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From Dislocation to Nano‐Precipitation: Evolution to Low Thermal

Conductivity and High Thermoelectric Performance in n‐Type PbTe

Article  in  Advanced Functional Materials · December 2020

DOI: 10.1002/adfm.202005479

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Full Paper
From Dislocation to Nano-Precipitation: Evolution to Low
Thermal Conductivity and High Thermoelectric
Performance in n-Type PbTe
Ping-Yuan Deng, Kuang-Kuo Wang, Jia-Yu Du, and Hsin-Jay Wu*
PbTe-based alloys have been widely used as mid-temperature thermoelectric
(TE) materials since the 1960s. Years of endeavor spurred the tremendous
advances in their TE performance. The breakthroughs for n-type PbTe have
been somewhat less impressive, which limits the overall conversion efficiency
of a PbTe-based TE device. In light of this obstacle, an n-type Ga-doped PbTe
via an alternative thermodynamic route that relies on the equilibrium phase
diagram and microstructural evolution is revisited. Herein, a plateau of zT = 1.2
is achieved in the best-performing Ga0.02Pb0.98Te in the temperature range of
550–673 K. Notably, an extremely high average zTave = 1.01 is obtained within
300 − 673 K. The addition of gallium optimizes the carrier concentration and
boosts the power factor PF  =  S2ρ−1. Meanwhile, the κL of Ga-PbTe reveals a
significantly decreasing tendency owing to the defect evolution that changes
from dislocation loop to nano-precipitation with increasing Ga content. The
pathway for both the κL reduction and defect evolution can be probed by an
equilibrium phase diagram, which opens up a new avenue for locating high zT
TE materials.
1. Introduction
To pursue environmental and economic sustainability, the
research trend seeks green and high-performance energy
resources, which aim to cut down the reliance on fossil fuel
while retaining technological development. To this end, ther-
moelectric (TE) materials and devices, which can convert
ejected heat into electricity via the Seebeck effect,[1–3] attract
research attention. Conventionally, the use of a figure-of-merit,
P.-Y. Deng, Prof. H.-J. Wu
Department of Materials Science and Engineering
National Chiao Tung University
Hsinchu 30010, Taiwan
E-mail: ssky0211@nctu.edu.tw
Dr. K.-K. Wang
Department of Materials and Optoelectronic science
National Sun Yat-sen University
Kaohsiung 80424, Taiwan
J.-Y. Du
Department of Chemical Engineering
National Tsing Hua University
Hsinchu 30010, Taiwan
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202005479.
DOI: 10.1002/adfm.202005479
Adv. Funct. Mater. 2020, 2005479 2005479  (1 of 11)
www.afm-journal.de
zT  = (S2σ/κ)T, gauges the thermal-to-
electricity conversion efficiency of a TE
alloy, in which S is the thermopower, σ the
electrical conductivity, κ the thermal con-
ductivity, and T the absolute temperature.
For decades, the conversion efficiency of
lead tellurides with dopants has steadily
improved alongside the development
of mid-temperature TE generators.[4–8]
Through the carrier optimization[9–12]
and the all-scale microstructure engi-
neering,[13–19] the zT values for both p-type
and n-type lead tellurides are enhanced.
Recently, the thermodynamic routes
emerged[20] as new paradigms to hunt
for the low-κ and high-zT TE alloys, in
which their TE performance is correlated
with the mutual solubilities of constituent
elements, the microstructure, and the
phase stability. The above thermodynamic
approach (or the so-called phase-boundary
mapping[21,22]) can be easily realized by an
equilibrium phase diagram, which might be overlooked by the
TE community for the past few years.
Compared with the extraordinary zT values in the p-type
lead tellurides, such as the PbTe-SrTe with a peak zT  ≈ 1.8
at 950 K,[23] the progress in zT enhancements of n-type lead
tellurides seems to be sluggish, with only a few studies on
the (Ag, La)-PbTe, Mn-PbTe, and (I, Sb)-PbTe that achieved
the zT  >  1.5 at T  >  773 K.[24–26] Herein, we aim to enhance
the TE performance of n-type PbTe through doping with gal-
lium that features with the electron donor nature.[27,28] Before
thermal/electronic transport property optimization, the solu-
bility limit of gallium in PbTe, as well as the neighboring
phase relations, shall be understood by using an equilibrium
phase diagram, in order to forecast the maximum dopant
concentration and the presence of secondary phases or even
the precipitates. The addition of Ga is expected to bring addi-
tional impurity energy levels falling way below the conduction
band maximum (CBM),[29] which act as electron reservoirs
that constrain the extra donor electrons inside deep energy
well.[30] Even under a thermal activation, the deep impu-
rity energy level helps to tune the electron carrier concentra-
tion and pins the Fermi level to an optimal position for n-type
conduction.[11,31]
In addition, defect engineering enables the reduction in
lattice thermal conductivity κL and raise the zT value pro-
foundly.[32–34] The presence of crystal defects, including the
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point defects, the dislocations, and the nano-precipitates, are
associated with the increased lattice strain fields, which could
