Journal of Alloys and Compounds 664 (2016) 369e377

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Consideration about the synthesis pressure effect on lattice defects of

Mg2Si using 1st principle calculations
Yoji Imai a, *, Yoshihisa Mori b, Shigeyuki Nakamura c, Ken-ichi Takarabe b
a
National Institute of Advanced Industrial Science and Technology, AIST Tsukuba Central 5, Higashi 1-1, Tsukuba, Ibaraki 305-8565, Japan
b
Okayama University of Science, Ridai-cho 1-1, Kita-ku, Okayama 700-0005, Japan
c
Tsuyama National College of Technology, Numa 624-1, Tsuyama, Okayama 708-8509, Japan

a r t i c l e i n f o a b s t r a c t

Article history: In order to understand the observed decrease in both of the absolute value of the Seebeck coefficient and
Received 13 April 2015 the electrical conductivity of n-type Mg2Si synthesized at high pressure, we have studied pressure
Received in revised form dependence of several kinds of lattice defect formation enthalpies of Mg2Si and also calculated their
2 September 2015
densities of states and band structures. Under the Mg-rich condition, the Mg atoms which occupy the
Accepted 13 September 2015
Available online 14 September 2015
interstitial sites of Mg2Si lattice, IMg, is the most dominant defect which causes the n-type conductivity,
and this defect seems to be energetically more favorable in the higher pressure. On the contrary, diva-
cancy of MgSi, VMgSi, which is electrically neutral, and Si substitution of the Mg site, whose contribution
Keywords:
Silicide
to the Seebeck coefficient would not be so large, are energetically favorable under the Si-rich conditions,
Electronic energy though IMg is still probable. Increase in pressure is favorable for stabilizing of IMg and unfavorable for that
Mg2Si of VMgSi and trivacancy (VMg2Si), the latter of which can be the possible origin of the p-type conductivity,
Defect though the probability that three vacancies (two VMg's and one VSi) associate would be small enough so
Ab-initio calculations as to cancel the effect of not-so-large defect formation enthalpy. The observed decrease in the n-type
Density of states defects in that material synthesized under higher pressure would probably be caused by lowering of the
synthesis temperature, which will be favorable for relaxation of the n-type defects.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction Simultaneous decrease in the absolute value of Seebeck coeffi-

Recently, Mg2Si has attracted renewed attention as one of the
eco-friendly thermoelectric semiconductors which would be useful
for recovering wasted heat at mid-temperature (600e900 K) such
as in the automotive industry. However, it has been known that
only n-type materials with relatively high thermoelectric perfor-
mance (TP) can be provided by conventional synthetic methods.
Since TP of Mg2Si-based p-type devices are inferior compared to TP
of the n-type materials, development of high-TP p-type materials
has been demanded.
Very recently, it was reported that electrical conductivity of n-
type Mg2Si synthesized at high pressure (1 GPa) is smaller than that
of Mg2Si synthesized by spark-plasma method under relatively low
pressure (ca. 0.03 GPa) by one order of magnitude, while the ab-
solute value of Seebeck coefficient of the former is much less than
that of the latter [1,2].
cient and electrical conductivity cannot be understood from the
conventional viewpoint of the carrier concentration dependence on
thermoelectric properties of doped semiconductors.1 However,
since electronic properties of undoped Mg2Si synthesize under
higher pressure seemed to come close to that of intrinsic semi-
conductors and to go away from impurity semiconductors, we
speculated that concentration of defects which are origins of the n-
type behavior of the undoped Mg2Si were decreased by
pressurization.
Main lattice defects included in the undoped Mg2Si synthesized
by using conventional processes are believed to be the excessive Mg
atoms which occupy interstitial sites (4b site by Wyckoff notation)
of the Mg2Si lattice. Since increase in pressure is generally favorable
for stabilization of interstitial defects, the observed behavior seems
to be contrary to the above speculation.

1
For example, electrical conductivity is assumed to increase with decrease in
* Corresponding author. absolute value of Seebeck coefficient, which is attributed to the increase in carrier
E-mail address: imai-y@aist.go.jp (Y. Imai). concentration in analysis using so-called Jonker plot.

