J Theor Appl Phys (2014) 8:123–134

DOI 10.1007/s40094-014-0141-9

RESEARCH

Estimation of lattice strain in ZnO nanoparticles: X-ray peak

profile analysis
P. Bindu • Sabu Thomas

Received: 4 March 2014 / Accepted: 22 June 2014 / Published online: 30 July 2014
Ó The Author(s) 2014. This article is published with open access at Springerlink.com

Abstract ZnO nanoparticles were synthesized from Keywords Nanostructured materials  ZnO
chitosan and zinc chloride by a precipitation method. The nanoparticles  X-ray diffraction  SEM  TEM 
synthesized ZnO nanoparticles were characterized by Photoluminescence emission
Fourier transform infrared spectroscopy, X-ray diffraction
peak profile analysis, Scanning electron microscopy,
Transmission electron microscopy and Photoluminescence. Introduction
The X-ray diffraction results revealed that the sample was
crystalline with a hexagonal wurtzite phase. We have The wide band gap semiconductors, viz. GaN, ZnO, InN,
investigated the crystallite development in ZnO nanopar- AlN, have gained more attention among semiconductor
ticles by X-ray peak profile analysis. The Williamson–Hall materials, because of their potential application in opto-
analysis and size–strain plot were used to study the indi- electronic devices in both the visible and UV regions, such
vidual contributions of crystallite sizes and lattice strain e as light emitting diodes (LEDs) and laser diodes. Zinc oxide
on the peak broadening of ZnO nanoparticles. The (ZnO) is a wide band gap semiconductor, which has been
parameters including strain, stress and energy density value studied extensively due to its fundamental and technological
were calculated for all the reflection peaks of X-ray dif- importance. It has wide band gap energy (3.37 eV), large
fraction corresponding to wurtzite hexagonal phase of ZnO exciton binding energy and excellent chemical stability; all
lying in the range 20°–80° using the modified form of these properties suggest a great possible practical applica-
Williamson–Hall plots and size–strain plot. The results tions viz. in gas sensors, ceramics, field-emission devices
showed that the crystallite size estimated from Scherrer’s and luminescent materials [1–3]. The large exciton binding
formula, Williamson–Hall plots and size–strain plot, and energy of ZnO allows an intense near-band-edge excitonic
the particle size estimated from Transmission electron emission at room temperature and higher temperatures [4].
microscopy analysis are very much inter-correlated. Both Recently, ZnO has gained interest for spintronic applications
methods, the X-ray diffraction and Transmission electron due to its ferromagnetic behavior at room temperature when
microscopy, provide less deviation between crystallite size doped with transition metals [5]. Recent reports from our lab
and particle size in the present case. [6, 7] revealed that ZnO nanoparticles can be used as rein-
forcing agent in polymers, activator and accelerator instead
of micro ZnO in the vulcanization of rubber materials, for
producing highly stable and improved properties of the final
products. Moreover, the ZnO content in vulcanized rubber
P. Bindu (&)  S. Thomas
School of Chemical Sciences, Mahatma Gandhi University, can be reduced to 10 times if nanosized ZnO is used instead
Priyadarshini Hills P.O, Kottayam 686 560, Kerala, India of the conventional micro ZnO [8], and this approach helps
e-mail: bindu_patanair@yahoo.com to reduce the release of toxic zinc metal into the environ-
ment [6].
P. Bindu  S. Thomas
Centre for Nanoscience and Nanotechnology, Mahatma Gandhi Particle size and crystal morphology play important
University, Kottayam 686 560, Kerala, India roles in these applications, which have driven the attention

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124 J Theor Appl Phys (2014) 8:123–134

