Theses and Dissertations
This collection includes both ASU Theses and Dissertations, submitted by graduate students, and the Barrett, Honors College theses submitted by undergraduate students.
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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 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
Description
Recent technology advancements in photovoltaics have enabled crystalline silicon (c-Si) solar cells to establish outstanding photoconversion efficiency records. Remarkable progresses in research and development have been made both on the silicon feedstock quality as well as the technology required for surface passivation, the two dominant sources of performance loss via recombination of photo-generated charge carriers within advanced solar cell architectures.
As these two aspects of the solar cell framework improve, the need for a thorough analysis of their respective contribution under varying operation conditions has emerged along with challenges related to the lack of sensitivity of available characterization techniques. The main objective of my thesis work has been to establish a deep understanding of both “intrinsic” and “extrinsic” recombination processes that govern performance in high-quality silicon absorbers. By studying each recombination mechanism as a function of illumination and temperature, I strive to identify the lifetime limiting defects and propose a path to engineer the ultimate silicon solar cell.
This dissertation presents a detailed description of the experimental procedure required to deconvolute surface recombination contributions from bulk recombination contributions when performing lifetime spectroscopy analysis. This work proves that temperature- and injection-dependent lifetime spectroscopy (TIDLS) sensitivity can be extended to impurities concentrations down to 109 cm-3, orders of magnitude below any other characterization technique available today. A new method for the analysis of TIDLS data denominated Defect Parameters Contour Mapping (DPCM) is presented with the aim of providing a visual and intuitive tool to identify the lifetime limiting impurities in silicon material. Surface recombination velocity results are modelled by applying appropriate approaches from literature to our experimentally evaluated data, demonstrating for the first time their capability to interpret temperature-dependent data. In this way, several new results are obtained which solve long disputed aspects of surface passivation mechanisms. Finally, we experimentally evaluate the temperature-dependence of Auger lifetime and its impact on a theoretical intrinsically limited solar cell. These results decisively point to the need for a new Auger lifetime parameterization accounting for its temperature-dependence, which would in turn help understand the ultimate theoretical efficiency limit for a solar cell under real operation conditions.
As these two aspects of the solar cell framework improve, the need for a thorough analysis of their respective contribution under varying operation conditions has emerged along with challenges related to the lack of sensitivity of available characterization techniques. The main objective of my thesis work has been to establish a deep understanding of both “intrinsic” and “extrinsic” recombination processes that govern performance in high-quality silicon absorbers. By studying each recombination mechanism as a function of illumination and temperature, I strive to identify the lifetime limiting defects and propose a path to engineer the ultimate silicon solar cell.
This dissertation presents a detailed description of the experimental procedure required to deconvolute surface recombination contributions from bulk recombination contributions when performing lifetime spectroscopy analysis. This work proves that temperature- and injection-dependent lifetime spectroscopy (TIDLS) sensitivity can be extended to impurities concentrations down to 109 cm-3, orders of magnitude below any other characterization technique available today. A new method for the analysis of TIDLS data denominated Defect Parameters Contour Mapping (DPCM) is presented with the aim of providing a visual and intuitive tool to identify the lifetime limiting impurities in silicon material. Surface recombination velocity results are modelled by applying appropriate approaches from literature to our experimentally evaluated data, demonstrating for the first time their capability to interpret temperature-dependent data. In this way, several new results are obtained which solve long disputed aspects of surface passivation mechanisms. Finally, we experimentally evaluate the temperature-dependence of Auger lifetime and its impact on a theoretical intrinsically limited solar cell. These results decisively point to the need for a new Auger lifetime parameterization accounting for its temperature-dependence, which would in turn help understand the ultimate theoretical efficiency limit for a solar cell under real operation conditions.
ContributorsBernardini, Simone (Author) / Bertoni, Mariana I (Thesis advisor) / Coletti, Gianluca (Committee member) / Bowden, Stuart (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2018
Description
Chemical Vapor Deposition (CVD) is the most widely used method to grow large-scale single layer graphene. However, a systematic experimental study of the relationship between growth parameters and graphene film morphology, especially in the industrially preferred cold wall CVD, has not been undertaken previously. This research endeavored to address this and provide comprehensive insight into the growth physics of graphene on supported solid and liquid Cu films using cold wall CVD.
A multi-chamber UHV system was customized and transformed into a cold wall CVD system to perform experiments. The versatile growth process was completely custom-automated by controlling the process parameters with LabVIEW. Graphene growth was explored on solid electrodeposited, recrystallized and thin sputter deposited Cu films as well as on liquid Cu supported on W/Mo refractory substrates under ambient pressure using Ar, H₂ and CH₄ mixtures.
