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Theoretical analysis of structure and formation energy of impurity-doped Mg2Si: Comparison

of first-principles codes for material properties

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Japanese Journal of Applied Physics 54, 07JC05 (2015) REGULAR PAPER
http://dx.doi.org/10.7567/JJAP.54.07JC05

Theoretical analysis of structure and formation energy of impurity-doped Mg2Si:

Comparison of first-principles codes for material properties
Naomi Hirayama1*, Tsutomu Iida1, Hiroki Funashima2, Shunsuke Morioka1, Mariko Sakamoto1,
Keishi Nishio1, Yasuo Kogo1, Yoshifumi Takanashi1, and Noriaki Hamada2
1
Tokyo University of Science, Katsushika, Tokyo 125-8585, Japan
2
Osaka University, Toyonaka, Osaka 560-0043, Japan
E-mail: hirayama@rs.tus.ac.jp
Received October 1, 2014; accepted March 4, 2015; published online June 17, 2015

We theoretically investigate the impurity doping effects on the structural parameters such as lattice constant, atomic positions, and site preferences
of impurity dopants for Al-doped magnesium silicide (Mg2Si) crystal using the first-principles calculation methods. We present comparison between
several codes: ABCAP, Quantum Espresso, and Machikaneyama2002 (Akai KKR), which are based on the full-potential linearized augmented
plane-wave method, the pseudopotential method, and KKR/GGA Green’s function method, respectively. As a result, any codes used in the
present study exhibit qualitative consistency both in the dependence of the lattice constants on the doping concentration and the energetic
preference of the Al atom for the following sites; substitutional Si and Mg sites, and interstitial 4b site; in particular, ABCAP, which is based on the
all-electron full-potential method, and Quantum Espresso, which is a code of the pseudopotential method, produce closely-resemble calculation
results. We also discuss the effects of local atomic displacement owing to the presence of impurities to the structural parameters of a bulk. Using
the analytical method considering the local atomic displacement, moreover, we evaluate the formation energy of Na- and B-doped systems as
examples of p-type doping in order to examine the possilbility of realizing p-type Mg2Si. © 2015 The Japan Society of Applied Physics

