Response of the Lattice across the Filling-Controlled Mott Metal-Insulator Transition of a Rare Earth Titanate.

The lattice response of a prototype Mott insulator, SmTiO_{3}, to hole doping is investigated with atomic-scale spatial resolution. SmTiO_{3} films are doped with Sr on the Sm site with concentrations that span the insulating and metallic sides of the filling-controlled Mott metal-insulator transition (MIT). The GdFeO_{3}-type distortions are investigated using an atomic resolution scanning transmission electron microscopy technique that can resolve small lattice distortions with picometer precision. We show that these distortions are gradually and uniformly reduced as the Sr concentration is increased without any phase separation. Significant distortions persist into the metallic state. The results present a new picture of the physics of this prototype filling-controlled MIT, which is discussed.

Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors.

A scarcity of stable n-type doping strategies compatible with facile processing has been a major impediment to the advancement of organic electronic devices. Localizing dopants near the cores of conductive molecules can lead to improved efficacy of doping. We and others recently showed the effectiveness of tethering dopants covalently to an electron-deficient aromatic molecule using trimethylammonium functionalization with hydroxide counterions linked to a perylene diimide core by alkyl spacers. In this work, we demonstrate that, contrary to previous hypotheses, the main driver responsible for the highly effective doping observed in thin films is the formation of tethered tertiary amine moieties during thin film processing. Furthermore, we demonstrate that tethered tertiary amine groups are powerful and general n-doping motifs for the successful generation of free electron carriers in the solid-state, not only when coupled to the perylene diimide molecular core, but also when linked with other small molecule systems including naphthalene diimide, diketopyrrolopyrrole, and fullerene derivatives. Our findings help expand a promising molecular design strategy for future enhancements of n-type organic electronic materials.

Schmitt trigger using a self-healing ionic liquid gated transistor.

Electrical double layer transistors using ionic liquids as the gate and ZnO as the semiconductor exhibit stable operation in the presence of redox active additives. The characteristics of the device enable single components with the response of a Schmitt trigger.

Rapid microwave preparation and ab initio studies of the stability of the complex noble metal oxides La2BaPdO5 and La2BaPtO5.

We present a rapid microwave-assisted solid-state approach to prepare complex platinum-group metal oxides with the formula La2BaMO5 (M = Pd, Pt). While conventional furnace-based preparations of these compounds take several days and often require oxidizing conditions, the microwave-assisted pathway enables the target compounds to be obtained with high phase purity in about 20 min of reaction time in air without the multiple regrindings that are required of conventional solid-state synthesis. These complex oxides are stable in various atmospheres up to 1000 °C unlike the simple noble metal oxides, which are reduced even at room temperature. Density functional theory-based calculations have been employed to establish the stability of these complex oxides and to understand the electronic structure origins of the stability, most notably the influence of electropositive cations. It is shown that the presence of electropositive ions in the oxide crystal structure "softens" the oxygen anion and results in more covalent (Pd/Pt)-O interactions.

Bonding structure of phenylacetylene on hydrogen-terminated Si(111) and Si(100): surface photoelectron spectroscopy analysis and ab initio calculations.

Interfaces between phenylacetylene (PA) monolayers and two silicon surfaces, Si(111) and Si(100), are probed by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and the results are analyzed using ab initio molecular orbital calculations. The monolayer systems are prepared via the surface hydrosilylation reaction between PA and hydrogen-terminated silicon surfaces. The following spectral features are obtained for both of the PA-Si(111) and PA-Si(100) systems: a broad π-π* shakeup peak at 292 eV (XPS), a broad first ionization peak at 3.8 eV (UPS), and a low-energy C 1s → π* resonance peak at 284.3 eV (NEXAFS). These findings are ascribed to a styrene-like π-conjugated molecular structure at the PA-Si interface by comparing the experimental data with theoretical analysis results. A conclusion is drawn that the vinyl group can keep its π-conjugation character on the hydrogen-terminated Si(100) [H:Si(100)] surface composed of the dihydride (SiH(2)) groups as well as on hydrogen-terminated Si(111) having the monohydride (SiH) group. The formation mechanism of the PA-Si(100) interface is investigated within cluster ab initio calculations, and the possible structure of the H:Si(100) surface is discussed based on available data.

Transformation of stable glasses into supercooled liquids: growth fronts and anomalously fast liquid diffusion.

