Article https://doi.org/10.

1038/s41467-023-
38446-0

Half-Heusler alloys as emerging high

power density thermoelectric cooling
materials

Received: 5 December Hangtian Zhu 1,2,3 , Wenjie Li1,3 , Amin

2022 1
Nozariasbmarz , Na Liu1, Yu Zhang 1
, Shashank
1 1
Accepted: 28 April 2023 Priya & Bed Poudel

To achieve optimal thermoelectric performance, it is crucial to

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manipulate the scattering processes within materials to decouple the
transport of phonons and electrons. In half-Heusler (hH) compounds,
selective defect reduction can significantly improve performance due to
the weak electron-acoustic phonon interaction. This study utilized Sb-
pressure controlled annealing process to modulate the microstructure
and point defects of Nb0.55Ta0.40Ti0.05FeSb compound, resulting in a
100% increase in carrier mobility and a maximum power factor of 78
µW cm−1 K−2, approaching the theoretical prediction for NbFeSb single
crystal. This approach yielded the highest average zT of ~0.86 among
hH in the temperature range of 300-873 K. The use of this material led
to a 210% enhancement in cooling power density compared to Bi2Te3-
based devices and a conversion efficiency of 12%. These results
demonstrate a pro- mising strategy for optimizing hH materials for near-
room-temperature ther- moelectric applications.

scattering centers to suppress phonon propagation also weakens

Thermoelectric (TE) is a solid-state energy conversion technology the electrical transport, such as
that enables the conversion between thermal and electrical
energy1–3. Electrons near the Fermi level in TE material carry
both charge and entropy and can migrate under the driving
electric field or tempera- ture field to realize the energy
transfer. However, in this process, a portion of energy will
inevitably be lost through heat conduction due to the
temperature gradient (ΔT) in the material. Therefore, the effi-
ciency of a TE device is lower than a Carnot engine and
depends pri- marily on the TE dimensionless figure of merit (zT),
where zT = [S2σ/ (κL + κe)]T; S, σ, κL, κe, and T are the Seebeck
coefficient, electrical conductivity, lattice and electronic
contribution of thermal con- ductivity, and absolute
temperature, respectively. Thermoelectric performance is the
result of a competition between electrical (power factor, PF =
S2σ) and thermal transport (κL + κe), both of which are heavily
affected by scattering processes within the material 4–6. In
recent years, to improve TE performance, researchers have
pursued reducing κL by introducing various scattering sources,
such as point defects7,8, grain boundaries9, dislocations10,11,
nanoprecipitations12, and porous structures13,14. However, adding

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 materials play a major role at low temperatures, so minimizing
reduced carrier mobility, which results in low PF and zT. In contamination and reducing defect density is crucial for
this sce- nario, balancing the beneficial and detrimental effects of achieving high TE performance near room temperature16.
the scattering source on TE transport becomes the essential Half-Heusler (hH) alloys are among the most promising TE
strategy for optimizing TE properties. Thus, the ratio of carrier materials for medium and high-temperature waste heat
mobility to lattice thermal conductivity (i.e., μ/κL) is critically recovery applications owing to their outstanding mechanical
important for enhancing TE performance 15. On the other hand, strength, ther- mal stability, and zT17,18. Due to the suppressed
mobility enhancement can be achieved by suppressing electron-acoustic phonon coupling in hH alloys, electron
collisions of charged carriers with different scattering sources, scattering from phonons is much weaker with the intrinsic low
including phonons, ionized impurities, defects, electromagnetic deformation potential19. Therefore, defects in hH alloys play a
fields, and other carriers4. Among them, structural defects in TE more important role in elec- tronic transport than that in other
TE materials20. It is possible to

1
Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802, USA. 2Present address: Beijing
National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China. 3These authors
contributed equally: Hangtian Zhu, Wenjie Li. e-mail: [email protected]; [email protected]; [email protected]; [email protected]

