Stephen Ducharme

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.

Efficiency enhancement in organic solar cells with ferroelectric polymers

The recombination of electrons and holes in semiconducting polymer-fullerene blends has been identified as a main cause of energy loss in organic photovoltaic devices. Generally, an external bias voltage is required to efficiently separate the electrons and holes and thus prevent their recombination. Here we show that a large, permanent, internal electric field can be ensured by incorporating a ferroelectric polymer layer into the device, which eliminates the need for an external bias. The electric field, of the order of 50 V μm(-1), potentially induced by the ferroelectric layer is tens of times larger than that achievable by the use of electrodes with different work functions. We show that ferroelectric polymer layers enhanced the efficiency of several types of organic photovoltaic device from 1-2% without layers to 4-5% with layers. These enhanced efficiencies are 10-20% higher than those achieved by other methods, such as morphology and electrode work-function optimization. The devices show the unique characteristics of ferroelectric photovoltaic devices with switchable diode polarity and tunable efficiency.

Electric energy density of dielectric nanocomposites

Dielectric materials with large electric energy density are actively pursued for many applications. The authors analyze the effective permittivity, breakdown strength, and electric energy density of dielectric nanocomposites using an effective medium approximation, modeling the nanocomposite as a three-phase material by the double-inclusion method. The addition of nanoparticles enhances the permittivity but reduces the breakdown strength, making the potential gain in electric energy density small. In addition, the interfacial interaction shifts the “percolation” threshold toward lower volume fraction of nanoparticles. The analysis suggests that the microstructure of nanocomposites must be carefully controlled to maintain high dielectric strength and therefore realize enhanced electric energy density.

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)].

Ferroelectric polymer Langmuir-Blodgett films for nonvolatile memory applications

We review the potential for integrating ferroelectric polymer Langmuir-Blodgett (LB) films with semiconductor technology to produce nonvolatile ferroelectric random-access memory (NV-FRAM or NV-FeRAM) and data-storage devices. The prototype material is a copolymer consisting of 70% vinylidene fluoride (VDF) and 30% trifluoroethylene (TrFE), or P(VDF-TrFE 70:30). Recent work with LB films and more conventional solvent-formed films shows that the VDF copolymers are promising materials for nonvolatile memory applications. The prototype device is the metal-ferroelectric-insulator-semiconductor (MFIS) capacitance memory. Field-effect transistor (FET)-based devices are also discussed. The LB films afford devices with low-voltage operation, but there are two important technical hurdles that must be surmounted. First, an appropriate method must be found to control switching dynamics in the LB copolymer films. Second, the LB technology must be scaled up and incorporated into the semiconductor-manufacturing process, but since there is no precedent for mass production of LB films, it is difficult to project how long this will take.

Piezoelectric and pyroelectric properties of ferroelectric Langmuir-Blodgett polymer films

The piezoelectric and pyroelectric responses of ferroelectric Langmuir–Blodgett polymer films are less than the largest values measured with bulk films of the same composition. The films of the crystalline copolymer poly(vinylidene fluoride trifluoroethylene) fabricated by the Langmuir–Blodgett technique are 30 ML thick (15 nm) and are highly crystalline and oriented with polarization perpendicular to the film. Both piezoelectric and pyroelectric measurements show reversible ferroelectric switching. The films are suitable for use in pyroelectric infrared imaging and in piezoelectric acoustic transducers.

Speed of the photorefractive effect in a BaTiO3 single crystal

We present data on the speed of light‐induced refractive index changes in a BaTiO3 single crystal. The light‐induced erasure rate of a refractive index grating is shown to depend on optical intensity as I x where x<1. The exponent x depends weakly on temperature and increases from 0.62±0.02 to 0.71±0.02 when the temperature is varied between 12 and 40 °C. The sublinear dependence of rate on intensity implies that higher optical intensity is required to achieve high‐speed operation of BaTiO3 devices than previously thought. The dark erasure rate has an anomolously strong temperature dependence; it increases by a factor of 50 over the same temperature range. We have also determined that the number density of photorefractive charge carriers is 6×1016 cm−3 in this crystal.

Tuning the Energy Level Offset between Donor and Acceptor with Ferroelectric Dipole Layers for Increased Efficiency in Bilayer Organic Photovoltaic Cells

Ultrathin ferroelectric polyvinylidene fluoride (70%)-tetrafluoroethylene (30%) copolymer film is inserted between the poly3(hexylthiophene) (P3HT) donor and [6,6]-phenyl-C61-butyric acid methylester (PCBM) acceptor layers as the dipole layer to tune the relative energy levels, which can potentially maximize the open circuit voltage of bilayer organic solar cells. In this work, the power conversion efficiency of P3HT/PCBM bilayer solar cells is demonstrated to be doubled with the inserted dipoles.

Altering the photorefractive properties of BaTiO 3 by reduction and oxidation at 650°C

The photorefractive properties of a nominally pure single crystal of BaTiO3 were altered by treating the crystal at 650°C in oxygen at different partial pressures. Treatment altered the effective density of photorefractive charge carriers in the crystal and could convert an inactive crystal into an active one. Treatment at low oxygen pressure (reduction) decreased the temperature of the tetragonal-to-cubic phase transition of the crystal and also decreased the measured optical band gap, implying that oxygen vacancies had been introduced into the bulk crystal. These oxygen vacancies are associated with negative photorefractive charge donors. Either hole transport or electron transport dominated, depending on whether the partial pressure of oxygen was greater than or less than ½ atm during treatment. The competing roles of electrons and holes are discussed.

Synthesis of Monodisperse TiO2−Paraffin Core−Shell Nanoparticles for Improved Dielectric Properties

Core-shell structures of oxide nanoparticles having a high dielectric constant, and organic shells with large breakdown field are attractive candidates for large electrical energy storage applications. A high growth temperature, however, is required to obtain the dielectric oxide nanoparticles, which affects the process of core-shell formation and also leads to poor control of size, shape, and size-distribution. In this communication, we report a new synthetic process to grow core-shell nanoparticles by means of an experimental method that can be easily adapted to synthesize core-shell structures from a variety of inorganic-organic or inorganic-inorganic materials. Monodisperse and spherical TiO2 nanoparticles were produced at room temperature as a collimated cluster beam in the gas phase using a cluster-deposition source and subsequently coated with uniform paraffin nanoshells using in situ thermal evaporation, prior to deposition on substrates for further characterization and device processing. The paraffin nanoshells prevent the TiO2 nanoparticles from contacting each other and also act as a matrix in which the volume fraction of TiO2 nanoparticles was varied by controlling the thickness of the nanoshells. Parallel-plate capacitors were fabricated using dielectric core-shell nanoparticles having different shell thicknesses. With respect to the bulk paraffin, the effective dielectric constant of TiO2-paraffin core-shell nanoparticles is greatly enhanced with a decrease in the shell thickness. The capacitors show a minimum dielectric dispersion and low dielectric losses in the frequency range of 100 Hz-1 MHz, which are highly desirable for exploiting these core-shell nanoparticles for potential applications.