The Role of Atomic Dynamics in Nanoscale

Transport and Thermodynamics

Olivier Delaire
Mechanical Engineering and Materials Science & Physics,
Duke University

Berkeley Nano Seminar

Oct 7th, 2016
 Outline

VO2 PbTe
Electron-phonon coupling: Strong anharmonicity:
FeSi: PNAS 2011, PRB 2011, PRB 2013 PbTe: Nature Materials 2011,
V3Si: PRL 2008, PRB 2008 SnSe Nature Physics 2015,
PRB 2012,
Ferroelectrics / Multiferroics: APEX 2014, PRL 2014
Pb-relaxors (Nature Comm. 2014),
BaTiO3 (PRB 2013), BiFeO3 (PRB 2012)
Defect scattering:
Phonon entropy: AgSbTe2:
VO2 (Nature 2014), FeV (PRL 2011) Nature Nanotechnology 2013,
PRB 2014

2
 Phonons in crystals (atomic vibrations)
Longitudinal Acoustic (LA)

All modes at 300K

Transverse Optic (TO)

Contribute entropy

Phonons transport energy

propagation wolf.ifj.edu.pl/~parlinsk/

Model 2-atom crystal, MA = 1.5 MB , KA = KB

3
 Phonons in crystals (atomic vibrations)
Quantum harmonic oscillator

En = (n +1 2)ω ; ω = K M

V(x)

ΔE = ω
Frequency
n = w/2p ~ THz

!! 1 !,! ! 1 !,!,! ! ! !
!= ! + !!! + ! Φ!,! !!! !! + ! Interesting
! !! !! !! + ⋯!
Ψ!,!,!complications…
2! 2! 3!
!,! !,!,!

4
 Phonons in crystals (atomic vibrations)

Phonons are quantized normal-modes of vibration of a (harmonic) crystal:

Dispersion relations Density of states

w = w(k,j) g(w)

LO
Wavevector

Frequency (THz)
Measured with neutrons/x-rays/optical
Frequency (THz)

k = 2p/l ~ Å-1
TO
Calculated from first-principles

Sound waves:
w = c k for kè0

(Similar dispersions for spin-waves)

5
Anharmonicity affects thermal properties

Anharmonic

!! 1 !,! ! 1 !,!,! ! !
!= ! + !!! + ! Φ!,! !!! !! +! ! Ψ!,!,! !!! !! !! + ⋯!
2! 2! 3!
!,! !,!,!

Thermal expansion, thermal resistivity

6
6
 Neutrons and X-rays probe
structure and dynamics
• neutron wavelength ~ interatomic distances
• neutron energy ~ phonon, magnon energies

Thermal neutrons:
E = 25meV
v = 2.2 km/s
λ = 1.8 Å

Physics Nobel prize 1994

Clifford Shull Bertram Brockhouse

7
Neutron and X-ray Scattering Sources
Spallation Neutron Source (ORNL) NIST Center for Neutron Research
nuclear reactor

Advanced Photon Source synchrotron (ANL) LCLS free-electron laser (SLAC)

8
 Neutron and X-ray Spectrometers
Neutron time-of-flight: Inelastic X-ray Spectrometer:

9m
Ef

3m

Ei
HERIX at APS: ~10 detectors.
beam ~30 μm ; Ei = 23.7 keV
ARCS at SNS: ~105 pixels, Resolution ~1.5 meV, constant with E
~104 time channels each.
beam ~ 5cm, DE/E ~5%
9
 Neutron spectrometers now enable
4D mapping of (Q,E) space Phonons in FeSi
single-crystal
Energy slice: meV measured at SNS

10
 First-principles modeling of S(Q,E)
Example: S(Q,E) in FeSi single-crystal

FeSi: neutron scattering FeSi: DFT simulation

Phonon energy, E (meV)

Qx

Qy

Momentum Q (fractional)
Measured intensities reflect phonon polarization vectors:
E
LA TA

G G G Qx

Qy

11
PNAS 2011, PRB 2013, PRB 2015
 Phase Stability:
the Role of Phonon Entropy
in the Metal-Insulator
Transition in VO2
Budai*, Hong*, Manley, Specht, Li, Tischler,
Abernathy, Said, Leu, Boatner, McQueeney, and O. Delaire
Nature 515, 535–539 (2014)

