Materials Research Bulletin 41 (2006) 590600

www.elsevier.com/locate/matresbu

Effect of solvents on the synthesis of nano-size zinc oxide

and its properties
K.G. Kanade a, B.B. Kale b,*, R.C. Aiyer c, B.K. Das b
a

Department of Chemistry, Mahatma Phule College, Pimpri, Pune 411017, India

Centre for Materials for Electronics Technology (C-MET), Department of Information Technology, Govt. of India,
Panchawati, Off Pashan Road, Pune 411008, India
c
Department of Physics, Pune University, Ganeshkhind, Pune 411007, India
Received 20 May 2004; received in revised form 23 August 2005; accepted 2 September 2005
Available online 29 September 2005

Abstract
The effect of the solvents on particle size and morphology of ZnO is investigated. The optical properties of nano ZnO were
studied extensively. During this study, zinc oxalate was prepared in aqueous and organic solvents using zinc acetate and oxalic acid
as precursors. The thermo-gravimetric analysis (TGA/DTA) showed formation of ZnO at 400 8C. Nano-size zinc oxide was
obtained by thermal decomposition of aqueous and organic mediated zinc oxalate at 450 8C. The phase purity was confirmed by
XRD and crystal size determined from transmission electron microscopy (TEM) was found to be 2225 nm for the aqueous and 14
17 nm in organic mediated ZnO. Scanning electron microscope (SEM) also revealed different nature of surfaces and microstructures for zinc oxide obtained in aqueous and organic solvents. The UVabsorption spectra showed sharp absorption peaks with a
blue shift for organic mediated ZnO, due to monodispersity and lower particle size. Sharp peaks and absence of any impurity peaks
in photoluminescence spectra (PLS) complement the above observations.
# 2005 Elsevier Ltd. All rights reserved.
Keywords: D. Optical properties; D. Crystal structure

1. Introduction
The development of nanocrystalline materials is a recent thrust area of research. ZnO is an important
semiconductor, which has a direct band gap (3.3 eVat room temperature), large bond strength, large excitation binding
energy (Eb = 60 meV) and high melting temperature (2248 K) [1]. ZnO is an exceptionally important material having
applications in pigments, rubber additive, gas sensor, varistors and optical devices [2]. The characteristics of ZnO
powder depend on its size and methods of preparation. Preparation of nano-size ZnO has been carried out by different
methods like aerosol, micro-emulsion, ultrasonic, solgel method, evaporation of solution and suspensions,
evaporative decomposition of solution (EDS), solid state reaction, conventional ceramic fabrication, wet chemical
synthesis and spray pyrolysis method [315]. Recently, synthesis of ZnO in the form of powder or film using metal
organic chemical vapour deposition (MOCVD) has been reported [16,17]. Lately, room temperature UV lasing from
ZnO nano-rod arrays [1820] was reported by Yang et al., highlighting the prospects for the methods of fabrication of

* Corresponding author. Tel.: +91 20 25899273; fax: +91 20 25898180.

E-mail addresses: kbbb1@yahoo.com, bbk@cmetindia.org (B.B. Kale).
0025-5408/$ see front matter # 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2005.09.002

