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- All Subjects: Materials Science
- Creators: Smith, David J.
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 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
Description
III-V-bismide semiconductor alloys are a class of materials with applications in the mid and long wave infrared spectrum. The quaternary alloy InAsSbBi is attractive because it can be grown lattice-matched to commercially available GaSb substrates, and the adjustment of the Bi and Sb mole fractions enables both lattice constant and bandgap to be tuned independently. This dissertation provides a comprehensive study of the surface morphology and the structural and chemical properties of InAsSbBi alloys grown by molecular beam epitaxy.
210 nm thick InAsSbBi layers grown at temperatures from 280 °C to 430 °C on (100) on-axis, (100) offcut 1° to (011), and (100) offcut 4° to (111)A GaSb substrates are investigated using Rutherford back scattering, X-ray diffraction, transmission electron microscopy, Nomarski optical microscopy, atomic force microscopy, and photoluminescence spectroscopy. The results indicate that the layers are coherently strained and contain dilute Bi mole fractions.
Large surface droplets with diameters and densities on the order of 3 µm and 106 cm-2 are observed when the growth is performed with As overpressures around 1%. Preferential orientation of the droplets occurs along the [011 ̅] step edges offcut (100) 1° to (011) substrate. The surface droplets are not observed when the As overpressure is increased to 4%. Small crystalline droplets with diameters and densities on the order of 70 nm and 1010 cm-2 are observed between the large droplets for the growth at 430°C. Analysis of one of the small droplets indicates a misoriented zinc blende structure composed of In, Sb, and Bi, with a 6.543 ± 0.038 Å lattice constant.
Lateral variation in the Bi mole fraction is observed in InAsSbBi grown at high temperature (400 °C, 420 °C) on (100) on-axis and (100) offcut 4° to (111)A substrates, but is not observed for growth at 280 °C or on (100) substrates that are offcut 1° to (011). Improved crystal and optical quality is observed in the high temperature grown InAsSbBi and CuPtB type atomic ordering on the {111}B planes is observed in the low temperature grown InAsSbBi. Strain induced tilt is observed in coherently strained InAsSbBi grown on offcut substrates.
210 nm thick InAsSbBi layers grown at temperatures from 280 °C to 430 °C on (100) on-axis, (100) offcut 1° to (011), and (100) offcut 4° to (111)A GaSb substrates are investigated using Rutherford back scattering, X-ray diffraction, transmission electron microscopy, Nomarski optical microscopy, atomic force microscopy, and photoluminescence spectroscopy. The results indicate that the layers are coherently strained and contain dilute Bi mole fractions.
Large surface droplets with diameters and densities on the order of 3 µm and 106 cm-2 are observed when the growth is performed with As overpressures around 1%. Preferential orientation of the droplets occurs along the [011 ̅] step edges offcut (100) 1° to (011) substrate. The surface droplets are not observed when the As overpressure is increased to 4%. Small crystalline droplets with diameters and densities on the order of 70 nm and 1010 cm-2 are observed between the large droplets for the growth at 430°C. Analysis of one of the small droplets indicates a misoriented zinc blende structure composed of In, Sb, and Bi, with a 6.543 ± 0.038 Å lattice constant.
Lateral variation in the Bi mole fraction is observed in InAsSbBi grown at high temperature (400 °C, 420 °C) on (100) on-axis and (100) offcut 4° to (111)A substrates, but is not observed for growth at 280 °C or on (100) substrates that are offcut 1° to (011). Improved crystal and optical quality is observed in the high temperature grown InAsSbBi and CuPtB type atomic ordering on the {111}B planes is observed in the low temperature grown InAsSbBi. Strain induced tilt is observed in coherently strained InAsSbBi grown on offcut substrates.
ContributorsKosireddy, Rajeev Reddy (Author) / Johnson, Shane R (Thesis advisor) / Smith, David J. (Committee member) / Alford, Terry L. (Committee member) / Soignard, Emmanuel (Committee member) / Arizona State University (Publisher)
Created2020
Description
Extended crystal defects often play a critical role in determining semiconductor device performance. This dissertation describes the application of transmission electron microscopy (TEM) and aberration-corrected scanning TEM (AC-STEM) to study defect clusters and the atomic-scale structure of defects in compound semiconductors.
