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     

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     

Enthalpy recovery of a glass-forming liquid constrained in a nanoporous matrix: Negative pressure effects

The T _g of organic liquids confined to nanoporous matrices and that of thin polymer films can decrease dramatically from the bulk value. One possible explanation for this phenomenon is the development of hydrostatic tension during vitrification under confinement that results in a concomitant increase in the free volume. Here we present experimental evidence and modeling results for ortho-terphenyl (o-TP) confined in pores as small as 11.6 nm that indicate that, although there is an important hydrostatic tension in the liquid in the pores, it does not develop until near the reduced T _g of the constrained material --well below the bulk T _g. Enthalpy recovery for the o-TP in the nanopores exhibits accelerated physical aging relative to the bulk, as well as a leveling off of the fictive temperature at equilibrium values greater than the aging temperature. An adaptation of the structural recovery model that incorporates vitrification under isochoric conditions is able to provide a quantitative explanation for the apparently anomalous aging observed in nanopore confined liquids and in thin polymeric films. The results strongly support the existence of an intrinsic size effect as the cause of the reduced T _g. Received 3 September 2001     

Magnetic and structural studies of the double perovskites Ba2REMoO6

A magnetic, electronic and structural study of the double perovskites Ba₂REMoO₆ (RE=Sm, Eu, Gd, Dy) has been performed. All materials crystallise in the cubic symmetry space group and the cell volume decreases as RE varies from Sm to Dy in accordance with Vegard's law. An antiferromagnetic transition is observed below T_N=130 and 112 K for RE=Sm and Eu, respectively. The Néel temperatures of these ordered rare earth molybdenum double perovskites are much higher than previously observed in double perovskites containing Eu or Sm and a 4d or 5d transition metal arranged in an ordered rock salt configuration. The high Néel temperatures arise due to a strong superexchange magnetic interaction via the Mo-O-RE-O-Mo pathway. All of the phases are electronically insulating and there is no evidence of magnetoresistance at any temperature.     

Magnetization curves of DyN clusters

Magnetic properties of isolated Dy_N clusters are studied in a molecular beam performing Stern-Gerlach experiments. The magnetizations μ _z of Dy_N are measured in dependence of the magnetic field strength B = 0-1.6 T and at nozzle temperatures T _n = 18 K and T _n = 300 K. At room temperature the magnetization augments linear with the field following a simple paramagnetic model. At T _n = 18 K the magnetization curves saturate at field strengths B ≥0.8 T. To explain the magnetization process at low temperatures two models are discussed: A model for adiabatic magnetization based on cluster rotation effects and a modified van-Vleck model. Received 30 November 2000     

Heterogeneous dynamics at the glass transition in van der Waals liquids, in the bulk and in thin films

It has been shown over the last few years that the dynamics close to the glass transition is strongly heterogeneous, both by measuring the diffusion coefficient of tagged particles or by NMR studies. Recent experiments have also demonstrated that the glass transition temperature of thin polymer films can be shifted as compared to the same polymer in the bulk. We propose here first a thermodynamical model for van der Waals liquids, which accounts for experimental results regarding the bulk modulus of polymer melts and the evolution of the density with temperature. This model allows us to describe the density fluctuations in such van der Waals liquids. Then, by considering the thermally induced density fluctuations in the bulk, we propose that the 3D glass transition is controlled by the percolation of small domains of slow dynamics, which allows to explain the heterogeneous dynamics close to T _g. We show then that these domains percolate at a lower temperature in the quasi-2D case of thin suspended polymer films and we calculate the corresponding glass transition temperature reduction, in quantitative agreement with experimental results of Jones and co-workers. In the case of strongly adsorbed films, we show that the strong adsorption amounts to enhance the slow domains percolation. This effect leads to 1) a broadening of the glass transition and 2) an increase of T _g in quantitative agreement with experimental results. For both strongly and weakly adsorbed films, the shift in T _g is given by a power law, the exponent being the inverse of that of the correlation length of 3D percolation. Received 21 March 2000 and Received in final form 4 December 2000     

