Time Evolution and Spatial Hierarchy of Crack Patterns.

Cracks generated due to desiccation of wet colloidal systems are ubiquitous, examples being nanomaterial films, painted walls, cemented floors, mud fields, river beds, and even giant rocks. In all such cases, crack patterns are often appreciably similar but for the length and time scales, which can be widely differing. In this work, we have examined the crack formation more closely to see if there exists some generality with regard to the length scale of parameters and the formation time. Specifically, using a commonly used colloidal dispersion and optimized conditions to form polygonal network patterns rather than isolated cracks (films of subcritical thickness), we have studied the time evolution of the pattern parameters, the area occupied by the cracks, their lengths, and the widths. As is well known, initially, a network of cracks forms, which we term as the primary generation, followed by interconnecting cracks inside the polygonal regions (secondary) and, later, cracks spreading in local regions (tertiary). We find that the area and the width increase nearly linearly with time with the change in the slope corresponding to the change in the generation. When normalized with respect to the final values, the trends obtained for different film thicknesses overlap, the only exception being the pattern containing unconnected cracks. Thus, the time evolution of cracks is shown to be predictable based on width filtering. Including the angle between cracks as further input into the recursive model, the possibility of identifying the hierarchy of crack segments is also shown. The approach may be useful in determining the age, authenticity, and details of old paintings, understanding the stress profile of geological rocks, and analyzing various natural and manmade hierarchical structures.

Transparent and Flexible Supercapacitors with Networked Electrodes.

Transparent and flexible energy storage devices have received immense attention due to their suitability for innovative electronics and displays. However, it remains a great challenge to fabricate devices with high storage capacity and high degree of transmittance. This study describes a simple process for fabrication of supercapacitors with ≈75% of visible transparency and areal capacitance of ≈3 mF cm-2 with high stability tested over 5000 cycles of charging and discharging. The electrodes consist of Au wire networks obtained by a simple crackle template method which are coated with MnO2 nanostructures by electrodeposition process. Importantly, the membrane separator itself is employed as substrate to bring in the desired transparency and light weight while additionally exploiting its porous nature in enhancing the interaction of electrolyte with the active material from both sides of the substrate, thereby enhancing the storage capacity. The method opens up new ways for fabricating transparent devices.

Solution-processed soldering of carbon nanotubes for flexible electronics.

We report a simple lithography-free, solution-based method of soldering of carbon nanotubes with Ohmic contacts, by taking specific examples of multi-walled carbon nanotubes (MWNTs). This is achieved by self-assembling a monolayer of soldering precursor, Pd(2+) anchored to 1,10 decanedithiol, onto which MWNTs could be aligned across the gap electrodes via solvent evaporation. The nanosoldering was realized by thermal/electrical activation or by both in sequence. Electrical activation and the following step of washing ensure selective retention of MWNTs spanning across the gap electrodes. The soldered joints were robust enough to sustain strain caused during the bending of flexible substrates as well as during ultrasonication. The estimated temperature generated at the MWNT-Au interface using an electro-thermal model is ∼150 °C, suggesting Joule heating as the primary mechanism of electrical activation. Further, the specific contact resistance is estimated from the transmission line model.

Field effect transistors and photodetectors based on nanocrystalline graphene derived from electron beam induced carbonaceous patterns.

We describe a transfer-free method for the fabrication of nanocrystalline graphene (nc-graphene) on SiO(2) substrates directly from patterned carbonaceous deposits. The deposits were produced from the residual hydrocarbons present in the vacuum chamber without any external source by using an electron beam induced carbonaceous deposition (EBICD) process. Thermal treatment under vacuum conditions in the presence of Ni catalyst transformed the EBIC deposit into nc-graphene patterns, confirmed using Raman and TEM analysis. The nc-graphene patterns have been employed as an active p-type channel material in a field effect transistor (FET) which showed a hole mobility of ~90 cm(2) V(-1) s(-1). The nc-graphene also proved to be suitable material for IR detection.

Metal anion-alkyl ammonium complexes as direct write precursors to produce nanopatterns of metals, nitrides, oxides, sulfides, and alloys.

