Phonons
5.1
Introduction
so far: we considered mainly a static crystal with the atom s at fixed position
~xs0
now: consider elastic vibrations of a crystal,
with atom s at position ~xs (t) = ~xs0 + ~us (t),
i.e. we consider (small) displacements ~us (t) that depend on time
and which are correlated to displacements of other atoms nearby
e.g. deformations or elongations of whole lattice planes.
Note:
Deformation of solids can be treated by the classical
theory of linear elasticity2 .
gives both the energies and dynamics associated with small deformations,
provided the wavelength of the deformations is large
in comparison with the lattice constants.
However, this (continuum) theory fails when the wavelength of deformations
becomes comparable to3 interatomic distances in the crystal lattice.
results:
collective excitations/vibrations of the atoms (at frequency )
~ propagating through the crystal
formation of waves (with wave vector K)
important questions:
what are the vibrating modes in a crystal lattice ?
~ ?
what is the relation (K)
how do the lattice vibrations interact with mechanical, electromagnetic
or other forces ?
in contrast to uncorrelated vibrations, e.g. due to thermal fluctuations, which was considered for
the derivation of the Debye-Waller factor that enters into the expression for the intensity of the Bragg
peak for x-ray diffraction
2
see e.g. Kittel Introduction to solid state physics (1966) at the end of chapter 3
3
or smaller than
81
82
Chapter 5 Phonons
lattice vibrations have particle-like character
quantum mechanical treatment (particle-wave-dualism):
propagating waves phonons with energy ~
(analogy to photons)
importance of phonons:
5.1
Introduction
83
Most simple situation is obtained in the [100], [110] and [111] propagation directions
of cubic crystals (correspond to directions along the cube edge, the face diagonal and
the body diagonal, respectively).
If a wave is propagating along one of these directions entire planes of atoms move in
phase with displacements either parallel (longitudinal) or perpendicular (transverse)
~
to the direction of the wavevector K
allows simple description of the displacement of a whole plane s from its equilibrium
position
1-dimensional problem
Each wavevector has three polarization modes one longitudinal (Fig.5.1) and two
transverse (Fig.5.2).
Figure 5.1: (Dashed lines) Planes of atoms when in equilibrium. (Solid lines) Planes
of atoms when displaced as for a longitudinal wave. The coordinate u measures the
displacement of the planes [from Kittel, Introduction to solid state physics (1996);
Fig.4.2].
Figure 5.2: Planes of atoms as displaced during passage of a transverse wave [from
Kittel, Introduction to solid state physics (1999); Fig.4.3].
84
Chapter 5 Phonons
5.2
(5.1)
(5.2)
d 2 us
M us = C(us+1 + us1 2us )
dt2
(5.3)
(0)
(5.4)
(5.5)
(5.6)
5.2
85
(5.7)
(with
4C Ka
sin
M
2
(5.8)
1 cos x = | sin(x/2)|)
Ka
K
1. Brillouin zone
a
a
connection between K values within and outside the 1. Brillouin zone:
us+1
0
i2n
ei(Ka2n) eiK a
= eiKa = e|{z}
us
=1
(5.9)
(5.10)
86
Chapter 5 Phonons
In other words:
The range of Ka covers all independent values of the exponential
eiKa = us+1 /us . I.e., saying that two adjacent atoms are out of phase by 0.3 or
2.3 has the same physical meaning, as shown in the figure below.
Figure 5.5: The wave represented by the solid curve conveys no information not given
by the dashed curve. Only wavelengths longer than 2a are needed to represent the
motion [from Kittel, Introduction to solid state physics (1996); Fig.4.5].
limit of long wavelength:
if K a wavelength 2/K a
one can approximate in (5.8) |sin(x)| x, i.e.
r
C
Ka K
M
(5.11)
n=1
= 2/Kmax = 2/(/a) = 2a
2d sin = 2a
n = 2a
q.e.d
5.2
87
group velocity:
The group velocity of a wave packet is given as the slope of the dispersion curve
(K)
d
~
or
~vg = gradK (K)
(5.12)
vg =
dK
(corresponds to the velocity of energy propagation in a crystal)
(5.13)
limit q
of long wavelength:
vg =
C
M
a = const.