of researchers on the synthesis of nanocrystalline ZnO. Photoluminescence (PL). The XPPA was carried out for
Many methods were reported [9] such as sol–gel, solo- estimating the crystallite size, lattice strain, lattice stress
chemical processes, precipitation, combustion synthesis, and lattice strain energy density of ZnO nanoparticles
DC thermal plasma synthesis, spray pyrolysis, pyrolysis, based on modified W–H plots using uniform deformation
and hydrothermal synthesis to prepare ZnO nanopowders. model (UDM), uniform stress deformation model (USDM),
The particle size and morphology of ZnO nanoparticles uniform deformation energy density model (UDEDM) and
will vary with the synthetic route adopted for the synthesis. another method viz. size–strain plot (SSP) and thereby
It was understood that a perfect crystal would extend in correlating them to the presently observed physicochemical
all directions to infinity; however, no crystals are perfect properties of nanocrystalline ZnO. Literature reports
due to their finite size. This deviation from perfect crys- revealed that a detailed study using these models on the
tallinity is the reason for broadening of the diffraction synthesized ZnO nanoparticles annealed at 550 °C is not
peaks of materials. There are two main properties extracted yet reported. This study reveals the importance of SSP and
from peak width analysis viz. crystallite size and lattice W–H models in the determination of crystallite size of ZnO
strain. Crystallite size is a measure of the size of a coher- nanomaterials.
ently diffracting domain, and the crystallite size of the
particles is not generally the same as the particle size due to
the presence of polycrystalline aggregates. The various Experimental details
techniques used for the measurement of particle size rather
than the crystallite size are direct light scattering (DLS), Materials
scanning electron microscopy (SEM), and transmission
electron microscopy (TEM) analysis. Lattice strain is a Chitosan was provided by M/s. India Sea Foods, Cochin,
measure of the distribution of lattice constants arising from Kerala, India. Zinc chloride and sodium hydroxide were
crystal imperfections, such as lattice dislocation. There are supplied by M/s. S. D. Fine Chem. Ltd. Mumbai, India.
other sources of strain, which are the grain boundary triple ZnO nanoparticles were synthesized from chitosan, zinc
junction, coherency stresses, contact or sinter stresses, chloride and sodium hydroxide.
stacking faults, etc. [10]. The X-ray line broadening is used
for the investigation of dislocation distribution. Synthesis of ZnO nanoparticles
X-ray peak profile analysis (XPPA) was used to estimate
the micro-structural quantities and correlate them to the ZnO nanoparticles were synthesized from zinc chloride and
observed material properties. Although XPPA is an aver- chitosan [16]. This is a new synthetic approach and in the
aging method, it still holds a dominant position in crys- present synthetic procedure, we have optimized the reac-
tallite size determination. XPPA is a simple and powerful tion conditions to facilitate the formation of Zn–chitosan
tool to estimate the crystallite size and lattice strain [11]. complex and also to increase the yield of the ZnO nano-
The crystallite size and lattice strain affect the Bragg peak particles. We have optimized the concentrations of ZnCl2,
in different ways and both these effects increase the peak chitosan and NaOH, pH of the reaction medium, reaction
width, peak intensity and shift the 2h peak position temperature and stirring time for complexation of Zn–
accordingly. There are other methods reported in the lit- chitosan complex and precipitation of Zn(OH)2 out of the
erature to estimate the crystallite size and lattice strain, complex. About 5 g of ZnCl2 was dissolved in 100 ml 1 %
which are the pseudo-Voigt function, Rietveld refinement, acetic acid to form 5 % solution, and another 1 % solution
and Warren-Averbach analysis [12–14]. However, the of chitosan was prepared in 1 % acetic acid. Both the
Williamson–Hall (W–H) analysis is a simplified integral solutions were mixed and stirred for 21 h. After this,
breadth method employed for estimating crystallite size stoichiometric amount of NaOH (5 %) was added drop
and lattice strain, considering the peak width as a function wise to the above reaction mixture with constant stirring.
of 2h [15]. The size–strain parameters can be also obtained The whole mixture was then allowed to digest for 24 h at
by considering an average ‘size–strain plot’ (SSP) method. room temperature. During this time, OH- and Cl- ions
The XPPA is an average method and is important for the were diffused through the medium and white gel-like
determination of crystallite size apart from TEM analysis. precipitate of Zn(OH)2 was formed. This was filtered and
The present work describes a facile route for the syn- washed thoroughly with distilled water to remove unre-
thesis of ZnO nanoparticles from chitosan and ZnCl2 by a acted chitosan and other by-product like NaCl. This was
precipitation method. We have found that this is a cost- then dried at 100 °C and annealed at 550 °C for 4 h in a
effective and new method for the synthesis of ZnO nano- muffle furnace to get ZnO nanocrystals. The yield of ZnO
particles. The structure and morphology of ZnO nanopar- nanocrystals obtained by this method is about 90 %. The
ticles were investigated by FTIR, XRD, SEM, TEM and new synthetic route has the following advantages: the

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J Theor Appl Phys (2014) 8:123–134 125

analyser. HRTEM was taken with JEOL-JEM 3010

instrument; the ZnO nanoparticles were dispersed in ace-
tone by ultrasonic bath and a drop of it was deposited on
carbon-coated copper grid and was analyzed under an
accelerating voltage of 200 kV. Photoluminescence (PL)
spectrum of ZnO nanoparticles was recorded at room
temperature using RF-5301 PC-Spectroflurophotometer-P/
N 206.81601 consisting of Xenon arc lamp as the excita-
tion source at excitation wavelength (kex = 355 nm). The
luminescence is dispersed with a monochromator and
recorded using a CCD detector.

