An investigation into the processes taking place at the surface interface of ferroelectric Pb(Zr1-x,Tix)O3 immersed in metal salt solution under ultraviolet illumination is presented. The semiconducting and switchable dipolar nature of this material allows the spatial separation and control of photo-induced reduction and oxidation across its surface interface. These properties can be of application in novel techniques such as the controlled growth of metallic nanoparticles across specific polar domains. 70nm thick Pb(Zr0.3,Ti0.7)O3 samples, PZT(30/70), are manufactured using the sol gel methodology, two crystallographic orientations being produced. The orientation being controlled by the substrate used; Si was used for [111] orientation and MgO for [100]. The initial work with wideband ultraviolet light shows that the reduction and growth of silver on the PZT surface is greatly influenced by the structure of the film. The crystallographic orientation of the film affects metal deposition such that on [111] films the metal deposits only on positive domains, where as the [100] films experience deposition on both positive and negative domains. This is shown to be due to the difference in width of the space charge region, Δw = 4.4nm, between the [111] and [100] samples so that the negative domain on [100] samples have 10 19 times higher chance of electron tunnelling compared to the [111]. It is also shown that grain boundaries have the greatest effect on the growth of metal, with a metal cluster growth rate 51 times faster than elsewhere on the surface. This increased rate of growth is due to the effect a grain boundary has on the surrounding area, the energy band bending at the boundary attracting charge carriers from the grains around it. The interface types ranked from greatest to lowest influence are grain boundaries, positive domains, domain boundaries and finally interphase boundaries.ii It is shown that the stern layer, strongly adsorbed charged ions of opposite sign to the surface charge, at the PZT/solution interface act as an insulating layer to metal reduction. The accumulation of photoexcited charge carriers at points along grain boundaries causes the surface potential gradient to alter and allows metal reduction and thus clusters to nucleate. The energy required to cause this variation is investigated by use of narrow band, 5nm bandwidth, ultraviolet. For energy from 4.4eV to 5 eV, it is found there is an increase in the average silver cluster cross sectional area by a ratio of ca 1.6 to 1 for both the [111] and [100] orientations of PZT. Finally it is shown that the type of metal salt used in the photochemical process affects the type of reaction that takes place at the sample surface. For a cation to reduce on positive domains its reduction potential needs to be below the bottom edge of the conduction band of PZT. Chloride salts, that sit above the conduction band, cause decomposition of the negative domains. Use is made of these effects to find the position of the bottom of the conduction band for PZT. It is found that across similar [111] PZT samples FeCl2 can both reduce on positive domains and decompose negative domains, this puts the bottom of the conduction band for PZT(30/70) between 4.06 and 4.36 eV from vacuum. It is also discovered that the type of anion affects the decomposition of the negative domains. Nitrate salts with cations above the conduction band cause no decomposition whereas chlorides do. The decomposition is shown to be the loss of Pb from the negative surface.

This dissertation details the study of band bending in n- and p-type GaN samples with a Kelvin probe utilizing different illumination geometries, ambients (air, oxygen, vacuum 10-6 mbar), and sample temperatures (77 – 650 K). The Kelvin probe, which is mounted inside an optical cryostat, is used to measure the surface potential. Illumination of the GaN surface with band-to-band light generates electron-hole pairs, which quickly separate in the depletion region due to a strong electric field caused by the near-surface band bending. The charge that is swept to the surface reduces the band bending and generates a surface photovoltage (SPV). Information about the band bending can be obtained by fitting the SPV measurements with a thermionic model based on the emission of charge carriers from bulk to surface and vice versa. The band bending in freestanding n-type GaN templates has been evaluated. The Ga-polar and N-polar surfaces exhibit upward band bending of about 0.74 and 0.57 eV, respectively. The surface treatment also plays a major role in the SPV behavior, where the SPV for mechanical polished surfaces restores faster than predicted by a thermionic model in dark. When measuring the photoluminescence (PL) signal, the PL from mechanically polished surfaces was about 4 orders of magnitude smaller than the PL from chemically mechanically polished surfaces. The PL and SPV behaviors were explained by the presence of a large density of defects near the surface, which quench PL and aid in the restoration of the SPV via electron hopping between defects. Temperature-dependent SPV studies have also been performed on doped n- and p-type GaN samples. In Si-doped n-type GaN, the estimated upward band bending was about 1 eV at temperatures between 295 and 500 K. However, in p-type GaN, the downward band bending appeared to increase with increasing temperature, where the magnitude of band bending increased from 0.8 eV to 2.1 eV as the temperature increased from 295 to 650 K. It appears that heating the p-type GaN samples allows for band bending values larger than 1 eV to fully restore. Pre-heating of samples was of paramount importance to measure the correct value of band bending in p-type GaN. The slope of the dependence of the SPV on excitation intensity at low temperatures was larger than expected; however, once the temperature exceeded 500 K, the slope began to reach values that are in agreement with a thermionic model.