either enhance the phonon scattering or cause the lattice sof-
tening.[35,36] For the phonon scattering, the phonon propagates
under a constant speed while the direction (vector) changes. In
comparison, the lattice softening is accompanied only with a
decrease in the phonon speed, which is even more critical for
the κL reduction in the anharmonic materials.[37–39] For most of
TE materials, the two mechanisms virtually co-exist, and both
account for the κL reduction.[40]
Most importantly, the present study provides the experi-
mental evidence for the defect evolution in the n-type Ga-PbTe
alloys, whose carrier concentrations are simultaneously opti-
mized. The formation of the dislocation loop and Ga-rich nano-
precipitate realize the significant reduction in κ. In particular,
an equilibrium Ga-Pb-Te phase diagram probes the narrow
compositional region where the defect evolution and κ reduc-
tion takes place. As a consequence, the n-type Ga-PbTe alloy
with a composition of Ga0.02Pb0.98Te achieves a peak zT ≈ 1.2 at
573 K, and yields a record-high zTave =  1.01 in the temperature
range of 300–673 K.
2. Results and Discussion
It is well known that the substitution of Pb by Ga in PbTe could
enhance the zT value.[31,41] The composition of Pb0.98Ga0.02Te
achieves a peak zT  = 1.34 at 766 K,[31] while a slightly Ga-
rich Pb0.97Ga0.03Te possess an zT  = 1.3 at 823 K.[41] To explore
the mechanism yielding the high zT values, we revisit the
GaxPb1−xTe alloys (x  = 0–0.06) using the Bridgman method.
The temperature-dependent zT curve (Figure 1a) of undoped
PbTe (x  = 0) declines with increasing temperature within
300–573 K. It then increases as the temperature is higher than
600 K. This dramatical change in temperature dependence is due
to the co-existence of electron and hole carriers in the undoped
PbTe that leads to the significant bipolar behavior at elevated tem-
perature. A similar behavior for the undoped PbTe is found in
Figure 1.  a) Temperature-dependent zT curves for the GaxPb1−xTe (x = 0–0.02), the Gay(PbTe)1−y (y = 0.004–0.012), and the GazPbTe1−z (z = 0.006, 0.01).
b) The averaged zT values calculated with 300–673 K, for various n-type PbTe with different dopants: the Sb-doped PbTe,[50] the Ag-doped PbTe,[44] the
Ga-doped PbTe,[31,41] the (I, Sb)-doped PbTe,[26] the Cu-doped PbTe,[6] and the (Ga, Ge)-doped PbTe.[55]
Adv. Funct. Mater. 2020, 2005479 2005479  (2 of 11)
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the previous study.[41] The lightly doped x = 0.004 also reveals a
similar temperature dependence trend of its zT curve.
As the Ga content (x) increases, the zT curves move upward
significantly. In the temperature range of 300–673 K, the
x  = 0.02 outperforms the rest of alloys, by not only yielding a
high peak zT  > 1.2 at 573 K but also showing an outstanding
average zT (zTave) ≈ 1.01. Compared with the previous Ga-
PbTe alloys,[31,41] our x  = 0.02 (Ga0.02Pb0.98Te) reveals a higher
zTave  = 1.01 within 300–673 K (Figure  1b). Further compared
with other n-type PbTe doped with Sb,[42] Ag,[24] Cu,[10] I/Sb,[26]
and Ga[31,41] (Figure  1b and Table S1, Supporting Information),
we found that our x  = 0.02 alloy possesses an extraordinary
zTave =  1.01,  which is by far one of the best-performing n-type
PbTe in the mid-temperature region (300–673 K). Even for the
less doped x = 0.01, the zTave is still as high as 0.84, suggesting
that Ga could be an ideal dopant for utilizing the high-perfor-
mance n-type PbTe materials. The reproducibility for the high
performance of x = 0.02 is verified by measuring three different
samples with an identical nominal composition (Figure S1,
Supporting Information). Additionally, thermal cycling between
300 and 673 K is conducted for one x = 0.02 sample (Figure S2,
Supporting Information) to confirm the thermal stability.
For comparison purposes, we prepared the other two
series of Ga-PbTe alloys, the Gay(PbTe)1−y (y  = 0.004–0.012),
and the GazPbTe1−z (z  = 0.006–0.01), respectively. As shown
in Figure  1a, the zT curves of Gay(PbTe)1−y move upward with
the increasing y, and a moderate peak zT ≈ 0.68 is reached in
y  = 0.012 at 650 K. However, a different tendency is revealed
for the GazPbTe1−z alloys whose zT curves go downwardly with
increasing z. The lightly doped z  = 0.006 achieves the highest
peak zT ≈ 0.72 at 625 K. In a previous case of I-PbTe,[43] the defi-
ciency of Te in a PbTe generally brings down the zT values as a
result of an increase in κ. That explains the declining zT values
in our GazPbTe1−z alloys.
The success in boosting the zTave from 0.84 (x  = 0.01) to
1.01 (x  = 0.02) within the mid-temperature region reveals that
the n-type lead tellurides could have a better TE performance
than what had been previously reported (Table S1, Supporting
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Figure 2.  a) The isothermal section of the ternary Pb-Te-Ga system at 673 K. b) The enlarged isothermal section superimposed with the color
contour of peak zT values at 673 K. The wavelength dispersive spectrum (WDS) maps for individual elements of Pb, Ga, and Te for c) alloy#33
(Ga-25.0at%Pb-55.0at%Te), and d) alloy#28 (Ga-10.0at%Pb-55.0at%Te) underwent a 30-day post-annealing at 673 K.

