Review

Cite This: ACS Appl. Energy Mater. 2020, 3, 2200−2213 www.acsaem.org

Critical Analysis of Single Band Modeling of Thermoelectric

Materials
Harshita Naithani† and Titas Dasgupta*,†
Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400076, India
*
S Supporting Information

ABSTRACT: Study of the electronic band structure of thermoelectric (TE)

materials is fundamental to both its understanding and further development.
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Currently theoretical models which assume a single-band-based charge

transport are utilized due to their predictive capabilities and ease of
implementation. However, most good thermoelectric materials have complex
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band structures with multiple bands near the band edge. The extent of
applicability of single-band models in such systems is questionable and forms
the objective of this study. To check this, we have chosen five well-known TE
materials and modeled their room temperature properties using the single
parabolic band (SPB) model and the single Kane band (SKB) model. The
room temperature experimental data for these materials were extracted from
literature reports, and the analysis was carried out on a relatively large sample
set (with over 350 data points spread across the various materials). Our
analysis indicates the failure of single-band models in situations where multiple near-degenerate bands are present close to the
band extrema. The associated errors are in the estimated density of states effective mass (mD*), Lorenz number (L), and lattice
thermal conductivity (κL), which in turn result in erroneous predictions of the optimum charge carrier concentration and zT
values. We also find that identifying whether the band edge is parabolic is difficult from a visual comparison of the SPB and SKB
Pisarenko plots since the observed variations are well within the acceptable limits of experimental error. To overcome this
problem, we propose an error analysis technique which can be used to find the best fit model. The error analysis can also be
useful in identifying the dominant charge carrier scattering mechanism as shown from our study. Overall, our work highlights
the need for implementation of multiband modeling while working with materials with complex band structures.
KEYWORDS: single parabolic band model (SPB), single Kane band model (SKB), thermoelectric materials, Seebeck coefficient,
Lorenz number, band mass

■ INTRODUCTION
Thermoelectric materials have the unique ability to directly
interconvert heat and electrical energy.1 Hence they have
immense application potential as solid state devices where they
can be used as generators, refrigerators, or temperature sensors.
In this world of ever rising demand for consumable energy,
harvesting waste heat to electricity would not only help in the
preservation of fossil fuels but also reduce our carbon footprint.
However, such thermoelectric heat harvesters are not
commonplace. This is due to their poor conversion efficiency
(commercially available thermoelectric devices have around
5−6%2). Current research in this field is therefore concen-
trated on improving the material properties.
The transport properties of a material such as the Seebeck
coefficient (S), electrical conductivity (σ), and hermal
conductivity (κ, the sum of electronic and lattice thermal
conductivities) contribute to a dimensionless number called
S 2σ
figure of merit, zT = κ T which in turn determines the
efficiency of a thermoelectric material. All of these parameters
depend upon the charge carrier concentration. Hence this
concentration needs to be optimized.1 These parameters can
be readily obtained from experiments. If the electronic band
structure of a material is known, the transport properties can
be predicted. But density functional theory predicts the band
structure at ground state, which does not reflect the actual state
of the material. Therefore, modeling of thermoelectric
materials becomes important. On the basis of the kind of
band which takes part in electrical transport, single parabolic
band (SPB) and singe Kane band (SKB) are the most
commonly used models. 3,4 They are applicable when
conduction is limited to just one band, parabolic or
nonparabolic, respectively. One can also go for modeling
which involves multiple bands; however, solving the equations
becomes relatively complex. Another parameter to keep in
mind is the scattering mechanism of charge carriers since these
models include it as well.5 These models use some
experimental data as input and return some important material
Special Issue: Thermoelectrics
Received: October 12, 2019
Accepted: November 21, 2019
Published: December 9, 2019

© 2019 American Chemical Society 2200 DOI: 10.1021/acsaem.9b02015

ACS Appl. Energy Mater. 2020, 3, 2200−2213
ACS Applied Energy Materials Review

Table 1. Single Band Expressions for Charge Carrier Concentration (n), Seebeck Coefficient (S), Hall Prefactor (rH), Lorenz
Number (L), Hall Mobility (μH), and Power Factor (S2σ) for the SPB and SKB Modelsa
property SPB SKB
(2mD*kBT )3/2 * kBT )3/2
(2mD0
n F1/2(η) (0F03/2(η))

ÅÄ ÑÉÑ
3π 2ℏ3 3π 3ℏ3
kB ijj 2F1(η) zy kB ÅÅÅÅ 1F −1 2(η) Ñ
jj − ηzzzz ÅÅ 0 1 − ηÑÑÑÑ
e jk F0(η) { e ÅÅÅÇ F −2(η) ÑÑ
ÑÖ
S

3 F −1/2(η) 3K (K + 2)(0F03/2)(0F −1/2

4 )
rH F1/2(η) 2

Ä É
2Å 2Ñ
4 F0 (η) (2K + 1)2 (0F −1 2)2
Å Ñ
ij kB yz 3F0(η)F2(η) − 4F12(η) ij kB yz ÅÅÅÅ 2F −1 2(η) jij 1F −1 2(η) zyz ÑÑÑÑ
jj zz jj zz ÅÅ 0 1 j z
je z j e z ÅÅ F (η) − jj 0F 1 (η) zz ÑÑÑÑ
2

k { k { ÅÅÇ −2 k −2 { ÑÑÖ
L
F0 2(η)
0 1
F −1/2(η) F −2(η)
μH μ0 rHμ0 0 3/2
2F0(η) F0 (η)

i * y ij 2F (η) yz i * y ij 1F 1 (η) yz
jij 8π zyzμ k 2jjj 2mDkBT zzz F0(η)jjjj 1 − ηzzzz jij 8π zyzμ k 2jjj 2mD0kBT zzz F −2(η)jjjj 0 −1 2 − ηzzzz
j z 0 B jj zz j z 0 B jj zz
3/2 2 3/2 2

k 3e { k h { k F0(η) { k 3e { k h { k F −2(η) {
S2σ 2 2
0 1

a
mD* represents the density of states effective mass of a parabolic band, while mD0
* is the density of states effective mass at the band extremum (E =
0) of a nonparabolic band. μ0 represents the mobility free parameter, and K is the ratio of the longitudinal to transverse effective mass.3,4.

