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COND-1 Tutorial Session

Heat Conduction at the Nanoscale:
Theoretical Approaches
Jennifer R. Lukes
Department of Mechanical Engineering and Applied Mechanics
University of Pennsylvania
Philadelphia, Pennsylvania USA
Eurotherm 103: Nanoscale and Microscale Heat Transfer IV
Lyon, France
14 October 2014

Philadelphia
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

University of Pennsylvania
•  Founded by Benjamin Franklin
•  Scientist, printer, postmaster, signer
of the Declaration of Independence,
first U.S. Ambassador to France

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Lukes Group Research
•  Goal:
•  To understand the thermal and fluid transport
processes that lead to unusual nanoscale behavior

•  Approach:
•  Computer simulations
•  Molecular dynamics
•  Monte Carlo
•  Lattice dynamics

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Introduction

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Macroscopic Heat Conduction
2

∂T
∂T
ρ Cp
=k 2
∂t
∂x
•  Classical heat equation
•  Derived from energy balance on control volume
•  Assumptions
•  Heat flux from Fourier law
•  Constant properties
6

Q = −k ∇T

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity: An Intrinsic Property
2

∂T
∂T
ρ Cp
=k 2
∂t
∂x
•  k is an intrinsic material property
•  Found in tables

7

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Size Dependent Nanowire Thermal Conductivity
Reduction in size further
reduces thermal
conductivity

Thermal conductivity of
nanowires is much less than that
of bulk materials
(Glassbrenner

and Slack,
Physical Review 1964)

3500
3000
2500

115 nm Diameter Si
Nanowire

2000
1500

(Li, et al. APL 2003)

1000
500
0

0

100
Temperature (K)

9

200

Thermal Conductivity (W/mK)

Thermal Conductivity (W/mK)

Bulk Silicon
50
40
30

Nanowire
(115 nm)

20

Nanowire
(56 nm)

10

Nanowire
(37 nm)

0
20

120

220

Temperature (K)

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

320

Size Dependent Nanotube Thermal
Conductivity

Thermal conductivity
decreases as diameter
increases
Opposite trend
compared to
nanowires
Yu et al., Proc. 2003 ASME Summer Heat
Transfer Conference, HT2003-47263, 1-6, 2003

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity: Not an Intrinsic Property!

•  Thermal conductivity of nanostructures depends
on size
•  Is not an intrinsic property after all!

•  This is in contrast to the classical macroscopic
picture

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Why Does the Macroscopic Description Fail?

•  Continuum assumption
no longer valid
~nm

Continuum

•  Need to consider heat
conduction from a more
fundamental perspective:
atoms / phonons

12

Quantum
Dot

Nanowire

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Discrete

Thin film

Atomic Structure of Materials
Magnesium diboride

http://www.bnl.gov/bnlweb/pubaf/pr/photos/
2002/MgB2-pic.jpg (Y. Zhu et al)

13

Single and bilayer graphene

http://www.nature.com/nmat/journal/v10/n3/
images/nmat2964-f1.jpg (K. Urban)

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

What is a Phonon?
•  Vibration of the crystal lattice that carries heat
•  Dominant carrier of heat in dielectric materials
Displacements in video scaled by 100

•  Characteristics of phonons
•  Can behave like waves and particles, in analogy to photons
•  Have a broad spectrum of frequencies and wavelengths
•  Travel in all directions
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Particle vs. Wave Transport

•  Typically thermal conductivity is calculated using
particle-based models for phonon transport
•  Assumes phonons are incoherent: wave effects such
as interference, tunneling and diffraction unimportant
•  Valid for many practical thermal transport situations

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Particle vs. Wave Transport
•  Recent works: coherent phonon transport may
be more important than previously thought
•  Luckyanova et al, Science, 338, 936, 2012
•  Ravichandran et al, Nature Materials 13, 168, 2014

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Overview of Tutorial

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Goals of This Tutorial
•  Review basic principles of sub-continuum heat
conduction in solid materials
•  Introduce various theoretical methods to
calculate thermal conductivity
•  Show how these methods can account for
nanoscale size effects