88
Chapter 5 Phonons
generalization to 3D:
we used Hookes law F = C u which is valid in that form only in one dimension;
in 3D this relation becomes more complex:
then: =C e ;
So far, we used the approximation of only nearest neighbor interactions, i.e. for
the force on atom s from the displacement of atom s + p we only considered
p = 1.
Particularly in metals the effective forces can be of quite long range, i.e. interactions of lattice planes up to 20 lattice spacings apart from each other (i.e. p = 20)
can be significant.
For that case one can find a generalization of the dispersion relation (5.7) to p
nearest neighbors as
2 X
2 =
Cp (1 cos pKa)
(5.14)
M p>0
Solving for the interplanar force constants Cp at range pa yields
Ma
Cp =
2
+/a
/a
2
dK K
cos pKa
(5.15)
5.3
5.3
89
(5.16)
Ansatz:
travelling waves, now with different amplitudes
us = u ei(sKat)
vs = v ei(sKat)
(5.17)
where the lattice constant a is defined as the distance between nearest neighbors of
atoms with same mass (for zero displacement).
Substitution of (5.17) in (5.16) yields
2 M1 u = Cv[1 + eiKa ] 2Cu
2 M2 v = Cu[1 + eiKa ] 2Cv
(5.18)
This system of linear equations has a solution only if the determinant of the coefficients
of the unknowns u, v vanishes
iKa
2C M1 2
C
[1
+
e
]
=0
(5.19)
det
C [1 + eiKa ]
2C M2 2
hence
(5.20)
90
Chapter 5 Phonons
solution for ka 1 :
with cos Ka 1 12 K 2 a2 + . . . one finds the two solutions
1
1
2
+
optical branch
2C
M1 M2
and
2
C
K 2 a2
2(M1 + M2 )
acoustical branch
(5.21)
(5.22)
2C
M1
and
2 =
2C
M2
(5.23)
The full dispersion relatione, including the discussed limiting cases is shown below for
the case M1 > M2 .
Figure 5.8: Optical and acoustical branches of the dispersion relation for a diatomic
linear lattice, showing the limiting frequencies at K = 0 and K = Kmax = a . The
lattice constant is a [from Kittel, Introduction to solid state physics (1996); Fig.4.7].
5.3
91
The figure below shows the atom displacements transverse to the K vector.
For certain frequencies here for (2C/M1 )1/2 < < (2C/M2 )1/2 there are no
wavelike solutions.
characteristic for polyatomic lattices
Note: the 2N degrees of freedom fit again into the 1. Brillouin zone.
92
Chapter 5 Phonons
5.4
3p
branches:
Figure 5.10: Phonon dispersion relations in the [111] direction: Left in germanium
at 80 K. The twoTA phonon branches are horizontal at the zone boundary position
12 21 12 . The LO and TO branches coincide at K = 0 ; this also is a conseKmax = 2
a
quence of the crystal symmetry of Ge. The results were obtained with neutron inelastic
scattering by G. Nielsson and G. Nelin. Right in KBr at 90 K, after A.D.B. Woods
et al. The extrapolation to K = 0 of the TO and LO branches are called T and L .
[from Kittel, Introduction to solid state physics (1996); Fig.4.8].
5.4
93
Example: Silicon
Si crystallizes in the diamond lattice with p = 2 atoms per cell. The figure below shows
the Brillouin zone of such a cubic crystal.
Figure 5.11: Brillouin zone of cubic crystals. Some points and lines of high symmetry are drawn. denotes the center
(0, 0, 0), the point X is given by 2
(0, 1, 0),
a
the point L by a (1, 1, 1) and the point
K by 3
(0, 1, 1) [from Bergmann-Schaefer,
2a
Lehrbuch der Experimentalphysik, Bd. 6
Festkorperphysik (1992); Abb.1.18].
Due to p = 2, silicon has 6 phonon branches which are degenerate along the lines
and .
Figure 5.12: Dispersion of phonons in Si. Shown is the phonon energy ~, with phonon
frequency . , X, K and L denote different points and , and different lines in
outside the Brillouin
the Brillouin zone, as defined in fig. 5.4. Extending the line K
zone one reaches a point which is equivalent to X. L and T means longitudinally
and transversely polarized wave, respectively, A, acoustical wave, and O optical wave.