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enhance mobility by reducing the scattering source, such as longevity, the maximum cooling heat flow density ma
) is of great
lattice defects in the hH materials, thereby achieving high PF. In (Qc importance, and it is governed by the x

this study, we demonstrate significantly enhanced TE relation27:

performance of
M1−xTixFeSb (M = Nb, Ta) compounds, one of the most 1
Qcmax ∼ 2 PF T 2
4T κ ð1Þ
promising p-type hH material families 21–24, by reducing point
defect density. The Nb\Ta ratio was tuned to improve the μ/κL
ratio, as it can introduce mass fluctuation without lattice stress A higher zT value does not necessarily result in higher heat
(Fig. S1). This is
due to the small difference in lattice constant of less than pumping, as it is not directly related to . Therefore, in order to
1% Qc
between NbFeSb and TaFeSb24. We developed an Sb-pressure
con- achieve better
Q max

cmax performance, it is important to have a large

trolled annealing process to reduce the concentration of PF, especially when the ΔT is small. Under extreme conditions
defects and drive grain growth (Fig. 1a). The microstructure when ΔT is
shows sub- millimeter-sized grains in p-type negative, a high PF and κ can further enhance heat pumping by
Nb0.55Ta0.40Ti0.05FeSb sample with reduced grain boundary com- bining active and passive cooling28. Currently, most TE
density (Fig. 1b). The minimized defects and grain boundary cooling devices use Bi2Te3 alloys and provide a small ΔT of 5–10
density enable substantial enhancement of mobility (Fig. 1a) K for high-power electronics thermal management. For the first
and thus double the PF up to ~78 μW cm−1 K−2 near room time, we demonstrate superior solid-state cooling power
temperature (Fig. 1c), which leads to the highest zT of ~0.4 at density in hH alloys that outper- forms the state-of-the-art
room temperature in hH alloys and the highest average zT of Bi2Te3-based modules. We have fabricated a uni-couple device
0.86 in the temperature range of 300–873 K among hH. This using YbAl3 as an n-type counterpart, which exhibits
enhancement is reflected in an excellent power conversion ~210% higher cooling density with a ΔT of 5 K compared to a
efficiency of ~12% under ΔT of 600 K. Bi2Te3- based device (Fig. 1d). This performance is highly
In the field of TE cooling technology, two important aspects relevant for high- power electronics thermal management such as
are the maximum temperature difference (ΔT) and the maximum laser sources and on- chip hot-spot.
cooling density under zero ΔT, which depend on specific
application require- ments. Over the past six decades, the Results and discussion
maximum ΔT has been estab- lished on Bi2Te3-based alloys due High-performance hH materials enabled by point defect
to their high zT near room temperature, which has yet to be and grain boundary density
significantly rivaled. However, for most TE applications that modulation Due to the weak acoustic scattering in hH alloy
require small ΔT and precise temperature control, such as in and the screening effect of free electrons, an increase in
electronics temperature control, and particularly for hot-spots carrier concentration drives the competition between optical
cooling25,26, the maximum cooling density under small ΔT is often and acoustic phonon scattering, which results in a peak in
more important. For instance, in laser diode cooling, where a carrier mobility29. For the p-type (Nb,Ta)FeSb matrix, which has
significant amount of heat is generated during operation and must a heavier
d
density of state effective mass of valence band (m*
be maintained at a specific temperature for optimal ~8me)6,22,23, an optimized light doping strategy of 5% Ti at Nb/ Ta
performance and site has been developed (Fig. S2). While ionized impurities can

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Fig. High performance of Nb0.55Ta0.4Ti0.05FeSb hH material and
pressed and annealed alloy. c Power factor as a function of temperature and
devices with sub-millimeter grains. a Schematic illustration of enhanced
zT near room temperature. d Cooling power of hH-YbAl3 uni-couple device
carrier transportation by Sb-pressure controlled annealing. Green: Nb/Ta/Ti;
and Bi2Te3- based device at ΔT of 5 K.
Gray: Fe; Yellow: Sb; White: point defects. b Electron backscattered
diffractometry (EBSD) images of as-hot-