parameters. Lattice thermal conductivity is one such parameter m* the band effective mass; or (b) nonparabolic (Kane

which can be obtained. Its knowledge would aid in further
reducing its value to increase the figure of merit.
The use of the SPB model is widespread for initial analysis of
materials due to its mathematical simplicity. However, it has
many shortcomings when used to analyze some material
systems over a wide range of charge carrier concentration. For
instance, for materials in which electronic transport takes place
through multiple near-degenerate bands, it is likely to fail. In
such a case multiband modeling would be ideal. Thus, there
are many questions associated with the applicability of present
and commonly used models to a particular material. How
different are SPB and SKB from each other? How accurate is a
scattering mechanism in describing the behavior of a material?
Which model best fits the experimental data? What can be the
error associated with the calculation of lattice thermal
conductivity? To answer these questions, a comparison of
the available models needs to be made. In this work we have
reviewed some common thermoelectric material systems and
analyzed them using the SPB and SKB models. In addition, we
have incorporated the use of a two-band model for transport
based on available literature to fit the data, which has provided
more insight into the nature of some materials.
i Ey
Ejjj1 + E zzz = 2m * , where Eg is the band gap of the material.4
type)the energy dispersion relation is of the type
k g{
ℏ2k 2
The quadratic energy term in this equation is to account for
the nonparabolic nature of the band. The direct consequence
of nonparabolicity is that the band mass (m*) is a function of
both energy (E) and band gap (thus temperature), unlike the
parabolic band where m* is constant. These two models are
commonly known as the single parabolic band model and the
single Kane band model, respectively.
The solutions of the various transport properties in the SPB
model3 involve integrals which are represented in terms of the
∞ ε j dε
“Fermi−Dirac” integral given by Fj(η) = ∫ .5 Here
0 1 + exp(ε − η)
ε represents the reduced energy (E/kT) and η the reduced
Fermi level (EF/kT). The term “j”, known as the index of the
integral, depends on both the transport property and energy
dependence of the relaxation time of the charge carriers.
Solution of a more complex integral4 is necessary to account
for band nonparabolicity in the SKB model, where the integral
is given by
∞i
jj− ∂f yzzε n(ε + αε 2)m (1 + 2αε)k dε
j z

k ∂ε {
Single Band Models (Parabolic and Kane Bands). The n m
F k (η , α) = ∫0
assumption that electrical transport of materials with complex
band structures can be modeled using a single energy (1)
dispersion curve is based on the fact that TE materials are Here the term “α” is known as the band nonparabolicity
heavily doped semiconductors. Thus, only the majority charge parameter and depends on the band gap of the material
carriers and hence the bands associated with them are relevant kT
(α = E ). The terms n, m, and k are indices of the integral
for electrical transport. Further, the majority carrier bands are G

