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Materials Letters 61 (2007) 3265 3268

www.elsevier.com/locate/matlet

Preparation and characterization of ZnO nanoparticles


by a novel solgel route
M. Vafaee a , M. Sasani Ghamsari b,
a
Department of Material Science and Engineering, Sharif University of Technology, 11365-9898, Tehran, Iran
b
Solid State Laser Division, Laser Research Center, 11365-8486, Tehran, Iran
Received 27 September 2006; accepted 9 November 2006
Available online 5 December 2006

Abstract

In this study, ZnO nanoparticles with 3 to 4 nm size and spherical shape have been prepared. For the first time, TEA (triethanolamine) as a
surfactant has been used for the preparation of ZnO nanoparticles. The best concentration of each component was adjusted through comparison
between different sol absorption spectra. The best sol regarding its optical property was subjected to analysis by photoluminescence spectroscopy.
TEM micrograph and electron diffraction pattern of these particles were obtained to represent the morphology and crystalline phase of the
particles, respectively. Experimental results have shown that the prepared zinc oxide nanoparticles by this method have higher photoluminescence
spectra as compared to other methods.
2006 Elsevier B.V. All rights reserved.

Keywords: ZnO nanoparticles; TEA; Surfactant; Photoluminescence spectra

1. Introduction preparation of zinc oxide nanoparticles. These procedures are


categorized as {ZnAc (zinc acetate dihydrate), 2-Methoxyetha-
Zinc oxide is a well-known semiconductor with a wide direct nol, MEA}, {ZnAc, 2-Propanol, DEA} and {ZnAc, Ethylene
band gap (3.37 eV) and a large exciton binding energy of 60 meV Glycol, glycerol, 1-Propanol,}. In this study and for the first
at room temperature [1]. It is used in many applications such as time, we have used TEA (triethanolamine) as a surfactant. There
surface acoustic wave devices (SAW), gas sensor devices, laser is no other research result on the preparation of ZnO nanoparticle
and optoelectronic devices [24,7]. in the presence of TEA. The best ratio of each component was
Zinc oxide nanoparticles can be prepared by different me- selected based on ZnO that gave better optical properties. Ac-
thods. From these methods, the solgel method is more popular cording to FTIR analyses, consequent reactions from dissolving
because of its cheapness, reliability, repeatability, and simplicity. of the ZnAc to formation of ZnO were suggested. Excitation of
In addition, the nanoparticles which are produced by this route, ZnO nanoparticles was studied based on their photolumines-
show good optical properties. But, this can be achieved only by cence spectra and their morphologies were presented by TEM
good control of the size and morphology of the particles. That is, analysis.
we have to carefully control the solgel process and the growth
of nuclei must be prevented. One of the ways that this can be 2. Experimental
done is by providing good absorption of the surfactant onto the
surface of the particles. For this purpose, in the preparation of In the preparation of ZnO sols, the following procedure was
ZnO nanoparticles, surfactants such as MEA (Monoethanola- carried out. First, the appropriate ratio of triethanolamine was
mine) and DEA (Diethanolamine) are employed [57]. There added to ethanol. After complete mixing by a magnetic stirrer,
are three procedures which have been frequently chosen for the zinc acetate dihydrate (ZnAc) was added as precursor. The
amounts of ZnAc in sols were varied to 0.25, 0.5 and 0.75 M in
Corresponding author. order to assess the best ratio, and also the molar ratio of TEA to
E-mail address: msghamsari@yahho.com (M.S. Ghamsari). ZnAc was adjusted to 3:5, 6:5 and 9:5 with the same aim. The
0167-577X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.11.089
3266 M. Vafaee, M.S. Ghamsari / Materials Letters 61 (2007) 32653268

