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Journal of Luminescence 129 (2009) 874878

Contents lists available at ScienceDirect

Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Synthesis, effect of capping agents, structural, optical and photoluminescence

properties of ZnO nanoparticles
A.K. Singh , V. Viswanath, V.C. Janu
Defence Institute of Advanced Technology, Girinagar, Pune 411025, India

a r t i c l e in f o

a b s t r a c t

Article history:
Received 28 June 2008
Received in revised form
13 February 2009
Accepted 21 March 2009
Available online 5 April 2009

Zinc oxide nanoparticles were synthesized using chemical method in alcohol base. During synthesis
three capping agents, i.e. triethanolamine (TEA), oleic acid and thioglycerol, were used and the effect of
concentrations was analyzed for their effectiveness in limiting the particle growth. Thermal stability of
ZnO nanoparticles prepared using TEA, oleic acid and thioglycerol capping agents, was studied using
thermogravimetric analyzer (TGA). ZnO nanoparticles capped with TEA showed maximum weight loss.
X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for structural and
morphological characterization of ZnO nanoparticles. Particle size was evaluated using effective mass
approximation method from UVvis spectroscopy and Scherrers formula from XRD patterns. XRD
analysis revealed single crystal ZnO nanoparticles of size 1220 nm in case of TEA capping. TEA, oleic
acid and thioglycerol capped synthesized ZnO nanoparticles were investigated at room temperature
photoluminescence for three excitation wavelengths i.e. 304, 322 and 325 nm, showing strong peaks at
about 471 nm when excited at 322 and 325 nm whereas strong peak was observed at 411 for 304 nm
excitation.
& 2009 Elsevier B.V. All rights reserved.

PACS:
71.35.Cc
78.55.Et
78.55m
Keywords:
ZnO
Capping agent
UVvis
Photoluminescence

1. Introduction
Zinc oxide (ZnO) is a wide band gap semiconductor, having
high exciton binding energy of 60 meV and has stable wurtzite
structure with lattice spacing a 0.325 nm and c 0.521 nm. It
has attracted intensive research efforts for its unique properties
and versatile applications in antireection coatings, transparent
electrodes in solar cells, ultraviolet (UV) light emitters, diode
lasers, varistors, piezoelectric devices, spin-electronics, surface
acoustic wave propagator [13], antibacterial agent [4], photonic
material [5] and for gas sensing [6]. Invisible thin lm transistors
(TFTs) using ZnO as an active channel, have shown much higher
eld effect mobility than amorphous silicon TFTs. These transistors can be widely used for display applications. ZnO has been
proposed to be a more promising UV emitting phosphor than GaN
because of its larger exciton binding energy leading to a reduced
UV lasing threshold and yielding higher UV emitting efciency at
room temperature [7]. Surface acoustic wave lters using ZnO
lms have already been used for video and radio frequency
circuits. Bulk and thin lms of ZnO nanoparticles have demonstrated high sensitivity to toxic gases [8]. Several authors have
reported high photoluminescence efciencies in ZnO nanostruc-

 Corresponding author. Tel.: +91 2024304173; fax: +91 2024389411.

E-mail address: draksingh@hotmail.com (A.K. Singh).

0022-2313/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jlumin.2009.03.027

tures [9,10]. Also, ZnO is an environment friendly material, which

is desirable especially for bioapplications. Due to the increasing
demands globally for green materials and processes, new and
efcient synthesis processes are desired. A large number of
techniques like spray pyrolysis, thermal decomposition, chemical
vapour deposition, laser ablation, etc. have been used for
synthesis of nanomaterials and structures. Chemical synthesis is
one of the important techniques which can be performed using a
range of precursors and synthesis conditions like temperature,
time, concentration, pH of reactants, etc. Optimization of these
parameters leads to nanoparticles of different size, shapes and
showing different optical properties.
In this study, ZnO nanoparticles are synthesized by wet
chemical method, which is a simple method, under ambient
atmosphere at room temperature, and characterized by UVvis,
X-ray diffraction (XRD), and scanning electron microscopy (SEM).
Concentration of TEA is varied and also the capping agent is
changed to oleic acid and thioglycerol and its effect on the size
and the properties of the particles is analyzed.

