In situ N K-edge XANES study of iron, cobalt and nickel nitride thin films.

A prototype in situ X-ray absorption near-edge structure (XANES) system was developed to explore its sensitivity for ultra-thin films of iron-nitride (Fe-N), cobalt-nitride (Co-N) and nickel-nitride (Ni-N). They were grown using DC-magnetron sputtering in the presence of an N2 plasma atmosphere at the experimental station of the soft XAS beamline BL01 (Indus-2, RRCAT, India). XANES measurements were performed at the N K-edge in all three cases. It was found that the N K-edge spectral shape and intensity are greatly affected by increasing thickness and appear to be highly sensitive, especially in low-thickness regions. From a certain thickness of ∼1000 Å, however, samples exhibit a bulk-like behavior. On the basis of the obtained results, different growth stages were identified. Furthermore, the presence of a molecular N2 component in the ultra-thin regime (<100 Å) was also obtained in all three cases studied in this work. In essence, this prototype in situ system reveals that N K-edge XANES is a powerful technique for studying ultra-thin films, and the development of a dedicated in situ system can be effective in probing several phenomena that remain hitherto unexplored in such types of transition metal nitride thin films.

Electronic structure modification and Fermi level shifting in niobium-doped anatase titanium dioxide thin films: a comparative study of NEXAFS, work function and stiffening of phonons.

The electronic structure and tuning of work function (WF) by electronic excitations (EEs) induced by swift heavy ions (SHIs) in anatase niobium-doped titanium dioxide (NTO) thin films is reported. The densities of EEs were varied using 80 MeV O, 130 MeV Ni and 120 MeV Ag ions for irradiation. The EE-induced modifications in electronic structure were studied by O K-edge and Ti L3,2 edge absorption spectra using near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The reduction of hybridized O 2p and Ti 3d unoccupied states in the conduction band with a decrease in energy of the crystal field strength of ∼ 480 meV and the correlated effect on the decrease in the WF value of ∼ 520 meV upon increasing the total energy deposition in the lattice are evident from the study of NEXAFS and scanning Kelvin probe microscopy (SKPM), respectively. The observed stiffening in the low frequency Raman mode (LFRM) of ∼ 9 cm(-1) further validates the electronic structure modification under the influence of EE-induced strain in TiO6 octahedra. The reduction of hybridized valence states, stiffening behavior of LFRM and decrease in WF by nano-crystallization followed by amorphization and defects in NTO lattice are explained in terms of continuous, discontinuous amorphous ion tracks containing intestinally created defects and non-stoichiometry in the lattice. These studies are very appropriate for better insights of electronic structure modification during phase transformation and controlled Fermi level shifting, which plays a crucial role in controlling the charge carrier injection efficiency in opto-electronic applications and also provides a deeper understanding of the involved physical processes.

Robust electronic and tunable magnetic states in Sm2 NiMnO6ferromagnetic insulator.

Ferromagnetic insulators (FM-Is) are the materials of interest for the new generation quantum electronic applications. Here, we have investigated the physical observables depicting FM-I ground states in epitaxial Sm2NiMnO6(SNMO) double perovskite thin films fabricated under different conditions to realize the different level of Ni/Mn anti-site disorders (ASDs). The presence of ASDs immensely influence the characteristic magnetic and anisotropy behaviors in SNMO system by introducing short scale antiferromagnetic interactions in predominant long range FM ordered host matrix. Charge disproportion between cation sites, in the form of Ni2++ Mn4+→ Ni3++ Mn3+, causes mixed valency in both Ni and Mn species, which is found insensitive to ASD concentrations. Temperature dependent photo emission, photo absorption measurements duly combined with cluster model configuration interaction simulations, suggest that the eigenstates of Ni and Mn cations can be satisfactorily described as a linear combination of the unscreeneddnand screeneddn+1L̲(L̲: O 2phole) states. The electronic structure across the Fermi level (EF) exhibits closely spaced Ni 3d, Mn 3dand O 2pstates. From occupied and unoccupied bands, estimated values of the Coulomb repulsion energy (U) and ligand to metal charge transfer energy (Δ), indicate charge transfer insulating nature, where remarkable modification in Ni/Mn 3d-O 2phybridization takes place across the FM transition temperature. Existence of ASD broadens the Ni, Mn 3dspectral features, whereas the spectral positions are found to be unaltered. Hereby, present work demonstrates SNMO thin film as a FM-I system, where the FM state can be tuned by manipulating ASD in the crystal structure, while the I state remains intact.

Mixed Mott-Hubbard and charge transfer nature of 4H-SrMnO3thin film on Si (100).

