Vibrational Spectroscopy 72 (2014) 90–96

Contents lists available at ScienceDirect

Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

Influence of crystal size on the electron–phonon coupling in ZnO

nanocrystals investigated by Raman spectroscopy
Animesh K. Ojha a,b,∗ , Manish Srivastava c , Sumeet Kumar a , Rasha Hassanein b , Jay Singh d ,
Manish K. Singh e , Arnulf Materny b
a
Department of Physics, Motilal Nehru National Institute of Technology, Allahabad, India
b
Center for Functional Materials and Nanomolecular Science, Jacobs University Bremen, 28759 Bremen, Germany
c
Department of Biotechnology, Delhi Technological University, Shahbad Daulatpur, Main Bawana Road, Delhi 110042, India
d
Department of Applied Chemistry, Delhi Technological University, Shahbad Daulatpur, Main Bawana Road, Delhi 110042, India
e
Department of Physics, The LNM Institute of Information Technology, Jaipur-302031, India

a r t i c l e i n f o a b s t r a c t

Article history: We have synthesized ZnO nanocrystals of different sizes (25–41 nm) using the sol–gel method and char-
Received 1 February 2013 acterized them using different techniques such as: transmission electron microscopy (TEM) and X-ray
Received in revised form 23 February 2014 diffraction (XRD). Raman spectra of different sizes of ZnO nanocrystals were recorded at two excita-
Accepted 24 February 2014
tion wavelengths, 514 and 647 nm, in the spectral range 300–1200 cm−1 . The vibrational modes were
Available online 3 March 2014
assigned on the basis of group theory analysis. The influence of mean crystallite size on the strength
of the electron–phonon coupling is experimentally estimated by the variation of relative intensities of
Keywords:
second order Raman band and the first order Raman band for ZnO nanocrystals of different sizes. We
ZnO
Nanocrystals
found that the intensity ratio of the 2E2 and 1E2 Raman bands decreases almost linearly for both exci-
Raman spectroscopy tation wavelengths with decreasing crystallite size, which reveals that the Fröhlich interaction plays a
Electron–phonon coupling dominant role in the electron–phonon coupling of the ZnO nanocrystals.
Fröhlich interaction © 2014 Elsevier B.V. All rights reserved.

1. Introduction Molecules and crystalline solids usually have well-defined

Recently, nanocrystal semiconductor materials have drawn
much attention due to their unique physical, chemical and optical
properties. Bulk ZnO is a well-known wide band-gap semicon-
ductor and one of the important candidates for high-performance
optoelectronic devices, such as ultraviolet (UV)-light-emitting
diodes, chemical or biological sensors, dye-sensitized solar cells
and piezoelectric devices because of its wide band gap (3.37 eV) and
its large exciton energy (60 meV) at room temperature. The optical
properties of nanometer scale devices can be controlled by tailoring
the average size of nanometer-sized crystals [1–5]. Here, also ZnO
nanostructures aroused great interest, since the mechanical, opti-
cal, and vibrational properties can be modified by size reduction,
shape and surface modifications [1].
∗ Corresponding author at: Motilal Nehru National Institute of Technology
(MNNIT), Allahabad, India. Tel.: +91 532 22771289.
E-mail addresses: animesh@mnnit.ac.in, animesh r1776@rediffmail.com
(A.K. Ojha).
structures and accordingly their potential energy is a function
of the nuclear coordinates with a global minimum. Further, the
electronic wave functions depend on the nuclear coordinates,
whereas the potential energy function for nuclear motion is pro-
duced by the much faster-moving electrons. If the energy difference
between two electronic states depends on a phonon coordinate,
electron–phonon coupling (EPC) can be observed in the crystals.
The nuclear equilibrium positions are different in the two states,
but the vibrational frequencies are unchanged [6].
The electron–phonon coupling is an important aspect in semi-
conductor materials due its significant influence on the optical
and electrical properties, such as the energy relaxation rate of
excited carriers and phonon reproduction of excitons in the lumi-
nescence as well as Raman spectra [7]. In a simple situation,
the radial electric field of the ionic nuclei in the crystal results
in a Coulomb interaction with the exciton, and the strength of
such an exciton–phonon coupling will be enhanced if the wave-
length of the phonon vibration is comparable to the spatial extent
of the exciton [8–13]. As per advances in material science, it is
possible to prepare semiconductor nanocrystals that occupy vol-
umes comparable with the size of the bulk exciton. Such quantum

