Surface ferroelectric phase transition in multilayer polymer Langmuir films

The ferroelectric phase transition on the free surface of a polymer ferroelectric Langmuir-Blodgett film was studied by the optical second harmonic generation (SHG) technique. A hysteresis in the temperature dependence of the SHG intensity observed for a multilayer film of a poly(vinylidene fluoride)-trifluoroethylene copolymer in the vicinity of T≈15°C is a manifestation of the first-order ferroelectric phase transition in the topmost surface monolayer of the film.     

Anisotropy of dipole-dipole interactions in ferroelectric langmuir films of poly(vinylidene fluoride-trifluoroethylene)

The Lorentz tensor components L _j for poly(vinylidene fluoride-trifluoroethylene, 70/30) Langmuir-Blodgett films in the ferroelectric phase are determined experimentally. The results indicate that intralayer dipole-dipole interaction between the segments of the polymer is stronger than interlayer interaction. This conclusion agrees with the absence of the critical film thickness below which ferroelectricity would cease to exist.     

Adsorbate/absorbate interactions with organic ferroelectric polymers

We discuss the interactions of adsorbates with the organic ferroelectric copolymer poly(vinylidene fluoride (PVDF)–trifluoroethylene (TrFE)). Range of molecular adsorbates is discussed from the smaller polar molecules like water, which is small enough to both adsorb and absorb, to the larger macrocyclic metal–organic metal phthalocyanines. The changes in local dipole orientation may affect the strength of the coupling between adsorbate or absorbate and the copolymer poly(vinylidene fluoride–trifluoroethylene). The interface dipole interactions may also affect device properties. The dipole interactions are implicated at the interface between copper phthalocyanine and poly(vinylidene fluoride with trifluoroethylene) affecting the band offsets and the diode properties.     

Pressure effect on phase transition in ferroelectic polymers

Pressure effects of phase transition behaviour in two kinds of ferroelectric polymers of poly(vinylidene fluoride), PVDF, and copolymers of vinylidene fluoride and trifluoroethylene, (VDF/TrFE), are discussed. In the case of PVDF, several high-pressure treatments including a high-pressure annealing and a uniaxial compression were shown to induce a crystal transformation from a non-polar Form II crystal to a polar Form I crystal, which has ferroelectric characteristics and high piezoelectric activity. In addition, substantial pressure effects on ferroelectric phase transition points as well as crystal structures were observed for (VDF/TrFE) copolymers with different VDF contents. The most significant pressure effects were observed for copolymer samples with unstable ferroelectric structures at atmospheric pressure. From high-pressure X-ray and Raman scattering studies, these pressure effects were suggested to originate from the pressure-induced conformational transition from gauche to trans in the molecular chains.     

Scaling of the coercive field in ferroelectrics at the nanoscale

The scaling of the coercive field in ferroelectric films at the nanoscale is investigated experimentally. The scaling in the films of copolymer vinylidene fluoride and BaTiO₃ with thickness equal by the order of value to the critical domain nucleus size 1–10 nm reveals deviation from the well-known Kay-Dunn law. At this thickness region coercive field does not depend on thickness and coincides with Landau-Ginzburg-Devonshire value.     

Effective medium approximation for optical bistability in nonlinear metal-dielectric composites

A general theory based on the spectral representation method and effective medium approximation is adopted to investigate the optical bistable behavior in a nonlinear two-phase composite with symmetrical microstructure, in which the metal particles of the volume fraction p and the dielectric particles of the volume fraction 1−p are randomly dispersed but oriented with respect to one another. The relation between the spatial average of local field squared and the external applied field is established through the spectral density function m(x), obtained from the modified Bruggeman effective medium approximation. We find that the optical bistability (OB) is dependent on the depolarization factor L of the components and the volume fraction p. For a given p, we predict that OB can be observed only when L is larger than the critical value L_c, and bistable behavior is more pronounced at large L. Moreover, numerical results show that both the upper threshold field and the width of OB region increase monotonically as L increases. The field-dependent reflectance at normal incidence R in random composites is also investigated.     

