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Journal of Crystal Growth 289 (2006) 102106 www.elsevier.com/locate/jcrysgro

Synthesis and optical properties of nanocrystalline ZnO powders by a simple method using zinc acetate dihydrate and poly(vinyl pyrrolidone)
Santi Maensiria,, Paveena Laokula, Vinich Promarakb
b

Department of Physics, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand Department of Chemistry, Faculty of Science, Ubon Ratchathani University, Varinchamrap, Ubon Ratchathani 34190, Thailand Received 7 September 2005; accepted 21 October 2005 Available online 5 January 2006 Communicated by D.P. Norton

Abstract This paper reports the synthesis and characterization of nanocrystalline ZnO powders by a simple method using zinc acetate dihydrate and polyvinyl pyrrolidone (PVP) as a chelating agent. The polymeric precursor was characterized by TG-DTA to determine the thermal decomposition and crystallization temperature which was found to be at 600 1C. The precursor was calcined at 600 1C for 1 h to obtain nanocrystalline ZnO powders. The morphology and crystalline size of the calcined powders characterized by SEM and TEM revealed that the powders consisted of the mixture of nanoparticles with particle sizes of $50100 nm and nanorods with diameters of $100200 nm and 200500 nm in length. The XRD and FTIR results indicated that the synthesized ZnO powders had the pure wurtzite structure with lattice parameters a and c of 0.3234470.00058 and 0.5184370.00211 nm, respectively. The synthesized powders exhibited the UV absorption at around 2.99 eV with the estimated direct bandgap (Eg) of 3.10 eV. Room temperature photoluminescence spectrum of the powders showed a strong UV emission band at $2.98 eV, a weak blue band at 2.82 eV, a week bluegreen band at 2.56 eV, and a weak green band at 2.34 eV, which indicated their high structural and optical quality. r 2005 Elsevier B.V. All rights reserved.
Keywords: A1. Characterization; A1. Crystal structure; A2. Growth from solutions; B1. Nanomaterials; B1. Zinc compounds; B2. Semiconducting IIVI materials

1. Introduction Zinc oxide (ZnO), a representative IIVI compound semiconductor, has attracted considerable attention over the last few years. Its many attractive properties, such as the direct wide bandgap (3.37 eV), large exciton binding energy (60 meV at room temperature), good piezoelectric characteristics, chemical stability and biocompatibility, suggest a host of possible practical applications, notably in the area of ultraviolet/blue emission devices [18]. So far, nanocrystalline ZnO with different particle morphologies and sizes have been obtained by several preparation approaches including thermal decomposition, vapor chemical deposition, solgel method, wet chemical synthesis, mechanochemical, electrodeposition, gas-phase reaction, hydrothermal synthesis and so
Corresponding author. Tel.: +66 43 2022229x2248; fax: +66 43 202374. E-mail address: sanmae@kku.ac.th (S. Maensiri).

on. An excellent review of recent progress on processing, properties and applications of ZnO was recently published elsewhere [9]. Among other established synthesis methods, simple and cost effective routes to synthesize nanocrystalline ZnO by utilization of cheap, nontoxic and environmentally benign precursors are still the key issues. In this paper, we report the synthesis and optical properties of nanocrystalline ZnO powders prepared by a simple method using zinc acetate dihydrate and polyvinyl pyrrolidone (PVP) as a chelating agent. The synthesized powders were characterized by TG-DTA, XRD, FT-IR, UV-VIS, SEM, and TEM. The photoluminescence properties of the powders were also investigated. 2. Experimental procedure In this study, zinc acetate dihydrate (Fluka, X99.5%) and PVP (M n 1 300 000, Aldrich) were used as the

0022-0248/$ - see front matter r 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.jcrysgro.2005.10.145