Smart windows

Ultrafast transistor application with metal-insulator

A VO2 film can respond to the environmental temperature
switching time <1picosecond
to intelligently regulate infrared transmittance while
maintaining visible transparency
Stöhr & Dürr, SLAC / Stanford
12
Gao Yanfeng, Shanghai University
 Metal-Insulator Transition in VO2

Temperature
Rutile “R”
Metal
T > 340K
Oxygen

Vanadium
TMIT=340K
ΔG = ΔH – TMIT ΔS = 0

Monoclinic “M1”
T < 340K
Insulator

13
 Thermal diffuse scattering
Large change in x-ray diffuse scattering signal between R and M1:

T Experiment Theory

TMIT=340K

M1

14 Measurements at APS 33-BM Simulations with VASP+Phonopy

 Phonon DOS shows softer R phase
• R phase spectrum shifted to lower energy than M1
• Peak at E=13meV abruptly disappears below 340K

T>340K (R)

Measurements
SNS (ARCS)

T<340K (M1)

T>340K (R)

First-principles calcs.
(AIMD run at NERSC)

T<340K (M1)

15
 IXS dispersions show broad TA modes

R-point TA1 mode

Tc

16
 Damped harmonic oscillator lineshapes
TA phonon spectral functions follow DHO lineshape

Bose

Bare phonon energy Damping

M point R point
Intensity (counts)

Energy E=ħω Energy E=ħω

17
 Phonon potentials are strongly
anharmonic and soft in R VO2
RMSD (Å) RMSD (Å)
0 0.02 0.04 0.06 0.08 0 0.02 0.04 0.06 0.08 0.1
100
Energy/f.u. (meV)

Energy/f.u. (meV)
150
80 R phase:
60 100 Anharmonic
40 50
20
R point 0 M point
0
0 0.3 0.6 0.9 1.2 1.5 0 0.3 0.6 0.9 1.2 1.5 Dots: DFT calculation
Mode disp (Å) x 10-1 Mode disp (Å) x 10-1
green: quadratic fit
RMSD (Å) RMSD (Å)
0 0.02 0.04 0.06 0.08 0.1 0 0.02 0.04 0.06 blue: quadratic + quartic
60 200
Energy/f.u. (meV)

Energy/f.u. (meV)

150
40 M1 phase:
100 Harmonic
20
50
G point C point
0 0
0 0.3 0.6 0.9 1.2 1.5 0 0.3 0.6 0.9 1.2 1.5
Mode disp (Å) x 10-1 Mode disp (Å) x 10-1

18
 Entropy change across MIT
• Phonon entropy ≈ 2/3 of the transition entropy
• Electronic entropy 3x smaller
• Large phonon entropy in Rutile competes with lower
electronic energy (gap opening) in M1

∆S (M1->R)
Experiment DFT
(kB/atom)
Good agreement
Phonon 0.33±0.03 0.34 between measurements
and simulations
Electron 0.1 (*) 0.09

Total 0.5 ± 0.05 (**) 0.43

*Berglund, C. N. et al, Phys. Rev. 185, 1022 (1969). **Park, J. H. et al. Nature 500, 431(2013).

19
 Summary: VO2

• Accounted for microscopic thermodynamics driving

the VO2 metal-insulator transition
• Phonons are sensitive probe of electronic structure

• Anharmonicity (non-linear lattice dynamics)

important for phase stability in oxides

20
 Phonon Transport in
Thermoelectrics
• O. Delaire, J. Ma et al., Nature Materials 10, 614 (2011)
• J. Ma*, O. Delaire*, et al., Nature Nanotechnology 8, 445 (2013).
• C. Li, O. Hellman, O. Delaire et al., Phys. Rev. Letters 112, 175501 (2014).
• C. Li, J. Ma, O. Delaire et al. Phys. Rev. B 90, 214303 (2014).

Solar thermoelectrics
Radioisotope Thermoelectric Generators Automobile industry

21
 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

22
 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

23
 PbTe: example of strong anharmonicity
• 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

24
 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
Anharmonicity? Temperature dependence?

softening

wavevector q
Sangyeop Lee et al. Nature Communications (2014)
25
 T-dependence of TO phonon in PbTe
PbTe TO mode spectra at G
Deviates strongly from quasi-
harmonic behavior:
• Broad TO (ferroelectric) mode 670K
at G, stiffens with increasing T. 500K

• Double-peak structure, with 300K

strong T-dependence. 200K
100K

300K

Delaire et al., Nature Materials 10, 614 (2011)

Confirmed by Jensen et al. PRB 86, 085313 (2012)
26
 Anharmonic calculations of PbTe / SnTe
PbTe experiment (INS) PbTe anharmonic (DFT)
T=300K T=300K
10