replaced with an equivalent band while working with single-
band models. The validity of this assumption is something that
will be discussed in the next section. Transport equations for
the single-band model are based on the Boltzmann transport
equation (BTE).5 Depending on the a priori information
obtained from the electronic band structure of the material
system, the single band is assumed to be either (a) parabolic
ℏ2k 2
the energy dispersion relation is given by E = 2m * , where ℏ is
the reduced Planck’s constant, k the Boltzmann constant, and
2201
whose values depend on the transport property and the charge
carrier scattering mechanism.
The solutions of both of these integrals require the
information on the energy dependence of scattering of the
charge carriers (depends on the scattering mechanism). In the
SPB model, the energy dependence of the relaxation time (τ)
is given by the equation τ = τ0ελ−1/2, where the value of λ
depends on the scattering mechanism. For TE modeling at
room temperature and above, it is assumed that acoustic
phonon scattering of the charge carriers is the dominant
DOI: 10.1021/acsaem.9b02015
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mechanism for which the λ value is zero.5 It is to be noted that
other scattering mechanisms or multiple mechanisms with the
same energy exponent can also be implemented in the model.
Energy dependence of relaxation time in the SKB model is
given by the expression4
1 n=
∝ [ε(1 + ε /εg)]−r ε1/2(1 + 2ε /εg)(1 + ε /εg)1/2
τ (2)
where the parameter r is equal to zero for scattering by
acoustic phonons.
The input variables to both of these models are the
experimental data of the Seebeck coefficient (S(T)), electrical
conductivity (σ(T)), thermal conductivity (κ(T)), and Hall
coefficient (RH(T)) at a given temperature (T). The solution
to the SPB model involves a sequential procedure where at
each step the number of unknown parameters is restricted to
one. An excellent review on the SPB modeling which details
the solution procedure can be found elsewhere.3 A similar
procedure is adopted for solving the SKB model6 which
additionally requires the information on the material band gap
as an input parameter.
In Table 1 various equations for SPB and SKB that have
been used in this work are provided. The corresponding
integrals for SPB and SKB are as discussed earlier. It has been
assumed that the charge carriers are scattered by acoustic
phonons in both models.
The applicability of the models to a given material system
can be ascertained from the variation of the experimental data
from the theoretically calculated values. Typically a plot of the
Seebeck coefficient versus the charge carrier concentration
known as the “Pisarenko plot”3 is drawn to check the band
edge characteristics. The plot consists of experimental data
points which represent the variation of the Seebeck coefficient
with charge carrier concentration at a given temperature. For
both the SPB and SKB models, an ideal fit would be a
theoretical line (with fixed m*D or m*D0 value) that passes
through all of the data points. Normally, the validity and hence
the applicability of the model are based on a visual judgment of
the Pisarenko plot. Any deviations from the theoretical
Pisarenko line is taken to be proof of band nonrigidity,
presence of multiple bands, or presence of special features in
the electronic band structure, e.g., resonant states.7 Additional
checks for model validity can be obtained from plots of charge
carrier mobility (μ) versus charge carrier concentration (n)
and zT versus n. It is to be noted that mostly the Pisarenko
plot provides the best fit between experiment and theory since
the Seebeck coefficient is independent of mobility (depends on
the energy dependence of mobility5) and hence largely
unaffected by microstructural features.
Solutions of the SPB and SKB equations involve solving the
Fermi integrals. This can be easily done numerically using
numeric computational packages such as MATLAB or
Octave.8 As an example, defining the Fermi integrals and
inverse solving to obtain the reduced Fermi level (η) from the
experimental Seebeck coefficient (S) value (which is the first
step for both models) using MATLAB is provided in the
Supporting Information (see Figure S1). Further steps to
obtain the various parameters can be defined from the
estimated η value.
Beyond Single Band Models. To analyze materials where
charge carriers from multiple bands contribute to electrical
transport properties, the single-band models are generally not
valid. Such a scenario can arise in semiconductors where there
2202
Review
are multiple near-degenerate bands close to the band edge or
at elevated temperatures where the contribution to transport
from the minority charge carriers cannot be neglected. For
such materials the various thermoelectric properties can be
obtained from9
∑ ni
i (3)
σ= ∑ σi
i (4)
∑i Siσi
S=
∑i σi (5)
∑i RHiσi 2
RH = 2
(∑i σi) (6)
σσ
i j
κE = ∑ κi + ∑ (Si − Sj)2 T
σi + σj
i i,j (7)
σ
L=
κET (8)
Here the indices i and j represent contributions from a given
band. The multiband expression for electronic contribution to
thermal conductivity (κE) has an additional summation term
(second term in the equation) which represents the
contribution due to interband transport. For mixed conduction
(e.g., one conduction and one valence band), this represents
the bipolar thermal transport which can be significant at
elevated temperatures. Modeling using multiband expressions
becomes complex as the expressions cannot be reduced to
provide a stepwise solution such as the single-band models.
Typically this involves simultaneous solution of the transport
equations or least-squares fitting to obtain the desired data.10
In this work, we have tried an inverse solution; i.e., from
reported data of the various intrinsic parameters, the values for
the transport properties were obtained and compared with
those from the single band models.
■
REVIEW OF LITERATURE DATA
In this section we review the reported experimental data for
five state-of-the-art thermoelectric materials. These materials
were chosen as examples of specific differences in the
electronic structure and are representative of contribution to
electrical transport coming from (i) a single parabolic band
(ZnSb), (ii) multiple (two) degenerate bands (Mg2Si0.3Sn0.7),
(iii) multiple near-degenerate bands (Mg2Si0.4Sn0.6 and
CoSb3), and (iv) a single nonparabolic band (PbTe). Reported
experimental data of S, σ, and RH at 300 K for these
compounds were used as input to the single-band models. The
data set used for the analysis is provided in the Supporting
Information. The methodology used for the analysis is
described first followed by the observation and results for
each material system.
Methodology. Experimental data were used as input for
the SPB and SKB models, and various intrinsic materials
parameters (η, rH, mD*, L, n, and μ0) were calculated for all data
points. From here on, the SKB m*D0 has been referred to as m*D.
Typical plots generated for various materials were (a) variation
of Seebeck coefficient (S) with the Hall carrier concentration
(nH) (Pisarenko Plot), (b) mD* as a function of nH, (c) power
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Figure 1. Representative plots showing (a) least-squares minimization of Seebeck coefficient error to obtain the mD*av value and (b) least-squares
minimization of μ error to obtain the μav
0 value.

Figure 2. (a) Schematic band structure of the conduction band edge of Mg2Si0.3Sn0.7. (b) Pisarenko plot showing variation of S with Hall carrier
concentration (nH). The lines indicate the theoretical data obtained from the various models. The inset shows a zoomed-in region highlighting the
near overlap of the various theoretical model lines. (c) Variation of mD* values with nH obtained from the SPB and SKB models. The dashed lines
indicate the average m*D values obtained from SPB and SKB models, respectively. (d) Experimental and theoretical data showing the variation of S2σ
with nH. (e) Experimental data plot of the estimated Lorenz number from the SPB model as a function of nH. The theoretical two-band L and the
SPB L (derived from the two-band data) are also plotted. The experimental data for the plots have been taken from refs 11−20.

factor (S2σ) as a function of nH, and (d) Lorenz number as a the Supporting Information. The mD*av value was used to
function of nH. To generate theoretical fits for the data, average generate the theoretical fit in the Pisarenko plot while both
values of m*Dav and μav 0 were calculated using a least-squares m*Dav and μav0 values were needed for generating the S σ plot. In
2

minimization technique. For the m*Dav calculation, the quantity
∑i(Sexp − Smodel)2 (where Sexp is the experimental data point,
Smodel is the value obtained from the single-band model, and i is
a data point) was minimized as a function of mD*. The mD* value
corresponding to the minimum S least-squares error was taken
as m*Dav (as shown in Figure 1a). Similarly, the μav 0 value was
obtained from the minimization of ∑i(μexp − μmodel)2 (μexp is
experimental data and μmodel is the value obtained from the
model; shown in Figure 1b). Additional details are provided in
2203
addition, to compare the goodness of fit for the SPB and SKB
model, the root-mean-square error of the Seebeck coefficient
data (Srms
error) was used as a metric.
Two parabolic band model equations (provided in the
previous section) were used to explain discrepancies in the
observed data. The parameters required for solving the
equations were taken from literature or generated from the
single-band models (explanation given in individual materials’
sections).
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Table 2. Estimated Srms

error Error Values for the Different Materials Obtained Using the SPB and SKB Models

