The efficiency of photoconversion systems, such as organic photovoltaic (OPV) cells, is largely controlled by a series of fundamental photophysical processes occurring at the interface before carrier collection. A profound understanding of ultrafast interfacial charge transfer (CT), charge separation (CS), and charge recombination (CR) is the key determinant to improving the overall performances of photovoltaic devices. The discussion in this dissertation primarily focuses on the relevant parameters that are involved in photon absorption, exciton separation, carrier transport, carrier recombination and carrier collection in organic photovoltaic devices. A combination of steady-state and femtosecond broadband transient spectroscopies was used to investigate the photoinduced charge carrier dynamics in various donor-acceptor systems. Furthermore, this study was extended to investigate some important factors that influence charge transfer in donor-acceptor systems, such as the morphology, energy band alignment, electronic properties and chemical structure. Interestingly, clear correlations among the steady-state measurements, time-resolved spectroscopy results, grain alignment of the electron transporting layer (ETL), carrier mobility, and device performance are found. In this thesis, we explored the significant impacts of ultrafast charge separation and charge recombination at donor/acceptor (D/A) interfaces on the performance of a conjugated polymer PTB7-Th device with three fullerene acceptors: PC71BM, PC61BM and IC60BA. Time-resolved laser spectroscopy and high-resolution electron microscopy can illustrate the basis for fabricating solar cell devices with improved performances. In addition, we studied the effects of the incorporation of heavy metals into π-conjugated chromophores on electron transfer by monitoring the triplet state lifetime of the oligomer using transient absorption spectroscopy, as understanding the mechanisms controlling intersystem crossing and photoinduced electron transfer dynamics is required to improve the device performance of solar cells. Here, we evaluated the effects of incorporating Pt(II) on intersystem crossing and photoinduced electron transfer by comparing and analyzing the photoexcited dynamics of DPP-Pt(II)(acac) and metal-free DPP with different acceptors such as TCNE, TMPyP, and TPyP.

The study of defects in semiconductors has been on-going for over 50 years. During this time, researchers have been studying the origins and identity of process induced defects, a task which has proved to be very demanding. While defects in silicon, the most widely used semiconductor, have been widely studied, there is more literature on n-type silicon than on p-type silicon. Compared to n-type silicon, p-type silicon is challenging to work with when it comes to making good Schottky diodes. A good rectifying device is essential for the performing of electrical characterisation techniques such as deep-level transient spectroscopy. In spite of this challenge p-silicon cannot be ignored. Many of the electronic devices are a combination of both n- and p-silicon therefore the need to understand the electronic properties of both materials. In this thesis, defects introduced in p-Si by electron beam deposition (EBD) were investigated. In order to understand these defects better, defects introduced by conditions of electron beam deposition (EBD) without metal deposition, were investigated. This process will be referred to as electron beam exposure (EBE). Finally, the defects were compared to defects induced by alpha-particle irradiation. EBD defects, introduced during electron beam deposition (EBD) of titanium (Ti) contacts on p-Si were investigated. The Schottky contacts were annealed within a temperature range of 200–400 oC. Current-voltage (I-V) measurements were conducted to monitor the change in electrical characteristics with every annealing step. Deep-level transient spectroscopy (DLTS) and Laplace-DLTS techniques were employed to identify the defects introduced after EBD and isochronal annealing of the Ti Schottky contacts. DLTS revealed that the main defects introduced during metallisation were hole traps with activation energy of 0.05 eV, 0.23 eV and 0.38 eV. Depth profiles of these defects showed that the formed close to the interface within a depth of 0.4 μm. Defects induced by EBE were studied by exposing samples for 50 minutes after which nickel (Ni) Schottky contacts were fabricated using resistive deposition. Only one defect with an activation energy of 0.55 eV was observed. This activation energy is similar to that of the I-defect. DLTS depth profiling revealed that the defect could be detected up to a depth of 0.8μm below the junction, which is significantly deeper than EBD defects. Defects induced when p-Si was irradiated by alpha particles from a 5.4 MeV americium (Am) 241 foil radioactive source with a fluence rate of 7×106 cm−2 s−1 at room temperature were investigated. After exposure at a fluence of 5.1×1010 cm−2, hole traps with the following activation energies were observed: 0.10 eV, identified as a tri-vacancy related defect, 0.33 eV, the interstitial carbon (Ci), 0.52 eV, a B-related defect and 0.16 eV. Low temperature irradiation experiments were also carried out using alpha- particles with the same fluence rate. Measurements were taken between 35 K and 120 K. The defect levels were at 0.10 eV, 0.14 eV and 0.18 eV. These levels were attributed to the boron-substitutional vacancy complex, the mono-vacancy and a vacancy-related defect, respectively. We conclude that EBD and EBE induced more complex defects than those induced by alpha-particle irradiation. / Thesis (PhD)--University of Pretoria, 2019. / Physics / PhD / Unrestricted