Results and discussion

The synthesized ZnO nanoparticles were characterized as

follows.

Structural studies

The IR spectrum of ZnO nanoparticles (Fig. 1a) was

recorded using KBr pellet. The bands correspond to m (Zn–O)
appeared at 1,018 and 488 cm-1.
The XRD pattern of prepared ZnO nanoparticles was
taken. All the XRD peaks were indexed by hexagonal
wurtzite phase of ZnO (JCPDS Card No. 01-089-0510) as
shown in Fig. 1b. XRD pattern indicates the formation of
hexagonal wurtzite phase of ZnO which is in agreement
with the electron diffraction results. The peak broadening
in the XRD pattern clearly indicates that small nanocrystals
are present in the samples. There is no evidence of bulk
Fig. 1 a FTIR spectrum of ZnO nanoparticles. b XRD pattern of remnant materials and impurity. Nine peaks appear at
ZnO nanoparticles different 2h values as shown in the Fig. 1b. The sharp
diffraction peaks indicate the good crystallinity of the
prepared particles.
reaction can be carried out under moderate conditions, As ZnO crystallizes in the wurtzite structure in which
yield of the product is very good and particles of nanometer the oxygen atoms are arranged in a hexagonal close packed
size can be attained, which make this method promising for type with zinc atoms occupying half the tetrahedral sites.
large-scale production. Zn and O atoms are tetrahedrally coordinated to each other
Chitosan is a linear polymine having reactive amino and have, therefore, an equivalent position. The zinc
groups and hydroxyl groups and hence can easily form structure is open with all the octahedral and half the tet-
chelates with transition metal ions. In the present reaction, rahedral sites empty. According to Bragg’s law [11],
chitosan acts as a chelating agent for Zn2? ions to form
nk ¼ 2d Sinh ð1Þ
Zn–chitosan complex.
where n is the order of diffraction (usually n = 1), k is the
Characterization methods X-ray wavelength and d is the spacing between planes of
given Miller indices h, k and l. In the ZnO hexagonal
FTIR (Schimadzu IR-470 IR spectrophotometer) spectrum structure, the plane spacing d is related to the lattice con-
of the ZnO nanoparticles was recorded in the range stants a, c and the Miller indices by the following relation
4000–400 cm-1 using KBr pellet. XRD was recorded with [11],
the help of Bruker D-8 Advance (k = 1.54060 Angstrom,  
1 4 h2 þ hk þ k2 l2
Cu-Ka9) machine, using pure Al2O3 as reference. SEM 2
¼ 2
þ 2 ð2Þ
dðhklÞ 3 a c
images were recorded using FE-SEM SUPRA-25 ZEISS

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126 J Theor Appl Phys (2014) 8:123–134