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Main Methods to be Covered

•  Boltzmann Transport Equation
•  Monte Carlo
•  Molecular Dynamics

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Briefly Discussed at the End
(as time permits)
•  State-of-the-Art Methods:
•  First Principles Thermal Conductivity Calculation
•  Deviational Monte Carlo
•  Hadjiconstantinou (has a chapter in arht)

•  Quantum Molecular Dynamics

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Not Covered in This Tutorial

•  Thermal transport in fluids
•  Thermal transport across interfaces
•  Coupled multi-carrier thermal conduction
•  Focus here is on lattice contribution to thermal
conductivity

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Level of Coverage

•  Time limitations preclude in-depth coverage of
each topic
•  Aim: cover main points of each method
•  References for more in-depth study are provided

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Review of Phonon Basics

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Important Phonon Characteristics

• 
• 
• 
• 
• 
• 

24

Wavevector
Frequency
Group Velocity
Energy
Specific Heat
Scattering Rate!

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Phonon Dispersion Relation
•  Relationship between phonon frequency and
wavevector (inverse wavelength)
•  Derived from analysis of wave propagation in the
crystal lattice
•  Essential features are highlighted for a classical
one-dimensional diatomic lattice

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

One-Dimensional Diatomic Lattice

γ!

n: lattice point index
a: period
γ: spring constant
x,y: displacement of mass M1,M2

•  Write equation of motion for each atom
d 2 xn
M1 2 = γ (yn + yn−1 − 2xn )
dt
d 2 yn
M 2 2 = γ (xn+1 + xn − 2yn )
dt
26

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

One-Dimensional Diatomic Lattice

γ!

n: lattice point index
a: period
γ: spring constant
x,y: displacement of mass M1,M2

•  Assume traveling wave solutions for x and y
•  Substitute into equations of motion

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

1D Diatomic Dispersion

http://www.lcst-cn.org/Solid%20State%20Physics/Ch43.files/image029.gif

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Optical vs. Acoustic Phonons
Different types of atomic motion
for optical and acoustic

Movie:
http://www.chembio.uoguelph.ca/
educmat/chm729/Phonons/
optmovie.htm

•  Optical
•  Atoms out of phase

•  Acoustic
•  Atoms in phase

Blakemore, Solid State Physics
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Diatomic Dispersion Relation - Diamond
Polarization:
Direction of wave
displacement
Longitudinal:
Displacement || q
Transverse:
Displacement ⊥ q
Blakemore, Solid State Physics

2 C atoms per basis.
3D x 2 atoms/basis = 6 branches

http://www.mgm.monschau.de/seismic/
images/artikel/raumwave.gif

(2 degenerate transverse branches)
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Nanowire Dispersion Relation
Torsional

Extensional

1.8
1.6
1.4

f

1.2
1
0.8

Flexural 1

0.6
0.4
0.2
0

0.2

0.4

0.6

0.8

1

1.2

k (1/nm)

Four lowest branches
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Flexural 2

Group Velocity
•  Measures how fast the
phonon is traveling
•  Can obtain from slope of
dispersion curve for any
branch p and any
wavevector q
∂ω ( q, p)
•  Given by vg ( q, p) =
∂q
Blakemore, Solid State Physics

32

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Energy
•  A phonon is the quantum of lattice vibrational
energy: !ω ( q, p)
•  Energy of vibrational mode is given by number of
phonons in that mode
!
1$
E ( q, p) = !ω ( q, p)# f ( q, p) + &
"
2%
•  At equilibrium, f is given by
Bose-Einstein distribution
33

f0 ( q, p,T ) =

1
! !ω ( q, p) $
exp #
& −1
" k BT %

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Specific Heat
•  Derivative of energy with respect to temperature
•  Needed for thermal conductivity calculation
•  Specific heat per mode

∂E ( q, p)
∂n ( q, p)
C=
= !ω ( q, p)
∂T
∂T
•  At equilibrium

34

C = kB x

2

ex
2

"#e x −1$%

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

!ω ( q, p)
x=
k BT

Scattering Events
•  Phonon-Phonon scattering
• 
• 
• 
• 

Due to anharmonicity
Dominant at high temperatures
May combine or split phonons
N- and U-processes