Information).[6,8,10,11,24–26,31,41–56] The breakthrough shall be
attributed to their microstructures and phases, in which a phase
diagram could interpret the relationship. Figure 2a shows
the isothermal section of ternary Pb-Te-Ga at 673 K, which is
constructed by an experimental approach. The phase bounda-
ries on three edges of Figure  2a are extracted from the binary
phase diagrams.[57–60] In order to determine the phase relation-
ships inside the ternary space, various Pb-Te-Ga ternary alloys
are thermally equilibrated by a post-annealing at 673 K for
30 days. The equilibrium phase compositions for those ther-
mally equilibrated alloys (Table S2 and Figure S3, Supporting
Information) are put together to construct the phase diagram.
Taking two alloys, the alloy#33 (Ga-25.0at%Pb-55.0at%Te)
and alloy#28 (Ga-10.0at%Pb-55.0at%Te), as examples. The WDS
elemental mapping results (Figure 2c,d) reveal the distribution
of Pb, Te, and Ga elements, inferring that the alloy #33 falls in
a PbTe + Ga6PbTe10 two-phase region while the alloy #28 locates
in a PbTe + Ga6PbTe10 three-phase region. The X-Ray diffrac-
tion (XRD) patterns (Figure S4, Supporting Information) for
selective thermally equilibrated alloys are in good agreement
with their metallographic observations (Figure S5, Supporting
Information). It is worth noting that the PbTe phase in a binary
Pb-Te phase diagram[58] covers a small yet non-stoichiometric
compositional homogeneity, which extends toward the Te-rich
side. With soluble Ga, the homogeneity region of PbTe still
retains asymmetric, as shown in the enlarged isothermal sec-
tion (Figure  2b). Notably, the nominal compositions for three
series of alloys (the GaxPb1−xTe (x  = 0–0.06), the Gay(PbTe)1−y
(y = 0.004–0.012), and the GazPbTe1−z (z = 0.006, 0.01)) fall inside
the PbTe single-phase region, except for the x = 0.06 alloy. The
magnified isothermal section is further superimposed with the
color contour of peak zT values at 673 K. The high-zT zone for
Ga-PbTe alloys falls across the maximum solubility of Ga in
Te-enriched PbTe.
Figure 3a shows the temperature dependence ρ(T) curves in
the temperature range of 300–673 K. For the x = 0 and x = 0.004
alloys, the ρ(T) curves transit from the metallic to semicon-
ductor conducting with increasing temperature. Meanwhile,
the S(T) curves for these two alloys (inset of Figure  3b) also
reveal the transition from p-type to n-type conducting. With the
increasing x and y, the ρ(T) curves move downward, implying
that the incorporation of Ga increases the electron carrier
concentration nH. Table 1 summarizes the room-temperature
nH for three series of alloys. For GaxPb1−xTe, the nH gradually
increases from nH =  3.03 × 1018 cm−3 (x = 0) to nH =  1.05 × 1019
(x  = 0.02), which explains the decreasing tendency in ρ. The
Gay(PbTe)1−y also reveals a similar increasing nH with increasing
y. Nevertheless, the increasing z in the Te-deficient GazPbTe1−z
oppositely leads to a decrease in nH, which corresponds to the
rise in their ρ(T) curves (Figure  3a). The mobility μH for all
the Ga-PbTe alloys is boosted compared with that of undoped
PbTe (x = 0), indicating that the incorporation of Ga plays a sig-
nificantly positive role upon the electrical transport properties.
Almost all the Ga-PbTe alloys reveal n-type conduction
within 300–673 K, as confirmed by their negative S values
(Figure  3b). For the GaxPb1−xTe and Gay(PbTe)1−y, the S(T)
curves declines with increasing Ga content, which are asso-
ciated with the increasing nH (Table  1). In contrast, the S(T)
curves of GazPbTe1−z show a downward shifting with increasing
z, owing to the decreasing nH. The thermoelectric power factor
(PF) = S2/ρ (Figure 3c), generally decreases with increasing tem-
perature. Among them, the PF curve of x  = 0.02 outperforms
the other alloys, which reaches a peak value of 4.4 mW m−1 K−2
at 300 K. This ultra-high PF value is 200% higher than that of
x  = 0 (PF = 2.0 mW m−1 K−2) at the same temperature. Fur-
thermore, a calculated PF curve (denoted as optimal PF) using
the single Kane band (SKB) model is added in Figure 3c. One
can conclude that the optimal PF curve describes a similar

