International Journal of NanoScience and Nanotechnology ISSN 0974 3081 Volume 1, Number 1-2 (2009), pp.

81-90 International Research Publications House http://www.irphouse.com/sci/ijnn.htm

Visible Emission from ZnO Nanorods Synthesized by a Simple Wet Chemical Method
P. K. Samanta*, S. K. Patra, A. Ghosh and P. Roy Chaudhuri Department of Physics& Meteorology, Indian Institute of Technology, Kharagpur *Corresponding author E-mail: pijush.samanta@gmail.com Abstract In this article, we report our investigation results of a strong visible emission from ZnO nanorods fabricated by us using a template-free aqueous solution based simple chemical route. Through repeated fabrication and characterization studies, the emission around 421 nm (violet) from the prepared nanorods is established. Attributed to the recombination of electron at Zn interstitial and a hole in the valance band, this emission is accompanying those caused by few weaker defect states emissions owing to several oxygen vacancies. This result has been further confirmed from the Raman shift measurements. UV-visible spectroscopy was also carried out for further studies of the optical properties of the nanorods. Our investigation, focused around this visible emission, therefore, makes useful contribution to the ZnO nanostructure studies, and can be used to explore potentials applications in luminescence, lasing, nano-photonic and optoelectronic devices. Key Words: ZnO nanorods; visible emission; photoluminescence; wet chemical method

Introduction
ZnO based nanostructure research has drawn considerable attention in the last few years as a multi-functional material due to its versatile properties like near UV [1] and visible (green [2], blue [3] and violet [4]) emission, optical transparency [5], electrical conductivity [6], piezoelectricity [7] and many others promising applications in electroacoustic transducers, gas sensors, transparent conducting coating materials, photovoltaic devices and optical solar cells [8]. With its wide band gap of 3.37 eV at room temperature and a large exiton bonding energy of 60 meV, it is being extensively investigated due to its short-wavelength light emitting, and room temperature ultraviolet lasing [9]. In this front, various ZnO nanostructures have been

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fabricated and their photoluminescence were studied by many researchers. The emission peak in the UV range that originates due to the band edge transition or the exciton transition is the characteristic emission for zinc oxide. But researchers had also shown the visible emissions from nanostructured ZnO that mainly originate from different defect states (several oxygen vacancies, Zn interstitials etc.) of ZnO. However, these emissions from ZnO depend highly on the shape and size of the nanostructures which indeed owe much to the technique in general, and the process variables, in particular, of fabrication. Low dimensional nanostructures are now being extensively explored for applications in advanced devices. Various methods such as chemical vapour deposition [10], laser ablation [11], vacuum arc deposition [12], sputtering [13], and hydrothermal process [14, 15] have already appeared in the literature to have been implemented for synthesizing ZnO nanostructures. But mostly these fabrication techniques appear to be involved process with many complex steps, require sophisticated equipments and rigorous experimental conditions. Therefore, it is important to develop a simple method to synthesize ZnO nanorods in laboratory environment with a view to characterizing such structures for a wide range of applications through repeated fabrication and modification. The wet chemical method provides a better route to fabricate multi-dimensional nanostructures in a large scale. It is an inexpensive technique which does not involve complicated processing or huge infrastructures/sophisticated equipments as needed in physical or chemical vapour deposition, pulsed laser deposition, molecular beam epitaxy. Furthermore, the fabrication based on this table-top experimental setup provides repeated preparation that enables one to varying the process conditions for an investigational study and repeatability in the yield. In our attempt, we have succeeded in realizing ZnO nanorods grown at room temperature that show strong emission in the visible window. In the following sections, we outline our experimental approach towards growing of a few targeted nanostructures followed by some typical characterization results of our experiments. We also discuss the possible growth mechanism of these ZnO-structures in the relevance of the chemical route of fabrication.

Experimental
Preparation of nanorods As an initial attempt, we started with the well-known basic fabrication technique as reported by Wu et al [16] and followed quantitatively almost the similar type of recipe. But the difference is that we have done our fabrication process at room temperature. So maintenance of a constant higher temperature is not required which makes the process much simpler. All the reagents we used were of analytical grade (MERCK) that did not necessitate any more purification. Under constant stirring of NaOH solution (1M) at room temperature, zinc nitrate solution of 0.5M was added dropwise for 15 min. Stirring was continued for 3 hours till a white precipitate deposited at the bottom of the flask. The precipitate was then filtered and washed 2-3 times with distilled water. Then the powdered sample was dried at 600C in a furnace for further characterizations. With this basic recipe, we then varied the key process parameters to provide different fabrication conditions in order to grow different

