A. V. Sorokin

Two-dimensional ferroelectric films

Ultrathin crystalline films offer the possibility of exploring phase transitions in the crossover region between two and three dimensions. Second-order ferromagnetic phase transitions have been observed in monolayer magnetic films,, where surface anisotropy energy stabilizes the two-dimensional ferromagnetic state at finite temperature. Similarly, a number of magnetic materials have magnetic surface layers that show a second-order ferromagnetic–paramagnetic phase transition with an increased Curie temperature. Ferroelectricity is in many ways analogous to ferromagnetism, and bulk-like ferroelectricity and finite-size modifications of it have been seen in nanocrystals as small as 250 Å in diameter, in perovskite films 100 Å thick and in crystalline ferroelectric polymers as thin as 25 Å (refs 7-10). But these results can be interpreted as bulk ferroelectricity suppressed by surface depolarization energies, and imply that the bulk transition has a minimum critical size. Here we report measurements of the ferroelectric transition in crystalline films of a random copolymer of vinylidene fluoride and trifluoroethylene just 10 Å (two monolayers) thick. We see a first-order ferroelectric phase transition with a transition temperature nearly equal to the bulk value, even in these almost two-dimensional films. In addition, we see a second first-order transition at a lower temperature, which seems to be associated with the surface layers only. The near-absence of finite-size effects on the bulk transition implies that these films must be considered as two-dimensional ferroelectrics.

Nonvolatile memory element based on a ferroelectric polymer Langmuir-Blodgett film

We report the operation of a potential nonvolatile bistable capacitor memory element consisting of a metal gate, a 170 nm thick ferroelectric Langmuir–Blodgett film of vinylidene fluoride (70%) with trifluoroethylene (30%) copolymer, and a 100 nm thick silicon-oxide insulating layer, all deposited on an n-type silicon semiconductor substrate. The device exhibited clear capacitance hysteresis as the gate voltage was cycled between ±25 V, with a capacitance dynamic range of 8:1 and threshold voltage shift of 2.8 V. The results are in good agreement with the model of Miller and McWhorter [J. Appl. Phys. 72, 5999 (1992)].

Nanoscale polarization manipulation and conductance switching in ultrathin films of a ferroelectric copolymer

We report the direct observation of induced molecular reorientation on a ferroelectric copolymer with a scanning tunneling microscope (STM). Ultrathin copolymer films of vinylidene fluoride (70%) with trifluoroethylene (30%) revealed a quasihexagonal close-packing structure with long-range polymer chain ordering. By flipping the polarity of the STM tip bias voltage, a reversal of local polarization was observed through an apparent lattice shift and was accompanied by an asymmetric “diode-like” character in tunneling current I(V). These results clearly demonstrated conductance switching behavior on nanoscale with local polarization reversal.

Determination of the optical dispersion in ferroelectric vinylidene fluoride (70%)/trifluoroethylene (30%) copolymer Langmuir–Blodgett films

We report measurements of the optical dispersion in ferroelectric Langmuir–Blodgett films of polyvinylidene fluoride (70%)-trifluoroethylene (30%) copolymer, using variable-angle spectroscopic ellipsometry over a wide spectral range from infrared to ultraviolet. Film thickness averaged 1.78±0.07 nm per deposition layer for films ranging from 5 to 125 deposition layers as determined from multi-sample analysis. This deposition rate was consistent with capacitance measurements, yielding a dielectric constant of 9.9±0.4 normal to the film, by quartz microbalance measurements, and by atomic force microscopy.

Water absorption and dielectric changes in crystalline poly(vinylidene fluoride-trifluoroethylene) copolymer films

Crystalline Langmuir–Blodgett copolymer films of vinylidene fluoride with trifluoroethylene (70%:30% and 80%:20%) absorb water. Water absorption is accompanied by film swelling, as indicated by an increase in lattice spacing, sometimes by as much as 5%. This water absorption, between 0 and 40 °C, is a result of intercalation or occupation of interstitial sites between the layers of the film, not just water molecules filling voids and defect sites alone. An increase in the film capacitance is observed, although the polymer chains retain all trans configuration of the ferroelectric phase.

