JOURNAL OF RAMAN SPECTROSCOPY

J. Raman Spectrosc. 2008; 39: 15781583

Published online 20 October 2008 in Wiley InterScience
(www.interscience.wiley.com) DOI: 10.1002/jrs.2106

Study on the applied limitation of the micro-crystal

model for Raman spectra
of nano-crystalline semiconductors
S. L. Zhang, S. N. Wu, Y. Yan, T. Hu, J. Zhao, Y. Song, Q. Qu and W. Ding
School of Physics, Peking University, Beijing 100871, China
Received 13 February 2008; Accepted 26 July 2008

The limitation in sample size and the choice in parameters for the application of the micro-crystal (MC)
model have been tested and discussed. The testing was performed through the fitting of calculated
Raman spectra by using the MC model with the observed Raman spectra for nearly uniform-sized nanocrystalline (NC)-Si of smaller than 2 nm. The results showed that the good fittings could not be obtained,
if the phonon dispersion curves !.q/ and Raman linewidths 0 of bulk-crystals (BCs) were used, i.e. if the
bulk-like approximation (BLA) was used in the fitting. Moreover, an analysis of the fitting results indicates
that when the size of NC-Si is smaller than about 4 nm, the MC model based on BLA will be invalid.
Copyright 2008 John Wiley & Sons, Ltd.

KEYWORDS: Raman spectrum; micro-crystal model; bulk-like approximation

INTRODUCTION
Nano-crystals have been the main focus of fundamental
study and technical applications for a long time, with
nano-crystalline (NC)-semiconductors forming a major part
of the study. In the study of NC-semiconductors, Raman
spectroscopy is one of the preferred choices in characterization and investigation.1,2 The Raman spectra of
NC-semiconductors usually exhibit new features different
from those of the corresponding bulk-crystalline (BC)semiconductors, in which the main differences are the
wavenumber shift and the linewidth broadening. For these
new features, the theoretical interpretation is very important as it will explore the nature of the new features. In the
Raman scattering theory of NC-semiconductors, the microscopic models for micro-crystallites and quantum dots have
been proposed and given good agreements with experiments, which lead to a deep understanding of the nature
of phonon modes of NC-semiconductors.3 5 However, the
microscopic theories are rather difficult to apply, especially
for many experimentalists. In order to overcome this difficulty, phenomenological models for subjects of small size
are proposed, among which the RWL model proposed by
Richter, Wang and Ley6 and the spatial correlation (SC)
Correspondence

to: S. L. Zhang, School of Physics, Peking

University, Beijing, China.
E-mail: slzhang@pku.edu.cn

Copyright 2008 John Wiley & Sons, Ltd.

model proposed by Juserand and Spariel,7 based on the

phonon confinement and phonon localization effects, respectively, are popular.
In 1986, Campbell and Fauchet8 tested and developed
RWL model further. The basic physical assumptions of
the RWL model are as follows: on the one hand, in small
crystallites, the periodicity of lattices still exists, meaning that
the translational symmetry and the momentum conservation
law still hold and, in fact, the bulk-like approximation
(BLA) is accepted; on the other hand, the small size of
the crystallites results in the spreading of momentum and
relaxation of the wave vector selection rule due to the
uncertainty principle. Based on the above assumptions, the
first order Raman intensity I
 in the RWL model is written
as follows:


d3 q jC
0, qj2
I


1
D
[

q]2 C
0 /22
where C
0, q is the Fourier coefficient of a weighting function
W
r, L, by which the function amplitude decays fast near the
boundary of crystallites.
q is the phonon dispersion and
0 is the linewidth. In the original RWL model suggested
in Refs 6,8,
q and 0 were all chosen as those in bulk
semiconductors, reflecting that the BLA has been adopted
practically.
The SC model was proposed for phonon localization
caused by alloying in Ga1
x Alx As.9 The authors proposed that

The applied limitation of the micro-crystal model

the phonon mode contributing to the total Raman spectrum

has a frequency equal to that of the corresponding bulk
phonon and its line-shape is Lorentzian. In the SC model,
the Raman intensity I
 is the weighted summation of the
intensity of all the contributing phonons and is expressed as
following:


I
 D

P
q
0

q/
dq
[

q]2 C
q2

2

where P
q is the weighting factor, representing the contribution probability of phonons for the whole spectrum. The
authors assumed that P
q is Lorentzian with a linewidth
and a peak center at q D 0 and is expressed as
p
q D

