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Charge and phonon transport in PbTe-based thermoelectric

materials
Yu Xiao1 and Li-Dong Zhao1

PbTe is a typical intermediate-temperature thermoelectric material, which has undergone extensive developments and achieved
excellent high thermoelectric performance. In this perspective we summarized several strategies that were successfully applied in
PbTe-based thermoelectric materials through manipulating charge and phonon transports, such as optimizing carrier density to
tune Fermi level, tailoring band structure to enhance effective mass, and designing all-scale hierarchical architectures to suppress
phonon propagation. Meanwhile, due to the different features of conduction and valence bands, we separately introduced the
approaches to enhance performance of p-type and n-type PbTe. In p-type PbTe, the strategies of band convergence, band
alignment and density of state (DOS) distortion are more effective to achieve high electrical transport properties. By contrast,
flattening conduction bands and introducing deep impurity level are more suitable for n-type PbTe. Lastly, several potential
strategies were proposed to further improve the thermoelectric performance of PbTe-based materials, which might be extended to
other thermoelectric systems.
npj Quantum Materials (2018)3:55 ; doi:10.1038/s41535-018-0127-y

INTRODUCTION hierarchical architecturing and band structure engineering. Based

With more than 60% of input energy being lost, most of which as on above strategies, many promising thermoelectric materials
waste heat, there is a compelling need for high performance emerged in an endless stream nowadays. Specifically, near room
thermoelectric materials that can directly and reversibly convert temperature (300–500 K) thermoelectrics include (Bi, Sb)2(Se,Te)3-
heat to electric energy. With continuing vigorous developments based alloys and MgAgSb alloys.12–15 Intermediate-temperature
over the past decade, encompassing diverse strategies to enhance (500–900 K) thermoelectrics include Pb(Te, Se, S),16–20 Sn(Se, S),21–
27
the power factor and reduce the thermal conductivity, the field of SnTe,28,29 GeTe,30 Cu2(Te, Se, S),31,32 Mg2(Si, Sn, Ge),33,34
thermoelectrics has truly reached its Renaissance era. However, BiCuSeO,35,36 Zn4Sb3,37 In4Se3,38 Ba8Ga16Ge30,39 skutterudites,40–
42
practical realization of thermoelectric materials is limited by and tetrahedrites.43 At high temperature (>900 K), SiGe,44 (Pr,
hitherto low dimensionless figure of merit, ZT, which is governed La)3Te4,45,46 Yb14MnSb11,47 and half-Heusler (HH) alloys48–50 are
by Carnot efficiency of waste heat conversion.1 Namely, ZT = S2σT/ very promising thermoelectric candidates.
κ, where S, σ, T, and κ denote the Seebeck coefficient, electrical Among well-known thermoelectric materials, PbTe is recog-
conductivity, working temperature in Kelvin, and thermal con- nized as a very promising compound for power generation in
ductivity, respectively.2 Apparently, a good thermoelectric mate- intermediate-temperature range. PbTe-based thermoelectric
rial simultaneously demands large Seebeck coefficient, high materials have successfully served in several NASA space
electrical conductivity and low thermal conductivity. However, missions.17 In 1960s, due to the technological limits, the thermal
the complex relationship among these thermoelectric parameters conductivity was overestimated, thus the maximum ZT (ZTmax)
makes it difficult to enhance the final ZT value. Therefore, values ~ 0.7–0.8 in PbTe were underestimated. After laser flash
countless efforts are aimed to improve the ZT value through method was provided to determine thermal diffusivity,51 the
balancing these interdependent thermoelectric parameters. ZTmax values in both n- and p-type PbTe were recognized to be as
After predicating and witnessing that narrow-gap semiconduc- high as ~1.4.52 Generally, the thermoelectric performance in PbTe-
tors were excellent thermoelectric materials, the development of based materials experienced a large progress especially in recent
thermoelectric materials experienced a slow progress.3,4 The idea decades, as shown in Fig. 1. The ZTmax values of p-type PbTe are
of “size effect” promotes a rapid progress due to dramatically boosted from ∼1.0 to ∼2.5,53 and the ZTmax values in n-type PbTe
enhanced thermoelectric performance through reducing lattice reach ~1.8–2.2.16,54,55 Notably, it is necessary to maximize the
thermal conductivity via nanostructuring.5,6 Before the “size effect” efficiency for a thermoelectric device through developing the
was employed in bulk materials, most reports focused on its well-matched performance for both p- and n-type PbTe.
quantum effects in low-dimensional materials such as superlattice Although PbTe is a simple binary compound, its performance
thin films and nanowires.7–9 When the “size effect” approaches stands out among intermediate-temperature thermoelectrics.
atomic-scale, quantum confinements will produce remarkable PbTe possesses several outstanding features that are typical
effects on charge and phonon transports in thermoelectric requirements for thermoelectrics, such as high Seebeck coefficient
materials.10,11 The idea of “size effect” substantially motivated due to its complicated electronic band structures, superior
researchers to optimize thermoelectric performance, such as electrical conductivity from high-symmetry cubic crystal structure,

