Article https://doi.org/10.

1038/s41467-022-33774-z

Evolution of defect structures leading to high

ZT in GeTe-based thermoelectric materials

Received: 21 July 2022 Yilin Jiang 1, Jinfeng Dong1, Hua-Lu Zhuang1, Jincheng Yu 1, Bin Su 1 ,
Hezhang Li2, Jun Pei 1, Fu-Hua Sun3, Min Zhou 4 , Haihua Hu1, Jing-Wei Li1,
Accepted: 1 October 2022
Zhanran Han1, Bo-Ping Zhang5, Takao Mori 2,6 & Jing-Feng Li 1,3

Check for updates GeTe is a promising mid-temperature thermoelectric compound but inevi-
tably contains excessive Ge vacancies hindering its performance maximiza-
1234567890():,;

tion. This work reveals that significant enhancement in the dimensionless

1234567890():,;

figure of merit (ZT) could be realized by defect structure engineering from

point defects to line and plane defects of Ge vacancies. The evolved defects
including dislocations and nanodomains enhance phonon scattering to reduce
lattice thermal conductivity in GeTe. The accumulation of cationic vacancies
toward the formation of dislocations and planar defects weakens the scatter-
ing against electronic carriers, securing the carrier mobility and power factor.
This synergistic effect on electronic and thermal transport properties
remarkably increases the quality factor. As a result, a maximum ZT > 2.3 at
648 K and a record-high average ZT (300-798 K) were obtained for
Bi0.07Ge0.90Te in lead-free GeTe-based compounds. This work demonstrates
an important strategy for maximizing the thermoelectric performance of
GeTe-based materials by engineering the defect structures, which could also
be applied to other thermoelectric materials.

Thermoelectric technology has received increasing attention due to Recently, a series of material systems with high ZT values have been
the capability of direct conversion from heat to electricity and vice reported, such as PbTe9,10, SnSe11,12, and Cu2Se13. It is acknowledged that
versa. It can increase energy efficiency by harvesting waste heat for PbTe-based materials are limited to special applications due to the
additional energy conversion1,2, as well as other promising general trend of pursuing environment-friendly materials. The latter
applications3,4. The thermoelectric conversion efficiency can be eval- two compounds possess high ZT at quite high temperatures, but show
uated by the dimensionless figure of merit (ZT) defined as ZT = S2σT/κ, inferior performance at medium temperatures compared to PbTe-
where σ, S, T, and κ are the electrical conductivity, Seebeck coefficient, based materials.
absolute temperature, and thermal conductivity, respectively. Here, κ GeTe, a non-toxic compound among the IV–VI families, is a p-type
can be mainly divided into electrical (κe) and lattice thermal con- semiconductor with thermoelectric performance rivaling that of PbTe.
ductivity (κL). Therefore, maximizing the power factor (PF = S2σ) or GeTe possesses a less symmetrical rhombohedral structure (space
minimizing κL is the basic rule for achieving high ZT values. Many group: R3m), which enables the formation of ferroelectric domains,
methods have been utilized to improve PF5,6 and suppress κL7,8. providing abundant microstructures14,15. Recent advances in solid-state

1
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China.
2
International Center for Materials Nanoarchitechtonics (WPI-MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba 305-0044,
Japan. 3Institute for Advanced Materials, Hubei Normal University, Huangshi 435002, China. 4Key Laboratory of Cryogenics, Technical Institute of
Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China. 5The Beijing Municipal Key Laboratory of New Energy Materials and
Technologies, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China. 6Graduate School of
Pure and Applied Sciences, University of Tsukuba, Tennoudai 1-1-1, Tsukuba 305-8671, Japan. e-mail: [email protected]; [email protected];
[email protected]; [email protected]