ω2 , k 2
ω1 , k 1

ω3 , k 3

•  Defects and Dislocations

UNSW

•  Isotopes and other defects in crystal structure

•  Boundaries
•  Grain boundaries
•  External boundaries
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UNSW

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Rough silicon nanowire
Hochbaum, et al. Nature 2008

Scattering Rate
•  How often the phonon scatters from
•  Boundaries, defects (impurities, isotopes,
dislocations, ...), other phonons
boundary

defect

phonon-phonon

•  Calculated using Mattheissen’s rule
•  Assumes independent scattering events

1
1
1
1
=
+
+
+...
τ eff τ boundary τ defect τ phonon−phonon
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Boltzmann Transport Equation

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Boltzmann Transport Equation

•  Particle based theoretical approach
•  Tracks number of particles as a function of
position, wavevector(momentum, velocity), time
•  First applied to phonons by Peierls (1929)
•  “Phonon gas” idea
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Boltzmann Transport Equation for Phonons

# ∂f &
∂f
+ vg .∇ r f = % (
$ ∂t 'scattering
∂t
•  f is the number of phonons in mode q at position r
at time t

f = f ( r, q, t )
•  Track f for each phonon polarization p
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Localized in r and q at a Snapshot in Time

dr

f = f ( r, q, t )
40

dq

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Boltzmann Transport Equation for Phonons

# ∂f &
∂f
+ vg .∇ r f = % (
$ ∂t 'scattering
∂t
•  vg is group velocity ∂ω / ∂q (not phase velocity ω / q )
•  Particle treatment ! phonons must be
localized within some Δr

Δr ~ 1 / Δq

•  Resulting spread of wavevectors Δq leads to
wavepackets that travel at vg
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Scattering Term

# ∂f &
∂f
+ vg .∇ r f = % (
$ ∂t 'scattering
∂t
•  Very complex to evaluate
•  Full solution requires coupling between all possible
initial and final phonon states
•  For phonon-phonon scattering processes this is
calculated using Fermi’s golden rule
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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Relaxation Time Approximation
" ∂f %
f − f0
≈−
$ '
# ∂t &scattering
τ eff
•  Exponential approach to equilibrium through
scattering
•  Effective scattering (relaxation) time: τeff
•  Gray assumption: no mode dependence
•  More detailed models include mode dependence of τeff

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Linearized Phonon Boltzmann Equation
•  For small perturbations from equilibrium we can
linearize the Boltzmann Transport Equation
•  Introduce deviation g = f – f0

1
f0 ( q, p,T ) =
! !ω ( q, p) $
exp #
& −1
" k BT %

•  At steady state, for negligible gradient of g this
yields

f = f0 − τ eff

44

∂f0
vg .∇ rT
∂T

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Heat Flux

•  Heat current

J = ∑ !ω ( q, p) f ( q, p) vg ( q, p)
q, p

J 1
Q = = ∑ !ω ( q, p) f ( q, p) vg ( q, p)
Ω Ω q, p

•  Heat flux

"

45

"

"Ω: unit cell volume

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity - 1
•  Express as ratio of heat flux to temperature
gradient via Fourier law

k = −Q / ∇T
•  Assumes local thermodynamic equilibrium

46

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity - 2
•  To obtain k:
•  First write linearized expression for f in terms of
specific heat per mode C (at equilibrium)
•  Then for simplicity, assume temperature gradient in x
direction:

C
dT
f = f0 −
vgτ eff

dx

47

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity - 3
•  Next, substitute linearized expression for f into Q
#
& dT
2
Q = −%∑ c ( q, p,T ) vg ( q, p) τ eff (
%$ q, p
(' dx

C
c=
Ω
c: volumetric
specific heat per mode

•  Finally we obtain thermal conductivity

k = ∑ c ( q, p,T ) vg2 ( q, p) τ eff
q, p

48

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Size Effects on Thermal Conductivity
k = ∑ c ( q, p,T ) vg2 ( q, p) τ eff
q, p

•  Now we can see the origin of the size effect
1
1
1
1
=
+
+
+...
•  Recall
τ eff τ boundary τ defect τ phonon−phonon

•  τ boundary ~ L / v . For small L,
•  τboundary is small
•  Boundary scattering dominates other scattering
mechanisms
49