http://dx.doi.org/10.1016/j.jallcom.2015.09.112
0925-8388/© 2015 Elsevier B.V. All rights reserved.
370 Y. Imai et al. / Journal of Alloys and Compounds 664 (2016) 369e377
In order to understand the above behaviors, it is quite important
to know how the density of various defects might be effected by
applied high pressures. Therefore, we tried to evaluate how the
defect concentrations would be affected by the applied pressure
using first-principle density-functional theory (DFT) calculations of
the formation enthalpies of various lattice defects of Mg2Si under
the supercell approximation.
The supercell approximation for isolated charged point defects
in semiconductors requires calculations for a system containing
more than a few hundred of atoms so as to obtain quantitatively
accurate results, since this approximation inevitably introduces
artificial long-range interactions between the periodic defects. The
systems which could be used in the present calculation might not
be large enough judging from this criteria. However, we used this
method since qualitative evaluation of the energies of the systems
containing defects can be performed by DFT which describes
accurately the crucial local rearrangements of bonding between
atoms and the underlying crystal structure.
2. Calculation details
2.1. Calculated structures
Mg2Si belongs to the space group of F m
3 m and the unit cell
consists of simple cubic sublattice of eight Mg atoms and face-
centered sublattice of four Si atoms (Mg8Si4). The Si atoms
occupy the 4a Wyckoff sites (0 0 0), and the Mg atoms occupy the 8c
(1/4 1/4 1/4) sites. There exist four interstitial sites corresponding to
the 4b Wyckoff sites (1/2 1/2 1/2), and occupation of these sites by
excessive Mg atoms are considered to be the main reason of the
quite persistent n-type conductivity of Mg2Si. This unit cell can be
reduced to the primitive rhombohedral Mg2Si cell if we adopt a set
of primitive vectors pointing from a corner site to any of the three
kinds of face-centering point of cubic lattice composed of Si atoms.
As for defects found in the Mg2Si lattice, Jund et al. [3] recently
performed systematic calculations.2 They calculated the formation
energies of the following eight kinds of defects; (1), an interstitial
Mg atom on the 4b site (IMg), (2), an interstitial Si atom on the 4b
site (ISi), (3), a vacancy on the Mg site (VMg), (4), a vacancy on the Si
site (VSi), (5), a Mg atom substituting the Si site (MgSi), (6), a Si atom
substituting the Mg site (SiMg), (7), a divacancy on adjacent one Mg
site and one Si site (VMgSi), and (8), a trivacancy on adjacent two Mg
sites and one Si site (VMg2Si).
Though they did not give the densities of states (DOS) curves of
the system containing these defects, they concluded that, (1),
Sequence of the defect formation energy will depend on the growth
condition (i.e., conditions rich in Mg or conditions poor in Mg), (2),
VSi, MgSi and ISi are energetically unfavorable in any condition, (3),
IMg will contribute to the n-type conductivity while VMg and VMg2Si
will contribute to the p-type conductivity, and (4), VMgSi and SiMg
have no doping effect.
In the present study, we re-evaluate the formation enthalpies of
those defects in the ambient and under the applied hydrostatic
pressure of 1 GPa so as to clarify the effect of the applied pressure
on the stability of various defects. In addition to the defects above,
we calculated an antisite defect of Mg and Si, where a pair of these
atoms exchange their positions. This antisite defect is regarded as
adjacent defects of (5) and (6). We have calculated this antisite
2
Very recently, Zwolenski et al. have published the results on relative stability of
Mg2Si containing statistically distributed point defects in the ambient pressure by
using coherent potential approximation (that is, without supercell approximation)
[4]. Comparison of the results by supercell approximation with theirs are left for
future studies.
defect since it has been known that adjacent coexistence of
different kind of defects, such as VMg and VSi, causes decrease in
defect formation energy.
The calculations of DOSs of defect-containing systems have been
performed for 3  3  3 supercell of the above rhombohedral
primitive cell composed of 81 atoms (Mg54Si27) which is accom-
panied by defects above stated. That is, calculated cells are as fol-
lows: Mg55Si27 for IMg, Mg53Si27 for VMg, Mg54Si28 for ISi, Mg54Si26
for VSi, Mg53Si26 for VMgSi, Mg52Si26 for VMg2Si, Mg53Si28 for SiMg,
Mg55Si26 for MgSi, and Mg54Si27 for the antisite defect. The relax-
ation of the cells caused by introduction of defects has not been
performed for DOS calculations since the optimization of these
structures took too much computational resources.
However, for energetic evaluations, we performed full-
optimization of the cells of more compact system which is based
on 2  2  2 supercell of the above rhombohedral cell containing 24
atoms (Mg16Si8) accompanied with the defects.3
2.2. Calculation methods
The calculation method is similar to that used in the previous
study on the Ca2SieMg2Si system [5,6]; calculations were per-
formed using CASTEP code developed by Payne et al. [7]. This is a
first-principle pseudopotential method based on DFT with a
pseudopotential description of the electronecore interaction and a
plane-wave expansion of the wavefunctions. The pseudopotential
used is the ultrasoft pseudopotential generated by the scheme of
Vanderbilt [8], where the Mg 2p state is explicitly treated as a part
of the valence. The PerdeweWang generalized gradient approxi-
mations (GGA) [9] are employed to approximate the DFT exchange
e correlation term.4
Self-consistent iteration convergence was assumed when the
total energy difference between successive cycles was less than
0.001 eV per atom. The kinetic cutoff energy for the plane-wave
expansion (Ecutoff) was set to 380 eV.5 The MonkhorstePacke
(M
P) scheme [12] was used for the k-point sampling with a
spacing of 0.5 nm
1 in reciprocal space, unless otherwise stated.
The DOS curves were obtained by broadening the discrete en-
ergy levels on a grid of M
P k-points using a Gaussian smearing
function of 0.07 eV full-width at half-maximum (FWHM). The en-
ergy is measured with respect to the Fermi level. The band struc-
ture (BS) along several high-symmetry lines in the Brillouin zone
have also been calculated for some of the systems.
In the calculations of the electronic energies, we performed a
geometrical optimization using the total energy minimization al-
gorithm and the BroydeneFletchereGoldfarbeShannon optimiza-
tion procedure, for which the criterion of convergence is as follows:
the energy change between two steps, the root-mean-square (rms)
residual force on movable atoms, the rms displacement of atoms
during the geometrical optimization process, and the rms residual
bulk stress must be smaller than 1 meV, 10
9 N, 10
4 nm, and
3
DOSs of optimized Mg16þxSi8þy accompanied with the defects have similar
shapes with corresponding unrelaxed Mg54þx, Si27þy, shown in the present paper,
but the location of Fermi level with respect to the energy gap have become
ambiguous due to too many localized energy levels generated above/between/
below the energy gap in most of cases.
4
Used method here may look relatively classical. For example, spin-orbit inter-
action, which is now considered to be of crucial importance in understanding the
dispersion relation of the top of valence bands [10], has not been directly treated.
However, we used the present method so as to maintain the consistency among our
series of related studies on silicide semiconductors. Electronic structure calcula-
tions of Mg2Si upto 2003, basically based on relatively classical methods, was
summarized in Refs. [5,11]. Recent studies on Mg2Si by more exquisite methods can
be found in, for example, references of [10].
5
Reasons for selecting this value have been described in the previous paper [6].
 Y. Imai et al. / Journal of Alloys and Compounds 664 (2016) 369e377 371