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physics theories and material preparation techniques have provided dislocations, and domain structures with planar vacancies to mesos-
various means of manipulating thermoelectric performance that prove cale grain boundaries were established in GeTe. This type of engi-
to be effective. The symmetry-breaking and adjustable band structure neered structure provides scattering sources at all relevant length
provide more opportunities to manipulate and optimize the carrier scales, achieving an extremely low κL of 0.48 Wm−1K−1 close to the
transport properties16,17. One of the conventional viewpoints is that PF Cahill amorphous limit. The evolution of Ge vacancies also improves
can be effectively improved by modulating the symmetry and hence the carrier transport properties, increasing the weighted mobility μw
the band structure, which was manifested by the use of Pb18,19, Cd20, (calculated from Supplementary Eq. S1) and the value of μw/κL (Fig. 1b).
In21,22, and Ti23 as dopants. The lattice thermal conductivity was These great merits represent a higher quality factor B (calculated from
simultaneously suppressed by introducing point defects24,25, stacking Supplementary Eq. S2) for Ge-deficient samples sintered at 873 K
faults26, and precipitates27,28. High thermoelectric properties at med- (Fig. 1c), showing considerable potential as high ZT thermoelectric
ium temperatures were achieved in GeTe, rendering it an important candidates. Finally, a peak ZT value of over 2.3 at 648 K and a ZTavg
compound with worldwide attention29–32. value of 1.56 was achieved in the carrier concentration-optimized
However, intrinsic Ge vacancies commonly exist in the stoi- sample (Bi0.07Ge0.90Te) sintered at 873 K. By adopting the proposed
chiometric GeTe, resulting in excessive holes, reaching a high strategy, the thermoelectric performance of GeTe compounds is
concentration (~1021 cm−3), which deviates far from the optimum significantly enhanced compared to the previously reported Bi-
value for thermoelectrics33. On the other hand, the intrinsic vacan- doped samples (without Ge deficiency), as shown in Supplementary
cies impeding the carrier transport usually deteriorate the electrical Fig. 1. The present work illustrates the positive role of Ge vacancies
properties. The dopants like Bi34,35, Sb36,37, and PbSe38, etc. positively in improving the thermoelectric performance of GeTe via rational
optimize carrier concentration by suppressing the Ge vacancies, manipulation.
but introducing exotic elements usually hampers the carrier trans-
port. It is expected that inevitable vacancies may have less impact Results and discussion
on carrier transport if they aggregate to form high-dimensional Vacancy manipulation in GeTe
defects39. Unlike point defects, these high-dimensional defects such According to the conventional view that Ge vacancies hinder the
as dislocations contribute to enhancing the phonon scattering propagation of carriers, their excess is considered detrimental to the
without sacrificing the carrier mobility40, thereby bringing oppor- thermoelectric performance of GeTe. This negative effect was also
tunities to achieve enhanced thermoelectric performance by discovered in the present work. It can be seen that the Hall mobility
actively controlling Ge vacancies. (μH) and μw are reduced by 54.9% and 26.1% in the Ge0.97Te sample
In this work, the defect structures of GeTe are engineered to sintered at 723 K (namely, Ge0.97Te-723), compared with the pristine
optimize the carrier and phonon transport behaviors. This defect GeTe sample (Table 1). By contrast, the κL only shows a 3.4% reduction
control strategy can be illustrated in the schematic diagram in Fig. 1a. at room temperature, meaning that a random distribution of Ge
The hierarchical structures from atomic-scale defects, nanoscale vacancies is not desirable for GeTe.

Fig. 1 | Synergistic control of the carrier and phonon transports via defect sintered at 873 K at the room temperature, as compared with samples sintered at
engineering. a The schematic diagram presenting the behaviors of carriers and 723 K. c ZT value as a function of reduced Fermi potential with different quality
phonons in the GeTe-based compounds with the presence of hierarchical struc- factors at 648 K.
tures. b The weighted mobility μw and the value of μw/κL of Ge-deficient samples

