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Description
As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an

As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.
ContributorsCavendish, Rio (Author) / Crozier, Peter (Thesis advisor) / Adams, James (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2012
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Description
In this dissertation, the surface interactions of fluorine were studied during atomic layer deposition (ALD) and atomic layer etching (ALE) of wide band gap materials. To enable this research two high vacuum reactors were designed and constructed for thermal and plasma enhanced ALD and ALE, and they were equipped for

In this dissertation, the surface interactions of fluorine were studied during atomic layer deposition (ALD) and atomic layer etching (ALE) of wide band gap materials. To enable this research two high vacuum reactors were designed and constructed for thermal and plasma enhanced ALD and ALE, and they were equipped for in-situ process monitoring. Fluorine surface interactions were first studied in a comparison of thermal and plasma enhanced ALD (TALD and PEALD) of AlF3 thin films prepared using hydrogen fluoride (HF), trimethylaluminum (TMA), and H2-plasma. The ALD AlF3 films were compared ¬in-situ using ellipsometry and X-ray photoelectron spectroscopy (XPS). Ellipsometry showed a growth rate of 1.1 Å/ cycle and 0.7 Å/ cycle, at 100°C, for the TALD and PEALD AlF3 processes, respectively. XPS indicated the presence of Al-rich clusters within the PEALD film. The formation of the Al-rich clusters is thought to originate during the H2-plasma step of the PEALD process. The Al-rich clusters were not detected in the TALD AlF3 films. This study provided valuable insight on the role of fluorine in an ALD process. Reactive ion etching is a common dry chemical etch process for fabricating GaN devices. However, the use of ions can induce various defects, which can degrade device performance. The development of low-damage post etch processes are essential for mitigating plasma induced damage. As such, two multistep ALE methods were implemented for GaN based on oxidation, fluorination, and ligand exchange. First, GaN surfaces were oxidized using either water vapor or O2-plasma exposures to produce a thin oxide layer. The oxide layer was addressed using alternating exposures of HF and TMG, which etch Ga2O3 films. Each ALE process was characterized using in-situ using ellipsometry and XPS and ex-situ transmission electron microscopy (TEM). XPS indicated F and O impurities remained on the etched surfaces. Ellipsometry and TEM showed a slight reduction in thickness. The very low ALE rate was interpreted as the inability of the Ga2O3 ALE process to fluorinate the ordered surface oxide on GaN (0001). Overall, these results indicate HF is effective for the ALD of metal fluorides and the ALE of metal oxides.
ContributorsMessina, Daniel C (Author) / Nemanich, Robert J (Thesis advisor) / Goodnick, Stephen (Committee member) / Ponce, Fernando A (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Layer structured two dimensional (2D) semiconductors have gained much interest due to their intriguing optical and electronic properties induced by the unique van der Waals bonding between layers. The extraordinary success for graphene and transition metal dichalcogenides (TMDCs) has triggered a constant search for novel 2D semiconductors beyond them. Gallium

Layer structured two dimensional (2D) semiconductors have gained much interest due to their intriguing optical and electronic properties induced by the unique van der Waals bonding between layers. The extraordinary success for graphene and transition metal dichalcogenides (TMDCs) has triggered a constant search for novel 2D semiconductors beyond them. Gallium chalcogenides, belonging to the group III-VI compounds, are a new class of 2D semiconductors that carry a variety of interesting properties including wide spectrum coverage of their bandgaps and thus are promising candidates for next generation electronic and optoelectronic devices. Pushing these materials toward applications requires more controllable synthesis methods and facile routes for engineering their properties on demand.

