in the vias. A stepped potential waveform was applied to move the Cu growth front from the bottom of the via to the top. Sample characterization was performed through mechanical cross-sections and X-ray computed tomography (CT) scans. The CT scans revealed small seam voids in the Cu electrodeposit, and process parameters were tuned accordingly to produce void-free Cu features. During the voltage-controlled experiments, measured current data showed a characteristic current minimum, which was identified as an endpoint detection method for Cu deposition in these vias. We believe this is the first report of this novel endpoint detection method for TSV filling.

We report on a nanoelectrode array sensor for the detection of gaseous iodine at levels below 20 ppb within short exposure times. The sensor is constructed on a free-standing anodic aluminum oxide wafer with 120 nm diameter, 50 um length nanopores. On each wafer surface, continuous metal films are deposited: on one surface, a gold film is deposited such that it covers the nanopores, and, on the opposite surface, a platinum film is deposited such that the nanopores remain open and their volumes in contact with the environment. The gold film serves as the working electrode and the platinum film serves as the auxiliary and pseudo-reference electrode. The nanopores are filled with a pH 9 buffer aqueous solution to create an array of billions/cm2 electrochemical cells in parallel. Ionic conductivity is maintained for environments with relative humidity levels greater than ~30%. Here we report on sensor performance improvements that allow using this sensor in more arid environments, as well as in the presence of other relevant interferent analytes (e.g. Cl2). The detection mechanism is the electrochemical oxidation of anionic species formed by the dissolution and subsequent hydrolysis of gas phase I2 in pH 9 buffer electrolyte. Gas phase I2 dissolves in the buffer following Henry's Law and then is hydrolyzed to several species, including the anionic species iodide and tri-iodide. The hydrolysis mechanism of I2 in the pH 9 buffer enables it to function as a concentrator for the anionic species. When the sensor is exposed to a gas stream containing iodine, continuous accumulation of the electrochemically detectable anionic species is possible, enabling preconcentration of the incoming flow-stream by several orders of magnitude. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

We report on a nanoelectrode array sensor for the detection of I2 (iodine gas) at levels as low as near 0,02 ppm within tens of seconds of exposure. The sensor is constructed on a free-standing anodic aluminum oxide wafer with nanopores of 120 nm diameter and 50 um length. On each wafer surface, continuous metal films of tens of nm thickness are deposited: on one surface, a gold film is deposited such that it covers the nanopores, and, on the opposite surface, a platinum film is deposited such that the nanopores remain open and their volumes in contact with the environment. The gold film serves as the working electrode and the platinum film serves as the auxiliary and pseudo-reference electrode. The nanopores are filled with a pH 9 buffer aqueous solution to create an array of electrochemical cells in parallel, and ionic conductivity is maintained for environments with relative humidity levels greater than about 30%. The detection mechanism is the electrochemical oxidation of anionic species of I2 that form from the dissolution and subsequent hydrolysis of gas phase I2 in the pH 9 buffer electrolyte: the gas phase I2 dissolves in the buffer in proportion to Henry's Law constant and then the dissolved I2 is hydrolyzed to several species, including the anionic species iodide and tri-iodide. The detection of I2 is achieved by measuring oxidizing current during the cyclic voltammetry technique bounded between -0,2 and 0,5 V vs the Pt pseudoreference electrode. The hydrolysis mechanism of I2 in the pH 9 buffer enables the buffer to function as a concentrator for the anionic species of I2. When the sensor is exposed to a gas stream containing I2, practically continuous accumulation of the electrochemically detectable anionic species of I2 is possible, with a saturation point where the pH 9 buffer contains > 100 ppm iodide anion. For context, the sensor can detect iodide anions in pH 9 buffer at levels as low as 0,01 ppm. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

AlGaN-channel high electron mobility transistors (HEMTs) were operated as visible- and solar-blind photodetectors by using GaN nanodots as an optically active floating gate. The effect of the floating gate was large enough to switch an HEMT from the off-state in the dark to an on-state under illumination. This opto-electronic response achieved responsivity >108 A/W at room temperature while allowing HEMTs to be electrically biased in the off-state for low dark current and low DC power dissipation. The influence of GaN nanodot distance from the HEMT channel on the dynamic range of the photodetector was investigated, along with the responsivity and temporal response of the floating gate HEMT as a function of optical intensity. The absorption threshold was shown to be controlled by the AlN mole fraction of the HEMT channel layer, thus enabling the same device design to be tuned for either visible- or solar-blind detection.

