Evolution of anatase phase for the TiO₂ nanocrystals at their laser irradiation is

researched by the method of combinational light dispersion. The observed changes of

intensity, frequency and halfwidth of TiO₂ phonon lines are interpreted taking into

account the effects of nonstoichiometry, superficial strains and phonon confinement. The

found out parameter changes in the low frequency Eg mode show that laser irradiation

results in substantial improvement of the structural ordering in the area of TiO₆

octahedrons bonds

Budzulyak, I.M

Budzulyak, S.I.

Ilnytsyy, R.V.

Kotsyubynskyy, V.O.

Segin, M.Ya.

Strelchuk, V.V

Yablon, L.S.

Semiconductor Physics Quantum Electronics & Optoelectronics

Наукова електронна бібліотека періодичних видань НАН України (Vernadsky National Library of Ukraine)

Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine309PACS 61.43.Gt; 82.47.Aa УДК 621.315.592Raman spectroscopy of the laser irradiated titanium dioxide1Strelchuk V.V., 1Budzulyak S.I., 2Budzulyak I.M., 2Ilnytsyy R.V.,2Kotsyubynskyy V.O., 2Segin M.Ya., 2Yablon L.S.1V. E. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,41, pr. Nauky, 03028, Kyiv, Ukraine2Vasyl Stefanuk Precarpatian National University,57, Shevchenko str., 76025, Ivano-Frankivsk UkraineAbstract. Evolution of anatase phase for the TiO2 nanocrystals at their laser irradiation is researched by the method of combinational light dispersion. The observed changes of intensity, frequency and halfwidth of TiO2 phonon lines are interpreted taking into account the effects of nonstoichiometry, superficial strains and phonon confinement. The found out parameter changes in the low frequency Eg mode show that laser irradiation results in substantial improvement of the structural ordering in the area of TiO6octahedrons bonds.Keywords: Titanium dioxide, Intercalation, Anatase, Raman spectroscopy.Manuscript received 04.05.10; accepted for publication 08.07.10; published online 30.09.10.1. IntroductionNowadays titanium dioxide is used as electrode material for the lithium power sources [1-3]. The nanodispersed forms of TiO2 are very important, as they give possibilities to carry out lithium intercalation in the “host”-material more effectively. However, even in the case of nanodispersed TiO2 using the availability of their «guest» positions is supposed to be improved. Therefore,the various external influences are used for their activation, which allow to increase «guest» loading and, accordingly, to form the power sources with higher specific power characteristics. 2. ExperimentalLaser radiation was used to activate “guest” positions in nanodispersed TiO2 of the firm «Aldrich» (average size of particles < 25 nm, anatase phase); laser radiation was made in vacuum (Р = 10-5 Torr) by using Nd:YAG-laser that operates in the mode of the modulated Q-factor (wavelength is  = 1.06 m, pulse duration is  = 10 ns, frequency of these pulses is f = 28 Hz, energy in the pulse is Е = 0.02-0.04 J, duration of irradiation is t = 4.5-5.5 min).Main structural transformations during laser radiation with nanodispersed titanium dioxide lie in a change of elementary cell parameters (Table 1) (experimental error ±0.0001…0.0005 Е) and Frenkel defects formation. At the same time, existent point defects get sufficient energy for their migration inside the bulk. Laser radiation has the biggest influence on materials with availability of native point defects and considerable heterogeneities (including other phases, interfaces, etc). Co-ordination disturbance of titanium and oxygen atoms is probably related to the appearance of fields of thermoelastic strains in their surrounding as a result of laser beam thermal influence. Localization of thermal energy causes the change in lattice parameters, which at the same time influences on the sizes and charge state of energy favorable «guest» positions for the intercalated lithium ions. The average size of coherent-scattering regions for different modes of laser irradiation did not change for the methodic error.X-ray researches were realized using the diffractometer STOE STADI P with the linear position-sensible detector (PSD) accordingly to the scheme of the modified Gin'e geometry, in the Bregg-Brentano mode (CuK1- radiation;  = 1.54060 Е; Iogann type Ge-bended monochromator [111]; scanning step is 0.015°2, scanning time in the step is 400 s).Raman spectra of nanodispersed titanium dioxide researches were carried out using the triple spectrometer of T64000 Jobin-Yvon (1800/mm, settling ability ≈ 1 cm-1) in geometry of reverse dispersion, using the line 488 nm of argon- krypton laser. With the purpose to eliminate local overheating the samples, laser radiation power did not exceed 1 mW/cm2.Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine310Table 1. Changes of tetragonal lattice parameters and the values of “guest” loading of TiO2 as a result of laserirradiation.Lattice parameters, Е№sampleEnergy in the impulse Е, Joule Irradiation time, min.а сLi+ “Guest”intercalation degreeCoherent-scattering region, Е1 0 0 3.7884 9.5086 1.87 952 0.02 4.5 3.7874 9.5057 1.43 953 0.02 5 3.7878 9.5039 2.65 934 0.02 5.5 3.7866 9.5027 1.78 935 0.03 4.5 3.7884 9.5034 2.07 956 0.03 5 3.7872 9.5054 2.32 947 0.03 5.5 3.7873 9.5050 2.12 958 0.04 4,5 3.7874 9.5042 2.11 949 0.04 5 3.7866 9.5016 1.47 9410 0.04 5.5 3.7877 9.5033 3.50 953. Results and discussionTiO2 with the anatase structure belongs to the spatial group of 194hD  symmetry. In this structure, the titanium ions are surrounded by six ions of oxygen that are located in vertexes of the partly distorted octahedron, at the same time three ions of metal that co-ordinate each of anions lie in the vertexes of semi-perfect triangle. Accordingly to the theoretical group analysis for tetragonal anatase structure, optical phonon modes active in the process of Raman scattering for G-points of Brillouin center zone ( q=0) can be presented by six nonreducible representations: G = 3Eg + 2B1g + A1g. As a result, it is possible to observe in the experimental Raman spectrum 3Eg nonpolar modes with frequency positions 143, 197 and 639 cm-1 [4] (see, Fig. 1 as Eg(1), Eg(2) and Eg(3), accordingly), 2B1g nonpolar modes at 399 and  519 cm-1 and A1g mode at  513 cm-1. Phonon B1g modes nearly  513 and  519 cm-1 are well spectrally separated only at low temperatures [5]. The narrow and very intense phonon band at 143 cm-1 Eg(1) corresponds to oscillation of bridges between the octahedrons of TiO6. Oscillations at 143, 197 cm-1(Eg(1), Eg(2) modes) and 393 cm-1 (B1g mode) are mainly O-Ti-O bending. The high-frequency bands at 639 cm-1(Eg(3) mode) and at 514 cm-1 (A1g mode) are Ti-O strain oscillation (valency).In our case for the unirradiated anatase, nc-ТіО2samples frequency position of Eg(1) phonon band is 145 cm-1, which is higher as compared to the bulk TiO2 (143 cm-1). This effect can be conditioned by decreasing of crystal size [6], increasing of superficial strains [7], nonstoichiometry of chemical composition and by surface oxidization of particles [8], change of the lattice parameter [9]. The size of TiO2 nanocrystals (found from the analysis of the low-frequency Eg(1) of phonon mode) is about 12 nm [6]. In addition, broadening and shifting frequency (143 cm-1 ) of Eg(1) mode in the paper [8] is connected to the «stoichiometry defects» in oxygen sublattice: at disturbance of the stoichiometry ratio O/Ti from 2.0 down to 1.89 there were broadening and high-frequency shift of Eg(1) mode more than by 10 cm-1 [10].The authors also studied the effect of laser irradiation with the energy influence in the ТіО2transparence area on its phonon spectra, which is not studied enough up tu date. From Fig. 1, we can see that with increasing the nanocrystalline (nc) TiO2 laser irradiation dose up to 0.04 J, the growth of integral intensity takes place for all phonon bands. The band intensity of Eg(1) mode increases almost 10-fold (Fig. 2) and B1g and Eg(2) mode – by 1.7 times. This effect of dominant intensity increase for Eg(1) mode can be conditioned by improvement of structural order in ТіО2inside the areas that connect ТіО6  octahedrons. It should be mentioned that with increase of the irradiated dose the frequency of Eg(1) of phonon mode decreases from 145.0 down tо 143/5 cm-1 with its practically stable halfwidth (  8.0…8.2 cm-1) (Fig. 3). This effect of changing parameters for other phonon bands of nc-ТіО2with the increase of irradiation dose is considerably lower. For example, for B1g mode  ≈ 397.8-396.8 cm-1and  ~ 21.0-21.6 cm-1, and for Eg(3) mode  ≈ 640.5 – 639.8 cm-1 ,  ~ 22,0-22,5 cm-1. One of the main reason of substantial broadening B1g and Eg(3) phonon modes in Raman spectra is the presence of defects in small crystallites [11], which shows their high sensitivity to the defects as compared to the intensity of 143 cm-1Eg(1) mode [12].It should be noted that the small