0.1 GPa, respectively.

Defect formation enthalpy of Mg16þxSi8þy, ⊿Hd, is defined as the
difference of calculated enthalpy of Mg16þxSi8þy and Href, the
enthalpy of the reference state defined by sum of (16 þ x)H(Mg)r
and (8 þ y)H(Si)r.
In Mg-rich conditions, H(Mg)r is equal to H(Mg), the calculated
enthalpy of bulk stable Mg with the hcp structure, and6

H(Si)r ¼ H(Mg2Si)
2H(Mg)

where H(Mg2Si) is the calculated enthalpy of Mg2Si. Href is proved

to be equal to

H(Mg16Si8) þ xH(Mg) þ yH(Si) þ (y/8)⊿HF (1)

where ⊿HF is the calculated formation enthalpy of Mg16Si8.7

In Si-rich conditions, H(Si)r is equal to H(Si), the calculated
enthalpy of bulk stable Si with the diamond structure, and
H(Mg)r ¼ 1/2 [H(Mg2Si)
H(Si)]. Href is proved to be equal to

H(Mg16Si8) þ xH(Mg) þ yH(Si) þ (x/16)⊿HF (2)

Fig. 1. Calculated densities of states (DOSs) of (a), Mg54Si27 without any lattice defect,
(b), Mg55Si27 with an interstitial Mg atom at 4b site, and (c), Mg53Si27 with a vacancy at
3. Results and discussions Mg site. Fermi level of each compound is aligned with 0.0 eV in this and succeeding
DOS curves.
3.1. Densities of states of defected structures

in the p-type conductivity. Occupancy by a Si atom, which is more

At first, we show the calculated DOSs of Mg2Si with/without an
positive than Ne and O, will cause the upward shift of the Fermi
interstitial Mg atom in the 4b site or a vacancy at the Mg site in
level, resulting in the n-type conductivity of the system.
Fig. 1. As is well known, Mg2Si (Mg54Si27) is an indirect semi-
In case a Si monovacancy (VSi) is introduced, the calculated DOS,
conductor with the gap value of ca. 0.77 eV and this is clearly
shown in Fig. 2b, also suggests the n-type conductivity. Therefore, it
demonstrated in Fig. 1a. Fermi level (0.0 eV) is located just between
is concluded that both excessive and deficient Si atoms will work as
the energy gap.8 In case an excessive Mg atom occupies the inter-
a source of the n-type conductivity.
stitial site of Mg2Si (IMg), new energy levels are generated between
The DOSs of the system with a divacancy on adjacent one Mg
this gap and the Fermi level is located on these states, as shown in
site and one Si site (VMgSi)and a trivacancy (VMg2Si)on adjacent two
Fig. 1b. DOS has a definite value at its Fermi level and this will
contribute to the n-type conductivity. In contrast, Fermi level of the
cell with a Mg vacancy (VMg) is located below the energy gap as
shown in Fig. 1c, which suggest the p-type conductivity of this
system.
Effect of occupancy of the interstitial site by a Si atom (ISi) is
shown in Fig. 2a. Since the Fermi level is located above the gap, this
defect must contribute to the n-type conductivity. This fact may
look strange if we take the fact into consideration that Si atoms will
attract electrons from Mg atoms in the Mg2Si crystal. However, Si
atoms at the interstitial sites can emit electrons into the Mg2Si
lattice. This is comparable to the cases where an inert neon (Ne)
atom or a negative oxygen (O) atom occupies the interstitial site. As
will be shown elsewhere, hypothetical occupation of the 4b site by
a Ne will cause no effect on the shape of DOS curve and the location
of the Fermi level, while hypothetical occupation of the 4b site by
an O atom causes the shift of Fermi level to below the gap, resulting

6
Chemical potentials of Mg and Si (mMg and mSi) depends on the atmosphere
where Mg2Si crystal is growing. If we assume a thermodynamic equilibrium among
Mg, Si, and Mg2Si, relation of 2mMg þ mSi ¼ mMg2 Si must hold. This relation leads to
the relation among enthalpies in case entropy contribution to the chemical po-
tentials can be disregarded [2].
7
Expression of Href by (1) and (2) are derived in Appendix 1.
8
Indirect energy gap value between the top of valence band at G point and the
bottom of the conduction band at X point was calculated to be 0.34 eV, which is
much smaller than the observed value, as is inferred from well-known LDA (and
GGA) problem. This value was a bit larger than that of our previous results using a
normal Mg2Si cell [5], perhaps due to (1), the increased cutoff frequency used, (2), Fig. 2. Calculated DOSs of (a), Mg54Si28 with an interstitial Si atom at 4b site, (b),
difference in lattice constants (observed value or optimized value), and/or (3), Mg53Si26 with a vacancy at Si site, (c), Mg53Si26 with a divacancy (VMgSi)on adjacent
difference in numerical errors caused by difference in calculated cell size (a normal one Mg and one Si site, and (d), Mg52Si26 with a trivacancy (VMg2Si)on adjacent two Mg
primitive cell or a supercell of 3  3  3), but is not discussed here. sites and one Si site.
372 Y. Imai et al. / Journal of Alloys and Compounds 664 (2016) 369e377

