This action might not be possible to undo. Are you sure you want to continue?
Chinese Journal of Aeronautics 20(2007) 162-167
Journal of Aeronautics
Magnetic and Optical Properties of the TiO2-Co-TiO2 Composite Films Grown by Magnetron Sputtering
LIU Fa-min*, DING Peng, SHI Wei-mei, WANG Tian-min
Department of Physics, School of Sciences, Beijing University of Aeronautics and Astronautics, Beijing 100083, China Received 10 August 2006; accepted 3 November 2006
Abstract The TiO2-Co-TiO2 sandwich films were successfully grown on glass and silicon substrata making alternate use of radio frequency reactive magnetron sputtering and direct current magnetron sputtering. The structures and properties of these films were identified with X-ray diffraction (XRD), Raman spectra and X-ray photoemission spectra (XPS). It is shown that the sandwich film consists of two anatase TiO2 films with an embedded Co nano-film. The fact that, when the Co nano-film thickens, varied red shifts appear in optical absorption spectra may well be explained by the quantum confinement and tunnel effects. As for magnetic properties, the saturation magnetization, remnant magnetic induction and coercivity vary with the thickness of the Co nano-films. Moreover, the Co nano-film has a critical thickness of about 8.6 nm, which makes the coercivity of the composite film reach the maximum of about 1413 Oe. Keywords: TiO2-Co-TiO2 sandwich films; surface structure and properties; optical and magnetic properties
Titanium dioxide (TiO2) is an attractive material in applications such as photo-catalyst and gate oxides in MOS transistors. Since the discovery of Matsumoto et al, Co/TiO2 thin films have drawn many researchers’ attention due to their very high Curie temperature (TC). While much work[4-10] has been done on the ferromagnetic properties of Co/TiO2 thin films grown by various methods, a few papers have been published on the magnetic properties of other 3d metals doped with TiO2. Also have been made public a lot of researches as to other dilute magnetic semiconductors[12-16], which are of considerable use to spin injectors in spintronic devices. However, so far very few studies over optical and magnetic properties of the TiO2*Corresponding author. Tel.: +86-10-82317935.
E-mail address: email@example.com Foundation items: Aeronautical Science Foundation of China (03G51069); Items of Engineering Research Institute, Peking University (ERIPKU-204031)
Co-TiO2 sandwich films have been performed. Recently, it is found that TiO2-Co-TiO2 sandwich films are able to be grown on glass and silicon substrata making alternate use of radio-frequency reactive (RFR) magnetron sputtering and direct current (DC) magnetron sputtering. This paper presents microstructures, optical and magnetic properties of these films, obtained by means of X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, UV-visible spectrophotometer and vibrating sample magnetometer. Moreover, a discussion is carried out about the influences of the Co nano-film and the substrate temperature on the optical and magnetic properties of the TiO2-Co-TiO2 sandwich films.
2 Experimental Procedure
The TiO2-Co-TiO2 sandwich films were deposited making alternate use of radio frequency reactive magnetic sputtering and direct current magnetron sputtering. Glass and silicon substrata in size of