The study explores the possibility of using metal anions complexed with tetraoctylammonium bromide (ToABr) as single-source direct write precursors in e-beam and soft lithography processes to obtain micro- and nanoscale patterns of various metals, i.e., Au, Pd, Pt, Ag, Pb and Cu, as well as of their alloys (AuCu), oxides (Co(3)O(4), ZnO), nitrides (CoN, InN, GaN), and sulfides (Ag(2)S). The extraction efficiency of ToABr for different metal anions is found to be varied (40-90%), but the obtained precursors are easily processable as they have reasonable solubility in common solvents and are obtainable as smooth films, both being important for high-resolution patterning. The e-resist action of the precursors originates from the extreme e-beam sensitivity of the hydrocarbon chain present in ToABr, while direct micromolding has been possible due to easy flow of the precursor solutions in capillaries. The interaction of the anion and ToABr being mainly electrostatic enables easy removal of the hydrocarbon from patterned regions by thermolysis on a hot plate in the ambient or in controlled atmosphere to form the desired product. This method can be easily generalized.

Charge storage in mesoscopic graphitic islands fabricated using AFM bias lithography.

Electrochemical oxidation and etching of highly oriented pyrolytic graphite (HOPG) has been achieved using biased atomic force microscopy (AFM) lithography, allowing patterns of varying complexity to be written into the top layers of HOPG. The graphitic oxidation process and the trench geometry after writing were monitored using intermittent contact mode AFM. Electrostatic force microscopy reveals that the isolated mesoscopic islands formed during the AFM lithography process become positively charged, suggesting that they are laterally isolated from the surrounding HOPG substrate. The electrical transport studies of these laterally isolated finite-layer graphitic islands enable detailed characterization of electrical conduction along the c-direction and reveal an unexpected stability of the charged state. Utilizing conducting-atomic force microscopy, the measured I(V) characteristics revealed significant non-linearities. Micro-Raman studies confirm the presence of oxy functional groups formed during the lithography process.

CNT manipulation: inserting a carbonaceous dielectric layer beneath using electron beam induced deposition.

Electron beam induced carbonaceous deposition has been carried out in the presence of water vapor at 0.4 torr pressure amidst residual hydrocarbons present in the SEM chamber. When performed at a CNT location on a Si substrate with low e beam energy (10 kV), the deposition was taking place beneath the CNT. While higher beam energy (25 kV) causing the deposition on the top surface of the CNT, in agreement with the earlier reports. The insertion of dielectric carbonaceous layer beneath the CNT allowed us to measure the I-V data along the length of the nanotube using CAFM.

Direct micromolding of Pd micro-stripes for electronic applications.

A simple, one-step direct micromolding process has been realised to produce highly conducting Pd micro-stripes over large areas on various substrates including flexible polyimide. Under a PDMS micromold, Pd octanethiolate served as a precursor at 250 degrees C, a temperature at which the precursor gets neatly metallised. Thus produced micro-stripes are robust under bending and can be utilised for flexible electronics. Hydrogen sensing by Pd micro-stripes is demonstrated. By electrolessly depositing Cu on the stripes, they can be made to peel off to form free standing Cu-Pd micro-ribbons.

Femtoliter silver cups as surface enhanced Raman scattering active containers.

Femtoliter capacity Ag cups formed by the pulsed laser ablation of an Ag foil have been tried out as substrates for surface enhanced Raman scattering (SERS) measurements. The cups are formed as the impinging droplets from the laser plume undergo a flow pattern before freezing into cup-like structures, resulting in a surface roughness (approximately 35 nm) that makes them ideal for SERS studies. The internal volume of the cups is in the femtoliter (10(-15) l) range, well suited for small-scale reactions, particularly in biological studies. The cups exhibit enhancement factors of the order of 10(6) with the analyte molecule thiophenol. Individual cups have been dosed attoliter quantities (10(-18) l) of the analyte and detected.

Local anodic oxidation patterning of Au deposited Si surfaces.

