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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 beam epitaxy (MBE) under virtually identical conditions on GaSb, InAs,

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.
ContributorsOuyang, Lu (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha (Committee member) / Ponce, Fernando (Committee member) / Chamberlin, Ralph (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2012
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Description
In this dissertation, various characterization techniques have been used to investigate many aspects of the properties of III-nitride materials and devices for optoelectronic applications.

The first part of this work is focused on the evolution of microstructures of BAlN thin films. The films were grown by flow-modulated epitaxy at 1010

In this dissertation, various characterization techniques have been used to investigate many aspects of the properties of III-nitride materials and devices for optoelectronic applications.

The first part of this work is focused on the evolution of microstructures of BAlN thin films. The films were grown by flow-modulated epitaxy at 1010 oC, with B/(B+Al) gas-flow ratios ranging from 0.06 to 0.18. The boron content obtained from X-ray diffraction (XRD) patterns ranges from x = 0.02 to 0.09, while Rutherford backscattering spectrometry (RBS) measures x = 0.06 to 0.16. Transmission electron microscopy indicates the sole presence of the wurtzite crystal structure in the BAlN films, and a tendency towards twin formation and finer microstructure for B/(B+Al) gas-flow ratios greater than 0.15. The RBS data suggest that the incorporation of B is highly efficient, while the XRD data indicate that the epitaxial growth may be limited by a solubility limit in the crystal phase at about 9%. Electron energy loss spectroscopy has been used to profile spatial variations in the composition of the films. It has also located point defects in the films with nanometer resolution. The defects are identified as B and Al interstitials and N vacancies by comparison of the observed energy thresholds with results of density functional theory calculations.

The second part of this work investigates dislocation clusters observed in thick InxGa1-xN films with 0.07 ≤ x ≤ 0.12. The clusters resemble baskets with a higher indium content at their interior. Threading dislocations at the basket boundaries are of the misfit edge type, and their separation is consistent with misfit strain relaxation due the difference in indium content between the baskets and the surrounding matrix. The base of the baskets exhibits no observable misfit dislocations connected to the threading dislocations, and often no net displacements like those due to stacking faults. It is argued that the origin of these threading dislocation arrays is associated with misfit dislocations at the basal plane that dissociate, forming stacking faults. When the stacking faults form simultaneously satisfying the crystal symmetry, the sum of their translation vectors does add up to zero, consistent with our experimental observations.
ContributorsWang, Shuo, Ph.D (Author) / Ponce, Fernando A. (Thesis advisor) / Menéndez, Jose (Committee member) / Rez, Peter (Committee member) / McCartney, Martha (Committee member) / Arizona State University (Publisher)
Created2018
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Description
The work described in this thesis explores the synthesis of new semiconductors in the Si-Ge-Sn system for application in Si-photonics. Direct gap Ge1-ySny (y=0.12-0.16) alloys with enhanced light emission and absorption are pursued. Monocrystalline layers are grown on Si platforms via epitaxy-driven reactions between Sn- and Ge-hydrides using compositionally graded

The work described in this thesis explores the synthesis of new semiconductors in the Si-Ge-Sn system for application in Si-photonics. Direct gap Ge1-ySny (y=0.12-0.16) alloys with enhanced light emission and absorption are pursued. Monocrystalline layers are grown on Si platforms via epitaxy-driven reactions between Sn- and Ge-hydrides using compositionally graded buffer layers that mitigate lattice mismatch between the epilayer and Si platforms. Prototype p-i-n structures are fabricated and are found to exhibit direct gap electroluminescence and tunable absorption edges between 2200 and 2700 nm indicating applications in LEDs and detectors. Additionally, a low pressure technique is described producing pseudomorphic Ge1-ySny alloys in the compositional range y=0.06-0.17. Synthesis of these materials is achieved at ultra-low temperatures resulting in nearly defect-free films that far exceed the critical thicknesses predicted by thermodynamic considerations, and provide a chemically driven route toward materials with properties typically associated with molecular beam epitaxy.

Silicon incorporation into Ge1-ySny yields a new class of Ge1-x-ySixSny (y>x) ternary alloys using reactions between Ge3H8, Si4H10, and SnD4. These materials contain small amounts of Si (x=0.05-0.08) and Sn contents of y=0.1-0.15. Photoluminescence studies indicate an intensity enhancement relative to materials with lower Sn contents (y=0.05-0.09). These materials may serve as thermally robust alternatives to Ge1-ySny for mid-infrared (IR) optoelectronic applications.

An extension of the above work is the discovery of a new class of Ge-like Group III-V-IV hybrids with compositions Ga(As1–xPx)Ge3 (x=0.01-0.90) and (GaP)yGe5–2y related to Ge1-x-ySixSny in structure and properties. These materials are prepared by chemical vapor deposition of reactive Ga-hydrides with P(GeH3)3 and As(GeH3)3 custom precursors as the sources of P, As, and Ge incorporating isolated GaAs and GaP donor-acceptor pairs into diamond-like Ge-based structures. Photoluminescence studies reveal bandgaps in the near-IR and large bowing of the optical behavior relative to linear interpolation of the III-V and Ge end members. Similar materials in the Al-Sb-B-P system are also prepared and characterized. The common theme of the above topics is the design and fabrication of new optoelectronic materials that can be fully compatible with Si-based technologies for expanding the optoelectronic capabilities of Ge into the mid-IR and beyond through compositional tuning of the diamond lattice.
ContributorsWallace, Patrick Michael (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Committee member) / Trovitch, Ryan (Committee member) / Arizona State University (Publisher)
Created2018
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Description
High-performance III-V semiconductors based on ternary alloys and superlattice systems are fabricated, studied, and compared for infrared optoelectronic applications. InAsBi is a ternary alloy near the GaSb lattice constant that is not as thoroughly investigated as other III-V alloys and that is challenging to produce as Bi has a

