Parameters Affecting Interfacial Assembly and Alignment of Nanotubes.

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.

Assembly and Alignment of High Packing Density Carbon Nanotube Arrays Using Lithographically Defined Microscopic Water Features.

High packing density aligned arrays of semiconducting carbon nanotubes (CNTs) are required for many electronics applications. Past work has shown that the accumulation of CNTs at a water-solvent interface can drive array self-assembly. Previously, the confining interface was a large-area, macroscopic feature. Here, we report on the CNT assembly on microscopic water features. Water microdroplets are formed on 10-100 µm wide hydrophilic stripes patterned on a substrate. Exposure to CNTs dispersed in solvent accumulates CNTs at the microdroplet-solvent interface, driving their alignment and deposition at the microdroplet-solvent-substrate contact line. Compared with macroscopic methods in which the contact line uncontrollably moves across the substrate as it is pulled out of the liquids, the hydrophilic patterns and microdroplets allow pinning of the contact line. As CNTs deposit, the contact line self-translates, allowing for dense CNT packing. We realize monolayer CNT arrays aligned within ±3.9° at density of 250 µm-1 and field effect transistors with a high current density of 1.9 mA µm-1 and transconductance of 1.2 mS µm-1 at -0.6 V drain bias and 60 nm channel length.

Aligned 2D carbon nanotube liquid crystals for wafer-scale electronics.

Semiconducting carbon nanotubes promise faster performance and lower power consumption than Si in field-effect transistors (FETs) if they can be aligned in dense arrays. Here, we demonstrate that nanotubes collected at a liquid/liquid interface self-organize to form two-dimensional (2D) nematic liquid crystals that globally align with flow. The 2D liquid crystals are transferred onto substrates in a continuous process generating dense arrays of nanotubes aligned within ±6°, ideal for electronics. Nanotube ordering improves with increasing concentration and decreasing temperature due to the underlying liquid crystal phenomena. The excellent alignment and uniformity of the transferred assemblies enable FETs with exceptional on-state current density averaging 520 µA µm−1at only −0.6 V, and variation of only 19%. FETs with ion gel top gates demonstrate subthreshold swing as low as 60 mV decade−1. Deposition across a 10-cm substrate is achieved, evidencing the promise of 2D nanotube liquid crystals for commercial semiconductor electronics.

Low-energy room-temperature optical switching in mixed-dimensionality nanoscale perovskite heterojunctions.

Long-lived photon-stimulated conductance changes in solid-state materials can enable optical memory and brain-inspired neuromorphic information processing. It remains challenging to realize optical switching with low-energy consumption, and new mechanisms and design principles giving rise to persistent photoconductivity (PPC) can help overcome an important technological hurdle. Here, we demonstrate versatile heterojunctions between metal-halide perovskite nanocrystals and semiconducting single-walled carbon nanotubes that enable room-temperature, long-lived (thousands of seconds), writable, and erasable PPC. Optical switching and basic neuromorphic functions can be stimulated at low operating voltages with femto- to pico-joule energies per spiking event, and detailed analysis demonstrates that PPC in this nanoscale interface arises from field-assisted control of ion migration within the nanocrystal array. Contactless optical measurements also suggest these systems as potential candidates for photonic synapses that are stimulated and read in the optical domain. The tunability of PPC shown here holds promise for neuromorphic computing and other technologies that use optical memory.