Davor Copic

Diverse 3D Microarchitectures Made by Capillary Forming of Carbon Nanotubes

A new technology called capillary forming enables transformation of vertically aligned nanoscale filaments into complex three-dimensional microarchitectures. We demonstrate capillary forming of carbon nanotubes into diverse forms having intricate bends, twists, and multidirectional textures. In addition to their novel geometries, these structures have mechanical stiffness exceeding that of microfabrication polymers, and can be used as masters for replica molding

Engineering of Micro‐ and Nanostructured Surfaces with Anisotropic Geometries and Properties

Widespread approaches to fabricate surfaces with robust micro- and nanostructured topographies have been stimulated by opportunities to enhance interface performance by combining physical and chemical effects. In particular, arrays of asymmetric surface features, such as arrays of grooves, inclined pillars, and helical protrusions, have been shown to impart unique anisotropy in properties including wetting, adhesion, thermal and/or electrical conductivity, optical activity, and capability to direct cell growth. These properties are of wide interest for applications including energy conversion, microelectronics, chemical and biological sensing, and bioengineering. However, fabrication of asymmetric surface features often pushes the limits of traditional etching and deposition techniques, making it challenging to produce the desired surfaces in a scalable and cost-effective manner. We review and classify approaches to fabricate arrays of asymmetric 2D and 3D surface features, in polymers, metals, and ceramics. Analytical and empirical relationships among geometries, materials, and surface properties are discussed, especially in the context of the applications mentioned above. Further, opportunities for new fabrication methods that combine lithography with principles of self-assembly are identified, aiming to establish design principles for fabrication of arbitrary 3D surface textures over large areas.

A monolithically-integrated μGC chemical sensor system.

Gas chromatography (GC) is used for organic and inorganic gas detection with a range of applications including screening for chemical warfare agents (CWA), breath analysis for diagnostics or law enforcement purposes, and air pollutants/indoor air quality monitoring of homes and commercial buildings. A field-portable, light weight, low power, rapid response, micro-gas chromatography (μGC) system is essential for such applications. We describe the design, fabrication and packaging of μGC on monolithically-integrated Si dies, comprised of a preconcentrator (PC), μGC column, detector and coatings for each of these components. An important feature of our system is that the same mechanical micro resonator design is used for the PC and detector. We demonstrate system performance by detecting four different CWA simulants within 2 min. We present theoretical analyses for cost/power comparisons of monolithic versus hybrid μGC systems. We discuss thermal isolation in monolithic systems to improve overall performance. Our monolithically-integrated μGC, relative to its hybrid cousin, will afford equal or slightly lower cost, a footprint that is 1/2 to 1/3 the size and an improved resolution of 4 to 25%.

Mass-Sensitive Microfabricated Chemical Preconcentrator

This paper describes a mass-sensitive microfabricated preconcentrator for use in chemical detection microsystems. The device combines mass sensing and preconcentration to create a smart preconcentrator (SPC) that determines when it has collected sufficient analyte for analysis by a downstream chemical microsystem. The SPC is constructed from a Lorentz-force-actuated pivot-plate resonator with an integrated heater. Subsequent to microfabrication, the SPC is coated with an adsorbent for collection of chemical analytes. The frequency of operation varies inversely with the mass of collected analyte. Such shifts can be measured by a back-EMF in the SPCs drive/transducer line. By using a calibrated vapor system, the limit of detection of the SPC was determined to be less than 50 ppb for dimethyl-methyl-phosphonate (DMMP) (actual limits of detection are omitted due to export control limitations). At 1 ppm of DMMP, 1-s collection was sufficient to trigger analysis in a downstream microsystem; other micropreconcentrators would require an arbitrary collection time, normally set at 1 min or longer. This paper describes the theory of operation, design, fabrication, coating, vapor system testing, and integration of the SPC into microanalytical systems. The theory of operation, which is applicable to other torsional oscillators, is used to predict a shear modulus of silicon (100) of G = 57.0 GPa plusmn2.2 GPa.

