We have investigated the electronic and magnetic properties of the pulsed laser deposited epitaxial thin films of undoped and Fe doped (4 at. %) anatase TiO2−d by photoemission, magnetization measurements, and ab-initio band structure calculations. These films show room temperature magnetic ordering. It is observed that Fe ions hybridize with the oxygen vacancy induced Ti3+ defect states. Our study reveals the formation of local magnetic moment at Ti and Fe sites to be responsible for magnetic ordering. A finite density of states at the Fermi level in both undoped and Fe doped films is also observed, suggesting their degenerate semiconducting nature.
We study the structural and electronic properties of Fe doped (4–8 at. %) and undoped TiO2 thin films deposited by pulsed laser deposition on Si(111) substrate. The films grow in single phase anatase structure of TiO2 as revealed by x-ray diffraction and Raman spectroscopy measurements. The Fe doped films reveal room temperature magnetic hysteresis behavior. We have probed the electronic environment of Fe in TiO2 matrix and its coupling to the cations, using photoelectron spectroscopy measurements. Photoelectron spectroscopic studies reveal the ionic state of Fe in TiO2, precluding the formation of Fe metal clusters. Valence band spectra of these films suggest that it primarily consists of O-2p derived state, however, Fe derived state is also observed in Fe doped films. Resonance photoelectron spectroscopy studies indicate that Fe ions are hybridized with Ti3+ defect states.
With the motive of unraveling the origin of native vacancy induced magnetization in ferroelectric perovskite oxide systems, here we explore the consequences of electronic structure modification in magnetic ordering of oxygen deficient epitaxial BaTiO 3−δ thin films. Our adapted methodology employs state-of-the-art experimental approaches viz. photoemission, photo-absorption spectroscopies, magnetometric measurements duly combined with first principles based theoretical methods within the frame work of density functional theory (DFT and DFT+U) calculations. Oxygen vacancy (O V ) is observed leading partial population of Ti 3d (t 2g ), which induces defect state in electronic structure near the Fermi level and reduces the band gap. The oxygen deficient BaTiO 2.75 film reveals Mott-Hubbard insulator characteristic, in contrast to the band gap insulating nature of the stoichiometric BaTiO 3 . The observed magnetic ordering is attributed to the asymmetric distribution of spin polarized charge density in the vicinity of O V site, which originates unequal magnetic moment values at first and second nearest neighboring Ti sites, respectively. Hereby, we present an exclusive method for maneuvering the band gap and on-site electron correlation energy with consequences on magnetic properties of BaTiO 3−δ system, which can open a gateway for designing novel single phase multiferroic system.
The electronic structure of CeO2 thin film grown by pulsed laser deposition on Si (100) substrate has been investigated using resonance photoemission spectroscopy (RPES). X-ray photoemission study on the film suggests that Ce has 3+ and 4+ valence states. Valence band spectra of the film show a feature at 2.1 eV of binding energy and a broad band at higher binding energy due to O 2p derived state. RPES measurements performed in the Ce 4d→4f photoabsorption region show maximum intensity for 2.1 eV feature at photon energy of 122 eV confirming it to be due to Ce3+ (4f1) state. RPES measurements also show maximum intensity for binding energy position of 4.4 eV in the broad band at photon energy of 125 eV, suggesting it to be due to Ce4+ (4f0) state. Constant initial state (CIS) versus photon energy plots also confirm these findings and suggest that the broad band is admixture of O 2p and Ce 4f and 5d derived states.
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