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591

ZnO-rods. It is rationally expected that some types of morphologies of ZnO would be promising for use in a roomtemperature UV laser. Therefore, the development of morphologically controlled ZnO nanoparticles by a simple and
economical method is an important issue. The effect of solvents (organic) are reported by Zhang et al. [21] and Kwon
et al. [22], who concluded that solvent not only controls the surface morphology, but also plays a vital role on the optoelectronic and electrical properties of nano-size ZnO.
We report a simple, economical and moderately low temperature (450 8C) solution route for the preparation of ZnO
nano powder. Precipitation of the intermediate (zinc oxalate) phase was obtained by the reaction of zinc acetate with
oxalic acid in aqueous and organic solvents. The decomposition of intermediate oxalate phase gave highly
monodispersed ZnO particles, exhibiting pure hexagonal crystal phase. The crystal phase, particle size and microstructure were examined using XRD, SEM and TEM. The process reported here is potentially cheaper, simple and
useful for large-scale production since the organic solvents can be regenerated and recycled.
2. Experimental
2.1. Sample preparation
The raw materials viz. zinc acetate [Zn(CH3COO)2
2H2O]; oxalic acid [H2C2O4
2H2O], methanol and ethylene
glycol (made by Aldrich) were used. Initially, to maximize the yield of the intermediate zinc oxalate phase, various
experiments were performed by reacting aqueous concentrations of zinc acetate in the range of 0.0080.1 M with
0.0120.18 M solution of oxalic acid at room temperature. It was found that the reaction between 0.1 M solution of
zinc acetate and 0.15 M solution of oxalic acid gave maximum yield of intermediate product as compared to other
ratios of the precursors. Therefore, this ratio of concentration of the precursor solution was used for rest of the work
reported here. Similar experiments were performed using methanol and ethylene glycol as a solvent in place of water
to study the effect of organic solvents on the properties and morphology of nano-size ZnO powders produced. The zinc
oxalate was obtained by slow addition of oxalic acid with constant stirring rate of 150 rpm for 12 h, at room
temperature. The precipitate obtained was filtered and washed with acetone for at least three times to remove
impurities, if any, and dried at 120 8C. The crystal phase of zinc oxalate synthesized in different solvents was
determined using X-ray diffraction (XRD) from the positions and intensities of XRD peaks using JCPDS card no. 251029 and JCPDS card no. 37-0718.
2.2. Characterisation
The thermal study of zinc oxalate synthesized in different solvents was carried out using Thermo Gravimetric
Analyzer (TGA-DTA, Metler-Toledo Star System make) up to 1000 8C in air at the heating rate of 10 8C/min. ZnO
prepared by decomposition of zinc oxalate at 450 8C was employed for the powder XRD studies. A scanning electron
microscope (SEM) with EDAX (Philips-XL-30) was used to study the surface morphology of the zinc oxide powder. A
transmission electron microscope (JEOL-1200EX) was used to measure the particle size. FTIR (Spectrum2000 PerkinElmer) was used to observe the stretching of metal oxygen bond. UVvis absorption spectra were recorded by using a
Hitachi-3200 Spectrophotometer at room temperature. Photoluminescence (PL) spectra at room temperature were
recorded by Spectroflurometer (Perkin-Elmer LS-50B Spectrophotometer) by using xenon arc lamp as the light source.
3. Results and discussion
The nano-size ZnO powder was prepared using zinc acetate and oxalic acid in aqueous and non-aqueous solvents.
Table 1 represents the details of the yield obtained for the zinc oxalate prepared using the procedure mentioned in
Table 1
Yield of intermediate and nano-size zinc oxide
S. No.

Solvents

% Yield of zinc oxalate

% Yield of zinc oxide from Zn-oxalate

1
2
3

Water
Methanol
Ethylene glycol

85.8
90
92

90
90
90

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Fig. 1. X-ray diffractograms corresponding to intermediate zinc oxalate prepared in: (a) aqueous, (b) methanol, (c) ethylene glycol solvents.

Section 2.1. The yield of the intermediate zinc oxalate was determined gravimetrically by assuming the stoichiometric
ratios as per the reaction. The reaction scheme can be presented as follows:
ZnCH3 COO2
2H2 O H2 C2 O4
2H2 O ! ZnC2 O4
2H2 O 2CH3 COOH 2H2 O

(1)