The results indicate that graphene grown on Cu films using cold wall CVD follows a classical two-dimensional nucleation and growth mechanism. The nucleation density decreases and average size of graphene crystallites increases with increasing dilution of the CH₄/H₂ mixture by Ar, decrease in total flow rate and decrease in CH₄:H₂ ratio at a fixed substrate temperature and chamber pressure. Thus, the resulting morphological changes correspond with those that would be expected if the precursor deposition rate was varied at a fixed substrate temperature for physical deposition using thermal evaporation. The evolution of graphene crystallite boundary morphology with decreasing effective C deposition rate indicates the effect of edge diffusion of C atoms along the crystallite boundaries, in addition to H₂ etching, on graphene crystallite shape.
The roles of temperature gradient, chamber pressure and rapid thermal heating in C precursor-rich environment on graphene growth morphology on thin sputtered Cu films were explained. The growth mechanisms of graphene on substrates annealed under reducing and non-reducing environment were explained from the scaling functions of graphene island size distribution in the pre-coalescence regime. It is anticipated that applying the pre-coalescence size distribution method presented in this work to other 2D material systems may be useful for elucidating atomistic mechanisms of film growth that are otherwise difficult to obtain.
A multi-chamber UHV system was customized and transformed into a cold wall CVD system to perform experiments. The versatile growth process was completely custom-automated by controlling the process parameters with LabVIEW. Graphene growth was explored on solid electrodeposited, recrystallized and thin sputter deposited Cu films as well as on liquid Cu supported on W/Mo refractory substrates under ambient pressure using Ar, H₂ and CH₄ mixtures.
The results indicate that graphene grown on Cu films using cold wall CVD follows a classical two-dimensional nucleation and growth mechanism. The nucleation density decreases and average size of graphene crystallites increases with increasing dilution of the CH₄/H₂ mixture by Ar, decrease in total flow rate and decrease in CH₄:H₂ ratio at a fixed substrate temperature and chamber pressure. Thus, the resulting morphological changes correspond with those that would be expected if the precursor deposition rate was varied at a fixed substrate temperature for physical deposition using thermal evaporation. The evolution of graphene crystallite boundary morphology with decreasing effective C deposition rate indicates the effect of edge diffusion of C atoms along the crystallite boundaries, in addition to H₂ etching, on graphene crystallite shape.
The roles of temperature gradient, chamber pressure and rapid thermal heating in C precursor-rich environment on graphene growth morphology on thin sputtered Cu films were explained. The growth mechanisms of graphene on substrates annealed under reducing and non-reducing environment were explained from the scaling functions of graphene island size distribution in the pre-coalescence regime. It is anticipated that applying the pre-coalescence size distribution method presented in this work to other 2D material systems may be useful for elucidating atomistic mechanisms of film growth that are otherwise difficult to obtain.
ContributorsDas, Shantanu, Ph.D (Author) / Drucker, Jeff (Thesis advisor) / Alford, Terry (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2018
Description
ABSTRACT
Autonomous smart windows may be integrated with a stack of active components, such as electrochromic devices, to modulate the opacity/transparency by an applied voltage. Here, we describe the processing and performance of two classes of visibly-transparent photovoltaic materials, namely inorganic (ZnO thin film) and fully organic (PCDTBT:PC70BM), for integration with electrochromic stacks.
Sputtered ZnO (2% Mn) films on ITO, with transparency in the visible range, were used to fabricate metal-semiconductor (MS), metal-insulator-semiconductor (MIS), and p-i-n heterojunction devices, and their photovoltaic conversion under ultraviolet (UV) illumination was evaluated with and without oxygen plasma-treated surface electrodes (Au, Ag, Al, and Ti/Ag). The MS Schottky parameters were fitted against the generalized Bardeen model to obtain the density of interface states (Dit ≈ 8.0×1011 eV−1cm−2) and neutral level (Eo ≈ -5.2 eV). These devices exhibited photoconductive behavior at λ = 365 nm, and low-noise Ag-ZnO detectors exhibited responsivity (R) and photoconductive gain (G) of 1.93×10−4 A/W and 6.57×10−4, respectively. Confirmed via matched-pair analysis, post-metallization, oxygen plasma treatment of Ag and Ti/Ag electrodes resulted in increased Schottky barrier heights, which maximized with a 2 nm SiO2 electron blocking layer (EBL), coupled with the suppression of recombination at the metal/semiconductor interface and blocking of majority carriers. For interdigitated devices under monochromatic UV-C illumination, the open-circuit voltage (Voc) was 1.2 V and short circuit current density (Jsc), due to minority carrier tunneling, was 0.68 mA/cm2.