1
School of Materials Science and Engineering, Beihang University, Beijing 100191, China
Correspondence: L-D. Zhao ([email protected])

Received: 29 May 2018 Revised: 19 September 2018 Accepted: 11 October 2018

Published in partnership with Nanjing University

 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
2
and low thermal conductivity caused by strong anharmonicity due In this perspective, we summarized the effective strategies to
to the Pb local off-center.56–58 To date, PbTe is still a research hot improve thermoelectric performance of PbTe-based systems,
spot in thermoelectric community. After a good perspective including optimizing carrier density to tune Fermi level, tailoring
summary in 2011,17 a large amount of achievements have been band structures to enhance effective mass, and designing all-scale
reported in PbTe-based thermoelectrics, which are evidenced by hierarchical architectures to suppress phonon propagation.
ZTmax ~ 2.2 in p-type PbTe-SrTe in 2012,59 ZTmax ~ 2.0 in p-type Considering the difference between valence and conduction
PbTe-MgTe in 2013,60 ZTmax > 2.0 in p-type PbTe-PbS in 2014,61 bands in PbTe, the special emphasis is given on the different
ZTmax ~ 2.5 in p-type PbTe-SrTe in 2016,53 ZTmax ~1.8 in n-type strategies to enhance effective mass and Seebeck coefficients by
PbTe-InSb,54 and ZTmax ~1.8 in n-type PbTe-Sb-I in 2017,55 et al. manipulating the band structures in p-type and n-type PbTe,
Therefore, it is essential to update these research progresses in respectively. In p-type PbTe, the convergence in light (L) and
PbTe-based thermoelectrics. heavy (Σ) valence bands and DOS distortion in valence band are
extensively utilized.61–64 Additionally, band alignment also plays a
positive role in maintaining carrier mobility when one second
phase is embedded in p-type PbTe.53,65 On the contrary, because
of the large offset between light (L) and heavy (Σ) conduction
bands, it is challenging to achieve conduction bands convergence
in n-type PbTe. However, the approaches of conduction band
flattening66 and introducing deep impurity level67,68 could boost
power factor in n-type PbTe. Apart from the discussions about
electrical transport properties, we also put emphasis on suppres-
sing phonon propagation through designing hierarchical archi-
tectures ranging from atomic-scale, nanoscale to mesoscale. We
believe that this perspective could provide useful insights into
PbTe-based systems, which can be extended to other thermo-
Fig. 1 Timeline of ZT values achieved in representative PbTe-based electric systems. At last, a discussion of future possible strategies is
1234567890():,;

thermoelectrics, including both p-type (orange ball) and n-type PbTe proposed to aim at further enhancing the thermoelectric
(green ball) performance in PbTe-based materials.