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Issues with Thermal Conductivity Calculation
k = ∑ c ( q, p,T ) vg2 ( q, p) τ eff
q, p

•  Parameters for each mode are required
•  These may not be known
•  vg can be obtained from detailed analysis of
dispersion relation
•  τeff is quite difficult to obtain
50

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Best-Known Approximate Models
for Thermal Conductivity
•  Approximate models are often used for thermal
conductivity calculation
•  Callaway (1959)
•  Starting point: Boltzmann transport equation
•  Assumes debye spectrum, simplified scattering times
•  Displaced normal phonon distribution

•  Holland (1963)
•  Separate treatment of transverse and longitudinal
phonons
51

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Solution of Boltzmann Transport Equation

# ∂f &
∂f
+ vg .∇ r f = % (
$ ∂t 'scattering
∂t
•  Boltzmann transport equation for phonons can
be solved numerically
•  Methods include
•  Variational method [Ziman, Electrons and Phonons, (1960)]
•  Finite volume method [Murthy et al, Int. J. for Multiscale
Computational Engineering, 3, 5 (2005)]

•  Iterative method [Omini and Sparavigna, Physica B, 212, 101 (1995)]
52

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Advantage / Disadvantage of BTE

•  Advantage
•  Established methods exist to solve this equation
•  Long history of solvers for photon, neutron, rarefied gas
transport
•  Increasing emphasis on more exact, iterative methods

•  Disadvantage
•  Difficult to treat irregular geometries

53

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Monte Carlo

54

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

(Kinetic) Monte Carlo
•  Probabilistic method for solving Boltzmann equation
•  Uses random numbers to describe
•  How often a phonon scatters
•  The type of phonon scattering
•  The change of a phonon’s trajectory, frequency, and mode
due to scattering events

•  Tracks a representative portion of the phonon
population over time
•  Frequency and propagation velocity are tracked for each
phonon

55

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Relaxation Time, τ!
•  Mean lifetime of a phonon between scattering
events
•  Depends on mode, frequency, and type of
scattering event
•  As in the Boltzmann Transport Equation
treatment, there are various ways to treat τ

56

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Tracking Phonons - 1
•  Initialize phonon distribution
•  Advance a time step (typically ~ ps). In that step:
•  Advance the phonon in a straight line a distance vg Δt
•  Determine whether it has crossed a boundary of the domain
•  If so, it undergoes specular or diffuse reflection

bath cells
on ends
have set T

periodic or specular
reflecting boundaries
cell population typ.
5000 - 8000 particles

LY

57

LX at the Nanoscale: Theoretical Approaches
J.R. Lukes Heat Conduction

Tracking Phonons - 2
•  After the phonon advances
•  Calculate relaxation time τeff

1
1
1
=
+
+...
τ eff τ defect τ phonon−phonon

note: no boundary term

•  Use τeff to compute probability that phonon scatters
via any mechanism (scattering probability Pscatter)

Pscatter = 1− e
58

# Δt
%−
% τ
$ eff

&
(
(
'

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Tracking Phonons - 3
•  Next, determine whether the phonon scatters
•  Generate a random number r1 between 0 and 1
•  If r1 < Pscatter then the phonon scatters
•  If not, it continues on a straight path

59

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Tracking Phonons - 4
•  Next, determine probability of defect scattering
Pdefect =

1/ τ defect
1/ τ eff

•  Generate a random number r2 between 0 and 1
•  If r2 < Pdefect then the phonon undergoes impurity
scattering
•  If not, it undergoes phonon-phonon scattering

60

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Tracking Phonons - 5
•  Next, determine probability of N-scattering
1/ τ N
PN =
1/ τ eff
•  Generate a random number r3 between 0 and 1
•  If r3 < PN then the phonon undergoes N-scattering
•  If not, it undergoes U-scattering

61

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Approach to Steady State
∇T

x!

cold
end

hot
end

•  Impose temperature gradient
•  Calculate energy flux across
a planar cross section

ERIGHT − E LEFT
Qx =
AmΔt
m : number of time steps

•  Run until a steady state is reached
•  Track Q. Steady ! Q is converged across domain
62

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity Calculation
∇T

x!

