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- All Subjects: Silicon alloys
- Genre: Academic theses
- Genre: Doctoral Dissertation
- Creators: Menéndez, Jose
Description
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.
ContributorsJuday, Reid (Author) / Ponce, Fernando A. (Thesis advisor) / Drucker, Jeff (Committee member) / Mccartney, Martha R (Committee member) / Menéndez, Jose (Committee member) / Shumway, John (Committee member) / Arizona State University (Publisher)
Created2013
Description
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.
ContributorsBeeler, Richard (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2012
Description
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.
ContributorsLi, Di (Author) / Ponce, Fernando (Thesis advisor) / Culbertson, Robert (Committee member) / Yu, Hongbin (Committee member) / Shumway, John (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2012
Description
ABSTRACT This thesis focuses on structural characterizations and optical properties of Si, Ge based semiconductor alloys. Two material systems are characterized: Si-based III-V/IV alloys, which represent a possible pathway to augment the optical performance of elemental silicon as a solar cell absorber layer, and Ge-based Ge1-ySny and Ge1-x-ySixSny systems which are applicable to long wavelength optoelectronics. Electron microscopy is the primary tool used to study structural properties. Electron Energy Loss spectroscopy (EELS), Ellipsometry, Photoluminescence and Raman Spectroscopy are combined to investigate electronic band structures and bonding properties. The experiments are closely coupled with structural and property modeling and theory. A series of III-V-IV alloys have been synthesized by the reaction of M(SiH3)3 (M = P, As) with Al atoms from a Knudsen cell. In the AlPSi3 system, bonding configurations and elemental distributions are characterized by scanning transmission electron microscopy (STEM)/EELS and correlated with bulk optical behavior. The incorporation of N was achieved by addition of N(SiH3)3 into the reaction mixture yielding [Al(As1-xNx)]ySi5-2yalloys. A critical point analysis of spectroscopic ellipsometry data reveals the existence of direct optical transitions at energies as low as 2.5 eV, well below the lowest direct absorption edge of Si at 3.3 eV. The compositional dependence of the lowest direct gap and indirect gap in Ge1-ySny alloys extracted from room temperature photoluminescence indicates a crossover concentration of yc =0.073, much lower than virtual crystal approximation but agrees well with large atomic supercells predictions. A series of Ge-rich Ge1-x-ySixSny samples with a fixed 3-4% Si content and progressively increasing Sn content in the 4-10% range are grown and characterized by electron microscopy and photoluminescence. The ternary represents an attractive alternative to Ge1-ySny for applications in IR optoelectronic technologies.
ContributorsJiang, Liying (Author) / Menéndez, Jose (Thesis advisor) / Kouvetakis, John (Thesis advisor) / Smith, David J. (Committee member) / Chizmeshya, Andrew V.G (Committee member) / Chamberlin, Ralph (Committee member) / Arizona State University (Publisher)
Created2014
Description
Group-IV semiconductor alloys are of interest for Si-integrated optoelectronic applications due to the band gap tunability and enhanced optical capabilities that can be achieved through compositional tuning. This work advances the field by presenting a systematic study of the optical and electronic properties of Ge1-ySny and analogous Ge1-x-ySixSny alloys.
The fundamental direct and indirect band gaps of Ge1-ySny materials are measured by room temperature photoluminescence in samples containing 0 ≤ y ≤ 0.11 and a transition to direct gap materials is found to occur at yc = 0.087. This result is enabled by the development of sample growth and processing protocols that produce high-quality materials epitaxially on Ge-buffered Si(100) substrates. Strategies to optimize the optical performance are explored by varying the film thickness, thermal and surface treatments, and n-type doping. The electrical and optical properties of diodes based on these materials are characterized by current-voltage, optical responsivity, and electroluminescence measurements. These show improved optical performance near yc with tunable emission out to 2500 nm. Measuring the carrier lifetimes in devices with strain relaxed and fully strained interfaces show significantly longer lifetimes in the fully strained case.
The direct and indirect band gaps of Sn-rich (y > x) Ge1-x-ySixSny materials are measured by room temperature photoluminescence on optimized samples. These data confirm a transition to direct gap materials occurs for the ternary alloy as well. Devices based on compositions 0.02 ≤ x ≤ 0.10 and 0.03 ≤ y ≤ 0.11 are characterized by current-voltage, optical responsivity, and electroluminescence measurements and show competitive performance with analogous devices based on Ge1-ySny materials. A detailed study of the direct gap in Ge1-xSix alloys gives parameters crucial en route to a global description of the Ge1-x-ySixSny fundamental band gaps.