Nanopatterning of Si(100) surfaces deposited with Au films from physical and chemical methods, has been carried out using a AFM set up mounted with a conducting tip. At a tip bias of -12 V, the LAO patterns drawn on various Au/SiOx surfaces have been compared with those on bare Si. The height of the oxide patterns is several times higher in the case of Au covered Si surfaces compared to patterns on bare Si surface. The enhancement in LAO is related to the catalytic activity of Au nanoparticulates at SiOx interface.

Electrical and hydrogen-sensing characteristics of field effect transistors based on nanorods of ZnO and WO2.72.

Top-gated field effect transistors (FETs) using Au-gap (5 microm) electrodes on glass substrate and SiO2/Si as gate have been fabricated with undoped and doped nanorods of ZnO as well as with WO2.72 nanorods as active semiconductor elements. The I-V characteristics at different gate voltages show that the nanorods are n-type semiconductors and the derived transfer characteristics show that the FET devices function in the depletion mode. Al-doping (3 at%) enhances the carrier mobility of ZnO nanorods to 128.6 cm2/V x s as against to 0.009 cm2/V x s estimated in the case of the undoped nanorods. Doping with Cd and Mg (3 at%) as well as N (approximately 1 at%) similarly increases the mobility although to a smaller extent. The Cd-doped ZnO nanorods exhibit the high sensitivity (defined as the ratio of the resistance in air to that in the hydrogen) (20) for 1000 ppm of hydrogen. Application of gate voltage decreases the recovery times of the nanorod sensors. FETs based on WO2.72 nanorods also show the depletion mode type characteristics and a carrier mobility of 8.38 cm2/V x s is obtained. The WO2.72 based FETs exhibit good sensitivity (approximately 10) for 1000 ppm hydrogen.

Surfactant-promoted formation of fractal and dendritic nanostructures of gold and silver at the organic-aqueous interface.

The effect of surfactants such as tetraoctylammoniumbromide (TOAB) and cetyltrimethylammoniumbromide (CTAB) on the type of nanostructures formed when gold ions present in the organic phase are reduced at the interface by hydrazine in the aqueous phase has been investigated. Extended fractal structures are formed at the liquid-liquid interface, the fractal structures themselves comprising cauliflower type units formed by gold nanorods. Accordingly, the nanostructures exhibit transverse and longitudinal plasmon adsorption bands in the 550 and 800 nm regions, respectively. Dendritic structures of silver are formed at the interface when Ag ions are reduced similarly in the presence of surfactants. The nanostructures consist of nanoparticles or nanorods with five-fold symmetry.

Gold nanostructuring on Si substrate by selective electroless deposition.

Gold deposition on Si(111) substrates has been carried out by electroless process from KAuCl4 in a fluorinated solution and the resulting nanostructures have been characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM). Deposition carried out under normal plating conditions produces an Au film with (111) orientation. The effect of additives such as poly(vinylpyrrolidone) (PVP) and mercaptoundecanoic acid (MUA) to the plating solution has been examined. While PVP induces amorphous deposition, MUA gives rise to flat (111) oriented islands. In order to produce individual nanostructures, we made use of octadecyltrichlorosilane (OTS) as a masking agent and carried out electroless deposition with an intermittent dip in OTS. By varying the durations of dip in the two solutions, various Au nanostructures-islands, cellular networks, and nanowires are obtained.

Dip-pen lithography using pens of different thicknesses.

A laboratory method to produce AFM tips of different sizes has been developed based on laser irradiation of the commercial silicon nitride tips. A few shots of 60 mJ at 355 nm were found adequate to induce the desired bluntness from 40 nm to 500 nm in a controlled way. Dip-pen nanolithography (DPN) has been performed with the blunt tips using a colloidal ink consisting of Pd nanocrystals coated with polyvinyl pyrrolidone. The line patterns drawn bear a direct relation with the tip morphology, wider the tip, broader are the patterns, in general. The rate of deposition also increases with the tip dimension, but is not as much proportional for larger tips. The study highlights the potential ability of DPN in integrating nano and microelectronics.

A hydrogen-bonded channel structure formed by a complex of uracil and melamine.

The structure of a 1:1 complex of uracil and melamine obtained by cocrystallization has been investigated. The structure involves hydrogen bonded layers with apertures stacked along the a and b directions giving rise to channels, unlike the complex of cyanuric acid with melamine.

