pubs.acs.

org/cm Article

Engineering Electronic Structure and Lattice Dynamics to Achieve

Enhanced Thermoelectric Performance of Mn−Sb Co-Doped GeTe
Ashutosh Kumar,* Preeti Bhumla, Taras Parashchuk, Stanislaw Baran, Saswata Bhattacharya,*
and Krzysztof T. Wojciechowski*
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ABSTRACT: GeTe, as a p-type semiconductor, has been

intensively studied in recent years as a promising lead-free mid-
temperature-range thermoelectric (TE) material. Herein, we report
an improved energy conversion efficiency (η) using a two-step TE
properties optimization in Mn−Sb co-doped GeTe by engineering
electronic structure and lattice dynamics. Mn−Sb co-doping
enhances the TE properties of GeTe, as evidenced from both
experiments and first-principles-based theoretical calculations. The
density functional theory (DFT) calculations indicate that Mn−Sb
co-doping improves the band convergence and optimizes the Fermi level position. This in turn helps in enhancing the Seebeck
coefficient (α). As a result of the optimized Seebeck coefficient and electrical conductivity (σ), an enhanced power factor (α2σ) is
obtained for the Mn−Sb co-doped system. Moreover, a significant reduction in the phonon (lattice) thermal conductivity (κph ∼
0.753 W/mK) at 748 K is observed for Ge0.87Mn0.05Sb0.08Te, attributed to the point-defect scattering and reduced phonon group
velocity. The synergistic improvement in α and reduction in κph result in a maximum figure-of-merit (zT) of 1.67 at 773 K, with an
average zT (zTav) of ∼ 0.9 for Ge0.87Mn0.05Sb0.08Te over a temperature range of 300−773 K, leading to an η of ∼12.7%.

1. INTRODUCTION parameters with a trade-off relationship is challenging to

Thermoelectric (TE) materials, capable of bidirectional achieve a high zT in a single system. In recent times,
conversion of heat energy to electrical power, are propitious advancement in the TE properties has been elicited by
remedies for the global energy problem.1,2 The promising innovative transport mechanisms: (a) optimization of the
application of TE devices requires a high conversion efficiency electrical transport performance5−9 and (b) reduction of
(η), defined as thermal conductivity in a single system.10−12
Among the promising TE materials, the IV−VI-based
ΔT 1 + zTav − 1 chalcogenides (GeTe, PbTe, SnTe) possess attractive TE
η= TC properties in the intermediate temperature range (∼500−800
TH 1 + zTav + TH (1) K) due to their unique band structure, high carrier mobility,
1 T and inherently low κph.13−15 However, the GeTe system
with a high zTav = TH − TC
∫T H zT dT across a wide temperature possesses intrinsic Ge vacancies, leading to a high hole carrier
concentration (n ∼ 1021 cm−3), large σ (∼8000 S/cm), and
C
difference (ΔT = TH − TC) between the hot (TH) and cold
(TC) temperature ends of the device, gauged using the TE small α ∼ 28 μV/K at 300 K, resulting in inferior TE
figure-of-merit (zT), which is determined using the intertwined properties. GeTe also displays a second-order phase transition
properties of the material,3 i.e., (∼700 K) from a high-temperature cubic (Fm-3m) to a low-
temperature rhombohedral (or hexagonal) structure (R3m).
α 2σ There has been a recent surge of interest in GeTe focusing on
zT = T
κ (2) optimizing the TE properties and suppressing the transition
temperature to achieve its better functionality during practical
where α and σ are the Seebeck coefficient and electrical
conductivity, respectively, κ = (κe + κph) is the thermal
conductivity [consisting of carrier thermal conductivity (κe) Received: January 29, 2021
and phonon (lattice) thermal conductivity (κph)], and T is the Revised: April 30, 2021
absolute temperature. A potential TE material should possess a Published: May 11, 2021
high α, large σ, and inferior κ (the “phonon−glass−electron−
crystal” concept suggested by Slack4) for promising practical
applications. However, the strong coupling between these