The development of gallium nitride (GaN) light emitting devices has reached extraordinary echelons. As such, the characterization and analysis of the behavior of GaN materials is essential to the advancement of GaN technology. In this thesis, the effect of temperature on the optical and electrical properties of p-type GaN is investigated. The GaN samples used in this work were grown by various methods and studied by Kelvin probe and photoluminescence (PL) techniques. Specifically, the surface photovoltage (SPV) behavior and PL data were analyzed at different temperatures and illumination intensities. Using the SPV results, we show that p-type GaN exhibits n-type conductivity at low temperatures (80 K). If the sample is heated beyond a characteristic temperature, TC, the conductivity reverts to p-type. This temperature of conversion can be tuned by varying the illumination intensity. We explain this conductivity conversion using a simple, one-acceptor phenomenological model. Temperature-dependent PL measurements taken on Mg-doped p-type GaN layers show abrupt and tunable thermal quenching of the PL intensity. This effect is explained by a more complex model but with the same assertions, that the system must undergo a change in conductivity at low temperatures and under UV illumination. It is necessary to understand the observed behaviors, since the implications of such could have an effect on the performance of devices containing p-type GaN materials.

There is an understanding of surface photovoltage (SPV) behavior for GaN, yet little is known about the SPV behavior for AlGaN. In this work, a Kelvin probe was used to measure the SPV for p-type AlGaN. Very slow SPV transients were found in AlGaN, which could not be explained with a simple thermionic model. A possible explanation of this behavior is the segregation of impurities to the surface, which causes significant reduction of the depletion region width (down to 2 nm), with carrier tunneling and hopping becoming the dominant mechanisms responsible for the SPV transients. To verify this assumption, the near-surface defective region (about 40 nm) has been removed through the ICP-RIE process. After the etching, the SPV transients became fast and increased in magnitude by about 0.6 eV. By using the thermionic model, band bending was estimated to be -1 eV.

Steady-state and transient surface photovoltages in undoped GaN are studied in various environments (air, nitrogen, oxygen, vacuum) at room temperature and 400 K with a Kelvin probe attached to an optical cryostat. The results are explained within a phenomenological model accounting for the accumulation of photo-generated holes at the surface, capture of free electrons from the bulk over the near-surface potential barrier, and emission of electrons from surface states into the bulk. Mechanisms of surface photovoltage are discussed in detail. Photoadsorption and photodesorption of negatively charged species will either increase or decrease the surface potential and thus band bending. Oxygen is the assumed species responsible for the SPV changes in air ambient during continuous UV illumination. This variation in SPV will be confirmed with photoluminescence measurements.

