Influência dos parâmetros de processo na deposição de nitreto de titânio por plasma em gaiola catódica

Titanium nitride films were grown on glass using the Cathodic Cage Plasma Deposition technique in order to verify the influence of process parameters in optical and structural properties of the films. The plasma atmosphere used was a mixture of Ar, N2 and H2, setting the Ar and N2 gas flows at 4 and 3 sccm, respectively and H2 gas flow varied from 0, 1 to 2 sccm. The deposition process was monitored by Optical Emission Spectroscopy (OES) to investigate the influence of the active species in plasma. It was observed that increasing the H2 gas flow into the plasma the luminescent intensities associated to the species changed. In this case, the luminescence of N2 (391,4nm) species was not proportional to the increasing of the H2 gas into the reactor. Other parameters investigated were diameter and number of holes in the cage. The analysis by Grazing Incidence X-Ray Diffraction (GIXRD) confirmed that the obtained films are composed by TiN and they may have variations in the nitrogen amount into the crystal and in the crystallite size. The optical microscopy images provided information about the homogeneity of the films. The atomic force microscopy (AFM) results revealed some microstructural characteristics and surface roughness. The thickness was measured by ellipsometry. The optical properties such as transmittance and reflectance (they were measured by spectrophotometry) are very sensitive to changes in the crystal lattice of the material, chemical composition and film thicknesses. Therefore, such properties are appropriate tools for verification of this process control. In general, films obtained at 0 sccm of H2 gas flow present a higher transmittance. It can be attributed to the smaller crystalline size due to a higher amount of nitrogen in the TiN lattice. The films obtained at 1 and 2 sccm of H2 gas flow have a golden appearance and XRD pattern showed peaks characteristics of TiN with higher intensity and smaller FWHM (Full Width at Half Maximum) parameter. It suggests that the hydrogen presence in the plasma makes the films more stoichiometric and becomes it more crystalline. It was observed that with higher number of holes in the lid of the cage, close to the region between the lid and the sample and the smaller diameter of the hole, the deposited film is thicker, which is justified by the most probability of plasma species reach effectively the sample and it promotes the growth of the film

Estudo da sinterabilidade de ligas de níquel obtidas por meio dos portadores de liga sic, si3n4 ou si metálico com grafita

Nickel alloys are frequently used in applications that require resistance at high temperatures associated with resistance to corrosion. Alloys of Ni-Si-C can be obtained by means of powder metallurgy in which powder mixtures are made of metallic nickel powders with additions of various alloying carriers for such were used in this study SiC, Si3N4 or Si metal with graphite. Carbonyl Ni powder with mean particle size of 11 mM were mixed with 3 wt% of SiC powders with an average particle size of 15, 30 and 50 μm and further samples were obtained containing 4 to 5% by mass of SiC with average particle size of 15 μm. Samples were also obtained by varying the carrier alloy, these being Si3N4 powder with graphite, with average particle size of 1.5 and 5 μm, respectively. As a metallic Si graphite with average particle size of 12.5 and 5 μm, respectively. The reference material used was nickel carbonyl sintered without adding carriers. Microstructural characterization of the alloys was made by optical microscopy and scanning electron microscopy with semi-quantitative chemical analysis. We determined the densities of the samples and measurement of microhardness. We studied the dissociation of carriers alloy after sintering at 1200 ° C for 60 minutes. Was evaluated also in the same sintering conditions, the influence of the variation of average particle size of the SiC carrier to the proportion of 3% by mass. Finally, we studied the influence of variation of the temperatures of sintering at 950, 1080 and 1200 ° C without landing and also with heights of 30, 60, 120 and 240 minutes for sintering where the temperature was 950 °C. Dilatometry curves showed that the SiC sintered Ni favors more effectively than other carriers alloy analyzed. SiC with average particle size of 15 μm active sintering the alloy more effectively than other SiC used. However, with the chemical and morphological analyzes for all leagues, it was observed that there was dissociation of SiC and Si3N4, as well as diffusion of Si in Ni matrix and carbon cluster and dispersed in the matrix, which also occurred for the alloys with Si carriers and metallic graphite. So the league that was presented better results containing Si Ni with graphite metallic alloy as carriers, since this had dispersed graphite best in the league, reaching the microstructural model proposed, which is necessary for material characteristic of solid lubricant, so how we got the best results when the density and hardness of the alloy

Estudo da molhabilidade de ligas de adição à base de prata sobre insertos cerâmicos para aplicação em brocas perfuração de poços de petróleo

Metal-ceramic interfaces are present in tricone drill bits with hard ceramic inserts for oil well drilling operations. The combination of actions of cutting, crushing and breaking up of rocks results in the degradation of tricone drill bits by wear, total or partial rupture of the drill bit body or the ceramic inserts, thermal shock and corrosion. Also the improper pressfitting of the ceramic inserts on the bit body may cause its total detachment, and promote serious damages to the drill bit. The improvement on the production process of metal-ceramic interfaces can eliminate or minimize some of above-mentioned failures presented in tricone drill bits, optimizing their lifetime and so reducing drilling metric cost. Brazing is a widely established technique to join metal-ceramic materials, and may be an excellent alternative to the common mechanical press fitting process of hard ceramic inserts on the steel bit body for tricone drill bit. Wetting phenomena plays an essential role in the production of metal/ceramic interfaces when a liquid phase is present in the process. In this work, 72Silver-28Copper eutectic based brazing alloys were melted onto zirconia, silicon nitride and tungsten carbide/Co substrates under high vacuum. Contact angle evolution was measured and graphically plotted, and the interfaces produced were analysed by SEM-EDX. The AgCu eutectic alloy did not wet any ceramic substrates, showing high contact angles, and so without chemical interaction between the materials. Better results were found for the systemns containing 3%wt of titanium in the AgCu alloy. The presence os titanium as a solute in the alloy produces wettable cand termodinamically stable compounds, increasing the ceramics wetting beahviour

