Contact line motion in dewetted polymer droplets on anisotropic nanopatterned surfaces.

Thin polymer films can become unstable and dewet on a non-wettable substrate leading to the formation of an array of droplets. This instability-mediated drop formation lacks spatial order on flat substrates, but it can be ordered for better combinatorial studies using patterned substrates. In this work, we studied the process of dewetting polystyrene (PS) films on grating patterned substrates upon solvent vapor exposure. The PS film thickness was commensurate with the grating pattern height (hP). Our findings show that the initial dewetting stages follow the direction of the underlying grating pattern with the formation of directional holes in the film. During the later stages of dewetting, there was a lateral coalescence of polymer threads across the grating stripes. The final morphology comprised smaller droplets or threads confined within the pattern grooves and anisotropic large drops covering several pattern stripes. Furthermore, the larger drops show a unique behavior of shape change from anisotropic to isotropic as a function of solvent vapor concentration (Cn) inside the dewetting chamber. The drop regained its anisotropic shape with an increase in Cn, and this transition continued, with the movement of the three-phase contact line (TPCL). While the capillary flow of the polymer causes anisotropy during high Cn, the local orientation of the contact line and a mismatch in the value of the equilibrium contact angle can drive the drop back into an isotropic shape as Cn reduces and capillary forces weaken. We also observed that the extent of anisotropy quantified as droplet distortion ratio (Dr) not only depends on the Cn during dewetting but also on solvent type and hP. This new-found dynamic behavior of dewetted polymeric drops can be studied in greater detail and potentially leveraged for applications in sensing and microfluidics.

Durability studies of underwater superoleophobic graphene oxide coated wire mesh.

Due to the increased industrial oily wastewater, developing a successful oil/water separation mechanism is a ubiquitous challenge. As oil/water separation is an interfacial phenomenon, a straightforward way is to utilize the special wettability of novel materials towards oil and water. In this work, we intend to construct a durable membrane/mesh that can have a selective response towards oil and water based on the difference in surface tension. Graphene oxide (GO) is one such material that exhibits in-air hydrophilicity and underwater superoleophobicity. GO-coated wire meshes can act as membranes with excellent efficiency for oil/water separation, but they lack long-term durability for repeated use under different environments. We created GO*-coated wire meshes by dip coating multiple layers of GO with intermediate air plasma treatment. While the multiple steps of coating ensured complete coverage of the mesh with GO, plasma treatment improved the binding of the GO coating to the wire mesh. After coating five GO layers, the mesh is subjected to mild plasma treatment to improve the porosity. The GO*-coated mesh is extremely hydrophilic in air, and the underwater oil contact angles (CA) are ≥125° for different oils. To test the long-term durability, the GO*-coated mesh is continuously immersed underwater in acidic and basic media, and the underwater oil CA is measured at different immersion times. The initial durability results are very promising and show that the GO*-coated mesh retains a significant level of underwater oleophobicity even after 60 days of continuous immersion in water.

Spin coating mediated morphology modulation in self assembly of peptides.

Controlling the morphology and nanostructure of self-assembled peptide molecules is of fundamental importance to chemistry and material science due to their bioactivity in both in vivo and in vitro settings, ability to act as templates for conjugating bio-recognition elements, hybrid supramolecular assembly, possible detection and treatment of diseases and so on. In this article, we show that spin coating, a widely utilized method for obtaining ultra-thin polymer films, has been utilised to modulate the self-assembly of peptide molecules, which has traditionally been achieved by chemical functionalisation of the molecules. With the specific example of diphenylalanine-based peptide molecules, we show that a variety of self-assembled architectures such as long fibrils, short fibrils, globules, nanodots, and so on, spanning over large areas can be obtained by simultaneously varying the spinning speed (RPM) and the solution concentration (Cp) during spin coating. We correlate the variation in morphology to a transition from spin dewetting at very low Cp (or high RPM) to the formation of continuous films at high Cp (or low RPM) during the initial stage of spin coating. We further show the generality of the approach by achieving distinct self-assembled morphologies with diphenylalanine analogues with different C-terminal and N-terminal groups by modulation of spin coating parameters, though the exact morphology obtained under identical coating conditions depends on the chemical nature of the peptide molecules. The work opens up a new possible route for creating complex peptide assemblies on demand by simultaneous control of molecular functionalisation and spin coating parameters vis - a - vis the applied centrifugal force.

High Temperature Durability of Oleoplaned Slippery Copper Surfaces.