calculate the structural properties. However, there have been

1. Introduction
The thermoelectric materials have recently been attracting
renewed interest owing to their potential for the energy
conversion systems. The increased interest has led to a great
number of developments to realize more efficient materials
than those currently available.
In recent years, much attention has been focusing on
Mg2Si1–9) as a promising candidate for mid-temperature
(600–900 K) thermoelectric applications, and it is therefore
expected to be suitable for use in a waste heat recovery
system in the automotive industry. This material also
possesses advantageous attributes for practical use in terms
of cost and environmental protection: it is cheap, lightweight,
nontoxic, and composed of elements abundant in the Earth’s
crust.10,11) Impurity doping is a well-established method for
improving the thermoelectric performance of Mg2Si and thus
necessary to optimize the thermoelectric properties for actual
applications.1) However, it is time-consuming and sometimes
difficult to obtain experimentally detailed and comprehensive
information about doping effects on structure, electronic and
transport properties of Mg2Si. Therefore, theoretical analyses
including first-principles calculation methods have been
recognized as potential tools that provide new insight into
the doping effects, and thereby they are expected to give
guidelines for further development.
In the present study, we have been focusing on the
structural change that occurs when a magnesium silicide
(Mg2Si) crystal is doped with an impurity atom. In particular,
changes in the lattice constant and localized distortion of the
crystal lattice due to the existence of impurity atoms can affect
the electronic physical properties, such as the band structure,
and thus the transport properties of the carrier. The energeti-
cally stable site of an impurity should be also important since
it is essentially related to the carrier concentration and its
temperature dependence of the impurity-doped system.
In order to obtain the impurity doping effects accurately,
of course, it is crucial to choose an appropriate method to
07JC05-1
few reports and discussions focusing on the differences
between theoretical approaches and their validity.
In order to address this issue, we investigate the structure
of Al-doped Mg2Si from the perspective of the total energy,
we use several codes that perform first-principles calcula-
tions, and the structural parameters obtained from them are
compared, as explained in Sect. 2. It has been reported that
Al is a potential dopant to Mg2Si to enhance stability and
environmental benignity.1) Theoretically, Al-doped Mg2Si
can be utilized for examining both n- and p-type systems,
since the conductivity type depends on the site occupied
by Al in a Mg2Si crystal; i.e., it is expected that substituting
Al for Mg and Si leads to n- and p-type conductivities,
respectively, based on their different valences: Al(III),
Mg(II), and Si(IV). It is noteworthy that in a real system,
Al-doped Mg2Si is known to exhibit n-type conductivity.
However, we theoretically examine both the cases of the Mg
and Si sites occupied by Al, which allows us to discuss the
behavior of n- and p-type Al-doped Mg2Si, respectively.
Calculated results indicate that all codes that are examined in
this study possess qualitatively consistent behavior when
considering the lattice constant and formation energy.
The paper is organized as follows. In Sect. 2, we outline
calculation methods and first-principles calculation codes
used in the present study. In Sect. 3.1, we show the
dependence of the lattice constant and the formation energy
on impurity concentration for Al-doped Mg2Si and compare
the calculation results obtained from different calculation
codes. In Sect. 3.2, we consider the localized shifting of
individual atoms inside cells from their average crystallo-
graphic positions owing to the existence of impurities and
examine practical implications of it for lattice constant and
formation energy. In Sect. 3.3, we discuss the cases of
incorporating Na and B into the crystal in order to assess the
feasibility of p-type doping on Mg2Si. Section 4 is devoted to
conclusions.
© 2015 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 54, 07JC05 (2015)
Fig. 1. (Color online) Mg2Si has the anti-fluorite (CaF2) crystal structure
belonging to Fm3m
space group. In a perfect crystal, Si and Mg atoms,
indicated as small (red) and large (blue) points, are located at the 4a and 8c
sites, respectively.
(a) (b)
(c)
