Matching Items (18)
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- All Subjects: Chemistry
- Genre: Doctoral Dissertation
- Creators: Kouvetakis, John
- Creators: Tao, Nongjian
Description
Metal hydride materials have been intensively studied for hydrogen storage applications. In addition to potential hydrogen economy applications, metal hydrides offer a wide variety of other interesting properties. For example, hydrogen-dominant materials, which are hydrides with the highest hydrogen content for a particular metal/semimetal composition, are predicted to display high-temperature superconductivity. On the other side of the spectrum are hydrides with small amounts of hydrogen (0.1 - 1 at.%) that are investigated as viable magnetic, thermoelectric or semiconducting materials. Research of metal hydride materials is generally important to gain fundamental understanding of metal-hydrogen interactions in materials. Hydrogenation of Zintl phases, which are defined as compounds between an active metal (alkali, alkaline earth, rare earth) and a p-block metal/semimetal, were attempted by a hot sintering method utilizing an autoclave loaded with gaseous hydrogen (< 9 MPa). Hydride formation competes with oxidative decomposition of a Zintl phase. The oxidative decomposition, which leads to a mixture of binary active metal hydride and p-block element, was observed for investigated aluminum (Al) and gallium (Ga) containing Zintl phases. However, a new phase Li2Al was discovered when Zintl phase precursors were synthesized. Using the single crystal x-ray diffraction (SCXRD), the Li2Al was found to crystallize in an orthorhombic unit cell (Cmcm) with the lattice parameters a = 4.6404(8) Å, b = 9.719(2) Å, and c = 4.4764(8) Å. Increased demand for materials with improved properties necessitates the exploration of alternative synthesis methods. Conventional metal hydride synthesis methods, like ball-milling and autoclave technique, are not responding to the demands of finding new materials. A viable alternative synthesis method is the application of high pressure for the preparation of hydrogen-dominant materials. Extreme pressures in the gigapascal ranges can open access to new metal hydrides with novel structures and properties, because of the drastically increased chemical potential of hydrogen. Pressures up to 10 GPa can be easily achieved using the multi-anvil (MA) hydrogenations while maintaining sufficient sample volume for structure and property characterization. Gigapascal MA hydrogenations using ammonia borane (BH3NH3) as an internal hydrogen source were employed in the search for new hydrogen-dominant materials. Ammonia borane has high gravimetric volume of hydrogen, and additionally the thermally activated decomposition at high pressures lead to a complete hydrogen release at reasonably low temperature. These properties make ammonia borane a desired hydrogen source material. The missing member Li2PtH6 of the series of A2PtH6 compounds (A = Na to Cs) was accessed by employing MA technique. As the known heavier analogs, the Li2PtH6 also crystallizes in a cubic K2PtCl6-type structure with a cell edge length of 6.7681(3) Å. Further gigapascal hydrogenations afforded the compounds K2SiH6 and Rb2SiH6 which are isostructural to Li2PtH6. The cubic K2SiH6 and Rb2SiH6 are built from unique hypervalent SiH62- entities with the lattice parameters of 7.8425(9) and 8.1572(4) Å, respectively. Spectroscopic analysis of hexasilicides confirmed the presence of hypervalent bonding. The Si-H stretching frequencies at 1550 cm-1 appeared considerably decreased in comparison with a normal-valent (2e2c) Si-H stretching frequencies in SiH4 at around 2200 cm-1. However, the observed stretching modes in hypervalent hexasilicides were in a reasonable agreement with Ph3SiH2- (1520 cm-1) where the hydrogen has the axial (3e4c bonded) position in the trigoal bipyramidal environment.