The magnetic properties were studied on an LDJ-model 9600 vibrating sample magnetometer at the room temperature. In order to produce a TiO2-Co-TiO2 sandwich film.1 is the X-ray diffraction patterns pertaining to a TiO2-Co-TiO2 sandwich film and an anatase TiO2 film grown on a glass substrate making alternate use of radio frequency reactive magnetron sputtering under the condition that the power equal to 250 W.999%) Ti plate Ø60 mm×3 mm thick was used as a target. All samples measured were calibrated with respect to the C1s peak at 284.0 sccm was introduced. The average grain size d of TiO2 can be estimated from the XRD profiles using Scherrer’s equation: d = kλ / β cosθ where k is a constant (shape factor. Every substrate was further inversely sputtered for 5 min before the high film deposited. The cell dimensions calculated from the diffracted lines are a = 0. In our experiment. only a stream of high purity (99.6 eV. the film was heated in situ at various temperatures (100-700 ℃) to ensure high-quality TiO2 films. the second anatase TiO2 is formed by the same route the first one has been made. As for the anatase TiO2. The TiO2-Co-TiO2 sandwich films were identified by X-ray diffraction (XRD).28 nm/s. The target was separated from the substrate 5 cm. (200).2 . alcohol.9999%) argon and oxygen (99. The film thickness d was determined by surface profilometry with a DEKTAK 3 α-step instrument. / Chinese Journal of Aeronautics 20(2007) 162-167 · 163 · 20 mm×20 mm were ultrasonically washed successively in acetone.5 nm line of Ar+ laser excitation at the room temperature. All spectra reported here were measured in backscattering geometry using the 514. (204). the mean particle size of 13. An output laser power of 200 mW was needed to avoid sample overheated. about 0. The XRD data accord with those of anatase TiO2 in Refs. In TiO2 film. (211). Optical absorption spectra without consideration of reflection loss were measured with a Perkin-Elmer λ9 double beam spectrophotometer in the range from 300 to 1 000 nm at the room temperature. The X-ray diffractometer was operated at a voltage of 40 kV and a current of 150 mA. are present. During sputtering.0 sccm and substrate temperature 500 ℃. Fig. and de-ionized water to achieve a clean surface before being placed in a vacuum chamber. the thickness of about 80 nm of TiO2 films of the TiO2-Co-TiO2 sandwich film was kept constant. (004). 3 Results and Discussion In our experiments. When the chamber was evacuated to a pressure of 5×10-5 Pa. λ is X-ray wavelength. X-ray photoemission spectra data were recorded with a VG ESCALAB MK II spectrometer using MgKα source (1 253.9). Then. the high anatase TiO2 was deposited by radio frequency reactive magnetron sputtering. X-ray diffraction (XRD) studies were carried out on a rotating anode of D/max-rB type. can be observed seven diffracted lines labeled by (101). a mixed stream of high purity (99. First. A high purity (99. Raman scattering and X-ray photoemission spectra (XPS).98 %) Co plate Ø60 mm×3 mm thick was used as a target. The direct current sputtering power was about 26 W.5 nm/min.LIU Fa-min et al. No diffracted lines characterized by other polymorphs of TiO2.6 eV) radiation of 12 kV and 20 mA.999 %) gases at a ratio of 50/5. 18].[17.9999%) argon gas was introduced. Raman scattering spectra were measured using a SPEX-1403 laser Raman spectrometer with a typical resolution of 1 cm-1 in the measured frequency region. The output voltage of the radio frequency sputter gun was 1 020 V. the sputtering rate of TiO2 was as large as ~2. the chamber pressure was maintained 2 Pa.154 nm) monochromated with a graphite sample. A computer-controlled sputtering system was used.951 nm. When the chamber was again evacuated to a pressure of 5×10-5 Pa. (220) and (215). Ar/O2 ratio 50/5. And thus a Co nano-film was grown onto TiO2 layer by direct current magnetron sputtering. rutile or brookite. β is full-width at half-maximum (FWHM) of the diffraction line and θ is a diffraction angle. and that of Co about 0.378 nm and c=0. The deposition rate was obtained by dividing d by sputtering time. while the thickness of Co film varied from 3 nm to 20 nm. A round high purity (99. CuKα1 radiation (λ=0.