Thermal expansion of orthorhombic and tetragonal phases of the highT c superconductors RE1Ba2Cu3O y (RE=Y,Gd, Dy)

Measurements of the coefficient of linear thermal expansion α have been carried out for the orthorhombic and tetragonal phases of RE₁Ba₂Cu₃O _y (RE=Y, Gd, Dy) compounds using a high resolution capacitance dilatometer in the temperature range 77–300 K. All the superconducting samples exhibit a jump Δα at their respective transition temperatures,T _c. Evidences of, sample-to-sample variation in α values and dependence of Δα on the sample preparation conditions, have been obtained. The non-superconducting samples, in general, exhibit lower values of α possibly because of lowering of oxygen content.     

Sm-Fe和Sm-Co非晶态合金薄膜的高场热磁效应

本文研究了Sm_xT_1-x(T=Fe,Co)非晶态薄膜的磁化强度σ与温度T的关系。发现在磁场H=7T下,对Sm_xCo_1-x样品(x=0.46,0.48,0.54,0.65)的升温过程测得的σ(T)曲线上有极大值,它对应的温度都在25—28K范围内,与成分关系不大。非晶态Sm_xFe_1-x(x=0.46,0.73)的结果与之不同,极大值对应的温度与成分有关。对上述样品,还发现在T≈6K附近σ(T)有极小值(和陡变),在近室温端,出现σ(T)下降缓慢的“拖尾巴”现象。我们认为,Sm-Co非晶态薄膜表现的高场热磁效应可能起源于Sm原子磁矩对磁化的贡献不可忽略,作用在Sm原子上的局域无规各向异性很强;这种各向异性在20—30K变化较大。而Sm-Fe薄膜的高场热磁效应可能起源于Fe原子磁矩的分散。σ(T)在6K附近的极小值(和陡变)及其在室温端变化缓慢的原因,可能是合金成分的涨落所致。 关键词：     

Rare earth doped cobalt ferrite thin films deposited by PLD

CoFe₂O₄ thin films with preferential texture structure, small grain size, and perpendicular magnetic anisotropy can be obtained by the pulsed laser deposition (PLD) technique. In this work, we studied the influence of the Fe³⁺ ions substitution by three elements from lanthanide group (Dy, La, and Gd) on the structural properties of the thin films. The samples were deposited by Nd:YAG laser (λ=532 nm, 10 ns) ablation of CoFe_1.8RE_0.2O₄, (RE=Dy, La, Gd) targets at various substrate temperatures ranging from room temperature to 600 °C. The microstructure and chemical composition of the thin films were investigated by Raman spectroscopy, XRD, SEM-EDS, and ToF-SIMS. The XRD patterns and Raman spectra of the thin films indicated the formation of a single spinel structure. Thus, the desired substitution of the iron ions in the spinel lattice with the RE elements was achieved in the thin films, although in the bulk material, their presence determined the formation of a residual phase with a perovskite-type structure.     

Quantum theory of the magneto-optical effect and magnetization of Nd-substituted yttrium iron garnet

The magneto-optical and magnetic properties of Nd ³⁺ ions in Y ₃Fe ₅O ₁₂ garnet are analyzed by using quantum theory. In the spontaneous state, the magneto-optical effects originate mainly from the intra-ionic electric dipole transitions between the 4 f ³ and 4 f ²5d states split by the spin-orbit, crystal field, and superexchange interactions. For the excited configuration, the coupling scheme of Yanase is extended to the Nd ³⁺ ion. The magneto-optical resonance frequencies are mainly determined by the splitting of the 5d states induced by the crystal field. The theoretical results of both Nd magnetization and Faraday rotation are in good agreement with experiments. The observed Faraday rotation is proved to be of the paramagnetic type. Although the value of the magneto-optical resonance frequency derived from a macroscopic analysis is approximately confirmed by our theoretical study, a new assignment about the transitions associated with this resonance is unambiguously determined. The spin-orbit coupling of the ground configuration has a great influence on both the Faraday rotation and magnetization, but, unlike the theoretical results obtained in some metals and alloys, the relation between the Faraday rotation and the spin-orbit coupling strength is more complex than a linear one. The magnitude of the magneto-optical coefficient increases as the spin-orbit interaction strength of the ground configuration decreases when the strength is not very weak. Finally, the temperature dependence of the magneto-optical coefficient and the effect of the mixing of different ground-term multiplets induced by the crystal field are analyzed. Received 8 November 2000     