Room temperature electronic structure of polycrystalline 4H-SrMnO3thin film grown on Si (100) substrate has been studied using resonance photo emission spectroscopy and soft x-ray absorption spectroscopy measurements. Presence of charge transfer screen Mn 3dnLfinal state along with the 3dn-1final state at the valence band edge of 4H-SrMnO3thin film confirms that the ground state is strongly mixed between Mn 3dand O 2pstates. The estimated equivalent values of on-site Coulomb interaction energy (U) and O 2pto Mn 3d- charge transfer energy (Δ) (U≈ Δ ≈ 4.8 eV) from the combination of occupied and unoccupied spectra further confirm the intermediate Mott-Hubbard and charge transfer insulator nature of 4H-SrMnO3film. Despite having similar Mn 4+ valence state in 4H-SrMnO3and cubic SrMnO3, 4H phase is observed to reveal much higher band gap ∼1.5 eV than the cubic phase (0.3 eV), which arises due to different MnO6octahedra environment.

Strain healing of spin-orbit coupling:a cause for enhanced magnetic moment in epitaxial SrRuO3 thin films.

Enhanced magnetic moment and coercivity in SrRuO3 thin films are significant issues for advanced technological usages and hence are researched extensively in recent times. Most of the previous reports on thin films with enhanced magnetic moment attributed it to the high spin state. Our magnetization results show high magnetic moment of 3.3 µB/Ru ion in the epitaxial thin films grown on LSAT substrate against 1.2 µB/Ru ion observed in bulk compound. Contrary to the previous reports the Ru ions are found to be in low spin state and the orbital moment is shown to be contributing significantly in the enhancement of magnetic moment. We employed x-ray absorption spectroscopy and resonant valance band spectroscopy to probe the spin state and orbital contributions in these films. The existence of strong spin-orbit coupling responsible for the de-quenching of the 4d orbitals is confirmed by the observation of the non-statistical large branching ratio at the Ru M2,3 absorption edges. X-ray magnetic circular dichroism studies performed at the Ru M2,3 edges provided direct evidence of significant contribution of orbital moment in the film grown on LSAT. The relaxation of orbital quenching by strain engineering provides a new tool for enhancing magnetic moment and strain disorder is shown to be an efficient mean to control the spin-orbit coupling.

Structural, optical and electronic properties of Ni1-x Co x O in the complete composition range.

Crystallographic and electronic structures of phase pure ternary solid solutions of Ni1-x Co x O (x = 0 to 1) have been studied using XRD, EXAFS and XAS measurements. The lattice parameter of the cubic rock-salt (RS) Ni1-x Co x O solid solutions increases linearly with increasing Co content and follows Vegard's law, in the complete composition range. A linear increase in the bond lengths (Ni/Co-O, Ni-Ni and Ni-Co) with "x", closely following the bond lengths determined from virtual crystal approximation (VCA), is observed, which implies that there is only a minimal local distortion of the lattice in the mixed crystal. The optical gap of the ternary solid solution determined from diffuse reflectivity measurements shows neither a linear variation with Co composition nor bowing, as observed in many ternary semiconductors. This trend in the variation of optical gaps is explained by probing the conduction band using XAS at the O K-edge. We have observed that the variation in the onset energy of the conduction band edge with "x" is very similar to the variation in the optical gap with "x", thus clearly indicating the dominant role played by the conduction band position in determining the optical gap. The variation in the intensities of the pre-edge peak in the XANES spectra measured at Ni and Co K-edges, and the L1/2 peak in XAS spectra measured at Ni and Co L-edges, is found to depend on the unoccupied O 2p-metal-(Ni/Co) 3d hybridized states and the bond lengths.

In situ soft x-ray absorption spectroscopic study of polycrystalline Fe/MgO interfaces.

Interfacial interactions between a layer of iron and MgO hold the key to various phenomena like tunnel magnetoresistance, perpendicular magnetic anisotropy, interlayer exchange coupling, observed in the system. Interface structure has been studied in situ during deposition of iron on MgO surface, using soft x-ray absorption spectroscopy (SXAS). Sub-monolayer sensitivity of SXAS, combined with in situ measurements as a function of iron layer thickness, allowed one to study the evolution of interface with film thickness. Two different substrates namely MgO (0 0 1) single crystal, and a polycrystalline MgO film on Si substrate have been used in order to elucidate the role of the state of MgO surface in controlling the interface structure. It is found that at the interface of iron and MgO film, about two monolayers of Fe3O4 are formed. Fe3O4 being the oxide of iron with the highest heat of formation, the reaction appears to be controlled thermodynamically. On the other hand, on the interface with MgO (0 0 1) surface, FeO is formed, suggesting that the reaction is limited by the availability of oxygen atoms. Magnetic behavior of the FeO layer gets modified significantly due to proximity effect of the bulk ferromagnetic iron layer.

