Excitation of "forbidden" guided-wave plasmon polariton modes via direct reflectance using a low refractive index polymer coupling layer.

A surface plasmon polariton (SPP) is an excitation resulting from the coupling of light to a surface charge oscillation at a metal-dielectric interface. The excitation and detection of SPPs is foundational to the operating mechanism of a number of important technologies, most of which require SPP excitation via direct reflectance, commonly achieved via Attenuated Total Reflection (ATR) using the Kretschmann configuration. As a result, the accessible modes are fundamentally high-loss "leaky modes," presenting a critical performance barrier. Recently, our group provided the first demonstration of "forbidden," or guided-wave plasmon polariton modes (GW-PPMs), collective modes of a MIM structure with oscillatory electric field amplitude in the central insulator layer with up to an order of magnitude larger propagation lengths than those of traditional SPPs. However, in that work, GW-PPMs were accessed by indirect reflectance using Otto configuration ATR, making them of limited applied relevance. In this paper, we demonstrate a technique for direct reflectance excitation and detection of GW-PPMs. Specifically, we replace the air gap used in traditional Otto ATR with a low refractive index polymer coupling layer, mirroring a technique previously demonstrated to access Long-Range Surface Plasmon Polariton modes. We fit experimental ATR data using a robust theoretical model to confirm the character of the modes, as well as to explore the potential of this approach to enable advantageous propagation lengths. The ability to excite GW-PPMs using a device configuration that does not require an air gap could potentially enable transformative performance enhancements in a number of critical technologies.

Versatile Method for Producing 2D and 3D Conductive Biomaterial Composites Using Sequential Chemical and Electrochemical Polymerization.

Flexible and conductive biocompatible materials are attractive candidates for a wide range of biomedical applications including implantable electrodes, tissue engineering, and controlled drug delivery. Here, we demonstrate that chemical and electrochemical polymerization techniques can be combined to create highly versatile silk-conducting polymer (silk-CP) composites with enhanced conductivity and electrochemical stability. Interpenetrating silk-CP composites were first generated via in situ deposition of polypyrrole during chemical polymerization of pyrrole. These composites were sufficiently conductive to serve as working electrodes for electropolymerization, which allowed an additional layer of CP to be deposited on the surface. This sequential method was applied to both 2D films and 3D sponge-like silk scaffolds, producing conductive materials with biomimetic architectures. Overall, this two-step technique expanded the range of available polymers and dopants suitable for the synthesis of mechanically robust, biocompatible, and highly conductive silk-based materials.

Characterizing ion profiles in dynamic junction light-emitting electrochemical cells.

Organic semiconductors have the unique ability to conduct both ionic and electronic charge carriers in thin films, an emerging advantage in applications such as light-emitting devices, transistors, and electrochromic devices, among others. Evidence suggests that the profiles of ions and electrochemical doping in the polymer film during operation significantly impact the performance and stability of the device. However, few studies have directly characterized ion profiles within LECs. Here, we present an in-depth study of the profiles of ion distributions in LECs following application of voltage, via time-of-flight secondary ion mass spectrometry. Ion distributions were characterized with regard to film thickness, salt concentration, applied voltage, and relaxation over time. Results provide insight into the correlation between ion profiles and device performance, as well as potential approaches to tuning the electrochemical doping processes in LECs.

Characterization of ion profiles in light-emitting electrochemical cells by secondary ion mass spectrometry.

Ion profiles in polymer light-emitting electrochemical cells are known to significantly affect performance and stability, but are not easily measured. Here, secondary ion mass spectrometry is used to investigate ion profiles in both dynamic and chemically fixed junction devices. Results indicate lower reversibility of dynamic junctions and a more significant time delay for ion redistribution than previously expected, but confirm the complete immobilization of ions in chemically fixed junction devices. When compared with prior studies analyzing the electric field profiles in similar devices, these results help to elucidate the roles of ion distribution and electrochemical doping in LECs.

Precise color tuning via hybrid light-emitting electrochemical cells.

We report color-tunable light-emitting devices employing CdSe/ZnS quantum dots (QDs) blended into a polymer light-emitting electrochemical cell (LEC) architecture. This novel structure circumvents the charge-tunneling barrier of QDs to achieve bright, uniform, and highly voltage-independent electroluminescence, with nearly all emission generated by the QDs. By blending varying ratios of two QD materials that emit at different wavelengths, we demonstrate precise color control in a single layer device structure.

Synthesis and utilization of perylene-based n-type small molecules in light-emitting electrochemical cells.

We report the synthesis of a soluble perylene-based small molecule for use as an n-type emissive material for organic optoelectronic device applications, and demonstrate the material in a light-emitting electrochemical cell configuration.