Applied Surface Science 253 (2007) 74977500 www.elsevier.

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Raman study of phase transformation of TiO2 rutile single crystal irradiated by infrared femtosecond laser
H.L. Ma *, J.Y. Yang, Y. Dai, Y.B. Zhang, B. Lu, G.H. Ma
Department of Physics, Instrumental Analysis & Research Center, Shanghai University, Shanghai 200444, PR China Received 23 August 2006; received in revised form 7 February 2007; accepted 22 March 2007 Available online 30 March 2007

Abstract Titanium dioxide (TiO2) rutile single crystal was irradiated by infrared femtosecond (fs) laser pulses with repetition rate of 250 kHz and phase transformation of rutile TiO2 was observed. Micro-Raman spectra show that the intensity of Eg Raman vibrating mode of rutile phase increases and that of A1g Raman vibrating mode decreases apparently within the ablation crater after fs laser irradiation. With increasing of irradiation time, the Raman vibrating modes of anatase phase emerged. Rutile phase of TiO2 single crystal is partly transformed into anatase phase. The anatase phase content transformed from rutile phase increased to a constant with increasing of fs pulse laser irradiation time. The study indicates the more stable rutile phase is transformed into anatase phase by the high pressure produced by fs pulse laser irradiation. # 2007 Elsevier B.V. All rights reserved.
PACS : 79.20.Ds; 64.60.i Keywords: Femtosecond laser; Titanium dioxide crystal; Raman spectroscopy

1. Introduction Titanium dioxide (TiO2) is a large-band gap semiconductor with important applications in corrosion-resistant coating, pigment, photocatalysis, gas sensors, medical implants and optical active coatings and solar energy conversion [14]. It is well known that TiO2 exists three natural phases: rutile, anatase, and brookite [5]. Every titanium is surrounded by six oxygens to form a TiO6 octahedron in the modications, but they have different networks composed of TiO6 octahedra. A lot of studies have been carried out on the formation of rutile and anatase crystals and lms [69]. At elevated pressures TiO2 has a rich phase diagram with a series of structural phase transformations. The structure and stability of the high-pressure phases of TiO2 are of particular interest in Earth sciences, for these phases are an accessible analog of minerals in the Earths mantle. Rutile TiO2 is particularly attractive in this context because it is expected to undergo a sequence of phase transformations with increasing pressure similar to that experienced by SiO2 in the Earths lower mantle. High pressure

* Corresponding author. Tel.: +86 21 66135267; fax: +86 21 66135030. E-mail address: mahl@staff.shu.edu.cn (H.L. Ma). 0169-4332/$ see front matter # 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2007.03.047

X-ray diffraction [1012] and Raman spectroscopy [1314] studies have revealed that rutile and anatase transform to a columbite structure at high pressure. Recently phase of TiO2 from anatase to rutile is studied by UV Raman spectroscopy excited by 325 and 244 nm lasers [15]. High uence neutron irradiation and proton irradiation induce similar variations of the frequency and intensity of Raman vibration modes in the rutile single crystals. But there are no attempts to phase transformation of TiO2 from rutile to anatase by using infrared femtosecond laser pulses. During the last decades, special interest was paid to the potential of ultrashort laser pulses with durations in the picosecond to femtosecond domain with respect to laserinduced phase transitions [1618] as well as to the fundamental processes during laser ablation. The femtosecond laser, because of ultrashort pulse and ultrahigh peak power, has exhibited great potentials in material processing and many microstructures in transparent materials have been fabricated, including optical wave guides, splitters, couples, three-dimensional data storage, and photon crystals [1923]. Femtosecond laser can be used to generate a number of nonlinear effects by multi-photon absorption and avalanche ionization in the focusing area of materials. Catalytic performance of TiO2 largely depends on the surface properties, especially the surface phase. The surface

