Bull. Mater. Sci., Vol. 32, No. 2, April 2009, pp. 165–168. © Indian Academy of Sciences.

Synthesis and optical characteristics of ZnO nanocrystals

D SRIDEVI* and K V RAJENDRAN

Department of Physics, Presidency College, Chennai 600 093, India

MS received 20 June 2008; revised 19 December 2008

Abstract. Zinc oxide nanomaterials with an average particle size of 20–30 nm are readily synthesized by the
reaction of zinc acetate and oxalic acid under hydrothermal conditions. The samples are characterized by
XRD, SEM, TEM, UV and photoluminescence (PL) studies. The average crystal size of the as prepared ZnO
nanopowder is determined by XRD and the values are in good agreement with the TEM analysis. UV absorp-
tion spectra revealed the absorption at wavelength < 370 nm indicating the smaller size of ZnO nanoparticles.
The quality and purity of ZnO nanomaterial crystalline samples are confirmed by photoluminescence spectra.

Keywords. Nanomaterials; optical materials; properties; ZnO.

1. Introduction water to remove impurities and dried over 120°C for 6 h

in order to remove water molecules.
ZnO is a wide bandgap semiconductor with optoelec-
H2O
tronic properties that make it an attractive candidate for a Zn(CH3COO)2⋅2H2O + H2C2O4⋅2H2O ––––→
variety of device applications. Zinc oxide is a versatile ZnC2O4.XH2O + CH3COOH + 2H2O
material that has achieved applications in photocatalysts,
solar cells, chemical sensors, piezoelectric transducers, ZnC2O4⋅XH2O → ZnO + CO + CO2 + XH2O.
transparent electrodes (Bauer et al 2001; Duran et al 2002),
electro luminescent devices, and ultraviolet laser diodes The calcination process is carried out over a temperature
(Johnson et al 2001; Zhang et al 2002). Compared to of 400–450°C in order to remove CO and CO2 from the
other semiconductors, ZnO has wide bandgap of 3⋅37 eV compound.
and other large excitation binding energy, which makes Thus obtained samples are characterized by powder
excitation stable even at room temperature. There are X-ray diffractometer XPERT PRO with CuKα X-ray
various methods in order to synthesize ZnO nanomaterials radiation (λ = 0⋅15496 nm). The crystalline nature of
viz. solvothermal synthesis, sol–gel (Li and Kanbunde ZnO samples is confirmed by sharp intense peaks. The
1992; Mondelaers et al 2002), combustion synthesis surface morphology of the sample is observed by scan-
(Vorkakpic and Matsaukas 1998; Hwang et al 2004), ning electron microscopy (SEM, JEOL, JSM-67001) and
spray analysis (Ko et al 2006), thermal hydrolysis (Kodas high-resolution transmission electron microscopy
1989), hydrothermal synthesis etc. Hydrothermal synthe- (HRTEM, HITACHI model H-800). The composition of
sis is one of the most extensively used and cost effective elements like Zn, O is confirmed by energy dispersive X-
methods for the preparation of nanomaterials. In this study, ray spectra (EDX). Optical absorption spectrum is taken
we have synthesized ZnO nanomaterials and their optical with SHIMA DZU UV-310PC, UV scanning spectropho-
and surface morphological properties are investigated. tometer. The room temperature photoluminescence
(PL) spectrum of ZnO is recorded with fluorescence
spectrometer (FLS920) using Xe lamp as the excitation
2. Experimental source at excitation wavelength (λex = 325 nm). The
luminescence is dispersed with a monochromator and
Zinc oxide is synthesized in aqueous solutions by taking recorded.
zinc acetate and oxalic acid under hydrothermal condi-
tions. 0⋅1 M solution of zinc acetate (AR) is taken in a
beaker containing 0⋅1 M solution of oxalic acid (AR ) and 3. Results and discussion
stirred for about 12 h. The white precipitates thus ob-
tained are filtered and washed with acetone and distilled Figure 1(a) shows the XRD patterns of ZnO nanocrysta-
lline powder. The sharp intense peaks of ZnO confirms
the good crystalline nature of ZnO and the peaks origi-
*Author for correspondence ([email protected]) nated from (100), (002), (101), (102), (110), (103), (200),
165
166 D Sridevi and K V Rajendran

