Matching Items (102)
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 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.
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
Description
Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis method, contain wrinkles affecting their gas separation characteristics and the method itself is difficult to scale up. Moreover, the production of graphene oxide membranes with fine-tuned interlayer spacing for improved molecular separation is still a challenge. These unsolved issues will affect their potential impact on industrial gas separation applications.
In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.
An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).
In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.
An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).
ContributorsIbrahim, Amr Fatehy Muhammad (Author) / Lin, Jerry Y.S. (Thesis advisor) / Mu, Bin (Committee member) / Lind, Mary (Committee member) / Green, Matthew (Committee member) / Wang, Qing (Committee member) / Arizona State University (Publisher)
Created2018
Description
Alloying in semiconductors has enabled many civilian technologies in optoelectronic, photonic fields and more. While the phenomenon of alloying is well established in traditional bulk semiconductors, owing to vastly available ternary phase diagrams, the ability to alloy in 2D systems are less clear. Recently anisotropic materials such as ReS2 and TiS3 have been extensively studied due to their direct-gap semiconductor and high mobility behaviors. This work is a report on alloys of ReS2 & ReSe2 and TiS3 &TiSe3.
Alloying selenium into ReS2 in the creation of ReS2xSe2-x, tunes the band gap and changes its vibrational spectrum. Depositing this alloy using bottom up approach has resulted in the loss of crystallinity. This loss of crystallinity was evidenced by grain boundaries and point defect shown by TEM images.
Also, in the creation of TiS3xSe3-x, by alloying Se into TiS3, a fixed ratio of 8% selenium deposit into TiS3 host matrix is observed. This is despite the vastly differing precursor amounts and growth temperatures, as evinced by detailed TEM, EDAX, TEM diffraction, and Raman spectroscopy measurements. This unusual behavior contrasts with other well-known layered material systems such as MoSSe, WMoS2 where continuous alloying can be attained. Cluster expansion theory calculations suggest that only limited composition (x) can be achieved. Considering the fact that TiSe3 vdW crystals have not been synthesized in the past, these alloying rejections can be attributed to energetic instability in the ternary phase diagrams estimated by calculations performed. Overall findings highlight potential means and challenges in achieving stable alloying in promising direct gap and high carrier mobility TiS3 materials.
Alloying selenium into ReS2 in the creation of ReS2xSe2-x, tunes the band gap and changes its vibrational spectrum. Depositing this alloy using bottom up approach has resulted in the loss of crystallinity. This loss of crystallinity was evidenced by grain boundaries and point defect shown by TEM images.
Also, in the creation of TiS3xSe3-x, by alloying Se into TiS3, a fixed ratio of 8% selenium deposit into TiS3 host matrix is observed. This is despite the vastly differing precursor amounts and growth temperatures, as evinced by detailed TEM, EDAX, TEM diffraction, and Raman spectroscopy measurements. This unusual behavior contrasts with other well-known layered material systems such as MoSSe, WMoS2 where continuous alloying can be attained. Cluster expansion theory calculations suggest that only limited composition (x) can be achieved. Considering the fact that TiSe3 vdW crystals have not been synthesized in the past, these alloying rejections can be attributed to energetic instability in the ternary phase diagrams estimated by calculations performed. Overall findings highlight potential means and challenges in achieving stable alloying in promising direct gap and high carrier mobility TiS3 materials.
ContributorsAgarwal, Ashutosh (Author) / Tongay, Sefaattin (Thesis advisor) / Green, Matthew (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2018
Description
Since the discovery of graphene, two dimensional materials (2D materials) have become a focus of interest for material research due to their many unique physical properties embedded in their 2D structure. While they host many exciting potential applications, some of these 2D materials are subject to environmental instability issues induced by interaction between material and gas molecules in air, which poses a barrier to further application and manufacture. To overcome this, it is necessary to understand the origin of material instability and interaction with molecules commonly found in air, as well as developing a reproducible and manufacturing compatible method to post-process these materials to extend their lifetime. In this work, the very first investigation on environmental stability on Te containing anisotropic 2D materials such as GaTe and ZrTe3 is reported. Experimental results have demonstrated that freshly exfoliated GaTe quickly deteriorate in air, during which the Raman spectrum, surface morphology, and surface chemistry undergo drastic changes. Environmental Raman spectroscopy and XPS measurements demonstrate that H2O molecules in air interact strongly on the surface while O2, N2, and inert gases don't show any detrimental effects on GaTe surface. Moreover, the anisotropic properties of GaTe slowly disappear during the aging process. To prevent this gas/material interaction based surface transformation, diazonium based surface functionalization is adopted on these Te based 2D materials. Environmental Raman spectroscopy results demonstrate that the stability of functionalized Te based 2D materials exhibit much higher stability both in ambient and extreme conditions. Meanwhile, PL spectroscopy, angle resolved Raman spectroscopy, atomic force microscopy measurements confirm that many attractive physical properties of the material are not affected by surface functionalization. Overall, these findings unveil the degradation mechanism of Te based 2D materials as well as provide a way to significantly enhance their environmental stability through an inexpensive and reproducible surface chemical functionalization route.