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starting chemicals. In a typical procedure, 7.5 g of PVP was rst dissolved into 500 ml de-ionized water under vigorous stir on hot plate stirrer (CERAMAC, Midi, USA) at 27 1C for 30 min. Subsequently, 5 g of zinc acetate was added to the PVP solution under vigorous stir at 60 1C for 30 min to obtain a well-dissolved solution. Then, the solution was evaporated by heating in water bath of 60 1C for a week to remove the water. The resulting solid precursor was dried in oven at 100 1C for 2 h. Finally, the dried precursor was calcined in box-furnace (Lenton, UK) at 600 1C for 1 h in air. The heating and cooling rate were 5 1C/min. The calcined precursor was ground and passed through 105 mm sieve to break up large agglomerates. The nal products obtained were white nanocrystalline powders. The as-synthesized ZnO nanoparticles were characterized by means of thermogravimetric-differential thermal analysis (TG-DTA) (Pyris Diamond TG-DTA, PerkinElmer Instrument, USA), The ne calcined particles were characterized for crystal phase identication by powder Xray diffraction (XRD) using a Philips X-ray diffractometer (PW3040, The Netherlands) with CuKa radiation l 0:15406 nm. Fourier transmission infared (FT-IR) spectra of the powders (as pellets in KBr) were recorded using a Fourier transmission infrared spectrometer (Spectrum One FT-IR Spectrometer, Perkin Elmer Instrument, USA) in the range of 4000400 cm1 with a resolution of 1 cm1. The optical absorption spectra were measured in the range of 200800 nm using a UV-3101PC UV-VIS-NIR scanning spectrometer (Shimadzu, Japan). The particle size and external morphology of the ne calcined powders were characterized by scanning electron microscopy, SEM (LEO SEM 1450VP, UK) and transmission electron microscopy, TEM (JEOL JEM 2010, Japan). Photoluminescence measurement was carried out on a luminescence spectrometer (PerkinElmer LS-55B, PerkinElmer Instrument, USA) using a Xenon lamp as the excitation source at room temperature. The sample was dispersed in dichloromethane and the excitation wavelength used in photo luminescence (PL) measurement was 325 nm. 3. Results and discussion The TG curve in Fig. 1 shows a major weight loss step from 400 up to about 550 1C with no further weight loss observed up to 1000 1C. The weight loss is related to the combustion of organic matrix. The clear plateau formed between 550 and 1000 1C on the TG curve indicates the formation of nanocrystalline ZnO as decomposition product, as conrmed by XRD and FT-IR analysis shown in Figs. 1 and 2. On the DTA curve (Fig. 1) a main exothermic effect was observed between 400 and 600 1C with a maximum at about 500 1C, indicating that the thermal events can be associated with the burnout of organic species involved in the precursor powders (organic mass remained from PVP), of the residual carbon or due to direct crystallization of nanocrystalline ZCO from the amorphous component. No further weight loss and no

30 20 10

-20 Weight Loss (%) -40

0 -60 -10 -80 -100 200 400 600 Temperature (C) 800 -20 -30 1000

Fig. 1. TG-DTA curves of thermal decomposition of nanocrystalline ZnO powder precursor at a heating rate of 15 1C/min in static air.

Intensity (a.u.)

(100) (002)

(101)

(110)

(103)

(112) (201) (004)

(102)

(200)

30

40

50 2 (degree)

60

70

(202) 80

Fig. 2. XRD patterns of nanocrystalline ZnO powders calcined in air at 600 1C for 1 h.

thermal effect were observed above 550 1C, indicating that no decomposition occurs above this temperature. XRD patterns of the calcined ZnO powders in Fig. 2 show typical peak patterns, which can be indexed as the ZnO wurtzite structure in the standard data (JCPDS, 361451). The wurtzite lattice parameters a and c calculated from the XRD spectra for the ZnO powders are a 0:32344 0:00058 nm and c 0:51843 0:00211 nm, and are close to those of lattice constants a 0:32488 nm and c 0:52066 nm in the standard data (JCPDS, 36-1451). The crystallite sizes of the powders were estimated from Xray line broadening using Scherrers equation [10] (i.e. D 0:89l=b cos y, where l is the wavelength of the Xray radiation, K is a constant taken as 0.89, y is the diffraction angle. b is the full width at half maximum (FWHM)), and were obtained to be 51721 nm.

DTA

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The formation of ZnO wurtzite structure in the synthesized ZnO powders was further supported by FTIR spectra as shown in Fig. 3. The FTIR spectra show main absorption bands at $3400, $2900, $1380 and 1600 cm1, which correspond to the OH mode, CH mode, and asymmetric and symmetric CQO stretching modes of zinc acetate, respectively. The absorption band at $490 cm1 is the stretching mode of ZnO [1113]. The morphology of the nanocrystalline ZnO powders as revealed by SEM (Fig. 4(a)) shows the mixture of nanoparticles with particle sizes of $50100 nm and nanorods with diameters of $100200 nm and 200500 nm in length. The morphology and structure of the powders were further investigated by TEM. It is clearly seen from the TEM bright eld image (Fig. 4(b)) that the ZnO powders consist of both nanoparticles and nanorods as seen in the SEM. The corresponding selected-area electron diffraction (SAED) pattern (Fig. 4(b)) of the ZnO powders shows spotty rings pattern without any additional diffraction spots and rings of second phases, revealing their highly crystalline ZnO wurtzite structure. According to the diffraction patterns in Fig. 4(b), lattice constants measured agree with those of (1 0 2), (1 1 0), (1 0 3), (0 0 4) and (2 0 2) planes in the XRD results and the standard data (JCPDS, 36-1451). The UV-VIS absorption spectrum of the nanocrystalline ZnO powders is shown in Fig. 5. The ZnO powders show a strong absorption below 400 nm (3.10 eV) with a welldened absorbance peak at around 300 nm (4.14 eV). The band edge for the ZnO sample appears at $415 nm (2.99 eV). The direct bandgap energy (Eg) for the ZnO powders is determined by tting the absorption data to the direct transition equation: ahn E D hn E g 1=2 , (1)

Fig. 4. Electron microscopy images of nanocrystalline ZnO powders calcined in air at 600 1C for 1 h: (a) SEM secondary electron image; (b) TEM bright eld image with corresponding selected-area electron diffraction (SAED) patterns.

where a is the optical absorption coefcient, hn is the

Transmittance (a.u)

C-H CO2 O-H

C=O

Absorbance (a.u.)