Structural, ferroelectric and dielectric properties of multiferroic YMnO3 synthesized via microwave assisted radiant hybrid sintering.

In this work, multiferroic YMnO3 ceramic samples prepared via microwave assisted radiant heating method (at 4 different microwave power percentage: 0, 15, 30 and 50) were studied to investigate their structural, ferroelectric and dielectric properties. In Raman measurement, the A1 Raman scattering line at ∼ 683 cm-1 is much stronger than other Raman modes and dominates the Raman spectra in all samples. The observed Raman modes identify the hexagonal YMnO3 type structure of studied samples. YMnO3 samples prepared at different microwave power displayed variation in ferroelectric polarization. The dielectric constant and dielectric loss tangent variation across different frequencies is also explored for these samples.

Elucidating the origin of magnetic ordering in ferroelectric BaTiO3- d thin film via electronic structure modification.

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[Formula: see text] thin films. Our adapted methodology employs state-of-the-art experimental approaches viz. photo-emission, 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[Formula: see text]) 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 BaTiO2.75 film reveals Mott-Hubbard insulator characteristic, in contrast to the band gap insulating nature of the stoichiometric BaTiO3. The observed magnetic ordering is attributed to the asymmetric distribution of spin polarized charge density in the vicinity of O[Formula: see text] 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[Formula: see text] system, which can open a gateway for designing novel single phase multiferroic system.

Excimer laser irradiation effects on soft magnetic properties of sputtered iron nitride thin films.

Effect of pulse laser irradiation on soft magnetic properties of reactively sputtered iron nitride thin film has been studied. The as-deposited films exhibit large coercivity in the range 54 Oe to 148 Oe. Laser irradiation results in remarkable decrease in the coercivity of the films, the minimum value achieved being 8 Oe. X-ray diffraction measurements evidence structural relaxation in the films, resulting in densification. Surface roughness of the films exhibits only a marginal increase after laser irradiation. The observed decrease in the coercivity may be attributed to the relaxation of some quenched-in stresses associated with structural relaxation in the films. Irradiation as a function of energy density of laser pulse shows that an optimum energy density is required to achieve the best soft magnetic properties, which can vary from sample to sample.

Grain size effect on lattice of ni nanocrystals prepared through polyol method.

Nanocrystalline nickel powders were prepared with grain size 'd' in the range 40-100 nm diameters through polyol method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used for characterization. XRD of the prepared samples consistently matched with standard fcc structure of nickel without any impurity peak. Detailed analysis and calculations using Scherrer equation for (111) peak revealed systematic increase in line width and peak shifting towards lower diffraction 2theta angles with decrease in nickel to ethylene glycol mole ratio. Different values of d estimated from various peaks of each sample suggested associated microstrains in the nanograins. Values of d estimated from X-ray diffraction patterns were compared with those obtained from atomic force microscopy and scanning electron microscopy results, and discussed. Observed lattice expansion is explained, on the basis of a theoretical model of linear elasticity.

Investigation of Ti layer thickness dependent structural, magnetic, and photoemission study of nanometer range Ti/Ni multilayer structures.

Structural, magnetic, and electronic properties of Ti/Ni multilayer (ML) samples as a function of Ti layer thickness are studied and reported in this paper. For this purpose [Ti (t nm)/Ni (5 nm)] x 10 ML samples, where t = 3, 5, and 7 nm have been deposited by using electron beam evaporation technique under UHV conditions at room temperature. Structure of ML samples were determined by using XRD (X-ray diffraction) technique and observed that Titanium is deposited mainly in amorphous nature with FCC structure at lower Ti layer thickness of 3 nm, which transform to crystalline HCP structures above than this Ti layer thickness. Corresponding fitted GIXRR (grazing incidence X-ray reflectivity) patterns shows asymmetric nature of Ti-Ni and Ni-Ti interfaces because of heavy intermixing and interdiffusion of Ni and Ti atoms at Ti-Ni interfaces at lower Ti layer thickness. The depth profiling core level and valence band measurements carried out by using XPS (X-ray photoelectron spectroscopy) technique confirms the interdiffusion and intermixing leading to Ti-Ni alloy phase formation at interfaces during deposition, particularly at lower Ti layer thickness of 3 nm. The corresponding magnetization behavior of ML samples has been investigated using Magneto-Optical Kerr Effect (MOKE) technique and observed that, coercitivity decreases while saturation magnetization increases with Ti layer thickness variations. These results are interpreted and discussed in terms of observed micro-structural changes due to Ti layer thickness vitiations in Ti/Ni multilayer samples.