ContributorsYang, Sijie (Author) / Tongay, Sefaattin (Thesis advisor) / Gould, Ian (Thesis advisor) / Trovitch, Ryan (Committee member) / Ghirlanda, Giovanna (Committee member) / Arizona State University (Publisher)
Created2017
Description
In this study, the differences in delivery of methylated and unmethylated prokaryotic
DNA in mammalian cells was investigated. 3 plasmids, DH5-α, ER2925 and
GM272 were extracted and transformed from E. coli bacteria. DH5-α is the regular
methylated plasmid, however,ER2925 and GM272 lack Dam and Dcm enzymes which
methylate adenine and internal cytosine in prokaryotes respectively, hence they are
unmethylated. The 3 plasmids were delivered via different delivery vectors in two
cell lines, UMUC3 and MDA-MB-231 which are human bladder cancer cell line and
human triple negative breast cancer cell line, respectively.
Luciferase and BCA assay were carried out to quantify transgene expression to
compare the efficacy of gene delivery in three aforementioned plasmids. In addition,
hydrodynamic diameter and zeta potential was measured for all delivery vectors, to
correlate with other transgene expression data. The results show that methylated
plasmid has significantly higher transgene expression in mammalian cell lines. This
can be either a result of smaller size and more positive zeta potential that the methylated
plasmid had, or a result of having Dam and Dcm enzymes which enhance binding
of DNA and transcription factors and enhance gene expression. Having smaller size
and more positive zeta potential was proven to be the case for the methylated plasmid
in this study. However the latter hypothesis should be investigated furthermore.
DNA in mammalian cells was investigated. 3 plasmids, DH5-α, ER2925 and
GM272 were extracted and transformed from E. coli bacteria. DH5-α is the regular
methylated plasmid, however,ER2925 and GM272 lack Dam and Dcm enzymes which
methylate adenine and internal cytosine in prokaryotes respectively, hence they are
unmethylated. The 3 plasmids were delivered via different delivery vectors in two
cell lines, UMUC3 and MDA-MB-231 which are human bladder cancer cell line and
human triple negative breast cancer cell line, respectively.
Luciferase and BCA assay were carried out to quantify transgene expression to
compare the efficacy of gene delivery in three aforementioned plasmids. In addition,
hydrodynamic diameter and zeta potential was measured for all delivery vectors, to
correlate with other transgene expression data. The results show that methylated
plasmid has significantly higher transgene expression in mammalian cell lines. This
can be either a result of smaller size and more positive zeta potential that the methylated
plasmid had, or a result of having Dam and Dcm enzymes which enhance binding
of DNA and transcription factors and enhance gene expression. Having smaller size
and more positive zeta potential was proven to be the case for the methylated plasmid
in this study. However the latter hypothesis should be investigated furthermore.
ContributorsMeraji, Seyedehmelika (Author) / Rege, Kaushal (Thesis advisor) / Nannegna, Brent (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2018
Description
Encapsulant is a key packaging component of photovoltaic (PV) modules, which protects the solar cell from physical, environmental and electrical damages. Ethylene-vinyl acetate (EVA) is one of the major encapsulant materials used in the PV industry. This work focuses on indoor accelerated ultraviolet (UV) stress testing and characterization to investigate the EVA discoloration and delamination in PV modules by using various non-destructive characterization techniques, including current-voltage (IV) measurements, UV fluorescence (UVf) and colorimetry measurements. Mini-modules with glass/EVA/cell/EVA/backsheet construction were fabricated in the laboratory with two types of EVA, UV-cut EVA (UVC) and UV-pass EVA (UVP).
