Paul A. Kohl

Anion-exchange membranes in electrochemical energy systems†

This article provides an up-to-date perspective on the use of anion-exchange membranes in fuel cells, electrolysers, redox flow batteries, reverse electrodialysis cells, and bioelectrochemical systems (e.g. microbial fuel cells). The aim is to highlight key concepts, misconceptions, the current state-of-the-art, technological and scientific limitations, and the future challenges (research priorities) related to the use of anion-exchange membranes in these energy technologies. All the references that the authors deemed relevant, and were available on the web by the manuscript submission date (30th April 2014), are included.

Interconnect opportunities for gigascale integration

Throughout the past four decades, semiconductor technology has advanced at exponential rates in both productivity and performance. In recent years, multilevel interconnect networks have become the primary limit on the productivity, performance, energy dissipation, and signal integrity of gigascale integration. Consequently, a broad spectrum of novel solutions to the multifaceted interconnect problem must be explored. Here we review recent salient results of this exploration. Based upon prediction of the complete stochastic signal interconnect length distribution of a megacell, optimal reverse scaling of each pair of wiring levels provides a prime opportunity to minimize cell area, clock period, power dissipation, or number of wiring levels. Using a heterogeneous version of Rents rule, a design methodology for the global signal, clock, and power/ground distribution networks for a system-on-a-chip has been derived. Wiring area, bandwidth, and signal integrity are the prime constraints on the design of the networks. Three-dimensional integration offers the opportunity to reduce the length of the longest global interconnects in a distribution by as much as 75%. Wafer-level batch fabrication of chip input/output interconnects and chip scale packages provides new benefits such as I/O bandwidth enhancement, simultaneous switching-noise reduction, and lower cost of packaging and testing. Microphotonic interconnects have long-term potential to reduce latency, power dissipation, and crosstalk while increasing bandwidth.

The effects of pulse charging on cycling characteristics of commercial lithium-ion batteries

The effects of a pulse charging technique on charge–discharge behavior and cycling characteristics of commercial lithium-ion batteries were investigated by comparison with the conventional direct current (dc) charging. The impedance spectra and cycling voltammograms of Li-ion batteries cycled by both protocols have been measured. The individual electrodes in the batteries have also been examined using XRD and SEM. The results show that pulse charging is helpful in eliminating concentration polarization, increasing the power transfer rate, and lowering charge time by removing the need for constant voltage charging in the conventional protocol. Pulse charging interrupts dc charging with short relaxation periods and short discharge pulses during charging, and also improves the active material utilization giving the battery higher discharge capacity and longer cycle life. Impedance measurements show that the magnitude of the interfacial resistance of the batteries cycled both by pulse charging and dc charging is small. However, at the same number of cycles, the interfacial resistance of the pulse charged battery is larger than that of dc charged. The batteries after 300 cycles charged by pulse charging show higher peak currents during both forward and reverse scans indicating higher reversibility of the electrodes. XRD and SEM studies of the individual electrodes indicate that pulse charging maintains the stability of the LiCoO2 cathode better than dc charging and inhibits the increase in the thickness of the passive film on the anode during cycling.

The Electrochemical Oxidation of Silicon and Formation of Porous Silicon in Acetonitrile

The photoelectrochemical oxidation and dissolution of silicon has been investigated in the absence of water and oxygen. The etch rate and photocurrent for n-Si in an anhydrous, HF-acetonitrile solution were directly proportional to light intensity. Four electrons were transferred per silicon oxidized, with a quantum yield greater than 3.3 due to electron injection. The anodic dissolution of p-Si, as Si(IV) without H 2 gas at up to 1.4 A/cm 2 , yielded a novel porous structure which exhibited electroluminescence and photoluminescence

Sacrificial polymers for nanofluidic channels in biological applications

Chip based bio/chemical analysis relies on networks of fluidic channels that are connected to reaction chambers and sensors. For sensitive detection it is important to scale down the size of the channels so that they approach the relevant length scales of the molecules of interest. Here we have made sealed channels on the 100 nm scale using nanoimprinting to pattern the sacrificial polymer polynorbornene over areas of several square centimetres. We have combined channels of different cross sections and we have shown that the nanochannels can be made hydrophilic with DNA transported electrophoretically in these self-sealed channels.

