Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams.

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

Surface-waves, stability, and scattering for a lined duct with flow

We consider a straight cylindrical duct with a steady subsonic axial flow and a reacting boundary (e.g. an acoustic lining). The wave modes are separated into ordinary acoustic duct modes, and surface modes confined to a small neighbourhood of the boundary. Many researchers have used a mass-spring-damper boundary model, for which one surface mode has previously been identified as a convective instability; however, we show the stability analysis used in such cases to be questionable. We investigate instead the stability of the surface modes using the Briggs-Bers criterion for a Flügge thin-shell boundary model. For modest frequencies and wavenumbers the thin-shell has an impedance which is effectively that of a mass-spring-damper, although for the large wavenumbers needed for the stability analysis the thin-shell and mass-spring-damper impedances diverge, owing to the thin shell's bending stiffness. The thin shell model may therefore be viewed as a regularization of the mass-spring-damper model which accounts for nonlocally-reacting effects. We find all modes to be stable for realistic thin-shell parameters, while absolute instabilities are demonstrated for extremely thin boundary thicknesses. The limit of vanishing bending stiffness is found to be a singular limit, yielding absolute instabilities of arbitrarily large temporal growth rate. We propose that the problems with previous stability analyses are due to the neglect of something akin to bending stiffness in the boundary model. Our conclusion is that the surface mode previously identified as a convective instability may well be stable in reality. Finally, inspired by Rienstra's recent analysis, we investigate the scattering of an acoustic mode as it encounters a sudden change from a hard-wall to a thin-shell boundary, using a Wiener-Hopf technique. The thin-shell is considered to be clamped to the hard-wall. The acoustic mode is found to scatter into transmitted and reflected acoustic modes, and surface modes strongly linked to the solid waves in the boundary, although no longitudinal or transverse waves within the boundary are excited. Examples are provided that demonstrate total transmission, total reflection, and a combination of the two. This thin-shell scattering problem is preferable to the mass-spring-damper scattering problem presented by Rienstra, since the thin-shell problem is fully determined and does not need to appeal to a Kutta-like condition or the inclusion of an instability in order to avoid a surface-streamline cusp at the boundary change.