ContributorsPuhakainen, Kati (Author) / Häussermann, Ulrich (Thesis advisor) / Seo, Dong (Thesis advisor) / Kouvetakis, John (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
Description
Human breath is a concoction of thousands of compounds having in it a breath-print of physiological processes in the body. Though breath provides a non-invasive and easy to handle biological fluid, its analysis for clinical diagnosis is not very common. Partly the reason for this absence is unavailability of cost effective and convenient tools for such analysis. Scientific literature is full of novel sensor ideas but it is challenging to develop a working device, which are few. These challenges include trace level detection, presence of hundreds of interfering compounds, excessive humidity, different sampling regulations and personal variability. To meet these challenges as well as deliver a low cost solution, optical sensors based on specific colorimetric chemical reactions on mesoporous membranes have been developed. Sensor hardware utilizing cost effective and ubiquitously available light source (LED) and detector (webcam/photo diodes) has been developed and optimized for sensitive detection. Sample conditioning mouthpiece suitable for portable sensors is developed and integrated. The sensors are capable of communication with mobile phones realizing the idea of m-health for easy personal health monitoring in free living conditions. Nitric oxide and Acetone are chosen as analytes of interest. Nitric oxide levels in the breath correlate with lung inflammation which makes it useful for asthma management. Acetone levels increase during ketosis resulting from fat metabolism in the body. Monitoring breath acetone thus provides useful information to people with type1 diabetes, epileptic children on ketogenic diets and people following fitness plans for weight loss.
ContributorsPrabhakar, Amlendu (Author) / Tao, Nongjian (Thesis advisor) / Forzani, Erica (Committee member) / Lindsay, Stuart (Committee member) / Arizona State University (Publisher)
Created2013
Description
The thesis studies new methods to fabricate optoelectronic Ge1-ySny/Si(100) alloys and investigate their photoluminescence (PL) properties for possible applications in Si-based photonics including IR lasers. The work initially investigated the origin of the difference between the PL spectrum of bulk Ge, dominated by indirect gap emission, and the PL spectrum of Ge-on-Si films, dominated by direct gap emission. It was found that the difference is due to the supression of self-absorption effects in Ge films, combined with a deviation from quasi-equilibrium conditions in the conduction band of undoped films. The latter is confirmed by a model suggesting that the deviation is caused by the shorter recombination lifetime in the films relative to bulk Ge. The knowledge acquired from this work was then utilized to study the PL properties of n-type Ge1-ySny/Si (y=0.004-0.04) samples grown via chemical vapor deposition of Ge2H6/SnD4/P(GeH3)3. It was found that the emission intensity (I) of these samples is at least 10x stronger than observed in un-doped counterparts and that the Idir/Iind ratio of direct over indirect gap emission increases for high-Sn contents due to the reduced gamma-L valley separation, as expected. Next the PL investigation was expanded to samples with y=0.05-0.09 grown via a new method using the more reactive Ge3H8 in place of Ge2H6. Optical quality, 1-um thick Ge1-ySny/Si(100) layers were produced using Ge3H10/SnD4 and found to exhibit strong, tunable PL near the threshold of the direct-indirect bandgap crossover. A byproduct of this study was the development of an enhanced process to produce Ge3H8, Ge4H10, and Ge5H12 analogs for application in ultra-low temperature deposition of Group-IV semiconductors. The thesis also studies synthesis routes of an entirely new class of semiconductor compounds and alloys described by Si5-2y(III-V)y (III=Al, V= As, P) comprising of specifically designed diamond-like structures based on a Si parent lattice incorporating isolated III-V units. The common theme of the two thesis topics is the development of new mono-crystalline materials on ubiquitous silicon platforms with the objective of enhancing the optoelectronic performance of Si and Ge semiconductors, potentially leading to the design of next generation optical devices including lasers, detectors and solar cells.
