Encyclopedia of

Nanoscience and
Nanotechnology

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Phonon Connement in
Nanostructured Materials
Akhilesh K. Arora, M. Rajalakshmi, T. R. Ravindran
Indira Gandhi Centre for Atomic Research, Kalpakkam, India

CONTENTS
1. Introduction
2. Optical Phonons
3. Results
4. Acoustic Phonons
5. Summary
Glossary
References

1. INTRODUCTION
There is considerable current interest in the physics of
nanostructured materials in view of their numerous technological applications [1, 2] in a variety of areas such as
catalysis [3], magnetic data storage [4], ferrouids [5], soft
magnets [6], machinable ceramics and metallurgy [7], nonlinear optical and optoelectronic devices [8], and sensors
[9]. In addition, obtaining an understanding of the properties of nanostructured materials is of interest from a fundamental point of view. Only a proper understanding of the
dependence of a given property on the grain/particle size can
lead to design/tailoring of the nanostructured material for
the related application. It is also important to understand
when a material could be considered as nanostructured.
Although one can in principle classify materials with grain
size less than 1000 nm as nanostructured, several properties
such as optical [10] and vibrational [11] properties do not
differ much from the corresponding bulk value unless the
grain/particle size is less than typically 20 nm. In view of this
it is reasonable to treat a material with a grain size smaller
than a certain value as nanostructured only if the property
of interest differs from the bulk value at least by a few percent. It is also possible that a material with nanometer grain
size may behave as nanostructured for a specic property
while it could act like bulk for other properties. In addition
to the grain size, the properties of the nanostructured materials may sometimes depend on the method of their synthesis. Generally nanostructured materials are synthesized in
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one of the three forms: (a) as isolated or loosely connected

nanoparticles in the form of powder [12], (b) as composites of nanoparticles dispersed in another host [13], or (c)
as compact collection of nanograins as pellets [14] or thin
lms [15]. The last form is also called nanophase material.
This chapter reviews the vibrational properties of the various forms of nanostructured materials.
Phonons are quanta of atomic vibrations in crystalline
solids. In a simple monoatomic solid with only one atom per
primitive cell (for example,
-iron, copper), one can have
only three acoustic phonon branches corresponding to the
three degrees of freedom of atomic motion. On the other
hand, for monoatomic solids with two atoms per primitive
cell such as diamond, magnesium, or diatomic compounds
such as GaAs, one also has three optic phonon branches in
addition to the three acoustic phonons [16]. In compounds
with a greater number of atoms and complex crystal structures, the number of optic phonons is more than three. If
the crystal unit cell contains N atoms, then 3N degrees of
freedom result in 3 acoustic phonons and 3N 3 optical
phonons. These phonons can propagate in the lattice of a
single crystal as a wave and exhibit dispersion depending
on their wavelength or equivalently their wavevector in the
Brillouin zone [17]. Phonon propagation is interrupted when
a grain boundary is encountered in a polycrystalline material. In an isolated grain the phonon can get reected from
the boundaries and remain conned within the grain. However, from the point of view of phonons, a well-crystallized
polycrystalline sample with several micrometer grain size can
be treated as a bulk/innite crystal for all practical purposes.
The consequences of phonon connement are noticeable in
the vibrational spectra only when the grain size is smaller
than typically 20 lattice parameters.
The atomic vibrational frequencies in crystalline solids
range from zero to about 100 THz. A more common
unit to describe the vibrational frequencies is wavenumber
(cm1  obtained by dividing the actual frequency by the
velocity of light or by inverting the wavelength. Acoustic
phonons have frequencies from zero to about a few hundred
Encyclopedia of Nanoscience and Nanotechnology
Edited by H. S. Nalwa
Volume 8: Pages (499512)

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Phonon Connement in Nanostructured Materials

wavenumbers while the optic phonons have higher frequencies. Hence the vibrational spectra could be probed using
infrared absorption/reectivity or using Raman spectroscopy
[18]. The wavevector of the IR photon for these energies is
of the order of 102 103 cm1 . On the other hand, in a Raman
scattering experiment the magnitude of scattering vector is
2k0 sin(/2), where k0 is the wavevector of the incident light
and  is the scattering angle. Thus the maximum value of the
scattering vector could at best be 2k0 (corresponding to the
backscattering geometry), which has a value 5104 cm1
for visible light. Hence the wavevector probed by either of
these two techniques is much smaller than the wavevector
q of the full phonon dispersion curve, which extends up to
the boundary of the Brillouin zone (/a 108 cm1 , where
a is the lattice parameter). Thus these techniques sample
only the optical phonons close to the zone center (q 0).
This q 0 selection rule is essentially a consequence of the
innite periodicity of the crystal lattice [19]. However, if the
periodicity of the crystal lattice is interrupted, as in the case
of nanocrystalline materials, this rule is relaxed and phonons
away from the Brillouin zone center also contribute to the
phonon lineshape observed in spectroscopic measurements.
This can be qualitatively explained in the following manner.
Consider the phonon dispersion curve of a typical diatomic
solid as shown in Figure 1. For a particle/grain of size d,
the phonon wavefunction must decay to a very small value
close to the boundary. This restriction on the spatial extent
of the wavefunction, via a relationship of the uncertainty
principle type, results in an uncertainty
q /d in the
wavevector of the zone-center optical phonon and a corresponding uncertainty 2 in its frequency [20]. Now the
light scattering can take place from quasi-zone-center optical phonons with wavevectors
q up to /d. This results in
asymmetric broadening of the phonon lineshape. In addition
to the changes in the optical phonon lineshape, connement
of acoustic phonons also leads to other interesting changes
in the spectra. A quantitative formalism of phonon connement will be discussed in subsequent sections.

1.1. Dimensionality of Connement

It is important to distinguish between the dimensionality of
the system and the dimensionality/degree of connement.
A bulk material is a 3D system and is unconned; that
is, dimensionality/degree of connement is zero. The rst
q/d
0

level of connement occurs in single- and multilayer thin

lms grown using layered deposition on substrates. Semiconductor superlattices, single-quantum well structures, and
multiple-quantum well structures [21] are well-known examples of 2D systems because the phonons and charge carriers
are conned within a plane, say, the x-y plane; however,
the degree of connement is 1D because phonons and
charge carriers are restricted along the z direction. Similarly, 2D connement occurs in nanowires [22] and in carbon
nanotubes [23], whereas the dimensionality of the system
reduces to 1D. The highest degree of connement (3D)
occurs in quantum dots [24] and nanoparticles [25, 26] where
the propagation is restricted in all three directions. Here the
dimensionality of the system is zero.