http://dx.doi.org/10.1016/j.vibspec.2014.02.013
0924-2031/© 2014 Elsevier B.V. All rights reserved.
 A.K. Ojha et al. / Vibrational Spectroscopy 72 (2014) 90–96
confined electronic systems differ strongly from their bulk coun-
terpart in their optical and electronic properties. Experimentally,
the magnitude of EPC is typically expressed through the Huang-
Rhys factor S, which is the ratio of one-phonon to zero-phonon
intensity in the low-temperature Raman spectrum. The factor S is
expressed as, S = 2 /2, where  is the displacement between the
ground and excited state potential minima along the dimension-
less phonon coordinate [14]. Few theoretical as well experimental
studies [7–16] have been done to estimate the electron–phonon
coupling strength and its dependence on mean crystallite size of
semiconductor nanocrystals. Theoretically, Schmitt et al. [9] sug-
gested that the electron–LO–phonon coupling should vanish with
decreasing size of the materials by using a simple charge neutral-
ity model [7]. However, sophisticated theoretical treatments using
the nonparabolicity of the bands showed an increasing coupling
strength with decreasing nanocrystal size [10,11]. Very recently,
Kelly [15] has performed theoretical investigations to determine
the electron–phonon coupling strength in CdSe nanocrystals using
an atomistic phonon model. In this investigation, the phonon fre-
quencies and eigenvectors, electron–phonon couplings, and the
associated resonance Raman spectra have been calculated for
approximately spherical, wurtzite form of CdSe nanocrystals hav-
ing radii 1.4 to 2.3 nm and containing 318 to 1498 atoms. The
Huang-Rhys factor was calculated for the different sizes for the
coupling of each phonon mode to the 1Se –1S3/2 and 1Se –2S3/2 exci-
tations. The results show that the Huang-Rhys factors are larger
for the acoustic phonon modes than those obtained for the optical
modes. They decrease with increasing crystal size, and the Huang-
Rhys factors for each group of modes are smaller for the 1Se –2S3/2
than for the 1Se –1S3/2 excitation. Further, a series of experimen-
tal studies in CdSe, CdS, and InP nanocrystals indicated that the
electron–phonon coupling diminishes with decreasing nanocrys-
tal size [6,12–14]. Moreover, Scamarcio et al. [17] reported an
increase in the Frohlich electron–LO phonon interaction strength
with decreasing size in CdSx Se1−x nanocrystals embedded in a
glass slab. In the studies [18,19] it was found that the strength
of the electron–phonon coupling is governed by 2 ∝ 1/R for the
deformation coupling. For the long-range Fröhlich interactions, the
electron–phonon coupling strength can be estimated by determin-
ing the ratio between the Raman intensity of the 2LO phonon line
and that of the fundamental LO phonon line, which is approxi-
mately proportional to the electron–LO–phonon coupling. Seong
et al. [20] indicated, by studying the Raman intensity ratio of the
LO phonon to its overtone in CdS and InP quantum dots, that the
electron–phonon coupling decreases with decreasing crystallite
size. Fan et al. investigated the electron–phonon coupling strength
for CuO nanocrystals and observed that their value decreases by
reducing the size of the nanocrystals. Wang et al. [7] studied the
electron–phonon coupling strength in ZnO nanorods using Raman
spectroscopy and they observed that the Fröhlich interactions play
an important role for the electron–phonon coupling. This shows
that the strength of the electron–phonon/electron–plasmon cou-
pling in ZnO nanocrystals decreases with reducing the crystallite
size. A similar kind of pattern for the variation of electron–phonon
coupling strength with the mean crystallite size has been observed
in earlier reports [7,8,12–14]. ZnO/Mg0.27 Zn0.73 O quantum wells
were synthesized on lattice-matched substrates which were grown
by laser molecular-beam epitaxy.
The dependence of the coupling between localized excitons
and longitudinal-optical phonons was estimated experimentally
by calculating the value of Huang-Rhys factor and found that its
value increases significantly with increasing the width of quantum
well [21]. Fan et al. [22] had synthesized ZnO nanocombs of vari-
ous sizes by simple thermal evaporation methods. The resonance
Raman measurements were performed for the synthesized sam-
ples to determine the strength of electron–phonon coupling and it
91
was found that its value increases with decreasing the particle size.
Phan et al. [23] had studied resonant Raman scattering (RRS) in ZnO
nanostructures annealed at various temperatures and the strength
of electron–phonon coupling is determined by calculating the
intensity ratio of 2LO to 1L. The value of intensity ratio was found to
be temperature dependent and showed a maximum value for the
samples synthesized at 800 ◦ C and at other temperatures, the value
of 2LO/1LO is decreased. The dependence of the intensity, energy,
and resonance effects of the longitudinal optical (LO) phonon on
laser excitation condition are discussed in the context of Fröhlich
interaction for ZnO nanocrystals embedded in a MgO/ZnO [24].
The optical phonon modes and its overtones was investigated in
ZnS and ZnO quantum dots using resonance Raman scattering and
their behaviour is discussed in somewhat more detailed [25]. Hsu
et al. [26] had studied the exciton–longitudinal–optical–phonon
interaction. They found that its value decreased with reducing ZnO
particle size to its exciton Bohr radius. ZnO quantum dots of con-
trolled sizes have been fabricated by a simple sol–gel method and
the resonance Raman measurements were done to estimate the
strength of electron–phonon coupling. In the study it was reported
that the strength of electron–phonon coupling diminishes with
reducing the diameter of ZnO quantum dots [27]. Electron–phonon
and spin–phonon interaction, and using a Green’s function tech-
nique. The authors studied mainly surface, size, and ion doping
effects on the phonon properties of ZnO nanoparticles nanopar-
ticles. They have shown that the electron–phonon and anharmonic
phonon–phonon interactions play an important role in pure ZnO
as well as transition metals doped ZnO nanoparticles [28].
For semi-conductor nanocrystals with smaller band gaps, such
as CdSe, CdS, and InP, the electron–phonon coupling has been inves-
tigated experimentally and theoretically in a greater detail, for
semi-conductor nanocrystals with wider band gaps, such as ZnO
(3.37 eV), size and shape dependence of the coupling are still not
completely understood. Therefore a systematic study of the size and
shape dependence of the electron–phonon coupling strengths in
ZnO nanocrystal is of a particular interest for the understanding the
fundamental physics of ZnO nanocrystals and for their application
in functional devices. The purpose of this report is to examine the
influence of the particle size on the evolution of phonon confine-
ment and the strength of electron–phonon coupling using Raman
spectroscopy.
2. Experimental
2.1. Materials
Zinc acetate (ZnAC2 ·2H2 O), 70% aqueous solution of glycolic
acid, 25% aqueous solution of ammonia and deionized-water were
used in the experiments. All the reagents were of analytical grade
and used without any further purification.
2.2. Synthesis of ZnO nanocrystals
The synthesis of ZnO nanocrystals was done following the
sol–gel method analogous to that described in our earlier report
[29]. A stoichiometric amount of zinc acetate was dissolved in
deionized water to prepare a 0.01 mol solution and subsequently
70% aqueous solution of glycolic acid was added with a molar ratio
of metal salts to glycolic acid of 1:2. Further, 25% aqueous solution
of ammonia was added dropwise into the prepared solution with
vigorous magnetic stirring to obtain a pH value of 8. At this stage, we
obtained a homogeneous solution. In the next step of the synthesis,
the obtained solution was slowly evaporated to remove the extra
amount of water within the temperature range of 65–70 ◦ C. Subse-
quently, the obtained solution was heated once again at 75 ◦ C under
92 A.K. Ojha et al. / Vibrational Spectroscopy 72 (2014) 90–96

