From anisotropic dots to smooth RFe 2 (110) single crystal layers (R = rare earth)

Single crystal RFe₂(110) films were grown by molecular beam epitaxy to a total thickness of 1000 ? at different substrate temperatures ranging from 450 ^° C to 660 ^° C. The first stages of growth and the surface morphology of the deposited layers have been studied using Reflection High Energy Electron Diffraction (RHEED) and Atomic Force Microscopy (AFM). The growth is first strained but further deposit induces the formation of three-dimensional fully relaxed islands. Subsequently, the morphology of the RFe₂(110) nanosystems evolves from anisotropic dots to a smooth surface, as a function of the preparation parameters, i.e. nominal thickness and substrate temperature. It also depends on the rare earth involved in the compound. Received 29 June 2000     

Strain effect on transport properties of <Emphasis Type="Bold">SrRuO</Emphasis><Subscript><Emphasis Type="Bold">3</Emphasis></Subscript> films grown by laser MBE

Transport properties of SrRuO₃ thin films were studied as a function of the epitaxial strain. SrRuO₃ films were grown on (100) SrTiO₃ substrates by the Pulsed Laser Deposition technique equipped with Reflection High Energy Electrons Diffraction (RHEED). Samples thickness has been varied from a few unit cells to above 1000 ? while monitoring RHEED intensity oscillations. In thicker films epitaxial strain was found to be progressively relaxed. SrRuO₃ relaxed films (thickness 1000 ?) show metallic behavior for the whole temperature range with a ferromagnetic ordering at about 150 K. For thinner films, ferromagnetic ordering occurs at progressively lower temperatures, until in films thinner than 400 ? it disappears. Films thinner than 80 ? show a semiconducting behavior at low temperatures. Our results provide direct evidence of the crucial role of the strain effect for conducting and magnetic properties of SrRuO₃. Received 16 July 2001 and Received in final form 22 October 2001     

Magnetic behavior and role of the antiphase boundaries in Fe3O4 epitaxial films sputtered on MgO (001)

Magnetite Fe₃O₄ films were grown on single crystal MgO (001) substrates using facing target sputtering technique. Conversion Electron M?ssbauer Spectroscopy and magneto optical polar Kerr spectra have confirmed the stoichiometric repartition of Fe cations corresponding to the inverse spinel structure and the electronic structure characteristic of bulk Fe₃O₄. Hysteresis loops carried out at room temperature show that, in a 1 T applied magnetic field, only 60% of the saturation magnetization is detected. This behavior is discussed in correlation to the antiphase boundaries (APBs) observed by electron microscopy. Magnetic force microscopy studies show that magnetic domains are larger than the mean distance between APBs. Received 2 July 2001     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

Morphologies of diblock copolymer thin films before and after crystallization

Spin-coated thin films of about 100nm of low-molecular-weight hydrogenated poly(butadiene-b- ethyleneoxide) (PB_h-PEO) diblock copolymers have been crystallized at various constant temperatures. Crystallization has been observed in real time by light microscopy. Detailed structural information was obtained by atomic force microscopy, mainly enabled by the large viscoelastic contrast between amorphous and crystalline regions. The behavior in thin films is compared to the bulk properties of the polymer. Crystallization started from an annealed microphase separated melt where optical microscopy indicated a lamellar orientation parallel to the substrate. A small difference in the length of the crystallizable block produced significantly different crystallization behavior, both in the bulk and in thin films. For thin films of the shortest diblock copolymer (45% PEO content) and for an undercooling larger than about 10 degrees, crystallization created vertically oriented lamellae. These vertical lamellae could be preferentially aligned over several micrometers when crystallization occurred close to a three-phase contact line. Annealing at temperatures closer to the melting point or keeping the sample at room temperature for several months allowed the formation of a lamellar structure parallel to the substrate. A tentative interpretation based on kinetically caused chain folding and relaxation within the crystalline state, with implications on general aspects of polymer crystallization, is presented. Received 19 March 1999 and Received in final form 14 December 1999     

Soft X-ray magnetic circular dichroism in Fe and Fe 0.50 Co 0.48 V 0.02 films: quantitative analysis of transmission

Magnetic circular dichroism (MCD) in X-ray absorption has been measured at the L _{2, 3} edges of Fe in ex-situ grown Fe and Fe _0.50 Co _0.48 V _0.02 films by means of the transmission method. A new approach is developed for fitting the observed transmittance, which describes the resonance lineshapes as (generalized) Fano profiles. Analytical integration of each single resonance allows a more reliable determination of the orbital and spin magnetic moments based on the MCD sum rules. The results are consistent with an increase of the Fe spin and orbital magnetic moment in Fe-Co alloys as obtained by other experiments and band structure calculations. Received 15 August 2000 and Received in final form 11 June 2001     

