Matching Items (15)
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- All Subjects: Materials Science
- Genre: Masters Thesis
- Creators: Tongay, Sefaattin
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 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.
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
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 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
Description
Microplastics are emerging to be major problem when it comes to water pollution and they pose a great threat to marine life. These materials have the potential to affect a wide range of human population since humans are the major consumers of marine organisms. Microplastics are less than 5 mm in diameter, and can escape from traditional wastewater treatment plant (WWTP) processes and end up in our water sources. Due to their small size, they have a large surface area and can react with chlorine, which it encounters in the final stages of WWTP. After the microplastics accumulate in various bodies of water, they are exposed to sunlight, which contains oxidative ultraviolet (UV) light. Since the microplastics are exposed to oxidants during and after the treatment, there is a strong chance that they will undergo chemical and/or physical changes. The WWTP conditions were replicated in the lab by varying the concentrations of chlorine from 70 to 100 mg/L in increments of 10 mg/L and incubating the samples in chlorine baths for 1–9 days. The chlorinated samples were tested for any structural changes using Raman spectroscopy. High density polyethylene (HDPE), polystyrene (PS), and polypropylene (PP) were treated in chlorine baths and observed for Raman intensity variations, Raman peak shifts, and the formation of new peaks over different exposure times. HDPE responded with a lot of oxidation peaks and shifts of peaks after just one day. For the degradation of semi-crystalline polymers, there was a reduction in crystallinity, as verified by thermal analysis. There was a decrease in the enthalpy of melting as well as the melting temperature with an increase in the exposure time or chlorine concentration, which pointed at the degradation of plastics and bond cleavages. To test the plastic response to
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UV, the samples were exposed to sunlight for up to 210 days and analyzed under Raman spectroscopy. Overall the physical and chemical changes with the polymers are evident and makes a way for the wastewater treatment plant to take necessary steps to capture the microplastics to avoid the release of any kind of degraded microplastics that could affect marine life and the environment.
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UV, the samples were exposed to sunlight for up to 210 days and analyzed under Raman spectroscopy. Overall the physical and chemical changes with the polymers are evident and makes a way for the wastewater treatment plant to take necessary steps to capture the microplastics to avoid the release of any kind of degraded microplastics that could affect marine life and the environment.
ContributorsKelkar, Varun (Author) / Green, Matthew D (Thesis advisor) / Tongay, Sefaattin (Committee member) / Halden, Rolf U. (Committee member) / Arizona State University (Publisher)
Created2017
Description
Doping is the cornerstone of Semiconductor technology, enabling the functionalities of modern digital electronics. Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have tunable direct bandgaps, strong many-body interactions, and promising applications in future quantum information sciences, optoelectronic, spintronic, and valleytronic devices. However, their wafer-scale synthesis and precisely controllable doping are challenging. Moreover, there is no fixed framework to identify the doping concentration, which impedes their process integration for future commercialization. This work utilizes the Neutron Transmutation Doping technique to control the doping uniformly and precisely in TMDCs. Rhenium and Tin dopants are introduced in Tungsten- and Indium-based Chalcogenides, respectively. Fine-tuning over 0.001% doping level is achieved. Precise analytical techniques such as Gamma spectroscopy and Secondary Ion Mass Spectrometry are used to quantify ultra-low doping levels ranging from 0.005-0.01% with minimal error. Dopants in 2D TMDCs often exhibit a broad stokes-shifted emission, with high linewidths, due to extrinsic effects such as substrate disorder and surface adsorbates. A well-defined bound exciton emission induced by Rhenium dopants in monolayer WSe2 and WS2 at liquid nitrogen temperatures is reported along with specific annealing regimes to minimize the defects induced in the Neutron Transmutation process. This work demonstrates a framework for Neutron Doping in 2D materials, which can be a scalable process for controlling doping and doping-induced effects in 2D materials.
