Vacuum 64 (2002) 233236

Characterization of aluminium doped zinc oxide thin lms deposited on polymeric substrates
E. Fortunato*, P. Nunes, D. Costa, D. Brida, I. Ferreira, R. Martins
Department of Materials Science/CENIMAT, Faculty of Sciences and Technology, New University of Lisbon and CEMOP-UNINOVA, Quinta da Torre, 2829-516 Caparica, Portugal

Abstract We report, for the rst time, results on transparent ZnO : Al thin lms deposited on polyester (Mylar type D, 100 mm thickness) substrates at room temperature by magnetron sputtering. The structural, optical and electrical properties of the deposited lms have been studied. The samples are polycrystalline with a hexagonal wurtzite structure and a strong crystallographic c-axis orientation (0 0 2) perpendicular to the substrate surface. The ZnO : Al thin lms with 83% transmittance in the visible region and a resistivity as low as 3.6 102 O cm have been obtained, as deposited. The obtained results are comparable to those obtained on glass substrates, opening a new eld of low cost, light weight, small volume, exible and unbreakable large area optoelectronic devices. r 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Zinc oxide; Thin lm; Polyester; Mylar; Magnetron sputtering

1. Introduction One of the main failure mechanisms of laptop computers, cellular phones, active matrix liquid crystal displays and similar portable devices is the breakage of the glass of the display. To solve this problem much research eorts are focused on the fabrication of thin lm electronic devices on plastic substrates to replace the glass, making these devices exible, lightweight and unbreakable. In this paper we present for the rst time results on transparent conducting zinc oxide doped with aluminium (ZnO : Al) deposited by rf magnetron sputtering at room temperature on polyester substrates. Although this oxide has been exten-

sively studied on glass substrates [1], no detailed work has been reported on polymeric/organic substrates. The lms grown under dierent rf powers were characterised by X-ray diraction (XRD), scanning electron microscope (SEM), Hall eect measurements and optical transmittance. In order to compare the results, the same lm was also deposited on a glass substrate, taken as reference. The overall properties of the produced lms are comparable with that of the lms deposited on glass substrates, which make them a good candidate for large area optoelectronic applications.

2. Experimental details
*Corresponding author. Tel.: +351-21-2948562; fax: +35121-2948558. E-mail address: emf@mail.fct.unl.pt (E. Fortunato).

The substrates used in this work are polyester (Mylar type D [2]) foils from Dupont with a

0042-207X/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 0 4 2 - 2 0 7 X ( 0 1 ) 0 0 3 1 9 - 0

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thickness of 100 mm. The main reason for choosing such polymer is that it presents a unique combination of physical, mechanical, electrical and chemical properties up to a maximum working temperature of 1501C. Besides these properties, it is transparent (similar to window glass, transmits in average 90% in the wavelength range from 0.4 to 2.4 mm) with a refractive index of 1.65. All these balanced properties make Mylar lms ideal for a broad array of applications, including the fabrication of exible, lightweight and unbreakable optoelectronic devices [3]. Before depositing the ZnO thin lms, the substrates were ultrasonically cleaned in a detergent bath, followed by isopropyl alcohol and dried in nitrogen. The substrates (10 cm 10 cm) were placed inside the chamber and then evacuated until a base pressure of 7 107 mbar. The ZnO : Al thin lms were produced by rf magnetron sputtering from a commercially available sintered ceramic ZnO : Al2O3 (98 : 2) target with 99.99% purity, from Cerac, of 50 mm diameter, placed at a distance of 20 cm from the substrate. The argon ow rate was regulated by a mass ow controller to 10 sccm and the deposition pressure was xed to 1.6 102 mbar (optimised deposition conditions for this chamber, see Ref. [4]), while the rf power was varied between 150 and 200 W. The lms were produced at room temperature and were not annealed after deposition. The structural and morphological properties of the lms were studied by XRD spectroscopy (Rigaku diractometer DMAX III-C series, with a copper cathode) and the morphological properties were analysed by SEM (Zeiss DSM 962). The optical transmittance measurements were performed with a Shimadzu UV/VIS 3100 PC double beam spectrophotometer in the wavelength from 300 to 1500 nm. The thickness of the lms was measured using a Sloan Dektak 3D prolometer. The resistivity, carrier concentration and Hall mobility were obtained from four-point probe (square conguration, 5 mm side) and Hall eect measurements using a BIORAD HL5500 system with a permanent magnet of 5 kG.

3. Results and discussion 3.1. Structural and morphological analysis The lms prepared in this work were physically stable and had good adherence to the polymeric substrate. The XRD measurements revealed that these ZnO : Al thin lms were polycrystalline and retained the hexagonal wurtzite structure, having lattice parameters corresponding to that of bulk ZnO. The XRD pattern of the ZnO : Al thin lms (normalised to the thickness) deposited for two rf powers are shown in Figs. 1(a) and (b). It is also possible to observe from the XRD measurements that the grains are strongly oriented along the caxis (presence of a singular peak (0 0 2) for 2y=34.341), indicating that we are in the presence

Fig. 1. X-ray diraction pattern for ZnO : Al thin lm deposited on Mylar type D substrate, at room temperature, for (a) 150 W and (b) 200 W.