2. OPTICAL PHONONS
As mentioned in the Introduction, only zone-center optical phonons can be observed in ideal single crystals using
optical techniques such as Raman spectroscopy. However,
this q = 0 selection rule is relaxed due to interruption of
lattice periodicity in a nanocrystalline material. In this section we present a phenomenological model of phonon connement in an isolated nanoparticle. The case of spherical
nanoparticle is considered rst.

2.1. Phenomenological Connement Model

A quantitative formalism for the conned-phonon lineshape
[27] involves taking into account the contributions of the
phonons over the complete Brillouin zone with appropriate
weight factors. Consider a spherical nanoparticle of diameter d as shown in Figure 2. A plane-wave-like phonon wavefunction cannot exist within the particle because the phonon
cannot propagate beyond the crystal surface. In view of this,
one must multiply the phonon wavefunction with a connement function or envelope function W r, which decays to
a very small value close to the boundary.
The wavefunction of a conned phonon of wavevector q0
can be written as
 q0  r = W ruq0  r expiq0 r


 q0  r =  q0  ruq0  r

(1)
(2)

(q)

W (r)

2/a

Figure 1. Schematic representation of the optical phonon dispersion

curve and the range
q of the wavevectors probed in Raman scattering
from a nanoparticle of diameter d. 2 is the corresponding range of
phonon frequencies that contribute to the rst-order Raman scattering.

Figure 2. The Gaussian connement function W r for a spherical

nanocrystal of diameter d.

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Phonon Connement in Nanostructured Materials

where the Fourier coefcients Cq0  q are given by

Cq0  q = 23   q0  r expiq rd 3 r

(5)

where the value of
decides how rapidly the wavefunction decays as one approaches the boundary. This gives
Cq0  q as
Cq0  q = expd 2 q q0 2 /4


(6)

Richter et al. (RWL model) [27] used the boundary condition that the phonon amplitude  2 W 2 r reduced to 1/e
at the boundary r = d/2 of the particle. This corresponds
to
= 2. Other values of
such as 8 2 used by Campbell
and Fauchet (CF model) [28] and 9.67 (bond polarizability
model) [29] have also been proposed. Thus   are the eigenfunctions of the phonons with wavevectors q in an interval
q q0  < /d centered at q0 and the weight factors Cq0  q
also have a Gaussian distribution. As one-phonon Raman
scattering probes zone-center phonons, one can set q0 = 0.
This yields
C0 q2 = expq 2 d 2 /2


(7)

The rst-order Raman spectrum is then given as

I =

C0 q2 d 3 q
 q2 + 0 /22

(8)

where q is the phonon dispersion curve and 0 is the

natural linewidth of the zone-center optical phonon in the
bulk. In order to simplify the calculations, one can assume a
spherical Brillouin zone and consider the phonon dispersion
curve to be isotropic. These assumptions are valid when only
a small region of the Brillouin zone, centered at  point,
contributes to the scattering. The optical phonon dispersion
curve could then be approximated to an analytical function
of the type
q = 0
 sin2 qa/4

(9)

where a is the lattice parameter, 0 is the zone-center optical phonon frequency, and
 is the width of the phonon
dispersion curve.
The calculated Raman lineshapes of 4- and 8-nm GaAs
nanoparticles are compared in Figure 3 with that of the
bulk. One can see that as the particle size reduces, the

40

4 nm

30
20

8 nm

10
Bulk

0
240

(4)

The particle (nanocrystal) phonon wavefunction is a superposition of plane waves with q vectors centered at q0 . Gaussian connement functions have been extensively used as the
connement function [2729]. One can write W r as
W r = exp
r 2 /d 2 

50

Intensity (arb units)

where uq0  r has the periodicity of the lattice. In order

to calculate the effect on the Raman spectrum, we expand
  q0  r in Fourier series:


  q0  r = Cq0  q expiq rd 3 q
(3)

280

320

360
-1

Raman shift (cm )

Figure 3. Calculated Raman spectra of conned LO phonon in GaAs

nanoparticles. The bulk spectrum is also shown for comparison. Note
the asymmetric broadening of the lineshape and also the shift of the
peak towards the low-frequency side.

Raman spectra develop marked asymmetry towards the lowfrequency side and exhibit marginal shift in the peak position also towards the same side. As the optical phonon
dispersion curves in most solids have negative dispersion, that is, phonon frequency decreases as a function of
wavenumber, the increased intensity in the wing of the
Raman spectra on the low-frequency side basically arises
from the contribution from the phonon branch away from
the zone center. The dependence of the peak shift and the
line broadening on the particle size is shown in Figure 4 for
the longitudinal optic phonon in GaAs. Note that both peak
shift and the linewidth increase as the particle size reduces.
However, the changes are marginal if the particle size is
larger than 10 nm.
It is sometimes useful to combine the results of Figure 4
into a single curve of peak shift versus line broadening. This
is particularly useful while analyzing data on nanocrystalline
systems where information about the particle size is not
available. For ion-implanted GaAs, Tiong et al. [30] argued
that crystallite size reduced due to irradiation-induced damage in the lattice; however, spatial correlation (size of
crystalline region) persisted over a small length. In view of
this the changes in the peak shift and line broadening as
a function of uence were ascribed to the residual spatial
correlation over the nanocrystalline grains in the implanted
sample. Figure 5 shows peak shift as a function of line
broadening for GaAs nanoparticles.
In addition to the Gaussian function, other analytic functions such as sinc and exponential have also been considered
as connement functions. In analogy with the ground-state
wavefunction of an electron in a spherical potential well, a
sinc sinx/x function was considered [28]:
WS r = sin2r/d/2r/d
=0

if r < d/2
otherwise

(10)

Here the wavefunction becomes zero at the boundary of the

particle. The Fourier coefcient in this case becomes [29]
CS 0 q

sinqd/2
q4 2 q 2 d 2 

(11)

Similarly, in analogy with the propagation of a wave in a

lossy medium, an exponential decay of phonon amplitude

502

Phonon Connement in Nanostructured Materials

has also been considered [28]. The connement function

used in this case was

20

LINE WIDTH (cm1)

WE r = exp4 2 r/d

(a)

16

The Fourier coefcient is then given by [28]

12

CE 0 q

0
10

(b)

PEAK SHIFT (cm1)

1
16 4 q 2 d 2 2

(13)

These connement functions yield different dependence of

peak shift on the line broadening. Figure 5 also compares
the dependencies for the sinc and exponential connement
functions with that of Gaussian. Note that each connement
function has a different shape of  versus  curve. From
the analysis of their data and other reported results [27, 31],
Campbell and Fauchet [28] have shown that a Gaussian connement with
= 8 2 ts best to the data. This corresponds to a strong/rigid connement of phonons within the
nanoparticle with zero amplitude near the boundary.
We now consider other connement geometries. As mentioned earlier, rodlike shape corresponds to 2D connement and platelike (thin-lm) shape gives 1D connement.
A rodlike particle is characterized by two length scales, its
diameter d1 being much smaller than its length d2 . Again
using
= 8 2 in Gaussian connement, the expressions for
the Fourier coefcients C(0, q1 q2  have been obtained [28]:

C0 q1  q2 2
expq12 d12 /16 2  expq22 d22 /16 2 


2

iq2 d2 

(14)
1 erf
32 

0
0

10

12

DIAMETER (nm)

Figure 4. The dependence of linewidth (a) and peak shift (b) of the
longitudinal optic phonon on the particle size for GaAs nanoparticles.
Dashed line is the linewidth of the bulk phonon.
8

GAUSS

SINC

(cm1)

(12)

On the other hand, a thin lm has only its thickness d as the

conning dimension. For a thin lm, the Fourier coefcient
is given by [28]


2

iqd 
C0 q2
expq 2 d 2 /16 2 1 erf
32 

(15)

The changes in the Raman lineshape, quantied in terms of

line broadening and peak shift, are compared in Figure 6
for 1-, 2-, and 3D conned systems within the framework
of Gaussian connement. Note that as the dimensionality of
connement reduces, the magnitude of peak shift and line
broadening reduce dramatically. The departure from bulk is
maximum for a particle while it is least for a thin lm of the
same dimension.

2.2. Bond Polarizability Model

EXP

10

(cm1)

20

Figure 5. The relationship between peak shift  and line broadening 

for the three different connement functions. Adapted with permission
from [28], I. H. Campbell and P. M. Fauchet, Solid State Commun. 58,
739 (1986). 1986, Elsevier Science.

In addition to the phenomenological models of phonon

connement, there have been some attempts to theoretically obtain [29] the Raman spectrum of nanocrystals using
bond polarizability model [32] within the framework of
partial density approximation [33]. In this method eigenvalues and eigenvectors are obtained by diagonalizing the
dynamical matrix, while the force constants are obtained
by using partial density approach. The eigenvectors thus
obtained are analyzed to give vibrational amplitude as a
function of distance from the center of the particle. The
phonon amplitude in a Si nanosphere was shown to closely

503

Phonon Connement in Nanostructured Materials

8
1.0

(a)

SPHERE

W2(r)

(cm1)

0.8
0.6
(1)
(2)

(3)

0.4

4
ROD

0.2
0.0
0.0

0.1

0.2

THIN FILM

r/d

0.3

0.4

0.5

1.0

(cm1)

(b)

20

Figure 6. The relationship between peak shift  and line broadening

 for three different shapes of the nanoparticles. In all the three curves
the open circles correspond to a size of 4 nm. Adapted with permission
from [28], I. H. Campbell and P. M. Fauchet, Solid State Commun. 58,
739 (1986). 1986, Elsevier Science.

resemble a sinc function or a Gaussian with
= 967 [29].

Amplitude at the boundary was calculated to be around
3.6%. This is much smaller than 1/e used by Richter et al.
[27] and much larger than exp4 2  used by Campbell
and Fauchet (CF) [28]. The Gaussian connement functions and the corresponding Fourier coefcients corresponding to three different
(2, 9.67, and 8 2  are compared in
Figure 7. Note that weight factor Cq2 for the Raman
intensity drops too rapidly for
= 2 and too slowly for
=
8 2 as one moves away from the Brillouin zone center. Consequently the RWL model predicts only a marginal change
in the Raman spectra while that of CF model causes maximum departure from the bulk for the same particle size. On
the other hand, the calculations of Zi et al. suggest an effect
intermediate between the two limiting cases. It is important
to point out that a large number of results have been satisfactorily explained on the basis of Gaussian connement
model using
= 8 2 [20, 3438].

3. RESULTS
In this section we discuss various results reported on phonon
connement in 1-, 2-, and 3D conned systems.

3.1. 1D Conned Systems

Superlattices consisting of alternate thin layers of a pair of
semiconducting materials such as GaAs and AlAs, grown
on a substrate using molecular beam epitaxy, have been
extensively studied [21] in view of their applications in lightemitting diodes and diode lasers [39]. In these superlattices
GaAs layer constitutes the quantum well while the AlAs
layer forms the barrier layer. It is important to point out
that the range of optical phonon frequencies of GaAs does
not overlap with that of AlAs. Hence the phonons of GaAs
layer cannot propagate into the neighboring AlAs layers and
vice versa. Thus phonons in each of the GaAs and AlAs

0.8

10

|C(q)|

0.6
0.4
0.2

(3)

(2)

(1)

0.0
0.0

0.2

0.4

0.6

0.8

1.0

(qa/)

Figure 7. Squares of the Gaussian connement functions W r (a) and

the corresponding Fourier transform Cq (b) for different values of
.
Curve (1)
= 20 (RWL model), (2)
= 967 (bond-polarizability
model), and (3)
= 8 2 (CF model). The phonon amplitude W 2 is
plotted up to the boundary of the particle (r = d/2) and C 2 up to the
Brillouin zone boundary q = /a.

layers are conned within those layers. The conned optical

phonons in such superlattices can be described as modes of
a thin slab, arising from the standing wave pattern formed
within each slab. A set of modes at discrete wavevectors
qj = j/d1 , where d1 is the thickness of the GaAs layer, are
allowed. The conned phonon frequencies j then correspond to the discrete qj points on the dispersion curve of
GaAs [40]. Similarly the conned optical phonons of AlAs
layer of thickness d2 correspond to the qj = j/d2 discrete
points on the AlAs dispersion curve. In GaAs/AlAs superlattices the conned optical phonons in the GaAs layers have
been observed only under resonant conditions, that is, when
the incident photon energy is close to that of an electronic
excitation of the GaAs quantum well [40]. Under nonresonant conditions the intensities of these modes are weak.
In many cases one of the layers is an alloy Alx Ga1x As
[21]. This mixed crystal system exhibits a two-mode behavior [41]; that is, it exhibits both GaAs-like and AlAs-like
modes. Hence AlAs-like phonons remain conned in the
barrier layer (Alx Ga1x As) in a GaAs/Alx Ga1x As superlattice. On the other hand, the GaAs-like modes of the
quantum-well layer (GaAs) can propagate in the barrier
layer and vice versa. In view of this one expects zone folding to take place with new periodicity of (d1 + d2  at qj =
j/(d1 + d2 ; however, this effect has not been observed for
propagating optical phonons in GaAs/Alx Ga1x As superlattices because of the highly dispersive character of the optical