Srms
error

SPB SKB
Mg2Si0.3Sn0.7 11.99 12.37
Mg2Si0.4Sn0.6 52.57 54.20
CoSb3 35.49 37.61
ZnSb 51.99 53.11
PbTe 12.52 (nH full range) 13.25 (nH full range)
19.33 (nH < 1025 m−3) 18.89 (nH < 1025 m−3)
6.85 (I-doped,69 nH full range) 6.67 (I-doped,69 nH full range)
4.79 (I-doped,69 nH > 1025 m−3) 5.20 (I-doped,69 nH > 1025 m−3)

Figure 3. (a) Schematic band structure showing the nearly degenerate conduction bands in Mg2Si0.4Sn0.6. (b) Pisarenko plot showing the variation
of S with nH. For both the SPB and SKB models, the theoretical lines were drawn using multiple mD* values. For better clarity, a zoomed-in image of
the encircled region is provided in the inset. (c) Variation of m*D values with nH obtained from the SPB and SKB models. The solid line represents
the mD* data obtained from SPB using the properties calculated from the two-band model as the input. The dashed lines indicate the mD* values of
the heavy and light bands. (d) Experimental and theoretical data showing the variation of S2σ with nH. (e) Experimental data of the estimated
Lorenz number from SPB model as a function of nH. Theoretical two-band L and SPB L are also plotted. The experimental data for the plots have
been taken from refs 23−31.

Mg2(Si0.3Sn0.7) (n-Type). Mg2Si1−xSnx solid solutions are
potential n-type thermoelectric materials. The high zT in these
materials is due to a combination of enhanced power factor
due to the convergence of conduction bands and reduced
lattice thermal conductivity due to alloy scattering.11 The best
TE performance is observed close to x ∼ 0.7 (Mg2(Si0.3Sn0.7)),
where the two conduction band minima at the X k-point in the
reciprocal space become degenerate. The schematic band
structure for this composition is shown in Figure 2a indicating
the two degenerate bands which contribute to the electrical
transport when this material is n-doped. In Figure 2b, the
Pisarenko plot is given showing the experimental data points
(round symbols) along with the theoretical plots (lines)
2204
obtained from different models. For the SKB model, the α
parameter was taken to be 0.0637 (on the basis of the reported
band gap21) and the K value is assumed to be 1. To generate
the two-band Pisarenko line, information on the density of
states mass and mobility of the two individual bands are
required. For the light band (band 1 in Figure 1a), data of m*D1
and μ01 were taken from literature (mD1 * = 1.1me, and μ01 =
0.0123 cm2/(V s)).22 These literature values were obtained
from SPB modeling in Mg2Si in which the light band alone
contributes to the electrical transport. To obtain the
information for the heavy band (mD2 * = 2.19me and μ02 =
0.0078 cm2/(V s)), the following equations were used:
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Figure 4. (a) Schematic band structure of the conduction band edge in CoSb3 which consists of two near-degenerate bands. (b) Pisarenko plot
showing the variation of the experimental and theoretically calculated S values as a function of nH. Three different average m*D values were
calculated for the SPB model (over the entire nH range, 2.7me; for nH < 1025 m−3, 1.4me; for nH > 1026 m−3, 3.7me). For the SKB model the average
over the entire nH range was used for the m*D calculation. (c) Variation of the experimental m*D (calculated using the SPB model) with nH. The
values of mD* used for the two-band calculation32 are shown as dashed lines. The solid line represents the mD* data obtained from the SPB model
using the two-band-calculated properties as input. (d) Variation of the experimental and calculated S2σ values as a function of nH. (e) Plot of
experimental data of the estimated Lorenz number from SPB model as a function of nH. The theoretical two-band L and SPB L are also plotted.
The experimental data for the plots have been taken from refs 32−55.

* = ((mD*av )3/2 − (mD1

mD2 * )3/2 )2/3
(mD*av )3/2 μ0av − (mD1* )3/2 μ
01
μ02 =
(mD*av )3/2 (10)
(where the m*D and
av
μav
0 values were obtained from the least-
squares minimization technique using the SPB model). As seen
from the data, the differences between the different models are
less compared to the experimental scatter in the data. This is
indicative of (a) validity of the SPB model in a degenerate two-
band scenario (the inset shows minor differences between the
SPB and two-band lines and is attributed to errors in defining
nH in a multiband scenario) and (b) difficulty in differentiating
parabolic from a Kane-type nonparabolic band. To find the
better fit, the root-mean-square error of the S data (Srms
error) were
(9) to an erroneous definition of nH in a multiband scenario). It is
to be noted that the SKB model predicts a lower optimum nH
compared to other models. This is attributed to the higher
value of the effective mass estimated from the SKB model. In
Figure 2e, the Lorenz number values are shown as a function of
nH. Both band models predict the same values of L in the
entire carrier concentration range.
It is to be noted that the close match between the SPB and
two-band data in Figure 2b,d,e is also a result of the way the
theoretical plots have been generated. The SPB n value has an
r
error due to the assumption of RH = neH which is invalid for a
two-band system. The associated error depends on the
mobility ratio of the bands (due to the
nμ +n μ
1
assumption n = (n 1μ 1+ n 2μ 2)2 ). The error in the SPB n value
1 1 2 2

