Infrared and Raman spectral signatures of aromatic nitration in thermoplastic urethanes

The spectral signatures of nitro attack of the aromatic portion of thermoplastic urethanes (TPU) were determined. Eight fragment molecules were synthesized that represent the nitrated and pristine methylenediphenyl section common to many TPUs. Infrared (IR) and Raman (785 nm illumination) spectra were collected and modeled using the B3LYP/6-31G(d)//B3LYP/6-31G(d) model chemistry. Normal mode animations were used to fully assign the vibrational spectra of each fragment. The vibrational assignment was used to develop a diagnostic method for aromatic nitro attack in thermoplastic urethanes. The symmetric NO(2) stretch coupled out of phase with the C-NO(2) stretch (1330 cm(-1)) was found to be free from spectral interferences. Spectral reference regions that enable correction for physical differences between samples were determined. The carbonyl stretch at 1700 cm(-1) was the best IR reference region, yielding a limit of quantitation (LOQ) of 0.66 +/- 0.02 g N/100 g Estane. Secondary IR reference regions were the N-H stretch at 3330 cm(-1) or the urethane nitrogen deformation at 1065 cm(-1). The reference region in the Raman was a ring stretching mode at 1590 cm(-1), giving an LOQ of 0.69 +/- 0.02 g N/100 g Estane. Raman spectroscopy displayed a larger calibration sensitivity (slope = 0.110 +/- 0.004) than IR spectroscopy (slope = 0.043 +/- 0.001) for nitration determination due to the large nitro Raman cross-section. The full spectral assignment of all eight molecules in the infrared and Raman is presented as supplemental material.     

Studying the surface of UHMWPE films modified with graphene nanoplatelets using a Raman mapping method

Abstract

This article discusses the nature of the distribution of intact polyaniline-functionalized graphene nanoplatelets (GNPs) in the surface layer of nanomodified films of ultra-high molecular weight polyethylene (UHMWPE) using a Raman mapping method. On the Raman maps, D, G, and 2D peaks can be observed for the 0.1?wt.% GNPs content in the UHMWPE. In the surface layer of the films containing 1.0?wt.% GNPs, these signals are not detected, thereby indicating the displacement of the nanomodifier into the polymer bulk. In contrast, the polyaniline-functionalized GNPs tend to migrate to the surface of the UHMWPE nanocomposite film and evenly distribute in the surface layer as the concentration increases from 0.1 to 2.0?wt.%.     

Annealing study of the electrical resistance and defect density in calcium films

Polycrystalline calcium films were deposited under ultrahigh vacuum onto a cooled silica substrate by thermal evaporation. During the growth process of the film a number of lattice defects are incorporated. In the present study, Vand's theory is applied and allows us to calculate the characteristic function F₀ expressing the law of distribution of the decay energies.     

Giant enhancement of the carrier mobility in silicon nanowires with diamond coating

We show theoretically that the low-field carrier mobility in silicon nanowires can be greatly enhanced by embedding the nanowires within a hard material such as diamond. The electron mobility in the cylindrical silicon nanowires with 4-nm diameter, which are coated with diamond, is 2 orders of magnitude higher at 10 K and a factor of 2 higher at room temperature than the mobility in a free-standing silicon nanowire. The importance of this result for the downscaled architectures and possible silicon-carbon nanoelectronic devices is augmented by an extra benefit of diamond, a superior heat conductor, for thermal management.     

On the determination of carrier mobility in compensated GaAs

The applicability of the Brooks-Herring and Conwell-Weisskopf formulas in calculations of the carrier mobility associated with scattering by ionized impurities is examined usingn-type GaAs as an example. The Brooks-Herring approximation is shown to be inapplicable at large compensation ratios, where the Conwell-Weisskopf formula is more accurate. The applicability limits of the two formulas are established for calculations of carrier mobility from dopant concentration and compensation ratio and for calculations of the concentration of ionized centers (compensation ratio) from carrier concentration and mobility. The predicted applicability limits are consistent with experimental data.     

Metal-insulator transition in graphite: A comparison to heterostructures with high carrier mobility

Conditions for a transition from the insulator (I) to metal (M) state in the electron system of highly oriented pyrolytic graphite (HOPG) have been studied by means of magnetotransport measurements in a broad temperature range (0.3–150 K). In magnetic fields below a certain critical value (B < B _c ≈ 0.05 T), HOPG exhibits the classical magnetoresistance, while for B > B _c, the temperature dependence of the resistance is determined by the state (insulator versus metal) of the electron system. The M-I transition in HOPG, by analogy with that in heterostructures with two-dimensional electron gas, obeys the power law T _c ∞ (B ? B _c) ^k (k = 0.25) and is related to the spin-orbit interaction of electron waves.     

The method of separation for evolutionary spectral density estimation of multi-variate and multi-dimensional non-stationary stochastic processes

The method of separation can be used as a non-parametric estimation technique, especially suitable for evolutionary spectral density functions of uniformly modulated and strongly narrow-band stochastic processes. The paper at hand provides a consistent derivation of method of separation based spectrum estimation for the general multi-variate and multi-dimensional case. The validity of the method is demonstrated by benchmark tests with uniformly modulated spectra, for which convergence to the analytical solution is demonstrated. The key advantage of the method of separation is the minimization of spectral dispersion due to optimum time- or space–frequency localization. This is illustrated by the calibration of multi-dimensional and multi-variate geometric imperfection models from strongly narrow-band measurements in I-beams and cylindrical shells. Finally, the application of the method of separation based estimates for the stochastic buckling analysis of the example structures is briefly discussed.     