Magnetic properties and structural chemistry of ternary silicides (RE,Th, U)Ru2Si2 (RE = RARE EARTH)

Ternary silicides (RE, Th, U)Ru₂Si₂ have been synthesized from the elements. All the compounds (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were found to be isotypic and to crystallize with the structure type of ThCr₂Si₂ (ordered derivative of the BaAl₄-type). The magnetic behavior of these alloys was studied in the temperature range 1.5 K < T < 1100 K. Magnetic susceptibilities at temperatures T > 300 K closely follow a typical Van Vleck paramagnetism of free RE³⁺-ions. In the case of CeRu₂Si₂ susceptibilities are well described for 20 K < T < 1100 K by a Van Vleck paramagnetism of widely spaced multiplets; the observed effective paramagnetic moment μ_eff = 2.12 BM indicates a high percentage (85%) of Ce³⁺. SmRu₂Si₂ yields an effective moment μ_eff = 0.54 BM, which compares reasonably well with the Hund's rule J = 5/2 ground level for free Sm⁺ and a low-lying excited level with J = 7/2. For temperatures T > 15 K the magnetic susceptibility as a function of temperature follows the “Van Vleck behavior” for free Sm³⁺. At low temperatures ferromagnetic ordering was encountered for (Pr, Nd, Ho, Er, Tm)Ru₂Si₂, whereas antiferromagnetic ordering was observed for (Sm, Gd, Tb, Dy)Ru₂Si₂. The ordering temperatures are generally below 55 K. No superconductivity was found for temperatures as low as 1.8 K.     

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.     

The microscope structures of amorphous phosphorus

The microscopic structures of thin films of amorphous phosphorus have been investigated by Raman scattering. The thin films were deposited by vacuum evaporation at substrate temperatures T_s between 300 and 510K. The Raman spectra of the films were compared with vibrational spectra of different allotropes of phosphorus: orthohombic black P, bulk amorphous red P and Hittorf's P. The structure of the films with T_s ? 300K is built up of double layers similar to those of orthorhombic black P. For T_s?510K the thin films have a structure similar to bulk amorphous red P based on the pentagonal tubes of Hittorf's P. A continuous transformation from one structure to the other is indicated by the Raman spectra of the films at intermediate T_s. The Raman measurements support early determinations of the structures of amorphous phosphorus inferred from radial distribution functions.     

Static and dynamic properties of supercooled thin polymer films

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular-dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), D, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT β-process. An analysis of the temperature dependence of the α-relaxation time suggests that the critical temperature, T _c, of MCT decreases with D. If the confinement is not too strong ( D≥10monomer diameter), the static structure factor of the film coincides with that of the bulk when compared for the same distance, T - T _c(D), to the critical temperature. This suggests that T - T _c(D) is an important temperature scale of our model both in the bulk and in the films. Received 12 September 2001     

Yrast bands in N = 91 isotones

The in-beam spectroscopy on N = 91 isotones has been carried out using the ¹²C + ¹⁵⁰Nd reaction. The νi _13/2 and νh _11/2 bands of ¹⁵³Sm have been extended up to 33/2⁺ and 31/2^-, respectively. Two new γ-rays have been located on the top of the unfavored band with νi _13/2 configuration in ¹⁵⁷Dy. Two identical relationships have been established in the low-spin region of the yrast νi _13/2 configuration between ¹⁵³Sm and ¹⁵⁵Gd, and between unfavored bands of ¹⁵⁵Gd and ¹⁵⁷Dy. Here all these nuclei have the same neutron number N = 91. Received: 28 June 2000 / Accepted: 20 October 2000     

Magnetization fluctuation analysis and superconducting parameters of , Sm, Gd, Dy, Ho, Yb) superconductor