Table 1 Interplanar spacing (dhkl) from XRD, JCPDS data card for to determine the instrumental broadening. The instrumental
corresponding hh k li planes, percentage of variation of d, and corrected broadening [17] bhkl corresponding to each dif-
FWHM
fraction peak of ZnO was calculated using the relation,
hh k li dXRD (Å) dJCPDS (Å) % of contraction FWHM
    1=2
in d (Degree) bhkl ¼ b2hkl Measured  b2hkl Instrumental ð6Þ
h100i 2.7964 2.8135 0.6078 0.295 In particular, the ZnO h101i diffraction peak is much
h002i 2.5871 2.6027 0.5994 0.289 stronger than the ZnO h002i peak. This indicates that the
h101i 2.4624 2.4751 0.5131 0.318 formed ZnO nanocrystals have a preferential crystallo-
h102i 1.9030 1.9106 0.3978 0.372 graphic h101i orientation. The average crystallite size was
h110i 1.6196 1.6244 0.2955 0.402 calculated from XRD peak width of h101i based on the
h103i 1.4727 1.4769 0.2844 0.447 Debye–Scherrer equation [18],
Kk
D¼ ð7Þ
bhkl Cosh
With the first-order approximation, n = 1;
    where bhkl is the integral half width, K is a constant equal
k2 4  2  a 22 to 0.90, k is the wave length of the incident X-ray
Sin2 h ¼ 2 h þ k2 þ hk þ l ð3Þ
4a 3 c (k = 0.1540 nm), D is the crystallite size, and h is the
The lattice constant a for h100i plane is calculated by Bragg angle. The average crystallite size calculated for
[11], synthesized ZnO nanoparticles was 27.49 nm. The crys-
tallite size is assumed to be the size of a coherently dif-
k fracting domain and it is not necessarily the same as
a ¼ pffiffiffi ð4Þ
3 Sinh particle size.
For the h002i plane, the lattice constant c is calculated The dislocation density (d), which represents the amount
by [11], of defects in the sample is defined as the length of dislo-
cation lines per unit volume of the crystal and is calculated
k
c¼ ð5Þ using the Eq. [18],
Sinh
1
The lattice constants (a = b = 3.2299 Angstrom and d¼ ð8Þ
c = 5.1755 Angstrom, c/a = 1.6024) and diffraction peaks D2
corresponding to the planes h100i, h002i, h101i, h102i, where D is the crystallite size. The dislocation density (d)
h110i, h103i obtained from X-ray diffraction data are is 14.76 9 10-4 (nm)-2.
consistent with the JCPDS data of ZnO. The interplanar The Zn–O bond length L is given by [19],
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
spacing (dh k l) calculated from XRD is compared with u
u a2  2 !
JCPDS data card and corresponding hh k li planes, per- 1
L ¼ t þ  u c2 ð9Þ
centage of variation of d and full width at half-maximum 3 2
(FWHM) values for some major XRD peaks are summa-
rized in Table 1. where u is the positional parameter in the wurtzite structure
and is a measure of the amount by which each atom is
Crystallite size and strain displaced with respect to the next along the ‘c’ axis. ‘u’ is
given by
Scherrer method
a2
u¼ þ 0:25 ð10Þ
XRD peak profile analysis is a simple and powerful method 3c2
to evaluate the peak broadening with crystallite size and The correlation between the c/a ratio and u is that when
lattice strain due to dislocation. The breadth of the Bragg the c/a ratio decreases, the u increases in such a way that
peak is a combination of both instrument and sample- those four tetrahedral distances remain nearly constant
dependent effects. For an accurate analysis for size and through a distortion of tetrahedral angles. The Zn–O bond
strain effects, the instrumental broadening must be length calculated is 1.9654 Å; whereas the reported Zn–O
accounted. The diffraction pattern from the line broadening bond length in the unit cell of ZnO and neighboring atoms
of a standard material such as alumina (Al2O3) was col- is 1.9767 Å [20]. The calculated bond length agrees with
lected to decouple the above-mentioned contributions and the Zn–O bond length in the unit cell.

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J Theor Appl Phys (2014) 8:123–134 127

Estimation of microstrain (e)

Williamson–Hall (W–H) methods

Uniform deformation model (UDM)

In Williamson–Hall approach, the line broadening due to

finite size of coherent scattering region and the internal
stress in the prepared film is also considered. According to
Williamson and Hall, the diffraction line broadening is due
to crystallite size and strain contribution. However, the
XPPA by W–H methods is a simplified method which
clearly differentiates between size-induced and strain-
induced peak broadening by considering the peak width as
a function of 2h [15]. The strain-induced broadening in Fig. 2 Plot of bhkl coshhkl versus 4sinhhkl
powders due to crystal imperfection and distortion was
calculated using the formula,
bhkl y-intercept, and the microstrain e, from the slope of the
e¼ ð11Þ linear fit (Fig. 2). The UDM for ZnO nanoparticles is
4tanh
shown in Fig. 2. This strain may be due to the lattice
From Eqs. (7) and (11), it was confirmed that the peak shrinkage that was observed in the calculation of lattice
1
width from crystallite size varies as Cos h
and strain varies parameters.
as tan h. Now, the total peak broadening is represented by
the sum of the contributions of crystallite size and strain Uniform stress deformation model (USDM)
present in the material and can be written as [21],
In many cases, the assumption of homogeneity and isotropy
bhkl ¼ bD þ be ð12Þ
is not fulfilled. To incorporate more realistic situation, an
where bD is due to the contribution of crystallite size, be is anisotropic approach is adopted. Therefore, Williamson–
due to strain-induced broadening and bhkl is the width of Hall equation is modified by an anisotropic strain e. In
the half-maximum intensity of instrumental corrected uniform stress deformation model (USDM), the lattice
broadening. The instrumental corrected broadening of each deformation stress is assumed to be uniform in all crystal-
diffraction peak is calculated using Eq. (6) as given above. lographic directions, and assuming a small microstrain to be
If we assume that the particle size and strain contributions present in the particles. In USDM, the Hooke’s law refers to
to line broadening are independent to each other and both the strain and there is a linear proportionality between the
have a Cauchy-like profile, the observed line breadth is the stress and strain as given by r = eYhkl or e = r/Yhkl, where
sum of Eqs. (7) and (11) and given as [22], r is the stress of the crystal, e is anisotropic microstrain, this
Kk will depend on the crystallographic directions and Yhkl is the
bhkl ¼ þ 4 e tanh ð13Þ modulus of elasticity or Young’s modulus. This equation is
Dcosh
just an approximation and is valid for a significantly small
By rearranging Eq. (13), we get strain; when strain is increased, the particles deviate from
Kk this linear proportionality. In this approach, the William-
bhkl cos hhkl ¼ þ 4e sinhhkl ð14Þ
D son–Hall equation is modified [22] by substituting the value
of e in Eq. (14), we get
The Eq. (14) is Williamson–Hall equation, which rep-
resents the uniform deformation model (UDM). Equation Kk 4rsinhhkl
bhkl cos hhkl ¼ þ ð15Þ
(14) assumes that the strain is uniform in all crystallo- D Yhkl
graphic directions and known as uniform deformation For a hexagonal crystal, Young’s modulus is given by
model (UDM). In this model the crystal is considered as the following relation [13, 14],
isotropic in nature and it is assumed that the properties of h
Þ2  2 i2
material are independent of the direction along which it is h2 þ ðhþ2k
3 þ alc
measured. The values of bhkl coshhkl on y-axis were plotted Yhkl ¼  2  4  
Þ2 Þ2 al2
s11 h2 þ ðhþ2k þs33 alc þð2s13 þ s44 Þ h2 þ ðhþ2k
as a function of 4sinhhkl on x-axis, and from the linear fit of 3 3 c