Archetypal laser device designs on Si are explored by fabricating degenerate pn junction diodes and highly doped waveguide devices based on high-quality Ge1-ySny materials. The diodes showed tunnel-like current-voltage characteristics and tailored electroluminescence based on the doping profile. The waveguides demonstrate emission under optical stimulation.
The fundamental direct and indirect band gaps of Ge1-ySny materials are measured by room temperature photoluminescence in samples containing 0 ≤ y ≤ 0.11 and a transition to direct gap materials is found to occur at yc = 0.087. This result is enabled by the development of sample growth and processing protocols that produce high-quality materials epitaxially on Ge-buffered Si(100) substrates. Strategies to optimize the optical performance are explored by varying the film thickness, thermal and surface treatments, and n-type doping. The electrical and optical properties of diodes based on these materials are characterized by current-voltage, optical responsivity, and electroluminescence measurements. These show improved optical performance near yc with tunable emission out to 2500 nm. Measuring the carrier lifetimes in devices with strain relaxed and fully strained interfaces show significantly longer lifetimes in the fully strained case.
The direct and indirect band gaps of Sn-rich (y > x) Ge1-x-ySixSny materials are measured by room temperature photoluminescence on optimized samples. These data confirm a transition to direct gap materials occurs for the ternary alloy as well. Devices based on compositions 0.02 ≤ x ≤ 0.10 and 0.03 ≤ y ≤ 0.11 are characterized by current-voltage, optical responsivity, and electroluminescence measurements and show competitive performance with analogous devices based on Ge1-ySny materials. A detailed study of the direct gap in Ge1-xSix alloys gives parameters crucial en route to a global description of the Ge1-x-ySixSny fundamental band gaps.
Archetypal laser device designs on Si are explored by fabricating degenerate pn junction diodes and highly doped waveguide devices based on high-quality Ge1-ySny materials. The diodes showed tunnel-like current-voltage characteristics and tailored electroluminescence based on the doping profile. The waveguides demonstrate emission under optical stimulation.
ContributorsGallagher, James Dennis (Author) / Menéndez, Jose (Thesis advisor) / Kouvetakis, John (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2015
Description
Sn-based group IV materials such as Ge1-xSnx and Ge1-x-ySixSny alloys have great potential for developing Complementary Metal Oxide Semiconductor (CMOS) compatible devices on Si because of their tunable band structure and lattice constants by controlling Si and/or Sn contents. Growth of Ge1-xSnx binaries through Molecular Beam Epitaxy (MBE) started in the early 1980s, producing Ge1-xSnx epilayers with Sn concentrations varying from 0 to 100%. A Chemical Vapor Deposition (CVD) method was developed in the early 2000s for growing Ge1-xSnx alloys of device quality, by utilizing various chemical precursors. This method dominated the growth of Ge1-xSnx alloys rapidly because of the great crystal quality of Ge1-xSnx achieved. As the first practical ternary alloy completely based on group IV elements, Ge1-x-ySixSny decouples bandgap and lattice constant, becoming a prospective CMOS compatible alloy. At the same time, Ge1-x-ySixSny ternary system could serve as a thermally robust alternative to Ge1-ySny binaries given that it becomes a direct semiconductor at a Sn concentration of 6%-10%. Ge1-x-ySixSny growths by CVD is summarized in this thesis. With the Si/Sn ratio kept at ~3.7, the ternary alloy system is lattice matched to Ge, resulting a tunable direct bandgap of 0.8-1.2 eV. With Sn content higher than Si content, the ternary alloy system could have an indirect-to-direct transition, as observed for Ge1-xSnx binaries. This thesis summarizes the development of Ge1-xSnx and Ge1-x-ySixSny alloys through MBE and CVD in recent decades and introduces an innovative direct injection method for synthesizing Ge1-x-ySixSny ternary alloys with Sn contents varying from 5% to 12% and Si contents kept at 1%-2%. Grown directly on Si (100) substrates in a Gas-phase Molecular Epitaxy (GSME) reactor, both intrinsic and n-type doped Ge1-x-ySixSny with P with thicknesses of 250-760 nm have been achieved by deploying gas precursors Ge4H10, Si4H10, SnD4 and P(SiH3)3 at the unprecedented low growth temperatures of 190-220 °C. Compressive strain is reduced and crystallinity of the Ge1-x-ySixSny epilayer is improved after rapid thermal annealing (RTA) treatments. High Resolution X-ray Diffraction (HR-XRD), Rutherford Backscattering Spectrometry (RBS), cross-sectional Transmission Electron Microscope (XTEM) and Atomic Force Microscope (AFM) have been combined to characterize the structural properties of the Ge1-x-ySixSny samples, indicating good crystallinity and flat surfaces.