The core levels of Co 2p1/2 and Co 2p3/2 are at 797.4 eV. Some feature diffraction peaks of anatase TiO2 and a Co (111) could be noticed in the TiO2-Co-TiO2 sandwich film.7 eV. respectively.1 X-ray diffraction patterns of the TiO2-Co-TiO2 sandwich film and the anatase TiO2 film. (b) the TiO2-Co-TiO2 sandwich film. Fig. Fig. level of the anatase TiO2 and the TiO2-Co-TiO2 sandwich film.1 and 782. and the others 515 cm-1 and 640 cm-1 to the Eg modes. the core levels of Co 2p3/2 and Co 2p1/2 in the anatase TiO2 have chemical shifts of 0. From it.4 shows XPS O 1s core level of (a) the anatase TiO2 and (b) the TiO2-Co-TiO2 sandwich film.2 Raman scattering spectra of the anatase TiO2 film and the TiO2-Co-TiO2 sandwich film. From it. In addition.3 shows the comparison of XPS Ti 2p core Fig. From it. However. and has a peak separation at 5. Fig.1 and 458. it is obvious Co in a metal state in the anatase TiO2. which. the core levels of Ti 2p1/2 and Ti 2p3/2 have a small shift of 0.43 eV. in approximate accordance with the main peak at 529.9 eV of TiO2. which indicates a strong interaction at the interface between the TiO2 film and the glass substrate. Fig. Fig. The XRD pattern of TiO2-Co-TiO2 sandwich films reveals that the film is a mixture of the anatase TiO2 and the cubic cobalt. (b) the TiO2-Co-TiO2 sandwich film.7 eV between them. / Chinese Journal of Aeronautics 20(2007) 162-167 nm is estimated.· 164 · LIU Fa-min et al.2 eV respectively. Weak XRD peak signals can be sourced back to very thin films (about 150 nm). having a peak separation of 14. These results are in good agreement with Ref. respectively.. there is another Raman peak of around 1 106 cm-1 attributable to the vibration mode of Ti-O-SiO2. Fig. the core level of O 1s is at line of 529. are ascribed to the Ti4+ (TiO2).42 eV and 0. in line with Ref.[21.3 XPS Ti 2p core level of (a) anatase TiO2.2.5 shows XPS Co 2p core level of the TiO2Co-TiO2 sandwich film.. The two of them are approximately 144 cm-1 and 400 cm-1 which are attributable to the B1g modes. Raman scattering spectra of the anatase TiO2 film and the TiO2-Co-TiO2 sandwich film are shown in Fig. Compared with Refs. which is assigned to the titanium dioxide at the surface. 22]. can be seen four Raman scattering peaks of the anatase TiO2.9 eV between them.4 XPS O 1s core level of (a) anatase TiO2. Compared to Ref. This demonstrates an interaction be- .1 eV.. the core levels of Ti 2p1/2 and Ti 2p3/2 are approximately at 464.
Fig.6 Optical absorption of the TiO2-Co-TiO2 sandwich films with different thicknesses of Co nano-film. The optical absorption spectra of the TiO2-Co. / Chinese Journal of Aeronautics 20(2007) 162-167 · 165 · tween Co and TiO2. in case of a Co nano-film embedded between two-anatase TiO2 films. presented in Fig.LIU Fa-min et al. The value of m (m = 2) is a characteristic value for the indirect allowed transition. which dominates over the optical absorption[24.8 Optical absorption spectra of the TiO2-Co-TiO2 sandwich film deposited at different substrate temperatures.7. Co atoms will diffuse into the matrix of TiO2 and change the band gap of the TiO2-Co-TiO2 sandwich films. The variation of band gap with the thickness d of the Co nano-film in the TiO2-Co-TiO2 sandwich films is Fig. These can be in- .2 nm. This indicates that the band gap of the anatase TiO2 narrows when the Co nano-film thickens. which correspond to the substrate temperatures of 300. Fig. 350 and 400 ℃ respectively. 12 and 48 nm.86 eV) in comparison with that of the bulk anatase TiO2 (3. respectively. the Ar/O2 ratio 50/5.6 nm. However.25]. It is observed that as the substrate temperature increases. 330.6. Fig. 333. It is shown that the threshold α of the fundamental absorption of the TiO2-Co-TiO2 sandwich film may be described by the expression: α = A ( E – Eg)m (1) where E is the optical band gap of the TiO2-Co-TiO2 sandwich film. which may well be explained by the quantum confinement effects.TiO2 sandwich films with different thicknesses of Co nano-layer are shown in Fig. are shown in Fig.5 and 345.0 sccm. the optical absorption of the TiO2-Co-TiO2 sandwich films red shift to 321.8. which correspond to the thickness of the Co nano-film of 3. 349.7.5 XPS Co 2p core level of the TiO2-Co-TiO2 sandwich film.8. The measured results of these optical absorption edges are about 339. Eg is the optical band gap of the pure anatase TiO2. From Fig. and A is a constant. The optical absorption spectra of the TiO2Co-TiO2 sandwich films deposited at different substrate temperatures under the condition that the power be 250 W. the optical absorption edge blue shifted to 320. 9. For nanocrystalline anatase TiO2 film with zero thickness of Co nano-layer.8 and 400.6.9 nm (3.7 Variation of band gap vs the thickness of Co-nanofilm in TiO2-Co-TiO2 sandwich films.4. the optical absorption edges see varied red shifts.20 eV).