the data, the crystalline size D was estimated from the ð16Þ

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128 J Theor Appl Phys (2014) 8:123–134

Fig. 3 Plot of bhkl coshhkl versus 4sinh/Yhkl Fig. 4 Plot of bhkl coshhkl versus 4sinhhkl (2/Yhk)1/2

where ‘a’ and ‘c’ are lattice parameters; s11, s13, s33 and s44 ued = (r2/2Yhkl). The lattice strain can be calculated by
are the elastic compliances of ZnO with values knowing the Yhkl value.
7.858 9 10-12, -2.206 9 10-12, 6.940 9 10-12 and 23.57
9 10-12 m2 N-1, respectively [23]. Young’s modulus, Yhkl, Size–strain plot (SSP)
for hexagonal ZnO nanoparticles was calculated as *127
GPa. Plotting bhkl coshhkl as a function of 4sinh/Yhkl The W–H plots described that the line broadening was
(Fig. 3), the uniform deformation stress r can be estimated basically isotropic. This emphasizes that the diffracting
from the slope of the linear fit and y-intercept gives the domains were isotropic due to the contribution of micro-
crystallite size. The strain e can be calculated if Young’s strain. In the cases of isotropic line broadening, a better
modulus, Yhkl, of hexagonal ZnO nanoparticles is known. evaluation of the size–strain parameters can be obtained by
considering an average ‘size–strain plot’ (SSP) [24]. This
Uniform deformation energy density model (UDEDM) method has a benefit that less importance is given to data
from reflections at high angles where the precision is
There is another model called the uniform deformation usually lower. In this method, it is assumed that the ‘strain
energy density model (UDEDM) that can be used to profile’ is explained by a Gaussian function and the
determine the energy density of a crystal. In Eq. (14), the ‘crystallite size’ profile by a Lorentzian function [25] and is
crystals are assumed to have a homogeneous, isotropic given by,
nature; however, in many cases, the assumption of homo- 1 2  ea 2
ðdhkl bhkl cos hhkl Þ2 ¼ dhkl bhkl cos hhkl þ ð18Þ
geneity and isotropy is not justified. Moreover, the con- Vs 2
stants of proportionality associated with the stress–strain
where dhkl is the lattice distance between the hh k li planes,
relation are no longer independent when the strain energy
Vs is the apparent volume weighted average size and ea is a
density ued is considered. For an elastic system that follows
measure of the apparent strain which is related to the root-
Hooke’s law, the energy density ued (energy per unit vol-
mean-square (RMS) strain eRMS,
ume) as a function of strain is ued = (e2Yhkl)/2. Then,  
Eq. (15) can be rewritten according to the energy and strain ea
heRMS i ¼ pffiffiffiffiffiffi ð19Þ
relation as [22], 2 2p
    !
Kk 2ued 1=2 For spherical crystallites the volume average true size is
bhkl coshhkl ¼ þ 4sinhhkl ð17Þ given by Dv = Vs 4/3.
D Yhkl
The corresponding SSP for ZnO nanoparticles was
Plot of bhkl coshhkl versus 4sinhhkl (2/Yhk)1/2 was done obtained by plotting (dhkl bhkl coshhkl)2 on y-axis with
(Fig. 4) and the anisotropic energy density ued was esti- respect to (d2hkl bhkl coshhkl) on the x-axis (Fig. 5) for all
mated from the slope of the linear fit and the crystallite size peaks of ZnO nanoparticles with the wurtzite hexagonal
D from the y-intercept. Previously, we knew that r = eYhkl phase from 2h = 208–808. In this method, the volume-
and ued = (e2Yhkl)/2, where the stress r was calculated as averaged true crystallite size Dv was estimated from the