Growth and properties of pulsed laser deposited thin films of Fe(3)O(4) on Si substrates of different orientation.

Fe(3)O(4) thin films were prepared by pulsed laser deposition on Si substrates of different orientations: (111), (100) and (110). X-ray diffraction studies revealed the spinel cubic structure of the films with preferential (111) orientation independent of the substrate orientation. Raman spectroscopy suggests the single-phase growth of Fe(3)O(4) films on these substrates, with minimum full width at half maxima being observed for the film grown on Si(111) substrate. These samples exhibit room-temperature ferromagnetism, as observed by magnetization hysteresis. The magnetization in these films saturates at a magnetic field value of approximately 0.2 T.

Giant Rashba effect at the topological surface of PrGe revealing antiferromagnetic spintronics.

Rashba spin-orbit splitting in the magnetic materials opens up a new perspective in the field of spintronics. Here, we report a giant Rashba spin-orbit splitting on the PrGe [010] surface in the paramagnetic phase with Rashba coefficient α R = 5 eVÅ. We find that α R can be tuned in this system as a function of temperature at different magnetic phases. Rashba type spin polarized surface states originates due to the strong hybridization between Pr 4f states with the conduction electrons. Significant changes observed in the spin polarized surface states across the magnetic transitions are due to the competition between Dzyaloshinsky-Moriya interaction and exchange interaction present in this system. Presence of Dzyaloshinsky-Moriya interaction on the topological surface give rise to Saddle point singularity which leads to electron-like and hole-like Rashba spin split bands in the [Formula: see text] and [Formula: see text] directions, respectively. Supporting evidences of Dzyaloshinsky-Moriya interaction have been obtained as anisotropic magnetoresistance with respect to field direction and first-order type hysteresis in the X-ray diffraction measurements. A giant negative magnetoresistance of 43% in the antiferromagnetic phase and tunable Rashba parameter with temperature makes this material a suitable candidate for application in the antiferromagnetic spintronic devices.

Electronic structure of Mo1-x Re x alloys studied through resonant photoemission spectroscopy.

We studied the electronic structure of Mo-rich Mo1-x Re x alloys ([Formula: see text]) using valence band photoemission spectroscopy in the photon energy range 23-70 eV and density of states calculations. Comparison of the photoemission spectra with the density of states calculations suggests that, with respect to the Fermi level E F, the d states lie mostly in the binding energy range 0 to -6 eV, whereas s states lie in the binding energy range -4 to -10 eV. We observed two resonances in the photoemission spectra of each sample, one at about 35 eV photon energy and the other at about 45 eV photon energy. Our analysis suggests that the resonance at 35 eV photon energy is related to the Mo 4p-5s transition and the resonance at 45 eV photon energy is related to the contribution from both the Mo 4p-4d transition (threshold: 42 eV) and the Re 5p-5d transition (threshold: 46 eV). In the constant initial state plot, the resonance at 35 eV incident photon energy for binding energy features in the range E F (BE = 0) to -5 eV becomes progressively less prominent with increasing Re concentration x and vanishes for x > 0.2. The difference plots obtained by subtracting the valence band photoemission spectrum of Mo from that of Mo1-x Re x alloys, measured at 47 eV photon energy, reveal that the Re d-like states appear near E F when Re is alloyed with Mo. These results indicate that interband s-d interaction, which is weak in Mo, increases with increasing x and influences the nature of the superconductivity in alloys with higher x.

Implication of local moment at Ti and Fe sites for the electrical and magneto-transport properties of degenerate semiconducting Ti1-xFexO2-d epitaxial films.

We have investigated the effect of local magnetic moment on the electrical and magneto-transport properties of thin films of the degenerate semiconductor Ti(1-x)Fe(x)O(2-d) (x = 0,0.04). The electrical measurements of these films reveal high temperature metallic behavior and resistivity minima. The behavior below the resistivity minimum temperature is ascribed to Kondo like scattering. The coupling between the local moment and the charge carriers is reflected in the magnetoresistance measurements in these films. This work indicates competition between the magnetic ordering mechanism by J(RKKY) and the moment screening mechanism by J(Kondo). Accordingly the role of carrier density in achieving the magnetic ordering in such materials either by defect engineering or by transition metal doping is discussed.