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Essentially, the randomly distributed vacancies enhance both the Microstructural evolution via the active control of Ge vacancies
carrier and phonon scattering, but the former is, unfortunately, more As discussed above, at the higher sintering temperature, the undesired
intensified and not desired. Interestingly, the carrier scattering could excessive Ge vacancies in GeTe are conducive to enhancing the
be weakened with further enhanced phonon scattering when the Ge transport properties. In order to reveal the underlying mechanism of
vacancies are actively controlled to form a hierarchical structure (the this unusual phenomenon, structure analysis was carried out as
details are presented in the following section). This active control of Ge follows.
vacancies is achieved by simple but effective heat treatment at 873 K, As for Ge0.97Te-723, the domain structure in the submicron
which helps to redistribute the Ge vacancies. As shown in Table 1, dimension is observed under a transmission electron microscope
higher μH and μw with a lower κL are achieved in the Ge0.97Te sample (TEM) (Fig. 2a and Supplementary Fig. 3a, b), together with a few dis-
sintered at 873 K (Ge0.97Te-873) compared to the Ge0.97Te-723 sample. locations and vacancy clusters inside some grains. As for the Ge-
The μw is increased by 19.6%, while the κL is decreased by 27.2%. deficient samples sintered at 873 K, typical nanodomain structures and
Consequently, the value of μw/κL is increased dramatically, leading to a high-density dislocations are observed in a randomly selected area
higher B and therefore higher thermoelectric potential in Ge-deficient (Fig. 2b). The high-resolution TEM (HRTEM) image (Fig. 2c) illustrates
samples. the special hierarchical structure with submicron domains, nanodo-
mains, and planar vacancies. Furthermore, dislocations and planar
Table 1 | Thermoelectric transport parameters at room tem- vacancies are also observed (Fig. 2e). The fast Fourier transformation
perature for the GeTe and Ge0.97Te samples (FFT) shows the special elongated diffraction spots of the planar
vacancy (Fig. 2f). Figure 2g–i show the inverse FFT (IFFT) image
Sample σ nH μH μw κL μw/κL
(Fig. 2g) and strain mapping along the xx direction (Fig. 2h) and xy
GeTe-723 5.61 5.28 66.3 376 1.75 215
direction (Fig. 2i) from Fig. 2e, revealing the high-density dislocations
Ge0.97Te-723 5.26 11.0 29.9 281 1.69 166 and the large strain fluctuation induced by dislocations and planar
Ge0.97Te-873 5.62 10.7 34.5 336 1.23 273 vacancies. As a result of the high-temperature sintering process, the
(Units: σ (103 S cm−1), nH (1020 cm−3), μH (cm2 V−1 s−1), μw (cm2 V−1 s−1), κL (W m−1 K−1), μw/κL (cm2 V−1 s−1/ metastable state can be easily broken, facilitating the evolution of
W m−1 K−1)). vacancies to higher-dimensional defects. In particular, the diffusion
and accumulation of these positively charged Ge vacancies give rise to

Fig. 2 | Microstructure evolution led by vacancies. a, b Low-magnification TEM dislocations and planar vacancies. f The FFT image for e. g The IFFT images of e.
images of the Ge-deficient samples sintered at 723 K and 873 K, respectively. c The Strain mapping along xx direction (h) and xy direction (i) confirmed by geometric
HRTEM image of a randomly selected region in b showing the domain walls and phase analysis (GPA). j The selected area electron diffraction (SAED) of d marked
planar vacancies in the sample sintered at 873 K. d Low-magnification TEM image of with a white dashed square. The enlarged images of the framed area in d with three
the dislocation network in the sample sintered at 873 K. e HRTEM image of  l g = ð111Þ, and m g = ð022Þ.
different diffraction conditions k g = ð002Þ, 