Fig. 2. (Color online) Three types of impurity site are depicted; such that
an impurity atom is substituted with (a) Mg and (b) Si atoms, and (c) it is
inserted into 4b site.
2. Theoretical methods
2.1 Structural description of pure and impurity-doped
Mg2Si
Mg2Si has an anti-fluorite (CaF2) crystalline structure,12) as
shown in Fig. 1; it belongs to the Fm3m
space group where
Si and Mg atoms are located at the 4a and 8c sites,
respectively.9) The atomic positions in the conventional unit
cell, in units of the lattice constant, are given by the following
coordinates: Si:ð0; 0; 0Þ; Mg:ð0:25; 0:25; 0:25Þ; and
Mg:ð0:75; 0:75; 0:75Þ. For the impurity-doped systems, we
consider three cases of the impurity site, as depicted in
Figs. 2(a)–2(c). These cases are generated by the substitution
of Si and Mg and the interstitial insertion of an impurity into
the 4b site, i.e., the ð0:5; 0:5; 0:5Þ position in the cell,
respectively.
2.2 Three first-principles calculation codes examined in
the present study
In this study, three first principles calculation codes
[ABCAP,13–15) Quntum Espresso,16,17) Machikaneyama2002
07JC05-2
N. Hirayama et al.
(Akai KKR)13,18–21)] were used to derive the two physical
properties: the lattice constant and the impurity site, for
impurity-doped Mg2Si and the results were then compared.
ABCAP is a program for calculating the electronic state
using the full-potential linear augmented plane wave
(FLAPW) method22,23) based on the local density approx-
imation (LDA)24,25) within density functional theory (DFT)
and is expected to offer the most reliable calculation, since
the all-electron full-potential method is used. On the other
hand, Quantum Espresso, which is a pseudopotential method
based on the DFT, requires less calculation time and makes it
relatively easy to conducting calculations with high calcu-
lation accuracy by considering a large basis set of plane
wave, as well as to handle systems with low impurity
concentrations which are generally doped in experiments
using a supercell that includes a large number of atoms. It
therefore can be expected to serve as a powerful means for
investigating the contribution of impurity additions to the
physical properties. We used a norm-conserving pseudopo-
tential with the Perdew–Burke–Ernzerhof (PBE) exchange–
correlation functional for calculations by Quantum Espresso.
Machikaneyama (AkaiKKR) is a calculation program based
on the Korringa–Kohn–Rostoker (KKR)-Green’s function
method within the framework of LDA or generalized gradient
approximation (GGA) of DFT and, like ABCAP, is a highly
accurate calculation technique based on the all-electron
calculation. If the impurity concentration is extremely low
(about 1% or lower), however, it is known to be incapable of
handling the system correctly in some cases. For analysis of
thermoelectric materials, therefore, the calculation accuracy
needs to be carefully considered when the Machikaneyama
method is used, since the impurity concentration is often
around 1% or lower. If the calculation accuracy is guaranteed,
however, this code would prove to be extremely beneficial
in the development of thermoelectric materials since it can
perform the all-electron calculation with overwhelmingly low
calculation cost even for low doping concentrations.
Using the codes, we optimized the lattice constant for
Mg2Si doped with Al by minimizing total energy of the
systems. Furthermore, we carried out variable-cell relaxation
by Quantum Espresso in order to examine the effect of
localized shifting of individual atoms inside cells from their
regular positions in a perfect crystal due to the existence of
impurity atoms. The calculation conditions are summarized
in Table I.
2.3 Supercell calculations
The doping concentration x is defined as the atomic
percentage of the dopant per all atoms in a cell. In order to
study cases of different x-values using ABCAP and Quantum
Espresso, calculations were performed for two lattice sizes:
the conventional unit cell, Mg8Si4 (Fig. 1), and a 2 × 2 × 2
cubic supercell, Mg64Si32, which consists of 8 conventional
unit cells stacked along each direction. For the former, a
simple-cubic (sc) lattice was considered. The atomic
percentages of the dopant, when it displaces one of the
atoms (8 Mg and 4 Si) in the cell, is 8.333 at. %. For the
supercell, two lattice types, namely face-centered-cubic (fcc)
and sc, were considered to define the positions substituted
by the dopant in the lattice. Thus, the doping concentrations x
are 4.167 and 1.042 at. %, respectively.
© 2015 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 54, 07JC05 (2015) N. Hirayama et al.

