Properties of a-C:H films deposited from a methane electron cyclotron wave resonant plasma

An electron cyclotron wave resonant methane plasma discharge was used for the high rate deposition of hydrogenated amorphous carbon (a-C:H). Deposition rates of up to ∼400 Å/min were obtained over substrates up to 2.5 in. in diameter with a film thickness uniformity of ∼±10%. The deposited films were characterised in terms of their mass density, sp3 and hydrogen contents, C-H bonding, intrinsic stress, scratch resistance and friction properties. The deposited films possessed an average sp3 content, mass density and refractive index of ∼58%, 1.76 g/cm3 and 2.035 respectively.Mechanical characterisation indicated that the films possessed very low steady-state coefficients of friction (ca. 0.06) and a moderate shear strength of ∼141 MPa. Nano-indentation measurements also indicated a hardness and elastic modulus of ∼16.1 and 160 GPa respectively. The critical loads required to induce coating failure were also observed to increase with ion energy as a consequence of the increase in degree of ion mixing at the interface. Furthermore, coating failure under scratch test conditions was observed to take place via fracture within the silicon substrate itself, rather than either in the coating or at the film/substrate interface. © 2003 Elsevier B.V. All rights reserved.

Engineering multi-step electron tunneling systems in proteins

Multi-step electron tunneling, or “hopping,” has become a fast-developing research field with studies ranging from theoretical modeling systems, inorganic complexes, to biological systems. In particular, the field is exploring hopping mechanisms in new proteins and protein complexes, as well as further understanding the classical biological hopping systems such as ribonuclease reductase, DNA photolyases, and photosystem II. Despite the plethora of natural systems, only a few biologically engineered systems exist. Engineered hopping systems can provide valuable information on key structural and electronic features, just like other kinds of biological model systems. Also, engineered systems can harness common biologic processes and utilize them for alternative reactions. In this thesis, two new hopping systems are engineered and characterized.

The protein Pseudomonas aeruginosa azurin is used as a building block to create the two new hopping systems. Besides being well studied and amenable to mutation, azurin already has been used to successfully engineer a hopping system. The two hopping systems presented in this thesis have a histidine-attached high potential rhenium 4,7-dimethyl-1,10-phenanthroline tricarbonyl [Re(dmp)(CO)3] + label which, when excited, acts as the initial electron acceptor. The metal donor is the type I copper of the azurin protein. The hopping intermediates are all tryptophan, an amino acid mutated into the azurin at select sites between the photoactive metal label and the protein metal site. One system exhibits an inter-molecular hopping through a protein dimer interface; the other system undergoes intra-molecular multi-hopping utilizing a tryptophan “wire.” The electron transfer reactions are triggered by excitation of the rhenium label and monitored by UV-Visible transient absorption, luminescence decays measurements, and time-resolved Infrared spectroscopy (TRIR). Both systems were structurally characterized by protein X-ray crystallography.

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.

I. Proton magnetic resonance of polynucleotides and transfer RNA. II. Electron spin relaxation studies of manganese (II) complexes in acetonitrile

Part I. Proton Magnetic Resonance of Polynucleotides and Transfer RNA.

Proton magnetic resonance was used to follow the temperature dependent intramolecular stacking of the bases in the polynucleotides of adenine and cytosine. Analysis of the results on the basis of a two state stacked-unstacked model yielded values of -4.5 kcal/mole and -9.5 kcal/mole for the enthalpies of stacking in polyadenylic and polycytidylic acid, respectively.

The interaction of purine with these molecules was also studied by pmr. Analysis of these results and the comparison of the thermal unstacking of polynucleotides and short chain nucleotides indicates that the bases contained in stacks within the long chain poly nucleotides are, on the average, closer together than the bases contained in stacks in the short chain nucleotides.

Temperature and purine studies were also carried out with an aqueous solution of formylmethionine transfer ribonucleic acid. Comparison of these results with the results of similar experiments with the homopolynucleotides of adenine, cytosine and uracil indicate that the purine is probably intercalating into loop regions of the molecule.

The solvent denaturation of phenylalanine transfer ribonucleic acid was followed by pmr. In a solvent mixture containing 83 volume per cent dimethylsulf oxide and 17 per cent deuterium oxide, the tRNA molecule is rendered quite flexible. It is possible to resolve resonances of protons on the common bases and on certain modified bases.

Part II. Electron Spin Relaxation Studies of Manganese (II) Complexes in Acetonitrile.

The electron paramagnetic resonance spectra of three Mn⁺² complexes, [Mn(CH₃CN)₆]⁺², [MnCl₄]^-2, and [MnBr₄]^-2, in acetonitrile were studied in detail. The objective of this study was to relate changes in the effective spin Hamiltonian parameters and the resonance line widths to the structure of these molecular complexes as well as to dynamical processes in solution.

Of the three systems studied, the results obtained from the [Mn(CH₃CN)₆]⁺² system were the most straight-forward to interpret. Resonance broadening attributable to manganese spin-spin dipolar interactions was observed as the manganese concentration was increased.

