ARTICLE

https://doi.org/10.1038/s41467-021-23569-z OPEN

Entropy engineering promotes thermoelectric

performance in p-type chalcogenides
Binbin Jiang 1,5, Yong Yu1,5, Hongyi Chen2, Juan Cui1, Xixi Liu1, Lin Xie1 & Jiaqing He 1,3,4 ✉

We demonstrate that the thermoelectric properties of p-type chalcogenides can be effec-

tively improved by band convergence and hierarchical structure based on a high-entropy-
1234567890():,;

stabilized matrix. The band convergence is due to the decreased light and heavy band energy
offsets by alloying Cd for an enhanced Seebeck coefficient and electric transport property.
Moreover, the hierarchical structure manipulated by entropy engineering introduces all-scale
scattering sources for heat-carrying phonons resulting in a very low lattice thermal con-
ductivity. Consequently, a peak zT of 2.0 at 900 K for p-type chalcogenides and a high
experimental conversion efficiency of 12% at ΔT = 506 K for the fabricated segmented
modules are achieved. This work provides an entropy strategy to form all-scale hierarchical
structures employing high-entropy-stabilized matrix. This work will promote real applications
of low-cost thermoelectric materials.

1 Shenzhen Key Laboratory of Thermoelectric Materials, Department of Physics, Southern University of Science and Technology, Shenzhen, China. 2 College of

Chemistry and Chemical Engineering, Central South University, Changsha, China. 3 Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-
Electrical Energy Materials and Devices, Southern University of Science and Technology, Shenzhen, China. 4 Key Laboratory of Energy Conversion and
Storage Technologies, Southern University of Science and Technology, Ministry of Education, Shenzhen, China. 5These authors contributed equally:
B. Jiang, Y. Yu. ✉email: [email protected]

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T
hermoelectric (TE) technologies can generate electricity distortion is usually the core phenomenon of high-entropy mate-
from waste heat and have drawn widespread attention rial—such distortion leads to strong scattering for heat-carrying
because of the possibility of increasing overall energy phonons and results in low lattice thermal conductivity18. Stabi-
efficiency1–5. However, its high cost and low conversion efficiency lizing single-phase structures by increasing entropy weakens the
weaken the competitiveness6–8. To achieve a high conversion phase-boundary electron scattering in multiphase high-entropy
efficiency, TE materials with a high figure-of-merit (zT) should be material, thus providing a beneficial contribution to improve
used9,10: electrical transport properties, i.e., entropy-driven structural
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi stabilization18,22. Therefore, the high-entropy-stabilized composi-
T h þT c
T  Tc 1 þ z 2  1 tion should work as a good matrix for further optimization of TE
ηmax ¼ h qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ; ð1Þ performance by integrating the traditional optimization strategy.
Th 1 þ z T h þT c þ T c PbSe is a promising alternative to expensive PbTe because of
2 Th
the earth-abundant element Se. Recently, the zT value of n-type
where Th and Tc are the hot- and cold-side temperatures. The PbSe has been largely improved to a high value of 1.8, which is
dimensionless figure-of-merit zT = S2σ/κ is given by the materi- comparable to n-type PbTe18,23,24. However, p-type PbSe still
al’s parameters. Here, the Seebeck coefficient is S, the electrical shows a much lower zT value than PbTe, which prevents its
conductivity is σ, and the thermal conductivity is κ. Many stra- possible commercial applications25–35. Here, we synthesized
tegies have been proposed to improve zT values, which aimed to high-entropy Pb0.975Na0.025Se0.5S0.25Te0.25 compositions whose
increase σ or S or decrease κ. For example, decreasing carrier structure was stabilized by increasing the entropy. This increased
effective mass and scattering is beneficial to increase σ because of the peak zT to a high value of 2.0 at 900 K with band convergence
the increased carrier mobility11,12. Band convergence and reso- and hierarchical structures (Fig. 1a). The hierarchical structures
nant level increase the density-of-states’ effective mass con- manipulated by introducing complicated elemental composition
tributing to a large S (refs. 13,14). Lattice defects and demonstrated different scales of lattice defects (Fig. 1c). These
nanostructures destroy the propagation path of heat-carrying scatter all-frequency phonons and contributed to a very low lat-
phonons resulting in a low κ (refs. 15–17). tice thermal conductivity (κL) of 0.33 Wm−1K−1 for
Recently, entropy engineering has been used as a novel strategy Pb0.935Na0.025Cd0.04Se0.5S0.25Te0.25 sample. Based on the high-
to optimize the electrical and thermal transport properties of TE performance high-entropy chalcogenides, we fabricated a seg-
materials18–20. By increasing element species, the mixing entropy mented TE module and realized an experimental conversion
in a material system increases quickly, and high-entropy materials efficiency of 12% at ΔT = 506 K, which is one of the highest
with over five principal elements will be formed21. Severe lattice results yet reported (Fig. 1b).