Functionalized polynorbornene dielectric polymers: Adhesion and mechanical properties

Within the microelectronics industry, there is an ongoing trend toward miniaturization coupled with higher performance. High glass-transition temperature polynorbornenes exhibit many of the key performance criteria necessary for these demanding applications. However, homopolynorbornene exhibits poor adhesion to common substrate materials, including silicon, silicon dioxide, aluminum, gold, and copper. In addition, this homopolymer is extremely brittle, yielding less than 1% elongation-to-break values. To address these issues, the homopolymer was functionalized to improve adhesive and mechanical properties. Attaching triethoxysilyl groups to the polymer backbone substantially improved the adhesion, but at the cost of increasing the dielectric constant because of the polarity of the functional group. Alkyl groups were also added to the backbone, which decreased the rigidity of the system, and resulted in significantly higher elongation-to-break values and a decrease in residual stress. The addition of an alkyl group slightly decreased the dielectric constant of the polymer as a result of an increase in molar volume. The coefficient of thermal expansion and modulus are also reported for the polynorbornene functionalized with triethoxysilyl groups using a multiple substrate approach.

Fabrication of air-channel structures for microfluidic, microelectromechanical, and microelectronic applications

A method is presented for fabricating micro-air-channel structures encapsulated by a dielectric material using a sacrificial polymer based on polynorbornene (PNB) chemistry. A spin-coated film of PNB was patterned to define the exact geometry of the air-channels using conventional lithographic and etching techniques. The sacrificial polymer was encapsulated with a permanent dielectric material. The composite was then raised to elevated temperatures to produce gaseous products which permeate through the encapsulating material (SiO/sub 2/, SiN/sub x/ or other polymer) leaving behind minimal solid residue. Air-channels integrated with metal interconnections can be formed via a Damascene, or in-lay process. After patterning the sacrificial polymer, copper was electroplated, followed by encapsulation with the dielectric. Various issues pertaining to the processing steps have been investigated and are discussed, such as type of encapsulants, feasible air-channel sizes, and processing conditions. Such air-channel structures are believed to have potential applications in microelectronics, displays, printers, multilevel wiring boards, microscale chemical reactors on a chip, and microelectromechanical devices.

Fabrication of microchannels using polycarbonates as sacrificial materials

The use of polycarbonates as thermally decomposable, sacrificial materials for the formation of microchannels is presented. Polycarbonates decompose in the temperature range of 200-300 °C. Two polycarbonates, polyethylene carbonate and polypropylene carbonate, have been used to fabricate microchannels in three different types of encapsulants: an inorganic glass (silicon dioxide), a thermoplastic polymer (Avatrel dielectric polymer) and a thermoset polymer (bisbenzoycyclobutene Cyclotene 3022-57). This paper presents the details of the fabrication process, a thermogravimetric analysis of the sacrificial materials, and the kinetic parameters for the decomposition process. The presence of oxygen or water was found to impact on the decomposition of the sacrificial material. This paper demonstrates the feasibility of forming buried air-cavities in a variety of encapsulants at a modest temperature, thus enabling the use of a wide range of dielectric materials with different thermal stabilities and properties.

Silver metallization for advanced interconnects

Silver metal has the highest room-temperature electrical conductivity of any substance; however, it has found limited acceptance in the electronic industry (e.g., silver filled epoxy) due to the high rate of metal corrosion and migration causing dendrites and electrical failures. With decreasing transistor feature sizes, device-operating voltages have scaled down considerably. In this paper, the reliability of silver and potential benefits of silver metallization are discussed in terms of future trends in microelectronic interconnections. Experimental data supports existing reliability models indicating that electrochemical migration failure modes may not be operative at low voltages. Silver metal corrosion and migration are studied under accelerated test conditions to obtain a qualitative understanding of the failure mechanism.

Low k, Porous Methyl Silsesquioxane and Spin-On-Glass

Low dielectric constant, porous silica was made from commercially available methyl silsesquioxane (MSQ) by the addition of a sacrificial polymer, substituted norbornene polymer containing triethoxysilyl groups (NB), to the MSQ. The silsesquioxane-NB polymer film mixture was thermally cured followed by decomposition of the NB at temperatures above 400°C. The dielectric constant of the MSQ was lowered from 2.7 to 2.3 by creating 70 nm pores in the MSQ. The voids created in the MSQ exhibited a closed-pore structure. The concentration of NB in the MSQ affected the number of pores but not their size. Porous films were also created in a methyl siloxane spin-on-glass and its dielectric constant was lowered from 3.1 to 2.7. Infrared spectroscopy was used to follow the curing of the MSQ and decomposition of the NB.