Electrical transport and electromigration studies on nickel encapsulated carbon nanotubes: possible future interconnects.

We nominate the nickel filled multiwalled carbon nanotubes (MWNTs) as potential candidates to cope with challenges in persistent scaling for future interconnect technology. The insights into electrical transport through nickel filled carbon nanotubes provide an effective solution for major performance and reliability issues such as the increasing resistivity of metals at reduced scales, electromigration at high current densities and the problem of diffusion and corrosion faced by the existing copper interconnect technology. Furthermore, the nickel filled MWNTs outperform their hollow counterparts, the unfilled MWNTs, carrying at least one order higher current density, with increased time to failure. The results suggest that metal filled carbon nanotubes can provide a twofold benefit: (1) the metal filling provides an increased density of states for the system leading to a higher current density compared to hollow MWNTs, (2) metal out-diffusion and corrosion is prevented by the surrounding graphitic walls.

Electrical transport and breakdown in graphene multilayers loaded with electron beam induced deposited platinum.

We demonstrate here the effect of electron beam induced deposited platinum on the electrical transport through multilayer graphene sheets. Platinum metal is deposited at different positions on the graphene multilayers, i.e., including as well as excluding the bottom contact sites and the change in electrical conductance of the same multilayer graphene sheets before and after platinum deposition is segregated. An improvement in electrical conductance is observed even if the metal is deposited at the part of the graphene sheets that does not touch the bottom gold electrodes, and hence this experimental approach directly demonstrates that the contact improvement is not the sole reason for the improved electrical conduction. The improvement in electrical performance of the graphene sheets is explained in terms of the doping of graphene sheets caused by the charge transfer between the deposited metal and the graphene and thereby modified density of states for electrical conduction. Metal deposition also leads to the increased interlayer interaction of the graphene sheets as revealed by the transmission electron microscopy analysis. Further, two types of breakdown behaviors viz. sharp and stepped breakdowns observed for these graphene devices are explained in terms of the effective graphene-metal contact area. These studies reveal the implications of top metal contact fabrication on graphene for electronic devices.

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.

Thinning of multilayer graphene to monolayer graphene in a plasma environment.

We present a facile approach to transform multilayer graphene to single-layer graphene in a gradual thinning process. Our technique is based upon gradual etching of multilayer graphene in a hydrogen and nitrogen plasma environment. High resolution transmission microscopy, selected area electron diffraction and Raman spectroscopy confirm the transformation of multilayer graphene to monolayer graphene at a substrate temperature of ∼ 400 °C. The shift in the position of the G-band peak shows a perfect linear dependence with substrate temperature, which indicates a controlled gradual etching process. Selected area electron diffraction also confirmed the removal of functional groups from the graphene surface due to the plasma treatment. We also show that plasma treatment can be used to engineer graphene nanomesh structures.

Studies on carbon nanotubes and fullerenes under extreme conditions.

Ion beam irradiation of materials can cause defect creation as well as defect annealing depending on the ion beam parameters such as ion fluence and the energy loss of ions in materials. In present review, we report the behaviour of carbon nanotubes under exteme conditions such as laser irradiation and ion irradiation. The reorientation of the crystalline planes in confined single crystal nickel nanorods inside carbon nano tube, induced by heavy ion irradiation, is reported. Axial buckling of nickel nanorods as well as walls of carbon nano tubes in nickel encapsulated carbon nano tubes under swift heavy ion irradiation at high fluence is observed. At high fluence, amorphization of nickel nanorods inside carbon nanotubes is also observed. Axial buckling and amorphization under ion irradiation at high fluence are dependent on the number of walls in carbon nanotubes. High resolution transmission electron microscopy was used to investigate the reorientations, buckling and amorphization of metal filled nanotubes. Synthesis of carbon nanowires by ion irradiation of fullerene and their field emission properties with comparison to that of unirradiated and irradiated carbon nanotubes are reported. An international scenario with future prospects of ion beam studies in carbon nanotube is briefed.

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.

Hydrogen in chemical vapour deposited carbon nanotubes: an active site for functionalization.

The presence of hydrogen in as-grown carbon nanotubes (CNTs) synthesized by microwave plasma (MP) chemical vapour deposition (CVD) technique is demonstrated. Our results showed that the MPCVD, as-grown CNTs were hydrogenated consisting of C-H bonds; whereas, the tubes synthesized by arc discharge consisted of non-hydrogenated multi-walled CNTs. Fourier transform infrared spectroscopy (FTIR) and micro-Raman spectroscopy techniques were used to detect C-H bonding in the as-grown CNTs. The effective functionalization of as-grown hydrogenated CNTs grown using a microwave CVD process is first time demonstrated by laser assisted CVD process. It was found that the laser-assisted CVD process resulted in the termination of hydrogen and the oxidation of as-grown CNT structure leading to the carboxylic group attachment. The FTIR results show the presence of -OH and C=O bonds in the functionalized samples. However, the non-hydrogenated CNTs could not be effectively functionalized by the same process, probably due to the fact that it did not contain active sites pre-requisite for functionalization, as did the CVD grown samples. The functionalization of CVD grown tubes is believed to take place at the 'active' hydrogen-terminated sites on the CNT surfaces.

Selective growth of vertically aligned carbon nanotubes by double plasma chemical vapour deposition technique.

The selective growth of vertically aligned carbon nanotubes (VACNTs) on large area copper substrates was carried out using a double plasma hot-filament chemical vapour deposition system. Three independent power supplies were used to produce two glow discharges within the vacuum reactor. The generation of two glow discharges and the efficient utilization of the electric fields, by controlling the key process parameters, enabled the production of VACNTs. Morphology, density and structure of carbon nanotubes were characterized using Scanning Electron Microscopy and Raman Spectroscopy.

