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ISSN: 0973-7464 Vol. XVI: No.

1 & 2 SB Academic Review 2009: 57-65

OPTICAL PROPERTIES OF ZnO NANOPARTICLES


Soosen Samuel M, Lekshmi Bose and George KC* ABSTRACT The synthesis of ZnO nanoparticles has attracted immense interest because of their unique properties and potential applications in optoelectronic devices. ZnO as a wide band gap semiconductor with large excitation energy becomes one of the most important functional material with near UV-emission, optical transparency, electric conductivity and piezoelectricity. ZnO nanoparticles were prepared by chemical method, using PVP as capping agent. The structure and morphology of the samples were investigated by X-ray diffraction and Scanning electron microscopy. X-ray diffraction revealed the wurtzite structure of ZnO. Percentage of lattice contraction and average particle size of the sample were also calculated from the XRD. SEM micrographs showed the spherical shape of ZnO nanoparticles. The UV-VIS absorption spectra showed blue shift in wavelength corresponding to bulk. Band gap energy of ZnO nanoparticles were determined from UV reflectance spectra and confirm quantum confinement. Keywords: ZnO nanoparticles. SEM, XRD, UV-VIS spectroscopy. INTRODUCTION Semiconductor compounds have drawn much attention during the last few years because of their novel optical and transport properties which have great potential for many optoelectronic applications. ZnO is a wide band gap semiconductor that displays high optical transparency and luminescent properties in the near ultra violet and the visible regions (Nunes et al. 1999). Due to these properties ZnO is a promising material for electronic and optoelectronic applications such as solar cells (anti-reflecting coating and transparent conducting materials), gas sensors, liquid crystal displays, heat mirrors, surface acoustic wave devices etc (Chopra 1983). The high exciton binding energy of ZnO (~ 60 meV) would allow for excitonic transitions even at room temperature, which could mean high radiative recombination efficiency for spontaneous emission as well as a lower threshold voltage for laser emission. Studies have been carried out to fine-tune the properties of ZnO to adopt it for different applications; for example, the band gap of ZnO is modified to use as UV detectors and
Department of Physics, S. B College, Changanassery, Kerala.686101, India. *Corresponding author: georgekalapura@gmail.com.

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ISSN: 0973-7464 Vol. XVI: No. 1 & 2 SB Academic Review 2009: 57-65

emitters. ZnO nanoparticles are widely employed in fundamental research and potential applications, such as hydrogen-storage, field emitters, ultraviolet lasers and diodes, piezoelectric devices and photo catalysts (Kim et al. 2000) fluorescence labels in medicine and biology, controlling units as UV photo detectors and as high-flame detectors (Chen et al. 2000) in cosmetic industry and as a component of sun screens (Zhang et al. 2002) Here, we report the synthesis of ZnO nanoparticles through chemical method, using PVP as capping agent. The structural and optical properties of the prepared ZnO particles have been confirmed using TEM, XRD and UV-VIS absorption spectroscopy. A model equation using the effective mass model (Brus 1986) has been developed in this work to calculate the particle size as a function of the peak absorbance wavelength. MATERIALS AND METHODS All the reagents used in the experiments were in analytical grade (purchased from Merck chemical Industrial company) and used without any further purification. The alkali solution of zinc was prepared by dissolving zinc nitrate [Zn (NO3)26H2O] and KOH in distilled water to form a 100 ml solution [Zn2+ =0.5M, OH =1.0 M]. Under constant stirring, the reaction solution was heated to 50oC temperature and keeping the PH 8. (Polyvinylpyrrollidone) PVP was used as capping agent. After few hours of reaction, the white precipitate deposited in the bottom of the flask was collected and washed it. Finally, the precipitate was centrifuged and dried at room temperature for 30 hours. The samples were stored at room temperature for measurements of optical absorption, and other structural properties. The morphology of the sample was examined by a Hitachi Model S-300H scanning electron microscope (SEM), whose maximum magnification is 300,000X and resolution is 3.5 nm. The crystal structure of the sample was characterized by Bruker A X S D8 Advance Xray diffractometer using CuK radiation. UV-VIS measurements were made by a T 90 + PG equipment UK spectrophotometer RESULTS AND DISCUSSION The morphology of the as prepared sample analyzed by SEM is shown in Fig.1. The SEM image demonstrates clearly the formation of spherical ZnO nanoparticles.