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significantly influence carrier mobility, the improvement in mobility migration rate (see Supplementary Information for details).
by reducing doping concentration is still limited. Microstructural The vacancy in the lattice of the samples, where internal energy
fea- tures, such as grain architecture and crystal quality, are is stored during the ball-milling and hot-pressing process, was
strongly cor- related with defect density and depend on the also minimized after both types of annealing processes, as
fabrication process. These features govern the electrical and confirmed by SEM and TEM results (Fig. 2e–h and Fig. S4i, j).
thermal transports by acting as scattering sources. Fast powder Figure 3a–c provides insight into the effect of Sb-pressure
consolidation typically leads to uniform polycrystalline samples con- trolled annealing on electron transport in the
with grain sizes of hundreds of nanometers9,23,30, while Nb0.55Ta0.40Ti0.05FeSb compound. The electrical conductivity is
annealing above the recrystallization tem- perature can lower substantially improved due to the enhanced carrier mobility
dislocation density and the number of grain boundaries due to resulting from the reduced point defects and grain boundary
the grain growth process. However, the large grain size in hH density as the grain size is increased during the Sb-pressure
samples is difficult to achieve by annealing22,31, owning to the controlled annealing process. The observed T−1.5 trend of the
alloys’ very high melting temperature (~1273 K) and good electrical conductivity suggests that the scattering of defects is
thermal stability, even though grain growth in hot-pressed minimized, indicating the dominance of acoustic phonon scattering
nanocrystals is thermodynamically favorable due to the reduction in the transport behavior of the sample annealed at high
in surface energy. By adding addition Ta into the temperature with controlled Sb-pressure (Fig. 3a). To distinguish
Nb0.55Ta0.40Ti0.05FeSb compound, the contribution of scattering from point defect and grain
its phase transition temperature decreases to 1173 K. boundary, we compared the samples before and after
Consequently, conventional vacuum annealing, where the point defects are
the hot-pressing for the Nb0.55Ta0.40Ti0.05FeSb sample can released with the unchanged grain size. The increase in
only be conducted at 1073 K, which is approximately 300 K lower mobility in the conventional vacuum-annealed sample can thus
than that of the NbFeSb compound, and no remarkable grain be attributed to the reduction of a point defect. In comparison,
growth was observed during the hot-pressing process (Fig. 2a). the elimination of point defects contributes ~25% of the total
Even after conventional vacuum annealing for 6 days at 1123 increase in carrier mobility (the first stage in Fig. 3c), while the
K, the grain size of the as-hot- pressed nano-crystalline reduction of grain boundaries contributes up to ~75% of the
Nb0.55Ta0.40Ti0.05FeSb sample did not increase significantly (Fig. total increase (the second stage in Fig. 3c), indicating the strong
S3). TEM investigation revealed (Fig. S4a–h) that the pinning scattering effect of the potential barrier at grain boundaries in hH
behavior of the Sb-rich phase imparts dynamic resis- tance to system20. Thus, a large PF of
grain growth at the grain boundary. To remove the excess Sb and ~78 µW cm−1 K−2 near room temperature is achieved (Fig. 3b),
provide an Sb-deficient environment, an Sb-pressure-controlled which is
annealing process was developed under different two times higher than that of the as-hot-pressed sample and
temperatures (see Supplementary Information for details). As close to the theoretical optimum PF ( ~90 µW cm−1 K−2) for
a result, no Sb-rich phase was observed at grain boundaries NbFeSb single crystal19.
after Sb-pressure controlled annealing at 1143 K for 2 days (Fig. The mean free path (λ) of phonon in hH is typically less
S4k, l), and grain sizes were sig- nificantly increased by three than 100 nm19, which is less than the grain size of materials
orders of magnitude, from ~200 nm to investigated in this study. Consequently, increasing the grain size
~150 μm (Fig. 2a–d), due to the substantially improved grain did not significantly
boundary

