Effects of alternating current voltage amplitude and oxide capacitance on mid-gap interface state defect density extractions in In0.53Ga 0.47As capacitors

This work looks at the effect on mid-gap interface state defect density estimates for In0.53Ga0.47As semiconductor capacitors when different AC voltage amplitudes are selected for a fixed voltage bias step size (100 mV) during room temperature only electrical characterization. Results are presented for Au/Ni/Al2O3/In0.53Ga0.47As/InP metal–oxide–semiconductor capacitors with (1) n-type and p-type semiconductors, (2) different Al2O3 thicknesses, (3) different In0.53Ga0.47As surface passivation concentrations of ammonium sulphide, and (4) different transfer times to the atomic layer deposition chamber after passivation treatment on the semiconductor surface—thereby demonstrating a cross-section of device characteristics. The authors set out to determine the importance of the AC voltage amplitude selection on the interface state defect density extractions and whether this selection has a combined effect with the oxide capacitance. These capacitors are prototypical of the type of gate oxide material stacks that could form equivalent metal–oxide–semiconductor field-effect transistors beyond the 32 nm technology node. The authors do not attempt to achieve the best scaled equivalent oxide thickness in this work, as our focus is on accurately extracting device properties that will allow the investigation and reduction of interface state defect densities at the high-k/III–V semiconductor interface. The operating voltage for future devices will be reduced, potentially leading to an associated reduction in the AC voltage amplitude, which will force a decrease in the signal-to-noise ratio of electrical responses and could therefore result in less accurate impedance measurements. A concern thus arises regarding the accuracy of the electrical property extractions using such impedance measurements for future devices, particularly in relation to the mid-gap interface state defect density estimated from the conductance method and from the combined high–low frequency capacitance–voltage method. The authors apply a fixed voltage step of 100 mV for all voltage sweep measurements at each AC frequency. Each of these measurements is repeated 15 times for the equidistant AC voltage amplitudes between 10 mV and 150 mV. This provides the desired AC voltage amplitude to step size ratios from 1:10 to 3:2. Our results indicate that, although the selection of the oxide capacitance is important both to the success and accuracy of the extraction method, the mid-gap interface state defect density extractions are not overly sensitive to the AC voltage amplitude employed regardless of what oxide capacitance is used in the extractions, particularly in the range from 50% below the voltage sweep step size to 50% above it. Therefore, the use of larger AC voltage amplitudes in this range to achieve a better signal-to-noise ratio during impedance measurements for future low operating voltage devices will not distort the extracted interface state defect density.

Investigation of electrically active defects at the interface of high-k dielectrics and compound semiconductors

As silicon based devices in integrated circuits reach the fundamental limits of dimensional scaling there is growing research interest in the use of high electron mobility channel materials, such as indium gallium arsenide (InGaAs), in conjunction with high dielectric constant (high-k) gate oxides, for Metal-Oxide-Semiconductor Field Effect Transistor (MOSFET) based devices. The motivation for employing high mobility channel materials is to reduce power dissipation in integrated circuits while also providing improved performance. One of the primary challenges to date in the field of III-V semiconductors has been the observation of high levels of defect densities at the high-k/III-V interface, which prevents surface inversion of the semiconductor. The work presented in this PhD thesis details the characterization of MOS devices incorporating high-k dielectrics on III-V semiconductors. The analysis examines the effect of modifying the semiconductor bandgap in MOS structures incorporating InxGa1-xAs (x: 0, 0.15. 0.3, 0.53) layers, the optimization of device passivation procedures designed to reduce interface defect densities, and analysis of such electrically active interface defect states for the high-k/InGaAs system. Devices are characterized primarily through capacitance-voltage (CV) and conductance-voltage (GV) measurements of MOS structures both as a function of frequency and temperature. In particular, the density of electrically active interface states was reduced to the level which allowed the observation of true surface inversion behavior in the In0.53Ga0.47As MOS system. This was achieved by developing an optimized (NH4)2S passivation, minimized air exposure, and atomic layer deposition of an Al2O3 gate oxide. An extraction of activation energies allows discrimination of the mechanisms responsible for the inversion response. Finally a new approach is described to determine the minority carrier generation lifetime and the oxide capacitance in MOS structures. The method is demonstrated for an In0.53Ga0.47As system, but is generally applicable to any MOS structure exhibiting a minority carrier response in inversion.

