Phonon anharmonicity near

structural transitions -
Scattering experiments and first-principles simulations

Olivier Delaire
Duke University

F20.00010
 Acknowledgements
ORNL: D. Pajerowski, S. Calder, D. Abernathy, G. Ehlers,T. Hong, S. Chi,
B. Winn, H. Cao, A. May, L. Boatner
ANL: M. Krogstad, R. Osborn, S. Rosenkranz, D.-Y. Chung, A. Said,
A. Alatas, Y. Ren,
Northwestern: M. Kanatzidis
UTK: H. Zhou
Dipanshu Bansal Jen Niedziela Mayank Gupta

Y19.00011 (Friday):
Anharmonic phonons,
superionic diffusion,
and ultralow thermal
conductivity in
Cu7PSe6

Tyson Xing He Shan Yang Jingxuan Ding

Lanigan Atkins

Funding: DOE Office of Science, Basic Energy Sciences, MSED

 Outline

• Mapping and modeling full S(Q,E)

neutron & x-ray scattering + DFT simulations to rationalize
intensities, renormalization, broadening

• Anharmonic phonons in CsPbBr3

extended overdamped zone-boundary modes

• Spin-phonon coupling in h-FeS

antiferromagnetism, coupled soft-phonons and metal-
insulator transition
 Outline

• Mapping and modeling full S(Q,E)

neutron & x-ray scattering + DFT simulations to rationalize
intensities, renormalization, broadening

• Anharmonic phonons in CsPbBr3

extended overdamped zone-boundary modes

• Spin-phonon coupling in h-FeS

antiferromagnetism, coupled soft-phonons and metal-
insulator transition
 Spectral signatures of anharmonicity
• Quasi-harmonic phonons: 𝛅 -functions on dispersions
• Stronger anharmonicity:
phonon peaks broadened (damping)
no-longer well-defined quasiparticles in extreme cases
Strongly Anharmonic:
Weakly Anharmonic: strong renormalization,
Harmonic: damped harmonic oscillators complex spectra (eg. satellites),
delta functions Lorentzian-like, shifted quasi-elastic from damped fluctuations
E E E E

Q Q Q Q
Q0 Q0 Q0 Q0
Nature Materials 10, 614 (2011) Nature Physics 15, 73 (2019)
PRL 112, 175501 (2014) PNAS 117, 3930 (2020)
Spectral lineshapes and phonon self-energy

Imaginary part of self-energy:

3-phonon interaction strength
(transition probability)

energy and momentum

conservation (phase space size
~ joint DOS)

Kramers-Kronig (Hilbert) transformation:

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

Li, Hellman… OD, Phys. Rev. Letters (2014)

 Anomalous phonon intensities in SrTiO3
• Acoustic branch disappears near ferroelectric quantum critical point
• Anomalous temperature dependence captured by simulations
S(Q,E) along (H,H,2) from HYSPEC at SNS

TO Triple-axis (HB-3): S(Q0 ,E) vs T

TA TA

TO
TO

no TA

Xing He, D.Bansal, B.Winn, S.Chi, L.Boatner, O.Delaire. Phys Rev Letters 124, 14 (2020)
 Phonon renormalization in SnS
• Continuous Pnma – Cmcm phase transition at 880K
• Soft-mode condensation at Cmcm zone-boundary (Y), doubling cell
• Strong renormalization of entire TA + TO phonon manifold, not only
at soft-mode wavevector
• Affects phonon scattering phase-space, thermal transport calculations

DFT INS

Pnma
T<880K

Cmcm
T>880K

AIMD (anharmonic)

T. Lanigan-Atkins*, S. Yang* ... OD, Nature Communications 11 (1), 1-9 (2020)

 Outline

• Mapping and modeling full S(Q,E)

neutron & x-ray scattering + DFT simulations to rationalize
intensities, renormalization, broadening

• Anharmonic phonons in CsPbBr3

extended overdamped zone-boundary modes

• Spin-phonon coupling in h-FeS

antiferromagnetism, coupled soft-phonons and metal-
insulator transition
 Lead halide perovskites
• Excellent optoelectronic properties - solar cells
and radiation detectors

• Very soft and anharmonic lattice dynamics[1,2]