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ISSN: 0973-7464 Vol. XVI: No. 1 & 2 SB Academic Review 2009: 57-65

Fig. 1: SEM image of ZnO nanoparticles.

Fig 2 (a-c) shows the XRD pattern of the ZnO nanoparticles annealed at room temperature, 300C and 600C respectively. All of the diffraction pattern can be indexed to the hexagonal ZnO phase (Wurtzite Structure) by comparison with the data from JCPDS card 36-1451. However, the XRD patterns of the nanoparticles are considerably broadened due to the very small size of these particles. The strong and narrow diffraction peaks indicated that the product has good crystallinity. Fig 2 (a-c): Pattern of the ZnO nanoparticles annealed at room temperature, 300C and 600C

Fig 2 (a-c .XRD spectra of ZnO nanoparticles at (a) RT (b) 3000C (c) 6000C. Average particle size calculated using the Sherrers formula, L= 0.9 / cos (Cullity B.D, 2001) and lattice constant a of the hexagonal wrutzite sample calculated by equation a = d [(h + k + l)] 1/2 are tabulated in table 1. With increasing annealing temperatures, the diffraction peaks are sharpened and enhanced, thereby indicating that the particles have grown and the crystal quality has been improved. 63

ISSN: 0973-7464 Vol. XVI: No. 1 & 2 SB Academic Review 2009: 57-65

Table 1. Particle size and lattice constant of ZnO nanoparticles annealed at different temperatures.

From table 1 we can easily notice the relationships of the annealing temperature with the changes of particle size and lattice parameter. In ZnO nanoparticles, there are a large number of vacancies of oxygen, vacancy clusters, and local lattice disorders present in the interface , which lead to an increase in c and decreases in a 64

ISSN: 0973-7464 Vol. XVI: No. 1 & 2 SB Academic Review 2009: 57-65

and the volume of the unit cell. The low-temperature annealing can lead to a relaxation in the interface structure, but cannot dispel the local lattice disorders or change the internal structure of the nanograins, so there are no apparent changes in the positions and intensities of XRD peaks. When the annealing temperature increases there is a rapid decrease in the density of vacant lattice sites, vacancy clusters, and local lattice disorders and a rapid resumption of lattice parameters and the volume of the unit cell towards normal values, and the grains begin to grow .Hence particle size increases with increasing temperature and lattice constant 'a' decreases with increasing temperature. For a real crystal, the calculated values of 'a' and 'c' are the same based on different crystal planes. However, the presence of a large number of vacant lattice sites and local lattice disorders may lead to serious reduction in the intensity or even the nearly disappearance of the XRD peaks of the corresponding lattice plane. This is the reason for why (102) plane is absent in 300oC and 600oC. Table 2. Percentage variation of'd' values at room temperature. Observed 2 value 31.8615 34.5012 36.3441 47.5958 56.6276 62.8945 Observed d value 2.80644 2.59709 2.4060 1.90899 1.62409 1.47648 d value Standard % of contraction 0.279 0.239 0.241 0.112 0.040 0.043 (h k l) 100 002 101 102 110 103

2.81430 2.60332 2.47592 1.91114 1.62472 1.47712

Table 3. Percentage variation of 'd' values at 3000C . Observed 2 value 31.919 34.582 36.402 56.744 63.033 Observed Standard % of lattice

d value
2.80154 2.59164 2.46612 1.62103 1.47367

d value
2.81430 2.60332 2.47592 1.62472 1.47712

contraction
0.453 0.448 0.395 0.227 0.233

(h k l)
100 002 101 110 103

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ISSN: 0973-7464 Vol. XVI: No. 1 & 2 SB Academic Review 2009: 57-65

