Applied Surface Science 257 (2011) 71797183

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Photocatalytic and superhydrophilicity properties of N-doped TiO2 nanothin lms

M. Chekini a , M.R. Mohammadizadeh a,b, , S.M. Vaez Allaei a
a b

Superconductivity Research Laboratory (SRL), Department of Physics, University of Tehran, North Karegar Ave., P.O. Box 14395-547, Tehran, Iran Departement of Physics, Brock University, St. Catharines, ON, L2S 3A1, Canada

a r t i c l e

i n f o

a b s t r a c t
Pure TiO2 and nitrogen doped titanium dioxide (N-TiO2 ) thin lms were prepared by solgel method through spin coating on soda lime glass substrates. TiCl4 and urea were used as Ti and N sources in the sol. XRD results showed nitrogen doping has retarded anatase to rutile phase transformation. The doping also leads to a decrease in roughness of the samples from 4 nm (TiO2 ) to 1 nm (N-TiO2 ). However, surface analysis by statistical methods reveals that both surfaces have self-afne structure. Optical band gap of thin lms was shifted from 3.65 eV (TiO2 ) to 3.47 eV (N-TiO2 ). Hydrophilic conversion and photocatalytic degradation properties of thin lms were investigated and exhibited that N-TiO2 thin lm has more preferable hydrophilicity and photocatalytic properties under UV illumination. 2011 Elsevier B.V. All rights reserved.

Article history: Received 22 December 2010 Received in revised form 27 February 2011 Accepted 16 March 2011 Available online 23 March 2011 PACS: 61.72.U81.16.Be 82.65.+r 82.30.Rs Keywords: Solgel N-doped TiO2 thin lm Spin coating Hydrophilic Photocatalytic

1. Introduction Titanium dioxide which has considerable benecial properties such as chemical stability, non-toxicity and low fabrication cost, has attracted lots of interests for industrial usages [1]. Additionally, titanium dioxide has found many industrial applications after discovery of its photoinduced photocatalytic and hydrophilic properties. Its common applications such as a medium for environmental cleanup, energy conversion, surfaces with antifogging, self cleaning and antimicrobial properties, are widely used in commercial products [2]. As TiO2 band gap is large and its absorption edge is placed in UV spectra, there is a great amount of attempt to reduce its band gap in order to have benecial use of solar spectra (visible light as far as its ultraviolet radiation). Several efforts such as transition metal doping, dye synthesizing, hydrogen-

Corresponding author at: Superconductivity Research Laboratory (SRL), Department of Physics, University of Tehran, North Karegar Ave., P.O. Box 14395-547, Tehran, Iran Tel.: +98 21 61118611/61118634/+1 905 688 5550x5785; fax: +98 21 88004781/+1 905 984 4857. E-mail addresses: zadeh@ut.ac.ir, rmohammadizadeh@brocku.ca (M.R. Mohammadizadeh). 0169-4332/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2011.03.084

plasma reduction, and coupling to other semiconductors (with low band gap) have been performed for narrowing the band gap of TiO2 [3,4]. In 2001, Asahi and his colleagues carried out density functional theory calculations to show how substitution of anionic species (C, N, P, S, and F) in O sites of TiO2 can lead to narrowing the band gap in TiO2 . In particular, substitutional nitrogen doping has an inuence in band structure by mixing N-2p and O-2p states, while interstitial doping is not effective [5]. On the other hand, Valentin et al. using electron paramagnetic resonance and X-ray photoelectron spectroscopy (XPS) measurements and density functional theory calculations revealed that interstitial doping of nitrogen can be effective due to the making of discrete levels above valance band edge [6]. Peng et al. also demonstrated that visible light activity of interstitial N-doping, which is characterized by XPS spectra as hyponitrite, is higher than substitutional N-doping [7]. As a physical effect, it is known that the topography of a surface can also play a leading role on its wettability [8,9]. The geometrical properties with respect to the chemical behavior of interface can control the hydrophilicity/hydrophobicity of a given interface [8,10]. Recently, in several reports it has been shown the possibility of fabrication of superhydrophobic surfaces by controlling the roughness of intrinsically hydrophilic interfaces [1014]. In

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Fig. 1. XRD pattern of N-TiO2 (up) and TiO2 (down) powders, where N-TiO2 shows only anatase (A) phase, while in TiO2 there are rutile (R) phase peaks, too.

addition, Sakar et al. have shown how self-afne fractal characteristics of an interface can basically play a role on its wetting [11]. Thus, characterization of surface topography is necessary for a comprehensive understanding from its wetting feature. Using AFM measurements, and statistical analysis of the results, these kinds of investigations can be utilized. In this paper, we study nitrogen doping effect on the fabrication of TiO2 thin lms. The structures of the samples were investigated by XRD, AFM, SEM, and UVvisible spectroscopy analysis to characterize the photocatalytic and hydrophilicity of the samples. We have also investigated statistical properties and roughness of the surfaces, to nd out their possible effects on the wettability of the systems.