Fig. 1 Improving TE performance in all-scale hierarchical structures through entropy engineering. a Temperature dependence of zT values for p-type
chalcogenides in this work. The results of p-type PbSe-based materials in the literature are also included25–35. b Temperature difference (ΔT) dependence
of maximum conversion efficiencies (ηmax) for chalcogenides-based segmented TE modules in this work. The results of Pb(Te,Se,S)/Bi2Te3-
based18,46,47,49–51, Skutterudite/Bi2Te3-based48,52–56, and half-Heusler/Bi2Te3-based57–59 TE modules in literature are also included (the pink area).
c Phonon mean free path dependence of accumulated lattice thermal conductivity κL (the red line) and schematic diagram of all-scale hierarchical
structures (point defects, planar defects, nanoprecipitates, and mesoscopic precipitates). The pink, orange, green, blue, and purple spheres represent
Pb, Na, Se, Te, and S atoms, respectively. The green and red grains represent CdS and high-entropy matrix, respectively.

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Fig. 2 Band convergence in p-type Cd-doped chalcogenides. a Powder XRD patterns (left), calculated lattice parameters (right), b room-temperature
infrared diffuse reflectance spectroscopy (left) and calculated band gaps (right) for Pb0.975−xCdxNa0.025Se0.5S0.25Te0.25 (x = 0, 0.01, 0.02, 0.03, 0.04,
0.05) samples. The spheres with different colors correspond to the lines with the same colors. c Calculated band structures of Pb27Se27, Pb27Se13Te7S7,
and Pb26CdSe13Te7S7. d Schematic diagram of band convergence by alloying S, Te, and Cd in PbSe. e Temperature dependence of Hall coefficients (the
orange arrows represent the decreased peak temperature), and f carrier concentration dependence of the Seebeck coefficients (the Pisarenko relationship)
for Pb0.975−xCdxNa0.025Se0.5S0.25Te0.25 (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05) samples (blue spheres). The black line and open symbols are from
reference27.

Results and improve the electrical properties18, which is similar to the

High-entropy composition and band structure. Powder X-ray improved atomic ordering in Cd-doped AgSbTe2 (ref. 36).
diffraction patterns at room temperature for all the samples are Meanwhile, the increased solubility of Te and S at anion sites
shown in Fig. 2a. The results reveal that the PbSe0.5S0.25Te0.25 from the increased entropy also extends phase space for perfor-
sample has split diffraction peaks, which come from the multi- mance optimization and largely distorts the lattice, resulting in
phase mixture with modulated composition. Upon introducing strong scattering for heat-carrying phonons. Based on this single-
Na, the split peaks converged into one peak illustrating the phase composition (Pb0.975Na0.025Se0.5S0.25Te0.25), we further
resulting single phase. This phenomenon was also observed in Sn- alloyed Cd at the Pb site to tune the band structure and micro-
alloyed (Pb,Sn)(Se,S,Te) system and can be well explained by the structure. The sharp peaks of the Pb0.975−xNa0.025Cdx-
entropy-driven structural stabilization18,22. The introduced Na Se0.5S0.25Te0.25 sample can be well indexed to rock salt PbSe
increased the mixing entropy resulting in a negative Gibbs free structure, which demonstrated that the single-phase matrix was
energy and stabilized structure. The stabilized structure can keep maintained upon introducing Cd.
the long-range order of atomic arrangement, thereby eliminating The alloyed Cd should change the band structure because of
the boundary phonon scattering around phase interfaces18. This the changed orbital hybridization31 and the compressed lattice
phenomenon of stabilized structure from entropy-driven struc- parameter (Fig. 2a), as proved by the diffuse reflectance spectra27.
tural stabilization can maintain the electrical transport framework Based on Kubelka–Munk relationship, the band gaps of all of the