504
modes [42]. It may be mentioned that the acoustic phonons,
whose dispersion curves overlap over a wide range of frequencies, propagate through both the layers exhibiting zonefolding effects due to new periodicity [43].
Conned optical phonons have been found also in single
GaAs quantum wells under resonant conditions [44]. Resonance was achieved at a xed photon energy by exploiting the temperature dependence of electronic excitations in
the quantum well. Recently, IR absorption measurements
have been used for studying conned optical phonons in
(PbTe)m /(EuTe)n superlattices [45]. The conned phonons
manifest themselves as minima in the transmission spectrum. In the normal incidence only transverse optic (TO)
phonons are observed, while in oblique incidence both TO
and longitudinal optic (LO) phonons are seen. From the
frequencies of these conned phonons the dispersion curve
along the 111 direction could be deduced. In contrast
to GaAs/Alx Ga1x As superlattices, zone-folding effects have
been observed in GaN/Alx Ga1x N superlattices [46]. As this
mixed crystal system exhibits one-mode behaviour, it is
argued that the overlap between the density of states in the
two layers is signicant. In superlattices and in quantumwell structures, interface optical phonons have also been
observed [47, 48]. Phenomenological models [49] predict
that these modes have frequencies between TO and LO
phonons of the constituent layers. If the interfaces are sharp,
the interface phonons are found to be weak [46].

3.2. 2D Conned Systems

Recently, several tens of micrometers long nanowires of a
variety of materials such as Si [22, 50], Ge [51], GaAs [52],
SiC [5355], and TiC [56] have been synthesized using laser
ablation [57] and other methods. The diameter of these
nanowires ranges from 5 to 50 nm. Their optical properties
are strongly inuenced by the connement of electrons and
holes in these 1D systems. In view of their unique properties,
they nd applications in several devices [56]. In analogy with
electron connement, phonon connement has also been
found to give rise to interesting changes in the vibrational
spectra.
Raman spectra of the F2g optical phonon in Si nanowires
show broadening and peak shifts [50] similar to those
predicted by Gaussian connement model. For a 10-nmdiameter nanowire the peak is found to shift to 505 cm1
from 519 cm1 and also broaden to 13 cm1 from 3.5 cm1 .
Additional peaks at 302 and 964 cm1 have also been
reported. These were assigned to overtones of the zoneboundary phonons [50]. Appearance of zone-boundary
phonons in crystals with large density of defects [58] or in
mixed crystals [59] has often been reported. This arises due
to the relaxation of the q = 0 selection rule due to the
presence of disorder in the crystal. Similarly, overtones and
combinations constitute the second-order spectra and these
also are enhanced in the presence of disorder. On the other
hand, Wang et al. [50] apply the phonon connement model
also to the overtones of zone-boundary phonon and try to
interpret their shifts and broadening. In fact, the changes in
the Raman spectra of overtones, etc., as a consequence of
reducing the nanowire diameter should only be ascribed to
higher defect density resulting in the appearance of peaks

Phonon Connement in Nanostructured Materials

corresponding to one- and two-phonon density of states.

Quite interestingly, Wang et al. also introduce a new term
phonon connement length (in analogy with exciton connement length). By this they imply a size of nanostructure
below which the phonon connement effects are noticeable
in the Raman spectra. In this context it is important to point
out that for a given material the connement effects may
be different for phonons of different symmetries [37], making such terms lose their physical signicance. This will be
discussed further in a subsequent section.
Germanium nanowires with an oxide layer coating have
been synthesized using laser ablation technique [51]. As
expected, larger core diameters in the range 2051 nm do
not exhibit any noticeable change in the Raman spectra. On
the other hand, nanowires with 617 nm core show asymmetric broadening; however, no quantitative analysis has
been carried out. Gallium arsenide nanowires with a GeOx
sheath have exhibited broad TO and LO phonon modes
[52]; however, the broadening was found to be nearly symmetric. Surprisingly, the red shift of the LO phonon was very
large, 40 cm1 for nanowires with diameters in the range
10120 nm with an average diameter of 60 nm. Such a large
shift cannot be accounted for based on phonon connement effect alone. Other factors such as defects and residual
stresses have been argued to contribute to the decrease of
LO phonon frequency. Silicon carbide nanowires of average
diameter 80 nm with a coating of 17 nm SiOx [53] have also
shown very broad Raman spectra that resemble those arising
from phonon density of states rather than from phonon connement effects. The red shifts of 12 to 34 cm1 for the TO
and LO phonons were attributed to connement effects and
internal stresses [53]. CdSe nanolaments incorporated in
brous magnesium silicate (chrysotile asbestos) have shown
polarized Raman spectrum [60].
Carbon nanotubes are unique one-dimensional systems
[61, 62], whose diameters are typically 12 nm and whose
lengths are up to several tens of micrometers. Vibrational
properties of these hollow tubes are quite different from
those of solid nanorods discussed earlier. A single-wall carbon nanotube (SWNT) can be described as a single atomic
layer of graphite rolled up into a seamless cylinder. A SWNT
is specied by a pair of indices (m, n) that represent the
number of unit vectors na1 and ma2 on the 2D hexagonal
honeycomb lattice contained in the chiral vector. Folding of
the graphite sheet is done such that the chiral vector is perpendicular to the axis of the nanotube (see, e.g., Fig. 1 of
[63]). The magnitude of the chiral vector gives its circumference. The diameter of the nanotube is related to the (m, n)
indices as
d = 31/2 m2 + mn + n2 1/2 acc /
where acc is the nearest-neighbor C-C distance (1.421
in graphite). The phonon dispersion relations in a carbon
nanotube are obtained from those of an isolated 2D graphite
layer (graphene sheet) by using the zone-folding approach
[64]. Zone folding of acoustic branches leads to several lowfrequency modes, whose frequencies depend strongly on the
diameter of the nanotube. Notable among these are the E2g
mode, the E1g , mode, and the A1g radial breathing mode.
For a (10, 10) nanotube of diameter 1.36 nm, these modes

