Structural study of TiO2 thin films by micro-Raman spectroscopy

The Raman spectroscopy method was used for structural characterization of TiO₂ thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125–425 °C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 °C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 °C and retained this phase even after annealing at 900 °C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 °C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.     

New opportunities for double rotation NMR of half-integer quadrupolar nuclei

A combined approach is presented which expands the applicability of double rotation (DOR) by overcoming its most prominent disadvantages: spinning stability and sensitivity. A new design using air-bearings for the inner rotor and a computer-assisted start-up procedure allows DOR operation over in principle unlimited time at outer rotor speeds of up to 2000Hz. Sensitivity enhancement of the DOR experiment is achieved by applying amplitude-modulated adiabatic pulses such as the double frequency sweep (DFS) before pulse excitation. Repeating the DFS enhancement and signal readout several times without allowing for spin-lattice relaxation leads to sensitivity enhancements of a factor 3 for (27)Al in various minerals. As a result, it becomes possible to study low sensitivity quadrupolar nuclei and various long duration 2D measurements can be performed routinely. Spinning is adequate to suppress residual homonuclear dipolar couplings in the spectral dimension of typical quadrupolar spin systems. In 2D-exchange spectroscopy, however, homonuclear correlation can still be established through dipolar-quadrupolar cross-terms.     

Atomic layer deposition of Cr2O3 thin films: Effect of crystallization on growth and properties

Atomic layer deposition of Cr₂O₃ thin films from CrO₂Cl₂ and CH₃OH on amorphous SiO₂ and crystalline Si(1 0 0) and -Al₂O₃() substrates was investigated, and properties of the films were ascertained. Self-limited growth with a rate of 0.05–0.1 nm/cycle was obtained at substrate temperatures of 330–420 °C. In this temperature range epitaxial eskolaite was formed on the -Al₂O₃() substrates. The predominant crystallographic orientation in the epitaxial films depended, however, on the growth temperature and film thickness. Sufficiently thick films grown on the SiO₂ and Si(1 0 0) substrates contained also the eskolaite phase, but thinner films deposited at 330–375 °C on these substrates were amorphous. The growth rate data of films with different phase composition allowed a conclusion that the crystalline phase grew markedly faster than the amorphous phase did. The amorphous, polycrystalline and epitaxial films had densities of 4.9, 5.1 and 5.1–5.3 g/cm³, respectively.     

Sensitivity enhancement in (13)C solid-state NMR of protein microcrystals by use of paramagnetic metal ions for optimizing (1)H T(1) relaxation

We discuss a simple approach to enhance sensitivity for (13)C high-resolution solid-state NMR for proteins in microcrystals by reducing (1)H T(1) relaxation times with paramagnetic relaxation reagents. It was shown that (1)H T(1) values can be reduced from 0.4-0.8s to 60-70 ms for ubiquitin and lysozyme in D(2)O in the presence of 10 mM Cu(II)Na(2)EDTA without substantial degradation of the resolution in (13)C CPMAS spectra. Faster signal accumulation using the shorter (1)H T(1) attained by paramagnetic doping provided sensitivity enhancements of 1.4-2.9 for these proteins, reducing the experimental time for a given signal-to-noise ratio by a factor of 2.0-8.4. This approach presented here is likely to be applicable to various other proteins in order to enhance sensitivity in (13)C high-resolution solid-state NMR spectroscopy.     

Vibrational spectra, ab initio calculations, and ring-puckering potential energy function for gamma-crotonolactone

The infrared and Raman spectra of liquid and vapor gamma-crotonolactone have been collected. Both the experimental data and ab initio calculations show that the molecule is rigidly planar in its electronic ground state. This conclusion agrees with the previously reported microwave studies and is attributed to the conjugation between the C=C and C=O double bonds of the ring. The ring-puckering potential energy function was generated from ab initio calculations and was confirmed by the vapor-phase Raman spectra to be nearly harmonic. Density functional theory (DFT) calculations predict a harmonic ring-puckering frequency of 203 cm(-1) as compared to the observed vapor-phase Raman value of 208 cm(-1). The DFT calculations were also used to compute the infrared and Raman spectra of gamma-crotonolactone, and these agree very well with the experimental spectra.     

Fluorescence and ultraviolet absorption spectra, and the structure and vibrations of 1,2,3,4-tetrahydronaphthalene in its S1(pi,pi*) state

The ultraviolet absorption spectra in the static vapor phase and the laser induced fluorescence spectra (both fluorescence excitation and single vibronic level fluorescence spectra) of jet-cooled 1,2,3,4-tetrahydronaphthalene have been used along with theoretical calculations to assign many of the vibronic levels in the S1(pi,pi*) state. These have been compared to the corresponding vibrational levels for the S0 ground state. Analysis of the upper states of the ring-twisting vibration nu(31) and three other low-frequency modes has allowed us to construct an energy map of the lowest vibrational quantum states for both S0 and S1. The molecule is highly twisted in both electronic states with high barriers to planarity, which are calculated to be 4811 cm(-1) for S0 and 5100 cm(-1) for S1. However, the experimental data show that the barrier should be lower in the S1 state.     

The determination of 17O NMR parameters of hydroxyl oxygen: a combined deuteration and DOR approach

The direct detection of hydroxyl oxygen (O-H) by (17)O double-rotation (DOR) NMR is very challenging because of the strong O-H dipole interaction. It is shown that deuteration of the hydroxyl site overcomes this using glycine.HCl as an illustration. Two well-separated sets of narrow (linewidth approximately 80-100 Hz) resonances with their spinning-sidebands are observed for the carboxyl and hydroxyl oxygens in the DOR spectrum of [(17)O,(2)H]glycine.HCl. The chemical shift anisotropy of these sites is obtained from a simulation of the DOR spinning-sideband intensities. The chemical shift span (Omega) for the carboxyl oxygen is found to be much larger than that of the hydroxyl oxygen, with Omega values of 540 +/- 15 and 210 +/- 10 ppm, respectively.     

Nonoscillation Characterizations of Second Order Linear Differential Equations

In this paper, we establish some nonoscillatory characterizations of solutions of the second order linear differential equation (pu′)′ + qu = 0. Using these characterizations, we give some comparison theorems improving the results of Hille , Wintner , Wong and Yu .     

Metal-polymer “superglue” for dirty polymer surfaces

Current methods of bonding metals to polymeric surfaces involve chemical reactions between atomically clean surfaces (S. Paul, Surface Coatings, Wiley, New York 1985). We propose a novel method of attaching metals to polymeric surfaces which does not require chemical bonding and is designed to be effective for polymeric surfaces which are not clean.