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Fig. 3 | Lattice thermal conductivity and Debye-Callaway model prediction. the prediction κL for Bi0.07Ge0.90Te-723 and Bi0.07Ge0.90Te-873 samples.
a Temperature-dependent κL for the BixGe0.97–xTe-723 and BixGe0.97–xTe-873 sam- d Calculated κs using the Debye-Callaway model with different scattering
ples, respectively. b The comparison of κL at room temperature for the Bix- mechanisms including the Umklapp process scattering (U), grain boundary scat-
Ge0.97–xTe-723 and BixGe0.97–xTe-873 samples. c Temperature-dependent κL for the tering (B), point defect scattering (PD), dislocation scattering (D), planar vacancy
Bi0.07Ge0.90Te-723 and Bi0.07Ge0.90Te-873 samples (symbols). The lines showing scattering (PV), domain boundary scattering (DB) at 300 K.

vacancy clusters and planar vacancies, where the negatively charged vectors of BD1, BD2, and BD3. According to the principle of minimum
nanoscale domain walls can be attracted to balance the electric field, energy, the dislocation in one orientation can be easily merged by the
thereby promoting the formation of nanodomain structures15,41,42. other two orientations43,44. As displayed in Supplementary Table 3, the
Additionally, the vacancy clusters can also collapse into closed loops of Burgers vectors are BD1 || a/2[110] or a=2½110, BD2 || a/2½101 or
edge dislocations. The vacancy diffusion could facilitate dislocation a/2[011], and BD3 || a/2[011]. According to the dislocation reaction, the
migration, thereby increasing the dislocation density. According to only solution is a/2½101 + a/2[011] = a/2[110], where BD1 || a/2[110],
our density functional theory (DFT) results of the present study BD2 || a=2½101, and BD3 || a/2[011]. This reaction satisfies the energy
(Supplementary Fig. 2), the formation energy of dislocations is nega- and geometry conditions. This type of network is made up of a large
tive, serving as evidence for the presence of abundant dislocations in number of dislocations45. By comparing the differences in micro-
the Ge-deficient samples. In addition, different sintering conditions structures among the samples sintered at 723 K, 773 K, 873 K, and
(the sintering temperatures: 723 K, 773 K, 873 K, and 923 K) were 923 K, it is clear that the supersaturated vacancies’ migration and
applied, and the corresponding TEM characterization was displayed in accumulation at high temperatures is key to activating the micro-
Supplementary Figs. 3–6, which show the evolution of defect struc- structural evolution, as displayed in Fig. 1a. The abundant micro-
tures in detail. The phase characterization was shown in Supplemen- structures, stemming from Ge vacancies, are the main reason for the
tary Figs. 7–9 and Supplementary Tables 1–2. enhanced quality factor in the Ge-deficient samples sintered at 873 K,
Figure 2d displays a typical dislocation network, and the corre- which will be investigated as follows.
sponding selected area electron diffraction pattern indicates fine
crystals in Fig. 2j. Here, as the interaxial angle α is close to 90° (Sup- Reduced lattice thermal conductivity via defect engineering
plementary Table 1), the same Burgers vector BD = a/2[011] for the Due to the formation of hierarchical domain structures and high-
perfect dislocation in PbTe system10 is adopted. The detailed disloca- density dislocations via the active control of Ge vacancies, κL sharply
tion structure is also presented in Supplementary Fig. 5, where the decreases by ~27% on average for the BixGe0.97–xTe-873 samples
white arrows follow a complete Burgers loop of the dislocation with (Fig. 3a). Here, κe is calculated according to the Wiedemann-Franz law,
the black arrow representing BD = a/2[011]. The IFFT images show the and κL is obtained by subtracting κe from κ (displayed in Supplemen-
extra half-planes of the dislocation (Supplementary Fig. 5). The BD of tary Fig. 10). The significantly reduced κL is related to the multiple
the individual dislocations were determined by comparing two-beam defect structures and Bi doping, as shown in Fig. 3b. The chemical
diffraction contrast images using different diffraction vectors g. compositions for the BixGe0.97–xTe-873 samples are shown in Supple-
Figure 2k–m shows the enlarged view of the white-circled area of mentary Table 4. Consequently, the minimum κL of 0.48 Wm−1K−1 is
 ð111Þ, and ð022Þ,
Fig. 2d in different diffraction vectors g of ð002Þ,  which achieved in the Bi0.07Ge0.90Te-873 sample, nearly approaching the
were utilized to determine the BD of entire dislocations sets. As dis- theoretically minimum κL of GeTe following the Cahill model46.
cussed above, GeTe consists of edge dislocations with BD = a=2h110i. To further understand the roles of the hierarchical domain
The inset images in Fig. 2k–m display a hexagon formed by the Burgers structure with planar vacancies and dense dislocations, the κL was