2
1
 q2 C 2

3

The above assumption implies that the Raman spectrum

can be regarded as the consequence of scattering of a wave
packet. This is consistent with the result based on the
assumption of the phonon momentum and wave vector
selection rule in the RWL model.
If we assume
q in Eqn (2) is independent of q and
p
q D jC
0, qj2 in Eqn (1), the RWL and SC models
are equivalent in forms. Therefore, one does not exactly
distinguish the RWL and SC models in practical applications.
In the following sections, we use the name micro-crystal
(MC) model to represent the above two models and the
discussion will be based on Eqn (1) for simplification.
In the last two decades, the MC model has been applied
extensively and successfully to crystallites and/or nanowires.6 18 However, there appear two problems. First, the
fitting is successful only if the parametersW
r, L,
q,
and 0 are chosen to be different from those suggested
in Refs 6,8. For instance, Yoshikawa et al.14 assumed that
the 0 is dependent on the particle size, Faraci et al.18 and

Zi et al.19 suggested to modify the integral range and to

adopt a new form of W
r, L. Paillard et al.17 proposed an
expression of
q, which takes the anisotropy into account,
instead of the conventional isotropic one-dimensional
q D 2/L.
Second, the query on the limitation of the MC model
in the size of the samples has been put forward. For
example, Zi et al.19 tested the MC model by comparing
the microscopic calculation, based on the partial-density
approach with the observed Raman spectra of Si spheres
and found that for Si spheres of very small size, the MC
model cannot give a satisfactory description. Paillard et al.17
and Adu et al.10 suggested that the size limitation of the
samples in the application of the MC model was 2.2 and
4 nm, respectively. Unfortunately, up-to-date, the size of
NC-Si used in experiments is mostly larger than 10 nm with
large size distribution. The smallest sizes of samples used
were 4.6 1 and 4.5 0.2 nm, which appeared in the works
done by Paillard et al.17 and Adu et al.10 respectively.
Owing to the above reasons, further and detailed
tests for the size limitation of samples and choice of
parameters in the MC model are needed urgently, especially
because of the sizes of the prepared NC-semiconductors
becoming smaller and smaller. In this paper, we report
on such testing by fitting the theoretical Raman spectra
calculated using the MC model with the experimental Raman
spectra of small-size NC-Si with nearly uniform size. The
physical nature reflected by our testing results will be
discussed.

FITTING PARAMETER CHOICE AND SAMPLE

SIZE
In the fitting, W
r, L,
q, and 0 are adjustable parameters
and the sample size L is not, as the sample is definite in
the experiments and thus the sample size L must be fixed
in the fitting. Besides, based on the requirement of this
(b)

(a)

Figure 1. PL spectrum (a) and Raman spectra excited at 488, 515, 633, and 785 nm (b) of NC-Si sample C.

Copyright 2008 John Wiley & Sons, Ltd.

J. Raman Spectrosc. 2008; 39: 15781583

DOI: 10.1002/jrs

1579

1580

S. L. Zhang et al.

testing, the size of the samples used should be very small,

say, less than 34 nm.10,17 In the Raman experiments of
NC-semiconductors, the sample size can be determined by
the resonant size selection effect (RSSE) when the Raman
spectrum is from the resonant Raman scattering (RRS) within
the electronic band gap.20,21
The photoluminescence (PL) spectrum and the Raman
spectra of the NC-Si sample C used in the fitting are shown
in Fig. 1(a) and (b), respectively.20
It is well known that the position and intensity of PL
spectra reflect the band gap energy Eg and the particle
number taking part in the NC-Si PL process. Figure 1(a)
shows us that the energy of the PL spectra covers a broad
visible range from the high energy side of 3.5 eV to the
low energy side of about 1.6 eV, which was from the
extension of the experimental spectrum. The above feature
confirms the presence of a strong quantum confinement
effect (QCE) on the electronic structure, as PL bands are
shifted from the infrared region in BC-Si to the blue region in
sample C. Besides, Fig. 1(a) also indicates that the Raman
spectra shown in Fig. 1(b), excited at 488 (2.54 eV), 515
(2.41 eV), and 633 (1.96 eV) nm lasers, are the RRS spectra,
indicating the nearly uniform-sized NC-Si that takes part
in the Raman process. For the Raman spectrum excited at
785 nm (1.59 eV), compared to the PL spectrum shown in
Fig. 1(a), the resonance did not happen or was very weak,
implying that the Si particles with different energies (i.e.
different sizes) including 1.59 eV (i.e. 2.1 nm) may be mainly
drawn into Raman scattering.
Based on the RSSE,20,21 using the relations between band
gap energy Eg and NC-Si size L22 and setting ELaser D Eg ,
the NC-Si size LOptic can be extracted for each resonant
Raman spectrum. The excited laser wavelength 0 , the
corresponding laser energy ELaser , and the RSSE selected
LOptic have been listed in Table 1. From Table 1, we can see
that the LOptic of the resonant samples are less than 2 nm,
matching the above requirement on sample size fitting.
On W
r, L, we learnt that the QCE on phonons is very
strong in systems of small size23 and thus we chose the sinc
function as a fitting form of W
r, L,19 and the traditional
Gaussian function,6,8 which give rise to zero and nonzero
vibrational amplitude at the boundary, respectively. Their
practical forms and the corresponding Fourier coefficient

