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Description
Silicon solar cells with heterojunction carrier collectors based on a-Si/c-Si heterojunction (SHJ) have a potential to overcome the limitations of the conventional diffused junction solar cells and become the next industry standard manufacturing technology of solar cells. A brand feature of SHJ technology is ultrapassivated surfaces with already demonstrated 750

Silicon solar cells with heterojunction carrier collectors based on a-Si/c-Si heterojunction (SHJ) have a potential to overcome the limitations of the conventional diffused junction solar cells and become the next industry standard manufacturing technology of solar cells. A brand feature of SHJ technology is ultrapassivated surfaces with already demonstrated 750 mV open circuit voltages (Voc) and 24.7% efficiency on large area solar cell. Despite very good results achieved in research and development, large volume manufacturing of high efficiency SHJ cells remains a fundamental challenge. The main objectives of this work were to develop a SHJ solar cell fabrication flow using industry compatible tools and processes in a pilot production environment, study the interactions between the used fabrication steps, identify the minimum set of optimization parameters and characterization techniques needed to achieve 20% baseline efficiency, and analyze the losses of power in fabricated SHJ cells by numerical and analytical modeling. This manuscript presents a detailed description of a SHJ solar cell fabrication flow developed at ASU Solar Power Laboratory (SPL) which allows large area solar cells with >750 mV Voc. SHJ cells on 135 um thick 153 cm2 area wafers with 19.5% efficiency were fabricated. Passivation quality of (i)a-Si:H film, bulk conductivity of doped a-Si films, bulk conductivity of ITO, transmission of ITO and the thickness of all films were identified as the minimum set of optimization parameters necessary to set up a baseline high efficiency SHJ fabrication flow. The preparation of randomly textured wafers to minimize the concentration of surface impurities and to avoid epitaxial growth of a-Si films was found to be a key challenge in achieving a repeatable and uniform passivation. This work resolved this issue by using a multi-step cleaning process based on sequential oxidation in nitric/acetic acids, Piranha and RCA-b solutions. The developed process allowed state of the art surface passivation with perfect repeatability and negligible reflectance losses. Two additional studies demonstrated 750 mV local Voc on 50 micron thick SHJ solar cell and < 1 cm/s effective surface recombination velocity on n-type wafers passivated by a-Si/SiO2/SiNx stack.
ContributorsHerasimenka, Stanislau Yur'yevich (Author) / Honsberg, C. (Christiana B.) (Thesis advisor) / Bowden, Stuart G (Thesis advisor) / Tracy, Clarence (Committee member) / Vasileska, Dragica (Committee member) / Holman, Zachary (Committee member) / Sinton, Ron (Committee member) / Arizona State University (Publisher)
Created2013
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Description
In this dissertation, far UV spectroscopy is applied to investigate the optical properties of dielectric thin films grown by atomic layer deposition. The far UV (120 – 200 nm) reflectance for several dielectric oxides and fluorides, including AlF3, Al2O3, Ga2O3, HfO2, and SiO2, was measured at variable angles and thicknesses.

In this dissertation, far UV spectroscopy is applied to investigate the optical properties of dielectric thin films grown by atomic layer deposition. The far UV (120 – 200 nm) reflectance for several dielectric oxides and fluorides, including AlF3, Al2O3, Ga2O3, HfO2, and SiO2, was measured at variable angles and thicknesses. Multiple optical calculation methods were developed for the accurate determination of the optical constants from the reflectance. The deduced optical constants were used for optical designs, such as high-reflectivity coatings, and Fabry-Perot bandpass interference filters. Three filters were designed for use at 157 nm, 212 nm, and 248 nm wavelengths, based on multilayer structures consisting of SiO2, Al2O3, HfO2, and AlF3. A thorough error analysis was made to quantify the non-idealities of the optical performance for the designed filters. Far UV spectroscopy was also applied to analyze material mixtures, such as AlF3/Al and h-BN/c-BN mixtures. Using far UV spectroscopy, different phases in the composite can be distinguished, and the volume concentration of each constituent can be determined. A middle UV reflective coating based on A2O3 and AlF3 was fabricated and characterized. The reflective coating has a smooth surface (?? < 1 nm), and a peak reflectance of 25 – 30 % at a wavelength of 196 nm. The peak reflectance deviated from the design, and an analysis of the AlF3 layer prepared by plasma-enhanced atomic layer deposition (PEALD) indicated the presence of Al-rich clusters, which were associated with the UV absorption. Complementary techniques, such as spectroscopic ellipsometry, and X-ray photoelectron spectroscopy, were used to verify the results from far UV spectroscopy. In conclusion, this Dissertation demonstrated the use of in-situ far UV spectroscopy to investigate the optical properties of thin films at short wavelengths. This work extends the application of far UV spectroscopy to ultrawide bandgap semiconductors and insulators. This work supports a path forward for far UV optical filters and devices. Various errors have been discussed with solutions proposed for future research of methods and materials for UV optics.
