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As crystalline silicon solar cells continue to get thinner, the recombination of carriers at the surfaces of the cell plays an ever-important role in controlling the cell efficiency. One tool to minimize surface recombination is field effect passivation from the charges present in the thin films applied on the cell

As crystalline silicon solar cells continue to get thinner, the recombination of carriers at the surfaces of the cell plays an ever-important role in controlling the cell efficiency. One tool to minimize surface recombination is field effect passivation from the charges present in the thin films applied on the cell surfaces. The focus of this work is to understand the properties of charges present in the SiNx films and then to develop a mechanism to manipulate the polarity of charges to either negative or positive based on the end-application. Specific silicon-nitrogen dangling bonds (·Si-N), known as K center defects, are the primary charge trapping defects present in the SiNx films. A custom built corona charging tool was used to externally inject positive or negative charges in the SiNx film. Detailed Capacitance-Voltage (C-V) measurements taken on corona charged SiNx samples confirmed the presence of a net positive or negative charge density, as high as +/- 8 x 1012 cm-2, present in the SiNx film. High-energy (~ 4.9 eV) UV radiation was used to control and neutralize the charges in the SiNx films. Electron-Spin-Resonance (ESR) technique was used to detect and quantify the density of neutral K0 defects that are paramagnetically active. The density of the neutral K0 defects increased after UV treatment and decreased after high temperature annealing and charging treatments. Etch-back C-V measurements on SiNx films showed that the K centers are spread throughout the bulk of the SiNx film and not just near the SiNx-Si interface. It was also shown that the negative injected charges in the SiNx film were stable and present even after 1 year under indoor room-temperature conditions. Lastly, a stack of SiO2/SiNx dielectric layers applicable to standard commercial solar cells was developed using a low temperature (< 400 °C) PECVD process. Excellent surface passivation on FZ and CZ Si substrates for both n- and p-type samples was achieved by manipulating and controlling the charge in SiNx films.
ContributorsSharma, Vivek (Author) / Bowden, Stuart (Thesis advisor) / Schroder, Dieter (Committee member) / Honsberg, Christiana (Committee member) / Roedel, Ronald (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Microwave dielectrics are widely used to make resonators and filters in telecommunication systems. The production of thin films with high dielectric constant and low loss could potentially enable a marked reduction in the size of devices and systems. However, studies of these materials in thin film form are very sparse.

Microwave dielectrics are widely used to make resonators and filters in telecommunication systems. The production of thin films with high dielectric constant and low loss could potentially enable a marked reduction in the size of devices and systems. However, studies of these materials in thin film form are very sparse. In this research, experiments were carried out on practical high-performance dielectrics including ZrTiO4-ZnNb2O6 (ZTZN) and Ba(Co,Zn)1/3Nb2/3O3 (BCZN) with high dielectric constant and low loss tangent. Thin films were deposited by laser ablation on various substrates, with a systematical study of growth conditions like substrate temperature, oxygen pressure and annealing to optimize the film quality, and the compositional, microstructural, optical and electric properties were characterized. The deposited ZTZN films were randomly oriented polycrystalline on Si substrate and textured on MgO substrate with a tetragonal lattice change at elevated temperature. The BCZN films deposited on MgO substrate showed superior film quality relative to that on other substrates, which grow epitaxially with an orientation of (001) // MgO (001) and (100) // MgO (100) when substrate temperature was above 500 oC. In-situ annealing at growth temperature in 200 mTorr oxygen pressure was found to enhance the quality of the films, reducing the peak width of the X-ray Diffraction (XRD) rocking curve to 0.53o and the χmin of channeling Rutherford Backscattering Spectrometry (RBS) to 8.8% when grown at 800oC. Atomic Force Microscopy (AFM) was used to study the topography and found a monotonic decrease in the surface roughness when the growth temperature increased. Optical absorption and transmission measurements were used to determine the energy bandgap and the refractive index respectively. A low-frequency dielectric constant of 34 was measured using a planar interdigital measurement structure. The resistivity of the film is ~3×1010 ohm·cm at room temperature and has an activation energy of thermal activated current of 0.66 eV.
ContributorsLi, You (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Singh, Rakesh (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Carrier lifetime is one of the few parameters which can give information about the low defect densities in today's semiconductors. In principle there is no lower limit to the defect density determined by lifetime measurements. No other technique can easily detect defect densities as low as 10-9 - 10-10 cm-3