The reaction (1) was carried out in the aqueous and organic media yielded the same amount of zinc oxalate.
During optimization of the process, it was observed that the reaction was faster in water than in organic solvent,
which may be attributed to the high polarity and dielectric constant of water as compared to its organic counterparts. This
ultimately results in slow and uniform crystal growth in organic media. However, the ethylene glycol (EG) may be acting
as a good dispersing agent during the reaction. The polarity and saturated vapor pressure of solvents were found to affect
the products under thermal conditions. The organic solvents are playing a key role for controlling the nucleation [22].
3.1. XRD analysis of intermediate
Fig. 1(ac) represents the typical XRD patterns of zinc oxalate prepared in aqueous, methanol and ethylene glycol
solvents. The important features of the XRD data pertaining to above patterns with reference to finger-printing with
reported data for monoclinic phase of zinc oxalate [JCPDS card no. 25-1029 and JCPDS card No. 37-0718] are
summarized below:
1. The XRD peaks in Fig. 1(a) at 19.58 (2u) display 100% intensity indicating the formation of a-ZnC2O4
2H2O.
2. The XRD peaks of Fig. 1(b and c) at 24.08 (2u) display 100% intensity indicating the formation of b-ZnC2O4.
The XRD peaks of organic mediated sample are better resolved than those of the aqueous mediated sample. The
zinc oxalate prepared in different solvents was further analyzed thermally to explore the decomposition temperature.
3.2. Thermal analysis
Fig. 2 depicts the TGA/DTA curves for decomposition of zinc oxalate synthesized in aqueous solvent. TGA showed
a weight loss in two steps at 120 and 400 8C and correspondingly DTA showed two endothermic peaks at these

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Fig. 2. TGA/DTA of aqueous mediated zinc oxalate.

temperatures. The endothermic peak at 120 8C was due to removal of water and the peak at 400 8C was due to
decomposition of zinc oxalate as per reaction:
ZnC2 O4
2H2 O 12O2 ! ZnO 2CO2 2H2 O

Fig. 3. X-ray diffractograms of: (a) aqueous, (b) methanol, (c) ethylene glycol mediated ZnO.

(2)

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Dehydration (excess water removal) of zinc oxalate at 120 8C is endothermic in nature. Further decomposition of
anhydrous zinc oxalate at 400 8C is also an endothermic process. The above TGA/DTA study also confirms the purity
and phase of zinc oxalate. The weight loss obtained at 400 8C matched with the calculated value using reaction (2)
shows complete formation of ZnO. TGA/DTA study of thermal decomposition of zinc oxalate prepared in methanol
solvent showed a one step weight loss at 400 8C and the corresponding DTA endothermic peak at the same temperature
due to decomposition of zinc oxalate. The absence of dehydration peak reveals that there was no excess water in zinc
oxalate powder made in methanol solvent after drying at 120 8C. Ethylene glycol mediated zinc oxalate showed a
weight loss in two steps at 250 and 400 8C, respectively. The corresponding DTA showed endothermic peaks at 250 8C
is due to removal of excess ethylene glycol solvent from zinc oxalate. The DTA peak at 400 8C is due to the
decomposition of zinc oxalate to form ZnO. As no extra salient features were observed in TGA/DTA data for the
intermediate products synthesized in organic solvents, only TGA/DTA of aqueous mediated zinc oxalate is furnished
here. Using TGA/DTA data, the zinc oxalate obtained from various solvents was decomposed at 450 8C and used for
further study.
3.3. XRD analysis of nano-size ZnO
Fig. 3(ac) depicts the X-ray diffraction patterns of ZnO prepared in aqueous, methanol and ethylene glycol (EG)
solvents. It shows a hexagonal wurtzite structure and the lattice constant values obtained from the XRD patterns of
zinc oxide powders were in good agreement with the reported values [23].

Fig. 4. SEM micrographs of nano ZnO powder prepared in: (a) aqueous, (b) methanol, (c) ethylene glycol solvents.

