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The widespread potential application of vertically aligned carbon nanotube (CNT) forests have stimulated recent work on large-area chemical vapor deposition growth methods, but improved control of the catalyst particles is needed to overcome limitations to the monodispersity and packing density of the CNTs. In particular, traditional thin-film deposition methods are not ideal due to their vacuum requirements, and due to limitations in particle uniformity and density imposed by the thin-film dewetting process. Here, a continuous-feed convective self-assembly process for manufacturing uniform mono- and multi-layers of catalyst particles for CNT growth is presented. Particles are deposited from a solution of commercially available iron oxide nanoparticles, by pinning the meniscus between a blade edge and the substrate. The substrate is translated at constant velocity under the blade so the meniscus and contact angle remain fixed as the particles are deposited on the substrate. Based on design of the particle solution and tuning of the assembly parameters, a priori control of CNT diameter and packing density is demonstrated. Quantitative relationships are established between the catalyst size and density, and the CNT morphology and density. The roll-to-roll compatibility of this method, along with initial results achieved on copper foils, suggest promise for scale-up of CNT forest manufacturing at commercially relevant throughput.
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A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. Here, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs. In particular, single- or few-walled CNT forests were achieved at very low oxygen loading, with single-to-multi-walled CNT diameters ranging from 4.8 ± 1.3 nm to 6.4 ± 1.1 nm over 0-800 ppm O2, and an expected variation in alignment, where both were related to the annealed catalyst morphology. Morphological differences were not the result of subsurface diffusion, but instead occurred via Ostwald ripening under several hundred ppm O2, and this effect was mitigated by high H2 concentrations and not due to water vapor (as confirmed in O2-free water addition experiments), supporting the importance of O2 specifically. Further characterization of the interface between the Fe catalyst and Al2O3 support revealed that either oxygen-deficit metal oxide or oxygen-adsorption on metals could be functional mechanisms for the observed catalyst nanoparticle evolution. Taken as a whole, our results suggest that the impacts of O2 and H2 on the catalyst evolution have been underappreciated and underleveraged in CNT synthesis, and these could present a route toward facile manipulation of CNT forest morphology through control of the reactive gaseous atmosphere alone.
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Additive manufacturing by layerwise photopolymerization, commonly called stereolithography (SLA), is attractive due to its high resolution and diversity of materials chemistry. However, traditional SLA methods are restricted to planar substrates and planar layers that are perpendicular to a single-axis build direction. Here, we present a robotic system that is capable of maskless layerwise photopolymerization on curved surfaces, enabling production of large-area conformal patterns and the construction of conformal freeform objects. The system comprises an industrial six-axis robot and a custom-built maskless projector end effector. Use of the system involves creating a mesh representation of the freeform substrate, generation of a triangulated toolpath with curved layers that represents the target object to be printed, precision mounting of the substrate in the robot workspace, and robotic photopatterning of the target object by coordinated motion of the robot and substrate. We demonstrate printing of conformal photopatterns on spheres of various sizes, and construction of miniature three-dimensional objects on spheres without requiring support features. Improvement of the motion accuracy and development of freeform toolpaths would enable construction of polymer objects that surpass the size and support structure constraints imparted by traditional SLA systems.
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The properties of carbon nanotube (CNT) networks and analogous materials comprising filamentary nanostructures are governed by the intrinsic filament properties and their hierarchical organization and interconnection. As a result, direct knowledge of the collective dynamics of CNT synthesis and self-organization is essential to engineering improved CNT materials for applications such as membranes and thermal interfaces. Here, we use real-time environmental transmission electron microscopy (E-TEM) to observe nucleation and self-organization of CNTs into vertically aligned forests. Upon introduction of the carbon source, we observe a large scatter in the onset of nucleation of individual CNTs and the ensuing growth rates. Experiments performed at different temperatures and catalyst particle densities show the critical role of CNT density on the dynamics of self-organization; low-density CNT nucleation results in the CNTs becoming pinned to the substrate and forming random networks, whereas higher density CNT nucleation results in self-organization of the CNTs into bundles that are oriented perpendicular to the substrate. We also find that mechanical coupling between growing CNTs alters their growth trajectory and shape, causing significant deformations, buckling, and defects in the CNT walls. Therefore, it appears that CNT-CNT coupling not only is critical for self-organization but also directly influences CNT quality and likely the resulting properties of the forest. Our findings show that control of the time-distributed kinetics of CNT nucleation and bundle formation are critical to manufacturing well-organized CNT assemblies and that E-TEM can be a powerful tool to investigate the mesoscale dynamics of CNT networks.
