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A Study of the Mechanical Behavior Of Nanocrystalline Metals Using Micro-Electro-Mechanical Systems (MEMS)

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The study of the mechanical behavior of nanocrystalline metals using microelectromechanical systems (MEMS) devices lies at the intersection of nanotechnology, mechanical engineering and material science. The extremely small grains that make up nanocrystalline metals lead to higher strength but lower

The study of the mechanical behavior of nanocrystalline metals using microelectromechanical systems (MEMS) devices lies at the intersection of nanotechnology, mechanical engineering and material science. The extremely small grains that make up nanocrystalline metals lead to higher strength but lower ductility as compared to bulk metals. Effects of strain-rate dependence on the mechanical behavior of nanocrystalline metals are explored. Knowing the strain rate dependence of mechanical properties would enable optimization of material selection for different applications and lead to lighter structural components and enhanced sustainability.

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2014-05

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Synthesis and band gap engineering in Ge₁-x-ySixSny Materials for Near-IR Wavelength Applications

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This thesis describes the fabrication of several new classes of Ge1-x-ySixSny materials with the required compositions and crystal quality to engineer the band gaps above and below that of elemental Ge (0.8 eV) in the near IR. The work initially

This thesis describes the fabrication of several new classes of Ge1-x-ySixSny materials with the required compositions and crystal quality to engineer the band gaps above and below that of elemental Ge (0.8 eV) in the near IR. The work initially focused on Ge1-x-ySixSny (1-5% Sn, 4-20% Si) materials grown on Ge(100) via gas-source epitaxy of Ge4H10, Si4H10 and SnD4. Both intrinsic and doped layers were produced with defect-free microstructure and viable thickness, allowing the fabrication of high-performance photodetectors. These exhibited low ideality factors, state-of-the-art dark current densities and adjustable absorption edges between 0.87 and 1.03 eV, indicating that the band gaps span a significant range above that of Ge. Next Sn-rich Ge1-x-ySixSny alloys (2-4% Si and 4-10% Sn) were fabricated directly on Si and were found to show significant optical emission using photoluminescence measurements, indicating that the alloys have direct band gaps below that of pure Ge in the range of 0.7-0.55 eV. A series of Sn-rich Ge1-x-ySixSny analogues (y>x) with fixed 3-4% Si content and progressively increasing Sn content in the 4-10% range were then grown on Ge buffered Si platforms for the purpose of improving the material's crystal quality. The films in this case exhibited lower defect densities than those grown on Si, allowing a meaningful study of both the direct and indirect gaps. The results show that the separation of the direct and indirect edges can be made smaller than in Ge even for non-negligible 3-4% Si content, confirming that with a suitable choice of Sn compositions the ternary Ge1-x-ySixSny reproduces all features of the electronic structure of binary Ge1-ySny, including the sought-after indirect-to-direct gap cross over. The above synthesis of optical quality Ge1-x-ySixSny on virtual Ge was made possible by the development of high quality Ge-on-Si buffers via chemical vapor deposition of Ge4H10. The resultant films exhibited structural and electrical properties significantly improved relative to state-of-the-art results obtained using conventional approaches. It was found that pure Ge4H10 facilitates the control of residual doping and enables p-i-n devices whose dark currents are not entirely determined by defects and whose zero-bias collection efficiencies are higher than those obtained from samples fabricated using alternative Ge-on-Si approaches.

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2013

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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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2013

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Synthesis and characterization of erbium compound nanowires as high gain optical materials

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Integrated photonics requires high gain optical materials in the telecom wavelength range for optical amplifiers and coherent light sources. Erbium (Er) containing materials are ideal candidates due to the 1.5 μm emission from Er3+ ions. However, the Er density in

Integrated photonics requires high gain optical materials in the telecom wavelength range for optical amplifiers and coherent light sources. Erbium (Er) containing materials are ideal candidates due to the 1.5 μm emission from Er3+ ions. However, the Er density in typical Er-doped materials is less than 1 x 1020 cm-3, thus limiting the maximum optical gain to a few dB/cm, too small to be useful for integrated photonics applications. Er compounds could potentially solve this problem since they contain much higher Er density. So far the existing Er compounds suffer from short lifetime and strong upconversion effects, mainly due to poor quality of crystals produced by various methods of thin film growth and deposition. This dissertation explores a new Er compound: erbium chloride silicate (ECS, Er3(SiO4)2Cl ) in the nanowire form, which facilitates the growth of high quality single crystals. Growth methods for such single crystal ECS nanowires have been established. Various structural and optical characterizations have been carried out. The high crystal quality of ECS material leads to a long lifetime of the first excited state of Er3+ ions up to 1 ms at Er density higher than 1022 cm-3. This Er lifetime-density product was found to be the largest among all Er containing materials. A unique integrating sphere method was developed to measure the absorption cross section of ECS nanowires from 440 to 1580 nm. Pump-probe experiments demonstrated a 644 dB/cm signal enhancement from a single ECS wire. It was estimated that such large signal enhancement can overcome the absorption to result in a net material gain, but not sufficient to compensate waveguide propagation loss. In order to suppress the upconversion process in ECS, Ytterbium (Yb) and Yttrium (Y) ions are introduced as substituent ions of Er in the ECS crystal structure to reduce Er density. While the addition of Yb ions only partially succeeded, erbium yttrium chloride silicate (EYCS) with controllable Er density was synthesized successfully. EYCS with 30 at. % Er was found to be the best. It shows the strongest PL emission at 1.5 μm, and thus can be potentially used as a high gain material.