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T _g, the relative strength of the glass transition, and the relative rate of physical aging below T _g in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T _g. Positive deviations from bulk T _g are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T _g are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm. Received 21 August 2001     

Structure-related infrared optical properties of BaTiO3 thin films grown on Pt/Ti/SiO2/Si substrates

BaTiO₃ thin films with different thickness have been grown on Pt/Ti/SiO₂/Si substrates by a modified sol-gel method. X-ray diffraction analyses show that the BaTiO₃ thin films are polycrystalline. The crystalline quality of the films is improved with increasing thickness. The infrared optical properties of the BaTiO₃ thin films have been investigated using an infrared spectroscopic ellipsometry in the wave number range of 800-4000 cm⁻¹ (2.5-12.5 μm). By fitting the measured pseudodielectric functions with a three-phase model (Air/BaTiO₃/Pt), and a derived classical dispersion relation for the thin films, the optical constants and thicknesses of the thin films have been simultaneously obtained. The refractive index of the BaTiO₃ thin films increases and on the other hand, the extinction coefficient does not change with increasing thickness in the entirely measured wave number range. The dependence of the refractive index on the film thickness has been discussed in detail and was mainly due to both the crystalline quality of the films and packing density. Finally, the absorption coefficient was calculated in the infrared region for applications in the pyroelectric IR detectors.     

Spin-cast, thin, glassy polymer films: Highly metastable forms of matter

Ultra thin films of glassy polymers such as polystyrene (PS) can show a) anomalously large thickness changes, b) unexpected dewetting properties, c) large shifts in the glass temperature T_g. The present discussion focusses mainly on point a). A certain cascade of metastable states is presented together with (tentative) explanations. Received 1 March 2001 and Received in final form 10 May 2001     

Effect of interfacial alloying on the surface plasmon resonance of nanocrystalline Au-Ag multilayer thin films

Nanocrystalline Au and Ag in multilayer thin film form with Au/Ag/Au structure were prepared by high pressure (∼40 Pa) d.c. sputtering techniques. The Ag concentrations in Ag_xAu_1-x films were changed from x = 0 to 1. These multilayer films with varying Ag concentration showed significant changes in microstructures obtained from TEM and XRD analyses. The optical absorption spectra of these multilayer films showed a single plasmon band confirming the formation of Au-Ag alloy. We ascribe this alloying to the interfacial reactions in nanophase limited at the Au-Ag interface. The red-shift and broadening of the plasmon bands with the increase in silver concentration could be associated to the increase in size of the nanoparticles and its distribution. The observed red shift in the plasmon band may be associated with the change in electronic structure at the Au-Ag interface due to configuration mixing of the atomic energy levels of Au and Ag. Received 17 October 2002 / Received in final form 26 February 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: msakp@mahendra.iacs.res.in     

Infrared transmission study of Pr<Subscript><Emphasis Type="Bold">2</Emphasis></Subscript>CuO<Subscript><Emphasis Type="Bold">4</Emphasis></Subscript> crystal-field excitations

We present an infrared crystal-field study of Pr₂CuO₄ single crystals and thin films. Excitations from the ground state multiplet ³H₄ to the ³H₅, ³H₆, ³F₂ and ³F₃ excited multiplets are observed in both single crystals and thin films. A precise set of crystal-field parameters, that reproduces the energy and the symmetry of the levels, is determined. Received 25 April 2001     

Studies on CdS nanoparticles dispersed in silica matrix prepared by sol-gel technique

SiO₂/CdS-nanoparticle composite films (SiO₂:CdS=85:15, 80:20, 75:25 and 70:30) were prepared by the sol-gel route. The films were characterized by studying microstructural (XRD and TEM) and optical (transmittance and photoluminescence) properties. Band gaps of these films annealed at different temperatures (373-473 K) for different times (10-120 min) indicated that the signature of nanocrystallinity is retained throughout the range of our experimental conditions. A thermal diffusion process controlled growth in the crystallite size with increasing annealing time and temperature. The average radii of the nanoparticles varied as the cube root of the annealing time but showed exponential dependence on the inverse of annealing temperature. Photoluminescence (PL) studies of the composite films indicated excitonic transitions. Theoretical analysis of the line shapes of the PL peaks recorded at 300 K and 80 K could be accounted for by the combined effects of size distribution and phonon broadening. It was observed that the deformation potential (E _d) effectively controlled the line shapes of the PL measurements. Received 24 May 2002 Published online 27 January 2003 RID="a" ID="a"e-mail: msakp@mahendra.iacs.res.in     

