Rabibrata Mukherjee

Selective Molecular Sieving in Self‐Standing Porous Covalent‐Organic‐Framework Membranes

Self-standing, flexible, continuous, and crack-free covalent-organic-framework membranes (COMs) are fabricated via a simple, scalable, and highly cost-effective methodology. The COMs show long-term durability, recyclability, and retain their structural integrity in water, organic solvents, and mineral acids. COMs are successfully used in challenging separation applications and recovery of valuable active pharmaceutical ingredients from organic solvents.

Control of morphology in pattern directed dewetting of thin polymer films

We investigate the creation of large area mesoscale structures by controlling the dewetting pathways of thin polymer films on physically heterogeneous substrates comprising a two-dimensional (2-D) array of square pillars. Depending on the initial configuration and thickness of the film, dewetting produces a variety of both ordered and disordered structures. The substrate pattern strongly influences the dewetting pathways as well as the organization and size of the polymer structures. The key findings are: (i) the lateral confinement imposed by the substrate pattern can reduce the length-scale of the dewetted structure by one to two orders of magnitude as compared to dewetting on the same homogeneous substrate. (ii) When the polymer film is thin ( 40 nm), dewetting progresses by nucleation of large holes, uncorrelated to the substrate pattern. The dewetted pattern in this case forms on multiple length-scales consisting of ∼10 μm droplets resulting from the coalescence of the holes and small (<1 μm) droplets at the interstitial locations due to stick–slip of the retracting contact line.

Stability and Dewetting of Metal Nanoparticle Filled Thin Polymer Films: Control of Instability Length Scale and Dynamics

We investigate the influence of gold nanoparticle addition on the stability, dewetting, and pattern formation in ultrathin polymer-nanoparticle (NP) composite films by examining the length and time scales of instability, morphology, and dynamics of dewetting. For these 10-50 nm thick (h) polystyrene (PS) thin films containing uncapped gold nanoparticles (diameter approximately 3-4 nm), transitions from complete dewetting to arrested dewetting to absolute stability were observed depending on the concentration of the particles. Experiments show the existence of three distinct stability regimes: regime 1, complete dewetting leading to droplet formation for nanoparticle concentration of 2% (w/w) or below; regime 2, partial dewetting leading to formation of arrested holes for NP concentrations in the range of 3-6%; and regime 3, complete inhibition of dewetting for NP concentrations of 7% and above. Major results are (a) length scale of instability, where lambdaH approximately hn remains unchanged with NP concentration in regime 1 (n approximately 2) but increases in regime 2 with a change in the scaling relation (n approximately 3-3.5); (b) dynamics of instability and dewetting becomes progressively sluggish with an increase in the NP concentration; (c) there are distinct regimes of dewetting velocity at low NP concentrations; (d) force modulation AFM, as well as micro-Raman analysis, shows phase separation and aggregation of the gold nanoparticles within each dewetted polymer droplet leading to the formation of a metal core-polymer shell morphology. The polymer shell could be removed by washing in a selective solvent, thus exposing an array of bare gold nanoparticle aggregates.

Chemically Delaminated Free-Standing Ultrathin Covalent Organic Nanosheets

Covalent organic nanosheets (CONs) are a new class of porous thin two-dimensional (2D) nanostructures that can be easily designed and functionalized and could be useful for separation applications. Poor dispersion, layer restacking, and difficult postsynthetic modifications are the major hurdles that need to be overcome to fabricate scalable CON thin films. Herein, we present a unique approach for the chemical exfoliation of an anthracene-based covalent organic framework (COF) to N-hexylmaleimide-functionalized CONs, to yield centimeter-sized free-standing thin films through layer-by-layer CON assembly at the air-water interface. The thin-layer fabrication technique presented here is simple, scalable, and does not require any surfactants or stabilizing agents.

Influence of substrate wettability on the morphology of thin polymer films spin-coated on topographically patterned substrates.