SnTe TO
SnTe
• c”(Q,E) computed from
3

(meV)
8 LA
2

anharmonic phonon
self-energy Σq(E)
6 0.1

Energy, E=
TA
7
6
4 5

• Reproduce TO phonon
4

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

splitting in PbTe, by
2

1010
including anharmonicity PbTe TO PbTe
8
(meV)
E (meV)

LA

6
Energy, E=

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 0.0 HH3 1.0 2.0
G X
HH3
Wavevector
HH3
q (rlu)

C. Li, O. Hellman, O. Delaire FIG.

et al.
1. Phys.
χ (Q, ΩRev. Letters 2014
!!
) measured with INS and computed with first-principles anharmonic latt
!!
TO mode at the zone center, Γ (arrows). (a,b) χ (Q, Ω ) of SnTe measured with CNCS, a
[H, H, 3] (intensities are integrated over ±0.1 r.l.u. along [0, 0, 1] and [1, 1, 0] directions, an
O. Delaire, J. Ma et al., Nature(d,e)
Materials 2011
Same for PbTe. Part of the data in (e) was shown in Ref. [8]. White lines are renormal
at T = 300 K. (c,f) Anharmonic χ!! (Q, Ω ) along [H, H, 3], computed from the phonon self-e
27 O. Hellman et al. Phys. Rev. B 2013
 Neutron spectra and phonon self-energy
(R. Cowley, Rep. Prog. Phys. 1968)
• Dynamical susceptibility:
NaI

• Look for minima in {…}

• Multiple crossings lead to multiple

peaks in the INS spectra for cq”(E)

• Dq,j(W) obtained from anharmonic

(meV2)
interatomic force-constants.

28
 Phonon “nesting” increases phase-space
for acoustic-optic scattering of TO mode
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

29
 Phonon “nesting” amplifies anharmonic
coupling in PbTe, compared to SnTe

• Phase-space size amplifies effect of anharmonic potential

• Nesting of phonon dispersions:

Joint DOS Spectral function S(E)

E0

E E
E0

è screen/design materials for favorable dispersions

30
 Summary: PbTe

• Strong anharmonicity near ferroelectric instability

• TO soft-mode couples strongly to acoustic modes,

suppressing thermal transport

• Opportunity for “thermoelectric-ferroelectrics”

31
 SnSe: bonding instability, phase
transition and anharmonicity

Li*, Hong*, May, Bansal, Ma, Hong, Chi, Ehlers, and Delaire,
Nature Physics 11, 1063 (2015)

Bansal, Hong, Li, May, and Delaire Phys. Rev. B 94, 054307
(2016)

Hong and Delaire, arxiv:1604.07077

32
 SnSe: anisotropy and phase transition
• Very high zT ~ 2.5 and very low thermal conductivity κlat < 1 Wm−1K−1
• Strongly anisotropic,
• Structural phase transition at ~805K
Pnma
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)

33
 SnSe: continuous phase transition
Pnma (low T): Cmcm (high T):
d2 ≠ d3 ; d4 ≠ d5 d2 = d3 ; d4 = d5
Se

Sn

Adouby, et al. Z. Kristallogr. 213, 343349 (1998).

Chattopadhyay, et al. J. Phys. Chem. Solids 47, 879 (1986).

34
 Neutron scattering First-principles simulations
10 10 10 10 10 10
300 K 300 K 300 K
8 8 8 8 8 8
Energy (meV)

Energy (meV)

Energy (meV)

Energy (meV)

Energy (meV)

Energy (meV)
6 6 6 6 6 6

4 4 4 4 4 4

2 2 2 2 2 2

0 0 0 0 0 0
2 3 4 5 6 -2 -1 0 1 2 -1.0 -0.5 0.0 0.5 1.0 2 3 4 5 6 -2 -1 0 1 2 -1.0 -0.5 0.0 0.5 1.0
H00 H20 H02 H00 H20 H02
10 10 10 10 10 10
300 K 300 K 300 K

8 8 8 8 8 8
Energy (meV)

Energy (meV)

Energy (meV)

Energy (meV)

Energy (meV)