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Fig. 4 | The electrical transport properties. Temperature-dependent a σ and b S temperature. d Temperature-dependent PF for our samples compared to other
for the BixGe0.97–xTe-723 and BixGe0.97–xTe-873 samples. c Hall carrier concentra- literatures34,48–51.
tion and μH for the BixGe0.97–xTe-723 and BixGe0.97–xTe-873 samples at room

fitted by the Debye-Callaway model (shown in Supplementary Mate- dislocations and domain structures with planar vacancies via defect
rials), which can provide useful insights into the phonon transport engineering in enhancing phonon scattering. The frequency-
behavior. Here, κL can be calculated from the following equation47: dependent accumulative reduction in κL is presented in Fig. 3d.
Grain boundaries are responsible for scattering the low-frequency

3 Z θD
kB kBT z 4 ez phonons, while point defects target the high-frequency phonons. By
κL = τ tot dz ð1Þ
2π 2 υs _ 0 ðez  1Þ2 contrast, dislocations and planar vacancies effectively reduce κL by
scattering the mid-frequency phonons in the mid-temperature range.
The integrand item, in conjunction with the coefficient of Eq. 1, is the Consequently, the phonon transport is suppressed by defect structure
spectral lattice thermal conductivity (κs), namely: engineering via active control of Ge vacancies, and a low κL was
achieved.

3
kB kBT z 4 ez
κs = τ tot ð2Þ
2π 2 υs _ ðe  1Þ2
z Electrical transport properties
The σ and S of the BixGe0.97–xTe-723 and BixGe0.97–xTe-873 samples are
where kB is the Boltzmann constant, νs is the average sound speed, _ is displayed in Fig. 4a, b. When subject to the higher sintering tempera-
the reduced Planck constant, θD is the Debye temperature, z = _ω=k B T ture, the σ shows a pronounced increase while S hardly changes, which
(ω denoting the phonon frequency) is the reduced phonon frequency deviates from the conventional compromising relationship between S
and τtot is the total relaxation time, namely: and σ. Therefore, the Hall measurement was carried out and the results
are shown in Fig. 4c; defect engineering does not modify the carrier
τ 1 1 1 1 1 1 1
tot = τ U + τ B + τ PD + τ PV + τ D + τ DB ð3Þ concentration but improves the μH. The almost constant S is ascribed
to the unchanged carrier concentration. At the same time, the
The sound velocities (longitudinal, transverse, and average sound increased electrical conductivity comes from the enhanced μH. The μH
velocity) of the BixGe0.97–xTe-723 and BixGe0.97–xTe-873 samples were for Bi0.07Ge0.90Te-873 reached 55.4 cm2 V−1 s−1, while a lower result of
measured and are displayed in Supplementary Fig. 10. Other 41.1 cm2 V−1 s−1 was obtained for Bi0.07Ge0.90Te-723. The extraordinarily
parameters are determined from earlier studies26,48. More details increased μH after defect engineering indicates that the formation of
about this model can be found in the Supplementary Materials. hierarchical structures instead of high-concentration vacancies has
As shown in Fig. 3c, κL is remarkably reduced via defect engi- less impact on electron transport, demonstrating that dislocations and
neering in the Bi0.07Ge0.90Te-873 sample. The solid blue line indicates planar vacancies are more favorable defects in thermoelectricity. The
the contribution from the Umklapp process scattering, the grain relationship between the carrier scattering and dislocations is descri-
boundary scattering, and point defect scattering (Ge vacancies and Bi bed by μH~T3/2 40 also showing negligible effects of dislocations on the
atoms). The orange line represents the contribution of a few disloca- carrier transport (Supplementary Figs. 11–12). Consequently, the
tions and domain structures in phonon transport. Given the defect improved σ leads to the increased PF (shown in Supplementary Fig. 13);
evolution process, the simulated decreased κL is displayed by the a high PF was obtained at 648 K via defect engineering, reaching
purple line. Notably, the simulated value is in good agreement with the 48 μW cm−1 K−2 and 45 μW cm−1 K−2 for Bi0.06Ge0.91Te-873 and
experimental value. The comparison manifests the significant role of Bi0.07Ge0.90Te-873, respectively. Compared with findings in the

