Carbon Nanotube-Based Ion Selective Sensors for Wearable Applications.

Wearable electronics offer new opportunities in a wide range of applications, especially sweat analysis using skin sensors. A fundamental challenge in these applications is the formation of sensitive and stable electrodes. In this article we report the development of a wearable sensor based on carbon nanotube (CNT) electrode arrays for sweat sensing. Solid-state ion selective electrodes (ISEs), sensitive to Na+ ions, were prepared by drop coating plasticized poly(vinyl chloride) (PVC) doped with ionophore and ion exchanger on CNT electrodes. The ion selective membrane (ISM) filled the intertubular spaces of the highly porous CNT film and formed an attachment that was stronger than that achieved with flat Au, Pt, or carbon electrodes. Concentration of the ISM solution used influenced the attachment to the CNT film, the ISM surface morphology, and the overall performance of the sensor. Sensitivity of 56 ± 3 mV/decade to Na+ ions was achieved. Optimized solid-state reference electrodes (REs), suitable for wearable applications, were prepared by coating CNT electrodes with colloidal dispersion of Ag/AgCl, agarose hydrogel with 0.5 M NaCl, and a passivation layer of PVC doped with NaCl. The CNT-based REs had low sensitivity (-1.7 ± 1.2 mV/decade) toward the NaCl solution and high repeatability and were superior to bare Ag/AgCl, metals, carbon, and CNT films, reported previously as REs. CNT-based ISEs were calibrated against CNT-based REs, and the short-term stability of the system was tested. We demonstrate that CNT-based devices implemented on a flexible support are a very attractive platform for future wearable technology devices.

Semiconductor nanorod-carbon nanotube biomimetic films for wire-free photostimulation of blind retinas.

We report the development of a semiconductor nanorod-carbon nanotube based platform for wire-free, light induced retina stimulation. A plasma polymerized acrylic acid midlayer was used to achieve covalent conjugation of semiconductor nanorods directly onto neuro-adhesive, three-dimensional carbon nanotube surfaces. Photocurrent, photovoltage, and fluorescence lifetime measurements validate efficient charge transfer between the nanorods and the carbon nanotube films. Successful stimulation of a light-insensitive chick retina suggests the potential use of this novel platform in future artificial retina applications.

Graphene supported nickel nanoparticle as a viable replacement for platinum in dye sensitized solar cells.

A platinum free counter electrode for dye sensitized solar cells was developed using graphene platelets (GP) supported nickel nanoparticles (NPs) as the active catalyst. Few layered GP were prepared by chemical oxidation of graphite powders followed by thermal exfoliation and reduction. The nanoparticles of nickel were deposited directly onto the platelets by pulsed laser ablation. The composite electrodes of GP and Ni nanoparticles (GP-Ni) thus obtained showed better performance compared to conventional Pt thin film electrodes (Std Pt) and unsupported Ni NPs. The efficiencies of the cells fabricated using GP-Ni, Std Pt and Ni NP CEs were 2.19%, 2% and 1.62%, respectively. The GP-Ni composite solar cell operated with an open circuit voltage of 0.7 V and a fill factor of 0.6. Electrochemical impedance spectroscopy using the I(3)(-)/I(-) redox couple confirms lower values of charge transfer resistance for the composite electrodes, 4.67 Ω cm(2) as opposed to 7.73 Ω cm(2) of Std Pt. The better catalytic capability of these composite materials is also reflected in the stronger I(3)(-) reduction peaks in cyclic voltammetry scans.

Graphene supported platinum nanoparticle counter-electrode for enhanced performance of dye-sensitized solar cells.