In the [MnCl₄]^-2 system, solvent fluctuations and dynamical ion-pairing appear to be significant in determining electron spin relaxation.

In the [MnBr₄]^-2 system, solvent fluctuations, ion-pairing, and Br- ligand exchange provide the principal means of electron spin relaxation. It was also found that the spin relaxation in this system is dependent upon the field strength and is directly related to the manganese concentration. A relaxation theory based on a two state collisional model was developed to account for the observed behavior.

A new strategy of enhancing two-photon absorption in benzothiazole-containing fluorene molecules: Introduction of auxiliary donor-acceptor effects

A series of benzothiazole-containing fluorene molecules have been designed and their one- and two-photon absorption properties have been investigated theoretically by using the ZINDO method. The effects of electron-excessive/deficient heterocyclic bridges as auxiliary donors (auxD)/acceptors (auxA) on TPA cross-sections were studied. The results show that the molecules with D-pi-auxA-A, D-aux D-pi-A, or D-auxD-pi-auxA-A structure types have large TPA cross-section, which can be a valuable strategy in the design of two-photon absorption materials. Also, a linear relationship between the first hyperpolarizability and the TPA cross-section is observed. (c) 2006 Elsevier B.V. All rights reserved.

First-principles prediction of doped graphane as a high-temperature electron-phonon superconductor.

We predict by first-principles calculations that p-doped graphane is an electron-phonon superconductor with a critical temperature above the boiling point of liquid nitrogen. The unique strength of the chemical bonds between carbon atoms and the large density of electronic states at the Fermi energy arising from the reduced dimensionality give rise to a giant Kohn anomaly in the optical phonon dispersions and push the superconducting critical temperature above 90 K. As evidence of graphane was recently reported, and doping of related materials such as graphene, diamond, and carbon nanostructures is well established, superconducting graphane may be feasible.

Dynamical behavior of damped driven coupled single electron simple harmonic oscillators

Coherent coupling between a large number of qubits is the goal for scalable approaches to solid state quantum information processing. Prototype systems can be characterized by spectroscopic techniques. Here, we use pulsed-continuous wave microwave spectroscopy to study the behavior of electrons trapped at defects within the gate dielectric of a sol-gel-based high-k silicon MOSFET. Disorder leads to a wide distribution in trap properties, allowing more than 1000 traps to be individually addressed in a single transistor within the accessible frequency domain. Their dynamical behavior is explored by pulsing the microwave excitation over a range of times comparable to the phase coherence time and the lifetime of the electron in the trap. Trap occupancy is limited to a single electron, which can be manipulated by resonant microwave excitation and the resulting change in trap occupancy is detected by the change in the channel current of the transistor. The trap behavior is described by a classical damped driven simple harmonic oscillator model, with the phase coherence, lifetime and coupling strength parameters derived from a continuous wave (CW) measurement only. For pulse times shorter than the phase coherence time, the energy exchange between traps, due to the coupling, strongly modulates the observed drain current change. This effect could be exploited for 2-qubit gate operation. The very large number of resonances observed in this system would allow a complex multi-qubit quantum mechanical circuit to be realized by this mechanism using only a single transistor.

Strength and drying shrinkage of reactive MgO modified alkali-activated slag paste

Conventional alkali-activated slag (AAS) cements suffer from significant drying shrinkage which hinders their widespread application. This paper investigates the potential of using commercial reactive MgO to reduce the drying shrinkage of AAS. Two different reactive MgOs were added at a content of 2.5-7.5 wt% of the slag, which was activated by sodium hydroxide and water-glass. The strength and the drying shrinkage of those reactive MgO modified AAS (MAAS) pastes were measured up to 90 days. It is found that MgO with high reactivity accelerated the early hydration of AAS, while MgO with medium reactivity had little effect. The drying shrinkage was significantly reduced by highly reactive MgO but it also generated severe cracking under the dry condition. On the other hand, medium-reactive MgO only showed observable shrinkage-reducing effect after one month, but the cement soundness was improved. The hydration products, analysed by X-ray diffraction, thermogravimetric analysis and scanning electron microscopy techniques, showed that Mg was mainly incorporated in the hydrotalcite-like phases. It is concluded that the curing conditions and the time of hydrotalcite-like phases formation and their quantity are crucial to the developed strength and shrinkage reduction properties of MAAS, which are highly dependent on the reactivity and content of reactive MgO. Crown Copyright © 2013 Published by Elsevier Ltd. All rights reserved.

Impact of donor traps on the 2DEG and electrical behavior of AlGaN/GaN MISFETs

As an important step in understanding trap-related mechanisms in AlGaN/GaN transistors, the physical properties of surface states have been analyzed through the study of the transfer characteristics of a MISFET. This letter focused initially on the relationship between donor parameters (concentration and energy level) and electron density in the channel in AlGaN/GaN heterostructures. This analysis was then correlated to dc and pulsed measurements of the transfer characteristics of a MISFET, where the gate bias was found to modulate either the channel density or the donor states. Traps-free and traps-frozen TCAD simulations were performed on an equivalent device to capture the donor behavior. A donor concentration of 1.14× 1013 ∼ cm-2 with an energy level located 0.2 eV below the conduction band edge gave the best fit to measurements. With the approach described here, we were able to analyze the region of the MISFET that corresponds to the drift region of a conventional HEMT. © 1980-2012 IEEE.