Table I. Calculation parameters for the calculation codes used in this

study are listed. As shown in the table, the cut-off energy and the number of
k-points are set to be larger as to Quantum Espresso. It is because the
pseudopotential method, which this code is based on, requires calculation
cost that is generally smaller than the FLAPW method, thereby it is easy to
increase values of the parameters.
Quantum
Parameter ABCAP Machikaneyama
Espresso
Cut-off energy (eV) 653 327 —
Number of k-points 888 666 888
Exchange correlation GGA LDA GGA
Threshold of total (a) (b)
force for cell relaxation 10−4 — —
(eV=bohr)

On the other hand, Machikaneyama, which is based on

the Green’s function method for the scattering problem, can
perform calculations without considering a supercell for any
doping concentration.

2.4 Evaluation of formation energy

Based on the obtained energetically stable systems, we
calculated the following formation energy in order to discuss
the site preferentially occupied by an impurity:
EðMg2 Si1 A Þ ¼ EðMg2 Si1 A Þ þ EðSiÞ
 EðMg2 SiÞ  EðAÞ;
EðMg2 SiA Þ ¼ EðMg2 SiA Þ þ EðMgÞ
 EðMg2 SiÞ  EðAÞ;
EðMg2 SiA Þ ¼ EðMg2 SiA Þ  EðMg2 SiÞ  EðAÞ: ð3Þ
Equations (1)–(3) correspond to the case of impurity atom A
occupying the Si, Mg, and 4b (interstitial) sites, respectively.
Here, ξE(A) denotes the total energy of single crystalline of
A per ξ mol.
3. Results and discussion
3.1 Calculation code comparisons
In the present study, we focus on the lattice constant and
impurity site as structural properties and numerically estimate
the dependence of these two physical properties on the
doping concentration of Al.
3.1.1 Lattice constant We have calculated the lattice
constant a for various doping concentrations x by minimizing
the total energy of a bulk. Here, the atomic coordinates inside
the cell were fixed as the coordinates of the perfect intact
crystal, so the volume of the cell, that is, only the lattice
constant, was optimized so as to minimize the total energy.
(The localized shifting of atomic positions is considered in
the following section.)
Figures 3(a)–3(c) depict graphs showing the x-dependence
of a for Al-doped Mg2Si calculated using the ABCAP,
Quantum Espresso, and Machikaneyama codes, respectively.
The plotted points a0 for x = 0, are the lattice constants of a
perfect crystal with no impurity added. The calculation
results have been fitted by the method of least square method.
This resulted in values listed in Table II for the R value, and
parameters a0 and a of the linear formula; a(x) = a0 + ax.
As shown in the figures, the lattice constant a exhibits
qualitatively consistent dependence on the doping concen-
(c)
Fig. 3. (Color online) Doping-concentration-dependence of the lattice
constants calculated using (a) the Quantum Espresso, (b) the ABCAP, and
(c) the Machikaneyama codes for Al-doped Mg2Si. The lattice constants
ð1Þ were optimized by minimizing the total energy of a bulk without considering
the localized shifting of atomic positions. In the figures, circles, triangles, and
diamonds correspond to three types of insertions of Al: Mg and Si
ð2Þ substitution, and 4b site insertion, respectively.
tration x for the three different codes. However, the
magnitudes of a, i.e., the intercepts of the graphs, a0, vary
depending on the code; such as 6.26, 6.350, and 6.354 Å for
ABCAP, Quantum Espresso, and Machikaneyama, respec-
tively. Here we note that the two latter codes exhibit similar
values to experimental results: 6.355–6.391 Å.26–28) Since
this code dependence of a0 can be mostly attributed to the
differences in the calculation methods these codes are based
on, such as the method used for handling electron–electron
interaction, it has little significance on the discussions of this
paper. In this study, we focus on the dependence of a on x,
i.e., the slopes of the graphs.
Although Quantum Espresso neglects the core states of
electrons by using the pseudopotential method, the result did
indicate x-dependence of a that was quantitatively close to
ABCAP, which performs all-electron calculations. Therefore,
we may conclude that Quantum Espresso is an effective
code not only in terms of calculation accuracy, but also in
calculation cost for examining the structural changes
occurring when an impurity is doped.
We also observe that the graphs of a(x) exhibit good
linearity, as shown in the figures. Hence, these theoretical
methods can be expected to analyze systems with low
impurity concentrations effectively, such as those used in
experiments. Generally, it is expensive to perform a supercell
calculation for impurity concentrations that are around 1% or
lower. However, the clear linearity observed in the high-
concentration region can be extrapolated to predict the
behavior of the system in the low-concentration region. There
07JC05-3 © 2015 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 54, 07JC05 (2015) N. Hirayama et al.

Table II. The dependence of the lattice constant a on the doping concentration of Al, x, shown in Fig. 3, have been fitted by the method of least square
method. This resulted in values R2, and parameters a0 and a of the linear formula; a(x) = a0 + ax.
Quantum Espresso
Impurity site Parameter ABCAP Machikaneyama
Cell relax. Volume relax.
a0 6.35 6.35 6.26 6.354
Si site a 0.0091 0.0096 0.0084 0.0073
R2 0.9999 1.0 0.9966 0.9975
a −0.0050 −0.0046 −0.0060 −0.0061
Mg site
R2 0.9971 0.9904 0.9449 0.9963
a 0.0114 0.0135 0.0144 0.0190
4b site
R2 0.0098 0.0098 1.0 0.9947

