Toward the Ultimate Limit of Analyte Detection, in Graphene-Based Field-Effect Transistors.

The ultimate sensitivity of field-effect-transistor (FET)-based devices for ionic species detection is of great interest, given that such devices are capable of monitoring single-electron-level modulations. It is shown here, from both theoretical and experimental perspectives, that for such ultimate limits to be approached the thermodynamic as well as kinetic characteristics of the (FET surface)-(linker)-(ion-receptor) ensemble must be considered. The sensitivity was probed in terms of optimal packing of the ensemble, through a minimal charge state/capacitance point of view and atomic force microscopy. Through the fine-tuning of the linker and receptor interaction with the sensing surface, a record limit of detection as well as specificity in the femtomolar range, orders of magnitude better than previously obtained and in excellent accord with prediction, was observed.

Modulation of Electrokinetic Potentials Using Graphene-Based Surfaces and Variable Substrate Charge Density.

Enhanced electrokinetic phenomena, manifested through the observation of a large streaming potential (Vs), were obtained in microchannels with single-layer graphene (SLG)-coated and few-layer graphene (FLG)-coated surfaces. In comparison to silicon microchannels, the Vs obtained for a given pressure difference along the channel (ΔP) was higher by 75% for the graphene-based channels, with larger values in the SLG case. Computational modeling was used to correlate the surface charge density, tuned through plasma processing, and related zeta potential to measured Vs. The implications related to deploying lower dimensional material surfaces for modulating electrokinetic flows were investigated.

Enhanced graphene surface plasmonics through incorporation into metallic nanostructures.

A methodology for enhancing the surface plasmon polariton (SPP) resonance associated with graphene, through nanoscale metal-dielectric-metal (MDM) gaps, is proposed. The modulation of the resonances, in the range of 0.7 µm to 1 µm was done through tuning the carrier density in graphene and has been shown to be of potential utility for surface analyte sensing. It was shown, from finite element simulations in the frequency domain, that the related hybrid SPP modes could be clearly delineated in far field spectroscopy.

The Modulation of Electrokinetic Streaming Potentials of Silicon-Based Surfaces through Plasma-Based Surface Processing.

A new plasma processing-based methodology for enhancing the streaming potential (Vs) that may be obtained in electrokinetic flows for a given pressure gradient over a silicon surface-based microchannel is indicated. The dependence of the Vs on both the surface zeta potential and the electrolyte slip length was carefully determined through a series of experiments involving the variation of CF4- and Ar-based plasma parameters, incorporating pressure, exposure time, and power. It was determined through analytical estimates that, while the zeta potential is always increased, the slip length may be diminished under certain conditions. A record value of ∼0.1 mV/Pa was obtained using CF4 plasma at 500 W, 10 mTorr, and 300 s of exposure. The implications of the work extend to the investigation of whether smooth surfaces may be effective for generating large Vs's for new modalities of electrical voltage sources in microfluidics-based applications.

Influence of Surface Texture on the Variation of Electrokinetic Streaming Potentials.

The electrokinetic streaming potential (Vs) obtained through electrolyte flow in a microchannel is shown to be related to the underlying surface pattern. Pillar, mesh, and groove patterns were studied for comparing the relative magnitudes of the Vs with air-/liquid-filled surfaces. A record value of the related figure of merit, in terms of the developed Vs per-unit applied pressure, of ∼0.127 mV/Pa, was observed in a mesh texture liquid-filled surface (LFS) impregnated with an electrolyte-immiscible oil. The study indicated that increasing the solid fraction of the pattern surface decreases the effective slip length while enhancing the overall channel ζ potential. Consequently, maximizing the obtained Vs implies a balancing of the slip with the surface potential, with plausibly more significance of the latter. The work has implications for higher-efficiency electrical voltage sources.

Interaction and hybridization of orthogonal Fabry-Pérot like surface plasmon modes in metal-dielectric grating structures.

The interaction of specific surface plasmon modes in metal-dielectric-metal arrangements is investigated, motivated by their relevance to device-based configurations. The absorption spectra of the relevant nanostructures considering geometrical variation, such as the width and height of the metal or dielectric, are probed considering such interactions. Frequency domain simulations are used to study related multiple surface plasmon polariton resonance modes. It is indicated that the resonant energy level interaction due to the coupling between modes in a horizontal dielectric layer and those in a vertical groove can be engineered and understood in terms of energy level hybridization.

Possibility of Obtaining Two Orders of Magnitude Larger Electrokinetic Streaming Potentials, through Liquid Infiltrated Surfaces.