We show that the morphology of a thin polymer film spin coated directly on to a topographically patterned substrate is strongly influenced by the wettability of the substrate, in addition to other well-known parameters such as concentration of the polymer solution (c(n)), spin speed (RPM), and spin duration. Similar to spin coating on a flat surface, (1, 2) on a topographically patterned substrate as well, a continuous film forms only above a critical polymer solution concentration (c(t)*), for a specific RPM and dispensed drop volume. It is believed that for c(n) > c(t)*, the resulting continuous film on a topographically patterned substrate has an undulating top surface, where the surface undulations are in phase with the underlying substrate patterns. (3) On the basis of experiments involving spin coating of polymer thin films on topographically patterned grating substrates, we show that the surface undulations on the film are in phase with the substrate patterns only when the substrate is completely wetted (CW) by the solvent. In contrast, when the substrate is partially wetted (PW) by the solvent, then the undulations are 180° out of phase with respect to the substrate patterns. We further show that for c(n) < c(t)*, a variety of ordered and disordered structures, like array of aligned droplets, isolated strips of polymers, etc., result on both CW and PW substrates, depending on c(n).

Selective Molecular Separation by Interfacially Crystallized Covalent Organic Framework Thin Films

Exponential interest in the field of covalent organic frameworks (COFs) stems from the direct correlation between their modular design principle and various interesting properties. However, existing synthetic approaches to realize this goal mainly result in insoluble and unprocessable powders, which severely restrict their widespread applicability. Therefore, developing a methodology for easy fabrication of these materials remains an alluring goal and a much desired objective. Herein, we have demonstrated a bottom-up interfacial crystallization strategy to fabricate these microcrystalline powders as large-scale thin films under ambient conditions. This unique design principle exploits liquid-liquid interface as a platform, allowing simultaneous control over crystallization and morphology of the framework structure. The thin films are grown without any support in free-standing form and can be transferred onto any desirable substrate. The porous (with Tp-Bpy showing highest SBET of 1 151 m2 g-1) and crystalline thin films, having high chemical as well as thermal stability, also hold the merit to tune the thickness as low as sub-100 nm. These nanostructured thin COF films demonstrate remarkable solvent-permeance and solute-rejection performance. A prominent instance is the Tp-Bpy thin film, which displays an unprecedented acetonitrile permeance of 339 L m-2 h-1 bar-1.

Tunable hydrodynamic characteristics in microchannels with biomimetic superhydrophobic (lotus leaf replica) walls.

The present work comprehensively addresses the hydrodynamic characteristics through microchannels with lotus leaf replica (exhibiting low adhesion and superhydrophobic properties) walls. The lotus leaf replica is fabricated following an efficient, two-step, soft-molding process and is then integrated with rectangular microchannels. The inherent biomimetic, superhydrophobic surface-liquid interfacial hydrodynamics, and the consequential bulk flow characteristics, are critically analyzed by the micro-particle image velocimetry technique. It is observed that the lotus leaf replica mediated microscale hydrodynamics comprise of two distinct flow regimes even within the low Reynolds number paradigm, unlike the commonly perceived solely apparent slip-stick dominated flows over superhydrophobic surfaces. While the first flow regime is characterized by an apparent slip-stick flow culminating in an enhanced bulk throughput rate, the second flow regime exhibits a complete breakdown of the aforementioned laminar and uni-axial flow model, leading to a predominantly no-slip flow. Interestingly, the critical flow condition dictating the transition between the two hydrodynamic regimes is intrinsically dependent on the micro-confinement effect. In this regard, an energetically consistent theoretical model is also proposed to predict the alterations in the critical flow condition with varying microchannel configurations, by addressing the underlying biomimetic surface-liquid interfacial conditions. Hence, the present research endeavour provides a new design-guiding paradigm for developing multi-functional microfluidic devices involving biomimetic, superhydrophobic surfaces, by judicious exploitation of the tunable hydrodynamic characteristics in the two regimes.

Ordered alternating binary polymer nanodroplet array by sequential spin dewetting.

