Rational design of silicon structures for optically controlled multiscale biointerfaces.

Silicon-based materials have been widely used. However, remotely controlled and interconnect-free silicon configurations have been rarely explored, because of limited fundamental understanding of the complex physicochemical processes that occur at interfaces between silicon and biological materials. Here, we describe rational design principles, guided by biology, for establishing intracellular, intercellular and extracellular silicon-based interfaces, where the silicon and the biological targets have matched properties. We focused on light-induced processes at these interfaces, and developed a set of matrices to quantify and differentiate the capacitive, Faradaic and thermal outputs from about 30 different silicon materials in saline. We show that these interfaces are useful for the light-controlled non-genetic modulation of intracellular calcium dynamics, of cytoskeletal structures and transport, of cellular excitability, of neurotransmitter release from brain slices, and of brain activity in vivo.

Alloy-assisted deposition of three-dimensional arrays of atomic gold catalyst for crystal growth studies.

Large-scale assembly of individual atoms over smooth surfaces is difficult to achieve. A configuration of an atom reservoir, in which individual atoms can be readily extracted, may successfully address this challenge. In this work, we demonstrate that a liquid gold-silicon alloy established in classical vapor-liquid-solid growth can deposit ordered and three-dimensional rings of isolated gold atoms over silicon nanowire sidewalls. We perform ab initio molecular dynamics simulation and unveil a surprising single atomic gold-catalyzed chemical etching of silicon. Experimental verification of this catalytic process in silicon nanowires yields dopant-dependent, massive and ordered 3D grooves with spacing down to ~5 nm. Finally, we use these grooves as self-labeled and ex situ markers to resolve several complex silicon growths, including the formation of nodes, kinks, scale-like interfaces, and curved backbones.

Heterogeneous silicon mesostructures for lipid-supported bioelectric interfaces.

Silicon-based materials have widespread application as biophysical tools and biomedical devices. Here we introduce a biocompatible and degradable mesostructured form of silicon with multi-scale structural and chemical heterogeneities. The material was synthesized using mesoporous silica as a template through a chemical vapour deposition process. It has an amorphous atomic structure, an ordered nanowire-based framework and random submicrometre voids, and shows an average Young's modulus that is 2-3 orders of magnitude smaller than that of single-crystalline silicon. In addition, we used the heterogeneous silicon mesostructures to design a lipid-bilayer-supported bioelectric interface that is remotely controlled and temporally transient, and that permits non-genetic and subcellular optical modulation of the electrophysiology dynamics in single dorsal root ganglia neurons. Our findings suggest that the biomimetic expansion of silicon into heterogeneous and deformable forms can open up opportunities in extracellular biomaterial or bioelectric systems.

A new silicon drift detector for high spatial resolution STEM-XEDS: performance and applications.

A newly designed, 100 mm2, silicon drift detector has been installed on an aberration-corrected scanning transmission electron microscope equipped with an ultra-high resolution pole piece, without requiring column modifications. With its unique, windowless design, the detector's active region is in close proximity to the sample, resulting in a dramatic increase in count rate, while demonstrating an increased sensitivity to low energy X-rays and a muted tilt dependence. Numerous examples of X-ray energy dispersive spectrometry are presented on relevant materials such as Al x Ga1-x N nanowires, perovskite oxides, and polycrystalline CdTe thin films, across both varying length scales and accelerating voltages.

Toward atomically-precise synthesis of supported bimetallic nanoparticles using atomic layer deposition.

Multi-metallic nanoparticles constitute a new class of materials offering the opportunity to tune the properties via the composition, atomic ordering and size. In particular, supported bimetallic nanoparticles have generated intense interest in catalysis and electrocatalysis. However, traditional synthesis methods often lack precise control, yielding a mixture of monometallic and bimetallic particles with various compositions. Here we report a general strategy for synthesizing supported bimetallic nanoparticles by atomic layer deposition, where monometallic nanoparticle formation is avoided by selectively growing the secondary metal on the primary metal nanoparticle but not on the support; meanwhile, the size, composition and structure of the bimetallic nanoparticles are precisely controlled by tailoring the precursor pulse sequence. Such exquisite control is clearly demonstrated through in situ Fourier transform infrared spectroscopy of CO chemisorption by mapping the gradual atomic-scale evolution in the surface composition, and further confirmed using aberration-corrected scanning transmission electron microscopy.

Investigation of Nucleation Mechanism and Tapering Observed in ZnO Nanowire Growth by Carbothermal Reduction Technique.

ZnO nanowire nucleation mechanism and initial stages of nanowire growth using the carbothermal reduction technique are studied confirming the involvement of the catalyst at the tip in the growth process. Role of the Au catalyst is further confirmed when the tapering observed in the nanowires can be explained by the change in the shape of the catalyst causing a variation of the contact area at the liquid-solid interface of the nanowires. The rate of decrease in nanowire diameter with length on the average is found to be 0.36 nm/s and this rate is larger near the base. Variation in the ZnO nanowire diameter with length is further explained on the basis of the rate at which Zn atoms are supplied as well as the droplet stability at the high flow rates and temperature. Further, saw-tooth faceting is noticed in tapered nanowires, and the formation is analyzed crystallographically.

DC photoelectron gun parameters for ultrafast electron microscopy.

We present a characterization of the performance of an ultrashort laser pulse driven DC photoelectron gun based on the thermionic emission gun design of Togawa et al. [Togawa, K., Shintake, T., Inagaki, T., Onoe, K. & Tanaka, T. (2007). Phys Rev Spec Top-AC 10, 020703]. The gun design intrinsically provides adequate optical access and accommodates the generation of approximately 1 mm2 electron beams while contributing negligible divergent effects at the anode aperture. Both single-photon (with up to 20,000 electrons/pulse) and two-photon photoemission are observed from Ta and Cu(100) photocathodes driven by the harmonics (approximately 4 ps pulses at 261 nm and approximately 200 fs pulses at 532 nm, respectively) of a high-power femtosecond Yb:KGW laser. The results, including the dependence of the photoemission efficiency on the polarization state of the drive laser radiation, are consistent with expectations. The implications of these observations and other physical limitations for the development of a dynamic transmission electron microscope with sub-1 nm.ps space-time resolution are discussed.

Synthesis and characterization of single-crystal strontium hexaboride nanowires.

Catalyst-assisted growth of single-crystal strontium hexaboride (SrB6) nanowires was achieved by pyrolysis of diborane (B2H6) over SrO powders at 760-800 degrees C and 400 mTorr in a quartz tube furnace. Raman spectra demonstrate that the nanowires are SrB6, and transmission electron microscopy along with selected area diffraction indicate that the nanowires consist of single crystals with a preferred [001] growth direction. Electron energy loss data combined with the TEM images indicate that the nanowires consist of crystalline SrB 6 cores with a thin (1 to 2 nm) amorphous oxide shell. The nanowires have diameters of 10-50 nm and lengths of 1-10 microm.