Atomic Layer Deposition of Alumina-Coated Thin-Film Cathodes for Lithium Microbatteries.

This work shows the electrochemical performance of sputter-deposited, binder-free lithium cobalt oxide thin films with an alumina coating deposited via atomic layer deposition for use in lithium-metal-based microbatteries. The Al2O3 coating can improve the charge-discharge kinetics and suppress the phase transition that occurs at higher potential limits where the crystalline structure of the lithium cobalt oxide is damaged due to the formation of Co4+, causing irreversible capacity loss. The electrochemical performance of the thin film is analysed by imposing 4.2, 4.4 and 4.5 V upper potential limits, which deliver improved performances for 3 nm of Al2O3, while also highlighting evidence of Al doping. Al2O3-coated lithium cobalt oxide of 3 nm is cycled at 147 µA cm-2 (~2.7 C) to an upper potential limit of 4.4 V with an initial capacity of 132 mAh g-1 (65.7 µAh cm-2 µm-1) and a capacity retention of 87% and 70% at cycle 100 and 400, respectively. This shows the high-rate capability and cycling benefits of a 3 nm Al2O3 coating.

Methods for latent image simulations in photolithography with a polychromatic light attenuation equation for fabricating VIAs in 2.5D and 3D advanced packaging architectures.

As demand accelerates for multifunctional devices with a small footprint and minimal power consumption, 2.5D and 3D advanced packaging architectures have emerged as an essential solution that use through-substrate vias (TSVs) as vertical interconnects. Vertical stacking enables chip packages with increased functionality, enhanced design versatility, minimal power loss, reduced footprint and high bandwidth. Unlocking the potential of photolithography for vertical interconnect access (VIA) fabrication requires fast and accurate predictive modeling of diffraction effects and resist film photochemistry. This procedure is especially challenging for broad-spectrum exposure systems that use, for example, Hg bulbs with g-, h-, and i-line UV radiation. In this paper, we present new methods and equations for VIA latent image determination in photolithography that are suitable for broad-spectrum exposure and negate the need for complex and time-consuming in situ metrology. Our technique is accurate, converges quickly on the average modern PC and could be readily integrated into photolithography simulation software. We derive a polychromatic light attenuation equation from the Beer-Lambert law, which can be used in a critical exposure dose model to determine the photochemical reaction state. We integrate this equation with an exact scalar diffraction formula to produce a succinct equation comprising a complete coupling between light propagation phenomena and photochemical behavior. We then perform a comparative study between 2D/3D photoresist latent image simulation geometries and directly corresponding experimental data, which demonstrates a highly positive correlation. We anticipate that this technique will be a valuable asset to photolithography, micro- and nano-optical systems and advanced packaging/system integration with applications in technology domains ranging from space to automotive to the Internet of Things (IoT).

Electrochemical Discrimination of Salbutamol from Its Excipients in VentolinTM at Nanoporous Gold Microdisc Arrays.

The emergence of specific drug-device combination products in the inhalable pharmaceutical industry demands more sophistication of device functionality in the form of an embedded sensing platform to increase patient safety and extend patent coverage. Controlling the nebuliser function at a miniaturised, integrated electrochemical sensing platform with rapid response time and supporting novel algorithms could deliver such a technology offering. Development of a nanoporous gold (NPG) electrochemical sensor capable of creating a unique fingerprint signal generated by inhalable pharmaceuticals provided the impetus for our study of the electrooxidation of salbutamol, which is the active bronchodilatory ingredient in VentolinTM formulations. It was demonstrated that, at NPG-modified microdisc electrode arrays, salbutamol is distinguishable from the chloride excipient present at 0.0154 M using linear sweep voltammetry and can be detected amperometrically. In contrast, bare gold microdisc electrode arrays cannot afford such discrimination, as the potential for salbutamol oxidation and chloride adsorption reactions overlap. The discriminative power of NPG originates from the nanoconfinement effect for chloride in the internal pores of NPG, which selectively enhances the electron transfer kinetics of this more sluggish reaction relative to that of the faster, diffusion-controlled salbutamol oxidation. Sensing was performed at a fully integrated three-electrode cell-on-chip using Pt as a quasi-reference electrode.

Advanced Solid State Nano-Electrochemical Sensors and System for Agri 4.0 Applications.

Global food production needs to increase in order to meet the demands of an ever growing global population. As resources are finite, the most feasible way to meet this demand is to minimize losses and improve efficiency. Regular monitoring of factors like animal health, soil and water quality for example, can ensure that the resources are being used to their maximum efficiency. Existing monitoring techniques however have limitations, such as portability, turnaround time and requirement for additional reagents. In this work, we explore the use of micro- and nano-scale electrode devices, for the development of an electrochemical sensing platform to digitalize a wide range of applications within the agri-food sector. With this platform, we demonstrate the direct electrochemical detection of pesticides, specifically clothianidin and imidacloprid, with detection limits of 0.22 ng/mL and 2.14 ng/mL respectively, and nitrates with a detection limit of 0.2 µM. In addition, interdigitated electrode structures also enable an in-situ pH control technique to mitigate pH as an interference and modify analyte response. This technique is applied to the analysis of monochloramine, a common water disinfectant. Concerning biosensing, the sensors are modified with bio-molecular probes for the detection of both bovine viral diarrhea virus species and antibodies, over a range of 1 ng/mL to 10 µg/mL. Finally, a portable analogue front end electronic reader is developed to allow portable sensing, with control and readout undertaken using a smart phone application. Finally, the sensor chip platform is integrated with these electronics to provide a fully functional end-to-end smart sensor system compatible with emerging Agri-Food digital decision support tools.

