The thesis studies new methods to fabricate optoelectronic Ge1-ySny/Si(100) alloys and investigate their photoluminescence (PL) properties for possible applications in Si-based photonics including IR lasers. The work initially investigated the origin of the difference between the PL spectrum of bulk Ge, dominated by indirect gap emission, and the PL spectrum of Ge-on-Si films, dominated by direct gap emission. It was found that the difference is due to the supression of self-absorption effects in Ge films, combined with a deviation from quasi-equilibrium conditions in the conduction band of undoped films. The latter is confirmed by a model suggesting that the deviation is caused by the shorter recombination lifetime in the films relative to bulk Ge. The knowledge acquired from this work was then utilized to study the PL properties of n-type Ge1-ySny/Si (y=0.004-0.04) samples grown via chemical vapor deposition of Ge2H6/SnD4/P(GeH3)3. It was found that the emission intensity (I) of these samples is at least 10x stronger than observed in un-doped counterparts and that the Idir/Iind ratio of direct over indirect gap emission increases for high-Sn contents due to the reduced gamma-L valley separation, as expected. Next the PL investigation was expanded to samples with y=0.05-0.09 grown via a new method using the more reactive Ge3H8 in place of Ge2H6. Optical quality, 1-um thick Ge1-ySny/Si(100) layers were produced using Ge3H10/SnD4 and found to exhibit strong, tunable PL near the threshold of the direct-indirect bandgap crossover. A byproduct of this study was the development of an enhanced process to produce Ge3H8, Ge4H10, and Ge5H12 analogs for application in ultra-low temperature deposition of Group-IV semiconductors. The thesis also studies synthesis routes of an entirely new class of semiconductor compounds and alloys described by Si5-2y(III-V)y (III=Al, V= As, P) comprising of specifically designed diamond-like structures based on a Si parent lattice incorporating isolated III-V units. The common theme of the two thesis topics is the development of new mono-crystalline materials on ubiquitous silicon platforms with the objective of enhancing the optoelectronic performance of Si and Ge semiconductors, potentially leading to the design of next generation optical devices including lasers, detectors and solar cells.

The work contained in this dissertation is focused on the optical properties of direct band gap semiconductors which crystallize in a wurtzite structure: more specifically, the III-nitrides and ZnO. By using cathodoluminescence spectroscopy, many of their properties have been investigated, including band gaps, defect energy levels, carrier lifetimes, strain states, exciton binding energies, and effects of electron irradiation on luminescence. Part of this work is focused on p-type Mg-doped GaN and InGaN. These materials are extremely important for the fabrication of visible light emitting diodes and diode lasers and their complex nature is currently not entirely understood. The luminescence of Mg-doped GaN films has been correlated with electrical and structural measurements in order to understand the behavior of hydrogen in the material. Deeply-bound excitons emitting near 3.37 and 3.42 eV are observed in films with a significant hydrogen concentration during cathodoluminescence at liquid helium temperatures. These radiative transitions are unstable during electron irradiation. Our observations suggest a hydrogen-related nature, as opposed to a previous assignment of stacking fault luminescence. The intensity of the 3.37 eV transition can be correlated with the electrical activation of the Mg acceptors. Next, the acceptor energy level of Mg in InGaN is shown to decrease significantly with an increase in the indium composition. This also corresponds to a decrease in the resistivity of these films. In addition, the hole concentration in multiple quantum well light emitting diode structures is much more uniform in the active region when Mg-doped InGaN (instead of Mg-doped GaN) is used. These results will help improve the efficiency of light emitting diodes, especially in the green/yellow color range. Also, the improved hole transport may prove to be important for the development of photovoltaic devices. Cathodoluminescence studies have also been performed on nanoindented ZnO crystals. Bulk, single crystal ZnO was indented using a sub-micron spherical diamond tip on various surface orientations. The resistance to deformation (the "hardness") of each surface orientation was measured, with the c-plane being the most resistive. This is due to the orientation of the easy glide planes, the c-planes, being positioned perpendicularly to the applied load. The a-plane oriented crystal is the least resistive to deformation. Cathodoluminescence imaging allows for the correlation of the luminescence with the regions located near the indentation. Sub-nanometer shifts in the band edge emission have been assigned to residual strain the crystals. The a- and m-plane oriented crystals show two-fold symmetry with regions of compressive and tensile strain located parallel and perpendicular to the ±c-directions, respectively. The c-plane oriented crystal shows six-fold symmetry with regions of tensile strain extending along the six equivalent a-directions.