We study the use of nanoelectrode arrays (NEAs), consisting of billions/cm2 of ~ 75 nm diameter electrodes, for the electrochemical analysis of ionic halogen species in water. Such NEA sensors were previously demonstrated to detect part-per-billion (ppb) levels of Pb-ions in aqueous solutions without supporting electrolytes. Briefly, the individual electrodes in the NEA can be tailored with sufficient separation coupled with pore-depth control so that each experiences non-overlapping hemispherical diffusion zones within which the ionic flux of an analyte is independent of time. This geometry is well-suited for trace-level detection, as fast voltage sweeps result in a large and steady-state current density. With optimized design, the additive response from the plethora of nanoelectrodes leads to an orders-of-magnitude analytical advantage for electrochemical detection compared to conventional (mm) sized disc electrodes using sweep or pulse voltammetric techniques. NEAs are fabricated by anodizing RF-sputter deposited Al films on a substrate-of-choice, resulting in billions/cm2 tailored with controllable pore diameters. Each nanopore is partially filled via electrochemical plating with an appropriate working electrode material, such as Au, Pt or Ni. A thin W film is beneath the nanopore template for both processing assistance and to provide a backside electrical contact in parallel to every nanoelectrode. In the case that the NEA is recessed within the porous alumina, a thin conducting film can be added to the topside to function as a counter/pseudo-reference electrode. In some situations, the counter electrode can also serve as an ion collector, preconcentrating ionic species near the pore openings prior to beginning an electrochemical measurement. Using such NEA sensors, we will demonstrate trace detection levels for both Cl and I ionic species in water, and compare the limits-of-detection with conventional electrodes. In addition, we explore the possibility of using NEA sensors to detect halogens in the gas phase. By manipulating the NEA structure, the monitoring capability may be extended to gas phase detection of Cl2 or I2. Such gas-phase detection is possible by utilizing the natural humidity in air condensing on the nanopore walls above the recessed working electrodes. Indirect sensing of such gases occurs after they dissolve in the pore water to form electrochemically detectable halogen species. Notably, the electrochemical measurement is achieved with simple, condensed humidity as the sole ionically conducting phase, without the need for a supporting electrolyte. This is because the high resistivity of water† is mitigated by the short ionic path length: the net solution resistance is small because of the sub-micron distance separating the NEA electrodes from the counter/pseudo-reference electrode sputtered upon the surface of the opposite (open) end of the pore. †The conductivity of humidity levels we consider in this study range from 10-6 S/m (humidity from DI water) to 10-3-10-4 S/m (conductivity range of natural humidity across the USA as monitored by the National Atmospheric Deposition Program’s National Trend Network). This work is supported by the Laboratory Directed Research and Development program at Sandia National Laboratories. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Microwave impedance microscopy (MIM) is a scanning probe technique to measure local changes in tip-sample admittance. The imaginary part of the reported change is calibrated with finite element simulations and physical measurements of a standard capacitive sample, and thereafter the output ΔY is given a reference value in siemens. Simulations also provide a means of extracting sample conductivity and permittivity from admittance, a procedure verified by comparing the estimated permittivity of polytetrafluoroethlyene (PTFE) to the accepted value. Simulations published by others have investigated the tip-sample system for permittivity at a given conductivity, or conversely conductivity and a given permittivity; here we supply the full behavior for multiple values of both parameters. Finally, the well-known effective medium approximation of Bruggeman is considered as a means of estimating the volume fractions of the constituents in inhomogeneous two-phase systems. Specifically, we consider the estimation of porosity in carbide-derived carbon, a nanostructured material known for its use in energy storage devices.

Gold electroplating, now over two centuries old(1), remains a mainstay of the electronic industry, where the good electrical and mechanical properties of hard gold in particular make for excellent contacts. Electrodeposited gold is hardened by the incorporation of minute amounts of inclusions, both metallic and non-metallic, which affect the microstructure of the growing film as well as its final surface(2). As previously demonstrated(3), the main contributor to hardening is the inclusions’ effect on decreasing grain size. In addition to the metal inclusions, carbon-containing by-products of the electroplating bath, particularly AuCN and CN-complexed cobalt have been found, affecting both hardness and wear resistance(4). In our work, we aim to better understand the inclusion mechanism in cobalt-hardened gold in particular, and by extension that of other additions such as nickel, and the resulting microstructure and properties. We will electrodeposit gold with systematically varying bath compositions under several deposition conditions, while measuring the nucleation rate using Tafel plots, and characterize the resulting films in terms of microstructure, hardness and wear resistance. The effect of thermal aging on the inclusion profile will be studied by Auger electron spectroscopy. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000. 1. Kohl PA. Electrodeposition of gold. In: Schlesinger M, Paunovic M, editors. Modern Electroplating, Fifth Edition. New York, NY, USA: Wiley; 2000. p. 201-25. 2. Okinaka Y. Significance of inclusions in electroplated gold films for electronics applications. Gold bulletin. 2000;33(4):117-27. 3. Lo CC, Augis JA, Pinnel MR. Hardening mechanisms of hard gold. Journal of Applied Physics. 1979;50(11):6887-91. 4. DeDonker R, Vanhumbeeck J. Cobalt in gold electrodeposits. Transactions of the Institute of Metal Finishing. 1985;63:59.

Microwave impedance microscopy (MIM) is a novel mode of near-field scanning probe microscopy that can measure topography and local electrical impedance simultaneously with nanometer spatial resolution. MIM is often used qualitatively to identify defects in nanodevices or to image ferroelectric domain walls, for example. We have chosen to use MIM to study the disordered pore networks of nanostructured carbon materials, such as carbidederived carbon (CDC) and onion-like carbon (OLC). In this work, we model MIM experiments by simulating the electrical response of some simple models of heterogeneous materials under an AFM tip which radiates an RF electromagnetic field. These models are designed to act as very basic approximations of more complicated structures measured with the MIM technique, with the eventual goal of correlating the electrical response with local structural parameters, such as porosity.

