Accepted Manuscript

Dramatically reduced lattice thermal conductivity of Mg2Si thermoelectric material

from nanotwinning

Guodong Li, Jiangang He, Qi An, Sergey I. Morozov, Shiqiang Hao, Pengcheng Zhai,
Qingjie Zhang, William A. Goddard, III, G. Jeffrey Snyder
PII: S1359-6454(19)30127-2
DOI: [Link]
Reference: AM 15164

To appear in: Acta Materialia

Received Date: 12 February 2019

Revised Date: 25 February 2019
Accepted Date: 25 February 2019

Please cite this article as: G. Li, J. He, Q. An, S.I. Morozov, S. Hao, P. Zhai, Q. Zhang, W.A. Goddard
III., G.J. Snyder, Dramatically reduced lattice thermal conductivity of Mg2Si thermoelectric material from
nanotwinning, Acta Materialia, [Link]

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

Dramatically reduced lattice thermal conductivity of Mg2Si

thermoelectric material from nanotwinning

Guodong Li a,b, Jiangang He b, Qi An c, Sergey I. Morozov d, Shiqiang Hao b, Pengcheng Zhai *,a,
Qingjie Zhang a, William A. Goddard III e, and G. Jeffrey Snyder *,b

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a
Hubei Key Laboratory of Theory and Application of Advanced Materials Mechanics, School of Science,
Wuhan University of Technology, Wuhan 430070, China.

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b
Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208,
USA.

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c
Department of Chemical and Materials Engineering, University of Nevada Reno, Reno, Nevada 89557,
USA
d
Department of Computer Simulation and Nanotechnology, South Ural State University, Chelyabinsk

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454080, Russia
e
Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125,
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USA.
*
Corresponding authors: pczhai@[Link]; [Link]@[Link]
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Abstract: Tuning phonon transport to reduce the lattice thermal conductivity (κL) is crucial for
advancing thermoelectrics (TEs). Traditional strategies on κL reduction focus on introducing
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scattering sources such as point defects, dislocations, and grain boundaries, that may degrade the
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electrical conductivity and Seebeck coefficient. We suggest here, a novel twin boundary (TB)
strategy that can decrease the κL of Mg2Si by ~90%, but which may not degrade the electrical
properties significantly. We validate this suggestion using density functional theory (DFT). We
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attribute the mechanism of TB induced κL reduction to (i) the lower phonon velocities and larger
Grüneisen parameter, (ii) “rattling” of the Mg−Mg pair induced soft acoustic and optical modes,
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(iii) shorter phonon lifetime and higher phonon scattering rate. We predict that the size of
nanotwinned structure should be controlled between 3 nm and 100 nm in the Mg2Si matrix for the
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most effective κL reduction. These results should be applicable for other TE or non TE energy
materials with desired low thermal conductivity, suggesting rational designs of high-performance
Mg2Si TE materials with low κL for the energy conversion applications.

Keywords: Mg2Si Thermoelectric Material; Thermal Conductivity; Nanotwinning; Density

Functional Theory

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1. INTRODUCTION

Since the 20th century, overconsumption of fuel oils and the resulting energy crisis has been
increasingly causing such environmental issues as global climate change, acid rain pollution, and
marine pollution. Solid-state thermoelectric (TE) technology, enabling direct conversion between

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heat and electricity without moving parts, offers the possibility for relieving the current energy
crisis [1,2]. The widespread application of TE technology requires TE materials with high
conversion efficiency, which is characterized by the materials’ dimensionless figure of merit zT,

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zT = S2σT/(κE+κL), where S, σ, κE, κL, and T are the Seebeck coefficient, electrical conductivity,
electronic thermal conductivity, lattice thermal conductivity and absolute temperature,

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respectively [1-5]. To achieve a high zT value, TE materials should have a high Seebeck
coefficient, a high electrical conductivity, and a low total (electronic and lattice) thermal
conductivity.

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The current strategies for enhancing the zT value are mainly focused either on improving the
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power factor (S2σ) by tailoring the electrical transport properties [6,7] or on reducing κL through
phonon scattering [8-11]. Due to the strong correlation between S, σ, and κE, traditional strategy
of carrier optimization is often not very effective in improving zT [1,12,13]. Two decades ago,
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Dresselhaus et al. proposed a concept of quantum confinement for effectively decoupling the
correlation between S, σ, and κE [14,15]. Then, various effective band modification approaches
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(such as band convergence [16-18], distortion [19], and nestification [20].) were developed to
decouple these three parameters and enhance the S2σ and zT. Alternatively, exploring effective
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reduction strategies for κL (the only independent parameter) or seeking low κL materials has
consistently led to advances in high-performance TE materials [21-26]. For example, the
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extraordinary ‘liquid-like’ behavior in Cu2-xSe results in an intrinsically low κL of

0.4 W m−1 K−1 and a zT of 1.5 at 1000 K [21]. In SnSe single crystals, The lattice anharmonicity
leads to an exceptionally low κL of 0.23 ± 0.03 W m−1 K−1 and an unprecedented zT of 2.6 ± 0.03 at
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923 K [22,23]. In such TE materials as MgAgSb [24], Ag5-δTe3 [25], and Ag8SnSe6 [26], the
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complex crystal structure or weak chemical bonds leads to low heat capacity or low speed of
sound, well explaining the low intrinsic κL of < 0.5 W m−1 K [24-26]. Introducing phonon
scattering sources such as point defects [27-29], dislocations [30-32], grain boundaries [33-35],
can effectively shorten phonon relaxation time, giving rise to reduction in κL. Multiple fillers in
CoSb3 can achieve broad-frequency phonon scattering, reducing κL to the glass limit value of
0.2 W m−1 K−1, and leading to an extremely high zT of 1.7 at 850 K [29]. Full-spectrum phonon
scattering, which was achieved through grain boundary, dense dislocation arrays, and point defect,