Fig. 2 a Crystal structure; b electronic band structure; c peak ZT values as a function of optimized carrier density in p-type PbTe systems: (1)
PbTe-Ge:Na,101 (2) PbTe:(Na, Bi),102 (3) PbTe-Sn:(Ag, Sb),103 (4) PbTe-Mn:Na,104 (5) PbTe-Se:K,105 (6) PbTe-Ca:Na,91 (7) PbTe-Cd:Na,92 (8) PbTe-S:K,61
(9) PbTe:Na,106 (10) PbTe:Na (Nano-precipitates),107 (11) PbTe-Ge,108 (12) PbTe-Se-S:Na,109 (13) PbTe-Hg: Na,110 (14) PbTe:Tl,64 (15) PbTe-Sn-Se-S:
Na,95 (16) PbTe-Yb:Na,111 (17) PbTe-Se:Na,62 (18) PbTe-Mn-Sr:Na,112 (19) PbTe-Mg:Na,60 (20) PbTe-Eu:Na,113 (21) PbTe-Sr:Na,59 (22) PbTe-S:Na,63
(23) PbTe-Sr:Na (Non-equilibrium);53 d peak ZT values as a function of optimized carrier density in n-type PbTe systems: (1) PbTe-Se:Cr,114 (2)
PbTe-Se-S:I,115 (3) PbTe-NaCl,116 (4) PbTe-Zn:I,117 (5) PbTe-Cd:I,118 (6) PbTe-Sn-Se:I,119 (7) PbTe-Mg:I,120 (8) PbTe-Se-S:Cl,121 (9) PbTe:Cd,122 (10)
PbTe:La,123 (11) PbTe:(I, In),67 (12) PbTe-S:Sb,66 (13) PbTe-Cu:I,98 (14) PbTe:(Sb, I),55 (15) PbTe:(Sb, In).54 That shows the large difference of
optimized carrier density between p-type (3 ~ 40 × 1019 cm−3) and n-type (0.4 ~ 4 × 1019 cm−3)

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 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
3

Fig. 3 a Schematic image of band convergence; b Schematic image of DOS distortion in PbTe; c theoretical Pisarenko line shows single
parabolic band with effective mass m* = 0.3me at 300 K, and the point data include PbTe-Se:Na (band convergence),62 PbTe-Mg:Na (band
convergence),60 and PbTe:Tl (resonant level);64 d graphic presentation of band alignment; e the ratio of carrier mobility to lattice thermal
conductivity as a function of SrTe content in PbTe-Sr:Na;59 f temperature-dependent ZT values of PbTe-Se:Na, PbTe-Mg:Na, PbTe:Tl, and PbTe-
Sr:Na

OPTIMIZATIONS OF CARRIER DENSITY PbTe, elements of I and Br (doping on Te site), Sb, Bi, Al, Ga, and In
PbTe possesses the NaCl-type crystal structure with space group (doping on Pb sites) are usually chosen as donor dopants, and the
of Fm-3m, which exhibits high symmetry. The unit cell is face- electron carrier density in superior n-type PbTe is in the range of
centered cube and all sites in the lattice have six coordinated 4–40 × 1018 cm−3, shown in Fig. 2d. Notably, the optimal carrier
atoms, as shown in Fig. 2a. The chemical bonds in PbTe are mixed density in p-type PbTe is an order of magnitude higher than that
ionic-covalent bonds, thus it is usually classified as polar in n-type PbTe.
semiconductor. The electronic band structure of PbTe in Fig. 2b
shows a typical semiconductor with a direct bandgap ~ 0.3 eV.65 MANIPULATIONS ON VALENCE BAND STRUCTURE IN P-TYPE
Distinct differences between valence band and conduction band PBTE
can be easily observed, and the offset of light valence band (L) In physics, quantum is the minimum unit to characterize physical
and heavy valence band (Σ) is ~ 0.15–0.20 eV,69 while a larger properties that involve interaction. In thermoelectric materials,
band offset ~ 0.45 eV exists in conduction band.70 charge is a quantum unit of carriers that is used to estimate the
To obtain p-type PbTe, theoretically, alkali metal in group-IA (Li, electrical transport properties. Since the quantum charge trans-
Na, K) can work as an acceptor dopant in Pb site and produce hole ports in crystalline materials are closely relevant to electronic band
carrier. Experimentally, most of the advanced p-type PbTe structure, manipulation on electronic band structure is an effective
materials in Fig. 2c are doped with Na and K, and the optimal strategy to optimize electrical transport properties. Manipulating
hole carrier density is in the range of 3–40 × 1019 cm−3. In n-type approaches on electronic band structure include band

