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- All Subjects: Materials Science
- Creators: Alford, Terry L.
- Creators: Adams, James
Description
As the 3rd generation solar cell, quantum dot solar cells are expected to outperform the first 2 generations with higher efficiency and lower manufacture cost. Currently the main problems for QD cells are the low conversion efficiency and stability. This work is trying to improve the reliability as well as the device performance by inserting an interlayer between the metal cathode and the active layer. Titanium oxide and a novel nitrogen doped titanium oxide were compared and TiOxNy capped device shown a superior performance and stability to TiOx capped one. A unique light anneal effect on the interfacial layer was discovered first time and proved to be the trigger of the enhancement of both device reliability and efficiency. The efficiency was improved by 300% and the device can retain 73.1% of the efficiency with TiOxNy when normal device completely failed after kept for long time. Photoluminescence indicted an increased charge disassociation rate at TiOxNy interface. External quantum efficiency measurement also inferred a significant performance enhancement in TiOxNy capped device, which resulted in a higher photocurrent. X-ray photoelectron spectrometry was performed to explain the impact of light doping on optical band gap. Atomic force microscopy illustrated the effect of light anneal on quantum dot polymer surface. The particle size is increased and the surface composition is changed after irradiation. The mechanism for performance improvement via a TiOx based interlayer was discussed based on a trap filling model. Then Tunneling AFM was performed to further confirm the reliability of interlayer capped organic photovoltaic devices. As a powerful tool based on SPM technique, tunneling AFM was able to explain the reason for low efficiency in non-capped inverted organic photovoltaic devices. The local injection properties as well as the correspondent topography were compared in organic solar cells with or without TiOx interlayer. The current-voltage characteristics were also tested at a single interested point. A severe short-circuit was discovered in non capped devices and a slight reverse bias leakage current was also revealed in TiOx capped device though tunneling AFM results. The failure reason for low stability in normal devices was also discussed comparing to capped devices.
ContributorsYu, Jialin (Author) / Jabbour, Ghassan E. (Thesis advisor) / Alford, Terry L. (Thesis advisor) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2011
Description
Silicon nanowires were grown epitaxially on Si (100) and (111) surfaces using the Vapor-Liquid-Solid (VLS) mechanism under both thermal and plasma enhanced growth conditions. Nanowire morphology was investigated as a function of temperature, time, disilane partial pressure and substrate preparation. Silicon nanowires synthesized in low temperature plasma typically curved compared to the linear nanowires grown under simple thermal conditions. The nanowires tended bend more with increasing disilane partial gas pressure up to 25 x10-3 mTorr. The nanowire curvature measured geometrically is correlated with the shift of the main silicon peak obtained in Raman spectroscopy. A mechanistic hypothesis was proposed to explain the bending during plasma activated growth. Additional driving forces related to electrostatic and Van der Waals forces were also discussed. Deduced from a systematic variation of a three-step experimental protocol, the mechanism for bending was associated with asymmetric deposition rate along the outer and inner wall of nanowire. The conditions leading to nanowire branching were also examined using a two-step growth process. Branching morphologies were examined as a function of plasma powers between 1.5 W and 3.5 W. Post-annealing thermal and plasma-assisted treatments in hydrogen were compared to understand the influences in the absence of an external silicon source (otherwise supplied by disilane). Longer and thicker nanowires were associated with longer annealing times due to an Ostwald-like ripening effect. The roles of surface diffusion, gas diffusion, etching and deposition rates were examined.
ContributorsJoun, Hee-Joung (Author) / Petuskey, William T. (Thesis advisor) / Drucker, Jeff (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2011
Description
Amorphous oxide semiconductors are promising new materials for various optoelectronic applications. In this study, improved electrical and optical properties upon thermal and microwave processing of mixed-oxide semiconductors are reported. First, arsenic-doped silicon was used as a model system to understand susceptor-assisted microwave annealing. Mixed oxide semiconductor films of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) were deposited by room-temperature RF sputtering on flexible polymer substrates. Thermal annealing in different environments - air, vacuum and oxygen was done. Electrical and optical characterization was carried out before and after annealing. The degree of reversal in the degradation in electrical properties of the thin films upon annealing in oxygen was assessed by subjecting samples to subsequent vacuum anneals. To further increase the conductivity of the IGZO films, Ag layers of various thicknesses were embedded between two IGZO layers. Optical performance of the multilayer structures was improved by susceptor-assisted microwave annealing and furnace-annealing in oxygen environment without compromising on their electrical conductivity. The post-processing of the films in different environments was used to develop an understanding of mechanisms of carrier generation, transport and optical absorption. This study establishes IGZO as a viable transparent conductor, which can be deposited at room-temperature and processed by thermal and microwave annealing to improve electrical and optical performance for applications in flexible electronics and optoelectronics.