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leads to a substantially lower κL of 0.33 W m−1 K−1 and a dramatic high zT of 1.86 at 320 K in
Bi0.5Sb1.5Te3 bulk alloys [30].
Twin boundaries (TBs), a thermodynamically stable planar defect, could provide another
phonon scattering source to effectively suppress κL [36-38]. Ren. et al. prepared nanotwinned
InSb and found that phonons can be scattered by TBs [36]. Shin. et al. found TB induced crystal

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defect reduced κL from 1.9 to 1.4 W m−1 K−1 for twin-contained Bi2Te3 nanowires [37]. Zhou et al.
found that nanotwins in PbTe can effectively reduce κL [38]. These findings suggest that TBs play

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significant roles in phonon scattering and κL reduction without degrading electronic transport
properties. However, the determining factors for TB induced κL reduction and the underlying

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scattering mechanisms remain unexplored.
To understand the role of TB on κL and the underlying phonon scattering mechanism, we
carried out DFT phonon calculations and solved the linearized Boltzmann equation to examine

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the phonon transport properties of single crystalline and nanotwinned Mg2Si. We find that TB can
reduce κL by ~ 90%, as shown in Fig. 1. At 300 K, the κL of nanotwinned Mg2Si is 1.42 and 1.20
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W m−1 K−1 along the a and c axis, respectively, only ~10% of that (11.8 W m−1 K−1) in single
crystalline Mg2Si. We attribute this remarkable κL reduction to the following three mechanisms:
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(i) lower phonon velocities and larger Grüneisen parameter, (ii) “rattling” of the Mg−Mg pair
induced soft acoustic and optical modes, (iii) shorter phonon lifetime and higher phonon
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scattering rate in nanotwinned Mg2Si.

The density of nanotwins is closed related to the various properties of nanotwins. Studying
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how density of nanotwins influences the κL requires large-scale atomic simulations such as
molecular dynamics. This will be considered as a future study.
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2. METHODOLOGY

All density functional theory (DFT) calculations were performed within the VASP code
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using the projector augmented wave (PAW) method [40-42]. The Perdew-Burke-Ernzerhof (PBE)
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version of the generalized gradient approximation (GGA) was adopted to describe the exchange
correlation interaction [43].
Г-centered symmetry reduced Monkhorst-Pack meshes with a fine resolution of 2π × 1/40
Å−1 were used to sample the k-points in the first Brillouin zone. An energy cutoff of 500 eV was
used for the plane-wave expansion, with the electronic energy and force convergence criteria of
1×10-6 eV and 1×10-2 eV/Å, respectively.

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Phonon dispersion calculations were carried out with the PHONOPY package using the
frozen phonon method [44]. The 3×3×3 supercell (81 atoms) for flawless Mg2Si and 3×3×1
supercell (162 atoms) for nanotwinned Mg2Si were chosen for the second order force constant
calculations. The third order force constants of the flawless and nanotwinned Mg2Si were
computed using the [Link] code with 3×3×3 and 2×2×1 supercells [45]. The phonon

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lifetime, scattering rate, and κL were carried out within the ShengBTE code by solving the
Boltzmann transport equation [46].

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3. RESULTS AND DISCUSSION

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Mg2Si crystalizes in a face centered cubic (FCC) structure with space group Fm 3 m (225).
The unit cell contains 8 × Mg and 4 × Si atoms with Mg occupying the (1/4, 1/4, 1/4) site and Si
occupying the (0, 0, 0) site (Fig. 2(a)). Each Mg atom is tetrahedrally coordinated to Si atoms

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with a Mg−Si bond length of 2.75 Å. The shared electron localization function (ELF) isosurfaces
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between Mg and Si atoms imply covalent character of the Mg−Si bond (Fig. 2(b)). Our optimized
lattice parameter is a = 6.359 Å, only 0.1% larger than the experimental value of 6.351 Å at room
temperature [47].
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Previous experimental results showed that the most stable coherent twin of Mg2Si is the
deformation twin with TBs along the {1-1-1} plane [48]. Here, we utilized DFT to relax the
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initial nanotwinned Mg2Si and then determined the stable atomic geometry, leading to the
structure shown in Fig. 2(c). The nanotwinned structure contains 24× Mg and 12 × Si atoms with
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lattice parameters a = 7.74 Å, b = 4.47 Å, c = 22.94 Å, α = β = γ = 90° (Fig. 2(c)) This leads to a

hexagonal primitive cell containing 12× Mg and 6 × Si atoms, as shown in Fig. S1 in the
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Supporting Material. The twin spacing is 1.15 nm with Si atoms sitting in the TB. Within the TB,
two Mg−Mg bonds form, coupling the upper and lower half of the twinned structure. This
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Mg−Mg length (2.55 Å) is shorter than the covalent bond length (2.85 Å) [50] and much shorter
than the metallic bond (3.20 Å) [51], implying covalent character for the Mg−Mg interaction in
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the TB. The Mg−Si bond length in the TBs is 2.88 Å, which is 0.13 Å longer than that (2.75 Å) in
single crystalline Mg2Si. This leads to a much weaker Mg−Si bond in the TBs than that in the
Mg2Si crystal. The upper half of the nanotwinned Mg2Si is the (1-1-1)[1-12] slip system, while
the lower half is (1-1-1)[-11-2]. Our previous DFT simulations suggested that the (1-1-1)[-11-2]
slip system is the most likely under pressure [49]. These results explain why the shear stress
induced during the synthetic processing can generate this deformation twin experimentally [48].