calculated as given in Table 2. The data are indicative of the
band being parabolic.
In Figure 2c, the calculated m*D values from both the SPB
and SKB values are given. As observed, the SKB model tends
to give a higher absolute value compared to the SPB model.
The mD* values are also observed to be independent of nH
indicative of the validity of models in the studied range. The
S2σ data (shown in Figure 2d) also indicate the validity of the
SPB model in a degenerate two-band scenario (minor
mismatch between SPB and the two-band plot is attributed
2205
further results in an error in the estimated m*Dav value. Since
* and μ02 were calculated on the basis of this mD*av value, the
mD2
two-band data generated from these values also contain this
error and result in a good match with the SPB data. This
however does not affect the calculated optimum S2σ and zT
absolute values since the experimental data are taken as input
and the errors in the intrinsic parameters (m*D and μ0) cancel
out when used to generate the theoretical values of S2σ and zT.
The observed effect is thus a translation of the plots along the
x-axis (n values). In principle, this indicates a failure of the SPB
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Figure 5. (a) Schematic band structure of the valence band edge in ZnSb. Generally only the light band (band 1) is considered while modeling its
TE properties; hence, the heavy band is shown with a question mark. (b) Pisarenko plot showing the variation of the experimental and theoretically
calculated S values as a function of nH. Two different average mD* values were calculated for both SPB and SKB models (over the entire nH range,
0.46me (SPB) and 0.58 me (SKB); for nH > 1025 m−3, 0.72me (SPB) and 0.91me (SKB)). (c) Variation of the experimental m*D (calculated using the
SPB model) with nH. The values of mD* used for the two-band calculation are shown as dashed lines. The solid line represents the mD* data obtained
from the SPB model using the two-band-calculated properties as input. (d) Variation of the experimental and calculated S2σ values as a function of
nH. Data for the plots are taken from refs 56−65.

model in predicting the intrinsic material parameters with
multiple degenerate bands; however, this in no way affects the
accuracy of the predicted optimum extrinsic properties. While
ways to overcome this problem can be the scope of future
study, in the present work this issue is not discussed any
further. In the Supporting Information, the extent of error in
the n values with material parameters of Mg2Si0.3Sn0.7 and
CoSb3 are provided (shown in Figure S2).
Overall, the results for Mg2Si0.3Sn0.7 reaffirm this material to
be a “canonical example” of applicability of SPB in a multiband
scenario, as mentioned by Uher et al.13
Mg2(Si0.4Sn0.6) (n-Type). The next material that we have
surveyed is Mg2(Si0.4Sn0.6), which also belongs to the
Mg2(Si1−xSnx) family. However, in this material the condition
of conduction band degeneracy is lifted (shown in Figure 3a),
resulting in two nearly degenerate bands at the conduction
band edge with a reported interband separation of 0.061 eV.21
In Figure 3b, the Pisarenko plot is shown. As seen from the
figure, unlike Mg2(Si0.3Sn0.7) the single-band lines do not fit
the data in the entire nH range. To get a better fit, two different
values of m*Dav were calculated (for both SPB and SKB
models), one using the data for the entire carrier concentration
range and the other for nH > 1026 m−3. As seen from the plot,
different m*Dav values result in a better fit over specific ranges of
nH. This is indicative of the variation of m*D with nH , and as
seen from Figure 3c, there is a systematic increase of m*D with
increasing nH. This trend of increasing mD* is similar for both
the SPB and SKB models. This observation also indicates that
2206
the nH dependence of m*D cannot be attributed to band
nonparabolicity (in which case the mD* calculated from SKB is
expected to be invariant to changes in nH). To probe the
possible influence of the two near-degenerate bands, two-band
calculations were performed using the same set of m*D and μ0
values as that of Mg2Si0.3Sn0.7. The Pisarenko line for the two-
band model provides a much better fit to the experimental data
as compared to the single-band models (shown in the inset of
Figure 3b). Further, the output from the two band analysis (S
and RH) was taken as the input data for SPB. As evident from
Figure 3c, the m*D values obtained from the two-band data
agree with those obtained from experimental data (S and RH),
indicating that it is indeed a two-band scenario.
The experimental data of S2σ as a function of nH is shown in
Figure 3d along with various theoretical calculations. The best
fit to the data is obtained for the two-band model, which also
indicates the influence of the two conduction bands on the
observed electrical properties. The predictions of S2σ and
optimum nH from the single-band models are seen to be
dependent on the nH range from which the m*D is estimated,
indicating the failure of single-band models. The other effect of
using the SPB model is the difference in the estimated Lorenz
number (compared to the two-band model) as seen in Figure
3e. The two-band model predicts a higher value of L in the
entire nH range. The effect of this on the calculated κL and zT
is discussed in the next section.
CoSb3 (n-Type). CoSb3-based materials are also well-
known TE materials. The conduction band edge of this
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Figure 6. (a) Schematic band structure showing the sole conduction band in PbTe. Generally, it is taken to be a Kane-type nonparabolic band, but
our results indicate otherwise. (b) Pisarenko plot showing the variation of S with nH for both SPB (solid line) and SKB (dashed line). A zoomed-in
image of the encircled region is provided in the inset. For lower nH values SKB gives a better fit than SPB, and for higher n values SPB gives a better
fit than SKB. (c) Variation of mD* values with nH obtained from the SPB and SKB models. mD* for SKB deviates more from the average SKB mD* at
higher nH. (d) Experimental and theoretical data showing the variation of S2σ with nH. (e) Experimental data of the estimated Lorenz number from
SPB and SKB models as a function of nH. The experimental data for the plots have been taken from refs 6, 67−76.