• Link between lattice dynamics and optoelectronic

properties still poorly understood

Use inelastic neutron/diffuse x-ray scattering

and ab-initio MD / DFT to probe lattice
dynamics and impact on electronic properties
Harmonic versus anharmonic
potentials [1]

T. Lanigan-Atkins*, X. He*, M. Krogstad, D. Pajerowski, D. Abernathy, G. Xu, Z. Xu, D.-Y.

Chung, M. Kanatzidis, S. Rosenkranz, R. Osborn and O. Delaire,
“Two-dimensional overdamped fluctuations of soft perovskite lattice in CsPbBr3”
Nature Materials (2021)
1. Katan, Mohite, and Even. Nature Materials 17.5 (2018): 377-379.
2. Simoncelli, Marzari, and Mauri. Nature Physics 15.8 (2019): 809-813.
Anharmonicity and electronic structure in CsPbBr3
• Electronic disorder potential dynamically shortened by Br motions and
reduces Urbach energy (sharp absorption edges)
[Gehrmann and Egger. Nature Commun. (2019)]

• Bandgap fluctuates in time with Pb-Br-Pb bond angle in AIMD, anharmonicity

extends carrier lifetimes by disrupting el-ph coupling and recombination
[Li, Vasenko, Tang, Prezhdo. J. Phys. Chem. Letters (2019)]
Prior experimental findings on CsPbBr3 phonons

• Large structural fluctuations often

linked to organic molecules in hybrid
halide perovskites

• Local polar fluctuations intrinsic to

inorganic lead-halide framework [1]

• Inelastic scattering measurements have

revealed damped modes in LHPs [2,3,4]
but limited by crystal size and measured
high-symmetry planes at limited Q-points

Low energy Raman spectra of

CsPbBr3 (b) and MAPbBr3 (a) [1]

1. Yaffe et al. Phys Rev Letters 118.13 (2017): 136001.

2. Songvilay et al. Physical Review Materials 3.9 (2019): 093602
3. Songvilay et al. Physical Review Materials 3.12 (2019): 125406.
4. Beecher et al. ACS Energy Letters 1.4 (2016): 880-887.
Prior experimental findings on CsPbBr3 phonons

• Large structural fluctuations often

linked to organic molecules in hybrid
halide perovskites

• Local polar fluctuations intrinsic to

inorganic lead-halide framework [1]

• Inelastic scattering measurements have

revealed damped modes in LHPs [2,3,4]
but limited by crystal size and measured CsPbBr3 single-crystal (m=5 grams)

high-symmetry planes at limited Q-points

We used large single-crystals to
map S(Q,E) with diffuse X-ray
scattering and high-resolution INS
1. Yaffe et al. Physical review letters 118.13 (2017): 136001.
2. Songvilay et al. Physical Review Materials 3.9 (2019): 093602
3. Songvilay et al. Physical Review Materials 3.12 (2019): 125406.
4. Beecher et al. ACS energy Letters 1.4 (2016): 880-887.
 CsPbBr3 structure and transitions

• Cubic at high temperature

• Tetragonal: in-plane (a-b) rotations of PbBr6 octahedra, in-phase

along c-axis

• Orthorhombic: octahedral tilts out-of-phase along c-axis

• Structural distortions overlap with phonon eigenvectors

T ≈ 361 K T ≈ 403 K

R-point eigenvector M-point eigenvector

 Extended diffuse scattering rods
a revealed
Orthorhombic
x-ray

• Mapped large volumes of S(Q,E) with XRD and INS (time-of-flight)

• Diffuse rods span edges of BZ connecting M-R points

• 2D correlated domains in real space, from fluctuating sheets of

collective PbBr6 octahedra rotations
neutron

(H,K,L=0.5) plane → superlattice Bragg peaks of cubic parent phase

d Cubic
a Orthorhombic b Tetragonal c Cubic
x-ray
x-ray x-ray x-ray

0.5

Intensity
-0.5
-1.5
-0.5 1.5
0.5 0.5
1.5 -0.5
neutron
neutron neutron neutron -1.5

d e f Cubic
Cubic Cubic
 Overdamped phonons along BZ edge
• Overdamped low-energy Br-dominated phonons (tetra & cubic phases)
• Causes strong quasi-elastic signal (around E=0 meV) in XRD and INS