© 2021 American Chemical Society https://doi.org/10.1021/acs.chemmater.1c00331

3611 Chem. Mater. 2021, 33, 3611−3620
Chemistry of Materials
applications.16−23 The realization of a high zT heavily depends
on an optimized carrier concentration (n ∼ 1019−1020 cm−3),
along with band engineering,24 and reducing the κph via
hierarchical architecture engineering,25 defect engineering,26 a
composite approach,27−29 and other multiscale scattering
centers.30,31
As mentioned above, several strategies, including alloying
and band-structure modifications, have been adopted to reduce
the high hole carrier concentration and improve the α in
GeTe.13,32−38 The aliovalent dopants like Bi3+ and Sb3+ at the
Ge2+ site reduce the carrier concentration and decrease κph due
to phonon scattering through solid-solution point defects.7
Such doping also reduces the phase transition temperature to
∼300 K for a doping concentration of ∼10%; however, large
aliovalent doping reduces the electrical conductivity signifi-
cantly.39−41 On the other hand, Mn doping in GeTe has been
an effective strategy to promote band convergence, viz. (i)
decreasing the energy difference between the light and heavy
hole bands and (ii) increasing the symmetry using hexagonal
to cubic transition lead to an increase in the carriers’ effective
mass.33 The Mn doping further improves the carrier
concentration (n) in GeTe. It is noted that the presence of
intrinsic vacancies in GeTe results in a high carrier
concentration (∼1021 cm−3) and deepens the Fermi level
(EF) in the valence band. With an increase in Mn doping in
GeTe, n improves and it further deepens the Fermi level in the
valence band, which is not beneficial for the TE performance.
Also, a higher Mn (∼10%) content at the Ge site reduces the
carrier mobility significantly due to induced spin scattering and
does not improve the overall zT.33,42 Hence, optimized co-
doping of Mn and Sb in GeTe is required for a synergistic
effect of enhanced band convergence and optimized Fermi
level position that improves the Seebeck coefficient, which is
essential for a high TE performance in GeTe. This study
demonstrates enhanced TE properties in Mn and Sb co-doped
GeTe via electronic structure (optimized Fermi level position,
carrier concentration, and band convergence) and lattice
dynamics (reduced phonon velocity) engineering. The precise
band-structure calculation for the Mn−Sb co-doped GeTe is
performed systematically to re-establish the experimental
results using density functional theory (DFT) calculations.
Furthermore, the phonon dispersion calculation considering
Ge vacancies in GeTe and Mn−Sb co-doped GeTe was carried
out to understand the atypical lowering of κph.
2. RESULTS AND DISCUSSION
2.1. Structural Characterization. The X-ray diffraction
(XRD) pattern for Ge1−x−yMnxSbyTe for the 0 ≤ x ≤ 0.05, 0 ≤
y ≤ 0.08 sample after pulsed electric current sintering (PECS)
is shown in Figure 1. All of the samples display a similar
diffraction pattern and indicate the single-phase formation.
The characteristic doublet peaks in the 2θ range from 23 to
27° and 41 to 45° confirm the rhombohedral structure at 300
K. A small impurity trace due to Ge is observed at 27° for x =
0.01, y = 0.01. The XRD patterns are further analyzed using
Reitveld refinement. The refinement pattern for the
Ge1−x−yMnxSbyTe sample for GeTe and Mn−Sb co-doped
GeTe is shown in Figure S1a−d; the corresponding refinement
parameters are shown in Table SI. It is noted that the lattice
parameters of the a-axis increase slightly with Mn doping at the
Ge site; however, the values of the c-axis decrease, which agrees
with the reports in the literature.41 This increase in the lattice
parameter of the a-axis is attributed to the higher ionic radius
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Figure 1. X-ray diffraction pattern for Ge1−x−yMnxSbyTe (0 ≤ x ≤
0.05, 0 ≤ y ≤ 0.08). Bragg’s position and corresponding Miller indices
are marked.
of Mn (0.140 nm) than that of Ge (0.125 nm). The lattice
parameter (c-axis) decreases with the increase in the Mn−Sb
co-doping in the system. The unit cell volume also reduces
accordingly, which agrees with the previous study on GeTe.33
The scanning electron microscope (SEM) images for
Ge1−x−yMnxSbyTe (0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08) are shown
in Figure S2a−f. The figure shows that the samples are
homogeneous in the microscale range, further confirming the
single-phase formation. The elemental composition obtained
from the energy-dispersive X-ray spectroscopy (EDXS)
measurement is shown in the respective SEM image’s inset
(Figure S2). The Ge deficiency (Ge0.962Te) is obtained from
the EDXS analysis and is attributed to the lower formation
energy for Ge vacancies.43 Further, the elemental compositions
for Mn and Sb doped samples are in approximate agreement
with the nominal composition, which further confirms the
samples’ homogeneous nature.
2.2. Electrical Transport Properties. TE material
homogeneity is essential for efficient energy conversion since
the large spatial variation in the Seebeck coefficient (α) due to
inhomogeneity can cause the formation of eddy currents,
leading to loss of energy. The spatial distribution of α is
measured on the Ge1−x−yMnxSbyTe (0 ≤ x ≤ 0.05, 0 ≤ y ≤
0.08) sample surface (3.0 mm × 3.0 mm) with a step size of 50
μm using the scanning thermoelectric microprobe (STM) and
is shown in Figure 2a−d. The distribution of α across the
sample surface is fitted using a Gaussian function. The narrow
distribution of α indicates the homogeneous nature of the
samples. The average value of α for GeTe at 300 K is 29 μV/K,
which increases for the Mn and Sb co-doped GeTe (44 μV/K
for x = 0.05, y = 0.00, 72 μV/K for x = 0.05, y = 0.05, and 86
μV/K for x = 0.05, y = 0.08).
The temperature-dependent electrical conductivity (σ) for
Ge1−x−yMnxSbyTe (0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08) is shown in
Figure 3a. The σ for all the samples decreases monotonically
with the increase in temperature, depicting the degenerate
semiconductor nature. Also, Mn doping at the Ge site
increases the carrier concentration (n). The overall atomic
ratio between cations (Ge + Mn) and anions (Te) decreases as
the Mn content increases, which means that the concentration
of Ge vacancies increases, resulting in an increase in the carrier
concentration from 8.9 × 1020 cm−3 for pristine GeTe to 1.23
× 1021 cm−3 for Ge0.95Mn0.05Te. However, σ decreases due to
https://doi.org/10.1021/acs.chemmater.1c00331
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Figure 2. Spatial variation of Seebeck coefficient (α) for Ge1−x−yMnxSbyTe: (a) x = 0.00, y = 0.00; (b) x = 0.05, y = 0.00; (c) x = 0.05, y = 0.05; and
(d) x = 0.05, y = 0.08 using the scanning thermoelectric microprobe at 300 K.

