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Epitaxy of group IV optical materials and synthesis of IV/III-V semiconductor analogs by designer hydride chemistries

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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

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.

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Date Created
2013

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Investigation of light absorption and emission in Ge and GeSn films grown on Si substrates

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Ge1-ySny alloys represent a new class of photonic materials for integrated optoelectronics on Si. In this work, the electrical and optical properties of Ge1-ySny alloy films grown on Si, with concentrations in the range 0 ≤ y ≤ 0.04, are

Ge1-ySny alloys represent a new class of photonic materials for integrated optoelectronics on Si. In this work, the electrical and optical properties of Ge1-ySny alloy films grown on Si, with concentrations in the range 0 ≤ y ≤ 0.04, are studied via a variety of methods. The first microelectronic devices from GeSn films were fabricated using newly developed CMOS-compatible protocols, and the devices were characterized with respect to their electrical properties and optical response. The detectors were found to have a detection range that extends into the near-IR, and the detection edge is found to shift to longer wavelengths with increasing Sn content, mainly due to the compositional dependence of the direct band gap E0. With only 2 % Sn, all of the telecommunication bands are covered by a single detector. Room temperature photoluminescence was observed from GeSn films with Sn content up to 4 %. The peak wavelength of the emission was found to shift to lower energies with increasing Sn content, corresponding to the decrease in the direct band gap E0 of the material. An additional peak in the spectrum was assigned to the indirect band gap. The separation between the direct and indirect peaks was found to decrease with increasing Sn concentration, as expected. Electroluminescence was also observed from Ge/Si and Ge0.98Sn0.02 photodiodes under forward bias, and the luminescence spectra were found to match well with the observed photoluminescence spectra. A theoretical expression was developed for the luminescence due to the direct band gap and fit to the data.

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Date Created
2011

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Synthesis of hybrid (III-V)y(IV)5-2y semiconductors: a new approach to extending the optoelectronic capabilities of Si and Ge technologies

Description

Modern semiconductor technologies have been dominated by group-IV materials and III-V analogues. The development of hybrid derivatives combining appropriate members of these systems has been of interest for the purpose of extending the optoelectronic capabilities of the state-of-the-art. Early work

Modern semiconductor technologies have been dominated by group-IV materials and III-V analogues. The development of hybrid derivatives combining appropriate members of these systems has been of interest for the purpose of extending the optoelectronic capabilities of the state-of-the-art. Early work on pseudo-binary (III-V)-IV alloys, described with the general formula (III-V)1-x(IV2)x,

showed limited progress due to phase segregation, auto-doping and compositional inhomogeneities. Recently, new techniques were introduced for synthesizing new classes of (III-V)-IV hybrid materials using reactions of V(IVH3)3 molecules [V = N, P, As and IV = Si, Ge] with group-III elements (B, Al, Ga, In). The reactions produce (III-V)-IV3 building blocks that interlink to form diamond-like

frameworks in which the III-V pairs incorporate as isolated units within the group-IV lattice. This approach not only precludes phase segregation, but also provides access to structures and compositions unattainable by conventional means. Entire new families of crystalline (III-V)-IV3 and (III-V)y(IV)5-y alloys with tunable IV-rich compositions, different from conventional (III-V)1-x(IV2)x systems, have been grown on Si(100) and GaP(100) wafers as well as Si1-xGex and Ge buffer layers which, in most cases, provide lattice matched templates for Si integration.

In this work, materials in the In-P-Ge, Ga-As-Ge and Ga-P-Si systems that would exhibit direct-gap behavior were targeted. A series of (InP)yGe5-2y alloys with tunable Ge contents above 60% were synthesized by reactions of P(GeH3)3 and indium atoms and were studied for bonding, structure, and optical response. (GaAs)yGe5-2y analogues were also grown and exhibited strong photoluminescence for applications in mid-IR photonics. The GaPSi3 alloy and Si-rich derivatives were produced via reactions of P(SiH3)3 and [H2GaNMe2]2 and exhibit enhanced absorption in the visible range. Quaternary analogues in the Al1-xBxPSi3 system were grown on Si via reactions of Al(BH4)3 and P(SiH3)3 leading to the formation crystalline materials with extended absorption relative to Si. This makes them imminently suitable for applications in Si-based photovoltaics. The work emphasized use of quantum-chemical simulations to elucidate structural, thermodynamic, and mechanical properties of the synthesized systems. The theory also included simulations of new synthetic targets such as BNC3, BNSi3, BPC3, and BPSi3 with interesting mechanical properties and strong covalent bonding.