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An inherently low κL generally arises from low phonon velocities (vs) and larger Grüneisen
parameters (γG). We first calculated the vs, extracted from the slope of phonon dispersion around
Г point (Fig. 3). As listed in Table. 1, we calculate that vs = 3915 m/s for nanotwinned Mg2Si to
be 13% lower than that (4427 m/s) of single crystalline Mg2Si. This decrease is probably because
the TB leads to a bond length (2.88 Å) 4.7% longer than that in the flawless crystal (Fig. 2). This

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weaker Mg−Si bonding interaction leads to a softer structural rigidity, resulting in lower vs in the
nanotwinned structure. To determine the structural stability of flawless and nanotwinned Mg2Si,

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We calculated the elastic matrix elements (See Table S1 in the SM) and used the Voigt-Reuss-
Hill relationship to calculate the B and G (Table. 1) [52]. We found that G = 32.4 GPa in
nanotwinned Mg2Si is significantly lower (36%) than that (50.6 GPa) in the flawless crystal. This

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indicates that the global structural rigidity of nanotwinned Mg2Si is weaker than that in flawless
Mg2Si, even though a covalent Mg−Mg bond forms in the nanotwinned structure. This provides

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another explanation of why the vs in nanotwinned Mg2Si is lower than that in its flawless crystal.
The Grüneisen parameter (γG) characterizes the strength of lattice anharmonicity, providing
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another intrinsic material parameter related to the physical nature of thermal transport behavior.
The γG of flawless Mg2Si is 1.38 (Table 1), which is higher than that of single crystalline CoSb3
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(0.92) [53]. This explains why flawless Mg2Si with simple unit cell, light elements and large
phonon velocity (4427 m/s) possesses a comparable κL (11.8 W/mK at room temperature) with
single crystalline CoSb3 (10 W/mK) [53]. The calculated γG of nanotwinned Mg2Si is 1.49 (Table
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1), higher than that of flawless Mg2Si. The larger γG reflects a higher lattice anharmonicity in the
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nanotwinned Mg2Si. As the nanotwinned Mg2Si is mechanically sheared, the antisymmetric

deformation of upper and lower half part leads to the distorted TB [49]. While the Mg-Si
framework uniformly resists the deformation in flawless Mg2Si [49]. Because of the weaker
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Mg−Si bond in the TB discussed above, the TB rigidity is much softer than the Mg-Si framework.
This explains why the nanotwinned Mg2Si exhibits a larger anharmonicity than the flawless
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crystal.
To determine the underlying mechanism of the extremely low κL for nanotwinned Mg2Si, we
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investigated the phonon dispersion along the high-symmetry directions and the phonon density of
states (PDOS) of single crystalline and nanotwinned Mg2Si, as shown in Fig. 3. We highlighted
the acoustic modes with different colors because they are expected to play significant roles in the
thermal transport. For frequencies less than 125 cm-1, the Mg and Si atom in flawless Mg2Si
contribute equally to acoustic phonon branches (Fig. 3(c)). However, at high frequencies (>125
cm-1), the longitudinal acoustic (LA) phonon branches strongly overlap with the optical phonon
modes along the Г – X and Г – K directions (Fig. 2(b)). We attribute these behaviors to the

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similar atom masses between Mg and Si elements. Avoided crossings between the LA and optical
branches along the Г – K and Г – L directions lead to suddenly decreased LA phonon energy.
This softening of the phonon mode arises from avoided crossings, providing another reason why
flawless Mg2Si possesses an κL comparable with CoSb3 [53]. In nanotwinned Mg2Si, we observed
similar avoided crossings along the Г – M and Г – K directions, leading to flat LA phonon

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dispersions with a maximum frequency of 115 cm-1. This value is much lower than the maximum
LA phonon frequency (288 cm-1) in flawless Mg2Si. As shown in Fig. 3(e), the transverse

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acoustic (TA’) phonons in nanotwinned Mg2Si are also flat and soft. The avoided crossings
induced acoustic phonon softening similar to that found in other low κL TE compound such as
full-Heusler Ba2AuBi [54] and filled CoSb3 [55]. Thus, we attribute the origin of low κL to the

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atomic rattling in these compounds. Analogously to clathrates, we attributed the flat and soft
acoustic modes to the Mg−Mg pair “rattling” in the TB (Fig. 3(f)). The Mg1 atoms in the TB are