ContributorsLakhavade, Sushant Sambhaji (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2023
Description
In the Rare-earth-Tri-telluride family, (RTe3s) [R=La, Ce, Nd, Sm, Gd, Tb, Dy, Er, Ho, Tm] the emergence of Charge Density Waves, (CDW) has been under investigation for a long time due to broadly tunable properties by either chemical substitution or pressure application. These quasi 2D Layered materials RTe3s undergo Fermi Surface Nesting leading to CDW instability. CDWs are electronic instabilities found in low-dimensional materials with highly anisotropic electronic structures. Since the CDW is predominantly driven by Fermi-surface (FS) nesting, it is especially sensitive to pressure-induced changes in the electronic structure. The FS of RTe3s is a function of p-orbitals of Tellurium atoms, which are arranged in two adjacent planes in the crystal structure. Although the FS and electronic structure possess a nearly four-fold symmetry, RTe3s form an incommensurate CDW.This dissertation is structured as follows: Chapter 1 includes basic ideas of Quantum materials, followed by an introduction to CDW and RTe3s. In Chapter 2, there are fundamentals of crystal growth by Chemical Vapor Transport, including various precursors, transport agent, temperature gradient, and rate of the reaction. After the growth, the crystals were confirmed for lattice vibrations by Raman, for composition by Energy Dispersive Spectroscopy; crystal structure and orientation were confirmed by X-ray Diffraction; magnetic ordering was established by Vibrating sample measurement. Detailed CDW study was done on various RTe3s by Raman spectroscopy. The basic mechanism and instrumentations used in these characterizations are explained in Chapter 3. Chapter 4 includes experimental data for crystal growth and results of these characterizations for Parent RTe3s. Chapter 5 includes fundamental insights on Cationic alloying of RTe3s, along with one alloy system’s crystal growth and characterization. This work tries to explain the behavior of CDW by a Temperature-dependent Raman study of RTe3s established the CDW transition temperature accompanied by Phonon softening; Angle-resolved Raman data confirming the nearly four-fold symmetry; thickness-dependent Raman spectroscopy resulting in the conclusion that as thickness decreases CDW transition temperature increases. Also, CDW transition is analyzed as a function of alloying.
ContributorsAttarde, Yashika (Author) / Tongay, Sefaattin (Thesis advisor) / Botana, Antia (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2021
Description
Metal-Oxide-Semiconductor (MOS) is essential to modern VLSI devices. In the past decades, a wealth of literature has been created to understand the impact of the radiation-induced charges on the devices, i.e., the creation of electron-hole pairs in the oxide layer which is the most sensitive part of MOS structure to the radiation effect. In this work, both MOS and MNOS devices were fabricated at ASU NanoFab to study the total ionizing dose effect using capacitance-voltage (C-V) electrical characterization by observing the direction and amounts of the shift in C-V curves and electron holography observation to directly image the charge buildup at the irradiated oxide film of the oxide-only MOS device.C-V measurements revealed the C-V curves shifted to the left after irradiation (with a positive bias applied) because of the net positive charges trapped at the oxide layer for the oxide-only sample. On the other hand, for nitride/oxide samples with positive biased during irradiation, the C-V curve shifted to the right due to the net negative charges trapped at the oxide layer. It was also observed that the C-V curve has less shift in voltage for MNOS than MOS devices after irradiation due to the less charge buildup after irradiation.
Off-axis electron holography was performed to map the charge distribution across the MOSCAP sample. Compared with both pre-and post-irradiated samples, a larger potential drop at the Si/SiO2 was noticed in post-irradiation samples, which indicates the presence of greater amounts of positive charges that buildup the Si/SiO2 interface after the TID exposure.
TCAD modeling was used to extract the density of charges accumulated near the SiO2/Si and SiO2/ Metal interface by matching the simulation results to the potential data from holography. The increase of near-interface positive charges in post-irradiated samples is consistent with the C-V results.
ContributorsChang, Ching Tao (Author) / Barnaby, Hugh (Thesis advisor) / Holbert, Keith (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2023
Description
In the past decade, 2D materials especially transition metal dichalcogenides (TMDc), have been studied extensively for their remarkable optical and electrical properties arising from their reduced dimensionality. A new class of materials developed based on 2D TMDc that has gained great interest in recent years is Janus crystals. In contrast to TMDc, Janus monolayer consists of two different chalcogen atomic layers between which the transition metal layer is sandwiched. This structural asymmetry causes strain buildup or a vertically oriented electric field to form within the monolayer. The presence of strain brings questions about the materials' synthesis approach, particularly when strain begins to accumulate and whether it causes defects within monolayers.The initial research demonstrated that Janus materials could be synthesized at high temperatures inside a chemical vapor deposition (CVD) furnace. Recently, a new method (selective epitaxy atomic replacement - SEAR) for plasma-based room temperature Janus crystal synthesis was proposed. In this method etching and replacing top layer chalcogen atoms of the TMDc monolayer happens with reactive hydrogen and sulfur radicals. Based on Raman and photoluminescence studies, the SEAR method produces high-quality Janus materials. Another method used to create Janus materials was the pulsed laser deposition (PLD) technique, which utilizes the interaction of sulfur/selenium plume with monolayer to replace the top chalcogen atomic layer in a single step.
The goal of this analysis is to characterize microscale defects that appear in 2D Janus materials after they are synthesized using SEAR and PLD techniques. Various microscopic techniques were used for this purpose, as well as to understand the
mechanism of defect formation. The main mechanism of defect formation was proposed to be strain release phenomena. Furthermore, different chalcogen atom positions within the monolayer result in different types of defects, such as the appearance of cracks or wrinkles across monolayers. In addition to investigating sample topography, Kelvin probe force microscopy (KPFM) was used to examine its electrical properties to see if the formation of defects impacts work function. Further study directions have been suggested for identifying and characterizing defects and their formation mechanism in the Janus crystals to understand their fundamental properties.
