等离子体效应对类氦氖Kα线系电偶极辐射的影响

采用离子球模型，通过自洽求解Boltzmann方程和Poisson方程，得到类氦氖离子Kα线系的两条电偶极辐射光谱能量随等离子体环境的漂移．结果显示，Kα线系电偶极谱线随等离子体电子密度增大发生红移，红移量与等离子体电子密度有近似的正比关系；随着等离子体电子温度的降低，光谱红移对等离子体电子密度的敏感性增大。另外，所研究的两条谱线间的能量间隔随等离子体电子密度的增大而减小，减小量随等离子体电子密度的变化也呈现出近似的线性规律。值得注意的是，类氦氖Kα线系中两条电偶极谱线分别为互组合线与共振谱线，而其能量差

双色激光场中激光强度和脉宽对线性多原子分子离子电离的影响

利用强激光场电离和离解分子来研究分子激发态的波包结构是强场物理的重要研究方向。利用短时指数传播子对称分割法和快速傅里叶变换技术。数值求解了一维含时Schr（oe）dinger方程，探讨了双色激光场中激光的基波和谐波强度之间的不同配比以及脉宽对线性多原子分子离子电离的影响。理论计算结果表明：基波和谐波的相对相位为π时，尽管随着激光的基波和谐波强度之间配比的变化，电离几率随原子间距变化的趋势基本保持不变，但在一定的激光基波强度下(1．2×10^13～1．2×10^15W／cm^2)，激光基波强度的变化可以明显

Earth-abundant materials for solar hydrogen generation

A critical challenge for the 21st century is shifting from the predominant use of fossil fuels to renewables for energy. Among many options, sunlight is the only single renewable resource with sufficient abundance to replace most or all of our current fossil energy use. However, existing photovoltaic and solar thermal technologies cannot be scaled infinitely due to the temporal and geographic intermittency of sunlight. Therefore efficient and inexpensive methods for storage of solar energy in a dense medium are needed in order to greatly increase utilization of the sun as a primary resource. For this purpose we have proposed an artificial photosynthetic system consisting of semiconductors, electrocatalysts, and polymer membranes to carry out photoelectrochemical water splitting as a method for solar fuel generation.

This dissertation describes efforts over the last five years to develop critical semiconductor and catalyst components for efficient and scalable photoelectrochemical hydrogen evolution, one of the half reactions for water splitting. We identified and developed Ni–Mo alloy and Ni₂P nanoparticles as promising earth-abundant electrocatalysts for hydrogen evolution. We thoroughly characterized Ni–Mo alloys alongside Ni and Pt catalysts deposited onto planar and structured Si light absorbers for solar hydrogen generation. We sought to address several key challenges that emerged in the use of non-noble catalysts for solar fuels generation, resulting in the synthesis and characterization of Ni–Mo nanopowder for use in a new photocathode device architecture. To address the mismatch in stability between non-noble metal alloys and Si absorbers, we also synthesized and characterized p-type WSe₂ as a candidate light absorber alternative to Si that is stable under acidic and alkaline conditions.

Phase-type quantum-dot-array diffraction grating

A novel phase-type quantum-dot-array diffraction grating (QDADG) is reported. In contrast to an earlier amplitude-type QDADG [C. Wang , Rev. Sci. Instrum. 78, 053503 (2007)], the new phase-type QDADG would remove the zeroth order diffraction at some certain wavelength, as well as suppressing the higher-order diffractions. In this paper, the basic concept, the fabrication, the calibration techniques, and the calibration results are presented. Such a grating can be applied in the research fields of beam splitting, laser probe diagnostics, and so on.

Controllable Kerr nonlinearity with perfect transparency in the existence of spontaneously generated coherence

We investigate the Kerr nonlinearity of a V-type three-level atomic system where the upper two states decay outside to another state and hence spontaneous generated coherence may exist. It is shown that dark state and hence perfect transparency present under certain conditions. Meanwhile, the Kerr nonlinearity can be controlled by manipulation of the decay rates and the splitting of the two excited states. Therefore, enhanced Kerr nonlinearity without absorption can be obtained under proper parameters.