Mg sites and one Si site are given in Fig. 2c and d, respectively.9 As is

clearly seen in Fig. 2c, Fermi level of the system with a divacancy is
located just in the gap of the DOS curve, while that of the system
with a trivacancy is located below the gap. This implies that the
former is electrically neutral and the latter has a p-type nature. It
should be noted that the ionic model of Mg2Si, where Mg works as a
divalent cation and Si works as a tetravalent anion, is not a good
description and an equal number of Mg atoms and Si atoms seem to
keep a balance in the Mg2Si lattice.
Effect of substitutional occupation of the Mg site by a Si atom,
SiMg, that of the Si site by Mg, MgSi, and coexisting of both of them
(or, the antisite defect), on the form of DOS curve is shown in Fig. 3a,
b, and c, respectively.
From Fig. 3b and c, MgSi and the antisite defect must contribute
to the n-type conductivity since their Fermi levels are located on
the generated defect levels. On the contrary, it is interesting that
the DOS curve of the system with SiMg has a clear gap and the Fermi
level is located just below the generated level between the gap, as Fig. 3. Calculated DOSs of (a), Mg53Si28 with a substituted Mg site by a Si atom, SiMg,
shown in Fig. 3a. Jund et al. supposed that the system with this (b), Mg55Si26 with a substituted Si site by a Mg atom, MgSi, and (c), Mg54Si27 with an
defect must be electrically neutral, though they did not show antisite defect of Si and Mg.
calculated DOS curve of the system. However, we take care that its
Fermi level seems to be located just above the valence band edge.
We suppose that the difference between Jund et al.'s and ours is
due to the number of k-point sampled for the DOS calculations. In
fact, if we use four k-points sampled from the irreducible part of the
Brillouin zone by M
K method for the DOS calculations, the Fermi
level of this cell is located just in the middle of the energy gap,
while the Fermi level is located at the lower edge of the gap in case
we use fourteen k-points, corresponding to the k-point spacing of
0.03 nm
1. This suggests that the location of the defect level on the
calculated DOS curve will vary with the sampled k-points for DOS
calculation, which causes difficulty in judgment whether this
defect will contribute to the n-type or the p-type conductivity from
the calculated DOS curve.
To obtain the information on the accurate location of the Fermi
level, we calculated band diagram of that system.
Fig. 4 shows comparison of the band structure diagram of Fig. 4. Comparison of the band diagrams of Mg53Si28 with the defect of SiMg, (a), and
Mg54Si27 without lattice defects, (b). Top of the defect level or the valence band is
Mg53Si28 with the defect of SiMg, (a), and the perfect crystal of Mg2Si
aligned with 0.0 eV in (a) and (b), respectively.
(Mg54Si27), (b)10. As for Mg54Si27 without defects, top of the valence
bands (the 108th band11 is located at G, while bottom of the con- excited electrons. Since the energy range of the defect band (the
duction bands (the 109th band) is at X. As for Mg53Si28, the 109th 109th band) of Mg53Si28 extends over wide energy range, it is a quite
band (defect band) is generated between the 108th and the 109th subtle problem whether carriers on this band works as an n-type or
band of Mg54Si27, and the energy of the defect level is varied with k a p-type carrier. Average number of the n-type or the p-type con-
from the value very close to the value of the 108th band at L~G to the ducting carriers will depend on the temperature of the ambience
value just below the bottom of the conduction band (110th band) at but the contribution to the Seebeck coefficient must be not so
X ~ K. remarkable, if any.13
Since all the valence electrons of Mg53Si28 will be just accom- As stated later, this defect is dominant under Si-rich conditions.
modated in the 108th and lower bands,12 the conductivity type will Perhaps this explains why Mg2Si, even if synthesized under prob-
be determined by what energy levels will be occupied by thermally ably lower chemical potential of Mg than that under the stoichio-
metric condition, does not work as a distinct p-type semiconductor.
Anticipation to obtain a p-type semiconductor by changing the
9
synthetic atmosphere would prove in vain.
DOSs of those multivacancies have been calculated since previous calculations
have shown that they may be energetically more stable than monovacancies (VMg
and VSi) [3].
10 3.2. Defect formation enthalpies of various defects
Band structure diagram of Mg54Si27 shown in Fig. 4b may look quite different
from that of normal Mg2Si. This is just ostensible difference caused by the reason
which is alike with the case of folding of the extended Brillouin zone scheme to the In this section, we give the calculated enthalpies of Mg16þxSi8þy
reduced Brillouin zone scheme, as shown in Appendix 2. where x ¼
2,
1, 0, or þ1, and y ¼ þ1, 0, or
1 under the hy-
11
Plotted numerical values in this and succeeding band structure diagrams are drostatic pressure of 0 GPa or 1 GPa in Table 1 with their optimized
the numbers which express the order, counted from the bottom of the valence
band. Because the Mg2p states are explicitly treated as a part of the valence in the
pseudopotential used, 159 (or 162) bands composed of Mg2p atomic orbitals are
13
present for Mg53Si28 (or Mg54Si27), respectively, but these bands are omitted from One may consider band structure diagram of Mg53Si28 (Si on Mg site) shown in
the numbering in this figures for simplicity. Thus, 108 bands are fully occupied by Fig. 4a is not consistent with a DOS curve shown in Fig. 3a with non-vanishing DOS
valence electrons of Mg54Si27. at the Fermi level. This is caused by the fact that the k-points sampled by M
P
12
Number of valence electrons will not be varied by substitution of Mg with Si, as scheme to draw a DOS curve are not on the high-symmetry lines in the Brillouin
stated in the discussion above. zone to draw a band structure diagram.
 Y. Imai et al. / Journal of Alloys and Compounds 664 (2016) 369e377 373

