Effects of high-temperature annealing on magnetic ordering in thin films of Bi2O3-CaO-Fe2O3

Magnetic properties of rf sputtered (0.5–x) Bi₂O₃-x CaO-0.5 Fe₂O₃ (x=0–0.5) have been studied through magnetization and ferromagnetic resonance (FMR) measurements. Films prepared in a mixed oxygen-argon atmosphere are amorphous and paramagnetic. Samples annealed in air at temperatures of 700–1000 K show a ferrimagnetic behavior even though X-ray diffraction data for the films do not indicate the precipitation of any crystalline ferrimagnetic compounds. The room-temperature saturation magnetization 4M and the uniaxial anisotropy field H _u , decrease with increasing x. The Curie temperature and the gyromagnetic ratio increase with increase in the concentration of CaO. Studies on the effects of sputtering atmospheres on magnetic parameters show that films sputtered in oxygen-rich atmospheres have a large 4M and H _u , and a relatively small and FMR line-width. Ordered amorphous clusters are suggested to give rise to the observed ferrimagnetic character in the annealed films.     

Lithium intercalation in MoO3: A comparison between crystalline and disordered phases

We report properties of lithium-intercalated MoO₃ crystalline and thin-film which are potential cathode materials for high energy density batteries. Discharge and charge reactions of MoO₃ electrodes in a non-aqueous Li⁺-electrolyte have been studied. The kinetically accessible discharge range amounts to 0x1.5 for Li insertion in Li _x MoO₃. Transport parameters such as the Li⁺ chemical diffusion coefficient, thermodynamic factor and ionic conductivity are investigated during the Li⁺ insertion process and discussed with respect to the crystallinity of the cathode material.     

Frictional and atomic-scale study of C60 thin films by scanning force microscopy

Scanning force microscopy (SFM) was employed to characterize C₆₀ island films in an ultra-high vacuum (UHV). The initial growth stage of C₆₀ on NaCl cleavage faces and nanotribological properties of this solid lubricant are investigated. In comparison to the NaCl(001) face, higher friction is measured on the C₆₀ islands, resulting in a ratio of friction of 13 for NaClC₆₀. The friction coefficient of the (111) oriented C₆₀ island is determined to be 0.15±0.05. High-resolution SFM images reveal the hexagonal lattice of the unreconstructed (111) top surfaces and the overgrowth relationships of the C₆₀ islands.     

Polymeric sheets in Mg4C60

We present preliminary results on the preparation and structure of Mg₄C₆₀, a new fulleride polymer. A series of Mg_xC₆₀ compositions (0<x<6) were prepared by solid state reaction. While most samples were multiphase, a single phase material was obtained at the nominal composition Mg₄C₆₀. The X-ray diffraction pattern of Mg₄C₆₀ was successfully indexed and fitted to a rhombohedral structure based on two-dimensional polymeric sheets of C₆₀ ions. This result extends the family of fulleride polymers to the salts of multiply charged cations and thus opens a new direction in this field.     

Raman-spectroscopy study of PbTiO3 thin films grown on Si substrates by metalorganic chemical vapor deposition

Raman spectra have been investigated in PbTiO₃ thin films grown on Si by metalorganic chemical vapor deposition. A large grazing-angle scattering technique was taken to measure the temperature dependence of Raman spectra below room temperature. All Raman modes in the thin films are assigned and compared with those in the bulk single crystal, a newA ₁(TO) soft mode at 104 cm^–1 was recorded which satisfies the Curie-Weiss relation ² =A(T _c –T). Intensities of theA ₁(1TO) andE(1TO) modes were anomalously strengthened with increasing temperature. Raman modes for the thin films exhibit remarkable frequency downshift and upshift which is related to the effect of internal stress.     

Study on the formation during the production of lead-free piezoceramics at the morphotropic phase boundary

Because of the environmental concerns, the manufacture of ceramics based on lead titanate zirconate [Pb(Zr_1−xTi_x)O₃−PZT] has been condemned because of the lead toxicity. In this context, the electromechanical properties of sodium, potassium and lithium niobate [(Na_0.5−x/2K_0.5−x/2Li_x)NbO₃−NKLN] at the morphotropic phase boundary granted these materials the position of most suitable candidate to replace PZT. However, the production of these ceramics is rather critical mainly because of a natural tendency of forming secondary phases. To help with the studies of the synthesis of this lead-free piezoceramic, this work presents an evaluation of the crystallization of the (Na_0.47K_0.47Li_0.06)NbO₃ phase by solid-state reactions. TG-DTA, XRD, dilatometric and ferroelectric hysteresis analyses indicated that a secondary phase (K₃Li₂Nb₅O₁₅) crystallizes at temperatures above 850 C and also during the sintering of the powders compacts at 1080 C. To prevent the formation of this phase, the addition of Na₂Nb₂O₆.nH₂O microfibers obtained through a microwave hydrothermal synthesis was performed in the sintering process. After to this addition, the suppression of the K₃Li₂Nb₅O₁₅ phase occurred and an increase of the NKLN electrical properties was then obtained.     