over the lms surfaces. Each contact angle is average of three measurements. The photocatalytic activity of the lms was determined by decomposition of methylene blue (MB). The degradation of the MB under UV light irradiation (810 W/cm2 ) was determined by measuring absorption spectra using a UVvis spectrophotometer (Bausch & Lamb 710). The initial concentration (C0 ) of the MB contamination was chosen 104 M. 3. Results and discussion Powder samples were used for XRD analysis. The pure TiO2 powder sample was white, and N-TiO2 powder had yellowish color which is in agreement with preceding reports [1518]. The results of XRD analysis (Fig. 1) show that N-TiO2 is in anatase structure. The dominant phase of TiO2 sample is anatase, as well. However, in pure TiO2 there are three rather small peaks of rutile phase. It seems that the existence of nitrogen has retarding effect on the transformation from anatase to rutile crystalline phase in these annealing temperatures [19,20]. Using Scherrers formula, crystallite sizes of the samples have been estimated 16 nm and 13 nm for TiO2 and N-TiO2 powder samples, respectively. SEM and AFM images of the pure and nitrogen doped TiO2 thin lms were presented in Fig. 2. To investigate the effect of nitrogen doping on decreasing magnitude of interface roughness we have calculated height distribution of the two samples, as shown in Fig. 3. As it is clearly seen, in N-TiO2 sample, the distribution of heights becomes localized over its mean value, and the interface has been smoother which it leads to a considerable change in roughness of interfaces, i.e. from 4 nm (TiO2 ) to 1 nm (N-TiO2 ). Using statistical methods, we have investigated structure of the surfaces to distinguish the effect of doping on the system. To achieve this, we have measured roughness exponent of the two interfaces and also we examined the scaling properties (self-afnity or multi-afnity) of the systems [21,22]. In order to characterize the topography of these two thin lms in details, we have utilized q-th order heightheight correlation function, Cq (r ) = |h(x) h(x + r )|q
x

2. Experimental details The N-TiO2 single layer thin lms were produced by the solgel on soda-lime glass substrate. One volume part of TiCl4 was added dropwisely under stirring to 10 part of ethanol while the temperature was kept constant at zero degree of Celsius. After nishing the exposure of white vapor, solution of urea in 6 part of deionized water was added to the initial sol. Urea/TiCl4 molar ratio in the nal sol was 4/1. Soda-lime glass substrates were coated with 50 L of sol, by spin coating with the rotational speed of 4000 rpm. For making pure TiO2 samples the same sol without urea was used (by adding of 6 part deionized water to initial sol instead of urea solution). Each sample was dried at 150 C for an hour then for forming anatase phase, samples were annealed at 300 and 450 C each one for 60 min. TiO2 and N-TiO2 powder samples were produced by drying the sol in 150 C for an hour and annealed at 300 and 450 C each one for 60 min. The XRD measurements were realized using a Philips PW 1390 diffractometer and a Cu K radiation source with a scan rate of 4 /min over a range of 20 70 . Transmittance and reectance spectra of the lms were measured in the UVvisible range (250900 nm) using a single-beam spectrophotometer Perkin Elmer, Lambda 950. Thickness of the lms was measured by the optical interference method. SEM (LEO 1455VP, by Platinum deposition) images were used for surface morphology studies. Surface roughness and morphology of the TiO2 lms were also evaluated by atomic force microscopy (AFM) using a NT-MDT instrument in a semi-contact mode. The contact angle of water droplet was extracted from the image contour of the droplet on the as prepared lms in the air. A CCD camera (Proline UK) was used to acquire images of the droplets and record of its spreading process

in which h(x) denoted to the surface height on the surface, and the average is over the surface area. To determine the roughness exponent of the two surfaces, we have calculated C2 (r) vs r, as was shown in Fig. 4 (the curve corresponding to q = 2). This curve follows the scaling relation C2 (r) r2 in length scales r < Rc 50 nm. Thus we can calculate the roughness exponent of the interfaces, which are 0.85 0.3 and 0.68 0.3 for TiO2 and N-TiO2 , respectively. These

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Fig. 2. AFM images of pure (up) and nitrogen doped (down) TiO2 thin lms.

exponents exhibit a meaningful change in the structure of the interfaces and can be related to its physical features [2123]. Based on these results, it seems TiO2 sample has a rough interface with larger roughness rather than N-TiO2 sample. To determine the structure of these surfaces in detail, using higher order of heightheight correlation function we have studied self-afnity (multi-afnity) of their structures. We have calculated Cq up to q = 10, and measured the generalized roughness exponent, i.e. q , according Cq (r) r q , for r < Rc 50 nm. In the case we have q q, there is a general roughness exponent, i.e. , in the system and it can be concluded that the interface is self-afne [21,22]. However, if there is no linear relation between q and q, this means that there is a multi-afne structure. Fig. 4 shows the calculated Cq (r) vs r for different values of q. Using these curves we have estimated all q which listed in Fig. 5, accordingly. Up to the errors in our estimations, we can conclude there is a linear feature in these diagrams and, consequently nitrogen doping has not lead to a cru-

Fig. 3. Height distribution of TiO2 and N-TiO2 thin lms.