Electron beam lithography assisted high-resolution pattern generation

This thesis details the top-down fabrication of nanostructures on Si and Ge substrates by electron beam lithography (EBL). Various polymeric resist materials were used to create nanopatterns by EBL and Chapter 1 discusses the development characteristics of these resists. Chapter 3 describes the processing parameters, resolution and topographical and structural changes of a new EBL resist known as ‘SML’. A comparison between SML and the standard resists PMMA and ZEP520A was undertaken to determine the suitability of SML as an EBL resist. It was established that SML is capable of high-resolution patterning and showed good pattern transfer capabilities. Germanium is a desirable material for use in microelectronic applications due to a number of superior qualities over silicon. EBL patterning of Ge with high-resolution hydrogen silsesquioxane (HSQ) resist is however difficult due to the presence of native surface oxides. Thus, to combat this problem a new technique for passivating Ge surfaces prior to EBL processes is detailed in Chapter 4. The surface passivation was carried out using simple acids like citric acid and acetic acid. The acids were gentle on the surface and enabled the formation of high-resolution arrays of Ge nanowires using HSQ resist. Chapter 5 details the directed self-assembly (DSA) of block copolymers (BCPs) on EBL patterned Si and, for the very first time, Ge surfaces. DSA of BCPs on template substrates is a promising technology for high volume and cost effective nanofabrication. The BCP employed for this study was poly (styrene-b-ethylene oxide) and the substrates were pre-defined by HSQ templates produced by EBL. The DSA technique resulted into pattern rectification (ordering in BCP) and in pattern multiplication within smaller areas.

Development of InAlN HEMTs for space application

This thesis investigates the emerging InAlN high electron mobility transistor (HEMT) technology with respect to its application in the space industry. The manufacturing processes and device performance of InAlN HEMTs were compared to AlGaN HEMTs, also produced as part of this work. RF gain up to 4 GHz was demonstrated in both InAlN and AlGaN HEMTs with gate lengths of 1 μm, with InAlN HEMTs generally showing higher channel currents (~150 c.f. 60 mA/mm) but also degraded leakage properties (~ 1 x 10-4 c.f. < 1 x 10-8 A/mm) with respect to AlGaN. An analysis of device reliability was undertaken using thermal stability, radiation hardness and off-state breakdown measurements. Both InAlN and AlGaN HEMTs showed excellent stability under space-like conditions, with electrical operation maintained after exposure to 9.2 Mrad of gamma radiation at a dose rate of 6.6 krad/hour over two months and after storage at 250°C for four weeks. Furthermore a link was established between the optimisation of device performance (RF gain, power handling capabilities and leakage properties) and reliability (radiation hardness, thermal stability and breakdown properties), particularly with respect to surface passivation. Following analysis of performance and reliability data, the InAlN HEMT device fabrication process was optimised by adjusting the metal Ohmic contact formation process (specifically metal stack thicknesses and anneal conditions) and surface passivation techniques (plasma power during dielectric layer deposition), based on an existing AlGaN HEMT process. This resulted in both a reduction of the contact resistivity to around 1 x 10-4 Ω.cm2 and the suppression of degrading trap-related effects, bringing the measured gate-lag close to zero. These discoveries fostered a greater understanding of the physical mechanisms involved in device operation and manufacture, which is elaborated upon in the final chapter.