In this dissertation, vapor phase transport is used to synthesize layer structured gallium chalcogenide nanomaterials with highly controlled structure, morphology and properties, with particular emphasis on GaSe, GaTe and GaSeTe alloys. Multiple routes are used to manipulate the physical properties of these materials including strain engineering, defect engineering and phase engineering. First, 2D GaSe with controlled morphologies is synthesized on Si(111) substrates and the bandgap is significantly reduced from 2 eV to 1.7 eV due to lateral tensile strain. By applying vertical compressive strain using a diamond anvil cell, the band gap can be further reduced to 1.4 eV. Next, pseudo-1D GaTe nanomaterials with a monoclinic structure are synthesized on various substrates. The product exhibits highly anisotropic atomic structure and properties characterized by high-resolution transmission electron microscopy and angle resolved Raman and photoluminescence (PL) spectroscopy. Multiple sharp PL emissions below the bandgap are found due to defects localized at the edges and grain boundaries. Finally, layer structured GaSe1-xTex alloys across the full composition range are synthesized on GaAs(111) substrates. Results show that GaAs(111) substrate plays an essential role in stabilizing the metastable single-phase alloys within the miscibility gaps. A hexagonal to monoclinic phase crossover is observed as the Te content increases. The phase crossover features coexistence of both phases and isotropic to anisotropic structural transition.

Overall, this work provides insights into the controlled synthesis of gallium chalcogenides and opens up new opportunities towards optoelectronic applications that require tunable material properties.
ContributorsCai, Hui, Ph.D (Author) / Tongay, Sefaattin (Thesis advisor) / Dwyer, Christian (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2018
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Description
This dissertation describes fundamental studies of hollow carbon nanostructures, which may be used as electrodes for practical energy storage applications such as batteries or supercapacitors. Electron microscopy is heavily utilized for the nanoscale characterization. To control the morphology of hollow carbon nanostructures, ZnO nanowires serve as sacrificial templates. The first

This dissertation describes fundamental studies of hollow carbon nanostructures, which may be used as electrodes for practical energy storage applications such as batteries or supercapacitors. Electron microscopy is heavily utilized for the nanoscale characterization. To control the morphology of hollow carbon nanostructures, ZnO nanowires serve as sacrificial templates. The first part of this dissertation focuses on the optimization of synthesis parameters and the scale-up production of ZnO nanowires by vapor transport method. Uniform ZnO nanowires with 40 nm width can be produced by using 1100 °C reaction temperature and 20 sccm oxygen flow rate, which are the two most important parameters.

The use of ethanol as carbon source with or without water steam provides uniform carbonaceous deposition on ZnO nanowire templates. The amount of as-deposited carbonaceous material can be controlled by reaction temperature and reaction time. Due to the catalytic property of ZnO surface, the thicknesses of carbonaceous layers are typically in nanometers. Different methods to remove the ZnO templates are explored, of which hydrogen reduction at temperatures higher than 700 °C is most efficient. The ZnO templates can also be removed under ethanol environment, but the temperatures need to be higher than 850 °C for practical use.

Characterizations of hollow carbon nanofibers show that the hollow carbon nanostructures have a high specific surface area (>1100 m2/g) with the presence of mesopores (~3.5 nm). The initial data on energy storage as electrodes of electrochemical double layer capacitors show that high specific capacitance (> 220 F/g) can be obtained, which is related to the high surface area and unique porous hollow structure with a thin wall.
ContributorsSong, Yian (Author) / Liu, Jingyue (Committee member) / Smith, David (Committee member) / McCartney, Martha (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2016
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Description
This dissertation presents research findings regarding the exploitation of localized surface plasmon (LSP) of epitaxial Ag islands as a means to enhance the photoluminescence (PL) of Germanium (Ge) quantum dots (QDs). The first step of this project was to investigate the growth of Ag islands on Si(100). Two distinct families

This dissertation presents research findings regarding the exploitation of localized surface plasmon (LSP) of epitaxial Ag islands as a means to enhance the photoluminescence (PL) of Germanium (Ge) quantum dots (QDs). The first step of this project was to investigate the growth of Ag islands on Si(100). Two distinct families of Ag islands have been observed. “Big islands” are clearly faceted and have basal dimensions in the few hundred nm to μm range with a variety of basal shapes. “Small islands” are not clearly faceted and have basal diameters in the 10s of nm range. Big islands form via a nucleation and growth mechanism, and small islands form via precipitation of Ag contained in a planar layer between the big islands that is thicker than the Stranski-Krastanov layer existing at room-temperature.

