Instrument for in situ hard x-ray nanobeam characterization during epitaxial crystallization and materials transformations.

Solid-phase epitaxy (SPE) and other three-dimensional epitaxial crystallization processes pose challenging structural and chemical characterization problems. The concentration of defects, the spatial distribution of elastic strain, and the chemical state of ions each vary with nanoscale characteristic length scales and depend sensitively on the gas environment and elastic boundary conditions during growth. The lateral or three-dimensional propagation of crystalline interfaces in SPE has nanoscale or submicrometer characteristic distances during typical crystallization times.

Phase Selection and Structure of Low-Defect-Density γ-AlO Created by Epitaxial Crystallization of Amorphous AlO.

A multistep phase sequence following the crystallization of amorphous AlO via solid-phase epitaxy (SPE) points to methods to create low-defect-density thin films of the metastable cubic γ-AlO polymorph. An amorphous AlO thin film on a (0001) α-AlO sapphire substrate initially transforms upon heating to form epitaxial γ-AlO, followed by a transformation to monoclinic θ-AlO, and eventually to α-AlO. Epitaxial γ-AlO layers with low mosaic widths in X-ray rocking curves can be formed via SPE by crystallizing the γ-AlO phase from amorphous AlO and avoiding the microstructural inhomogeneity arising from the spatially inhomogeneous transformation to θ-AlO.

Radiation-induced segregation in a ceramic.

Radiation-induced segregation is well known in metals, but has been rarely studied in ceramics. We discover that radiation can induce notable segregation of one of the constituent elements to grain boundaries in a ceramic, despite the fact that the ceramic forms a line compound and therefore has a strong thermodynamic driving force to resist off-stoichiometry. Specifically, irradiation of silicon carbide at 300 °C leads to carbon enrichment near grain boundaries, whereas the enrichment diminishes for irradiation at 600 °C.

Surface Coating Structure and Its Interaction with Cytochrome in EG-Coated Nanoparticles Varies with Surface Curvature.

The composition, orientation, and conformation of proteins in biomolecular coronas acquired by nanoparticles in biological media contribute to how they are identified by a cell. While numerous studies have investigated protein composition in biomolecular coronas, relatively little detail is known about how the nanoparticle surface influences the orientation and conformation of the proteins associated with them. We previously showed that the peripheral membrane protein cytochrome adopts preferred poses relative to negatively charged 3-mercaptopropionic acid (MPA)-gold nanoparticles (AuNPs).

High-Ge-Content SiGe Alloy Single Crystals Using the Nanomembrane Platform.

The growth of single crystals of Ge-rich SiGe alloys in an extended composition range is demonstrated using the nanomembrane (NM) platform and III-V growth substrates. Thin films of high-Ge-content SiGe films are grown on GaAs(001) to below the kinetic critical thickness and released from the growth substrate by selectively etching a release layer to relax the strain. The resulting crystalline nanomembranes at the natural lattice constant of the alloy are transferred to a new host and epitaxially overgrown at similar compositions to make a thicker single crystal.

Density Functional Theory Study of the Gas Phase and Surface Reaction Kinetics for the MOVPE Growth of GaAsBi.

The kinetics of chemical reactions occurring during the metal-organic vapor phase epitaxy (MOVPE) of GaAsBi have been studied using density functional theory (DFT). GaAsBi is a metastable semiconductor alloy that has potential applications in high-performance long-wavelength emitters. Its growth is complicated by the low solubility of Bi within the GaAs lattice, which leads to phase segregation under conventional III-V semiconductor growth conditions.

Peripheral Membrane Proteins Facilitate Nanoparticle Binding at Lipid Bilayer Interfaces.

Molecular understanding of the impact of nanomaterials on cell membranes is critical for the prediction of effects that span environmental exposures to nanoenabled therapies. Experimental and computational studies employing phospholipid bilayers as model systems for membranes have yielded important insights but lack the biomolecular complexity of actual membranes. Here, we increase model membrane complexity by incorporating the peripheral membrane protein cytochrome c and studying the interactions of the resulting membrane systems with two types of anionic nanoparticles.

Distinct Nucleation and Growth Kinetics of Amorphous SrTiO on (001) SrTiO and SiO/Si: A Step toward New Architectures.

Integration of emerging complex-oxide compounds into sophisticated nanoscale single-crystal geometries faces significant challenges arising from the kinetics of vapor-phase thin-film epitaxial growth. A comparison of the crystallization of the model perovskite SrTiO (STO) on (001) STO and oxidized (001) Si substrates indicates that there is a viable alternative route that can yield three-dimensional epitaxial synthesis, an approach in which STO is crystallized from an amorphous thin film by postdeposition annealing. The crystallization of amorphous STO on single-crystal (001) STO substrates occurs via solid-phase epitaxy (SPE), without nucleation and with a temperature-dependent amorphous/crystalline interface velocity.

