Proceedings of 2011 IEEE International Conference on Applied Superconductivity and Electromagnetic Devices Sydney, Australia, December 14-16, 2011

ID128

Deposition of Nanocrystalline TiO2 Thin Films on Poly(Ethylene Terephthalate) at 130C

Huynh Chau Pham, Dorian Amir Henry Hanaor, Julian Michael Cox*, Charles Christopher Sorrell
School of Materials Science and Engineering, University of New South Wales, Sydney, NSW 2052, Australia * School of Chemical Engineering, University of New South Wales, Sydney, NSW 2052, Australia
AbstractA sol-gel method was used to produce thin films of the anatase polymorph of titania on poly(ethylene Terephthalate) (PET). This was done at a temperature of only 130C, which demonstrates the feasibility of the fabrication of flexible photocatalyts, solar cells, and other semiconducting materials. The films were ~570 nm thick and were comprised of grains of 15-25 nm diameter; these grains themselves consisted of crystallites of 5-10 nm diameter. Keywords-anatase; titania; sol-gel; thin film; PET

In beaker 1, 6 mL of propanol and 25 mL of TTIP were added and mixed for ~1 min. In beaker 2, 150 mL of deionised water and 1.7 mL of concentrated nitric acid were added and mixed for ~5 min. Initial peptisation to form the sol involved transferring the contents of beaker 1 to a burette and adding dropwise over ~90 min to the contents of beaker 2 with continuous stirring. A dilute solution (H2O/TTIP molar ratio ~83:1) was used because this was expected to promote hydrolysis [10]. Final peptisation involved transferring the sol to a glass bottle with a loosely fitting lid, placing it in a water bath at 95-96C, stirring for ~8 h, adding sufficient deionised water to regain the original volume, loose sealing of the bottle, and refluxing for another 8 h (without additional significant water loss). Gelled coatings were produced on both PET and glass using a motorised dip-coater. The coating process involved initial coating and subsequent air drying for ~30-60 min and oven drying at 130C for ~15 min, followed by a second coating and the same drying procedure except that the final drying was for ~15 h instead of ~15 min. Surface compositions of the coatings and substrates were determined by X-ray photoelectron spectroscopy (XPS; Thermo Scientific ESCALAB250Xi spectrometer, with monochromated Al-K source). Film thicknesses were determined using single-beam focussed ion beam milling (FIB; FEI XP200, with initial gold sputtered [~20 nm]) using the cross-sections of milled holes. The morphology and structure of the films were analysed using high-resolution scanning electron microscopy (HRSEM; FEI, NovaNano SEM 230). The film topography was examined by atomic force microscopy (AFM; Nanoscope IIIA Multimode SPM, Veeco Instruments). The structure and crystallography of the films were studied using high-resolution transmission electron microscopy (HRTEM; FEI CM200-FEG microscope). The crystallography was determined by X-ray diffraction (XRD; Philips Xpert Multipurpose Diffractometer). Additional phase analysis was carried out using a laser Raman microspectrometer (Renishaw Invia Raman microscope) equipped with an Ar laser.

I.

INTRODUCTION

It is well known that crystallinity is required for photocatalytic activity in TiO2 [1,2] and that the metastable anatase phase usually exhibits photocatalytic activity superior to that of the equilibrium rutile phase [3-5]. This phase transformation temperature often is observed to occur at ~600C [6,7], although temperatures in the range 400-1200C have been observed [5]. Thus, retention of anatase below 400C is considered a desirable goal in the processing of TiO2 thin films. Most thin-film fabrication methods require heating at temperatures in excess of 400C so as to recrystallise the films [8,9]. This limitation in high-temperature processing impacts on the potential to retain anatase as well as the types of substrates that can be used to support the thin films. That is, almost no polymers can withstand these temperatures, so ceramics and metals are the alternatives. Thus, the development of TiO2 coating methods at low temperatures would make possible the production of flexible light-weight coatings on polymers. The present work was designed to obtain crystalline TiO2 at temperatures sufficiently low to avoid the anataserutile phase transformation and charring/melting of polymeric substrates. II. EXPERIMENTAL PROCEDURE

The following materials were used: Substrate Polymeric Film Melinex 516 polyethylene teraphthalate (PET) film (Dupont Corp.) Titanium Source Titanium tetra-isopropoxide (TTIP; 97 wt%, Sigma-Aldrich) Other Chemicals Propanol (AlanaR, 99.7 wt%) Nitric acid (Univar, 70 wt%)

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III.

