Interfacial Electron Beam Lithography Converts an Insulating Organic Monolayer to a Patterned Single-Layer Conductor with Puzzling Charge Transport Performance.

The direct generation of conducting paths within an insulating surface represents a conceptually unexplored approach to single-layer electrical conduction that opens vistas for exciting research and applications fundamentally different from those based on specific layered materials. Herein we report surface channels with single-layer -COOH functionality patterned on insulating n-octadecyltrichlorosilane monolayers on silicon that exhibit unusual ionic-electronic conduction when equipped with ion-releasing silver electrodes. The strong dependence of charge transport in such channels on their lateral dimensions (nanosize, macro-size), the type (p, n) and resistivity (doping level) of the underlying silicon substrate, the nature of the insulating spacer layer between the conducting channel and the silicon surface, and the postpatterning chemical manipulation of channel's -COOH functionality allows designing channels with variable resistivities, ranging from that of a practical insulator to some unexpectedly low values. The unusually low resistivities displayed by channels with nanometric widths and micrometer-millimeter lengths are attributed primarily to enhanced electronic transport within ultrathin nanowire-like silver metal films formed along their conductive paths. Function-structure correlations derived from a comprehensive analysis of electrical, atomic force microscopy, and Fourier transform infrared spectral data suggest an unconventional mode of conduction in these channels, which has yet to be elucidated, apparently involving coupled ionic-electronic transport mediated and enhanced by interfacial electrical interactions with charge carriers located outside the conducting channel and separated from those carrying the measured current. These intriguing findings hint at effects akin to Coulomb pairing in the proposed mechanisms of excitonic superconductivity in interfacial nanosystems structurally related to the present metalized surface channels.

Self-assembly of water-filled molecular saddles to generate diverse morphologies and high proton conductivity.

The design of single-component organic compounds acting as efficient solid-state proton conduction (SSPC) materials has been gaining significant traction in recent times. Molecular design and controlled self-assembly are critical components in achieving highly efficient SSPC. In this work, we report the design, synthesis, and self-assembly of an organic macrocyclic aza-crown-type compound, P2Mac, which complements synthetic ease with efficient SSPC. P2Mac is derived from the pyridine-2,6-dicarboxamide (PDC) framework and contains polar amide and amine residues in its inner region, while aromatic residues occupy the periphery of the macrocycle. The crystal structure analysis revealed that P2Mac adopts a saddle-shaped geometry. Each P2Mac molecule interacts with one water molecule that is present in its central polar cavity, stabilized by a network of five hydrogen bonds. We could self-assemble P2Mac in a variety of unique, aesthetically pleasing morphologies such as micron-sized octahedra, hexapods, as well as hollow nanoparticles, and microrods. The water-filled polar channels formed through the stacking of P2Mac allow attaining a high proton conductivity value of 21.1 mS cm-1 at 27 °C under a relative humidity (RH) of 95% in the single crystals of P2Mac, while the as-prepared P2Mac pellet sample exhibited about three-orders of magnitude lower conduction under these conditions. The low activation energy of 0.39 eV, calculated from the Arrhenius plot, indicates the presence of the Grotthus proton hopping mechanism in the transport process. This report highlights the pivotal role of molecular design and self-assembly in creating high-performance SSPC organic materials.

Microfluidics based bioimaging with cost-efficient fabrication of multi-level micrometer-sized trenches.

Microfluidic devices, through their vast applicability as tools for miniaturized experimental setups, have become indispensable for cutting edge research and diagnostics. However, the high operational cost and the requirement of sophisticated equipment and clean room facility for the fabrication of these devices make their use unfeasible for many research laboratories in resource limited settings. Therefore, with the aim of increasing accessibility, in this article, we report a novel, cost-effective micro-fabrication technique for fabricating multi-layer microfluidic devices using only common wet-lab facilities, thereby significantly lowering the cost. Our proposed process-flow-design eliminates the need for a mastermold, does not require any sophisticated lithography tools, and can be executed successfully outside a clean room. In this work, we also optimized the critical steps (such as spin coating and wet etching) of our fabrication process and validated the process flow and the device by trapping and imaging Caenorhabditis elegans. The fabricated devices are effective in conducting lifetime assays and flushing out larvae, which are, in general, manually picked from Petri dishes or separated using sieves. Our technique is not only cost effective but also scalable, as it can be used to fabricate devices with multiple layers of confinements ranging from 0.6 to more than 50 µm, thus enabling the study of unicellular and multicellular organisms. This technique, therefore, has the potential to be adopted widely by many research laboratories for a variety of applications.

Bioinspired Design of an Uncharged Ambipolar Helical Scaffold To Achieve Efficient Solid-State Proton Conduction.

This work demonstrates highly efficient solid-state proton conduction in helical organic scaffolds inspired by the biomolecule gramicidin A. The scaffold, 1, derived from a pyridine-2,6-dicarboxamide (PDC) residue adopts a helical conformation that is stabilized by a network of strong bifurcated intramolecular H-bonds between the polar residues that align the inner (concave) face of the molecule, while the aromatic units in 1 are oriented outwards. As a result, the helix attains an ambipolar nature just like gramicidin A. Two different solid forms of 1 could be isolated: a yellow solid from high-polarity solvents and an orange solid from low-polarity solvents. Single-crystal X-ray diffraction (SCXRD) studies showed that in the former, molecules of 1 are stacked in a homochiral fashion, while in the latter heterochiral stacks of 1 were present. The yellow form exhibited an almost ∼300-fold higher conductivity (of up to 0.12 mS cm-1 at 95 °C and 95 % relative humidity) than the orange form as a result of closer intermolecular proximity and lower activation energy of 0.098 eV, thus indicating a Grotthus mechanism of proton transport. This study establishes the key role of bioinspired design and controlled stereo-organization of such discrete uncharged organic molecules in achieving efficient solid-state proton conduction.