[from Bergmann-Schaefer, Lehrbuch der Experimentalphysik, Bd. 6 Festkorperphysik
(1992); Abb.1.19].
94
Chapter 5 Phonons
Figure 5.13: Left: Brillouin zones of the body-centered tetragonal (top) and simple
tetragonal (bottom) lattices. The symmetry directions along which the dispersion
curves are displayed are indicated with
heavy
lines. For the body-centered tetragonal
a2
5.5
5.5
95
1
E = n+
~
2
with n: number of quantum particles; n = 0, 1, 2, . . .
electromagnetic (light) wave: Quantum particle = Photon
lattice vibrations: Quantum particle = Phonon
here:
E = (n+ 12 )~ is the energy of an elastic mode of frequency when the mode is excited
to the quantum number n,
i.e. the mode is occupied by n phonons.
For n = 0 E = ~/2 = zero point energy of the mode.
Occurs for both phonon and photon due to their equivalence to a quantum mechanical harmonic oscillator of frequency
Phonon momentum:
~ can interact with particles as if it had a momentum p~ = ~K
~
A phonon of wavevector K
However, a phonon does not carry a physical momentum
~ = 0, corresponding to the translation of a crystal as a whole)
(except for K
~ is only defined modulo a reciprocal lattice vector G.
~
Note: K
Explanation (in the particle picture):
~ during Bragg
the crystal as a whole can change its momentum by ~G
reflection (recoil);
~ 2 /2Mcrystal very small, since Mcrystal very large
Recoil energy Erecoil = (~K)
possible interactions of phonons with:
electrons, neutron, photons,. . .
other phonons (due to anharmonic terms in the elastic energy)
selection rules in a crystal:
govern allowed transitions between quantum states,
e.g. for elastic scattering of an x-ray photon by a crystal we found
~k 0 = ~k + G
~
(5.25)
96
Chapter 5 Phonons
inelastic scattering by phonons:
scattering of a photon with a phonon involved can be described by either
~k 0 + K
~ = ~k + G
~
(5.26)
~ or by
i.e. the creation (emission) of a phonon of wavevector K
~k 0 = ~k + K
~ +G
~
(5.27)
(5.28)
(: creation/anihilation of a phonon)
~ is chosen such that K
~ lies in the 1. Brillouin zone.
Here, G
conservation of energy:
02
2
~2 kneutron
~2 kneutron
=
~ph
2mn
2mn
(5.29)
(: creation/anihilation of a phonon)
~ is based on the two conservation laws (5.28),
Experimental determination of (K)
(5.29).
Then in the experiment, one needs to find the energy gain or energy loss of the
scattered neutrons as a function of the scattering direction ~k ~k 0 .
5.5
97
Figure 5.14: Phonon dispersion in GaAs as obtained from neutron scattering (after
Strauch and Dorner). The different points and lines on/along the wave vector axis
are defined in Fig.5.11; is the frequency [from Bergmann-Schaefer, Lehrbuch der
Experimentalphysik, Bd. 6 Festkorperphysik (1992); Abb.1.30].
98
Chapter 5 Phonons
5.6
5.6.1
1
e(En )/kB T
+1
1
~)
2
= fermions,
(5.30)
Here, is the(chemical potential), which has to be determined in such
a way that the number of particles in the system (e.g. all electrons in the
crystal) is conserved.
particles with integer spin (e.g. 0~, 1~) = bosons,
e.g. photons, phonons:
f (En ) =
1
e(En )/kB T
(5.32)
5.6
99
XX
p
~k
1
~
BT
e~(K)/k
~
~(K)
(5.33)
determination of D():
consider cube with length L, plus periodic boundary conditions
possible vibrating states
(compare to linear chain with L = N a where we found K = 2n/N a):
Kx = 0, 2/L, 4/L, . . . ; Ky , Kz analog
1 state per
2
L
8 3
V
(5.34)
4 3 V
K 3
3
8
(5.35)
dNK dK
V K 2 dK
dNK
=
d
dK d
2 2 d
(5.36)
100
Chapter 5 Phonons
(5.37)
V 2
2 2 vs3
(5.38)
Remark :
Debye model is o.k. for acoustical phonons;
at sufficiently low temperature 6 mainly those phonons are excited
~
(energy of the optical phonons is large for all K!)