Physical vapor deposition onto substrates near 0.85T(g) can prepare organic glasses with low enthalpy, high density, and high thermal stability. Isotopically labeled multilayer films of tris(naphthyl)benzene and indomethacin stable glasses were prepared and secondary ion mass spectrometry was used to study the evolution of these materials upon heating above T(g). In contrast to ordinary glasses, when stable glasses are held above T(g) they transform to a liquid via a growth front mechanism. In these experiments, growth fronts are initiated at the free surface of the glass and in some cases at the glass/substrate interface or an internal interface in the glass. For tris(naphthyl)benzene, the velocity of this growth front is observed to be nearly independent of the stability of the glass. Diffusion in the liquid that results from the growth front is initially 2-5 times faster than for the equilibrium supercooled liquid at the same temperature; the nature of this liquid is unclear. Under some circumstances, the slow evolution of this unusually mobile liquid into the equilibrium supercooled liquid can be observed.

Self-diffusion of supercooled tris-naphthylbenzene.

We have measured self-diffusion coefficients for deeply supercooled tris-naphthylbenzene using secondary ion mass spectrometry. Isotopically labeled multilayer films were prepared by vapor deposition. For samples deposited within a few K of T(g), the evolution of the concentration profile was observed to be Fickian on all accessible length and time scales. Diffusion is enhanced by a factor of approximately 100 at 338 K when compared to the prediction of the Stokes-Einstein model. In combination with previous neutron reflectivity experiments, these measurements quantify the length scale at which dynamics cross over to non-Fickian behavior in supercooled TNB. Comparisons are made between this diffusion data and other measurements of dynamics in supercooled TNB, including probe diffusion and crystal growth rates. An earlier report of self-diffusion coefficients for TNB was in error because the samples were prepared by vapor deposition at T(g) - 50 K, creating very stable glasses in which the concentration profile does not evolve by Fickian diffusion.

Stable glass transformation to supercooled liquid via surface-initiated growth front.

Highly stable glasses of tris-naphthylbenzene transform into a liquid when annealed above the glass transition temperature T_{g}. In contrast to the predictions of standard models, the observed transformation is spatially inhomogeneous. Secondary ion mass spectrometry experiments on isotopically labeled multilayer films show that the liquid grows into the stable glass with sharp growth fronts initiated at the free surface and at the interface with the substrate. For the free surface, the growth velocity is constant in time and has the same temperature dependence as self-diffusion in the equilibrium supercooled liquid. These stable glasses are packed so efficiently that surfaces and interfaces are required to initiate the transformation to the liquid even well above T_{g}.

Metals and the integrity of a biological coating: the cuticle of mussel byssus.

The cuticle of mussel byssal threads is a robust natural coating that combines high extensibility with high stiffness and hardness. In this study, fluorescence microscopy and elemental analysis were exploited to show that the 3,4-dihydroxyphenyl-L-alanine (dopa) residues of mussel foot protein-1 colocalize with Fe and Ca distributions in the cuticle of Mytilus galloprovincialis mussel byssal threads. Chelated removal of Fe and Ca from the cuticle of intact threads resulted in a 50% reduction in cuticle hardness, and thin sections subjected to the same treatment showed a disruption of cuticle integrity. Dopa-metal complexes may provide significant interactions for the integrity of composite cuticles deformed under tension.

Structural characterization of an elevated lipid bilayer obtained by stepwise functionalization of a self-assembled alkenyl silane film.

This work reports a novel tethered lipid membrane supported on silicon oxide providing an improved model cell membrane. There is an increasing need for robust solid supported fluid model membranes that can be easily deposited on soft cushions. In such architecture the space between the membrane and the substrate should be tunable in the nanometer range. For this purpose a SiO(2) surface was functionalized with poly(ethylene glycol) (PEG)-lipid tethers and further modified with poly(ethylene glycol) making a biologically passivated substrate available for lipid bilayer deposition. First, a short chain self-assembled alkenyl silane film was oxidized to yield terminal COOH groups and then functionalized with amino-terminated PEG-lipids via N-hydroxysuccinimide chemistry. The functionalized silane film was then additionally passivated by functionalization of unreacted COOH groups with amino-terminated PEG of variable chain length. X-ray photoelectron spectroscopy (XPS) analysis of dry films, carried out near the C 1s ionization edge to characterize chemical groups formed in the near-surface region, confirmed binding of PEG-lipid tethers to the silane film. XPS further indicated that backfilling with PEG caused the lipid tails to stick up above the PEG layer which was confirmed by the x-ray reflectivity measurements. Lipid vesicle fusion on these surfaces in the presence of excess water resulted in the formation of supported membranes characterized by very high homogeneity and long range mobility, as confirmed by fluorescence bleaching experiments. Even after repeated drying-hydrating cycles, these robust surfaces provided good templates for high fluidity elevated membranes. X-ray reflectivity measurements of the tethered membranes, with a resolution of 0.6 nm in water, showed that these fluid membranes are elevated up to 8 nm above the silicon oxide surface.

