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Abstract The assembly of a two-dimensional (2D) nematic liquid crystal at an interface between two liquids can be exploited to assemble densely packed and highly aligned arrays of rod-like nanoparticles. This method is especially relevant to creating arrays of semiconducting carbon nanotubes (CNTs) for high-performance electronics. When a dense solvent containing CNTs flows over a less dense water subphase in a confined channel, the locally aligned arrays of nanoparticles align globally with the flow direction and can be transferred to the substrate. For large substrates and long channels, the dense solvent tends to slow and create a pool, which then drops through the interface and disturbs the delicate deposition process. Understanding this phenomenon is critical to improving and scaling up similar manufacturing processes. Here, data are collected, and an empirical model is developed to understand and predict the pooling behavior of a suspended fluid flowing over a less dense subphase. The model is demonstrated with two different solvents and proves to be accurate within +/− 15%. With a better understanding of the physics governing the system, the model is then used to suggest methods for minimizing pooling behavior.more » « less
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Tangential flow interfacial self-assembly (TaFISA) is a promising scalable technique enabling uniformly aligned carbon nanotubes for high-performance semiconductor electronics. In this process, flow is utilized to induce global alignment in two-dimensional nematic carbon nanotube assemblies trapped at a liquid/liquid interface, and these assemblies are subsequently deposited on target substrates. Here, we present an observational study of experimental parameters that affect the interfacial assembly and subsequent aligned nanotube deposition. We specifically study the water contact angle (WCA) of the substrate, nanotube ink composition, and water subphase and examine their effects on liquid crystal defects, overall and local alignment, and nanotube bunching or crowding. By varying the substrate chemical functionalization, we determine that highly aligned, densely packed, individualized nanotubes deposit only at relatively small WCA between 35 and 65°. At WCA (< 10°), high nanotube bunching or crowding occurs, and the film is nonuniform, while aligned deposition ceases to occur at higher WCA (>65°). We find that the best alignment, with minimal liquid crystal defects, occurs when the polymer-wrapped nanotubes are dispersed in chloroform at a low (0.6:1) wrapper polymer to nanotube ratio. We also demonstrate that modifying the water subphase through the addition of glycerol not only improves overall alignment and reduces liquid crystal defects but also increases local nanotube bunching. These observations provide important guidance for the implementation of TaFISA and its use toward creating technologies based on aligned semiconducting carbon nanotubes.more » « less
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Hexagonal boron nitride (h-BN) is a promising material for next-generation electronics due to its unique optoelectronic and electronic properties. While the synthesis of h-BN on metallic substrates has been studied extensively, h-BN synthesis on CMOS-compatible substrates like Ge has not. Here, we report the growth of h-BN on Ge(001) from borazine via high-vacuum chemical vapor deposition. We find that the sublimation of Ge under high vacuum inhibits h-BN growth. To overcome this challenge, we place two Ge substrates face-to-face and achieve the growth of aligned h-BN islands and monolayer h-BN films.more » « less
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The directed self-assembly (DSA) of block copolymers (BCPs) can be used to produce nanoscale patterns without the cost and process complexity of state-of-the-art optical lithography. Thus, DSA may be useful in a wide variety of semiconductor applications such as fin field-effect transistors and biosensors. To create technologically useful patterns with aligned BCP domains, conventional DSA mechanisms often rely on topographically complex structures or high-resolution chemical patterns to direct the self-assembly, that are difficult to fabricate. In comparison, a newly discovered mechanism for DSA, termed boundary-directed epitaxy (BDE), utilizes chemical contrast at the boundaries between a substrate and relatively wide chemical stripe. Here, we demonstrate the use of BDE to template the fabrication of sub-10 nm features for the first time. BDE is used in conjunction with selective infiltration to create ultranarrow line-space arrays of alumina. These results demonstrate a proof-of-concept for BDE as a method for ultrahigh-resolution feature formation.more » « less