vigorous magnetic stirring to obtain the slurry type product. At the (a) ZnO

(101)
(100)
last stage of the synthesis process the obtained product was poured

(110)
(002)

(103)
(102)

(112)
(201)
(200)
in a silica crucible for calcinations process. The samples were cal-
cined at 500, 600, 700, 800, and 900 ◦ C for 10 h and the mean size of
41 nm

Normalized Intensity
the particle obtained at these calcinations temperatures was found
to be 25, 29, 35, 37 and 41 nm, respectively. 37 nm

2.3. XRD, TEM, and Raman measurements

35 nm

The synthesized products were characterized using XRD, TEM,

and Raman spectroscopy. XRD measurements of the samples
29 nm
were carried out using an X-ray diffraction powder diffractometer
(XPERT-PRO PW3050/60) equipped with a copper target and nickel
filter operated at 30 kV and 30 mA. The X-ray wavelength used in 25 nm
this study was 0.15406 nm (Cu K-alpha). The structural morphol-
30 40 50 60 70
ogy and mean crystallite size of the synthesized nanocrystals was Degree (2 )
investigated by TEM measurements using a Tecnai G2 S-Twin elec-
tron microscope. The Raman spectra of the ZnO nanocrystals of
(b)

(101)
ZnO
different sizes were recorded at two excitation wavelengths, 514

(100)

(002)
and 647 nm. The Raman spectra of the ZnO nanocrystals of dif-
ferent sizes with 514.5 nm excitation wavelength were measured 41 nm