On the relaxation ofμ + SR signal and diffusive neutron scattering in AF phase of HTSC

We consider the antiferromagnetic (AF) state of high-T _c compounds and assume the existence of the localized magnetic two-level systems (TLS) with the relatively small energyE in the AF copper planes, which is compatible with a series of experimental data implying low-energy scale in these systems. It is shown in our previous paper that these TLS are formed, if one accepts Aharony et al. suggestion that the small doping results in the holes' localization on the oxygen ions in CuO₂ planes. Randomly distributed, these TLS cause partial disorder in the average values of AF copper spins. The manifestation of this effect in the ⁺ SR experiments and the elastic neutron scattering is discussed. Our results are in a qualitative agreement with the temperature dependence and the magnitude of the line shift and the relaxation rate of ⁺ SR signal. The elastic diffusive neutron scattering at the small wave-vectors near 2D AF Bragg point (1/2, 1/2,l) and near the point (0, 0,l) is predicted. However, the temperature dependence of this scattering, observed in the experiments with YBa₂Cu₃O_6+x atx=0.38, isn't met by our formulae, obtained for a small doping. It is shown, that SR data give stronger confidence to the frustrated bond rather and frustrated plaquette case of the hole localization.     

Raman spectra of samarium-fullerene intercalation compounds

Samarium-fullerene intercalation compounds of nominal composition Sm_xC₆₀ (x=1,2,…,6) have been synthesized by a solid-state reaction method. We obtain a Sm_2.75C₆₀ superconducting phase with orthogonal structure and a Sm₆C₆₀ phase with body-centered cubic structure. The broadening and weakening of Raman peaks of the Sm_xC₆₀ compounds are due to the distortion of C₆₀ and electron-phonon interaction. The Raman measurements reveal that the distortion of C₆₀ decrease in Sm_xC₆₀ (x=3,4,5) exposed to air, although the fulleride solids have transformed into an amorphous state. The Raman results also show that the distortion of C₆₀ is still very large in the Sm₆C₆₀ exposed to air, or the C₆₀ molecules have been destroyed and become some amorphous carbide.     

Characterization of stoichiometric LiNbO3 grown from melts containing K2O

The growth of LiNbO₃ single crystals from a melt with the Li/Nb ratio of 0.946, to which 6 wt.% K₂O has been added, leads to stoichiometric specimens, essentially free of potassium, with (50±0.15) mol% Li₂O in the crystal. This is established by studying the composition dependence of the following properties: linewidths of the electron paramagnetic resonance (EPR) of Fe³⁺, energy of the fundamental absorption edge, Raman linewidths of phonon modes, and dispersion of the optical birefringence. Comparison of the results with relevant calibration scales leads to the above composition. In all cases the Li₂O content was found to be closer to 50% than that of a LiNbO₃ crystal vapor-phase equilibrated to 49.9mol% Li₂O. The photorefractive effect at light intensities I10⁷ W/m² is suppressed in this stoichiometric material. The features of the ternary system K₂O-Li₂O-Nb₂O₅, which are possibly responsible for the unexpected growth of stoichiometric LiNbO₃ from the indicated melts, are discussed.     

Properties of RF sputtered ZnxCd1−xS thin films

Zn _x Cd_1–x S thin films (0x0.20) were prepared using rf sputtering in argon atmosphere and characterized using X-ray diffraction, optical transmission, electrical resistivity and photoconductive decay measurements. The films were found to possess hexagonal structure. The crystallite size and degree of preferential orientation were found to decrease with the increase ofx and to improve upon annealing in vacuum at 250 °C. The transmission edge shifted towards shorter wavelengths with the increase ofx in agreement with the expected shift in the energy band gap. The films were found to exhibit room temperature resistivity in the range 100–1000 cm. The obtained values of long wavelength transmission (70–80%) and minority carrier diffusion length (30 m) are high enough for the application of these films in the field of solar cells.     