An extensive effort was made to identify specific locations of crystal defects in epitaxial CdTe that might contribute to degraded light-conversion efficiency. Electroluminescence (EL) mapping and the creation of surface etch pits through chemical treatment were combined in attempts to identify specific structural defects for subsequent TEM examination. Observations of these specimens revealed only surface etch pits, without any visible indication of extended defects near their base. While chemical etch pits could be helpful for precisely locating extended defects that intersect with the treated surface, this study concluded that surface roughness surrounding etch pits would likely mitigate against their usefulness.
Defect locations in GaAs solar-cell devices were identified using combinations of EL, photoluminescence, and Raman scattering, and then studied more closely using TEM. Observations showed that device degradation was invariably associated with a cluster of extended defects, rather than a single defect, as previously assumed. AC-STEM observations revealed that individual defects within each cluster consisted primarily of intrinsic stacking faults terminated by 30° and 90° partial dislocations, although other defect structures were also identified. Lomer dislocations were identified near locations where two lines of strain contrast intersected in a large cluster, and a comparatively shallow cluster, largely constrained to the GaAs emitter layer, contained 60° perfect dislocations associated with localized strain contrast.
In another study, misfit dislocations at II-VI/III-V heterovalent interfaces were investigated and characterized using AC-STEM. Misfit strain at ZnTe/GaAs interfaces, which have relatively high lattice mismatch (7.38%), was relieved primarily through Lomer dislocations, while ZnTe/InP interfaces, with only 3.85% lattice mismatch, were relaxed by a mixture of 60° perfect dislocations, 30° partial dislocations, and Lomer dislocations. These results were consistent with the previous findings that misfit strain was relaxed primarily through 60° perfect dislocations that had either dissociated into partial dislocations or interacted to form Lomer dislocations as the amount of misfit strain increased.
An extensive effort was made to identify specific locations of crystal defects in epitaxial CdTe that might contribute to degraded light-conversion efficiency. Electroluminescence (EL) mapping and the creation of surface etch pits through chemical treatment were combined in attempts to identify specific structural defects for subsequent TEM examination. Observations of these specimens revealed only surface etch pits, without any visible indication of extended defects near their base. While chemical etch pits could be helpful for precisely locating extended defects that intersect with the treated surface, this study concluded that surface roughness surrounding etch pits would likely mitigate against their usefulness.
Defect locations in GaAs solar-cell devices were identified using combinations of EL, photoluminescence, and Raman scattering, and then studied more closely using TEM. Observations showed that device degradation was invariably associated with a cluster of extended defects, rather than a single defect, as previously assumed. AC-STEM observations revealed that individual defects within each cluster consisted primarily of intrinsic stacking faults terminated by 30° and 90° partial dislocations, although other defect structures were also identified. Lomer dislocations were identified near locations where two lines of strain contrast intersected in a large cluster, and a comparatively shallow cluster, largely constrained to the GaAs emitter layer, contained 60° perfect dislocations associated with localized strain contrast.
In another study, misfit dislocations at II-VI/III-V heterovalent interfaces were investigated and characterized using AC-STEM. Misfit strain at ZnTe/GaAs interfaces, which have relatively high lattice mismatch (7.38%), was relieved primarily through Lomer dislocations, while ZnTe/InP interfaces, with only 3.85% lattice mismatch, were relaxed by a mixture of 60° perfect dislocations, 30° partial dislocations, and Lomer dislocations. These results were consistent with the previous findings that misfit strain was relaxed primarily through 60° perfect dislocations that had either dissociated into partial dislocations or interacted to form Lomer dislocations as the amount of misfit strain increased.
ContributorsMcKeon, Brandon (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Thesis advisor) / Liu, Jingyue (Committee member) / Zhang, Yong-Hang (Committee member) / Arizona State University (Publisher)
Created2020
Description
A new nanoparticle deposition technique, Aerosol Impaction-Driven Assembly (AIDA), was extensively characterized for material structures and properties. Aerogel films can be deposited directly onto a substrate with AIDA without the long aging and drying steps in the sol-gel method. Electron microscopy, pore size analysis, thermal conductivity, and optical measurements show the nanoparticle (NP) films to be similar to typical silica aerogel. Haze of nanoparticle films modeled as scattering sites correlates strongly with pore size distribution. Supporting evidence was obtained from particle sizes and aggregates using electron microscopy and small-angle X-ray scattering. NP films showed interlayers of higher porosity and large aggregates formed by tensile film stress.
