Disorder-Induced Magnetotransport Anomalies in Amorphous and Textured Co1-xSix Semimetal Thin Films.

In recent times the chiral semimetal cobalt monosilicide (CoSi) has emerged as a prototypical, nearly ideal topological conductor hosting giant, topologically protected Fermi arcs. Exotic topological quantum properties have already been identified in CoSi bulk single crystals. However, CoSi is also known for being prone to intrinsic disorder and inhomogeneities, which, despite topological protection, risk jeopardizing its topological transport features. Alternatively, topology may be stabilized by disorder, suggesting the tantalizing possibility of an amorphous variant of a topological metal, yet to be discovered. In this respect, understanding how microstructure and stoichiometry affect magnetotransport properties is of pivotal importance, particularly in case of low-dimensional CoSi thin films and devices. Here we comprehensively investigate the magnetotransport and magnetic properties of ≈25 nm Co1-xSix thin films grown on a MgO substrate with controlled film microstructure (amorphous vs textured) and chemical composition (0.40 < x < 0.60). The resistivity of Co1-xSix thin films is nearly insensitive to the film microstructure and displays a progressive evolution from metallic-like (dρxx/dT > 0) to semiconducting-like (dρxx/dT < 0) regimes of conduction upon increasing the silicon content. A variety of anomalies in the magnetotransport properties, comprising for instance signatures consistent with quantum localization and electron-electron interactions, anomalous Hall and Kondo effects, and the occurrence of magnetic exchange interactions, are attributable to the prominent influence of intrinsic structural and chemical disorder. Our systematic survey brings to attention the complexity and the challenges involved in the prospective exploitation of the topological chiral semimetal CoSi in nanoscale thin films and devices.

DC magnetron sputtered polyaniline-HCl thin films for chemical sensing applications.

Thin films of conducting polymers exhibit unique chemical and physical properties that render them integral parts in microelectronics, energy storage devices, and chemical sensors. Overall, polyaniline (PAni) doped in acidic media has shown metal-like electronic conductivity, though exact physical and chemical properties are dependent on the polymer structure and dopant type. Difficulties arising from poor processability render production of doped PAni thin films particularly challenging. In this contribution, DC magnetron sputtering, a physical vapor deposition technique, is applied to the preparation of conductive thin films of PAni doped with hydrochloric acid (PAni-HCl) in an effort to circumvent issues associated with conventional thin film preparation methods. Samples manufactured by the sputtering method are analyzed along with samples prepared by conventional drop-casting. Physical characterization (atomic force microscopy, AFM) confirm the presence of PAni-HCl and show that films exhibit a reduced roughness and potentially pinhole-free coverage of the substrate. Spectroscopic evidence (UV-vis, FT-IR, and X-ray photoelectron spectroscopy (XPS)) suggests that structural changes and loss of conductivity, not uncommon during PAni processing, does occur during the preparation process. Finally, the applicability of sputtered films to gas-phase sensing of NH(3) was investigated with surface plasmon resonance (SPR) spectroscopy and compared to previous contributions. In summary, sputtered PAni-HCl films exhibit quantifiable, reversible behavior upon exposure to NH(3) with a calculated LOD (by method) approaching 0.4 ppm NH(3) in dry air.

Additive Lithography-Organic Monolayer Patterning Coupled with an Area-Selective Deposition.

The combination of area-selective deposition (ASD) with a patternable organic monolayer provides a versatile additive lithography platform, enabling the generation of a variety of nanoscale feature geometries. Stearate hydroxamic acid self-assembled monolayers (SAMs) were patterned with extreme ultraviolet (λ = 13.5 nm) or electron beam irradiation and developed with ASD to achieve line space patterns as small as 50 nm. Density functional theory was employed to aid in the synthesis of hydroxamic acid derivatives with optimized packing density to enhance the imaging contrast and improve dose sensitivity. Near-edge X-ray absorption fine structure spectroscopy and infrared spectroscopy reveal that the imaging mechanism is based on improved deposition inhibition provided by the cross-linking of the SAM to produce a more effective barrier during a subsequent deposition step. With patterned substrates composed of coplanar copper lines and silicon spacers, hydroxamic acids selectively formed monolayers on the metal portions and could undergo a pattern-wise exposure followed by ASD in the first combination of a patternable monolayer with ASD. This material system presents an additional capability compared to traditional ASD approaches that generally reflect a starting patterned surface. Furthermore, this bottoms-up additive approach to lithography may be a viable alternative to subtractive nanoscale feature generation.

Surface Initiated Polymer Thin Films for the Area Selective Deposition and Etching of Metal Oxides.

The area selective growth of polymers and their use as inhibiting layers for inorganic film depositions may provide a valuable self-aligned process for fabrication. Polynorbornene (PNB) thin films were grown from surface-bound initiators and show inhibitory properties against the atomic layer deposition (ALD) of ZnO and TiO2. Area selective control of the polymerization was achieved through the synthesis of initiators that incorporate surface-binding ligands, enabling their selective attachment to metal oxide features versus silicon dielectrics, which were then used to initiate surface polymerizations. The subsequent use of these films in an ALD process enabled the area selective deposition (ASD) of up to 39 nm of ZnO. In addition, polymer thickness was found to play a key role, where films that underwent longer polymerization times were more effective at inhibiting higher numbers of ALD cycles. Finally, while the ASD of a TiO2 film was not achieved despite blanket studies showing inhibition, the ALD deposition on polymer regions of a patterned film produced a different quality metal oxide and therefore altered its etch resistance. This property was exploited in the area selective etch of a metal feature. This demonstration of an area selective surface-grown polymer to enable ASD and selective etch has implications for the fabrication of both micro- and nanoscale features and surfaces.