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Fig. 5 | Thermoelectric properties and conversion efficiency. Temperature- previously reported typical GeTe-based materials18,22,26,34,50,60–62. Current-dependent
dependent a figure of merit ZT for BixGe0.97–xTe-723 and BixGe0.97–xTe-873 samples c output power and d efficiency of the single-leg GeTe thermoelectric device.
and b the average ZT for the Bi0.07Ge0.90Te-873 sample compared with the

previous literatures34,48–51, the sample in the present study displays a and the low κL reported for high-entropy GeTe samples51, the κL in the
much higher PF in Bi-doped GeTe samples, verifying the validity of the present work is at a modest level indicating that there is still scope for
proposed strategy in manipulating electrical transport properties. enhancing the thermoelectric performance of GeTe by optimizing κL.
More details about the electrical transport properties are provided in A high theoretical conversion efficiency approaching 15% (Tcold =
Supplementary Tables 5–6. 300 K) was simulated for the single-leg thermoelectric Bi0.07Ge0.90Te
The μw can be calculated from Supplementary Eq. S152. The Bix- module at 798 K, as shown in Supplementary Fig. 16. The high output
Ge0.97–xTe-873 samples show much higher μw than the BixGe0.97–xTe- power of 144 mW with a power density of 1.82 W cm−2 was obtained at a
723 samples (Fig. 1 and Supplementary Tables 5–6), which also indi- temperature difference (ΔT) of 498 K (Fig. 5c). The high output power
cates that superior electrical transport properties can be achieved by and power density are strongly correlated with the high PF at elevated
actively controlling Ge vacancies. It is found that minimal Bi substitu- temperatures. However, during the efficiency test at an elevated
tion (≤7 at.%) shows limited effects on μw. The mean free path temperature using the mini-PEM module testing system, thermal
lengths of phonons and carriers are summarized in Supplementary radiation significantly impacted on the test of the heat flow Qc, which is
Table 7, where the shorter mean free path of phonons and longer mean difficult to be measured accurately. Hence, the heat flow through the
free path of carriers are presented. Furthermore, the value of μw/κL for device was overestimated54,55. The heat flow was calibrated with the
the BixGe0.97–xTe-873 samples is at a higher value (Supplementary simulated Qc data in Fig. 5d, leading to energy conversion efficiency up
Tables 5–6), manifesting a higher B, as shown in Fig. 1c. to 11% at ΔT = 498 K.
In summary, this study reveals that defect evolution can be
ZT value and conversion efficiency induced by actively controlling the Ge vacancies in GeTe-based com-
In the present work, the phonons are selectively scattered through the pounds to form high-dimensional defects, which favors the phonon
active control of defect structures, which breaks the long-standing scattering without affecting the carrier transport. Controlling Ge
bottleneck of defect engineering, leading to high mobility and PF. As a vacancies is achieved by the high-temperature heat treatment, which
consequence, the thermoelectric performance is greatly improved. promotes the transformation of supersaturated vacancies, giving rise
Figure 5a displays the temperature dependence of ZT. A maximum ZT to dense dislocations and dislocation networks. Meanwhile, the posi-
of over 2.3 at 648 K is obtained in the Bi0.07Ge0.90Te-873 sample, tively charged Ge vacancies can be attracted by the negatively charged
compared to the maximum ZT of 1.9 at 723 K for the Bi0.07Ge0.90Te-723 nanoscale domain walls, which induces hierarchical nanodomain
sample. A high average ZT value of 1.56 was also achieved at the tem- structures with planar vacancies, further strengthening the scattering
perature range of 300 K to 798 K (Fig. 5b), which is comparable to that of the mid-frequency phonons. More prominently, higher carrier
of the Pb-doped samples, and is also a record-high value in lead-free mobility demonstrates the effective role of such a defect structure in
GeTe-based compounds. Our samples show good reproductivity dur- breaking the conventional relationship of S and σ. As a result, the
ing the cycling measurement (Supplementary Figs. 14–15). However, as Bi0.07Ge0.90Te-873 sample holds a maximum PF of 45 μ W cm−1 K−2 at
for phonon transport properties, compared with the theoretical 648 K and a minimum κL of 0.48 W m−1 K−1. A peak ZT value over 2.3 at
amorphous limit (≈0.28 Wm−1K−1 calculated by the diffusion model53) 648 K and a high average ZT of 1.56 within the range of 300–798 K are