To better understand film stress and NP adhesion, chemical bonding analyses were performed for samples annealed up to 900 °C. Analysis revealed that about 50% of the NP surfaces are functionalized by hydroxyl (-OH) groups, providing for hydrogen bonding. Ellipsometric porosimetry was used to further understand the mechanical properties by providing a measure of strain upon capillary pressure from filling pores. Upon annealing to 200 °C, the films lost water resulting in closer bonding of NPs and higher Young’s modulus. Upon further annealing up to 900 °C, the films lost hydroxyl bonds while gaining siloxane bonds, reducing Young’s modulus. The application of ellipsometric porosimetry to hydrophilic coatings brings into question the validity of pore size distribution calculations for materials that hold onto water molecules and result in generally smaller calculated pore sizes.
Doped hydrogenated microcrystalline silicon was grown on crystalline silicon NPs, as a test case of an application for NP films to reduce parasitic absorption in silicon heterojunction solar cells. Parasitic absorption of blue light could be reduced because microcrystalline silicon has a mix of direct and indirect bandgap, giving lower blue absorption than amorphous silicon. Using Ultraviolet Raman spectroscopy, the crystallinity of films as thin as 13 nm was determined rapidly (in 1 minute) and non-destructively. A mono-layer of nanocrystals was applied as seeds for p-doped microcrystalline silicon growth and resulted in higher crystallinity films. Applications of the method could be explored for other nanocrystalline materials.
To better understand film stress and NP adhesion, chemical bonding analyses were performed for samples annealed up to 900 °C. Analysis revealed that about 50% of the NP surfaces are functionalized by hydroxyl (-OH) groups, providing for hydrogen bonding. Ellipsometric porosimetry was used to further understand the mechanical properties by providing a measure of strain upon capillary pressure from filling pores. Upon annealing to 200 °C, the films lost water resulting in closer bonding of NPs and higher Young’s modulus. Upon further annealing up to 900 °C, the films lost hydroxyl bonds while gaining siloxane bonds, reducing Young’s modulus. The application of ellipsometric porosimetry to hydrophilic coatings brings into question the validity of pore size distribution calculations for materials that hold onto water molecules and result in generally smaller calculated pore sizes.
Doped hydrogenated microcrystalline silicon was grown on crystalline silicon NPs, as a test case of an application for NP films to reduce parasitic absorption in silicon heterojunction solar cells. Parasitic absorption of blue light could be reduced because microcrystalline silicon has a mix of direct and indirect bandgap, giving lower blue absorption than amorphous silicon. Using Ultraviolet Raman spectroscopy, the crystallinity of films as thin as 13 nm was determined rapidly (in 1 minute) and non-destructively. A mono-layer of nanocrystals was applied as seeds for p-doped microcrystalline silicon growth and resulted in higher crystallinity films. Applications of the method could be explored for other nanocrystalline materials.
ContributorsCarpenter, Joe Victor (Author) / Holman, Zachary C (Thesis advisor) / Bertoni, Mariana I (Committee member) / Chan, Candace K. (Committee member) / Smith, David J. (Committee member) / Arizona State University (Publisher)
Created2020
Description
Wide bandgap semiconductors are of much current interest due to their superior electrical properties. This dissertation describes electron microscopy characterization of GaN-on-GaN structures for high-power vertical device applications. Unintentionally-doped (UID) GaN layers grown homoepitaxially via metal-organic chemical vapor deposition on freestanding GaN substrates, were subjected to dry etching, and layers of UID-GaN/p-GaN were over-grown. The as-grown and regrown heterostructures were examined in cross-section using transmission electron microscopy (TEM). Two different etching treatments, fast-etch-only and multiple etches with decreasing power, were employed. The fast-etch-only devices showed GaN-on-GaN interface at etched location, and low device breakdown voltages were measured (~ 45-95V). In comparison, no interfaces were visible after multiple etching steps, and the corresponding breakdown voltages were much higher (~1200-1270V). These results emphasized importance of optimizing surface etching techniques for avoiding degraded device performance.