ContributorsSinha, Shantanu (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2022
Description
Many important technologies, including electronics, computing, communications, optoelectronics, and sensing, are built on semiconductors. The band gap is a crucial factor in determining the electrical and optical properties of semiconductors. Beyond graphene, newly found two-dimensional (2D) materials have semiconducting bandgaps that range from the ultraviolet in hexagonal boron nitride to the terahertz and mid-infrared in bilayer graphene and black phosphorus, visible in transition metal dichalcogenides (TMDs). These 2D materials were shown to have highly controllable bandgaps which can be controlled by alloying. Only a small number of TMDs and monochalcogenides have been alloyed, though, because alloying compromised the material's Van der Waals (Vdw) property and the stability of the host crystal lattice phase. Phase transition in 2D materials is an interesting phenomenon where work has been done only on few TMDs namely MoTe2, MoS2, TaS2 etc.In order to change the band gaps and move them towards the UV (ultraviolet) and IR (infrared) regions, this work has developed new 2D alloys in InSe by alloying them with S and Te at 10% increasing concentrations. As the concentration of the chalcogens (S and Te) increased past a certain point, a structural phase transition in the alloys was observed. However, pinpointing the exact concentration for phase change and inducing phase change using external stimuli will be a thing of the future. The resulting changes in the crystal structure and band gap were characterized using some basic characterization techniques like scanning electron microscopy (SEM), X-ray Diffraction (XRD), Raman and photoluminescence spectroscopy.
ContributorsYarra, Anvesh Sai (Author) / Tongay, Sefaattin (Thesis advisor) / Yang, Sui (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2022
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 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.
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
Description
Two-dimensional quantum materials have garnered increasing interest in a wide
variety of applications due to their promising optical and electronic properties. These
quantum materials are highly anticipated to make transformative quantum sensors and
biosensors. Biosensors are currently considered among one of the most promising
solutions to a wide variety of biomedical and environmental problems including highly
sensitive and selective detection of difficult pathogens, toxins, and biomolecules.
However, scientists face enormous challenges in achieving these goals with current
technologies. Quantum biosensors can have detection with extraordinary sensitivity and
selectivity through manipulation of their quantum states, offering extraordinary properties
that cannot be attained with traditional materials. These quantum materials are anticipated
to make significant impact in the detection, diagnosis, and treatment of many diseases.
Despite the exciting promise of these cutting-edge technologies, it is largely
unknown what the inherent toxicity and biocompatibility of two-dimensional (2D)
materials are. Studies are greatly needed to lay the foundation for understanding the
interactions between quantum materials and biosystems. This work introduces a new
method to continuously monitor the cell proliferation and toxicity behavior of 2D
materials. The cell viability and toxicity measurements coupled with Live/Dead
fluorescence imaging suggest the biocompatibility of crystalline MoS2 and MoSSe
monolayers and the significantly-reduced cellular growth of defected MoTe2 thin films
and exfoliated MoS2 nanosheets. Results show the exciting potential of incorporating
kinetic cell viability data of 2D materials with other assay tools to further fundamental
understanding of 2D material biocompatibility.
variety of applications due to their promising optical and electronic properties. These
quantum materials are highly anticipated to make transformative quantum sensors and
biosensors. Biosensors are currently considered among one of the most promising
solutions to a wide variety of biomedical and environmental problems including highly
sensitive and selective detection of difficult pathogens, toxins, and biomolecules.
However, scientists face enormous challenges in achieving these goals with current
technologies. Quantum biosensors can have detection with extraordinary sensitivity and
selectivity through manipulation of their quantum states, offering extraordinary properties
that cannot be attained with traditional materials. These quantum materials are anticipated
to make significant impact in the detection, diagnosis, and treatment of many diseases.
Despite the exciting promise of these cutting-edge technologies, it is largely
unknown what the inherent toxicity and biocompatibility of two-dimensional (2D)
materials are. Studies are greatly needed to lay the foundation for understanding the
interactions between quantum materials and biosystems. This work introduces a new
method to continuously monitor the cell proliferation and toxicity behavior of 2D
materials. The cell viability and toxicity measurements coupled with Live/Dead
fluorescence imaging suggest the biocompatibility of crystalline MoS2 and MoSSe
monolayers and the significantly-reduced cellular growth of defected MoTe2 thin films
and exfoliated MoS2 nanosheets. Results show the exciting potential of incorporating
kinetic cell viability data of 2D materials with other assay tools to further fundamental
understanding of 2D material biocompatibility.
ContributorsTran, Michael, Ph.D (Author) / Tongay, Sefaattin (Thesis advisor) / Green, Matthew (Thesis advisor) / Muhich, Christopher (Committee member) / Arizona State University (Publisher)
Created2019