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J Theor Appl Phys (2014) 8:123–134 129

a given sample, W–H plots can be plotted using Eqs. (6, 7,

11–17). Furthermore, the average crystallite sizes esti-
mated from the y-intercept of the graphs for the UDM,
USDM, UDEDM models were found to be 35.35, 36.28
and 36.09 nm, respectively. The average values of crys-
tallite size obtained from UDM, UDSM, and UDEDM are
almost similar, which indicate that the inclusion of strain in
various forms of W–H methods has a very small effect on
the average crystallite size of ZnO nanoparticles. However,
the average crystallite size obtained from Scherrer’s for-
mula and W–H analysis shows a small variation because of
the difference in averaging the particle size distribution. It
can be noted that the values of the average crystallite size
obtained from the above three methods are in good
Fig. 5 Plot of (dhkl bhkl coshhkl)2 versus (d2hkl bhkl coshhkl) agreement with the results of the TEM analysis (Table 2).
Our results are more appropriate than the reported literature
[27]. We suggest that these three methods are also suitable
slope of the linear fit, and the RMS strain estimated from models for the evaluation of the crystallite size of ZnO
the intercept was negligible (Table 2). nanoparticles. Rosenberg et al. [28] observed that for
According to the literature report [26], the Williamson– metallic samples with cubic structures, the uniform defor-
Hall plot showed that, the line broadening was essentially mation energy model is suitable. We have made a com-
isotropic and that the least-squares line through the points parison of the estimated microstrain e values of ZnO
had a positive slope and a non-zero intercept. This indi- nanoparticles annealed at 450 °C reported by Dole et al.
cates that diffracting domains are isotropic and there is also [29] by W–H models, with that of our present values. The
a microstrain contribution. For a better evaluation of the higher values of estimated microstrain e in our case indi-
size–strain parameters, an average ‘size–strain plot’ (SSP) cate polycrystalline nature of the films. The polycrystalline
method was considered as explained above. Comparing films will show a larger value of e indicating more strain on
W–H and SSP methods in the present case, the lattice strain the lattice. As the annealing temperature of ZnO nano-
e calculated from the W–H and SSP methods was found to crystal is at 550 °C, the microstrain e is high and the films
be comparable and in agreement with each other (Table 2). are more polycrystalline in nature. This study reveals the
Moreover, the crystallite size D obtained from the SSP importance of models in the determination of particle size
method is in good agreement with the values obtained from of ZnO nanoparticles. The average crystallite size and the
W–H models and TEM (Table 2). However, the SSP strain values obtained from UDM, UDSM, UDEDM and
method is the most suitable one compared to W–H meth- SSP methods were found to be accurate and comparable, as
ods, because less importance is given to data from reflec- the entire high-intensity points lay close to the linear fit.
tions at high angles and the data points lay very close to the
linear fit. Estimation of RMS strain
Comparing the 3 W–H models, UDM considers the
homogeneous isotropic nature of the crystal, whereas The Wilson method [30] was employed to compute the
USDM and UDEDM models consider the anisotropic nat- maximum or upper-limit ehkl, and root-mean-square (RMS)
ure of the crystallites. In USDM and UDEDM, it may be microstrains eRMS along the hh k li crystallographic
noted that though both Eqs. (15) and (17) are taken into directions using the following relations:
account in the anisotropic nature of the elastic constant,  
Ddhkl
they are essentially different. According to Eq. (15), it is ehkl ¼ ð20Þ
d0hkl
assumed that the deformation stress has the same value in
all crystallographic directions allowing ued to be aniso-  1=2
2
tropic, while in Eq. (17), it is assumed that the deformation heRMS i ¼ ehkl ð21Þ
p
energy to be uniform in all crystallographic directions
treating the deformation stress r to be anisotropic. How- The upper-limit microstrain was derived from the
ever, it was understood from the plots (Figs. 3, 4) using Bragg’s law by Wilson [30, 31] and the root-mean-square
Eqs. (15) and (17) that, a given sample may result in dif- microstrain was derived from the upper-limit microstrain
ferent values for lattice strain and crystallite size. Thus, for with the assumption of a Gaussian microstrain distribution.