Nanostructured tungsten trioxide photoanodes for solar energy conversion

Nanostructured tungsten trioxide (WO₃) photoelectrodes are potential candidates for the anodic portion of an integrated solar water-splitting device that generates hydrogen fuel and oxygen from water. These nanostructured materials can potentially offer improved performance in photooxidation reactions compared to unstructured materials because of enhancements in light scattering, increases in surface area, and their decoupling of the directions of light absorption and carrier collection. To evaluate the presence of these effects and their contributions toward energy conversion efficiency, a variety of nanostructured WO₃ photoanodes were synthesized by electrodeposition within nanoporous templates and by anodization of tungsten foils. A robust fabrication process was developed for the creation of oriented WO₃ nanorod arrays, which allows for control nanorod diameter and length. Films of nanostructured WO₃ platelets were grown via anodization, the morphology of the films was controlled by the anodization conditions, and the current-voltage performance and spectral response properties of these films were studied. The observed photocurrents were consistent with the apparent morphologies of the nanostructured arrays. Measurements of electrochemically active surface area and other physical characteristics were correlated with observed differences in absorbance, external quantum yield, and photocurrent density for the anodized arrays. The capability to quantify these characteristics and relate them to photoanode performance metrics can allow for selection of appropriate structural parameters when designing photoanodes for solar energy conversion.

R6G单分子表面增强共振拉曼散射光谱探测研究

以共焦显微系统为平台，研究了不同浓度的R6G银溶胶的表面增强共振拉曼散射（SERRS）光谱，结果表明不同浓度溶液中的R6G分子表现出了不同的光谱特性。在浓度为10^-13mol·L^-1的R6G银溶胶中得到了R6G单分子的表面增强共振拉曼散射光谱，观察到了一些光谱非均匀变化现象，如谱色散、谱线的强度起伏、拉曼谱的偏振化以及分子的闪烁等，并对这些现象进行了分析，证明得到的是R6G单分子的SERRS光谱。文章还对单分子检测中的一些关键问题进行了分析与讨论，确定了单分子SERRS光谱检测的适当条件。

Reflection and transmission of Gaussian beam from a uniaxial crystal slab

We investigate the characteristics of Gaussian beams reflected and transmitted from a uniaxial crystal slab with an arbitrary orientation of its optical axis. The formulas of the total electric and magnetic fields inside and outside the slab are derived by use of Maxwell's equations and by matching the boundary conditions at the interfaces. Numerical simulations are presented and the field values as well as the power densities are computed. Negative refractions are demonstrated when the beam is transmitted through a uniaxial crystal slab. Beam splitting of the reflected beam is observed and is explained by the resonant transmission for plane waves. Dependences of the lateral shift on the incident angle and beam width are discussed. Negative and positive lateral shifts are observed due to the spatial anisotropic properties.

I. Spectroscopic evidence for slow vibrational relaxation in excited electronic states of diatomics in rare gas solids. II. Static crystal field effects in the electronic spectra of isotopically mixed benzene crystals

Part I

Studies of vibrational relaxation in excited electronic states of simple diatomic molecules trapped in solid rare-gas matrices at low temperatures are reported. The relaxation is investigated by monitoring the emission intensity from vibrational levels of the excited electronic state to vibrational levels of the ground electronic state. The emission was in all cases excited by bombardment of the doped rare-gas solid with X-rays.

The diatomics studied and the band systems seen are: N₂, Vegard-Kaplan and Second Positive systems; O₂, Herzberg system; OH and OD, A ²Σ⁺ - X²II_i system. The latter has been investigated only in solid Ne, where both emission and absorption spectra were recorded; observed fine structure has been partly interpreted in terms of slightly perturbed rotational motion in the solid. For N₂, OH, and OD emission occurred from v' > 0, establishing a vibrational relaxation time in the excited electronic state of the order, of longer than, the electronic radiative lifetime. The relative emission intensity and decay times for different v' progressions in the Vegard-Kaplan system are found to depend on the rare-gas host and the N₂ concentration, but are independent of temperature in the range 1.7°K to 30°K.

Part II

Static crystal field effects on the absorption, fluorescence, and phosphorescence spectra of isotopically mixed benzene crystals were investigated. Evidence is presented which demonstrate that in the crystal the ground, lowest excited singlet, and lowest triplet states of the guest deviate from hexagonal symmetry. The deviation appears largest in the lowest triplet state and may be due to an intrinsic instability of the ³B_1u state. High resolution absorption and phospho- rescence spectra are reported and analyzed in terms of site-splitting of degenerate vibrations and orientational effects. The guest phosphorescence lifetime for various benzene isotopes in C₆D₆ and sym-C₆H₃D₃ hosts is presented and discussed.

Physical characterization of the rack effect and hydrogen bond networks in blue copper proteins

A summary of previous research is presented that indicates that the purpose of a blue copper protein's fold and hydrogen bond network, aka, the rack effect, enforce a copper(II) geometry around the copper(I) ion in the metal site. In several blue copper proteins, the C-terminal histidine ligand becomes protonated and detaches from the copper in the reduced forms. Mutants of amicyanin from Paracoccus denitrificans were made to alter the hydrogen bond network and quantify the rack effect by pK_a shifts.