material is similar to that of Mg2Si0.4Sn0.6 with two near-
degenerate bands (shown in Figure 4a). The reported
interband separation is 0.08 eV and the density of states
mass being 0.7me and 4.8me, respectively.32 This material was
studied to check the repeatability of the observed trends for the
two near-degenerate band scenarios. The plots in Figure 4b−e
are similar to those for Mg2Si0.4Sn0.6 (compare Figure 3b−e).
For the two-band model, necessary parameters were taken
from the work of Snyder et al.32 (we restrict our model to two
bands (2 CB) as compared to three bands (2 CB + 1 VB) since
our calculation is restricted to 300 K). The obtained overall
trends in the Pisarenko plot and variations of m*D, S2σ, and L
with nH are similar to those of Mg2Si0.4Sn0.6. Finer differences,
e.g., the extent of swing in the L data, exist between the two
materials and possible causes for them are discussed in the next
section. Estimation of Srms
error values for this material system is
given in Table 2, which indicates the SPB model has a better fit
to the data compared to the SKB model.
ZnSb (p-Type). ZnSb is a well-known TE material, and its
electrical properties are generally modeled assuming a single
parabolic band (band 1 in Figure 5a). The Pisarenko plot for
this material is shown in Figure 5b. As seen from the figure,
single-band models (both SPB and SKB) do not fit the
experimental data over the entire nH range. This is because of
the increase of the mD* values with increasing doping level
(shown in Figure 5c). This has been attributed to the effect of
2207
impurity band conduction based on studies of low-doped
specimens.56 However, the observed increase of mD* even at
heavy doping levels and the similarity to previous examples
indicate the possibility of two-band conduction. A recent DFT
electronic band structure calculation66 reveals the presence of a
heavy hole band around 0.8 eV below the valence band
maximum. To verify the possibility of multiband conduction, a
two-band model was used to fit the experimental data. Due to a
lack of literature reports on the properties of the heavy band,
required data were extracted from the high nH range. It should
be noted that our results only highlight the possibility of two-
band conduction in this material and further studies are
required to get accurate properties of the heavy band. As seen
from the data, the two-band model provides a better fit
(compared to the single-band models) to the S versus nH and
m*D versus nH variations. In Figure 5d, the S2σ data are shown
as a function of nH. Theoretical single-band fits using different
average m*D values highlight the difference in the predicted
optimum S2σ and doping level while working with data at
different nH ranges. The estimation of Srms error values for this
material is provided in Table 2, which indicates the SPB model
has a better fit to the data compared to that of the SKB model.
PbTe (n-Type). Lastly, we have analyzed PbTe. n-type
PbTe is taken to be the model example of materials in which
the sole conduction band is nonparabolic and therefore the
applicability of the SKB model4(schematically represented in
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Figure 6a). Here both SKB and SPB have been applied to the
experimental data, and the results were surprising. Throughout
this work, a parameter called Srms error (described in the preceding
section) has been used to compare SPB and SKB models. A
lower value of Srmserror for a model is indicative of that model
giving a better fit. In Figure 6b, it is difficult to visually
compare SKB and SPB. When the entire range of charge carrier
concentration is taken into consideration, it is found that SPB
25 −3
gives a better fit (lower Srms
error than SKB). But for nH < 10 m ,
it is found that SKB gives a better fit. To eliminate the errors
arising from taking the experimental data with different
dopants, test equipment, and synthesis methods, data from a
single research work6 were taken separately and analyzed as
shown in Figure 7. For the entire range of charge carrier
Figure 7. Experimental and theoretically generated Pisarenko plot for
iodine-doped PbTe, with data taken from ref 6. The Srms error values
calculated in different nH ranges are provided.
concentration, SKB gave a lower value of Srms error, but for the
range above 1025 m−3, SPB Srms error was lower. In any case, for
higher charge carrier concentrations, SPB gives a better fit,
suggesting that on moving away from the band minima the
band becomes parabolic. This is also evident from the m*D
versus nH plot (Figure 6c), which shows a higher deviation of
the effective mass from the average value at higher charge
carrier concentration, indicating a failure of the SKB at higher
doping levels. These findings certainly raise a question
regarding the absolute validity of the Kane band model over
the entire range of charge carrier concentration in PbTe. The
effective mass and Lorenz number calculated from these two
different models are different (Figure 6c,e). Thus, by using the
wrong model, it is possible to end up with wrong values for the
optimum charge carrier concentration and lattice thermal
conductivity. It is important to stress upon this gradual shift
from the Kane-type nonparabolic to the parabolic nature in the
conduction band because the optimum zT is achieved within a
narrow range of n. Thus, identifying the correct model in that
range (or coming up with a new model altogether) to get the
right concentration is important. p-type PbTe and other
materials with a known nonparabolic band edge could be
studied in a similar way to get more insight into the nature of
the extent of this nonparabolicity.
■ DISCUSSION
The materials analysis in the previous section highlights certain
systematic deviations and errors when a multiband material is
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Review
modeled using single-band models. Systematic deviations from
the theoretical models are observed in the Pisarenko plot and
mD* dependence on nH when plotted over a wide carrier
concentration range. Both of these observations are related to
changes in the interband charge carrier distribution and are
indicative of multiband conduction. The extent of the observed
deviation in the Pisarenko plot is also an indicator (of
multiband conduction) because the difference between the
SPB and SKB lines as observed from our analysis is minimal.
The only scenario when multiband conduction can be modeled
by single-band models is for multiple degenerate bands with
similar effective band masses as observed in Mg2Si0.3Sn0.7.
From our analysis, the errors associated with modeling a
multiband material with single-band models are in the
estimated (a) Lorenz number (which in turn affects the
estimated κL value), (b) optimal doping concentration, and (c)
predictions of maximum S2σ (also zT).
In this section, we aim to provide further insight into these
systematic deviations and errors on the basis of the study of a
two-parabolic-band model. Two possible ratios of the band
effective mass are studied; (i) both the DOS band masses (m1
and m2) are the same and equal to the electron rest mass, and
(ii) a large difference in the DOS band masses with m1 = 0.7me
and m2 = 4.8me (values taken for that of CoSb3). In both of
these cases calculations were performed for interband
separations of 0 and 0.1 eV, i.e., for conditions of degenerate
and near-degenerate bands.
Interpretation of mD* Plot. In Figure 8, the variation of
m*D with n for the two different cases are shown. The m*D values
Figure 8. Variation in the calculated mD* with n using the SPB model
on a two-band material. The upper panel data are for equal band
masses, while the lower panel data are that of different band masses.
In both cases the constant value (solid line) represents the degenerate
scenario.
were obtained from the SPB model using the generated two-
band data as input. It is thus similar to studying the measured
data of a two-band material using SPB model. In both cases,
degenerate bands result in constant values of mD* given by mD* =
(Nv1m3/21 + Nv2m3/2
2 )
2/3
(here the band degeneracies Nv1 and
Nv2 are assumed to be unity). For this situation, the SPB model
is valid since the criterion of constant mD* with changing doping
level (known as rigid band) is satisfied. This also results in an
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Figure 9. (a) Difference in Lorenz number calculated using the two-band and SPB models as a function of charge carrier concentration. The upper
panel data are for equal band masses, while the lower panel data are those of different band masses. In both cases the interband separation is taken
to be 0.1 eV. (b) Error in the estimated κL (using SPB generated L) plotted as a function of carrier concentration.

