The theory of long distance electron transfer reactions

The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

Silicide formation and the interaction of metals with polycrystalline Si

The main factors affecting solid-phase Si-metal interactions are reported in this work. The influence of the orientation of the Si substrates and the presence of impurities in metal films and at the Si-metal interface on the formation of nickel and chromium silicides have been demonstrated. We have observed that the formation and kinetic rate of growth of nickel silicides is strongly dependent on the orientation and crystallinity of the Si substrates; a fact which, up to date, has never been seriously investigated in silicide formation. Impurity contaminations in the Cr film and at the Si-Cr interface are the most dominant influencing factors in the formation and kinetic rate of growth of CrSi₂. The potentiality and use of silicides as a diffusion barrier in metallization on silicon devices were also investigated.

Two phases, Ni₂Si and NiSi, form simultaneously in two distinct sublayers in the reaction of Ni with amorphous Si, while only the former phase was observed on other substrates. On (111) oriented Si substrates the growth rate is about 2 to 3 times less than that on <100> or polycrystalline Si. Transmission electron micrographs establish-·that silicide layers grown on different substrates have different microcrystalline structures. The concept of grain-boundary diffusion is speculated to be an important factor in silicide formation.

The composition and kinetic rate of CrSi₂ formation are not influenced by the underlying Si substrate. While the orientation of the Si substrate does not affect the formation of CrSi₂ , the purity of the Cr film and the state of Si-Cr interface become the predominant factors in the reaction process. With an interposed layer of Pd₂Si between the Cr film and the Si substrate, CrSi₂ starts to form at a much lower temperature (400°C) relative to the Si-Cr system. However, the growth rate of CrSi₂ is observed to be independent of the thickness of the Pd2Si layer. For both Si-Cr and Si-Pd₂Si-Cr samples, the growth rate is linear with time with an activation energy of 1.7 ± 0.1 ev.

A tracer technique using radioactive ³¹Si (T_1/2 = 2.26 h) was used to study the formation of CrSi₂ on Pd₂Si. It is established from this experiment that the growth of CrSi₂ takes place partly by transport of Si directly from the Si substrate and partly by breaking Pd₂Si bonds, making free Si atoms available for the growth process.

The role of CrSi₂ in Pd-Al metallization on Si was studied. It is established that a thin CrSi₂ layer can be used as a diffusion barrier to prevent Al from interacting with Pd₂Si in the Pd-Al metallization on Si.

As a generalization of what has been observed for polycrystalline-Si-Al interaction, the reactions between polycrystalline Si (poly Si) and other metals were studied. The metals investigated include Ni, Cr, Pd, Ag and Au. For Ni, Cr and Pd, annealing results in silicide formation, at temperatures similar to those observed on single crystal Si substrates. For Al, Ag and Au, which form simple eutectics with Si annealing results in erosion of the poly Si layer and growth of Si crystallites in the metal films.

Backscattering spectrometry with 2.0 and 2.3 MeV ⁴He ions was the main analytical tool used in all our investigations. Other experimental techniques include the Read camera glancing angle x-ray diffraction, scanning electron, optical and transmission electron microscopy. Details of these analytical techniques are given in Chapter II.

Theory of s-d exchange scattering in dilute magnetic alloys

The problem of s-d exchange scattering of conduction electrons off localized magnetic moments in dilute magnetic alloys is considered employing formal methods of quantum field theoretical scattering. It is shown that such a treatment not only allows for the first time, the inclusion of multiparticle intermediate states in single particle scattering equations but also results in extremely simple and straight forward mathematical analysis. These equations are proved to be exact in the thermodynamic limit. A self-consistent integral equation for electron self energy is derived and approximately solved. The ground state and physical parameters of dilute magnetic alloys are discussed in terms of the theoretical results. Within the approximation of single particle intermediate states our results reduce to earlier versions. The following additional features are found as a consequence of the inclusion of multiparticle intermediate states;

(i) A non analytic binding energy is pre sent for both, antiferromagnetic (J < o) and ferromagnetic (J > o) couplings of the electron plus impurity system.

(ii) The correct behavior of the energy difference of the conduction electron plus impurity system and the free electron system is found which is free of unphysical singularities present in earlier versions of the theories.

(iii) The ground state of the conduction electron plus impurity system is shown to be a many-body condensate state for J < o and J > o, both. However, a distinction is made between the usual terminology of "Singlet" and "Triplet" ground states and nature of our ground state.

(iv) It is shown that a long range ordering, leading to an ordering of the magnetic moments can result from a contact interaction such as the s-d exchange interaction.

(v) The explicit dependence of the excess specific heat of the Kondo systems is obtained and found to be linear in temperatures as T→ o and T ℓnT for 0.3 T_K ≤ T ≤ 0.6 T_K. A rise in (ΔC/T) for temperatures in the region 0 < T ≤ 0.1 T_K is predicted. These results are found to be in excellent agreement with experiments.

(vi) The existence of a critical temperature for Ferromagnetic coupling (J > o) is shown. On the basis of this the apparent contradiction of the simultaneous existence of giant moments and Kondo effect is resolved.

