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Microelectronics Journal 40 (2009) 239241

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Microelectronics Journal
journal homepage: www.elsevier.com/locate/mejo

Optical properties of ZnO thin lms prepared by solgel process

J. Petersen a, C. Brimont a, M. Gallart a, O. Cregut a, G. Schmerber a, P. Gilliot a, B. Honerlage a, C. Ulhaq-Bouillet a, J.L. Rehspringer a, C. Leuvrey a, S. Colis a, A. Slaoui b, A. Dinia a,
a b

Institut de Physique et Chimie des Materiaux de Strasbourg, IPCMS UMR 7504 du CNRS, ULP-ECPM, 23 rue du Lss, B.P. 43, 67034 Strasbourg Cedex 2, France InESS-CNRS-ULP, 23 rue du Loess, B.P. 43, 67037 Strasbourg Cedex 2, France

a r t i c l e in fo
Available online 19 September 2008 Keywords: ZnO Photoluminescence Solgel Thin lm Excitons

abstract
The present study focused on ZnO thin lms fabricated by solgel process and spin coated onto Si (1 0 0) and quartz substrates. ZnO thin lms have a hexagonal wurtzite structure with a grain diameter about 50 nm. Optical properties were determined by photoluminescence (PL) and absorption spectroscopy. The absorption spectrum is dominated by a sharp excitonic peak at room and low temperatures. At room temperature, two transitions were observed by PL. One near to the prohibited energy band in ultraviolet (UV) region and the other centered at 640 nm, characteristic of the electronic defects in the band-gap. The spectrum at 6 K is dominated by donor-bound exciton lines and donoracceptor pair transition. LO-phonon replica and two-electron satellite transitions are also observed. These optical characteristics are a signature of high-quality thin lms. & 2008 Elsevier Ltd. All rights reserved.

1. Introduction ZnO is a direct wide band-gap semiconductor with Eg 3.37 eV (at room temperature) and a strong exciton binding energy of 60 meV [1] that allows efcient excitonic emission even at room temperature. It is a promising material for opto-electronic applications in the ultraviolet (UV) and visible regions. ZnO is a natural n-type semiconductor, chemically stable and environmentally friendly. ZnO thin lms show a versatile combination of interesting optical, electrical and magnetic properties. Consequently, this material plays a role in various technological domains such as solar cells [2], transparent conducting oxide thin lms/electrodes [3], diluted magnetic semiconductor [4,5], acoustic optical devices [6] and it has excellent piezoelectric properties [7]. Various methods have been used to prepare ZnO nanostructures such as molecular beam epitaxy (MBE) [8], magnetron sputtering [9], laser ablation [10], hydrothermal synthesis [11,12], co-precipitation [13], spray pyrolysis [14], metal-organic vaporphase epitaxy (MOVPE) [15] and solgel technique [16,17]. For a large use of ZnO thin lms for opto-electronic devices a better understanding of the relationship between the growth technique and optical properties is necessary. The optical properties of ZnO have been studied under different form of powders, thin lms, single crystals or nanostructures [18]. According to the literature, two transitions are usually observed on ZnO, one near to the

band-gap in the UV region at 370 nm and the other is a green luminescence band centered at about 500 nm. The origin of the green luminescence is still subject of debates but is generally assigned to the presence of ionized oxygen vacancies and zinc interstitial in ZnO matrix. In this study, we investigated optical properties of ZnO thin lm prepared by solgel process. This process is much cheaper and easier to use for growing ZnO thin lms with comparable optical properties like the above-mentioned much sophisticated techniques. We employed solgel technique and spin-coating to prepare ZnO thin lms on Si (1 0 0) and quartz substrates. Structural properties have been studied by X-ray diffraction (XRD). Films have the ZnO wurtzite structure with a preferential orientation along the c-axis and had no impurity phase. Photoluminescence (PL) and UVvisible measurements have been carried out to investigate the optical properties at room and low temperatures.

2. Experimental procedure ZnO thin lms were fabricated by zinc acetate (Zn(O2CCH3)2(H2O)2) with a concentration of 0.3 mol/l dissolved in n-propanol and glycerol, respectively. After stirring the solution for 45 min at 100 1C using a magnetic stirrer, a homogeneous and transparent solution was obtained. The substrates were pre-cleaned using acetone, ethanol and surface oxidation before the deposition of the lms. The lms were spin-coated on the substrate at 2000 rpm for 5 min, and then a heat treatment at 300 1C during 10 min was performed. We repeated three times this manipulation to

Corresponding author. Tel.: +33 3 88 10 70 67; fax: +33 3 88 10 72 49.

E-mail address: aziz.dinia@ipcms.u-strasbg.fr (A. Dinia). 0026-2692/$ - see front matter & 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.mejo.2008.07.061

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evaporate the organic components. Finally, we deposited a last layer with a heat treatment at 700 1C for 10 min, so to obtain the desired structure with a thickness of 180 nm. Nanocrystals structure and shape of ZnO thin lms were characterized by XRD using the monochromatic CuKa1 (l 1.54056 A) radiation and scanning electron microscopy (SEM). Room-temperature absorption properties of ZnO thin lm were investigated using a conventional UV spectrometer. Lowtemperature absorption was performed using a tungsten lamp and a spectrometer and recorded by a charge-coupled device (CCD) camera. PL was recorded using a YAG Laser with an excitation wavelength at 355 nm at room temperature. The PL signal from the samples is analyzed through the same detection system as the absorption signal. Low-temperature experiments have been performed at 6 K, on an Oxford MG11 device in which the sample was surrounded by cold gaseous helium. The temperature of the sample was thus precisely monitored and controlled, and any surface heating resulting from the optical excitation was immediately dissipated.