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achieved. The thermoelectric energy conversion efficiency of a single- ensemble) using the Nose-Hoover thermostat at 300 K. The projector
leg Bi0.07Ge0.90Te module reaches up to 11% at ΔT = 498 K. This study augmented wave potentials are used to describe the interaction
demonstrates that defect structure engineering through actively between electrons and ions. Generalized gradient approximation in
controlling the Ge vacancies is a simple and effective approach for the scheme of Perdew–Burke–Ernzerhof59 is employed to describe
fabricating high-performance GeTe-based materials, qualifying them the exchange and correlation function. The cutoff energy was set to
to be promising lead-free candidate compounds at mid- 400 eV, and the total energy converged to 1.0 × 10−5 eV per atom. A
temperature range. typical edge dislocation in GeTe rhombohedral phase with R3m
space group was simulated using a supercell containing 285 atoms.
Methods The dislocation formation energy was calculated using the following
P P
Synthesis equation: E f = ðE tot  nα E α Þ= nα 10, where Etot represents the
Raw materials, germanium (granules, 2–5 mm, 99.999%), tellurium total energy of the system, nα denotes the number of α atoms, and Eα
(powder, 99.999%), and bismuth (powder, 99.99%) were weighed in is the total energy of an α atom in its ground-state bulk phase.
the glove box and loaded into tungsten carbide jars according to the
stoichiometric ratios of BixGe0.97–xTe (x = 0, 0.03, 0.06, 0.07). First, the Reporting summary
mixture was reacted via mechanical alloying in a planetary ball mill at Further information on research design is available in the Nature
460 rpm for 12 h, with argon (>99.5%) as the protective gas. Then, the Research Reporting Summary linked to this article.
obtained powders were densified by spark plasma sintering (SPS 211Lx,
Fuji Electronic, Japan) at 723 K, 773 K, 873 K, or 923 K for 5 min under a Data availability
pressure of 60 MPa. The data that support the findings of this study are available from the
corresponding author on request.
Characterization
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Acknowledgements Peer review information Nature Communications thanks Iris Nandha-

J.F.L., Y.L.J., J.F.D., H.L.Z., J.C.Y., B.S., J.P., F.H.S., M.Z., H.H.H., J.W.L., kumar, Pengfei Qiu and the other anonymous reviewer(s) for their con-
Z.R.H., and B.P.Z. acknowledge the Basic Science Center Project of tribution to the peer review of this work.
NSFC no. 51788104 and the National Key R&D Program of China no.
2018YFB0703603. T.M. and H.Z.L. acknowledge support from JST Mirai Reprints and permission information is available at
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