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We present the design of a concentric tube (CT) reactor for roll-to-roll chemical vapor deposition (CVD) on flexible substrates, and its application to continuous production of graphene on copper foil. In the CTCVD reactor, the thin foil substrate is helically wrapped around the inner tube, and translates through the gap between the concentric tubes. We use a bench-scale prototype machine to synthesize graphene on copper substrates at translation speeds varying from 25 mm/min to 500 mm/min, and investigate the influence of process parameters on the uniformity and coverage of graphene on a continuously moving foil. At lower speeds, high-quality monolayer graphene is formed; at higher speeds, rapid nucleation of small graphene domains is observed, yet coalescence is prevented by the limited residence time in the CTCVD system. We show that a smooth isothermal transition between the reducing and carbon-containing atmospheres, enabled by injection of the carbon feedstock via radial holes in the inner tube, is essential to high-quality roll-to-roll graphene CVD. We discuss how the foil quality and microstructure limit the uniformity of graphene over macroscopic dimensions. We conclude by discussing means of scaling and reconfiguring the CTCVD design based on general requirements for 2-D materials manufacturing.
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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.
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Commercialization of materials utilizing patterned carbon nanotube (CNT) forests, such as hierarchical composite structures, dry adhesives, and contact probe arrays, will require catalyst patterning techniques that do not rely on cleanroom photolithography. We demonstrate the large scale patterning of CNT growth catalyst via adaptation of a laser-based electrostatic printing process that uses magnetic ink character recognition (MICR) toner. The MICR toner contains iron oxide nanoparticles that serve as the catalyst for CNT growth, which are printed onto a flexible polymer (polyimide) and then transferred to a rigid substrate (silicon or alumina) under heat and mechanical pressure. Then, the substrate is processed for CNT growth under an atmospheric pressure chemical vapor deposition (CVD) recipe. This process enables digital control of patterned CNT growth via the laser intensity, which controls the CNT density; and via the grayscale level, which controls the pixelation of the image into arrays of micropillars. Moreover, virtually any pattern can be designed using standard software (e.g., MS Word, AutoCAD, etc.) and printed on demand. Using a standard office printer, we realize isolated CNT microstructures as small as 140 µm and isolated catalyst â³pixelsâ³ as small as 70 µm (one grayscale dot) and determine that individual toner microparticles result in features of approximately 5-10 µm . We demonstrate that grayscale CNT patterns can function as dry adhesives and that large-area catalyst patterns can be printed directly onto metal foils or transferred to ceramic plates. Laser printing therefore shows promise to enable high-speed micropatterning of nanoparticle-containing thin films under ambient conditions, possibly for a wide variety of nanostructures by engineering of toners containing nanoparticles of desired composition, size, and shape.
RESUMEN
While many promising applications have been demonstrated for vertically aligned carbon nanotube (CNT) forests, lack of consistency in results (e.g., CNT quality, height, and density) continues to hinder knowledge transfer and commercialization. For example, it is well known that CNT growth can be influenced by small concentrations of water vapor, carbon deposits on the reactor wall, and experiment-to-experiment variations in pressure within the reaction chamber. However, even when these parameters are controlled during synthesis, we found that variations in ambient lab conditions can overwhelm attempts to perform parametric optimization studies. We established a standard growth procedure, including the chemical vapor deposition (CVD) recipe, while we varied other variables related to the furnace configuration and experimental procedure. Statistical analysis of 280 samples showed that ambient humidity, barometric pressure, and sample position in the CVD furnace contribute significantly to experiment-to-experiment variation. We investigated how these factors lead to CNT growth variation and recommend practices to improve process repeatability. Initial results using this approach reduced run-to-run variation in CNT forest height and density by more than 50%.
Asunto(s)
Cristalización/métodos , Interpretación Estadística de Datos , Modelos Químicos , Modelos Estadísticos , Nanotubos de Carbono/química , Nanotubos de Carbono/ultraestructura , Simulación por Computador , Sustancias Macromoleculares/química , Ensayo de Materiales , Modelos Moleculares , Conformación Molecular , Tamaño de la Partícula , Propiedades de SuperficieRESUMEN
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.