Energy (meV)
6 6 6 6 6 6

4 4 4 4 4 4

2 2 2 2 2 2

0 0 0 0 0 0
1.0 1.5 2.0 2.5 3.0 -0.4 -0.2 0.0 0.2 0.4 -1.0 -0.5 0.0 0.5 1.0 1.0 1.5 2.0 2.5 3.0 -0.4 -0.2 0.0 0.2 0.4 -1.0 -0.5 0.0 0.5 1.0
0K0 0K2 4K0 0K0 0K2 4K0
10 10 10 10 10 10
300 K 300 K 300 K

LDA more accurate than

8 8 8 8 8 8
Energy (meV)

Energy (meV)

Energy (meV)

Energy (meV)

Energy (meV)
Energy (meV)

6 6 6 6 6 6

4 4
GGA (PBE) 4 4 4 4

2 2 2 2 2 2

0 0 0 0 0 0
1.0 1.5 2.0 2.5 3.0 1.0 1.5 2.0 2.5 3.0 -1.0 -0.5 0.0 0.5 1.0 1.0 1.5 2.0 2.5 3.0 1.0 1.5 2.0 2.5 3.0 -1.0 -0.5 0.0 0.5
00L 40L 02L 00L 40L 02L

Important to preserve information

about the polarization vectors
35
 SnSe: S(Q,E) for c-polarized modes -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 / LDA but GGA
-2
10

4
underestimates phonon frequencies. -3
10
2

0
-1.0 -0.5 0.0 0.5 1.0 -0.2 0.0 0.2
Li*, Hong*, May, Bansal, Ma, Hong, Chi, Ehlers, Γ Χ Γ Χ Γ (Y‹—) Γ
0K2 (r.l.u.)
(—›Y)
H02 (r.l.u.)
and Delaire, Nature Physics 11, 1063 (2015)
k // [100] k // [010]

36 CNCS @ SNS (12meV)

 SnSe soft-mode behavior of TOc(G)
SnSe zone-center TOc
• Many acoustic and optical phonons a (0,0,1.95)
show strong temperature dependence.

6
5x10

6
4x10
HB-3
CNCS cuts
• Lowest zone-center TOc mode softens
at the phase transition.

4
850K

3
825K
• Confirms strong anharmonicity.
800K

3
χ'' (a.u.)
775K

χ'' (a.u.)
2
750K

2
700K

650K

1
600K

1
500K

300K

0
0
100K

1 2 3 4 5 6 7 2
Li*, Hong*, May, Bansal, Ma, Hong, Chi, Ehlers, Energy (meV)

and Delaire, Nature Physics 11, 1063 (2015)

HB3 @ HFIR
CNCS @ SNS
37
 Anharmonicity and thermal transport
k convergence vs cutoff
• SnSe thermal conductivity computed
SnSe from first-principles.
• 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

<011>
<011> Li*, Hong*, May, Bansal, Ma, Hong, Chi, Ehlers, and
Cutoff radius for Y3
~ <100>rocksalt Delaire, Nature Physics 11, 1063 (2015)

38
*W. Li Comput. Phys. Commun. 185, 17471758 (2014)
 Anharmonicity from bonding instability
Electron Localization Function
High-T Cmcm Low-T Pnma
• Electronic instability (Jahn-Teller)
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.

• We have identified several

strongly anharmonic materials
near Jahn-Teller / Peierls
instabilities. Cmcm

Hong and Delaire, Pnma

arxiv:1604.07077

39
 Conclusions
• Need to understand atomic dynamics to control
microscopic thermal transport and thermodynamics.

➤ Emerging design rules for phonon dispersions and

electronic structure to favor strong anharmonicity

➤ Look for phases near Jahn-Teller/Peierls distortions,

displacive phase transitions.

➤ Great complementarity between neutron / x-ray

scattering, and first-principles simulations of dynamics.

40
 Acknowledgements
Jie Ma Chen Li Jiawang Hong Dipanshu Bansal Jen Niedziela
Former postdoc Former postdoc Former postdoc Postdoc Postdoc

ORNL: A. May, M. McGuire B. Sales (Sample Synthesis),

J. Budai, E. Specht (Scattering and ThermoPhysics Group)
D. Abernathy, G. Ehlers, M. Stone, T. Hong, S. Chi, H. Cao (Neutron scattering)
Jiao Lin, V. Lynch, D. Singh, X. Chen, CAMM-group (Computing)

MIT: Gang Chen, Yang Shao-Horn Linköping U.: Olle Hellman

Funding:
• DOE Office of Science Early Career Award, DOE BES-MSED
• DOE Energy Frontier Research Center (S3TEC)
• Center for Accelerating Materials Modeling from SNS data (CAMM)
41