Investigation of electrochromic tungsten trioxide thin films prepared by the ILGAR method

An ion layer gas reaction dip coating process for the deposition of tungsten trioxide has been developed. Thin films of electrochromic tungsten trioxide with thicknesses of up to 150 nm were prepared. The films were found to be microcrystalline by X-ray diffraction analysis. The growth rate of the films was measured by profilometry. The chemical diffusion coefficient of lithium was investigated as a function of the concentration of lithium by the electrochemical galvanostatic intermittent titration technique. The chemical diffusion coefficient was found to increase slightly from 7×10⁻¹² to 3×10⁻¹ cm²/s, with x increasing from 0.2 to 0.8 in Li _x WO₃.     

Enhanced luminescence from spontaneously ordered Gd2O3:Eu based nanostructures

Nanostructured Gd₂O₃:Eu³⁺ and Li⁺ doped Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The effects of annealing and Li⁺ doping on the structural, morphological, optical and luminescent properties are discussed. X-ray diffraction and Micro-Raman investigations indicate a phase transformation from amorphous to nanocrystalline phase and an early crystallization was observed in Li⁺ doped Gd₂O₃:Eu³⁺ thin films on annealing. AFM images of Li⁺ doped Gd₂O₃:Eu³⁺ films annealed at different temperatures especially at 973 K show a spontaneous ordering of the nanocrystals distributed uniformly all over the surface, with a hillocks (or tips) like self-assembly of nanoparticles driven by thermodynamic and kinetic considerations. Enhanced photoemission from locations corresponding to the tips suggest their use in high resolution display devices. An investigation on the photoluminescence of Gd_2−xEu_xO₃ (x=0.10) and Gd_2−x−yEu_xLi_yO₃ (x=0.10, y=0.08) thin films annealed at 973 K reveals that the enhancement in luminescence intensity of about 3.04 times on Li⁺ doping is solely due to the increase in oxygen vacancies and the flux effect of Li⁺ ions. The observed decrease in the values of asymmetric ratio from the luminescence spectra of Li⁺ doped Gd₂O₃:Eu³⁺ films at high temperature region is discussed in terms of increased EuO bond length as a result of Li⁺ doping.     

Multi-exponential analysis of DLTS

Deep-level transient spectroscopy (DLTS), which is widely used to characterize deep impurity centers in semiconductors, assumes a single exponential wave form for the transient junction capacitance. When there are several closely spaced energy levels this assumption is no more valid, and the conventional DLTS may lead to errorneous results. To overcome this difficulty we propose here a novel method which we call the multi-exponential DLTS(MEDLTS). The transient wave form of the junction capacitance is directly analysed into multi-exponential compouents using the nonlinear least-squares analysis program DISCRETE developed by Provencher. The resolved time constants of these components are then displayed in the form of aT ²–1/T plot. According to the results of simulation with various parameters MEDLTS is shown quite effective to resolve closely spaced energy levels which can not be resolved by the conventional DLTS. As an example of the application of this method deep levels in Si: Au were investigated. The results have shown that a single peak in conventional DLTS actually consists of two adjacent levels with activation energies and capture cross-sectionsE _B1=0.49 eV, _B1=1.1×10^–14cm² andE _B2=0.46 eV, _B2=1.3×10^–15 cm² and with amplitude ratio 11.     

Ion irradiation—a technique providing a criterion to distinguish between amorphous and nanocrystalline In1−x Pd x films

In_1–x Pd _x films with 0.2x0.75 have been prepared by vapour quenching at 4.2 K or 77 K, respectively. To test whether amorphous (a-) phases can be obtained in this way, the resistance behavior and the electron diffraction patterns of the as-prepared and annealed films were studied insitu. For films withx=0.25 additional information could be acquired from their superconducting behavior. Combining these results one concludes that a-phases exist for the compositional range 0.2x0.6, which are stable up to crystallization temperaturesT _x within the range 250 KT _x 420 K. Irradiation of the crystallized films at low temperatures (4.2 K or 77 K) with heavy ions (350 keV Ar⁺ or Kr⁺) leads to complete re-amorphization. Forx=0.67 corresponding to InPd₂ a nanocrystalline (n-) phase is obtained by vapour quenching at 77 K as inferred from x-ray diffraction. AtT _x =700 K, thesen-films exhibit a drop of the electrical resistance indicating the beginning of significant grain growth. After recooling, Kr⁺ bombardment at 77 K does not restore the high electrical resistance of the as-quenchedn-film. This result can be used as a criterion when studying quenched films withx=0.625 corresponding to In₃Pd₅. In this case, a resistance drop is found atT _x =600 K, but the diffraction techniques do not allow an uniquevocal distinction between amorphous and nanocrystalline. This becomes possible by low temperature ion irradiation after annealing atT>T _x . The bombardment results in resistance changes, which saturate well-below the value of the as-quenched sample implying nanocrystallinity for the latter. Based on this criterion, a phase-diagram for quenched In_1–x Pd _x is provided with 0x1 containing the newly detecteda- andn-phases.     