ContributorsGrzybowski, Gordon (Author) / Kouvetakis, John (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2013
Description
Group IV alloy films exhibit the ability to tune both band structure and lattice parameters and have recently attracted attention for their potential applications in Si-photonics and photovoltaics. In this work, several new approaches to produce these alloys directly on Si(100) and Ge(100) wafers are developed. For photovoltaics, use of Ge-buffered Si(100) wafers as a low cost platform for epitaxy of In1-xGaxAs layers was explored. The results indicate that this approach has promise for transitioning from bulk Ge platforms to virtual substrates for a significant cost reduction. The electrical and optical properties of Ge and Ge1-ySny layers produced using several different techniques were explored via fabrication of high performance heterostructure photodiodes. First, a new CVD approach to Ge-like materials was developed in which germanium is alloyed with very small amounts of tin. These alloys exhibited no significant difference in their structural properties or band gap compared to pure Ge, however superior photo response and reduced dark currents were observed from fabricated devices relative to pure Ge on Si reference diodes. Additionally, pure Ge/Si(100) photodiodes were fabricated using layers grown via reactions of Ge4H10 on Si(100) and found to exhibit low dark current densities with high collection efficiencies. Ge1-x-ySixSny materials represent the newest member of group IV alloy family. The ability to decouple the lattice constant and the band gap in this system has led to strong interest both for strain/confinement layers in quantum well structures, and as the possible "missing" 1 eV junction in multijunction photovoltaics. Recent progress in this field has allowed for the first time growth, fabrication and measurement of novel photodiodes based on Ge1-x-ySixSny. This work presents the material, electrical and optical properties of Ge1-x-ySixSny layers and photodiodes grown directly on Ge and Si wafers using two different synthetic approaches. A series of photodiodes containing Sn concentrations from 1-5%, all lattice matched to Ge, was fabricated. The devices exhibited low dark current densities with high collection efficiencies as required for photovoltaics. By measuring the photoresponse, tunable band gaps ranging from 0.85 eV to 1.02 eV were observed.
ContributorsBeeler, Richard (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2012
Description
This thesis describes the fabrication of several new classes of Ge1-x-ySixSny materials with the required compositions and crystal quality to engineer the band gaps above and below that of elemental Ge (0.8 eV) in the near IR. The work initially focused on Ge1-x-ySixSny (1-5% Sn, 4-20% Si) materials grown on Ge(100) via gas-source epitaxy of Ge4H10, Si4H10 and SnD4. Both intrinsic and doped layers were produced with defect-free microstructure and viable thickness, allowing the fabrication of high-performance photodetectors. These exhibited low ideality factors, state-of-the-art dark current densities and adjustable absorption edges between 0.87 and 1.03 eV, indicating that the band gaps span a significant range above that of Ge. Next Sn-rich Ge1-x-ySixSny alloys (2-4% Si and 4-10% Sn) were fabricated directly on Si and were found to show significant optical emission using photoluminescence measurements, indicating that the alloys have direct band gaps below that of pure Ge in the range of 0.7-0.55 eV. A series of Sn-rich Ge1-x-ySixSny analogues (y>x) with fixed 3-4% Si content and progressively increasing Sn content in the 4-10% range were then grown on Ge buffered Si platforms for the purpose of improving the material's crystal quality. The films in this case exhibited lower defect densities than those grown on Si, allowing a meaningful study of both the direct and indirect gaps. The results show that the separation of the direct and indirect edges can be made smaller than in Ge even for non-negligible 3-4% Si content, confirming that with a suitable choice of Sn compositions the ternary Ge1-x-ySixSny reproduces all features of the electronic structure of binary Ge1-ySny, including the sought-after indirect-to-direct gap cross over. The above synthesis of optical quality Ge1-x-ySixSny on virtual Ge was made possible by the development of high quality Ge-on-Si buffers via chemical vapor deposition of Ge4H10. The resultant films exhibited structural and electrical properties significantly improved relative to state-of-the-art results obtained using conventional approaches. It was found that pure Ge4H10 facilitates the control of residual doping and enables p-i-n devices whose dark currents are not entirely determined by defects and whose zero-bias collection efficiencies are higher than those obtained from samples fabricated using alternative Ge-on-Si approaches.