accurate prediction of S2σ and optimum n as shown in Figure LσT). In Figure 9b, the estimated errors in κL (ΔκL) if the SPB
2d,e. Thus, the SPB model can be used in multiband scenarios model is applied to a two-band material is given. The ΔκL
where the bands are degenerate and can be expected to values peak at intermediate doping levels (∼1026 m−3) which is
provide accurate information on L, κL, nopt, and zTopt. also where optimum zT values lie (shown in Figure 10). The
In case of near-degenerate bands (in this example 0.1 eV),
the observed mD* variation with n shows a sharp change at
intermediate n values, which plateaus at higher and lower
carrier concentrations. The near-constant m*D values at lower n
are indicative of charge transport dominated by the lower
band. As the doping level increases, there is an increase in
charge transfer to the upper band resulting in a rising mD* value.
At very high doping levels (when all electrons participating in
charge transport can access the upper band) the m*D value
again becomes constant because there is no net change in the
charge distribution with increasing n value. Thus, modeling any
two (or multi)band material using the SPB model would
exhibit this feature if there are multiple doped samples spread
over a wide range of n. In such cases, the SPB model can be
used as an indicator for the presence of multiple bands near the
Fermi level. Even when the two masses are equal, the observed
rise in m*D is ∼50% (and becomes higher if the band masses are
unequal) and hence can be easily observed from experiments.
Errors in Lorenz Number and Its Effect on Lattice
Thermal Conductivity. Lorenz number as a function of
charge carrier concentration was calculated using both the two-
band and SPB models (using the two-band S data as input). In
Figure 9a, the difference between them is plotted as a function
of n. At low doping levels L values from the two-band model
are higher compared to the SPB values. With a rise in doping
level, both the two-band and SPB L initially increase which is
followed by a sharp decrease of the two-band L value until it Figure 10. Variation of zT with n as calculated by the SPB and two-
merges with the SPB line. The downward swing in the two- band models. The upper panel represents the data when the band
band L value is seen to occur at n values where interband mass ratio is unity. In the lower panel the data for the different band
charge transfer is prominent (see Figure 8). masses are shown. Here the SPB calculations were carried out using
The reason for this difference in the L values (calculated three different sets of m*D and μ0 values.
using the two models) is the additional interband charge
transfer component of the electronic thermal conductivity (κine ) estimated peak errors in ΔκL also depend on the band mass
which is accounted for in the two-band model. The κein ratios with deviation from unity leading to larger errors. As
contribution is higher at low doping levels and is expected to seen from our example it can be as high as 15% though further
fall sharply as the upper band gets populated. Thus, using the studies (with varying band mass ratio and interband
SPB model is expected to result in erroneous L values in separation) are necessary to check the possible upper limits.
materials with multiple near-degenerate bands. This in turn The ΔκL values are smaller at low doping levels (even though
influences the calculated lattice thermal conductivity (κL = κ − the difference in L is large) because of the low σ values, while
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at higher n this is due to the similar L values predicted by both
models. Overall, this study indicates that κL values are
overestimated when using the SPB model on a multiband
near-degenerate system.
Errors in Optimal Charge Carrier Concentration and
zT. The effect of modeling a two-band material with near-
degenerate bands using SPB results in errors in mD*, L, and κL
as discussed previously. The cumulative effect of this can be
seen in the difference in the calculated zT values from the two
models. For the SPB calculations, data generated from the two-
band model was used to derive average m*D and μ0 values using
the least-squares minimization technique. In the case of
identical mass of the two bands (upper panel of Figure 10) the
SPB model predicts a higher value of the zTmax value and a
lower value of the optimum charge carrier concentration. The
differences between the SPB and two-band zTmax become more
pronounced when the mass of the two bands are different as
seen from the lower panel of Figure 10. The origin of this
difference lie in the charge carrier dependence of m*D in two-
band systems. Thus, working with a fixed mD* for zT calculation
(in th SPB model) results in errors depending on the doping
concentration of the specimen used for m*D extraction. As
shown in the lower panel of Figure 10, if m*D and μ0 values are
extracted from the averaging over the entire n-range, the
obtained zTmax (dotted line) is significantly lower than the
two-band zTmax value. Similarly, using the doping level which
results in the optimum zT from the two-band model results in
a much higher predicted zTmax (dashed−dotted line). A further
zT plot (dashed line) is shown in the figure which represents
the effect of data extraction from a low-doped sample (n = 1024
m−3). These results highlight one of the biggest drawback of
using the SPB model in multiband systems. The general
practice while using the SPB model has been to use a single
composition to extract experimental data for the model. While
this works perfectly in materials with a single band contributing
to charge transport or, as shown in this work, in materials with
multiple degenerate bands, it would result in erroneous
predictions in multiband systems with near-degenerate bands.
Identification of Scattering Mechanism. As mentioned
earlier, a parameter called Srms
error has been used as a statistical
tool to determine how suitable a model is for the experimental
data. This approach was used to identify the extent of
applicability of SPB and SKB to a given material. But it can
also be used within SPB to identify the scattering mechanism
which gives the best fit to the experimental data since the SPB
equations employ the scattering parameter λ. The idea is that
the theoretical Pisarenko plot which results in lowest Srms error is
the most suitable and so is the corresponding λ. Generalized
SPB equations with λ as an additional variable were used. For
different values of λ, the theoretical Pisarenko plots were
generated (shown in Figure 11) and Srms error was evaluated. Here,
Mg2Si0.3Sn0.7 experimental data were used because, among all
of the materials surveyed, SPB fits best to this material (Srms error