This thesis concerns new hydrogen- and polarity-related effects in the photoluminescence of ZnO single crystal wafers and the relationship between surface electron accumulation and surface hydroxyl coverage on different ZnO surfaces. A comparative study of the low temperature photoluminescence of various types of hydrothermal and melt-grown ZnO wafers revealed several new hydrogen-related exciton recombination lines and a number of consistent polarity-related differences in the PL emission from different crystallographic surfaces. Temperature-dependent PL measurements were extensively used to distinguish the ground and excited state transitions involved in these effects. ZnO samples of different surface polarity were annealed in oxygen and nitrogen gases and in hydrogen-containing forming gas mixtures in an attempt to identify the origin of these new PL features. The well known aluminium-related I_₆ recombination line was resolved into two separate features in hydrothermal ZnO, and the new component I6-H (3.36081 eV) was found to repeatedly quench and then re-emerge after annealing in oxygen and forming gas, respectively. A model involving an aluminium - lithium - hydrogen defect complex was proposed for I6-H and further tested via hydrogen and deuterium implantation experiments on hydrothermal ZnO wafers with different lithium concentrations. These experiments also provided evidence for the involvement of a different lithium-hydrogen defect complex in other hydrogen-related emission lines I₄b,c (3.36219 eV and 3.36237 eV) unique to hydrothermal ZnO. In addition, a broad Gaussian-shaped feature observed in the near-band-edge PL emission from the O-polar (000‾1), a-plane (11‾20) and r-plane (1‾102) faces of ZnO was shown to be surface sensitive and also related to hydrogen. The involvement of hydrogen in the chemical and electronic properties of different ZnO surfaces was also investigated. The thermal stability of the hydroxyl termination and the associated downward surface band bending on the polar and non-polar surfaces of ZnO was studied by synchrotron and real-time photoelectron spectroscopy, both during and after annealing and subsequent H₂O/H₂ dosing in ultra-high vacuum conditions. On the O-polar face, the band bending could be reversibly switched over a range of approximately 0.8 eV by adjusting the surface H-coverage using simple UHV heat treatments and atmospheric exposure. A transition from electron accumulation to electron depletion on the O-polar face was observed at a H-coverage of approximately 0.9 monolayers. In contrast, the downward band bending on the Zn-polar face was significantly more resilient and electron-depleted surfaces could not be prepared by heat treatment alone. This was also the case for in situ cleaving in UHV conditions which failed to produce hydroxyl-free surfaces due to migration of hydrogen from the bulk to the cleaved surface. Interestingly, the thermal stability of the hydroxyl termination on the a-plane (11‾20) and m-plane (10‾10) surfaces was signiifcantly lower than on the polar faces due to the availability of a lower energy desorption pathway and the electrostatic stability of these non-polar surfaces in their clean, bulk terminated form. The surface band bending on the non-polar ZnO surfaces was also found to be directly related to their OH coverage with a transition from downward to upward band bending, similar to that observed on the O-polar face, as the OH coverage was reduced. Thermal admittance spectroscopy and deep level transient spectroscopy was used to investigate the effect of lithium removal on the defect nature of hydrothermal ZnO. A number of new defects were introduced by the high temperature (1100-1400°C) annealing/re-polishing process used to reduce the lithium concentration, particularly E₁₉₀ (also known as T2) which is thought to be related to Zn vacancies. Significantly, both the E₅₀ defect level and the I6-H PL emission line were absent after lithium (and hydrogen) removal suggesting an association of both these features with the same aluminium - lithium - hydrogen defect complex.