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At present, focus of the SiC crystal growth development is on improving the crystalline quality without polytype inclusions, micropipes and the occurrence of extended defects. The purity of the grown material, as well as intentional doping must be well controlled and the processes understood. High-quality substrates will significantly improve device performance and yield. One of the aims of the thesis is further understanding of polytype inclusion formation as well as impurity control in SiC bulk crystals grown using PVT method also termed seeded sublimation method. Carbonization of the source was identified as a major reason behind the polytype inclusion occurrence during the growth. The aim of this work was further understanding of sublimation growth process of 4H-SiC bulk crystals in vacuum, in absence of an inert gas. For comparison growth in argon atmosphere (at 5 mbar) was performed. The effect of the ambient on the impurity incorporation was studied for different growth temperatures. For better control of the process in vacuum, tantalum as a carbon getter was utilized. The focus of the SiC part of the thesis was put on further understanding of the PVT epitaxy with an emphasis on the high growth rate and purity of grown layers. High resistivity 4H-SiC samples grown by sublimation with high growth rate were studied. The measurements show resistivity values up to high 104 cm. By correlation between the growth conditions and SIMS results, a model was applied in which it is proposed that an isolated carbon vacancy donor-like level is a possible candidate responsible for compensation of the shallow acceptors in p-type 4H-SiC. A relation between cathodoluminescence (CL) and DLTS data is taken into account to support the model. To meet the requirements for high voltage blocking devices such as high voltage Schottky diodes and MOSFETs, 4H-SiC epitaxial layers have to exhibit low doping concentration in order to block reverse voltages up to few keV and at the same time have a low on-state resistance (Ron). High Ron leads to enhanced power consumption in the operation mode of the devices. In growth of thick layers for high voltage blocking devices, the conditions to achieve good on-state characteristics become more challenging due to the low doping and pronounced thicknesses needed, preferably in short growth periods. In case of high-speed epitaxy such as the sublimation, the need to apply higher growth temperature to yield the high growth rate, results in an increased concentration of background impurities in the layers as well as an influence on the intrinsic defects. On-state resistance Ron estimated from current density-voltage characteristics of Schottky diodes on thick sublimation layers exhibits variations from tens of mΩ.cm2 to tens of Ω.cm2 for different doping levels. In order to understand the occurrence of high on-state resistance, Schottky barrier heights were first estimated for both forward and reverse bias with the application of thermionic emission theory and were in agreement with literature reported values. Decrease in mobility with increasing temperature was observed and its dependencies of T–1.3 and T–2.0 for moderately doped and low doped samples, respectively, were estimated. From deep level measurements by Minority Carrier Transient Spectroscopy (MCTS), an influence of shallow boron related levels and D-center on the on-state resistance was observed, being more pronounced in low doped samples. Similar tendency was observed in depth profiling of Ron. This suggests a major role of boron in a compensation mechanism. In the second part of the thesis growth and characterization of GaN is presented. Excellent electron transport properties with high electron saturate drift velocity make GaN an excellent candidate for electronic devices. Especially, AlGaN/GaN based high electron mobility transistors (HEMT) have received an increased attention in last years due to their attractive properties. The presence of strong spontaneous and piezoelectric polarization due to the lattice mismatch between AlGaN and GaN is responsible for high free electrons concentrations present in the vicinity of the interface. Due to the spatial separation of electrons and ionized donors or surface states, 2DEG electron gas formed near the interface of the heterostructure exhibits high sheet carrier density and high mobility of electrons. Al0.23Ga0.77N/GaN based HEMT structures with an AlN exclusion layer on 100 mm semiinsulating 4H-SiC substrates have been grown by hot-wall MOCVD. The electrical properties of the two-dimensional electron gas (2DEG) such as electron mobility, sheet carrier density and sheet resistance were obtained from Hall measurements, capacitance-voltage and contact-less eddy-current techniques. The effect of different scattering mechanisms on the mobility have been taken into account and compared to the experimental data. Hall measurements were performed in the range of 80 to 600 K. Hall electron mobility is equal to 17140 cm2(Vs)-1 at 80 K, 2310 cm2(Vs)-1 at room temperature, and as high as 800 cm2(Vs)-1 at 450 K, while the sheet carrier density is 1.04x1013 cm-2 at room temperature and does not vary very much with temperature. Estimation of different electron scattering mechanisms reveals that at temperatures higher than room temperature, experimental mobility data is mainly limited by optical phonon scattering. At relevant high power device temperature (450 K) there is still an increase of mobility due to the AlN exclusion layer. We have studied the behaviour of Ga-face GaN epilayers after in-situ thermal treatment in different gas mixtures in a hot-wall MOCVD reactor. Influence of N2, N2+NH3 and N2+NH3+H2 ambient on the morphology was investigated in this work. The most stable thermal treatment conditions were obtained in the case of N2+NH3 gas ambients. We have also studied the effect of the increased molar ratio of hydrogen in order to establish proper etching conditions for hot-wall MOCVD growth.

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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.

Das Halbleitermaterial Zinkselenid (ZnSe) wurde mit Deep Level Transient Spectroscopy (DLTS) untersucht. Fuer planar N-dotierte, MO-CVD-gewachsene ZnSe-Schichten auf p-GaAs wurden vorwiegend breite Zustandsverteilungen, aber auch tiefe Niveaus gefunden. In kristallin gezuechtetem, undotiertem ZnSe wurden tiefe Stoerstellen nachgewiesen.