With N primitive cells in the crystal volume V :
The total number of acoustic phonon modes is N
From (5.35) we know then that all N vibrating states are located within the volume
(in K space)
V 4
V 4
N = 3 K 3 = 3 (/vs )3
(5.39)
8 3
8 3
This relation defines a maximum frequency, or cutoff frequency
D =
6 2 vs3 N
V
31
(Debye frequency)
(5.40)
With the dispersion relation one gets the corresponding cutoff wavevector
D
KD =
=
vs
6 2 N
V
13
(5.41)
Note: D and KD depend only on the density N/V , which is physically reasonable.
5.6
101
~
kB T
(5.43)
and
xD
~D
kB T
T
(5.44)
6 2 N
V
31
(5.45)
e 1
0
(5.46)
with N atoms in the specimen. Thus, the heat capacity (plotted in Fig.5.15)) is
U
= 9N kB
Cv =
T
3 Z xD
T
x4 e x
dx x
(e 1)2
0
(5.47)
Figure 5.15: Heat capacity CV of a solid, according to the Debye approximation. [from
Kittel, Introduction to solid state physics (1996); Fig.5.7].
102
Chapter 5 Phonons
xD
0
3 4 N kB T 4
U=
53
x3
dx x
e 1
dx
4
x3
=
ex 1
15
12 4 N kB T 3
and cv =
234N kB
53
cV T 3
(5.48)
3
T
(Debyes T 3 law)
(5.49)
(5.50)
simple explanation:
We have 3N possible modes (N : number of primitive cells).
Only those modes having ~ < kB T will be excited at low temperature to an energy
close to kB T .
~ space only a fraction (T /D )3 = (T /)3 will
Hence, from the available volume in K
be occupied by excited modes.
T 3
;
number of excited phonons 3N
each phonon has energy kB T
energy 3N kB T (T /)3 , and CV 12N kB (T /)3
The range of validity of the T 3 is below 0.1.
For T the heat capacity approaches the classical value 3N kB .
Typical values for :
Li
C
Au
K
: 334 K
: 2230 K
: 165 K
: 91 K
Figure 5.16: Heat capacity of silicon and germanium. Not the decrease at low temperatures. To convert a value in cal/molK to J/MolK, multiply by 4.186. [from Kittel,
Introduction to solid state physics (1996); Fig.5.8].
5.6
103
(5.51)
Thermal energy:
U = 3N
~0
~
/k
0
BT
e
heat capacity:
Cv = 3N kB
as plotted in the figure below
~0
kB T
3 due to polarization
e~0 /kB T
(e~0 /kB T 1)2
(5.52)
(5.53)
Figure 5.17: Comparison of experimental values of the heat capacity of diamond with
values calculated on the earliest quantum (Einstein) model, using the characteristic
temperature E = ~/kB = 1320 K. To convert to J/MolK, multiply by 4.186. [from
Kittel, Introduction to solid state physics (1996); Fig.5.11].
For low temperature: Cv e~0 /kB T
(not as good as Debye model which is in better agreement with experimental data)
For high temperature: Cv 3N kB
(reproducing the Dulong-Petit value, as the Debye model does)
104
Chapter 5 Phonons
With the perpendicular distance dK between the surfaces of constant and constant
+ d (see next figure) one gets:
Z
Z
3
d k = dS dk
(5.55)
shell
5.6
105
dS dK = dS
D() =
V
8 3
=const.
Note:
~ space
Integral goes over area of constant in K
D() can contain singularity points = Van-Hove singularities,
if the group velocity vg = 0
(this is e.g. the case at Brillouin zone boundary)
Figure 5.20: Density of states as a function of frequency for (a) a solid according to
the Debye model and (b) an actual crystal structure. The spectrum for the crystal
starts as 2 for small , but discontinuities develop at singular points [from Kittel,
Introduction to solid state physics (1996); Fig.5.14].
106
Chapter 5 Phonons
5.6.2
So far, we only considered a linear force-displacement relation to describe lattice vibrations (Hooks law).
This leads to a potential energy which is quadratic in the interatomic displacements
(harmonic theory).