cold
end

hot
end

•  Average temperature in each “x-bin”
•  Average: 100s – 1000s of timesteps

•  Compute k from
temperature gradient

T

Q
k =−
dT / dx
63

J.R.
Zuckerman
Lukes Heat
and Lukes,
Conduction
ASMEatJ.the
Heat
Nanoscale:
Transfer, Theoretical
136, 012401
Approaches
(2014)

bin

Common Features of MC Models

•  Assumption: elastically isotropic
•  Only TA and LA modes treated
•  No optical modes
•  The contribution of optical modes is ~ 5–10% of the
total flux [Goicochea et al, ASME J. Heat Transfer, 132, 012401]

64

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Scale Factor
•  The actual number of phonons is too large to
handle computationally
•  Simulations treat a small portion of the complete
phonon population
•  A scale factor W is used to scale the results
W=

•  W ~ 103-104
65

actual phonon population
simulated phonon population
[Mazumder and Majumdar, ASME J. Heat Transfer,
123, 749 (2001)]

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Some Previous Literature

66

Model

End
Boundary
Type
(for ∇T)

Applicable
Temperature
Range for τ
equations

Multiple
Modes

Phonon
Dispersion

PhononPhonon
Scattering

Impurity
Scattering

Superlattice
+ Grain
Boundary
Scattering

Klitsner 1988

Radiative

Low

Yes

No

No

No

No

Peterson 1994

Thermal
Bath

High

No

No,variable
ω only

Yes

No

No

Mazumder 2001

Radiative

Low

Yes

Yes

Yes

Yes

No

Lacroix 2005

Thermal
Bath

Low

Yes

Yes

Yes

Yes

No

Y. Chen 2005

Thermal
Bath

Low

Yes

Yes

Yes

Yes

No

Jeng 2008

Radiative

no restriction
(very simple)

No
(gray)

No

Yes
(implicit)

Yes
(implicit)

Yes

Randrianalisoa
2008

Radiative

Low

Yes

Yes

Yes

Yes

No

Zuckerman
2014

Thermal
Bath

High

Yes

Yes

Yes

Yes

Yes

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

High-Temperature Phonon-Phonon
Scattering Rates
•  Most MC models use expressions valid below
200 K: [P. G. Klemens 1951, 1958]
−1
τ 3-phonon
∝ ωT
TA mode

−1
τ 3-phonon
∝ ω 2T
LA mode

•  Sharma and Rose presented approximate
expressions for higher T [J. Solid State Chem., 73, 92 (1988)]
−1
m
−1
2 m
τ

ω
T
τ 3-phonon ∝ ω T
3-phonon
LA mode

TA mode

•  Also, first principles approaches can provide
quantitative relaxation times
67

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

MC Modeling of Phonon Transport
In-plane conduction, thin film

Transverse
Mode

Longitudinal
Mode

+∇T

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J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Advantages / Disadvantages of MC
•  Advantages
•  Irregular boundaries easy to implement
•  Spectral dependencies easily handled via relaxation time
expressions

•  Disadvantages
•  Convergence can be challenging to achieve
•  Convergence strongly depends on the details of the phonon
transport and scattering rules

•  Care must be taken with choice of time step size
•  Single-step drift distance of the shortest-lifetime phonons must
be kept well below their mean free path
•  Time step needs to be small enough so that a particle cannot
drift over an entire cell during a single time step

69

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Molecular Dynamics

70

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Molecular Dynamics (MD) Overview
•  Computational technique that
models
•  Physical properties of materials
•  Dynamical behavior of materials
Liquid

•  Basis: classical mechanics of
interacting particles
•  Can treat vapor, liquid, solid
phases
•  The focus of this talk will be solids
71

(FCC
J.R. Lukes Heat Conduction at the Nanoscale: TheoreticalSolid
Approaches

crystal structure)

How Does It Work?
•  Compute trajectories of each particle in the system
•  Required inputs:
•  Initial positions (crystal structure), initial velocities (temperature)

•  System evolution:
•  Interatomic potential function (“spring”) gives force
•  Position is determined from force, velocity, and previous position
Displacements in video scaled by 100

72

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Potential Energy of the System
•  Most general (multibody) form:
φ = ∑ v1 (ri ) + ∑∑ v2 (ri , rj ) + ∑∑
i

i

external
field term

j >i

pair potential term

i

∑ v (r , r , r ) + ...
3

i

j

k

j >i k > j >i

three-body potential term

higher order
terms

•  Often the potential energy is treated as
two-body or three-body in form, with other
terms neglected
73

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Where Do the Potential Functions Come From?
•  Fitted to
•  Experimental data (empirical), First principles simulation data

•  Potentials have been developed for many materials
•  Multiple potentials may exist for a given material
•  Example: over 30 different potentials for silicon!