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Fig. 2 | Growth of grain in Nb0.55Ta0.40Ti0.05FeSb samples with Sb-

where green, gray, yellow, and white indicate the Nb/Ta/Ti, Fe, Sb, and point
pressure control. a–d The SEM images of samples under different heat defects of vacancies. e–h HRTEM images along ½112 axis and defect analysis
treatment condi- tions: as-hot-pressed at 1123 K for 5 min consisting of grain of the as-hot- pressed sample (e, f) and the sample annealed at 1143 K with
size of 200–300 nm (average ~250 nm) (a), annealing with Sb-pressure Sb-pressure control
control for 2 days at 1073 K consisting of grain size of 2–10 µm (average (g, h). The actual Wyckoff positions of vacancy are unable to be distinguished
~6 µm) (b), at 1113 K exhibiting grain size of 5–30 µm (average ~20 µm) due to the similar atomic weight of the two sites (Nb0.55Ta0.4Ti0.05 =
(c), and at 1143 K exhibiting grain size of 125.8710, Sb = 121.7600).
20–200 µm (average ~150 µm) (d). The crystal structures are inserted in (a) and
(d),

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Fig. 3 | Enhanced TE performance of (Nb,Ta,Ti)FeSb sample. a, b The

and crystal boundary for the mobility enhancement is marked by blue and
electrical conductivity (a) and PF (b) as a function of temperature under
pink in (a–c), respectively. d, e The temperature-dependent thermal
different annealing conditions. c The carrier mobility-dependent PF under
conductivity (d) and zT values (e). f The average zT compared with state-of-
different annealing condi- tions near room temperature. The contribution of
the-art p-type hH material22,23,40–42.
optimization of point defects

improve the lattice thermal conductivity κL due to the weak

directly proportional to the PF of the material where ΔT is equal
phonon scattering from the grain boundary15, which has also been to 0. The parameters of p-type Nb 0.55Ta0.40Ti0.05FeSb and p-
observed in Mg3(Bi,Sb)2 system32,33. As a result, this led to a type Bi0.33Sb1.67Te3 materials considered in Eq. 2 are listed in
substantially increased μ=κL ratio, resulting in ~200% enhanced Table S2 for reference.
zT value near room tem- perature compared to other hH Benefiting from the ultra-high PF and the decent z value
materials (Fig. 3e and Fig. S5). near room temperature, Nb0.55Ta0.40Ti0.05FeSb exhibits
Remarkably, a record-high average zT of ~0.86 was achieved enhanced perfor- mance compared to that of Bi2Te3-based TE
from room temperature to 873 K (Fig. 3e, f). The materials in terms of low ΔT heat pumping. The YbAl3 alloy
reproducibility of the performance Nb0.55Ta0.40Ti0.05FeSb sample with an extremely high PF of
was verified in Fig. S6, and the round-robin test was also ~110 µW cm−1 K−2 at room temperature (Fig. S9), which is
conducted at Oak Ridge national laboratory (Fig. S7), which compatible with p-type Nb0.55Ta0.40Ti0.05FeSb, was used as the n-
confirmed the transport data reported here. type counterpart to construct the uni-couple cooling device (hH-
YbAl3). Figure 4b shows the simulated cooling performance of
High cooling capacity hH module performance hH-YbAl3 device. Considering the extremely high electrical and
The Bi2Te3-based materials have been widely used in commercial thermal conductivity of YbAl3, the cross-section of the YbAl3 leg
solid- state cooling devices with a cooling power density of up to should be four times smaller than that of p-type hH to optimize the
~45 W cm−2 (based on leg lengths of ~0.2 mm, Table S1)34. performance of the device, which makes the construction and
However, it is not suffi- cient for advanced cooling applications, measurement of the device extremely difficult. Thus, the cross-
such as electronic cooling and thermal management for laser section ratio (Ap/An) was reduced to 1.4, leading to slightly lower
devices and hot-spot, which require higher cooling power performance than that of the device with optimized geometry.
densities up to ~100 W cm−2. The most crucial
parameter for high-power TE cooling is PF, which determines The measured ma of the hH-YbAl3 device at ΔT of 5 K was found to
x
the Qc be
maximum cooling power density of the module (Q cmax ) 3.6 W cm (with a leg length of 7.7 mm), which is twice that of
−2

as: the Bi2Te3-based device, 1.7 W cm−2, with the same leg length
and ΔT
ðT 2 - 2ΔT =zÞPF ðPFT 2 - (Fig. 4b, c and Fig. S10). The maximum cooling power density of
2ΔTκÞ the
Qc = c = c ð2Þ
max
2l 2l negligible. When PF is doubled (e.g., from
~35 µW cm−1 K−2 for Bi2Te3-based materials to ~80 µW cm−1K−2
where Tc is the cold side temperature, and l is the length of the for the
leg. For the materials with the same z (PF=κtol ) value, Qcmax is
mainly deter- mined by PF, particularly under small ΔT. For
instance, as shown in Fig. 4a, under a ΔT of 5 K, Qcmax shows a
linear relationship with PF, while the effect of κ is almost