is of course no guarantee that the function a(x) obtained in

the high-concentration system can be applied in the low-
concentration system with the same accuracy; but the fact
that an approximate idea about the properties of the low-
concentration region can be obtained from accurate calcu-
lations, such as the all-electron calculation, is advantageous
for the analysis of experimental results.
Furthermore, the calculation results derived using the
Machikaneyama method, as shown in Fig. 3(c), display a
trend that is close to those of the other two codes. As
described earlier, the calculation accuracy of low-concen- (a) (b)
tration-doped systems needs to be scrutinized with particular
care when the KKR method is used. This result, however,
proves the validity of the Machikaneyama method, at least
for a qualitative discussion on the effect of Al-doping on the
system considered in this study.

3.1.2 Formation energy An impurity site is a structural

property that is important for adding impurities. The site
preference for the impurity atoms when adding Al will be
considered here.
The dependences of the formation energy E on the
impurity concentration x obtained using the ABCAP,
Quantum Espresso, and Machikaneyama methods are shown
in Figs. 4(a)–4(c), respectively. Furthermore, the slopes of
the E(x) graphs, i.e., the rate of the formation energy variation
to the impurity concentration variation are shown in
Table III.
The three calculation codes in this study exhibited the
same trend for the site preferences of Al. In other words, Al
has the highest energy preference for substitutions at Mg site,
which will bring about n-type conductivity. Furthermore, the
validity of the Quantum Espresso method was qualitatively
verified, since it yielded the slopes of the E(x) graphs very
close to those of ABCAP, which is a all-electron calculation.
This raised our expectations for the investigation of the
impurity concentration dependence in even finer detail and
the behavior at even lower impurity concentrations using the
Quantum Espresso, which impose lower calculation loads.
3.2 Disorder in the crystal: Localized shifting of atomic
positions
In the preceding section, we focused on the lattice constants
and impurity sites as structural parameters. The existence of
impurity atoms inside crystals was considered in numerically
estimating the impact on these two physical properties. Here
we consider the effect of localized shifting of individual
07JC05-4
(c)
Fig. 4. (Color online) Doping-concentration-dependence of the formation
energy calculated using (a) the Quantum Espresso, (b) the ABCAP, and
(c) the Machikaneyama codes for Al-doped Mg2Si. In the figures, circles,
triangles, and diamonds correspond to three types of insertions of an
impurity: Mg and Si substitution, and 4b site insertion, respectively.
atoms inside cells from their positions in a perfect crystal by
the force they are subjected to because of the existence of
impurity atoms.
We reported previously that the localized shifting of
atomic positions was greatest for the nearest-neighbor atoms
of impurity atoms, being about 1 to 5%, according to a
structural relaxation calculation (variable-cell relaxation) of
the atomic positions inside cells using the Quantum Espresso
code.29) Here we investigated the contribution to the lattice
constants. The dotted line in Fig. 5(a) indicates the results.
A comparison of the solid and dotted lines (without and
with structural relaxation, respectively) in Fig. 5(a) reveals
that the impurity concentration dependence of the lattice
constants depends very little on the localized shifting of
atomic positions.
Furthermore, the impact of the shifting of atomic positions
can be ignored in discussions of the site preference of
© 2015 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 54, 07JC05 (2015) N. Hirayama et al.

Table III. The dependence of the formation energy E on the doping concentration of Al, x, shown in Fig. 4, have been fitted by the method of least square
method. The slope of the graph EA and the R2 are listed.
Quantum Espresso
Impurity site Parameter ABCAP Machikaneyama
Cell relax. Volume relax.
0.1490 0.1484 0.1561 0.2131 0.1490
Si site
1.0 1.0 — 0.9998 1.0
0.0823 0.0877 0.0919 0.0580 0.0823
Mg site
1.0 0.9998 — 0.9998 1.0
0.1477 0.1609 0.1081 0.3211 0.1477
4b site
0.978 0.9761 — 0.9945 0.978

Volume relaxation Cell Relaxation These results suggest that when considering the contribu-
tion of Al or other impurities that have similar ionic radii to
Mg2Si structure, the impact of the atomic positions can be
ignored, and only an analysis of the lattice constant is
necessary.