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Allotaxonometry and rank-turbulence divergence: a universal instrument for comparing complex systemsAbstract Complex systems often comprise many kinds of components which vary over many orders of magnitude in size: Populations of cities in countries, individual and corporate wealth in economies, species abundance in ecologies, word frequency in natural language, and node degree in complex networks. Here, we introduce ‘allotaxonometry’ along with ‘rank-turbulence divergence’ (RTD), a tunable instrument for comparing any two ranked lists of components. We analytically develop our rank-based divergence in a series of steps, and then establish a rank-based allotaxonograph which pairs a map-like histogram for rank-rank pairs with an ordered list of components according to divergence contribution. We explore the performance of rank-turbulence divergence, which we view as an instrument of ‘type calculus’, for a series of distinct settings including: Language use on Twitter and in books, species abundance, baby name popularity, market capitalization, performance in sports, mortality causes, and job titles. We provide a series of supplementary flipbooks which demonstrate the tunability and storytelling power of rank-based allotaxonometry.more » « less
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We examine if the bundling of semiconducting carbon nanotubes (CNTs) can increase the transconductance and on-state current density of field effect transistors (FETs) made from arrays of aligned, polymer-wrapped CNTs. Arrays with packing density ranging from 20 to 50 bundles μm −1 are created via tangential flow interfacial self-assembly, and the transconductance and saturated on-state current density of FETs with either (i) strong ionic gel gates or (ii) weak 15 nm SiO 2 back gates are measured vs the degree of bundling. Both transconductance and on-state current significantly increase as median bundle height increases from 2 to 4 nm, but only when the strongly coupled ionic gel gate is used. Such devices tested at −0.6 V drain voltage achieve transconductance as high as 50 μS per bundle and 2 mS μm −1 and on-state current as high as 1.7 mA μm −1 . At low drain voltages, the off-current also increases with bundling, but on/off ratios of ∼10 5 are still possible if the largest (95th percentile) bundles in an array are limited to ∼5 nm in size. Radio frequency devices with strong, wraparound dielectric gates may benefit from increased device performance by using moderately bundled as opposed to individualized CNTs in arrays.more » « less
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Remote epitaxy is promising for the synthesis of lattice-mismatched materials, exfoliation of membranes, and reuse of expensive substrates. However, clear experimental evidence of a remote mechanism remains elusive. Alternative mechanisms such as pinhole-seeded epitaxy or van der Waals epitaxy can often explain the resulting films. Here, we show that growth of the Heusler compound GdPtSb on clean graphene/sapphire produces a 30° rotated (R30) superstructure that cannot be explained by pinhole epitaxy. With decreasing temperature, the fraction of this R30 domain increases, compared to the direct epitaxial R0 domain, which can be explained by a competition between remote versus pinhole epitaxy. Careful graphene/substrate annealing and consideration of the relative lattice mismatches are required to obtain epitaxy to the underlying substrate across a series of other Heusler films, including LaPtSb and GdAuGe. The R30 superstructure provides a possible experimental fingerprint of remote epitaxy, since it is inconsistent with the leading alternative mechanisms.more » « less
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Controlling the deposition of polymer-wrapped single-walled carbon nanotubes (s-CNTs) onto functionalized substrates can enable the fabrication of s-CNT arrays for semiconductor devices. In this work, we utilize classical atomistic molecular dynamics (MD) simulations to show that a simple descriptor of solvent structure near silica substrates functionalized by a wide variety of self-assembled monolayers (SAMs) can predict trends in the deposition of s-CNTs from toluene. Free energy calculations and experiments indicate that those SAMs that lead to maximum disruption of solvent structure promote deposition to the greatest extent. These findings are consistent with deposition being driven by solvent-mediated interactions that arise from SAM-solvent interactions, rather than direct s-CNT-SAM interactions, and will permit the rapid computational exploration of potential substrate designs for controlling s-CNT deposition and alignment.more » « less
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