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hH-YbAl 3 device remains competitive with that of Bi2Te3-based negative Seebeck coefficient for the n-type leg) would result in
devices up to ΔT of 20 K. Improved n-type material would be a higher cooling capacity across a wider ΔT range of 46 K (Fig.
able to provide even higher performance at high ΔT. For 4b).
example, a hypothetical device made using both legs with The COP of the hH-YbAl3 device, which is determined by the
similar properties to Nb0.55Ta0.40Ti0.05FeSb (which has a zT
current hH materials), ma is enhanced by ~250%. The effect of z value, ΔT, and current I, is demonstrated in Fig. 4d. The current
x
Qc value applied
on ma and the coefficient of performance (COP) corresponding to the device determines heat load, as shown in Fig. 4c.
x
Qc to Practically
Qcma gradually decreases with a decrease of ΔT (Fig. S8). It is also when TE cooling devices work under a high heat load, the COP
x
worth PFT
2 is
noting that the maximum cooling capacity of a device, = 2l c , usually lower than its maximum value at low cooling density (Fig.
max
Qc is S10c,

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Fig. 4 | Theoretical and experimental cooling performance of the hH-YbAl3

based materials and device is described in Figs. S10 and S11, and Table S2.
TE device. a The theoretical maximum Qc as a function of PF (under different
The hypothetical hH device is calculated using the same TE properties of
κ) and κ
Nb0.55Ta0.40Ti0.05FeSb for both n- and p-type legs. f The calculated
(under different PF) calculated using Eq. 2. b The cooling ΔT dependent Q of
c
max projection of
different hH-YbAl3 devices. c, d The calculated and measured cooling power
Qcmax of hH-YbAl3 module under different leg heights as a comparison with a
den- sity (c) and COP (d) of hH-YbAl3 device with different ΔT. e The state- of-the-art commercial cooling device. The fill fraction (FF), electrical
calculated and measured cooling density as a function of COP at ΔT of 5 K. (Rc), and
The leg height of hH- YbAl3 and Bi2Te3-based modules are the same at 7.7 thermal (κc) contact resistance used for calculation are listed in the figure.
mm. The details of Bi2Te3-

d)35. Under small ΔT, the hH-YbAl3 device demonstrates a

that of the Nb0.95Ti0.05FeSb/Zr0.44Hf0.44Ti0.12NiSn0.9Sb0.01 module
significantly higher cooling density (Qc) compared to that of a
developed in our previous work, even though the PF of
traditional Bi2Te3- based module under the same COP up to the
Nb0.95Ti0.05FeSb compound near room temperature (~100 µW
magnitude of 2 (Fig. 4e). It also exhibits a slower COP
cm−1 K−2) is higher than that of our p-type Nb0.55Ta0.40Ti0.05FeSb
degradation trend with an increase of cooling density as
compound. This result is mainly attributed to the better
compared to that of Bi2Te3-based device36. The
matching of electrical conductivity and
maximum ma of ~88 W cm−2 can be achieved for the hH-YbAl3 thermal conductivity between the p-Nb0.55Ta0.40Ti0.05FeSb
Qc
x
device and
when the length of the TE leg is projected to be 0.2 mm (Fig. 4f), Supplementary Materials and Fig. S12). During the three cycles of
which is ~210% higher than that of commercial Bi2Te3-based measurement, the performance of the device was stable and
modules. This illustrates that hH-YbAl3 devices are more consistent with theoretical prediction, indicating good stability of
effective under small ΔT (e.g., 5 K). the device and accuracy of the measurement (Fig. 5e, f). It is worth
noting that the output power of the hH uni-couple module is also
High efficiency for power generation higher than
The outstanding performance of the developed hH material with a
high average zT has also been verified by the device power
generation mode. A high conversion efficiency of ~12%, which is
~40% higher compared to our previous work37, was achieved at a
hot-side temperature of 923 K for the hH uni-couple module (Fig.
5). This result is due to the superior performance of p-type hH
leg with high average zT. The agreement between prediction and
experimental internal resistance (Ri) and open voltage (Voc) of uni-
couple devices indicates that the experimental electrical
contact resistance is negligible since the electrical contact
resistance was not considered in the prediction (Fig. 5b, c). As
shown in Fig. 5d, the slightly higher experimental Qcond
compared to that of prediction results from the thermal
radiation effect, which was observed in our previous work38.
Thus, thermal radiation calibration was performed using a
dummy module for accurate efficiency mea- surement (see