The accelerated UV testing was performed in a UV chamber equipped with UV lights at an ambient temperature of 50°C, little or no humidity and total UV dosage of 400 kWh/m2. The mini-modules were maintained at three different temperatures through UV light heating by placing different thickness of thermal insulation sheets over the backsheet. Also, prior to thermal insulation sheet placement, the backsheet and laminate edges were fully covered with aluminum tape to prevent oxygen diffusion into the module and hence the photobleaching reaction.
The characterization results showed that mini-modules with UV-cut EVA suffered from discoloration while the modules with UV-pass EVA suffered from delamination. UVf imaging technique has the capability to identify the discoloration region in the UVC modules in the very early stage when the discoloration is not visible to the naked eyes, whereas Isc measurement is unable to measure the performance loss until the color becomes visibly darker. YI also provides the direct evidence of yellowing in the encapsulant. As expected, the extent of degradation due to discoloration increases with the increase in module temperature. The Isc loss is dictated by both the regions – discolored area at the center and non-discolored area at the cell edges, whereas the YI is only determined at the discolored region due to low probe area. This led to the limited correlation between Isc and YI in UVC modules.
In case of UVP modules, UV radiation has caused an adverse impact on the interfacial adhesion between the EVA and solar cell, which was detected from UVf images and severe Isc loss. No change in YI confirms that the reason for Isc loss is not due to yellowing but the delamination.
Further, the activation energy of encapsulant discoloration was estimated by using Arrhenius model on two types of data, %Isc drop and ΔYI. The Ea determined from the change in YI data for the EVA encapsulant discoloration reaction without the influence of oxygen and humidity is 0.61 eV. Based on the activation energy determined in this work and hourly weather data of any site, the degradation rate for the encaspulant browning mode can be estimated.
The accelerated UV testing was performed in a UV chamber equipped with UV lights at an ambient temperature of 50°C, little or no humidity and total UV dosage of 400 kWh/m2. The mini-modules were maintained at three different temperatures through UV light heating by placing different thickness of thermal insulation sheets over the backsheet. Also, prior to thermal insulation sheet placement, the backsheet and laminate edges were fully covered with aluminum tape to prevent oxygen diffusion into the module and hence the photobleaching reaction.
The characterization results showed that mini-modules with UV-cut EVA suffered from discoloration while the modules with UV-pass EVA suffered from delamination. UVf imaging technique has the capability to identify the discoloration region in the UVC modules in the very early stage when the discoloration is not visible to the naked eyes, whereas Isc measurement is unable to measure the performance loss until the color becomes visibly darker. YI also provides the direct evidence of yellowing in the encapsulant. As expected, the extent of degradation due to discoloration increases with the increase in module temperature. The Isc loss is dictated by both the regions – discolored area at the center and non-discolored area at the cell edges, whereas the YI is only determined at the discolored region due to low probe area. This led to the limited correlation between Isc and YI in UVC modules.
In case of UVP modules, UV radiation has caused an adverse impact on the interfacial adhesion between the EVA and solar cell, which was detected from UVf images and severe Isc loss. No change in YI confirms that the reason for Isc loss is not due to yellowing but the delamination.
Further, the activation energy of encapsulant discoloration was estimated by using Arrhenius model on two types of data, %Isc drop and ΔYI. The Ea determined from the change in YI data for the EVA encapsulant discoloration reaction without the influence of oxygen and humidity is 0.61 eV. Based on the activation energy determined in this work and hourly weather data of any site, the degradation rate for the encaspulant browning mode can be estimated.
ContributorsDolia, Kshitiz (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Green, Matthew (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Arizona State University (Publisher)
Created2018
Description
An urgent need for developing new chemical separations that address the capture of dilute impurities from fluid streams are needed. These separations include the capture of carbon dioxide from the atmosphere, impurities from drinking water, and toxins from blood streams. A challenge is presented when capturing these impurities because the energy cost for processing the bulk fluid stream to capture trace contaminants is too great using traditional thermal separations. The development of sorbents that may capture these contaminants passively has been emphasized in academic research for some time, producing many designer materials including metal-organic frameworks (MOFs) and polymeric resins. Scaffolds must be developed to effectively anchor these materials in a passing fluid stream. In this work, two design techniques are presented for anchoring these sorbents in electrospun fiber scaffolds.