ContributorsHuang, Zhiyu (Author) / Nemanich, Robert (Thesis advisor) / Ponce, Fernando (Committee member) / Menéndez, Jose (Committee member) / Holman, Zachary (Committee member) / Arizona State University (Publisher)
Created2021
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Description
CdTe/MgCdTe double heterostructures (DHs) integrated with a heavily-doped a-Si:H layer as the hole contact was demonstrated a record open-circuit voltage (VOC) of 1.11 V and an active-area efficiency of 20% in 2016. Despite this significant progress, some of the underlying device physics has not been fully understood. The first part

CdTe/MgCdTe double heterostructures (DHs) integrated with a heavily-doped a-Si:H layer as the hole contact was demonstrated a record open-circuit voltage (VOC) of 1.11 V and an active-area efficiency of 20% in 2016. Despite this significant progress, some of the underlying device physics has not been fully understood. The first part of this dissertation reports a systematic study of the CdTe/MgCdTe DH devices. The CdTe/MgCdTe DHs are grown on InSb(001) substrates. The vertical transport mechanisms across the CdTe and InSb heterovalent interface are investigated with N-CdTe/n-InSb and N-CdTe/p-InSb heterostructures. A transport model including tunneling through CdTe barrier and InSb interband transition is developed to explain the different temperature dependent current-voltage characteristics of these two heterostructures. Different p-type layers are integrated with the CdTe/MgCdTe DHs to form solar cells with different VOC values and efficiencies. The low VOC of devices with ZnTe:Cu and ZnTe:As hole contacts is attributed to the low built-in voltage and reduced minority carrier lifetime in the CdTe absorber, respectively. The critical requirements for reaching high VOC values are analyzed. A novel epitaxial lift-off technology for monocrystalline CdTe is developed using a water-soluble and nearly lattice-matched MgTe sacrificial layer grown on InSb substrate. The freestanding CdTe/MgCdTe DH thin films obtained from the lift-off process show improved optical performance due to enhanced light extraction efficiency and photo-recycling effect. This technology enables the possible development of monocrystalline CdTe thin-film solar cells and 1.7/1.1-eV MgCdTe/Si or MgCdTe/Cu(InGa)Se2 tandem solar cells. The monocrystalline CdTe thin-film solar cells and 1.7-eV MgCdTe DH solar cells have been demonstrated with a power conversion efficiency of 9.8% and an active-area efficiency as high as 15.2%, respectively. Additionally, a study of the radiation effects on CdTe DHs under 68-MeV proton irradiation is performed and showed their superior radiation tolerance. All these findings indicate that the monocrystalline CdTe thin-film solar cells are reasonably expected to have low weight, high-efficiency and high power density, ideal for space applications.