Measuring the capacitance of individual semiconductor nanowires for carrier mobility assessment

Capacitance-voltage characteristics of individual germanium nanowire field effect transistors were directly measured and used to assess carrier mobility in nanowires for the first time, thereby removing uncertainties in calculated mobility due to device geometries, surface and interface states, and gate dielectric constants and thicknesses. Direct experimental evidence showed that surround-gated nanowire transistors exhibit higher capacitance and better electrostatic gate control than top-gated devices, and are the most promising structure for future high performance nanoelectronics.     

Local frequency estimation for the fringe pattern with a spatial carrier: principle and applications

A local frequency estimation approach for the fringe pattern with a spatial carrier by which the 2D spatial frequencies at a certain pixel are estimated from its neighborhood is presented. The applications of this approach in the fringe pattern analyses are also introduced. First, a 2D spatial carrier phase-shifting algorithm is derived. With it the detuning errors induced by frequency mismatching are avoided, and the stronger phase deformations can be successfully coped with. Second, a novel aperture extrapolation method is developed by which the phase accuracies of the Fourier-transform method at the aperture boundaries are effectively improved.     

Observation of Raman g-peak split for graphene nanoribbons with hydrogen-terminated zigzag edges

Raman scattering of individual hydrogen-terminated zigzag-edged graphene nanoribbons (Z-GNRs) was studied with focus on the G-peak. In addition to the bulk graphene G-peak appearing at ～1594 cm(-1) (G(+)), an edge-related G-peak at ～1583 cm(-1) (G(-)) was observed for Z-GNRs. This additional Raman vibrational mode originates from the zigzag edges where localized metallic edge states are present. The relative intensity ratio G(-)/G(+) displays a strong dependence on the ribbon width (W). It increases gradually with decreasing W, and the G(+) finally vanishes at W = 5(±3) nm. Polarized Raman scattering was also employed to confirm the four-fold symmetry of the split TO modes, and the results are in good agreement with previous theoretical predictions. Our work offers the first direct experimental evidence to confirm the validity of predicted Raman scattering of GNRs.     

Effects of strain on the carrier mobility in silicon nanowires

We investigate electron and hole mobilities in strained silicon nanowires (Si NWs) within an atomistic tight-binding framework. We show that the carrier mobilities in Si NWs are very responsive to strain and can be enhanced or reduced by a factor >2 (up to 5×) for moderate strains in the ± 2% range. The effects of strain on the transport properties are, however, very dependent on the orientation of the nanowires. Stretched 100 Si NWs are found to be the best compromise for the transport of both electrons and holes in ≈10 nm diameter Si NWs. Our results demonstrate that strain engineering can be used as a very efficient booster for NW technologies and that due care must be given to process-induced strains in NW devices to achieve reproducible performances.     

Transient photocurrents as a spatially resolved probe of carrier transport and defect distributions in silicon thin films

Transient photocurrent spectroscopy (TPC) yields the energetic distribution of localised states in disordered semiconductors from an analysis of the decay of photocurrent with time following a short laser pulse. By comparing results at different laser excitation wavelengths, and hence absorption depths, information on spatial non-uniformities may also be inferred. Here we investigate the use of TPC as a spatial probe with reference to two thin-film silicon systems; amorphous silicon subjected to various light-induced degradation regimes, and microcrystalline silicon grown on a range of ‘seed’ layers. Computer simulation is used to support experimental findings, and to identify sensitivity and resolution limitations.     

Raman spectral analysis of TiO₂ thin films doped with rare-earth samarium

TiO₂ thin films doped with rare-earth samarium were prepared on a quartz plate by the sol-gel/spin-coating technique. The samples were annealed at 700?°C to 1100?°C, and the Raman spectra of the samples were obtained. Analyses of Raman spectra show that samarium doping can inhibit the anatase-rutile phase transition. Samarium doping can refine grains of TiO₂ thin films and increase the internal stress, thereby preventing lattice vibration. Nanocrystalline TiO₂ thin films obviously show the phonon confinement effect, i.e., the blueshift of characteristic Raman peak and full width at half-height increase, and the peak shapes asymmetrically broaden with a decrease in the grain sizes of the samples.     

Probing the nature of defects in graphene by Raman spectroscopy

Raman spectroscopy is able to probe disorder in graphene through defect-activated peaks. It is of great interest to link these features to the nature of disorder. Here we present a detailed analysis of the Raman spectra of graphene containing different type of defects. We found that the intensity ratio of the D and D' peak is maximum (～13) for sp(3)-defects, it decreases for vacancy-like defects (～7), and it reaches a minimum for boundaries in graphite (～3.5). This makes Raman Spectroscopy a powerful tool to fully characterize graphene.     

Direct spectral power density estimation from a discrete-time representation of stochastic analog quantization for an analog random process

Raising the performance is considered for the direct estimation of spectral power density for analog random processes. The solution is based on using sign analog-stochastic quantization of the random processes. Experimental results are presented. Translated from Izmeritel’naya Tekhnika, No. 3, pp. 13–17, March, 2009.