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linked with each other with a strong Mg−Mg covalent bond of 2.55 Å (Fig. 2(b) and Fig. 3(f)),
but the Mg1 interacts more weakly with the Si1 atom with the longer Mg−Si bond of 2.88 Å (Fig.
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2(b) and Fig. 3(f)). Thus we suggest that the Mg−Mg pair behaves as a rattling center that scatters
heat-carrying phonons, similar to the guest atom in clathrate CoSb3. This is consistent to the
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PDOS (Fig. 3(f)), which shows clearly that the Mg1 atom in the TB dominates the contribution of
low energy phonons (65 to 115 cm-1). In addition, the lattice distortion caused by the Mg−Mg pair
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also leads to low frequency optical phonons. The lowest optical phonon is only 25 cm-1 at A point
(Fig. 3(e)). This value is much lower than that of flawless Mg2Si (145 cm-1), and even lower than
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that of other low κL TE compounds, such as filled CoSb3 (42 cm-1) [55]. These soft acoustic and
optical phonons in nanotwinned Mg2Si demonstrate the “rattling” of the Mg−Mg pair as a
mechanism by which the TB lowers κL of Mg2Si.
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To further understand the role of TBs on thermal transport, we calculated the phonon
lifetime as a function of frequency for nanotwinned and flawless Mg2Si at room temperature, as
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shown in Fig. 4. The phonon lifetimes show the general trend that low frequency acoustic
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phonons have longer lifetimes than high frequency optical phonons [56]. We find that the phonon
lifetimes of nanotwinned Mg2Si are much shorter than those of flawless Mg2Si. This indicates
much stronger scattering in nanotwinned Mg2Si, which we attribute mainly to resonant scattering
caused by the Mg−Mg pair “rattling” in the TB. In nanotwinned Mg2Si, acoustic phonon lifetimes
show a dip at the frequency of 82 cm-1 and 115 cm-1 which corresponds to the flat LA and TA’
phonons as shown in Fig. 3(e). This is another indication that soft LA and TA’ phonons enhance
the phonon scattering.

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The shorter phonon lifetimes are due to higher scattering rate, as shown in Fig. 5. Here the
three-phonon interaction of absorption (Г+: λ + λ’→λ’’) and emission (Г-: λ→λ’ + λ’’) processes
for flawless Mg2Si and nanotwinned Mg2Si are displayed. The peaks in Fig. 5 represent the
scattering rate of a phonon with wavelength λ and frequency ω scattered by another phonon with
wavelength λ’ and frequency ω’. Due to the Mg−Mg pair “rattling” (Fig. 3(f)), nanotwinned

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Mg2Si shows much stronger scattering than flawless Mg2Si in both Г+ and Г- processes. In the Г+
process, the soft and flat LA and TA’ phonons (Fig. 3(e)) lead to scattering peaks of nanotwinned

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Mg2Si that are much lower than those of Mg2Si. In the Г- process, the high frequency modes of
nanotwinned Mg2Si decompose to low frequency phonons more easily. This shows that the
“rattling” can interacts further with the high frequency optical modes, suppressing the heat

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transport carried by them. Fig. 5 shows clearly that the phonon-phonon interaction in
nanotwinned Mg2Si is much stronger than that of flawless Mg2Si, another source of lower κL in

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nanotwinned Mg2Si.
To examine the impact of the phonon mean free paths (MFPs) on κL, Fig. 6 displays the
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cumulative κL as a function of MFP in flawless and nanotwinned Mg2Si at room temperature. The
cumulative κL shows a crossover at a MFP of 2~3 nm. For the high frequency phonon modes with
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small MFPs, it is the avoided crossings between LA and optical modes (Fig. 3(b)) that are
responsible for the cumulative κL of flawless Mg2Si being lower than that of nanotwinned Mg2Si.
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For the low frequency phonon modes with large MFPs, the resonant scattering originating from
the Mg−Mg pair “rattling” leads to a much lower cumulative κL of nanotwinned Mg2Si than that
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of flawless Mg2Si. At the MFP of ~100 nm, the cumulative κL for flawless Mg2Si is 9.5 W/mK,
80% of the κL (11.8 W/mK) for nanotwinned Mg2Si. This suggests that for effective κL reduction,
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the size of this nanotwin in the Mg2Si matrix should be controlled to lie between 3 nm and 100
nm.
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4. CONCLUSIONS
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In Summary, we applied DFT to determine the role of nanotwins on the κL of Mg2Si TE

material. We found that the κL of nanotwinned Mg2Si (1.42 and 1.20 W m−1 K−1 along the a and c
axis) is decreased 10 fold from that (11.8 W m−1 K−1) in single crystalline Mg2Si. We attribute this
κL reduction to three aspects:
(i) The weak Mg−Si bond leads to the low phonon velocity in nanotwinned Mg2Si. In
addition, the TB induced lattice mismatch leads to the large anharmonicity.

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(ii) The resonant scattering originated from “rattling” of Mg−Mg bond pair leads to soft
acoustic and optical modes in nanotwinned Mg2Si.
(iii) The shorter phonon lifetime and higher scattering rates indicate a stronger phonon-
phonon interaction in nanotwinned Mg2Si.
For the maximum effect in reducing κL, the size of this nanotwin Mg2Si should be controlled to

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lie between 3 nm and 100 nm in the Mg2Si matrix.

ACKNOWLEDGEMENTS

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This work is partially supported by the 111 Project of China under Project no. B07040. Q.A.