Quantifying the Electrostatics of Polycation-Lipid Bilayer Interactions.

Mechanistic insight into how polycations disrupt and cross cell membranes is needed for understanding and controlling polycation-membrane interactions, yet such information is surprisingly difficult to obtain at the molecular level. We use second harmonic and vibrational sum frequency generation spectroscopies along with quartz crystal microbalance with dissipation monitoring and computer simulations to quantify the interaction of poly(allylamine) hydrochloride (PAH) and its monomeric precursor allylamine hydrochloride (AH) with lipid bilayers. We find PAH adsorption to be reversible and nondisruptive to the bilayer under the conditions of our experiments.

Atomic Layer Deposited MgO: A Lower Overpotential Coating for Li[NiMnCo]O Cathode.

An ultrathin MgO coating was synthesized via atomic layer deposition (ALD) to improve the surface properties of the Li[NiMnCo]O (NMC) cathode. An in-situ quartz crystal sensor was used to monitor the "self-limiting" surface reactions during ALD process and estimate the density of the deposited film. The electrochemical performance of the MgO-coated NMC cathode was evaluated in a half-cell assembly and compared to other ALD-based coatings, such as AlO and ZrO.

Resonantly Enhanced Nonlinear Optical Probes of Oxidized Multiwalled Carbon Nanotubes at Supported Lipid Bilayers.

With production of carbon nanotubes surpassing billions of tons per annum, concern about their potential interactions with biological systems is growing. Herein, we utilize second harmonic generation spectroscopy, sum frequency generation spectroscopy, and quartz crystal microbalance with dissipation monitoring to probe the interactions between oxidized multiwalled carbon nanotubes (O-MWCNTs) and supported lipid bilayers composed of phospholipids with phosphatidylcholine head groups as the dominant component. We quantify O-MWCNT attachment to supported lipid bilayers under biogeochemically relevant conditions and discern that the interactions occur without disrupting the structural integrity of the lipid bilayers for the systems probed.

Atomic Layer Deposition of Al2O3-Ga2O3 Alloy Coatings for Li[Ni0.5Mn0.3Co0.2]O2 Cathode to Improve Rate Performance in Li-Ion Battery.

Metal oxide coatings can improve the electrochemical stability of cathodes and hence, their cycle-life in rechargeable batteries. However, such coatings often impose an additional electrical and ionic transport resistance to cathode surfaces leading to poor charge-discharge capacity at high C-rates. Here, a mixed oxide (Al2O3)1-x(Ga2O3)x alloy coating, prepared via atomic layer deposition (ALD), on Li[Ni0.

Lipopolysaccharide Density and Structure Govern the Extent and Distance of Nanoparticle Interaction with Actual and Model Bacterial Outer Membranes.

Design of nanomedicines and nanoparticle-based antimicrobial and antifouling formulations and assessment of the potential implications of nanoparticle release into the environment requires understanding nanoparticle interaction with bacterial surfaces. Here we demonstrate the electrostatically driven association of functionalized nanoparticles with lipopolysaccharides of Gram-negative bacterial outer membranes and find that lipopolysaccharide structure influences the extent and location of binding relative to the outer leaflet-solution interface. By manipulating the lipopolysaccharide content in Shewanella oneidensis outer membranes, we observed the electrostatically driven interaction of cationic gold nanoparticles with the lipopolysaccharide-containing leaflet.

Tuning Acid-Base Properties Using Mg-Al Oxide Atomic Layer Deposition.

Atomic layer deposition (ALD) was used to coat γ-Al2O3 particles with oxide films of varying Mg/Al atomic ratios, which resulted in systematic variation of the acid and base site areal densities. Variation of Mg/Al also affected morphological features such as crystalline phase, pore size distribution, and base site proximity. Areal base site density increased with increasing Mg content, while acid site density went through a maximum with a similar number of Mg and Al atoms in the coating.

Control of thickness and chemical properties of atomic layer deposition overcoats for stabilizing Cu/γ-Al2 O3 catalysts.

Whereas sintering and leaching of copper nanoparticles during liquid-phase catalytic processing can be prevented by using atomic layer deposition (ALD) to overcoat the nanoparticles with AlOx , this acidic overcoat leads to reversible deactivation of the catalyst by resinification and blocking of the pores within the overcoat during hydrogenation of furfural. We demonstrate that decreasing the overcoat thickness from 45 to 5 ALD cycles is an effective method to increase the rate per gram of catalyst and to decrease the rate of deactivation for catalysts pretreated at 673 K, and a fully regenerable copper catalyst can be produced with only five ALD cycles of AlOx . Moreover, although an overcoat of MgOx does not lead to stabilization of copper nanoparticles against sintering and leaching during liquid-phase hydrogenation reactions, the AlOx overcoat can be chemically modified to decrease acidity and deactivation through the addition of MgOx , while maintaining stability of the copper nanoparticles.

