Joseph A. Dura

Hybrid bilayer membranes in air and water: infrared spectroscopy and neutron reflectivity studies.

In this report we describe the fabrication and characterization of a phospholipid/alkanethiol hybrid bilayer membrane in air. The bilayer is formed by the interaction of phospholipid with the hydrophobic surface of a self-assembled alkanethiol monolayer on gold. We have characterized the resulting hybrid bilayer membrane in air using atomic force microscopy, spectroscopic ellipsometry, and reflection-absorption infrared spectroscopy. These analyses indicate that the phospholipid added is one monolayer thick, is continuous, and exhibits molecular order which is similar to that observed for phospholipid/phospholipid model membranes. The hybrid bilayer prepared in air has also been re-introduced to water and characterized using neutron reflectivity and impedance spectroscopy. Impedance data indicate that when moved from air to water, hybrid bilayers exhibit a dielectric constant and thickness that is essentially equivalent to hybrid bilayers prepared in situ by adding phospholipid vesicles to alkanethiol monolayers in water. Neutron scattering from these samples was collected out to a wave vector transfer of 0.25 A(-1), and provided a sensitivity to changes in total layer thickness on the order of 1-2 A. The data confirm that the acyl chain region of the phospholipid layer is consistent with that observed for phospholipid-phospholipid bilayers, but suggest greater hydration of the phospholipid headgroups of HBMs than has been reported in studies of lipid multilayers.

AND/R: Advanced neutron diffractometer/reflectometer for investigation of thin films and multilayers for the life sciences

An elastic neutron scattering instrument, the advanced neutron diffractometer/reflectometer (AND/R), has recently been commissioned at the National Institute of Standards and Technology Center for Neutron Research. The AND/R is the centerpiece of the Cold Neutrons for Biology and Technology partnership, which is dedicated to the structural characterization of thin films and multilayers of biological interest. The instrument is capable of measuring both specular and nonspecular reflectivity, as well as crystalline or semicrystalline diffraction at wave-vector transfers up to approximately 2.20 Å(-1). A detailed description of this flexible instrument and its performance characteristics in various operating modes are given.

First-Principles Determination of Hybrid Bilayer Membrane Structure by Phase-Sensitive Neutron Reflectometry

The application of a new, phase-sensitive neutron reflectometry method to reveal the compositional depth profiles of biomimetic membranes is reported. Determination of the complex reflection amplitude allows the related scattering length density (SLD) profile to be obtained by a first-principles inversion without the need for fitting or adjustable parameters. The SLD profile so obtained is unique for most membranes and can therefore be directly compared with the SLD profile corresponding to the chemical compositional profile of the film, as predicted, for example, by a molecular dynamics simulation. Knowledge of the real part of the reflection amplitude, in addition to enabling the inversion, makes it possible to assign a spatial resolution to the profile for a given range of wavevector transfer over which the reflectivity data are collected. Furthermore, the imaginary part of the reflection amplitude can be used as a sensitive diagnostic tool for recognizing the existence of certain in-plane inhomogeneities in the sample. Measurements demonstrating the practical realization of this phase-sensitive technique were performed on a hybrid bilayer membrane (self-assembled monolayer of thiahexa (ethylene oxide) alkane on gold and a phospholipid layer) in intimate contact with an aqueous reservoir. Analysis of the experimental results shows that accurate compositional depth profiles can now be obtained with a spatial resolution in the subnanometer range, primarily limited by the background originating from the reservoir and the roughness of the films supporting substrate.

Phase determination and inversion in specular neutron reflectometry

Abstract We present results testing the experimental feasibility of recently discovered solutions of the dynamical phase problem for specular reflection. Using layers of Cu, Ni, and Mo as references, the real and imaginary parts of the complex reflection amplitude were measured from neutron reflectivities for an asymmetric composite film consisting of deuterated polystyrene and Si. The reflection amplitude was also measured from neutron reflectivity without references for a symmetric deuterated polystyrene film. These amplitudes were inverted using the Gel’fand–Levitan–Marchenko equation to produce scattering length density profiles for the films studied. The inverted profiles compared reasonably well to the expected potentials. We conclude that such methods are practical with current instrumentation.

Determination of the Effective Transverse Coherence of the Neutron Wave Packet as Employed in Reflectivity Investigations of Condensed-Matter Structures. I. Measurements

The primary purpose of this investigation is to determine the effective coherent extent of the neutron wave packet transverse to its mean propagation vector k, when it is prepared in a typical instrument used to study the structure of materials in thin film form via specular reflection. There are two principal reasons for doing so. One has to do with the fundamental physical interest in the characteristics of a free neutron as a quantum object while the other is of a more practical nature, relating to the understanding of how to interpret elastic scattering data when the neutron is employed as a probe of condensed matter structure on an atomic or nanometer scale. Knowing such a basic physical characteristic as the neutrons effective transverse coherence can dictate how to properly analyze specular reflectivity data obtained for material film structures possessing some amount of in-plane inhomogeneity. In this study we describe a means of measuring the effective transverse coherence length of the neutron wave packet by specular reflection from a series of diffraction gratings of different spacings. Complementary non-specular measurements of the widths of grating reflections were also performed which corroborate the specular results. (Part I principally describes measurements interpreted according to the theoretical picture presented in Part II.) Each grating was fabricated by lift-off photo-lithography patterning of a nickel film (approximately 1000 Angstroms thick) formed by physical vapor deposition on a flat silicon crystal surface. The grating periods ranged from 10 microns (5 microns Ni stripe, 5 microns intervening space) to several hundred microns. The transverse coherence length, modeled as the width of the wave packet, was determined from an analysis of the specular reflectivity curves of the set of gratings.