Slippery surfaces, inspired by the functionality of trapping interfaces of specialized leaves of pitcher plants, have been widely used in self-cleaning, anti-icing, antifrost, and self-healing surfaces. They can be fabricated on metallic surfaces as well, presenting a more durable and low-maintenance anticorrosive surface on metals. However, the lack of studies on the durability of these slippery surfaces at high temperature prohibits their practical deployment in real industrial applications where thermal effects are critical and high temperature conditions are inevitable. We present here a unique fabrication technique of a copper-based oleoplaned slippery surface that has been tested for high temperature durability under repeated thermal cycles. Their slipperiness at high temperatures has also been tested in the absence of the Leidenfrost effect. Our findings suggest that these new substrates can be used for fabricating low maintenance surfaces for high temperature applications or even where the surface undergoes repeated thermal cycles like heat exchanger pipes, utensils, engine casings, and outdoor metallic structures.

Durability of submerged hydrophobic surfaces.

Hydrophobic and superhydrophobic surfaces have gained wide popularity due to their potential in various areas such as in self-cleaning and anti-fouling materials, drag reduction and microfluidics. However, for all practical applications, the long term durability of these surfaces is extremely important, yet not often investigated. Of particular interest is the long term durability of soft hydrophobic surfaces that remain submerged underwater for a prolonged duration. In this article, we explore how the chemical durability of flat and patterned crosslinked PDMS surfaces (polydimethylsiloxane, a preferred material for microfabrication) change as a function of time when submerged in acidic, basic and neutral media for different durations over a prolonged period of time. Based on contact angle measurements, atomic force microscopy, confocal microscopy and SEM analysis of the surfaces, we checked if there is any change in the morphology of the surface due to deposition or etching. We created a biomimetic positive replica of a lotus leaf that exhibited super-hydrophobicity and Cassie state of wetting with a static water contact angle (θ) > 150°, and compared the degradation with a negative replica of lotus leaf (θ ∼ 127°), a grating patterned surface that exhibited Wenzel state of wetting (θ ∼ 110°) and a flat crosslinked PDMS surface (θ ∼ 105°). The positive replica maintained reasonable hydrophobicity (θ > 90°) for up to a month, but lost its super-hydrophobic property. The surface hydrophobicity degraded the most in the case of basic solution due to deposition.

Reversible morphological switching and deformation hysteresis in electric field mediated instability of thin elastic films.

Reversible morphology switching in a soft elastic film sandwiched between two parallel electrodes when subject to an externally applied electric field is reported herein. In contrast to electric field mediated instability of a thin liquid film, where the instability patterns remain permanent, in the present case the patterns debond completely or partially when the electric field is switched off, depending on whether the gap spacing (dG) between the film and the top electrode is >100 nm or not. The onset of instability is marked with the appearance of isotropic columns when the applied field strength (U) exceeds a critical value (Uc). The subsequent increase in U leads to the gradual transition of the instability patterns from pillars to bi-continuous labyrinths to an array of holes. Complete conformal contact is established between the film and the top electrode at U = UF. When U is reduced, the morphology changes in a reverse sequence. There is a significant level of hysteresis between the bonding and debonding stages, including persistence of the features at much lower voltages due to pinning of the patterns to the top electrode. Complete detachment occurs at a lower voltage UD when dG > 100 nm. The holes fluctuate before complete contact between the film and the top electrode due to competition between the destabilizing electric field and restoring forces due to stretching of the crosslinked polymer matrix.

Enhanced performance of hybrid self-biased heterojunction photodetector on soft-lithographically patterned organic platform.

Nanopatterning of the active layer with feature size comparable to the wavelength of visible light is a popular strategy for improving the performance of optoelectronic devices, as these structures enhance the optical path length by light trapping due to combined contribution of multiple scattering, diffraction, and antireflection. Here, we report the fabrication of ZnO/CdS self-biased heterojunction photodetectors on soft lithographically patterned PEDOT:PSS layers with grating geometry. The present study combines the robustness of inorganic devices along with the convenience of easy patterning capability of an organic PEDOT:PSS layer. Patterns with two different line widths (L P = 350 nm, and Lp = 750 nm) have been used in this study to understand the influence of feature dimension on the device performance. We observe enhanced photoluminescence on patterned devices, in comparison to devices fabricated on flat PEDOT:PSS films, which is attributed to the increased interfacial area between the organic and inorganic layers. The spectral response [R( λ )] and specific detectivity [D * ( λ )] are found to be higher for the devices with Lp = 350 nm as compared to other devices due to enhanced absorption within the structures due to confinement of light, which also results in reduced reflectance in devices with Lp = 350 nm.