Nitride semiconductors have wide applications in electronics and optoelectronics technologies. Understanding the nature of the optical recombination process and its effects on luminescence efficiency is important for the development of novel devices. This dissertation deals with the optical properties of nitride semiconductors, including GaN epitaxial layers and more complex heterostructures. The emission characteristics are examined by cathodoluminescence spectroscopy and imaging, and are correlated with the structural and electrical properties studied by transmission electron microscopy and electron holography. Four major areas are covered in this dissertation, which are described next. The effect of strain on the emission characteristics in wurtzite GaN has been studied. The values of the residual strain in GaN epilayers with different dislocation densities are determined by x-ray diffraction, and the relationship between exciton emission energy and the in-plane residual strain is demonstrated. It shows that the emission energy increases withthe magnitude of the in-plane compressive strain. The temperature dependence of the emission characteristics in cubic GaN has been studied. It is observed that the exciton emission and donor-acceptor pair recombination behave differently with temperature. The donor-bound exciton binding energy has been measured to be 13 meV from the temperature dependence of the emission spectrum. It is also found that the ionization energies for both acceptors and donors are smaller in cubic compared with hexagonal structures, which should contribute to higher doping efficiencies. A comprehensive study on the structural and optical properties is presented for InGaN/GaN quantum wells emitting in the blue, green, and yellow regions of the electromagnetic spectrum. Transmission electron microscopy images indicate the presence of indium inhomogeneties which should be responsible for carrier localization. The temperature dependence of emission luminescence shows that the carrier localization effects become more significant with increasing emission wavelength. On the other hand, the effect of non-radiative recombination on luminescence efficiency also varies with the emission wavelength. The fast increase of the non-radiative recombination rate with temperature in the green emitting QWs contributes to the lower efficiency compared with the blue emitting QWs. The possible saturation of non-radiative recombination above 100 K may explain the unexpected high emission efficiency for the yellow emitting QWs Finally, the effects of InGaN underlayers on the electronic and optical properties of InGaN/GaN quantum wells emitting in visible spectral regions have been studied. A significant improvement of the emission efficiency is observed, which is associated with a blue shift in the emission energy, a reduced recombination lifetime, an increased spatial homogeneity in the luminescence, and a weaker internal field across the quantum wells. These are explained by a partial strain relaxation introduced by the InGaN underlayer, which is measured by reciprocal space mapping of the x-ray diffraction intensity.

Group IV alloy films exhibit the ability to tune both band structure and lattice parameters and have recently attracted attention for their potential applications in Si-photonics and photovoltaics. In this work, several new approaches to produce these alloys directly on Si(100) and Ge(100) wafers are developed. For photovoltaics, use of Ge-buffered Si(100) wafers as a low cost platform for epitaxy of In1-xGaxAs layers was explored. The results indicate that this approach has promise for transitioning from bulk Ge platforms to virtual substrates for a significant cost reduction. The electrical and optical properties of Ge and Ge1-ySny layers produced using several different techniques were explored via fabrication of high performance heterostructure photodiodes. First, a new CVD approach to Ge-like materials was developed in which germanium is alloyed with very small amounts of tin. These alloys exhibited no significant difference in their structural properties or band gap compared to pure Ge, however superior photo response and reduced dark currents were observed from fabricated devices relative to pure Ge on Si reference diodes. Additionally, pure Ge/Si(100) photodiodes were fabricated using layers grown via reactions of Ge4H10 on Si(100) and found to exhibit low dark current densities with high collection efficiencies. Ge1-x-ySixSny materials represent the newest member of group IV alloy family. The ability to decouple the lattice constant and the band gap in this system has led to strong interest both for strain/confinement layers in quantum well structures, and as the possible "missing" 1 eV junction in multijunction photovoltaics. Recent progress in this field has allowed for the first time growth, fabrication and measurement of novel photodiodes based on Ge1-x-ySixSny. This work presents the material, electrical and optical properties of Ge1-x-ySixSny layers and photodiodes grown directly on Ge and Si wafers using two different synthetic approaches. A series of photodiodes containing Sn concentrations from 1-5%, all lattice matched to Ge, was fabricated. The devices exhibited low dark current densities with high collection efficiencies as required for photovoltaics. By measuring the photoresponse, tunable band gaps ranging from 0.85 eV to 1.02 eV were observed.