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 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
4
convergence, DOS distortion and resonant state, band alignment PbTe-SrTe53,59 etc. In the valence bands of PbTe, valley
between matrix and second phase, band flattening, and introdu- degeneracy at L point is 4, while the valley degeneracy at Σ point
cing impurity level, etc. is 12.62 Therefore, when two valence bands jointly carry carriers at
a close energy range, the effective mass m* can get a dramatic
Band convergence enhancement, as shown in Fig. 3c. It is readily seen that the
effective masses in PbTe-PbSe and PbTe-MgTe systems are larger
In p-type PbTe, the small offset between light valence band (L)
than the Pisarenko line that is derived from the single parabolic
and heavy valence band (Σ) facilitates charge redistribution from
band (SPB) model with an effective mass m* = 0.3me, evidencing a
single band to multiple bands. Elements alloying could enclose
larger effective mass contributed by multiple valence bands.
the light and heavy valence bands, called band convergence.
Converging valence bands could enhance effective mass through
increasing valley degeneracy numbers.3,71 Recently, the approach DOS distortion and resonant state
of band convergence was revisited along with nanostructuring Another alternative mechanism to increase effective mass and
technology, which is one powerful synergistic strategy to enhance Seebeck coefficient is to produce distortion energy level into the
thermoelectric performance in p-type PbTe.62,72 Band conver- conduction or valence bands. The effect of locally increased DOS
gence can achieve a high valley degeneracy number (Nv) to to improve Seebeck coefficient can be explained by the Mott
enlarge the effective mass (m*), defined as m
¼ Nv m
b , where
2=3
expression as follows:64
m
b denotes the local band effective mass. Because the carrier n o
π2 k 2 T
mobility μ is proportional to 1=m
b , the mobility is nominally S ¼ 3qB d½lnðdE σ ðE ÞÞ
E¼Ef
unaffected by Nv. Even though the carrier mobility may be n o (1)
π 2 kB2 T 1 dnðE Þ 1 dμðEÞ
deteriorated by the inter-valley scattering, the enhancement in ¼ 3q n dE þ μ dE
E¼Ef
effective mass overcomes the loss in carrier mobility, resulting in
an enhanced net ZT. where q is unit charge, kB is Boltzmann constant, σ(E) denotes
It should be noted that the multiple electronic bands can be energy-dependent electrical conductivity, n denotes carrier
activated only when the band energy offsets are small enough density, μ is carrier mobility and T is working temperature. From
and comparable to several kBT, where kB is the Boltzmann Eq. (1), we can understand that the enhancement in Seebeck
constant. In p-type PbTe, the light (L) and heavy (Σ) bands in coefficient induced by resonant level arises from two mechanisms:
valence band are ~0.15–0.20 eV, as shown in Fig. 3a, and the small (1) an excess density of states n(E) near Fermi level, and (2)
energy offset makes the multiple valence bands easily converge. increased energy-dependent μ(E), known as “resonant scatter-
Typically, several superior p-type PbTe-based systems are ing”.73 The first mechanism is an intrinsic feature that is slightly
achieved through manipulating electronic band structures, and temperature-dependent, and it will predominate with rising
typical examples are PbTe-PbSe,62 PbTe-PbS,61,63 PbTe-MgTe,60 temperature. The second mechanism only works well at cryogenic

Fig. 4 a Schematic band flattening after S or Mn alloying in n-type PbTe; b Pisarenko line shows the different effective masses with doping
and alloying; c comparisons of effective mass and carrier mobility for the I- and La-doped n-type PbTe; d temperature-dependent of ZT values
for I- and La-doped PbTe, n-type PbTe1−xSx and Pb1−xMnxTe66,77,79