Non-equilibrium cation distribution and enhanced spin disorder in hollow CoFe2O4 nanoparticles.

We present magnetic properties of hollow and solid CoFe(2)O(4) nanoparticles that were obtained by annealing of Co(33)Fe(67)/CoFe(2)O(4) (core/shell) nanoparticles. Hollow nanoparticles were polycrystalline whereas the solid nanoparticles were mostly single crystal. Electronic structure studies were performed by photoemission which revealed that particles with hollow morphology have a higher degree of inversion compared to solid nanoparticles and the bulk counterpart. Electronic structure and the magnetic measurements show that particles have uncompensated spins. Quantitative comparison of saturation magnetization (M(S )), assuming bulk Néel type spin structure with cationic distribution, calculated from quantitative XPS analysis, is presented. The thickness of uncompensated spins is calculated to be significantly large for particles with hollow morphology compared to solid nanoparticles. Both morphologies show a lack of saturation up to 7 T. Moreover magnetic irreversibility exists up to 7 T of cooling fields for the entire temperature range (10-300 K). These effects are due to the large bulk anisotropy constant of CoFe(2)O(4) which is the highest among the cubic spinel ferrites. The effect of the uncompensated spins for hollow nanoparticles was investigated by cooling the sample in large fields of up to 9 T. The magnitude of horizontal shift resulting from the unidirectional anisotropy was more than three times larger than that of solid nanoparticles. As an indication signature of uncompensated spin structure, 11% vertical shift for hollow nanoparticles is observed, whereas solid nanoparticles do not show a similar shift. Deconvolution of the hysteresis response recorded at 300 K reveals the presence of a significant paramagnetic component for particles with hollow morphology which further confirms enhanced spin disorder.

Optimization of protein patterns for neuronal cell culture applications.

In the present study, we fabricated two-component extracellular matrix protein patterned substrates with fibronectin (FN) and laminin (LN) because of our interest in the mechanism of axonal regeneration and injury in the central and peripheral nervous systems. The authors investigated how the patterning order and method of attachment affected the spatial distribution and biological activity of the immobilized proteins. Micro-contact printing (µCP) techniques in concert with reactive surface chemistry were used to modify glass substrates with one- and two-component films of FN and LN, including micrometer-scale patterns of FN and LN. The composition and spatial distributions of both proteins on the patterned surfaces were characterized by x ray photoelectron spectroscopy, epi-fluorescence microscopy, atomic force microscopy, and time-of-flight secondary-ion mass spectrometry. The authors also characterized the biological activity of the top-most protein layer in a two-layer protein system as well as the ability of the top-most protein layer to mask the biological activity of an underlying protein layer using a fluorescence-based enzyme-linked immunosorbent assay. The order of protein deposition significantly affected the relative biological activity of the upper-most and underlying immobilized proteins. As a result of these optimization studies, maximum biological activity per surface protein was achieved by first immobilizing FN from solution, followed by µCP of LN on the FN. Addition of µCP LN films was able to mask ∼84% of the underlying FN activity, whereas µCP FN films were only able to mask ∼27% of the underlying LN activity.

Development of an analytical method for distinguishing ammonium bicarbonate from the products of an aqueous ammonia CO2 scrubber.

The link between anthropogenic emissions of carbon dioxide, increasing atmospheric CO2 levels, and concomitantly increasing global temperatures is established and accepted. The use of aqueous ammonia, to capture CO2 and produce an inexpensive nitrogen fertilizer, ammonium bicarbonate (ABC), is believed to be a feasible approach to CO2 sequestration. Due to the varying concentrations of reactants and varying reaction conditions, different ammonia-carbon compounds may be produced. ABC is the ideal product for maximizing NH3 utilization in CO2 capture; therefore, identification and quantification of ABC in the reaction products is mandatory. Various analytical techniques were used to distinguish and quantify the ABC. Fourier transform infrared spectroscopy can only be used to distinguish ammonium carbamate, and. X-ray diffraction can be used to qualitatively distinguish ABC from the other possible products of the CO2 capture reaction. Carbon-hydrogen-nitrogen elemental analysis and near-infrared (NIR) spectroscopy were used to quantify ABC, with both techniques giving +/-5% agreement for ABC concentrations for 8 of 13 samples from a bench-scale aqueous ammonia CO2 scrubbing system. An additional 3 of the 13 samples were within +/-12%. Results indicate that NIR will be an ideal tool for real-time, on-line measurements of ABC in a full-scale aqueous ammonia CO2 scrubber. The ABC in 11 samples from the bench-scale scrubber at Western Kentucky University was determined by these techniques and assessed to have very good quality as a fertilizer in accordance with GB-3559-92, the Agricultural Ammonium Bicarbonate National Standard of China.