The first technique involves imbedding sorbent particles inside the fibers: forming particle-embedded fibers. It is demonstrated that particles will spontaneously coat themselves in the fibers at dilute loadings, but at higher loadings some get trapped on the fiber surface. A mathematical model is used to show that when these particles are embedded, the polymeric coating provided by the fibers may be designed to increase the kinetic selectivity and/or stability of the embedded sorbents. Two proof-of-concept studies are performed to validate this model including the increased selectivity of carbon dioxide over nitrogen when the MOF ZIF-8 is embedded in a poly(ethylene oxide) and Matrimid polymer blend; and that increased hydrothermal stability is realized when the water-sensitive MOF HKUST-1 is embedded in polystyrene fibers relative to pure HKUST-1 powder.
The second technique involves the creation of a pore network throughout the fiber to increase accessibility of embedded sorbent particles. It is demonstrated that the removal of a blended highly soluble polymer additive from the spun particle-containing fibers leaves a pore network behind without removing the embedded sorbent. The increased accessibility of embedded sorbents is validated by embedding a known direct air capture sorbent in porous electrospun fibers, and demonstrating that they have the fastest kinetic uptake of any direct air capture sorbent reported in literature to date, along with over 90% sorbent accessibility.
The first technique involves imbedding sorbent particles inside the fibers: forming particle-embedded fibers. It is demonstrated that particles will spontaneously coat themselves in the fibers at dilute loadings, but at higher loadings some get trapped on the fiber surface. A mathematical model is used to show that when these particles are embedded, the polymeric coating provided by the fibers may be designed to increase the kinetic selectivity and/or stability of the embedded sorbents. Two proof-of-concept studies are performed to validate this model including the increased selectivity of carbon dioxide over nitrogen when the MOF ZIF-8 is embedded in a poly(ethylene oxide) and Matrimid polymer blend; and that increased hydrothermal stability is realized when the water-sensitive MOF HKUST-1 is embedded in polystyrene fibers relative to pure HKUST-1 powder.
The second technique involves the creation of a pore network throughout the fiber to increase accessibility of embedded sorbent particles. It is demonstrated that the removal of a blended highly soluble polymer additive from the spun particle-containing fibers leaves a pore network behind without removing the embedded sorbent. The increased accessibility of embedded sorbents is validated by embedding a known direct air capture sorbent in porous electrospun fibers, and demonstrating that they have the fastest kinetic uptake of any direct air capture sorbent reported in literature to date, along with over 90% sorbent accessibility.
ContributorsArmstrong, Mitchell (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Seo, Dong (Committee member) / Lackner, Klaus (Committee member) / Holloway, Julianne (Committee member) / Arizona State University (Publisher)
Created2018
Description
Recently, two-dimensional (2D) materials have emerged as a new class of materials with highly attractive electronic, optical, magnetic, and thermal properties. However, there exists a sub-category of 2D layers wherein constituent metal atoms are arranged in a way that they form weakly coupled chains confined in the 2D landscape. These weakly coupled chains extend along particular lattice directions and host highly attractive properties including high thermal conduction pathways, high-mobility carriers, and polarized excitons. In a sense, these materials offer a bridge between traditional one-dimensional (1D) materials (nanowires and nanotubes) and 2D layered systems. Therefore, they are often referred as pseudo-1D materials, and are anticipated to impact photonics and optoelectronics fields.
This dissertation focuses on the novel growth routes and fundamental investigation of the physical properties of pseudo-1D materials. Example systems are based on transition metal chalcogenide such as rhenium disulfide (ReS2), titanium trisulfide (TiS3), tantalum trisulfide (TaS3), and titanium-niobium trisulfide (Nb(1-x)TixS3) ternary alloys. Advanced growth, spectroscopy, and microscopy techniques with density functional theory (DFT) calculations have offered the opportunity to understand the properties of these materials both experimentally and theoretically. The first controllable growth of ReS2 flakes with well-defined domain architectures has been established by a state-of-art chemical vapor deposition (CVD) method. High-resolution electron microscopy has offered the very first investigation into the structural pseudo-1D nature of these materials at an atomic level such as the chain-like features, grain boundaries, and local defects.