ContributorsDing, Jia (Author) / Zhang, Yong-Hang (Thesis advisor) / Vasileska, Dragica (Committee member) / Johnson, Shane (Committee member) / Holman, Zachary (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Cubic boron nitride (c-BN), hexagonal boron nitride (h-BN), and semiconducting diamond all have physical properties that make them ideal materials for applications in high power and high frequency electronics, as well as radiation detectors. However, there is limited research on the unique properties and growth of c-BN or h-BN thin

Cubic boron nitride (c-BN), hexagonal boron nitride (h-BN), and semiconducting diamond all have physical properties that make them ideal materials for applications in high power and high frequency electronics, as well as radiation detectors. However, there is limited research on the unique properties and growth of c-BN or h-BN thin films. This dissertation addresses the deposition of c-BN via plasma enhanced chemical vapor deposition (PECVD) on boron doped diamond substrates. In-Situ X-ray photoelectron spectroscopy (XPS) is used to characterize the thickness and hexagonal to cubic ratio of boron nitride thin films. The effects of hydrogen concentration during the deposition of boron nitride are investigated. The boron nitride deposition rate is found to be dependent on the hydrogen gas flow. The sp2 to sp3 bonding is also found to be dependent on the hydrogen gas flow. Preferential growth of h-BN is observed when an excess of hydrogen is supplied to the reaction, while h-BN growth is suppressed when hydrogen flow is reduced to be the limiting reactant. Reduced hydrogen flow is also observed to promote preferential growth of c-BN. The hydrogen limited reaction is used to deposit c-BN on single crystal (100) boron-doped diamond substrates. In-situ ultra-violet photoelectron spectroscopy (UPS) and XPS are used to deduce the valence band offset of the diamond/c-BN interface. A valence band offset of -0.3 eV is measured with the diamond VBM above the VBM of c-BN. This value is then discussed in context of previous experimental results and theoretical calculations. Finally, UPS and XPS are used to characterize the surface states of phosphorus-doped diamond. Variations within the processing parameters for surface preparation and the effects on the electronic surface states are presented and discussed.
ContributorsBrown, Jesse (Author) / Nemanich, Robert J (Thesis advisor) / Alarcon, Ricardo (Committee member) / Lindsay, Stuart (Committee member) / Zaniewski, Anna (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Patterning technologies for micro/nano-structures have been essentially used in a variety of discipline research areas, including electronics, optics, material science, and biotechnology. Therefore their importance has dramatically increased over the past decades. This dissertation presents various advanced patterning processes utilizing cross-discipline technologies, e.g., photochemical deposition, transfer printing (TP), and nanoimprint

Patterning technologies for micro/nano-structures have been essentially used in a variety of discipline research areas, including electronics, optics, material science, and biotechnology. Therefore their importance has dramatically increased over the past decades. This dissertation presents various advanced patterning processes utilizing cross-discipline technologies, e.g., photochemical deposition, transfer printing (TP), and nanoimprint lithography (NIL), to demonstrate inexpensive, high throughput, and scalable manufacturing for advanced optical applications. The polymer-assisted photochemical deposition (PPD) method is employed in the form of additive manufacturing (AM) to print ultra-thin (< 5 nm) and continuous film in micro-scaled (> 6.5 μm) resolution. The PPD film acts as a lossy material in the Fabry-Pérot cavity structures and generates vivid colored images with a micro-scaled resolution by inducing large modulation of reflectance. This PPD-based structural color printing performs without photolithography and vacuum deposition in ambient and room-temperature conditions, which enables an accessible and inexpensive process (Chapter 1). In the TP process, germanium (Ge) is used as the nucleation layer of noble metallic thin films to prevent structural distortion and improve surface morphology. The developed Ge-assisted transfer printing (GTP) demonstrates its feasibility transferring sub-100 nm features with up to 50 nm thickness in a centimeter scale. The GTP is also capable of transferring arbitrary metallic nano-apertures with minimal pattern distortion, providing relatively less expensive, simpler, and scalable manufacturing (Chapter 2). NIL is employed to fabricate the double-layered chiral metasurface for polarimetric imaging applications. The developed NIL process provides multi-functionalities with a single NIL, i.e., spacing layer, planarized surface, and formation of dielectric gratings, respectively, which significantly reduces fabrication processing time and potential cost by eliminating several steps in the conventional fabrication process. During the integration of two metasurfaces, the Moiré fringe based alignment method is employed to accomplish the alignment accuracy of less than 200 nm in both x- and y-directions, which is superior to conventional photolithography. The dramatically improved optical performance, e.g., highly improved circular polarization extinction ratio (CPER), is also achieved with the developed NIL process (Chapter 3).
