Crystallizaton Characteristics of the Alternating Tetrafluoroethylene-Ethylene Copolymer

The alternating tetrafluoroethylene-ethylene (TFE-E) copolymer has been studied with respect to its crystallization by using differential scanning calorimetry and optical microscopy. The value of the specific surface energy σ at the melt/crystal interface is calculated to be about 2 · 10⁻³ J/m². The nucleating activity Φ of TiO₂ particles introduced into TFE-E copolymer is estimated to be approximately 0.9. The temperature dependence of the nucleation rate and of the linear growth velocity are constructed in the whole region from the melting temperature T_m to the vitrification temperature T_g. The minimum cooling rate for the formation of a crystal-free TFE-E copolymer glass is calculated and its value amounts to 10⁴ K · min⁻¹.     

ELECTROOPTIC EFFECTS OF THICK FREELY SUSPENDED FERROELECTRIC LIQUID CRYSTAL FILM AND CELL

Abstract

Electrooptic effects of thick freely suspended ferroelectric liquid crystal films and conventional cells that are thicker than helical pitch have been studied. A very slow molecular motion was observed in the case of the thick films that have no solid surface.     

Vacuum-evaporated ferroelectric films and heterostructures of vinylidene fluoride/trifluoroethylene copolymer

The potential of the vacuum method for preparing ferroelectric films and photonic heterostructures from organic materials is studied. Vacuum-evaporated films of fluoropolymers and heterostructures on their basis are obtained and their ferroelectric and spectral properties are studied. In particular, homogeneous films of the well-known piezoelectric polymer polyvinylidene fluoride and ferroelectric material vinylidene fluoride/trifluoroethylene copolymer (P(VDF/TFE)) are produced. Experimental studies of vacuum-evaporated P(VDF/TFE) films confirmed their ferroelectric properties. The heterostructures composed of alternating layers of P(VDF/TFE) copolymer molecules and azodye molecules are fabricated by vacuum evaporation. Owing to the controlled layer thickness and a significant difference in the refractive indices of the P(VDF/TFE) copolymer and azodyes, these heterostructures exhibit properties of photonic crystals. This finding is confirmed by the occurrence of a photonic band in the absorption spectra of the heterostructures.     

Second-harmonic generation in vinylidene fluoride-trifluoroethylene copolymers doped with donor-acceptor molecules

The temperature dependence of the second-harmonic generation in a vinylidene fluoride-trifluoroethylene ferroelectric copolymer doped with 5 wt % of a noncentrosymmetric 4-anilino-4′-nitroazobenzene chromophore is analyzed. The second-order susceptibility χ⁽²⁾ in the ferroelectric phase of these copolymers appears to be twice as high as in the poly(methyl methacrylate) with the same chromophore content. The effect is attributed to the presence in ferroelectrics of a local electric field associated with the spontaneous polarization. The intensity of the second-harmonic generation in both ferroelectric and paraelectric phases correlates with the variation of the surface potential.     

Isothermal liquid phase epitaxy of A 3 B 5 compounds under excessive vapor pressure of the B 5 component

A mathematical model has been developed of isothermal epitaxial growth of A³B⁵ films on the A³B⁵ substrates from flux by creating the excessive pressure of diatomic vapors of the B ⁵ component. The model is based on the diffusion equation with the nonlinear boundary condition at the evaporation surface and the thirdkind condition at the crystallization surface. The problem is solved numerically on a computer.     