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structural yields. The resulting nano-powders were characterized repeatedly for studying their optical luminescence properties. Characterizations of the nanorods The X-ray diffraction data were collected on a RIGAKU diffractometer using Cu Kradiation over an angular range 200< 2<600. The morphology of the sample was observed in field emission scanning electron microscopy (FESEM) using ZEISS scanning electron microscope. Transmission Electron microscopy was carried out in a JEOL JEM-2100F microscope with the accelerating voltage of 200 kV. For TEM study a very small amount of the powder sample was first dispersed in acetone by ultra-sonication. A drop of that solution was taken on a carbon coated grid for TEM imaging. The room temperature PL spectrum was recorded in PERKIN ELMER LS55 with a Xenon lamp with the excitations of 275 nm, 300 nm and 325nm. Reinshaw Raman System: RM-1000B (coupled with LEICA microscope DMLM) was deployed to carry out the Raman shift measurement of the sample. As the excitation source, a 20mW Argon ion laser was used which operated at 514nm wavelength using an edge filter of 200/cm as cut-off. UV-visible absorption data of the sample was collected in Perkin-Elmer Lambda-45 spectrophotometer in the wavelength range 380-800 nm to study further the optical absorption.

Results and Discussions

X-ray diffraction A typical XRD pattern of the prepared nanorods (powders) is shown in figure 1. The pattern is indexed with hexagonal unit cell structure (JCPDS card no.36-1451). We also compare the observed relative peak intensities to that of their standard values (see table-1).There is a small difference in the relative peak intensities of the (100) to (002) as observed in our case imply that the ZnO nanorods fabricated by different methods exhibit different preferred orientations. Further more no impurities were found in the XRD pattern. Also the diffraction peaks are intensive and very sharp. Thus high purity hexagonal ZnO nanocrystals could be obtained by this synthesis process. Field emission scanning electron microscopy Figure 2 shows the morphology of the as prepared ZnO nanorods. It reveals the most striking feature of the as obtained product is ZnO nanorods. The powder contains ZnO nanorods of diameter ~30-50 nm and length ~ (100-150) nm. We have taken the FESEM images from different region of the distributed sample and it was observed that the rods are randomly distributed in the powder sample and gathered together. Growth mechanism The growth mechanism has been proposed by several researchers according to the condition of the experiments [17, 18]. In the context of our synthesis, we depict the mechanism of ZnO nanorod formation as follows: When zinc nitrate solution is added with the NaOH solution under constant stirring it produces Zn(OH)2 colloidal

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particles. During the hydrothermal decomposition, a part of this colloidal Zn(OH)2 dissolves into Zn2+ and OH- and it continues further to form Zn(OH)42-. When their concentration reaches to the degree of supersaturation, ZnO nuclei form. The basic reactions are: Zn( NO3 ) 2 .6 H 2O + 2 NaOH = Zn(OH ) 2 + 2 NaNO3 + 6 H 2O
+ Zn(OH ) 2 + 2 H 2O = Zn 2+ + 2OH + 2 H 2O = Zn(OH ) 2 4 + 2H

Zn(OH ) 2 4 = ZnO + H 2O + 2OH

Transmission electron microscopy study Further studies on the structure of the ZnO nanorods were done using transmission electron microscopy. Figure 3(A-C) shows the TEM image of the fabricated nanorods. The length of the nanorods varies from 100-200 nm and their diameters lies between 20-40 nm. The corresponding selected area electron diffraction (SAED) pattern is also shown in figure 3D, which reveals the single crystalline nature of the nanorods. Raman shift measurement Nanocrystals or quantum dots, produced by chemical methods, normally have more defects than corresponding bulk crystals. Raman spectra of such nanocrystalline semiconductors are red shifted and broadened due to the relaxation of the selection rule for the q-vector (conservation of crystal momentum) due to small crystallite size of the nanocrystals. The phonon uncertainty roughly goes as q ~ 1/d, d being the diameter of the nanocrystals [19]. The phonon scattering will not be limited to the center of the Brillouin zone and phonon dispersion near the center of the Brillouin zone should be taken into consideration .Thus, symmetry forbidden modes will also be observed along with the shifting and broadening of the first-order optical phonon scattering modes. ZnO has hexagonal wurtzite structure which falls in the space group C46v with two formula units per primitive cell and the Raman- active modes predicted by the group theory for wurtzite ZnO are A1 + 2E2 +E1 . The polar modes A1 and E1 can split into transverse optical (TO) and longitudinal optical (LO) modes. The nonpolar E2 mode is composed of two modes with a low and high frequency. Figure 4 shows the Raman spectra of the ZnO nanorods. Three prominent vibration peaks are observed at 334, 441 and 583 cm-1. The peak at 583 cm-1, positioned between A1 (LO) and E1 (LO) optical phonon mode can be attributed to the oxygen deficiency. It is in good agreement with the theoretical calculations of Fonoberov and Balandin [20]. The peak at 441cm-1 corresponds to the nonpolar E2 optical phonon mode. The 334 cm-1 peak is attributed to the second order Raman process and is assigned to the 2E2 mode. The strong intensity of this peak reveals that the ZnO nanorods grown at room temperature have several oxygen deficiencies. No TO phonons are observed in the nonresonant Raman spectrum of the grown ZnO nanorods. Photoluminescence Spectroscopy Room temperature photoluminescence (PL) was recorded with the excitation wavelengths of 275 nm, 300 nm and 325nm respectively. In figure 5 the strong