Chemically Controlled Bending of Compositionally Anisotropic Microcylinders

Soft materials that can undergo mechanical actuation in response to external stimuli, such as changes in temperature, light, pH value, or ionic strength, have attracted increasing attention because of their potential use as thinfilm actuators, smart sutures, and soft robots. These materials typically require specialty polymers, such as shape-memory polymers or use macroscopically layered films. In layered films, the anisotropic distribution of two polymers, or a polymer and a metal, is essential. This creates a mismatch in mechanical properties that gives rise to a defined bending. In principle, this concept is not limited to macroscopic multilayer films, but can be achieved with colloidal materials, as long as the required anisotropy can be realized and different parts of the colloidal object will respond differently to the external stimulus. In recent years, compositionally anisotropic microand nanoparticles have been devised using a range of different synthesis methods including microfluidic and lithographic techniques, particle replication in low surface energy templates, selective crosslinking of polybutadiene segments in terpolymers, lithographic patterning of microspheres, electrochemical and photochemical reduction, templating of porous membranes and nanotubes, surfactant aided growth, graft polymerization, and processes based on controlled surface nucleation. Alternatively, electrohydrodynamic co-jetting is a method to prepare particles and fibers with multiple compartments by transferring fluids through a set of capillaries that can process dissimilar materials. In the past, electrohydrodynamic co-jetting has resulted in particles with multiple compartments that contain different polymer blends, dyes, low-molecular weight additives, reactive molecules and even inorganic nanoparticles. If a reactive additive, such as a functionalized polymer, is added to one of the compartments, selective surface modification is possible and can result in spatially controlled immobilization of proteins or peptides. Because different compartments can be loaded with dissimilar materials, entirely new sets of functions can arise from unique synergistic effects, not just from the addition of the properties of the individual compartments. Herein, we report a new type of compositionally anisotropic microcylinders, where defined compartments within the same microcylinder undergo differential expansion due to the site-selective growth of a surface layer. The asymmetric expansion creates surface stresses resulting in significant and controllable bending of the microcylinders, which depends on the particle geometry and the architecture of the surface layers. Using finite element simulations, we verify the observed bending trends and derive a family of performance curves that predict a wide-range tunability of the actuation stroke based on the cylinder geometry and the amount of swelling. The microcylinders are fabricated based on electrohydrodynamic co-jetting followed by microsectioning. In brief, an electric field is applied to a compound droplet comprising two or more polymer solutions generated by laminar flow from a side-by-side arrangement of capillary needles. We have previously demonstrated the synthesis of particles and fibers from chloroform-based solutions of lactic acid polymers. In the case of fibers, high viscosities, combined with high solvent volatility and low charge-to-volume ratios, can result in an extremely linear and controlled jet migration without the bending and whipping instabilities commonly observed in charged jets. This situation enables the production of multicompartmental microfibers, which not only exhibit monodispersity with respect to diameter, but can also be aligned on rotating collectors. Such highly aligned fiber scaffolds can then be cut into monodisperse microcylinders. Importantly, particle diameters are controlled by altering the solution and process parameters during electrohydrodynamic co-jetting, while control over cylinder length is achieved by the microsectioning step. Spatioselective functionalization of one or more compartments of the cylinders has been achieved by incorporation of poly(lactide-co-propargyl glycolide) as an additive during fabrication of the microcylinders, and subsequent modification with biotin and streptavidin by click chemistry. As shown in the Supporting Information, Figure S1, we incorporated a poly[lactide-co[*] Dr. S. Saha, N. Clay, A. Donini, Prof. J. Lahann Department of Chemical Engineering University of Michigan, Ann Arbor, MI 48109 (USA) E-mail: lahann@umich.edu

Direct fabrication of graphene on SiO2 enabled by thin film stress engineering

We demonstrate direct production of graphene on SiO2 by CVD growth of graphene at the interface between a Ni film and the SiO2 substrate, followed by dry mechanical delamination of the Ni using adhesive tape. This result is enabled by understanding of the competition between stress evolution and microstructure development upon annealing of the Ni prior to the graphene growth step. When the Ni film remains adherent after graphene growth, the balance between residual stress and adhesion governs the ability to mechanically remove the Ni after the CVD process. In this study the graphene on SiO2 comprises micron-scale domains, ranging from monolayer to multilayer. The graphene has >90% coverage across centimeter-scale dimensions, limited by the size of our CVD chamber. Further engineering of the Ni film microstructure and stress state could enable manufacturing of highly uniform interfacial graphene followed by clean mechanical delamination over practically indefinite dimensions. Moreover, our findings suggest that preferential adhesion can enable production of 2-D materials directly on application-relevant substrates. This is attractive compared to transfer methods, which can cause mechanical damage and leave residues behind.