Antiferroelectric and ferroelectric switching of a liquid crystal in Langmuir-Blodgett films under strong confinement conditions

An antiferroelectric liquid-crystal (LC) material formed of banana-shaped molecules in the sandwich metal-thin Langmuir-Blodgett film-metal geometry, which is typical of solid-state technology, is investigated. Upon heating the thin-film elements, the material passes to the high-temperature (68–127°C) LC B ₂ phase, which, despite severe limitation on the film thickness (∼100 nm or less), exhibits antiferroelectric switching, which was previously observed only in bulk samples (10 μm thick) of the LC studied. At film thicknesses smaller than ∼40 nm, ferroelectric switching is observed, which is caused by the stabilization of the ferroelectric LC phase by the boundary surfaces. The largest values of the switched polarization of films (∼400 nC/cm²) are comparable with the polarization of bulk samples. The coercive field increases with decreasing film thickness and reaches ∼10⁶ V/cm for the thinnest films. This value corresponds to the intrinsic coercive field of the ferroelectric under conditions of a strong surface effect, which suppresses domain processes. Published in Russian in Kristallografiya, 2006, Vol. 51, No. 5, pp. 898–905. Dedicated to the 60th Birthday of M.V. Kovalchuk The text was submitted by the authors in English.     

Growth,structure and some properties of oriented Sb (S,O) I films

X-ray and electron microprobe analyses of Sb(S, O)I films structure and composition have been performed. The films under investigation were prepared by crystallization from the melt in close spacing. It was revealed that the SbS_0.8O_0.2I structure was isomorphic t the SbSI one. The ferroelectric phase transition was observed at 75°C. The electromechanical coupling factor was 0.3 at 50°C.     

Physicochemical investigation into the specific features of the phase transformations in electrodeposited nanocrystalline oxotungstate films

The structure of oxotungstate films (as-deposited and subjected to heat treatment at temperatures of up to 600°C) prepared through electrodeposition on platinum and gold polycrystalline substrates is investigated using different physicochemical methods. It is shown that the oxotungstate films consist of X-ray amorphous hydrated mixtures of isopoly compounds, predominantly in the form of paratungstates with [H₂W₁₂O₄₂]¹⁰⁻ anions. The structural transformation with an increase in the temperature in air is accompanied by the loss of water, the transformation of paratungstate anions into more oxidized forms, their destruction, and the crystallization of nonstoichiometric hydroxylated oxide phases.

     

On two-dimensional ferroelectricity in layered polymer films on substrates

A simple model for describing structural phase transitions in thin ferroelectric copolymer films on solid substrates obtained by the Langmuir-Blodgett method has been suggested. It is shown that the polymer-substrate interaction and surface tension considerably influence these transitions and, in particular, can induce additional low-temperature first-and second-order phase transitions depending on the material parameters and the film thickness. The main dimensionless parameter and its critical value, which control the formation of the additional order in very thin films, are determined.     

Surface Chemical Bonding States and Ferroelectricity of Pb(Zr0.52Ti0.48)O3 Thin Films

The surface chemical bonding states and the ferroelectric properties of sol‐gel deposited lead zirconate titanate [Pb(Zr_0.52Ti_0.48)O₃, PZT] thin films coated on (111)Pt/Ti/SiO₂/Si substrates were investigated. X‐ray photoelectron spectroscopy (XPS) was used to determine the oxidation state of the surface and the chemical composition as a function of depth in ferroelectric PZT thin layers. Values for the dielectric constant and dissipation factor at 1 kHz for the 300 nm‐thick film were 1214 and 0.014 for the film annealed at 520 °C, and 881 and 0.015 for a film annealed at 670 °C. Measured values for the remanent polarization (P_r) and coercive field (E_c), from polarization‐electric field (P‐E) hysteresis loops biased at 10 V at a frequency of 100 Hz, were 16.7, 14.4 μC/cm² and 60, 41.7 kV/cm for 520 °C and 670 °C. The leakage current density (J) was 72 and 96 nA/cm² at an applied field of 100 kV/cm. It was found that the bonding states of lead and oxygen in the surface regions could be correlated with the ferroelectric properties of the integrated thin layers.     

