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- All Subjects: Chemistry
- Genre: Doctoral Dissertation
- Creators: Chizmeshya, Andrew
Description
Natural photosynthesis features a complex biophysical/chemical process that requires sunlight to produce energy rich products. It is one of the most important processes responsible for the appearance and sustainability of life on earth. The first part of the thesis focuses on understanding the mechanisms involved in regulation of light harvesting, which is necessary to balance the absorption and utilization of light energy and in that way reduce the effect caused by photooxidative damage. In photosynthesis, carotenoids are responsible not only for collection of light, but also play a major role in protecting the photosynthetic system. To investigate the role of carotenoids in the quenching of the excited state of cyclic tetrapyrroles, two sets of dyads were studied. Both sets of dyads contain zinc phthalocyanine (Pc) covalently attached to carotenoids of varying conjugation lengths. In the first set of dyads, carotenoids were attached to the phthalocyanine via amide linkage. This set of dyads serves as a good model for understanding the molecular "gear-shift" mechanism, where the addition of one double bond can turn the carotenoid from a nonquencher to a very strong quencher of the excited state of a tetrapyrrole. In the second set of dyads, carotenoids were attached to phthalocyanine via a phenyl amino group. Two independent studies were performed on these dyads: femtosecond transient absorption and steady state fluorescence induced by two-photon excitation. In the transient absorption study it was observed that there is an instantaneous population of the carotenoid S1 state after Pc excitation, while two-photon excitation of the optically forbidden carotenoid S1 state shows 1Pc population. Both observations provide a strong indication of the existence of a shared excitonic state between carotenoid and Pc. Similar results were observed in LHC II complexes in plants, supporting the role of such interactions in photosynthetic down regulation. In the second chapter we describe the synthesis of porphyrin dyes functionalized with carboxylate and phosphonate anchoring groups to be used in the construction of photoelectrochemical cells containing a porphyrin-IrO2·nH2O complex immobilized on a TiO2 electrode. The research presented here is a step in the development of high potential porphyrin-metal oxide complexes to be used in the photooxidation of water. The last chapter focuses on developing synthetic strategies for the construction of an artificial antenna system consisting of porphyrin-silver nanoparticle conjugates, linked by DNA of varied length to study the distance dependence of the interaction between nanoparticles and the porphyrin chromophore. Preliminary studies indicate that at the distance of about 7-10 nm between porphyrin and silver nanoparticle is where the porphyrin absorption leading to fluorescence shows maximum enhancement. These new hybrid constructs will be helpful for designing efficient light harvesting systems.
ContributorsPillai, Smitha (Author) / Moore, Ana (Thesis advisor) / Moore, Thomas (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2011
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
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
[FeFe]-hydrogenases are enzymes for the reduction of protons to hydrogen. They rely on only the earth abundant first-row transition metal iron at their active site (H cluster). In recent years, a multitude of diiron mimics of hydrogenases have been synthesized, but none of them catalyzes hydrogen production with the same exquisite combination of high turnover frequency and low activation energy as the enzymes. Generally, model complexes fail to include one or both of two features essential to the natural enzyme: an intricate array of outer coordination sphere contacts that constrain the coordination geometry to attain a catalytically optimal conformation, and the redox non-innocence of accessory [FeS] clusters found at or near the hydrogen-activating site. The work presented herein describes the synthesis and electrocatalytic characterization of iron-dithiolate models designed to incorporate these features. First, synthetic strategies are developed for constructing peptides with artificial metal-binding motifs, such as 1,3-dithiolate and phosphines, which are utilized to append diiron-polycarbonyl clusters onto a peptide. The phosphine-functionalized peptides are shown to be better electrocatalysts for proton reduction in water/acetonitrile mixtures than in neat acetonitrile. Second, we report the impact of redox non-innocent ligands on the electrocatalytic properties of two types of [FeFe]-hydrogenase models: dinuclear and mononuclear iron complexes. The bidentate, redox non-innocent α-diimine ligands (N-N), 2,2'-bipyridine and 2,2' bipyrimidine, are used to create complexes with the general formula (μ-SRS)Fe2(CO)4(N-N), new members of the well known family of asymmetric diiron carbonyls. While the 2,2'-bipyridine derivatives can act as electrocatalysts for proton reduction, surprisingly, the 2,2'-bipyrimidine analogues are found to be inactive towards catalysis. Electrochemical investigation of two related Fe(II) complexes, (bdt)Fe(CO)P2 for bdt = benzene-1,2-dithiolate and P2 = 1,1'-diphenylphosphinoferrocene or methyl-2-{bis(diphenylphosphinomethylamino}acetate, related to the distal iron in [FeFe]-hydrogenase show that these complexes catalyze the reduction of protons under mild conditions. However, their reactivities toward the external ligand CO are distinguished by gross geometrical differences.