ContributorsXu, Chi (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Drucker, Jeffrey (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2013
Description
Monitoring of air pollutants is critical for many applications and studies. In
order to access air pollutants with high spatial and temporal resolutions, it is
necessary to develop an affordable, small size and weight, low power, high
sensitivity and selectivity, and wireless enable device that can provide real time
monitoring of air pollutants. Three different kind of such devices are presented, they
are targeting environmental pollutants such as volatile organic components (VOCs),
nitrogen dioxide (NO2) and ozone. These devices employ innovative detection
methods, such as quartz crystal tuning fork coated with molecularly imprinted
polymer and chemical reaction induced color change colorimetric sensing. These
portable devices are validated using the gold standards in the laboratory, and their
functionality and capability are proved during the field tests, make them great tools
for various air quality monitoring applications.
order to access air pollutants with high spatial and temporal resolutions, it is
necessary to develop an affordable, small size and weight, low power, high
sensitivity and selectivity, and wireless enable device that can provide real time
monitoring of air pollutants. Three different kind of such devices are presented, they
are targeting environmental pollutants such as volatile organic components (VOCs),
nitrogen dioxide (NO2) and ozone. These devices employ innovative detection
methods, such as quartz crystal tuning fork coated with molecularly imprinted
polymer and chemical reaction induced color change colorimetric sensing. These
portable devices are validated using the gold standards in the laboratory, and their
functionality and capability are proved during the field tests, make them great tools
for various air quality monitoring applications.
ContributorsChen, Cheng, Ph.D (Author) / Tao, Nongjian (Thesis advisor) / Kiaei, Sayfe (Committee member) / Zhang, Yanchao (Committee member) / Tsow, Tsing (Committee member) / Arizona State University (Publisher)
Created2014
Description
Hydrogenases catalyze the interconversion of protons, electrons, and hydrogen according to the reaction: 2H+ + 2e- <-> H2 while using only earth abundant metals, namely nickel and iron for catalysis. The enzymatic turnover of Clostridium acetobutylicum [FeFe]-hydrogenase has been investigated through the use of electrochemical and scanning probe techniques. Scanning tunneling microscopy (STM) imaging revealed sub-monolayer surface coverage. Cyclic voltammetry yielded a catalytic, cathodic hydrogen production signal similar to that observed for a platinum electrode. From the direct observation of single enzymes and the macroscopic electrochemical measurements obtained from the same electrode, the apparent turnover frequency (TOF) per single enzyme molecule as a function of potential was determined. The TOF at 0.7 V vs. Ag/AgCl for the four SAMs yielded a decay constant for electronic coupling (β) through the SAM of ~ 0.82 Å -1, in excellent agreement with published values for similar SAMs. One mechanism used by plants to protect against damage is called nonphotochemical quenching (NPQ). Triggered by low pH in the thylakoid lumen, NPQ leads to conversion of excess excitation energy in the antenna system to heat before it can initiate production of harmful chemical species by photosynthetic reaction centers. Here a synthetic hexad molecule that functionally mimics the role of the antenna in NPQ is described. When the hexad is dissolved in an organic solvent, five zinc porphyrin antenna moieties absorb light, exchange excitation energy, and ultimately decay by normal photophysical processes. However, when acid is added, a pH-sensitive dye moiety is converted to a form that rapidly quenches the first excited singlet states of all five porphyrins, converting the excitation energy to heat and rendering the porphyrins kinetically incompetent to perform useful photochemistry. Charge transport was also studied in single-molecule junctions formed with a 1,7-pyrrolidine-substituted 3,4,9,10-Perylenetetracarboxylic diimide (PTCDI) molecule. A reduction in the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbitals energy gap due to the electronic properties of the substituents is seen when compared to an unsubstituted-PTCDI. The small HOMO-LUMO energy gap allows for switching between electron- and hole-dominated charge transport with a gate voltage, thus demonstrating a single-molecule ambipolar field effect transistor.