ContributorsChoi, Shinhyuk (Author) / Wang, Chao (Thesis advisor) / Yu, Hongbin (Committee member) / Holman, Zachary (Committee member) / Hwa, Yoon (Committee member) / Arizona State University (Publisher)
Created2023
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Description
This work correlates microscopic material changes to short- and long-term performance in modern, Cu-doped, CdTe-based solar cells. Past research on short- and long-term performance emphasized the device-scale impact of Cu, but neglected the microscopic impact of the other chemical species in the system (e.g., Se, Cl, Cu), their distributions, their

This work correlates microscopic material changes to short- and long-term performance in modern, Cu-doped, CdTe-based solar cells. Past research on short- and long-term performance emphasized the device-scale impact of Cu, but neglected the microscopic impact of the other chemical species in the system (e.g., Se, Cl, Cu), their distributions, their local atomic environments, or their interactions/reactions. Additionally, technological limitations precluded nanoscale measurements of the Cu distributions in the cell, and microscale measurements of the material properties (i.e. composition, microstructure, charge transport) as the cell operates. This research aims to answer (1) what is the spatial distribution of Cu in the cell, (2) how does its distribution and local environment correlate with cell performance, and (3) how do local material properties change as the cell operates? This work employs a multi-scale, multi-modal, correlative-measurement approach to elucidate microscopic mechanisms. Several analytical techniques are used – including and especially correlative synchrotron X-ray microscopy – and a unique state-of-the-art instrument was developed to access the dynamics of microscopic mechanisms as they proceed. The work shows Cu segregates around CdTe grain boundaries, and Cu-related acceptor penetration into the CdTe layer is crucial for well-performing cells. After long-term operation, the work presents strong evidence of Se migration into the CdTe layer. This redistribution correlates with microstructural changes in the CdTe layer and limited charge transport around the metal-CdTe interface. Finally, the work correlates changes in microstructure, Cu atomic environment, and charge collection as a cell operates. The results suggest that, as the cell ages, a change to Cu local environment limits charge transport through the metal-CdTe interface, and this change could be influenced by Se migration into the CdTe layer of the cell.
ContributorsWalker, Trumann (Author) / Bertoni, Mariana I (Thesis advisor) / Holman, Zachary (Committee member) / Chan, Candace (Committee member) / Colegrove, Eric (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Diamond as a wide-bandgap (WBG) semiconductor material has distinct advantages for power electronics applications over Si and other WBG materials due to its high critical electric field (> 10 MV/cm), high electron and hole mobility (??=4500 cm2/V-s, ??=3800 cm2/V-s), high thermal conductivity (~22 W/cm-K) and large bandgap (5.47 eV). Owing

Diamond as a wide-bandgap (WBG) semiconductor material has distinct advantages for power electronics applications over Si and other WBG materials due to its high critical electric field (> 10 MV/cm), high electron and hole mobility (??=4500 cm2/V-s, ??=3800 cm2/V-s), high thermal conductivity (~22 W/cm-K) and large bandgap (5.47 eV). Owing to its remarkable properties, the application space of WBG materials has widened into areas requiring very high current, operating voltage and temperature. Remarkable progress has been made in demonstrating high breakdown voltage (>10 kV), ultra-high current density (> 100 kA/cm2) and ultra-high temperature (~1000oC) diamond devices, giving further evidence of diamond’s huge potential. However, despite the great success, fabricated diamond devices have not yet delivered diamond’s true potential. Some of the main reasons are high dopant activation energies, substantial bulk defect and trap densities, high contact resistance, and high leakage currents. A lack of complete understanding of the diamond specific device physics also impedes the progress in correct design approaches. The main three research focuses of this work are high power, high frequency and high temperature. Through the design, fabrication, testing, analysis and modeling of diamond p-i-n and Schottky diodes a milestone in diamond research is achieved and gain important theoretical understanding. In particular, a record highest current density in diamond diodes of ~116 kA/cm2 is demonstrated, RF characterization of diamond diodes is performed from 0.1 GHz to 25 GHz and diamond diodes are successfully tested in extreme environments of 500oC and ~93 bar of CO2 pressure. Theoretical models are constructed analytically and inii Silvaco ATLAS including incomplete ionization and hopping mobility to explain space charge limited current phenomenon, effects of traps and Mott-Gurney dominated diode ???. A new interpretation of the Baliga figure of merit for WBG materials is also formulated and a new cubic relationship between ??? and breakdown voltage is established. Through Silvaco ATLAS modeling, predictions on the power limitation of diamond diodes in receiver-protector circuits is made and a range of self-heating effects is established. Poole-Frenkel emission and hopping conduction models are also utilized to analyze high temperature (500oC) leakage behavior of diamond diodes. Finally, diamond JFET simulations are performed and designs are proposed for high temperature – extreme environment applications.
