Enhanced photoluminescence of rare-earth doped films prepared by off-axis pulsed laser deposition

Alternate pulsed laser deposition from the host (Al₂O₃) and dopant (Er, Yb) targets has been used to prepare artificially nanostructured films in which the rare earth ion-ion separation is controlled in the nanometer scale in order to control energy transfer between ions. One series of films was prepared in the standard on-axis configuration, i.e. a static substrate being centred with respect to the plasma expansion axis. A second series of films was prepared by rotating the substrate with respect to a shifted axis parallel to the plasma expansion one (off-axis configuration). The latter configuration leads to films with enhanced thickness and Er related photoluminescence intensity uniformity. More interestingly, the Er related photoluminescence lifetime in as-grown films increases up to 2.5 ms, which is much higher than the maximum value of 1 ms obtained for the on-axis configuration films. This enhancement is discussed in terms of a decrease of defect density when using the off-axis configuration.     

Electron-stimulated desorption of D (H) from condensed D2O (H2O) films

The electron-stimulated desorption (ESD) of D⁻ and H⁻ ions from condensed D₂O and H₂O films is investigated. Three low-energy peaks are observed in the ESD anion yield, which are identified as arising from excitation of ²B₁, ²A₁ and ²B₂ dissociative electron attachment (DEA) resonances. Additional structure is observed between 18 and 32 eV, which may be due to ion pair formation or to DEA resonances involving the 2a₁ orbital. The ion yield resulting from excitation of the ²B₁ resonance increases as the film is heated. We attribute the increase in the ion yield to thermally induced hydrogen bond breaking near the surface, which enhances the lifetimes of the excited states that lead to desorption.     

Modeling techniques for analysis and interpretation of electron magnetic resonance (EMR) data for transition ions at low symmetry sites in crystals—A primer for experimentalists

Electron magnetic resonance (EMR) studies of paramagnetic centers exhibiting monoclinic and triclinic local site symmetry have gained renewed importance, since such centers occur often in various technologically important materials and biological systems. The intricate low symmetry aspects, which arise for such centers, bear on meaningful interpretation of EMR data and their correlation with structural data. This review provides a primer for experimentalists who wish to utilize efficiently the modeling techniques for analysis and interpretation of EMR data for transition ions, especially ions located at low symmetry sites in crystals. This requires proper understanding of the low symmetry effects observable in EMR spectra as well as related theoretical questions concerning, e.g., (i) existence of physically equivalent zero-field splitting (ZFS) parameter sets, (ii) clear definitions of the axis systems, (iii) proper forms of spin Hamiltonians, and (iv) distinction between apparent and actual low symmetry cases. The question (i) involves consideration of the orthorhombic standardization, which provides basis for standardization of monoclinic and triclinic ZFS parameters. Thus, the aspects pertaining to orthorhombic site symmetry are also outlined. To solve other questions several modeling techniques have been utilized and related computer packages have recently been developed in our group: (1) the superposition model calculations of the zero-field splitting parameters (ZFSPs) in arbitrary symmetry, (2) the procedure for diagonalization of the 2nd-rank ZFSPs and transformation of respective 4th- and 6th-rank ZFSPs, (3) the pseudosymmetry axes method for approximation of the 4th- and 6th-rank ZFSPs to higher symmetry, and (4) the closeness factors and norm ratios for quantitative comparisons of various ZFSP sets. These modeling techniques enable deeper analysis and interpretation of the low symmetry aspects involved in the fitted and theoretical ZFSPs. The computer packages facilitate extracting useful structural information inherent in monoclinic and triclinic ZFSP sets. Illustrative examples taken from recent studies of low symmetry ion-host systems are discussed.     

Theoretic 3-D study of the high-frequency magnetic moment dynamics in thin ferromagnetic films with in-plane uniaxial anisotropy by considering eddy-current generation

In the present paper, theoretic investigations of polarisation vector precession trajectories represented by a macro spin in ferromagnetic films with in-plane uniaxial anisotropy were realised. For this purpose, the Landau–Lifschitz–Gilbert differential equation (LLG) in combination with the Maxwell equations were solved for three dimensions by considering a linear progression of the magnetisation or polarisation with an external field. The frequency and time dependent polarisation trajectories illustrate how a magnetic moment precesses if effective damping and eddy-currents impacts its motion. For computation, typical parameter values like the saturation polarisation J_s=μ₀·M_s=1.4 T and in-plane uniaxial anisotropy μ₀·H_u=4.5 mT were employed. The main focus of simulation was on the variation of the effective damping parameter α_eff between 0.01 and 0.05 and ferromagnetic film thickness t_m between 200 nm and 1200 nm. The frequency-dependent calculations were carried out between 50 MHz and 6 GHz. The time-dependent simulations were done for a duration between 5 and 30 ns.     