2. Synthesis methodology
Zincacetatedihydrate, Zn(Ac)2  2H2O dissolved in dimethylsulpoxide (DMSO) and potassiumhydroxide (KOH) dissolved in
ethanol is used to synthesize ZnO and then triethanolamine (TEA)

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A.K. Singh et al. / Journal of Luminescence 129 (2009) 874878

is added as capping agent. Zincacetatedihydrate of 0.2 M,

Zn(Ac)2  2H2O, is prepared in 20 ml dimethylsulpoxide and stirred
till it is completely dissolved and forms a clear solution.
Potassium hydroxide solution of 1.2 M in 10 ml ethanol is added
to the solution of zinc acetate drop wise till the solution becomes
milky white under slow stirring condition until it is uniformly
white. Intended capping agents, i.e. TEA, oleic acid, thioglycerol, in
required concentration, is added and stirring is continued for
proper mixing of the capping agent in the milky white solution.
The precipitate is separated by centrifugation and then washed at
least three times and then naturally dried to get ne white
powder. All the chemicals used were purchased from the leading
suppliers without further purication.

3. Measurements and analysis

UVvis absorption study has been carried out using Nanodrop
1000 spectrophotometer by dispersing nanoparticles in methanol.
Photoluminescence (PL) measurements have been done at room
temperature using Perkin Elmer (LS-55) Luminescence Spectrophotometer. Thermogravimetric analysis (TGA) has been done
using Du Pont analyzer, model 951. Analysis of crystal structure,
crystal size and morphology has been carried out by X-ray
diffraction and scanning electron microscopy. Stoichiometric
analysis has been done using EDAX. The energy corresponding
to the exciton absorption peak has been converted in terms of
particle size using the effective mass approximation [11]


1
1
1:8e2
2

Smaller term
(1)

E Eg h p2
me mh
4p0 0 0 R

respectively. From Eq. (1) size of the particle is found to be

between 30 and 4 nm. As seen from Fig. 1 and Table 1, the
absorption spectra for all the samples are blue shifted to, from
375 nm absorption wavelength (expected for bulk ZnO having
direct band gap of 3.3 eV) and showing sharp excitonic peaks.
3.1. Effect of TEA concentration
To analyze the effect of concentration of capping agent,
concentration of TEA is increased i.e. 2, 50 and 75 times of the
initial concentration (0.12 ml). Observation of Fig. 1 shows that
there is gradual blue shift in the UV absorption spectra,
correspondingly the size of ZnO has decreased to 1520, 34
and 34 nm, respectively, as obtained from the mass approximation. Observation of Table 1 also shows that the effect of increase
in concentration of TEA is only up to certain level i.e. 50 times,
after which increase in TEA concentration becomes ineffective.
3.2. Effect of capping agents on the size of particle
To analyze the effect of various capping agents, TEA has been
replaced rst with oleic acid and then with thioglycerol. The
concentration used is 0.24 ml of oleic acid and 0.12 ml of
thioglycerol, respectively, and the UV absorption spectra observed
is shown in Fig. 2 for all the samples. Observation of gure shows
that thioglycerol is more effective capping agent than TEA. It is
seen that to achieve 34 nm size of ZnO, 9.0 ml of TEA is required
or 0.24 ml of oleic acid against 0.12 ml of thioglycerol. This can be
attributed to the greater steric effect on nitrogen of TEA, which

where E is band gap of synthesized particle, Eg is bulk band gap of

ZnO (3.3 eV), R is radius of the particle, me is effective mass of
electron (0.28 mo), mh is effective mass of the hole (0.49 mo), e0 is
dielectric constant of material (9.1), e0 0 is permittivity of free
space, h is Plancks constant. From Scherrers formula [12] using
FWHM of XRD patterns, size of particles is
0:9l
b cos y

1
TEA 0.24 ml (double)

0.9

TEA 6.0 ml (50 times)

0.8
Absorption (a.u.)

875

(2)

where l is wavelength of X-ray source, b is full-width at halfmaximum in radians, y is Braggs diffraction angle.

TEA 0.12 ml

0.7

TEA 9.0 ml (75 times)

0.6
0.5
0.4
0.3
0.2

3. Results and discussion

0.1
Table 1 summarizes the synthesis results of ZnO, effect of
capping agents on excitonic peaks and particle size estimated
from mass approximation Eq. (1). Fig. 1 shows the UV absorption
spectra of ZnO capped with different concentrations of TEA.
Absorption peaks corresponding to 0.12, 0.24, 6.0 and 9.0 ml
concentrations of TEA are obtained at 360, 357, 338 and 337 nm,

0
200

300

400
500
600
Wavelength (nm)

700

800

Fig. 1. UVvis absorption spectra of ZnO powder capped with 0.12, 0.24, 6.0 and
9.0 ml concentrations of TEA.