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2013

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Characterization of strain in core-shell nanowires: a Raman spectroscopy study

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Raman scattering from Ge-Si core-shell nanowires is investigated theoretically and experimentally. A theoretical model that makes it possible to extract quantitative strain information from the measured Raman spectra is presented for the first time. Geometrical and elastic simplifications are introduced

Raman scattering from Ge-Si core-shell nanowires is investigated theoretically and experimentally. A theoretical model that makes it possible to extract quantitative strain information from the measured Raman spectra is presented for the first time. Geometrical and elastic simplifications are introduced to keep the model analytical, which facilitates comparison with experimental results. In particular, the nanowires are assumed to be cylindrical, and their elastic constants isotropic. The simple analytical model is subsequently validated by performing numerical calculations using realistic nanowire geometries and cubic, anisotropic elastic constants. The comparison confirms that the analytic model is an excellent approximation that greatly facilitates quantitative Raman work, with expected errors in the strain determination that do not exceed 10%. Experimental Raman spectra of a variety of core-shell nanowires are presented, and the strain in the nanowires is assessed using the models described above. It is found that all structures present a significant degree of strain relaxation relative to ideal, fully strained Ge-Si core-shell structures. The analytical models are modified to quantify this strain relaxation.

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2011

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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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2011

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Polarization effects in group III-nitride materials and devices

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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

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.

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2012

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Structural characterization of II-VI and III-V compound semiconductor heterostructures and superlattices

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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

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.

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2012

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A study of two high efficiency energy conversion processes: semiconductor photovoltaics and semiconductor luminescence refrigeration

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As the world energy demand increases, semiconductor devices with high energy conversion efficiency become more and more desirable. The energy conversion consists of two distinct processes, namely energy generation and usage. In this dissertation, novel multi-junction solar cells

As the world energy demand increases, semiconductor devices with high energy conversion efficiency become more and more desirable. The energy conversion consists of two distinct processes, namely energy generation and usage. In this dissertation, novel multi-junction solar cells and light emitting diodes (LEDs) are proposed and studied for high energy conversion efficiency in both processes, respectively. The first half of this dissertation discusses the practically achievable energy conversion efficiency limit of solar cells. Since the demonstration of the Si solar cell in 1954, the performance of solar cells has been improved tremendously and recently reached 41.6% energy conversion efficiency. However, it seems rather challenging to further increase the solar cell efficiency. The state-of-the-art triple junction solar cells are analyzed to help understand the limiting factors. To address these issues, the monolithically integrated II-VI and III-V material system is proposed for solar cell applications. This material system covers the entire solar spectrum with a continuous selection of energy bandgaps and can be grown lattice matched on a GaSb substrate. Moreover, six four-junction solar cells are designed for AM0 and AM1.5D solar spectra based on this material system, and new design rules are proposed. The achievable conversion efficiencies for these designs are calculated using the commercial software package Silvaco with real material parameters. The second half of this dissertation studies the semiconductor luminescence refrigeration, which corresponds to over 100% energy usage efficiency. Although cooling has been realized in rare-earth doped glass by laser pumping, semiconductor based cooling is yet to be realized. In this work, a device structure that monolithically integrates a GaAs hemisphere with an InGaAs/GaAs quantum-well thin slab LED is proposed to realize cooling in semiconductor. The device electrical and optical performance is calculated. The proposed device then is fabricated using nine times photolithography and eight masks. The critical process steps, such as photoresist reflow and dry etch, are simulated to insure successful processing. Optical testing is done with the devices at various laser injection levels and the internal quantum efficiency, external quantum efficiency and extraction efficiency are measured.

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2010

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Material properties of MBE Grown ZnTe, GaSb and their heterostructures for optoelectronic device applications

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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)

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.

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2012