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samples with different Cd contents were measured as shown in conductivity (κe) based on the Wiedemann–Franz law2,3, term κL
Fig. 2b. The band gap increased from 0.28 to 0.37 eV, when the was calculated and plotted in Fig. 3d. Clearly, κL is largely
Cd content increased from 0 to 0.05. The band structure based on depressed to a low value in the entire temperature range for the
density functional theory (DFT) was calculated to determine the high-entropy Pb0.975Na0.025Se0.5S0.25Te0.25 sample, which was even
effect of the increased band gap on band structure. As shown in much lower than that of the nanostructure PbSe27,29,30,34, such as
Fig. 2c, the valence band maximum was pushed down, and the the green line for Pb0.935Na0.025Cd0.04Se in this work and the
conduction band minimum was pushed up because of the reported Pb0.95Na0.02Cd0.03Se in previous literature27,34. Further-
increased band gap with introducing Cd; the other band valleys more, we introduced Cd to produce nanoprecipitates using this
remained unchanged. As a result, the energy difference (ΔEL − Σ) high-entropy-stabilized composition as a matrix material, resulting
between the light (L) and heavy (Σ) valence bands will be in a very low κL in the whole temperature range. This temperature-
decreased, as shown in the schematic diagram in Fig. 2d. For p- independent trend of κL largely deviates from the T−1 relation for
type chalcogenides without alloying Cd, the Fermi level only pass Umklapp phonon scattering3,5,7, demonstrating that the scattering
through L band because of the large ΔEL − Σ. But the Fermi level from a high-entropy matrix and nanostructure dominates the
in Cd-doped materials should be deep into both the L and Σ phonon transport process. The low κL (0.33 Wm−1K−1) is close to
bands due to the decreased ΔEL − Σ, which leads to the increased the theoretical minimum value (0.31 Wm−1K−1) based on Cahill
valley degeneracy Nv (band convergence)27,28. PbSe is well known model44, illustrating that the phonon mean free path is very small
as a typical incipient metal with a unique bonding mechanism and similar to the atomic distance. The full-spectrum phonons
called metavalent bonding (MVB)37. MVB is mainly formed by p- should be strongly scattered by wide-scale scattering sources
orbitals in a σ-bonding configuration in chalcogenides, which considering the temperature-independent trend of κL and atomic-
shows high electron mobility because of the small conductivity scale phonon mean free path45.
effective mass and weak s–p hybridization38. In our experiment, The highest zT value was largely improved to 2.0 at 900 K
alloying Cd at Pb site will strengthen s–p hybridization between (Fig. 3e) by combining the improved PF from band convergence
cation and anion because of the increased charge sharing37,39. and the depressed κL from full-spectrum phonon scattering
Thus, the band gap opens and band effective mass of a single presented above. This is a high value in p-type PbSe-based
valley (mb*) increases, resulting in the reduced charge carrier materials and comparable to expensive p-type PbTe13,45–47. The
mobility (Fig. S1d)40. In this regard, alloying Cd should zT value of high-entropy Pb0.935Na0.025Cd0.04Se0.5S0.25Te0.25
deteriorate the electrical transport property based on a single sample has been improved by 100% and 67%, respectively, versus
parabolic band model. However, the enlarged band gap decreases Pb0.975Na0.025Se and Pb0.935Na0.025Cd0.04Se with only band
the energy separation between L and Σ bands, and promotes the convergence and nanostructure.
band convergence as verified by our DFT calculations. The
participation of Σ band in electrical transport process leads to the
TE module. Although discussions in the TE community often
multiple band behavior13. As a consequence, the valley
focuses on the development of zT value, the conversion efficiency of
degeneracy Nv and density-of-states effective mass m* (m* =
the module is more valuable to evaluate the the TE
Nv2/3mb*) will be largely increased (the Pisarenko line in Fig. 2f)13,
performance18,46,47. In this work, we fabricated a segmented module
resulting in the enhanced S and power factor (PF = S2σ).
based on this p-type Pb0.935Na0.025Cd0.04Se0.5S0.25Te0.25 and n-type
Pb0.89Sb0.012Sn0.1Se0.5S0.25Te0.25 as in our previous work18 along with
commercial p-type Bi1.5Sb0.5Te3 and n-type Bi2Te2.7Se0.318. This
TE properties of high-entropy materials. The changed band
eight-couple module had a dimension of 20 mm by 20 mm by 13.5
structure from the band convergence is largely tuned along the
mm (inset in Fig. 3f). The output properties of the fabricated module
electrical transport properties. As shown in Fig. 3a, the electrical
were measured under different operating temperatures by PEM-2
conductivity (σ) decreased and the Seebeck coefficient (S)
(Fig. S2). Based on the measured voltage (U) and current (I), the
increased with increasing Cd content due to the decreased carrier
output power (P) can be calculated as P = UI. A maximum P of 2.7
concentration (Fig. S1a). There was an obvious plateau in the
W was obtained under a temperature difference ΔT = 506 K (ΔT =
temperature-dependent curves of S for the Cd-alloyed samples,
Th − Tc. Th, the temperature at hot side; Tc, the temperature at cold
which showed enhancement of S.
side; Fig. S2c). The conversion efficiency can be obtained as η = P/(P
We performed the Hall measurement to analyze the origin of
+ Qc) (Fig. 3f) by measuring the heat flow at the cold side (Qc, Fig.
the increased S (Fig. 2e and Fig. S1). The Hall coefficient had an
S2d)18,48. The measured η reached a maximum value of 12% under
increased peak with increasing Cd content ~500 K (Fig. 2e),
ΔT = 506 K, which is among the reported highest values for all the
illustrating that the hole transport changed from single- to two-
TE systems18,46–59. In this experiment, the height ratio of PbSe- and
band behavior28. Generally, the Hall coefficient is expected to be
Bi2Te3-based legs (HPbSe/HBT) was set at 1.5 and the cross-sectional
temperature independent when the Fermi level only passes
area ratio of the p- and n-legs (Ap/An) was set at 1.0, which were not
through single band. However, the monotonous trend turns into
fully optimized. Therefore, further improvements can be realized by
complex behavior because of the redistribution of holes in the two
optimizing the leg geometry factors. Meanwhile, the electrical and
bands29–31. The participated contribution of both heavy and light
thermal losses at various interfaces (electrical and thermal contact
bands to the hole transport process increased the band
resistance, thermal radiation and convection) will also degrade the
degeneracy (Nv) and overall density-of-states resulting in the
conversion efficiency, which demand optimization for the assembly
enhanced S13,28–31. Therefore, the peak PF was largely increased
approach of the TE module48.
to 16.5 μWcm−1K−2 for the Pb0.955Na0.025Cd0.02Se0.5S0.25Te0.25
sample, which is 22% higher than that of Pb0.975Na0.025-
Se0.5S0.25Te0.25 sample (Fig. 3b). All-scale hierarchical structures. The very low lattice thermal
Entropy engineering is an effective strategy to tune lattice conductivity from atomic-scale phonon mean free path is the
thermal conductivity (κL)18–20,41–43, which also worked in this main contribution to the largely improved zT value and con-
system. The total thermal conductivity (κ) largely decreased from 5 version efficiency in this work. To analyze the origin of phonon
to 2 Wm−1K−1 when the composition changed from low-entropy scattering, we performed transmission electron microscopy
Pb0.975Na0.025Se to high-entropy Pb0.975Na0.025Se0.5S0.25Te0.25 (TEM) studies on the high-performance Pb0.935Na0.025Cd0.04-
(Fig. 3c). By subtracting the contribution of the electronic thermal Se0.5S0.25Te0.25 sample (Fig. 4 and Figs. S3–S5). As shown in