High-performance III-V semiconductors based on ternary alloys and superlattice systems are fabricated, studied, and compared for infrared optoelectronic applications. InAsBi is a ternary alloy near the GaSb lattice constant that is not as thoroughly investigated as other III-V alloys and that is challenging to produce as Bi has a tendency to surface segregate and form droplets during growth rather than incorporate. A growth window is identified within which high-quality droplet-free bulk InAsBi is produced and Bi mole fractions up to 6.4% are obtained. Photoluminescence with high internal quantum efficiency is observed from InAs/InAsBi quantum wells. The high structural and optical quality of the InAsBi materials examined demonstrates that bulk, quantum well, and superlattice structures utilizing InAsBi are an important design option for efficient infrared coverage.

Another important infrared material system is InAsSb and the strain-balanced InAs/InAsSb superlattice on GaSb. Detailed examination of X-ray diffraction, photoluminescence, and spectroscopic ellipsometry data provides the temperature and composition dependent bandgap of bulk InAsSb. The unintentional incorporation of approximately 1% Sb into the InAs layers of the superlattice is measured and found to significantly impact the analysis of the InAs/InAsSb band alignment. In the analysis of the absorption spectra, the ground state absorption coefficient and transition strength of the superlattice are proportional to the square of the electron-hole wavefunction overlap; wavefunction overlap is therefore a major design parameter in terms of optimizing absorption in these materials. Furthermore in addition to improvements through design optimization, the optical quality of the materials studied is found to be positively enhanced with the use of Bi as a surfactant during molecular beam epitaxy growth.

A software tool is developed that calculates and optimizes the miniband structure of semiconductor superlattices, including bismide-based designs. The software has the capability to limit results to designs that can be produced with high structural and optical quality, and optimized designs in terms of maximizing absorption are identified for several infrared superlattice systems at the GaSb lattice constant. The accuracy of the software predictions are tested with the design and growth of an optimized mid-wave infrared InAs/InAsSb superlattice which exhibits superior optical and absorption properties.
ContributorsWebster, Preston Thomas (Author) / Johnson, Shane R (Thesis advisor) / Zhang, Yong-Hang (Committee member) / Menéndez, Jose (Committee member) / Vasileska, Dragica (Committee member) / Arizona State University (Publisher)
Created2016
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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 on pseudo-binary (III-V)-IV alloys, described with the general formula (III-V)1-x(IV2)x,

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.
ContributorsSims, Patrick Edward (Author) / Kouvetakis, John (Thesis advisor) / Chizmeshya, Andrew V. G. (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2017
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Description
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

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.
ContributorsWu, Songnan (Author) / Zhang, Yong-Hang (Thesis advisor) / Menéndez, Jose (Committee member) / Ponce, Fernando (Committee member) / Belitsky, Andrei (Committee member) / Schroder, Dieter (Committee member) / Arizona State University (Publisher)
Created2010
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Description
A highly uniform and repeatable method for synthesizing the single-layer transition metal dichalcogenides (TMDs) molybdenum disulfide, MoS2, and tungsten disulfide, WS2, was developed. This method employed chemical vapor deposition (CVD) of precursors in a custom built cold-wall reaction chamber designed to allow independent control over the growth parameters. Iterations of

A highly uniform and repeatable method for synthesizing the single-layer transition metal dichalcogenides (TMDs) molybdenum disulfide, MoS2, and tungsten disulfide, WS2, was developed. This method employed chemical vapor deposition (CVD) of precursors in a custom built cold-wall reaction chamber designed to allow independent control over the growth parameters. Iterations of this reaction chamber were employed to overcome limitations to the growth method. First, molybdenum trioxide, MoO3, and S were co-evaporated from alumina coated W baskets to grow MoS2 on SiO2/Si substrates. Using this method, films were found to have repeatable coverage, but unrepeatable morphology. Second, the reaction chamber was modified to include a pair of custom bubbler delivery systems to transport diethyl sulfide (DES) and molybdenum hexacarbonyl (MHC) to the substrate as a S and Mo precursors. Third, tungsten hexacarbonyl (WHC) replaced MHC as a transition metal precursor for the synthesis of WS2 on Al2O3, substrates. This method proved repeatable in both coverage and morphology allowing the investigation of the effect of varying the flow of Ar, varying the substrate temperature and varying the flux of DES to the sample. Increasing each of these parameters was found to decrease the nucleation density on the sample and, with the exception of the Ar flow, induce multi-layer feature growth. This combination of precursors was also used to investigate the reported improvement in feature morphology when NaCl is placed upstream of the substrate. This was found to have no effect on experiments in the configurations used. A final effort was made to adequately increase the feature size by switching from DES to hydrogen sulfide, H2S, as a source of S. Using H2S and WHC to grow WS2 films on Al2O3, it was found that increasing the substrate temperature and increasing the H2S flow both decrease nucleation density. Increasing the H2S flow induced bi-layer growth. Ripening of synthesized WS2 crystals was demonstrated to occur when the sample was annealed, post-growth, in an Ar, H2, and H2S flow. Finally, it was verified that the final H2S and WHC growth method yielded repeatability and uniformity matching, or improving upon, the other methods and precursors investigated.
ContributorsLunceford, Chad (Author) / Drucker, Jeff (Thesis advisor) / Menéndez, Jose (Committee member) / Smith, David J. (Committee member) / Rez, Peter (Committee member) / Arizona State University (Publisher)
Created2019