Mason A. Wolak

Enhanced breakdown strength of multilayered films fabricated by forced assembly microlayer coextrusion

There is a need in electronic systems and pulsed power applications for capacitors with high energy density. From a material standpoint, capacitive energy density improves with increasing dielectric constant and/or breakdown strength. Current state-of-the-art polymeric capacitors are, however, limited in that their dielectric constant is low (2–4). Our approach to improve polymer film capacitors is to combine, through microlayer coextrusion, two polymers with complementary properties: one with a high breakdown strength (polycarbonate) and one with a high dielectric constant (polyvinylidene fluoride-hexafluoropropylene). As opposed to the monolith controls, multilayered films with various numbers of layers and compositions subjected to a pulsed voltage exhibit treeing patterns that hinder the breakdown process. Consequently, substantially enhanced breakdown strengths are measured in the mutilayered films. It is further shown, by varying the overall film thickness, that the charge at the tip of the needle electrode is a key parameter that controls treeing. Based on the acquired data, a breakdown mechanism is formulated to explain the increased dielectric strengths. Using the understanding gained from these systems, selection and optimization of future layered structures can be carried out to obtain additional property enhancements.

Dielectric response of structured multilayered polymer films fabricated by forced assembly

The effect of introducing a multilayer microstructure on the dielectric properties of polymer materials is evaluated in 32- and 256-layer films with alternating polycarbonate (PC) and polyvinylidene-hexafluoropropylene (coPVDF) layers. The permittivity, dielectric loss, dielectric strength, and energy density were measured as a function of the relative PC/coPVDF volume concentrations. The permittivity follows an effective medium model while the dielectric strength was typically higher than that predicted by a volume fraction based weighted average of the components. Energy densities as high as ∼14J∕cm3, about 60% greater than that of the component polymers, are measured for 50% PC/50% coPVDF films.

Internal field distributions in multilayer polycarbonate/poly(vinylidene fluoride)-hexafluoropropylene films at onset of breakdown

Multilayer polymer films comprising alternating layers of polycarbonate (PC) and polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) show enhanced dielectric strength relative to single component films of either source polymer. Previous failure analysis on films subjected to breakdown under divergent field conditions revealed that multilayer films produced distinct surface treeing patterns whereas monolithic films did not. The choice of surface layer (PC or PVDF-HFP) contacted by a needle electrode influenced the nature of these treeing patterns. Additionally, damage within the film was largely localized to the interfaces between layers. To help explain these empirical results, we model the divergent field based on the geometry of our experimental setup and calculate the internal electric field distribution using the boundary integral equation method (BIEM). All fundamental charges, including: free, bound, trapped, and space charges are accounted for in the calculations, based on current and voltage data recorded during prior breakdown measurements. The calculations show that when PC is used as the surface layer in contact with the needle anode, there is significant field intensification in the top PC layer, in excess of 2000 V/μm. This is many times higher than the measured dielectric strength of monolithic PC and is at least partially due to charge injection from the needle anode. In contrast, the PVDF-HFP sub-layer in this configuration has very low field. These observations are consistent with breakdown occurring near the surface of the film, resulting in large-range surface treeing. When PVDF-HFP is the top layer, field intensification occurs deeper in the film, which is again consistent with the observed optical and FIB/SEM imaging results where less surface treeing and more internal damage is observed. The calculations suggest that the large contrast in field between adjacent layers generates a nexus for localized breakdown at the layer interfaces, again consistent with large internal voids formed by layer delamination in films subjected to divergent field breakdown.

Energy transfer and excitation migration in a doped organic semiconductor

We have studied energy transfer to a dioxolane-substituted pentacene derivative, 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (TP-5), from tris(8-hydroxyquin-8-olinato) aluminum(III) (Alq3) by steady state and time-resolved photoluminescence (PL) spectroscopy. The Förster transfer radius is 27 Å, calculated from the fluorescence spectrum of Alq3 and the absorption spectrum of TP-5. We find that pentacene emission dominates the PL spectra of TP-5:Alq3 guest-host films, even at concentrations where the typical guest separation is significantly larger than the Förster transfer radius. Monte Carlo simulations of energy transfer to randomly dispersed guest molecules in the host matrix show that Förster-type energy transfer cannot completely account for the PL dynamics of the guest and host. Exciton diffusion within the Alq3 host followed by fluorescence of the host molecules or energy transfer to the guest explains the PL spectra and dynamics.

Imaging cellular membrane potential through ionization of quantum dots

Recent interest in quantum dots (QDs) stems from the plethora of potential applications that arises from their tunable absorption and emission profiles, high absorption cross sections, resistance to photobleaching, functionalizable surfaces, and physical robustness. The emergent use of QDs in biological imaging exploits these and other intrinsic properties. For example, quantum confined Stark effect (QCSE), which describes changes in the photoluminescence (PL) of QDs driven by the application of an electric field, provides an inherent means of detecting changes in electric fields by monitoring QD emission and thus points to a ready mean of imaging membrane potential (and action potentials) in electrically active cells. Here we examine the changing PL of various QDs subjected to electric fields comparable to those found across a cellular membrane. By pairing static and timeresolved PL measurements, we attempt to understand the mechanism driving electric-field-induced PL quenching and ultimately conclude that ionization plays a substantial role in initiating PL changes in systems where QCSE has traditionally been credited. Expanding on these findings, we explore the rapidity of response of the QD PL to applied electric fields and demonstrate changes amply able to capture the millisecond timescale of cellular action potentials.

Energy transfer and excitation migration in organic semiconductors

Energy transfer plays a key role in various applications of organic semiconductors such as electroluminescence, photovoltaics, and sensors. We have carried out a study combining transient and continuous wave (CW) optical spectroscopy with modeling. The fluorescence spectra and dynamics of a functionalized pentacene doped into a fluorescent host (Alq3) were measured and simulated by a Monte Carlo model incorporating distributed dopants and exciton migration. For nonluminescent materials, transient absorption spectroscopy provides insight into excitation migration. Singlet diffusion rates in C60 were determined by probing delayed charge transfer to ZnPc in films with a layered nanostructure.