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n-Zr (Fig. S13).
In summary, by minimizing chemical vacancies and reducing
grain boundaries, the superior enhancement in power factor and
average zT value in Nb0.55Ta0.40Ti0.05FeSb has been achieved. It
was accomplished by controlling the Sb pressure during
annealing to promote the growth of large grain size and reduce
defects. The power factor of the materials was greatly improved
by doubling room temperature carrier mobility and optimizing
dopant concentration leading to the remarkable near- room
temperature zT of ~0.4 and the highest average zT of ~0.86
(300–873 K) for hH TE materials. A 210% higher cooling
capacity was achieved compared to that of the Bi2Te3 device
under ΔT of 5 K by deploying the high PF hH material. The
hH-YbAl3 device has the advantage of maximum cooling density
with ΔT ≤ 20 K and is even more efficient under low ΔT of 5 K
and high cooling power density of 1-3.5 W cm−2. In the
power generation mode, the measured energy conversion
efficiency of the uni-couple hH module reached ~12% at ΔT of
600 K. This work successfully demonstrates the effectiveness of
low- defect design in improving hH performance and the great
potential of Nb0.55Ta0.40Ti0.05FeSb in high heat flux thermal
management.

Methods
Synthesis of hH materials
The p-type (Nb,Ta,V,Ti)FeSb alloys were synthesized by ball
milling. The niobium (99.9%, foil), tantalum (99.9%, shot),
vanadium (99.99%, piece), titanium (99.9%, sponge), iron
(99.99%, slug), and antimony

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Fig. 5 | Power generation performance of hH devices. a Photo of the

efficiency (η) (f) obtained using optimal current as a function of hot side
measure- ment setup for the high-performance hH uni-couple module. b–f
tem- perature (Th)22,42–44. The radiation in the heat flow measurement was
Internal resis- tance (Ri) (b), open voltage (Voc) (c), heat flow at zero calibrated by the standard sample38 (Fig. S12).
current (Qcond) (d), the power density of TE legs (ω) (normalized to the
length of 2 mm) (e), and conversion

(99.9999%, shot) constituents were weighted in their in quartz tubes under high vacuum and annealed at 973 K for 30
stoichiometric ratio inside the glove box. Elements with a total min.
mass of 15 g were loaded into a stainless-steel ball-milling jar in a
glove box under an Ar atmosphere. The high-energy ball milling
was conducted for 24 hours using SPEX mixer/mill (Model
8000D, SPEX SamplePrep, Metuchen, NJ). The ball-milled
powders were consolidated by SPS (SPS, Dr. Sinter- 625V, Fuji,
Japan) at 1073 K under a pressure of 80 MPa for 5 min. The hot-
pressed pellets were sealed with Nb foil in quartz tubes under a
high vacuum. The Nb foil was used to control the Sb pressure
during the annealing.
The n-type Zr0.44Hf0.44Ti0.12NiSn0.9Sb0.01 materials were
synthe- sized by induction melting under an argon
atmosphere38. The zirco- nium (99.9%, slug), hafnium (99.9%,
piece), titanium (99.9%, wire),
nickel (99.995%, slug), tin (99.95%, wire), and antimony
(99.9999%, shot) constituents were weighted in their
stoichiometric ratio and loaded into tungsten crucible. The
induction melting was performed under an argon atmosphere for
3 min and re-melted 3 times to ensure homogeneity. Then the
ingots were transferred into stainless steel jar inside the glove
box. The high-energy ball milling was conducted for 4 h using
SPEX mixer/mill (Model 8000D, SPEX SamplePrep, Metuchen,
NJ). The grinded nanopowders were consolidated by SPS at 1373 K
under a pressure of 80 MPa for 5 min.

