DIET in the bulk: evidence for hot electron cleavage of Si---H bonds in SiO2 films

The observed increase in leakage current through SiO₂ films after hot electron exposure is ascribed to dissociation induced by electronic transitions (“DIET”) of bulk Si---H bonds, producing mobile hydrogen. We use ab initio supercell bandstructure calculations at the local density functional level to locate features produced by hydrogen-containing defects in -SiO₂. The edge of the Si---H σ* resonance is found to be about 2.7 eV above the conduction band rise, in good agreement with the observed threshold for hot electron induced damage in amorphous SiO₂ films grown on Si substrates. The O---H σ* resonance is almost 4 eV higher. Removing H from O---H in the supercell does not affect the gap region (---O⁻ forms); however, removing H from Si---H produces a mid-gap state, suggesting leakage current by hopping conductivity between Si dangling bonds. A Morse potential model is used to explore the dynamics of bond scission by short-lived (<1 fs) hot electron σ* capture. Supercell calculations on interstitial atomic hydrogen indicate the energy cost to break an embedded Si---H bond is about 0.6 eV less than in the gas phase. The DIET yield is substantially increased by reducing both ground and electron-attached state binding by this amount. While uncertainty over the displaced equilibrium in the electron-attached excited state remains, the computed DIET cross-section for reasonable parameters is ≈10⁻¹⁸ cm², and is in agreement with the semi-empirically derived value for trap creation. Comparisons are made to surface DIET processes involving Si---H bonds.     

Temperature-dependent pressure broadened line shape measurements in the ν 1+ν 3 band of acetylene using a diode laser referenced to a frequency comb

Using an extended cavity diode laser referenced to a femtosecond frequency comb, the P(11) absorption line in the ?? ₁+?? ₃ combination band of the most abundant isotopologue of pure acetylene was studied at temperatures of 296, 240, 200, 175, 165, 160, 155, and 150?K to determine pressure-dependent line shape parameters at these temperatures. The laser emission profile, the instrumental resolution, is a Lorentz function characterized by a half width at half the maximum emission (HWHM) of 8.3×10^?6?cm^?1 (or 250?kHz) for these measurements. Six collision models were tested in fitting the experimental data: Voigt, speed-dependent Voigt, Rautian?CSobel??man, Galatry, and two Rautian?CGalatry hybrid models (with and without speed-dependence). Only the speed-dependent Voigt model was able to fit the data to the experimental noise level at all temperatures and for pressures between 3 and nearly 360?torr. The variations of the speed-dependent Voigt profile line shape parameters with temperature were also characterized, and this model accurately reproduces the observations over their entire range of temperature and pressure.     

Polyatomic ions in inductively coupled plasma–mass spectrometry: Part II: Origins of N2H and HxCO ions using experimental measurements combined with calculated energies and structures

Several polyatomic ions in inductively coupled plasma–mass spectrometry are studied experimentally and by computational methods. Novel calculations based on spin-restricted open shell second order perturbation theory (ZAPT2) and coupled cluster (CCSD(T)) theory are performed to determine the energies, structures and partition functions of the ions. These values are combined with experimental data to evaluate a dissociation constant and gas kinetic temperature (T_gas) value. In our opinion, the resulting T_gas value can sometimes be interpreted to deduce the location where the polyatomic ion of interest is generated. The dissociation of N₂H⁺ to N₂⁺ leads to a calculated T_gas of 4550 to 4900 K, depending on the computational data used. The COH⁺ to CO⁺ system yields a similar temperature, which is not surprising considering the similar energies and structures of COH⁺ and N₂H⁺. The dissociation of H₂CO⁺ to HCO⁺ leads to a much lower T_gas (< 1000 to 2000 K). Finally, the dissociation of H₂COH⁺ to HCOH⁺ generates a T_gas value between those from the other H_xCO⁺ ions studied here. All of these measured T_gas values correspond to formation of extra polyatomic ion in the interface or extraction region. The computations reveal the existence of isomers such as HCO⁺ and COH⁺, and H₂CO⁺ and HCOH⁺, which have virtually the same m/z values and need to be considered in the interpretation of results.     

AC Stark detection of optical-optical double resonance in CH2

A new scheme for the detection of double resonance spectra of chemical intermediates involves negligible population transfer but the detection of electric field-induced energy shifts in unpopulated levels.     

High-cooperativity coupling of electron-spin ensembles to superconducting cavities

Electron spins in solids are promising candidates for quantum memories for superconducting qubits because they can have long coherence times, large collective couplings, and many qubits could be encoded into spin waves of a single ensemble. We demonstrate the coupling of electron-spin ensembles to a superconducting transmission-line cavity at strengths greatly exceeding the cavity decay rates and comparable to the spin linewidths. We also perform broadband spectroscopy of ruby (Al?O?:Cr(3+)) at millikelvin temperatures and low powers, using an on-chip feedline. In addition, we observe hyperfine structure in diamond P1 centers.