has the saturation magnetization of about 4. remnant magnetic induction and coercivity vary with the thickness of Co nano-films. Fig.10 A hysteresis loop of another TiO2-Co-TiO2 sandwich film in magnetic field.6 nm of the Co nano-film can be noticed in this kind of composite films which have the maximum coercivity of about 1 413 Oe. Fig. From Fig. It is clear that the coercivity of 9 nm Co-em- . The Co nano-film has a critical thickness of about 8.6 nm. The saturation magnetization. which makes the coercivity of the composite film reach the maximum value of about 1 413 Oe. 4 Conclusions The TiO2-Co-TiO2 sandwich films were successfully grown on glass and silicon substrates making alternate use of radio frequency reactive magnetic sputtering and direct current magnetron sputtering. which originated from the quantum confinement effects. the thicknesses of the Co films. the remnant magnetic induction of 1.11 The coercivity of the TiO2-Co-TiO2 sandwich films vs. Fig.11 shows the coercivity of the TiO2-Co-TiO2 sandwich films versus varied thicknesses of Co nano-films. Fig. / Chinese Journal of Aeronautics 20(2007) 162-167 terpreted by the decrease of the band gaps of TiO2-Co-TiO2 sandwich films with an ever-increasing number of Co atoms diffusing into the matrix of TiO2 caused by increased substrate temperature.10 illustrates a hysteresis loop of another TiO2-Co-TiO2 sandwich film in magnetic field. It demonstrates ferromagnetic properties possessed by the TiO2-Co-TiO2 sandwich film. This may well be accredited to the quantum interface effects.· 166 · LIU Fa-min et al. Its loop is parallel to the film plane as well. bedded film is higher than that of the 12 nm Co-embedded one.6 Oe. The structures and the properties of these films were investigated with XRD. The sandwich films comprise two anatase TiO2 films and an embedded Co nano-film. Fig. composed of two 80 nm TiO2 layers and an embedded Co film 12 nm thick. The films show ferromagnetic properties at the room temperature. The film has an embedded Co film about 9 nm thick and coercivity of about 1 399.9 A hysteresis loop of a TiO2-Co-TiO2 sandwich film in magnetic field parallel to the film plane.11. which is parallel to the film plane. Raman spectra and X-ray photoemission spectra (XPS).02 emu/g and the coercivity of 569. Transmission absorption spectra see varied red shifts as the Co nano-film thickens.9 shows a hysteresis loop of a TiO2Co-TiO2 sandwich film in magnetic field.35 emu/g. a critical thickness of about 8.2 Oe at the room temperature. and the solid line the Gaussian fit. where circle points present the experimental data. This film. Fig.
Perkin-Elmer: Eden Praitie. Surf & Coat Technol 2001. Room-temperature ferromag          netism in Mn-doped SnO2 diluted magnetic semiconductor. Nonlinear optical properties of nanocrystalline GaSb-SiO2 composite film. Tay M. / Chinese Journal of Aeronautics 20(2007) 162-167 · 167 · References  Choi W. He will Now he has published more than 60 papers in various pe- get his Master degree in 2007. et al. Appl Phys Lett 2004. 79(21): 3467-3469. 34(22): 4810-4815. Electrical and optical properties of TiO2 anatase thin films. He is doing research work on functional thin films. 268(1/2): 159-164. 33(8): 912-916. 54(1): 369-372. Room-temperature ferromagnetism in transparent transition metal-doped titanium dioxide. Sakai J.  Kimura H. 37(10): 5852-5856. 2005. Ren M J.buaa. The effect of Mn disorder on the electronic and magnetic properties of (Ga. Epitaxial growth of ferromagnetic Co:TiO2 thin films by co-sputtering. Kawai T. [in Chinese]  Hong N H. Saito H. male. 83(15): 3129-3131.07O2 anatase. 