RESULTS AND DISCUSSION

XPS data for the coatings, shown in Fig. 1, exhibited relatively intense Ti2p peaks. The Ti2p3/2 and Ti2p3/1 peaks of titanium are located at 458.9 eV and 464.7 eV, respectively.

The Ti2p3/2 binding energy exceeds that of Ti metal (454.0 eV), TiO (455.0 eV) and Ti2O3 (456.7 eV) and is typical of that of TiO2 [11,12]. Also, the doublet separation between the 2p3/2 and 2p3/1 peaks of ~5.7 eV is typical of TiO2 [12].

Figure 1. XPS data for TiO2 coating on: (a) PET and (b) enlargement of Ti2p peaks.

Fig. 2 shows optical and HRSEM images. The former revealed the presence of some pinholes; the latter indicated that the films were comprised of uniform anhedral and equiaxed particles, with diameters in the range 15-25 nm. FIB analysis showed film thicknesses of the order of 570 20 nm. AFM data shows that the film surfaces had a mean roughness of ~1.5 nm, although this is not very meaningful as it is well below the probe diameter of 10 nm.

dimensions in the range 5-10 nm and disordered crystallite interfaces. It is likely that the particle sizes observed using HRSEM and AFM correspond to agglomerates of the crystallites observed with HRTEM.

Figure 2. Micrographs of TiO2 coatings on PET by: (a) laser Raman microspectroscopy and (b) HRSEM.

Figure 3. Micrographs of TiO2 coatings: (a) on PET, using AFM and (b) on glass, using HRTEM.

Fig. 3 shows AFM and HRTEM micrographs of the films. The former confirmed the HRSEM data; the latter revealed the presence of lattice fringes of randomly oriented crystallites of

Fig. 4 shows XRD and laser Raman microspectroscopy data that confirmed that the films were crystalline. The small XRD peak at ~31 2 and the labelled Raman peak indicate the presence of a small amount of the metastable TiO2 polymorph brookite.

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(a)

(b)

Figure 4. Mineralogy of TiO2: (a) XRD and (b) laser Raman microspectroscopy.

IV.

SUMMARY AND CONCLUSIONS

The HRTEM, XRD, and laser Raman microspectroscopy data confirm that these materials consisted of nanocrystalline anatase, although it is unknown if they recrystallised in the sol at 95-96C or during drying at 130C. In contrast, conventional sol-gel processing studies typically require annealing temperatures of 500-800C [8,9]. It is likely that the reasons for this difference in recrystallisation tempeatures derive from the high level of water used and the use of refluxing, neither of which is used in typical sol-gel studies. The physical reasons for this are unknown. However, it may be significant that these sols remained stable for as long as 6 months instead of the typical period of ~1 month for conventional sol-gel studies. The two phenomena of lowtemperature crystallisation and sol stability are likely to derive from the same origin, which is a function of the high stability of the TiO2-based system. Further, another difference between the present work and that of conventional sol-gel studies is that the sols in the former were transparent and probably crystalline while those in the latter typically were white and probably amorphous. This difference is likely to lie in the nature of the degree of hydrolysis, which would be complete in the former but incomplete in the latter. It is well known that decreasing crystallite size causes a blue shift to shorter wavelengths in the absorption edge of these photocatalytic materials. Thus, the small crystallite sizes obtained in the present work are assumed to be suboptimal for photocatalytic activity. Therefore, modification of the water level and refluxing conditions may result in superior results through ageing and grain growth. ACKNOWLEDGMENTS The authors would like to thank the following organisations for making the present work possible: Ministry of Agriculture of Viet Nam,

Australian Research Council, UNSW node of the Australian Microscopy Microanalysis Research Facility (AMMRF). REFERENCES

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