505

Phonon Connement in Nanostructured Materials

have frequencies of 17, 118, and 165 cm1 [63]. For tube
diameters ranging between 0.6 and 1.4 nm, a power law
dependence of the mode frequencies has been found [65].
The exponent for the E1g and A1g modes is close to 1 while
that for the lowest energy E2g mode is close to 2. Figure 8
shows the dependence of the frequencies of several Raman
active modes on the index n for (n, n armchair nanotubes
[66]. The inverse dependence of the radial breathing mode
frequency on the tube diameter serves as a secondary characterization to estimate the mean diameter of SWNTs. In
addition to these features, the internal modes associated
with the hexagonal ring stretching vibration of the graphite
sheet around 1581 cm1 exhibits splitting into A1g + Eg .
This splitting arises due to the curvature of the nanotube
graphene sheet. A novel feature of the Raman spectra of
SWNTs is the diameter selective scattering at different excitation energies, arising from the 2D quantum connement
of electrons. Resonance Raman spectroscopic studies in the
energy range 14.8 eV have proved to be a powerful probe
of these quasi-1D materials [6769]. Depending on its chirality (i.e., n and m), an individual SWNT could be semiconducting or metallic. Any sample of SWNTs is a mixture of
1/3 metallic and 2/3 semiconducting tubes. Raman excitations at different energies could selectively probe either of
these sets of tubes.
Specic-heat measurements at low temperature have
shown evidence of quantized phonon spectrum of SWNT
[70]. The data show the expected linear T dependence and
were found to be signicantly different from that of 3D
graphite and 2D graphene. The analysis also yielded an
energy of 4.3 meV for the lowest quantized phonon subband.
The nanotubes that are produced in either an electric arc or
pulsed laser vaporization are mostly in the form of bundles,
where nanotubes are aligned in a close-packed triangular
lattice. Intertube interactions that arise in the lattice are usually weak and are approximated by van der Waals interaction. This is similar to coupling between adjacent graphene
layers in 3D crystalline graphite. This coupling causes a
slight increase (7%) in the frequency of radial breathing

mode, independent of the tube diameter. This arises from

additional restoring force due to the nearest-neighbor tubetube interaction [71].

3.3. 3D Conned Systems

Isolated or loosely connected nanoparticles as selfsupporting powders and nanoparticles dispersed in other
hosts have been the most extensively studied nanostructured
systems. In many investigations quantitative tting of
phonon lineshape has also been carried out [20, 38, 72].
The extent of peak shift and line broadening is expected to
depend on the shape of the dispersion curve. For phonon
branches with less dispersion the effects are expected to be
small. On the other hand, the phonons that exhibit large
dispersion would get modied signicantly. This was demonstrated for the rst time [37] in the case of zinc oxide
nanoparticles by examining the phonons of different symmetries (irreducible representations). Zinc oxide has wurtzite
structure and consequently has phonons of symmetries A1 ,
E1 , and E2 at 393, 591, and 465 cm1 , respectively. For
a 4-nm particle size, E1 -LO mode exhibited a change in
linewidth from 18 to 38 cm1 whereas E2 mode showed
an increase of only 2 cm1 . Figure 9 shows the tted lineshape for 4-nm particles along with the data. Because of
insufcient intensity, A1 mode was not analyzed in detail.
The widely different behavior of E1 and E2 phonons could
be understood when the widths of the corresponding dispersion curves
 were taken into account. Table 1 shows
the peak shift and line broadening data for these modes in
4-nm particles.
There are a number of Raman spectroscopic studies on
nanocrystalline powders which exhibit broadening and peak
shifts similar to those expected for phonon connement
[7375]; however, quantitative analyses have not been carried out. In the case of composites synthesized either as thin
lms using co-sputtering [15] or by doping melt-quenched
oxide glasses [76], nanocrystalline precipitates form during
annealing at elevated temperatures [77, 78]. A departure
of LO phonon frequency from the expected behavior for

1400

E2

1200

12

1000

Intensity (arb. units)

MODE FREQUENCY (cm-1)

1600

800
600
400

E1
A1

200
0

4
0

10

15

20

n
400

Figure 8. Dependence of the vibrational frequencies of (n, n) armchair

single-walled carbon nanotubes on the index n. The diameter of the
nanotube is dn = 1357n . The frequencies of the A1g radial breathing
mode and other low-frequency modes depend strongly on the diameter.
Adapted with permission from [66], P. C. Eklund et al., Carbon 33, 959
(1995). 1995, Elsevier Science.

600

500

700

Raman Shift (cm1)

Figure 9. Raman spectrum of 4-nm ZnO nanoparticles. The continuous

curve is the calculated spectrum from Gaussian connement model.
Adapted with permission from [37], M. Rajalakshmi et al., J. Appl. Phys.
87, 2445 (2000). 2000, American Institute of Physics.

506

Phonon Connement in Nanostructured Materials

Phonon

 (cm1 

0 (cm1 

 (cm1 

 (cm1 

E2
E1 -LO

12
60

12
18

14
38

1
7

Note:
 is the width of the dispersion curve and 0 is the natural linewidth
of the phonon.

CdS nanoparticles smaller than 5 nm dispersed in GeO2

matrix has been attributed to defects [79]. Evidence of the
presence of CdO surface capping layer on pulsed laser
deposited CdS nanoparticles in SiO2 matrix has been found
from the presence of its characteristic peak in the Raman
spectrum [80]. A comparison of the Raman spectra of Si
doped SiO2 lms with those of theoretically calculated vibrational density of states of Si33 and Si45 clusters suggested
the presence of such clusters in SiO2 [81]. Semiconductor mixed crystals such as CdSx Se1x [82] and Cd1x Znx S
[77] dispersed in oxide glasses as nanocrystalline precipitates have been extensively studied in view of their interesting optical properties and applications as long-pass optical
lters. The system CdSx Se1x exhibits two-mode behavior
and both CdSe-like and CdS-like conned LO phonons
are observed [20]. On the other hand, Cd1x Znx S system
exhibits single-mode behavior. The shift of the LO phonon
frequency during late stage of annealing of Cd1x Znx S
nanoparticles dispersed in oxide glass host containing 20%
ZnO suggested a change in the stoichiometry (x in the
nanoparticle [77]. A few monolayers of AlSb deposited on
GaAs substrate using molecular beam epitaxy are found to
self-assemble in the form of platelike quantum dots during
annealing at 500  C [83]. In addition to phonon connement
effects, sometimes compressive stresses also play a role in
determining Raman lineshapes [84]. Nanopores of zeolites
have also been used to capture nanoparticles of Se and Te
[85]. Raman spectra showed evidence of trapping of either
a molecular Se8 or Te8 or formation of an irregular array
of chains and clusters depending on the size and connectivity of pores. The lifetime of phonons in nanocrystalline Si
has also been measured and found to be more than that in
amorphous Si [86].
As pointed out earlier, in most of the systems the optical phonon frequency decreases as one moves away from
the Brillouin zone center; that is, the optical phonon branch
exhibits negative dispersion. In this context, thorium oxide
is a unique system, whose optical phonon branch splits
into two components; one exhibits a negative dispersion
with
 = 50 cm1 , while the other undergoes a positive
dispersion of
 = +160 cm1 [87]. For nanocrystalline
thorium oxide both the branches are expected to contribute to the Raman lineshape. Recently, Raman spectra of nanocrystalline ThO2 have been reported, which are
found to be less asymmetric as compared to other crystals
[88]. This is attributed to the broadening arising on the left
and the right side of the peak from the contributions from
branches of the dispersion curve with negative and positive
dispersions, respectively.
In addition to the conned optic phonons, the presence
of surface phonons in the Raman spectra of nanostructured
materials has been reported in a number of systems