in a micro Raman setup (back-scattering geometry) using a Triax
single monochromator (TRIAX 550, Jobin Yvon, France) equipped
with three interchangeable holographic gratings (600, 1200, and
2400 grooves/mm) and a liquid nitrogen cooled CCD detector. An
Olympus microscope with a 50× objective was used focus the laser
light onto the samples and to collect the Raman scattered light.
The scattered signal was filtered by a holographic super-notch fil-
ter for Rayleigh scattering rejection before focusing it onto the
100 ␮m entrance slit of the spectrometer. The monochromator’s
1200 grooves/mm holographic grating was used for signal disper-
sion. Spectral calibration was performed using Si Raman modes.
During the measurement, the samples were kept in the form of
powder on an aluminum foil covering a glass slide, which was
mounted on the microscope XY table to avoid background signal
from the glass. The laser power on the samples was kept constant
at 20 mW. The data acquisition time for each Raman measurement
was 60 s with two averaged signal accumulations.
2.4. XRD and TEM studies of the synthesized products
The X-ray diffraction patterns of the synthesized ZnO nanocrys-
tals are shown in Fig. 1(a) and (b).
All the observed diffraction peaks were indexed with help of
standard JCPDS (card no. 36-1451) analysis. The peaks correspond-
ing to (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), and (1 1 2) planes
are in agreement with the typical wurtzite type structure of bulk
ZnO crystals. Moreover, no peaks corresponding to any unknown
phase could be observed in the XRD spectra, which confirm the
high purity of the obtained ZnO products. The mean crystallite size
of ZnO nanocrystals is determined by taking the FWHM values of
the four most intense diffraction peaks for each sample using the
Scherrer expression, d = 0.941 /B cos , where  is the wavelength,
B is the FWHM of the diffracted peak, and  is the Bragg angle. The
values of the crystallite sizes thus obtained are averaged. The aver-
age crystallite sizes for the five samples were determined to be 25,
29, 35, 37, and 41 nm. In order to show the dependence of the full
width at half maximum (FWHM) of the diffraction peaks on size
of the nanocrystals, the magnified XRD patterns corresponding to
the three most intense peaks are shown in Fig. 1(b). One can eas-
Normalized Intensity
37 nm
35 nm
29 nm
25 nm
32 33 34 35 36 37
Degree (2 )
Fig. 1. XRD patterns of ZnO nanocrystals of different crystal sizes (a) and magnified
XRD patterns for the most intense XRD peaks at each crystal size (b).
with increasing crystallite size may be explained in terms of lattice
expansion due to the relaxation in strain for the crystallite size cal-
cined at higher temperature. It could also be confirmed by variation
in the values of lattice constants with increasing the crystallite size
(see Table 1). Further, the XRD peaks corresponding to (0 0 2) and
(1 0 1) planes for crystallite size 35, 37 and 41 nm show a notice-
able asymmetry towards higher 2 values. In order to deconvolute
the XRD peaks, we have fitted these two planes using Lorentzian
function. The 2 value thus obtained by fitting the asymmetri-
cal feature was tried to indexed using JCPDS card. The obtained
2 value corresponding to asymmetrical feature could not match
with the plane associated to the any other phases of ZnO. Thus,
the appearance of asymmetry in XRD peaks could be described
by two ways. First, it may be appeared due to the reflection from
(0 0 2) and (1 0 1) planes by K␣1 and K␣2 as reported in the ear-
lier study [30]. In the study [30], the authors reported a method to
determine the defect structure in hyper-stoichiometric UO2+x using
Table 1
Calculated values of lattice constants for each particle size.
Particle size (nm) Lattice constants (nm)

ily notice that the FWHMs gradually increase on going from top to a=b c
bottom of the XRD patterns. This broadening is the first confirma- 25 3.22331 5.2101
tion that the synthesized ZnO products possess nano dimension. 29 3.22367 5.1714
Here, it is worthy to note that the planes (1 0 0), (0 0 2) and (1 0 1) 35 3.2335 5.18194
show a consistent decrease of 0.08◦ in 2 values upon going from 37 3.22623 5.17196
41 3.2284 5.17504
crystallite size 25 to 41 nm. The decrease of 2 values of XRD peaks
 A.K. Ojha et al. / Vibrational Spectroscopy 72 (2014) 90–96 93

Fig. 2. TEM micrographs of ZnO nanocrystals of particle sizes 41 nm (a) and 29 nm (b). PSD curves for 41 nm (c) and 29 nm (d) ZnO nanocrystals.

XRD and Raman spectroscopic techniques. They found a sequence quantitatively by fitting it using the following Gaussian function
of phase transition from cubic to tetragonal symmetry with increas- [32]
ing degree of non-stoichiometry. However in the present report if  
it is true, the asymmetry should have been appeared in the XRD A (D − Dm )2
P (D) =  exp −
peaks for each crystallite size. Second, the appearance of asym- 2D 2D2
metry in the XRD peaks at higher crystallite size may be due to
the high value of calcination temperature at which the particles where, D is the standard deviation of the diameter and Dm is
of smaller crystallite size combined together to form particle of the mean diameter. The mean crystallite sizes thus calculated are
large crystallite size. In the formation of particle of larger size, the 25 ± 1, 29 ± 1, 35 ± 1, 37 ± 1, and 41 ± 1 nm. TEM micrographs of
growth of these two planes may take place slight differently as two samples and their corresponding PSD curves are shown in
it was grown in case of smaller crystallite size. In a study [31] panels (a) and (b) of Fig. 2 and (c) and (d) of the same figure,
different techniques were used to study transformation of CdS respectively.
platelets during grinding and under hydrostatic pressure using XRD The mean crystallite size calculated based on the TEM
and Raman spectroscopic measurements. XRD and TEM measure- micrographs is in good agreement with the mean crys-
ments revealed that the platelets included zinc blende (cubic) CdS tallite size calculated from XRD data. The lattice param-
nanodomains dispersed in a wurtzite (hexagonal) single-crystalline eter of each sample was calculated using the following
matrix. Extended grinding led to a decrease of the grain size and relationship
to a progressive transformation of the hexagonal stacking into a
cubic one. The FWHM of the XRD peaks is increasing with decrease 1 h2 + k2 l2
2
= 2
+ 2
of crystalline size. FWHM of XRD peaks represents the distribu- d a c
tion of lattice parameter around a given value. It could originate 
from stresses, crystallite size or sum of the effects. In the present where c/a = 8/3 and a = b =
/ c. The calculated mean crystallite
study, it could be originated due to the variation in crystallite size and lattice parameters are summarized in Table 1.
size.
In order to support the findings based on the XRD pat- 3. Results and discussion
terns, we have also determined the crystallite sizes of the
samples through TEM images. A particle size distribution curve The normalized Raman spectra of ZnO nanocrystals recorded for
was drawn for each sample. The size distribution was analyzed the spectral region 300–1200 cm−1 using an excitation wavelength
94 A.K. Ojha et al. / Vibrational Spectroscopy 72 (2014) 90–96