It is shown that the magnitude of the streaming potential (Vs) can be significantly enhanced from ∼0.02 V to as much as ∼1.6 V, in electrokinetic flows through microchannels. This was done through flows on liquid-filled surfaces, where the grooves were filled with oils of viscosity in the range 30-3000 mPa·s. The presence of immiscible oils and the improved slip are both factors that could significantly increase the Vs. The analytical relationship between streaming potential and filled liquid viscosity was derived and verified through corresponding experimental results. The work yields novel insights into complex electrolyte flows and indicates avenues for more efficient energy harvesting.

Modulation of the Streaming Potential and Slip Characteristics in Electrolyte Flow over Liquid-Filled Surfaces.

A significant enhancement in the streaming potential ( Vs) was obtained in experiments considering the flow of electrolyte over liquid-filled surfaces (LFSs), where the grooves in patterned substrates are filled with electrolyte immiscible oils. Such LFSs yield larger Vs (by a factor of 1.5) compared to superhydrophobic surfaces, with air-filled grooves, and offer tunability of electrokinetic flow. It is shown that the density, viscosity, conductivity, as well as the dielectric constant of the filling oil, in the LFS, determine Vs. Relating a hydrodynamic slip length to the obtained Vs offers insight into flow characteristics, as modulated by the liquid interfaces in the LFS.

High-performance flexible hydrogen sensor made of WS2 nanosheet-Pd nanoparticle composite film.

We report a flexible hydrogen sensor, composed of WS2 nanosheet-Pd nanoparticle composite film, fabricated on a flexible polyimide substrate. The sensor offers the advantages of light-weight, mechanical durability, room temperature operation, and high sensitivity. The WS2-Pd composite film exhibits sensitivity (R 1/R 2, the ratio of the initial resistance to final resistance of the sensor) of 7.8 to 50,000 ppm hydrogen. Moreover, the WS2-Pd composite film distinctly outperforms the graphene-Pd composite, whose sensitivity is only 1.14. Furthermore, the ease of fabrication holds great potential for scalable and low-cost manufacturing of hydrogen sensors.

Enhanced Power Conversion Efficiency of Graphene/Silicon Heterojunction Solar Cells Through NiO Induced Doping.

We report a doping strategy, where nickel oxide (NiO) nanoparticle film coating is employed for graphene/Si heterojunction solar cells to improve the power conversion efficiency (PCE). NiO doping has been shown to improve the short circuit current (J(SC)) by 12%, open circuit voltage (V(OC)) by 25% and fill factor (FF) by 145% of the cells, in turn increasing the PCE from 1.37% to 4.91%. Furthermore, NiO doped graphene/Si solar cells don't show any significant performance degradation over 10 days revealing that NiO doping can be a promising approach for practical applications of graphene in solar cells.

Surface Composites Synthesized through the Incorporation of Atomic Layer Deposited AlOx into Nanoporous Fuzzy Tungsten.

The incorporation of energetic helium gaseous species into materials such as tungsten (W) imparts intrinsic surface fragility, yielding fuzzy tungsten. To enhance the robustness of the surface layers, aluminum oxide (AlOx) was deposited by atomic layer deposition into the fuzzy W. The conformally deposited ceramic yields a new class of surface composites. Structural characterization of the fuzzy W-AlOx composites through nanoindentation testing indicated enhanced indentation modulus (Eind) and hardness (Hind) and was modeled through various rules of mixtures approaches. The distribution of AlOx in fuzzy W was explored and a systematic study of the extent of incorporation of the AlOx into the fuzzy W was carried out. The synthesized composites may be utilized for improved structural characteristics, e.g., in reducing crack initiation and fracture.

Enhanced Corrosion Resistance in Aluminum-Based Electrolyzer Components via Stoichiometry Tuned Atomic Layer-Deposited TiOx Films.

Titanium (Ti) is widely used as anode current collectors in proton exchange membrane (PEM)-based water electrolyzers due to its self-passivated oxide layer, which protects it from corrosion in acidic solutions. However, the cost of the material and machining process for Ti is high. A wider utilization of water electrolyzers to produce hydrogen could be favored by the use of less expensive coated aluminum (Al) substrates, which could potentially replace high-cost Ti-based components. It is shown here by depositing a pinhole-free oxygen vacancy-rich titanium oxide (TiOx) protection layer by atomic layer deposition (ALD), the corrosion resistance of Al substrates in acidic environments at oxygen evolution potentials can be enhanced. The optimization of the oxygen vacancy concentration is accomplished by tuning the ALD parameters to achieve ideal stoichiometry and conformal coating on rough substrates. The robustness of the coatings was evaluated at high potentials (2.4 V vs NHE = normal hydrogen electrode) in low pH conditions. A low TiOx dissolution rate of the order of ∼6 nm year-1 was observed. By testing under industrially relevant conditions, i.e., high applied voltages (2.4 V) and low pH, an Al loss at around the zero ppb level was achieved using optimized ALD parameters. It is proposed that a 40 nm TiOx coating on Al may be adequate to provide 60,000 h of durability in a PEM water electrolyzer anode current collector.

