Block copolymer self-assembly is an innovative technology capable of patterning technologically relevant substrates with nanoscale precision for a range of applications from integrated circuit fabrication to tissue interfacing, for example. In this article, we demonstrate a microwave-based method of rapidly inducing order in block copolymer structures. The technique involves the usage of a commercial microwave reactor to anneal block copolymer films in the presence of appropriate solvents, and we explore the effect of various parameters over the polymer assembly speed and defect density. The approach is applied to the commonly used poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) and poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) families of block copolymers, and it is found that the substrate resistivity, solvent environment, and anneal temperature all critically influence the self-assembly process. For selected systems, highly ordered patterns were achieved in less than 3 min. In addition, we establish the compatibility of the technique with directed assembly by graphoepitaxy.

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The creation of gold surfaces modified by single- or double-stranded DNA self-assembled monolayers (SAMs) is shown to produce heterogeneous surface packing densities through the use of electrochemical studies coupled with fluorescence imaging. The modified surfaces created by direct adsorption of thiolate DNA [followed by passivation with mecaptohexanol (MCH)] resulted in regions covered by a monolayer of DNA SAM and other regions that were coated by large particles of DNA. The difference in fluorescence intensity measured from these regions was dramatic. More importantly, a regional variance in fluorescence intensity in response to electrochemical potential was observed: the large aggregates showing a significantly different modulation of fluorescence intensity than the monolayer-coated regions. Electrochemical desorption and detection of the fluorescently tagged DNA provided clear evidence of a complete surface modification. These studies have implications for biosensor/biochip development using DNA SAMs. A modification in the method used to produce the DNA SAMs resulted in a significantly different surface with much fewer aggregates and more significant electromodulation of the fluorescence intensity, though at much lower DNA surface density (ca. 1% of maximum theoretical coverage). This method for forming the modified surfaces has clear advantages over the currently accepted practice and emphasizes the importance of studying the nonaveraged nature of the sensor surface using in situ imaging tools like electrofluorescence microscopy.

A new class of comb‐shaped polymers for use as a proton conducting membrane is presented. The polymer is designed to combine the beneficial physical, chemical, and structural attributes of fluorinated Nafion‐like materials with higher‐temperature, polyaromatic‐based polymer backbones. The comb‐shaped polymer unites a rigid, polyaromatic, hydrophobic backbone with lengthy hydrophilic polymer side chains; this combination affords direct control over the polymer nanostructure within the membrane and results in distinct microphase separation between the opposing domains. The microphase separation serves to compartmentalize water into the hydrophilic polymer side chain domains, resulting in effective membrane water management and excellent proton conductivities.

The self-assembly of block copolymer (BCP) thin films is a versatile method for producing periodic nanoscale patterns with a variety of shapes. The key to attaining a desired pattern or structure is the annealing step undertaken to facilitate the reorganization of nanoscale phase-segregated domains of the BCP on a surface. Annealing BCPs on silicon substrates using a microwave oven has been shown to be very fast (seconds to minutes), both with and without contributions from solvent vapor. The mechanism of the microwave annealing process remains, however, unclear. This work endeavors to uncover the key steps that take place during microwave annealing, which enable the self-assembly process to proceed. Through the use of in situ temperature monitoring with a fiber optic temperature probe in direct contact with the sample, we have demonstrated that the silicon substrate on which the BCP film is cast is the dominant source of heating if the doping of the silicon wafer is sufficiently low. Surface temperatures as high as 240 °C are reached in under 1 min for lightly doped, high resistivity silicon wafers (n- or p-type). The influence of doping, sample size, and BCP composition was analyzed to rule out other possible mechanisms. In situ temperature monitoring of various polymer samples (PS, P2VP, PMMA, and the BCPs used here) showed that the polymers do not heat to any significant extent on their own with microwave irradiation of this frequency (2.45 GHz) and power (∼600 W). It was demonstrated that BCP annealing can be effectively carried out in 60 s on non-microwave-responsive substrates, such as highly doped silicon, indium tin oxide (ITO)-coated glass, glass, and Kapton, by placing a piece of high resistivity silicon wafer in contact with the sample-in this configuration, the silicon wafer is termed the heating element. Annealing and self-assembly of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCPs into horizontal cylinder structures were shown to take place in under 1 min, using a silicon wafer heating element, in a household microwave oven. Defect densities were calculated and were shown to decrease with higher maximum obtained temperatures. Conflicting results in the literature regarding BCP annealing with microwave are explained in light of the results obtained in this study.

