thermoelectrics. Nat. Mater. 11,
422–425 (2012).
72. He, Y. et al. High thermoelectric performance in non-toxic Earth-abundant
copper sulfide. Adv. Mater. 26, 3974–3978 (2014).
73. Stapfer, G. & Truscello, V. C. Development of the data base for a
degradation model of a selenide RTG. In Proc. 12th Intersociety Energy
Conversion Engineering Conference 1271–1278 (American Nuclear Society,
1997).
74. Olvera, A. A. et al. Partial indium solubility induces chemical stability and
colossal thermoelectric figure of merit in Cu2Se. Energy Environ. Sci. 10,
1668–1676 (2017).
75. Tang, H. et al. Graphene network in copper sulfide leading to enhanced
thermoelectric properties and thermal stability. Nano Energy 49, 267–273
(2018).
76. Yang, D. et al. Blocking ion migration stabilizes the high thermoelectric
performance in Cu2Se composites. Adv. Mater. 32, 2003730 (2020).
77. Brown, S. R., Kauzlarich, S. M., Gascoin, F. & Snyder, G. J. Yb14MnSb11: new
high efficiency thermoelectric material for power generation. Chem. Mater.
18, 1873–1877 (2006).
78. Cerretti, G., Villalpando, O., Fleurial, J. P. & Bux, S. K. Improving electronic
properties and mechanical stability of Yb14MnSb11 via W compositing. J.
Appl. Phys. 126, 175102 (2019).
79. Vasilyeva, I. G., Nikolaev, R. E., Abdusaljamova, M. N. & Kauzlarich, S. M.
Thermochemistry study and improved thermal stability of Yb14MnSb
alloyed by Ln3+ (La–Lu). J. Mater. Chem. C 4, 3342–3348 (2016).
80. Black, D. et al. Power generation from nanostructured half-Heusler
thermoelectrics for efficient and robust energy harvesting. ACS Appl. Energy
Mater. 1, 5986–5992 (2018).
81. Macdonald, R. A. & Macdonald, W. M. Thermodynamic properties of fcc
metals at high temperatures. Phys. Rev. B 24, 1715–1724 (1981).
82. Moruzzi, V. L., Janak, J. F. & Schwarz, K. Calculated thermal properties of
metals. Phys. Rev. B 37, 790–799 (1988).
83. Scudder, M. R. et al. Highly efficient transverse thermoelectric devices with
Re4Si7 crystals. Energy Environ. Sci. 14, 4009–4017 (2021).
84. Xie, K. & Gupta, M. C. High-temperature thermoelectric energy conversion
devices using Si–Ge thick films prepared by laser sintering of nano/micro
particles. IEEE Trans. Electron Devices 67, 2113–2119 (2020).
85. Liu, L. C., Cao, Z. P., Chen, M. & Jiang, J. Microstructure and
thermoelectric properties of (Bi0.48Sb1.52)Te3 thick films prepared with tape
casting method. Electronics 10, 140 (2021).
86. Dong, Z. Y. et al. Facile fabrication of paper-based flexible thermoelectric
generator. npj Flex. Electron. 5, 459 (2021).
87. Hikage, Y. et al. Thermal expansion properties of thermoelectric generating
device component. In 2007 26th International Conference on Thermoelectrics
331–335 (IEEE, 2007).
88. Ferreres, X. R., Aminorroaya Yamini, S., Nancarrow, M. & Zhang, C.
One-step bonding of Ni electrode to n-type PbTe—a step towards
fabrication of thermoelectric generators. Mater. Des. 107, 90–97
(2016).
89. Li, G. et al. Micro- and macromechanical properties of thermoelectric lead
chalcogenides. ACS Appl. Mater. Interfaces 9, 40488–40496 (2017).
512
Nature Materials
90. Tan, G. et al. All-scale hierarchically structured p-type PbSe alloys with
high thermoelectric performance enabled by improved band degeneracy.
J. Am. Chem. Soc. 141, 4480–4486 (2019).
91. Springholz, G. & Bauer, G. Substrate materials. In Growth and Structuring
437–438 (Springer, 2013).
92. Wu, C.-F., Wang, H., Yan, Q., Wei, T.-R. & Li, J.-F. Doping of thermoelectric
PbSe with chemically inert secondary phase nanoparticles. J. Mater. Chem.
C 5, 10881–10887 (2017).
93. Shi, X. et al. Multiple-filled skutterudites: high thermoelectric figure of
merit through separately optimizing electrical and thermal transports.
J. Am. Chem. Soc. 133, 7837–7846 (2011).
94. Rogl, G. et al. New bulk p-type skutterudites DD0.7Fe2.7Co1.3Sb12-xXx (X =
Ge, Sn) reaching ZT > 1.3. Acta Mater. 91, 227–238 (2015).
95. Ravi, V. et al. Thermal expansion studies of selected high-temperature
thermoelectric materials. J. Electron. Mater. 38, 1433–1442 (2009).
96. Guo, J. Q. et al. Development of skutterudite thermoelectric materials and
modules. J. Electron. Mater. 41, 1036–1042 (2012).
97. Rogl, G. et al. Thermal expansion of skutterudites. J. Appl. Phys. 107,
043507 (2010).
98. Dahal, T. et al. Thermoelectric and mechanical properties on misch
metal filled p-type skutterudites Mm0.9Fe4-xCoxSb12. J. Appl. Phys. 117,
055101 (2015).
99. Liu, Z. et al. Mechanical properties of nanostructured thermoelectric
materials α-MgAgSb. Scr. Mater. 127, 72–75 (2017).