ContributorsRoy, Souvik (Author) / Jones, Anne K (Thesis advisor) / Moore, Thomas (Committee member) / Trovitch, Ryan (Committee member) / Arizona State University (Publisher)
Created2013
Description
Developing a system capable of using solar energy to drive the conversion of an abundant and available precursor to fuel would profoundly impact humanity's energy use and thereby the condition of the global ecosystem. Such is the goal of artificial photosynthesis: to convert water to hydrogen using solar radiation as the sole energy input and ideally do so with the use of low cost, abundant materials. Constructing photoelectrochemical cells incorporating photoanodes structurally reminiscent of those used in dye sensitized photovoltaic solar cells presents one approach to establishing an artificial photosynthetic system. The work presented herein describes the production, integration, and study of water oxidation catalysts, molecular dyes, and metal oxide based photoelectrodes carried out in the pursuit of developing solar water splitting systems.
ContributorsSherman, Benjamin D (Author) / Moore, Thomas (Thesis advisor) / Moore, Ana (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2013
Description
This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached.
ContributorsAnsari, Younes (Author) / Angell, Charles A (Thesis advisor) / Richert, Ranko (Committee member) / Chizmeshya, Andrew (Committee member) / Wolf, George (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
Exploration of long-range conductance in non-redox-active proteins at the single molecule scale is aided by the development of innovative, tailor-made quantitative data analysis techniques. This thesis details the rationale behind the proposed approaches, the steps taken to design and implement every method, and the validation of the methodologies using appropriate experiments, benchmarks, and rigorous statistical data analysis. The first chapter conducts a thorough literature review, sets the stage for the subsequent investigation, and underscores the importance of the research questions addressed in this thesis. The second chapter describes the solvent effects on the electronic conductance of a series of Consensus Tetratricopeptide Repeat proteins (CTPR) measured with Scanning Tunneling Microscopy (STM). The study reveals a reversible reduction in electronic conductance when water (H2O) is replaced with heavy water (D2O) due to a ~6-fold decrease in the carrier diffusion constant as proteins become solvated by D2O. Similar observations are made in a ~7 nm long tryptophan zipper protein, while a phenylalanine zipper protein of comparable length remains unchanged in D2O, highlighting the critical role of aromatic residues in proteins lacking redox cofactors. As an extension to this finding, the third chapter describes the development of a machine-learning model to detect the presence of a protein and identify essential features helping in the detection. For this purpose, a solid-state device was engineered to measure the conductance of CTPR-16 protein wires. This approach addresses the limitations in characterizing the STM gap, enables the collection of stable current vs. time data, and provides a statistical understanding of the electronic transport through a protein. The final chapter investigates real-time changes in conductance in response to protein conformation alterations. A deoxyribonucleic acid (DNA) polymerase Φ29 was chosen for its potential utility as a single-molecule DNA sequencing device. The modified enzyme was bound to electrodes functionalized with streptavidin. Φ29 connected by one biotinylated contact and a second nonspecific contact showed rapid small fluctuations in current when activated. Signals were greatly enhanced with two specific contacts. Features in the distributions of conductance increased by a factor of 2 or more over the open-to-closed conformational transition of the polymerase.
ContributorsMukherjee, Sohini (Author) / Lindsay, Stuart (Thesis advisor) / Moore, Thomas (Committee member) / Qing, Quan (Committee member) / Arizona State University (Publisher)
Created2023
Description
Optoelectronic and microelectronic applications of germanium-based materials have received considerable research interest in recent years. A novel method for Ge on Si heteroepitaxy required for such applications was developed via molecular epitaxy of Ge5H12. Next, As(GeH3)3, As(SiH3)3, SbD3, S(GeH3)2 and S(SiH3)2 molecular sources were utilized in degenerate n-type doping of Ge. The epitaxial Ge films produced in this work incorporate donor atoms at concentrations above the thermodynamic equilibrium limits. The donors are nearly fully activated, and led to films with lowest resistivity values thus far reported.
Band engineering of Ge was achieved by alloying with Sn. Epitaxy of the alloy layers was conducted on virtual Ge substrates, and made use of the germanium hydrides Ge2H6 and Ge3H8, and the Sn source SnD4. These films exhibit stronger emission than equivalent material deposited directly on Si, and the contributions from the direct and indirect edges can be separated. The indirect-direct crossover composition for Ge1-ySny alloys was determined by photoluminescence (PL). By n-type doping of the Ge1-ySny alloys via P(GeH3)3, P(SiH3)3 and As(SiH3)3, it was possible to enhance photoexcited emission by more than an order-of-magnitude.
The above techniques for deposition of direct gap Ge1-ySny alloys and doping of Ge were combined with p-type doping methods for Ge1-ySny using B2H6 to fabricate pin heterostructure diodes with active layer compositions up to y=0.137. These represent the first direct gap light emitting diodes made from group IV materials. The effect of the single defected n-i¬ interface in a n-Ge/i-Ge1-ySny/p-Ge1-zSnz architecture on electroluminescence (EL) was studied. This led to lattice engineering of the n-type contact layer to produce diodes of n-Ge1-xSnx/i-Ge1-ySny/p-Ge1-zSnz architecture which are devoid of interface defects and therefore exhibit more efficient EL than the previous design. Finally, n-Ge1-ySny/p-Ge1-zSnz pn junction devices were synthesized with varying composition and doping parameters to investigate the effect of these properties on EL.