Heterojunction diode fabrication from polyaniline and a ferroelectric polymer

We have fabricated a p–n heterojunction diode by vapor depositing a thin film of polyaniline on top of the crystalline copolymer: poly(vinylidene fluoride with trifluoroethylene). The formation of a diode is expected from the band offsets of the two polymers near the Fermi level. The interface between the two components was investigated, and an abrupt interface was found that is very different from the inorganic analog.

Thickness dependence of switching for ferroelectric Langmuir films

Abstract Switchable ferroelectric Langmuir-Blodgett films prepared from the ferroelectric copolymer of vinylidene fluoride with trifluoroethylene P(VDF-TrFE) manifest the true bistability for films thicker than 15 monolayers; thinner films are still switchable but monostable. The crossover of the switching behaviour presents the first estimation of the ferroelectric correlation length, ξ ≈ 75 A .

Pyroelectric study of polarization switching in Langmuir-Blodgett films of poly(vinylidene fluoride trifluoroethylene)

The ferroelectric switching in Langmuir-Blodgett films of poly(vinylidene fluoride trifluoroethylene) is studied. The films have a distribution of switching times several decades wide. Nearly a half of the film volume may be switched faster than 1ms, though complete switching of a whole sample may require 100s or more. The switching occurs through a domain nucleation and growth mechanism. The decay of polarization at zero bias is logarithmic in time, with a constant rate below 5% per decade at room temperatures. The coercive voltage may be as low as 5V, which makes the films promising for use in nonvolatile random-access data storage.

Effects of an external electric field on the ferroelectric-paraelectric phase transition in polyvinylidene fluoride-trifluoroethylene copolymer Langmuir-Blodgett films

X-ray diffraction and capacitance measurements have been employed to study the structural and dielectric behavior of the ferroelectric-paraelectric phase transition under the influence of a large external electric field. The samples under study are ultrathin (15–100nm) Langmuir–Blodgett films of a copolymer of vinylidene fluoride (70%) with trifluoroethylene (30%) deposited on aluminum-coated silicon. In situ θ-2θ x-ray diffraction was used to measure the change in interlayer spacing perpendicular to the film surface, corresponding to the (110) direction and indicating that the polymer chains along (001) lie predominantly in the plane, while capacitance measurements were used to monitor the behavior of the dielectric constant of the film. Application of a large electric field, up to 265MV∕m, raises the phase transition temperature and can convert the nonpolar trans-gauche paraelectric phase to the polar all-trans ferroelectric phase in a reversible manner.

Investigation of Ferroelectricity in Poly(methyl vinylidene cyanide)

The ferroelectric and piezoelectric properties of newly synthesized polymer systems have been studied. To date PVDF and its copolymers P(VDF-TrFE) have provided the bulk of the knowledge pertaining to ferroelectricity in polymers. Recently, ultrathin ferroelectric films of P(VDF-TrFE) 70:30 have been fabricated using the Langmuir-Blodgett technique [4]. In this study, various new polymers have been synthesized by chemically altering the PVDF structure. This alteration was performed in order to enhance the amphiphilic nature of the polymer and thus improve the LB film quality and control. Various chemical groups have been used to replace the electropositive hydrogen and electronegative fluorine found in the traditional PVDF chemical structure, including Nitrile, Ester, and Methyl groups. In all cases the resulting chemical structure provides for a net dipole moment directed from the electronegative side of the monomer to the electropositive side. However, to obtain ferroelectricity these microscopic dipoles must first pack in a manner such that a reversible macroscopic dipole is obtained. Both structural and dielectric studies have been performed on a number of newly synthesized systems. The structural properties of these new materials were probed using both temperature-dependent x-ray diffraction and differential scanning calorimetry, while dielectric properties were investigated using electric field and temperature-dependent capacitance and polarization measurements. Communicated by Dr. George W. Taylor (Originally presented at the 10th European Meeting on Ferroelectricity; Cambridge; UK; August 3-8, 2003)