This work examines extended, point, and surface defects in GaN by means of electric force microscopy, photoluminescence and deep-level transient spectroscopy. Modeling of the surface band bending, its origin, and the effects of fabrication processing steps are discussed in the first part of the dissertation. Experimental results indicate that spontaneous polarization does not play a predominant role in GaN band bending. An increase of surface band bending due to annealing and etching was observed, while passivation did not produce changes. However, passivation did reduce reverse-bias leakage current by one to two orders of magnitude in GaN Schottky diodes. The optical properties of GaN were found to be sensitive to fabrication processing steps, most likely due to changes in the total density of surface states.The second part of this dissertation concerns the reduction of extended defects and associated deep levels in layers of GaN grown on different templates. Templates employing a low temperature GaN nucleation layer, epitaxial lateral overgrowth, and SiNx nanonetwork are compared in terms of deep level concentrations in the resulting GaN films. The concentrations of two types of traps, A (Ec-ET ~ 0.54-0.58 eV) and B (Ec-ET ~ 0.20-0.24 eV), were the highest for the sample with a low temperature nucleation layer and lowest for a sample with a 6 min SiNx deposition time. We surmise that the defects responsible for the dominant trap A are located along dislocation lines and form clusters.In the last part we investigate the piezoelectric and ferroelectric properties of PZT in Pb(Zr, Ti)O3(PZT)/GaN structures, and the effects of interface states. Sol-gel derived thin PZT films on GaN and Pt/Ti/SiO2/Si surfaces were studied by piezoresponse force microscopy (PFM), where quantitative characterization of piezoelectric properties of PZT films was performed. Superior piezoelectric properties of PZT/GaN/sapphire structures as compared to PZT/ Pt/Ti/SiO2/Si structures were observed and explained by a different preferred orientation of PZT. Despite the possible existence of a strong depolarization field at the PZT/GaN interface, we confirm with PFM the presence of a remanent polarization in PZT/GaN/sapphire structures.

Multilayer epitaxial graphene has been shown to contain "massless Dirac fermions" and is believed to provide a possible route to industrial-scale graphene electronics. We used scanning tunneling microscopy (STM) and spectroscopy (STS) in high magnetic fields to obtain local information on these fermions. A new STS technique was developed to directly measure graphene's energy-momentum relationship and resulted in the highest precision measurement of graphene's Dirac cone. STS spectra similar to ideal graphene were observed, but additional anomalies were also found. Extra peaks and an asymmetry between electron and hole states were shown to be caused by the work function difference between the Iridium STM tip and graphene. This tip effect was extracted using modeled potentials and performing a least square fit using degenerate perturbation theory on graphene's eigenstates solved in the symmetric gauge. Defects on graphene were then investigated and magnetic field effects were shown to be due to a mixture of potential effect from defects and the tip potential. New defect states were observed to localize around specific defects, and are believed to interact with the STM tip by Stark shifting in energy. This Stark shift gives a direct measurement of the capacitive coupling between the tip and graphene and agrees with the modeled results found when extracting the tip potential.

No description available.

Der Einfluss der Modifikation der technologisch relevanten GaAs(100) Oberfläche durch Chalkogene, i.e. Selen, Schwefel und Tellur, wird in dieser Arbeit untersucht. Es wird ein Modell vorgestellt, das die Eigenschaften der modifizierten Oberfläche beschreibt. In einem zweiten Schritt werden die so modifizierten Oberflächen mit Metallen unterschiedlicher Reaktivität und verschiedenen Elektronegativitäten bedampft. Die Bandbreite dieser Eigenschaften wird durch die Metalle Indium und Silber, das Alkalimetall Natrium, das Erdalkalimetall Magnesium und das Halbmetall Antimon abgebildet. Die Untersuchung des Einflusses der Chalkogene auf die chemischen Eigenschaften und die Barrierenhöhe der Metall/GaAs(100) Grenzfläche bilden einen weiteren Schwerpunkt. Die Änderung der Barrierenhöhe wird dabei mit Hilfe des Modells metallinduzierter Bandlückenzustände (metal induced gap states) erklärt. Als experimentelle Techniken werden Photoemissionsspektroskopie, Raman Spektroskopie und Strom-Spannungsmessungen verwendet. / The influence of a modification of the technological relevant GaAs(100) surface by chalcogens, i.e. selenium, sulphur and tellurium, is evaluated in this work. A model is proposed, which describes the properties of the modified surface. In a second step metals of different reactivity and electronegativity have been evaporated onto these modified surfaces. Among these materials were the metals indium and silver, the alkali metal sodium, the earth alkali metal magnesium and the half metal antimony. The investigation of the influence of chalcogens on the chemical properties and the barrier height of the metal/GaAs(100) interface is another point of interest. The change in barrier height is explained by the model of metal induced gap states (MIGS). Photoemission spectroscopy, Raman spectroscopy and current-voltage-measurement have been used as experimental techniques.