Table 1
Calculated energy (enthalpy) and optimized cell volume of Mg2Si with/without lattice defects.

Compound Composition External pressure Calculated total energy (E) Cell volume (10
3 nm3) Volume per atom (10
3 nm3)
and enthalpy (H), (eV)

Mg (hcp) Mg2 0 GPa E ¼
1957.051 46.76 23.23

¼
978.526/Mg1
1 GPa E ¼
1957.061 45.40 22.70
H ¼
1956.778
¼
978.389/Mg1
Si (diamond structure) Si2 0 GPa E ¼
217.455 38.79 19.40
¼
108.727/Si1
1 GPa E ¼
217.455 38.38 19.19
H ¼
217.213
¼
108.607/Si1
stoichiometric Mg2Si Mg16Si8 0 GPa E ¼
16530.059 510.16 21.26
1 GPa E ¼
16530.043 500.9７ 20.87
H ¼
16526.916
Defected Mg2Si Kind of defect
IMg Mg17Si8 0 GPa E ¼
17507.287 521.54 20.86
1 GPa E ¼
17507.298 513.96 20.56
H ¼
17504.089
VMg Mg15Si8 0 GPa E ¼
15549.685 505.89 22.00
1 GPa E ¼
15549.686 497.02 21.61
H ¼
15546.583
ISi Mg16Si9 0 GPa E ¼
16636.540 519.22 20.77
1 GPa E ¼
16636.511 509.39 20.37
H ¼
16633.331
VSi Mg16Si7 0 GPa E ¼
16419.382 509.00 22.13
1 GPa E ¼
16419.393 498.25 21.66
H ¼
16416.283
VMgSi Mg15Si7 0 GPa E ¼
15440.188 502.20 22.83
1 GPa E ¼
15440.170 492.29 22.38
H ¼
15437.097
VMg2Si Mg14Si7 0 GPa E ¼
14460.270 504.55 24.03
1 GPa E ¼
14460.277 494.11 23.53
H ¼
14457.193
MgSi Mg17Si7 0 GPa E ¼
17397.619 526.61 21.94
1 GPa E ¼
17397.553 516.47 21.52
H ¼
17394.329
SiMg Mg15Si9 0 GPa E ¼
15658.658 504.33 21.01
1 GPa E ¼
15658.628 494.65 20.61
H ¼
15655.540
MgSi and SiMg Mg16Si8 0 GPa E ¼
16526.720 516.40 21.52
1 GPa E ¼
16526.674 506.31 21.10
H ¼
16523.513

cell volumes. Next, we give an example of the calculation of defect formation

The formation enthalpy of the perfect crystal of Mg2Si (Mg16Si8)
is
46.2 kJ/(mol of Mg2Si) at 0 GPa, as follows, using the values in
Table 1.
The enthalpy of the left-hand side of the following chemical
reaction formula,
16 Mg þ 8Si / Mg16Si8,
is
16526.228 eV by using the value of H(Mg) ¼
978.526 eV/Mg1
and H(Si) ¼
108.727 eV/Si1. The enthalpy of the right-hand side is
H(Mg16Si8) ¼
16530.059 eV/Mg16Si8. Therefore, the enthalpy
change of the reaction, or the formation enthalpy of Mg16Si8, is
⊿HF ¼
3.830 eV /Mg16Si8,
which leads to the value of
0.479 eV/Mg2Si or
46.2 kJ/(mol of
Mg2Si)
This value is only 60% of the observed value,
79.3 kJ/(mol of
Mg2Si) [13], as is often experienced in the GGA (and local density
approximation (LDA) to DFT), but we used this approximation since
it has been known that GGA gives relatively good results so as to
evaluate the energy differences among different types of structure,
at least, qualitatively.
enthalpy per atom.
H(Mg17Si8), the enthalpy of Mg17Si8 where one of the 4b sites of
Mg8Si4 is interstitially occupied by a Mg atom, is _ 17507.287 eV, as
shown in Table 1. Since H(Mg) ¼
978.526 eV and H(Si) ¼

2066.257 _ 2* (
978.526) ¼
109.206 eV under Mg-rich condi-
tion, the enthalpy of the reference state, Href (¼ 17H(Mg)þ8H(Si)),
is
17508.584 eV, which is equal to the sum of enthalpy of Mg16Si8
without defects (¼
16530.059 eV) and that of Mg (¼
978.526 eV)
according to Eq. (1) where x ¼ 1 and y ¼ 0.
Therefore, ⊿Hd, defined by the difference of this value (Href) and
H(Mg17Si8) above is
þ1.298 eV/Mg17Si8 ¼ þ0.0519 eV/Mg0.68Si0.32.
In contrast, under Si-rich condition, H(Si) ¼
108.727 eV and
HðMgÞ ¼ 1=2½HðMg2 SiÞ
HðSiÞ
¼ 1=2½ð
16530:059=8Þ
ð
108:727Þ
¼ 978:765 eV:
Therefore, Href (¼17H(Mg)þ8H(Si)) is
17508.8241 eV, which is
equal to the sum of enthalpy of Mg16Si8 without defects
(¼
16530.059 eV), that of Mg (¼
978.526 eV), and 1/16 of ⊿HF
374 Y. Imai et al. / Journal of Alloys and Compounds 664 (2016) 369e377

(¼
3.830 eV) according to Eq. (2).

