Phonons Near Lattice Instabilities in

Thermoelectrics SnSe, SnTe, and PbTe

Olivier Delaire1,2,
C.Li2, J. Hong2, D. Bansal2, J. Ma2, A. May2,
B. Sales2, D. Abernathy2, G. Ehlers2, S. Chi2, T. Hong2
1Duke University, 2Oak Ridge National Laboratory

Funding:
• DOE Early Career Award
• DOE S3TEC Energy Frontier Research Center
 Thermal conductivity in thermoelectrics
• Suppress lattice thermal conductivity klat to optimize
thermoelectric efficiency:
(σ S 2T ) S: Seebeck ; s: el. conductivity
zT =
(κ el + κ lat ) k: thermal conductivity

• Rationalize microscopic origins of klat to gain control

over phonon transport:
1
κ q, j = C q, j vq,2 j τ q, j
3
Specific Phonon lifetimes:
heat Phonon group many possible scattering
velocities processes combined

All quantities can be obtained from neutron/x-ray scattering measurements

and also computed from first-principles (for moderately complex cells).
2
Microscopic understanding of thermal
conductivity from phonon linewidths
INS / IXS measures dynamical structure factor, S(Q,E)
providing details of dispersions and linewidths:
Intensity (arb.u.)

PbTe single-crystal PbTe

Neutron measurement Transverse-acoustic phonon
Linewidth:

Intensity (counts)
2Gq,j = 1/tq,j

Phonon
energy (meV)

Q (fractional) Phonon energy (mev)

Estimate thermal conductivity from INS Matthiessen’s rule:

1 2
κ = ∑κ q, j = ∑ C v τ
q, j q, j q, j
τ tot−1 = τ anh
−1 −1
+ τ el−ph −1
+ τ defect −1
+ τ boundary +...
q, j 3 q, j

3
 First-principles modeling of INS
Example: S(Q,E) for phonons in FeSi crystal Fe

Si
FeSi: neutron scattering FeSi: DFT simulation
Phonon energy (meV)

Momentum Q (fractional)

Delaire et al. PNAS 2011, PRB 2013, PRB 2015

4
 Anharmonicity in thermoelectrics: PbTe
• Large figure-of-merit ZTmax~ 2 (Pei Nature 2011, Biswas Nature 2012)
Pb
• Low thermal conductivity klat=2 W/m/K at 300K
Te
• Strongly anharmonic transverse-optic (TO) mode.
• 5x suppression in klat from optic-acoustic scattering (Shiga PRB 2012, Tian PRB 2012)

PbTe experiment (INS) PbTe calculation (DFT, harmonic)

10

Energy (meV)

0
wavevector G K X

Delaire, Ma et al., Nature Materials 2011

5
 PbTe, SnTe near-ferroelectricity:
resonant bonding in rock-salts
Long-ranged interactions in [100]
from unsaturated Te p-states with
large polarizability.
Resonant Te p-state network vs more ionic solid
(PbTe) (NaCl)
Optical phonon dispersion:
Softening at zone-center
Interatomic force-constant vs distance

softening

wavevector q
Sangyeop Lee et al. Nature Communications (2014)
6
 Anharmonic phonon spectral functions
PbTe experiment (INS) PbTe anharmonic (DFT)
T=300K T=300K
10

SnTe TO
SnTe
• Ab-initio MD + TDEP
3

(meV)
8 LA
2

reproduces strong 6
anharmonic effects 0.1

Energy, E=
TA
7
6
4 5

• c”(Q,E) computed from

4

3
(a) 300K
50K (b) 300K
(b)
300K 300K
(c) 300K (c) 30

anharmonic phonon
2

1010
self-energy Σq(E) PbTe TO PbTe
8
(meV)
E (meV)

LA
• Reproduce TO phonon 6

splitting in PbTe, by
Energy, E=

including anharmonicity 4 TA
Energy

2
300K
(e) 300K
(d) 50K
300K
(f) 300K
(e) 300K
(f) 3

00 0.4 0.6 0.8 1.0 1.2 1.4 1.6 0.4 0.6 0.8 1.0 1.2 1.4 1.6
0.0 HH3
1.0 2.0 X 0.0 HH3 1.0 2.0
GHH3 Wavevector
HH3
q (rlu)
FIG. 1. χ!! (Q, Ω ) measured with INS and computed with first-principles anharmonic latti
TO mode at the zone center, Γ (arrows). (a,b) χ!! (Q, Ω ) of SnTe measured with CNCS, a
C. Li, O. Hellman, O. Delaire [H,
etH,al. Phys. Rev. Letters 2014
3] (intensities are integrated over ±0.1 r.l.u. along [0, 0, 1] and [1, 1, 0] directions, an
(d,e) Same for PbTe. Part of the data in (e) was shown in Ref. [8]. White lines are renormal
TDEP: O. Hellman et al. Phys. at TRev.
= 300 B
K. 2013
(c,f) Anharmonic χ!! (Q, Ω ) along [H, H, 3], computed from the phonon self-en
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 Phonon “nesting” amplifies anharmonic
coupling in PbTe, compared to SnTe
Imaginary part of self-energy (damping):
3-phonon interaction strength
(transition probability)
Kinematic constraints for
conserving energy and
momentum
(phase space size
~ joint DOS)
Real and imaginary parts of self-energy related by
Kramers-Kronig (Hilbert) transformation:

PbTe
PbTe
H
SnTe
SnTe
H [d(x)] = 1/x

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 SnSe: new thermoelectric compound
• Recently identified as most efficient thermoelectric material
• Very high zT ~ 2.5 and very low thermal conductivity κlat < 1 Wm−1K−1
• Strongly anisotropic (rocksalt derived)
Pnma
• Structural phase transition at ~805K
T<805K
Zhao et al. Nature (2014),

Cmcm
T>805K

Zhao et al. Nature (2014), Zhao et al. Science (2016),

Chen et al. J. Mater. Chem. 2014, Carrete et al. APL (2014)

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 SnSe: phonon dispersions -1
Qx (Å )
-1
Qy (Å )
-0.5 0.0 0.5-0.5 0.0 0.5
10
DFT 100 K DFT 100 K
a ε // c b ε // c
8 DFT DFT
• Measured phonons with neutron scattering

Energy (meV)
on single-crystals at 100K < T < 850K 6

• Mapped all crystallographic directions 2

(orthorombic a≠b≠c) 0
c 100 K d 100 K
INS 100K INS 100K
8
• Observe strong softening with increasing

Energy (meV)
6
temperature (up to Pnma – Cmcm phase
transition) 4

• Especially anharmonic modes with 0

e 648 K f 648 K
polarizations along c-axis. 8 INS 648K INS 648K

Energy (meV)
6
• Good agreement with DFT simulations for
-2
10

4
Pnma phase. -3
10
2

0
Li*, Hong*, May, Bansal, Ma, Hong, Chi, Ehlers, -1.0 -0.5 0.0 0.5 1.0 -0.2 0.0 0.2
Γ Χ Γ Χ Γ (Y‹—) Γ (—›Y)
and Delaire, Nature Physics 11, 1063 (2015) H02 (r.l.u.) 0K2 (r.l.u.)

k // [100] k // [010]

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 SnSe soft-mode behavior of TOc(G)
SnSe zone-center TOc
• Many acoustic and optical phonons a (0,0,1.95) b (0.5,0,2)

6
5x10

6
4x10
show strong temperature HB-3
CNCS cuts
850K

dependence. 825K

4
850K
• Lowest zone-center TOc mode softens 800K

3
825K
at the phase transition. 800K
775K

3
750K
• Confirms strong anharmonicity.

χ'' (a.u.)
775K

χ'' (a.u.)
2
750K 700K

• Anharmonic potential also seen in

2
700K
650K
DFT. 650K
600K

1
600K

1
500K

Energy (meV)
500K
300K
300K

0
0

100K
100K

1 2 3 4 5 6 7 2 3 4 5
Energy (meV) Energy (meV)
Li*, Hong*, May, Bansal, Ma, Hong, Chi, Ehlers,
and Delaire, Nature Physics 11, 1063 (2015)

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 Anharmonicity and thermal transport
k convergence vs cutoff
• SnSe thermal conductivity computed
SnSe from first-principles (ShengBTE*)
• Strong influence of cubic terms Y
k/k0

within Sn 1NN coordination polyhedron

for triplet with Se-Se distance ~6Å
Grüneisen parameter

6Å

Sn Connect with
Se structure and
bonding

Cutoff radius for Y3

*W. Li Comput. Phys. Commun. 185, 17471758 (2014)

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 SnSe anharmonicity from bonding
instability
High-T Cmcm Low-T Pnma
• Electronic instability (Jahn-Teller) ELF
of high-T Cmcm phase:
Se Se Se Se
Resonantly-bonded high-symmetry
Cmcm phase distorts to Pnma to Sn Sn
lower electronic energy.
Se Se Se Se
• Results in double-well anharmonic
potential for ions.

• Opportunity for other strongly

anharmonic systems: look for
materials near Jahn-Teller/Peierls
distortions. Cmcm

Pnma
Hong and Delaire, submitted.

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 Conclusions

• Combined scattering experiments and DFT

simulations provide powerful insights.
• Strong anharmonicity near ferroelectric-like
instabilities in chalcogenide thermoelectrics.
➤ Look for phases near Jahn-Teller/Peierls
distortions, displacive phase transitions.

Thank You
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