3.3 Feasibility of p-type Mg2Si

Synthesizing p-type Mg2Si30–33) is known to present
difficulties in many cases. If more stable p-type conductivity
can be achieved by impurity doping, then p- and n-type
Mg2Si together would contribute significantly to the
manufacture of thermoelectric modules. We will therefore
investigate the feasibility of p-type doped Mg2Si in this
section as a practical example of the cell-relaxation method of
Quantum Espresso.
Figure 6 shows the calculated formation energy of the
(a) system to which B and Na have been added with a doping
concentration of 1.042 at. %. Here, crystallographic informa-
Volume relaxation Cell Relaxation tion for rhombohedral B34) was used to evaluate the total
energy of single-crystalline B in Eqs. (1)–(3). These results
revealed that the formation energy was lowest with B at the
Si site and with Na at the Mg site. Thus, the substitution sites
that exhibit p-type conductivity were realized.

(b)
Fig. 5. (Color online) Comparison of the results obtained using Quantum
Espresso codes without and with structural relaxation (solid and dotted lines,
respectively) for (a) the lattice constant and (b) the formation energy of Al-
doped Mg2Si. It reveals that the impurity concentration dependence of the
lattice constants and the formation energies depend very little on the
localized shifting of atomic positions.
impurities as well, as illustrated in Fig. 5(b). This is because
that considering the localized shifting of atomic positions, the
change in the total energy is much smaller than the difference
in the formation energy at the various impurity sites.
07JC05-5
4. Conclusions
We investigated the structure of Al-doped Mg2Si from the
perspective of the total energy using several codes that
perform first-principles calculations: ABCAP, Quantum
Espresso, and Machikaneyama2002 (Akai KKR), which are
based on the full-potential linearized augmented plane-wave
method, the pseudopotential method, and the KKR=GGA
Green’s function method, respectively. The structural pa-
rameters obtained from the codes were compared.
ABCAP is the high-accuracy and high-throughput code
among the all-electron first-principles calculation codes.
Notwithstanding such favorable features, the applicability
of this code (and also, in general, other FLAPW methods) is
practically limited by the large amount of computing time
required to solve self-consistent field calculations, which is
the central issue in the case of light-doping systems that
demand a large supercell calculation. The results of this
work has indicated that a similar or qualitatively consistent
dependencies of both the lattice constant and the formation
energy on the impurity concentrations can be obtained by
using any codes mentioned above. In particular, the
calculation results obtained from ABCAP and Quantum
Espresso have been found to resemble each other closely.
This has suggested that by using Quantum Espresso, the
© 2015 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 54, 07JC05 (2015)
(a)
(b)
Fig. 6. Formation energies of (a) Na-doped and (b) B-doped Mg2Si are
shown. These results indicate that the formation energy is lowest when Na
and B atoms are located at the Mg and Si sites, respectively, which suggests
that p-type conductivity is realized by doping these impurities.
computing time is drastically reduced in the calculations of
impurity-doped Mg2Si without sacrificing much accuracy.
The calculations performed in this study also show high
linearity in the dependence of the lattice constants on
impurity concentration. This implies that it may be possible
to use the results obtained in this study for the high-
concentration regions as the first step toward the interpreta-
tion of experiments performed in lower-concentration
regions.
In addition, we examined how the structural properties are
affected by the local displacement of atoms caused by the
presence of impurities. As a result, the shifting of atomic
positions contributed little to both the lattice constant and the
formation energy.
As a practical example of the method examined in this
study, we examined the formation energies of B- and Na-
doped Mg2Si using the cell-relaxation method of Quantum
Espresso. The results showed that substitution sites that
exhibit p-type conductivity have been achieved.
Acknowledgments
The present authors are grateful to Professor H. Akai and
07JC05-6
N. Hirayama et al.
Professor M. Geshi for their professional guidance and
insightful comments. This research was partially supported
by JSPS KAKENHI Grand Number 26820099.
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