Study of amorphous thin films of (Ti, Nb)O2 solid solutions by X-ray absorption at the Ti K edge

As the (Ti, Nb)O₂ amorphous thin films cannot be prepared under a self-supported form, we have recorded the X-ray reflectivity. A new program which allows extraction of the X-ray absorption from the reflectivity is briefly described. The correction of the anomalous dispersion effect is effective, particularly near the edge within 200 eV. Hence, it has allowed a comparison between the amorphous layers and the crystalline analogues for which the X-ray absorption has been recorded by transmission. In the amorphous state, the TiO₆ group is smaller than in the crystalline state because of the relaxation of the crystallographic constraints. The oxygen coordination octahedron is almost regular in the films. On the other hand, in both cases, an electron transfer takes place from Nb to Ti.     

Spin-wave resonance as a tool for probing surface anisotropies in ferromagnetic thin films: Application to the study of (Ga,Mn)As

In this paper we provide a concise review of present achievements in the study of spin-wave resonance (SWR) in ferromagnetic semiconductor (Ga,Mn)As thin films. The theoretical treatment of the experimental SWR data obtained so far concentrates specifically on the spherical surface pinning (SSP) model, in which the surface spin pinning energy is expressed by configuration angles (the out-of-plane polar angle $?$ and the in-plane azimuthal angle $\phi$) defining the direction of surface magnetization in the considered thin film. The model is based on a series expansion of the surface spin pinning energy; the terms in the series represent the respective pinning contributions from the cubic anisotropy as well as uniaxial anisotropies. Comparing theory with the reported experimental studies of SWR in thin films of the ferromagnetic semiconductor (Ga,Mn)As, we find that besides the first-order cubic anisotropy, higher-order cubic anisotropies (in the second and third orders) as well as uniaxial anisotropies (perpendicular in the first and second orders, and in-plane diagonal) occur on the surface of this material. We use our results to plot a 3D hypersurface visualizing the angle dependence of the surface spin pinning energy in configurational space. An advantage of this spatial representation is that the shape of the obtained hypersurface allows us to predict new SWR effects that have not yet been observed experimentally. Prospective experimental studies for the verification of this surface pinning model would bring new insight into the surface anisotropy phenomenon in (Ga,Mn)As thin films and help complete the knowledge in this field, the shortage of which in the literature available to date is becoming bothersome.     

Synthesis of P-type transparent conducting silver:indium oxide (AIO) thin films by reactive electron beam evaporation technique

Present paper reports the synthesis, electrical and optical properties of p-type conducting and transparent silver indium oxide (AIO) thin films prepared on glass substrates by reactive electron beam evaporation technique at three substrate temperatures (50, 200 and 250 °C) and at five evaporation rates (0.05 to 16.0 nm/s). The source material is pure powders of Ag₂O:In₂O₃=50:50 mol%. The AIO films are amorphous. The films, though not corresponding to Delafossite crystal structure, exhibit p-type conductivity, when prepared at an evaporation rate of 0.05 nm/s at all the three substrate temperatures. With increasing filament current, it is observed that (i) the electrical resistivity decreases and (ii) the refractive index of the films (at 632.8 nm, and is in the range: 1.219-1.211) decreases. The work function (effective Fermi level) has been measured on these samples by Kelvin Probe method. The results are explained on the basis of partial ionic charge and localization of covalent bonds in the AIO thin films.     

Structural elucidation of Cu(II) ion doped in hexaaquozincdiaquobis(malonato)zincate host by EPR spectroscopy

In order to understand the structural behaviour of Cu(II) in a variety of ligand environments, single crystal electron paramagnetic resonance studies of Cu(II) doped in hexaaquazincdiaquabis(malonato)zincate [Zn(H₂O)₆][Zn(mal)₂(H₂O)₂] are carried out at 300 K. Angular variation of copper hyperfine lines in three orthogonal planes shows the presence of single site, with spin Hamiltonian parameters as g_xx=2.034, g_yy=2.159, g_zz=2.388, A_xx=3.39 mT, A_yy=4.89 mT and A_zz=13.72 mT. The g/A tensor direction cosines are compared with various Zn-O directions in the host lattice, which confirm that Cu(II) enters substitutionally in the lattice. The low value of A_zz has been explained by considering admixture of d_²x−²y ground state with d_²z excited state. EPR powder spectra at 300 and 77 K give identical spin Hamiltonian parameters (g_∥=2.367, g_⊥=2.088, A_∥=11.47 mT, A_⊥=2.63 mT). IR, UV-vis and powder XRD data confirm the structure and symmetry of the Cu(II) ion in the host lattice.     