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130 J Theor Appl Phys (2014) 8:123–134

By substituting the value of ehkl in Eq. (21), the root-mean-

D (nm)
TEM square (RMS) lattice strain is given by the equation:

30
 1=2  
2 Ddhkl
r (MPa)
heRMShkl i ¼ ð22Þ

160.71
p d0hkl
Here, d and d0 represent the observed and ideal inter-
eRMS 9 10-3

planar spacing values, respectively. Figure 6 shows the plot

of RMS strain against variation in the interplanar spacing
0.2519

for the uniform deformation energy density model. Theo-

retically, if the strain values agree, all the points should lie
ea 9 10-3

on a straight line with an angle of 45° to the x-axis. The

1.2629

RMS strain linearly varies with the strain calculated from

Size–strain plot

the interplanar spacing, which indicates that there is no

e

discrepancy on the hh k li planes in the nanocrystalline

Dv (nm)

nature [21]. The lattice strain in the nanocrystalline ZnO

34.55

nanoparticles may arise from the excess volume of grain

boundaries due to dislocations. The X-ray diffraction line
ued (KJm-3)

broadening arises from dislocations and plastic deforma-

tion. The non-uniform strains are pictured as a distribution
48.23

of d-spacings and lead to XRD peak broadening. It was

already mentioned that the XRD peak broadening is mainly
r (MPa)

due to microstrains, small grain sizes (\100 nm), stacking

110.79

faults and machine limitation. The XRD peak broadening

was considered to be only a function of crystallite size,
e 9 10-3

microstrains and instrumental broadening. The develop-

0.8706

ment of lattice strain is caused by varying displacement of

the atoms with respect to their reference-lattice positions.
UDEDM
D (nm)

In other words, the origin of microstarin is related to lattice

36.09

‘misfit’. The diffraction peak shape is related to crystallite

Table 2 Geometric parameters for synthesized ZnO nanoparticles calcined at 550 °C

size and the crystallite size is related to root-mean-square

r (MPa)

(RMS) strain. The higher the RMS strain, the smaller is the
222.94

crystallite size, and the RMS strain is a measure of the

lattice distortion.
e 9 10-3

1.7518

Texture coefficient

The quantitative information concerning the preferential

D (nm)
USDM

36.28

crystal orientation can be obtained from the texture coef-

Williamson–Hall method

ficient, TC, which can be defined as [32],

e 9 10-3

IðhklÞ X IðhklÞ
1.6200

TChkl ¼ =N 1 ð23Þ
I0ðhklÞ I
n 0ðhklÞ

where TC(hkl) is the texture coefficient, I(hkl) is the intensity

D (nm)
UDM

35.35

of the XRD of the sample and n is the number of diffraction

peaks considered. I0(hkl) is the intensity of the XRD refer-
Scherrer method

ence of the randomly oriented grains. If TC(hkl) & 1 for all

the hhkli planes are considered, then the nanoparticles are
with a randomly oriented crystallite similar to the JCPDS
D (nm)

27.49

reference, while values higher than 1 indicate the abun-

dance of grains in a given hhkli direction. Values
0 < TC(hkl) < 1 indicate the lack of grains oriented in that
Sample

550 °C

direction. As TC(hkl) increases, the preferential growth of

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J Theor Appl Phys (2014) 8:123–134 131