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Figure 3.  The temperature-dependent a) electrical resistivity (ρ(T)) curves, b) Seebeck coefficient (S(T)) curves, c) the PF(T) = S2σ curves for
the GaxPb1−xTe (x = 0–0.02), the Gay(PbTe)1−y (y = 0.004–0.012), and the GazPbTe1−z (z = 0.006, 0.01). d) The average power factor calculated within
300–673 K, for various n-type PbTe with different dopants: the Ag-doped PbTe,[44] the Sb-doped PbTe,[50] the Ga-doped PbTe,[31,41] the (Ga, Ge)-doped
PbTe,[55] the (I, Sb)-doped PbTe,[26] and the Cu-doped PbTe.[6]

Table 1.  Electrical resistivity, Seebeck coefficient, thermal conductivity, Hall carrier concentration, and mobility for the GaxPb1−xTe (x  = 0–0.02), the
Gay(PbTe)1−y (y = 0.004–0.012), and the GazPbTe1−z (z = 0.006, 0.01) measured at 300 K.

Sample Electrical resistivity(ρ) Seebeck coefficient(S) Thermal conductivity(κ) Carrier concentration(nH) Carrier mobility(μH)
[mΩ cm] [μV K−1] [W m−1 K−1] [1018 cm−3] [cm2 V−1 s−1]
x = 0 3.11 298.91 2.30 3.03 1202.50
x = 0.004 3.29 328.48 2.31 0.83 1033.00
x = 0.006 4.66 −187.53 2.33 2.31 1291.78
x = 0.008 2.45 −234.17 2.53 5.16 1347.20
x = 0.01 0.88 −190.90 2.68 8.27 1688.00
x = 0.02 0.41 −132.83 2.52 10.50 1916.00
x = 0.06 0.96 −131.64 4.39 31.39 264.80
y = 0.004 3.72 −218.37 1.97 2.49 1903.00
y = 0.008 1.77 −222.35 2.14 4.50 1395.00
y = 0.012 1.12 −211.10 3.65 8.52 1777.00
z = 0.006 1.18 −173.48 2.15 5.32 1252.00
z = 0.01 1.73 −204.96 2.69 4.26 1955.25