ContributorsHu, Ding (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Committee member) / Trovitch, Ryan (Committee member) / Arizona State University (Publisher)
Created2019
Description
This dissertation covers my doctoral research on the cathodoluminescence (CL) study of the optical properties of III-niride semiconductors.
The first part of this thesis focuses on the optical properties of Mg-doped gallium nitride (GaN:Mg) epitaxial films. GaN is an emerging material for power electronics, especially for high power and high frequency applications. Compared to traditional Si-based devices, GaN-based devices offer superior breakdown properties, faster switching speed, and reduced system size. Some of the current device designs involve lateral p-n junctions which require selective-area doping. Dopant distribution in the selectively-doped regions is a critical issue that can impact the device performance. While most studies on Mg doping in GaN have been reported for epitaxial grown on flat c-plane substrates, questions arise regarding the Mg doping efficiency and uniformity in selectively-doped regions, where growth on surfaces etched away from the exact c-plane orientation is involved. Characterization of doping concentration distribution in lateral structures using secondary ion mass spectroscopy lacks the required spatial resolution. In this work, visualization of acceptor distribution in GaN:Mg epilayers grown by metalorganic chemical vapor deposition (MOCVD) was achieved at sub-micron scale using CL imaging. This was enabled by establishing a correlation among the luminescence characteristics, acceptor concentration, and electrical conductivity of GaN:Mg epilayers. Non-uniformity in acceptor distribution has been observed in epilayers grown on mesa structures and on miscut substrates. It is shown that non-basal-plane surfaces, such as mesa sidewalls and surface step clusters, promotes lateral growth along the GaN basal planes with a reduced Mg doping efficiency. The influence of surface morphology on the Mg doping efficiency in GaN has been studied.
The second part of this thesis focuses on the optical properties of InGaN for photovoltaic applications. The effects of thermal annealing and low energy electron beam irradiation (LEEBI) on the optical properties of MOCVD-grown In0.14Ga0.86N films were studied. A multi-fold increase in luminescence intensity was observed after 800 °C thermal annealing or LEEBI treatment. The mechanism leading to the luminescence intensity increase has been discussed. This study shows procedures that significantly improve the luminescence efficiency of InGaN, which is important for InGaN-based optoelectronic devices.
The first part of this thesis focuses on the optical properties of Mg-doped gallium nitride (GaN:Mg) epitaxial films. GaN is an emerging material for power electronics, especially for high power and high frequency applications. Compared to traditional Si-based devices, GaN-based devices offer superior breakdown properties, faster switching speed, and reduced system size. Some of the current device designs involve lateral p-n junctions which require selective-area doping. Dopant distribution in the selectively-doped regions is a critical issue that can impact the device performance. While most studies on Mg doping in GaN have been reported for epitaxial grown on flat c-plane substrates, questions arise regarding the Mg doping efficiency and uniformity in selectively-doped regions, where growth on surfaces etched away from the exact c-plane orientation is involved. Characterization of doping concentration distribution in lateral structures using secondary ion mass spectroscopy lacks the required spatial resolution. In this work, visualization of acceptor distribution in GaN:Mg epilayers grown by metalorganic chemical vapor deposition (MOCVD) was achieved at sub-micron scale using CL imaging. This was enabled by establishing a correlation among the luminescence characteristics, acceptor concentration, and electrical conductivity of GaN:Mg epilayers. Non-uniformity in acceptor distribution has been observed in epilayers grown on mesa structures and on miscut substrates. It is shown that non-basal-plane surfaces, such as mesa sidewalls and surface step clusters, promotes lateral growth along the GaN basal planes with a reduced Mg doping efficiency. The influence of surface morphology on the Mg doping efficiency in GaN has been studied.
The second part of this thesis focuses on the optical properties of InGaN for photovoltaic applications. The effects of thermal annealing and low energy electron beam irradiation (LEEBI) on the optical properties of MOCVD-grown In0.14Ga0.86N films were studied. A multi-fold increase in luminescence intensity was observed after 800 °C thermal annealing or LEEBI treatment. The mechanism leading to the luminescence intensity increase has been discussed. This study shows procedures that significantly improve the luminescence efficiency of InGaN, which is important for InGaN-based optoelectronic devices.
ContributorsLiu, Hanxiao (Author) / Ponce, Fernando A. (Thesis advisor) / Zhao, Yuji (Committee member) / Newman, Nathan (Committee member) / Fischer, Alec M (Committee member) / Arizona State University (Publisher)
Created2020