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 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
5
temperature when the phonon–electron scattering is weak. When alignment in p-type PbTe-SrTe.65 Because the energy of valence
phonon–electron scattering dominates in elevated temperature band in SrTe is comparable to that of p-type PbTe, when second
range, “resonant scattering” plays an ignorable role in enhancing phase SrTe precipitates out in p-type PbTe matrix, the carrier
Seebeck coefficient. Therefore, resonant state is very sensitive to mobility will be slightly deteriorated but phonon scattering is
temperature and it can only play a significant role in enhancing intensified by precipitates, which is considered as a typical
Seebeck coefficient near and below room temperature range.73 example of well-known “phonon glass-electron crystal” proposed
Fig. 3b schematically presents the effects of resonant level on the by Slack.76 To quantitatively evaluate the contribution of band
electronic energy distribution in PbTe matrix, which could cause a alignment to thermoelectric performance, one can calculate the
sharp increase of DOS near Fermi level. This phenomenon has
ratio of carrier mobility to lattice thermal conductivity (μ/κlat), as
been observed in p-type Tl-doped PbTe system,51 and the Tl
shown in Fig. 3e. The large increase in μ/κlat indicates that SrTe
resonant level in valence band of PbTe indeed contributes to a
distinct increase of Seebeck coefficient shown in Fig. 3c. When phases in p-type PbTe matrix scatter phonon stronger than carrier.
coming to carrier mobility issue, it should be noted that DOS The final enhancements in ZT values for p-type PbTe by
distortion will cause a larger carrier mobility deterioration than synergistic approaches are well elucidated in Fig. 3f, which reveals
that caused by band convergence. The DOS distortion enhances that the methods of band convergence, resonant level and band
the total effective mass through producing larger local band alignment are pretty effective to enhance the electrical transport
effective mass, however, the band convergence enhances the properties in p-type PbTe. More importantly, these approaches are
total effective mass through increasing valley degeneracy number. also promising to be extensively applied in thermoelectric
community as a general route.
Band alignment between PbTe matrix and nanostructured second
phases
It is well-known that introducing defects in a host material not
only intensifies phonon scattering, but also deteriorates carrier MANIPULATIONS ON CONDUCTION BAND STRUCTURE IN N-
mobility. When nanostructured second phase exists in matrix, it is TYPE PBTE
crucial to maintain high carrier mobility. One of the most effective
approaches is to introduce the exotic phase with small band offset Flattening band structure
compared with matrix, namely band alignment. Actually, band In n-type PbTe, conduction band flattening can distinctly enlarge
alignment works very well in solar cell community to maintain the effective mass, thereby optimizing Seebeck coefficient.77 For
carrier mobility,74,75 which was firstly well elucidated in PbTe an SPB, the local band effective mass m
b near the band edge is
system.65 Fig. 3d schematically presents the function of band sensitive to the band shape. From the energy dispersion

Fig. 5 Diagram schematically describes the deep impurity level in n-type PbTe: a deep impurity level localizes in bandgap and traps electrons
at 300 K; b deep impurity level releases electrons into conduction band at elevated temperature; c carrier density in both In- and Ga-doped n-
type PbTe increases with increasing temperature; d temperature-dependent ZT values in In- and Ga-doped n-type PbTe67,82

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 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
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relationship, the m
b is defined by following equation: valence band to form a resonant level in p-type PbTe, as we
 2 1 discussed above.64 Fig. 5a schematically describes the deep

2 ∂ E ðk Þ impurity level in n-type PbTe produced by introducing Ga and In.
mb ¼ h (2)
∂k 2 Interestingly, Ga and In (+3) substitutions on Pb (+2) sites do not
where ћ is reduced Planck constant, E(k) and k denotes energy boost the carrier density of PbTe. At low temperature, the impurity
dispersion function and wave vector, respectively, in the reciprocal levels produced by Ga and In could trap free electrons and work
space. The Eq. (2) demonstrates flat band shape will lead to high as a charge reservoir.67,82 With rising temperature, the trapped
effective mass, as shown in Fig. 4a. Experimentally, elements S or electrons will be released from the deep impurity levels into
Mn alloying in n-type PbTe could produce an obvious band conduction band, finally increasing the carrier density as shown in
flattening and thereby an enhancement in carrier effective mass in Fig. 5b. In the n-type PbTe with In doping, the carrier density
Fig. 4b. Typically, the ZTmax values of n-type PbTe are largely undergoes an order of magnitude enhancement from ~5 × 1018
boosted from ~1.1 to ~1.4 at 923 K and ~1.6 at 723 K through cm−3 at 300 K to ~2.8 × 1019 cm−3 at 773 K in Fig. 5c, exhibiting a
flattening conduction bands.66,77 In fact, as suggested by Kane kind of dynamic doping behavior. As for the PbTe with a single
band model, the energy dispersion is closely related to the conduction band, this anomalous variation in carrier density is
bandgap Eg, and broadening bandgap will flatten conduction related to the changing charge states of Ga and In. With increasing
band in PbTe following the relationship below:69,78 temperature, the mixed charge states (+1 and +3) of Ga and In
  will change to fully +3 states.80 Consequently, the dynamic
h2 k 2 E doping extends ZTmax in a larger temperature range, resulting in a
¼E 1þ (3)
2m
b Eg large average ZT (ZTave).67,82 The ZTave over the entire working
temperature range is important as it determines the thermo-
It is noteworthy to point out that carrier mobility μ will also be electric conversion efficiency.22 Similarly, Cr,83 Fe,84 Ti,85 Sc86 etc.
inevitably deteriorated due to the relationship of μ ∝ 1/mb* after can introduce impurity states in PbTe, however, these resonant
conduction band flattening. Therefore, it should be careful to
impurity levels in conduction band are localized and contribute
balance carrier effective mass and carrier mobility. Typically,
less to the carrier transports.85
combination of lower effective mass and higher carrier mobility in
Fig. 4c leads to a high ZTmax value in I-doped PbTe (~1.4 at 723 K),
which is 40% higher than that in La-doped PbTe (~1.0 at 723 K),79 CHARGE TRANSPORTS IN PBTE-BASED SUPERLATTICE
as shown in Fig. 4d.
Theoretical prediction shows that low-dimensional materials such
as superlattice thin films and nanowires can significantly enhance
Deep impurity level thermoelectric performance.7,9 Quantum confinement offers one
Impurity levels caused by adding group-IIIA elements (Ga, In, Tl) in special way to manipulate carrier transports because of the close
PbTe are systematically investigated.80,81 At room temperature, Ga relationship between electronic band structure and dimension-
and In elements can from a deep impurity level in the forbidden ality. For the thermoelectric materials with quantum dots, the
bandgap. On the contrary, Tl impurity level will enter into the band offset and/or strain field between quantum dots and matrix