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emission peak around 421nm can be assigned to the recombination of an electron at zinc interstitial and a hole in the valance band. Some other peaks are also observed at 406nm (3.05eV), 456nm (2.72eV), 485nm (2.59eV), and 527nm (2.35eV) which are attributed to different defect state emissions. Vanheusden et al [2] had reported that the visible luminescence of ZnO mainly originates from different defect states such as oxygen vacancies and Zn interstitials. Oxygen, in general, exhibit three types of charge states of oxygen vacancies such as Vo0, Vo+, and Vo2+. The oxygen vacancies are located below the bottom of the conduction band (CB) in the sequence of Vo0, Vo+, and Vo2+, from top to bottom. The peak around 527 nm can be related to singly ionised oxygen vacancy. The green emission is the results of the recombination of a photogenerated hole with a singly ionised charged state of the specific defect. Shallow acceptor levels are created at 0.3eV and 0.4eV above the top of the valance band (VB) due to zinc vacancy (VZn) and oxygen interstitial (Oi) respectively. Again, Zinc interstitial (Zni) produces a shallow donor level at 0.5ev below the bottom of CB [21, 22, 23]. The positions of different defect levels are schematically shown in figure 6. From figure 6, the emission at 421nm can be assigned to the recombination of an electron at Zni and a hole in the VB. We also observed that the PL intensity decreases with the increase of the excitation wavelength. The peak positions were almost same but a very small blue-shift was observed which may be resulting due to the polydispersity in the shape of the tips of the nanorods.
UV-visible spectroscopy UV-visible spectroscopy was carried out to study further the optical property of the nanorods. The room temperature UV-absorption spectra of the ZnO nanorods dispersed in tetrahydrofuran is shown in figure 7. It shows a prominent exciton band at 382 nm corresponds to the ZnO nanostructures. This absorption peak is red shifted as compared to the bulk exciton absorption of ZnO (373 nm) [22] which is due to the size effect of the nanostructures. This absorption in the visible range of wavelength implies that there exist more defect energy levels in the synthesized ZnO nanostructures that are due to the specific experimental synthesis conditions. Table 1: Comparison of the X-ray diffraction peak intensities of the standard JCPDS data and the observed data. XRD peak (hkl) (100) (002) (101) (102) (110) 2 (degree) from JCPDS 31.770 34.422 36.253 47.539 56.603 2 (degree) observed 31.811 34.495 36.307 47.501 56.565 Intensity from JCPDS 57 44 100 23 32 Intensity observed 61.95 68.84 100 30.63 47.67

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Intensity (a.u.)

(100)

(002)

(101)

20

30

40

(102)

50

(110)
60

2 (degree)

Figure 1: X-ray diffraction of the ZnO nanorods prepared at room temperature.

Figure 2: Field emission scanning electron microscopy image of the ZnO nanorods.

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Figure 3: (a)Transmission microscope image of the grown nanorods. (b) The SAED pattern of the nanorods.

441

Intensity (a.u.)

583 334

300

400

500

600
-1

700

Raman Shift (cm )

Figure 4: Raman scattering spectrum of the ZnO nanorods grown at room temperature.

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300

250

421

----- 275 nm ___ 300 nm -ooo- 325 nm

Intensity(a.u.)

200

150

485

100

527

50 400 450 500 550

Wavelength(nm)

Figure 5: Room temperature photoluminescence spectrum of the ZnO nanorods.

Figure 6: A schematic illustration of different defect levels of ZnO [22].

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3.0 381 2.8

Absorbance (a.u.)

2.6

2.4

2.2

2.0 400 450 500

Wavelength (nm)
Figure 7: UV-visible absorption spectroscopy of the nanorods.

Conclusions
We report here the implementation of chemical reaction based nanostructure fabrication method in the laboratory atmosphere with extensive studies to achieve repeatability and structure optimization. This approach offered producing a large quantity of ZnO nanorods at relatively high purity and with very low cost. We discuss here in this occasion a possible formation mechanism of these structures. An important observation is that, ZnO nanorods have a very strong photoluminescence (PL) band at visible range accompanied by few weaker defect states emissions which agrees well the measurements from Raman spectroscopy. Further studies on the optical properties of the nanorods agree well with the standard reported data. Thus our experimental nanostructure studies would help exploring more potential applications in luminescent, nano-photonic and optoelectronic devices.

Acknowledgements
The authors sincerely acknowledge IIT Kharagpur for providing research facilities. Two of the authors, P. K. Samanta, S. K. Patra sincerely acknowledge University

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Grant Commission (UGC), Govt. of India and Council of scientific & Industrial Research (CSIR) respectively for the financial support to carryout this work.

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