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.

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.

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).

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.

Diamond and cubic boron nitride (c-BN) are ultra wide band gap semiconductors (Eg>3.4 eV) and share similar properties in various aspects, including being isoelectronic, a 1% lattice mismatch, large band gap, high thermal conductivity. Particularly, the negative electron affinity (NEA) of diamond and c-BN is an unusual property that has led to effects such as p-type surface conductivity, low temperature thermionic emission, and photon enhanced thermionic emission. In this dissertation, the interface chemistry and electronic structure of dielectrics on diamond and c-BN are investigated with X-ray and ultraviolet photoemission spectroscopy (XPS and UPS). The first study established that the surface conductive states could be established for thin Al2O3 on diamond using a post deposition H-plasma process. At each step of the atomic layer deposition (ALD) and plasma processing, the band alignment was characterized by in situ photoemission and related to interface charges. An interface layer between the diamond and dielectric layer was proposed to explain the surface conductivity. The second study further investigated the improvement of the hole mobility of surface conductive diamond. A thin layer of Al2O3 was employed as an interfacial layer between surface conductive hydrogen-terminated (H-terminated) diamond and MoO3 to increase the distance between the hole accumulation layer in diamond and negatively charged states in acceptor layer. With an interfacial layer, the ionic scattering, which was considered to limit the hole mobility, was reduced. By combining two oxides (Al2O3 and MoO3), the hole mobility and concentration were modulated by altering the thickness of the Al2O3 interfacial layer. The third study focused on the electronic structure of vanadium-oxide-terminated c-BN surfaces. The vanadium-oxide-termination was formed on c-BN by combining vanadium deposition using molecular beam deposition (MBD) and oxygen plasma treatment. After thermal annealing, a thermally stable NEA was achieved on c-BN. A model was proposed based on the deduced interface charge distribution to explain the establishment of an NEA.

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.

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.

GaN and AlGaN have shown great potential in next-generation power and RF electronics. However, these devices are limited by reliability issues such as leakage current and current collapse that result from surface and interface states on GaN and AlGaN. This dissertation, therefore, examined these electronic states, focusing on the following two points:

First, the surface electronic state configuration was examined with regards to the polarization bound 1013 charges/cm2 that increases with aluminum content. This large bound charge requires compensation either externally by surface states or internally by the space charge regions as relates to band bending. In this work, band bending was measured after different surface treatments of GaN and AlGaN to determine the effects of specific surface states on the electronic state configuration. Results showed oxygen-terminated N-face GaN, Ga-face GaN, and Ga-face Al0.25Ga0.75N surface were characterized by similar band bending regardless of the polarization bound charge, suggesting a Fermi level pinning state ~0.4-0.8 eV below the conduction band minimum. On oxygen-free Ga-face GaN, Al0.15Ga0.85N, Al0.25Ga0.75N, and Al0.35Ga0.65N, band bending increased slightly with aluminum content and thus did not exhibit the same pinning behavior; however, there was still significant compensating charge on these surfaces (~1013 charges/cm2). This charge is likely related to nitrogen vacancies and/or gallium dangling bonds.

In addition, this wozrk investigated the interface electronic state configuration of dielectric/GaN and AlGaN interfaces with regards to deposition conditions and aluminum content. Specifically, oxygen plasma-enhanced atomic layer deposited (PEALD) was used to deposit SiO2. Growth temperature was shown to influence the film quality, where room temperature deposition produced the highest quality films in terms of electrical breakdown. In addition, the valence band offsets (VBOs) appeared to decrease with the deposition temperature, which likely related to an electric field across the Ga2O3 interfacial layer. VBOs were also determined with respect to aluminum content at the PEALD-SiO2/AlxGa1-xN interface, giving 3.0, 2.9, 2.9, and 2.8 eV for 0%, 15%, 25%, and 35% aluminum content, respectively—with corresponding conduction band offsets of 2.5, 2.2, 1.9, and 1.8 eV. This suggests the largest difference manifests in the conduction band, which is in agreement with the charge neutrality level model.

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.