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You are on page 1of 108

**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

2

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

3

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

4

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

Introduction

5

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

8

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

10

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

11

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

14

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

15

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

16

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

Overview of Tutorial

17

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

18

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

Main Methods to be Covered

**• Boltzmann Transport Equation
**

• Monte Carlo

• Molecular Dynamics

19

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

20

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

21

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

22

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

Review of Phonon Basics

23

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

25

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

27

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

28

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
**

29

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)
**

30

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
**

31

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

35

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

36

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

Boltzmann Transport Equation

37

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

38

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

39

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

41

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

42

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

43

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

!ω

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

68

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

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