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temperature dependence trend compared with that of the
x  = 0.01 and x  = 0.02 alloys. In addition to the high peak PF
value, the x = 0.02 also presents an extraordinarily high average
PF (PFave) of 3.37 mW m−1 K−2 in the temperature range of
300–673 K (Figure  3d). This value is higher than most of
the previously reported n-type PbTe alloys, including the hot-
pressed Cu-PbTe (PFave  ≈ 3.01 mW m−1 K−2) and the sparkle-
plasma-sintering Ga-PbTe (PFave  ≈ 2.99 mW m−1 K−2), within
the same temperature range.[6,31]
Although extrinsic doping offers an effective way of carrier
optimization and zT enhancement, it inevitably brings con-
cern on whether the band structure and mechanism of car-
rier scattering are affected. For example, the substitution of Pb
by a cation, such as the Bi,[60] Ti,[61] I,[62] in n-type PbTe would
lower the carrier mobility due to the deterioration of conduc-
tion band. In contrast, the intercalation of copper in n-type
PbTe (CuxPbTe1−x)[6] yields the best n-type performance, as a
result of retaining the electronic band structure. Nevertheless,
the gallium, which is known to have electron donor nature,
could create a deep impurity level, which pins the Fermi level
on an optimal position even under the thermal activation.[31]
The existence of this impurity level explains the temperature-
insensitive and low-lying ρ(T) curves (Figure 3a), and therefore
results in the extraordinary PF and PFave.
In order to validate the scattering mechanism in our
Ga-PbTe alloys, the Pisarenko curves using the single para-
bolic band (SPB) and the SKB model with the same effective
mass of 0.3 me are shown together in Figure 4a, in which the
experimental data are further superimposed. At 300 K, the
experimentally determined S and nH from this work (denoted
by filled circles) and by others[24,31,41] are in good agreement
with that of SKB and SPB-estimated curves, especially when
nH  >  5 × 1018 cm−3. Figure  4b summarizes the experimentally
determined μH and nH for our Ga-PbTe alloys and the other
n-type PbTe alloys.[24,31,41] A solid curve from the SKB model is
superimposed to guide the nH–μH relationship, which generally
gives a satisfactory estimation for our Ga-PbTe alloys especially
when nH is close to 1019 cm−3. The deviation between the SKB
Figure 4.  a) Pisarenko relation of Ga-PbTe at 300 K, compared the predicted results (curves) with the effective mass of 0.3 me according to the single
parabolic model and SKB model. Note that the literature data (La-PbTe,[24] Ga-PbTe[31,41])fits with the curve of 0.3 me. b) The relation between Hall
mobility (μH) and carrier concentration (nH) at 300 K.
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curve and experimental results is observed, presumably owing
to the complex electronic band structure[31] and co-existence of
dual carriers in those lightly doped or overly doped Ga-PbTe
alloys. Nevertheless, our best-performing x  = 0.02 alloy falls
in an optimal region of nH ≈ 1019 cm−3, whose electronic trans-
port properties can be predicted by the SPB and SKB model. In
other words, the remarkable PF and PFave in our x = 0.02 alloy
are due to the optimal nH and enhanced μH (1916 cm2 V−1 s−1)
that combinatorially lead to high electrical conductivity (σ = ρ−1).
Details of SKB and SPB models can be found in the Supporting
Information as well as in the previous work done by Su et al.[31]
The thermal conductivity κ for all the Ga-PbTe alloys are
measured within 300–673 K (Figure 5a). As known, the κ com-
prises two primary contributors, the electronic thermal con-
ductivity κe and the lattice thermal conductivity κL, respectively.
Based on the Weidemann–Franz law, the κe can be expressed
as κe = LTρ−1, whereas the Lorenz number L falls in the range
of 2.44  × 1018 to 1.5  × 1018 WΩ K−2 for degenerate to non-
degenerate semiconductors. Herein, we use the SPB model to
calculate the L number (Figure S6, Supporting Information),
to ensure the accuracy in the estimation of κL  =  κ  −  LTρ−1
(Figure  5b). At 300 K, the κ increases with increasing doping
content for all the Ga-PbTe alloys, owing to the increasing
κe (Figure  5d). As the temperature elevates, the κ(T) and
κL(T) curves decline except for that of undoped x  = 0. For the
x = 0.01 and x = 0.02 alloys, their κ(T) curves move down sig-
nificantly with the increasing temperature, become the lowest
ones among all the alloys as T > 573 K, and reach an extremely
low κ = 1.25 W m−1 K−1 at 673 K. Notably, the κL(T) curve of the
x  = 0.02 (Figure  5b) remains low lying within 300–673 K, and
achieves an ultra-low κL = 0.85 W m−1 K−1 at 673 K.
The specific heat Cp for all the Ga-PbTe alloys are measured
within 350–575 K (upper panel of Figure  5c), and the values
locate in the similar range as that calculated by an equation:
Cp/kB per atom = 3.07 + (0.00047 × (T − 300)).[46,47] Good agree-
ment is achieved between the experimentally determined Cp
and calculated Cp,[46,47] suggesting that the ultra-low κ and
κL for x  = 0.02 alloys are convincible. The x  = 0.06 exhibits a
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Figure 5.  Temperature-dependent a) thermal conductivity (κ(T)) curves, b) lattice thermal conductivity (κL(T)), c) specific heat capacity (Cp(T)), and
d) electrical thermal conductivity (κe(T)) curves for the GaxPb1−xTe (x  = 0–0.02), the Gay(PbTe)1−y (y  = 0.004–0.012), and the GazPbTe1−z (z = 0.006,
0.01). The inset in (b) showed enlarged section of (κL(T)) curves within the high-temperature region. The κ(T) calculated by the Debye–Callaway model
is superimposed in (b). The high-temperature lattice thermal conductivity (κL) of Ga0.02Pb0.98Te approach the amorphous limit of cubic structure
(≈0.4 W m−1 K−1).

high-rise κ(T) curve, presumably due to the co-existence of
PbTe and Ga6PbTe10, as suggested by the isothermal and further
confirmed by experimental results (Figure S7, Supporting Infor-
mation). On the contrary, the x = 0.01 and x = 0.02 appear to be
single phase of PbTe (Figure S7, Supporting Information).
Nevertheless, the transmission electron microscope (TEM)
analyses discussed below uncover a different story.
Figure 6a–g shows the TEM analyses results for the x = 0.01
alloy. The bright-field (BF) image (Figure 6a) corresponds to the
diffraction vector g = 2 20 in the [111] zone axis, revealing that the
PbTe matrix is embedded with a large number of dislocations.
The diffraction pattern (Figure  6c) affirms the cubic structure
of the matrix phase. Nevertheless, the energy dispersive spec-
trum (EDS) (Figure  6d) suggests a small yet detachable solu-
bility of Ga within the measured area. Moreover, the linear
and enclosed dislocations (aka dislocation loop) are uniformly
dispersed (Figure  6a), which originate from the lattice imper-
fections. The dark-field (DF) image is suitable for disloca-
tion imaging, as the bright region in the DF mode represents
the bending lattice near the dislocation cores. By taking the
diffraction spot of (220) in Figure 6c, the DF image (Figure 6b)
reveals the bright streaks and spots, which correspond to the
linear dislocation and dislocation loops in Figure 6a. The high-
resolution image (Figure 6e) reveals a closer observation upon
the dislocation loop, which suggests a severe lattice distortion.
In order to quantify the distortion, the lattice profiles
(Figure 6g) are analyzed across the edge and center of the dis-
location loop, as denoted by green and blue lines in Figure 6e,
respectively. The peaks are overlapping and broadening when
the line-scan is across the distorted area (upper panel of
Figure 6g), indicating that the lattice shrinks gradually along the
111 direction. As a comparison, the lower panel in Figure  6g
suggests the less-distortion area, as the peaks are sharp and are
separated with nearly an equal space. Moreover, another sample
of x  = 0.01 is analyzed by TEM, and its BF image (Figure  6f)
also confirms the presence of dislocation loops. Good reproduc-
ibility in the TEM analysis results can be achieved in different
samples of x = 0.01 alloy.
With the increasing Ga content, the defects are likely to
transform from 2D dislocations to 3D nano-precipitation.