Role of triple bond in 1,2-diphenylacetylene crystal: A combined experimental and theoretical study.

We have performed a combined experimental and theoretical study of the molecular system of 1,2-diphenylacetylene. The occurrence of two different geometries of the molecule in the crystal structure, one being planar and the other tilted by approximately 6 degrees , has been investigated in relation to the nature of the acetylenic linker. The experimental charge density analysis shows that the acetylenic linker exhibits a noncylindrical density reminiscent of the strong conjugation present in the molecule. The pi-orbitals of the acetylenic linker derived from density functional theory (DFT) calculations are found to sustain a variety of conjugation lengths between the phenyl rings, thereby giving flexibility to the molecule to arrange itself in various packing conformations in the crystal. It is interesting that the energy involved for such distortions is only kBT, allowing several polymorphic forms of the crystal structure as reported in the literature. The distortions entertained by the molecule and the corresponding changes in the charge density distribution and energy are all relevant to molecular electronics.

A facile method of producing femtoliter metal cups by pulsed laser ablation.

Cuplike structures of Au, Ag, Cu, Zn, Nb, Cd, Al, In, and Sn in the size range of 300 nm to a few micrometers with an internal volume of a few femtoliters have been produced by the laser ablation of metal targets in a vacuum, by optimizing, in each case, the laser fluence and the substrate temperature. The metal droplets impinging on the substrate seem to undergo a hydraulic jump driven by the surface tension forces before solidifying into cups. The cups are robust and can be functionalized with biomarkers, filled with nanoparticle sols, oxidized to crucibles, or detached from the substrate without causing any deformation. We envisage their potential applications as femtoliter metal containers.

Pyramidal nanostructures of zinc oxide.

Zinc oxide (ZnO) nanostructures have been prepared by pulsed laser deposition of the oxide onto Si(100) substrate at 600 degrees C. An examination of the morphology using atomic force microscopy and scanning electron microscopy reveals well formed pyramidal structures consistent with the growth habit of ZnO. A domain matched epitaxy across the interface makes the ZnO pyramids orient along the axes of Si(100) surface. The pyramidal nanostructures signify an intermediate state in the growth of hexagonal nanorods of ZnO. The hardness of the nanostructures as well as their response to oxygen gas have been investigated using nanoindentation and conducting probe methods respectively. ZnO nanostructures are much harder than their bulk. The hardness of ZnO pyramids obtained by nanoindentation is 70 +/- 10 GPa which is about one order more that of bulk ZnO. Besides, the nanostructures exhibit high sensitivity towards oxygen. A 70% increase in the resistance of ZnO nanostructures is observed when exposed to oxygen atmosphere.

Nature and properties of ultrathin nanocrystalline gold films formed at the organic-aqueous interface.

Ultrathin nanocrystalline films of gold formed at different temperatures at the organic-aqueous interface have been investigated by X-ray diffraction, electron microscopy, atomic force microscopy, and electronic spectroscopy. The films are smooth and continuous over relatively large length scales and are generally approximately 100 nm thick. The size of the nanocrystals is sensitive to the reaction temperature, which also determines whether the film is metallic or an activated conductor. The surface plasmon band of gold is highly red-shifted in the films. Alkanethiols perturb the structure of the films, with the magnitude of the effect depending on the chain length. Accordingly, the position of the plasmon band and the electrical resistance of the films are affected by interaction with alkanethiols; the plasmon band approaches that of isolated nanocrystals in the presence of long-chain thiols.

Gold-coated conducting-atomic force microscopy probes.

Some aspects of the performance of gold-coated conductive probes used in conducting atomic force microscopy (C-AFM) technique are discussed. The resistance of the nanocontact between the gold-coated AFM tip and the graphite substrate has been monitored at various applied forces. For small forces (<50 nN), resistance on the order of a few kiloohms was observed. Minimal contact resistance was observed for forces in the range 100-150 nN, beyond which the tip seems to undergo plastic deformation. The resistance of the nanocontact increased when current on the order of 100 microA was allowed to pass through, finally resulting in melting of the gold coating.