Ultra-high optical absorption efficiency from the ultraviolet to the infrared using multi-walled carbon nanotube ensembles.

The optical absorption efficiencies of vertically aligned multi-walled (MW)-carbon nanotube (CNT) ensembles are characterized in the 350-7000 nm wavelength range where CNT site densities > 1 × 10(11) /cm(2) are achieved directly on metallic substrates. The site density directly impacts the optical absorption characteristics, and while high-density arrays of CNTs on electrically insulating and non-metallic substrates have been commonly reported, achieving high site-densities on metals has been challenging and remains an area of active research. These absorber ensembles are ultra-thin (<10 µm) and yet they still exhibit a reflectance as low as ∼0.02%, which is 100 times lower than the reference; these characteristics make them potentially attractive for high-sensitivity and high-speed thermal detectors. In addition, the use of a plasma-enhanced chemical vapor deposition process for the synthesis of the absorbers increases the portfolio of materials that can be integrated with such absorbers due to the potential for reduced synthesis temperatures. The remarkable ruggedness of the absorbers is also demonstrated as they are exposed to high temperatures in an oxidizing ambient environment, making them well-suited for extreme thermal environments encountered in the field, potentially for solar cell applications. Finally, a phenomenological model enables the determinatiom of the extinction coefficients in these nanostructures and the results compare well with experiment.

Graphene and Two-Dimensional Materials for Biomolecule Sensing.

An ideal biosensor material at room temperature, with an extremely large surface area per unit mass combined with the possibility of harnessing quantum mechanical attributes, would be comprised of graphene and other two-dimensional (2D) materials. The sensing of a variety of sizes and types of biomolecules involves modulation of the electrical charge density of (current through) the 2D material and manifests through specific components of the capacitance (resistance). While sensitive detection at the single-molecule level, i.e., at zeptomolar concentrations, may be achieved, specificity in a complex mixture is more demanding. Attention should be paid to the influence of inevitably present defects in the 2D materials on the sensing, as well as calibration of obtained results with acceptable standards. The consequent establishment of a roadmap for the widespread deployment of 2D material-based biosensors in point-of-care platforms has the potential to revolutionize health care.

Band-to-Band Tunneling Leakage Current Characterization and Projection in Carbon Nanotube Transistors.

Carbon nanotube (CNT) transistors demonstrate high mobility but also experience off-state leakage due to the small effective mass and band gap. The lower limit of off-current (IMIN) was measured in electrostatically doped CNT metal-oxide-semiconductor field-effect transistors (MOSFETs) across a range of band gaps (0.37 to 1.19 eV), supply voltages (0.5 to 0.7 V), and extension doping levels (0.2 to 0.8 carriers/nm). A nonequilibrium Green's function (NEGF) model confirms the dependence of IMIN on CNT band gap, supply voltage, and extension doping level. A leakage current design space across CNT band gap, supply voltage, and extension doping is projected based on the validated NEGF model for long-channel CNT MOSFETs to identify the appropriate device design choices. The optimal extension doping and CNT band gap design choice for a target off-current density are identified by including on-current projection in the leakage current design space. An extension doping level >0.5 carrier/nm is required for optimized on-current.

Remote Oxygen Scavenging of the Interfacial Oxide Layer in Ferroelectric Hafnium-Zirconium Oxide-Based Metal-Oxide-Semiconductor Structures.

Discovery of ferroelectricity in HfO2 has sparked a lot of interest in its use in memory and logic due to its CMOS compatibility and scalability. Devices that use ferroelectric HfO2 are being investigated; for example, the ferroelectric field-effect transistor (FEFET) is one of the leading candidates for next generation memory technology, due to its area, energy efficiency and fast operation. In an FEFET, a ferroelectric layer is deposited on Si, with an SiO2 layer of ∼1 nm thickness inevitably forming at the interface. This interfacial layer (IL) increases the gate voltage required to switch the polarization and write into the memory device, thereby increasing the energy required to operate FEFETs, and makes the technology incompatible with logic circuits. In this work, it is shown that a Pt/Ti/thin TiN gate electrode in a ferroelectric Hf0.5Zr0.5O2 based metal-oxide-semiconductor (MOS) structure can remotely scavenge oxygen from the IL, thinning it down to ∼0.5 nm. This IL reduction significantly reduces the ferroelectric polarization switching voltage with a ∼2× concomitant increase in the remnant polarization and a ∼3× increase in the abruptness of polarization switching consistent with density functional theory (DFT) calculations modeling the role of the IL layer in the gate stack electrostatics. The large increase in remnant polarization and abruptness of polarization switching are consistent with the oxygen diffusion in the scavenging process reducing oxygen vacancies in the HZO layer, thereby depinning the polarization of some of the HZO grains.

