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In this dissertation, the interface chemistry and electronic structure of plasma-enhanced atomic layer deposited (PEALD) dielectrics on GaN are investigated with x-ray and ultraviolet photoemission spectroscopy (XPS and UPS). Three interrelated issues are discussed in this study: (1) PEALD dielectric growth process optimization, (2) interface electronic structure of comparative PEALD

In this dissertation, the interface chemistry and electronic structure of plasma-enhanced atomic layer deposited (PEALD) dielectrics on GaN are investigated with x-ray and ultraviolet photoemission spectroscopy (XPS and UPS). Three interrelated issues are discussed in this study: (1) PEALD dielectric growth process optimization, (2) interface electronic structure of comparative PEALD dielectrics on GaN, and (3) interface electronic structure of PEALD dielectrics on Ga- and N-face GaN. The first study involved an in-depth case study of PEALD Al2O3 growth using dimethylaluminum isopropoxide, with a special focus on oxygen plasma effects. Saturated and self-limiting growth of Al2O3 films were obtained with an enhanced growth rate within the PEALD temperature window (25-220 ºC). The properties of Al2O3 deposited at various temperatures were characterized to better understand the relation between the growth parameters and film properties. In the second study, the interface electronic structures of PEALD dielectrics on Ga-face GaN films were measured. Five promising dielectrics (Al2O3, HfO2, SiO2, La2O3, and ZnO) with a range of band gap energies were chosen. Prior to dielectric growth, a combined wet chemical and in-situ H2/N2 plasma clean process was employed to remove the carbon contamination and prepare the surface for dielectric deposition. The surface band bending and band offsets were measured by XPS and UPS for dielectrics on GaN. The trends of the experimental band offsets on GaN were related to the dielectric band gap energies. In addition, the experimental band offsets were near the calculated values based on the charge neutrality level model. The third study focused on the effect of the polarization bound charge of the Ga- and N-face GaN on interface electronic structures. A surface pretreatment process consisting of a NH4OH wet chemical and an in-situ NH3 plasma treatment was applied to remove carbon contamination, retain monolayer oxygen coverage, and potentially passivate N-vacancy related defects. The surface band bending and polarization charge compensation of Ga- and N-face GaN were investigated. The surface band bending and band offsets were determined for Al2O3, HfO2, and SiO2 on Ga- and N-face GaN. Different dielectric thicknesses and post deposition processing were investigated to understand process related defect formation and/or reduction.
ContributorsYang, Jialing (Author) / Nemanich, Robert J (Thesis advisor) / Chen, Tingyong (Committee member) / Peng, Xihong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2014
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Description
In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate

In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate stack structures have been prepared using a reactive electron beam system and a plasma enhanced atomic layer deposition system. Three interrelated issues represent the central themes of the research: 1) the interface band alignment, 2) candidate high-k materials, and 3) band bending, internal electric fields, and charge transfer. 1) The most highlighted issue is the band alignment of specific high-k structures. Band alignment relationships were deduced by analysis of XPS and UPS spectra for three different structures: a) HfO2/VO2/SiO2/Si, b) HfO2-La2O3/ZnO/SiO2/Si, and c) HfO2/VO2/ HfO2/SiO2/Si. The valence band offset of HfO2/VO2, ZnO/SiO2 and HfO2/SiO2 are determined to be 3.4 ± 0.1, 1.5 ± 0.1, and 0.7 ± 0.1 eV. The valence band offset between HfO2-La2O3 and ZnO was almost negligible. Two band alignment models, the electron affinity model and the charge neutrality level model, are discussed. The results show the charge neutrality model is preferred to describe these structures. 2) High-k candidate materials were studied through comparison of pure Hf oxide, pure La oxide, and alloyed Hf-La oxide films. An issue with the application of pure HfO2 is crystallization which may increase the leakage current in gate stack structures. An issue with the application of pure La2O3 is the presence of carbon contamination in the film. Our study shows that the alloyed Hf-La oxide films exhibit an amorphous structure along with reduced carbon contamination. 3) Band bending and internal electric fields in the gate stack structure were observed by XPS and UPS and indicate the charge transfer during the growth and process. The oxygen plasma may induce excess oxygen species with negative charges, which could be removed by He plasma treatment. The final HfO2 capping layer deposition may reduce the internal potential inside the structures. The band structure was approaching to a flat band condition.
ContributorsZhu, Chiyu (Author) / Nemanich, Robert (Thesis advisor) / Chamberlin, Ralph (Committee member) / Chen, Tingyong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2012
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Description
The electronic states of semiconductor interfaces have significant importance for semiconductor device performance, especially due to the continuing miniaturization of device technology.