Stabilization of copper catalysts for liquid-phase reactions by atomic layer deposition.

Atomic layer deposition (ALD) of an alumina overcoat can stabilize a base metal catalyst (e.g., copper) for liquid-phase catalytic reactions (e.

InAs nanowires grown by metal-organic vapor-phase epitaxy (MOVPE) employing PS/PMMA diblock copolymer nanopatterning.

Dense arrays of indium arsenide (InAs) nanowire materials have been grown by selective-area metal-organic vapor-phase epitaxy (SA-MOVPE) using polystyrene-b-poly(methyl methacrylate) (PS/PMMA) diblock copolymer (DBC) nanopatterning technique, which is a catalyst-free approach. Nanoscale openings were defined in a thin (~10 nm) SiNx layer deposited on a (111)B-oriented GaAs substrate using the DBC process and CF4 reactive ion etching (RIE), which served as a hard mask for the nanowire growth. InAs nanowires with diameters down to ~ 20 nm and micrometer-scale lengths were achieved with a density of ~ 5 × 10(10) cm(2).

Attachment of pathogenic prion protein to model oxide surfaces.

Prions are the infectious agents in the class of fatal neurodegenerative diseases known as transmissible spongiform encephalopathies, which affect humans, deer, sheep, and cattle. Prion diseases of deer and sheep can be transmitted via environmental routes, and soil is has been implicated in the transmission of these diseases. Interaction with soil particles is expected to govern the transport, bioavailability and persistence of prions in soil environments.

Mixed semiconductor alloys for optical devices.

There is an increasing technological need for a wider array of semiconducting materials that will allow greater control over the physical and electronic structure within multilayer heterostructures. This need has led to an expansion in the range of semiconducting alloys explored and used in new applications. These alloy semiconductors are often complicated by a limited range of miscibility.

Chemical characterization of DNA-immobilized InAs surfaces using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure.

Single-stranded DNA immobilized on an III-V semiconductor is a potential high-sensitivity biosensor. The chemical and electronic changes occurring upon the binding of DNA to the InAs surface are essential to understanding the DNA-immobilization mechanism. In this work, the chemical properties of DNA-immobilized InAs surfaces were determined through high-resolution X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS).

A low-cost, portable, and quantitative spectral imaging system for application to biological tissues.

The ability of diffuse reflectance spectroscopy to extract quantitative biological composition of tissues has been used to discern tissue types in both pre-clinical and clinical cancer studies. Typically, diffuse reflectance spectroscopy systems are designed for single-point measurements. Clinically, an imaging system would provide valuable spatial information on tissue composition.

Low-threshold thin-film III-V lasers bonded to silicon with front and back side defined features.

A III-V thin-film single-quantum-well edge-emitting laser is patterned on both sides of the epitaxial layer and bonded to silicon. Injected threshold current densities of 420 A/cm(2) for gain-guided lasers with bottom p-stripes and top n-stripes and 244 A/cm(2) for index-guided bottom p-ridge and top n-stripe lasers are measured with a lasing wavelength of approximately 995 nm. These threshold current densities, among the lowest for thin-film edge-emitting lasers on silicon reported to date (to our knowledge), enable the implementation of integrated applications such as power-efficient portable chip-scale photonic sensing systems.

A strategy for quantitative spectral imaging of tissue absorption and scattering using light emitting diodes and photodiodes.

A diffuse reflectance spectroscopy system was modified as a step towards miniaturization and spectral imaging of tissue absorption and scattering. The modified system uses a tunable source and an optical fiber for illumination and a photodiode in contact with tissue for detection. Compared to the previous system, it is smaller, less costly, and has comparable performance in extracting optical properties in tissue phantoms.

Cost-effective diffuse reflectance spectroscopy device for quantifying tissue absorption and scattering in vivo.

A hybrid optical device that uses a multimode fiber coupled to a tunable light source for illumination and a 2.4-mm photodiode for detection in contact with the tissue surface is developed as a first step toward our goal of developing a cost-effective, miniature spectral imaging device to map tissue optical properties in vivo. This device coupled with an inverse Monte Carlo model of reflectance is demonstrated to accurately quantify tissue absorption and scattering in tissue-like turbid synthetic phantoms with a wide range of optical properties.

Continuously phase-matched terahertz difference frequency generation in an embedded-waveguide structure supporting only fundamental modes.

We demonstrate an all-single mode structure which enables continuous phase matching of difference frequency generated THz light from the near-IR. This structure provides a long interaction length by way of well-confined collinear propagation of pumps and product without diffraction, resulting in high conversion efficiency. A LiNbO(3) version of this structure achieved a power-normalized conversion efficiency of 1.