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

An 8x8 thermopile based uncooled infrared sensor

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Low temperature magneto-photoluminescence characterization of high purity gallium arsenide and indium phosphide

Low-temperature magneto-photoluminescence is a very powerful technique to characterize high purity GaAs and InP grown by various epitaxial techniques. These III-V compound semiconductor materials are used in a wide variety of electronic, optoelectronic and microwave devices. The large binding energy differences of acceptors in GaAs and InP make possible the identification of those impurities by low-temperature photoluminescence without the use of any magnetic field. However, the sensitivity and resolution provided by this technique rema1ns inadequate to resolve the minute binding energy differences of donors in GaAs and InP. To achieve higher sensitivity and resolution needed for the identification of donors, a magneto-photoluminescence system 1s installed along with a tunable dye laser, which provides resonant excitation. Donors 1n high purity GaAs are identified from the magnetic splittings of "two-electron" satellites of donor bound exciton transitions 1n a high magnetic field and at liquid helium temperature. This technique 1s successfully used to identify donors 1n n-type GaAs as well as 1n p-type GaAs in which donors cannot be identified by any other technique. The technique is also employed to identify donors in high purity InP. The amphoteric incorporation of Si and Ge impurities as donors and acceptors in (100), (311)A and (3ll)B GaAs grown by molecular beam epitaxy is studied spectroscopically. The hydrogen passivation of C acceptors in high purity GaAs grown by molecular beam epitaxy (MBE) and metalorganic chemical vapor deposition (MOCVD) 1s investigated using photoluminescence. Si acceptors ~n MBE GaAs are also found to be passivated by hydrogenation. The instabilities in the passivation of acceptor impurities are observed for the exposure of those samples to light. Very high purity MOCVD InP samples with extremely high mobility are characterized by both electrical and optical techniques. It is determined that C is not typically incorporated as a residual acceptor ~n high purity MOCVD InP. Finally, GaAs on Si, single quantum well, and multiple quantum well heterostructures, which are fabricated from III-V semiconductors, are also measured by low-temperature photoluminescence.

Deposition of Intrinsic a-Si:H by ECR-CVD to Passivate the Crystalline Silicon Heterointerface in HIT Solar Cells

We have deposited intrinsic amorphous silicon (a-Si:H) using the electron cyclotron resonance (ECR) chemical vapor deposition technique in order to analyze the a-Si:H/c-Si heterointerface and assess the possible application in heterojunction with intrinsic thin layer (HIT) solar cells. Physical characterization of the deposited films shows that the hydrogen content is in the 15-30% range, depending on deposition temperature. The optical bandgap value is always comprised within the range 1.9- 2.2 eV. Minority carrier lifetime measurements performed on the heterostructures reach high values up to 1.3 ms, indicating a well-passivated a-Si:H/c-Si heterointerface for deposition temperatures as low as 100°C. In addition, we prove that the metal-oxide- semiconductor conductance method to obtain interface trap distribution can be applied to the a-Si:H/c-Si heterointerface, since the intrinsic a-Si:H layer behaves as an insulator at low or negative bias. Values for the minimum of D_it as low as 8 × 10^10 cm^2 · eV^-1 were obtained for our samples, pointing to good surface passivation properties of ECR-deposited a-Si:H for HIT solar cell applications.

Models and Simulations of Diamond-like Carbon for large-area high voltage power diodes

Silicon-based discrete high-power devices need to be designed with optimal performance up to several thousand volts and amperes to reach power ratings ranging from few kWs to beyond the 1 GW mark. To this purpose, a key element is the improvement of the junction termination (JT) since it allows to drastically reduce surface electric field peaks which may lead to an earlier device failure. This thesis will be mostly focused on the negative bevel termination which from several years constitutes a standard processing step in bipolar production lines. A simple methodology to realize its counterpart, a planar JT with variation of the lateral doping concentration (VLD) will be also described. On the JT a thin layer of a semi insulating material is usually deposited, which acts as passivation layer reducing the interface defects and contributing to increase the device reliability. A thorough understanding of how the passivation layer properties affect the breakdown voltage and the leakage current of a fast-recovery diode is fundamental to preserve the ideal termination effect and provide a stable blocking capability. More recently, amorphous carbon, also called diamond-like carbon (DLC), has been used as a robust surface passivation material. By using a commercial TCAD tool, a detailed physical explanation of DLC electrostatic and transport properties has been provided. The proposed approach is able to predict the breakdown voltage and the leakage current of a negative beveled power diode passivated with DLC as confirmed by the successfully validation against the available experiments. In addition, the VLD JT proposed to overcome the limitation of the negative bevel architecture has been simulated showing a breakdown voltage very close to the ideal one with a much smaller area consumption. Finally, the effect of a low junction depth on the formation of current filaments has been analyzed by performing reverse-recovery simulations.