Neutron reflectometry, x-ray reflectometry, and spectroscopic ellipsometry characterization of thin SiO2 on Si

We present here a comparison of neutron reflectometry, x-ray reflectometry, and spectroscopic ellipsometry on a thin oxide film. These three probes each independently determine the structure of the film as a function of depth. We find an excellent agreement between the three techniques for measurements of thicknesses and interfacial roughnesses for both the SiO2 and surface contamination layers found in the sample. Realistic models based on interface parameters measured herein indicate that as the SiO2 layers decrease to sizes projected for future generations of electronic devices, both spectroscopic ellipsometry and neutron reflectometry can easily measure SiO2 films to 2 nm thick or less.

Porous Mg formation upon dehydrogenation of MgH2 thin films

The hydrogenation and dehydrogenation of a thin film of Mg with a Pd cap layer was measured using neutron reflectometry. Upon hydrogenation, (at 373 K and 0.2 MPa H2), the Mg film swelled in the surface normal direction by an amount roughly equal to the difference in volume between MgH2 and Mg. After dehydrogenation (at 343–423 K), the Mg film returned to a composition of Mg but retained the swelled thickness by incorporating voids. The presence of the voids is confirmed by SEM micrographs. The voids may explain some of the changes in absorption kinetics after full cycling of Mg films.

Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes

Using molecular dynamics simulations, small-angle neutron scattering, and a variety of spectroscopic techniques, we evaluated the ion solvation and transport behaviors in aqueous electrolytes containing bis(trifluoromethanesulfonyl)imide. We discovered that, at high salt concentrations (from 10 to 21 mol/kg), a disproportion of cation solvation occurs, leading to a liquid structure of heterogeneous domains with a characteristic length scale of 1 to 2 nm. This unusual nano-heterogeneity effectively decouples cations from the Coulombic traps of anions and provides a 3D percolating lithium-water network, via which 40% of the lithium cations are liberated for fast ion transport even in concentration ranges traditionally considered too viscous. Due to such percolation networks, superconcentrated aqueous electrolytes are characterized by a high lithium-transference number (0.73), which is key to supporting an assortment of battery chemistries at high rate. The in-depth understanding of this transport mechanism establishes guiding principles to the tailored design of future superconcentrated electrolyte systems.

Highly reversible zinc metal anode for aqueous batteries

Metallic zinc (Zn) has been regarded as an ideal anode material for aqueous batteries because of its high theoretical capacity (820 mA h g–1), low potential (−0.762 V versus the standard hydrogen electrode), high abundance, low toxicity and intrinsic safety. However, aqueous Zn chemistry persistently suffers from irreversibility issues, as exemplified by its low coulombic efficiency (CE) and dendrite growth during plating/ stripping, and sustained water consumption. In this work, we demonstrate that an aqueous electrolyte based on Zn and lithium salts at high concentrations is a very effective way to address these issues. This unique electrolyte not only enables dendrite-free Zn plating/stripping at nearly 100% CE, but also retains water in the open atmosphere, which makes hermetic cell configurations optional. These merits bring unprecedented flexibility and reversibility to Zn batteries using either LiMn2O4 or O2 cathodes—the former deliver 180 W h kg–1 while retaining 80% capacity for >4,000 cycles, and the latter deliver 300 W h kg–1 (1,000 W h kg–1 based on the cathode) for >200 cycles.Metallic zinc is an ideal anode material for aqueous batteries but suffers from irreversibility issues. An aqueous electrolyte based on Zn and lithium salts using either LiMn2O4 or O2 cathodes now brings unprecedented flexibility and reversibility to Zn batteries.

X‐ray reflectivity determination of interface roughness correlated with transport properties of (AlGa)As/GaAs high electron mobility transistor devices

To explore the role of interface scattering in high electron mobility transistor (HEMT) device performance, a series of samples consisting of both a superlattice and a HEMT structure were grown by molecular beam epitaxy (MBE) at temperatures ranging from 500 to 630 °C. Hall measurements indicate a trend toward higher mobilities in samples grown at higher temperatures. Subsequent x‐ray reflectivity measurements were made, and the data were fitted by least‐squares refinement of a calculated reflectivity curve determined from a model of the sample structure to obtain the composition profile along the growth direction. These results indicate smoother interfaces for the samples with higher mobilities.