Person:

Bell, David

We report the closure of nanopores to single-digit nanometer dimensions by ion sculpting in a range of amorphous materials including insulators (SiO(2) and SiN), semiconductors (a-Si), and metallic glasses (Pd({80})Si(_{20})) — the building blocks of a single-digit nanometer electronic device. Ion irradiation of nanopores in crystalline materials (Pt and Ag) does not cause nanopore closure. Ion irradiation of c-Si pores below 100 °C and above 600 °C, straddling the amorphous-crystalline dynamic transition temperature, yields closure at the lower temperature but no mass transport at the higher temperature. Ion beam nanosculpting appears to be restricted to materials that either are or become amorphous during ion irradiation.

Nanostructures, which have sizes comparable to biological functional units involved in cellular communication, offer the potential for enhanced sensitivity and spatial resolution compared to planar metal and semiconductor structures. Silicon nanowire (SiNW) field-effect transistors (FETs) have been used as a platform for biomolecular sensors, which maintain excellent signal-to-noise ratios while operating on lengths scales that enable efficient extra- and intracellular integration with living cells. Although the NWs are tens of nanometers in diameter, the active region of the NW FET devices typically spans micrometers, limiting both the length and time scales of detection achievable with these nanodevices. Here, we report a new synthetic method that combines gold-nanocluster-catalyzed vapor–liquid–solid (VLS) and vapor–solid–solid (VSS) NW growth modes to produce synthetically encoded NW devices with ultrasharp (<5 nm) n-type highly doped ((n^{++})) to lightly doped (n) transitions along the NW growth direction, where (n^{++}) regions serve as source/drain (S/D) electrodes and the n-region functions as an active FET channel. Using this method, we synthesized short-channel (n^{++}/n/n^{++}) SiNW FET devices with independently controllable diameters and channel lengths. SiNW devices with channel lengths of 50, 80, and 150 nm interfaced with spontaneously beating cardiomyocytes exhibited well-defined extracellular field potential signals with signal-to-noise values of ca. 4 independent of device size. Significantly, these “pointlike” devices yield peak widths of (\sim 500 \mu s), which is comparable to the reported time constant for individual sodium ion channels. Multiple FET devices with device separations smaller than (2 \mu m) were also encoded on single SiNWs, thus enabling multiplexed recording from single cells and cell networks with device-to-device time resolution on the order of a few microseconds. These short-channel SiNW FET devices provide a new opportunity to create nanoscale biomolecular sensors that operate on the length and time scales previously inaccessible by other techniques but necessary to investigate fundamental, subcellular biological processes.

Nature has evolved hierarchical structures of hybrid materials with excellent mechanical properties. Inspired by nacre’s architecture, a ternary nanostructured composite has been developed, wherein stacked lamellas of 1D vanadium pentoxide nanofibres, intercalated with water molecules, are complemented by 2D graphene oxide (GO) nanosheets. The components self-assemble at low temperature into hierarchically arranged, highly flexible ceramic-based papers. The papers’ mechanical properties are found to be strongly influenced by the amount of the integrated GO phase. Nanoindentation tests reveal an out-of-plane decrease in Young’s modulus with increasing GO content. Furthermore, nanotensile tests reveal that the ceramic-based papers with 0.5 wt% GO show superior in-plane mechanical performance, compared to papers with higher GO contents as well as to pristine V2O5 and GO papers. Remarkably, the performance is preserved even after stretching the composite material for 100 nanotensile test cycles. The good mechanical stability and unique combination of stiffness and flexibility enable this material to memorize its micro- and macroscopic shape after repeated mechanical deformations. These findings provide useful guidelines for the development of bioinspired, multifunctional systems whose hierarchical structure imparts tailored mechanical properties and cycling stability, which is essential for applications such as actuators or flexible electrodes for advanced energy storage.

