Room temperature ferromagnetism is observed in undoped TiO2 films deposited on Si substrates using pulsed laser deposition (PLD). The ferromagnetic properties of the samples depend on the oxygen partial pressure during the PLD synthesis. The appearance of higher binding energy component (HBEC) in the oxygen 1s core peak from x-ray photoelectron spectroscopy (XPS) suggests the presence of oxygen vacancies in these samples. The amount of oxygen during the synthesis determines the vacancy concentration in the samples which is directly related to the magnetic behavior of the samples. The magnetic moment decreases with oxygen vacancy concentration in the samples. Valence band measurements were performed to study the electronic structure of both stoichometric and reduced TiO2. The analyses show the presence of Ti 3d band near the Fermi level in reduced TiO2 samples. These bands are otherwise empty in stoichiometric TiO2 and reside in the conduction band which makes them unobservable by XPS. The existence of this Ti 3d band near the Fermi level can possibly lead to Stoner splitting of the band.Comment: 20 pages, 9 figur

We have determined the electronic and atomic structure of N doped TiO 2 using a combination of hard x-ray photoelectron spectroscopy (HAXPES) and first-principles density functional theory calculations. Our results reveal that N doping of TiO 2 leads to the formation of oxygen vacancies and the combination of both N impurity and oxygen vacancies accounts for the observed visible light catalytic behavior of N doped TiO 2 .Titanium dioxide (TiO 2 ) is widely studied for applications such as photocatalysis [1,2], photovoltaics [3], and dilute magnetic semiconductor [4,5]. One of the most promising applications of TiO 2 is its catalytic capability of splitting water into oxygen and hydrogen [6]. However, due to its large band gap (3 and 3.2 eV for rutile and anatase, respectively), pure TiO 2 is only activated by ultraviolet light, lowering the efficiency of its catalytic process. Doping of TiO 2 can introduce energy levels in the band gap [7,8], effectively tailoring its electronic structure to absorb light in the visible region. Recently N doped TiO 2 has been synthesized and its catalytic properties demonstrated with visible light [9,10]. This success, however, is riddled with controversies concerning the

We report stabilization of magnetic glassy state in non-stoichiometric nickel ferrite thin films prepared by pulse laser deposition. Details of electronic structure of the films are presented and compared with stoichiometric bulk counterpart. Hard x-ray photoelectron spectroscopy shows significant amount of oxygen vacancies and enhanced cationic inversion for thin films. Films show spin glass (SG) features which is contrary to the usual ferrimagnetic response of the bulk nickel ferrite. Films exhibit spin freezing temperature which is above room temperature in low fields (0.1 T) and shifts to lower temperature (∼250 K) in the presence of a large applied field of 3 T. An exceptionally large exchange bias (EB) of 170 Oe at a significantly higher temperature (∼50 K) is measured in cooling field of 3 T. In comparison, bulk samples do not show exchange bias and magnetic irreversibility vanishes in significantly weaker fields (i.e., few kOe). Role of oxygen vacancies is to induce spin canting by destabilizing indirect super exchange interaction. Consequently, the spin-glass like behavior occurs that is coupled with huge suppression in saturation magnetization in the thin films. Observation of exchange bias is explained to be due to oxygen vacancies (hence non-stoichiometry) which generates random anisotropy in exchange coupled grains.

Recent applications of hard x-ray photoelectron spectroscopy (HAXPES) demonstrate its many capabilities in addition to several of its limitations. Examples are given, including measurement of buried interfaces and materials under in-situ or in-operando conditions, as well as measurements under x-ray standing-wave and resonant excitation. Physical considerations that differentiate HAXPES from photoemission measurements utilizing soft and ultraviolet x rays are also presented.

Nickel ferrite thin films were synthesized by pulsed laser deposition. It was determined that the monotonic increase in saturation magnetization and the non-monotonic increase in electrical conductivity depend on the oxygen partial pressure during the growth of the thin films. A substantial reduction in magnetization was found which ranged between 0.4% and 40% of the bulk value as the oxygen partial pressure increased from 0.2 × 10−6 Torr to 500 mTorr during the deposition of the films. There was a three orders of magnitude increase in conductivity for the sample prepared under the most oxygen deficient environment (partial pressure of oxygen 0.2 × 10−6 Torr). These variations in saturation magnetization and conductivity are described within the framework of cation/oxygen vacancies in an inverse spinel nickel ferrite structure. The changes in the electronic structure due to the presence of the vacancies were investigated using x-ray photoelectron spectroscopy, which confirmed the formation of lower valent Ni for the samples prepared in an oxygen deficient atmosphere.

We report the crystallization study of CoFeB/MgO/CoFeB magnetic tunnel junctions using in-situ, time-resolved synchrotron-based x-ray diffraction and transmission electron microscopy. It was found that the crystallization of amorphous CoFeB electrodes occurs on a time scale of seconds during the postgrowth high temperature annealing. The crystallization can be well fit by the Johnson-Mehl-Avrami model and the effective activation energy of the process was determined to be 150 kJ/mol. The solid-state epitaxy mode of CoFeB was found to involve separate crystallization at different locations followed by subsequent merging of small grains, instead of layer-by-layer growth of CoFeB film along the MgO template.

We find a new 5 eV satellite in the Ti 1s photoelectron spectrum of the transition-metal oxide SrTiO 3 . This satellite appears in addition to the well-studied 13 eV structure that is typically associated with the Ti 2p core line. We give direct experimental evidence that the presence of two satellites is due to the crystal-field splitting of the metal 3d orbitals. They originate from ligand 2p t 2g → metal 3d t 2g and ligand 2p e g → metal 3d e g monopole charge-transfer excitations within the sudden approximation of quantum mechanics. This assignment is made by the energetics of the resonant and high-energy threshold behaviors of the Ti K-L 2 L 3 Auger decay that follows Ti 1s photo-ionization.

Silver nanoparticles were synthesized by an inert gas condensation method using flowing helium in the process chamber. Nucleation, growth mechanism, and the kinetics of nanoparticle formation in vapor phase are studied. Effect of process parameters, such as evaporation temperature and inert gas pressure, on the particle crystallinity, morphology, and size distribution are examined. Particles were synthesized at evaporation temperatures of 1123, 1273, and 1423 K and at helium pressures of 0.5, 1, 5, 50, and 100 Torr. Synthesized silver nanoparticles were characterized by x-ray diffraction (XRD) and transmission electron microscopy (TEM). The particle size ranged from 9 to 32 nm, depending on the growth conditions. At lower evaporation temperature and inert gas pressure, smaller particles with spherical shape showing less agglomeration are formed. Based on the experimental results and theoretical model of surface free energy and undercooling as a function of evaporation temperature and inert gas pressure, particle formation is analyzed. A simple operating map for nanoparticle synthesis is presented. The theoretical model is well supported by the experimental data.