ContributorsMadden, Christopher (Author) / Moore, Thomas A. (Thesis advisor) / Jones, Anne (Committee member) / Tao, Nongjian (Committee member) / Arizona State University (Publisher)
Created2012
Description
Studying charge transport through single molecules tethered between two metal electrodes is of fundamental importance in molecular electronics. Over the years, a variety of methods have been developed in attempts of performing such measurements. However, the limitation of these techniques is still one of the factors that prohibit one from gaining a thorough understanding of single molecule junctions. Firstly, the time resolution of experiments is typically limited to milli to microseconds, while molecular dynamics simulations are carried out on the time scale of pico to nanoseconds. A huge gap therefore persists between the theory and the experiments. This thesis demonstrates a nanosecond scale measurement of the gold atomic contact breakdown process. A combined setup of DC and AC circuits is employed, where the AC circuit reveals interesting observations in nanosecond scale not previously seen using conventional DC circuits. The breakdown time of gold atomic contacts is determined to be faster than 0.1 ns and subtle atomic events are observed within nanoseconds. Furthermore, a new method based on the scanning tunneling microscope break junction (STM-BJ) technique is developed to rapidly record thousands of I-V curves from repeatedly formed single molecule junctions. 2-dimensional I-V and conductance-voltage (G-V) histograms constructed using the acquired data allow for more meaningful statistical analysis to single molecule I-V characteristics. The bias voltage adds an additional dimension to the conventional single molecule conductance measurement. This method also allows one to perform transition voltage spectra (TVS) for individual junctions and to study the correlation between the conductance and the tunneling barrier height. The variation of measured conductance values is found to be primarily determined by the poorly defined contact geometry between the molecule and metal electrodes, rather than the tunnel barrier height. In addition, the rapid I-V technique is also found useful in studying thermoelectric effect in single molecule junctions. When applying a temperature gradient between the STM tip and substrate in air, the offset current at zero bias in the I-V characteristics is a measure of thermoelectric current. The rapid I-V technique allows for statistical analysis of such offset current at different temperature gradients and thus the Seebeck coefficient of single molecule junctions is measured. Combining with single molecule TVS, the Seebeck coefficient is also found to be a measure of tunnel barrier height.
ContributorsGuo, Shaoyin (Author) / Tao, Nongjian (Thesis advisor) / Bennett, Peter (Committee member) / Ning, Cun-Zheng (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2012
Description
In today's world there is a great need for sensing methods as tools to provide critical information to solve today's problems in security applications. Real time detection of trace chemicals, such as explosives, in a complex environment containing various interferents using a portable device that can be reliably deployed in a field has been a difficult challenge. A hybrid nanosensor based on the electrochemical reduction of trinitrotoluene (TNT) and the interaction of the reduction products with conducting polymer nanojunctions in an ionic liquid was fabricated. The sensor simultaneously measures the electrochemical current from the reduction of TNT and the conductance change of the polymer nanojunction caused from the reduction product. The hybrid detection mechanism, together with the unique selective preconcentration capability of the ionic liquid, provides a selective, fast, and sensitive detection of TNT. The sensor, in its current form, is capable of detecting parts per trillion level TNT in the presence of various interferents within a few minutes. A novel hybrid electrochemical-colorimetric (EC-C) sensing platform was also designed and fabricated to meet these challenges. The hybrid sensor is based on electrochemical reactions of trace explosives, colorimetric detection of the reaction products, and unique properties of the explosives in an ionic liquid (IL). This approach affords not only increased sensitivity but also selectivity as evident from the demonstrated null rate of false positives and low detection limits. Using an inexpensive webcam a detection limit of part per billion in volume (ppbV) has been achieved and demonstrated selective detection of explosives in the presence of common interferences (perfumes, mouth wash, cleaners, petroleum products, etc.). The works presented in this dissertation, were published in the Journal of the American Chemical Society (JACS, 2009) and Nano Letters (2010), won first place in the National Defense Research contest in (2009) and has been granted a patent (WO 2010/030874 A1). In addition, other work related to conductive polymer junctions and their sensing capabilities has been published in Applied Physics Letters (2005) and IEEE sensors journal (2008).