Fig. 6 Plot of eRMS versus ehkl

the crystallites in the direction perpendicular to the hhkli

plane is greater.
Fig. 7 SEM image of ZnO nanoparticles
Morphological studies

The SEM image of ZnO nanoparticles is shown in Fig. 7. in electron excitation from the valence band to the con-
The individual ZnO nanoparticles have the length about duction band. Excited electrons may lose their energy by a
90–185 nm range and the diameter 20–90 nm range. non-radiative recombination and radiative recombination
The bright field TEM images of ZnO nanoparticles are process. In photoluminescence, the radiative recombination
shown in Fig. 8. The size parameters from TEM images of free carriers will result.
indicate that the morphology of ZnO nanoparticles is The PL study at room temperature provides information
identical to that observed in SEM image. The HRTEM of different energy states available between valence and
images of ZnO nanoparticles and the corresponding conduction bands responsible for irradiative recombina-
selected area electron diffraction (SAED) were shown in tion. Figure 9 shows the PL emission (kex = 355 nm) from
Figs. 8a, b, respectively. The SAED ring pattern indicates our synthesized ZnO nanoparticles. Two emission bands
that the phase of ZnO nanoparticles was polycrystalline in are clearly shown in Fig. 9. One is a relatively narrow and
structure, and the distance between crystalline planes was weak UV emission band, which is observed about 390 nm.
consistent with the standard pattern for a wurtzite ZnO The other one is a stronger and broader visible emission
crystal structure. However, HRTEM lattice image (Fig. 8c) band about 470 nm.
showed that each particle has a single crystalline structure. The UV emission is originated from excitonic recom-
The particle size distribution of ZnO nanoparticles varies bination corresponding to the near band gap emission of
from 20 to 90 nm with an average particle size of 30 nm. ZnO. The intensity of UV emission was negligible in this
Figure 8d represents particle size distribution based on experiment. The short life time of free exciton arises from
TEM images. However, the diffraction lines clearly indi- the high oscillator strength of the transition and the fast
cate the nanoscale crystallinity of the ZnO particles with non-radiative trapping of excited charge carriers. This fact
randomly oriented polycrystalline. Compared to bulk ZnO suggests that the exciton emission is greatly affected by the
crystal, the ZnO nanoparticles have large fraction of atoms trapping of charge carries at the surface sites. Thus, the
occupying the surface sites and the presence of imperfect weak UV emission in this experiment resulted from the
lattice. higher trapping rate of charge carriers at the surface sites
relative to the fast radiative recombination rate.
Photoluminescence (PL) The visible emissions of ZnO nanoparticles were origi-
nated from the intrinsic defects such as oxygen vacancy,
PL is the emission of light as a result of excitation by a oxygen interstitial, zinc vacancy, zinc interstitial and an-
light source. The sample absorbs photon from a mono- tisite oxygen in ZnO crystal. The blue band at 470 nm may
chromatic source such as a laser or Xe lamp, which results appear due to lattice defects related to oxygen and zinc

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132 J Theor Appl Phys (2014) 8:123–134

Fig. 8 a HRTEM image of

ZnO nanoparticles,
b corresponding selected area
electron diffraction (SAED),
c image of individual particles
(Lattice image), d particle size
distribution (from TEM images)

vacancies or interstitials [33]. The stronger the intensity of size and lattice strain. The peak broadening was analyzed
the blue luminescence, the more the intrinsic defects by the Scherrer’s equation, SSP and modified forms of W–
(oxygen and zinc vacancies or interstitials). The intensity H models viz. UDM, UDSM, and UDEDM. The lattice
of the visible emission is mainly depend on the surface strain e calculated from the W–H and SSP methods was
states. Shalish et al. [34] have reported that below a certain found to be comparable and in agreement with each other,
size the luminescence properties are entirely dominated by and the crystallite size D obtained from the SSP method is
properties of the surface. The intense visible peak at room in good agreement with the values obtained from W–H
temperature photoluminescence spectrum indicates that the methods and TEM. The SSP method is found to be the
large surface area of ZnO was exposed to air and that a most suitable one for the estimation of lattice strain e and
large amount of surface states related to oxygen vacancies. crystallite size D compared with W–H methods. Among
The room temperature photoluminescence spectroscopy W–H methods, UDM considers the homogeneous isotropic
indicates that large amount of surface states related to nature of the crystal where as USDM and UDEDM models
oxygen vacancies are present in the sample. consider the anisotropic nature of the crystallites. The
average values of crystallite size obtained from UDM,
UDSM, and UDEDM are almost similar, which indicate
Conclusions the inclusion of strain in various forms of W–H analysis
has a very small effect on the average crystallite size of
ZnO nanoparticles with hexagonal wurtzite structure were ZnO nanoparticles. It was also observed that, a small var-
synthesized from ZnCl2 and chitosan by a precipitation iation in the average crystallite size obtained from Scher-
method and characterized by FTIR, powder XRD, SEM, rer’s formula and W–H analysis was due to the difference
TEM and PL. The X-ray peak broadening of ZnO nano- in averaging the particle size distribution. The above-
particles annealed at 550 °C was due to the small crystallite explained methods were helpful in determining the

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J Theor Appl Phys (2014) 8:123–134 133

Open Access This article is distributed under the terms of the

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