⊿Hd, the difference of this value and H(Mg17Si8)
(¼
17507.287 eV) is þ1.537 eV/Mg17Si8 ¼ þ0.0615 eV/Mg0.68Si0.32.
Similar calculations have been performed for other defects.
Defect formation enthalpies per atom per defected site of IMg,
V , I , VSi, VMgSi, VMg2Si, SiMg, MgSi, and the antisite defect under
Mg Si

Si-rich condition and Mg-rich condition at 0 GPa, are shown as the

function of the composition of the system in Fig. 5 and Fig. 6,
respectively.
Fig. 5 indicates that, under the Si-rich condition, all the defect
formation enthalpies are positive, as is expected, but those of VMgSi,
VMg2Si and SiMg are relatively small compared to those of other
defects.
⊿Hd of IMg is not so positive, either, and this can be present from
energetic point of view.
It should be noted that defect formation enthalpies of VMgSi is
located below the connecting lines of those of VMg and VSi, as
shown by a black downward arrow, which means that this defect is
energetically stabilized by adjacence of VMg and VSi. This is also the
case of VMg2Si which is below the connecting line of VMg and VMgSi,
and the case of the antisite defect which is below the connecting
line of SiMg and MgSi. Therefore, defects can be energetically sta-
Fig. 6. Defect formation enthalpy per atom per defected site under the Mg-rich con-
bilized by adjacency. Defects will have a tendency to aggregate dition at 0 GPa.
from energetic point of view, though configurational entropy due to
the random configuration of defects will have opposite effect on the
free energies of the system. Thus, it is doubtful whether high and the occupancy of the Mg site tends to decrease with increasing
concentration of trivacancy of VMg2Si is realized. The most probable x. They also concluded that the Si occupancy was almost 100% for
defects expected in the Si-rich conditions are VMgSi and SiMg. From all the samples irrespective x and interstitial Si at 4b sites would be
the speculation in the previous section, this suggest the subtleness unlikely as well as vacancies at Si sites. These seem to be consistent
of the type of conductivity of Mg2Si synthesized under Si-rich to our results here, though their analysis did not take the possible
conditions in spite of our expectation of the p-type conductivity. substitutional defects and the multi-vacancies into account.
It should be mentioned here that defect formation enthalpies of The corresponding defect formation enthalpies under the Mg-
IMg and VMg are relatively small while those of ISi and VSi are large, rich condition are shown in Fig. 6. All the defect formation en-
though VSi may be stabilized by pairing with VMg. Recent report by thalpies are positive, as in the case under the Si-rich condition.
Kubouchi et al. [14] showed that assumption of interstitial occu- However, in contrast to Fig. 5, formation enthalpy of IMg is the
pancy by a Si atom or a mono-vacancy at a Si site is not necessary so smallest next to VMgSi. Since VMgSi is electrically neutral, the n-type
as to explain the results of X-ray measurement of the atomic dis- conductivity caused by IMg is determining, which is consistent with
tribution in the Mg2Si lattice. They stated that all the Mg-deficient the observed n-type behavior of Mg2Si.
samples, Mg2-XSi, contain about 0.5% IMg regardless of compositions These results stated in this section are consistent with the
previous report [3].

3.3. Effect of applied pressure on the defect formation enthalpies

In this section, we give the results on the effect of synthetic

pressure on the defect formation enthalpies.
Fig. 7 shows the comparison of the defect formation enthalpies
at 0 GPa (shown by open circles, B) or at 1 GPa (shown by closed
circles, C) under Mg-rich condition, a), or Si-rich condition, b).
Here, lines connecting each symbol have no physical meaning and
are drawn just so as to make it clear which defect is energetically
stable at assumed compositions.
As are shown, defect formation enthalpies of vacancies (VMg, VSi,
VMgSi, and VMg2Si) are increased if synthesized at higher pressure,
while defect formation enthalpies of interstitial defect (IMg and ISi)
are decreased. This can be understood if we take the following
thermodynamic relation into consideration [15]:

