The electrical properties of eumelanin, a ubiquitous natural pigment, have fascinated scientists since the late 1960s. For several decades, the hydrationdependent electrical properties of eumelanin have mainly been interpreted within the amorphous semiconductor model. Recent works undermined this paradigm. Here we study protonic and electronic charge carrier transport in hydrated eumelanin in thin film form. Thin films are ideal candidates for these studies since they are readily accessible to chemical and morphological characterization and potentially amenable to device applications. Current−voltage (I-V) measurements, transient current measurements with proton-transparent electrodes, and electrochemical impedance spectroscopy (EIS) measurements are reported and correlated with the results of the chemical characterization of the films, performed by X-ray photoelectron spectroscopy. We show that the electrical response of hydrated eumelanin films is dominated by ionic conduction (10 −4 −10 −3 S cm −1 ), largely attributable to protons, and electrochemical processes. To propose an explanation for the electrical response of hydrated eumelanin films as observed by EIS and I-V, we considered the interplay of proton migration, redox processes, and electronic transport. These new insights improve the current understanding of the charge carrier transport properties of eumelanin opening the possibility to assess the potential of eumelanin for organic bioelectronic applications, e.g. protonic devices and implantable electrodes, and to advance the knowledge on the functions of eumelanin in biological systems.

Eumelanin pigments show hydration-dependent conductivity, broad-band UV-vis absorption, and chelation of metal ions. Solution-processing of synthetic eumelanins opens new possibilities for the characterization of eumelanin in thin film form and its integration into bioelectronic devices. We investigate the effect of different synthesis routes and processing solvents on the growth, the morphology, and the chemical composition of eumelanin thin films using atomic force microscopy and X-ray photoelectron spectroscopy. We further characterize the films by transient electrical current measurements obtained at 50% to 90% relative humidity, relevant for bioelectronic applications. We show that the use of dimethyl sulfoxide is preferable over ammonia solution as processing solvent, yielding homogeneous films with surface roughnesses below 0.5 nm and a chemical composition in agreement with the eumelanin molecular structure. These eumelanin films grow in a quasi layer-bylayer mode, each layer being composed of nanoaggregates, 1-2 nm high, 10-30 nm large. The transient electrical measurements using a planar two-electrode device suggest that there are two contributions to the current, electronic and ionic, the latter being increasingly dominant at higher hydration, and point to the importance of time-dependent electrical characterization of eumelanin films.

Eumelanin is a ubiquitous pigment in the human body, animals, and plants, with potential for bioelectronic applications because of its unique set of physical and chemical properties, including strong UV‐vis absorption, mixed ionic/electronic conduction, free radical scavenging and anti‐oxidant properties. Herein, a detailed investigation is reported of eumelanin thin films grown on substrates patterned with gold electrodes as a model system for device integration, using electrical measurements, atomic force microscopy, scanning electron microscopy, fluorescence microscopy, and time‐of‐flight secondary ion mass spectroscopy. Under prolonged electrical biasing in humid air, one can observe gold dissolution and formation of gold‐eumelanin nanoaggregates, the assembly of which leads to the formation of dendrites forming conductive pathways between the electrodes. Based on results collected with eumelanins from different sources, a mechanism is proposed for the formation of the nanoaggregates and dendrites, taking into account the metal binding properties of eumelanin. The surprising interaction between eumelanin and gold points to new opportunities for the fabrication of eumelanin‐gold nanostructures and biocompatible memory devices and should be taken into account in the design of devices based on eumelanin thin films.

A detailed investigation of the diffusion of triplet excitons in a layer of N , NЈ-di-1-naphthalenyl-N , NЈ-diphenyl-͓1,1Ј :4Ј ,1Љ :4Љ ,1ٞ-quaterphenyl͔-4,4ٞ-diamine ͑4P-NPD͒ incorporated in organic light-emitting diodes is presented. An appropriate method to measure the triplet diffusion length in fluorescent host materials is the spatial separation of the site of exciton generation from the site of radiative triplet decay by inserting a host spacer layer of varying thickness. However, cavity effects, the quenching and blocking of excitons at the boundaries of the spacer layer, and direct charge-carrier recombination in the sensing layer need to be taken into account. We use a specially designed layer stack, which excludes the influence of cavity effects on the measurements and a strongly quenching sensing layer, which ensures well-defined boundary conditions. The quenching of excitons by the sensing layer, the generation zone, and direct charge-carrier recombination are investigated experimentally and their influence on the extracted diffusion length are discussed. The significance of triplet-triplet annihilation in this analysis is estimated by a current-dependent evaluation. An analytic model for the dependence of the sensing layer emission on the spacer thickness is presented, which includes the important effects. By this means, we find a triplet diffusion length of 11Ϯ 3 nm in 4P-NPD.

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