Line patterns produced by lamellae- and cylinder-forming block copolymer (BCP) thin films are of widespread interest for their potential to enable nanoscale patterning over large areas. In order for such patterning methods to effectively integrate with current technologies, the resulting patterns need to have low defect densities, and be produced in a short timescale. To understand whether a given polymer or annealing method might potentially meet such challenges, it is necessary to examine the evolution of defects. Unfortunately, few tools are readily available to researchers, particularly those engaged in the synthesis and design of new polymeric systems with the potential for patterning, to measure defects in such line patterns. To this end, we present an image analysis tool, which we have developed and made available, to measure the characteristics of such patterns in an automated fashion. Additionally we apply the tool to six cylinder-forming polystyrene-block-poly(2-vinylpyridine) polymers thermally annealed to explore the relationship between the size of each polymer and measured characteristics including line period, line-width, defect density, line-edge roughness (LER), line-width roughness (LWR), and correlation length. Finally, we explore the line-edge roughness, line-width roughness, defect density, and correlation length as a function of the image area sampled to determine each in a more rigorous fashion.

Highly ordered nanopatterns are obtained at sub‐5 nm periodicities by the graphoepitaxial directed self‐assembly of monodisperse, oligo(dimethylsiloxane) liquid crystals. These hybrid organic/inorganic liquid crystals are of high interest for nanopatterning applications due to the combination of their ultrasmall feature sizes and their ability to be directed into highly ordered domains without additional annealing.

materials and is desired for untethered multi-responsive soft robotics, opening a new range of applications, expanding from remotely controlled motion to possible locomotion. However, a facile approach to combining multi-stimulus response into one device without imposing dramatic mechanical or chemical changes to the system remains a challenge. Grasping devices making use of stimuli-responsive actuation have already been reported [9][10][11][12][13][14][15] and a present goal in this field is to free these stimuli-responsive soft robotic grippers from the necessity of manual manipulation for movement.Combining soft materials and stimuliresponsive reagents for the development of functional materials is a present endeavor. [16] Liquid crystal networks (LCNs) are attractive materials for fabricating soft actuators since they operate in dry environments, and their deformation can be programmed within the LC network by the 3D organization of the molecular building blocks. The versatility of liquid crystal (LC) networks has allowed for the development of several functional, responsive actuators with diverse fabrication techniques, such as 3D printing, [17] and operating with a variety of triggers, including light, [18][19][20][21][22] heat, [23] humidity, [24,25] and magnetic, [26,27] and electric [28] fields. Among the triggers studied in the development of LC actuators, light is highly appealing for untethered motion as it provides instantaneous stimulus, resulting in a fast response Here, a remotely controlled dual magneto-and photoresponsive soft robotic gripper is reported, capable of loading, transport, rotation, and release of cargo. The untethered soft actuator consists of a magnetically responsive polydimethylsiloxane layer containing magnetic iron powder coated onto the central region of a light-responsive liquid crystal polymer film hosting photochromic azobenzene dyes. Light is used to trigger the actuator to autonomously grab and pick up cargo with a high degree of control. Magnetic response is employed to conduct the locomotion as magnetic guidance, allowing the gripper to have both translational freedom and rotational freedom in its locomotion, differentiating the device from other soft robotic grippers. Control can be attained even in enclosed and/or confined spaces, through solely remote actuation. Through combined video, mechanical, and thermal analyses, the actuation mechanism of the light-responsive liquid crystal network is investigated, shedding light on the decisive role of the temperature evolution in governing both rate of motion and deformation amplitude of the light-responsive soft actuator.