measurement from the STM. The rise in α with Mn doping is

attributed to the band convergence increase (discussed later).
The Sb doping reduces the carrier concentration and optimizes
the Fermi level position, improving the Seebeck coefficient.
The α increases with an increase in temperature for all of the
samples and is consistent with the decrease in σ.
The dependence of α on carrier concentration (n) at 300 K
with different effective masses using the two-band model is
shown by the solid lines in Figure 3c. The α as a function of n
is determined using the Kane model and two-band
approximation and assuming the acoustic phonons (r = 0) as
the primary scattering mechanism.46 For calculations, the
degree of the band-structure nonparabolicity is accounted for
using a parameter β = kBT/eg,47 where kB is the Boltzmann
constant, T is the temperature, and eg is the band gap. The
Seebeck coefficient in the two-band approximation is defined

ÄÅ 1 ÉÑ
by the expression48

kB ÅÅÅÅ Ir + 1/2(η*, β) ÑÑ
Ñ
α=− ÅÅ 0 − η*ÑÑÑ
e ÅÅÅÇ Ir + 1/2(η*, β) ÑÑ
ÑÖ
Figure 3. Temperature-dependent (a) electrical conductivity (σ), (b)
Seebeck coefficient (α), (c) room-temperature carrier concentration (3)
(n) dependence of α (Pisarenko plot), compared with literature
(Zheng et al.,33 Perumal et al.,39 Lee et al.,41 and Li et al.44), and (d) where e is the charge of the electron, r is the scattering
temperature-dependent power factor (α2σ) for Ge1−x−yMnxSbyTe (0 parameter, η* = (EF − EV)/kBT is the reduced Fermi energy,
p,k(n*, β) are two-parametric Fermi integrals
48
≤ x ≤ 0.05, 0 ≤ y ≤ 0.08). and Im
∞i
jj− df yzz x (x + βx ) dx
j z
m 2 p

k dx { (1 + 2βx)
the reduced carrier mobility (μ) caused by induced spin I pm, k(η*, β) = ∫0 k
scattering.42 Further, Mn−Sb co-doped GeTe samples also (4)
show a reduction in σ at 300 K (∼7400 S/cm for GeTe to With the obtained values of η* for the nonparabolic valence
∼3796 S/cm in Ge 0.95 Mn 0.05 Te to 1150 S/cm for band, the carrier concentration (n) could be defined by the
Ge0.87Mn0.05Sb0.08Te). The decrease in σ with Sb doping is following expression
ascribed to a reduction in the carrier concentration from ∼1.23
× 1021 cm−3 in Ge0.95Mn0.05Te to ∼3.74 × 1020 cm−3 in (2md,0kBT )3/2 0
Ge0.87Mn0.05Sb0.08Te at 300 K. n= I3/2,0(η* , β )
The temperature-dependent Seebeck coefficient (α) of the 2π 2h3 (5)
Ge1−x−yMnxSbyTe (0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08) samples is where md,0 = N2/3V (mn*) (m⊥
1/3
*)2/3 is the band-edge density of
shown in Figure 3b. The Seebeck coefficient of the samples states effective mass and NV is the band degeneracy.47,48 The
indicates the p-type nature of transport and is consistent with carrier concentration increases with Mn doping (solid black
the previous studies.45 A small α (∼27 μV/K) is observed for circles in Figure 3c) and indicates an improvement in the
GeTe at 300 K and is consistent with the STM analysis. The α effective mass on the Pisarenko plot. Further, the Mn−Sb co-
increases with the increase of Mn and Sb content in GeTe doping shows a lowering of the carrier concentration (solid red
(from 27 μV/K (GeTe) to 46 μV/K (Ge0.95Mn0.05Te) to 93 star in Figure 3c), and the effective mass seems to be higher in
μV/K (Ge0.87Mn0.05Sb0.08Te) at 300 K). The change in α with the co-doped case. In the present study, the effective mass
Mn−Sb co-doping in GeTe at 300 K re-establishes the increases with Mn and Sb doping in GeTe. It increases from
3613 https://doi.org/10.1021/acs.chemmater.1c00331
Chem. Mater. 2021, 33, 3611−3620
Chemistry of Materials pubs.acs.org/cm Article

