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Photo-Catalytic Properties of Titanium Dioxide Sputtered on a Nano Structured Substrate

Photo-Catalytic Properties of Titanium Dioxide Sputtered on a Nano Structured Substrate

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01/20/2011

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Photocatalytic properties of titanium dioxide sputteredon a nanostructured substrate
I. Turkevych
, Y. Pihosh, M. Goto, A. Kasahara, M. Tosa, S. Kato,K. Takehana, T. Takamasu, G. Kido, N. Koguchi
 National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
Available online 27 April 2007
Abstract
The effective one-step physical approach is demonstrated for the fabrication of anatase titanium dioxide nanotubes through r.f. magnetronsputtering of TiO
2
on a highly ordered nanoporous anodic alumina template. The nanostructured TiO
2
benefited from the combination of unique properties of both the sputtering technique that provided well-controlled environment for the fabrication of anatase phase TiO
2
and the porousanodic alumina (PAA) that provided uniform and ordered nanopores. The photocatalytic properties of TiO
2
films were characterized following thedegradation of methylene blue molecules under UV light irradiation. The photocatalytic activity of the nanostructured TiO
2
films has been foundto be approximately twice higher in comparison with the flat TiO
2
films fabricated at the same conditions.© 2007 Elsevier B.V. All rights reserved.
 Keywords:
Photocatalysis; TiO
2
; Nanoporous alumina; Magnetron sputtering
1. Introduction
Titanium dioxide TiO
2
is a very attractive material foapplications in photocatalysis[1]because of its efficiency in promoting a variety of important chemical processes and itsstabilityagainstownphotochemicaldecomposition.Thetitaniumdioxide has attracted extensive interest as a nontoxic, highlystable, low-cost catalyst for chemical waste remediation[2
4].Due to the wide band gap, TiO
2
is activated by near ultraviolet light and has a strong oxidation power of generated holes, whichreact with water and produce hydroxyl radicals (OH
). Both theholes and the (OH
) radicals act as oxidation agents, which areable to decompose most of organic contaminants.Avariety of physical[5]and chemical[6]approaches for the fabrication of TiO
2
thin films have been developed up to date.Although the chemical processes usually result in rough filmswith high specific area, they require post-treatment annealing inorder to achieve a good crystal structure and a long-termstability of the film. The annealing however cannot be performed when a soft polymeric substrate is used. Physicalapproaches are suitable with soft substrates, give better crystalstructure and stability, but lead to the formation of dense andsmooth films containing few structural flaws. In order toenhance an overall catalytic performance, a high specific area of the catalyst is required.Over the past several years, a variety of methods have beendeveloped to synthesize TiO
2
materials in a form of nanos-tructures such as nanoparticles[7], nanowhiskers[8], nanowires [9]andnanobelts[10].TiO
2
nanotubes[11]havebeenfabricated by pressure impregnating of a nanoporous template withtitanium isopropoxide and then oxidatively decomposingthe reagent at 500 °C. Although the specific area of thesenanostructures was usually high enough to meet the require-ments of most applications, their fabrication methods however still caused the issues mentioned above. The chemical ap- proaches require high annealing temperatures and have further  problems arising of residual impurities incorporation fromorganic precursors and blends. On the other hand fabrication of nanostructures by physical approaches involves specific pat-terning of the deposited material, which is time consuming,
 Available online at www.sciencedirect.com
Thin Solid Films 516 (2008) 2387
2391www.elsevier.com/locate/tsf 
Corresponding author. National Institute for Materials Science, Sakura 3-13,Tsukuba, Ibaraki, 305-0003, Japan. Tel.: +81 29 863 5539; fax: +81 29 8635539.
 E-mail address:
Ivan.Turkevych@nims.go.jp(I. Turkevych).0040-6090/$ - see front matter © 2007 Elsevier B.V. All rights reserved.doi:10.1016/j.tsf.2007.04.083
 