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Fig. 3 TE performance of chalcogenide-based materials and modules. Temperature dependences of a electrical conductivity σ (the left black arrow), the
Seebeck coefficient S (the right black arrow), b power factor PF, c total thermal conductivity κ, d lattice thermal conductivity κL, and e zT values of
Pb0.975Na0.025Se, Pb0.935Na0.025Cd0.04Se, and Pb0.975−xCdxNa0.025Se0.5S0.25Te0.25 (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05) samples. The dash lines in e were
calculated by the modified Debye–Callaway model. U, NP, PD, and SF represent Umklapp process, nanoprecipitates, point defects, and stacking faults
scattering for phonons, respectively. f Current dependence of conversion efficiency under different operating temperatures (Th, temperature at hot side; Tc,
temperature at cold side) for the fabricated segmented TE module (the inset photograph).

Fig. 4a, high-density nanoprecipitates can be observed throughout indexing diffraction spots in Fig. 4b, c, we found that the nano-
the sample, whose size is distributed in a large range from several precipitates showed the same rock salt (face-centered cubic)
nanometers to several hundred nanometers. We then used structure as the PbSe-based matrix. The difference between the
energy-dispersive spectroscopy and selected area electron dif- two phases was the lattice constant, which is inversely propor-
fraction (SAED) to study the elemental composition and crystal tional to the reciprocal-space distance of spots in SAED patterns.
structure of the nanoprecipitates. Figures S3 and S4 show that the The interfaces between the nanoprecipitates and matrix were
nanoprecipitates are enriched with Cd and S, which is consistent semi-coherent (Fig. 4d), resulting in the periodic stacking faults
with their dark contrast. Generally, CdS exhibits covalent bond- due to the same crystal structure, but different lattice constants.
ing, which shows different physical properties, such as optical The high-density stacking faults within the nanoprecipitates
dielectric constant, effective coordination numbers, and Born resulted in dense lattice strains, which were proved by the
effective charge compared with MVB materials Pb(Se,S,Te)37–39. geometric phase analysis (GPA) as the insets in Fig. 4d–f show.
Thus, there should be large phonon scattering at the MVB/ In traditional nanocomposites, the lattice strains usually exist
covalent heterointerfaces due to the very different spring constant around the phase interfaces rather than within the
of chemical bonds, contributing to the ultralow κL (ref. 60). By grains15,17,27,45,53,61,62. Therefore, the size of the nanoprecipitates