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Figure 6.  The TEM analyses of Ga0.01Pb0.99Te (x  = 0.01) in the [111] zone axis, and the corresponding a) BF image, b) the dark-field (DF) image in
the [ 220 ] two-beam condition, c) the diffraction pattern. d) The EDS of the whole specimen. e) The high-resolution TEM image in the [112 ] zone axis.
f) The BF image of another x = 0.01 sample in the [111] zone axis. g) Lattice profiles of both lines in the [ 1 1 1] direction of (e).

Figure 7a–l summarizes the TEM analyses results for the
x  = 0.02 alloy. The BF images (Figure  7a,d) are taken in two
different zone axes of [001] and [021], respectively, in different
regions for the x = 0.02 specimen, which both reveal the square-
shaped nano-precipitate with a characteristic size of 20–40 nm.
The diffraction patterns (Figure 7b,e) also confirm the existence
of cubic structure. Bright regions in the DF images (Figure 7c,f)
further imply the presence of the strain field induced by the
nano-precipitate. In particular, the DF image (Figure  7f) is
obtained using the satellite spot nearing the (400) reflection,
as highlighted in an inset of Figure  7f. That suggests the co-
existence of two cubic structures with very similar lattice con-
stants. It is, therefore, speculated that the nano-precipitate also
crystallizes in a cubic structure and possesses a similar lattice
constant compared with that of PbTe matrix. Another evidence
for the structural similarity between the nano-precipitation and
matrix PbTe is revealed by the splitting of diffraction spots from
high-order reflections (444) and (224) (Figure 7k,l).
Upon closer observation, the interface between the nano-
precipitate and PbTe matrix (region A in Figure  7a) is nearly
coherent, as shown by a high-resolution image (Figure  7g). In
order to validate the formation of nano-precipitate, the high-
angle annular dark-field (HAADF) images in the [001] zone
axis are taken (Figure  7h,i), by using the scanning transmis-
sion electron microscope (STEM) mode. Consistently, the low-
magnification STEM-HAADF images uncover the uniform
dispersion of nano-precipitate. Since a HAADF image reflects the
difference in mass density, the darker nano-precipitate, by all
means, possesses a lighter atomic mass compared with that of
matrix PbTe. Given that Ga is lighter than Pb and Te, the nano-
precipitation is likely to be a Ga-rich cubic phase. There are
two types of Ga ions, the Ga+(0.81 Å) and Ga3+(0.62 Å), which
both possess a smaller ionic radius than Pb2+(1.2 Å). No matter
which Ga ion substitutes the Pb2+, it is expected that a lattice
mismatch takes places and therefore induces the formation of
defects.[55,63] Nevertheless, it still acquires more experimental
evidence to determine whether the Ga ions would substitute
the Pb2+ and which Ga ion (Ga+ or Ga3+) plays an essential role.
Meanwhile, the HAADF images confirm the presence of nano-
scale mass fluctuations, contributing from two identical cubic

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Figure 7.  The TEM analyses of Ga0.02Pb0.98Te including the a) BF image, b) diffraction pattern, and c) dark-field (DF) image in the [001] zone axis, d)
BF image, e) diffraction pattern, and f) DF image in the [021] zone axis, showing aligned nano-precipitate with rectangular-shaped region embedded in
the PbTe matrix. g) The high-resolution TEM image of the rectangular-shaped region in (a) in the [001] zone axis, indicating a well-connecting boundary
between precipitate and PbTe matrix. h,i) The STEM, HAADF images with two scales of magnification of the PbTe in the [001] zone axis, providing the
aspect to observe the mass contrast. j) The EDS of the whole specimen. k,l) Splitting spots appeared in the high-order diffracted plane, which were
444 and 224, respectively.

3 θ D /T
structures (matrix PbTe and nano-precipitate) with slightly dif- kB  kBT  x 4e x
ferent mass density, which benefits κ reduction.
κL =  
2π 2υ    ∫τ
0
tot (x )
(e x
− 1)
2 dx (1)