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phase of TiO2 should be responsible for its photocatalytic activity because not only the photo-induced reactions take place on the surface but also the photo-excited electrons and the holes might migrate through the surface region. 2. Experimental The laser system based on a regenerative Ti:sapphire amplier using chirped pulse amplication technique (RegA 9000, Coherent) provides high-intensity femtosecond laser pulses for the experiments. The system emitted linearly polarized 150 fs laser pulses at a center wavelength of 800 nm (photon energy 1.55 eV). A mechanical shutter was used to select laser pulses from a pulse-train with a repetition rate of 250 kHz. The Gaussian laser pulses were was focused onto the surface of the sample with a spot size of approximately 5 mm by using an optical microscope (Olympus BX51) with a 20 objective lens and a numerical aperture of 0.46. The average output power can reach 1.5 W and can be changed continuously with a Glan polarizer. An aperture is used to provide a round beam at the workpiece and improve the nal feature quality. The sample, rutile TiO2 single crystal, is prepared in optical oating zone systems (Z-T-10000-H-VI-PSH, Japan), It is 40 mm in diameter and 1.5 mm thick. It is polished on both sides. The specimen was mounted on a motorized xyz-translation stage and positioned perpendicular to the direction of laser incidence. Fig. 1 shows two arrays of visible laser damage spots on the surface of rutile single crystal induced by femtosecond laser pulses, where laser average power on the surface of the sample is 300 MW (laser energy 1.2 mJ) and the irradiation time is different from 1/63 to 400 s, which corresponds to from 4000 to 108 laser pulses, respectively. The interaction of a laser with matter at intensity above the ionization threshold proceeds in a way similar for all

Fig. 1. Microscope photograph of visible laser damage spots formed on the surface of rutile single crystal.

the materials. The plasma generated in the focal region increases the absorption coefcient and produces a fast energy release in a very small volume. A strong shock wave is generated in the interaction region and this propagates into the surrounding cold material. The shock wave propagation is accompanied by compression of the solid material at the wave front and decompression behind it, which leads to the formation of an ablation crater on the surface. Because of the accumulation effect, with the pulse number increasing, the temperature in the focal volume would rise accordingly, and then the thermal energy diffuses from the focal point to the outer area and the heated region begins melting and expanding. Due to the high temperature and pressure formed in the focal volume, the material at the edge of the modied region is compressed between the expanding region and the unheated one, and the refractive index of the compressed region increases, while the density of the expanding region reduces. Signicantly, when the exposure time is long enough, the density and the thermal conductivity of the expanding region decreases to extent that the deposited energy cannot transfer

Fig. 2. The phase of TiO2 studied here: rutile (a), and anatase (b). Red spheres represent the Ti ions, grey spheres the O ions.

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into the outer region smoothly. The energy deposits in the central region, then another circular structure with high refractive index emerges between the expanding region and the unheated one. Repeating the process several times, a series of circular structure can be observed under the natural light, which results from the refractive index changing alternately. The high temperature and strong pressure elds created by a femtosecond laser pulse should be sufcient to rearrange structures. In order to identify structural changes within the laser irradiated regions, micro-Raman spectroscopy was used. The Raman scattering experiment was performed with a Renishaw inVia-plus Spectrometer system. The ablated surface regions were excited using the 514 nm emission line of a cw Ar+ laser (Spectra Physics) operating at a power level of 20 mW. A 50 objective lens was used to focus the beam onto the sample. The scattered light was then collected, dispersed and detected by a Standard CCD array detector. The Rayleigh scattered light was reduced by a notch lter. Spectra were recorded at room temperature. The spectra were recorded using

Table 1 Observed Raman shift (cm1) of TiO2 single crystal and their assignment This article Rutile 140.2 235.5 445.8 609.8 825.5 Anatase n1 n2 n3 n4 n5 n6 140.9 196.3 396.0 515.4 515.4 632.7 143 236 447 612 826 144 197 399 516 516 639 B1g Multi-photon process Eg A1g B2g Eg Eg B1g A1g B1g Eg Arsov et al. [24] Assignment [25]

