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Journal of the Korean Physical Society, Vol. 55, No. 5, November 2009, pp.

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Structural, Optical, and Electronic Properties of ZnO Nanoparticles Formed on Al2 O3 Substrates by Using Spin Coating and Thermal Treatment
Dong Ick Son
Department of Information Display Engineering, Hanyang University, Seoul 133-791

Young Soo No, Su Youn Kim, Do Hyun Oh, Won Tae Kim and Tae Whan Kim
Department of Electronics and Computer Engineering, Hanyang University, Seoul 133-791 (Received 2 September 2008, in nal form 1 March 2009) ZnO nanoparticles were formed on Al2 O3 (0001) substrates by using a spin coating and thermal treatment method. Scanning electron microscopy images showed that ZnO nanoparticles were formed on the Al2 O3 substrates. X-ray diraction patterns showed that ZnO nanoparticles annealed at 350 and 450 C had a strong c-axis orientation and that those annealed at 550 C had various orientations. Photoluminescence spectra for the ZnO nanoparticles formed on Al2 O3 substrates showed that the dominant emission peak related to the band edge transitions was shifted to higher energy with increasing annealing temperature. X-ray photoelectron spectroscopy proles showed O 1s and the Zn 2p peaks corresponding to the ZnO nanoparticles.
PACS numbers: 78.55.Et, 78.66.Sq, 78.67.Bf Keywords: ZnO nanoparticle, Optical property, Structural property, Al2 O3 DOI: 10.3938/jkps.55.1973

I. INTRODUCTION Semiconductor nanoparticles have become particularly attractive because of interest in investigating their fundamental physical properties and their potential applications in many promising devices [15]. Because ZnO semiconductor materials are wide gap semiconductors with unique physical properties of large exciton binding energies and excellent chemical stabilities [6, 7], they are particularly interesting due to their potential applications in optoelectronic devices, such as light-emitting diodes [8], laser diodes [9], and solar cells [10]. In particular, ultraviolet lasers fabricated utilizing ZnO materials and operating at room temperature have emerged as potential candidates for potential applications in next-generation promising optoelectronic devices [1113]. Even though some works concerning ZnO nanoparticles formed on various substrates have been reported [1418], almost all of the reported materials have been formed by using molecular beam epitaxy, metalorganic chemical vapor deposition, pulsed laser deposition, and sputtering methods. Even though some studies on the formation and the physical properties of ZnO nanoparticles via a simple method have been performed [1921], systematic studies concerning the structural, the optical, and the electronic properties of ZnO nanoparti E-mail:

cles grown on Al2 O3 substrates by using spin coating and thermal treatment are still necessary to fabricate higheciency optoelectronic devices based on ZnO nanoparticles. Furthermore, investigations of the structural, the optical and the electronic properties of ZnO nanoparticles are very important for enhancing the eciency of optoelectronic devices operating in the blue and the ultraviolet regions of the spectrum. This paper reports data for the structural, the optical, and the electronic properties of ZnO nanoparticles formed on Al2 O3 substrates by using a spin-coating and thermal treatment method. Scanning electron microscopy (SEM) and X-ray diraction (XRD) measurements were carried out to investigate the surface and the structural properties of the ZnO nanoparticles. Photoluminescence (PL) measurements were performed to investigate the optical properties of the ZnO nanoparticles. X-ray photoelectron spectroscopy (XPS) measurements were carried out to study the electronic properties of the ZnO nanoparticles.