Fig. 6 a Schematic cross section of quantum-dot superlattice structure; b field-emission scanning electron microscope (FE-SEM) image of
quantum-dot superlattice structure;87 c relationship between Seebeck coefficient and carrier density for bulk PbTe and the new PbTe-based
quantum-dot superlattice structures; d comparison of ZT as a function of carrier density between bulk PbTe and PbSeTe/PbTe quantum-dot
superlattice structures (data taken from ref. 87) (b adapted from ref. 87 with permission, copyright Springer Nature 2000)

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 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
7

Fig. 7 a Diagram schematically describes all-scale hierarchical architecture to scatter phonon; b accumulated contributions to reduce lattice
thermal conductivity with respect of phonon mean free path in PbTe

modification due to quantum confinement. Figure 6d elucidates

that the ZTmax value can be enhanced through designing PbSeTe/
PbTe superlattice, indicating that reducing dimensionality of a
given material is a potential possibility to enhance thermoelectric
performance.

MANIPULATIONS ON PHONON TO REDUCE LATTICE THERMAL

CONDUCTIVITY
Apart from electrical transport properties, low thermal conductiv-
ity is required to preserve large temperature gradient, which is a
vital factor to realize high thermoelectric conversion efficiency.
Heat transport is regarded as elementary vibrational motion, and
the atom oscillation can be quantitatively evaluated using a
quantum description “phonon”. Phonon propagation and disper-
sion in crystalline materials are closely related to the mean free
path (MFP), which ranges from atomic-scale, nano-scale to
mesoscale. Since the MFP of PbTe is predominated in nano-scale,
therefore, nanostructuring is widely applied to reduce lattice
thermal conductivity in PbTe.16,59 When the defect sizes are
comparable to the MFP range, the phonon scattering can be
dramatically intensified and therefore lead to a very low lattice
thermal conductivity.54,55 Based on this idea, artificially designing
defects with all-scale hierarchical architectures are put forward to
considerably reduce lattice thermal conductivity.
Figure 7a is a schematic description of all-scale hierarchical
structures including atomic-scale point defects, nanoscale pre-
cipitates and mesoscale grain boundaries. The contributions of
reduced lattice thermal conductivity from these all-scale defects
can be quantitatively estimated by:88,89
Fig. 8 Phase diagram to guide all-scale hierarchical architecture: a  3 Z θD =T
eutectic phase diagram; b spinodal decomposition diagram. The kB kB T x 4 ex
κl ¼ 2 τ c ðxÞ dx (5)
targeted microstructures (right inserts) can be obtained if the 2π ν  h 0 ðe  1Þ2
x
synthesis process in given composition can be well controlled
where v is average phonon-group velocity, T is working
could act as a confining potential. Therefore, the electronic density temperature, θD is Debye temperature, x = hω/κBT, and τ is
of states (dN/dE) has the shape of a Dirac delta function87 relaxation time. Here, the relaxation time is treated as an
X integration of various process including Umklapp process (τU),
dN=dE / δðE  εi Þ (4) normal process (τN), grain boundary process (τG), nano-precipitate
εi process (τNP) and point defect process (τPD):89,90
where εi is discrete energy levels and δ is the Dirac function. Figure 1 1 1 1 1 1
¼ þ þ þ þ (6)
6a schematically shows the PbSeTe/PbTe superlattice structures τ c τ U τ N τ G τ NP τ PD
prepared by molecular beam epitaxy (MBE). The field emission When all above mechanisms contribute to the scattering of
scanning electron microscope (FE-SEM) in Fig. 6b shows individual phonon propagation, the lattice thermal conductivity is accumu-
quantum dots in white massively distribute in planar arrays. latively suppressed as shown in Fig. 7b. The lattice thermal
Compared with the state-of-the-art PbTe bulks, the artificial conductivity can be described as κl = 1/3Cvl, where C denotes
superlattice structures could produce much larger Seebeck heat capacity per unit volume, v is average speed of lattice
coefficient in Fig. 6c. The increased Seebeck coefficient arises vibration, l is mean free path. When l reaches interatomic distance,
from larger effective mass caused by the band structure the lattice thermal conductivity can approach the theoretical