0.69 (GeTe) to 1.84 for Ge0.95Mn0.05Te to 2.35 for To quantify the effect of Mn−Sb co-doping on the electrical
Ge0.87Mn0.05Sb0.08Te (Table 1). This indicates that the Sb transport in GeTe, the effective mass for the carriers has been
calculated using the experimental α and n measured at 300 K
Table 1. Transport Parameters (Electrical Conductivity (σ), for Ge1−x−yMnxSbyTe (0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08) and is
Seebeck Coefficient (α), Carrier Concentration (n), shown in Table 1. The increase in the effective mass is
Mobility (μ), and Effective Mass (m*/m0)) Obtained at 300 observed for Mn-doped and Mn−Sb co-doped samples and
K for Ge1−x−yMnxSbyTe (0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08) further supports the increase in the Seebeck coefficient in both
cases.
σ α n μ
sample (S/cm) (μV/K) (1020 cm−3) (cm2/(V·s)) m*/m0 The temperature variation of the power factor (α2σ) is
x = 0.00, 7408 27 8.90 52.0 0.69
shown in Figure 3d. The power factor for the Mn-doped
y = 0.00 sample increases with an increase in temperature, attributed to
x = 0.01, 5894 32 7.38 49.1 0.78 the enhancement of α with minimal reduction in σ. A slight
y = 0.00 decrease of σ is obtained in the present study for x = 0.05.
x = 0.02, 4745 41 10.50 28.2 1.40 However, a higher Mn addition in GeTe reduces σ significantly
y = 0.00
due to the increased spin scattering that reduces carrier
x = 0.05, 3796 46 12.30 19.3 1.84
y = 0.00 mobility.33 Further, the power factor for Mn−Sb co-doped
x = 0.01, 5087 35 6.31 50.3 0.79 samples increases due to a noticeable increase in α. The power
y = 0.01 factor for Ge0.87Mn0.05Sb0.08Te at 300 K is 995 μW/m·K2 and
x = 0.02, 3242 54 4.21 48.1 1.12 reaches a maximum of 3361 μW/m·K2 at 673 K. The
y = 0.02 enhancement in α2σ with the temperature rise for co-doped
x = 0.05, 1632 76 4.11 24.8 1.87 samples is ascribed to an increase in the Seebeck coefficient
y = 0.05
x = 0.05, 1151 93 3.74 19.2 2.35 with temperature.
y = 0.08 To understand the experimental observation regarding the
electronic transport properties in the Mn−Sb co-doped GeTe
doping also improves the effective mass due to the dominating system, density functional theory (DFT) calculations were
conduction of the heavy hole valence band over the light hole performed to estimate the electronic band structure and
valence band.40 The Sb doping shows a higher effective mass density of states for pristine, Mn-doped, and Mn−Sb co-doped
(as shown in the Pisarenko plot) in the literature.39,44 GeTe. In the present calculations, the principal valence band
However, it is worth noting that it is hard to compare the (light hole) maximum (VBM) and conduction band minimum
precise values of effective mass obtained directly by different (CBM) occur at the Γ point due to the folding of the L point
approximations (e.g. the single parabolic band model and Kane onto Γ. For the electronic structures of cubic and
model) and the usually unknown values of the band gap, the rhombohedral Ge24Te24, we obtain a band gap (eg) of 0.22
offset between bands, etc. used for calculations. The improve- and 0.52 eV, respectively, which agree with the earlier
ment in α with the Mn doping is attributed to the increase in theoretical calculations and experimental results.40,49 Since
the band degeneration.46 The increase in α with Mn−Sb co- the pristine GeTe shows a high hole carrier concentration due
doping is corroborated by the simultaneous effect of a decrease to intrinsic Ge vacancies, the same has been considered for
in carrier concentration and enhanced band degeneracy. estimating the electronic structure. The experimental carrier

Figure 4. Electronic band structures of rhombohedral (a) Ge22Te24, (b) Ge21MnTe24, (c) Ge20MnSbTe24, and (d) Ge19MnSb2Te24. The Ge
vacancies are considered during the calculation to attest to the high carrier concentration. The band gap appears at the Γ point in a 2 × 2 × 2
supercell containing 48 atoms. The VBM and CBM occur at the L point in the pristine GeTe fold onto the Γ point in the supercell. (e) Density of
states of pristine GeTe (Ge24Te24), GeTe with Ge vacancies (Ge22Te24), Mn-doped GeTe (Ge21MnSb24), and Mn−Sb co-doped GeTe
(Ge20MnSbTe24, Ge19MnSb2Te24) samples.