On the variation of the 2DEG charge density with the density of the surface donor traps in AiGaN/GaN transistors

Gallium nitride (GaN) has a bright future in high voltage device owing to its remarkable physical properties and the possibility of growing heterostructures on silicon substrates. GaN High Electron Mobility Transistors (HEMTs) are expected to make a strong impact in off line applications and LED drives. However, unlike in silicon-based power devices, the on-state resistance of HEMT devices is hugely influenced by donor and acceptor traps at interfaces and in the bulk. This study focuses on the influence of donor traps located at the top interface between the semiconductor layer and the silicon nitride on the 2DEG density. It is shown through TCAD simulations and analytical study that the 2DEG charge density has an 'S' shape variation with two distinctive 'flat' regions, wherein it is not affected by the donor concentration, and one linear region. wherein the channel density increases proportionally with the donor concentration. We also show that the upper threshold value of the donor concentration within this 'S' shape increases significantly with the AIGaN thickness and the Al mole fraction and is highly affected by the presence of a thin GaN cap layer. © 2013 IEEE.

Strength and hydration products of reactive MgO-silica pastes

The reaction between MgO and microsilica has been studied by many researchers, who confirmed the formation of magnesium silicate hydrate. The blend was reported to have the potential as a novel material for construction and environment purposes. However, the characteristics of MgO vary significantly, e.g., reactivity and purity, which would have an effect on the hydration process of MgO-silica blend. This paper investigated the strength and hydration products of reactive MgO and silica blend at room temperature up to 90 days. The existence of magnesium silicate hydrate after 7 days' curing was confirmed with the help of infrared spectroscopy, thermogravimetric analysis and X-ray diffraction. The microstructural and elemental analysis of the resulting magnesium silicate hydrate was conducted using scanning electron microscopy and energy dispersive spectroscopy. In addition, the effect of characteristics of MgO on the hydration process was discussed. It was found that the synthesis of magnesium silicate hydrate was highly dependent on the reactivity of the precursors. MgO and silica with higher reactivity resulted in higher formation rate of magnesium silicate hydrate. In addition, the impurity in the MgO affects the pH value of the blends, which in turn determines the solubility of silica and the formation of magnesium silicate hydrate. © 2014 Elsevier Ltd. All rights reserved.

Electric tunable of electron spin polarization in hybrid magnetic-electric barrier structures

Electron spin-dependent transport properties have been theoretically investigated in two-dimensional electron gas (2DEG) modulated by the magnetic field generated by a pair of anti-parallel magnetization ferromagnetic metal stripes and the electrostatic potential provided by a normal metal Schottky stripe. It is shown that the energy positions of the spin-polarization extremes and the width of relative spin conductance excess plateau could be significantly manipulated by the electrostatic potential strength and width, as well as its position relative to the FM stripes. These interesting features are believed useful for designing the electric voltage controlled spin filters. (C) 2008 Elsevier B.V. All rights reserved.

Spin-orbit splitting of a hydrogenic donor impurity in GaAs/GaAlAs quantum wells

The electronic states of a hydrogenic donor impurity in GaAs/GaAlAs quantum wells are investigated theoretically in the framework of effective-mass envelope function theory, including the effect of Rashba spin-orbit coupling. The splits of electron energy levels are calculated. The results show that (1) the split energy of the excited state is larger than that of the ground state; (2) the split energy peak appears as the GaAs well width increases from zero; and (3) the maximum split energy reaches about 1.6 meV. Our results are useful for the application of Rashba spin-orbit coupling to photoelectric devices. (c) 2008 American Institute of Physics.

Electron and hole states in diluted magnetic semiconductor quantum dots

The electronic structure of a diluted magnetic semiconductor (DMS) quantum dot (QD) is studied within the framework of the effective-mass theory. We find that the energies of the electron with different spin orientation exhibit different behavior as a function of magnetic field at small magnetic fields. The energies of the hole decreases rapidly at low magnetic fields and saturate at higher magnetic field due to the sp-d exchange interaction between the carriers and the magnetic ions. The mixing effect of the hole states in the DMS QD can be tuned by changing the external magnetic field. An interesting crossing behavior of the hole ground state between the heavy-hole state and the light-hole state is found with variation of the QD radius. The strength of the interband optical transition for different circular polarization exhibts quite different behavior with increasing magnetic field and QD radius.

Measurement of single electron spin with submicron Hall magnetometer

Submicron Hall magnetometry has been demonstrated as an efficient technique to probe extremely weak magnetic fields. In this letter, we analyze the possibility of employing it to detect single electron spin. Signal strength and readout time are estimated and discussed with respect to a number of practical issues. (C) 2005 American Institute of Physics.