As one of its consequences there should be no thermal expansion which we will consider
now:
Naive view: solid expands, while atoms oscillate
about their equilibrium position.
but: if one considers only harmonic oscillations, the average position of
the atom remains unchanged, no matter how large the amplitude
of oscillation is.
thermal expansion of solids results from anharmonic potential
Quantitatively:
Taylor expansion of the potential energy of an atom in the crystal potential
(equilibrium position shall be at x = 0)
(consider 1-dim. solid)
U (x) = cx2 gx3 f x4 . . .
(5.56)
hxi =
dx x eU (x)
dx e
(5.57)
U (x)
with = kB1T . The denominator is a normalization factor; normalizes the total probability to 1.
5.6
107
Z
Z
3 g 3/2
U (x)
cx2
4
5
dx xe
dx e
(x + gx + f x ) =
4 c5/2
r
Z
Z
U (x)
cx2
dx e
dxe
=
c
3g
kB T
2c2
thermal expansion proportional to T due to 3. order term in the potential
hxi
(5.58)
Measurements of the lattice constant a vs. temperature of solid argon are shown below.
The slope da/dT is proportional to the thermal expansion coefficient (vanishes at low
T ), which is significant at high T .
Figure 5.21: Lattice constant of solid argon as a function of temperature [from Kittel,
Introduction to solid state physics (1996); Fig.5.15].
108
5.6.3
Chapter 5 Phonons
dT
dx
(5.59)
dT
dT
`=
hvx i
dx
dx
ju = nhvx2 ic
(5.60)
(5.61)
with ` = v and C = nc
dT
1
jU = Cvl
|3 {z } dx
=KU
(q.e.d.)
(5.62)
5.6
109
(5.63)
110
Chapter 5 Phonons
Figure 5.23: (top) Flow of gas molecules in a state of drifting equilibrium down a long
open tube with frictionless walls. Elastic collision processes among the gas molecules do
not change the momentum or energy flux of the gas because in each collision the velocity
of the center of mass of the colliding particles and their energy remain unchanged.
Thus energy is transported from left to right without being driven by a temperature
gradient. Therefore the thermal resistivity is zero and the thermal conductivity is
infinite. (bottom) The usual definition of thermal conductivity in a gas refers to
a situation where no mass flow is permitted. Here the tube is closed at both ends,
preventing the escape or entrance of molecules. With a temperature gradient the
colliding pairs with above-average center of mass velocities will tend to be directed to
the right, those with below-average velocities will tend to be directed to the left. A
slight concentration gradient, high on the right, will be set up to enable the net mass
transport to be zero while allowing a net energy transport from the hot to the cold
end. [from Kittel, Introduction to solid state physics (1999); Fig.5.16a].
5.6
111
Figure 5.24: top: In a crystal we may arrange to create phonons chiefly at one end,
as by illuminating the left end with a lamp. From that end there will be a net flux
of phonons toward the right end of the crystal. If only N processes (K1 + K2 = K3 )
occur, the phonon flux is unchanged in momentum on collision and some phonon flux
will persist down the length of the crystal. On arrival of phonons at the right end we
can arrange in principle to convert most of their energy to radiation, thereby creating a
sink for the phonons. Just as in Fig.5.23(top) the thermal resistivity is zero. bottom:
In U processes there is a large net change in phonon momentum in each collision event.
An initial net phonon flux will rapidly decay as we move to the right. The ends may act
as sources and sinks. Net energy transport under a temperature gradient occurs as in
Fig.5.23(bottom) [after Kittel, Introduction to solid state physics (1999); Fig.5.16cd].
very high temperatures T > :
all phonon modes are excited and the phonon density n T (compare with
Bose-Einstein statistics)
U processes will provide relaxation to thermal equilibrium
mean free path ` 1/n 1/T KU 1/T
low temperatures:
number of phonons which are suited to U processes decreases e/T
K e/T
112
Chapter 5 Phonons
example (NaF):
Figure 5.25: Thermal conductivity of a highly purified crystal of sodium fluoride (NaF),
after H.E. Jackson, C.T. Walker and T.F. McNelly [from Kittel, Introduction to solid
state physics (1999); Fig.5.18].
Final remarks:
in metals:
additional (strong) heat transport due to electrons
some insulators (e.g. sapphire, Al2 O3 ):
have nevertheless a thermal conductivity which is comparable to metals,
e.g. maximum 200 W/(cmK) at 30 K for sapphire
for comparison:
maximum thermal conductivity of copper is 100 W/(cmK)
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