We report a facile technique for fabricating an ordered array of nearly equal-sized mesoscale polymer droplets of two constituent polymers (polystyrene, PS and poly(methyl methacrylate), PMMA) arranged in an alternating manner on a topographically patterned substrate. The self-organized array of binary polymers is realized by sequential spin dewetting. First, a dilute solution of PMMA is spin-dewetted on a patterned substrate, resulting in an array of isolated PMMA droplets arranged along the substrate grooves due to self-organization during spin coating itself. The sample is then silanized with octadecyltrichlorosilane (OTS), and subsequently, a dilute solution of PS is spin-coated on to it, which also undergoes spin dewetting. The spin-dewetted PS drops having a size nearly equal to the pre-existing PMMA droplets position themselves between two adjacent PMMA drops under appropriate conditions, forming an alternating binary polymer droplet array. The alternating array formation takes place for a narrow range of solution concentration for both the polymers and depends on the geometry of the substrate. The size of the droplets depends on the extent of confinement, and droplets as small as 100 nm can be obtained by this method, on a suitable template. The findings open up the possibility of creating novel surfaces having ordered multimaterial domains with a potential multifunctional capability.

Creating self-organized submicrometer contact instability patterns in soft elastic bilayers with a topographically patterned stamp.

The surface of a thin elastic bilayer becomes spontaneously unstable when it is brought in proximity to another rigid contactor. The instability patterns, which are random and isotropic, exhibit a dominant lateral length scale of instability λ, which linearly scales with the bilayer thickness (h) as: λ = R(F)h. It is known that for an elastic bilayer, R(F) exhibits a nonlinear dependence on the ratios of individual film thicknesses (H) and shear moduli (M) of the two constituent layers, and can have values as low as 0.5 under specific conditions. This is in contrast to a near constant value of R(F) ≈ 3 for a single layer elastic film. (1) These isotropic contact instability patterns in a bilayer can be ordered, aligned and modulated using a topographically patterned stamp. The precise morphology of the aligned structures depends on commensuration between λ and the stamp periodicity (λ(P)), and on the intersurface separation distance. A variety of patterns, like an array of circular holes, double periodic channels, etc., in addition to a positive and a negative replica of the stamp pattern, can be engineered with a simple stamp having 1D grating structure. A lower value of R(F) in a bilayer allows generating patterns with sub 500 nm lateral resolution, which is impossible to create by elastic contact lithography (ECL) of a single layer film due to strong surface tension effects in ultrathin films. Thus, control of elastic instability in a bilayer with a patterned stamp represents a flexible soft lithography tool allowing modulation of length scales, morphology, and order.

Ordered to Isotropic Morphology Transition in Pattern-Directed Dewetting of Polymer Thin Films on Substrates with Different Feature Heights

Controlled dewetting of a thin polymer film on a topographically patterned substrate is an interesting approach for aligning isotropic dewetted structures. In this article, we investigate the influence of substrate feature height (H(S)) on the dewetting pathway and final pattern morphology by studying the dewetting of polystyrene (PS) thin films on grating substrates with identical periodicity (λ(P) = 1.5 μm), but H(S) varying between 10 nm and 120 nm. We identify four distinct categories of final dewetted morphology, with different extent of ordering: (1) array of aligned droplets (H(S) ≈ 120 nm); (2) aligned undulating ribbons (H(S) ≈ 70-100 nm); (3) multilength scale structures with coexisting large droplets uncorrelated to the substrate and smaller droplets/ribbons aligned along the stripes (H(S) ≈ 40-60 nm); and (4) large droplets completely uncorrelated to the substrate (H(S) < 25 nm). The distinct morphologies across the categories are attributed to two major factors: (a) whether the as-cast film is continuous (H(S)≤ 80 nm) or discontinuous (H(S)≥ 100 nm) and (b) in case of a continuous film, whether the film ruptures along each substrate stripe (H(S)≥ 70 nm) or with nucleation of random holes that are not correlated to the substrate features (H(S)≤ 60 nm). While the ranges of H(S) values indicated in the parentheses are valid for PS films with an equivalent thickness (h(E)) ≈ 50.3 nm on a flat substrate, a change in h(E) merely alters the cut-off values of H(S), as the final dewetted morphologies and transition across categories remain generically unaltered. We finally show that the structures obtained by dewetting on different H(S) substrates exhibits different levels of hydrophobicity because of combined spatial variation of chemical and topographic contrast along the surface. Thus, the work reported in this article can find potential application in fabricating surfaces with controlled wettability.