The pK_a's of mutant amicyanins have been measured by pH-dependent electrochemistry. P94F and P94A mutations loosen the Northern loop, allowing the reduced copper to adopt a relaxed conformation: the ability to relax drives the reduction potentials up. The measured potentials are 265 (wild type), 380 (P94A), and 415 (P94F) mV vs. NHE. The measured pK_a's are 7.0 (wild type), 6.3 (P94A), and 5.0 (P94F). The additional hydrogen bond to the thiolate in the mutants is indicated by a red-shift in the blue copper absorption and an increase in the parallel hyperfine splitting in the EPR spectrum. This hydrogen bond is invoked as the cause for the increased stability of the C-terminal imidazole.

Melting curves give a measure of the thermal stability of the protein. A thermodynamic intermediate with pH-dependent reversibility is revealed. Comparisons with the electrochemistry and apoamicyanin suggest that the intermediate involves the region of the protein near the metal site. This region is destabilized in the P94F mutant; coupled with the evidence that the imidazole is stabilized under the same conditions confirms an original concept of the rack effect: a high energy configuration is stabilized at a cost to the rest of the protein.

Conical emission of Ti : sapphire femtosecond laser pulses propagating in water

Conical emission is investigated for Ti:sapphire femtosecond laser pulses propagating in water. The colored rings can be observed in the forward direction due to the constructive and destructive interference of transverse wavevector, which are induced by the spatio-temporal gradient of the free-electron density. With increasing input laser energy, due to filamentation and pulse splitting induced by the plasma created by multiphoton excitation of electrons from the valence band to the conduction band, the on-axis spectrum of the conical emission is widely broadened and strongly modulated with respect to input laser spectrum, and finally remains fairly constant at higher laser energy due to intensity clamping in the filaments.

Functionalization of Si(111) surfaces and the formation of mixed monolayers for the covalent attachment of molecular catalysts in photoelectrochemical devices

The functionalization of silicon surfaces with molecular catalysts for proton reduction is an important part of the development of a solar-powered, water-splitting device for solar fuel formation. The covalent attachment of these catalysts to silicon without damaging the underlying electronic properties of silicon that make it a good photocathode has proven difficult. We report the formation of mixed monolayer-functionalized surfaces that incor- porate both methyl and vinylferrocenyl or vinylbipyridyl (vbpy) moieties. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy (XPS), electro- chemical, and photoelectrochemical measurements. The functionalized Si surfaces were well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surfaces were stable toward atmospheric and electrochemical oxidation. The surface coverage of ferrocene or bipyridine was controllably varied from 0 up to 30% of a monolayer without loss of the underlying electronic properties of the silicon. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH₃CN. The immobilized bipyridine ligands bound transition metal ions, and thus enabled the assembly of metal complexes on the silicon surface. XPS studies demonstrated that [Cp∗Rh(vbpy)Cl]Cl, [Cp∗Ir(vbpy)Cl]Cl, and Ru(acac)₂vbpy were assembled on the surface. For the surface prepared with iridium, x-ray absorption spectroscopy at the Ir L_III edge showed an edge energy and post-edge features virtually identical to a powder sample of [Cp∗Ir(bipy)Cl]Cl (bipy is 2,2 ́-bipyridyl). Electrochemical studies on these surfaces confirmed that the assembled complexes were electrochemically active.

Nonlinear X-wave formation and conical emission at different powers of a femtosecond laser pulse in water

Nonlinear X-wave formation at different pulse powers in water is simulated using the standard model of nonlinear Schrodinger equation (NLSE). It is shown that in near field X-shape originally emerges from the interplay between radial diffraction and optical Kerr effect. At relatively low power group-velocity dispersion (GVD) arrests the collapse and leads to pulse splitting on axis. With high enough power, multi-photon ionization (NIPI) and multi-photon absorption (MPA) play great importance in arresting the collapse. The tailing part of pulse is first defocused by MPI and then refocuses. Pulse splitting on axis is a manifestation of this process. Double X-wave forms when the split sub-pulses are self-focusing. In the far field, the character of the central X structure of conical emission (CE) is directly related to the single or double X-shape in the near field. (c) 2007 Elsevier B.V. All rights reserved.