[72, 8991]. Surface phonons are expected to have frequencies between TO and LO phonons [72]. As the fraction of
surface atoms increases as the grain size of a nanostructured
material reduces, the surface phonons are observed with
noticeable intensity for small size particles. The dependence
of surface phonon frequency on the dielectric constant of
the surrounding medium has also been examined [90]. In
the nanoparticles of mixed crystals such as CdSx Se1x , two
surface phonons, one each of CdSe-like and CdS-like, have
been reported [89].
Porous-silicon (p-Si), obtained from electrochemical etching of Si [92], has been a subject of considerable interest in
view of its efcient photo- and electroluminescence at ambient temperature [93]. The pore diameter and consequently
the size of interconnected Si-nanostructure depends on the
electrochemical conditions [94]. Raman spectrum of p-Si
consists of an asymmetrically broadened F2g phonon line
characteristic of nanocrystalline Si and an overlapping broad
peak at 480 cm1 associated with amorphous Si [95, 96]. Fitting of the Raman spectrum to a conned phonon lineshape
has frequently been carried out to estimate the average particle size [97]. Conned phonons of p-Si have been found
to be responsible for the photoluminescence arising from
radiative recombination of carriers across the indirect transition [98] similar to that found in crystalline Si.
As mentioned earlier, if the phonon spectrum of the
particle overlaps signicantly with that of the surrounding medium, phonons of the particles can propagate into
the surrounding medium. In such cases a strong connement model of the Gaussian type is not expected to be
satisfactory. This was indeed found to be true [99] in the
case of nanocrystalline diamond particles surrounded by
amorphous-carbon region. Figure 10 shows the Raman spectrum of nanocrystalline diamond embedded in amorphouscarbon matrix. The observed linewidth was found to be
much more than expected for a Gaussian connement
model. In order to understand these results, an alternate
connement model was proposed, which took into account
the reection of the phonon from the dielectric/elastic
boundary of the particle. This leads to the existence of a
500

400

Intensity (arb. units)

Table 1. Peak shift  and line broadening  data for optical phonons
of different symmetries for 4-nm zinc oxide nanoparticles.

300

200

100

0
1280

1300

1320

1340

1360

1380

Raman shift (cm1)

Figure 10. Raman spectrum of 26-nm diamond particles embedded in

amorphous-carbon host. The continuous curve is the calculated spectrum based on the discrete model of phonon connement. Adapted
with permission from [99], A. K. Arora et al., Diamond Relat. Mater. 10,
1477 (2001). 2001, Elsevier Science.

507

Phonon Connement in Nanostructured Materials

4. ACOUSTIC PHONONS
Similar to the optical phonons, the acoustic phonons also
get conned within the particles. In the elastic continuum
limit, the connement of long-wavelength acoustic phonons

1.5

Diameter = 1.6 nm
Experimental

Normalized Intensity

calculated

0.5

0
1.5

Diameter = 6 nm
calculated
experimental

Normalized Intensity

standing wave pattern in the particle with phonon wavevector sampling the Brillouin zone at discrete points qn =
nQB /N (1 n N , where Na is the size of the particle. The
intensities In from the discrete phonons qn  were taken to
vary according to a power law In b n (b < 1). The discrete
model of the phonon connement yielded a satisfactory t
to the experimental phonon lineshape.
In order to probe the changes in the electron-phonon
interaction, resonance Raman scattering from conned
optical phonons has been investigated in a number of
systems. Effect of valence band mixing, arising from the
degeneracy at  point in the Brillouin zone of zinc-blende
semiconductors, on the electron phonon coupling has been
studied [100] in GaP nanoparticles. Surface phonons with
angular momentum l = 2 were found to participate in the
resonance Raman scattering, while in another study [101]
only the transitions with l = 0 2 have been argued to contribute to the resonance Raman scattering. In addition to the
LO phonons, zone-boundary TO phonons and their overtones have also been observed [102] in the nanoparticles of
indirect gap semiconductor AgBr under resonant conditions.
Using a phenomenological model, the ratio of intensities
of the overtone and the fundamental Raman spectra have
been analyzed [103] and the results suggested that electronphonon coupling decreased as the particle size reduced.
Interference effects in the resonance Raman efciency prole [104] of 1- and 2-LO conned phonons in Cd1x Znx S
mixed crystal nanoparticles, arising from a nonresonant contribution to the polarizability, have also been reported.
A detailed theory [105] of the one-phonon resonance
Raman scattering from spherical nanoparticles has shown
that in the dipole approximation, only l = 0 phonon modes
couple to the photon. On the other hand, in the electric quadrupole approximation l = 1 phonon modes can be
excited and their polarizability amplitude is proportional to
the wavevector of the photon.
In most of the analyses of the phonon lineshapes, the
bulk phonon dispersion curves have been assumed to be still
applicable. However, this is not guaranteed for very small
particles. Recent studies have shown that use of bulk phonon
dispersion in Gaussian connement model gives a good
agreement for 6-nm CdS particle; on the other hand, for
1.6-nm particles the predicted lineshape is more asymmetric
(Fig. 11) than that observed [106]. This disagreement has
been attributed to the inapplicability of the bulk phonon dispersion curves. It may be pointed out that the phonon density of states (DOS) of nanocrystalline iron [107] measured
using neutron scattering exhibits smearing of sharp features
and broadening on both low- and high-frequency side as
compared to the bulk. Molecular dynamics simulations show
that the increased density of states at low energies arises
from the vibrations of atoms at surface/grain boundaries
[108], whereas the increase in the DOS at high frequencies
has been attributed to shortening of bond length [109] and
lifetime broadening [110] due to anharmonic effects.

0.5

0
260

280

300

320

340

Raman Shift (cm1)

Figure 11. Raman spectra of CdS nanoparticles of diameter 1.6 and

6 nm. The disagreement of the calculated lineshape and the data for
the 1.6-nm particles suggests inapplicability of bulk phonon dispersion
curves. Reprinted with permission from [106], P. Nandakumar et al.,
Physica E 11, 377 (2001). 2001, Elsevier Science.

(sound waves) leads to the emergence of discrete modes

of particle which depend on the elastic properties through
the longitudinal and transverse sound velocities [111]. These
are spheroidal and torsional modes of the particle and their
frequencies depend on the angular momentum associated
with the vibration. We now briey describe the procedure to
obtain the frequencies of these modes.