shift of frequency and change in the halfwidth of phonon lines Eg and B1gin Raman spectra are not necessary conditioned by the change of TiO2 nanoareas. In each case, the change of Raman phonon spectra can have its own peculiarities, which is determined by nonstoichiometry of elemental and phase composition as well as by dispersion of dimensions. Important factors that influence on the Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine311frequency position of phonon lines in TiO2 nanocrystals can be vacancies in the oxygen sublattice, internal microstrains, conditions at the particle surface, type and concentration of different active superficial centers, related to the adsorbed oxygen and hydroxyl molecular complexes, etc. For example, one of the reason of internal microstrain changes can be nc-TiO2 surface oxidation due to oxygen that appears when reducing the coordinate-unsaturated cations Ті4+ under irradiation by visible light with the wavelength 600 up to 800 nm [8].150 300 450 600 75023,4Eg(2)Eg(3)A1gB1gIntensity (a.u.)Raman shift, cm-1Eg(1)1Fig. 1. Raman spectra of nc-ТіО2 : initial (curve 1) andirradiated by laser irradiation with the dose of 0.02, 0.03, 004 J(curves 2, 3, 4, accordingly). Т = 300 К; λexc = 488.0 nm.120 135 150 165Eg(1)432Intensity (a.u.)Raman shift, сm-11Fig. 2. Еg(1) mode of nc-TiO2 at 144 cm-1: spectra of initial(curve 1) and irradiated by laser irradiation with the dose 0.02, 0.03, 0.04 J (curves 2, 3, 4, accordingly). Т = 300 К. λexc = 488.0 nm.024680.00 0.01 0.02 0.03 0.04640.0640.58.08.5Intensity, I/I0(b)(a)Eg(3), В1gEg(1)Halfwidth, Eg(1)Frequency, Eg(1)Power, J Fig. 3. Relative intensity change Еg(1), Еg(3), В1g of phononmode (a), frequency and halfwidth of Еg(1) mode vs laser irradiation power (b). Т = 300 К. λexc = 488.0 nm.Also, we researched the influence of the process of electrochemical intercalation in ТіО2 on its phonon spectra at different stages of х intercalation. The nonpolar mode with the frequency positions 144, 168 and 774 cm−1 (Eg(1), Eg(2) and Eg(3), accordingly), 2B1gnonpolar mode at 444 cm−1 and A1g mode at 604 cm−1 are observed in the experimental Raman spectrum(Fig. 4).Fig. 4. Raman spectra of nc-ТіО2 intercalated by lithium at х = 0.05 (curve 1), х = 0.10 (curve 2) and х = 0.15 (curve 3). Т = 300 К, λ = 488.0 nm.Accordingly to Fig. 4, at the increase of intercalation degree х for nc-TiO2 to up to 0.15 the decreasing of all phonon bands integral intensities takes Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 3. P. 309-313.© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine312place. The intensity of the band for Eg(1) mode decreases almost by 3.5 times (Fig. 5), and B1g, Eg(2) modes by  2 times. This effect of dominant decrease in the Eg(1) mode intensity can be conditioned by TiO2deformation in the TiO6 coordination octahedron bonding structure areas during lithium intercalation [13], the degree of which grows gradually. In our case (Fig. 5), for the intercalated samples of anatase nc-ТіО2with х = 0.15 the frequency position of the phonon band Eg(1) mode is 145 cm-1, which is some higher as compared to the samples intercalated to х = 0.05 (144 cm-1). This effect can be conditioned by the lattice parameter changes as a result of lithium diffusion [14] and increase of superficial strains. It is important to note that the change of Eg(1) phonon lines halfwidth in the Raman spectrum with the change of the intercalated lithium amount can be determined by the phase composition nonstoichiometry of intercalated titanium, which proves the uneven filling the vacant positions by lithium atoms in the bulk of anatase nanocrystal particles.Fig. 5. Еg(1) mode 144 cm-1 of nc-ТіО2 intercalated by lithiumat х = 0.05 (curve 1), х = 0.10 (curve 2) and х = 0.15 (curve 3). Т = 300 К. λ = 488.0 nm.4. ConclusionsConsiderable growth of the Eg(1) mode intensity can be conditioned by the laser irradiated TiO2 structural arrangement improvement, and reason of considerable broadening of B1g and Eg(3) phonon modes in the Raman spectrum is the small crystals defects. 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Raman spectroscopy of the laser irradiated titanium dioxide

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Raman spectroscopy of the laser irradiated titanium dioxide

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Наукова електронна бібліотека періодичних видань НАН України (Vernadsky National Library of Ukraine)