3614 https://doi.org/10.1021/acs.chemmater.1c00331
Chem. Mater. 2021, 33, 3611−3620
Chemistry of Materials
concentration typically varies from 8 × 1020 to 1.5 × 1021 cm−3
for pure GeTe, roughly corresponding to the 4.3−8.1% Ge
vacancies, respectively, if we consider one hole per atom.45
The electronic band structure for Ge22Te24 is shown in
Figure 4a. Further, systematically, (i) one Mn (Figure 4b), (ii)
one Mn and one Sb (Figure 4c), (iii) one Mn, and two Sb
atoms in place of Ge in the GeTe supercell were substituted
(Figure 4d). A new impurity/donor band arises from the Mn
state33 in Mn-doped GeTe, which reduces the band gap of
GeTe. For the Mn−Sb co-doped case, the energies of the two
configurations were calculated (Figure S3), showing that (i)
Mn and Sb atoms are close to each other, and (ii) they are far
from each other in other cases. The latter configuration is
lower in energy than the former, making it more stable, and
hence the calculations proceeded with the second config-
uration.40 The co-doping of Mn and Sb at Ge in GeTe
(Ge19MnSb2Te24) further decreases the energy separation
between the two valence bands, ΔEΓ, to 0.09 eV. Therefore,
the carrier transport is strongly affected by the heavy holes.
Hence, these calculation results show that Mn−Sb co-doping
in GeTe enhances the valence band convergence and confirms
the obtained increase in the Seebeck coefficient.
To gain further insights, we plotted the density of states
(DOS) of pristine Ge24Te24, Ge22Te24 (with Ge vacancies),
Ge21MnTe24 (Mn-doped), Ge20MnSbTe24, and
Ge19MnSb2Te24 (Mn−Sb co-doped) as shown in Figure 4e.
The Fermi level position is critical to optimize the TE
performance of any system. A high hole carrier concentration
due to the intrinsic Ge vacancies in GeTe deepens its Fermi
level in the valence band. Hence, the charge carriers below the
Fermi level compensate for the energy transported by the
charge carriers above the Fermi level, leading to a lower α.50
The density of states (DOS) plot reveals that the Fermi level
lies in the middle of the band gap for pristine Ge24Te24;
however, with the Ge vacancies, the Fermi level lies deep in the
valence band and is in line with the high carrier concentration
obtained in GeTe. The Mn doping in GeTe also increases the
carrier concentration, resulting in the positioning of EF deeper
in the valence band. The decrease in the energy offset between
the valence band edges with Mn doping results in a band
convergence, as shown in the band-structure calculations.
Therefore, the combination of both the factors, viz. band
convergence and the Fermi level’s deeper positioning, explains
the increase in the Seebeck coefficient with the increase in
carrier concentration in Mn-doped GeTe. The Sb doping
forms donor states below the conduction band of pure GeTe
and the Fermi level shifts toward the valence band edge, and
hence a decrease in the hole carrier concentration is observed
(Table 1). A similar nature of DOS is shown for Sb−Bi co-
doped GeTe.40 Moreover, Mn−Sb co-doping makes the DOS
steeper, especially near the valence band edge. This sharper
DOS feature signifies a higher effective mass and is beneficial
for improving the Seebeck coefficient.42 The Fermi level lies in
the valence band for both Mn and Sb co-doping, which is due
to the larger Ge vacancies considered during theoretical
calculations.45
The experimental measurements of the Seebeck coefficient
agree well with the DFT calculations. For the pristine GeTe,
the heavy hole band is located ∼0.21 eV deeper than the light
hole band. Even for high carrier concentrations (up to 1021
cm−3), the carrier transport is defined by the light hole band
because the estimated position of the Fermi level is only
∼0.091 eV (the effect of the heavy hole band is negligible). As
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a result, we observed a high electrical conductivity, relatively
low effective mass, and low Seebeck coefficient at 300 K for
pristine GeTe (Table 1). With the Mn doping, the energy
offset between the valence band edges (heavy and light bands)
decreases with the simultaneous increase of the concentration.
As a result of the joint transport of heavy and light holes, we
observed the logical increase of the effective mass and
enhancement of the Seebeck coefficient. On the other hand,
Mn-doped GeTe samples show a significant decrease in
mobility (Table 1) due to increased effective mass and
introduction of spin scattering due to the Mn state.42 The
utilization of co-doping with Sb shifts the Fermi level toward
the conduction band due to the self-compensation effect of
holes by electrons. Finally, the Mn−Sb co-doped GeTe system
significantly enhances the Seebeck coefficient. Therefore, the
synergistic effects of Mn and Sb co-doping ameliorate the TE
performance of GeTe.
2.3. Thermal Transport Properties. The temperature
dependence of thermal conductivity (κ) for Ge1−x−yMnxSbyTe
for 0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08 is shown in Figure 5a. The κ of
Figure 5. Temperature-dependent (a) total thermal conductivity (κ)
and (b) phonon thermal conductivity (κph) for Ge1−x−yMnxSbyTe 0 ≤
x ≤ 0.05, 0 ≤ y ≤ 0.08. The inset shows κph as a function of the Mn
and Sb contents in the GeTe system at 300 K. The κph is fitted using
the Debye−Callaway model for Mn-doped GeTe.
the pristine GeTe rapidly decreases with increasing temper-
ature until it reaches the transition temperature, which is above
700 K.33 The decrease in κ is observed with Mn substitution. It
further reduces with the increase in temperature. The κ for the
Mn−Sb co-doped GeTe samples also shows a similar behavior
with temperature. However, the decrease in κ is prominent for
the Mn−Sb co-doped samples.
Since κ consists of lattice thermal conductivity (κph) and