The morphology of GaN-on-GaN devices after reverse-bias electrical stressing to breakdown was investigated. All failed devices had irreversible structural damage, showing large surface craters (~15-35 microns deep) with lengthy surface cracks. Cross-sectional TEM of failed devices showed high densities of threading dislocations (TDs) around the cracks and near crater surfaces. Progressive ion-milling across damaged devices revealed high densities of TDs and the presence of voids beneath cracks: these features were not observed in unstressed devices. The morphology of GaN substrates grown by hydride vapor-phase epitaxy (HVPE) and by ammonothermal methods were correlated with reverse-bias results. HVPE substrates showed arrays of surface features when observed by X-ray topography (XRT). All fabricated devices that overlapped with these features had typical reverse-bias voltages less than 100V at a leakage current limit of 10-6 A. In contrast, devices not overlapping with such features reached voltages greater than 300V. After etching, HVPE substrate surfaces showed defect clusters and macro-pits, whereas XRT images of ammonothermal substrate revealed no visible features. However, some devices fabricated on ammonothermal substrate failed at low voltages. Devices on HVPE and ammonothermal substrates with low breakdown voltages showed crater-like surface damage and revealed TDs (~25µm deep) and voids; such features were not observed in devices reaching higher voltages. These results should assist in developing protocols to fabricate reliable high-voltage devices.
ContributorsPeri, Prudhvi Ram (Author) / Smith, David J. (Thesis advisor) / Alford, Terry (Committee member) / Mccartney, Martha R (Committee member) / Nemanich, Robert (Committee member) / Zhao, Yuji (Committee member) / Arizona State University (Publisher)
Created2021
Description
The evolution of defects at different stages of strain relaxation in low-mismatched GaAs/GaAs1-xSbx/GaAs(001) (x ~ 0.08) heterostructures, and the underlying relaxation mechanisms, have been comprehensively studied primarily using transmission electron microscopy (TEM). Aberration-corrected scanning transmission electron microscopy (STEM) has been used for atomic-scale study of interfacial defects in low-mismatched GaAs(001)-based and high-mismatched GaSb/GaAs(001) heterostructures.Three distinct stages of strain relaxation were identified in GaAs/GaAs1-xSbx/GaAs(001) (x ~ 0.08) heterostructures with GaAsSb film thicknesses in the range of 50 to 4000 nm capped with 50-nm-thick GaAs layers. Diffraction contrast analysis with conventional TEM revealed that although 60° dislocations were primarily formed during the initial sluggish Stage-I relaxation, 90° dislocations were also created. Many curved dislocations, the majority of which extended into the substrate, were formed during Stage-II and Stage-III relaxation. The capping layers of heterostructures with larger film thickness (500 nm onwards) exhibited only Stage-I relaxation. A decrease in dislocation density was observed at the cap/film interface of the heterostructure with 4000-nm-thick film compared to that with 2000-nm-thick film, which correlated with smoothening of surface cross-hatch morphology. Detailed consideration of plausible dislocation sources for the capping layer led to the conclusion that dislocation half-loops nucleated at surface troughs were the main source of threading dislocations in these heterostructures.
Aberration-corrected STEM imaging revealed that interfacial 60° dislocations in GaAs/GaAsSb/GaAs(001) and GaAs/GaAsP/GaAs(001) heterostructures were dissociated to form intrinsic stacking faults bounded by 90° and 30° Shockley partial dislocations. The cores of the 30° partials contained single atomic columns indicating that these dislocations primarily belonged to glide set. Apart from isolated dissociated 60° dislocations, Lomer-Cottrell locks, Lomer dislocations and a novel type of dissociated 90° dislocation were observed in GaAs/GaAsSb/GaAs heterostructures.
The core structure of interfacial defects in GaSb/GaAs(001) heterostructure was also investigated using aberration-corrected STEM. 90° Lomer dislocations were primarily formed; however, glide-set perfect 60° and dissociated 60° dislocations were also observed. The 5-7 atomic-ring shuffle-set dislocation, the left-displaced 6-8 atomic-ring glide-set and the right-displaced 6-8 atomic-ring glide-set dislocations were three types of Lomer dislocations that were identified, among which the shuffle-set type was most common.
ContributorsGangopadhyay, Abhinandan (Author) / Smith, David J. (Thesis advisor) / Bertoni, Mariana (Committee member) / Crozier, Peter A. (Committee member) / King, Richard R. (Committee member) / McCartney, Martha R. (Committee member) / Arizona State University (Publisher)
Created2021