Fig. 4. Cq (r) vs r for different values of q, for TiO2 (up) and N-TiO2 (down).

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Fig. 8. Changes in water contact angle on glass, TiO2 , and N-TiO2 thin lms under UV (810 W/cm2 ) illumination in ambient condition.

Fig. 5. Plot of q vs q, which shows there is a linear dependence and consequently self-afnity behavior in these surfaces.

Fig. 9. Degradation of MB under UV illumination by TiO2 (Blue) and N-TiO2 (red) thin lms.

Fig. 6. Transmittance and reectance spectra of TiO2 and N-TiO2 samples.

cial change on the self-afnity of the interface; just a change in roughness exponent of the surface was observed. Transmittance and reectance spectra (Fig. 6) of both titanium dioxide and nitrogen doped titania thin lms were used to obtain adsorption coefcient () as reported in references [24,25]. Optical band gap of thin lms was calculated from t on linear relation of (h )0.5 versus incident photons energy (h ) plot [2427]. Thickness of thin lm is 111 6 nm for TiO2 sample and 118 9 nm for N-TiO2 sample. The estimated optical band gap of TiO2 thin lm is 3.67 eV in agreement with those reported for thin lms (3.46 up to 3.98 eV [28]) and for N-TiO2 thin lm is 3.49 eV (Fig. 7). N-doping has reduced the band gap as 0.18 eV. The photoinduced hydrophilicity was evaluated by the water contact angle measurement in ambient conditions under UV illu-

mination of 810 W/cm2 . Variation of water contact angle under UV exposure was shown in Fig. 8. The N-TiO2 thin lm shows an angle reduction from about 50 to 7 degree in 80 min and TiO2 thin lm shows from about 60 to 7 degree in 120 min. It seems that the N-TiO2 thin lm shows better hydrophilicity character under UV illumination. Other reports claim that nitrogen doping is undermining UV-induced hydrophilicity [29]. However, it seems the change in roughness, roughness exponent of the lms, slightly red shift, and also different lm structural phases lead to show a better hydrophilic property in nitrogen doped samples [30]. Visible light-induced hydrophilicity test was performed on both samples with power saving lamp by ltering its UV light. According to titanium dioxides big band gap, no hydrophilic conversion was seen by TiO2 sample. Unpromisingly, N-TiO2 sample did not show any hydrophilic conversion, too. The problem may is corresponding to the large band gap of thin lms which are still in the ultraviolet region. Photocatalytic properties of thin lm samples were studied by changes of C/C0 (where C0 and C stand for the contamination concentration before and after UV illumination, respectively) of MB deposited on thin lms as a function of UV irradiation time (Fig. 9). Although, we expect N-TiO2 degradation rate is less than TiO2 under UV illumination [31], it seems the nitrogen doped sample is an

Fig. 7. (h )0.5 plots versus h for pure and nitrogen doped titanium dioxide lms for band gap calculation.

Fig. 10. Decomposition rate of MB under UV illumination by TiO2 and N-TiO2 thin lms.

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active photocatalyst as well as the undoped sample and the average time for complete decomposition of MB by N-doped sample is evidently less than pure TiO2 . The ln(C0 /C) versus irradiation time plot in Fig. 10 suggests that decomposition of MB has a linear relation in time and it follows the pseudo rst order kinetics [32]. 4. Conclusions Pure and nitrogen doped titanium dioxide thin lms were synthesized by the solgel spin coating method. Investigation of those lms has reveals that existence of nitrogen hindered the transformation of anatase to rutile phase. Both samples have a self-afne surface structure, while surface roughness of doped sample is lower than the pure one. In addition, roughness exponent of the surfaces decreased from 0.85 (TiO2 ) to 0.68 (N-TiO2 ). The band gaps of thin lms were deduced 3.67 and 3.49 for TiO2 and N-TiO2 thin lms, respectively. The N-doping has decreased the band gap energy, but not as much to shift to visible region. The contact-angle measurement and photocatalytic degradation of MB, under UV illumination, showed nitrogen doped thin lm has more preferable superhydrophilicity and photocatalysis characteristics than pure titania thin lm. Acknowledgment Partial nancial support by the Research Council of the University of Tehran is acknowledged. MRM would like to appreciate F. Razavis support during his sabbatical in Brock University. References
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