The pseudodielectric functions of epitaxial Ag islands on Si(100) substrates were investigated with spectroscopic ellipsometry. Comparing the experimental pseudodielectric functions obtained for Si with and without Ag islands clearly identifies a plasmon mode with its dipole moment perpendicular to the surface. This observation is confirmed using a simulation based on the thin island film (TIF) theory. Another mode parallel to the surface may be identified by comparing the experimental pseudodielectric functions with the simulated ones from TIF theory. Additional results suggest that the LSP energy of Ag islands can be tuned from the ultra-violet to the infrared range by an amorphous Si (α-Si) cap layer.

Heterostructures were grown that incorporated Ge QDs, an epitaxial Si cap layer and Ag islands grown atop the Si cap layer. Optimum growth conditions for distinct Ge dot ensembles and Si cap layers were obtained. The density of Ag islands grown on the Si cap layer depends on its thickness. Factors contributing to this effect may include the average strain and Ge concentration on the surface of the Si cap layer.

The effects of the Ag LSP on the PL of Ge coherent domes were investigated for both α-Si capped and bare Ag islands. For samples with low-doped substrates, the LSPs reduce the Ge dot-related PL when the Si cap layer is below some critical thickness and have no effect on the PL when the Si cap layer is above the critical thickness. For samples grown on highly-doped wafers, the LSP of bare Ag islands enhanced the PL of Ge QDs by ~ 40%.
ContributorsKong, Dexin (Author) / Drucker, Jeffery (Thesis advisor) / Chen, Tingyong (Committee member) / Ros, Robert (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Carbon nanomaterials have caught tremendous attention in the last few decades due to their unique physical and chemical properties. Tremendous effort has been made to develop new synthesis techniques for carbon nanomaterials and investigate their properties for different applications. In this work, carbon nanospheres (CNSs), carbon foams (CF), and single-walled

Carbon nanomaterials have caught tremendous attention in the last few decades due to their unique physical and chemical properties. Tremendous effort has been made to develop new synthesis techniques for carbon nanomaterials and investigate their properties for different applications. In this work, carbon nanospheres (CNSs), carbon foams (CF), and single-walled carbon nanotubes (SWNTs) were studied for various applications, including water treatment, energy storage, actuators, and sensors.

A facile spray pyrolysis synthesis technique was developed to synthesize individual CNSs with specific surface area (SSA) up to 1106 m2/g. The hollow CNSs showed adsorption of up to 300 mg rhodamine B dye per gram carbon, which is more than 15 times higher than that observed for conventional carbon black. They were also evaluated as adsorbents for removal of arsenate and selenate from water and displayed good binding to both species, outperforming commercial activated carbons for arsenate removal in pH > 8. When evaluated as supercapacitor electrode materials, specific capacitances of up to 112 F/g at a current density of 0.1 A/g were observed. When used as Li-ion battery anode materials, the CNSs achieved a discharge capacity of 270 mAh/g at a current density of 372 mA/g (1C), which is 4-fold higher than that of commercial graphite anode.

Carbon foams were synthesized using direct pyrolysis and had SSA up to 2340 m2/g. When used as supercapacitor electrode materials, a specific capacitance up to 280 F/g was achieved at current density of 0.1 A/g and remained as high as 207 F/g, even at a high current density of 10 A/g.

A printed walking robot was made from common plastic films and coatings of SWNTs. The solid-state thermal bimorph actuators were multifunctional energy transducers powered by heat, light, or electricity. The actuators were also investigated for photo/thermal detection. Electrochemical actuators based on MnO2 were also studied for potential underwater applications.