We report observation of catalyst-free hydride vapor phase epitaxy growth of InN nanorods. Characterization of the nanorods with transmission electron microscopy, and X-ray diffraction show that the nanorods are stoichiometric 2H–InN single crystals growing in the [0001] orientation. The InN rods are uniform, showing very little variation in both diameter and length. Surprisingly, the rods show clear epitaxial relations with the c-plane sapphire substrate, despite about 29% of lattice mismatch. Comparing catalyst-free with Ni-catalyzed growth, the only difference observed is in the density of nucleation sites, suggesting that Ni does not work like the typical vapor–liquid–solid catalyst, but rather functions as a nucleation promoter by catalyzing the decomposition of ammonia. No conclusive photoluminescence was observed from single nanorods, while integrating over a large area showed weak wide emissions centered at 0.78 and at 1.9 eV.

We report nanoscale patterning of graphene using a helium ion microscope configured for lithography. Helium ion lithography is a direct-write lithography process, comparable to conventional focused ion beam patterning, with no resist or other material contacting the sample surface. In the present application, graphene samples on (Si/SiO_2) substrates are cut using helium ions, with computer controlled alignment, patterning, and exposure. Once suitable beam doses are determined, sharp edge profiles and clean etching are obtained, with little evident damage or doping to the sample. This technique provides fast lithography compatible with graphene, with ~15 nm feature sizes.

We report on the etching of graphene devices with a helium ion beam, including in situ electrical measurement during lithography. The etching process can be used to nanostructure and electrically isolate different regions in a graphene device, as demonstrated by etching a channel in a suspended graphene device with etched gaps down to about 10 nm. Graphene devices on silicon dioxide ((SiO_2)) substrates etch with lower He ion doses and are found to have a residual conductivity after etching, which we attribute to contamination by hydrocarbons.

Silicon nanowires (NWs) could enable low-cost and efficient photovoltaics, though their performance has been limited by nonideal electrical characteristics and an inability to tune absorption properties. We overcome these limitations through controlled synthesis of a series of polymorphic core/multishell NWs with highly crystalline, hexagonally-faceted shells, and well-defined coaxial Graphic (p/n) and p/intrinsic/n (p/i/n) diode junctions. Designed 200–300 nm diameter p/i/n NW diodes exhibit ultralow leakage currents of approximately 1 fA, and open-circuit voltages and fill-factors up to 0.5 V and 73%, respectively, under one-sun illumination. Single-NW wavelength-dependent photocurrent measurements reveal size-tunable optical resonances, external quantum efficiencies greater than unity, and current densities double those for silicon films of comparable thickness. In addition, finite-difference-time-domain simulations for the measured NW structures agree quantitatively with the photocurrent measurements, and demonstrate that the optical resonances are due to Fabry-Perot and whispering-gallery cavity modes supported in the high-quality faceted nanostructures. Synthetically optimized NW devices achieve current densities of 17 mA/cm2 and power-conversion efficiencies of 6%. Horizontal integration of multiple NWs demonstrates linear scaling of the absolute photocurrent with number of NWs, as well as retention of the high open-circuit voltages and short-circuit current densities measured for single NW devices. Notably, assembly of 2 NW elements into vertical stacks yields short-circuit current densities of 25 mA/cm2 with a backside reflector, and simulations further show that such stacking represents an attractive approach for further enhancing performance with projected efficiencies of > 15% for 1.2 μm thick 5 NW stacks.

Utilizing solar energy to fix carbon dioxide (CO2) with water into chemical fuels and oxygen, a mimic process of photosynthesis in nature, is becoming increasingly important but still challenged by the low selectivity and activity, especially in CO2 electrocatalytic reduction. Here we report transition metal atoms coordinated in graphene shell as active centers for aqueous CO2 reduction to carbon monoxide (CO), with high Faradaic efficiencies over 90 % under significant currents up to ~ 60 mA/mg (12 mA/cm2). Three-dimensional atom probe tomography was employed to directly identify the single Ni atomic sites in graphene vacancies. Theoretical simulations suggest that compared to metallic Ni, the Ni atomic sites present significantly different electronic structures which facilitate CO2 to CO conversion and suppress the competing hydrogen evolution reaction dramatically.