Chemical sensors and biosensors in liquid environment based on microcantilevers with amplified quality factor

A new technique is presented for bio/chemical sensors, based on microcantilevers, for detection in liquid environment. The low quality factor of the cantilever in liquid is increased up to three orders of magnitude by using Q-control. This enables AC detection that is immune to the long-term drift of the DC cantilever response in liquids, and to temperature variations. This technique has been applied for the detection of ethanol in aqueous solution by using the microbalance method, and for antibody/antigen recognition by the surface stress method. The results show the feasibility and very high sensitivity of these novel devices.     

Grammar engineering for multiple front-ends for Python

In this paper, we describe our experience in grammar engineering to construct multiple parsers and front ends for the Python language. We present a metrics-based study of the evolution of the Python grammars through the multiple versions of the language in an effort to distinguish and measure grammar evolution and to provide a basis of comparison with related research in grammar engineering. To conduct this research, we have built a toolkit, pygrat , which builds on tools developed in other research. We use pygrat to build a system that automates much of the process needed to translate the Python grammars from EBNF to a formalism acceptable to the bison parser generator. We exploit the suite of Python test cases, used by the Python developers, to validate our parser generation. Finally, we describe our use of the menhir parser generator to facilitate the parser and front-end construction, eliminating some of the transformations and providing practical support for grammar modularisation.     

Self‐Assembly of Atomically Thin Chiral Copper Heterostructures Templated by Black Phosphorus

The fabrication of 2D systems for electronic devices is not straightforward, with top‐down low‐yield methods often employed leading to irregular nanostructures and lower quality devices. Here, a simple and reproducible method to trigger self‐assembly of arrays of high aspect‐ratio chiral copper heterostructures templated by the structural anisotropy in black phosphorus (BP) nanosheets is presented. Using quantitative atomic resolution aberration‐corrected scanning transmission electron microscopy imaging, in situ heating transmission electron microscopy and electron energy‐loss spectroscopy arrays of heterostructures forming at speeds exceeding 100 nm s^?1 and displaying long‐range order over micrometers are observed. The controlled instigation of the self‐assembly of the Cu heterostructures embedded in BP is achieved using conventional electron beam lithography combined with site specific placement of Cu nanoparticles. Density functional theory calculations are used to investigate the atomic structure and suggest a metallic nature of the Cu heterostructures grown in BP. The findings of this new hybrid material with unique dimensionality, chirality, and metallic nature and its triggered self‐assembly open new and exciting opportunities for next generation, self‐assembling devices.     

Tuning Memristivity by Varying the Oxygen Content in a Mixed Ionic–Electronic Conductor

The rising interest shown for adaptable electronics and brain‐inspired neuromorphic hardware increases the need for new device architectures and functional materials to build such devices. The rational design of these memory components also benefits the comprehension and thus the control over the microscopic mechanisms at the origin of memristivity. In oxide‐based valence‐change memories, the control of the oxygen drift and diffusion kinetics is a key aspect in obtaining the gradual analog‐type change in resistance required for artificial synapse applications. However, only a few devices are designed with this in mind, as they are commonly built around ionic insulating active materials. This shortcoming is addressed by using a mixed ionic–electronic conductor as functional memristive material. This work demonstrates how the oxygen content in La₂NiO_4+δ (L2NO4), tuned through post‐annealing treatments, has a critical influence on the memory characteristics of L2NO4‐based memristive devices. The presence of interstitial oxygen point defects in L2NO4 affects both its structure and electrical properties. High oxygen stoichiometry in the pristine state leads to an increased electrical conductivity, ultimately resulting in an improved memory window with highly multilevel, analog‐type memory programing capabilities, desirable for analog computing and synaptic applications in particular.     