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and W.A.G were supported by the National Science Foundation CMMI program under grant no.
1727428. S.M. is thankful for the support by Act 211 Government of the Russian Federation,
under No. 02.A03.21.0011 and by the Supercomputer Simulation Laboratory of South Ural State

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University [57].
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Supplementary Material: Primitive cell of nanotwinned Mg2Si after relaxation; Average
phonon velocity (vs), Grüneisen parameter (γG) calculation method; Calculated Elastic matrix (Cij)
of single crystalline and nanotwinned Mg2Si.
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REFERENCES
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[1] G. J. Snyder and E. S. Toberer, Complex thermoelectric materials. Nat. Mater. 7 (2), 105 (2008).
TE

[2] J. He and T. M. Tritt, Advances in thermoelectric materials research: Looking back and moving
forward. Science 357, 1369 (2017).
[3] C. Chang, M. H. Wu, D. S. He, Y. L. Pei, C. F. Wu, X. F. Wu, H. L. Yu, F. Y. Zhu, K. D. Wang, Y.
EP

Chen, L. Huang, J. F. Li, J. Q. He, and L. D. Zhao, 3D charge and 2D phonon transports leading to
high out-of-plane ZT in n-type SnSe crystals. Science 360 (6390), 778 (2018).
[4] T. J. Zhu, Y. T. Liu, C. G. Fu, J. P. Heremans, J. G. Snyder, and X. B. Zhao, Compromise and
C

Synergy in High-Efficiency Thermoelectric Materials. Adv. Mater. 29 (14), 1605884 (2017).

AC

[5] W. G. Zeier, J. Schmitt, G. Hautier, U. Aydemir, Z. M. Gibbs, C. Felser, and G. J. Snyder,

Engineering half-Heusler thermoelectric materials using Zintl chemistry. Nat. Rev. Mater. 1 (6),
16032 (2016).
[6] J. W. Zhang, L. R. Song, G. K. H. Madsen, K. F. F. Fischer, W. Q. Zhang, X. Shi, and B. B. Iversen,
Designing high-performance layered thermoelectric materials through orbital engineering. Nat.
Commun. 7, 10892 (2016).

8
 ACCEPTED MANUSCRIPT

[7] G. D. Li, U. Aydemir, M. Wood, W. A. Goddard, P. C. Zhai, Q. J. Zhang, and G. J. Snyder, Defect-
Controlled Electronic Structure and Phase Stability in Thermoelectric Skutterudite CoSb3. Chem.
Mater. 29 (9), 3999 (2017).
[8] He, J. Q.; Girard, S. N.; Zheng, J. C.; Zhao, L. D.; Kanatzidis, M. G.; Dravid, V. P., Strong Phonon
Scattering by Layer Structured PbSnS2 in PbTe Based Thermoelectric Materials. Adv. Mater. 24 (32),
4440 (2012).

PT
[9] Liu, W. S.; Zhang, B. P.; Li, J. F.; Zhao, L. D., Effects of Sb compensation on microstructure,
thermoelectric properties and point defect of CoSb3 compound. J. Phys. D: Appl. Phys. 40 (21), 6784

RI
(2007).
[10] He, J. Q.; Blum, I. D.; Wang, H. Q.; Girard, S. N.; Doak, J.; Zhao, L. D.; Zheng, J. C.; Casillas, G.;
Wolverton, C.; Jose-Yacaman, M.; Seidman, D. N.; Kanatzidis, M. G.; Dravid, V. P., Morphology

SC
Control of Nanostructures: Na-Doped PbTe-PbS System. Nano. Lett. 12 (11), 5979 (2012).
[11] Wu, H. J.; Carrete, J.; Zhang, Z. Y.; Qu, Y. Q.; Shen, X. T.; Wang, Z.; Zhao, L. D.; He, J. Q., Strong
enhancement of phonon scattering through nanoscale grains in lead sulfide thermoelectrics. NPG.

U
Asia. Mater. 6, e108 (2014).
AN
[12] B. A. Xu, T. L. Feng, M. T. Agne, L. Zhou, X. L. Ruan, G. J. Snyder, and Y. Wu, Highly Porous
Thermoelectric Nanocomposites with Low Thermal Conductivity and High Figure of Merit from
Large-Scale Solution-Synthesized Bi2Te2.5Se0.5 Hollow Nanostructures. Angew. Chem. Int. Edit. 56
M

(13), 3546 (2017).

[13] Y. Z. Pei, A. D. LaLonde, N. A. Heinz, X. Y. Shi, S. Iwanaga, H. Wang, L. D. Chen, and G. J. Snyder,
Stabilizing the Optimal Carrier Concentration for High Thermoelectric Efficiency. Adv. Mater. 23
D

(47), 5674 (2011).

TE

[14] Goldsmid, H. J. Introduction to Thermoelectricity, Springer, Heidelberg, Germany (2009).

[15] L. D. Hicks and M.S. Dresselhaus, Effect of Quantum-Well Structures on the Thermoelectric Figure
of Merit. Phys. Rev. B 47, 12727 (1993).
EP

[16] L. D. Hicks, T. C. Harman, X. Sun, M. S. Dresselhaus, Experimental study of the effect of quantum-
well structures on the thermoelectric figure of merit. Phys. Rev. B 53, 10493 (1996).
[17] H. S. Kim, N. A. Heinz, Z. M. Gibbs, Y. L. Tang, S. D. Kang, and G. J. Snyder, High thermoelectric
C

performance in (Bi0.25Sb0.75)(2)Te-3 due to band convergence and improved by carrier concentration

control. Mater. Today. 20 (8), 452 (2017).
AC

[18] Y. Z. Pei, X. Y. Shi, A. LaLonde, H. Wang, L. D. Chen, and G. J. Snyder, Convergence of electronic
bands for high performance bulk thermoelectrics. Nature 473 (7345), 66 (2011).
[19] Y. L. Tang, Z. M. Gibbs, L. A. Agapito, G. Li, H. S. Kim, M. B. Nardelli, S. Curtarolo, and G. J.
Snyder, Convergence of multi-valley bands as the electronic origin of high thermoelectric
performance in CoSb3 skutterudites. Nat. Mater. 14 (12), 1223 (2015).