In short, the defect transits from the dislocation loop to

nano-precipitation with increasing Ga solubility in PbTe.
That demonstrates two scattering mechanisms, as shown
in Figure 8a,b, respectively. If the dislocation loop forms as
a major defect, the speed of phonon would be slowed down
while the direction of phonons (a vector) is unchanged when
they travel through the distortion area. That also refers to the
phonon softening, as shown in Figure  8a and found in our
x  = 0.01 alloy. Nevertheless, those soluble Ga (blue atom in
Figure  8a,b) could also induce the phonon scattering that
lowers the κL. The presence of nano-precipitate fulfills the typ-
ical phonon scattering mechanism, as illustrated in Figure 8b
and demonstrated in our x  = 0.02 alloy. The color contour
of κL at 673 K is superimposed on the isothermal section
(Figure 8c), and the superposition suggests that the decreasing
tendency in κL could be mapped out by a phase diagram. The
x  = 0.01 and x  = 0.02 alloys, which contained different types
of defects, achieve the ultra-low κL  ≈ 0.99 (W m−1 K−1) and
κL ≈ 0.85 (W m−1 K−1) at 673 K, and κL ≈ 2.12 (W m−1 K−1) and
κL ≈ 1.19 (W m−1 K−1) at 300 K, showing a great reduction com-
pared with the undoped PbTe. Moreover, a theoretical model
for κL based on the Debye approximation[64] offers a rational
way to compute the individual contribution of each type of
defect on the κL reduction:
In Equation (1), the kB, ν, ℏ, θD refers to the Boltzman con-
stant, the average speed of sound, the reduced Planck constant,
and the Debye temperature, respectively. The x  =  ℏω/kBT con-
tains the angular frequency ω. The τtotal is the total relaxation
time that comprises the scattering of the normal (N process,
τN), the Umklapp phonon–phonon (U process, τU), the point
defect (PD) (τP),[65,66] the interface (I) (τI),[67] the dislocation core
(DC) (τDC),[68] and the dislocation strain field (DS) (τDS)[69] via
the relation:
1 1 1 1 1 1 1 (2)
= + + + + +
τ total τ N τ U τ P τ I τ DC τ DS
Details of κL calculation based on the Debye approximation
is included in the Supporting Information. Parameters for κL
calculation are listed in Table S3,[70,71] Supporting Information.
It should be noted that the density of dislocation and interface
is estimated mainly from the TEM analysis results (Figures  6
and 7). A similar κL calculation has also been performed for the
p-type (Na, Eu)-PbTe.[67] Emphasis needs to be made that the
umklapp and normal (UN) process stands for the combined
contribution of U process and N process, while the interface I
scattering is mainly due to the nanostructuring.

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Figure 8.  Schematic illustration of phonon scattering and softening due to a) dislocation loop and b) nano-precipitation, were generated in the samples
of x = 0.01 and x = 0.02, respectively. c) The mapping of lattice thermal conductivity (κL) at 673 K superimposed with enlarged isothermal section of
Ga-Pb-Te. d) The experimentally determined κL of pristine PbTe (x = 0), Ga0.01Pb0.99Te (x = 0.01), and Ga0.02Pb0.98Te (x = 0.02) superimposed with the
Debye–Callaway models that consider the normal scattering (N process), the Umklapp phonon–phonon scattering (U process), the PD scattering,
and the interface scattering (I), respectively.

Figure 8d summarizes the temperature-dependent κL curves
for x = 0, x = 0.01, and x = 0.02 alloys, superimposed with the
calculated κL curves based on Equations (1) and (2). The pres-
ence of dislocation loops (i.e., point defect, x  = 0.01) dramati-
cally reduces the κL by 40–60% compared with x  = 0, while
the formation of nano-precipitation (x  = 0.02) further leads to
another 40% and 10% drop in the κL at 300 and 673 K, respec-
tively. The experimentally determined κL curves of x = 0.01 and
x  = 0.02 alloys fit very well with the model predictions that
consider the UN + PD process and the UN + PD + I process,
respectively, inferring that in addition to the U and N process,
the dislocation loop (point defect, PD) and the nano-precipitate
(nanostructuring interface, I) indeed enhance the phonon scat-
tering in these two alloys. Moreover, there is a noticeable devia-
tion between the experimentally determined κL and the UN
process in the x = 0 (undoped PbTe) as T > 400 K, reflecting the
possibility of existence of bipolar thermal conductivity κb.
3. Conclusion
In summary, a successful paradigm of reduced κL via defeat
evolution and carrier optimization is elaborated in n-type
Ga-PbTe alloys. Through phase diagram engineering, a specific
compositional region reveals the decreasing trend in κL with
increasing Ga content, in which the defects transits from the
dislocation loop to nano-precipitation. Experimental evidence
suggests that the coherency strains increase across the perfect
match of interfaces between those defects and the matrix PbTe,
and hence the transporting phonons are severely scattered
while the electrons pass without much interruption.
Astonishingly, the interplay of an ultra-high average
PF = S2ρ−1  ≈ 3.37 mW m−1 K−2, and low-lying κL curves result
in a high-rise plateau of zT ≈ 1.2 within 573–673 K, yielding an
extraordinary average zT  = 1.01 in n-type Ga0.02Pb0.98Te, in the
temperature range of 300–673 K.
4. Experimental Section
Synthesis: Thirty-six ternary alloys underwent a 30-day post-annealing
determined the Ga-Pb-Te isothermal section at 673 K. In a total of 1  g,
the high-purity elements of Ga (99.999%, Alfa Aesar), Pb (99.95%,
Alfa Aesar), and Te (99.999%, Alfa Aesar) were weighed according
to the predetermined nominal compositions as listed in Table S2,
Supporting Information and were sealed in a quartz tube under vacuum