ðvH=vPÞT ¼ V
TðvV=vTÞp

where H, P, T, and V are atomic enthalpy, pressure, absolute tem-

Fig. 5. Defect formation enthalpy per atom per defected site under the Si-rich con-
dition at 0 GPa. Black downward arrows in this and the following figures indicate the
enthalpy change in case two defects are coupled. See the body of the text.
perature (here, T ¼ 0) and atomic volume, respectively.
V is small for the systems with an interstitial defect and large for
the system with a vacancy (Compare the following values:
V ¼ 20.86 nm3 for the crystal with IMg and V ¼ 20.77 nm3 for the
crystal with ISi are smaller than V ¼ 21.26 nm3 for perfect crystal of
 Y. Imai et al. / Journal of Alloys and Compounds 664 (2016) 369e377
Fig. 7. Effect of synthetic pressure on the defect formation enthalpy under the Mg-rich
and the Si-rich condition.
Mg16Si8, while V ¼ 22.00 nm3 for the crystal with VMg,
V ¼ 22.13 nm3 for the crystal with VSi, V ¼ 22.83 nm3 for the crystal
with VMgSi, and V ¼ 24.06 nm3 for the crystal with VMg2Si are larger
than V ¼ 21.16 nm3 for perfect crystal of Mg16Si8, as given in
Table 1).
Therefore, increase in enthalpy with pressure is larger for the
systems with vacancies and smaller for the systems with interstitial
atoms.14
From this figure, we can anticipate that concentration of IMg,
origin of the n-type conductivity, would be increased by pressuri-
zation while concentration of SiMg, dominant defect under Si-rich
condition, would not be affected so much.
The above energetic speculation is not consistent with the
observed fact that pressurization in synthesis process seemed to
cause decrease in the concentration of the n-type defects.
Therefore, in order to understand the observed fact, we must
also take kinetic effect of the pressure on the defect formation into
the consideration.
It is generally accepted that pressurization will decrease the
solid state transformation, because higher pressure will retard
atomic diffusion.15 Therefore, relaxation of distorted lattice crystal
due to the lattice defects will be retarded in case high pressure is
applied if the rate is determined by diffusion of atoms.
This is also the case where the defect relaxation will proceed
without atomic diffusion, or in other words, by a ‘martensitic
(diffusionless16)’ process. In that case, the rate of relaxation will be
determined by activation volume of the relaxation reaction, but
since the volume change of the following reaction is positive, the
14
This rule holds for one of substitutional defects, MgSi, but the pressure effect on
the other substitutional defect, SiMg, seems to be beyond this simple consideration.
15
An example of the pressure dependence of diffusion can be seen in Ref. [16].
16
A “diffusionless transformation” here means a phase transformation that occurs
without the long-range diffusion of atoms but rather by some form of cooperative,
homogeneous movement of many atoms that results in a change in the crystal
structure. Individual atomic movements are small, usually less than the interatomic
distances, and the atoms maintain their relative relationships [17].
375
activation volume of this relaxation reaction,
Mg17Si8 / Mg16Si8 þ Mg (3)
must be positive, or in other words, the relaxation rate is decreased
by an increased pressure if we assume the similar relation to the
well-known BrønstedeEvansePolanyi principle17 will also hold for
the relation between the activation volume and the volume change
of the reaction.
Thus, energetic and kinetic effect of pressure considered so far
are not able to explain the reason for the observed possible
decrease in the n-type defects.
Remaining possible reason not considered at this stage is the
lowering of the growth temperature in case of high pressure syn-
thesis. In fact, crystal growth of Mg2Si by spark-plasma method
proceeded at the temperature of 1113 K, while that under high
pressure proceeded at 673 K. Since the enthalpy change of the re-
action (3) is negative, this reaction must be exothermic and the
system readjusts itself to (partially) counteract the effect of the
applied change according to the Le Chatelier's principle. Therefore,
this relaxation reactions must have a tendency to progress to the
direction of the right-hand side in lower temperature. Thus, lower
temperature process is favorable for preparation of Mg2Si with less
n-type defects.
We speculate, at present, that this effect is the main reason why
Mg2Si with a low Seebeck coefficient and a low electrical conduc-
tivity has been prepared at higher pressure. High temperature
process is unfavorable for emitting Mg atom from the supersatu-
rated state of Mg atom in the Mg2Si lattice. It seems to be necessary
that the relaxation reaction proceeds under the moderate low
temperature where the temperature is not so low for the reaction to
be frozen.
If this explanation is justifiable, Mg2Si synthesized at lower
temperatures must have low n-type defect density. To our knowl-
edge, measurements of thermoelectric properties of Mg2Si pre-
pared at low temperature is limited to the work by Ogawa et al. [18],
who prepared Mg2Si thick films with (110) orientation on (001)
sapphire substrate at 573 K using radiofrequency magnetron
sputtering. They found both p-type and n-type characteristics of as-