A fully organic bulk heterojunction photovoltaic device, composed of poly[N-9’-heptadecanyl-2,7-carbazole-alt-5,5-(4’,7’-di-2-thienyli2’,1’,3’-benzothiadiazole)]:phenyl-C71-butyric-acidmethyl (PCDTBT:PC70BM), with corresponding electron and hole transport layers, i.e., LiF with Al contact and conducting
on-conducting (nc) PEDOT:PSS (with ITO/PET or Ag nanowire/PDMS contacts; the illuminating side), respectively, was developed. The PCDTBT/PC70BM/PEDOT:PSS(nc)/ITO/PET stack exhibited the highest performance: power conversion efficiency (PCE) ≈ 3%, Voc = 0.9V, and Jsc ≈ 10-15 mA/cm2. These stacks exhibited high visible range transparency, and provided the requisite power for a switchable electrochromic stack having an inkjet-printed, optically-active layer of tungsten trioxide (WO3), peroxo-tungstic acid dihydrate, and titania (TiO2) nano-particle-based blend. The electrochromic stacks (i.e., PET/ITO/LiClO4/WO3 on ITO/PET and Ag nanowire/PDMS substrates) exhibited optical switching under external bias from the PV stack (or an electrical outlet), with 7 s coloration time, 8 s bleaching time, and 0.36-0.75 optical modulation at λ = 525 nm. The devices were paired using an Internet of Things controller that enabled wireless switching.
Autonomous smart windows may be integrated with a stack of active components, such as electrochromic devices, to modulate the opacity/transparency by an applied voltage. Here, we describe the processing and performance of two classes of visibly-transparent photovoltaic materials, namely inorganic (ZnO thin film) and fully organic (PCDTBT:PC70BM), for integration with electrochromic stacks.
Sputtered ZnO (2% Mn) films on ITO, with transparency in the visible range, were used to fabricate metal-semiconductor (MS), metal-insulator-semiconductor (MIS), and p-i-n heterojunction devices, and their photovoltaic conversion under ultraviolet (UV) illumination was evaluated with and without oxygen plasma-treated surface electrodes (Au, Ag, Al, and Ti/Ag). The MS Schottky parameters were fitted against the generalized Bardeen model to obtain the density of interface states (Dit ≈ 8.0×1011 eV−1cm−2) and neutral level (Eo ≈ -5.2 eV). These devices exhibited photoconductive behavior at λ = 365 nm, and low-noise Ag-ZnO detectors exhibited responsivity (R) and photoconductive gain (G) of 1.93×10−4 A/W and 6.57×10−4, respectively. Confirmed via matched-pair analysis, post-metallization, oxygen plasma treatment of Ag and Ti/Ag electrodes resulted in increased Schottky barrier heights, which maximized with a 2 nm SiO2 electron blocking layer (EBL), coupled with the suppression of recombination at the metal/semiconductor interface and blocking of majority carriers. For interdigitated devices under monochromatic UV-C illumination, the open-circuit voltage (Voc) was 1.2 V and short circuit current density (Jsc), due to minority carrier tunneling, was 0.68 mA/cm2.
A fully organic bulk heterojunction photovoltaic device, composed of poly[N-9’-heptadecanyl-2,7-carbazole-alt-5,5-(4’,7’-di-2-thienyli2’,1’,3’-benzothiadiazole)]:phenyl-C71-butyric-acidmethyl (PCDTBT:PC70BM), with corresponding electron and hole transport layers, i.e., LiF with Al contact and conducting
on-conducting (nc) PEDOT:PSS (with ITO/PET or Ag nanowire/PDMS contacts; the illuminating side), respectively, was developed. The PCDTBT/PC70BM/PEDOT:PSS(nc)/ITO/PET stack exhibited the highest performance: power conversion efficiency (PCE) ≈ 3%, Voc = 0.9V, and Jsc ≈ 10-15 mA/cm2. These stacks exhibited high visible range transparency, and provided the requisite power for a switchable electrochromic stack having an inkjet-printed, optically-active layer of tungsten trioxide (WO3), peroxo-tungstic acid dihydrate, and titania (TiO2) nano-particle-based blend. The electrochromic stacks (i.e., PET/ITO/LiClO4/WO3 on ITO/PET and Ag nanowire/PDMS substrates) exhibited optical switching under external bias from the PV stack (or an electrical outlet), with 7 s coloration time, 8 s bleaching time, and 0.36-0.75 optical modulation at λ = 525 nm. The devices were paired using an Internet of Things controller that enabled wireless switching.