Band engineering of Ge was achieved by alloying with Sn. Epitaxy of the alloy layers was conducted on virtual Ge substrates, and made use of the germanium hydrides Ge2H6 and Ge3H8, and the Sn source SnD4. These films exhibit stronger emission than equivalent material deposited directly on Si, and the contributions from the direct and indirect edges can be separated. The indirect-direct crossover composition for Ge1-ySny alloys was determined by photoluminescence (PL). By n-type doping of the Ge1-ySny alloys via P(GeH3)3, P(SiH3)3 and As(SiH3)3, it was possible to enhance photoexcited emission by more than an order-of-magnitude.
The above techniques for deposition of direct gap Ge1-ySny alloys and doping of Ge were combined with p-type doping methods for Ge1-ySny using B2H6 to fabricate pin heterostructure diodes with active layer compositions up to y=0.137. These represent the first direct gap light emitting diodes made from group IV materials. The effect of the single defected n-i¬ interface in a n-Ge/i-Ge1-ySny/p-Ge1-zSnz architecture on electroluminescence (EL) was studied. This led to lattice engineering of the n-type contact layer to produce diodes of n-Ge1-xSnx/i-Ge1-ySny/p-Ge1-zSnz architecture which are devoid of interface defects and therefore exhibit more efficient EL than the previous design. Finally, n-Ge1-ySny/p-Ge1-zSnz pn junction devices were synthesized with varying composition and doping parameters to investigate the effect of these properties on EL.
ContributorsSenaratne, Charutha Lasitha (Author) / Kouvetakis, John (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2016
Description
Transparent conductive oxides (TCO) comprise a class of materials that exhibit unique combination of high transparency in the visible region along with high electrical conductivity. TCOs play an important role as transparent electrodes for optoelectronic devices such as solar cell panels, liquid crystal displays, transparent heat mirrors and organic light emitting devices (OLED). The most commonly used transparent electrodes in optoelectronic applications is indium tin oxide (ITO) due to its low resistivity (~ 10−4 Ω-cm) and high transmittance (~ 80 %). However, the limited supply of indium and the growing demand for ITO make the resulting fabrication costs prohibitive for future industry. Thus, cost factors have promoted the search for inexpensive materials with good electric-optical properties.
The object of this work is to study the structure-property-processing relationship and optimize a suitable transparent electrode with the intent to optimize them for flexible optoelectronics applications. The work focuses on improved processing of the mixed oxide (indium gallium zinc oxide, IGZO) thin films for superior optical and electrical properties. The study focuses on two different methods of post-deposition annealing-microwave and conventional. The microwave annealing was seen to have the dual advantage of reduced time and lower temperature, as compared to conventional annealing. Another work focuses on an indium free transparent composite electrode (TCE) where a very thin metal layer is inserted between the two TCO layers. A novel Nb2O5/Ag/Nb2O5 multilayered structure can exhibit better electrical and optical properties than a single layered TCO thin film. The focus for low cost alternative leads to a TiO2/metal/TiO2 based TCE. A systematic study was done to understand the effect of metal thickness and substituting different metals (Ag, Cu or Au) on the opto-electrical properties of the TCEs. The TiO2/Ag/TiO2 with mid Ag thickness 9.5 nm has been optimized to have a sheet resistance of 5.7 Ohm/sq. average optical transmittance of 90 % at 550 nm and figure of merit with 61.4 ×10-3 Ω-1. The TCEs showed improved optical and electrical properties when annealed in forming gas and vacuum. These dielectric/metal/dielectric multilayer TCEs have lower total thickness and are more efficient than a single-layer ITO film.
The object of this work is to study the structure-property-processing relationship and optimize a suitable transparent electrode with the intent to optimize them for flexible optoelectronics applications. The work focuses on improved processing of the mixed oxide (indium gallium zinc oxide, IGZO) thin films for superior optical and electrical properties. The study focuses on two different methods of post-deposition annealing-microwave and conventional. The microwave annealing was seen to have the dual advantage of reduced time and lower temperature, as compared to conventional annealing. Another work focuses on an indium free transparent composite electrode (TCE) where a very thin metal layer is inserted between the two TCO layers. A novel Nb2O5/Ag/Nb2O5 multilayered structure can exhibit better electrical and optical properties than a single layered TCO thin film. The focus for low cost alternative leads to a TiO2/metal/TiO2 based TCE. A systematic study was done to understand the effect of metal thickness and substituting different metals (Ag, Cu or Au) on the opto-electrical properties of the TCEs. The TiO2/Ag/TiO2 with mid Ag thickness 9.5 nm has been optimized to have a sheet resistance of 5.7 Ohm/sq. average optical transmittance of 90 % at 550 nm and figure of merit with 61.4 ×10-3 Ω-1. The TCEs showed improved optical and electrical properties when annealed in forming gas and vacuum. These dielectric/metal/dielectric multilayer TCEs have lower total thickness and are more efficient than a single-layer ITO film.
ContributorsDhar, Aritra (Author) / Alford, Terry L. (Thesis advisor) / Petuskey, William (Thesis advisor) / Krause, Stephen (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2015