Diblock copolymer surfactant transport across the interface between two homopolymers.

Dynamics of adsorption and desorption of a diblock copolymer to an interface between two homopolymers was measured using dynamic secondary-ion mass spectrometry (SIMS). Thin films were constructed consisting of a layer of saturated polybutadiene with 90% 1,2-addition (sPB90), followed by a layer of saturated polybutadiene with 63% 1,2-addition (sPB63), and finally by another layer of the sPB90 homopolymer. A sPB90-sPB63 diblock copolymer was initially included only in the top sPB90 layer of the film at a volume fraction of 0.05. The thin films were annealed at ambient temperature for times ranging between 0.2 and 108 h, and the concentration profiles of the diblock copolymer through the films were measured using SIMS. The dynamics of adsorption and desorption of the diblock copolymer at the two sPB90-sPB63 interfaces was gauged by comparing the different transient concentration profiles. The sorption process was modeled as diffusion in an external field, generated from self-consistent field theory (SCFT). All parameters for the model were determined independently. Although the model neglects the dynamics of conformational change, experimental results matched theory very well.

Exploring gradients of halogens and zinc in the surface and subsurface of Nereis jaws.

The outstanding mechanical properties of impact-bearing tissues, such as Nereis jaws, make their morphology and chemical composition a subject of particular interest. The complex structure of the jaw was recently reported to exhibit molecular gradients that were closely correlated with stiffness and hardness.(18) Accordingly, we have explored the spatial distribution and bonding chemistries of Zn and the halogens in the surface structure of the jaws. Using secondary ion mass spectrometry (SIMS) and scanning electron microscopy (SEM), we found that Cl, Br, and I distributions are enhanced in surface layers of the basal protected portion of the jaw but are shifted to greater depths toward the exposed jaw tip. There are thus two complementary halogen gradients in the jaw: one on the surface that decreases from the base to the tip, coupled to an increasing one in the subsurface layers. The outer surface coating appeared to have granular morphology, in contrast to the anisotropic, fibrous core that dominates the subarchitecture. Using X-ray photoelectron spectroscopy (XPS), we discovered that Zn, I, and Br in the jaws have single chemical environments whereas chlorine is present in two distinct modes (Cl-Zn and Cl-C). Given the inverse relationship between surface exposure and halogen abundance in the jaws, it is unlikely that the halogens contribute directly to mechanical properties such as wear and hardness.

Molecular recognition in structured matrixes: control of guest localization in block copolymer films.

We demonstrate the use of molecular recognition to control the spatial distribution of guest molecules within block copolymer films. Block copolymers bearing recognition units were combined with complementary and noncomplementary molecules, and the extent of segregation of these molecules into the different domain types within microphase-separated thin films was quantitatively analyzed using dynamic secondary ion mass spectrometry (SIMS). Complementarity between the guest molecules and the polymer functionalities proved to be a key factor and an efficient tool for directing the segregation preference of the molecules to the different domain types. The effect of segregation preference on the glass transition temperature was studied using differential scanning calorimetry (DSC), and the results corroborate the SIMS findings. In a complementary study, guests with tunable sizes (via dendron substituents) were used to control block copolymer morphology. Morphological characterization using transmission electron microscopy (TEM) and X-ray diffraction reveal that selectivity differences can be directly translated into the ability to obtain different morphologies from recognition unit-functionalized block copolymer scaffolds.

Preparing contamination-free mica substrates for surface characterization, force measurements, and imaging.

Due to its perfect cleavage that provides large areas of molecularly smooth, chemically inert surfaces, mica is the most commonly used natural substrate in measurements with the surface forces apparatus (SFA), in atomic force microscopy (AFM), and in many adsorption studies. However, preparing mica surfaces that are truly clean is not easy since mica is a high-energy surface that readily adsorbs water, organic contaminants, and gases from the atmosphere. Mica can also become charged on cleaving, which makes it prone to picking up oppositely charged particles or mica flakes from the surroundings. High refractive index particles, such as metals, will adhere to mica through van der Waals forces. Recent articles have demonstrated that particle contamination is obtained when inappropriate cutting and handling procedures for the mica are used. In this paper, we show that both particle and other critical contamination is easy to detect and provide proper steps to take during the sample preparation process.