ContributorsAzhar, Ebraheem (Author) / Yu, Hongbin (Thesis advisor) / Dey, Sandwip (Thesis advisor) / Goryll, Michael (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2018
Description
Interconnection methods for IBC photovoltaic (PV) module integration have widely been explored yet a concrete and cost-effective solution has yet to be found. Traditional methods of tabbing and stringing which are still being used today impart increased stress on the cells, not to mention the high temperatures induced during the soldering process as well. In this work and effective and economical interconnection method is demonstrated, by laser welding an embossed aluminum (Al) electrode layer to screen-printed silver (Ag) on the solar cell. Contact resistivity below 1mΩ.cm2 is measured with the proposed design. Cross-sectional analysis of interfaces is conducted via Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDXS) methods. Typical laser weld phenomenon observed involves Al ejection at the entrance of the weld, followed by Al and Ag fusing together mid-way through the weld spot, as revealed by cross-sectional depth analysis. The effects of voltage and lamp intensity are also tested on the welding process. With the range of voltages tested, 240V seems to show the least process variability and the most uniform contact between Al and Ag layers, upon using an Ethylene-Vinyl Acetate (EVA) encapsulant. Two lamp intensities were also explored with a Polyolefin (POE) encapsulant with Al and Ag layers seen welded together as well. Smaller effect sizes at lamp 2 intensity showed better contact. A process variability analysis was conducted to understand the effects of the two different lamps on welds being formed. Lamp 2 showed a bi-modal size distribution with a higher peak intensity, with more pulses coupling into the sample, as compared to lamp 1.
ContributorsSukumar Mony, Sujyot (Author) / Holman, Zachary (Thesis advisor) / Alford, Terry (Committee member) / Yu, Zhengshan (Committee member) / Arizona State University (Publisher)
Created2019
Description
Nanocrystalline (NC) materials are of great interest to researchers due to their multitude of properties such as exceptional strength and radiation resistance owing to their high fraction of grain boundaries that act as defect sinks for radiation-induced defects, provided they are microstructurally stable. In this dissertation, radiation effects in microstructurally stable bulk NC copper (Cu)- tantalum (Ta) alloys engineered with uniformly dispersed Ta nano-precipitates are systematically probed. Towards this, both ex-situ and in-situ irradiations using heavy (self) ion, helium ion, and concurrent dual ion beams (He+Au) followed by isochronal annealing inside TEM were utilized to understand radiation tolerance and underlying mechanisms of microstructure evolution in stable NC alloys. With systematic self-ion irradiation, the high density of tantalum nanoclusters in Cu-10at.%Ta were observed to act as stable sinks in suppressing radiation hardening, in addition to stabilizing the grain boundaries; while the large incoherent precipitates experienced ballistic mixing and dissolution at high doses. Interestingly, the alloy exhibited a microstructure self-healing mechanism, where with a moderate thermal input, this dissolved tantalum eventually re-precipitated, thus replenishing the sink density. The high stability of these tantalum nanoclusters is attributed to the high positive enthalpy of mixing of tantalum in copper which also acted as a critical driving force against atomic mixing to facilitate re-precipitation of tantalum nanoclusters. Furthermore, these nanoclusters proved to be effective trapping sites for helium, thus sequestering helium into isolated small bubbles and aid in increasing the overall swelling threshold of the alloy. The alloy was then compositionally optimized to reduce the density of large incoherent precipitates without compromising on the grain size and nanocluster density (Cu-3at.%Ta) which resulted in a consistent and more promising response to high dose self-ion irradiation. In-situ helium and dual beam irradiation coupled with isochronal annealing till 723 K, also revealed a comparable microstructural stability and enhanced ability of Cu-3Ta in controlling bubble growth and suppressing swelling compared to Cu-10Ta indicating a promising improvement in radiation tolerance in the optimized composition. Overall, this work helps advancing the current understanding of radiation tolerance in stable nanocrystalline alloys and aid developing design strategies for engineering radiation tolerant materials with stable interfaces.
ContributorsSrinivasan, Soundarya (Author) / Solanki, Kiran (Thesis advisor) / Peralta, Pedro (Committee member) / Alford, Terry (Committee member) / Darling, Kristopher (Committee member) / Arizona State University (Publisher)
Created2021