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Date Created
2017

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Chemical vapor deposition of metastable germanium based semiconductors for optoelectronic applications

Description

Optoelectronic and microelectronic applications of germanium-based materials have received considerable research interest in recent years. A novel method for Ge on Si heteroepitaxy required for such applications was developed via molecular epitaxy of Ge5H12. Next, As(GeH3)3, As(SiH3)3, SbD3, S(GeH3)2 and

Optoelectronic and microelectronic applications of germanium-based materials have received considerable research interest in recent years. A novel method for Ge on Si heteroepitaxy required for such applications was developed via molecular epitaxy of Ge5H12. Next, As(GeH3)3, As(SiH3)3, SbD3, S(GeH3)2 and S(SiH3)2 molecular sources were utilized in degenerate n-type doping of Ge. The epitaxial Ge films produced in this work incorporate donor atoms at concentrations above the thermodynamic equilibrium limits. The donors are nearly fully activated, and led to films with lowest resistivity values thus far reported.

Band engineering of Ge was achieved by alloying with Sn. Epitaxy of the alloy layers was conducted on virtual Ge substrates, and made use of the germanium hydrides Ge2H6 and Ge3H8, and the Sn source SnD4. These films exhibit stronger emission than equivalent material deposited directly on Si, and the contributions from the direct and indirect edges can be separated. The indirect-direct crossover composition for Ge1-ySny alloys was determined by photoluminescence (PL). By n-type doping of the Ge1-ySny alloys via P(GeH3)3, P(SiH3)3 and As(SiH3)3, it was possible to enhance photoexcited emission by more than an order-of-magnitude.

The above techniques for deposition of direct gap Ge1-ySny alloys and doping of Ge were combined with p-type doping methods for Ge1-ySny using B2H6 to fabricate pin heterostructure diodes with active layer compositions up to y=0.137. These represent the first direct gap light emitting diodes made from group IV materials. The effect of the single defected n-i¬ interface in a n-Ge/i-Ge1-ySny/p-Ge1-zSnz architecture on electroluminescence (EL) was studied. This led to lattice engineering of the n-type contact layer to produce diodes of n-Ge1-xSnx/i-Ge1-ySny/p-Ge1-zSnz architecture which are devoid of interface defects and therefore exhibit more efficient EL than the previous design. Finally, n-Ge1-ySny/p-Ge1-zSnz pn junction devices were synthesized with varying composition and doping parameters to investigate the effect of these properties on EL.

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Date Created
2016

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Evaluation of k4-diimine nickel and cobalt hydrofunctionalization catalysts

Description

The search for highly active, inexpensive, and earth abundant replacements for existing transition metal catalysts is ongoing. Our group has utilized several redox non-innocent ligands that feature flexible arms with donor substituents. These ligands allow for coordinative flexibility about the

The search for highly active, inexpensive, and earth abundant replacements for existing transition metal catalysts is ongoing. Our group has utilized several redox non-innocent ligands that feature flexible arms with donor substituents. These ligands allow for coordinative flexibility about the metal centre, while the redox non-innocent core helps to overcome the one electron chemistry that is prevalent in first row transition metals. This dissertation focuses on the use of Ph2PPrDI, which can adopt a κ4-configuration when bound to a metal. One reaction that is industrially useful is hydrosilylation, which allows for the preparation of silicones that are useful in the lubrication, adhesive, and cosmetics industries. Typically, this reaction relies on highly active, platinum-based catalysts. However, the high cost of this metal has inspired the search for base metal replacements. In Chapter One, an overview of existing alkene and carbonyl hydrosilylation catalysts is presented. Chapter Two focuses on exploring the reactivity of (Ph2PPrDI)Ni towards carbonyl hydrosilylation, as well as the development of the 2nd generation catalysts, (iPr2PPrDI)Ni and (tBu2PPrDI)Ni. Chapter Three presents a new C-O bond hydrosilylation reaction for the formation of silyl esters. It was found the (Ph2PPrDI)Ni is the most active catalyst in the literature for this transformation, with turnover frequencies of up to 900 h-1. Chapter Four explores the activity and selectivity of (Ph2PPrDI)Ni for alkene hydrosilylation, including the first large scope of gem-olefins for a nickel-based catalyst. Chapter Five explores the chemistry of (Ph2PPrDI)CoH, first through electronic structure determinations and crystallography, followed by an investigation of its reactivity towards alkyne hydroboration and nitrile dihydroboration. (Ph2PPrDI)CoH is the first reported cobalt nitrile dihydroboration catalyst.

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Date Created
2018