SWNTs were also used to fabricate printable electrodes for trace Cr(VI) detection, which displayed sensitivity up to 500 nA/ppb for Cr(VI). The limit of detection was shown to be as low as 5 ppb. A flow detection system based on CNT/printed electrodes was also demonstrated.
ContributorsWang, Chengwei, Ph.D (Author) / Chan, Candace K. (Thesis advisor) / Tongay, Sefaattin (Committee member) / Wang, Qing Hua (Committee member) / Seo, Dong (Committee member) / Arizona State University (Publisher)
Created2015
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Description
This thesis presents systematic studies on angle dependent Raman and Photoluminescence (PL) of a new class of layered materials, Transition Metal Trichalcogenides (TMTCs), which are made up of layers possessing anisotropic structure within the van-der-Waals plane. The crystal structure of individual layer of MX3 compounds consists of aligned nanowire like

This thesis presents systematic studies on angle dependent Raman and Photoluminescence (PL) of a new class of layered materials, Transition Metal Trichalcogenides (TMTCs), which are made up of layers possessing anisotropic structure within the van-der-Waals plane. The crystal structure of individual layer of MX3 compounds consists of aligned nanowire like 1D chains running along the b-axis direction. The work focuses on the growth of two members of this family - ZrS3 and TiS3 - through Chemical Vapor Transport Method (CVT), with consequent angle dependent Raman and PL studies which highlight their in-plane optically anisotropic properties. Results highlight that the optical properties of few-layer flakes are highly anisotropic as evidenced by large PL intensity variation with polarization direction (in ZrS3) and an intense variation in Raman intensity with variation in polarization direction (in both ZrS3 and TiS3).

Results suggest that light is efficiently absorbed when E-field of the polarized incident excitation laser is polarized along the chain (b-axis). It is greatly attenuated and absorption is reduced when field is polarized perpendicular to the length of 1D-like chains, as wavelength of the exciting light is much longer than the width of each 1D chain. Observed PL variation with respect to the azimuthal flake angle is similar to what has been previously observed in 1D materials like nanowires. However, in TMTCs, since the 1D chains interact with each other, it gives rise to a unique linear dichroism response that falls between 2D and 1D like behavior. These results not only mark the very first demonstration of high PL polarization anisotropy in 2D systems, but also provide a novel insight into how interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of Quasi-1D materials. The presented results are anticipated to have impact in technologies involving polarized detection, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light.
ContributorsPant, Anupum (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry Lynn (Committee member) / He, Ximin (Committee member) / Arizona State University (Publisher)
Created2016
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Description
A new class of layered materials called the transition metal trichalcogenides (TMTCs) exhibit strong anisotropic properties due to their quasi-1D nature. These 2D materials are composed of chain-like structures which are weakly bound to form planar sheets with highly directional properties. The vibrational properties of three materials from the TMTC

A new class of layered materials called the transition metal trichalcogenides (TMTCs) exhibit strong anisotropic properties due to their quasi-1D nature. These 2D materials are composed of chain-like structures which are weakly bound to form planar sheets with highly directional properties. The vibrational properties of three materials from the TMTC family, specifically TiS3, ZrS3, and HfS3, are relatively unknown and studies performed in this work elucidates the origin of their Raman characteristics. The crystals were synthesized through chemical vapor transport prior to mechanical exfoliation onto Si/SiO¬2 substrates. XRD, AFM, and Raman spectroscopy were used to determine the crystallinity, thickness, and chemical signature of the exfoliated crystals. Vibrational modes and anisotropic polarization are investigated through density functional theory calculations and angle-resolved Raman spectroscopy. Particular Raman modes are explored in order to correlate select peaks to the b-axis crystalline direction. Mode III vibrations for TiS3, ZrS3, and HfS3 are shared between each material and serves as a unique identifier of the crystalline orientation in MX3 materials. Similar angle-resolved Raman studies were conducted on the novel Nb0.5Ti0.5S3 alloy material grown through chemical vapor transport. Results show that the anisotropy direction is more difficult to determine due to the randomization of quasi-1D chains caused by defects that are common in 2D alloys. This work provides a fundamental understanding of the vibrational properties of various TMTC materials which is needed to realize applications in direction dependent polarization and linear dichroism.
ContributorsKong, Wilson (Author) / Tongay, Sefaattin (Thesis advisor) / Wang, Liping (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Satisfying the ever-increasing demand for electricity while maintaining sustainability and eco-friendliness has become a key challenge for humanity. Around 70% of energy is rejected as heat from different sectors. Thermoelectric energy harvesting has immense potential to convert this heat into electricity in an environmentally friendly manner. However, low efficiency and