Recently a new materials platform consisting of semiconductors grown on GaSb and InAs substrates with lattice constants close to 6.1 A was proposed by our group for various electronic and optoelectronic applications. This materials platform consists of both II-VI (MgZnCdHg)(SeTe) and III-V (InGaAl)(AsSb) compound semiconductors, which have direct bandgaps spanning the entire energy spectrum from far-IR (~0 eV) up to UV (~3.4 eV). The broad range of bandgaps and material properties make it very attractive for a wide range of applications in optoelectronics, such as solar cells, laser diodes, light emitting diodes, and photodetectors. Moreover, this novel materials system potentially offers unlimited degrees of freedom for integration of electronic and optoelectronic devices onto a single substrate while keeping the best possible materials quality with very low densities of misfit dislocations. This capability is not achievable with any other known lattice-matched semiconductors on any available substrate. In the 6.1-A materials system, the semiconductors ZnTe and GaSb are almost perfectly lattice-matched with a lattice mismatch of only 0.13%. Correspondingly, it is expected that high quality ZnTe/GaSb and GaSb/ZnTe heterostructures can be achieved with very few dislocations generated during growth. To fulfill the task, their MBE growth and material properties are carefully investigated. High quality ZnTe layers grown on various III-V substrates and GaSb grown on ZnTe are successfully achieved using MBE. It is also noticed that ZnTe and GaSb have a type-I band-edge alignment with large band offsets (delta_Ec=0.934 eV, delta_Ev=0.6 eV), which provides strong confinement for both electrons and holes. Furthermore, a large difference in refractive index is found between ZnTe and GaSb (2.7 and 3.9, respectively, at 0.7 eV), leading to excellent optical confinement of the guided optical modes in planar semiconductor lasers or distributed Bragg reflectors (DBR) for vertical-cavity surface-emitting lasers. Therefore, GaSb/ZnTe double-heterostructure and ZnTe/GaSb DBR structure are suitable for use in light emitting devices. In this thesis work, experimental demonstration of these structures with excellent structural and optical properties is reported. During the exploration on the properties of various ZnTe heterostructures, it is found that residual tensile strains exist in the thick ZnTe epilayers when they are grown on GaAs, InP, InAs and GaSb substrates. The presence of tensile strains is due to the difference in thermal expansion coefficients between the epilayers and the substrates. The defect densities in these ZnTe layers become lower as the ZnTe layer thickness increases. Growth of high quality GaSb on ZnTe can be achieved using a temperature ramp during growth. The influence of temperature ramps with different ramping rates in the optical properties of GaSb layer is studied, and the samples grown with a temperature ramp from 360 to 470 C at a rate of 33 C/min show the narrowest bound exciton emission peak with a full width at half maximum of 15 meV. ZnTe/GaSb DBR structures show excellent reflectivity properties in the mid-infrared range. A peak reflectance of 99% with a wide stopband of 480 nm centered at 2.5 um is measured from a ZnTe/GaSb DBR sample of only 7 quarter-wavelength pairs.