(112) and (201) reflections of hexagonal ZnO (Yang et al dium. The orientation growth of ZnO crystal in water is
2005). The size of the particles is calculated by Debye higher (Kwon et al 2002). And the spherical shaped
Scherrer’s formula. The average crystal size is calculated morphology is observed in the micrograph as shown in
by the formula figure 2. The SEM pictures show distinguished spherical
morphology with a self-aligned prismatic nanoparticles.
D = k(λ/βcosθ),
The transmission electron micrograph of the ZnO sample
K is a constant equal to 0⋅89, λ the X-ray wavelength is given in figure 3. The figure clearly indicates the
(0⋅154095 nm), β the full wavelength at half maximum morphology of the particles to be roughly spherical and
and θ the half diffraction angle. homogeneous. Some of the particles are agglomerates.
The distribution of particles obtained from the TEM
The crystal size of the ZnO nanoparticles calculated from image is given in figure 4.
FWHM was tabulated in table 1. Figure 5 shows the optical absorption spectrum of ZnO
Energy dispersive X-ray spectra displayed in figure nanopowder prepared under aqueous conditions. The UV
1(b) and table 2 furnish the composition of various ele- visible spectra for ZnO nanoparticles synthesized in
ments in the prepared sample. aqueous media displayed excitonic absorption peak at
Figure 2 represents the scanning electron micrographs 363 nm which implies the lower particle size ZnO. The
of ZnO nanomaterials synthesized under aqueous me-

Table 1. Particle size estimated from the diffraction spectrum

in figure 1 by using half maximum widths.
Particle
Phase Width 2θ (deg) (hkl) size (nm)

ZnO 0⋅42 31⋅750 100 21

0⋅37 34⋅380 002 24
0⋅39 36⋅180 101 25
0⋅39 47⋅500 102 24
0⋅40 56⋅540 110 24
0⋅35 62⋅780 103 32
0⋅30 66⋅310 200 29
0⋅41 67⋅840 112 26
0⋅29 68⋅910 201 35

Table 2. Composition of elements in ZnO sample.

Element Wt% At%

OK 24⋅44 56⋅93
ZnK 75⋅56 43⋅07
Total 100⋅00 100⋅00

Figure 1. (a) XRD pattern of ZnO nanoparticles after calcina-

tion at 450°C and (b) EDX spectrum of ZnO nanoparticles. Figure 2. SEM image of ZnO nanocrystals.
 Synthesis and optical characteristics of ZnO nanocrystals 167

bandgap calculated from the UV cut-off is found to be observed in PL spectra, due to recombination of photo
3⋅41 eV ZnO nanoparticle. These band gap values blue generated holes with singly ionized charge state of spe-
shifted relative to the bulk zinc oxide of 3⋅37 eV (Huang cific defect (Hsieh et al 2003). However, absence of the
et al 2001). green yellow emission in our samples indicates the poten-
Figure 6 depicts the photoluminescence spectrum of tial of our synthetic strategy to produce a low concentra-
nanosize ZnO synthesized in aqueous medium. Strong tion of oxygen defects and high optical quality of single
emission peak centred at 397 nm was observed in ZnO. crystal ZnO (Zu et al 1997; Gao et al 2005).
The ZnO sample exhibits only UV bandgap lumines-
cence but no oxygen defects luminescence was observed.
4. Conclusions
(In general, it is observed around 530 nm, i.e. green–
yellow emission). Generally, a green–yellow emission is
ZnO nanomaterials have been successfully synthesized by
hydrothermal method using zinc acetate and oxalic acid
as the reactants. The XRD pattern reveals that the synthe-
sized materials are crystalline in nature. The size of the
particles determined by XRD is in good agreement with
TEM analysis. The optical properties of ZnO nanomaterials
are studied by absorption and photoluminescence spectra.

Figure 3. TEM image of ZnO nanocrystals.

Figure 5. UV absorption spectrum of obtained sample.

Figure 4. Particle distribution obtained from TEM image. Figure 6. PL spectrum of obtained sample.
168 D Sridevi and K V Rajendran

The high crystalline and purity of the ZnO nanomaterials Hwang C C and Wu T Y 2004 Mater. Sci. Engg. B, Solid State
are confirmed by photoluminescence spectra. Mater. Adv. Technol. 111 197
Johnson J C, Yan H, Schaller R D, Haber L H, Saykally R J and
Yang P 2001 J. Phys. Chem. B105 11387
Acknowledgement Ko T S, Yang S, Su H C H, Chu C P, Lin H F and Liao S C
2006 Mater. Sci. Engg. B, Solid State Mater. Adv. Technol.
The authors are grateful to the University Grants Com- 134 54
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Kwon Y J, Kin K H, Lim C S and Shim K B 2002 J. Ceram.
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