•  Different potentials arise from fitting to different
properties or applying different functional forms
•  No single potential function replicates all physical
properties well
74

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Common Intermolecular Potentials

•  Two-Body
•  Lennard-Jones
•  Argon model system

•  Three-Body
•  Stillinger-Weber
•  Silicon, germanium, carbon (group IV)

75

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Lennard-Jones Argon Potential
•  Often used in MD for preliminary, qualitative
studies of material behavior
•  Advantages

φ ( rij )

•  Agreement with experimental data
•  Simple two-body form:

'- σ *12 - σ *6 $
!+ ( + ( !
φ (rij ) = 4ε &+ ( − + ( #
!%, rij ) , rij ) !"

σ!

ε!

•  Physically meaningful parameters
76

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

rij

Equations of Motion (Two-Body Potential)

Force

f ijn = −

velocity Verlet algorithm

( )

dφ rijn
drijn

1 Fio
= vio +
Δt
2 mi

Fin = ∑ f ijn , j ≠ i
j

1 Fin
vin = v1/ 2 +
Δt
2 mi

Velocity

v1/ 2

Position

1 Fio
(Δt )2
rin = rio + vio Δt +
2 mi

Other integration algorithms are also used such as Gear 5th order, Runge-Kutta, etc.
Usually explicit integration is performed due to time savings
77

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Boundary Conditions

78

Periodic

Free

• phonon-phonon scattering

• phonon-phonon and
phonon-boundary scattering

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

More Things to Note
•  1 µm 3 "! ~10 billion atoms!
•  Limited to short length scales
•  Max. 10s-100s of nm

•  Short time steps required for
stability of algorithm
•  Max. 100s of ns
•  Time step should be < 0.1*vibrational
period of ‘spring’ (~ 1fs in solids)

Maximum wavelength

•  Results are influenced by boundary conditions and
size effects
•  Periodic BC: unphysical cutoff of long wavelength phonons
•  Non-periodic BC: physically meaningful confinement
79

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

A Fundamentally Different Approach
•  Molecular dynamics is fundamentally different
from BTE and MC:
•  Instead of particles, atoms are tracked
•  Coherent and incoherent phonon effects are
represented

•  All that is needed is interatomic potential
•  Don’t need to calculate frequencies, velocities,
dispersion directly
•  One can get this information from MD, though
80

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Property Calculations
with Molecular Dynamics

81

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity Calculation Methods
•  Equilibrium MD (Green-Kubo method*)
•  Direct Nonequilibrium MD
•  Homogeneous Nonequilibrium MD (Evans
method**)

*Kubo, J. Phys. Soc. Japan, 12, 570-86, 1957.
**Evans, Phys. Lett., 91A, 457-60,
1982.
82
J.R. Lukes
Heat Conduction at the Nanoscale: Theoretical Approaches

Equilibrium MD (Green-Kubo method*)

•  Compute and store heat current (J)
!
! ! !
! 1
J = ∑ ε i vi + ∑∑ Fij ⋅ vi rij
2 i j
i

(

)

!" "
Q = J /V

2-body potential

•  Integrate heat current (J) autocorrelation

1
kαβ =
VkBT 2
83

Jα (t)J β (0) dt

0

*Kubo,
J. Phys.
Japan, at
12,the
570-86,
1957.Theoretical Approaches
J.R. Lukes
HeatSoc.
Conduction
Nanoscale:

Test Case: (10,10) Single Wall
Carbon Nanotube

http://www.photon.t.u-tokyo.ac.jp/~maruyama/agallery/nanotubes/1010vib.gif

•  REBO
potential*

E pot = ∑ ∑ uB (rij ) = ∑ ∑[VR (rij )− BijVA (rij )]
i

j>i

i

j>i

•  1 fs time step
Brenner, J. Phys.: Condens. Matter 14, pp. 783-802, 2002.
84

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity vs.
Length and Temperature
EMD Calculation