ContributorsGadre, Mandar (Author) / Alford, Terry L. (Thesis advisor) / Schroder, Dieter (Committee member) / Krause, Stephen (Committee member) / Theodore, David (Committee member) / Arizona State University (Publisher)
Created2011
Description
Ge1-ySny alloys represent a new class of photonic materials for integrated optoelectronics on Si. In this work, the electrical and optical properties of Ge1-ySny alloy films grown on Si, with concentrations in the range 0 ≤ y ≤ 0.04, are studied via a variety of methods. The first microelectronic devices from GeSn films were fabricated using newly developed CMOS-compatible protocols, and the devices were characterized with respect to their electrical properties and optical response. The detectors were found to have a detection range that extends into the near-IR, and the detection edge is found to shift to longer wavelengths with increasing Sn content, mainly due to the compositional dependence of the direct band gap E0. With only 2 % Sn, all of the telecommunication bands are covered by a single detector. Room temperature photoluminescence was observed from GeSn films with Sn content up to 4 %. The peak wavelength of the emission was found to shift to lower energies with increasing Sn content, corresponding to the decrease in the direct band gap E0 of the material. An additional peak in the spectrum was assigned to the indirect band gap. The separation between the direct and indirect peaks was found to decrease with increasing Sn concentration, as expected. Electroluminescence was also observed from Ge/Si and Ge0.98Sn0.02 photodiodes under forward bias, and the luminescence spectra were found to match well with the observed photoluminescence spectra. A theoretical expression was developed for the luminescence due to the direct band gap and fit to the data.
ContributorsMathews, Jay (Author) / Menéndez, Jose (Thesis advisor) / Kouvetakis, John (Thesis advisor) / Drucker, Jeffery (Committee member) / Chizmeshya, Andrew (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2011
Description
This thesis discusses the use of low temperature microwave anneal as an alternative technique to recrystallize materials damaged or amorphized due to implantation techniques. The work focuses on the annealing of high-Z doped Si wafers that are incapable of attaining high temperatures required for recrystallizing the damaged implanted layers by microwave absorption The increasing necessity for quicker and more efficient processing techniques motivates study of the use of a single frequency applicator microwave cavity along with a Fe2O3 infused SiC-alumina susceptor/applicator as an alternative post implantation process. Arsenic implanted Si samples of different dopant concentrations and implantation energies were studied pre and post microwave annealing. A set of as-implanted Si samples were also used to assess the effect of inactive dopants against presence of electrically active dopants on the recrystallization mechanisms. The extent of damage repair and Si recrystallization of the damage caused by arsenic and Si implantation of Si is determined by cross-section transmission electron microscopy and Raman spectroscopy. Dopant activation is evaluated for the As implanted Si by sheet resistance measurements. For the same, secondary ion mass spectroscopy analysis is used to compare the extent of diffusion that results from such microwave annealing with that experienced when using conventional rapid thermal annealing (RTA). Results show that compared to susceptor assisted microwave annealing, RTA caused undesired dopant diffusion. The SiC-alumina susceptor plays a predominant role in supplying heat to the Si substrate, and acts as an assistor that helps a high-Z dopant like arsenic to absorb the microwave energy using a microwave loss mechanism which is a combination of ionic and dipole losses. Comparisons of annealing of the samples were done with and without the use of the susceptor, and confirm the role played by the susceptor, since the samples donot recrystallize when the surface heating mechanism provided by the susceptor is not incorporated. Variable frequency microwave annealing was also performed over the as-implanted Si samples for durations and temperatures higher than the single frequency microwave anneal, but only partial recrystallization of the damaged layer was achieved.
ContributorsVemuri, Rajitha (Author) / Alford, Terry L. (Thesis advisor) / Theodore, David (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
Description
Programmable metallization cell (PMC) technology is based on an electrochemical phenomenon in which a metallic electrodeposit can be grown or dissolved between two electrodes depending on the voltage applied between them. Devices based on this phenomenon exhibit a unique, self-healing property, as a broken metallic structure can be healed by applying an appropriate voltage between the two broken ends. This work explores methods of fabricating interconnects and switches based on PMC technology on flexible substrates. The objective was the evaluation of the feasibility of using this technology in flexible electronics applications in which reliability is a primary concern. The re-healable property of the interconnect is characterized for the silver doped germanium selenide (Ag-Ge-Se) solid electrolyte system. This property was evaluated by measuring the resistances of the healed interconnect structures and comparing these to the resistances of the unbroken structures. The reliability of the interconnects in both unbroken and healed states is studied by investigating the resistances of the structures to DC voltages, AC voltages and different temperatures as a function of time. This work also explores replacing silver with copper for these interconnects to enhance their reliability. A model for PMC-based switches on flexible substrates is proposed and compared to the observed device behavior with the objective of developing a formal design methodology for these devices. The switches were subjected to voltage sweeps and their resistance was investigated as a function of sweep voltage. The resistance of the switches as a function of voltage pulse magnitude when placed in series with a resistance was also investigated. A model was then developed to explain the behavior of these devices. All observations were based on statistical measurements to account for random errors. The results of this work demonstrate that solid electrolyte based interconnects display self-healing capability, which depends on the applied healing voltage and the current limit. However, they fail at lower current densities than metal interconnects due to an ion-drift induced failure mechanism. The results on the PMC based switches demonstrate that a model comprising a Schottky diode in parallel with a variable resistor predicts the behavior of the device.