Fig. 1. Fresh sols absorption spectra. The molar ratios of TEA:ZnAc are for Fig. 3. The effect of adding each component on chemical vibration bonds
(---): 3:5, (): 6:5 and (full line): 9:5. (black colour: EtOHTEAZnAc; blue colour: EtOHTEA; green colour:
EtOH). (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
solutions were stirred in about 30 min by heating to 5060 C.
Each sol was studied considering their stability by aging them
for one to two months. Absorption spectroscopy and Fourier- their absorption onset. The particle size for all sols is around 2 to 3 nm.
transform infrared (FTIR) spectroscopy were performed using The two other sols did not show this particular phenomenon which is
Hitachi U-3410 and Bruker (Vector 22) instruments respectively due to the semiconductors special ability. It is possible that these sols
on sols. The ability of emission excitation of ZnO nanoparticles contain particles with a low percentage of ZnO and surely a huge
amount of organic complexes. To sum up, the ratio of TEA to ZnAc
was investigated using Cary Eclipse photoluminescence
must be 3:5 according to absorption spectra. In order to demonstrate the
analyzer. Transmission electron microscopy was carried out
influence of ZnAc concentration on the optical properties of sols three
using Philips (3M200) instrument. other sols have been prepared which contained various molarities of
ZnAc (0.25, 0.5 and 0.75). But the molar ratio of TEA was fixed to 3:5
3. Result and discussion similar to the first experiment. To evaluate the bonds energy differences
between sols with different amounts of ZnAc and absolutely TEA,
This study was performed with the hope that ZnO nanoparticles with FTIR analyses were carried out on fresh sols. The resultant spectra are
good optical properties can be obtained. This can be achieved by shown in Fig. 2. TEA to ZnAc molar ratio was fixed to 3:5. The broad
preparing ZnO nanoparticles which will have good characteristic peak in the range of 3000 to 3500 cm 1 is attributed to water of hydra-
absorption and sharp luminescence spectrum. Three different ratios of tion present in the solution. The peaks which are located at 2885 and
both ZnAc and TEA were chosen to determine the best sol considering 2937 cm 1 are due to symmetric and asymmetric CH bonds respec-
their optical properties. First, for ZnAc of 0.5 M three different amounts tively. CH bonds are present in monoacetate groups as intermediate
of TEA were added. After completion, the sol's absorption was mea- products [5]. 1565 and 1380 cm 1 peaks are attributed to asymmetric
sured at various wavelengths. The absorption spectra are shown in and symmetric C_O bonds vibrations respectively, and these bonds
Fig. 1. modified form vibrate at 1330 and 1260 cm 1. CN bonds vibrate at
The sol whose TEA:ZnAc molar ratio was 3:5 shows a charac- 1010, 1060 and 1140 cm 1 [5,1013]. OH vibrations become sharper
teristic absorption spectrum around 275 nm. But the others have no and all the other vibrations are moderated due to the increase in ZnAc
peak and their absorption spectra arise drastically. This peak cor- molar ratio. According to these curves, it seems that the nature of the
responds to electronhole conjunctions [8]. According to quantum bonds in sols changes when the molar ratios increase. In Fig. 3, the
calculations by Brus [9] we can estimate the particle radius based on effect of adding each component is represented in order through FTIR
analyses.
There is no important vibration in ethanol FTIR spectrum except in
the range of CH bonds, but when TEA is being added, three OH
bonds of TEA can be recognized with regard to vibrations in the range
of 3000 to 3500 cm 1. When TEA is added, it will bring three numbers
of OH into the solution, so vibrations at this state will be boosted. CH

Fig. 2. FTIR spectra obtained from fresh sols. The amounts of ZnAc are
indicated above each spectrum. Fig. 4. Photoluminescence spectrum of ZnO nanoparticles in 0.75 M ZnAc sol.
M. Vafaee, M.S. Ghamsari / Materials Letters 61 (2007) 32653268 3267

green emissions, on the other hand, are assigned to transition of photo-


generated electrons from the conduction band edge to a trap level near
the conduction band [16]. These peaks do not obey the quantum con-
finement size effect and their intensity and shape are dominated by
surface structure of particles [17].
In order to elucidate the as-prepared ZnO nanoparticles morphol-
ogies, transmission electron microscopy (TEM) was performed on the
sol with 0.75 M ZnAc content. For the purpose of having a better
chance to obtain the appropriate number of particles, the amount of
ZnO nanoparticles related to solvent in the sol was increased by
evaporating some amount of the solvent in air. As it can be seen in
Fig. 5, there is no aggregation between nanoparticles, but the dense
structure due to evaporation process was formed. The particles tend to
have a minimum value of energy according to their spherical shape.
The average particle size in this image was estimated to be 4 nm by
applying the cross line method. After measuring the radius of the
circles and comparing it to JCPDS data [18], the crystal phase of these
Fig. 5. Transmission electron microscope micrograph of ZnO nanoparticles. particles was recognized. Nanoparticles in such sols were crystallized
in wurtzite ZnO.

and C_O bonds are also formed. It is clear from the curves that ethanol
4. Conclusion
and triethanolamine do not react. By ZnAc addition CN and C_O
bonds shifted to higher wave numbers in comparison with FTIR
spectrum related to ZnAc. It is proposed that in the process of ZnO According to absorption spectra, the best ratio for sols with
synthesis of ZnAc and a surfactant, an intermediate product called zinc good optical properties was chosen. Possible reactions which
monoacetate is obtained. The following reactions which represent the may occur during ZnO nanoparticles synthesis were proposed
process of ZnO formation from sol's component are suggested con- based on FTIR spectra. Different shapes of UV and green peaks
sidering the FTIR spectra. in the photoluminescence spectra of these particles suggest the
possible use of these particles in monochromatic excitation
CH3 COH2 OOZnOCOH2 OCH3 CH3 COOZn applications. The morphology of the particles and their crystal
OCOCH3  2H 2OH 1 structure were evaluated via TEM micrographs and diffraction
In the above reaction, zinc acetate dihydrate was changed to zinc pattern respectively.
monoacetate. But in the following reaction, a new complex is formed.
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