Alan W. Nicholls

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.

Ferroelasticity in mixed conducting LaCoO3 based perovskites: a ferroelastic phase transition

Abstract The defect structure of LaCoO 3 based ferroic perovskites has been studied by TEM. The dynamics of the temperature-induced ferroelastic to paraelastic phase transition was directly monitored by in-situ TEM during thermal cycles from room temperature to 700 °C. Different types of structural features of LaCoO 3 based perovskites have been observed, such as twins, antiphase domains, stacking faults, and dislocations. Domain motion and de-twinning during heating, and the reappearance of twins during cooling have been demonstrated. This is important for the understanding of ferroelastic hysteretic behavior of LaCoO 3 based perovskite ceramics.

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 multiscale structural and chemical heterogeneities. The material was synthesized using mesoporous silica as a template through a chemical-vapor-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.

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.

Examining Elemental Surface Enrichment in Ultrafine Aerosol Particles Using Analytical Scanning Transmission Electron Microscopy

The surface structure and chemistry of ultrafine aerosol particles (typically particles smaller than 100 nm in diameter) play key roles in determining physical and chemical behavior, and is relevant to fields as diverse as nanotechnology and aerosol toxicity. Analytical scanning transmission electron microscopy (STEM) is one of the few analytical methods available that is potentially capable of characterizing ultrafine particles at subnanometer resolution. We propose a method that enables STEM to characterize and quantify elemental surface enrichment within radially symmetrical particles at a spatial resolution of less than 1 nm when used in conjunction with electron energy loss spectroscopy (EELS) and X-ray energy dispersive spectroscopy (EDS). Although the method relies on a number of assumptions for complete particle characterization, estimation of the depth of an outer layer of elemental enrichment should be possible with relatively few assumptions. A preliminary investigation of the method has been carried out using particles from gas metal arc welding on mild steel. Using the analysis method, we were able to characterize Si and O enrichment in a number of particles. Two particles were investigated extensively using EELS and EDS analysis. Both techniques allowed surface enrichment of Si to be identified and quantified in the particles, although the relatively poor sensitivity of EDS was a limiting factor in the analysis. EELS allowed rapid data collection and enabled surface enrichment of Si and O to be characterized. Using a simple model to describe elemental composition with radial position, it was estimated that Si and O were enriched in an outer layer around the particle approximately 1 nm deep.

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 detectors 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.

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.

BORON NANOWIRES AND NOVEL TUBE-CATALYTIC PARTICLE-WIRE HYBRID BORON NANOSTRUCTURES

Catalyst-assisted growth of boron nanowires and novel tube–catalytic particle–wire hybrid boron nanostructures were achieved by pyrolysis of diborane at 820–890°C and ~ 200 mTorr in a quartz tube furnace. Electron microscopy imaging and diffraction analysis reveal that most of the nano-structures are amorphous. Elemental analysis by EELS and EDX shows that the nanostructures consist of boron with a small amount of oxygen and carbon. Possible growth mechanisms for the tube–catalytic particle–wire hybrid boron nanostructures are discussed.

Excited-state thermionic emission in III-antimonides: Low emittance ultrafast photocathodes

The normalized rms transverse emittance of an electron source is shown to be proportional to m*, where m* is the effective mass of the state from which the electron is emitted, by direct observation of the transverse momentum distribution for excited-state thermionic emission from two III-V semiconductor photocathodes, GaSb and InSb, together with a control experiment employing two-photon emission from gold. Simulations of the experiment using an extended analytical Gaussian model of electron pulse propagation are in close agreement with the data.

Electron Microscope Visualization of Multiphase Fluids Contained in Closed Carbon Nanotubes

Aqueous multiphase fluids trapped in closed multiwall carbon nanotubes are visualized with high resolution using transmission electron microscopy (TEM). The hydrothermally synthesized nanotubes have inner diameter of 70 nm and wall thickness 20 nm, on average. The nanotubes are hydrophilic due to oxygen groups attached on their wall surfaces. Segregated liquid inclusions contained in the nanotubes under high pressure can be mobilized by heating. A resistive heating stage is utilized to heat a thin membrane inside a nanotube, causing the membrane to evaporate slowly and eventually pinch off. Focused electron beam heating is employed as a second means of thermal stimulation, which results in localized heating. With the latter method, gas/liquid interface motion is observed inside the thin channel of a carbon nanotube. Experiments like the ones presented herein may help understand the dynamics of fluids contained in nanoscale channels.