In this work we report the analysis of magnetization experimental data of the , Sm, Gd, Dy, Ho, Yb) superconducting system. The data are analyzed in terms of thermal fluctuations on the magnetization excess ΔM(T) for different values of temperature in each one of the samples. We describe a procedure for extracting the penetration depth and the coherence length parameters from the magnetization, as a function of the applied magnetic field. This procedure was performed for polycrystalline samples of La_0.5RE_0.5BaCaCu₃O_7-δ by using the theory of Bulaevskii, Ledvij and Kogan, which analyzes the vortex fluctuation in superconducting materials within the Lawrence–Doniach framework. These data allowed to determine the characteristic temperature value T^* (73, 58, 48, 57, 56, 71 K, for RE=Y, Sm, Gd, Dy, Ho, Yb, respectively) in the magnetization curves for several magnetic fields. We calculated the data of magnetization excess from the curves of magnetization as a function of logarithm of applied field. We notice that the values for these superconducting parameters are in agreement with the reports for high temperature superconductors. The obtained value of superconducting volumetric fraction is compared with that obtained through the measure of the Meissner effect.     

Properties magnetiques des composes terres rares-plomb TPb3(T = Pr,Nd, Sm,Tb, Dy,Ho)

We have studied the low field susceptibility of TPb₃ compounds (T = Pr, Nd, Sm, Tb, Dy, Ho) between 3 and 300 K. All these compounds except SmPb₃ follow a Curie-Weiss law with a paramagnetic moment close to the free ion value. The compounds with Sm, Tb, Dy and Ho order antiferromagnetically.The magnetization of the three last compounds has been studied in static magnetic fields up to 85 koe.     

Magnetic properties of R3Co29Si4B10 (R=La, Ce, Pr, Nd, Sm, Gd and Dy) borides

The crystal structure and magnetic properties of quaternary rare-earth intermetallic borides R₃Co₂₉Si₄B₁₀ with R=La, Ce, Pr, Nd, Sm, Gd and Dy have been studied by X-ray powder diffraction and magnetization measurements. All compounds crystallize in a tetragonal crystal structure with the space group P4/nmm. Compounds with R=La, Ce, Pr, Nd and Sm are ferromagnets, while ferrimagnetic behavior is observed for R=Gd and Dy. The Curie temperatures vary between 149 K and 210 K. The Curie temperatures in R₃Co₂₉Si₄B₁₀ (R=Ce, Pr, Nd, Sm, Gd, Dy) compounds are roughly proportional to the de Gennes factors.     

R3(Fe,Mo)29Nx的晶体学特性和内禀磁性

研究了R₃(Fe,Mo)₂₉(R=Ce,Nd,Sm,Gd,Tb,Dy,Y)氮化物的晶体学特性和内禀磁性.主要研究内容为：氮化对R₃(Fe,Mo)₂₉金属间化合物的点阵参数、居里温度T_C、饱和磁化强度σ_s和各向异性场B_a的影响. 关键词：     

ZnSe films deposited on crystalline GaAs and amorphous quartz substrates by means of pulsed laser ablation technique

ZnSe films were deposited by pulsed laser ablation on a crystalline GaAs substrate and on an amorphous quartz substrate. The deposition process was performed with the same growth parameters. The films were investigated by means of X-ray diffraction, reflectance and photoluminescence spectroscopy. The X-ray diffraction spectra have demonstrated that the films grow in a highly oriented way but having different orientations, i.e. the films deposited on GaAs grow (100)-oriented and the films deposited on quartz grow (111)-oriented. Reflectance spectra as a function of the temperature have been analysed by means of the classical oscillator model, in order to obtain the temperature dependence of the band gap energy. This gives results comparable to those of ZnSe single crystals for ZnSe on GaAs, but it is red-shifted for ZnSe on quartz, because of lattice and thermal strains. The photoluminescence measurements at T = 10 K confirm the better quality of ZnSe deposited on GaAs and show that pulsed laser ablation is a promising technique to grow films having intrinsic luminescence even on an amorphous substrate. Received 29 May 2002 Published online 31 October 2002 RID="a" ID="a"e-mail: giuseppe.perna@ba.infn.it