data provided in Table 3). It was found that, for λ = 0.5, Srms error
was the lowest (although marginally). Since the same data are
used as the input to SPB with different λ values, it is argued
here that the marginal differences in Srms error should be attributed
to the accuracy of the model in describing the behavior of the
material rather than to experimental errors. This result
indicates that neutral scattering mechanism could actually be
the dominant mechanism of electron scattering at room
temperature or there could be a mixing of different
mechanisms. Findings of Kim et al.77 for Mg2Si0.1Sn0.9 (on
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Review
Figure 11. Pisarenko plots for Mg2Si0.3Sn0.7 with theoretical fits
generated using different values of λ. The insets show the differences
between theoretical fits. Data are taken from refs 11−20.
Table 3. Srms
error Obtained for Various λ Values in Mg2Si0.3Sn0.7
λ mD* (/me) Srms
error
0 (acoustic phonons) 2.68 11.99
0.5 (neutral impurity) 1.79 11.87
1 (polar optical phonons) 1.37 12.00
2 (ionized impurity) 0.96 12.72
the basis of experimental data) further support our result that it
is possible for this material to have λ = 0.5. A very important
point to note is that even though the differences in Srms error are
marginal, the mD* calculated from these values are very different
from each other. Thus, identifying the correct mechanism is of
utmost importance for calculation of material properties.
It is thus evident that single-band models have limitations
when applied to materials with complex band structures.
However, they can serve as an indicator of the presence of
multiple bands on the basis of the charge carrier variation of
the calculated properties. Thus, unlike common practice, it is
advisable to have multiple compositions spread over a few
orders of magnitude to check for the validity of a single-band
approximation. Another observation from this work is the
marginal difference between the SPB and SKB Pisarenko plots
in all of the studied materials. For all of the cases, the
difference is less than the scatter in the experimental data,
making it visually impossible to identify the correct model. We
have shown that statistical error analysis might be a useful tool
to identify the better model, but further work is necessary for a
confirmation. Thus, elimination of other possible sources of
scatter in experimental data (dopant material, synthesis
process, and measurement setup) is recommended to check
for band parabolicity when studying unknown material
systems. Choosing the correct model (parabolic or non-
parabolic) becomes relevant due to the significant difference in
the estimated properties (e.g., mD*, L, S2σ, and optimum n)
between the two models. The assumption of acoustic phonon
scattering being the dominant mechanism is also something
that is used as a default in SPB modeling. Our results show the
possibility of identifying the suitable λ values on the basis of an
error analysis of the Pisarenko plot. Further studies are
required on this due to the significant scatter observed in the
experimental data.
Overall, our work highlights various shortcomings of single-
band models and indicates the need for multiband modeling
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while addressing thermoelectric materials with complex band
structures. Another issue that is highlighted is the significant
scatter in the reported data which limits the predictive accuracy
of any such band models. Better quality experimental data and
thus better measurement practices are therefore required while
working with band structure modeling of TE materials.78
■
CONCLUSION
We have looked at the applicability of single-band models to
various thermoelectric materials with complex band structures.
The studied material systems were chosen to represent
different possible features of the band edge, namely, a single
parabolic band, two degenerate parabolic bands, two near-
degenerate parabolic bands, and a single nonparabolic band.
Both SPB and SKB models were used to analyze the data using
standard procedures. To interpret the observed deviations
from the single-band models, fitting was carried out using two-
parabolic-band equations. SPB works well for materials with
multiple degenerate bands (especially if the band masses are
similar). In the case of near-degenerate bands, application of
the SPB model results in errors in the calculated Lorenz
number, lattice thermal conductivity, the predicted optimum
charge carrier concentration, and zT values. The magnitude of
the error depends on the ratio of the band masses and the
interband separation. Differences between SPB and SKB
Pisarenko plots are also found to be marginal, making it
difficult to predict the nature of the band edge on the basis of
these models. We show the possibility of using statistical error
analysis in such instances for identifying the best fit.
Interestingly, applying this analysis to PbTe which is known
to have a nonparabolic band edge indicates a transition from a
Kane-type to a parabolic one on increasing the doping level.
This approach can be used to identify the scattering
mechanism in materials and was attempted in Mg2Si0.3Sn0.7.
The best fit was obtained for a λ value of 0.5. While further
studies are necessary to verify its applicability, this poses the
question whether acoustic scattering of charge carriers can be
considered as the default mechanism while using these models.
Overall, our study indicates the need for multiband modeling
while dealing with complex band structures and the single-and
models remain effective tools while working with multiple
degenerate bands at best.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.9b02015.
Initial steps of single band model solutions; experimental
data used for analysis; various material parameters used
for the models; procedure for calculation of mD*av and μav
0 J. Korean Phys. Soc. 2013, 63, 2153−2157.
and their values; comparison of two cases of degenerate
bands (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: titas.dasgupta@iitb.ac.in.
ORCID
Harshita Naithani: 0000-0001-9138-8431
Titas Dasgupta: 0000-0002-8261-9784
Author Contributions
†
H.N. and T.D. contributed equally to this work.
2211
Review
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We acknowledge the financial support provided by the
Department of Science and Technology (DST), Government
of India (Grant SERB/F/I0565/2017-2018). We also acknowl-
edge Dr. J. de Boor (DLR) for providing valuable suggestions
and discussions.
■ ABBREVIATIONS
rms
Serror ,
root-mean-square of the error of the Seebeck
coefficient data
SKB, single Kane band
SPB, single parabolic band
■
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