• INS with high E-resolution reveals slow fluctuations (not static)

aa bb cc
Orthorhombic
Orthorhombic Tetragonal
Tetragonal Cubic
Cubic
Experiments

M
M R
R M
M R
R

dd ee ff
Simulation

M
M R
R M
M R
R

(simulations with
AIMD / TDEP)
T-evolution of overdamped PbBr6 rotation modes

S(E) spectra from INS at M-point

 Distortion energetics and electronic bandgap

• M- and R-distortions show double-wells [1,2]

• Similar energetics → no preference in planar

stacking sequence (in-phase vs out-of-phase),
short correlations

• Wide Pb-Br-Pb angle distribution at 500K

• Band gap increased by large-amplitude

octahedra rotations

1. Yang, Ruo Xi, et al. Journal of physical chemistry letters 8.19 (2017): 4720-4726.
2. Bechtel and Van der Ven. Physical Review Materials 2.2 (2018): 025401.
 CsPbBr3 summary

• Revealed extended 3D network of diffuse scattering rods,

previously missed
• Originates from overdamped anharmonic Br-dominated
phonons → distortions correspond to phase transitions
(PbBr6 rotations)
• Large amplitude fluctuations impact electronic structure

T. Lanigan-Atkins*, X. He*, M. Krogstad, D. Pajerowski, D. Abernathy, G. Xu, Z. Xu, D.-Y.

Chung, M. Kanatzidis, S. Rosenkranz, R. Osborn and O. Delaire,
“Two-dimensional overdamped fluctuations of soft perovskite lattice in CsPbBr3”
Nature Materials (2021)
 Outline

• Mapping and modeling full S(Q,E)

neutron & x-ray scattering + DFT simulations to rationalize
intensities, renormalization, broadening

• Anharmonic phonons in CsPbBr3

extended overdamped zone-boundary modes

• Spin-phonon coupling in h-FeS

antiferromagnetism, coupled soft-phonons and metal-
insulator transition
 Magnetically-driven phonon instability
enables metal-insulator transition in h-FeS
• NiAs parent structure
• AFM ordering (~600K), distortion + MIT (~410K)
• Distinct from isostructural NiS, which undergoes
Mott MIT without structural or magnetic transitions
• FeS is magnetoelectric but no net polarization [1]

How are spins and phonons involved in

metal-insulator transition?

[1] Ricci & Bousquet PRL 116, 227601 (2016)

Bansal, Niedziela… Delaire, Nature Physics 16, 669–675 (2020)

 Phase transitions in hexagonal FeS
T < Tb (~ 600K) : AFM ordering in metallic phase
T < Ta (~ 410K) : metal-to-insulator transition with distortion

Neutron diffraction (powder): nuclear, magnetic

Heat capacity
 Phase transitions in hexagonal FeS

T < Ta

Ta < T < Tb
 IXS reveals zone-boundary soft modes
IXS spectra at wavevectors of soft-modes Q = H (similar at K point)

Temperature evolution of
soft-mode energies
Q = (4,0,-7)
Ta = 380K in our single-crystals

Q = (4,0,-3)

Soft-modes in agreement with prediction

of Ricci & Bousquet PRL 2016
 Dispersions from IXS
soft modes at H points
transverse branch [1,0,-3] transverse branch [1,0,1]

T > Ta
(simulations with
AIMD / TDEP)

Ta = 380K in
single-crystals

T < Ta
AFM order triggers the phonon instabilities
Frozen phonon potential energy surface

non-magnetic

antiferromagnetic
Type equation here.Entropy of phase
transitions

~∆S!"#
 h-FeS magnetic spectra
Sequoia at SNS
 Spin-lattice-charge coupling in h-FeS

• Identified coupling between AFM ordering and instabilities of

two zone-boundary soft phonons in metallic phase (H and K)
• Condensation of soft phonons couples to zone-center mode,
which drives lattice distortion opening electronic band gap
• Spin-lattice coupling opens gap in magnon spectrum that
controls entropy change across MIT

Bansal, Niedziela… Delaire, Nature Physics 16, 669–675 (2020)

 Summary

• neutron & x-ray scattering combined with

simulations enable us to rationalize S(Q,E):
intensities, renormalization, broadening

• strong phonon anharmonicity often found near

phase transitions

• can couple to electronic and magnetic degrees of

freedom

Thank you