Synthesis of YbAl3 materials

The YbAl3 materials were synthesized by induction melting
under an argon atmosphere. The mixtures of the high-purity
metals of ytter- bium (99.9%, slug) and aluminum (99.99%,
slug) with a nominal com- position of YbAl3.2 were loaded into a
tungsten crucible. The induction melting was performed under an
argon atmosphere for 3 min and re- melted 3 times to ensure
homogeneity. Then the ingots were ball- milled for 4 h, and the
grinded nanopowders were consolidated by SPS at 773 K under a
pressure of 80 MPa for 5 min. The obtained pellets were sealed

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Synthesis of Bi2Te3-based materials
The p-type Bi0.33Sb1.67Te3 and n-type Bi2Te2.7Se0.3 were
synthesized by the high energy ball milling method. The
antimony (99.9%, shot), bis- muth (99.9%, pieces), tellurium
(99.9%, lumps), and selenium (99.9%, pellets) constituents
were weighted in their stoichiometric ratios inside the
glovebox, and sealed in a sealed quartz tube and melted for 24
hours at 1000 °C inside a conventional furnace following by
quenching. The ingot was then loaded into a hardened steel vial
along with steel balls with the ball to powder ratio of 1:1 and
ball milled for 3 hours using a SPEX mixer/mill (Model 8000D,
SPEX SamplePrep) to obtain a homogeneous powder. The
powders were then consolidated in a cylindrical graphite die
using spark plasma sintering (SPS) at 520 °C (for p-type) and
450 °C (for n-type) under constant 30 MPa pressure for 2 min.

Measurement of thermoelectrical (TE) properties

The electrical conductivity and Seebeck coefficient were
measured simultaneously (ULVAC-RIKO ZEM-3 system, Japan).
High- temperature thermal properties were determined by
measuring thermal diffusivity with a laser flash system (LFA-
467 HT Hyper- Flash®, Germany). Specific heat was
measured with a differential scanning calorimeter (Netzsch
DSC 214, Germany). The thermal
conductivity, κ, was calculated from κ = α . Cp . ρ, where α, ρ,
and Cp
are thermal diffusivity, density, and specific heat. The density
is measured using the Archimedes method. The uncertainties
in elec- trical conductivity, thermal conductivity, Seebeck
coefficient, and zT are ±5, ±2, ±5, and ±7%, respectively. The
microstructure of alloys and uni couple module junctions is
characterized by field emission scanning electron microscopy
(FESEM, FEI Verios G4), energy dis- persive spectroscopy
(EDS, Oxford Aztec), and electron back- scattered
diffractometry (EBSD, FEI Apero S, Oxford AztecCrystal). The
carrier density and mobility were measured by LakeShore Hall
Effect System (8400 Series HMS, LakeShore). The TEM is
performed using FEI Titan G2.