Theory of ultrafast optical manipulation of electron spins in quantum wells

Based on a multiparticle-state stimulated Raman adiabatic passage approach, a comprehensive theoretical study of the ultrafast optical manipulation of electron spins in quantum wells is presented. In addition to corroborating experimental findings [Gupta , Science 292, 2458 (2001)], we improve the expression for the optical-pulse-induced effective magnetic field, in comparison with the one obtained via the conventional single-particle ac Stark shift. Further study of the effect of hole-spin relaxation reveals that, while the coherent optical manipulation of electron spin in undoped quantum wells would deteriorate in the presence of relatively fast hole-spin relaxation, the coherent control in doped systems can be quite robust against decoherence. The implications of the present results on quantum dots will also be discussed. (c) 2005 American Institute of Physics.

Free radial oscillation of a sphere in relativistic elasticity theory

The spherically symmetric free radial oscillation in the first post-Newtonian approximation for a homogeneous and isotropic elastic sphere with a constant density is studied. Based on the Xu, Wu, and Soffel formalism, the relation of the oscillation frequency of the sphere with the radius, mass density, and elastic constants of the sphere is derived by using the successive approximation method.

Influence of annealed ohmic contact metals on electron mobility of strained AlGaN/GaN heterostructures

The influence of annealed ohmic contact metals on the electron mobility of a two dimensional electron gas (2DEG) is investigated on ungated AlGaN/GaN heterostructures and AlGaN/GaN heterostructure field effect transistors (AlGaN/GaN HFETs). Current-voltage (I-V) characteristics for ungated AlGaN/GaN heterostructures and capacitance-voltage (C-V) characteristics for AlGaN/GaN HFETs are obtained, and the electron mobility for the ungated AlGaN/GaN heterostructure is calculated. It is found that the electron mobility of the 2DEG for the ungated AlGaN/GaN heterostructure is decreased by more than 50% compared with the electron mobility of Hall measurements. We propose that defects are introduced into the AlGaN barrier layer and the strain of the AlGaN barrier layer is changed during the annealing process of the source and drain, causing the decrease in the electron mobility.

Theory of the near K-edge structure in electron energy loss spectroscopy

Arguments are given that lead to a formalism for calculating near K-edge structure in electron energy loss spectroscopy (EELS). This is essentially a one electron picture, while many body effects may be introduced at different levels, such as the local density approximation to density functional theory or the GW approximation to the electron self-energy. Calculations are made within the all electron LMTO scheme in crystals with complex atomic and electronic structures, and these are compared with experiment. (c) 2004 Elsevier B.V. All rights reserved.

R-matrix theory of electron molecule scattering

This paper presents an overview of R-matrix theory of electron scattering by diatomic and polyatomic molecules. The paper commences with a detailed discussion of the fixed-nuclei approximation which in recent years has been used as the basis of the most accurate ab initio calculations. This discussion includes an overview of the computer codes which enable electron collisions with both diatomic and polyatomic molecules to be calculated. Nuclear motion including rotational and vibrational excitation and dissociation is then discussed. In non-resonant energy regions, or when the scattered electron energy is not close to thresholds, the adiabatic-nuclei approximation can be successfully used. However, when these conditions are not applicable, non-adiabatic R-matrix theory must be used and a detailed discussion of this theory is given. Finally, recent applications of the theory to treat electron scattering by polyatomic molecules are reviewed and a detailed comparison of R-matrix calculations and experimental measurements for water is presented.

Single-shot characterisation of independent femtosecond extreme ultraviolet free electron andf infrared laser pulses

Two-color above threshold ionization of helium and xenon has been used to analyze the synchronization between individual pulses of the femtosecond extreme ultraviolet (XUV) free electron laser in Hamburg and an independent intense 120 fs mode-locked Ti:sapphire laser. Characteristic sidebands appear in the photoelectron spectra when the two pulses overlap spatially and temporally. The cross-correlation curve points to a 250 fs rms jitter between the two sources at the experiment. A more precise determination of the temporal fluctuation between the XUV and infrared pulses is obtained through the analysis of the single-shot sideband intensities. ©2007 American Institute of Physics

Operation of a free-electron laser from the extreme ultraviolet to the water window

We report results on the performance of a free-electron laser operating at a wavelength of 13.7 nm where unprecedented peak and average powers for a coherent extreme-ultraviolet radiation source have been measured. In the saturation regime, the peak energy approached 170 J for individual pulses, and the average energy per pulse reached 70 J. The pulse duration was in the region of 10 fs, and peak powers of 10 GW were achieved. At a pulse repetition frequency of 700 pulses per second, the average extreme-ultraviolet power reached 20 mW. The output beam also contained a significant contribution from odd harmonics of approximately 0.6% and 0.03% for the 3rd (4.6 nm) and the 5th (2.75 nm) harmonics, respectively. At 2.75 nm the 5th harmonic of the radiation reaches deep into the water window, a wavelength range that is crucially important for the investigation of biological samples.

Plasma emission spectroscopy of solids irradiated by intense XUV pulses from a free electron laser

The FLASH XUV-free electron laser has been used to irradiate solid samples at intensities of the order 10(16) W cm(-2) at a wavelength of 13.5 nm. The subsequent time integrated XUV emission was observed with a grating spectrometer. The electron temperature inferred from plasma line ratios was in the range 5-8 eV with electron density in the range 10(21)-10(22) cm(-3). These results are consistent with the saturation of absorption through bleaching of the L-edge by intense photo-absorption reported in an earlier publication. (C) 2009 Elsevier B.V. All rights reserved.