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 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
8

Fig. 9 a TEM image of nano-precipitates with size distribution histogram as the inset in PbTe-4%InSb;54 b the HADDF image of Sb precipitates
in the PbTe0.998I0.002-3%Sb, the insets are the EDS elemental maps of one selected precipitates; c the in suit HADDF images of Sb precipitates
in the PbTe0.998I0.002-3%Sb with temperature rising from 373 K to 663 K;55 microstructure observation in n-type PbTe-Cu2Te sample: d grain
boundary in mesoscale; e precipitates in nanoscale; f point defects of Cu interstitial.98 (a adapted from ref. 54 with permission, copyright John
Wiley and Sons 2017) (b and c adapted from ref. 55 with permission, copyright Royal Society of Chemistry 2017) (d, e, and f adapted from ref. 98
with permission, copyright American Chemical Society 2017)

minimum κmin. It should be pointed out that the MFP range is Regardless eutectic phase diagram and spinodal decomposition,
related to the lattice-vibration frequency, which is temperature- when A and B possess similar crystal structure and comparable
dependent, implying that more scattering mechanisms may be lattice parameter, a coherent or semi-coherent interface between
involved in a given temperature. matrix and nano-precipitates will be formed, which will reduce the
Usually, nano-precipitates experience continuous steps of carrier scattering and facilitate carrier transport between phase
nucleation and growth, thus nano-precipitates range from several interfaces.94 The nano-precipitates with coherent or semi-
nanometers to hundreds of nanometers. Both eutectic phase coherent interfaces have been widely observed in PbTe-PbQ (Q
diagram and spinodal decomposition phase diagram in Fig. 8 = Se, S) solid solutions.61,63,95,96 Interestingly, the shapes and sizes
show two representative ways to obtain nanostructures B in A of nano-precipitates in a given thermoelectric system are also
matrix. In Fig. 8a, the A and B will be homogeneously melting at sensitive to the processing parameters during synthesizing, such
high temperature, when B exceeds its solubility limit in A, it will as cooling rate, annealing temperature and annealing time,
precipitate out as nanostructures, which are well elucidated in etc.53,97
PbTe-MTe (M = Mg, Ba, Sr, Ca and Cd) systems.59,60,91–93 Fig. 8b
exhibits a miscibility gap where thermodynamic phase separation Internal structure designs in PbTe-based thermoelectric materials
will occur through metastable nucleation and growth, which is Most of superior PbTe-based thermoelectric materials are
called spinodal decomposition process. Spinodal decomposition obtained by reducing lattice thermal conductivity through
can also produce different nano-precipitates, which is similar to scattering phonons via designing special microstructures. To
that of eutectic process, as shown in the right column of Fig. 8. match the high-performance p-type PbTe, the approach of

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 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
9

Fig. 10 a Temperature dependence of lattice thermal conductivity; b temperature dependence of ZT values in PbTe with the all-scale
hierarchical architecture

Fig. 11 Synergistic strategy to obtain high thermoelectric performance in PbTe-SrTe: a the band structure changing with varying SrTe fraction
in PbTe; b the relative band positions of valence band at L, Σ point, and the conduction band; c band alignment between SrTe second phase
and PbTe matrix to facilitate carrier transport; d SEM image showing micro-size grains; e low magnification TEM image showing ubiquitous
nano-precipitates in PbTe matrix; f the ZT values as a function of temperature in PbTe-SrTe.53 (a, b, c, d, e, and f adapted from ref. 53 with
permission, copyright Springer Nature 2016)