1E2 1E2

2E2 2E2 41 nm
41 nm
Normalized Raman Intensity

Normalized Raman Intensity

37 nm
37 nm

35 nm

35 nm

29 nm
29 nm

25 nm

25 nm

1200 1125 1050 400 300

-1
Wavenumber / cm
1200 1000 800 600 400
-1
Wavenumber / cm Fig. 4. Raman spectra of ZnO nanocrystals recorded using a 647 nm excitation wave-
length in the spectral ranges 300–1200 cm−1 for different crystal sizes.
Fig. 3. Raman spectra of ZnO nanocrystals recorded using a 514 nm excitation wave-
length in the spectral range 300–1200 cm−1 for different crystal sizes.
intensity is observed for samples of larger particle sizes. The bands
at 540 and 584 cm−1 wavenumber correspond to A1 and E1 sym-
of 514 for the mean crystallite sizes 25, 29, 35, 37, and 41 nm are metry species of the longitudinal optical phonon, respectively. A
shown in Fig. 3. very weak peak at 658 cm−1 is associated with an oxygen deficiency
The normalized Raman spectra for the crystallite sizes 25, 29, in the ZnO lattices. The Raman bands at 1105 and 1152 cm−1 are
35, 37, and 41 nm recorded at 647 nm excitation wavelength are assigned to second order overtone bands of E2 and the combination
shown in Fig. 4 for the spectral range 300–1200 cm−1 . of A1 and E1 Raman bands, respectively. The intensities of the low
The Raman spectra of the ZnO nanocrystals show nine Raman wavenumber bands at 329, 380, and 410 cm−1 show a consistent
bands out of which seven bands are in the low wavenumber region decrease upon reducing the mean crystal size from 41 to 25 nm for
and the remaining two bands are in the higher wavenumber region the Raman spectra recorded at 514 and 647 nm excitation wave-
for all the crystallite sizes. No more high-order peaks could be lengths. In addition to their change in intensity, the bands at 383
observed in the region above 1200 cm−1 . In order to determine the and 538 cm−1 become broader with decreasing crystallite size. For
exact wavenumber positions and intensities of the Raman bands at both excitation wavelengths, the Raman band at 1152 cm−1 has a
each crystallite size, the Raman bands in the spectra were fitted by noticeable asymmetry towards the low wavenumber side for each
a convolution of Gaussian and Lorentzian functions. The wavenum- crystal size. The asymmetrical feature keeps on developing upon
ber positions of the Raman bands obtained for both excitation going from mean crystal size 25 to 41 nm. In order to get exact band
wavelengths along with their symmetries determined on the basis positions and intensities, the band at 1152 cm−1 is fitted assuming
of group theory analysis are presented in Table 2. We do not see any
significant change in the Raman band wavenumbers with crystal-
lite size. Bulk ZnO has a wurtzite type structure, which belongs Table 2
Wavenumber position and symmetries of the vibrational modes in Raman spectrum
to the space group C4 6␯ with two formula units per primitive cell, of ZnO nanocrystals of size 41 nm recorded at the excitation wavelengths 514 and
where all atoms occupy C3␯ sites. The Raman active zone-center 647 nm.
optical phonons predicted by the group theory are A1 + 2E2 + E1 .
Wavenumber (cm−1 ) Symmetry Process Ref.
The phonons of A1 and E1 symmetry are polar phonons and, hence,
[7]
exhibit different frequencies for the transverse-optical (TO) and 514 (nm) 647 (nm)
longitudinal-optical (LO) phonons. The low wavenumber Raman 329 ± 1 327 ± 2 A1 Acoust. overtone 331
bands at 329 is assigned to acoustic mode. The Raman bands at 380 ± 2 377 ± 3 A1(TO) First process 383
380 and 410 cm−1 are assigned to overtone of A1 and E1 transverse 410 ± 0.8 407 ± 2 E1 (TO) First process 410
436 ± 1 433 ± 3 E2 First process 438
optical phonon. However, in study [33] the appearance of these two 538 ± 2 536 ± 3 A1 (LO) First process 540
modes was explained in terms of a multi-phonon process and they 585 ± 1 582 ± 2 E1 (LO) First process 584
were assigned to the TA (M) and 2-E2 (M) modes, respectively. The 658 ± 1 659 ± 2 A1 Acoust. overtone 660
peak at 438 cm−1 corresponds to the E2 mode, typical to the hexag- 1105 ± 1 1106 ± 3 E2 Acoust. comb. 1101
1152 ± 2 1149 ± 3 A1, E1 Opt. overtone 1154
onal phase of ZnO [34–36]. A remarkable increase in the E2 mode
 A.K. Ojha et al. / Vibrational Spectroscopy 72 (2014) 90–96 95