Transition from Spin Dewetting to continuous film in spin coating of Liquid Crystal 5CB.

Spin dewetting refers to spontaneous rupture of the dispensed solution layer during spin coating, resulting in isolated but periodic, regular sized domains of the solute and is pre-dominant when the solute concentration (C n ) is very low. In this article we report how the morphology of liquid crystal (LC) 5CB thin films coated on flat and patterned PMMA substrate transform from spin dewetted droplets to continuous films with increase in C n . We further show that within the spin dewetted regime, with gradual increase in the solute concentration, periodicity of the isotropic droplets (λ D ) as well as their mean diameter (d D ), gradually decreases, till the film becomes continuous at a critical concentration (C n *). Interestingly, the trend that λ D reduces with increase in C n is exact opposite to what is observed in thermal/solvent vapor induced dewetting of a thin film. The spin dewetted droplets exhibit transient Radial texture, in contrast to Schlieren texture observed in elongated threads and continuous films of 5CB, which remains in the Nematic phase at room temperature. Finally we show that by casting the film on a grating patterned substrate it becomes possible to align the spin dewetted droplets along the contours substrate patterns.

Transfer printing of colloidal crystals based on UV mediated degradation of a polymer thin film.

A versatile colloidal transfer printing method that can be used to transfer any type of particles (polymeric/inorganic) to any type of surface (hydrophobic/hydrophilic; smooth/rough) is reported. The method relies on UV mediated degradation of a sacrificial thin film of polymethylmethacrylate (PMMA), and does not necessitate the use of a transfer medium or modification of the target substrate.

Capillary Force Lithography Pattern-Directed Self-Assembly (CFL-PDSA) of Phase-Separating Polymer Blend Thin Films.

We report capillary force lithography pattern-directed self-assembly (CFL-PDSA), a facile technique for patterning immiscible polymer blend films of polystyrene (PS)/poly(methyl methacrylate) (PMMA), resulting in a highly ordered phase-separated morphology. The pattern replication is achieved by capillary force lithography (CFL), by annealing the film beyond the glass transition temperature of both the constituent polymers, while confining it between a patterned cross-linked poly(dimethyl siloxane) (PDMS) stamp and the silicon substrate. As the pattern replication takes place because of rise of the polymer meniscus along the confining stamp walls, higher affinity of PMMA toward the oxide-coated silicon substrate and of PS toward cross-linked PDMS leads to well-controlled vertically patterned phase separation of the two constituent polymers during thermal annealing. Although a perfect negative replica of the stamp pattern is obtained in all cases, the phase-separated morphology of the films under pattern confinement is strongly influenced by the blend composition and annealing time. The phase-separated domains coarsen with time because of migration of the two components into specific areas, PS into an elevated mesa region and PMMA toward the substrate, because of preferential wetting. We show that a well-controlled, phase-separated morphology is achieved when the blend ratio matches the volume ratio of the elevated region to the base region in the patterned films. The proposed top-down imprint patterning of blends can be easily made roll-to-roll-compatible for industrial adoption.

Directed ordering of phase separated domains and dewetting of thin polymer blend films on a topographically patterned substrate.

Substrate pattern guided self-organization of ultrathin and confined polymeric films on a topographically patterned substrate is a useful approach for obtaining ordered meso and nano structures over large areas, particularly if the ordering is achieved during film preparation itself, eliminating any post-processing such as thermal or solvent vapor annealing. By casting a dilute solution of two immiscible polymers, polystyrene (PS) and polymethylmethacrylate (PMMA), from a common solvent (toluene) on a topographically patterned substrate with a grating geometry, we show the formation of self-organized meso patterns with various degrees of ordering. The morphology depends on both the concentration of the dispensed solution (Cn) and the blend composition (RB). Depending on the extent of dewetting during spin coating, the final morphologies can be classified into three distinct categories. At a very low Cn the solution dewets fully, resulting in isolated polymer droplets aligned along substrate grooves (Type 1). Type 2 structures comprising isolated threads with aligned phase separated domains along each substrate groove are observed at intermediate Cn. A continuous film (Type 3) is obtained above a critical concentration (Cn*) that depends on RB. While the extent of ordering of the domains gradually diminishes with an increase in film thickness for Type 3 patterns, the size of the domains remains much smaller than that on a flat substrate, resulting in significant downsizing of the features due to the lateral confinement imposed on the phase separation process by the topographic patterns. Finally, we show that some of these structures exhibit excellent broadband anti-reflection (AR) properties.