The research described in this dissertation has involved the use of transmission electron microcopy (TEM) to characterize the structural properties of II-VI and III-V compound semiconductor heterostructures and superlattices. The microstructure of thick ZnTe epilayers (~2.4 µm) grown by molecular beam epitaxy (MBE) under virtually identical conditions on GaSb, InAs, InP and GaAs (100) substrates were compared using TEM. High-resolution electron micrographs revealed a highly coherent interface for the ZnTe/GaSb sample, and showed extensive areas with well-separated interfacial misfit dislocations for the ZnTe/InAs sample. Lomer edge dislocations and 60o dislocations were commonly observed at the interfaces of the ZnTe/InP and ZnTe/GaAs samples. The amount of residual strain at the interfaces was estimated to be 0.01% for the ZnTe/InP sample and -0.09% for the ZnTe/GaAs sample. Strong PL spectra for all ZnTe samples were observed from 80 to 300 K. High quality GaSb grown by MBE on ZnTe/GaSb (001) virtual substrates with a temperature ramp at the beginning of the GaSb growth has been demonstrated. High-resolution X-ray diffraction (XRD) showed clear Pendellösung thickness fringes from both GaSb and ZnTe epilayers. Cross-section TEM images showed excellent crystallinity and smooth morphology for both ZnTe/GaSb and GaSb/ZnTe interfaces. Plan-view TEM image revealed the presence of Lomer dislocations at the interfaces and threading dislocations in the top GaSb layer. The defect density was estimated to be ~1 x107/cm2. The PL spectra showed improved optical properties when using the GaSb transition layer grown on ZnTe with a temperature ramp. The structural properties of strain-balanced InAs/InAs1-xSbx SLs grown on GaSb (001) substrates by metalorganic chemical vapor deposition (MOCVD) and MBE, have been studied using XRD and TEM. Excellent structural quality of the InAs/InAs1-xSbx SLs grown by MOCVD has been demonstrated. Well-defined ordered-alloy structures within individual InAs1-xSbx layers were observed for samples grown by modulated MBE. However, the ordering disappeared when defects propagating through the SL layers appeared during growth. For samples grown by conventional MBE, high-resolution images revealed that interfaces for InAs1-xSbx grown on InAs layers were sharper than for InAs grown on InAs1-xSbx layers, most likely due to a Sb surfactant segregation effect.

Group III-nitride semiconductors have wide application in optoelectronic devices. Spontaneous and piezoelectric polarization effects have been found to be critical for electric and optical properties of group III-nitrides. In this dissertation, firstly, the crystal orientation dependence of the polarization is calculated and in-plane polarization is revealed. The in-plane polarization is sensitive to the lateral characteristic dimension determined by the microstructure. Specific semi-polar plane growth is suggested for reducing quantum-confined Stark effect. The macroscopic electrostatic field from the polarization discontinuity in the heterostructures is discussed, b ased on that, the band diagram of InGaN/GaN quantum well/barrier and AlGaN/GaN heterojunction is obtained from the self-consistent solution of Schrodinger and Poisson equations. New device design such as triangular quantum well with the quenched polarization field is proposed. Electron holography in the transmission electron microscopy is used to examine the electrostatic potential under polarization effects. The measured potential energy profiles of heterostructure are compared with the band simulation, and evidences of two-dimensional hole gas (2DHG) in a wurtzite AlGaN/ AlN/ GaN superlattice, as well as quasi two-dimensional electron gas (2DEG) in a zinc-blende AlGaN/GaN are found. The large polarization discontinuity of AlN/GaN is the main source of the 2DHG of wurtzite nitrides, while the impurity introduced during the growth of AlGaN layer provides the donor states that to a great extent balance the free electrons in zinc-blende nitrides. It is also found that the quasi-2DEG concentration in zinc-blende AlGaN/GaN is about one order of magnitude lower than the wurtzite AlGaN/GaN, due to the absence of polarization. Finally, the InAlN/GaN lattice-matched epitaxy, which ideally has a zero piezoelectric polarization and strong spontaneous polarization, is experimentally studied. The breakdown in compositional homogeneity is triggered by threading dislocations with a screw component propagating from the GaN underlayer, which tend to open up into V-grooves at a certain thickness of the InxAl1-xN layer. The V-grooves coalesce at 200 nm and are filled with material that exhibits a significant drop in indium content and a broad luminescence peak. The structural breakdown is due to heterogeneous nucleation and growth at the facets of the V-grooves.