ContributorsDiaz Aguilar, Alvaro (Author) / Tao, Nongjian (Thesis advisor) / Tsui, Raymond (Committee member) / Barnaby, Hugh (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2012
Description
The work described in this thesis explores the synthesis of new semiconductors in the Si-Ge-Sn system for application in Si-photonics. Direct gap Ge1-ySny (y=0.12-0.16) alloys with enhanced light emission and absorption are pursued. Monocrystalline layers are grown on Si platforms via epitaxy-driven reactions between Sn- and Ge-hydrides using compositionally graded buffer layers that mitigate lattice mismatch between the epilayer and Si platforms. Prototype p-i-n structures are fabricated and are found to exhibit direct gap electroluminescence and tunable absorption edges between 2200 and 2700 nm indicating applications in LEDs and detectors. Additionally, a low pressure technique is described producing pseudomorphic Ge1-ySny alloys in the compositional range y=0.06-0.17. Synthesis of these materials is achieved at ultra-low temperatures resulting in nearly defect-free films that far exceed the critical thicknesses predicted by thermodynamic considerations, and provide a chemically driven route toward materials with properties typically associated with molecular beam epitaxy.
Silicon incorporation into Ge1-ySny yields a new class of Ge1-x-ySixSny (y>x) ternary alloys using reactions between Ge3H8, Si4H10, and SnD4. These materials contain small amounts of Si (x=0.05-0.08) and Sn contents of y=0.1-0.15. Photoluminescence studies indicate an intensity enhancement relative to materials with lower Sn contents (y=0.05-0.09). These materials may serve as thermally robust alternatives to Ge1-ySny for mid-infrared (IR) optoelectronic applications.
An extension of the above work is the discovery of a new class of Ge-like Group III-V-IV hybrids with compositions Ga(As1–xPx)Ge3 (x=0.01-0.90) and (GaP)yGe5–2y related to Ge1-x-ySixSny in structure and properties. These materials are prepared by chemical vapor deposition of reactive Ga-hydrides with P(GeH3)3 and As(GeH3)3 custom precursors as the sources of P, As, and Ge incorporating isolated GaAs and GaP donor-acceptor pairs into diamond-like Ge-based structures. Photoluminescence studies reveal bandgaps in the near-IR and large bowing of the optical behavior relative to linear interpolation of the III-V and Ge end members. Similar materials in the Al-Sb-B-P system are also prepared and characterized. The common theme of the above topics is the design and fabrication of new optoelectronic materials that can be fully compatible with Si-based technologies for expanding the optoelectronic capabilities of Ge into the mid-IR and beyond through compositional tuning of the diamond lattice.
Silicon incorporation into Ge1-ySny yields a new class of Ge1-x-ySixSny (y>x) ternary alloys using reactions between Ge3H8, Si4H10, and SnD4. These materials contain small amounts of Si (x=0.05-0.08) and Sn contents of y=0.1-0.15. Photoluminescence studies indicate an intensity enhancement relative to materials with lower Sn contents (y=0.05-0.09). These materials may serve as thermally robust alternatives to Ge1-ySny for mid-infrared (IR) optoelectronic applications.
An extension of the above work is the discovery of a new class of Ge-like Group III-V-IV hybrids with compositions Ga(As1–xPx)Ge3 (x=0.01-0.90) and (GaP)yGe5–2y related to Ge1-x-ySixSny in structure and properties. These materials are prepared by chemical vapor deposition of reactive Ga-hydrides with P(GeH3)3 and As(GeH3)3 custom precursors as the sources of P, As, and Ge incorporating isolated GaAs and GaP donor-acceptor pairs into diamond-like Ge-based structures. Photoluminescence studies reveal bandgaps in the near-IR and large bowing of the optical behavior relative to linear interpolation of the III-V and Ge end members. Similar materials in the Al-Sb-B-P system are also prepared and characterized. The common theme of the above topics is the design and fabrication of new optoelectronic materials that can be fully compatible with Si-based technologies for expanding the optoelectronic capabilities of Ge into the mid-IR and beyond through compositional tuning of the diamond lattice.
ContributorsWallace, Patrick Michael (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Committee member) / Trovitch, Ryan (Committee member) / Arizona State University (Publisher)
Created2018