thermal conductivity due to charge carriers (κe), i.e., κ = κe +
κph, it indicates that the reduction in κ is due to the decrease in
σ (κe) and κph. The κe is determined using the Wiedemann−
Franz law: κe = LσT, where L is the Lorenz number and is
2Å 2
Ä ÉÑ
ij kB yz ÅÅÅÅ Ir + 1/2(η*, β) Ir1+ 1/2(η*, β) ÑÑÑ
calculated using the formula
L = jjj zzz ÅÅ 0 ÑÑ
k e { ÅÅÅÇ Ir + 1/2(η*, β) Ir + 1/2(η*, β) ÑÑÑÑÖ
− 0
(6)
The reduced Fermi energy (η*) can be derived by fitting α
using eq 3 for the acoustic phonon scattering of charge carriers.
Further, κph is extracted by subtracting κe from κ. The
temperature-dependent Lorenz number (L) calculated and the
corresponding electronic thermal conductivity (κe) are shown
in Figure S4.
The temperature-dependent κph for Ge1−x−yMnxSbyTe (0 ≤
x ≤ 0.05, 0 ≤ y ≤ 0.08) is shown in Figure 5b. It decreases
with an increase in temperature for all of the samples. The κph
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Chem. Mater. 2021, 33, 3611−3620
Chemistry of Materials
Figure 6. Phonon dispersion curve for (a) Ge24Te24 and (b) Ge21MnSb2Te24 in a rhombohedral structure.
decreases with Mn doping from 3.80 W/m·K (GeTe) to 2.52
W/m·K (Ge0.95Mn0.05Te) at 300 K due to the increased point-
defect scattering.42 This decrease in κph with Mn doping is
analyzed using the Debye−Callaway model.51,52 The point-
defect scattering in solid solution is originated due to both
mass fluctuation and strain field fluctuations. The ratio of
phonon thermal conductivity of the materials with point
defects (κph) to the parent system (κpph), above the Debye
κ ph tan−1(u)
temperature (θD), is given by the expression p
κ ph
= u
.
1/2
π 2θDΩ
Here, the parameter u is defined as u = ( hva2
p
κ ph Γ)
where Ω, h, and va are the average volume per atom, Planck
constant, and average sound velocity, respectively.50 The
scattering parameter Γ, which signifies the strength of the
point-defect scattering, consists of two parts: scattering
parameter due to mass (ΓM) and strain field (ΓS) fluctuation
with a adjustable parameter ϵ included due to uncertainty in
ΓS, i.e., Γ = ΓM + ϵΓS.51 The scattering parameters obtained for
the Mn-doped samples are shown in Table SII. The phonon
thermal conductivity calculated using the Debye−Callaway
model for Mn-doped GeTe (shown by the solid line in the
inset of Figure 5b) is in excellent agreement with the
experimentally observed values, which confirms that the
point-defect scattering due to mass and strain field fluctuation
in Mn-doped GeTe leads to reduced phonon thermal
conductivity. The κph reduces significantly in Mn−Sb co-
doped samples compared to single Mn doping at 300 K (inset
of Figure 5b). This suggests that the phonon scattering is
enhanced for Mn−Sb co-doped GeTe.
The origin of reduction in the lattice thermal conductivity in
the Mn−Sb co-doped GeTe can be understood using the
phonon dispersion curve. The phonon dispersion calculation
for pristine GeTe and Mn−Sb co-doped GeTe was performed.
Firstly, to examine the thermal stability, the phonon
dispersions of both rhombohedral and cubic GeTe using the
phonopy code were plotted.53 It is worth noting that the
phonon dispersion of cubic GeTe exhibits various imaginary
modes (Figure S5) in the Brillouin zone, due to which cubic
GeTe is generally unstable at ambient conditions. On the
contrary, real modes are present in the rhombohedral phase,
making it thermodynamically stable. Therefore, further doping
studies were performed on the rhombohedral phase. The
phonon dispersion curve considering Ge vacancies (similar to
the one used for electronic band-structure calculations) for
pristine GeTe (Ge22Te24) is shown in Figure S6. The
corresponding ω vs k curve is slightly lower than that of the
pubs.acs.org/cm Article
pristine GeTe (Figure 6a) and is attributed to the defect
(vacancy) scattering. However, due to technical challenges in
accommodating so many defects inside a supercell to compute
the phonon band structure accurately for Mn−Sb co-doped
GeTe considering Ge vacancies, the phonon dispersion curve
i s c a l c u l a te d o n l y f o r Mn− S b c o - d o p e d G e T e
(Ge21MnSb2Te24). Nevertheless, a similar effect of these two
Ge vacancies for the Mn−Sb co-doped system on the
dispersion curve is expected as obtained in the case of
Ge22Te24 (Figure S6) if one computes the same with intrinsic
Ge vacancies.
, Figure 6a,b shows the phonon dispersion plot for Ge24Te24
and Ge21MnSb2Te24, respectively, in the rhombohedral
structure. The phonon dispersion curve for pristine GeTe is
consistent with the previous studies.42,54 The Mn doping in
GeTe (Ge23MnTe24) does not alter the phonon dispersion
curve, including acoustic and optical modes at lower
frequencies, and agrees with the results shown by Liu et al.42
However, the phonon dispersion curve for Mn−Sb co-doped
GeTe (Ge21MnSb2Te24) shows a substantial decrease in the
phonon dispersion curve slope, as shown in Figure 6b. In
general, the phonon dispersion is indicated by the ω vs k plot,
and the gradient of ω vs k curve gives the vg (phonon group
velocity), where vg = dω/dk. As shown in Figure 6b, the
gradient or slope of the phonon curve for the Mn−Sb co-
doped system is lower than that of pristine GeTe. This
suggests that the mean phonon group velocity decreases for a
Mn−Sb co-doped sample compared to pristine GeTe, resulting
in a lower lattice thermal conductivity. The decrease in the
slope of the phonon dispersion curve for Sb doping can be
attributed to the large mass (M) of Sb, as ω ∝ M−1/2. Further,
to get insights into the charge transfer, the charge density
contours for Ge24Te24 and Ge21MnSb2Te24 are shown in
Figure S7. It may be noted that there is a charge transfer
between Sb and Ge atoms, which further stabilizes the bond.
This tightly coupled bond due to the charge transfer hinders