Sub-Nanometer Interfacial Oxides on Highly Oriented Pyrolytic Graphite and Carbon Nanotubes Enabled by Lateral Oxide Growth.

A new generation of compact and high-speed electronic devices, based on carbon, would be enabled through the development of robust gate oxides with sub-nanometer effective oxide thickness (EOT) on carbon nanotubes or graphene nanoribbons. However, to date, the lack of dangling bonds on sp2 oriented graphene sheets has limited the high precursor nucleation density enabling atomic layer deposition of sub-1 nm EOT gate oxides. It is shown here that by deploying a low-temperature AlOx (LT AlOx) process, involving atomic layer deposition (ALD) of Al2O3 at 50 °C with a chemical vapor deposition (CVD) component, a high nucleation density layer can be formed, which templates the growth of a high-k dielectric, such as HfO2. Atomic force microscopy (AFM) imaging shows that at 50 °C, the Al2O3 spontaneously forms a pinhole-free, sub-2 nm layer on graphene. Density functional theory (DFT) based simulations indicate that the spreading out of AlOx clusters on the carbon surface enables conformal oxide deposition. Device applications of the LT AlOx deposition scheme were investigated through electrical measurements on metal oxide semiconductor capacitors (MOSCAPs) with Al2O3/HfO2 bilayer gate oxides using both standard Ti/Pt metal gates as well as TiN/Ti/Pd gettering gates. In this study, LT AlOx was used to nucleate HfO2 and it was shown that bilayer gate oxide stacks of 2.85 and 3.15 nm were able to achieve continuous coverage on carbon nanotubes (CNTs). The robustness of the bilayer was tested through deployment in a CNT-based field-effect transistor (FET) configuration with a gate leakage of less than 10-8 A/µm per CNT.

Elastic response of carbon nanotube forests to aerodynamic stresses.

The ability to determine static and (hydro)dynamic properties of carbon nanotubes (CNTs) is crucial for many applications. While their static properties (e.g., solubility and wettability) are fairly well understood, their mechanical responses (e.g., deflection under shear) to ambient fluid flow are to a large extent unknown. We analyze the elastic response of single-walled CNT forests, attached to the bottom wall of a channel, to the aerodynamic loading exerted by both laminar and turbulent flows. Our analysis yields analytical expressions for velocity distributions, the drag coefficient, and bending profiles of individual CNTs. This enables us to determine flexural rigidity of CNTs in wind-tunnel experiments. The model predictions agree with laboratory experiments for a large range of channel velocities.

Toxicity issues in the application of carbon nanotubes to biological systems.

Carbon nanotubes (CNTs) have recently emerged as a new option for possible use in methodologies of cancer treatment, bioengineering, and gene therapy. This review analyzes the potential, through possible toxicologic implications, of CNTs in nanomedicine. Generally, proven success in other fields may not translate to the use of CNTs in medicine for reasons including inconsistent data on cytotoxicity and limited control over functionalized-CNT behavior, both of which restrict predictability. Additionally, the lack of a centralized toxicity database limits comparison between research results. To better understand these problems, we seek insight from currently published toxicity studies, with data suggesting postexposure regeneration, resistance, and mechanisms of injury in cells, due to CNTs. FROM THE CLINICAL EDITOR: Carbon nanotubes (CNTs) have recently emerged as a new option for cancer treatment, bioengineering, and gene therapy. Inconsistent data on cytotoxicity and limited control over functionalized-CNT behavior currently restrict predictability of such applications.

Iron redox pathway revealed in ferritin via electron transfer analysis.

Ferritin protein is involved in biological tissues in the storage and management of iron - an essential micro-nutrient in the majority of living systems. While there are extensive studies on iron-loaded ferritin, its functionality in iron delivery is not completely clear. Here, for the first time, differential pulse voltammetry (DPV) has been successfully adapted to address the challenge of resolving a cascade of fast and co-occurring redox steps in enzymatic systems such as ferritin. Using DPV, comparative analysis of ferritins from two evolutionary-distant organisms has allowed us to propose a stepwise resolution for the complex mix of concurrent redox steps that is inherent to ferritins and to fine-tune the structure-function relationship of each redox step. Indeed, the cyclic conversion between Fe3+ and Fe2+ as well as the different oxidative steps of the various ferroxidase centers already known in ferritins were successfully discriminated, bringing new evidence that both the 3-fold and 4-fold channels can be functional in ferritin.