FTIR spectroscopy of multiwalled carbon nanotubes: a simple approach to study the nitrogen doping.

The nitrogen doped multiwalled carbon nanotubes (MWNTs) were synthesized by microwave plasma chemical vapor deposition (MPCVD) technique. In this paper, we report the results of FTIR, Raman, and TGA studies to confirm the presence of N-doping inside carbon nanotubes. Fourier transform infrared (FTIR) studies were carried out in the range 400-4000 cm(-1) to study the attachment of nitrogen impurities on carbon nanotubes. FTIR spectra of the virgin sample of MWNTs show dominant peaks which are corresponding to Si-O, C-N, N-CH3, CNT, C-O, and C-Hx, respectively. The Si-O peak has its origin in silicon substrate whereas the other peaks are due to the precursor gases present in the gas mixture. The peaks are sharp and highly intense showing the chemisorption nature of the dipole bond. The intensity of the peaks due to N-CH3, C-N, and C-H reduces after annealing. It is interesting to note that these peaks vanish on annealing at high temperature (900 degrees C). The presence of C-N peak may imply the doping of the MWNTs with N in substitution mode. The position of this intense peak is in agreement with the reported peak in carbon nitride samples prepared by plasma CVD process, since the Raman modes are also expected to be delocalized over both carbon and nitrogen sites it was found that the intensity ratio of the D and G peaks, I(D)/I(G), varies as a function of ammonia concentration. The TGA measurements, carried out under argon flow, show that the dominant weight loss of the sample occurs in the temperature range 400-600 degrees C corresponding to the removal of the impurities and amorphous carbon.

RF sputter deposited nanocrystalline (110) magnetite thin film from alpha-Fe2O3 target.

Nanocrystalline magnetite thin film was prepared on to fused quartz substrate by sputtering at an rf power of 50 W. X-ray diffraction study showed that the sputtered film was (110) oriented. The stoichiometry in the thin film has been confirmed through a variety of characterization techniques. The room temperature spontaneous magnetization value (4piMs) of the film was 5100 G. This is about 85% of the bulk value. The resistivity of the film showed a sharp change around 120 K, indicative of the Verwey transition.

Single crystalline nickel nanorods inside carbon nanotubes: growth behavior, structure, and magnetic properties.

Nickel nanorods with diameters ranging from 5 to 10 nm, encapsulated inside the carbon nanotubes, are prepared using microwave plasma chemical vapor deposition. High-resolution transmission electron microscopy (HRTEM) studies reveal the perfect crystalline nature of the rods with d-spacing closely matching the (111) interplanar spacing of Ni. The (111) planes of the Ni nanorods are always aligned at 39.6 degrees with respect to the graphite planes of the nanotubes. The cosine component of the d-spacing along the direction of the graphite planes is found to be 1.6 A; exactly half the d-spacing between the graphite planes. The electron diffraction pattern shows clear spots corresponding to Ni structure. The field cooled and zero field cooled magnetization data reveal the reversibility of the magnetization of the Ni nanorods and show a blocking temperature of 195 K, which correspond to energy barrier of 0.4 eV/(V).

Ni and Ni/Pt filling inside multiwalled carbon nanotubes.

Multiwalled carbon nanotubes are grown by microwave plasma chemical vapor deposition with CH4 and H2 as precursor gases. Ni and Ni/Pt electroplated layers are used as catalysts for the synthesis of the tubes. We observe that a very efficient filling of the tubes takes place with Ni. In some cases Ni/Pt filling is also observed inside the tubes. High-resolution transmission electron microscopy (HRTEM) studies, coupled with energy-dispersive X-ray analyses of the tubes, indicate Ni nanorods with a highly symmetrical cylindrical structure. The diameter of the cylindrical nanorods is on the order of 40 nm, and their length is 660 nm. The nano area diffraction pattern of the nanorods reveals the cubic structure of nickel, and electron diffraction spots corresponding to (111), (200), (220) planes are evident. The lattice constant of Ni measured from the diffraction spots was found to be 0.347 +/- 0.0013 nm. This should be compared with 0.352 nm, the value of "a" in bulk Ni. The decrease in the lattice constant may be due to the strain experienced inside the tubes. Raman spectroscopy shows the typical signature of the tangential breathing mode present in the tubes at 1580 cm-1 that shifts to a new position when the C12 is replaced by 13C. The shift, however, is too small and is difficult to explain on the basis of mass difference. HRTEM experiments indicate the presence of Ni3C in the samples dominantly in the interfacial region.

Characterization of enterotoxin produced by four Yersinia enterocolitica strains of pig origin.

All four isolates of Yersinia enterocolitica and one isolate of Y. frederiksenii from pigs were found to be enterotoxigenic. Whole-cell preparations of Y. enterocolitica isolates did not induce any change in the rabbit ligated gut test after 6 and 18 h of inoculation, but Y. frederiksenii on the other hand showed a positive gut response at 18 h. Cell-free supernatant (CFS) of all five isolates induced dilatation in the rabbit gut up to 6 h, after which Y. enterocolitica became negative, while Y. frederiksenii continued to show a reaction up to 18 h. CFS of all five isolates were also found positive with the infant mouse test. Of the five isolates of Yersinia, three gave a positive reaction for the permeability factor on rabbit skin. Yersinia enterotoxin could be concentrated by methanol extraction. It was stable at 100 degrees C for 20 min and at 120 degrees C for 15 min. However, its activity was lost at low (2.0) and high pH (10.0). Enterotoxic preparations of Y. enterocolitica lost part of their enterotoxic activity upon dialysis.