Metastable surface phase for NaxC60

Na_xC₆₀ thin films with Na concentration 0 ? x ? 3 were investigated using angle-dependent photoelectron spectroscopy. For low doping we observed two distinct fulleride phases coexisting with regions of pristine C₆₀. One of these fulleride phase is predominantly formed close to the surface and disappears after annealing and further addition of Na. At higher doping a phase with stoichiometry of x = 3 is formed.     

On the asymptotics of occurrence times of rare events for stochastic spin systems

We consider translation-invariant attractive spin systems. LetT _,x ^v be the first time that the average spin inside the hypercube reaches the valuex when the process is started from an invariant measure with density smaller thanx. We obtain sufficient conditions for (1) ¦¦^–1 logT _,x ^v (x) in distribution as ¦¦ , and ¦¦^–1 logT _,x ^v (x) as ¦¦ , where (x):= –lim ¦¦^–1 log {(average spin inside ) x. And (2)T _,x ^v /ET _,x ^v converges to a unit mean exponential random variable as ¦¦ . Both (1) and (2) are proven under some type of rapid convergence to equilibrium. (1) is also proven without extra conditions for Ising models with ferromagnetic pair interactions evolving according to an attractive reversible dynamics; in this case is a thermodynamic function. We discuss also the case of finite systems with boundary conditions and what can be said about the state of the system at the timeT _,x ^v .On leave from São Paulo University.     

Thermal conductivity of C60 and C70 crystals

We have performed thermal conductivity measurements on C₆₀ and C₇₀ crystals grown by sublimation. For single crystal C₆₀, the thermal conductivity k is 0.4 W/m K at room temperature and is nearly temperature independent down to 260K. We observed a sharp orientational phase transition at 260K, indicated by a 25% jump in k. Below 90K, k is time dependent, which manifests itself as a shoulder-like structure at 85K. The temperature and time dependence of k below 260K can be described by a simple model which accounts for the thermally activated hopping of C₆₀ molecules between two nearly degenerate orientations, separated by an energy barrier of 240 meV. It is found that solvents have a strong influence on the physical properties of C₇₀ crystals. For solvent-free C₇₀ crystal, k is about constant above 300K. There is a broad first-order phase transition in k at 300K with a 25% jump. We associate this transition with the aligning of the fivefold axes of the C₇₀ molecules along the c-axis of the hexagonal lattice. Upon further cooling, k increases and is time independent.     

Scaling solutions of Smoluchowski's coagulation equation

We investigate the structure of scaling solutions of Smoluchowski's coagulation equation, of the formc _k (t)s(t)^– (k/s(t)), wherec _k (t) is the concentration of clusters of sizek at timet,s(t) is the average cluster size, and(x) is a scaling function. For the rate constantK(i, j) in Smoluchowski's equation, we make the very general assumption thatK(i, j) is a homogeneous function of the cluster sizesi andj:K(i,j)=a ^– K(ai,aj) for alla>0, but we restrict ourselves to kernels satisfyingK(i, j)/j0 asj. We show that gelation occurs if>1, and does not occur if1. For all gelling and nongelling models, we calculate the time dependence ofs(t), and we derive an equation for(x). We present a detailed analysis of the behavior of(x) at large and small values ofx. For all models, we find exponential large-x behavior: (x)A x ^– e ^–x asx and, for different kernelsK(i, j), algebraic or exponential small-x behavior: (x)Bx ^– or (x)=exp(–Cx ^–|| + ...) asx0.     

Y1Ba2Cu3O7-δ thin films from KrF laser ablation with substrate heating and in situ patterning by CO2 laser radiation

Y₁Ba₂Cu₃O_7– thin films were deposited by KrF laser ablation while replacing conventional contact heating by cw CO₂ laser irradiation of the substrate front surface. The HTSC films obtained on (100)ZrO₂ showed T _c(R=0)=90 K, T(90–10%)=0.5 K, j _c=2.5 × 10⁶ A/cm², a sharp transition in the ac susceptibility X(T), and pure c-axis orientation. Micrographs of thin films (< 0.5 m) showed a smooth morphology while thick films (>1 m) contained many crystallites sticking in the bulk material. Furthermore, in situ patterning was achieved during deposition by local laser heating of a selected substrate surface area. The resulting planar films contained amorphous, semiconducting parts only 1 mm or less apart from crystalline material showing the above HTSC quality.Presented at LASERION '91, June 12–14, 1991, München (Germany)