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e 38446-0
67, 69–147 (2018).
The module preparation 5. Pei, Y. Z. et al. Convergence of electronic bands for high
The p-type Nb0.55Ta0.40Ti0.05FeSb leg with a height of 7.7 mm perfor- mance bulk thermoelectrics. Nature 473, 66–69
and cross-section of 3.6 mm2 was used to fabricate both power (2011).
generation and cooling devices. The 6. He, R. et al. Achieving high power factor and output power
Zr0.44Hf0.44Ti0.12NiSn0.9Sb0.01 material with the same height (7.7 density in p-type half-Heuslers Nb1-xTixFeSb. Proc. Natl Acad.
mm) and cross-section (3.6 mm2) was used for the n-type leg of Sci. USA 113, 13576–13581 (2016).
power generation uni-couple device. The n-type YbAl3 leg with a
height of 7.7 mm and a cross-section of 2.53 mm2 was used for
the cooling device. With the aim of minimizing the relative error
from heat flow measurement, the cross-section Bi2Te3 legs were
adjusted to match the maximum heat flow of the hH-YbAl3
device at ΔT of 5 K. Therefore, p-type Bi0.33Sb1.67Te3 leg
(height of 7.7 mm and cross- section of 6.4 mm2) and n-type
Bi2Te2.7Se0.3 leg (height of 7.7 mm and cross-section of 7 mm2)
were used to fabricate the Bi2Te3 based cooling device.
AlN-based direct bonding copper (DBC) and copper plate
were used as the substrate of the module. Ga-based liquid metal,
which could provide extremely low electrical and thermal contact
resistance, was used as the interfacial material between the hH
legs and the substrate for the TE module. Due to the reaction
between YbAl3 and liquid metal, YbAl3 legs were connected to the
substrate by reflow soldering with Al–Zn-based solder at 673 K
(Fig. S14). The custom-built scanning probe measurement system
was used to analyze the contact resistance37–39.

Heat flow measurement

The heat flow (Q) was measured using a Q-meter, which is a
standard material (copper, brass, or graphite are commonly
used) with a cylindrical or rectangular shape connected to the
heat sink. The tem- perature gradient along the Q-meter (copper
and graphite were used for power generation and cooling
measurement in this work, respec- tively) was measured by using
four thermocouples located at specific
distances39. Then Q can be calculated by Q = κdx. A . dT, where κ,
A, and
dT/dx are the thermal conductivity, cross-sectional area, and the
slope of temperature difference versus distance on the Q-
meter.

The thermal radiation calibration

In the process of power generation measurement with hot-side
tem- perature up to 923 K, the Q-meter absorbs the radiation
energy from the high-temperature heater, resulting in the heat
flow measurement error. In order to calibrate the thermal
radiation, a dummy uni-couple device made of two legs of the
Zr0.44Hf0.44Ti0.12NiSn0.9Sb0.01 material was fabricated and
measured. The thermocouples were soldered on the DBC
substrates to measure the temperature on both sides of the leg.
The thermal flow was calculated based on the thermal conductivity
of Zr0.44Hf0.44Ti0.12NiSn0.9Sb0.01 material and the temperature
of two sides of the leg (Fig. S12).

Data availability
All data are available in the main text and the Supplementary
Materials.

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39. Nozariasbmarz, A. et al. High power density body heat Competing interests
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to the peer review of this work. A peer review file is available.
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Thermo- electric Modules: A Pathway toward Practical
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Publisher’s note Springer Nature remains neutral with regard to
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Acknowledgements
Open Access This article is licensed under a Creative Commons
Funding. We acknowledge Dr. Hsing Wang for the round-robin
Attribution 4.0 International License, which permits use, sharing,
test of thermoelectric materials and Kai Wang for the crystal
adaptation, distribution and reproduction in any medium or format,
structure drawing. H.Z. acknowledges the financial support
as long as you give appropriate credit to the original author(s)
through the Office of Defense Advanced Research Projects
and the source, provide a link to the Creative Commons license,
Agency (DARPA) under the pro- ject of Nano Engineered
and indicate if changes were made. The images or other third
Thermoelectric Systems (NETS). W.L. and B.P. acknowledge the
party material in this article are included in the article’s Creative
financial support through the Office of Naval Research through
Commons license, unless indicated otherwise in a credit line to
grant number N00014-20-1-2602. This effort (A.N. and S.P.),
the material. If material is not included in the article’s Creative
including the data analysis and interpretation, was supported as
Commons license and your intended use is not permitted by
part of the Center for 3D Ferroelectric Microelectronics (3DFeM), an
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Energy Frontier Research Center funded by the U.S.
to obtain permission directly from the copyright holder. To view
Department of Energy (DOE), Office of Science, Basic Energy
a copy of this license, visit http://creativecommons.org/
Sciences under Award Number DE-SC0021118. N.L.
licenses/by/4.0/.
acknowledges the support from National Science Foundation (NSF)
planning grant, TERRM. Y.Z. acknowledges the support from the
© The Author(s) 2023
Army SBIR program supported by NanoOhmics.

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