Solid-state reaction in Ti/Ni multilayers studied by magneto-optical and optical spectroscopies, and X-ray diffraction

Comparative study of the solid-state reaction (SSR) in a series of Ti/Ni multilayered films (MLF) with a bilayer period of 0.65-22.2 nm and a constant Ti to Ni sublayer thickness ratio has been performed by using the experimental and computer-simulated magneto-optical (MO) and optical spectroscopies as well as X-ray diffraction (XRD). It was shown that alloyed-like regions in an amorphous structure is spontaneously formed near the interfaces between pure elements during the film deposition. The thickness of this region was estimated as 2-3.8 nm on the basis of the MO and optical studies. The SSR in the Ti/Ni MLF caused by an annealing at 580 K for 60 min increases the thickness of these interfacial amorphous regions. It was shown that SSR takes place mainly in the Ti/Ni MLF with relatively “thick” sublayers. The existence of a threshold nominal Ni-sublayer thickness for observing the equatorial Kerr effect of about 3.0 and 4.5 nm for the as-deposited and annealed Ti/Ni MLF, respectively, is explained by formation of the nonmagnetic alloyed regions between pure components during the film deposition as a result of the SSR. For the case of Ti/Ni MLF, the MO and optical approaches turn out to be more sensitive in determining the thickness of the reacted zone, while XRD is more useful for the structural analysis. It was also shown that the very thin nonreacted Ni sublayers have different MO properties (and hence electronic structure) from the bulk. Received 2 May 2001 and Received in final form 21 November 2001     

Isotope effect for transport and magnetic properties of La 0.35 Pr 0.35 Ca 0.3 MnO 3 thin films

The effect of ¹⁶ O → ¹⁸ O isotope substitution on electrical resistivity, magnetoresistance, and ac magnetic susceptibility was studied for La_0.35Pr_0.35Ca_0.3MnO₃ epitaxial thin films deposited onto LaAlO₃ and SrTiO₃ substrates. For the films on LaAlO₃, the isotope substitution resulted in the reversible transition from a metal-like to insulating state. The applied magnetic field ( H ≥ 2 T) transformed the sample with ¹⁸O back to the metallic state. The films on SrTiO₃ remained metallic at low temperatures for both ¹⁶O and ¹⁸O, but the shift of the resistivity peak corresponding to onset of metallic state exceeded 63 K after ¹⁶ O → ¹⁸ O substitution. The temperature dependence of both resistivity and magnetic susceptibility was characterized by hysteresis, especially pronounced in the case of the films on LaAlO₃. Such a behavior gives certain indications of the phase separation characteristic of interplay between ferromagnetism and charge ordering. Received 11 February 2000 and Received in final form 13 September 2000     

Corrosion behaviour of sintered NdFeB coated with Al/Al2O3 multilayers by magnetron sputtering

Al/Al₂O₃ multilayers were deposited on sintered NdFeB magnets to improve the corrosion resistance. The amorphous Al₂O₃ films were used to periodically interrupt the columnar growth of the Al layers. The structure of the multilayers was investigated by Scanning Electron Microscopy (SEM) and High Resolution Transmission Electron Microscopy (HRTEM). It was found that the columnar structure was effectively inhibited in the multilayers. Subsequent corrosion testing by potentiodynamic polarization in 3.5 wt.% NaCl and neutral salt spray test (NSS) revealed that the Al/Al₂O₃ multilayers had much better corrosion resistance than the Al single layer. Furthermore, for multilayers with similar thickness, the corrosion resistance was improved as the period decreased.     

Branched crystal morphology of linear polyethylene crystallized in a two-dimensional diffusion-controlled growth field

The branched crystal morphology of linear polyethylene formed at various temperatures from thin films has been studied by atomic-force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) pattern and polymer decoration technique. Two types of branched patterns, i.e. dendrite and seaweed patterns, have been visualized. The fractal dimension d _f = 1.65 of both dendrite and some of seaweed patterns was obtained by using the box-counting method, although most of the seaweed patterns are compact. Selected-area ED patterns indicate that the fold stems tilt about 34.5^° around the b-axis and polymer decoration patterns show that the chain folding direction and regularity in two (200) regions are quite different from each other. Because of chain tilting, branched crystals show three striking features: 1) the lamella-like branches show two (200) regions with different thickness; 2) the crystals usually bend towards the thin region; 3) the thick region grows faster by developing branches, thus branches usually occur outside the thick region. The branched patterns show a characteristic width w, which gives a linear relationship with the crystallization temperature on a semilogarithmic plot. Received 15 March 2002 and Received in final form 29 April 2002     