3. Results and discussion XRD pattern of ZnO thin lm on Si (1 0 0) substrate is shown in Fig. 1(a). The pattern shows diffraction peaks corresponding to the ZnO hexagonal wurtzite structure and the sample is polycrystalline. The fact that the (0 0 2) peak at 2y 34.451 is the most intense one, while it is expected to present half of the intensity of the (1 0 1) peak, indicates that the lms are oriented preferentially with the c-axis perpendicular to the lm plane. By means of the Scherrer formula on the peak (0 0 2), the average grain size of the nanocrystals has been determined to be 45 nm. Fig. 1(b) shows SEM image of nanocrystal thin lm on Si (1 0 0) substrate which reveals an homogeneous lm with a size of 50 nm in agreement with X-ray data. Fig. 2 displays the absorption and PL spectra, on the UV and visible ranges, at room temperature, of the ZnO lm deposited on quartz substrate. The absorption spectrum exhibits a sharp structure at 370 nm, which is characteristic of an excitonic absorption. The presence of this excitonic peak on the absorption spectrum reveals a good structural quality of the ZnO layer. On the PL spectrum, the peaks at 350 and 700 nm are the excitation lines from the laser and its second order. A sharp line at 379 nm is related to the recombination of free and shallow bound excitons. This line is accompanied by its second-order replica at 760 nm. We will focus thereafter on this UV emission and give a detailed analysis of its ne structure based on the low-temperature PL. In the visible range, a broad band is centered at 640 nm. Earlier work indicated that ZnO exhibited two PL bands centered on 510 and

640 nm, labeled green and yellow bands, respectively [19]. Here, only the yellow band is noticeable. Whereas the green band emission is commonly associated with the presence of ionized oxygen vacancies and zinc interstitial in ZnO matrix, orange luminescence was detected for ZnO samples with an excess of oxygen. For these reasons, the green and yellow bands cannot be observed simultaneously. We now focus our attention on the ne structure of the UV emission by performing low-temperature PL. Fig. 3 shows such spectrum for ZnO thin lm at low temperature. The high spectral resolution associated with the low temperature, allows resolving structures on the main PL line. The absorption spectrum, also taken at low temperatures, is also plotted for comparison. It exhibits an excitonic line at 3.374 eV. The full-width at halfmaximum (FWHM) of this peak, close to 20 meV, is larger than the expected energy splitting between A and B excitons [20]. Thus, the main absorption peak is certainly the sum of the contributions from the two excitons. On the PL spectrum, a small bump in the high-energy side of the spectrum is resonant with the maximum of the absorption spectrum. We attribute this line to recombination of free A excitons. Another line at 22 meV below the free exciton line, labeled D0X, is related to the recombination of exciton bound to a neutral donor. The line at 3.303 eV is rather broad and is probably the superposition of two components: as it lies 72 meV below the free exciton line, it includes the LO-phonon replica of the free exciton [21]. The second component is the twoelectron satellite (TES) of the D0X. TES are commonly observed in

Fig. 2. Absorption and PL spectra excited by YAG laser at 355 nm of ZnO on quartz substrate measured at room temperature.

700 600 Intensity (counts) 500 400 300 200 100 35 40 45 100 101 002

102

50

55

110

60

2 (degrees)
Fig. 1. XRD pattern (a) and SEM image (b) of ZnO thin lm fabricated by the solgel process.

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were observed too. In summary, using solgel process, we have grown ZnO thin lms with low default density and optical properties equivalent to those measured on samples grown by using more sophisticated techniques. References
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Fig. 3. Absorption and PL spectra of ZnO thin lm at 6 K excited at 351 nm by argon laser.

PL spectra of high-quality ZnO [22]. This emission peak is caused by the recombination of the donor-bound exciton leaving the donor in an excited state. Thus, the difference in energy between the D0X line and its TES is 3/4 the donor binding energy. In the present case, this energy difference is close to 50 meV, which corresponds to the value reported for the indium in ZnO [23].

4. Conclusion We have investigated the structural and optical properties of ZnO thin lms fabricated by solgel process. XRD pattern reveals that the compound is polycrystalline with a preferential orienta tion with the wurtzite c-axis perpendicular to the lm plane. The absorption spectrum is dominated, at low and room temperatures, by a strong excitonic line which is the overlap of A and B excitonic lines. The PL at room temperature shows an emission in the UV region at 3.271 eV (379 nm), dominated by free exciton recombination, and a broad visible emission centered at 1.937 eV (640 nm). The PL spectrum at 6 K is characteristic of good quality ZnO. It exhibits sharp peaks associated with the radiative recombination of free and donor-bound excitons. LOphonon replicas with characteristic energy of 72 meV and TES