II. EXPERIMENTAL DETAILS The samples used in this work were formed on Al2 O3 (0001) substrates by using a spin coating and thermal treatment method. Zinc acetate dihydrate was used as a starting material, and a methanol solution was used

twk@hanyang.ac.kr; Fax: +82-2-2292-4135

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Journal of the Korean Physical Society, Vol. 55, No. 5, November 2009

as a solvent [22]. After the zinc acetate dihydrate had been dissolved in the methanol solution at 27 C, the saturated solution was stirred at 60 C for 1 h to obtain a clear and homogeneous solution. The prepared solution was dropped onto Al2 O3 substrates and then rotated by using a spin coater at 7000 rpm for 30 s. After the zinc acetate dihydrate had been deposited by spin coating, the samples were dried on a hot-plate for 10 min in order to remove the solvent and the organic residuals. The samples were annealed in an air atmosphere at 350, 450, or 550 C for 1 h. ZnO nanoparticles were formed from the vaporization of the acetate acid by the thermal treatment. The size of the ZnO nanoparticles could be controlled by changing annealing temperature. XRD patterns were measured by using a Rigaku D/MAX-B diractometer with Cu K radiation. The PL measurements were carried out using a 50-cm monochromator equipped with an RCA 31034 photomultiplier tube. The excitation source was the 3250- A line of a He-Cd laser, and the sample temperature was kept at 300 K. X-ray photoelectron spectroscopy (XPS) proles were measured by using an ESCALAB system, and the excitation source for the XPS proles was a Mg K X-ray source.

III. RESULTS AND DISCUSSION Figure 1 shows SEM images of ZnO nanoparticles formed on Al2 O3 substrates and annealed at (a) 350, (b) 450, and (c) 550 C. The SEM images show ZnO nanoparticles are formed on Al2 O3 substrates by using the spin-coating method and subsequently annealed at 350, 450, and 550 C for 1 h. The average diameters of the annealed ZnO nanoparticles formed on Al2 O3 substrates are between approximately 15 and 100 nm. The average diameter of the ZnO nanoparticles formed on Al2 O3 substrates increases with increasing annealing temperature due to the coalescence of the nanoparticles resulting from the higher thermal energy. Figure 2 shows XRD data for the ZnO nanoparticles on Al2 O3 substrates annealed at (a) 350, (b) 450, and (c) 550 C. The XRD curves for the ZnO nanoparticles on Al2 O3 substrates annealed at 350 and 450 C clearly show the (0002) K1 diraction peak corresponding to the ZnO (0001) nanoparticles, together with the (0006) diraction peak related to the Al2 O3 (0001) substrate. The intensity of the XRD pattern related to the ZnO (0001) nanoparticles for the ZnO/Al2 O3 heterostructures annealed at 450 C is larger than that for the samples annealed at 350 C, and the full width at half maximum for the (0002) ZnO diraction peak for the ZnO/Al2 O3 heterostructures annealed at 450 C is smaller than that for the samples annealed at 350 C. The XRD patterns for the ZnO nanoparticles formed on the Al2 O3 (0001) substrates annealed at 350 and 450 C indicate that the annealed ZnO nanoparticles have a

Fig. 1. Scanning electron microscopy images of ZnO nanoparticles formed on Al2 O3 substrates annealed at (a) 350, (b) 450, and (c) 550 C.

strong c-axis orientation. The relative intensity of the ZnO (0002) diraction peak signicantly increases with increasing annealing temperature up to 450 C, indicative of the c-axis enhancement of ZnO nanoparticles due to the increasing annealing temperature, as shown in Figures 2(a) and 2(b). However, the XRD curve for the ZnO nanoparticles on the Al2 O3 substrates annealed at 550 C shows that the (002), (101), and (100) K diraction peaks corresponding to the ZnO nanoparticles appear. The XRD curve for the ZnO nanoparticles on the Al2 O3 substrates annealed at 550 C shows that the ZnO nanoparticles have various orientations [23]. The signicant enhancement of the intensity which corresponds to the (002) K diraction peak with increasing annealing temperature is attributed to the smaller lattice matching between the ZnO nanoparticles and the Al2 O3 sub-

Structural, Optical, and Electronic Properties of Dong Ick Son et al.

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Fig. 2. X-ray diraction pattern of ZnO nanoparticles formed on Al2 O3 substrates annealed at (a) 350, (b) 450, and (c) 550 C.