Fabrication of high-aspect-ratio polymer microstructures and hierarchical textures using carbon nanotube composite master molds

Scalable and cost effective patterning of polymer structures and their surface textures is essential to engineer material properties such as liquid wetting and dry adhesion, and to design artificial biological interfaces. Further, fabrication of high-aspect-ratio microstructures often requires controlled deep-etching methods or high-intensity exposure. We demonstrate that carbon nanotube (CNT) composites can be used as master molds for fabrication of high-aspect-ratio polymer microstructures having anisotropic nanoscale textures. The master molds are made by growth of vertically aligned CNT patterns, capillary densification of the CNTs using organic solvents, and capillary-driven infiltration of the CNT structures with SU-8. The composite master structures are then replicated in SU-8 using standard PDMS transfer molding methods. By this process, we fabricated a library of replicas including vertical micro-pillars, honeycomb lattices with sub-micron wall thickness and aspect ratios exceeding 50:1, and microwells with sloped sidewalls. This process enables batch manufacturing of polymer features that capture complex nanoscale shapes and textures, while requiring only optical lithography and conventional thermal processing.

Hierarchical Assemblies of Carbon Nanotubes for Ultraflexible Li-Ion Batteries.

The flexible batteries that are needed to power flexible circuits and displays remain challenging, despite considerable progress in the fabrication of such devices. Here, it is shown that flexible batteries can be fabricated using arrays of carbon nanotube microstructures, which decouple stress from the energy-storage material. It is found that this battery architecture imparts exceptional flexibility (radius ≈ 300 μm), high rate (20 A g(-1) ), and excellent cycling stability.

Corrugated Paraffin Nanocomposite Films as Large Stroke Thermal Actuators and Self-Activating Thermal Interfaces

High performance active materials are of rapidly growing interest for applications including soft robotics, microfluidic systems, and morphing composites. In particular, paraffin wax has been used to actuate miniature pumps, solenoid valves, and composite fibers, yet its deployment is typically limited by the need for external volume constraint. We demonstrate that compact, high-performance paraffin actuators can be made by confining paraffin within vertically aligned carbon nanotube (CNT) films. This large-stroke vertical actuation is enabled by strong capillary interaction between paraffin and CNTs and by engineering the CNT morphology by mechanical compression before capillary-driven infiltration of the molten paraffin. The maximum actuation strain of the corrugated CNT-paraffin films (∼0.02-0.2) is comparable to natural muscle, yet the maximum stress is limited to ∼10 kPa by collapse of the CNT network. We also show how a CNT-paraffin film can serve as a self-activating thermal interface that closes a gap when it is heated. These new CNT-paraffin film actuators could be produced by large-area CNT growth, infiltration, and lamination methods, and are attractive for use in miniature systems due to their self-contained design.

Growth of primary motor neurons on horizontally aligned carbon nanotube thin films and striped patterns

OBJECTIVE Carbon nanotubes (CNTs) are attractive for use in peripheral nerve interfaces because of their unique combination of strength, flexibility, electrical conductivity and nanoscale surface texture. Here we investigated the growth of motor neurons on thin films of horizontally aligned CNTs (HACNTs). APPROACH We cultured primary embryonic rat motor neurons on HACNTs and performed statistical analysis of the length and orientation of neurites. We next presented motor neurons with substrates of alternating stripes of HACNTs and SiO2. MAIN RESULTS The neurons survived on HACNT substrates for up to eight days, which was the full duration of our experiments. Statistical analysis of the length and orientation of neurites indicated that the longest neurites on HACNTs tended to align with the CNT direction, although the average neurite length was similar between HACNTs and glass control substrates. We observed that when motor neurons were presented with alternating stripes of HACNTs and SiO2, the proportion of neurons on HACNTs increases over time, suggesting that neurons selectively migrate toward and adhere to the HACNT surface. SIGNIFICANCE The behavior of motor neurons on CNTs has not been previously investigated, and we show that aligned CNTs could provide a viable interface material to motor neurons. Combined with emerging techniques to build complex hierarchical structures of CNTs, our results suggest that organised CNTs could be incorporated into nerve grafts that use physical and electrical cues to guide regenerating axons.