two peaks and the wavenumber positions of the two fitted peaks
turn out to be 1105 and 1152 cm−1 for the 41 nm crystal size. Also 514 nm
the line shapes of the other vibrational bands, recorded using the
647 nm
514 and 647 nm excitation wavelengths become asymmetric and
some Raman bands shift to lower wavenumber with decreasing 0.18
crystal size. This red shift of the Raman bands may be due the lattice
expansion of the nanocrystals going from smaller to larger crystal-
lite size, which is also reflected in the XRD data. Compared to the
Raman spectra of the bulk form, the line broadening and asymme-
try of the first order optical phonon seen in the Raman spectra of
the nanocrystals can be explained in terms of a relaxation of the 0.17

I(2E ) / I(1E )
2
selection rules. In the bulk samples the K = 0 momentum selection
rule is satisfied for the first order Raman spectrum. However, when
the crystal is reduced to nanometer dimension, this selection rule

2
is relaxed and thus the phonon having a wavevector K = K ± 2/L,
where K is the wavevector of the incident light and L is the size of
the nanocrystal, also starts participating to the first order Raman 0.16
scattering. This means that now the Raman scattering is not only
limited to the phonon at the  point, but also the phonon close
to  contributes, which essentially results in a wavenumber shift,
broadening and asymmetry of the first order Raman bands. The
Raman intensity I (ω) for the spherical nanoparticles is defined by
integral of a superposition of weighted Lorentzian contributions 0.15
over the whole Brillouin zone and expressed as;
  
C(0, k)2
I(ω) =  2 2
 d3 k 25 30 35 40
(ω − ω(k)) + (0 /2) Mean particle size (nm)
where ω(k) is the phonon dispersion relation,  0 is the nat- Fig. 5. Variation of the ratio I2E2 /I1E2 (integrated intensities) with the size of the ZnO
ural linewidth (FWHM) and C(0, k) is the Fourier coefficient nanocrystals calculated for the excitation wavelengths 514 and 647 nm.
of the phonon confinement function and expressed as; |C(0,
k)|2 = exp(−k2 d2 /162 ), where d is the average size of the nanopar- crystallite size has been observed in earlier reports [7,8,12–14]. The
ticles. value of electron–phonon/electron–plasmon coupling strength
Wang et al. [7] have pointed out that the phonon confinement estimated in the present study for ZnO nanocrystals of mean
plays an important role for the determination of the wavenum- crystallite size 25–41 nm matches nicely with values calculated
ber shift, broadening and asymmetry in first order Raman bands of for the ZnO nanorods of diameters ranging from 20–40 nm [7]. In
nanocrystals. The dispersion behaviour of Raman scattering cross earlier studies [7,8,13,14] authors have extensively investigated
section phonon bands in bulk ZnO crystals had been very nicely the nature of electron–phonon/electron–plasmon coupling and
investigated by Callender et al. [37] through resonance Raman scat- its size dependence in CdS, CdSe, InP, CuO nanocrystals and ZnO
tering using a wide range of excitation energies. These authors nanorods by the method used in the present report. The ratio
found that the intensity of the E1 phonon band is enhanced signifi- of second and first order Raman scattering intensities could be
cantly under the resonance condition. However, all the TO phonon estimated theoretically by the following relationship as proposed
bands are almost unaffected when varying the excitation wave- by Klein et al. [39]:
lengths. Further, they also reported that the ratio of second to first
order scattering cross section of the E1 band changes from 2 to
e2
24
1/3 1 1 1