complex and still can result in contamination by incident ion beams and chemical or reactive ion etching during lithography.Thispaperreportsasimpleone-stepphysicalapproachforthefabrication of anatase titanium dioxide nanotubes through r.f.magnetron sputtering of TiO
2
on a highly ordered two-dimensional nanoporous patterns of anodic alumina. The basicidea comes from the combination of unique properties of boththe sputtering technique and the porous anodic alumina (PAA).The reactive sputtering[12
15]is one of the most utilizedmethods for obtaining TiO
2
thin films with well-controlledstoichiometry, density, adhesion and good thickness uniformityover a large area. The pressures of reactive gases, evaporationrate and moderate variation of substrate temperature can be usedto control the crystalline structure and optical properties of TiO
2
14]. The porous alumina prepared by aluminum anodiza-tion[16]consists of uniform columnar pores with high aspect ratio. The geometry of the porous structure, such as interporedistance, pore diameter and length, can be varied ina widerange by adjusting the conditions of aluminum anodization and post-anodizing treatment. Besides vertical aligning, nanopores tendto form ordered hexagonal arrays under specific conditions[17].Therefore the reactive sputtering of TiO
2
over the PAA templatecan result in the formation of vertically aligned and spatiallyordered TiO
2
nanotubes, which replicates the underlyingstructure of nanopores. This approach is expected to enhancethe photocatalytic activity of the TiO
2
prepared by reactivesputteringdue tobettercouplingof light andhigher specific areaof the nanostructure augmenting reaction kinetics.
2. Experimental
The highly ordered porous alumina templates were fabricat-ed through a typical two step anodization process[18]with99.999% pure aluminum substrates as anode in a 0.3 M oxalicacid electrolyte. The aluminum substrates were first electro- polished in the mixture of perchloric acid and ethanol 1:4 toobtain a smooth mirror-like surface. The anodization was performed under the constant potential of 40 V in a constant-temperature bath at 5 °C. The first anodization lasted 18 h, after which the thick porous layer was selectively dissolved in amixture of chromic (1.8 wt.%) and phosphoric (6 wt.%) acidsleaving a well-ordered concave patterns on the aluminumsubstrate, which acted as pore nucleation centers during thesecond anodization step. The second anodization was per-formed under the same parameters, except different anodizationtime was used to prepare the PAA templates with the thicknessof 300 nm. This process yielded highly ordered nanoporoustemplates with the pore diameter of 30 nm and interpore spacingof 100 nm. The diameter of nanopores was then increased to60 nm by the isotropic etching of aluminum oxide in 5% phosphoric acid at room temperature. Finally the PAA templateswere ultrasonically cleaned in distilled water for 15 min toremove the traces of chemicals used during their fabrication.TiO
2
was deposited on the top of unheated PAA templates bymeans of r.f. magnetron sputtering of a TiO
2
disk target (Furuuchi Chemical Corp., purity 99.9%).The r.f. generator (RFX 600A) operating at a frequency of 13.56 MHz and a power of 100 W was used for plasma initiation[19]. Theworking chamber was evacuated down to 10
6
Pa beforesputtering and a mixture of O
2
(20%) and Ar (80%) gases wasused as a working gas. The total pressure
tot 
of the O
2
/Ar mixture has been varied from 1.7 to 2.3 Pa to find the conditionsfor the fabrication of TiO
2
with anatase structure. The TiO
2
nanostructures have been studied by X-ray diffraction (XRD,Rigaku Co. RINT-2500) and observed in Field EmissionScanning Electron Microscope (FE-SEM, JEOL-6500F).The resulted TiO
2
coating was glued with 4 wt.% solution of  polymethylmethacrylate (PMMA) to an alumina silicate glasssubstrate, as shown inFig. 1. Then both the aluminum substrateand the PAA template were consequently dissolved in saturated
Fig. 1. Schematic diagram of nanostructured TiO
2
films fabrication by the aid of porous anodic alumina (PAA) templates.2388
I. Turkevych et al. / Thin Solid Films 516 (2008) 2387 
 – 
2391
 
HgCl
2
and 0.1% NaOH solutions respectively leaving TiO
2
nanotubes standing vertically with respect to the glass substrate plane.The photocatalytic properties of nanostructured TiO
2
werestudied by following transmittance of 0.05 mM methylene blue(C
16
H
18
 N
3
SCl) solution during its catalytic decompositionunder UV light irradiation with
λ
=254 nm. The UV light wastransferred to the TiO
2
nanostructure through the optical polymer fiber attached to the rear side of the glass substrate.The alumina silicate substrate was found to transmit 95% of UVlight and the transmittance was decreased slightly to 87% whenthe substrate was connected to the optical fiber due to losses inthe polymer glue. The transmittance of the methylene bluesolutions was measured each 24 h during 7 days using USB-2000-FLG spectrometer (Ocean Optics Inc.). Every PAAsubstrate used for the deposition of TiO
2
had its counterpart in a form of an alumina silicate glass substrate. The depositionof the TiO
2
onto the glass substrates resulted in the formation of flat TiO
2
films used as reference samples during studies of  photocatalytic properties.
3. Results
Stepwise growth of the TiO
2
films has been studied by theSEM observation of TiO
2
layers of different thickness preparedunder the same deposition parameters.Fig. 2shows the tiltedview SEM image of empty PAA template (a) and the top viewimages of TiO
2
gradually covering the surface of the PAA. Thesurface of the empty PAA is very smooth and during the initialgrowth stage both the top of the template and the inner walls of the pores are covered by amorphous TiO
2
in an isotropicmanner. After the deposition time of 15 min and the increasingof the TiO
2
layer thickness to approximately 10 nm thecolumnar structure starts to develop. It is clearly seen that theTiO
2
columns tend to nucleate and grow along the preferabledirections at the PAA top surface rather than on the walls of thenanopores. Therefore the growthof the TiO
2
nanostructure has atubular phase with the finite wall thickness of around 10 nm.Further growth results in a formation of a TiO
2
porous layer  built over the PAA template and replicating the morphology andarrangement of the underplaying PAA nanopores. It is inter-esting to note that the TiO
2
layer finally develops the columnar structure with pyramid like top morphology remaining open the pores in the TiO
2
layer. The enlarged top view of the TiO
2
shown in the inset of Fig. 3(d) reveals that each nanopore in theTiO
2
layer is formed by six triangular columns with the size of 80 nm.The evidence for the anatase phase of TiO
2
can be observedon the XRD spectra of TiO
2
layers deposited at various total pressure of the working O
2
/Ar mixture. Both the anatase (A)and the rutile (R) crystalline structures are present in the layer and the ratio of both phases depends on the
tot 
. The rutile
Fig. 2. (a) FE-SEM image of the empty PAA template; (b), (c) and (d) are the FE-SEM images of the top surface morphology of the TiO
2
layer sputtered on the PAAtemplate during 15, 60 and 90 min of sputtering respectively. The inset in (d) demonstrates the columnar structure of the TiO
2
layer with triangular morphology.2389
 I. Turkevych et al. / Thin Solid Films 516 (2008) 2387 
 – 
2391

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