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of a columnar growth [5]. With increasing the rf power the intensity of the peak increases. This means that the crystallinity of the resulting lms is improved when the rf power is higher. Nevertheless, by comparing the results with the same lm deposited onto glass substrates the intensity of the diraction peaks is not so intense, which might be due to the surface roughness exhibited by the polymer. This was also investigated by SEM analysis (see Figs. 2(a) and (c)), where it is possible to observe some irregularities related to the polymer surface. Since these irregularities have dimensions of the order of 0.2 mm (same order of magnitude of the ZnO thin lm thickness) it is possible to have some discontinuities along the covered surface. 3.2. Optical properties Fig. 3 shows the transmittance as a function of wavelength in the range from 300 to 900 nm, for two typical samples deposited with a rf power of 150 and 200 W. The average transmittance is of the order of 83% for both lms. A slight improvement of the transmittance is observed for the lm deposited at 200 W, because the thickness is lower. From the transmittance data it is possible to infer the optical gaps of the lms by plotting (ahn)2 vs. hn (where a is the absorption coecient, and hn the photon energy) and by extrapolating the straightline portion of this plot to the energy axis. These plots yield optical gaps of 3.09 and 3.02 eV for the lms deposited at 150 and 200 W, respectively. The obtained values are not consistent with the optical gap of ZnO : Al thin lms (the typical optical gap is around 3.23.3 eV for lms deposited on glass substrates [6]). This means that these values are due to the optical properties of the polymer substrate, which is partly absorbing in the high energy range of the visible spectrum. Even with this disadvantage, but with its good heat resistance and good electrical properties for the obtained lms, the Mylar substrate is still a candidate for
c Fig. 2. SEM micrographs of (a) ZnO : Al thin lm deposited onto 100 mm Mylar; (b) ZnO : Al thin lm deposited onto glass substrate and (c) Mylar type D surface.

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Table 1 Summary of the electrical properties presented by the ZnO : Al thin lms deposited by rf magnetron sputtering at room temperature Rf power (W) 150 200 () Thickness (A 1300 1100 Electrical resistivity (O cm) 7.0 102 3.6 102 Carrier concentration (cm3) 5.0 1019 5.4 1019 Hall mobility (cm2/Vs) 1.74 3.15

4. Conclusions ZnO : Al thin lms with good optical, electric and mechanical properties have been prepared on polymeric (Mylar type D) substrates by magnetron sputtering at room temperature. The samples are polycrystalline with a hexagonal wurtzite structure and a strong crystallographic c-axis orientation (0 0 2) perpendicular to the substrate surface. The ZnO : Al thin lms, with 83% transmittance in the visible region and a resistivity as low as 3.6 102 O cm have been obtained as deposited.

Fig. 3. Optical transmittance as a function of wavelength for two ZnO : Al thin lms deposited at room temperature. Solid squares: rf power of 200 W; solid circles: rf power of 150 W.

Acknowledgements *o This work was supported by the Fundac a # para a Ciencia e a Tecnologia through Pluriannual Contracts with CENIMAT and by the projects: POCTI/1999/ESE/35578 and POCTI/ 1999/CTM/35440.

ZnO : Al transparent conducting lm deposition. Similar eect was found in Ref. [7]. 3.3. Electrical properties Table 1 shows a summary of the electrical properties presented by the ZnO : Al thin lms deposited by rf magnetron sputtering at room temperature. All the lms exhibited an n-type behaviour, which is in conformity with the type of conduction mechanism associated with these, doped oxide semiconductors. By increasing the rf power from 150 to 200 W we observe a decrease (half) on the electrical resistivity associated to a increase on the carrier concentration as well as on the Hall mobility. The low values obtained for the Hall mobility are mainly due to the fact that the lms were grown at room temperature. The observed values obtained for the electrical properties (conductivity and carrier concentration) are correlated to a high degree of crystallinity (see Fig. 1) instead of high values of Hall mobility.

References
[1] Hartnagel HL, Dawar AL, Jain AK, Jagadish C. In: Semiconducting transparent thin lms. Bristol: Institute of Physics Publishing, 1995. [2] Technical information from Dupont at: http://www.dupontteijinlms.com. [3] Fortunato E, Ferreira I, Giuliani F, Wurmsdobler P, Martins R. J Non-Cryst Solids 2000;266269:1213. [4] Nunes P, Costa D, Fortunato E, Martins R. J Vac Sci 2002;64:2937. [5] Privato C, Antonaia A, Addolnizio ML, Di Nocera A, Loreti S, Terzini E. Proceedings of the 13th European Photovoltaic Solar Energy Conference, Nice, France 1995. p. 1623. [6] Sarkar A, Ghosh S, Chaudhuri S, Pal AK. Thin Solid Films 1991;204:255. [7] Ma J, Zhang D, Li S, Zhao J, Ma H. Jpn J Appl Phys 1998;37:5614.