Field amplification and ferroelectric switching in a bilayer linear insulator-ferroelectric heterostructure

Langmuir-Blodgett thin-film heterostructures consisting of molecular layers of the ferroelectric copolymer poly(vinylidene fluoride-trifluoroethylene) and an insulator (the azo dye) are prepared and studied. A physical model is proposed for amplification of a local electric field in regions of arrangement of the dye and ferroelectric molecules. Experimental studies of the ferroelectric switching confirm that, in the heterostructures, the effective external coercive voltage decreases and the switched polarization increases.     

Different approaches to adjusting band offsets at intermolecular interfaces

We show that at the hetero-molecular interface, the molecular band offsets can be modified by either adjusting the dopant or dopant concentration of one or both molecular layers or by changing the dipole orientation at the intermolecular interface. Photoemission studies reveal the changes in electronic structure and diode devices exhibit conduction properties that are altered in response to changes to the molecular band offsets. As a demonstration, thin film copper phthalocyanine to crystalline ferroelectric copolymer poly(vinylidene fluoride with trifluoroethylene) heterojunction diodes, without additional dopants, are compared with doped polyaniline layers on the crystalline ferroelectric copolymer poly(vinylidene fluoride with trifluoroethylene).     

Structure formation in crystallizing ferroelectric polymers

The structure of ferroelectric copolymers of vinylidene fluoride with hexafluoropropylene is investigated using wide-angle x-ray diffraction. It is shown that the crystallization of extruded films of vinylidene fluoride-hexafluoropropylene copolymers brings about the formation of the nonpolar α modification and, possibly, the polar α_p modification. An increase in the hexafluoropropylene content in the copolymer leads to a decrease in the degree of perfection of the α (α_p) phase, on the one hand, and a reduction of its volume fraction, on the other hand.     

Ferroelectric properties of vinylidene fluoride copolymers

Ferroelectric properties of copolymers of vinylidene fluoride with trifluoroethylene and tetrafluoroethylene are described with special interest in their polarization reversal and phase transition behavior. The ferroelectric phase consists of all-trans molecules packed in a parallel fashion while molecules adopt irregular TT, TG, T[Gbar] conformations in the paraelectric phase. In the ferroelectric phase, polarization reversal occurs at very high fields (> 100 MV/m) as a result of eventual 180° rotations of individual chain molecules around their axes. The switching time ranges from sec to nsec depending upon the strength of the applied field according to an exponential law with a particularly large activation field (～ 1 GV/m). The value of the observed remnant polarization is consistent with prediction from a simple dipole sum implying a minor contribution from the Coulomb interaction. The ferroelectric-to-paraelectric transition appears most clearly for copolymers containing 50-80 mol% vinylidene fluoride at temperatures from 70 to 140°C. The transition accompanies cooperative dipole motions associated with elementary trans-gauche transformations. Changes in various properties as well as in structures in the vicinity of the Curie point are consistent with an order-disorder transition of first order. Detailed characteristics specifying their ferroelectricity are summarized and discussed in relation to the molecular, crystalline, and higher-order structures inherent to ferroelectric polymers.     

Near field optical spectroscopy of colored centers stripes written in lithium fluoride by electron-beam lithography

Electron-beam lithography has been used to define color center stripes of about one hundred micrometers length and variable width (100 v nm to 5 v m) in lithium fluoride. These structures have for the first time been illustrated and spectrally characterized in near field optical microscopy (SNOM) operating in local illumination mode with an optical fiber probe and far field fluorescence detection.     