1 w x4 2 + x2 2
2
24 by varying the excitation wavelength from 350.7 to 356.4 nm.
In another study [38] ZnO nanoparticles were characterized using
resonant Raman scattering. It was found that the frequency of the
E2 phonon decreases with decreasing mean particle size while its
linewidth increases.
In order to determine the strength of the electron–phonon cou-
pling and its size dependence for ZnO nanocrystals from Raman
spectra, as done previously in case of CdSe, InP, CdS, CuO nanocrys-
tals and ZnO nanorods [7,8,12–14], the ratio of the integrated
intensities of the second order phonon Raman scattering to the
intensity of first order phonon Raman scattering is determined
for the crystallite sizes 41, 37, 35, 29, and 25 nm and the values
of the intensity ratios I2E2 /I1E2 have been plotted as a function of
mean particle size for both excitation wavelengths, 514 and 647 nm
(Fig. 5). It is quite evident from Fig. 5 that the values of the inten-
sity ratio I2E2 /I1E2 decrease almost linearly with reducing the mean
crystallite size from 41 to 25 nm.
This shows that the strength of the electron–
phonon/electron–plasmon coupling in ZnO nanocrystals decreases
with reducing the crystallite size. A similar kind of pattern for the
variation of electron–phonon coupling strength with the mean
 = −  4 dx
a  ωLO ε∞ ε0 w 1 + x2
0
where w = (32 )1/2 a0 /a with a0 and a being the exciton radius
and lattice parameter, respectively. Using the above relation, Wang
et al. [7] had calculated the value of  for bulk ZnO material and its
value turns out to be 2.85, which is well supported by the experi-
mental value 2.78 calculated using the ratio of second to first order
Raman scattering intensity of ZnO.
Our earlier report [40] on size dependence of the
electron–phonon coupling strength in Li0.5 Co0.1 Fe2.4 O4 nanocrys-
tals was in good agreement with the theoretical study done by
Takagahara [19]. However, in the present study, the strength of the
electron–phonon coupling is decreased with decreasing the size
of the nanoparticles. Mainly two mechanisms, the deformation
potential and the Fröhlich potential are responsible for the size
dependence of the electron–phonon coupling. In case of polar
semiconductors, both short range deformation potential and the
long range Fröhlich potential contribute to LO Raman scattering. On
the other hand, TO Raman scattering cross section is governed by
the deformation potential that involves the short-range interaction
96 A.K. Ojha et al. / Vibrational Spectroscopy 72 (2014) 90–96
between phonons and the electrons. However, here we find that the
TO phonon band is almost insensitive to the excitation wavelength.
We believe that the enhancement of electron–phonon coupling
strength with increasing mean crystallite size for ZnO nanocrystals
may be attributed to the competition of deformation and Fröhlich
interaction. In addition to size, the deformation and Fröhlich poten-
tial also depends on geometry (shape) of the nanoparticles and thus
the shape of the nanocrystals also plays an important role in the
determination of electron–phonon coupling strength. Therefore,
a detailed study of the shape dependence of the electron–phonon
coupling in different semi-conductor nanocrystals has been started.
4. Conclusions
In the present report, impurity-free ZnO nanocrystals of differ-
ent crystal sizes were synthesized using the sol–gel method. The
crystal phase and mean crystal size were determined using XRD and
TEM measurements. The Raman spectra of these ZnO nanocrystals
were recorded using two excitation wavelengths, 514 and 647 nm,
in the spectral range of 300–1200 cm−1 . The ratio of the intensi-
ties of the second order phonon band and the first order phonon
band was calculated for each crystal size and used to estimate the
strength of the electron–phonon coupling and its size dependence.
The values of the ratio I2E2 /I1E2 decrease with decreasing particle
size, which indicates that also the strength of the electron–phonon
coupling decreased when the mean crystallite size is reduced. This
behaviour may be attributed to the existence of Fröhlich interac-
tion. Further studies also taking variations of the crystallite shapes
into account will be required.