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Decreased peak intensities in organic mediated samples indicated that ZnO prepared in aqueous media is more
crystalline. XRD patterns of Fig. 3(ac) showed broadening of the peaks indicative of the ultra fine nature of the
crystallites. The crystallite sizes calculated from FWHM using Scherrers formula [24] for the (1 0 0), (0 0 2) and
(1 0 1) XRD peaks were found to be 2022, 1416 and 1315 nm for aqueous, methanol and ethylene glycol mediated
ZnO, respectively.
3.4. Particle morphology by SEM and TEM
Fig. 4(ac) represents scanning electron micrographs of aqueous, methanol and ethylene glycol mediated ZnO,
respectively. The SEM micrographs clearly show micro-structural homogeneities and remarkably different
morphologies for ZnO prepared in different solvents. An aqueous mediated ZnO displayed rectangular chunk shape
morphology (Fig. 4a), rod like ZnO was found in methanol-mediated sample (Fig. 4b), whereas more or less of
spherical crystallites were seen in ethylene glycol mediated ZnO (Fig. 4c). An agglomeration of particles was observed

Fig. 5. TEM micrographs with ED pattern: (a) aqueous, (b) methanol, (c) ethylene glycol mediated ZnO.

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Fig. 5. (Continued ).

in all the cases due to prolonged reaction time [21,25]. Agglomeration effect was very prominent in aqueous media as
compared to organic solvents because organic solvents have better dispersing ability [22]. The lower particle size with
different morphology was obtained in methanol and in EG mediated ZnO. The lower particle size is originating from
the oxalates prepared in different medium. The lower particle size and different morphology reveals that organic
solvents are playing a key role in controlling the nucleation and crystal orientation [22]. The particles obtained with
ethylene glycol mediated samples are most ultra-fine owing to its better dispersing ability as compared to others.
Fig. 5(ac) represents the transmission electron micrographs (TEM) of aqueous, methanol and ethylene glycol
mediated ZnO along with corresponding electron diffraction (ED) patterns. TEM pictures showed agglomerated
spherical and rod like morphology in methanol mediated ZnO, where as in EG-mediated ZnO, the particles were
regular and spherical in shape. TEM study also shows that the solvent plays a key role in controlling the morphology of
nanocrystalline zinc oxide [21]. In water, the reaction disperses more homogeneously than in organic solvents and the
growth of crystal nucleus is subjected to less confinement in boiling droplet of solvent. Therefore, it is liable to form
mixed rectangular and trigonal morphology in water. Further oriented growth of ZnO crystal is apparent with slightly
larger size. When a solvent with higher saturated vapor pressure such as methanol is utilized as a reaction media, the
amalgamation of the nucleus is not intense due to the lower boiling point of the solvent, which results in mixed
spherical and rod like particle morphology in case of methanol mediated ZnO. EG acts as a surfactant to efficiently

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stabilize the surface of the particles at high temperature and favor the formation of monodisperse ZnO crystals with
good dispersivity. Furthermore, the oriented growth of the ZnO crystal is controlled; hence the size obtained is smaller
in organic mediated ZnO. The ZnO powder appears aggregated with an average particle size of about 25, 17 and 15 nm
in water; methanol and EG mediated ZnO, respectively. These results matched with the particle size, calculated using
XRD data. The ED patterns given in Fig. 5(ac) provide the d spacing consistent with those obtained from XRD. These
observations lead us to the conclusion that the selection of the solvent is a key factor for obtaining high quality ZnO
nanocrystals.
3.5. Optical properties
Fig. 6(ac) represents the UV absorption spectra of aqueous, methanol and ethylene glycol mediated ZnO,
respectively. The sharpness of UV absorption peaks for organic mediated ZnO shows the magnitude of
monodisperseness of particles. The absorption edge cut off observed at 372 and 362 nm for aqueous and organic
mediated ZnO. Blue shift was observed in case of organic mediated samples implying lower particle size of ZnO. Band
gaps 3.34 and 3.43 eV was obtained for aqueous and organic mediated ZnO, respectively. These band gaps are
reasonably matching with the reported value of 3.37 eV [26].
Fig. 7(ac) depicts the photoluminescence spectra of nano-size ZnO synthesized in water, methanol and ethylene
glycol (EG) solvent, respectively. The PL measurements were performed at three excitation wavelengths of 250, 325
and 350 nm. Strong emission peaks centered at 394.4, 393.4 and 397.6 nm for above mentioned excited wavelengths
were observed in an aqueous mediated ZnO. Similarly, in methanol mediated ZnO, the emission peaks were centered

Fig. 6. UV-spectrum of nano ZnO powder (hexagonal phase) prepared in: (a) aqueous, (b) methanol, (c) ethylene glycol solvents.