4.1. Vibrational Modes of a Small Particle

By considering a spherical particle to be a homogeneous
elastic body, its free vibrations can be obtained by solving
the equation of motion [111113],
*+ 2 D/+t 2 = . + /0 0 D + /0 2 D

(16)

508

Phonon Connement in Nanostructured Materials

where D is the displacement, * is the density, and . and /

are Lames constants. The solutions are obtained by introducing scalar and vector potentials and by using appropriate boundary conditions for spheroidal and torsional modes.
The eigenvalue equation for the spheroidal modes is [111]
212 + l 1l + 21jl+1 1/jl 1 l + 1
2jl+1 2/jl 2 21 14 + l 12l + 112
+ 12 2ll 1l + 21jl+1 1/jl 1 = 0

(17)

where l is the angular momentum, 1 = R/ct and 2 =

1ct /cl are dimensionless variables,  is the spheroidal mode
frequency, R is the radius of the particle, and ct and cl
are the transverse and longitudinal sound velocities, respectively. jl (1) is the spherical Bessel function of the rst kind.
The angular momentum quantum number l can take values 0 1 2     The eigenvalue equation for torsional modes
is [114]
jl+1 1

l 1
jl 1 = 0
1

for l 1

(18)

Solving these equations for discrete values of l results in

S
T
a set of eigenvalues for each l, labeled as 1l
n and 1l n
for spheroidal and torsional modes, respectively. The index
n represents the branch number. It may be mentioned that
l = 0 torsional mode has null displacement. In addition,
the eigenvalues of the torsional modes do not depend on
the material, whereas those of spheroidal modes are completely determined by the ratio cl /ct . The eigenvalues of
these modes have been reported for many materials with
widely different values of the velocity ratio, such as 1.54
(MgAl2 O4 ) [115], 2.00 (Se) [38], 2.28 (CdS) [116, 114], 2.32
(CdSe) [117], 2.51 (Pb) [111], and 2.77 (In) [111]. The lowest eigenvalues for n = 0 for both spheroidal and torsional
modes correspond to the surface modes. These modes have
large amplitude near the surface. The subsequent eigenvalues (n 1) correspond to the inner modes. These discrete
modes for different values of l are essentially similar to the
acoustic phonons at discrete q-points in the Brillouin zone
given by l + 1/2/R up to a maximum value /a at the zone
boundary [111]. These modes modify the density of states of
the bulk [118] and have been argued to be responsible for
excess specic heat of small particles at low temperatures
[119, 120].
The symmetries of the particle vibrations correspond to
the irreducible representations of the rotation inversion
group O(3) of the sphere. The spheroidal modes transform
g
g
according to the irreducible representations D1  D2u  D3    
[121]. The subscripts represent the angular momentum, and
the superscripts g and u imply symmetry and antisymmetry
with respect to inversion. In addition, the components of
electric dipole moment transform according to D1u . On the
other hand, the components of the symmetric polarizability tensor for Raman scattering will transform according to
the irreducible representations resulting from the symmetric
g
g
product D1u D1u sym = D0 + D2 . Therefore the only allowed
g
Raman active modes are the spherical mode D0 and the
g
quadrupolar mode D2 . The torsional modes are not Raman
active [121]. This is different from the assignment by other

researchers [114, 122] based only on the parity of the wavefunctions, where all spheroidal modes with even l and all
torsional modes of odd l were argued to be Raman active.
In addition to the elastic continuum model, a microscopic
lattice dynamical calculation of conned acoustic phonons
in nanocrystalline Si has been carried out [123]. For this
the bond polarizability model within the partial density
approximation has been used, similar to the conned optical
phonon calculation [29]. The disagreement of the calculated
conned acoustic phonon frequencies with the experimental data [124] was attributed to the fact that the calculations
were carried out for free Si particles while the data was
for Si nanoparticles dispersed in SiO2 matrix. On the other
hand, studies of the effect of host matrix on the spheroidal
mode frequencies [111, 125] suggest only marginal changes.
In a recent formalism the linewidth of the conned acoustic phonon has also been taken into account by making the
eigenvalue complex [126].

4.2. Low-Frequency Raman Scattering

The frequencies of the spheroidal and torsional modes can
S
T
be calculated from the eigenvalues 1l
n and 1l n , respectively, as
S
Sl n = 1l
n ct /R

(19a)

T
Tl n = 1l
n ct /R

(19b)

and

In order to express the vibrational frequencies in cm1 , one

can divide Eqs. (19) by the velocity of light in vacuum c. In
most materials, for particles of diameter less than 10 nm,
these frequencies lie in the range of 5 to 50 cm1 . Hence
it is possible to observe the modes, allowed by the selection
rules, in the low-frequency Raman scattering. It is noteworthy that Brillouin spectroscopy is extensively used for probing the acoustic phonon branch close to the zone center in
crystalline solids. The Brillouin shifts of the order of 1 cm1
are conveniently measured by interferometric techniques
using FabryPerot etalon. However, the range of conned
acoustic phonon frequencies makes Brillouin spectroscopy
unsuitable for this purpose. On the other hand, the particle
modes were observed for the rst time by Duval et al. [115]
in the spinal (MgAl2 O4 ) particles dispersed in oxide glass
in the low-frequency Raman scattering. The inverse dependence of the mode frequencies on the particle size was also
established experimentally. Subsequently, conned acoustic
phonons have been reported in metal [127129] and semiconductor [124, 130, 131] nanoparticles.
Often the assignment of the peaks observed in the lowfrequency Raman spectrum in terms of angular momentum
quantum number l and branch number n may be tricky and
nonunique. In order to obtain unambiguous assignment, it
is useful to know the size of the particle from independent
measurements such as high-resolution transmission electron
microscopy (HRTEM) [122], X-ray diffraction (XRD) [132],
or small-angle X-ray scattering (SAXS) [117] and plot the
observed mode frequencies as a function of inverse diameter
along with the theoretically expected linear dependencies

509

Phonon Connement in Nanostructured Materials

PARTICLE SIZE (nm)

(b)
6

MODE FREQUENCY (cm1)