Introduction: Early studies in piezoelectricity,pyroelectricity, and ferroelectricity in polymers

Studies on piezoelectricity and pyroelectricity in polymers were initiated in materials of biological origin. A variety of polysaccharides, proteins and DNA were found to exhibit piezolectricity. Synthetic polymers such as polypeptides and optically-active polymers were also found to be piezoelectric. The piezolectricity and pyroelectricity in bone and tendon aroused interests in orthopaedists and led to studies on the electrical stimulation of osteogenesis. The discovery of large piezoelectricity in poled polyvinylidene fluoride opened a new field of research towards ferroelectric polymers. The Curie temperature was confirmed in the copolymers of vinylidene fluoride and trifluoroethylene. The characteristic changes of molecular conformation and associated crystalline structure were revealed at the temperature range of the phase transition. Piezoelectric and ferroelectric-like properties were found in the copolymers of vinylidenecyanide and vinylacetate, which are amorphous and transparent.     

Optically (solar) pumped oxygen-iodine lasers

We present the results of theoretical and experimental studies demonstrating the possibility of developing an oxygen-iodine laser (OIL) with direct optical pumping of molecular oxygen involving inter-molecular interaction with charge transfer from donor molecule (buffer gas) to acceptor molecule (oxygen). This interaction lifts degeneracy of the lower energy states of molecular oxygen and increases its absorption cross section in the visible spectral region and the UV Herzberg band, where high quantum yield of singlet oxygen is achieved (QY ～ 1 and QY ～ 2, respectively) at the same time. A pulse-periodic optical pump sources with pulse energy of ～50 kJ, pulse duration of ～25 μs, and repetition rate of ～10 Hz, which are synchronized with the mechanism of singlet oxygen generation, are developed. This allows implementation of a pulse-periodic oxygen-iodine laser with an efficiency of ～25%, optical efficiency of ～40%, and parameter L/T ～ 1/1.5, where T is the thermal energy released in the laser active medium upon generation of energy L. It is demonstrated that, under direct solar pumping of molecular oxygen, the efficiency parameter of the OIL can reach L/T ～ 1/0.8 in a wide range of scaling factors.     

Dielectric and optical properties of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)<Subscript>0.8</Subscript>Ti<Subscript>0.2</Subscript>O<Subscript>3</Subscript> (PMNT-0.2) ferroelectric relaxor single crystals

The dielectric and optical (optical transmission, small-angle light scattering, birefringence) properties of PMNT-0.2 single crystals and their variation induced by a dc electric field have been studied. The birefringence was found to increase anomalously at the transition from the rhombohedral ferroelectric to the inhomogeneous relaxor phase (the spontaneous ferroelectric transition temperature T_sp). Below T_sp, the dielectric and optical properties were observed to exhibit anomalies originating from reorientation and growth of domains in size. Unlike ferroelectric relaxors of the type of PbB′_1/3B′_2/3O₃ and PbB′_1/2B′_1/2O₃, in PMNT-0.2 neither induction of the ferroelectric phase by an electric field nor thermally stimulated destruction of the ferroelectric state occurs through the percolation mechanism (i.e., they are not accompanied by anomalously narrow maxima in small-angle light scattering). This is attributed to the inhomogeneous structure of the relaxor phase, as a result of which the phase transition does not take place simultaneously in various regions of the crystal.     

Distribution and amplification of an electric field in ferroelectric-dye heterostructures

The distribution of an electric field has been investigated in Langmuir-Blodgett thin-film heterostructures prepared by sequentially transferring layers of the ferroelectric copolymer poly(vinylidene fluoride-trifluoroethylene) P(70% VDF 70% ?C30% TrFE) and the azo dye. An alternating-current voltage applied to the electrodes is unevenly distributed across layers of the dye and the copolymer in accordance with a constant induction along the normal to the heterostructure. The electric-field-induced shift of the absorption spectrum of the dye serves as a probe of the electric field and reveals a noticeable amplification of the electric field in the dye layers (by a factor of 2?C7). The electric field in the ferroelectric is directed opposite to the direction of the electric field applied to the electrodes of the heterostructure.     

