Why Ferroelectric Polyvinylidene Fluoride is Special

Ferroelectric polymers entail a number of constraints, which together limit the useful compositional variations. These constraints include the following: a stable molecular dipole moment, compact crystal structure, conformational flexibility, and minimal steric hindrance. They are well satisfied by the prototype ferroelectric polymer, polyvinylidene fluoride, and yet almost every other conceivable molecular structure is limited by comparison

Polarization patterning by laser-induced phase change in ferroelectric polymer films

Polarization patterns were written on ferroelectric poly(vinylidene- trifluoroethylene) copolymer Langmuir–Blodgett films by heating into the paraelectric phase by laser illumination using two methods. In the first method, patterns were produced by direct writing by a focused continuouswave laser beam that was moved across the sample. This method affords the greatest flexibility. In the second method, the patterns were generated simultaneously with a pulsed laser using a beam interference method. This method produces highly regular patterns quickly over large areas and affords higher patterning resolution. The patterns produced by both methods could be erased and rewritten, making this technique useful for producing reconfigurable nonvolatile memories, infrared imaging sensors, or acoustic imaging transducers

Ferroelectric characterization and growth optimization of thermally evaporated vinylidene fluoride thin films

Organic thin films have numerous advantages over inorganics in device processing and price. The large polarization of the organic ferroelectric oligomer vinylidene fluoride (VDF) could prove useful for both device applications and the investigation of fundamental physical phenomena. A VDF oligomer thin film vacuum deposition process, such as thermal evaporation, preserves film and interface cleanliness, but is challenging, with successful deposition occurring only within a narrow parameter space. We report on the optimal deposition parameters for VDF oligomer thin films, refining the parameter space for successful deposition, resulting in a high yield of robust ferroelectric films. In particular, we investigate the influence of deposition parameters on surface roughness, and the role that roughness plays in sample yield. The reliable production of ferroelectric films allowed us to perform detailed measurements of previously unreported properties, including the Curie temperature, the temperature and thickness dependence of the coercive field, the melting temperature, and the index of refraction. The ability to successfully grow robust, switchable, well-characterized films makes VDF oligomer a viable candidate in the field of organic ferroelectrics

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 1 ms, though complete switching of a whole sample may require 100 s 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 5 V, which makes the films promising for use in nonvolatile random-access data storage

Observation of the photorefractive effect in a polymer

We report the first observation of the photorefractive effect in a polymeric material, the electro-optic polymer bisphenol-A-diglycidylether 4-nitro-1,2-phenylenediamine made photoconductive by doping with the hole-transport agent diethylamino-benzaldehyde diphenylhydrazone. The gratings formed exhibit dynamic writing and erasure, strong electric-field dependence, polarization anisotropy, and estimated space-charge fields up to 26 kV/cm at an applied field of 126 kV/cm. Application of similar concepts should provide a broad new class of easily fabricated photorefractive materials

Polarization imaging in ferroelectric polymer thin film capacitors by pyroelectric scanning microscopy

A Pyroelectric Scanning Microscopy system, which uses laser-induced thermal modulation for mapping the pyroelectric response, has been used to image a bipolar domain pattern in a ferroelectric polymer thin film capacitor. This system has achieved a resolution of 660±28 nm by using a violet laser and high f-number microscope objective to reduce the optical spot size, and by operating at high modulation frequencies to reduce the thermal diffusion length. The results agree well with a thermal model implemented numerically using finite element analysis

Ferroelectricity and the phase transition in large area evaporated vinylidene fluoride oligomer thin films

Organic ferroelectric materials, including the well-known poly(vinylidene fluoride) and its copolymers, have been extensively studied and used for a variety of applications. In contrast, the VDF oligomer has not been thoroughly investigated and is not widely used, if used at all. One key advantage the oligomer has over the polymer is that it can be thermally evaporated in vacuum, allowing for the growth of complex heterostructures while maintaining interfacial cleanliness. Here, we report on the ferroelectric properties of high-quality VDF oligomer thin films over relatively large areas on the order of mm2. The operating temperature is identified via differential scanning calorimetry and pyroelectric measurements. Pyroelectric measurements also reveal a stable remanent polarization for these films which persists over very long time scales, an important result for nonvolatile data storage. Temperature dependent pyroelectric and capacitance measurements provide compelling evidence for the phase transition in these films. Capacitance-voltage and currentvoltage measurements are used to confirm ferroelectricity, quantify the dielectric loss, and calculate the spontaneous polarization. Finally, piezoresponse force microscopy is used to demonstrate large area, low-voltage ferroelectric domain reading/writing in VDF oligomer thin films. This work enables new channels for VDF oligomer applications and research

Manifestation of a Ferroelectric Phase Transition

Temperature dependences of the dielectric properties of ultrathin polyvinylidene fluoride films prepared using the Langmuir-Blodgett method were studied by linear and nonlinear dielectric spectroscopy. It is shown that ultrathin Langmuir films of polyvinylidene fluoride exhibit a manifestation of a first-order ferroelectric phase transition, which can be assigned to the interaction between the spontaneous polarization and the surfaces bounding the film. As the film thickness increases, the effect of the surfaces decreases and the ferroelectric phase transition shifts to high temperatures to vanish altogether when the temperature region of the transition rises above the melting point

Switching kinetics of ferroelectric polymer nanomesas

The switching dynamics and switching time of ferroelectric nanomesas grown from the paraelectric phase of ultrathin Langmuir–Blodgett vinylidene fluoride and trifluoroethylene copolymer films are investigated. Ferroelectric nanomesas are created through heat treatment and self-organization and have an average height of 10 nm and an average diameter of 100 nm. Ferroelectric nanomesas are highly crystalline and are in the ferroelectric phase and switch faster than 50 μs. The dependence of switching time on applied voltage implies an extrinsic switching nature

Mini‐review: The Promise of Piezoelectric Polymers

Recent advances provide new opportunities in the field of polymer piezoelectric materials. Piezoelectric materials provide unique insights to the fundamental understanding of the solid state. In addition, piezoelectric materials have a wide range of applications, representing billions of dollars of commercial applications. However, inorganic piezoelectric materials have limitations that polymer ferroelectric materials can overcome, if certain challenges can be addressed. This mini-review is a practical summary of the current research and future directions in the investigation and application of piezoelectric materials with an emphasis on polymeric piezoelectric materials. We will assume that the reader is well versed in the subject of polymers, however, not as familiar with piezoelectric materials