Optical designs for improved solar cell performance

The solar resource is the most abundant renewable resource on earth, yet it is currently exploited with relatively low efficiencies. To make solar energy more affordable, we can either reduce the cost of the cell or increase the efficiency with a similar cost cell. In this thesis, we consider several different optical approaches to achieve these goals. First, we consider a ray optical model for light trapping in silicon microwires. With this approach, much less material can be used, allowing for a cost savings. We next focus on reducing the escape of radiatively emitted and scattered light from the solar cell. With this angle restriction approach, light can only enter and escape the cell near normal incidence, allowing for thinner cells and higher efficiencies. In Auger-limited GaAs, we find that efficiencies greater than 38% may be achievable, a significant improvement over the current world record. To experimentally validate these results, we use a Bragg stack to restrict the angles of emitted light. Our measurements show an increase in voltage and a decrease in dark current, as less radiatively emitted light escapes. While the results in GaAs are interesting as a proof of concept, GaAs solar cells are not currently made on the production scale for terrestrial photovoltaic applications. We therefore explore the application of angle restriction to silicon solar cells. While our calculations show that Auger-limited cells give efficiency increases of up to 3% absolute, we also find that current amorphous silicion-crystalline silicon heterojunction with intrinsic thin layer (HIT) cells give significant efficiency gains with angle restriction of up to 1% absolute. Thus, angle restriction has the potential for unprecedented one sun efficiencies in GaAs, but also may be applicable to current silicon solar cell technology. Finally, we consider spectrum splitting, where optics direct light in different wavelength bands to solar cells with band gaps tuned to those wavelengths. This approach has the potential for very high efficiencies, and excellent annual power production. Using a light-trapping filtered concentrator approach, we design filter elements and find an optimal design. Thus, this thesis explores silicon microwires, angle restriction, and spectral splitting as different optical approaches for improving the cost and efficiency of solar cells.

Design strategies for ultra-high efficiency photovoltaics

While concentrator photovoltaic cells have shown significant improvements in efficiency in the past ten years, once these cells are integrated into concentrating optics, connected to a power conditioning system and deployed in the field, the overall module efficiency drops to only 34 to 36%. This efficiency is impressive compared to conventional flat plate modules, but it is far short of the theoretical limits for solar energy conversion. Designing a system capable of achieving ultra high efficiency of 50% or greater cannot be achieved by refinement and iteration of current design approaches.

This thesis takes a systems approach to designing a photovoltaic system capable of 50% efficient performance using conventional diode-based solar cells. The effort began with an exploration of the limiting efficiency of spectrum splitting ensembles with 2 to 20 sub cells in different electrical configurations. Incorporating realistic non-ideal performance with the computationally simple detailed balance approach resulted in practical limits that are useful to identify specific cell performance requirements. This effort quantified the relative benefit of additional cells and concentration for system efficiency, which will help in designing practical optical systems.

Efforts to improve the quality of the solar cells themselves focused on the development of tunable lattice constant epitaxial templates. Initially intended to enable lattice matched multijunction solar cells, these templates would enable increased flexibility in band gap selection for spectrum splitting ensembles and enhanced radiative quality relative to metamorphic growth. The III-V material family is commonly used for multijunction solar cells both for its high radiative quality and for the ease of integrating multiple band gaps into one monolithic growth. The band gap flexibility is limited by the lattice constant of available growth templates. The virtual substrate consists of a thin III-V film with the desired lattice constant. The film is grown strained on an available wafer substrate, but the thickness is below the dislocation nucleation threshold. By removing the film from the growth substrate, allowing the strain to relax elastically, and bonding it to a supportive handle, a template with the desired lattice constant is formed. Experimental efforts towards this structure and initial proof of concept are presented.

Cells with high radiative quality present the opportunity to recover a large amount of their radiative losses if they are incorporated in an ensemble that couples emission from one cell to another. This effect is well known, but has been explored previously in the context of sub cells that independently operate at their maximum power point. This analysis explicitly accounts for the system interaction and identifies ways to enhance overall performance by operating some cells in an ensemble at voltages that reduce the power converted in the individual cell. Series connected multijunctions, which by their nature facilitate strong optical coupling between sub-cells, are reoptimized with substantial performance benefit.

Photovoltaic efficiency is usually measured relative to a standard incident spectrum to allow comparison between systems. Deployed in the field systems may differ in energy production due to sensitivity to changes in the spectrum. The series connection constraint in particular causes system efficiency to decrease as the incident spectrum deviates from the standard spectral composition. This thesis performs a case study comparing performance of systems over a year at a particular location to identify the energy production penalty caused by series connection relative to independent electrical connection.