Evidence for a solid phase of dodecahedral C 20

Evidence is presented for the formation of a solid phase based on the smallest fullerene, C₂₀, in thin diamond-like carbon films deposited by ultraviolet laser ablation from diamond onto nickel substrates at room temperature in the presence of 10^-4 torr of cyclohexane or benzene. Laser desorption mass spectrometry from the films shows the presence of C₂₀, C₂₁ and C₂₂ species, while micro-Raman spectroscopy and electron diffraction from selected particles together with first principle density-functional calculations, indicate a cubic solid with dodecahedral C₂₀ cages as building blocks. Unlike solid C₆₀ and fully protonated C₂₀, which are bound by van der Waals forces, the proposed structure is stabilized by linking of the C₂₀ dodecahedra with bridging carbon atoms at interstitial tetrahedral sites to form a face-centered-cubic lattice with 22 carbon atoms per unit cell. Received 10 October 2002 / Received in final form 24 December 2002 Published online 6 March 2003 RID="a" ID="a"e-mail: zafar.iqbal@njit.edu     

Mobility in thin polymer films ranging from local segmental motion, Rouse modes to whole chain motion: A coupling model consideration

Large increases of mobility of local segmental relaxation observed in polymer films as the film thickness is decreased, as evidenced by decreases of the glass temperature, are not found for relaxation mechanisms that have longer length scales including the Rouse relaxation modes and the diffusion of entire polymer chains. We show that the coupling model predictions, when extended to consider polymer thin films, are consistent with a large increase of the mobility of the local segmental motions and the lack of such a change for the Rouse modes and the diffusion of entire polymer chains. There are two effects that can reduce the coupling parameter of the local segmental relaxation in thin films. One is the chain orientation that is induced parallel to the surface when the film thickness h becomes smaller than the end-to-end distance of the chains and the other is a finite-size effect when h is no longer large compared to the cooperative length scale. Extremely thin ( ≈ 1.5 nm) films obtained by intercalating a polymer into layered silicates have thickness significantly less than the cooperative length scale near the bulk polymer glass transition temperature. As a result, the coupling parameter of the local segmental relaxation in such thin films is reduced almost to zero. With this plausible assumption, we show the coupling model can explain quantitatively the large decrease of the local segmental relaxation time found experimentally. Received 1 August 2001 and Received in final form 1 December 2001     

Preparation, magnetoresistance and magnetocaloric effect of two-layered perovskite La 2.5- x K 0.5+ x Mn 2 O 7+δ

Polycrystalline two-layered perovskite La_2.5-xK_0.5+xMn₂O _{7 + δ} (0 < x < 0.5) samples have been prepared by a modified sol-gel method and their magnetoresistance and magnetocaloric effects have been studied. A large deviation between the metal-insulator (MI) transition temperature (T _ρ ) and the magnetic transition temperature (T_C) is observed. Large magnetoresistance (MR) effects with Δρ/ρ of ∼40% at 12 kOe are obtained in wide temperature ranges. The maximum of the magnetic entropy change peaks at its Curie temperature (T_C), far above its MI transition temperature (T _ρ ). The large magnetic entropy change (∼1.4 J/kg.K) is obtained in the sample La_2.5-xK_0.5+xMn₂O _{7 + δ} (x = 0.35) upon 10 kOe applied magnetic field. Received 2 May 2002 / Received in final form 1st October 2002 Published online 19 December 2002 RID="a" ID="a"e-mail: wzhong@ufp.nju.edu.cn     

Temperature dependence of the YBa2Cu3O7 energy gap in differently oriented tunnel junctions

We have applied the break-junction technique to highly biepitaxial c-axis oriented YBa₂Cu₃O₇ thin films with T _C (ρ=0) = 91 K. Mechanically adjustable junctions with a good stability and tunneling current favored along the ab-planes have been realized. The conductance characteristics of these junctions show the presence of gap related maxima that move towards zero bias for increasing temperatures. Considering the misorientation angle α≈ 45 ^° ± 5 ^° of the junction, a maximum gap value at the Fermi level Δ ≈ 22 meV is inferred at T = 13 K. The temperature dependence of the gap related structures, shows a quasilinear behavior for T > 0.4 T _C similar to that observed in c-axis oriented, S-I-N type YBa₂Cu₃O₇ planar junctions. Received 20 July 2001