ContributorsBaliga, Sunil Ravindranath (Author) / Kozicki, Michael N (Thesis advisor) / Schroder, Dieter K. (Committee member) / Chae, Junseok (Committee member) / Alford, Terry L. (Committee member) / Arizona State University (Publisher)
Created2011
Description
This thesis focuses on the theoretical work done to determine thermodynamic properties of a chalcopyrite thin-film material for use as a photovoltaic material in a tandem device. The material of main focus here is ZnGeAs2, which was chosen for the relative abundance of constituents, favorable photovoltaic properties, and good lattice matching with ZnSnP2, the other component in this tandem device. This work is divided into two main chapters, which will cover: calculations and method to determine the formation energy and abundance of native point defects, and a model to calculate the vapor pressure over a ternary material from first-principles. The purpose of this work is to guide experimental work being done in tandem to synthesize ZnGeAs2 in thin-film form with high enough quality such that it can be used as a photovoltaic. Since properties of photovoltaic depend greatly on defect concentrations and film quality, a theoretical understanding of how laboratory conditions affect these properties is very valuable. The work done here is from first-principles and utilizes density functional theory using the local density approximation. Results from the native point defect study show that the zinc vacancy (VZn) and the germanium antisite (GeZn) are the more prominent defects; which most likely produce non-stoichiometric films. The vapor pressure model for a ternary system is validated using known vapor pressure for monatomic and binary test systems. With a valid ternary system vapor pressure model, results show there is a kinetic barrier to decomposition for ZnGeAs2.
ContributorsTucker, Jon R (Author) / Van Schilfgaarde, Mark (Thesis advisor) / Newman, Nathan (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2011
Description
Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization compatible with gallium arsenide (GaAs) was required in the development of high-powered radio frequency (RF) compound semiconductor devices operating at higher current densities and elevated temperatures. Gold-based metallization was implemented on GaAs devices because it uniquely forms a very low resistance ohmic contact and gold interconnects have superior electrical and thermal conductivity properties. Gold (Au) was also believed to have improved resistance to electromigration due to its higher melting temperature, yet electromigration reliability data on passivated Au interconnects is scarce and inadequate in the literature. Therefore, the objective of this research was to characterize the electromigration lifetimes of passivated Au interconnects under precisely controlled stress conditions with statistically relevant quantities to obtain accurate model parameters essential for extrapolation to normal operational conditions. This research objective was accomplished through measurement of electromigration lifetimes of large quantities of passivated electroplated Au interconnects utilizing high-resolution in-situ resistance monitoring equipment. Application of moderate accelerated stress conditions with a current density limited to 2 MA/cm2 and oven temperatures in the range of 300°C to 375°C avoided electrical overstress and severe Joule-heated temperature gradients. Temperature coefficients of resistance (TCRs) were measured to determine accurate Joule-heated Au interconnect film temperatures. A failure criterion of 50% resistance degradation was selected to prevent thermal runaway and catastrophic metal ruptures that are problematic of open circuit failure tests. Test structure design was optimized to reduce resistance variation and facilitate failure analysis. Characterization of the Au microstructure yielded a median grain size of 0.91 ìm. All Au lifetime distributions followed log-normal distributions and Black's model was found to be applicable. An activation energy of 0.80 ± 0.05 eV was measured from constant current electromigration tests at multiple temperatures. A current density exponent of 1.91 was extracted from multiple current densities at a constant temperature. Electromigration-induced void morphology along with these model parameters indicated grain boundary diffusion is dominant and the void nucleation mechanism controlled the failure time.
ContributorsKilgore, Stephen (Author) / Adams, James (Thesis advisor) / Schroder, Dieter (Thesis advisor) / Krause, Stephen (Committee member) / Gaw, Craig (Committee member) / Arizona State University (Publisher)
Created2013
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