Carrier lifetime is one of the few parameters which can give information about the low defect densities in today's semiconductors. In principle there is no lower limit to the defect density determined by lifetime measurements. No other technique can easily detect defect densities as low as 10-9 - 10-10 cm-3 in a simple, contactless room temperature measurement. However in practice, recombination lifetime τr measurements such as photoconductance decay (PCD) and surface photovoltage (SPV) that are widely used for characterization of bulk wafers face serious limitations when applied to thin epitaxial layers, where the layer thickness is smaller than the minority carrier diffusion length Ln. Other methods such as microwave photoconductance decay (µ-PCD), photoluminescence (PL), and frequency-dependent SPV, where the generated excess carriers are confined to the epitaxial layer width by using short excitation wavelengths, require complicated configuration and extensive surface passivation processes that make them time-consuming and not suitable for process screening purposes. Generation lifetime τg, typically measured with pulsed MOS capacitors (MOS-C) as test structures, has been shown to be an eminently suitable technique for characterization of thin epitaxial layers. It is for these reasons that the IC community, largely concerned with unipolar MOS devices, uses lifetime measurements as a "process cleanliness monitor." However when dealing with ultraclean epitaxial wafers, the classic MOS-C technique measures an effective generation lifetime τg eff which is dominated by the surface generation and hence cannot be used for screening impurity densities. I have developed a modified pulsed MOS technique for measuring generation lifetime in ultraclean thin p/p+ epitaxial layers which can be used to detect metallic impurities with densities as low as 10-10 cm-3. The widely used classic version has been shown to be unable to effectively detect such low impurity densities due to the domination of surface generation; whereas, the modified version can be used suitably as a metallic impurity density monitoring tool for such cases.
ContributorsElhami Khorasani, Arash (Author) / Alford, Terry (Thesis advisor) / Goryll, Michael (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of

Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of an OLED are emissive molecules that generate light in response to electrical stimulation. Ideal emitters are efficient, compatible with existing materials, long lived, and produce light predominantly at useful wavelengths. Developing an understanding of the photophysical processes that dictate the luminescent properties of emissive materials is vital to their continued development. Chapter 1 and Chapter 2 provide an introduction to the topics presented and the laboratory methods used to explore them. Chapter 3 discusses a series of tridentate platinum complexes. A synthetic method utilizing microwave irradiation was explored, as well as a study of the effects ligand structure had on the excited state properties. Results and techniques developed in this endeavor were used as a foundation for the work undertaken in later chapters. Chapter 4 introduces a series of tetradentate platinum complexes that share a phenoxy-pyridyl (popy) motif. The new molecular design improved efficiency through increased rigidity and modification of the excited state properties. This class of platinum complexes were markedly more efficient than those presented in Chapter 3, and devices employing a green emitting complex of the series achieved nearly 100% electron-to-photon conversion efficiency in an OLED device. Chapter 5 adapts the ligand structure developed in Chapter 4 to palladium. The resulting complexes exceed reported efficiencies of palladium complexes by an order of magnitude. This chapter also provides the first report of a palladium complex as an emitter in an OLED device. Chapter 6 discusses the continuation of development efforts to include carbazolyl components in the ligand. These complexes possess interesting luminescent properties including ultra-narrow emission and metal assisted delayed fluorescence (MADF) emission.
ContributorsTurner, Eric (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Thin films of ever reducing thickness are used in a plethora of applications and their performance is highly dependent on their microstructure. Computer simulations could then play a vital role in predicting the microstructure of thin films as a function of processing conditions. FACET is one such software tool designed

Thin films of ever reducing thickness are used in a plethora of applications and their performance is highly dependent on their microstructure. Computer simulations could then play a vital role in predicting the microstructure of thin films as a function of processing conditions. FACET is one such software tool designed by our research group to model polycrystalline thin film growth, including texture evolution and grain growth of polycrystalline films in 2D. Several modifications to the original FACET code were done to enhance its usability and accuracy. Simulations of sputtered silver thin films are presented here with FACET 2.0 with qualitative and semi-quantitative comparisons with previously published experimental results. Comparisons of grain size, texture and film thickness between simulations and experiments are presented which describe growth modes due to various deposition factors like flux angle and substrate temperature. These simulations provide reasonable agreement with the experimental data over a diverse range of process parameters. Preliminary experiments in depositions of Silver films are also attempted with varying substrates and thickness in order to generate complementary experimental and simulation studies of microstructure evolution. Overall, based on the comparisons, FACET provides interesting insights into thin film growth processes, and the effects of various deposition conditions on thin film structure and microstructure. Lastly, simple molecular dynamics simulations of deposition on bi-crystals are attempted for gaining insight into texture based grain competition during film growth. These simulations predict texture based grain coarsening mechanisms like twinning and grain boundary migration that have been commonly reported in FCC films.
ContributorsRairkar, Asit (Author) / Adams, James B (Thesis advisor) / Krause, Stephen (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process

Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process focused on identifying materials that do not produce volatile components when exposed to high temperatures and high sulfur pressures. Once the materials were identified and design was completed, the ultra–high vacuum growth system was constructed and tested.

Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back–scattering Spectrometry (RBS), X–Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near–IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural–quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV.
ContributorsWalimbe, Aditya (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Singh, Rakesh (Committee member) / Arizona State University (Publisher)
Created2016
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Description
I studied the properties of novel Co2FeAl0.5Si0.5 (CFAS), ZnGeAs2, and FeS2 (pyrite) thin films for microelectronic applications ranging from spintronic to photovoltaic. CFAS is a half metal with theoretical spin polarization of 100%. I investigated its potential as a spin injector, for spintronic applications, by studying the critical steps involved

I studied the properties of novel Co2FeAl0.5Si0.5 (CFAS), ZnGeAs2, and FeS2 (pyrite) thin films for microelectronic applications ranging from spintronic to photovoltaic. CFAS is a half metal with theoretical spin polarization of 100%. I investigated its potential as a spin injector, for spintronic applications, by studying the critical steps involved in the injection of spin polarized electron populations from tunnel junctions containing CFAS electrodes. Epitaxial CFAS thin films with L21 structure and saturation magnetizations of over 1200 emu/cm3 were produced by optimization of the sputtering growth conditions. Point contact Andreev reflection measurements show that the spin polarization at the CFAS electrode surface exceeds 70%. Analyses of the electrical properties of tunnel junctions with a superconducting Pb counter-electrode indicate that transport through native Al oxide barriers is mostly from direct tunneling, while that through the native CFAS oxide barriers is not. ZnGeAs2 is a semiconductor comprised of only inexpensive and earth-abundant elements. The electronic structure and defect properties are similar in many ways to GaAs. Thus, in theory, efficient solar cells could be made with ZnGeAs2 if similar quality material to that of GaAs could be produced. To understand the thermochemistry and determine the rate limiting steps of ZnGeAs2 thin-film synthesis, the (a) thermal decomposition rate and (b) elemental composition and deposition rate of films were measured. It is concluded that the ZnGeAs2 thin film synthesis is a metastable process with an activation energy of 1.08±0.05 eV for the kinetically-limited decomposition rate and an evaporation coefficient of ~10-3. The thermochemical analysis presented here can be used to predict optimal conditions of ZnGeAs2 physical vapor deposition and thermal processing. Pyrite (FeS2) is another semiconductor that has tremendous potential for use in photovoltaic applications if high quality materials could be made. Here, I present the layer-by-layer growth of single-phase pyrite thin-films on heated substrates using sequential evaporation of Fe under high-vacuum followed by sulfidation at S pressures between 1 mTorr and 1 Torr. High-resolution transmission electron microscopy reveals high-quality, defect-free pyrite grains were produces by this method. It is demonstrated that epitaxial pyrite layer was produced on natural pyrite substrates with this method.
ContributorsVahidi, Mahmoud (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Singh, Rakesh (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Transparent conductive oxides (TCOs) are used as electrodes for a number of optoelectronic devices including solar cells. Because of its superior transparent and conductive properties, indium (In) tin (Sn) oxide (ITO) has long been at the forefront for TCO research activities and high-volume product applications. However, given the

Transparent conductive oxides (TCOs) are used as electrodes for a number of optoelectronic devices including solar cells. Because of its superior transparent and conductive properties, indium (In) tin (Sn) oxide (ITO) has long been at the forefront for TCO research activities and high-volume product applications. However, given the limited supply of In and potential toxicity of Sn-based compounds, attention has shifted to alternative TCOs like ZnO doped with group-III elements such as Ga and Al. Employing a variety of deposition techniques, many research groups are striving to achieve resistivities below 1E-4 ohm-cm with transmittance approaching the theoretical limit over a wide spectral range. In this work, Ga-doped ZnO is deposited using pulsed laser deposition (PLD). Material properties of the films are characterized using a number of techniques. For deposition in oxygen at pressures >1 mTorr, post-deposition annealing in forming gas (FG) is required to improve conductivity. At these higher oxygen pressures, thermodynamic analysis coupled with a study using the Hall effect measurements and photoluminescence spectroscopy suggest that conductivity is limited by oxygen-related acceptor-like defects in the grains that compensate donors, effectively reducing the net carrier concentration and creating scattering centers that reduce electron mobility. Oxygen is also responsible for further suppression of conductivity by forming insulative metal oxide regions at the grain edges and oxygen-related electron traps at the grain boundaries. The hydrogen component in the FG is thought to passivate the intra-grain acceptor-like defects and improve carrier transport across these grain boundaries. Given this deleterious effect of oxygen on conductivity, depositions are performed in pure argon (Ar), i.e., the only oxygen species in the growth ambient are those ejected directly from the PLD solid source target. Ga-doped ZnO deposited in Ar at 200 °C and 10 mTorr have resistivities of 1.8E-4 ohm-cm without the need for post deposition annealing. Average transmittance of the Ga-doped films is 93% over the visible and near infrared (IR) spectral regions, but free carrier absorption is a limiting factor further into the IR. After annealing in FG at 500 °C, a 300 nm Ar film has a Haacke figure of merit of 6.61E-2 sq. ohm.
ContributorsScott, Robin Charis (Author) / Zhang, Yong Hang (Thesis advisor) / Alford, Terry (Committee member) / Krause, Stephen (Committee member) / Leedy, Kevin (Committee member) / Arizona State University (Publisher)
Created2011