Elimination of Oxygen Interference in the Electrochemical Detection of Monochloramine, Using In Situ pH Control at Interdigitated Electrodes.

Disinfection of water systems by chloramination is a method frequently used in North America as an alternative to chlorination. In such a case, monochloramine is used as the primary chlorine source for disinfection. Regular monitoring of the residual concentrations of this species is essential to ensure adequate disinfection. An amperometric sensor for monochloramine would provide fast, reagent-free analysis; however, the presence of dissolved oxygen in water complicates sensor development. In this work, we used in-situ pH control as a method to eliminate oxygen interference by conversion of monochloramine to dichloramine. Unlike monochloramine, the electrochemical reduction of dichloramine occurs outside the oxygen reduction potential window and is therefore not affected by the oxygen concentration. Potential sweep methods were used to investigate the conversion of monochloramine to dichloramine at pH 3. The pH control method was used to calibrate monochloramine concentrations between 1 and 10 ppm, with a detection limit of 0.03 ppm. Tests were carried out in high alkalinity samples, wherein it was found that the sensitivity of this method effectively remained unchanged. Monochloramine was also quantified in the presence of common interferents (copper, phosphate, and iron) which also had no significant impact on the analysis.

Pyrrolidinium Containing Ionic Liquid Electrolytes for Li-Based Batteries.

Ionic liquids are potential alternative electrolytes to the more conventional solid-state options under investigation for future energy storage solutions. This review addresses the utilization of IL electrolytes in energy storage devices, particularly pyrrolidinium-based ILs. These ILs offer favorable properties, such as high ionic conductivity and the potential for high power drain, low volatility and wide electrochemical stability windows (ESW). The cation/anion combination utilized significantly influences their physical and electrochemical properties, therefore a thorough discussion of different combinations is outlined. Compatibility with a wide array of cathode and anode materials such as LFP, V2O5, Ge and Sn is exhibited, whereby thin-films and nanostructured materials are investigated for micro energy applications. Polymer gel electrolytes suitable for layer-by-layer fabrication are discussed for the various pyrrolidinium cations, and their compatibility with electrode materials assessed. Recent advancements regarding the modification of typical cations such a 1-butyl-1-methylpyrrolidinium, to produce ether-functionalized or symmetrical cations is discussed.

Ionic Liquid Based Polymer Gel Electrolytes for Use with Germanium Thin Film Anodes in Lithium Ion Batteries.

Thermally stable, flexible polymer gel electrolytes with high ionic conductivity are prepared by mixing the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (C4mpyrTFSI), LiTFSI and poly(vinylidene difluoride-co-hexafluoropropylene (PVDF-HFP). FT-IR and Raman spectroscopy show that an amorphous film is obtained for high (60 %) C4mpyrTFSI contents. Thermogravimetric analysis (TGA) confirms that the polymer gels are stable below ∼300 °C in both nitrogen and air environments. Ionic conductivity of 1.9×10-3 S cm-2 at room temperature is achieved for the 60 % ionic liquid loaded gel. Germanium (Ge) anodes maintain a coulombic efficiency above 95 % after 90 cycles in potential cycling tests with the 60 % C4mpyrTFSI polymer gel.

Energy scavenging for long-term deployable wireless sensor networks.

The coming decade will see the rapid emergence of low cost, intelligent, wireless sensors and their widespread deployment throughout our environment. While wearable systems will operate over communications ranges of less than a meter, building management systems will operate with inter-node communications ranges of the order of meters to tens of meters and remote environmental monitoring systems will require communications systems and associated energy systems that will allow reliable operation over kilometers. Autonomous power should allow wireless sensor nodes to operate in a "deploy and forget" mode. The use of rechargeable battery technology is problematic due to battery lifetime issues related to node power budget, battery self-discharge, number of recharge cycles and long-term environmental impact. Duty cycling of wireless sensor nodes with long "SLEEP" times minimises energy usage. A case study of a multi-sensor, wireless, building management system operating using the Zigbee protocol demonstrates that, even with a 1 min cycle time for an 864 ms "ACTIVE" mode, the sensor module is already in SLEEP mode for almost 99% of the time. For a 20-min cycle time, the energy utilisation in SLEEP mode exceeds the ACTIVE mode energy by almost a factor of three and thus dominates the module energy utilisation thereby providing the ultimate limit to the power system lifetime. Energy harvesting techniques can deliver energy densities of 7.5 mW/cm(2) from outdoor solar, 100 microW/cm(2) from indoor lighting, 100 microW/cm(3) from vibrational energy and 60 microW/cm(2) from thermal energy typically found in a building environment. A truly autonomous, "deploy and forget" battery-less system can be achieved by scaling the energy harvesting system to provide all the system energy needs. In the building management case study discussed, for duty cycles of less than 0.07% (i.e. in ACTIVE mode for 0.864 s every 20 min), energy harvester device dimensions of approximately 2 cm on a side would be sufficient to supply the complete wireless sensor node energy. Key research challenges to be addressed to deliver future, remote, wireless, chemo-biosensing systems include the development of low cost, low-power sensors, miniaturised fluidic transport systems, anti-bio-fouling sensor surfaces, sensor calibration, reliable and robust system packaging, as well as associated energy delivery systems and energy budget management.