Table 1
Summary of synthesis of results and effect of capping agents on UV absorption peak and particle size.
S. No.

Capping agent

Quantity of capping
agent (ml)

UV absorption
peak (nm)

Size of particles obtained

from Eq. (1) (nm)

1
2
3
4
5
6

Triethanolamine
Triethanolamine
Triethanolamine
Triethanolamine
Oleicacid
Thioglycerol

0.12
0.24 (2 times)
6 (50 times)
9 (75 times)
0.24
0.12

360
357
338
337
344
335

2030
1525
34
34
45
3

7
8

Annealing at 423 K for 3 h for sample ZnO with TEA (S. No. 1)

364

4045

Solution temperature raised to 70 1C for ZnO with TEA as capping agent (S. No. 1)

350

1520

(TEA)
(TEA)
(TEA)
(TEA)

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A.K. Singh et al. / Journal of Luminescence 129 (2009) 874878

TEA
Thioglycerol
Oleic acid

100

Capping agent: Oleicacid 0.24ml

0.9

Absorption (a.u.)

Weight Loss (%)

Capping agent : Thioglycerol 0.12ml

0.8

Capping agent:TEA 0.12 ml

0.7
0.6
0.5
0.4

80
60
40
20

0.3
0.2

0.1

0
200

300

400
500
600
Wavelength (nm)

700

100

800

200
300
400
Temperature (C)

500

600

Fig. 4. Thermograph of capping agents.

Fig. 2. Comparison of UVvis absorption spectra with different capping agents i.e.
TEA, oleic acid, thioglycerol.

700

(101)

600
Intensity (a.u.)

106
ZnO nanoparticles capped with TEA

104

ZnO nanoparticles capped with Oleicacid

ZnO nanoparticles capped with Thioglycerol

102

ZnO commercial

Weight Loss (%)

100

(110)

500

(103)
(002)
(100)

400

(112)
(102)

300
200

98

100

96

0
20

30

94

40

50

60

70

80

(2)

92

Fig. 5. X-ray diffractogram of zinc oxide nanoparticles capped with 0.12 ml of TEA.

90
88
86
0

200

400
600
Temperature (C)

800

1000

Fig. 3. Thermograph of commercial ZnO powder and ZnO nanoparticles capped

with TEA, oleic acid, thioglycerol.

makes it less effective capping agent as compared to sulphur of

thioglycerol which is lesser hindered. The size of sulphur in
thioglycerol is also larger than nitrogen of TEA which makes it
more effective capping agent as compared to TEA. TGA of ZnO
nanoparticles prepared using various capping agents is shown in
Fig. 3 along with the thermograph of pure ZnO powder whereas
Fig. 4 shows the thermograph of capping agents. TGA of
nanoparticles and of capping agents not only provides
information about the stability of nanoparticles but can also be
used to evaluate yield of ZnO in nal product [13]. ZnO
nanoparticles capped with TEA showed maximum weight loss.

3.3. Crystal structure and morphology

Before discussing photoluminescence of ZnO nanoparticles it is
useful to consider their crystal structure and morphology. Fig. 5
shows the X-ray diffraction pattern of 0.12 ml TEA capped ZnO
nanoparticle. These peaks at scattering angles (2y) of 31.3, 33.1,
35, 46.3, 55.3, 61.6 and 66.7 correspond to the reection from:
100, 002, 101, 102, 110, 103 and 112 crystal planes, respectively.

XRD of the ZnO nanoparticles indicates that they possess a

hexagonal wurtzite type of crystallographic stricter. The XRD
pattern shows broadening of the peaks indicating ultra-ne
nature of the crystallites. The peaks assigned to diffractions
from various planes correspond to hexagonal structure of ZnO.
The crystallite size estimated for the same sample from Scherrers
formula using FWHM [12] from XRD patterns is of the order of
1220 nm from different peaks, giving average size of 15.4 nm
from all the peaks. Fig. 6 shows the energy dispersive analysis of
X-rays (EDAX) used to nd the composition of zinc oxide sample.
It shows zinc and oxygen to be almost in stoichiometric ratio.
Fig. 7 shows SEM images of ZnO capped with 0.12 ml of TEA for
two magnications. Observation of gure shows that ZnO
particles are spherical in nature and size of the particles is
in the range 4050 nm (size resolved from SEM is about 50 nm,
Fig. 5b).

