Vertical organic electrochemical transistor platforms for efficient electropolymerization of thiophene based oligomers.

Organic electrochemical transistors (OECTs) have emerged as promising candidates for various fields, including bioelectronics, neuromorphic computing, biosensors, and wearable electronics. OECTs operate in aqueous solutions, exhibit high amplification properties, and offer ion-to-electron signal transduction. The OECT channel consists of a conducting polymer, with PEDOT:PSS receiving the most attention to date. While PEDOT:PSS is highly conductive, and benefits from optimized protocols using secondary dopants and detergents, new p-type and n-type polymers are emerging with desirable material properties. Among these, low-oxidation potential oligomers are highly enabling for bioelectronics applications, however the polymers resulting from their polymerization lag far behind in conductivity compared with the established PEDOT:PSS. In this work we show that by careful design of the OECT geometrical characteristics, we can overcome this limitation and achieve devices that are on-par with transistors employing PEDOT:PSS. We demonstrate that the vertical architecture allows for facile electropolymerization of a family of trimers that are polymerized in very low oxidation potentials, without the need for harsh chemicals or secondary dopants. Vertical and planar OECTs are compared using various characterization methods. We show that vOECTs are superior platforms in general and propose that the vertical architecture can be expanded for the realization of OECTs for various applications.

Downsizing the Channel Length of Vertical Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) are promising building blocks for bioelectronic devices such as sensors and neural interfaces. While the majority of OECTs use simple planar geometry, there is interest in exploring how these devices operate with much shorter channels on the submicron scale. Here, we show a practical route toward the minimization of the channel length of the transistor using traditional photolithography, enabling large-scale utilization. We describe the fabrication of such transistors using two types of conducting polymers. First, commercial solution-processed poly(dioxyethylenethiophene):poly(styrene sulfonate), PEDOT:PSS. Next, we also exploit the short channel length to support easy in situ electropolymerization of poly(dioxyethylenethiophene):tetrabutyl ammonium hexafluorophosphate, PEDOT:PF6. Both variants show different promising features, leading the way in terms of transconductance (gm), with the measured peak gm up to 68 mS for relatively thin (280 nm) channel layers on devices with the channel length of 350 nm and with widths of 50, 100, and 200 µm. This result suggests that the use of electropolymerized semiconductors, which can be easily customized, is viable with vertical geometry, as uniform and thin layers can be created. Spin-coated PEDOT:PSS lags behind with the lower values of gm; however, it excels in terms of the speed of the device and also has a comparably lower off current (300 nA), leading to unusually high on/off ratio, with values up to 8.6 × 104. Our approach to vertical gap devices is simple, scalable, and can be extended to other applications where small electrochemical channels are desired.

Direct measurement of oxygen reduction reactions at neurostimulation electrodes.

Objective. Electric stimulation delivered by implantable electrodes is a key component of neural engineering. While factors affecting long-term stability, safety, and biocompatibility are a topic of continuous investigation, a widely-accepted principle is that charge injection should be reversible, with no net electrochemical products forming. We want to evaluate oxygen reduction reactions (ORR) occurring at different electrode materials when using established materials and stimulation protocols.Approach. As stimulation electrodes, we have tested platinum, gold, tungsten, nichrome, iridium oxide, titanium, titanium nitride, and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate). We use cyclic voltammetry and voltage-step amperometry in oxygenated versus inert conditions to establish at which potentials ORR occurs, and the magnitudes of diffusion-limited ORR currents. We also benchmark the areal capacitance of each electrode material. We use amperometric probes (Clark-type electrodes) to quantify the O2and H2O2concentrations in the vicinity of the electrode surface. O2and H2O2concentrations are measured while applying DC current, or various biphasic charge-balanced pulses of amplitude in the range 10-30µC cm-2/phase. To corroborate experimental measurements, we employ finite element modelling to recreate 3D gradients of O2and H2O2.Main results. All electrode materials support ORR and can create hypoxic conditions near the electrode surface. We find that electrode materials differ significantly in their onset potentials for ORR, and in the extent to which they produce H2O2as a by-product. A key result is that typical charge-balanced biphasic pulse protocols do lead to irreversible ORR. Some electrodes induce severely hypoxic conditions, others additionally produce an accumulation of hydrogen peroxide into the mM range.Significance. Our findings highlight faradaic ORR as a critical consideration for neural interface devices and show that the established biphasic/charge-balanced approach does not prevent irreversible changes in O2concentrations. Hypoxia and H2O2can result in different (electro)physiological consequences.

Infinite Selectivity of Wet SiO2 Etching in Respect to Al.

We propose and demonstrate an unconventional method suitable for releasing microelectromechanical systems devices containing an Al layer by wet etching using SiO2 as a sacrificial layer. We used 48% HF solution in combination with 20% oleum to keep the HF solution water-free and thus to prevent attack of the Al layer, achieving an outstanding etch rate of thermally grown SiO2 of ≈1 µm·min-1. We also verified that this etching solution only minimally affected the Al layer, as the chip immersion for ≈9 min increased the Al layer sheet resistance by only ≈7.6%. The proposed etching method was performed in an ordinary fume hood in a polytetrafluorethylene beaker at elevated temperature of ≈70 °C using water bath on a hotplate. It allowed removal of the SiO2 sacrificial layer in the presence of Al without the necessity of handling highly toxic HF gas.

Simple and Efficient AlN-Based Piezoelectric Energy Harvesters.

In this work, we demonstrate the simple fabrication process of AlN-based piezoelectric energy harvesters (PEH), which are made of cantilevers consisting of a multilayer ion beam-assisted deposition. The preferentially (001) orientated AlN thin films possess exceptionally high piezoelectric coefficients d33 of (7.33 ± 0.08) pC∙N-1. The fabrication of PEH was completed using just three lithography steps, conventional silicon substrate with full control of the cantilever thickness, in addition to the thickness of the proof mass. As the AlN deposition was conducted at a temperature of ≈330 °C, the process can be implemented into standard complementary metal oxide semiconductor (CMOS) technology, as well as the CMOS wafer post-processing. The PEH cantilever deflection and efficiency were characterized using both laser interferometry, and a vibration shaker, respectively. This technology could become a core feature for future CMOS-based energy harvesters.

Significance thresholds for the assessment of contaminated groundwater: perfluorinated and polyfluorinated chemicals.

BACKGROUND: Per- and polyfluorinated chemicals (PFC) do not occur naturally in the environment and are, therefore, of anthropogenic origin. As a consequence of their wide range of everyday applications and their extreme persistence in the environment, PFC have become ubiquitous in nature and can, therefore, be detected in groundwater as well as in many other environmental matrices. The German States' Water and Soil Consortia have compiled 'significance thresholds' (GFS) to assess groundwater contaminated with PFC. The GFS serve as criteria for the decision whether actions to remediate polluted groundwater are necessary. Thirteen of these PFC had been detected in groundwater at levels above their limit of quantitation and were assigned first priority. RESULTS: The data regarding human health effects were sufficient to derive guide values according to the criteria of the German Drinking Water Ordinance for 7 of the 13 first-priority PFC. With regard to available ecotoxicological data, predicted no-effect concentration values from official risk assessments existed for 2 of the 13 first-priority PFC. A predicted no-effect concentration for protection of the aquatic biocenosis could be derived for eight more substances. CONCLUSIONS: After evaluation of data from available literature regarding both human health and ecotoxicological effects, significance thresholds ranging from 0.06 to 10.0 µg/L could be derived for 7 of the 13 priority PFC in groundwater. As a practical guide valid solely for human health-based values, a summation rule was proposed for exposures to mixtures of these seven PFC.