Atom geometry of nanostructured Fe films grown on c(2 × 2)-N/Cu(1 0 0) surface: An investigation by X-ray absorption spectroscopy with multishell analysis

We investigated the growth of Fe nanostructured films on c(2 × 2)-N/Cu(1 0 0) surface with Fe K-edge X-ray absorption fine structure (XAFS) in the near edge and in the extended energy region. The high photon flux of the incident X-rays allowed us to perform multishell analysis of the XAFS oscillations for Fe coverage Θ_Fe < 1 ML. This data analysis yields a detailed investigation of the atom geometry and some insights in the film morphology. At Θ_N < 0.5 ML (N saturation coverage) there is absence of contribution to XAFS from N atoms. First shell analysis of linearly polarized XAFS gives Fe-Fe (or Fe-Cu) bond length values varying between R₁ = 2.526 ± 0.006 Å at the highest Fe coverage (3 ML ) and R₁ = 2.58 ± 0.01 Å at Θ_Fe = 0.5 ML, Θ_N = 0.3 ML, with incidence angle Θ = 35°. These values are different from the case of bcc Fe (R = 2.48 Å), and compatible with fcc Fe (R₁ = 2.52 Å) and fcc Cu (R₁ = 2.55 Å). At the Fe lowest coverage (Θ_Fe = 0.5 ML) the dependence of R₁ on the incidence angle indicates expansion of the outmost layer. Near edge spectra and multishell analysis can be well reproduced by fcc geometry with high degree of static disorder. At N saturation pre-coverage (Θ_N = 0.5 ML) the XAFS analysis has to keep into account the Fe-N bonding. The results suggest two different adsorption sites: one with Fe in a fcc hollow site, surrounded by other metal atoms as nearest neighbours, and one resulting from an exchange with a Cu atom underneath the N layer.     

Theoretical investigation of ESR spectra and local structure for VO in Ba2Zn(HCOO)6(H2O)

The electron spin resonance spectra (characterized by g factors g_, g_⊥ and hyperfine structure constants A_ and A_⊥) of Ba₂Zn(HCOO)₆(H₂O) (BZFA): VO²⁺ crystal are calculated from high order perturbation formulas. The calculated results are in good agreement with the observed values. The local structure parameters of [VO(H₂O)₅]²⁺ clusters are also obtained from the calculation. The magnitudes of the metal-ligand distances parallel and perpendicular to the C₄-axis are, respectively, R_≈0.163 nm and R_⊥≈0.210 nm. It is shown that the local structure around the V⁴⁺ ion possesses a compressed tetragonal distortion along C₄-axis.     

Effects of Cu/In ratio of electrodeposited precursor on post-sulfurization process in fabricating quaternary CuIn(S,Se)2 thin films

This paper reports the analysis of S diffusion into electrodeposited CuInSe₂ (CISe) precursors during post-sulfurization treatment at 500 °C in an Ar/H₂S ambient. The characterizations of the sulfurized films by X-ray diffraction, grazing-incidence X-ray diffraction, Auger electron spectroscopy and micro-Raman spectroscopy allow the observation of the strong dependence of S incorporation into these films on the Cu/In ratio of the precursor. AES profiles reveal higher S content along the depth of Cu-rich film than Cu-poor film after sulfurization. Raman Scattering shows that copper sulfoselenides Cu-(Se,S) are only detected in Cu-rich samples. The re-crystallization of films during sulfurization was analyzed and it is presumed that quasi-liquid Cu-Se phases, which are related to Cu/In ratio of precursor, promote continuous incorporation of S into these films.     

Spectroscopic properties of Fe ions at tetragonal sites—Crystal field effects and microscopic modeling of spin Hamiltonian parameters for Fe (S=2) ions in K2FeF4 and K2ZnF4

Magnetic and spectroscopic properties of the planar antiferromagnet K₂FeF₄ are determined by the Fe²⁺ ions at tetragonal sites. The two-dimensional easy-plane anisotropy exhibited by K₂FeF₄ is due to the zero field splitting (ZFS) terms arising from the orbital singlet ground state of Fe²⁺ ions with the spin S=2. To provide insight into the single-ion magnetic anisotropy of K₂FeF₄, the crystal field theory and the microscopic spin Hamiltonian (MSH) approach based on the tensor method is adopted. Survey of available experimental data on the crystal field energy levels and free-ion parameters for Fe²⁺ ions in K₂FeF₄ and related compounds is carried out to provide input for microscopic modeling of the ZFS parameters and the Zeeman electronic ones. The ZFS parameters are expressed in the extended Stevens notation and include contributions up to the fourth-order using as perturbation the spin-orbit and electronic spin-spin couplings within the tetragonal crystal field states of the ground ⁵D multiplet. Modeling of the ZFS parameters and the Zeeman electronic ones is carried out. Variation of these parameters is studied taking into account reasonable ranges of the microscopic ones, i.e. the spin-orbit and spin-spin coupling constants, and the energy level splittings, suitable for Fe²⁺ ions in K₂FeF₄ and Fe²⁺:K₂ZnF₄. Conversions between the ZFS parameters in the extended Stevens notation and the conventional ones are considered to enable comparison with the data of others. Comparative analysis of the MSH formulas derived earlier and our more complete ones indicates the importance of terms omitted earlier as well as the fourth-order ZFS parameters and the spin-spin coupling related contributions. The results may be useful also for Fe²⁺ ions at axial symmetry sites in related systems, i.e. Fe:K₂MnF₄, Rb₂Co_1−xFe_xF₄, Fe²⁺:Rb₂CrCl₄, and Fe²⁺:Rb₂ZnCl₄.