a 1800 groove mm1 grating giving a spectral resolution better than 1 cm1. The spectrum scattering detection region ranges from 100 to 900 cm1. The rutile structure, illustrated in Fig. 2(a), belongs to the P42/mnm tetragonal space group. The unit cell is dened by the lattice vectors a and c and contains two TiO2 units with Ti ions at (0, 0, 0) and (1/2, 1/2, 1/2) and O ions at (u, u, 0) and (1/ 2 + u, 1/2 u, 1/2). Therefore, there are ve Raman active modes: B1g, multi-photon process, Eg, A1g and B2g. Fig. 3 shows the Raman spectra before irradiation and after irradiation by using femtosecond laser pulses. In Fig. 3(a), the bottom line is the Raman shifts of rutile crystal before irradiation, exhibiting dominant peaks at 140.2, 235.5, 445.8, 609.5, and 825.5 cm1, which are assigned to the ve Raman active modes of rutile single crystal. The observed Raman shifts are listed in Table 1 with previous results for comparison [24]. B2g Raman mode disappears after laser irradiation. The relative intensities of Eg and A1g are different between before and after laser irradiation. After irradiation by femtosecond laser pulses, the intensity of Raman mode Eg increases and up to nearly equal to that of A1g when laser irradiation time is 0.125 s (about 3.1 104 pulses). Fig. 3(b) shows, the Raman active modes of TiO2 anatase crystal emerge with increasing of fs pulse laser irradiation time. The anatase structure, shown in Fig. 2(b), is characterized by 9 the tetragonal space group DI 4h I 4=amd . The unit cell contains two TiO2 units with Ti ions at (0, 0, 0) and (0, 1/2, 1/4) and O ions at (0, 0, u), 0; 0; u, (0, 1/2, u + 1/4), and (0, 1/2, 1/2 u). Factor group analysis indicates there are six Raman active modes: 1A1g + 2B1g + 3Eg. The intensities of Raman band in anatase phase change depending on the laser irradiation time. With increase in laser irradiation time, the intensities of some of them, n1, n3, n4 + n5, increase and then keep stable till n6 band emerges when laser irradiation time longer than 10 s. 3. Discussion

Fig. 3. Raman spectra of TiO2 single crystal irradiated by femtosecond laser pulses with 800 nm, 150 fs, and 250 kHz repetition rate at different irradiation time. The relative intensities of Eg and A1g of rutile crystal before and after laser irradiation (a), Eg and A1g Raman vibration modes of rutile are shown in the insert (view along c axis). With the irradiation time increases longer than 0.5 s, the Raman vibration modes of anatase emerged (b).

For any given value of pressure, P, all structural degrees of freedom are optimized, therefore, giving the predicted equilibrium geometry by minimizing the enthalpy function H: H = E + PV, with respect to all structural degrees. E is the

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there are no changes of the relative intensities and the frequencies of Raman active modes and no phase transformation. Our experiments indicate the more stable rutile phase is transformed into the anatase phase in the high pressure. The extreme conditions produced in the micro-explosions can serve as a novel phase transformation study for high pressure and high temperature, and the material processing.

Acknowledgements This research supported by Shanghai Leading Academic Discipline Project (no. T0104), the Shanghai Nano-technology Promotion Center and Science & Technology of Shanghai Municipality (no. 0652nm005) Science Foundation of Shanghai Municipal Commission Education and Science and Technology Commission of Shanghai Municipal (Grant 06PJ14042).

Fig. 4. Raman spectra of TiO2 lm annealed at 800 8C for 3 h. Before laser irradiation (the dotted line) and after irradiation (the upper solid line) by using femtosecond laser pulses for 10 s.

internal energy of the system and V is the unit cell volume. The local-density approximation (LDA) calculation [26] predicted rutile to be more stable than anatase, the calculated energy difference (dH = Hrutile Hanatase) between rutile and anatase is 2.11 kJ/mol, whereas the generalized gradient approximation calculation yielded anatase as the more stable phase by dH 4.82 kJ/mol. A plane-wave-LDA study [27] found that the relative stability of the two phases is sensitive to the pseudopotential even when small-core (SC) pseudopotential are used. Two different SC pseudopotentials were tested, with one type yielding rutile to be more stable than anatase by dH 4.598 kJ/mol (Teter pseudopotential) and the other nding anatase to be more stable than rutile by dH 5.852 kJ/mol (Troulier Martin pseudopotential). Our experiments found that some rutile phase is transformed into anatase phase when TiO2 rutile single crystal was irradiated by infrared femtosecond laser. It indicates the anatase phase is more stable than rutile phase in the high pressure. In order to identify whether anatase is transformed into rutile at the same experimental condition, TiO2 lm with the thickness of 0.5 mm, prepared by electronbeam evaporation method, was annealed at 800 8C for 3 h and then was irradiated by infrared femtosecond laser at average power of 300 mW (laser energy 1.2 mJ) for 10 s. Fig. 4 indicates that n1, n2, n3, n4, n5, n6 are the Raman active modes of anatase after annealed at 800 8C for 3 h, and the relative intensities and the frequencies of Raman active modes do not change and no new phase emerges after fs pulse laser irradiation. In conclusion, we nd that tightly focused 150 fs pulse laser initiate some TiO2 rutile phase transformation into anatase produced by the high pressure due to micro-explosions on the TiO2 surface. For TiO2 anatase lm irradiated by fs pulse laser,

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