ContributorsSurdi, Harshad (Author) / Goodnick, Stephen M (Thesis advisor) / Nemanich, Robert J (Committee member) / Thornton, Trevor J (Committee member) / Lyons, James R (Committee member) / Arizona State University (Publisher)
Created2022
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Description
In this dissertation, atomic layer processing and surface characterization techniques were used to investigate surface conditions of wide band gap materials, gallium nitride (GaN) and gallium oxide (Ga2O3). These studies largely focused on mitigation and removal of defect formation induced by ions used in conventional plasma-based dry etching techniques. Band

In this dissertation, atomic layer processing and surface characterization techniques were used to investigate surface conditions of wide band gap materials, gallium nitride (GaN) and gallium oxide (Ga2O3). These studies largely focused on mitigation and removal of defect formation induced by ions used in conventional plasma-based dry etching techniques. Band bending measured by x-ray photoelectron spectroscopy (XPS) was used to characterize charge compensation at the surface of GaN (0001) and determine densities of charged surface states produced by dry etching. Mitigation and removal of these dry-etch induced defects was investigated by varying inductively coupled plasma (ICP) etching conditions, performing thermal and plasma-based treatments, and development of a novel low-damage, self-limiting atomic layer etching (ALE) process to remove damaged material. Atomic layer deposition (ALD) and ALE techniques were developed for Ga2O3 using trimethylgallium (TMG). Ga2O3 was deposited by ALD on Si using TMG and O2 plasma with a growth rate of 1.0 ± 0.1 Å/cycle. Ga2O3 films were then etched using HF and TMG using a fully thermal ALE process with an etch rate of 0.9 ± Å/cycle. O2 plasma oxidation of GaN for surface conversion to Ga2O3 was investigated as a pathway for ALE of GaN using HF and TMG. This process was characterized using XPS, in situ multi-wavelength ellipsometry, and transmission electron microscopy. This study indicated that the etch rate was lower than anticipated, which was attributed to crystallinity of the converted surface oxide on GaN (0001).