(h)2 a.u. 2

3 4 5 Photon Energy (eV)

Zn-O 200 4000 3500 3000 2500 2000 1500 Wavenumber (cm-1) 1000 500
Fig. 5. Room temperature optical absorbance spectra of nanocrystalline ZnO powders calcined in air at different temperatures for 1 h. The inset shows plot of (ahn)2 as a function of photon energy, Eg, for the ZnO powders.

300

400

500 600 Wavelength (nm)

700

800

Fig. 3. FT-IR spectra of nanocrystalline ZnO powders calcined in air at 600 1C for 1 h.

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photon energy, Eg is the direct bandgap, and ED is a constant [14]. Plotting (ahn)2 as a function of photon energy, and extrapolating the linear portion of the curve to absorption equal to zero as shown in the inset of Fig. 5, gives the value of the direct bandgap (Eg) to be 3.10 eV. This value is lower than that of $3.37 eV reported in literature [1]. The difference in the bandgap values ranging from 3.1 to 3.3 eV is one of the curious features of the literature on ZnO. Srikant and Clarke [15] investigated the optical bandgap of ZnO single crystals at room temperature using a variety of optical techniques (i.e. conventional reection and transmission absorption measurement, spectroscopic ellipsometry, Fourier transform infared spectroscopy and photoluminescence) and reported three different Eg values of 3.1, 3.2 and 3.3 eV. They concluded that the room temperature bandgap of ZnO was 3.3 eV, whereas the reports of an apparent bandgap at 3.1 and 3.2 eV were due to the existence of a valence band-donor transition at 3.15 eV which can dominate the absorption spectrum when the bulk, as distinct from the surface, of a single crystal is probed. Therefore, the low value bandgap of 3.10 eV in our ZnO sample may be resulted from the presence of single crystal ZnO nanorods in the powders. Room temperature PL spectrum of the nanocrystalline ZnO powders measured using an Xenon laser of 325 nm as excitation source is shown in Fig. 6. The spectrum of the ZnO powders mainly consists of four emission bands: a strong UV emission band at $416 nm (2.98 eV), a weak blue band at $440 nm (2.82 eV), a week bluegreen band at 485 nm (2.56 eV), and a green band at 530 nm (2.34 eV). The strong UV emission corresponds to the exciton recombination related near-band edge emission of ZnO [1619]. The weak blue and weak bluegreen emissions are

possibly due to surface defect in the ZnO powders as in the case of ZnO nanowires reported by Wang and Gao [20]. The week green band emission corresponds to the singly ionized oxygen vacancy in ZnO, and this emission results from the recombination of a photo-generated hole with the singly ionized charge state of the specic defect [2123]. The low intensity of the green emission may be due to the low density of oxygen vacancies during the preparation of the ZnO powders, whereas the strong room temperature UV emission intensity should be attributed to the high purity with perfect crystallinity of the synthesized ZnO powders. 4. Conclusion Nanocrystalline ZnO powders have been synthesized by a simple method using Zn acetate and PVP. The XRD patterns and FTIR spectra suggested the formation of wurtzite nanocrystals in the synthesized powders after calcination the precursor at 600 1C for 1 h. The powders consisted of the mixture of nanoparticles with particle sizes of $50100 nm and nanorods with diameters of $100200 nm and 200500 nm in length, obtained by SEM and TEM. The synthesized powders exhibited the UV absorption below 2.99 eV and the direct bandgap (Eg) was determined to be 3.10 eV. The powders also exhibited room temperature PL, having a strong UV emission band at $2.98 eV, a weak blue band at 2.82 eV, a week bluegreen band at 2.56 eV, and a weak green band at 2.34 eV. The strong UV emission with weak green emission which is typically associated with defects indicates very good crystal quality of the synthesized ZnO powders. The current simple synthesis method using cheap precursors can be extended to prepare nanocrystalline powders of other interesting metal oxide powders. Acknowledgments The authors would like to thank the Department of Chemistry for providing TG-DTA and FTIR facilities, the Faculty of Science Electron Microscopy Unit for providing SEM facilities, and the Science and Technology Service Center (Chiang Mai University) for providing TEM facilities. This work is supported by the Postgraduate Education Development (PED) in Physics Program, The Commission on Higher Education, The Ministry of Education, Thailand.

3.55 eV

3.10 eV 416 nm

2.67 eV

2.48 eV

2.26 eV

2.07 eV

440 nm

Intensity (a.u.)

485 nm

530 nm

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350

400

450 500 Wavelength (nm)

550

600

Fig. 6. Room temperature photoluminescence spectra of the synthesized nanocrystalline ZnO powders under 325 nm light excitation.

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