Experiment

Maximum wavelength
Yu et al., Proc. 2003 ASME Summer Heat
Transfer Conference, HT2003-47263, 1-6, 2003

•  Thermal conductivity increases with nanotube length. Why?
•  More long wavelength modes are supported
•  EMD conductivity decreases with increasing temperature--trend
does not match experiments! Why?
•  MD is purely classical. Only valid at high temperature
85

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Direct Nonequilibrium MD

•  Compute local time averaged
temperatures
•  Compute temperature gradient
and use Fourier law to obtain
thermal conductivity

T

Q
k =−
dT dx
86

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

x

Calculation of Temperature Profile
•  Kinetic temperature is calculated
via equipartition
•  Equate kinetic energy to 3/2 kBT
N

T(t) = ∑ mi (t )vi2 (t ) 3Nk B
i =1

•  Temperature is time average of
kinetic temperature

T

T = T(t)
•  Temperature can be computed in
local regions to obtain
temperature distribution
87

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

x

Checking Local Thermodynamic Equilibrium
x,y,z velocity component distributions plotted
against Maxwell distribution
avgd. over
10,000 steps

(a)

(b)

avgd. over
30,000 steps

(c)

(d)

~ 2 nm x 2 nm
cross section

88

Averaging for longer time and
over larger numbers of atoms
→ local kinetic temperature
approaches local
thermodynamic equilibrium

~ 3 nm x 3 nm
cross section

T* = 0.5
t=1 fsHeat Conduction at the Nanoscale: Theoretical Approaches
J.R. Δ
Lukes

Nonequilibrium MD Temperature Profiles

320

κ = 58.32 W/m-K
5 nm

310

T (K)

T (K)

320

300

280

280
10

15

20

25

30

Planar number

0

35

10

320

κ = 148.97 W/m-K
20 nm

310

T (K)

T (K)

300
290

320

89

310

290

5

κ = 97.62 W/m-K
10 nm

300

280

280
40

60

80

100

40

50

60

300
290

20

30

κ = 223.32 W/m-K
40 nm

310

290

0

20

Planar number

0

20 40 60 80 100 120 140 160 180

number
J.R. Lukes
Heat Conduction at the Nanoscale: Theoretical Planar
Approaches
Planar
number

Homogeneous Nonequilibrium MD*
•  Perturb equilibrium equations of motion
•  Add terms containing a perturbation (Fe) to the force
calculation

•  Compute the heat current as before
•  Take the long-time average of heat current and
take the limit Fe → 0 to obtain macroscopic thermal
conductivity
!"
!
*Evans, Phys. Lett., 91A, 457-60, 1982.

90

< J α (Fe ,t) >
kα = !"
lim
lim
!
Fe →0 t→∞
FeTV

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

HNEMD Equilibration Time
Fe = 0.4
Fe = 0.2
Fe = 0.1

400
350

J/Fe (Arbitrary Unit)

300
250
200
150
100
50
0
0

2

4

6

8

10

Time (ps)
Heat flux for a 20nm SWNT at 300K with HNEMD
91

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thermal Conductivity Dependence on Perturbation
•  Extrapolate to Fe = 0
to get thermal
conductivity
#  Values depend on
curve fit:
•  exp(-x) gives listed
values

#  Significant questions
remain about this
method

92

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Density of States Calculation
Density of States is not directly needed for thermal
conductivity calculation

D(ω) = dte

93

−iωt

< v(t )• v(0) >

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Phonon Density of States

11
10
9
8
7
6
5
4
3
2
1
00

40 nm, free boundaries, 300K

peak

10

20

30

40

Frequency (THz)

50

60

800!

1600!

3200!

6400!

L (nm)!

5!

10!

20!

40!

2.25!

1.25!

0.75!

0.5!

ν (THz)!
Longitudinal D.O.S. (arbitrary units)

Longitudinal D.O.S. (arbitrary units)

Dz (ω ) = ∫ dte−iωt < vz (t )gvz (0) >

Atoms!