Programmable Nanopatterns by Controlled Debonding of Soft Elastic Films.

We report a facile patterning technique capable of creating nanostructures with different feature heights (hS), periodicities (λS), aspect ratios (AR), and duty ratios (DR), using a single grating stamp with fixed feature height hP and periodicity λP. The proposed method relies on controlling the extent of debonding and morphology of the contact instability features, when a rigid patterned stamp is gradually debonded from a soft elastic film to which it was in initial conformal contact. Depending on whether the instability wavelength (λF scales with the film thickness hF as λF ≈ 3hF) and the periodicity of the stamp feature (λP) are commensurate or not, it is possible to obtain features along each stamp protrusion when λF ≈ λP or patterns that span several stripes of the stamp when λF > λP. In both cases, the patterns fabricated during debonding are taller than the original stamp features (hS > hP). We show that hS can be modulated by controlling the extent of debonding as well as the shear modulus of the film (µ). Additionally, when λF > λP, progressive debonding leads to the gradual peeling of replicated features, which, in turn, allows possible tuning of the duty ratio (DR) of the patterns. Finally we show that by the simultaneous modulation of AR, DR, and hS, it becomes possible to create surfaces with controlled wettability.

Confinement induced ordering in dewetting of ultra-thin polymer bilayers on nanopatterned substrates.

We report the dewetting of a thin bilayer of polystyrene (PS) and poly(methylmethacrylate) (PMMA) on a topographically patterned nonwettable substrate comprising an array of pillars, arranged in a square lattice. With a gradual increase in the concentration of the PMMA solution (Cn-PMMA), the morphology of the bottom layer changes to: (1) an aligned array of spin dewetted droplets arranged along substrate grooves at very low Cn-PMMA; (2) an interconnected network of threads surrounding each pillar at intermediate Cn-PMMA; and (3) a continuous bottom layer at higher Cn-PMMA. On the other hand the morphology of the PS top layer depends largely on the nature of the pre-existing bottom layer, in addition to Cn-PS. An ordered array of PMMA core-PS shell droplets forms right after spin coating when both Cn-PMMA and Cn-PS are very low. Bilayers with all other initial configurations evolve during thermal annealing, resulting in a variety of ordered structures. Unique morphologies realized include laterally coexisting structures of the two polymers confined within the substrate grooves due to initial rupture of the bottom layer on the substrate followed by a squeezing flow of the top layer; an array of core-shell and single polymer droplets arranged in an alternating order etc., to highlight a few. Such structures cannot be fabricated by any stand-alone lithography technique. On the other hand, in some cases the partially dewetted bottom layer imparts stability to an intact top PS layer against dewetting. Apart from ordering, under certain specific conditions significant miniaturization and downsizing of dewetted feature periodicity and dimension as compared to dewetting of a single layer on a flat substrate is observed. With the help of a morphology phase diagram we show that ordering is achieved over a wide combination of Cn-PMMA and Cn-PS, though the morphology and dewetting pathway differs significantly with variation in the thickness of the individual layers.

Differential Behavior of Normal and Fibrotic Fibroblasts under the Synergistic Influence of Micropillar Topography and the Rigidity of Honey/Silk-Fibroin Substrates.

We report differential proliferation behavior of normal and fibrosis associated human oral fibroblasts on micropillar honey embedded silk fibroin substrates (HSF). Oral fibroblasts of different origins manifest differences in proliferation rate, morphology, and the cytoskeletal arrangement on HSF substrates with distinct topography (H, D, and S), stiffness, and honey concentration. It is observed that the proliferation rate is maximized for normal and inhibited for fibrosis associated fibroblasts on a HSF substrate surface with moderate height of ∼8.5 µm and 2% honey concentration. Molecular expression analysis reveals decrease in c-myc and p53 expression in later cells validating the inhibition of their proliferation rate, which is further correlated with the decreased Col I and Col III expression on this substrate. A substrate with enhanced interspacing and intermediate mechanical stiffness (0.57 ± 0.32 µN/nm) favors strong adhesion and stable cell-matrix interaction for normal cells, while exhibiting negative influence on fibrotic fibroblasts with poor adhesion and spreading capability. Decrease in vimentin, fibronectin expression, and cytoskeleton reorganization justify the poor stability of later cells on the optimized substrate, thereby allowing selective modulation of normal and fibrosis associated fibroblasts under the synergistic influence of honey concentration, topography, and rigidity of HSF substrates. The work highlights the possible therapeutic efficacy of honey based micropatterned substrates as smart patches for fast wound healing and in minimizing the chances of recurrence of precancer post oral tumor resection surgeries.