he accurate simulation of many-body quantum systems is a challenge for computational physics. Quantum Monte Carlo methods are a class of algorithms that can be used to solve the many-body problem. I study many-body quantum systems with Path Integral Monte Carlo techniques in three related areas of semiconductor physics: (1) the role of correlation in exchange coupling of spins in double quantum dots, (2) the degree of correlation and hyperpolarizability in Stark shifts in InGaAs/GaAs dots, and (3) van der Waals interactions between 1-D metallic quantum wires at finite temperature. The two-site model is one of the simplest quantum problems, yet the quantitative mapping from a three-dimensional model of a quantum double dot to an effective two-site model has many subtleties requiring careful treatment of exchange and correlation. I calculate exchange coupling of a pair of spins in a double dot from the permutations in a bosonic path integral, using Monte Carlo method. I also map this problem to a Hubbard model and find that exchange and correlation renormalizes the model parameters, dramatically decreasing the effective on-site repulsion at larger separations. Next, I investigated the energy, dipole moment, polarizability and hyperpolarizability of excitonic system in InGaAs/GaAs quantum dots of different shapes and successfully give the photoluminescence spectra for different dots with electric fields in both the growth and transverse direction. I also showed that my method can deal with the higher-order hyperpolarizability, which is most relevant for fields directed in the lateral direction of large dots. Finally, I show how van der Waals interactions between two metallic quantum wires change with respect to the distance between them. Comparing the results from quantum Monte Carlo and the random phase approximation, I find similar power law dependance. My results for the calculation in quasi-1D and exact 1D wires include the effect of temperature, which has not previously been studied.

The chemical sensitivity and spatial resolution of Raman spectroscopy, combined with the sensitivity of modern systems that can easily detect single atomic layers, have made this technique a preferred choice for the strain characterization of complex systems such as nanoscale complementary metal-oxide-semiconductor - CMOS - devices. A disadvantage of Raman spectroscopy, however, is that the shifts associated with strain are not related to the geometrical deformations in any obvious way, so that careful calibrations are needed to determine the anharmonic coefficients (p, q and r) that relate strain to Raman shifts. A new set of measurements of the Raman shift in strained Ge films grown on relaxed SiGe buffer layers deposited on Si substrates is presented, and thereby, a new consistent set of values for the parameters p and q for Ge has been proposed. In this dissertation the study of the vibrational properties of Ge1-xSnx alloys has also been reported. The temperature dependence of the Raman spectrum of Ge-rich Ge1-x Snx and Ge1-x-ySi xSny alloys has been determined in the 10 K - 450 K range. The Raman line shift and width changes as a function of temperature are found to be virtually identical to those observed in bulk Ge. This result shows that the anharmonic decay process responsible for the temperature dependence is extremely robust against the alloy perturbation.

Nanofluidic devices in which one single-walled carbon nanotube (SWCNT) spans a barrier between two fluid reservoirs were constructed, enabling direct electrical measurement of the transport of ions and molecules. Ion current through these devices is about 2 orders of magnitude larger than that predicted from the bulk resistivity of the electrolyte. Electroosmosis drives excess current, carried by cations, and is found to be the origin of giant ionic current through SWCNT as shown by building an ionic field-effect transistor with a gate electrode embedded in the fluid barrier. Wetting of inside of the semi-conducting SWCNT by water showed the change of its electronic property, turning the electronic SWCNT field-effect transistor to "on" state. These findings provide a new method to investigate and control the ion and molecule behavior at nanoscale.