Pressure-dependent Raman spectroscopy and DFT calculations have investigated the origin of the Raman vibrational modes in TiS3 and TaS3, and discovered the unusual pressure response and its effect on Raman anisotropy. Interestingly, the structural and vibrational anisotropy can be retained in the Nb(1-x)TixS3 alloy system with the presence of phase transition at a nominal Ti alloying limit. Results have offered valuable experimental and theoretical insights into the growth routes as well as the structural, optical, and vibrational properties of typical pseudo-1D layered systems. The overall findings hope to shield lights to the understanding of this entire class of materials and benefit the design of 2D electronics and optoelectronics.
This dissertation focuses on the novel growth routes and fundamental investigation of the physical properties of pseudo-1D materials. Example systems are based on transition metal chalcogenide such as rhenium disulfide (ReS2), titanium trisulfide (TiS3), tantalum trisulfide (TaS3), and titanium-niobium trisulfide (Nb(1-x)TixS3) ternary alloys. Advanced growth, spectroscopy, and microscopy techniques with density functional theory (DFT) calculations have offered the opportunity to understand the properties of these materials both experimentally and theoretically. The first controllable growth of ReS2 flakes with well-defined domain architectures has been established by a state-of-art chemical vapor deposition (CVD) method. High-resolution electron microscopy has offered the very first investigation into the structural pseudo-1D nature of these materials at an atomic level such as the chain-like features, grain boundaries, and local defects.
Pressure-dependent Raman spectroscopy and DFT calculations have investigated the origin of the Raman vibrational modes in TiS3 and TaS3, and discovered the unusual pressure response and its effect on Raman anisotropy. Interestingly, the structural and vibrational anisotropy can be retained in the Nb(1-x)TixS3 alloy system with the presence of phase transition at a nominal Ti alloying limit. Results have offered valuable experimental and theoretical insights into the growth routes as well as the structural, optical, and vibrational properties of typical pseudo-1D layered systems. The overall findings hope to shield lights to the understanding of this entire class of materials and benefit the design of 2D electronics and optoelectronics.
ContributorsWu, Kedi (Author) / Tongay, Sefaattin (Thesis advisor) / Zhuang, Houlong (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2018
Description
There has been a surge in two-dimensional (2D) materials field since the discovery of graphene in 2004. Recently, a new class of layered atomically thin materials that exhibit in-plane structural anisotropy, such as black phosphorous, transition metal trichalcogenides and rhenium dichalcogenides (ReS2), have attracted great attention. The reduced symmetry in these novel 2D materials gives rise to highly anisotropic physical properties that enable unique applications in next-gen electronics and optoelectronics. For example, higher carrier mobility along one preferential crystal direction for anisotropic field effect transistors and anisotropic photon absorption for polarization-sensitive photodetectors.
This dissertation endeavors to address two key challenges towards practical application of anisotropic materials. One is the scalable production of high quality 2D anisotropic thin films, and the other is the controllability over anisotropy present in synthesized crystals. The investigation is focused primarily on rhenium disulfide because of its chemical similarity to conventional 2D transition metal dichalcogenides and yet anisotropic nature. Carefully designed vapor phase deposition has been demonstrated effective for batch synthesis of high quality ReS2 monolayer. Heteroepitaxial growth proves to be a feasible route for controlling anisotropic directions. Scanning/transmission electron microscopy and angle-resolved Raman spectroscopy have been extensively applied to reveal the structure-property relationship in synthesized 2D anisotropic layers and their heterostructures.
This dissertation endeavors to address two key challenges towards practical application of anisotropic materials. One is the scalable production of high quality 2D anisotropic thin films, and the other is the controllability over anisotropy present in synthesized crystals. The investigation is focused primarily on rhenium disulfide because of its chemical similarity to conventional 2D transition metal dichalcogenides and yet anisotropic nature. Carefully designed vapor phase deposition has been demonstrated effective for batch synthesis of high quality ReS2 monolayer. Heteroepitaxial growth proves to be a feasible route for controlling anisotropic directions. Scanning/transmission electron microscopy and angle-resolved Raman spectroscopy have been extensively applied to reveal the structure-property relationship in synthesized 2D anisotropic layers and their heterostructures.
ContributorsChen, Bin, 1968- (Author) / Tongay, Sefaattin (Thesis advisor) / Bertoni, Mariana (Committee member) / Chang, Lan-Yun (Committee member) / Arizona State University (Publisher)
Created2018
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 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.
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