Fig. 4. X-ray photoelectron spectroscopy (a) Zn and (b) O spectra of ZnO nanoparticles formed on Al2 O3 substrates. Fig. 3. Photoluminescence spectra at 10 K of ZnO nanoparticles formed on Al2 O3 substrates annealed at (a) 350, (b) 450, and (c) 550 C. Filled rectangles, circles, and triangles represent the samples annealed at 350, 450, and 550 C, respectively.

strates. The ZnO nanoparticles formed on the Al2 O3 substrates have a strong c-axis orientation, that orientation giving the lowest surface free energy [24]. Figure 3 shows that PL spectra at 300 K for the ZnO nanoparticles formed on the Al2 O3 substrates annealed at 350, 450, and 550 C. The dominant excitonic peaks were shifted to higher energy with increasing annealing temperature due to the quantum-connement effect resulting from the decrease in the size of the ZnO nanoparticles and due to the stress relaxation of the ZnO nanoparticles. The PL spectra for the ZnO nanoparticles on the Al2 O3 substrates annealed at 350, 450, and 550 C show two dominant emission peaks corresponding to the ZnO nanoparticles. The peak at 3.25 eV corresponds to the band-to-band transition, and the peak at 2.5 eV is related to the subband transitions. The PL emission peaks at lower energy correspond to zinc vacancies (VZn ) and to antisite defects (OZn ) [25, 26]. The PL peaks

corresponding to defects exist for the ZnO nanoparticles grown on the Al2 O3 substrates annealed at 350, 450, and 550 C, and those for the defects of the annealed samples do not disappear regardless of the increased annealing temperature. The PL intensities of the exciton peaks for the ZnO nanoparticles formed on Al2 O3 substrates signicantly increase with increasing annealing temperature, indicative of an improvement of the ZnO nanoparticles, which is in reasonable agreement with the XRD patterns. The PL spectra for the ZnO nanoparticles formed on Al2 O3 substrates annealed at 550 C reveal a dominant emission related to the band edge transition peak together with diused subband transition peaks. Figure 4 shows that XPS spectra for the ZnO nanoparticles formed on the Al2 O3 substrates annealed at 350 C. The XPS peaks at 1021.6 and 1043.7 eV correspond to the Zn 2p3/2 and Zn 2p1/2 , respectively, as shown in Figure 4(a) [27]. Since the O 1s peak for the XPS spectra is asymmetric, at least two oxygen species exist in the XPS spectra. The two oxygen species are separated by using Gaussian ts. The O 1s peak at 531.6 eV in the XPS spectra observed in Figure 4(b) is attributed to ox-

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ide ions in the ZnO crystal lattice [28]. The peak around 529.6 eV in Figure 4(b) is related to the Zn-O binding energy, and that peak corresponds to oxygen decient states of the ZnO nanoparticles [29]. When the annealing temperature of the materials is 350 C, the OH or watercovered ZnO nanoparticles might be negligible. When the stoichiometry of the samples is compared with that of ZnO powders, the nanoparticles are ZnO [15]. These results indicate that ZnO nanoparticles are formed on the Al2 O3 substrates.

IV. SUMMARY AND CONCLUSIONS The structural, optical, and electronic properties of ZnO nanoparticles formed on Al2 O3 substrates by utilizing a spin-coating and thermal treatment method were investigated. SEM images for the annealed samples showed that ZnO nanoparticles were formed on Al2 O3 substrates. XRD patterns showed that the ZnO nanoparticles annealed at 350 and 450 C had a strong c-axis orientation and that those annealed at 550 C had various orientations. The PL spectra for the ZnO nanoparticles on Al2 O3 substrates annealed at 450 and 550 C showed that dominant exciton peaks related to the near band emission peak were shifted to higher energy with increasing annealing temperature. XPS proles corresponding to the O 1s and the Zn 2p peaks of the ZnO nanoparticles were observed These results can help to improve understanding of the surface, the structural, and the optical properties of ZnO nanoparticles formed on Al2 O3 substrates by using a spin coating and thermal treatment method.

ACKNOWLEDGMENTS This work was supported by the Korea Science and Engineering Foundation (KOSEF) grant funded by the Korea government (MEST) (No. R0A-2007-000-200440).

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