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Fig. 4 Microstructure of Pb0.935Cd0.04Na0.025Se0.5S0.25Te0.25 sample. a Medium magnification STEM image shows the coexistence of nanoprecipitates
and mesoscopic precipitates. Electron diffraction spots along b (001) and c (110) orientations. The green and red arrows represent spots from PbSe and
CdS structures, respectively. d, e HAADF images of two typical nanoprecipitates that contain high-density stacking faults. The insets are the GPA results
along the xy directions. f The enlarged image of the selected area in e image. The GPA result shows the tense lattice strains around the stacking faults.
g Calculated surface energy (γ) of PbSe/CdS and PbSe0.5S0.25Te0.25/CdS interfaces. h Calculated deformation energy of rock salt CdS phase in PbSe and
PbSe0.5S0.25Te0.25 lattice. The crystal structures in g and h represent the calculation model.

should be as small as possible to obtain high surface–volume matrix, the surface energy (γ) between matrix and nanoprecipi-
ratios in nanocomposites for strengthening phonon scattering. tates will be decreased (Fig. 4g). The decreased γ will lower the
The large precipitates will have less of a contribution to reducing deformation energy of rock salt CdS and stabilized this structure
lattice thermal conductivity than the small precipitates17,63. In at room temperature (Fig. 4h). The same atomic arrangement of
this sample, however, the high-density stacking faults within large rock salt PbSe0.5S0.25Te0.25 and CdS resulted in a continuous
nanoprecipitates induced dispersed lattice strains not only around lattice and indistinct interfaces. As a result, the strains from lattice
interfaces, but also inside the whole particle, which offers strong mismatch had to be released by forming stacking faults.
scattering for heat-carrying phonons. The resulting stacking faults worked as an important role in the
The high-density stacking faults within nanoprecipitates were phonon-scattering process. Scattering sources from high-entropy
interesting and were not reported in previous Cd-doped PbQ- composition are usually distributed at the atomic scale (<1 nm)18
based (Q = S,Se,Te) systems. In previous reports, Cd(S/Se) was hindering the propagation of high-frequency phonons. However,
stabilized as zinc blende (face-centered cubic) or wurtzite nano- and meso-precipitates usually scatter low-frequency
(hexagonal) structure at room temperature, which shows a phonons because of their large size (from a few nanometers to
different atomic arrangement with PbQ (rock salt structure, face- several hundred nanometers)27,61. Therefore, the resulting
centered cubic)27,29,30,64. Therefore, the lattice around the stacking faults with a scale of 1–10 nm provided effective
interfaces between Cd(S/Se) and PbQ should be discontinuous. scattering sources for middle-frequency phonons65,66. To clarify
The lattice strains from mismatches were released by the the contributions of different scattering sources to κL, we
interfaces rather than within the nanoprecipitates. However, calculated the temperature-dependent κL based on the modified
upon replacing PbSe by high-entropy PbSe0.5S0.25Te0.25 as a Debye–Callaway model (Fig. 3d). The calculation details can be

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Additional information
Supplementary information The online version contains supplementary material
bismuth telluride/Skutterudite segmented modules through full-parameter
available at https://doi.org/10.1038/s41467-021-23569-z.
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Correspondence and requests for materials should be addressed to J.H.
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thermoelectric devices based on n-type PbTe and p-type TAGS-85 Peer review information Nature Communications thanks Matthias Wuttig and the
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through grain boundary engineering of Skutterudite-based nanocomposites. Attribution 4.0 International License, which permits use, sharing,
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55. Chu, J. et al. Electrode interface optimization advances conversion efficiency appropriate credit to the original author(s) and the source, provide a link to the Creative
and stability of thermoelectric devices. Nat. Common. 11, 3723 (2020). Commons license, and indicate if changes were made. The images or other third party
56. Fu, C. et al. Realizing high figure of merit in heavy-band p-type half-Heusler material in this article are included in the article’s Creative Commons license, unless
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57. Xing, Y. et al. High-efficiency half-Heusler thermoelectric modules enabled by article’s Creative Commons license and your intended use is not permitted by statutory
self-propagating and topologic structure optimization synthesis. Energy regulation or exceeds the permitted use, you will need to obtain permission directly from
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