3.4. Photoluminescence
Generally, ZnO shows four PL emissions [14]: (a) near band
edge emission at around 390 nm (UV emission), attributed to freeexciton recombination (b) blue emission at around 460 nm is
because of intrinsic defects such as oxygen and zinc interstitials
(c) green emission at around 540 nm is known to be a deep level
emission which is caused by impurities, a structural defects in the
crystal such as oxygen vacancies, zinc interstitials, etc. and (d) red
emission at around 630 nm due to oxygen and zinc anti-sites.
Fig. 8 shows the room temperature photoluminescence spectra
of ZnO nanoparticles excited at three different wavelengths

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877

Fig. 6. EDAX of ZnO nanoparticles capped with 0.12 ml of TEA.

Fig. 7. SEM of the ZnO nanoparticles obtained with 0.12 ml of TEA capped agent.

350

350
Excitation at 325 nm
Excitation at 322 nm
Excitation at 304 nm

ZnO capped with Thioglycerol

250

517.5

250
200
150
100
50
0
350

ZnO capped with TEA

471.5

300

Intensity (a.u.)

Intensity (a.u.)

300

409.5

200

392.5

470.5

150
100

400

450

500 550 600 650

Wavelength (nm)

700

750

800

Fig. 8. PL emission spectra of ZnO nanoparticles capped with TEA at 304, 322 and
325 nm excitation wavelengths.

i.e. 304, 322 and 325 nm. At later two excitation wavelengths,
photoluminescence spectra are found to be of similar nature
showing strong peak at about 471 nm. ZnO nanoparticles excited
at 325 nm exhibited four prominent emission PL bands at around
390, 411, 471 and 517 nm. The PL results as shown in Fig. 8 are
similar to those reported previously [14,15]. The PL peak at 411 is
attributed to zinc vacancies [15] which is intense and sharp when
excited with 304 nm. This peak intensity is increased at the
expense of band edge emission. This showed that the probability

50
0
300

400

500
600
Wavelength (nm)

700

800

Fig. 9. Room temperature PL emission spectra of ZnO nanoparticles capped with

TEA and thioglycerol.

of trapping and giving the PL emission by zinc vacancies at the

excitation of 304 nm is more as compared to 325 nm excitation.
The peak around 470 nm i.e. blue emission is attributed to
intrinsic defects such as oxygen and zinc interstitials [14]. This
blue emission is common for all excitation wavelengths, but for
322 and 325 nm excitation blue emission is prominent. The green

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A.K. Singh et al. / Journal of Luminescence 129 (2009) 874878

band emission corresponds to the singly ionized oxygen vacancy

in ZnO in the bulk of nanoparticles and excess oxygen on the
surface, which might be in the form of OH ions and results from
the recombination of photo-generated hole with single ionized
charge state of this defect [13,16]. The weak green emission also
implies that there are few surface defects in ZnO nanoparticles.
Fig. 9 shows the room temperature photoluminescence spectra
of ZnO nanoparticles excited at 322 nm wavelength for two
different surfactants in same quantity (0.12 ml), i.e. TEA and
thioglycerol, indicating the effect of particle size on PL intensity. It
shows that PL intensity is higher when thioglycerol is used as
surfactant due to the formation of smaller ZnO nanoparticles as
compared to TEA. However, no blue shift has been observed in
photoluminescence spectra due to size effect. Similar results have
been reported by Ghosh et al. [14], Tan et al. [17]. This is because
the PL emission generally comes from the ZnO nanocrystals, and
the blue shift in the optical absorption spectra is due to the
amorphous phase in the material [17].

4. Conclusion
ZnO nanoparticles have been successfully synthesized using
zinc acetate, DMSO and KOH in ethanol at room temperature
using three capping agents, i.e. TEA, oleic acid and thioglycerol. It
has been found that thioglycerol is more effective capping agent
as compared to oleic acid and TEA, giving nanoparticles of size
3 nm. ZnO nanoparticles capped with thioglycerol show high
intensity luminescence. Blue emission at 471 nm is common for
all excitation wavelengths, but for 322 and 325 nm excitation blue
emission is prominent whereas for 304 nm excitation, emission at
411 is prominent.

Acknowledgements
Authors are thankful to Vice-Chancellor, DIAT, Pune for granting
permission to publish this work. Authors would like to thank Prof.
SK Kulkarni, Department of Physics, University of Pune, for
providing Photoluminescence facility and technical discussions;
and Director, DMSRDE, Kanpur, for SEM and EDAX of samples.
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