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at 387.8, 386.6 and 392.7 nm. Ethylene glycol mediated ZnO exhibited strong emission peaks at 388.9, 387.6 and
393.0 nm. The PL studies clearly showed that the blue shift in organic mediated ZnO was due to lower particle size and
uniform particle morphology. All the samples conferred only UV band gap luminescence and no luminescence due to
oxygen defects (observed generally around 530 nm, i.e., greenyellow emission) was observed. Generally, a green
yellow emission is observed in PL spectra, due to recombination of photo generated holes with singly ionized charge
state of specific defect [27]. However, absence of the greenyellow emission in our sample indicates the potential to
produce a low concentration of oxygen defects and high optical quality of single crystal ZnO. Higher intensity of
fluorescence observed in organic mediated ZnO as compared to aqueous mediated ZnO insinuates a lower particle size
in organic medium. The sharp peaks of photoluminescence spectra (PLS) indicate the good quality of ZnO. The
maximum of the fluorescence band shifted as the excitation wavelength changed, which is a different behavior from
that of crystalline semiconductor [27].
Fig. 8(ac) represents the FTIR of aqueous, methanol and ethylene glycol mediated ZnO. The IR band for ZnO
bonding corresponding to the bulk particle is observed at 580 cm1. Furthermore, this peak is shifted to 375 and
419 cm1 for the aqueous and organic mediated ZnO, respectively. This indicates the influence of solvent on synthesis
of nano-sized ZnO and also reveals that smaller particle lose their long-range order and prefer the local order with

Fig. 7. PL spectra of nano-size ZnO powder prepared in: (a) aqueous, (b) methanol, (c) ethylene glycol solvents.

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Fig. 7. (Continued ).

Fig. 8. Infra-red spectrum of: (a) aqueous, (b) methanol, (c) ethylene glycol mediated ZnO.

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octahedral symmetry [28]. The absence of stretching peaks due to acetates and oxalates indicating the complete
formation of zinc oxide.
4. Conclusions
The nano-size ZnO powder was obtained from zinc acetate through oxalate route using aqueous and organic
solvents. Thermal analysis results showed the complete conversion of zinc oxalate to zinc oxide at 400 8C. XRD
results confirmed the hexagonal crystal structure of ZnO. The particle size observed was in the range of 2225 nm for
an aqueous mediated ZnO and 1417 nm for organic mediated ZnO, which was also confirmed by TEM. The SEM and
TEM micrographs clearly show microstructural homogeneities and remarkably different agglomerates morphology in
different solvents implying that the selection of solvents is a key factor for obtaining high quality of nano-size ZnO via
the solution route. The UV and PL absorption spectra showed that the absorption edge was shifted to a shorter
wavelength in case of organic mediated ZnO, due to decrease in crystal size. Absence of the greenyellow emission
shows potential to produce a low concentration of oxygen defects and high optical quality of single crystal ZnO using
our simple method.
Acknowledgements
We gratefully acknowledge UGC, Government of India for the financial assistance through Minor Research
Project. We thank the Principal of Mahatma Phule College, Pimpri, Pune 411017 and the staff members of the
Nanocrystalline materials/glass group of C-MET Pune, for their kind support in carrying out the above research. We
also thank Mrs. Renu Pasricha and Dr. Mohan Bhadbadhe of the National Chemical Laboratory (NCL) Pune, for the
TEM analysis.
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