Table 4: Observed 2 value 31.891 34.553 36.368 47.687 56.717

Percentage variation of 'd' values at 6000C. Observed Standard % of lattices

d value
2.80388 2.59374 2.46836 1.90554 1.62174

d value
2.81430 2.60332 2.47592 1.9114 1.62472

contraction
0.370 0.367 0.305 0.306 0.184

(h k l)
100 002 101 110 103

Tables 2, 3 and 4 show the percentage of lattice contraction at different temperatures. The origin of the lattice relaxation (contraction or expansion) is due to the presence of dangling bonds in the surface layer of ZnO nanoparticles. The ions on the surface of ZnO nanoparticles are incompletely coordinated and possess the unpaired electron orbitals. Each of these dangling bonds (Zn + and O ions) forms an electric dipole resulting in a parallel array of dipoles originating in the boundary layer of each nanoparticle lies in this surface and experience a repulsive force. ZnO has the property of adsorbing Oand O ions in the surface; hence the repulsive inter dipolar force decreases and the attractive electrostatic interaction between Zn+ and O ions increases. Due to this electrostatic attraction lattice is slightly contracted Fig.3 represents the UV-VIS reflectance spectrum of ZnO nanoparticles. From which, we can calculate the band gap energy using Tauc relation. UV-VIS reflectance spectrum has less effect in scattering than absorption. The sudden decrease of reflectance at a particular wavelength, corresponding to the optical band gap means that the particles are almost uniformly distributed in the sample. Fig 3: Reflectance spectrum of ZnO nanoparticles.

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Fig 4: Band gap energy of ZnO nanoparticles.

The direct band gap energy (Eg) for the ZnO nanoparticles is determined by fitting the reflection data to the direct transition equation h=ED (h- Eg) , where is the optical absorption coefficient, h is the photon energy, Eg is the direct band gap and ED is a constant. Plotting (h) 2 as a function of photon energy and extrapolating the linear portion of the curve to absorption equal to zero gives the value of the direct band gap to be 3.4 eV .This value is higher than that of 3.3 eV reported in the literature (Berger et al. 1997). Band gap energy increases with decreasing particle size due to quantum size effects. Fig.5: Absorption spectrum of ZnO nanoparticles.

Fig. 5 shows the absorption spectrum of ZnO nanoparticles at different annealing temperatures. A typical exciton absorption at 362 nm is observed in the absorption spectrum at room temperature, which is blue shifted with respect to the bulk 67

ISSN: 0973-7464 Vol. XVI: No.1 & 2 SB Academic Review 2009: 57-65

absorption edge appearing at 380nm (Virendra et al. 2006) at room temperature. It is clear that the absorption edge systematically shifts to the lower wavelength or higher energy with decreasing size of the nanoparticle. This pronounced and systematic shift in the absorption edge is due to the quantum size effect. Thus the average particle size can be determined from the inflection point in the absorption vs. wavelength spectrum (Pesika 2003). The following Eqn. (1) derived using the effective mass model describe the particle size (r, radius) as a function of peak absorbance wavelength ( p) for monodispersed ZnO nanoparticles,

0.3049 + 26.23012 + r (nm) =

10240.72 p (nm) 2483.2 6.3829 + p (nm)

(1)

During the derivation of Eqn. (1), we have used me = 0.26 mo, mh = 0.59mo, mo is the free electron mass, = 8.5, and Egbulk = 3.3 eV. The prepared ZnO nanoparticles show peak absorbance at 362nm which corresponds to average particle size of 5-8 nm. Table 5. Determination of particle size from UV -VIS absorption spectrum. ZnO nano particle Annealed at Room temperature 300C 600C Peak absorbance wavelength 362 373 381 Particle size 2 r (nm) 4.74 5.84 7.42

Table 5. shows that the particle size increases with increasing temperature. As temperature increases, the peak absorbance wavelength become red shifted due to decreasing quantum confinement with increasing particle size.

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ISSN: 0973-7464 Vol. XVI: No.1 & 2 SB Academic Review 2009: 57-65

CONCLUSION In this work, we have reported the synthesis of ZnO nanoparticles by simple chemical method. The structural and optical properties of the prepared ZnO nanoparticles have been confirmed using TEM, XRD and UV-VIS spectroscopy. According to Scherer's formula, the average particle size of the sample is 16.3nm. Nanoparticle shows lattice contraction due to high attractive electrostatic interaction between Zn 2+ and O2- ions. Band gap energy of ZnO nanoparticle is 3.4eV, obtained from the UV-VIS reflectance spectra, which is higher than that of the bulk. Absorption peak of the prepared sample is 262nm which is highly blue shifted as compared to the bulk (360nm). Large band gap energy and highly blue shifted absorption edge confirm that the prepared ZnO nanoparticle exhibit strong quantum confinement effect. The average sizes of the sample have also been determined to be 5 to 8 nm from the peak absorbance wavelength and using the equation derived from the effective mass model. As temperature increases the particle size of the sample is found to be increases. REFERENCE
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