Satisfying the ever-increasing demand for electricity while maintaining sustainability and eco-friendliness has become a key challenge for humanity. Around 70% of energy is rejected as heat from different sectors. Thermoelectric energy harvesting has immense potential to convert this heat into electricity in an environmentally friendly manner. However, low efficiency and high manufacturing costs inhibit the widespread application of thermoelectric devices. In this work, an inexpensive solution processing technique and a nanostructuring approach are utilized to create thermoelectric materials. Specifically, the solution-state and solid-state structure of a lead selenide (PbSe) precursor is characterized by different spectroscopic techniques. This precursor has shown promise for preparing thermoelectric lead selenide telluride (PbSexTe1-x) thin films. The precursor was prepared by reacting lead and diphenyl diselenide in different solvents. The characterization reveals the formation of a solvated lead(II) phenylselenolate complex which deepens the understanding of the formation of these precursors. Further, using slightly different chemistry, a low-temperature tin(II) selenide (SnSe) precursor was synthesized and identified as tin(IV) methylselenolate. The low transformation temperature makes it compatible with colloidal PbSe nanocrystals. The colloidal PbSe nanocrystals were chemically treated with a SnSe precursor and subjected to mild annealing to form conductive nanocomposites. Finally, the room temperature thermoelectric characterization of solution-processed PbSexTe1-x thin films is presented. This is followed by a setup development for temperature-dependent measurements and preliminary temperature-dependent measurements on PbSexTe1-x thin films.
ContributorsVartak, Prathamesh Bhalchandra (Author) / Wang, Robert Y. (Thesis advisor) / Wang, Liping (Committee member) / Trovitch, Ryan J. (Committee member) / Tongay, Sefaattin (Committee member) / Goodnick, Stephen M. (Committee member) / Arizona State University (Publisher)
Created2020
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Description
More recently there have been a tremendous advancement in theoretical studies showing remarkable properties that could be exploited from transition metal dichalcogenide (TMDC) Janus crystals through various applications. These Janus crystals are having a proven intrinsic electrical field due to breaking of out-of-plane inversion symmetry in a conventional TMDC when

More recently there have been a tremendous advancement in theoretical studies showing remarkable properties that could be exploited from transition metal dichalcogenide (TMDC) Janus crystals through various applications. These Janus crystals are having a proven intrinsic electrical field due to breaking of out-of-plane inversion symmetry in a conventional TMDC when one of the chalcogenides atomic layer is being completely replaced by a layer of different chalcogen element. However, due to lack of accurate processing control at nanometer scales, key for creating a highly crystalline Janus structure has not yet been familiarized. Thus, experimental characterization and implication of these Janus crystals are still in a state of stagnation. This work presents a new advanced methodology that could prove to be highly efficient and effective for selective replacement of top layer atomic sites at room temperature conditions.

This is specifically more focused on proving an easy repeatability for replacement of top atomic layer chalcogenide from a parent structure of already grown TMDC monolayer (via CVD) by a post plasma processing technique. Though this developed technique is not limited to only chalcogen atom replacement but can be extended to any type of surface functionalization requirements.

Basic characterization has been performed on the Janus crystal of SeMoS and SeWS where, creation and characterization of SeWS has been done for the very first time, evidencing a repeatable nature of the developed methodology.
ContributorsTrivedi, Dipesh (Author) / Tongay, Sefaattin (Thesis advisor) / Green, Matthew (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2019