Composites of few layered graphene (G) and platinum (Pt) nanoparticles (NP) with different loadings of Pt were used as counter electrode (CE) in dye-sensitized solar cell (DSSC). NPs were deposited directly on to G using pulsed laser ablation method (PLD). DSSCs formed using the composite CEs show improved performance compared to conventional Pt thin film electrode (Std Pt) and unsupported Pt NPs. Composite with 27% loading of Pt shows 45% higher efficiency (η = 2.9%), greater short circuit current (J(sc) = 6.67 mA cm(-2)), and open circuit voltage (V(oc) = 0.74 V) without any loss of the fill factor (FF = 58%) as compared to the cells fabricated using Std Pt electrodes. Values of η, J(sc) and V(oc) for DSSC using Std Pt CE were 2%, 5.05 mA cm(-2) and 0.68 V, respectively. Electrochemical impedance spectroscopy using I(-)(3)/I(-) redox couple confirm lower values of charge transfer resistance for the composite electrodes, e.g., 2.36 Ω cm(2) as opposed to 7.73 Ω cm(2) of Std Pt. The better catalytic activity of these composite materials is also reflected in the stronger I(-)(3) reduction peaks in cyclic voltammetry scans.

Facile one-step transfer process of graphene.

Chemical vapour deposition (CVD) is emerging as a popular method for growing large-area graphene on metal substrates. For transferring graphene to other substrates the technique generally used involves deposition of a polymer support with subsequent etching of the metal substrate. Here we report a simpler one-step transfer process. Few-layer graphene (FLG) grown on a Cu substrate were transferred to a silanized wafer by just pressing them together. Hydrogen bonding between the hydroxyl group on FLG and the amine group on silane molecules facilitate the transfer.

Enhanced field emission and improved supercapacitor obtained from plasma-modified bucky paper.

The surface morphology of bucky papers (BPs) made from single-walled carbon nanotubes (CNTs) is modified by plasma treatment resulting in the formation of vertical microstructures on the surface. The shapes of these structures are either pillarlike or conelike depending on whether the gas used during plasma treatment is Ar or CH(4) . A complex interplay between different factors, such as the electric field within the plasma sheath, polarization of the CNT, intertubular cohesive forces, and ion bombardment, result in the formation of these structures. The roles played by these factors are quantitatively and qualitatively analyzed. The final material is flexible, substrate-free, composite-free, made only of CNTs, and has discrete vertically aligned structures on its surface. It shows enhanced field emission and electrochemical charge-storage capabilities. The field enhancement factor is increased by 6.8 times, and the turn-on field drops by 3.5 times from an initial value of 0.35 to 0.1 V µm(-1) as a result of the treatment. The increase in Brunauer-Emmett-Teller surface area results in about a fourfold improvement in the specific capacitance of the BP electrodes. Capacitance values before and after the treatments are 75 and 290 F g(-1) , respectively. It is predicted that this controlled surface modification technique could be put to good use in several applications based on macroscopic CNT films.

Healing of broken multiwalled carbon nanotubes using very low energy electrons in SEM: a route toward complete recovery.

We report the healing of electrically broken multiwalled carbon nanotubes (MWNTs) using very low energy electrons (3-10 keV) in scanning electron microscopy (SEM). Current-induced breakdown caused by Joule heating has been achieved by applying suitably high voltages. The broken tubes were examined and exposed to electrons of 3-10 keV in situ in SEM with careful maneuvering of the electron beam at the broken site, which results in the mechanical joining of the tube. Electrical recovery of the same tube has been confirmed by performing the current-voltage measurements after joining. This easy approach is directly applicable for the repairing of carbon nanotubes incorporated in ready devices, such as in on-chip horizontal interconnects or on-tip probing applications, such as in scanning tunneling microscopy.

Dramatic enhancement of the emission current density from carbon nanotube based nanosize tips with extremely low onset fields.

Nanostructures based on multiwalled carbon nanotubes (MWNTs) are fabricated using plasma of the mixture of hydrogen and nitrogen gases. The plasma-sharpened tips of nanotubes contain only a few tubes at the apex of the structure and lead to the dramatic enhancement in the emission current density by a factor >10(6) with the onset field as low as 0.16 V/microm. We propose that the nature of the tunneling barrier changes significantly for a nanosize tip at very high local electric field and may lead to the saturation in the emission current density.