Humidity- tunable liquefaction of Cr thin-film and its application to patterning.

Electric field induced liquefaction of chromium (Cr) thin-films, being a surface-based process, is affected by the moisture content in the surroundings. The said process is an electrochemical reaction, which takes place on an electrically stressed Cr thin-film. The reaction results in a liquid region, which appears to flow out radially from the tip of the cathode. A proper understanding of the phenomenon is warranted as it is applied for performing a nanolithography process, electrolithography (ELG). In this study we have focused on the effect of relative humidity (RH) on the material formation and transport on electrically stressed Cr thin-film. Varying the RH over a wide range, the phenomenon is studied using different levels of DC stress. The effect of the applied DC stress coupled with varying levels of RH showed trends which are explained qualitatively and quantitatively. The results indicate that RH could be a pivotal parameter affecting the above-mentioned phenomenon on electrically stressed Cr thin-films and could significantly alter the minimum feature size attainable by ELG. To demonstrate the effect of RH on ELG, lines are drawn at various humidity levels resulting in greater than 100% increase in the attainable line width when RH is increased by about 40%.

Manipulating liquid metal flow for creating standalone structures with micro-and nano-scale features in a single step.

Standalone structures with periodic surface undulations or ripples can be spontaneously created upon flowing a liquid metal, e.g. Ga, over a metallic film, e.g. Pt, Au, etc, through a complex 'wetting-reaction'-driven process. Due to the ability of 3-dimensional patterning at the small length scale in a single step, the liquid metal 'ripple' flow is a promising non-conventional patterning technique. Herein, we examine the effect of a few process parameters, such as distance away from the liquid reservoir, size of the liquid reservoir, and the geometry, thickness, and width of substrate metal film, on the nature of the ripple flow to produce finer patterns with feature sizes of ≤ 2µm. The height and the pitch of the pattern decrease with distance from the liquid reservoir and decrease in the reservoir volume. Furthermore, a decrease in the thickness and width of the substrate film also leads to a decrease in the height and pitch of the ripples. Finally, the application of an external electric field also controls the ripple patterns. By optimizing various parameters, standalone ripple structures of Ga with the height and pitch of ≤ 500 nm are created. As potential applications, the ripple patterns with micro-and nano-scopic features are demonstrated to produce a diffraction grating and a die for micro-stamping.

Spontaneous Formation of Structures with Micro- and Nano-Scopic Periodic Ripple Patterns.

We report the first study on the formation of structures with micro- and nano-scopic periodic surface patterns created by the spontaneous flow of liquid metal over thin metallic solid films. Minute details of the flow of liquid gallium over gold are captured in situ at very high magnifications using a scanning electron microscope, and a series of experiments and microstructural characterization are performed to understand the underlying principles of the liquid flow and the pattern formation. This phenomenon is solely driven by wetting, with little influence of gravity, and is aided by a tenacious semi-solidus envelope of the intermetallic compound formed due to the reaction between the liquid metal and the metallic substrate. This complex flow creates highly periodic patterns with features ranging from hundreds of nanometers to tens of micrometers, which can be tuned a priori. We propose a model capturing the essential mechanics of the ripple formation and apply it to simulate the formation of a single ripple, along with its essential asymmetry, that forms the basis for generating the observed patterns.

Kinematics and kinetics of alternating electric field induced liquid mass transport on chromium thin films.

Long range mass transport driven by an electric field has many applications in the fields of nanoscience and technology. Liquid-phase mass transport ranging from the micrometer to the millimeter scale and its application to nanopatterning have been demonstrated on chromium (Cr) thin films using a DC electric field. Under the influence of an electric field, the metal seems to undergo a chemical reaction, and the resulting liquid material flows out radially in all directions. In this study, we have explored the effect of an alternating (AC) electric field on this kind of liquid-phase material transport. Within the scope of this work, mass transport has been studied on Cr films 30 nm thick using an alternating square waveform with frequencies ranging from 100 Hz to 1000 Hz in steps of 50 Hz. The dependence of the material's formation, flow distance, and flow velocity on frequency, for a constant applied root mean square (RMS) voltage, was studied in detail. An analytical model is presented to explain the experimental results. This study, in particular the frequency parameter and the intermittent nature of the applied bias, will help us get a better control over the mass flow process, will lead to better resolutions for the electrolithography process.

Electrolithography--A New and Versatile Process for Nano Patterning.

We report a new lithography technique based on electromigration driven material transport for drawing patterns at nanometer scales in ambient conditions. We use a thin metal film as a masking layer and a polymer layer beneath it as a pattern transfer layer. The desired pattern is drawn in the metal layer by etching the metal with a conducting scanning probe assisted by liquid electromigration. The pattern drawn on the metal layer is transferred to the polymer layer by etching the polymer with an appropriate solvent. Subsequently, the pattern is transferred to the desired material layer using a film deposition technique followed by conventional lift-off process. Using this simple technique, we have achieved pattern resolutions of 9 nm on the polymer and 40 nm on transferring the pattern to another material. Based on the ease of use and process costs, this technique promises to be competitive to e-beam lithography that employs high energy and ultra-high vacuum, or the industrial standard ultra-violet light photolithography that employs extremely expensive implements to reach nano-scale resolutions. We also demonstrate direct mask writing using this technique and explain the fundamentals behind the workings of the developed method.