100. Hanninger, G., Ipser, H., Terzieff, P. L. & Komarek, K. The Co–Sb phase
diagram and some properties of NiAs-type Co1 ± xSb. J. Less-Common Met.
166, 103–114 (1990).
101. Fu, C. et al. Realizing high figure of merit in heavy-band p-type
half-Heusler thermoelectric materials. Nat. Commun. 6, 8144 (2015).
102. Rogl, G. et al. Mechanical properties of half-Heusler alloys. Acta Mater.
107, 178–195 (2016).
103. Mao, J. et al. Manipulation of ionized impurity scattering for achieving high
thermoelectric performance in n-type Mg3Sb2-based materials. Proc. Natl
Acad. Sci. USA 114, 10548 (2017).
104. Liu, Z. et al. Understanding and manipulating the intrinsic point defect in
α-MgAgSb for higher thermoelectric performance. J. Mater. Chem. A 4,
16834–16840 (2016).
105. Agne, M. T. et al. Heat capacity of Mg3Sb2, Mg3Bi2, and their alloys at high
temperature. Mater. Today Phys. 6, 83–88 (2018).
106. Li, J. et al. Point defect engineering and machinability in n-type
Mg3Sb2-based materials. Mater. Today Phys. 15, 100269 (2020).
107. Martinez-Ripoll, M., Haase, A. & Brauer, G. The crystal structure of
α-Mg3Sb2. Acta Crystallogr. B 30, 2006–2009 (1974).
108. Wiedemeier, H. & Csillag, F. J. The thermal expansion and high
temperature transformation of SnS and SnSe. Z. Kristallogr. Cryst. Mater.
149, 17 (1979).
109. Liu, G., Zhou, J. & Wang, H. Anisotropic thermal expansion of SnSe from
first-principles calculations based on Grüneisen’s theory. Phys. Chem. Chem.
Phys. 19, 15187–15193 (2017).
110. Tyagi, K. et al. Crystal structure and mechanical properties of spark plasma
sintered Cu2Se: an efficient photovoltaic and thermoelectric material. Solid
State Commun. 207, 21–25 (2015).
111. Ding, Y. F. et al. High performance n-type Ag2Se film on nylon membrane
for flexible thermoelectric power generator. Nat. Commun. 10, 841 (2019).
112. Rauscher, J. F. et al. Synthesis, structure, magnetism, and high temperature
thermoelectric properties of Ge doped Yb14MnSb11. Dalton Trans. 39,
1055–1062 (2010).
113. Zhao, L.-D. et al. Thermoelectric and mechanical properties of
nano-SiC-dispersed Bi2Te3 fabricated by mechanical alloying and spark
plasma sintering. J. Alloys Compd. 455, 259–264 (2008).
114. Zheng, Y. et al. Mechanically robust BiSbTe alloys with superior
thermoelectric performance: a case study of stable hierarchical
nanostructured thermoelectric materials. Adv. Energy Mater. 5, 1401391
(2015).
115. Kim, S. I. et al. Dense dislocation arrays embedded in grain boundaries
for high-performance bulk thermoelectrics. Science 348, 109–114
(2015).
116. Zhu, B. et al. Realizing record high performance in n-type Bi2Te3-based
thermoelectric materials. Energy Environ. Sci. 13, 2106–2114 (2020).
117. Fu, L. et al. Large enhancement of thermoelectric properties in n-type PbTe
via dual-site point defects. Energy Environ. Sci. 10, 2030–2040 (2017).
118. Tan, G. et al. Non-equilibrium processing leads to record high
thermoelectric figure of merit in PbTe–SrTe. Nat. Commun. 7, 12167
(2016).
119. Zhao, H. et al. High thermoelectric performance of MgAgSb-based
materials. Nano Energy 7, 97–103 (2014).
120. Liu, Y. et al. Demonstration of a phonon-glass electron-crystal strategy in
(Hf,Zr)NiSn half-Heusler thermoelectric materials by alloying. J. Mater.
Chem. A 3, 22716–22722 (2015).
Nature Materials | VOL 21 | May 2022 | 503–513 | www.nature.com/naturematerials
Nature Materials
121. Wang, B. L., Guo, Y. B. & Zhang, C. W. Cracking and thermal shock
resistance of a Bi2Te3 based thermoelectric material. Eng. Fract. Mech. 152,
1–9 (2016).
122. Pavlova, L. M., Shtern, Y. I. & Mironov, R. E. Thermal expansion of
bismuth telluride. High Temp. 49, 369–379 (2011).
123. Kirkham, M. J. et al. Ab initio determination of crystal structures of the
thermoelectric material MgAgSb. Phys. Rev. B 85, 144120 (2012).
124. Wang, J.-F. et al. Structural, elastic, electronic, and thermodynamic
properties of MgAgSb investigated by density functional theory. Chin. Phys.
B 25, 086302 (2016).
Acknowledgements
TE materials research at NTU is supported by Singapore MOE AcRF Tier 2 under
grant nos. 2018-T2-1-010, Singapore A*STAR Pharos Program SERC 1527200022 and
Singapore A*STAR project A19D9a0096. Basic TE materials research at Northwestern
University is supported by the US Department of Energy, Office of Science and Office of
Basic Energy Sciences, under award no. DE-SC0014520.
Nature Materials | VOL 21 | May 2022 | 503–513 | www.nature.com/naturematerials
Review Article
Author contributions
The manuscript was written with contributions from both authors. Both authors have
approved the final version of the manuscript.
Competing interests
The authors declare no competing interests.
Additional information
Correspondence should be addressed to Mercouri G. Kanatzidis.
Peer review information Nature Materials thanks Joseph P. Heremans, Takao Mori and
the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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