C(0,q) are written, respectively, as:

W
r, L D exp

r2 /L2 
2

jC
0, qj exp

q L /2

0 (nm)
ELaser (eV)
L (nm)

q
cm
1 
q
/a

488

514

633

785

2.54
0.8
16
0.35

2.41
0.9
15
0.29

1.96
1.2
9
0.22

1.59
2.1
8
0.09

Copyright 2008 John Wiley & Sons, Ltd.

5

where is the adjustable parameter and L is fixed at LOptic .

W
r, L D

 sin
2r/L
2r/L
0

jC
0, qj2 D

if r < L/2
if

6

r L/2

sin2
qL/2
4L4
4 2

2 q
42
q2 L2 2

7

The bulk
q was adopted first, which is isotropic and

located in a spherical Brillouin zone6,8 and is expressed as24
2
q D C C D cos
aq/4,

0  q  /a

8

is the lattice constant of Si, C D 1.714

where a D 5.3 A
105 cm
2 , and D D 1.000 105 cm
2 .
q with anisotropy
proposed by Paillard et al.17 was also used. Moreover,
q
reported by Hu and Zi25 was used, of which the features
are the distinct characteristic in momentum and the smear
characteristic in energy.
Two kinds of linewidth 0 were used. One is a constant of
4.5 cm
1 and another is dependent on the phonon moment q.

RESULTS AND DISCUSSION

The fitting work is performed in three ways as listed in
Table 2. The first method corresponds to choice 1, in which
the bulk
q and 0
D 4.5 cm
1  were chosen and W
r, L
was Gaussian. In the second method, only one parameter
was changed in each choice as listed in choices 25. In the
third method, the
q was chosen as that suggested by Hu
and Zi25 and the 0 was dependent on q, simultaneously,
W
r, L was chosen in two function forms as listed in choices
6 and 7.
The fitting results are shown in Fig. 2, in which the
calculated and observed Raman spectra are shown in solid
Table 2. Different choices for weighting function W
r, L,
dispersion curve
q, and linewidth 0 in the fitting by the MC
model
Choice

Table 1. Excited laser wavelength 0 , corresponding laser

energy ELaser , RSSE selected L, fitted linewidth
q, and wave
vector range q of Eff
q for NC-Si sample C

4

2 2

1
p

W
r, L Gaussian
Sinc19

q

0
Fig. 2

24

Bulk
Paillard et al.17
Hu and Zi25

1

Constant D 4.5 cm
Adjustable

2
p
p

3
p

4
p

5
p

6
p

7
p

J. Raman Spectrosc. 2008; 39: 15781583

DOI: 10.1002/jrs

The applied limitation of the micro-crystal model

Figure 2. Observed (dotted lines) and calculated (solid lines) Raman spectra by using MC model, in which (a), (b), (c), (d), (e), and
(f) correspond to choices 1, 2, 3, 4, 5, and 6 listed in Table 2, respectively, for NC-Si sample C.

and dotted lines and Fig. 2(a)(f) correspond to choices 16

in order.
From Fig. 2(a), we see at once that the result gives a
bad fitting for the resonant spectra and a good fitting for
the spectrum excited at 785 nm. This indicates that choice 1
cannot obtain a good fitting for the spectrum of the nearly
uniform-sized NC-Si, and the better fitting occurred in the
size-dispersive NC-Si. The latter coincides only with the
recognized viewpoint that the MC model is suitable for the
size-dispersive samples.15 A similar phenomenon could be
seen in all spectra excited at 785 nm in Fig. 1(b)(f), giving
the earlier argument a solid confirmation again.
Figure 2(b) does not show an obvious improvement when
compared with Fig. 2(a), reflecting that the different choices
of W
r, L do not have a significant impact on the result.
In Fig. 2(c)(e), the fitting results do not show any essential improvement when compared with Fig. 1(a) and (b).
The fitting results of choices 6 and 7 are similar; therefore
we have only shown the fitting result of choice 6 in Fig. 2(f).

Copyright 2008 John Wiley & Sons, Ltd.