9
 ACCEPTED MANUSCRIPT

[20] J. P. Heremans, V. Jovovic, E. S. Toberer, A. Saramat, K. Kurosaki, A. Charoenphakdee, S.

Yamanaka, and G. J. Snyder, Enhancement of thermoelectric efficiency in PbTe by distortion of the
electronic density of states. Science 321 (5888), 554 (2008).
[21] S. Q. Lin, W. Li, Z. W. Chen, J. W. Shen, B. H. Ge, and Y. Z. Pei, Tellurium as a high-performance
elemental thermoelectric. Nat. Commun. 7, 10287(2016).
[22] H. L. Liu, X. Shi, F. F. Xu, L. L. Zhang, W. Q. Zhang, L. D. Chen, Q. Li, C. Uher, T. Day, and G. J.

PT
Snyder, Copper ion liquid-like thermoelectrics. Nat. Mater. 11 (5), 422 (2012).
[23] L. D. Zhao, S. H. Lo, Y. S. Zhang, H. Sun, G. J. Tan, C. Uher, C. Wolverton, V. P. Dravid, and M. G.

RI
Kanatzidis, Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals.
Nature 508 (7496), 373 (2014).
[24] C. W. Li, J. Hong, A. F. May, D. Bansal, S. Chi, T. Hong, G. Ehlers, and O. Delaire, Orbitally driven

SC
giant phonon anharmonicity in SnSe. Nature Physics 11 (12), 1063 (2015).
[25] P. J. Ying, X. Li, Y. C. Wang, J. Yang, C. G. Fu, W. Q. Zhang, X. B. Zhao, and T. J. Zhu,
Hierarchical Chemical Bonds Contributing to the Intrinsically Low Thermal Conductivity in alpha-

U
MgAgSb Thermoelectric Materials. Adv. Funct. Mater. 27 (1), 1604145 (2017).
AN
[26] X. Y. Zhang, Z. W. Chen, S. Q. Lin, B. Q. Zhou, B. Gao, and Y. Z. Pei, Promising Thermoelectric
Ag5-delta Te3 with Intrinsic Low Lattice Thermal Conductivity. ACS. Energy. Lett. 2 (10), 2470
(2017).
M

[27] W. Li, S. Q. Lin, B. H. Ge, J. Yang, W. Q. Zhang, and Y. Z. Pei, Low Sound Velocity Contributing to
the High Thermoelectric Performance of Ag8SnSe6. Adv. Sci. 3 (11), 1600196 (2016).
[28] W. Li, L. L. Zheng, B. H. Ge, S. Q. Lin, X. Y. Zhang, Z. W. Chen, Y. J. Chang, and Y. Z. Pei,
D

Promoting SnTe as an Eco-Friendly Solution for p-PbTe Thermoelectric via Band Convergence and
TE

Interstitial Defects. Adv. Mater. 29 (17), 1605887 (2017).

[29] L. W. Fu, M. J. Yin, D. Wu, W. Li, D. Feng, L. Huang, and J. Q. He, Large enhancement of
thermoelectric properties in n-type PbTe via dual-site point defects. Energ. Environ. Sci. 10 (9), 2030
EP

(2017).
[30] X. Shi, J. Yang, J. R. Salvador, M. F. Chi, J. Y. Cho, H. Wang, S. Q. Bai, J. H. Yang, W. Q. Zhang,
and L. D. Chen, Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through
C

Separately Optimizing Electrical and Thermal Transports. J. Am. Chem. Soc. 133 (20), 7837 (2011).
[31] S. I. Kim, K. H. Lee, H. A. Mun, H. S. Kim, S. W. Hwang, J. W. Roh, D. J. Yang, W. H. Shin, X. S.
AC

Li, Y. H. Lee, G. J. Snyder, and S. W. Kim, Dense dislocation arrays embedded in grain boundaries
for high-performance bulk thermoelectrics. Science 348 (6230), 109 (2015).
[32] Z. W. Chen, Z. Z. Jian, W. Li, Y. J. Chang, B. H. Ge, R. Hanus, J. Yang, Y. Chen, M. X. Huang, G. J.
Snyder, and Y. Z. Pei, Lattice Dislocations Enhancing Thermoelectric PbTe in Addition to Band
Convergence. Adv. Mater. 29 (23), 1606768 (2017).

10
 ACCEPTED MANUSCRIPT

[33] Z. W. Chen, B. H. Ge, W. Li, S. Q. Lin, J. W. Shen, Y. J. Chang, R. Hanus, G. J. Snyder, and Y. Z.
Pei, Vacancy-induced dislocations within grains for high-performance PbSe thermoelectrics. Nat.
Commun. 8, 13828 (2017).
[34] B. Poudel, Q. Hao, Y. Ma, Y. C. Lan, A. Minnich, B. Yu, X. A. Yan, D. Z. Wang, A. Muto, D.
Vashaee, X. Y. Chen, J. M. Liu, M. S. Dresselhaus, G. Chen, and Z. F. Ren, High-thermoelectric
performance of nanostructured bismuth antimony telluride bulk alloys. Science 320 (5876), 634

PT
(2008).
[35] Q. H. Zhang, Z. X. Zhou, M. Dylla, M. T. Agne, Y. Z. Pei, L. J. Wang, Y. S. Tang, J. C. Liao, J. Li, S.