Efficient Oxygen Evolution and Gas Bubble Release Achieved by a Low Gas Bubble Adhesive Iron–Nickel Vanadate Electrocatalyst

Surface chemistry is a pivotal prerequisite besides catalyst composition toward advanced water electrolysis. Here, an evident enhancement of the oxygen evolution reaction (OER) is demonstrated on a vanadate‐modified iron–nickel catalyst synthesized by a successive ionic layer adsorption and reaction method, which demonstrates ultralow overpotentials of 274 and 310 mV for delivering large current densities of 100 and 400 mA cm^?2, respectively, in 1 m KOH, where vigorous gas bubble evolution occurs. Vanadate modification augments the OER activity by i) increasing the electrochemical surface area and intrinsic activity of the active sites, ii) having an electronic interplay with Fe and Ni catalytic centers, and iii) inducing a high surface wettability and a low‐gas bubble‐adhesion for accelerated mass transport and gas bubble dissipation at large current densities. Ex situ and operando Raman study reveals the structural evolution of β‐NiOOH and γ‐FeOOH phases during the OER through vanadate‐active site synergistic interactions. Operando dynamic specific resistance measurement evidences an accelerated gas bubble dissipation by a significant decrease in the variation of the interfacial resistance during the OER for the vanadate‐modified surface. Achievement of a high catalytic turnover of 0.12 s^?1 suggests metallic oxo‐anion modification as a versatile catalyst design strategy for advanced water oxidation.     

Improving design engineers’ performance through novelly structured design guidelines: a study in and with industry

Forschung im Ingenieurwesen - Engineering design guidelines are a means of sharing knowledge and information explicitly. Past work points out that the structure of a design...     

Energetic Control of Redox-Active Polymers toward Safe Organic Bioelectronic Materials

Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side-products. This is particularly important for bioelectronic devices, which are designed to operate in biological systems. While redox-active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side-reactions with molecular oxygen during device operation. Here, electrochemical side reactions with molecular oxygen are shown to occur during organic electrochemical transistor (OECT) operation using high-performance, state-of-the-art OECT materials. Depending on the choice of the active material, such reactions yield hydrogen peroxide (H₂O₂), a reactive side-product, which may be harmful to the local biological environment and may also accelerate device degradation. A design strategy is reported for the development of redox-active organic semiconductors based on donor–acceptor copolymers that prevents the formation of H₂O₂ during device operation. This study elucidates the previously overlooked side-reactions between redox-active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte-gated devices in application-relevant environments.     

Side Chain Redistribution as a Strategy to Boost Organic Electrochemical Transistor Performance and Stability

A series of glycolated polythiophenes for use in organic electrochemical transistors (OECTs) is designed and synthesized, differing in the distribution of their ethylene glycol chains that are tethered to the conjugated backbone. While side chain redistribution does not have a significant impact on the optoelectronic properties of the polymers, this molecular engineering strategy strongly impacts the water uptake achieved in the polymers. By careful optimization of the water uptake in the polymer films, OECTs with unprecedented steady-state performances in terms of [μC^*] and current retentions up to 98% over 700 electrochemical switching cycles are developed.     

In Situ and Operando Characterization of Proton Exchange Membrane Fuel Cells

For proton exchange membrane fuel cells (PEMFCs) to become a mainstream energy source, significant improvements in their performance, durability, and efficiency are necessary. To improve their durability, there must be a solid understanding of how the structural and electrochemical processes are affected during operation to propose mitigation strategies. To this aim, in situ and operando characterization techniques can locally identify structural and electrochemical processes, which cannot be captured using conventional techniques. Linking these properties in the same geometric area has been challenging due to its inherent limitations, such as sample size and imaging resolution. This has created a knowledge gap in structure‐to‐electrochemical performance relationships as operation and degradation unevenly affect different areas of the cell. In the recent past, catalyst layer degradation, hot spots, and water management have been structurally and electrochemically visualized in the same geometric area, revealing new interactions. To further the research in this direction, these interconnected fields are reviewed, followed by a roadmap for in situ characterization of PEMFCs, treating structural and electrochemical processes as a unified subject. With this approach, the knowledge of the degradation of PEMFCs will be significantly improved.     

The Advantage of Nanowire Configuration in Band Structure Determination

Earth-abundant and environmentally friendly semiconductors offer a promising path toward low-cost mass production of solar cells. A critical aspect in exploring new semiconducting materials and demonstrating their enhanced functionality consists in disentangling them from the artifacts of defects. Nanowires are diameter-tailored filamentary structures that tend to be defect-free and thus ideal model systems for a given material. Here, an additional advantage is demostrated, which is the determination of the band structure, by performing high energy and spatial resolution electron energy-loss spectroscopy in aloof and inner beam geometry in a scanning transmission electron microscope. The experimental results are complemented by spectroscopic ellipsometry and are excellently correlated with first principles calculations. This study opens the path for characterizing the band structure of new compounds in a non-destructive and prompt manner, strengthening the route of new materials discovery.