deposited films using the Hall coefficient and the Seebeck coeffi-
cient measurements, though there was no significant difference in
the characteristics of the films showing the p-type and the n-type
conductivity within the limits of the investigation of the Mg/Si ratio
and the remaining lattice strain. Their results imply the possibility
of preparation of the p-type Mg2Si-based materials under low
temperature and Si-rich condition, but also seem to imply the
subtleness of conductivity type of Mg2Si prepared.
4. Summary
In summary, we have performed studies on densities of states,
band structures, and energetic calculations of Mg2Si with/without
several kinds of lattice defects.
Though the system used here may not be large enough to say
anything quantitatively accurate results, we could conclude as
follows.
The Mg atoms which occupy the interstitial sites of Mg2Si lattice,
IMg, is the most dominant defect in the Mg-rich condition and
causes the n-type conductivity. This defect seems to be
17
This principle is usually referred to as ‘Linear Free Energy Relationship (LFER)’,
which means that the differences in activation energies among reactions of the
same family are proportional to the differences of their enthalpy changes of the
reactions.
376 Y. Imai et al. / Journal of Alloys and Compounds 664 (2016) 369e377
Fig. 8. Comparison of the band structures near the Fermi levels (BSs) of normal Mg2Si
with that of Mg16Si8, or 2  2  2 superlattice of Mg2Si. (a): BS of Mg2Si, (b): BS of
Mg16Si8, (c): BS of Mg16Si8 along the path of (1 1 1) to (0 0 0) of the reciprocal space of
Mg16Si8, which corresponds to the path of (1/2 1/2 1/2) to (0 0 0) of the reciprocal
space of Mg2Si.
energetically more favorable in the higher pressure. Divacancy of
MgSi, VMgSi, which is electrically neutral, and Si substitution of the
Mg site whose contribution to the Seebeck coefficient would not be
so large, are energetically favorable in the Si-rich conditions,
though the interstitial Mg atoms occupying the interstitial sites of
the Mg2Si lattice is still probable. Increase in pressure is favorable
for stabilizing of IMg, origin of the n-type conduction, and unfa-
vorable for that of VMgSi, and trivacancy (VMg2Si), the latter of which
is the possible origin of the p-type conductivity. The observed
decrease in the n-type defects in the material synthesized under
higher pressure may be caused by decrease in synthesis tempera-
ture, which will be favorable for relaxation of the n-type defects.
From above considerations, we cannot expect to obtain p-type
Mg2Si material by further pressurization and we will have to
formulate additional device.
Appendix 1
Eqs. (1) and (2) can be derived as follows:
Definition of Href is
Href ¼ (16 þ x)H(Mg)r þ (8 þ y)H(Si)r.
In Mg-rich conditions;
H(Mg) r ¼ H(Mg) and H(Si)r ¼ H(Mg2Si) _
2H(Mg).
Since H(Mg2Si) can be rewritten as 2*H(Mg) þ H(Si)þ D HF of
Mg2Si,
Href ¼ (16 þ x) H(Mg) þ (8 þ y)*[H(Mg2Si)
2H(Mg)]
¼16H(Mg) þ xH(Mg) þ (8 þ y)*
[2H(Mg) þ H(Si) þ DHF(Mg2Si)
2H(Mg)]
¼16H(Mg) þ xH(Mg) þ(8 þ y)* [H(Si) þ DHF(Mg2Si)]
¼16H(Mg) þ 8H(Si) þ 8 DHF(Mg2Si) þ xH(Mg) þ yH(Si)
þ y DHF(Mg2Si)
Since DHF(Mg16Si8) ¼ 8 DHF(Mg2Si),
Href ¼ [16H(Mg) þ 8H(Si) þ DHF(Mg16Si8) ] þ xH(Mg) þ yH(Si)
þ (y/8) DHF(Mg16Si8)
¼H(Mg16Si8) þ xH(Mg) þyH(Si) þ (y/8) DHF(Mg16Si8) (1)
In Si-rich conditions,
H(Mg) r ¼ 1/2{H(Mg2Si)
H(Si)} and H(Si)r ¼ H(Si).
Therefore, Href ¼ (16 þ x)H(Mg)r þ (8 þ y)H(Si)r
¼ (16 þ x) *[1/2{H(Mg2Si)
H(Si)}] þ (8 þ y) H(Si)
¼ (16 þ x) *[(1/2){2H(Mg) þ H(Si) þ DHF(Mg2Si)}
eH(Si)}] þ 8H(Si)þy H(Si)
¼ 16H(Mg) þ xH(Mg) þ 16*(1/2) DHF(Mg2Si) þ(x/2)*
DHF(Mg2Si) þ 8H(Si)þy H(Si)
¼ {16H(Mg) þ8* DHF(Mg2Si) þ 8H(Si)}þxH(Mg) þ (x/2)*
DHF(Mg2Si)þ y* H(Si)
¼ H(Mg16Si8) þ xH(Mg) þyH(Si) þ (x/16)⊿HF(Mg16Si8) (2)
Appendix 2
In order to show how the band structure (BS) diagram of the
superlattice of Mg2Si is related to that of normal Mg2Si, we compare
the latter, shown in Fig. 8a, with the former, shown in Fig. 8b which
describes the BS diagram of Mg16Si8, 2  2  2 superlattice of Mg2Si
near their Fermi levels. The 2  2  2 superlattice were selected so
as to simplify the explanation.
It should be noted that the lengths of the primitive vectors of the
reciprocal space of Mg16Si8 are one half of those of Mg2Si. Therefore,
we double the range of drawing on the k-axis so as for the corre-
spondence to be seen more clearly.
Fig. 8c shows the BS diagram along the path which return to (0
0 0) via (1/2 1/2 1/2) from (1 1 1) of the reciprocal space of Mg16Si8,
which correspond to the path from L (1/2 1/2 1/2) to G (0 0 0) of the
reciprocal space of Mg2Si. The points that were set ‘A’, ‘C’ and ‘B’ in
Fig. 8c are folded in Fig. 8b and correspond to those in Fig. 8a.
It should be noted that the point X(1/2 0 1/2) in Fig. 8a also
correspond to G ((0 0 0) in Fig. 8b. Thus, Mg2Si may appear to be a
direct semiconductor at first glance when a calculation is per-
formed using a Mg16Si8 lattice. This does not occur when using a
Mg54Si27 lattice. Similarly, the point ‘D’ in Fig. 8a corresponds to ‘D’
in Fig. 8b along the path G (0 0 0) to X(1/2 0 1/2) in Fig. 8a and (0
0 0) to (1 0 1) of the reciprocal space of Mg16Si8, though not shown
here.
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