American Institute of Physics. Acta Medica Okayama 0021-8979 109 4 2011 Spectroscopic evidence of the formation of (V,Ti)O₂ solid solution in VO₂ thinner films grown on TiO₂(001) substrates 043702-1 043702-6 EN Y. Muraoka K. Saeki R. Eguchi T. Wakita M. Hirai T. Yokoya S. Shin We have prepared VO2 thin films epitaxially grown on TiO2(001) substrates with thickness systematically varied from 2.5 to 13 nm using a pulsed laser deposition method, and studied the transport property and electronic states of the films by means of resistivity and in situ synchrotron photoemission spectroscopy (SRPES). In resistivity measurements, the 13-nm-thick film exhibits a metal-insulator transition at around 290 K on cooling with change of three orders of magnitudes in resistivity. As the film thickness decreases, the metal-insulator transition broadens and the transition temperature increases. Below 4 nm, the films do not show the transition and become insulators. In situ SRPES measurements of near the Fermi level valence band find that the electronic state of the 2.5-nm-thick film is different than that of the temperature-induced insulator phase of VO2 itself although these two states are insulating. Ti 2p core-level photoemission measurements reveal that Ti ions exist near the interface between the films and TiO2 substrates, with a chemical state similar to that in (V,Ti)O-2 solid solution. These results indicate that insulating (V,Ti)O-2 solid solution is formed in the thinner films. We propose a simple growth model of a VO2 thin film on a TiO2(001) substrate. Near the interface, insulating (V,Ti) O-2 solid solution is formed due to the diffusion of Ti ions from the TiO2 substrate into the VO2 film. The concentration of Ti in (V,Ti) O-2 is relatively high near the interface and decreases toward the surface of the film. Beyond a certain film thickness (about 7 nm in the case of the present 13-nm-thick film), the VO2 thin film without any Ti ions starts to grow. Our work suggests that developing a technique for preparing the sharp interface between the VO2 thin films and TiO2 substrates is a key issue to study the physical property of an ultrathin film of "pure" VO2, especially to examine the presence of the novel electronic state called a semi-Dirac point phase predicted by calculations. No potential conflict of interest relevant to this article was reported.

Elsevier Acta Medica Okayama 0368-2048 181 2-3 2010 Angle-resolved photoemission spectroscopy for VO₂ thin films grown on TiO₂ (0 0 1) substrates 249 251 EN Y Muraoka K Saeki Y Yao T Wakita M Hirai T Yokoya R Eguchi S Shin We present the results of angle-resolved photoemission spectroscopy (ARPES) measurements of metallic VO₂ thin films. The VO₂ thin films have been grown on TiO₂ (0 0 1) single crystal substrates using pulsed laser deposition. The films exhibit a first-order metal–insulator transition (MIT) at 305 K. In the ARPES spectra of the metallic phase for the films, the O 2p band shows highly dispersive feature in the binding energy range of 3–8 eV along the „C–Z direction. The periodicity of the dispersive band is found to be 2.2 Å^-1 which is almost identical with the periodicity expected from the c-axis length of the VO₂ thin films. The overall feature of the experimental band structure is similar to the band structure calculations, supporting that we have succeeded in observing the dispersive band of the O 2p state in the metallic VO₂ thin film. The present work indicates that the ARPES measurements using epitaxial thin films are promising for determining the band structure of VO₂. No potential conflict of interest relevant to this article was reported.