[72, 114]. In addition, making a polarized measurement is

useful in the assignment, as the spheroidal mode appears
only in the polarized geometry while the quadrupolar mode
occurs in both polarized and depolarized geometry.
Silver nanoparticles dispersed in different hosts such as
alkali halides [128], soda-lime glass [129], SiO2 [122, 127],
and ZrO2 [132] have been studied in great detail. Fuji et al.
found the frequencies of Ag particles of sizes between 2 and
5 nm close to those expected for l = 0 and l = 2 spheroidal
modes [122]. The strong Raman signal was attributed
to resonance associated with localized surface plasmons.
The growth of Ag nanoparticles in SiO2 during isochronal
annealing has been recently examined [127]. In view of its
depolarized characteristics, the Raman peak was assigned
to the l=2 quadrupolar mode. The average size thus estimated was found to be consistent with that obtained from
the width of the surface plasmon absorption. Quadrupolar
mode has been observed also for Ag nanoparticles dispersed
in soda-lime glass [129]. Silver nanoparticles synthesized in
ZrO2 by annealing a polycrystalline pellet coated with Ag,
at 1073 K exhibited as many as four peaks in the Raman
spectra [132] which were assigned to the quadrupolar mode.
These were interpreted as arising from a multimodal distribution of particle sizes ranging between 3.5 and 7 nm.
However, the average particle diameters obtained from the
width of the XRD peak and TEM were of the order of
23 nm. The quadrupolar mode frequency corresponding to
such a large average size is much smaller and not expected
to be observed in the low-frequency Raman spectrum. This
makes their assignment to quadrupolar modes doubtful. The
average size of gold clusters found in SiO2 due to ion beam
mixing and subsequent annealing has been estimated to be
around 4 nm from low-frequency Raman scattering [133].
Semiconductor nanoparticles dispersed in oxide glass
[77, 116, 134], SiO2 [135], and GeO2 [114] have been extensively studied. Many of these composites are synthesized
by doping the glass by the semiconductor up to about
2% in the melt and rapidly cooling to room temperature.
The solid solution thus formed is supersaturated and semiconductor nanoparticles nucleate and grow upon annealing the semiconductor doped glass above 500  C [136].
Synthesis of composites in the form of thin lms is carried out using the technique of co-sputtering. There have
been several studies on commercial long-pass optical lters such as GG495, GG475, and RG630 from SCHOTT,
which contain CdSx Se1x mixed crystals dispersed in oxide
glass [137]. In the early studies the lowest energy surface
mode and the lowest energy breathing mode were identied in the Raman spectra [116]. The frequencies of these
modes were found to decrease during annealing, suggesting
growth of particles [117]. Figure 12 shows the dependence
of spheroidal mode frequency and the estimated particle
size on the annealing temperature in Cd1x Znx S095 Se005
nanoparticles dispersed in oxide glass. During annealing the
zinc concentration x in the nanoparticle was reported to
increase, if the host glass contained ZnO as one of the
constituents [77]. Some studies have revealed very large
width of the conned acoustic phonon 2 2 in semiconductor doped glass GG495 [134]. This has been attributed
to the existence of a log-normal particle size distribution.
In addition, resonance enhancement of the quadrupolar

16

14

(a)

12
500

600

700

ANNEALING TEMP (C)

Figure 12. Dependence of conned acoustic phonon frequencies

(a) and average particle size (b) of CdS1x Sex nanoparticles dispersed
in borosilicate glass (GG475) on annealing temperature. Symbols
and
represent the corresponding values for the unannealed lter.
Reprinted with permission from [77], M. Rajalakshmi et al., J. Phys.:
Condens. Matter 9, 9745 (1997). 1997, IOP Publishing.

mode was found for excitation with green wavelength but

not with blue line. For CdS nanoparticles dispersed in GeO2
glass, a linear dependence of conned phonon frequencies
on inverse diameter has been reported [114]. From this analysis the mode was identied as the l = 0 spheroidal mode.
In addition to the conned acoustic phonons, another broad
peak called boson peak arising from the glassy host has
been observed in the low-frequency Raman spectra of semiconductor doped glasses [72]. Conned acoustic phonons
have also been reported in selenium nanoparticles dispersed
in a polymer host [38].

5. SUMMARY
In this chapter we have examined the consequences of
connement of the optical and acoustic phonons within a
grain of nanostructured materials on the vibrational spectra.
These are the shift and asymmetric broadening of the optical phonon lineshape and the appearance of spheroidal and
quadrupolar modes of the nanoparticle in the low-frequency
Raman spectra. Among the conned acoustic phonons, only
the spherical mode with angular momentum l = 0 and
quadrupolar mode with l = 2 are Raman active. The inverse
dependence of the particle mode frequencies on its diameter
is useful as a secondary method for the estimation of particle size. Changes in the optical phonon Raman lineshape
arise from the contribution of phonon with nite wavevector
whose magnitude is of the order of inverse diameter of the

510
grain. Noticeable differences in the spectra are found only
when the particle/grain size is smaller than about 20 lattice
parameters. Furthermore, the effect of connement is least
for 1D connement and maximum for 3D connement. For
very small grain size the phenomenological models that use
the bulk phonon dispersion curves as inputs fail because for
these sizes, phonon density of states differs signicantly from
that of the bulk. Detailed theoretical studies are required to
obtain a full understanding of the vibrational spectra of very
small size particles.

GLOSSARY
Acoustic phonons Phonons created by atoms vibrating in
phase with each other.
Anharmonic effects Effects such as thermal expansion,
arising from non-parabolic nature of interaction potential
between atoms. Parabolic atomic potential leads to harmonic atomic vibrations.
Brillouin scattering Inelastic scattering of photons by
acoustic phonons in a solid.
Brillouin zone Unit cell formed in the reciprocal space by
reciprocal lattice vectors.
Carbon nanotube A graphene layer rolled up into a tube
of diameter of the order of a few nanometers and length
several micrometer.
Chiral vector A vector formed from the superposition of
integral multiples of unit vectors of a 2D-hexagonal plane
of graphite. This vector is perpendicular to the axis of the
carbon nano-tube, and its magnitude determines the circumference of the tube.
Dispersion curve Plot of phonon frequency versus
wavevector for a phonon of specic symmetry.
Long-pass lter An optical lter that allows light longer
than a given wavelength to pass through.
Nanowire Wire/rod of a few nanometers diameter and several micrometer length.
Optical phonon Phonons in the high frequency region created by atoms in a crystal vibrating out-of-phase with each
other.
Phonon Quantum of atomic vibrations in crystalline solids.
Quantum dot A small particle surrounded by vacuum or a
material of larger band gap, capable of exhibiting effects of
quantum mechanical connement of charge carriers.
Quantum well A thin layer of a material of smaller band
gap sandwiched between adjacent layers of another material
with larger band gap, capable of exhibiting effects of quantum mechanical connement of charge carriers.
Raman scattering Inelastic scattering of photons by
atomic vibrations or other elementary excitations in
solids/molecules.
Resonance Raman scattering Enhancement of efciency
of Raman scattering when the incident photon energy is
close to one of the electronic transitions in a solid/molecule.
Scattering vector Wavevector transferred in the scattering
of light by elementary excitations.
Superlattice A periodic arrangement formed by depositing
thin alternate layers of two materials on a substrate.

Phonon Connement in Nanostructured Materials

Wavevector A vector in the direction of propagation of

phonon with a magnitude that is inverse of wavelength of
the phonon.

ACKNOWLEDGMENTS
It is a pleasure to acknowledge very fruitful collaborations
with Professors S. Mahamuni, D. S. Misra, B. R. Mehta, and
C. Vijayan. We also thank Dr. B. Viswanathan for interest in
the work, Dr. Baldev Raj for support, and Mr. S. B. Bhoje
for encouragement.

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