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.
Roll and spray coating methods have been employed for the fabrication of highly oxidation resistant transparent and conducting electrodes (TCEs) by a simple solution process using crackle lithography ...technique. We have spray-coated a crackle paint-based precursor to produce highly interconnected crackle network on PET roll mounted on a roll coater with web speed of 0.6 m/min. Ag TCE with a transmittance of 78% and sheet resistance of ∼20 Ω/□ was derived by spraying Ag precursor ink over the crackle template followed by lift-off and annealing under ambient conditions. The Ag wire mesh was stable toward bending and sonication tests but prone to oxidation in air. When electrolessly coated with Pd, its robustness toward harsh oxidation conditions was enhanced. A low-cost transparent electrode has also been realized by using only small amounts of Ag as seed layer and growing Cu wire mesh by electroless method. Thus, made Ag/Cu meshes are found to be highly stable for more than a year even under ambient atmosphere.
Palladium hexadecylthiolate is shown to serve as a negative-tone direct-write electron resist to produce nanopatterns down to 30 nm. The written patterns do not deviate much from the precursor in ...composition, while a post-treatment at 230 °C in air produced metallic Pd nanowires with residual carbon less than 10% and resistivity close to the bulk value, a desirable property of interconnects in nanocircuitry. The as-written patterns contain small nanocrystals (<5 nm) in a hydrocarbon matrix, which upon annealing aggregate to form well-connected networks of larger nanocrystals (5–15 nm), thus giving rise to metallic conductivity.
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 (Co3O4, ZnO), nitrides (CoN, InN, GaN), and sulfides (Ag2S). 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.
Flexible resistive strain sensors have been fabricated by micromolding Pd alkanethiolate on polyimide substrates and subjecting to thermolysis in air. Thus produced stripes were ∼1 μm wide with ...spacing of ∼0.5 μm and contained Pd nanoparticles in carbon matrix. The nanoparticle size and the nature of carbon are much dependent on the thermolysis temperature as is also the resistance of the microstripes. Generally, lower thermolysis temperatures (<230 °C) produced stripes containing small Pd nanoparticles with significant fraction of carbon from the precursor decomposition. The stripes were poorly conducting yet interestingly, exhibited change of resistance under tensile and compressive strain. Particularly noteworthy are the stripes produced from 195 °C thermolysis, which showed a high gauge factor of ∼390 with strain sensitivity, 0.09%. With molding at 230 °C, the stripes obtained were highly conducting, and amazingly did not change the resistance with strain even after several bending cycles. The latter are ideal as flexible conduits and interconnects. Thus, the article reports a method of producing flexible sensitive strain sensors on one hand and on the other, flexible conduits with unchanging resistance, merely by fine-tuning the precursor decomposition under the molding conditions.
Metal nanowire patterning in the form of grating structures has been carried out using a wide range of lithography techniques, and many hybrid methods derived from them. The challenge is to achieve ...sub-100 nm linewidths with controllable spacing and thickness over large areas of substrates with high throughput. In particular, the patterns with linewidth and spacing of a few tens of nm offer properties of great interest in optoelectronics and plasmonics. Crossbar grating structures-two gratings patterned perpendicular to each other-will play an important role as ultra-high density electrode grids in memristive devices for non-volatile memory.
Metal nanowire grating patterns (MNGPs) produced by various lithography methods find diverse applications, as highlighted in this minireview.
Four new iron(III) complexes of the bis(phenolate) ligands N,N-dimethyl-N‘,N‘-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine H2(L1), N,N-dimethyl-N‘,N‘-bis(2-hydroxy-4-nitrobenzyl)ethylenediamine ...H2(L2), N,N‘-dimethyl-N,N‘-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine H2(L3), and N,N‘-dimethyl-N,N‘-bis(2-hydroxy-4-nitrobenzyl)ethylenediamine H2(L4) have been isolated and studied as structural and functional models for the intradiol-cleaving catechol 1,2-dioxygenases (CTD). The complexes Fe(L1)Cl (1), Fe(L2)(H2O)Cl (2), Fe(L3)Cl (3), and Fe(L4)(H2O)Cl (4) have been characterized using absorption spectral and electrochemical techniques. The single-crystal X-ray structures of the ligand H2(L1) and the complexes 1 and 2 have been successfully determined. The tripodal ligand H2(L1) containing a N2O2 donor set represents the metal-binding region of the iron proteins. Complex 1 contains an FeN2O2Cl chromophore with a novel trigonal bipyramidal coordination geometry. While two phenolate oxygens and an amine nitrogen constitute the trigonal plane, the other amine nitrogen and chloride ion are located in the axial positions. In contrast, 2 exhibits a rhombically distorted octahedral coordination geometry for the FeN2O3Cl chromophore. Two phenolate oxygen atoms, an amine nitrogen atom, and a water molecule are located on the corners of a square plane with the axial positions being occupied by the other nitrogen atom and chloride ion. The interaction of the complexes with a few monodentate bases and phenolates and differently substituted catechols have been investigated using absorption spectral and electrochemical methods. The effect of substituents on the phenolate rings on the electronic spectral features and FeIII/FeII redox potentials of the complexes are discussed. The interaction of the complexes with catecholate anions reveals changes in the phenolate to iron(III) charge-transfer band and also the appearance of a low-energy catecholate to iron(III) charge-transfer band similar to catechol dioxygenase−substrate complexes. The redox behavior of the 1:1 adducts of the complexes with 3,5-di-tert-butylcatechol (H2DBC) has been also studied. The reactivities of the present complexes with H2DBC have been studied and illustrated. Interestingly, only 2 and 4 catalyze the intradiol-cleavage of H2DBC, the rate of oxygenation being much faster for 4. Also 2, but not 4, yields an extradiol cleavage product. The reactivity of the complexes could be illustrated not on the basis of the Lewis acidity of the complexes alone but by assuming that the product release is the rate-determining phase of the catalytic reaction.
Electron beam-induced carbonaceous deposition (EBICD) derived from residual hydrocarbons in the vacuum chamber has many fascinating properties. It is known to be chemically complex but robust, ...structurally amorphous, and electrically insulating. The present study is an attempt to gain more insight into its chemical and electrical nature based on detailed measurements such as Raman, XPS, TEM, and electrical. Interestingly, EBIC patterns are found to be blue fluorescent when excited with UV radiation, a property which owes much to sp2 carbon clusters amidst sp3 matrix. Temperature-dependent Raman and electrical measurements have confirmed the graphitization of the EBICD through the decomposition of functional groups above 300 °C. Finally, graphitized EBIC patterns have been employed as active p-type channel material in the field-effect transistors to obtain mobilities in the range of 0.2–4 cm2/V s.
By the reaction of the appropriate organometallic precursors and tetrakishydroxymethyl phosphonium chloride (THPC) at the toluene−water interface, we have prepared nanocrystalline films of Au−Ag and ...Au−Cu alloys with a range of compositions. The films have been characterized by X-ray diffraction, electron microscopy, optical spectroscopy, and other techniques, besides compositional analysis. The particle size of the nanocrystals in the films varies with the composition. The surface plasmon band of the alloy films as well as of the organosols obtained by the disintegration of the films by the addition of an alkanethiol show the expected composition dependence. It has been possible to prepare the nanocrystalline films of a ternary Au−Ag−Cu alloy.
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.
Fractal and dendritic nanostructures of gold and silver are formed at the liquid–liquid interface in the presence of surfactants.