Solvent-vapor-assisted dewetting of prepatterned thin polymer films: control of morphology, order, and pattern miniaturization.

Ultrathin (<100 nm) unstable polymer films exposed to a solvent vapor dewet by the growth of surface instability, the wavelength (λ) of which depends on the film thickness (h(f)). While the dewetting of a flat polymer thin film results in random structures, we show that the dewetting of a prepatterned film results in myriad ordered mesoscale morphologies under specific conditions. Such a film undergoes rupture over the thinnest parts when the initial local thickness of these zones (h(rm)) is lower than a limiting thickness h(lim) ≈ 10 nm. Additionally, the width of the pattern grooves (l(s)) must be wider than λ(s) corresponding to a flat film having a thickness of h(rm) for pattern-directed dewetting to take place over surface-tension-induced flattening. We first present an experimentally obtained morphology phase diagram that captures the conditions where a transition from surface-tension-induced flattening to pattern-directed-rupture takes place. Subsequently, we show the versatility of this technique in achieving a variety of aligned mesopatterns starting from a prepatterned film with simple grating geometry. The morphology of the evolving patterns depends on several parameters such as the initial film thickness (h(f)), prepattern amplitude (h(st)), duration of solvent vapor exposure (SVE), and wettability of the stamp used for patterning. Periodic rupture of the film at regular intervals imposes directionality on the evolving patterns, resulting in isolated long threads/cylindrical ridges of polymers, which subsequently disintegrate into an aligned array of droplets due to Rayleigh-Plateau instability under specific conditions. Other patterns such as a double periodic array of droplets and an array of holes are also possible to obtain. The evolution can be interrupted at any intermediate stage by terminating the solvent vapor annealing, allowing the creation of pattern morphology on demand. The created patterns are significantly miniaturized in size as compared to features obtained from dewetting a flat film with the same hf.

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.

Thermally tailored gradient topography surface on elastomeric thin films.

We report a simple method for creating a nanopatterned surface with continuous variation in feature height on an elastomeric thin film. The technique is based on imprinting the surface of a film of thermo-curable elastomer (Sylgard 184), which has continuous variation in cross-linking density introduced by means of differential heating. This results in variation of viscoelasticity across the length of the surface and the film exhibits differential partial relaxation after imprinting with a flexible stamp and subjecting it to an externally applied stress for a transient duration. An intrinsic perfect negative replica of the stamp pattern is initially created over the entire film surface as long as the external force remains active. After the external force is withdrawn, there is partial relaxation of the applied stresses, which is manifested as reduction in amplitude of the imprinted features. Due to the spatial viscoelasticity gradient, the extent of stress relaxation induced feature height reduction varies across the length of the film (L), resulting in a surface with a gradient topography with progressively varying feature heights (hF). The steepness of the gradient can be controlled by varying the temperature gradient as well as the duration of precuring of the film prior to imprinting. The method has also been utilized for fabricating wettability gradient surfaces using a high aspect ratio biomimetic stamp. The use of a flexible stamp allows the technique to be extended for creating a gradient topography on nonplanar surfaces as well. We also show that the gradient surfaces with regular structures can be used in combinatorial studies related to pattern directed dewetting.

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.

Lithographic Tuning of Polymeric Thin Film Surfaces by Stress Relaxation.

We report a facile soft lithography (SL) technique that allows fabrication of patterned polymeric surfaces with feature height varying between 0 and h0, using a single stamp. The method relies on the partial relaxation of the applied stress in a viscoelastic polymer thin film imprinted under a transient external load using a flexible stamp. The applicability of the technique is demonstrated for thermosetting (rubbery) as well as thermoplastic (glassy) polymers over a wide range of lateral dimensions. The lateral dimension and the periodicity of imprinted patterns remain identical to that of the original stamp. The method has potential applications in creating templates for performing combinatorial experiments related to wetting and dewetting studies, adhesion, nanotribology, microfluidics, etc.