Single-walled carbon nanotube (SWCNT) aerogels produced by critical-point-drying of wet-gel precursors exhibit unique properties, such as high surface-area-to-volume and strength-to-weight ratios. They are free-standing, are binder-free, and can be scaled to thicknesses of more than 1mm. Here, we examine the electric double layer capacitive behavior of these materials using a common room temperature ionic liquid electrolyte, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI). Electrochemical performance is assessed through galvanostatic cycling, cyclic voltammetry and impedance spectroscopy. Results indicate stable capacitive performance over 10,000 cycles as well as an impressive performance at high charge and discharge rates, due to accessible pore networks and enhanced electronic and ionic conductivities of SWCNT aerogels. These materials can find applications in mechanically compressible and flexible supercapacitor devices with high power requirements.

Microwave impedance microscopy (MIM) is a novel scanning probe technique used to measure local electrical impedance under an AFM tip operating at some fixed electrical resonant frequency. Each point in the surface scan records sample elevation and power return loss, thus generating a topographical image with an overlaid impedance map. Various high specific surface area (SSA) carbon materials, recently demonstrated to have excellent performance as electrochemical capacitor electrodes, were investigated via MIM. Results of MIM studies on these materials may be used to provide additional understanding of transport properties and complement conventional methods of surface area measurement.

Considerable interest in understanding interfacial phenomena occurring across nanostructured solid oxide fuel cell (SOFC) membrane electrode assemblies has increased demand for in situ characterization techniques with higher resolution. We briefly outline recent advancements in atomic force microscopy (AFM) instrumentation and subsystems in realizing real time imaging at high temperatures and ambient pressures, and the use of these in situ, multi-stimuli probes in collecting local information related to physical and fundamental processes. Here we demonstrate direct probing of local surface potential gradients related to the ionic conductivity of yttria-stabilized zirconia (YSZ) within symmetric SOFCs under intermediate operating temperatures (500–600 °C) via variable temperature scanning surface potential microscopy (VT-SSPM). The conductivity values obtained at different temperatures are then used to estimate the activation energy. These locally collected conductivity and activation energy values are subsequently compared to macroscopic electrochemical impedance results and bulk literature values, thus supporting the validity of the approach.

Two graphene-like carbide derived carbons (CDC-Gs) were produced by chlorination of SiC nanosheets obtained by magnesio-thermal reduction at moderate temperature of silica/graphene oxide nanocomposites. These CDC-Gs were evaluated as supercapacitor electrode materials in an organic electrolyte. Starting from a low SiO2/GO ratio in the precursor, the resulting CDC-G nanosheets are composed of a few layers of graphite, partially coated with microporous CDC. In contrast, a high SiO2/GO ratio leads to micropores generated on the basal plane of individual carbon nanosheets. The latter CDC-G shows a remarkable high power capability with 76 % of retention of the initial capacity at scan rates up to 3Vs−1. Notably, the equivalent series resistance (ESR) and time constant of the cell were found to be extremely low at 0.45Ω·cm2 and 0.4s, respectively, thanks to the unique 2D open surface and enhanced access to micropores. These features were attributed to the unique nanostructure of the microporous graphene.

The potential pathways to increase the energy storage in electric double-layer (EDL) supercapacitors using room-temperature ionic liquid electrolytes and carbon-based nanostructured electrodes are explored by molecular dynamics simulations. A systematic comparison of capacitances obtained on nanoparticles of various shape and dimensions showed that when the electrode curvature and the length scale of the surface roughness are comparable to ion dimensions, a noticeable improvement in the capacitive storage is observed. The nanoconfinement of the electrolyte in conductive electrode pores further enhances the capacitance due to mismatch in ion-electrode surface interactions and strong electrostatic screening. We show that nanoporous structures made of arrays of conductive carbon chains represent a synergy of all three favorable factors (that is, high curvature, atomic scale roughness, and nanoconfinement) and can generate non-Faradic capacitance ranging from 260 to 350 F/g, which significantly exceeds the performance of the current generation of nanostructured electrodes.

Microporous carbon materials are widely used in gas storage, sorbents, supercapacitor electrodes, water desalination, and catalyst supports. While these microporous carbons usually have a particle size in the 1100 m range, here the synthesis of porous carbide-derived carbon (CDC) with particle diameters around 30 nm by extraction of titanium from nanometer-sized titanium carbide (TiC) powder at temperatures of 200 degrees C and above is reported. Nanometer-sized CDCs prepared at 200400 degrees C show a disordered structure and the presence of CN sp1 bonds. Above 400 degrees C, the CN bond disappears with the structure transition to disordered carbon similar to that observed after synthesis from carbide micropowders. Compared to CDCs produced from micrometer-sized TiC, nano-CDC has a broader pore size distribution due to interparticle porosity and a large contribution from the surface layers. The material shows excellent electrochemical performance due to its easily accessible pores and a large specific surface area.