the free vibration of atoms and results in lowering the phonon
group velocity. The sound velocities measured for all samples
are shown in Table SIII. The longitudinal and transverse sound
velocities experimentally obtained for pristine GeTe are 3490
and 2230 m/s, respectively, which decrease to 3220 and 1870
m/s for the co-doped sample with x = 0.05, y = 0.08. This
further confirms that the Mn and Sb doping decreases the
sound velocities, leading to a reduction in the lattice thermal
conductivity.
2.4. Thermoelectric Figure-of-Merit and Efficiency.
Using the TE parameters α, σ, and κ, the figure-of-merit (zT)
3616 https://doi.org/10.1021/acs.chemmater.1c00331
Chem. Mater. 2021, 33, 3611−3620
Chemistry of Materials
is calculated for Ge1−x−yMnxSbyTe for 0 ≤ x ≤ 0.05, 0 ≤ y ≤
0.08 samples, and is shown in Figure 7a. It is observed that the
Figure 7. (a) Temperature-dependent figure-of-merit (zT), (b)
average figure-of-merit (zTav) for Ge1−x−yMnxSbyTe for 0 ≤ x ≤ 0.05,
0 ≤ y ≤ 0.08, (c) comparison of zTav obtained in the present study
with the reports in literature for similar systems,11,33,41,55 and (d) the
energy conversion efficiency (η) for Ge1−x−yMnxSbyTe for 0 ≤ x ≤
0.05, 0 ≤ y ≤ 0.08.
maximum value of zT obtained for GeTe is ∼0.9 at 720 K and
is consistent with the report in the literature.39 The addition of
Mn doping in GeTe also increases the zT; however, the
increase in zT is prominent for the Mn−Sb co-doped samples.
This is corroborated by the simultaneous increase in the
Seebeck coefficient and a decrease in thermal conductivity.
The maximum zT of 1.67 is observed for the
Ge0.87Mn0.05Sb0.08Te sample at ∼773 K.
For practical application, the average zT (zTav) is essential
rather than the maximum zT. In the present study, using the
lower and higher limits of the temperature as 300 and 773 K,
respectively, zTav is calculated and is shown in Figure 7b. The
maximum value of zT a v (∼ 0.9) is obtained for
Ge0.87Mn0.05Sb0.08Te for a ΔT of 473 K, which is promising
for making practical TE devices. Comparison of the zTav
obtained in the present study with the literature reports is
shown in Figure 7c. Further, the theoretical energy conversion
efficiency (η) is calculated for Ge0.87Mn0.05Sb0.08Te (p-type) by
assuming a similar n-type leg for a temperature difference
(ΔT) of 473 K, as shown in Figure 7d. The maximum
efficiency (η) obtained in the present study is ∼12.7% for
Ge0.87Mn0.05Sb0.08Te, higher than for several other systems
reported in the literature.11,20,33,41,55−58
3. CONCLUSIONS
This study demonstrates the enhanced thermoelectric proper-
ties in Mn−Sb co-doped GeTe, explained using the electronic
structure and lattice dynamics engineering. The samples
synthesized using the melting−quenching−sintering process
show a single-phase formation. The scanning electron
microscopy and energy-dispersive x-ray spectroscopy analyses
indicate the sample’s homogeneous nature, which is further
established using a scanning thermoelectric microprobe
(STM) analysis of the Seebeck coefficient (α). The average
3617
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value of α, obtained from the STM analysis at 300 K, increases
with Mn and Sb doping in GeTe. The experimental
observation shows an increase in α and decreased electrical
conductivity with Mn and Sb doping in GeTe. These are
ascribed to the simultaneous effect of an improved band
convergence (higher effective mass of carriers) and a reduced
carrier concentration. The first-principles density functional
theory (DFT) calculations suggest that Mn−Sb co-doping
sharpens the density of states and improves the band
convergence along with an optimized Fermi level position,
hence indicating an increase in α. The power factor for all of
the samples increases with temperature and is attributed to an
increase in α. The total thermal conductivity (κ) decreases
with Mn−Sb doping at 300 K and also with increase in
temperature. The phonon thermal conductivity (κph) at 300 K
suggests that the phonon scattering is strong for Mn and Sb co-
doped samples and agrees with the reduced phonon group
velocity obtained from the phonon dispersion curve and sound
velocity measurement. The reduction in κ and increase in α
result in a maximum zT of ∼ 1.67 at 773 K for
Ge0.87Mn0.05Sb0.08Te with an average zT (zTav) of ∼ 0.9
from 300 to 773 K, leading to a maximum efficiency (η) of
12.7%. This work shows the potential to enhance the TE
performance of GeTe by the simultaneous effect of electronic
structure and phonon dynamics engineering.
4. EXPERIMENTAL METHODS
4.1. Synthesis and Structural Characterization. The synthesis
of Ge1−x−yMnxSbyTe for 0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08 was carried out by
direct melting of elements (Ge, Mn, Sb, and Te) with purity >99.99%
(Alfa Aesar) in evacuated quartz ampoules. The ampoules were
heated at 1273 K for 10 h at a heating rate of 100 K/h followed by
quenching in water. The obtained ingots were ground to mixed
homogeneously. The samples for measurement were then compacted
in a cylindrical form having 10 mm diameter and 12−13 mm height
using the pulsed electric current sintering (PECS) technique. The
sintering was done in Ar (5N) atmosphere using the following
parameters: heating rate of 70 K/min and sintering temperature of
873 K with a hold time of 20 min at an uniaxial pressure of 50 MPa.
The sintered pellets were further cut to proper dimensions for
electrical and thermal transport measurements. The surface
morphology and chemical analysis were performed on the polished
surface using a scanning electron microscope (SEM) with an EDXS
analyzer. After sintering, the X-ray diffraction of samples was obtained
using the D8 ADVANCE (BRUKER) diffractometer (λ = 1.5406 Å).
The obtained XRD pattern was further analyzed by Rietveld