RI
Q. Bai, W. Jiang, L. D. Chen, and G. J. Snyder, Realizing High-performance Thermoelectric Power
Generation through Grain Boundary Engineering of Skutterudite-based Nanocomposites. Nano.
Energy 41, 501 (2017).

SC
[36] X. L. Su, P. Wei, H. Li, W. Liu, Y. G. Yan, P. Li, C. Q. Su, C. J. Xie, W. Y. Zhao, P. C. Zhai, Q. J.
Zhang, X. F. Tang, and C. Uher, Multi-Scale Microstructural Thermoelectric Materials: Transport
Behavior, Non-Equilibrium Preparation, and Applications. Adv. Mater. 29 (20), 1602013 (2017).

U
[37] J. Mao, Y. M. Wang, Z. H. Liu, B. H. Ge, and Z. F. Ren, Phonon scattering by nanoscale twin
AN
boundaries. Nano. Energy. 32, 174 (2017).
[38] H. S. Shin, S. G. Jeon, J. Yu, Y. S. Kim, H. M. Park, and J. Y. Song, Twin-driven thermoelectric
figure-of-merit enhancement of Bi2Te3 nanowires. Nanoscale. 6 (11), 6158 (2014).
M

[39] Y. G. Zhou, J. Y. Yang, L. Cheng, and M. Hu, Strong anharmonic phonon scattering induced giant
reduction of thermal conductivity in PbTe nanotwin boundary. Phys. Rev. B. 97 (8), 085304 (2018).
[40] J. Tani and H. Kido, Thermoelectric properties of bi-doped Mg2Si semiconductors. Physica. B. 364,
D

218, (2005).
TE

[41] G. Kresse and J. Furthmuller, Efficiency of ab-initio total energy calculations for metals and
semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15 (1996).
[42] G. Kresse and J. Furthmuller, Efficient iterative schemes for ab initio total-energy calculations using a
EP

plane-wave basis set. Phys. Rev. B. 54, 11169 (1996).

[43] G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method.
Phys. Rev. B. 59, 1758 (1999).
C

[44] J. P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev.
Lett. 77, 3865 (1996).
AC

[45] A. Togo, F. Oba, I. Tanaka, First-principles calculations of the ferroelastic transition between rutile-
type and CaCl2-type SiO2 at high pressures. Phys. Rev. B. 78, 134106 (2008).
[46] W. Li, L. Lindsay, D. A. Broido, D. A. Stewart, and N. Mingo, Thermal conductivity of bulk and
nanowire Mg2SixSn1-x alloys from first principles. Phys. Rev. B. 86, 174307 (2012).
[47] W. Li, J. Carrete, N. A. Katcho, and N. Mingo, ShengBTE: A solver of the Boltzmann transport
equation for phonons. Comput. Phys. Commun. 185 (6), 1747 (2014).

11
 ACCEPTED MANUSCRIPT

[48] G. S. Nolas, D. Wang, M. Beekman, Transport properties of polycrystalline Mg2Si1-ySby (0 <= y <
0.4). Phys. Rev. B. 76, 235204 (2007).
[49] J. I. Jang, J. E. Lee, B. S. Kim, S. D. Park, and H. S. Lee, Twinning and its formation mechanism in a
binary Mg2Si thermoelectric material with an anti-fluorite structure. Rsc. Adv. 7 (35), 21671 (2017).
[50] G. D. Li, Q. An, S. I. Morozov, B. Duan, W. A. Goddard, P. C. Zhai, Q. J. Zhang, and G. J. Snyder,
Mechanical softening of thermoelectric semiconductor Mg2Si from nanotwinning. Scripta. Mater. 157,

PT
90 (2018).
[51] S. P. Green, C. Jones, A. Stasch, Stable magnesium(I) compounds with Mg-Mg bonds. Science 318,

RI
1754 (2007).
[52] R. S. Busk, Effect of Temperature on the Lattice Parameters of Magnesium Alloys. J. Met. 4, 207
(1952).

SC
[53] D. H. Chung, Elastic Moduli of Single Crystal and Polycrystalline [Link]. Mag. 8, 833 (1963).
[54] T. Caillat, A. Borshchevsky, J. P. Fleurial, Properties of single crystalline semiconducting CoSb3. J.
Appl. Phys. 80, 4442 (1996).