Adv. Funct. Mater. 2020, 2005479 2005479  (9 of 11) © 2020 Wiley-VCH GmbH
www.advancedsciencenews.com
(3.0 × 10−3 Pa). The ampoules were homogenized at 1273 K for 5 h and
were subsequently quenched in ice water to retain the fine solidification
microstructures. Subsequently, the sample ampoules were annealed at
673 K for 30 days and were quenched in the water again. Those thermally
equilibrated alloys were subjected to metallographic observations and
crystal structure analysis to identify the types and compositions of the
equilibrium phases.
As for the thermoelectric property assessments, the Bridgman
method was chosen to grow the fully dense Ga-PbTe alloys whose
relative density is larger than 99%. Three series of Ga-PbTe alloys,
the GaxPb1−xTe (x  = 0 – 0.06), the Gay(PbTe)1−y (y  = 0.004–0.012), and
the GazPbTe1−z (z  = 0.006–0.01) were prepared through the Bridgman
method. The pure elements of Ga, Pb, and Te in a total of 8  g were
loaded in a carbon-coated quartz tube that was subsequently sealed
under vacuum (3.0 × 10−3 Pa). The sample ampoules were slowly heated
up to 1273 K in a furnace over 20 h, homogenized at this temperature for
12 h, and were solidified by a water-quenching process. At the beginning
of the Bridgman growth, the as-solidified ingots were placed in the top
and high-temperature region (T = 1213 K) of a Bridgman furnace where
the temperature was intentionally set to be higher than the materials’
melting points. Once the ingot became a melt, the sample ampoule
moved downward with a constant growth rate of 1.1 (K h−1) while rotated
axially until it reached to a low-temperature zone (T  = 1163 K) where
the melt solidified completely. The as-grown TE alloys were polished
and subjected for the following characterization and TE property
measurement.
Characterization: Microstructure analysis and phase identification
were conducted on both the thermally equilibrated and Bridgman-grown
alloys. Before the metallographic observation, the alloys were mounted
in the epoxy resin and polished with a series of SiC papers, ranging
from#1000 to #4000, and with Al2O3 powder with the particle size of
0.1 and 0.05 µm, respectively. The microstructure was observed using
a field-emission scanning microscope (FESEM, JEOL 6330) equipped
with a backscattered electron (BSE) detector, while the composition
of the phase was obtained through a field-emission electron probe
microanalyzer (EPMA, JXA-8530F, JEOL). The crystal structure was
determined by the X-ray diffraction pattern acquired by a powder X-ray
diffractometer (XRD, Siemens D-5000) with a Cu Kα source at angles of
20–90o. The high zT x  = 0.01 and x  = 0.02 alloys were further examined
by a field-emission transmission electron microscopy (FETEM, FEI E.O
Tecnai F20 G2) equipped with EDS. Prior to the TEM analysis, a focused
ion beam (NX2000, Hitachi, Japan) with the Ga+ as the ion source was
used for sample milling. In order to minimize the damage from the
ion-thinning process, a Pt layer of 3 µm thicknesses was sputtered
on the targeted region. With 200 KV acceleration electron voltage,
the TEM analysis including the BF, the DF, the high angular area
dark-field image under the STEM mode, and the diffraction patterns
under the selected-area diffractions (SAD) mode was performed.
Thermoelectric Property Measurements: The Bridgman-growth alloy
was sliced into a rod (7.0  mm in diameter and 15mm  in height) and a
pellet (7.0  mm in diameter and 1.5  mm in thickness) specimen, which
are subjected for the power factor S2ρ−1 evaluation and the thermal
conductivity κ measurement in the temperature range of 300–673 K,
respectively. The electrical resistivity (ρ) and (S) within 300–673 K
were measured by a commercial apparatus (ZEM-3, ULVAC, Japan)
in a helium-filled atmosphere. The κ was obtained from the following
equation: κ  =  D  × CP  × d, whereas the thermal diffusivity (D) was
measured by the laser flash method (LFA-467, NETZSCH, Germany)
within 300–673 K. The heat capacity (Cp) was obtained from the
differential scanning calorimetry (DSC 3500 Sirius, NETZSCH, Germany)
with a constant heat rate of 10 K min−1. Mass density (d) was obtained
via the Archimedes method.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Adv. Funct. Mater. 2020, 2005479 2005479  (10 of 11)
www.afm-journal.de
Acknowledgements
The authors acknowledged the financial support from the Young Scholar
Fellowship Program by the Ministry of Science and Technology (MOST)
in Taiwan, under the Grant MOST 109-2636-E-009-016.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
dislocation, nano-precipitation, n-type PbTe, thermal conductivity,
thermodynamic approaches
Received: June 30, 2020
Revised: July 21, 2020
Published online:
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