Electrocaloric effect in ferroelectric polymers

The electrocaloric effect (ECE) of poly (vinyledene fluoride?Ctrifluoroethylene) (P(VDF?CTrFE)) 55/45?mol% copolymers was directly measured, which confirms the results deduced from Maxwell relation. The adiabatic temperature change ??T under a given electric field peaks at the ferroelectric?Cparaelectric (FE?CPE) transition. Away from it, ECE becomes small. ??T versus applied electric field can be described well by a modified Belov?CGoryaga equation. The ECE in ferroelectric polymers, especially near FE?CPE transition where larger ECE is observed, are analyzed under different boundary conditions employing phenomenological theory and constitutive equations. The secondary pyroelectricity is found to play a significant role which enhances ECE in ferroelectric polymers.     

Nanometer-scale characterization and manipulation of ferroelectric films using scanning probe microscopy

Ferroelectric domain structures in Pb(Ni_0.04Zr_0.28Ti_0.68)O₃ and SrBi₂Ta₂O₉ ferroelectric thin films have been non-destructively observed using various scanning probe microscopy (SPM) modes. Using the SPM, it has been shown that it is possible to not only image but also manipulate the local domain structure on a nanometer scale by biasing the SPM tip. In addition, the SPM was applied to measure dC/dV–V spectra on individual ferroelectric grains. The examples illustrate the possibility of using an SPM-based datastorage read/write system.     

Ferroelectric characteristics of MFIS structure with P(VDF–TrFE)/BaTiO3 nanocomposite as ferroelectric layer

A metal–ferroelectric–insulator–semiconductor (MFIS) structure has been made using poly(vinylidene difluoride–trifluoroethylene)/barium titanate [P(VDF–TrFE)/BaTiO₃] nanocomposite as ferroelectric layer, on silicon/silicon dioxide (Si/SiO₂) substrate. Different concentrations of BaTiO₃ were added to P(VDF–TrFE) polymer using bath sonication method, and the films were prepared using spin coating method. The structure was annealed to 120 °C for 2 h and then the top aluminium electrode was deposited by thermal evaporation method. Capacitance–voltage shows an increase in accumulation capacitance as the BaTiO₃ nanoparticle concentrations increases. Dielectric constant was estimated from the capacitance voltage (C–V) characteristics and found to be changing as the concentration of BaTiO₃ is varied. Polarization–electric field analyses show hysteresis behaviour of the nanocomposite. A comparison of MFIS and metal–ferroelectric–semiconductor structures was done with varying ferroelectric film thicknesses. All these results suggest that this polymer nanocomposite can be a promising material which can be used in non-volatile memory devices.     

In fact,L-threonine

It is shown that three papers published recently by Allen Moses et al. on “L-threoninium phosphate”, “L-threoninium sodium fluoride” and “L-threoninium tartrate” are completely erroneous. In fact, only crystals of L-threonine were obtained in all cases.     

Effect of the mechanical stretching on the ferroelectric properties of a (VDF/TrFE) (75/25) copolymer film

The transition phase behaviour of a vinylidene fluoride-trifluoroethylene (VDF-TrFE) copolymer film was studied after being subjected to different mechanical stretching levels in both longitudinal (L) and transversal (T) directions relatively to the initial extrusion direction. Both ferroelectric-paraelectric (FE-PE) and melting transitions were detected in the films by differential scanning calorimetry, that were not affected by L stretching. This suggests that sliding mechanism along the c-axis of such films during plastic deformation influences slightly the all-trans chain conformations and the CF₂ dipole orientation. On the other hand, the FE-PE peak decreases in area and temperature upon T stretching, indicating a damage of the ferroelectric phase. However, the melting peak maintains unchanged. This fact provides evidence that the mechanical stretching do not change the total degree of crystallinity. The results suggest that the stretching induces a FE-PE phase transformation, without affecting the degree of crystallinity.