Hybrid lead-halide perovskites as novel materials for thin film direct and flexible ionizing radiation detectors

Ionizing radiations are important tools employed every day in the modern society. For example, in medicine they are routinely used for diagnostic and therapy. The large variety of applications leads to the need of novel, more efficient, low-cost ionizing radiation detectors with new functionalities. Personal dosimetry would benefit from wearable detectors able to conform to the body surfaces. Traditional semiconductors used for ionizing radiation direct detectors offer high performance but they are intrinsically stiff, brittle and require high voltages to operate. Hybrid lead-halide perovskites emerged recently as a novel class of materials for ionizing radiation detection. They combine high absorption coefficient, solution processability and high charge transport capability, enabling efficient and low-cost detection. The deposition from solution allows the fabrication of thin-film flexible devices. In this thesis, I studied the detection properties of different types of hybrid perovskites, deposited from solution in thin-film form, and tested under X-rays, gamma-rays and protons beams. I developed the first ultraflexible X-ray detector with exceptional conformability. The effect of coupling organic layers with perovskites was studied at the nanoscale giving a direct demonstration of trap passivation effect at the grain boundaries. Different perovskite formulations were deposited and tested to improve the film stability. I report about the longest aging studies on perovskite X-ray detectors showing that the addition of starch in the precursors’ solution can improve the stability in time with only a 7% decrease in sensitivity after 630 days of storage in ambient conditions. 2D perovskites were also explored as direct detector for X-rays and gamma-rays. Detection of 511 keV photons by a thin-film device is here demonstrated and was validated for monitoring a radiotracer injection. At last, a new approach has been used: a 2D/3Dmixed perovskite thin-film demonstrated to reliably detect 5 MeV protons, envisioning wearable dose monitoring during proton/hadron therapy treatments.

Kinetics of photogenerated carriers in nanostructured semiconductor heterojunctions for solar water splitting

This thesis aims to investigate the fundamental processes governing the performance of different types of photoelectrodes used in photoelectrochemical (PEC) applications, such as unbiased water splitting for hydrogen production. Unraveling the transport and recombination phenomena in nanostructured and surface-modified heterojunctions at a semiconductor/electrolyte interface is not trivial. To approach this task, the work presented here first focus on a hydrogen-terminated p-silicon photocathode in acetonitrile, considered as a standard reference for PEC studies. Steady-state and time-resolved excitation at long wavelength provided clear evidence of the formation of an inversion layer and revealed that the most optimal photovoltage and the longest electron-hole pair lifetime occurs when the reduction potential for the species in solution lies within the unfilled conduction band states. Understanding more complex systems is not as straight-forward and a complete characterization that combine time- and frequency-resolved techniques is needed. Intensity modulated photocurrent spectroscopy and transient absorption spectroscopy are used here on WO3/BiVO4 heterojunctions. By selectively probing the two layers of the heterojunction, the occurrence of interfacial recombination was identified. Then, the addition of Co-Fe based overlayers resulted in passivation of surface states and charge storage at the overlayer active sites, providing higher charge separation efficiency and suppression of recombination in time scales that go from picoseconds to seconds. Finally, the charge carrier kinetics of several different Cu(In,Ga)Se2 (CIGS)-based architectures used for water reduction was investigated. The efficiency of a CIGS photocathode is severely limited by charge transfer at the electrode/electrolyte interface compared to the same absorber layer used as a photovoltaic cell. A NiMo binary alloy deposited on the photocathode surface showed a remarkable enhancement in the transfer rate of electrons in solution. An external CIGS photovoltaic module assisting a NiMo dark cathode displayed optimal absorption and charge separation properties and a highly performing interface with the solution.