ContributorsHatch, Kevin Andrew (Author) / Nemanich, Robert J (Thesis advisor) / Ponce, Fernando A (Committee member) / Smith, David J (Committee member) / Zhao, Yuji (Committee member) / Arizona State University (Publisher)
Created2021
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Description
In this dissertation, the surface interactions of fluorine were studied during atomic layer deposition (ALD) and atomic layer etching (ALE) of wide band gap materials. To enable this research two high vacuum reactors were designed and constructed for thermal and plasma enhanced ALD and ALE, and they were equipped for

In this dissertation, the surface interactions of fluorine were studied during atomic layer deposition (ALD) and atomic layer etching (ALE) of wide band gap materials. To enable this research two high vacuum reactors were designed and constructed for thermal and plasma enhanced ALD and ALE, and they were equipped for in-situ process monitoring. Fluorine surface interactions were first studied in a comparison of thermal and plasma enhanced ALD (TALD and PEALD) of AlF3 thin films prepared using hydrogen fluoride (HF), trimethylaluminum (TMA), and H2-plasma. The ALD AlF3 films were compared ¬in-situ using ellipsometry and X-ray photoelectron spectroscopy (XPS). Ellipsometry showed a growth rate of 1.1 Å/ cycle and 0.7 Å/ cycle, at 100°C, for the TALD and PEALD AlF3 processes, respectively. XPS indicated the presence of Al-rich clusters within the PEALD film. The formation of the Al-rich clusters is thought to originate during the H2-plasma step of the PEALD process. The Al-rich clusters were not detected in the TALD AlF3 films. This study provided valuable insight on the role of fluorine in an ALD process. Reactive ion etching is a common dry chemical etch process for fabricating GaN devices. However, the use of ions can induce various defects, which can degrade device performance. The development of low-damage post etch processes are essential for mitigating plasma induced damage. As such, two multistep ALE methods were implemented for GaN based on oxidation, fluorination, and ligand exchange. First, GaN surfaces were oxidized using either water vapor or O2-plasma exposures to produce a thin oxide layer. The oxide layer was addressed using alternating exposures of HF and TMG, which etch Ga2O3 films. Each ALE process was characterized using in-situ using ellipsometry and XPS and ex-situ transmission electron microscopy (TEM). XPS indicated F and O impurities remained on the etched surfaces. Ellipsometry and TEM showed a slight reduction in thickness. The very low ALE rate was interpreted as the inability of the Ga2O3 ALE process to fluorinate the ordered surface oxide on GaN (0001). Overall, these results indicate HF is effective for the ALD of metal fluorides and the ALE of metal oxides.
ContributorsMessina, Daniel C (Author) / Nemanich, Robert J (Thesis advisor) / Goodnick, Stephen (Committee member) / Ponce, Fernando A (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2021
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Description
The application of silicon thin films in solar cells has evolved from their use in amorphous silicon solar cells to their use as passivating and carrier-selective contacts in crystalline silicon solar cells. Their use as carrier-selective contacts has enabled crystalline silicon solar cell efficiencies above 26%, just 3% shy of

The application of silicon thin films in solar cells has evolved from their use in amorphous silicon solar cells to their use as passivating and carrier-selective contacts in crystalline silicon solar cells. Their use as carrier-selective contacts has enabled crystalline silicon solar cell efficiencies above 26%, just 3% shy of the theoretical efficiency limit. The two cell architectures that have exceeded 26% are the silicon heterojunction and tunnel oxide passivating contact cell. These two cell architectures use two different forms of silicon thin films. In the case of the silicon heterojunction, the crystalline wafer is sandwiched between layers of intrinsic amorphous silicon, which acts as the passivation layer, and doped amorphous silicon, which acts as the carrier-selective layer. On the other hand, the tunnel oxide passivating contact cell uses a thin silicon oxide passivation layer and a doped polycrystalline silicon layer as the carrier-selective layer. Both cell structures have their distinct advantages and disadvantages when it comes to production. The processing of the silicon heterojunction relies on a low thermal budget and leads to high open-circuit voltages, but the cost of high-vacuum processing equipment presents a major hurdle for industrial scale production while the tunnel oxide passivating contact can be easily integrated into current industrial lines, yet it requires a higher thermal budgets and does not produce as high of an open-circuit voltage as the silicon heterojunction. This work focuses on using both forms of silicon thin films applied as passivating and carrier-selective contacts to crystalline silicon thin films.First, a thorough analysis of the series resistivity in silicon heterojunction solar cells is conducted. In particular, variations in the thickness and doping of the individual ii contact layers are performed to reveal their effect on the contact resistivity and in turn the total series resistivity of the cell. Second, a tunnel oxide passivated contact is created using a novel deposition method for the silicon oxide layer. A 21% efficient proof-of-concept device is presented demonstrating the potential of this deposition method. Finally, recommendations to further improve the efficiency of these cells is presented.
ContributorsWeigand, William (Author) / Holman, Zachary (Thesis advisor) / Yu, Zhengshan (Committee member) / Bertoni, Mariana (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2023