Acknowledgements
AKO is thankful to the Alexander von Humboldt Stiftung for the
award of a research fellowship. MS is thankful to MNNIT, Allahabad
for granting a senior research fellowship. J.S. acknowledges the
Department of Science & Technology, Govt of India for awarding
the DST-INSPIRE Fellowship [IFA-13 CH-105] 2013 and DST Young
Scientist award (CS-393/2012).
References
[1] H. Xu, Ya. Guo, W. Sun, Z. Liao, T. Burgess, H. Lu, Q. Gao, H. Tan, C. Jagadish, J.
Zou, Nanoscale Res. Lett. 7 (2012) 589–596.
[2] M. Rajalakshmi, A.K. Arora, B.S. Bendre, S. Mahamuni, J. Appl. Phys. 87 (2000)
2445–2450.
[3] Y. Yang, H. Yan, Z. Fu, B. Yang, J. Zuo, Appl. Phys. Lett. 88 (2006) 191909–191911.
[4] J.G. Lu, Z.Z. Ye, Y.Z. Zhang, Q.L. Liang, S.Z. Fujita, Z.L. Wang, Appl. Phys. Lett. 89
(2006) 023122–23124.
[5] P.M. Chassaing, F. Demangeot, V. Paillard, A. Zwick, N. Combe, C. Pagès, M.L.
Kahn, A. Maisonnat, B. Chaudret, Appl. Phys. Lett. 91 (2007) 053108–53111.
[6] A.M. Kelley, J. Phys. Chem. Lett. 1 (2010) 1296–1300.
[7] R.P. Wang, G. Xu, P. Jin, Phys. Rev. B: Condens. Matter 69 (2004)
113303–113306.
[8] A.P. Alivisatos, T.D. Harris, P.J. Carroll, M.L. Steigerwald, L.E. Brus, J. Chem. Phys.
90 (1989) 3463–3468.
[9] S. Schmitt-Rink, D.A.B. Miller, D.S. Chemla, Phys. Rev. B: Condens. Matter 35
(1987) 8113–8125.
[10] J.C. Marini, B. Stebe, E. Kartheuser, Phys. Rev. B: Condens. Matter 50 (1994)
14302–14308.
[11] S. Nomura, T. Kobayashi, Phys. Rev. B: Condens. Matter 45 (1992) 1305–1316.
[12] J.J. Shiang, S.H. Risbud, A.P. Alivisatos, J. Chem. Phys. 98 (1993) 8432–8442.
[13] J.J. Shiang, R.H. Wolters, J.R. Heath, J. Chem. Phys. 106 (1997) 8981–8994.
[14] H. Fan, B. Zou, Y. Liu, S. Xie, Nanotechnology 17 (2006) 1099–1103.
[15] A.M. Kelley, ACS Nano 5 (2011) 5254–5262.
[16] F. Murphy-Armando, G. Fagas, J.C. Greer, Nano Lett. 10 (2010) 869–873.
[17] G. Scamarcio, V. Spagnolo, G. Ventruti, M. Lugara, G.C. Righini, Phys. Rev. B:
Condens. Matter 53 (R10) (1996) 489–492.
[18] M.P. Chamberlain, C. Trallero-Giner, M. Cardona, Phys. Rev. B: Condens. Matter
51 (1995) 1680–1693.
[19] T. Takagahara, J. Lumin. 70 (1996) 129–143.
[20] M.J. Seong, O.I. Micic, A.J. Nozik, A. Mascarenhas, H.M. Cheong, Appl. Phys. Lett.
82 (2003) 185–187.
[21] T. Makino, K. Tamura, C.H. Chia, Y. Segawa, M. Kawasaki, A. Ohtomo, H.
Koinuma, Phys. Rev. B: Condens. Matter 66 (2002) 233305–233308.
[22] D. Fan, R. Zhang, Z. Rong, H. Peng, Physica B 407 (2012) 3510–3514.
[23] T.L. Phan, S.C. Yu, N.X. Nghia, V.D. Lam, J. Korean Phys. Soc. 57 (2010) 1569–1573.
[24] J.D. Ye, P. Parkinson, F.F. Ren, S.L. Gu, H.H. Tan, C. Jagadish, Opt. Express 20
(2012) 23281–23289.
[25] A.G. Milekhin, N.A. Yeryukov, L.L. Sveshnikova, T.A. Duda, C. Himsinschi,
E.I. Zenkevich, D.R.T. Jahn, Appl. Phys. A—Mater. Sci. Process. 107 (2012)
275–278.
[26] W.T. Hsu, K.F. Lin, W.F. Hsieh, Appl. Phys. Lett. 91 (2007) 181913–181915.
[27] H.M. Cheng, K.F. Lin, H.C. Hsu, W.F. Hsieh, Appl. Phys. Lett. 88 (2006)
261909–261911.
[28] J.M. Wesselinowa, A.T. Apostolov, J. Appl. Phys 108 (2010) 044316–044319.
[29] M. Srivastava, A.K. Ojha, S. Chaubey, P.K. Sharma, A.C. Pandey, Mater. Sci. Eng.,
B 175 (2010) 14–21.
[30] H. He, D. Shoesmith, Phys. Chem. Chem. Phys. 12 (2010) 8108.
[31] T.T.K. Chi, G. Gouadec, Ph. Colomban, G. Wang, L. Mazerolles, N.Q. Liern, J. Raman
Spectrosc. 42 (2011) 1007.
[32] M. Srivastava, A.K. Ojha, S. Chaubey, J. Singh, P.K. Sharma, A.C. Pandey, J. Alloys
Compd. 500 (2010) 206–210.
[33] J.M. Calleja, M. Cardona, Phys. Rev. B: Condens. Matter 16 (1977) 3753–3761.
[34] G. Xiong, U. Pal, J.G. Serrano, J. Appl. Phys. 101 (2007) 024317–024323.
[35] G.J. Exarhos, S.V. Sharma, Thin Solid Films 270 (1995) 27–32.
[36] Y.J. Xing, Z.H. Xi, Z.Q. Xue, X.D. Zhang, J.H. Song, R.M. Wang, J. Xu, Y. Song, S.L.
Zhang, D.P. Yu, Appl. Phys. Lett. 83 (2003) 1689–1691.
[37] R.H. Callender, S.S. Sussman, M. Selders, R.K. Chang, Phys. Rev. B: Condens.
Matter 7 (1973) 3788–3798.
[38] M. Yoshikawa, K. Inoue, T. Nakagawa, H. Ishida, N. Hasuike, H. Harima, Appl.
Phys. Lett. 92 (2008) 113115–113117.
[39] M.C. Klein, F. Hache, D. Ricard, C. Flyzanis, Phys. Rev. B: Condens. Matter 42
(1990) 11123–11132.
[40] M. Srivastava, N. Vyas, A.K. Ojha, Vib. Spectrosc. 56 (2011) 19–25.