Preparation and the growth mechanism of zinc blende structure tin sulfide films by successive ionic layer adsorption and reaction

Zinc blende structure tin sulfide (SnS) films have been prepared by successive ionic layer adsorption and reaction (SILAR) method. It is found that both the annealing and addition of NH₄Cl or NaCl to cation solution during the SILAR process can promote the crystallization of SnS films. The growth mechanism for this novel structure considered that the initial distribution of cations on the substrate surface during the cation adsorption process is the crucial factor that determines the structure of the final production. Because Cl⁻ anions can complex with Sn²⁺ cations, when the concentration of Cl⁻ in the cation precursor solution increases, more [SnCl]⁺ complex ions are adsorbed on the substrate. These [SnCl]⁺ ions assemble more orderly than Sn²⁺ ions because of the polarity of ions, so crystallized SnS films can be obtained when NH₄Cl or NaCl is added to the cation solution.     

Electro-Optic Hysteresis in Ferroelectric Polymer Langmuir–Blodgett Films

The hysteresis and kinetics of the electro-optic response of multilayer ferroelectric polymer Langmuir–Blodgett films have been investigated.

     

Orientation control of LaNiO3 thin films by RF magnetron sputtering with different oxygen partial pressure

Highly (1 1 0)- and (1 0 0)-oriented LaNiO₃ (LNO) thin films were successfully grown on Si (1 0 0) substrate using radio frequency (RF) magnetron sputtering at room temperature (RT). Effects of oxygen partial pressures on the orientation, film composition, surface morphology, and electrical properties of the films were investigated. The nearly complete (1 0 0) orientation was first achieved with oxygen partial pressure beyond 15% in the sputtering gas. The preferred (1 0 0) orientation of growing films is determined by uniform distribution of Ni³⁺ and La/Ni ratio in the films caused by oxygen during sputtering, as well as the lowest surface energy of the films in the crystalline process. LNO films with controlled orientation have low resistivity of 7.0×10⁻⁶ Ω m which is a good basis for integrating ferroelectric capacitors.     

Signatures of Ge2Sb2Te5 film at structural transitions

Ge₂Sb₂Te₅ (GST) films, one of the most suitable Chalcogenide alloys for Phase change Random Access Memory applications are studied for changes in sheet resistance, optical transmission, morphology and surface science by annealing at various transition temperatures. The crystallization leads to an increase of grain size and roughness in the films and the resistance changes to three orders of magnitude. Optical studies on GST films show distinct changes during phase transitions and the optical parameters are calculated. An increase of Tauc parameters B^1/2 indicates a reduction in disorder during phase transition. It is confirmed from XPS studies that Ge-Te, Sb-Te bonds are present in both amorphous and crystalline phases whereas Sb-Ge, Te-Te, Sb-Sb bonds are absent.     

Study of the growth and switching kinetics on ferroelectric nanocrystals of copolymer vinylidene fluoride and trifluoroethylene on an atomic force microscope

The growth of nanocrystals obtained from Langmuir-Blodgett films of ferroelectric copolymer consisting of 70% vinylidene fluoride and 30% trifluoroethylene has been investigated by atomic force microscopy (AFM). The radius and concentration of nanocrystals are found to depend on the annealing time of the film. A model for nanocrystal growth is proposed which yields adequate time dependences for nanocrystal size parameters. The switching kinetics of individual ferroelectric nanocrystals with an average diameter of 100–200 nm and a height of 15–20 nm has been investigated in the piezoelectric response mode. It is shown that the switching of nanocrystals has an activation character.     

Substitution effects on ferroelectric,leakage current and anti‐fatigue characteristic of Bi4‐xSbxTi3O12 thin films

Bi_4‐xSb_xTi₃O₁₂ (BSTO) (x = 0, 0.03, 0.04, 0.05, 0.06 and 0.07) thin films have been fabricated on Pt/Ti/SiO₂/Si substrates by sol‐gel method. The effects of various Sb³⁺ content on microstructure and ferroelectric properties of systems are investigated. XRD show that Bi_4‐xSb_xTi₃O₁₂ (x≠0) thin films prefer (117) orientation. The substitution Sb³⁺ for Bi³⁺ reduces the grain size of the film surface. Compared to the BTO (x = 0) film, Bi_4‐xSb_xTi₃O₁₂ films display exciting electric properties. Especially when x = 0.04, the film Bi_3.96Sb_0.04Ti₃O₁₂ has achieved the max 2Pr value of 87μC/cm². This film also has a better anti‐fatigue characteristic, which can be up to 10¹⁰ switching cycles without fatigue. The leakage current density improved with J = 8×10⁻⁸ A/cm².     