79(7): 988-990. 291: 854-856. 84(15): 2832-2834. Stickle W F. et al. Fukumura T. Prasad K.  Matsumoto Y. Okada N. Zhu J. Wolf G K. et al. Appl Phys Lett 2002. He Y L. Fe. Surf Sci 2001. Size effect on the ferroelectric phase transition in the PbTiO3 ultrafine particles. Hong S J. [in Chinese] Guo X G. Tasca M. et al.cn DING Peng Born in 1983. Ishikawa K. J Magnet Mater 2004. Thevuthasan S. Wang X. Mardare D. et al. male. et al.  Cui M L. On the structural properties and optical transmittance of TiO2 r. J Phys D: Appl Phys 2000. 81(13): 2421-2423.  Ando K. et al.  Ueda K.and Ni-doped TiO2 thin films grown on LaAlO3 and SrTiO3 substrates by laser ablation. 78(18): 2700-2702. et al.f. Appl Phys Lett 2001. Handbook of X-ray photoelectron spectroscopy. et al.  Kennedy R J. et al. Zhang W F. Professor. New York: Geology Society of America. Appl Surf Sci 2000. Synthesis and characterization of titania films on Mo(110).  Hong N H. His main research interests are in dilute magnetic semiconductor oxides and functional thin film. Zhang L D. Enviro Sci Technol 2000. et al.edu. riodicals. J Appl Phys 1994. 74(21): 3143-3145. graduate student. et al.  Kuang A L. Guo Q. Zhong X Y. Yoshikawa K. Co distribution in ferromagnetic rutile Co-doped TiO2 thin films grown by laser ablation on silicon substrates. Murakami M. X-ray powder data for ore minerals. Wang T M. sputtered thin films. Acta Physica Sinica 2005. Appl Phys Lett 1999. Science 2001.  Han G C. Zhang M S. 487: 1-8. Prellier W. 75(4): 2042-2047. 51(1): 183-186. Liu X C. Lee K W. Sobol P E. Epitaxial growth and properties of ferromagnetic co-doped TiO2 anatase. Appl Phys Lett 2001. 84(15): 2850-2852. Chang Y S. E-mail: fmliu@buaa. Appl Phys Lett 2004.edu. Stampe P A.  Chambers S A. Farrow R F C. 54(6): 2934-2937. [in Chinese] Biography: LIU Fa-min Born in 1961. Chen X S. Liu C Y. et al. 156: 200-206. Tang H.04O2 thin films and their ferromagnetism. Min B K. Sun Y L. Appl Phys Lett 2003. et al. Sakai J. Mn) As: a first principles study. et al.  Lee B H. Lai X. Thompson R M. et al. 85(10): 1698-1670.  Kim D H. Raman scattering study on anatase TiO2 nanocrystals. Jeon Y.96Co0. 80(1): 94-96. E-mail: firstname.lastname@example.orgCo0.  Song H Q. Phys Rev B 1988. Yang J S. et al. Liu F M. Shono T. 1962. Kawasaki M. Wu Y H. Formation of Co nanoclusters in epitaxial Ti0. Effects of interfacial layer growth on the electrical characteristics of thin titanium oxide films on silicon. Prellier W. Chen Y X. Hopping transport in TiO2:Co: signature of multiphase behavior. Sanjines R. Appl Phys Lett 2002. et al. et al. Zawadzki K. Photocatalytic degradation of polychlorinated dibenzo-p-dioxins on TiO2 film under UV or solar light irradiation. Appl Phys Lett 2001. Acta Physica Sinica. et al.LIU Fa-min et al. Hu E H. Tabata H. Jin Z. Appl Phys Lett 2004. 53(5): 1516-1519. Large magneto-optical effect in an oxide diluted magnetic semiconductor Zn1–xCoxO. Acta Physica Sinica 2002. Study of ferromagnetic semiconductor films: Ti1–xCoxO2. Acta Physica Sinica 2004. Magnetic and electric properties of transition-metal-doped ZnO films. Surface properties of silver doped titanium oxide films. et al. 1992. [in Chinese] Berry L G. Moudler J F. Zhang F. Delibas M. Rutile-type oxide-diluted magnetic semiconductor: Mn-doped SnO2.cn . Cobalt valence in epitaxial Ti0. 148: 65-70.
This action might not be possible to undo. Are you sure you want to continue?
We've moved you to where you read on your other device.
Get the full title to continue listening from where you left off, or restart the preview.