11
10
9
8
7
6
5
4
3
2
1
00

40 nm, periodic boundaries, 300K

no peak

10

20

30

40

50

60

Frequency (THz)

•  Low frequency vibrational peaks found for tubes with free
boundaries
•  Similar low frequency modes for small particles with free surfaces
found by Dickey and Paskin (Phys. Rev. B, 1, 851-7, 1970)
94

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Spectral Energy Density from MD
•  A method to obtain phonon mode information
from molecular dynamics
•  Dispersion relation
•  Phonon lifetime

•  Use this information to compute thermal
conductivity in the BTE formulation
k = ∑ c ( q, p,T ) vg2 ( q, p) τ
q, p

Thomas et al. Phys. Rev. B, 81, 081411 (2010)
95

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Advantages / Disadvantages of MD
•  Advantages
•  User-friendly: just need potential function
•  No need to track individual modes to compute thermal
conductivity
•  Handles anharmonic scattering processes

•  Disadvantages
•  Not valid at low temperature: assumes classical high
temperature occupation of phonon modes
•  Difficult to track trajectories of individual phonos

96

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Summary
•  Molecular dynamics simulation can provide a
rich array of thermal transport information
• 
• 
• 
• 
• 
• 

97

Temperature
Thermal conductivity
Density of states
Dispersion relation
Phonon lifetime
Phonon scattering phase functions

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Some Other Approaches for k Calculation
•  Green’s function method (nanowires)
•  Mingo and Yang, Phys Rev B 68, 245406 (2003)

•  Anharmonic Lattice Dynamics
•  Turney et al., Phys Rev B 79, 064301 (2009)

98

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

State-of-the-Art Methods
(brief mention, time permitting)

99

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

State-of-the-Art Methods

•  First Principles Thermal Conductivity Calculation
•  Deviational Monte Carlo
•  Quantum Molecular Dynamics

100

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

First Principles k Calculation: Main Idea
•  Derive interatomic force constants (‘springs’)
from density functional perturbation theory
•  2nd order constants: group velocities
•  3rd order constants: three-phonon lifetimes

•  Calculate thermal conductivity iteratively using
Boltzmann Transport Equation
Mingo et al., “Ab Initio Thermal Transport,” in Length-Scale Dependent Phonon
Interactions, Topics in Applied Physics 128, Shindé and Srivastava (eds.) (2014)
Esfarjani et al., “Modeling Heat Conduction from First Principles,” in Annual
Review of Heat Transfer, Vol. 17 (in press)
101

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Deviational Monte Carlo: Main Idea
•  New Monte Carlo approach for phonons
•  Tracks only the portion of the phonon population
that has a deviation from the gradient-free
(equilibrium) distribution
•  Most suitable for cases with small deviation from
equilibrium
•  Reduced computational cost
Péraud et al., “Monte Carlo Methods for Solving the Boltzmann Transport
Equation,” in Annual Review of Heat Transfer, Vol. 17 (in press)
102

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Quantum Molecular Dynamics: Main Idea
•  Electronic structure computed from density
functional theory
•  Forces on ions computed from electronic
structure
•  Ions advanced based on these forces
•  Few thermal transport studies because of
computational cost
Car and Parrinello, “Unified Approach for Molecular Dynamics and Density-Functional
Theory,” Phys Rev Lett 55, 2471 (1985)
Recoules and Crocombette, “Ab initio determination of electrical and thermal conductivity
of liquid aluminum,” Phys Rev B 72 (2005)
103

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Summary

104

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Goals of This Tutorial
•  Review basic principles of sub-continuum heat
conduction in solid materials
•  Introduce various theoretical methods to
calculate thermal conductivity
•  Show how these methods can account for
nanoscale size effects

105

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Main Methods Covered

•  Boltzmann Transport Equation
•  Monte Carlo
•  Molecular Dynamics

106

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Briefly Discussed at the End
(as time permits)
•  State-of-the-Art Methods:
•  First Principles Thermal Conductivity Calculation
•  Deviational Monte Carlo
•  Hadjiconstantinou (has a chapter in arht)

•  Quantum Molecular Dynamics

107

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches

Thank You for Your Attention

108

J.R. Lukes Heat Conduction at the Nanoscale: Theoretical Approaches