Published in partnership with Nanjing University npj Quantum Materials (2018) 55

 Charge and phonon transport in PbTe-based thermoelectric materials
Y Xiao and L-D Zhao
10
designing microstructures in n-type PbTe is highly sought since manipulating charge and phonon transports. One can see that
conduction bands are less complex than its valence bands. most reports focused on p-type PbTe, but few reports on n-type
Recently, a record high ZTmax ~ 1.8 at 773 K was obtained in n-type PbTe, which is urgent to be developed to match its high
PbTe-InSb with special nanostructures,54 as shown in Fig. 9a. Both performance p-type counterpart. The high performance n-type
electrical and thermal transport properties are improved in PbTe is expected to be realized through using following
nanostructured n-type PbTe. Seebeck coefficients are enhanced approaches: obtaining higher carrier mobility through reducing
due to carriers filtering by the energy barrier caused by intrinsic vacancies; scattering all-length phonons through design-
nanostructures, which also contribute to extremely low lattice ing all-scale hierarchical architectures; facilitating charge trans-
thermal conductivity due to strong phonon scattering.54 Sb ports through aligning conduction bands; suppressing the bipolar
doping in n-type PbTe (Fig. 9b) also exhibits very interesting diffusion through enlarging bandgap; enhancing effective mass
behaviors. Sb-contained endotaxial nano-precipitates can be through tailoring conduction band structures.
clearly observed at room temperature, but Sb will dissolve into
PbTe matrix with rising temperature as shown in Fig. 9c.55 The
solubility limit of Sb in PbTe is temperature-dependent, which ACKNOWLEDGEMENTS
could produce the dynamic doping and phonon scattering, thus This work was supported by National Key Research and Development Program of
both electrical and thermal transport properties are improved.55 China under Grant No. 2018YFB0703600, National Natural Science Foundation of
The idea of all-scale hierarchical architectures is confirmed as an China under Grant Nos. (51772012, 51571007 and 51632005), the Beijing Municipal
Science & Technology Commission under Grant No. Z171100002017002, 111 Project
effective approach to enhance thermoelectric performance in p-
(B17002) and the Academic Excellence Foundation of BUAA for PhD Students. The
type PbTe-SrTe through reducing lattice thermal conductivity.59 authors are grateful to Professors M.G. Kanatzidis, C. Wolverton, D.P. Vinayak, C. Uher,
The hierarchical architectures could also be realized in n-type J.-F. Li, J.Q. He, L. Huang, G.J. Tan, S.Q. Hao, H.J. Wu, S.J. Pennycook, Y.S. Zhang, S.H. Lo,
PbTe just through introducing Cu,98 as shown in Fig. 9d–f. The H. Sun, and H. Chi for their plentiful discussions and fruitful collaborations.
lattice thermal conductivity could be reduced as low as
~0.38 Wm−1 K−1 in PbTe-5.5% Cu2Te. Interestingly, as shown in
Fig. 9f, massive Cu interstitials would induce local lattice distortion. AUTHOR CONTRIBUTIONS
Moreover, apart from the hierarchical architecturing, these Cu Y.X. and L.-D.Z. drafted this perspective. L.-D.Z. offered important idea of the figures.
interstitials are inclined to vibrate in a large displacement, which Y.X. created the central idea of this review, constructed this framework. Both authors
could further suppress the lattice thermal conductivity. contributed to the writing of the manuscript.
Figure 10 shows the temperature-dependent lattice thermal
conductivity and ZT values in several typical PbTe systems. From
this comparison, it is obviously seen that the sample with all-scale ADDITIONAL INFORMATION
defects possesses the lowest lattice thermal conductivity, which is Competing interests: The authors declare no competing interests.
comparable to the theoretical minimum value (κmin ~
0.36 Wm−1 K−1) in Fig. 10a. The ZTmax value achieves ~2.2 at Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims
915 K in p-type PbTe-Na-4%SrTe and ~1.8 at 773 K in n-type in published maps and institutional affiliations.
PbTe0.998I0.002-3%Sb, as shown in Fig. 10b.55,59
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