refinement using FullProf software.
4.2. Electrical and Thermal Transport Properties. The spatial
distribution of the Seebeck coefficient (α) on the Ge1−x−yMnxSbyTe
(0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08) sample surface was analyzed using a
scanning thermoelectric microprobe (STM) at 300 K with a step size
of 50 μm. The temperature-dependent electrical conductivity (σ) and
α were measured simultaneously using an SBA 458 (NETSCH)
apparatus under Ar (5N) atmosphere (50 mL/min). The sample
dimensions for this measurement were 10 mm × 10 mm × 2 mm.
Thermal conductivity (κ = DCpρ) was obtained from the thermal
diffusivity (D), specific heat (Cp), and sample density (ρ) of the
cylindrical pellets with 10 mm diameter and ∼2 mm thickness. The D
and Cp measurements were performed simultaneously using the laser
flash technique (LFA-457, NETSCH). The Cp was measured using
the Pyroceram 9606 (NETSCH) sample as reference material. The
sample density (ρ) was measured using the mass of the pellet and its
volume. The uncertainty in the measurement of α and σ is 7 and 5%,
respectively; the estimated uncertainty in κ is 7%. The carrier
concentration (n) of the samples was determined by Hall measure-
ment at 300 K with the applied magnetic field changing gradually
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Chem. Mater. 2021, 33, 3611−3620
Chemistry of Materials
between −5.0 and 5.0 T, using the physical properties measurement
system (PPMS, Quantum Design).
4.3. Theoretical Methods. All of the density functional theory
(DFT)59,60 calculations were performed using the plane-wave-based
pseudopotential approach, as implemented in the Vienna Ab initio
Simulation Package (VASP).61,62 The self-consistency loop was
converged with a total energy threshold of 0.01 meV. The structures
were fully relaxed until the Heymann−Feynman forces on each atom
were less than 10−5 eV/Å for both pure and doped configurations.
The effects of doping were considered by substituting Mn and Sb
atoms at the specific sites of Ge atoms in a 2 × 2 × 2 supercell
(originally in rhombohedral phase) consisting of 48 atoms. The
structural optimization was carried out using generalized gradient
approximation (GGA) expressed by the Perdew−Burke−Ernzerhof
(PBE)63,64 exchange-correlation functional. Spin−orbit coupling
interactions owing to heavy atoms were included when calculating
the electronic structures. A 6 × 6 × 2 k-mesh was used for Brillouin
zone sampling. The electron wave function was expanded in a plane-
wave basis set with an energy cutoff of 600 eV. Phonon calculations
were obtained within the harmonic approximation and using a finite
displacement method.65 A 2 × 2 × 2 supercell was set for the cubic
GeTe containing 64 atoms, whereas, for the rhombohedral phase, a 3
× 3 × 1 supercell containing 54 atoms was built. In the Mn−Sb co-
doped rhombohedral system, we used a 2 × 2 × 1 supercell consisting
of 96 atoms. The starting parameters for the calculations were the
values obtained from the refinement.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.chemmater.1c00331.
Rietveld refinement pattern, SEM images, Lorenz
number and electronic thermal conductivity for
Ge1−x−yMnxSbyTe (0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.08),
phonon dispersion curve for pristine cubic GeTe, GeTe
considering Ge vacancies in rhombohedral structure,
charge density plot for Ge24Te24 and Ge21MnSb2Te24,
lattice parameter (a, c) and refinement parameters
obtained from the Rietveld refinement of the XRD
pattern for Ge1−x−yMnxSbyTe (0 ≤ x ≤ 0.05, 0 ≤ y ≤
0.08), scattering parameters obtained using Debye−
Callaway model for Ge1−xMnxTe, longitudinal and
transverse sound velocities for Ge1−x−yMnxSbyTe (0 ≤
x ≤ 0.05, 0 ≤ y ≤ 0.08) (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Ashutosh Kumar − Lukasiewicz Research NetworkKrakow
Institute of Technology, Kraków 30-418, Poland;
orcid.org/0000-0002-0355-0142;
Email: ashutosh.kumar@kit.lukasiewicz.gov.pl
Saswata Bhattacharya − Department of Physics, Indian
Institute of Technology Delhi, New Delhi 110016, India;
orcid.org/0000-0002-4145-4899; Email: saswata@
physics.iitd.ac.in
Krzysztof T. Wojciechowski − Faculty of Materials Science
and Ceramics, AGH University of Science and Technology,
Kraków 30-059, Poland; orcid.org/0000-0002-2459-
9957; Email: wojciech@agh.edu.pl
Authors
Preeti Bhumla − Department of Physics, Indian Institute of
Technology Delhi, New Delhi 110016, India
Taras Parashchuk − Lukasiewicz Research Network
Krakow Institute of Technology, Kraków 30-418, Poland
3618
pubs.acs.org/cm Article
Stanislaw Baran − M. Smoluchowski Institute of Physics,
Jagiellonian University, Kraków 30-348, Poland;
orcid.org/0000-0003-1819-5603
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemmater.1c00331
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to thank the Foundation for Polish
Science for financial support (TEAM-TECH/2016-2/14 grant
“New approach for the development of efficient materials for
direct conversion of heat into electricity”) under the European
Regional Development Fund. The beneficiary institution of the
grant is the Lukasiewicz Research NetworkKrakow Institute
of Technology, Poland. The research was partially carried out
with the equipment purchased through the financial support of
the European Regional Development Fund in the framework
of the Polish Innovation Economy Operational Program
(Contract No. POIG.02.01.00-12-023/08). P.B. acknowledges
UGC, India, for the junior research fellowship [1392/(CSIR-
UGC NET JUNE 2018)]. S. Bhattacharya acknowledges the
financial support from SERB under the core research grant
(Grant No. CRG/2019/000647). S. Bhattacharya and P.B.
thank HPC IIT Delhi for providing the computing hours.
■
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