Electron-beam lithography of cinnamate polythiophene films: conductive nanorods for electronic applications.

We report the electron-beam induced crosslinking of cinnamate-substituted polythiophene proceeding via excited state [2+2]-cycloaddition. Network formation in thin films is evidenced by infrared spectroscopy and film retention experiments. For the polymer studied herin, the electron-stimulated process appears to be superior to photo (UV)-induced crosslinking as it leads to less degradation. Electron beam lithography (EBL) patterns cinnamate-substituted polythiophene thin films on the nanoscale with a resolution of around 100 nm. As a proof of concept, we fabricated nanoscale organic transistors using doped and cross-linked P3ZT as contact fingers in thin film transistors.

Spatiotemporal Measurement of Arterial Pulse Waves Enabled by Wearable Active-Matrix Pressure Sensor Arrays.

Wearable pressure sensors have demonstrated great potential in detecting pulse pressure waves on the skin for the noninvasive and continuous diagnosis of cardiac conditions. However, difficulties lie in positioning conventional single-point sensors on an invisible arterial line, thereby preventing the detection of adequate signal amplitude for accurate pulse wave analysis. Herein, we introduce the spatiotemporal measurements of arterial pulse waves using wearable active-matrix pressure sensors to obtain optimal pulse waveforms. We fabricate thin-film transistor (TFT) arrays with high yield and uniformity using inkjet printing where array sizes can be customizable and integrate them with highly sensitive piezoresistive sheets. We maximize the pressure sensitivity (16.8 kPa-1) and achieve low power consumption (101 nW) simultaneously by strategically modulating the TFT operation voltage. The sensor array creates a spatiotemporal pulse wave map on the wrist. The map presents the positional dependence of pulse amplitudes, which allows the positioning of the arterial line to accurately extract the augmentation index, a parameter for assessing arterial stiffness. The device overcomes the positional inaccuracy of conventional single-point sensors, and therefore, it can be used for medical applications such as arterial catheter injection or the diagnosis of cardiovascular disease in daily life.

Beyond p-Hexaphenylenes: Synthesis of Unsubstituted p-Nonaphenylene by a Precursor Protocol.

The synthesis of unsubstituted oligo-para-phenylenes (OPP) exceeding para-hexaphenylene-in the literature often referred to as p-sexiphenyl-has long remained elusive due to their insolubility. We report the first preparation of unsubstituted para-nonaphenylenes (9PPs) by extending our precursor route to poly-para-phenylenes (PPP) to a discrete oligomer. Two geometric isomers of methoxylated syn- and anti-cyclohexadienylenes were synthesized, from which 9PP was obtained via thermal aromatization in thin films. 9PP was characterized via optical, infrared and solid-state 13 C NMR spectroscopy as well as atomic force microscopy and mass spectrometry, and compared to polymeric analogues. Due to the lack of substitution, para-nonaphenylene, irrespective of the precursor isomer employed, displays pronounced aggregation in the solid state. Intermolecular excitonic coupling leads to formation of H-type aggregates, red-shifting emission of the films to greenish. 9PP allows to study the structure-property relationship of para-phenylene oligomers and polymers, especially since the optical properties of PPP depend on the molecular shape of the precursor.

Light-Emitting Electrochemical Cells Based on Conjugated Ion Gels.

π-conjugated gels are potentially useful for organic electronic applications. We present a π-conjugated ion gel, composed of substituted poly(para-phenyleneethynylene) (PPE) and an ionic liquid. This combination is well suited as an active material in a light-emitting electrochemical cells (LECs). The nanosegregated structure of the gels achieves a large interface between the polymer and ionic liquid (IL) and allows-by nature of its structure-facile ion conduction and continuous electrical conduction paths. Efficient doping significantly improves the response time. This concept should be applicable to other π-conjugated gels, and it allows the construction of gel-LECs.

Pristine Poly( para-phenylene): Relating Semiconducting Behavior to Kinetics of Precursor Conversion.

We investigated unsubstituted poly( para-phenylene) (PPP), a long-desired prototype of a conjugated polymer semiconductor. PPP was accessed via thermal aromatization of a precursor polymer bearing kinked, solubility-inducing dimethoxycyclohexadienylene moieties. IR spectroscopy and Vis ellipsometry studies revealed that the rate of conversion of the precursor to PPP increases with temperature and decreases with film density, indicating a process with high activation volume. The obtained PPP films were analyzed in thin-film transistors to gain insights into the interplay between the degree of conversion and the resulting p-type semiconducting properties. The semiconducting behavior of PPP was further unambiguously proven through IR and transistor measurements of molybdenum trioxide p-doped films.

Measuring the lateral charge-carrier mobility in metal-insulator-semiconductor capacitors via Kelvin-probe.

We report a Kelvin-probe method to investigate the lateral charge-transport properties of semiconductors, most notably the charge-carrier mobility. The method is based on successive charging and discharging of a pre-biased metal-insulator-semiconductor stack by an alternating voltage applied to one edge of a laterally confined semiconductor layer. The charge carriers spreading along the insulator-semiconductor interface are directly measured by a Kelvin-probe, following the time evolution of the surface potential. A model is presented, describing the device response for arbitrary applied biases allowing the extraction of the lateral charge-carrier mobility from experimentally measured surface potentials. The method is tested using the organic semiconductor poly(3-hexylthiophene), and the extracted mobilities are validated through current voltage measurements on respective field-effect transistors. Our widely applicable approach enables robust measurements of the lateral charge-carrier mobility in semiconductors with weak impact from the utilized contact materials.

Influence of interfacial area on exciton separation and polaron recombination in nanostructured bilayer all-polymer solar cells.

The macroscopic device performance of organic solar cells is governed by interface physics on a nanometer scale. A comb-like bilayer all-polymer morphology featuring a controlled enhancement in donor-acceptor interfacial area is employed as a model system to investigate the fundamental processes of exciton separation and polaron recombination in these devices. The different nanostructures are characterized locally by SEM/AFM, and the buried interdigitating interface of the final device architecture is statistically verified on a large area via advanced grazing incidence X-ray scattering techniques. The results show equally enhanced harvesting of photoexcitons in both donor and acceptor materials directly correlated to the total enhancement of interfacial area. Apart from this beneficial effect, the enhanced interface leads to significantly increased polaron recombination losses both around the open-circuit voltage and maximum power point, which is determined in complement with diode dark current characteristics, impedance spectroscopy, and transient photovoltage measurements. From these findings, it is inferred that a spatially optimized comb-like donor-acceptor nanonetwork alone is not the ideal morphology even though often postulated. Instead, the energetic landscape has to be considered. A perfect morphology for an excitonic solar cell must be spatially and energetically optimized with respect to the donor-acceptor interface.