The application of ultra high vacuum (UHV) enables the preparation and characterization of fresh and cleaned interfaces. In a UHV environment, photoemission spectroscopy (PES) provides a non-destructive method to

The electronic states of semiconductor interfaces have significant importance for semiconductor device performance, especially due to the continuing miniaturization of device technology.

The application of ultra high vacuum (UHV) enables the preparation and characterization of fresh and cleaned interfaces. In a UHV environment, photoemission spectroscopy (PES) provides a non-destructive method to measure the electronic band structure, which is a crucial component of interface properties.

In this dissertation, three semiconductor interfaces were studies to understand different effects on electronic states. The interfaces studied were freshly grown or pre-treated under UHV. Then in-situ PES measurements, including x-ray photoemission spectroscopy (XPS) and ultra-violet photoemission spectroscopy (UPS), were conducted to obtain electronic states information.

First, the CdTe/InSb (100) heterointerface was employed as a model interface for II-VI and III-V heterojunctions. It was suggested that an interface layer formed, which consisted of In-Te bonding. The non-octal bonding between In and Te atoms has donor-like behavior, which was proposed to result in an electron accumulation layer in InSb. A type-I heterointerface was observed. Second, Cu/ZnO interfaces were studied to understand the interface bonding and the role of polarization on ZnO interfaces. It was shown that on O-face ZnO (0001) and PEALD ZnO, copper contacts had ohmic behavior. However, on Zn-face ZnO (0001), a 0.3 eV Schottky barrier height was observed. The lower than expected barrier heights were attributed to oxygen vacancies introduced by Cu-O bonding during interface formation. In addition, it is suggested that the different barrier heights on two sides of ZnO (0001) are caused by the different behavior for the ZnO (0001) faces. Last, a pulse mode deposition method was applied for P-doped diamond growth on (100) diamond surfaces. Pretreatment effects were studied. It is suggested that an O/H plasma treatment or a short period of H-plasma and CH4/H2 plasma could yield a higher growth rate. PES measurements were conducted on H-terminated intrinsic diamond surface and P-doped/intrinsic diamond (100) interfaces. It was suggested that electronic states near the valence band maximum caused Fermi level pinning effects, independent of the diamond doping.
ContributorsWang, Xingye (Author) / Nemanich, Robert J (Thesis advisor) / Chan, Candace (Committee member) / Ponce, Fernando (Committee member) / Holman, Zachary (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Cubic boron nitride (c-BN) has potential for electronic applications as an electron emitter and serving as a base material for diodes, transistors, etc. However, there has been limited research on c-BN reported, and many of the electronic properties of c-BN and c-BN interfaces have yet to be reported. This dissertation

Cubic boron nitride (c-BN) has potential for electronic applications as an electron emitter and serving as a base material for diodes, transistors, etc. However, there has been limited research on c-BN reported, and many of the electronic properties of c-BN and c-BN interfaces have yet to be reported. This dissertation focused on probing thin film c-BN deposited via plasma enhanced chemical vapor deposition (PECVD) with in situ photoelectron spectroscopy (PES). PES measurements were used to characterize the electronic properties of c-BN films and interfaces with vacuum and diamond. First, the interface between c-BN and vacuum were characterized with ultraviolet PES (UPS). UPS measurements indicated that as-deposited c-BN, H2 plasma treated c-BN, and annealed c-BN post H2 plasma treatment exhibited negative electron affinity surfaces. A dipole model suggested dipoles from H-terminated N surface sites were found to be responsible for the NEA surface. Then, Si was introduced into c-BN films to realize n-type doped c-BN. The valence structure and work function of c-BN:Si films were characterized with XPS and UPS measurements. Measurements were unable to confirm n-type character, and it is concluded that silicon nitride formation was the primary effect for the observations. Finally, XPS measurements were employed to measure the band offsets at the c-BN/diamond interface. Measurements indicated the valence band maximum (VBM) of c-BN was positioned ~0.8 eV above the VBM of diamond.
ContributorsShammas, Joseph (Author) / Nemanich, Robert J (Thesis advisor) / Ponce, Fernando (Committee member) / Chen, Tingyong (Committee member) / Chamberlin, Ralph (Committee member) / Arizona State University (Publisher)
Created2016