U
[55] J. G. He, M. Amsler, Y. Xia, S. S. Naghavi, V. I. Hegde, S. Q. Hao, S. Goedecker, V. Ozolins, and C.
AN
Wolverton, Ultralow Thermal Conductivity in Full Heusler Semiconductors. Phys. Rev. Lett. 117,
046602 (2016).
[56] B. L. Huang and M. Kaviany, Filler-reduced phonon conductivity of thermoelectric skutterudites: Ab
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initio calculations and molecular dynamics simulations. Acta. Mater. 58, 4516 (2010).
[57] Z. T. Tian, J. Garg, K. Esfarjani, T. Shiga, J. Shiomi, and G. Chen, Phonon conduction in PbSe, PbTe,
and PbTe1-xSex from first-principles calculations. Phys. Rev. B. 85, 184303 (2012).
D

[58] Kostenetskiy, P. S.; and Safonov, A.Y., SUSU Supercomputer Resources. Proceedings of the 10th
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Annual International Scientific Conference on Parallel Computing Technologies (Arkhangelsk, Russia,

2016).
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Table:

Table. 1 Calculated phonon velocities (vLA/TA/TA’, vs), Grüneisen parameter (γG), bulk modulus (B), and
shear modulus (G) of single crystalline and nanotwinned Mg2Si, respectively. vLA/TA/TA’ is calculated by

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fitting the slope of the acoustic phonon dispersion around the Г point. The calculation method for vs and γG
are shown in eqn. S1 and S2 in the SM.
vLA vTA vTA’ vs B G

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System γG
(m/s) (m/s) (m/s) (m/s) (GPa) (GPa)
Single crystalline Mg2Si 7410 4036 3895 4427 1.38 54.6 50.6

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Nanotwinned Mg2Si 6754 3555 3444 3915 1.49 50.6 32.4

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Figures:

Figure 1:

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Figure 1. Lattice thermal conductivity (κL) of single crystalline and nanotwinned Mg2Si as a function of
temperature, and a comparison with experimental value of bulk Mg2Si [39].
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Figure 2:

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Figure 2. Atomic Structures of single crystalline and nanotwinned Mg2Si. (a) Crystal structure of single
crystalline Mg2Si showing the FCC unit cell. (b) Atomic structure of Mg2Si (with calculated isosurfaces at
a value of 0.78 of ELF) along the a-c plane. (c) Atomic structure of nanotwinned Mg2Si (ELF = 0.78) with
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the TB along the {1-1-1} plane.

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Figure 3:

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Figure 3. The phonon transport of nanotwinned and flawless Mg2Si. (a) Brillouin zone and high-symmetry
paths in FCC Mg2Si. (b) Phonon band structures and (c) Phonon density of state (PDOS) of flawless Mg2Si.
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(d) Brillouin zone and high-symmetry paths in hexagonal nanotwinned Mg2Si. (e) Phonon band structures
and (f) PDOS of nanotwinned Mg2Si.
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Figure 4:

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Figure 4. Phonon lifetimes as a function of phonon frequencies for nanotwinned and flawless Mg2Si at
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Figure 5:

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Figure 5. Phonon scattering rates of three-phonon absorption (Г+) and emission (Г-) processes for (a)
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flawless Mg2Si and (b) nanotwinned Mg2Si, respectively. This shows that the scattering rates are
dramatically faster for the nanotwinned Mg2Si.
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Figure 6:

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Figure 6. Cumulative contributions to thermal conductivity as a function of phonon MFP at room

temperature for flawless and nanotwinned Mg2Si.
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Supplementary Material

Dramatically reduced lattice thermal conductivity of Mg2Si

thermoelectric material from nanotwinning

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Guodong Li a,b, Jiangang He b, Qi An c, Sergey I. Morozov d, Shiqiang Hao b, Pengcheng Zhai *,a,
Qingjie Zhang a, William A. Goddard III e, and G. Jeffrey Snyder *,b

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a
Hubei Key Laboratory of Theory and Application of Advanced Materials Mechanics, School of Science,

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Wuhan University of Technology, Wuhan 430070, China.
b
Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208,
USA.

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c
Department of Chemical and Materials Engineering, University of Nevada Reno, Reno, Nevada 89557,
USA
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Department of Computer Simulation and Nanotechnology, South Ural State University, Chelyabinsk
454080, Russia
e
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Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125,
USA.
*
Corresponding authors: pczhai@[Link]; [Link]@[Link]
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Primitive cell of nanotwinned Mg2Si after relaxation

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Figure S1. Primitive cell of nanotwinned Mg2Si along the (a) a-c plane and (b) a-b plane, respectively.
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Average phonon velocity (vs), Grueneisen parameter (γG) calculation method

The average phonon velocity (vs) is calculated using the following equation [1]:

−1
1 1 1 1 
3

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vs =   3 + 3 + 3   Eqn. S1
 3  vLA vTA vTA '  

where vLA, vTA, vTA’ is the three acoustic phonon velocities which is the slope of acoustic phonon

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dispersions.

The Gruneisen parameter (γG) is calculated using the following equation [1]:

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3  3vLA
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− 4vs2 
γG =  2  Eqn. S2
2  vLA + 2vs2 

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Calculated Elastic matrix (Cij) of single crystalline and nanotwinned Mg2Si

Table S1. Calculated elastic matrix (Cij) of single crystalline and nanotwinned Mg2Si. The unit of elastic

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constants is GPa.

System C11 C12 C13 C22 C23 C33 C44 C55 C66

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Flawless Mg2Si 117.0 23.45 - - - - 45.37 - -

Nanotwinned Mg2Si 88.4 33.4 22.9 - - 122.2 27.6 26.7 -

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REFERENCES:

[1] P. J. Ying, X. Li, Y. C. Wang, J. Yang, C. G. Fu, W. Q. Zhang, X. B. Zhao, and T. J. Zhu, Adv. Funct.
Mater. 27 (1), 1604145 (2017).

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