PHOTOISOMERISING EFFECTS IN NITROAZO FERROELECTRIC DYE GUEST HOST SYSTEMS

Abstract

The effect of a photoisomerising dye in a ferroelectric liquid crystal host has been investigated. A nitroazo dye incorporating the same three-siloxane unit as an organosiloxane ferroelectric host has been used to insure good miscibility and high dye concentrations. The effect of photoisomerisation by 300–400 nm UV of up to 430 mW. cm^?2 has been investigated in two mixtures with 25% and 50% molar weight of dye. The 25% mixture has an I-SmC*-crystal phase sequence, while the 50% mixture has I-SmA*-SmC*-crystal. Transition temperatures of both the mixtures are reduced by increased UV illumination. For the first mixture at a constant temperature, the spontaneous polarisation in the ferroelectric phase is reduced by UV illumination. For the second mixture both the spontaneous polarisation and tilt angle of the SmC* phase are reduced by UV illumination and the phase is changed from SmC* to SmA* at temperatures close to the transition. The change of tilt angle and observations of micrograph textures indicate that this is a macroscopic change of the material rather than any phase separation of the dye and host materials.     

The Photorefractive and Photovoltaic Properties of a Composite Based on Ferroelectric Polymer Doped with Carbon Nanotubes

The photorefractive effect is obtained in a composite of a ferroelectric polymer (polyvinylidene fluoride with trifluoroethylene (P(VDF/TrFE)) and single-walled carbon nanotubes (SWCNTs), which serve simultaneously as non-linear optical chromophores and spectral sensitizers to a 1064-nm laser beam. It is established that the presence of internal field in the ferroelectric makes it possible to measure the photorefractive effect in the absence of applied external field. Undoped films of VDF/TrFE copolymer are not photosensitive and do not exhibit the bulk photovoltaic effect (BPE). BPE is observed (along with the photosensitivity) in polarized samples, when carbon nanotubes are introduced into the copolymer.     

Nucleation and grain growth in as deposited and ion implanted GeTe thin films

The crystallization dynamic of amorphous GeTe 50 nm thick films deposited on a SiO₂/Si substrate by RF magnetron sputtering, either ion implanted by Ge⁺ ions or not, has been analyzed in situ by optical microscopy during annealing in the 143-155 °C temperature range. Raman spectroscopy has been also performed in as deposited, ion implanted (i.i.) and melt quenched (m.q.) amorphous samples to compare the local order among the different amorphous structure. Nucleation and growth rates, for i.i. and as deposited samples, have been observed and directly compared by optical microscopy in a region of about 5 × 10⁴ μm². From these data, the activation energy and pre-exponential terms of each process have been calculated. The nucleation rate and growth velocity of the i.i. films increased by a factor thirteen and a factor three with respect to the as deposited samples. This evidence, in agreement with Raman spectroscopy data, suggests that implantation, providing kinetic energy by collision cascade, induces a local atomic rearrangement towards more relaxed amorphous states. As a result the crystallization kinetic is enhanced by the reduction of wrong bonds formed during sputter deposition, a process which occurs far from equilibrium conditions.     

Spectroscopy of smooth deuterated carbon films redeposited from plasma discharge in the tokamak T-10

Smooth deuterated carbon films redeposited from a deuterium plasma discharge in the tokamak T-10 vacuum chamber have been investigated by different spectroscopic methods and temperature measurements. The photoluminescence excitation spectra of sp ³-sp ² nanostructures of tokamak films and sp ² nanostructures of fullerite C60 films are compared. The effect of defect states on the photoluminescence and its temperature quenching is discussed. It is concluded that the mechanism of thermal luminescence quenching for smooth deuterated tokamak films is close to the corresponding mechanism for amorphous a-C:H films.