Considering the only difference between choices 6 and 7 is

the choice of weighting function W
r, L, the above similarity
indicates once again that the form of weighting function has
no significant influence.
From Fig. 2(f), at a glance, a better fitting was obtained
for all spectra excited at four wavelengths except for the low
wavenumber region around 480 cm
1 . It has been pointed
out that an amorphous silicon oxide thin outer layer covers
the surface of NC-Si samples, which has a Raman band
peaked at 480 cm
1 .26 If we consider that sample C is one of
those Si NW samples and its Raman spectrum should deduct
the component from the amorphous silicon oxide thin outer
layer, the fitting shown in Fig. 1(f) should be regarded as
the best fitting. This result confirms that the MC model is
applicable if the dispersion curve and linewidth do not use
those of the BC simultaneously. In other words, the choice of
the parameters
q and 0 based on BLA are not appropriate
in the application of the MC model for nearly uniform-sized
small NC-Si.

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S. L. Zhang et al.

It will be possible, in exploring the physical nature of

the fitting results, to learn the fitted dispersion curve and
linewidth used in the best fitting shown in Fig. 2(f). The best
fitted dispersion curves here represent the frequency and
corresponding wavevector q of the scattered phonons, which
we called effective dispersion curve and labeled Eff
q. Coordinately, the best fitted linewidth was called effective linewidth
and was labeled Eff
q. The Eff
q, the corresponding wave
vector range q of Eff
q, and the best fitting linewidth
Eff
q for the spectra excited at different wavelengths, are
shown in Fig. 3(a) in solid lines and are listed in Table 1,
respectively. The values of the best fitted Eff
q and q on
sample sizes L are put and drawn in Fig. 3(b) and (c), respectively. The lines in Fig. 3(b) and (c) were drawn by the fitting
of the least square method.
From Fig. 3(a), one can find that Eff
q is absent in the
region near the Brillouin zone center, implying that the
phonons at and near the zone center did not participate in
the Raman scattering event for nearly uniform-sized small Si
crystallites. In fact, by examining the observed spectra shown
in Fig. 1(b) closely, one can see that the above feature of Eff
q
coincides with the feature of observed Raman spectra: the
scattering intensity from the phonons of 520 cm
1 at and
near q D 0 are obviously very weak for the spectra excited at
488, 515, and 633 nm lasers. The results presented here are
contrary to the predication by the BLA theory that Raman
scattering is mainly from the phonons in the region near
q D 0 for crystallites of small size.

From Fig. 3(b) and (c), we found that the dependence

of Eff
q and q on L were exponential and could be
expressed as:
1.48 exp

L/0.29 for Eff
q
0.92 exp

L/0.72 for q

9

10

From Eqns (9) and (10), we learnt that Eff
q and q
were, respectively, about 0.04 /a and 7.61 cm
1 at infinite L,
which are basically consistent with q 0 and 0 7 cm
1
in BC-Si,6,7 confirming the reliability of Eqns (9) and (10).
The exponential dependence of q on L is inconsistent
with the well-known linear dependence of q on L,
q D 2/L, derived from the BLA.27 Moreover from formula
(10), we found that when q approaches the value of BC-Si,
the L 3.9 nm, implying that about 4 nm is the size limitation
of the MC model based on the BLA. This coincides with the
disappearing size of the QCE on electrons22,28 and phonons23
of Si particles, 45 nm.

CONCLUSIONS
In summary, we performed the fitting of the theoretical
Raman spectra calculated by using the MC model with the
experimental Raman spectra. From the fitting, it is found
that the MC model is invalid for Si crystallites smaller than
4 nm with nearly uniform size if the dispersion curve

q and linewidth
q are chosen based on the BLA.

Figure 3. (a) The best fitted dispersion curve Eff
q (thick solid lines) and corresponding BC-Si dispersion curve (dashed lines),
(b) dependence of best fitted linewidth
q on sample size L, where /a is half the size of Brillouin zone, (c) dependence of
wavevector range q of Eff
q on sample size L, for NC-Si sample C.

Copyright 2008 John Wiley & Sons, Ltd.

J. Raman Spectrosc. 2008; 39: 15781583

DOI: 10.1002/jrs

The applied limitation of the micro-crystal model

Additionally, we discovered that the features of
q and

q appeared in the best fitting are different from those
predicated by the BLA. The above results indicate that the
present modifications within the BLA frame for the MC
model are not appropriate and the microscopic theory is
needed for very small crystallites of nearly uniform size.

Acknowledgements
We acknowledge the financial support from NSFC under Grants
No. 60290083, 50334040, 50272017, and 10774006, and from RGC of
Hong Kong under the Grant No. 401003, as well as the Beijing Key
Laboratory for Nano-Photonics and Nano-Structure. The technical
support from the nano-chemistry group in Peking University is also
appreciated. We thank Dr S. K. Hark for helpful discussion and
assistance in writing.

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