Lattice pulling effect and strain relaxation in axial (In, Ga)N/GaN nanowire heterostructures grown on GaN-buffered Si(111) substrate

Transmission electron microscopy and spatially resolved electron energy-loss spectroscopy have been applied to investigate the indium distribution and the interface morphology in axial (In,Ga)N/GaN nanowire heterostructures. The ordered axial (In,Ga)N/GaN nanowire heterostructures with an indium concentration up to 80% are grown by molecular beam epitaxy on GaN-buffered Si(111) substrates. We observed a pronounced lattice pulling effect in all the nanowire samples given in a broad transition region at the interface. The lattice pulling effect becomes smaller and the (In,Ga)N/GaN interface width is reduced as the indium concentration is increased in the (In,Ga)N section. The result can be interpreted in terms of the increased plastic strain relaxation via the generation of the misfit dislocations at the interface.

Post-CMOS compatible high-throughput fabrication of AIN-based piezoelectric microcantilevers

A post-complementary metal oxide semiconductor (CMOS) compatible microfabrication process of piezoelectric cantilevers has been developed. The fabrication process is suitable for standard silicon technology and provides low-cost and high-throughput manufacturing. This work reports design, fabrication and characterization of piezoelectric cantilevers based on aluminum nitride (AlN) thin films synthesized at room temperature. The proposed microcantilever system is a sandwich structure composed of chromium (Cr) electrodes and a sputtered AlN film. The key issue for cantilever fabrication is the growth at room temperature of the AlN layer by reactive sputtering, making possible the innovative compatibility of piezoelectric MEMS devices with CMOS circuits already processed. AlN and Cr have been etched by inductively coupled plasma (ICP) dry etching using a BCl3–Cl2–Ar plasma chemistry. As part of the novelty of the post-CMOS micromachining process presented here, a silicon Si (1 0 0) wafer has been used as substrate as well as the sacrificial layer used to release the microcantilevers. In order to achieve this, the Si surface underneath the structure has been wet etched using an HNA (hydrofluoric acid + nitric acid + acetic acid) based solution. X-ray diffraction (XRD) characterization indicated the high crystalline quality of the AlN film. An atomic force microscope (AFM) has been used to determine the Cr electrode surface roughness. The morphology of the fabricated devices has been studied by scanning electron microscope (SEM). The cantilevers have been piezoelectrically actuated and their out-of-plane vibration modes were detected by vibrometry.

Electron tomography of (In,Ga)N insertions in GaN nanocolumns grown on semi-polar (11(2)over-bar2) GaN templates

We present results of scanning transmission electron tomography on GaN/(In,Ga)N/GaN nanocolumns (NCs) that grew uniformly inclined towards the patterned, semi-polar GaN( 112̄ 2 ) substrate surface by molecular beam epitaxy. For the practical realization of the tomographic experiment, the nanocolumn axis has been aligned parallel to the rotation axis of the electron microscope goniometer. The tomographic reconstruction allows for the determination of the three-dimensional indium distribution inside the nanocolumns. This distribution is strongly interrelated with the nanocolumn morphology and faceting. The (In,Ga)N layer thickness and the indium concentration differ between crystallographically equivalent and non-equivalent facets. The largest thickness and the highest indium concentration are found at the nanocolumn apex parallel to the basal planes.

Electro-optical characterization of IC compatible microcantilevers

The aim of this work is to simulate and optically characterize the piezoelectric performance of complementary metal oxide semiconductor (CMOS) compatible microcantilevers based on aluminium nitride (AlN) and manufactured at room temperature. This study should facilitate the integration of piezoelectric micro-electro-mechanical systems (MEMS) such as microcantilevers, in CMOS technology. Besides compatibility with standard integrated circuit manufacturing procedures, low temperature processing also translates into higher throughput and, as a consequence, lower manufacturing costs. Thus, the use of the piezoelectric properties of AlN manufactured by reactive sputtering at room temperature is an important step towards the integration of this type of devices within future CMOS technology standards. To assess the reliability of our fabrication process, we have manufactured arrays of free-standing microcantilever beams of variable dimension and studied their piezoelectric performance. The characterization of the first out-of-plane modes of AlN-actuated piezoelectric microcantilevers has been carried out using two optical techniques: laser Doppler vibrometry (LDV) and white light interferometry (WLI). In order to actuate the cantilevers, a periodic chirp signal in certain frequency ranges was applied between the device electrodes. The nature of the different vibration modes detected has been studied and compared with that obtained by a finite element model based simulation (COMSOL Multiphysics), showing flexural as well as torsional modes. The correspondence between theoretical and experimental data is reasonably good, probing the viability of this high throughput and CMOS compatible fabrication process. To complete the study, X-ray diffraction as well as d33 piezoelectric coefficient measurements were also carried out.

IN-SITU ELECTRICAL, MECHANICAL AND ELECTROCHEMICAL CHARACTERIZATIONS OF ONE-DIMENSIONAL NANOSTRUCTURES

One-dimensional nanostructures initiated new aspects to the materials applications due to their superior properties compared to the bulk materials. Properties of nanostructures have been characterized by many techniques and used for various device applications. However, simultaneous correlation between the physical and structural properties of these nanomaterials has not been widely investigated. Therefore, it is necessary to perform in-situ study on the physical and structural properties of nanomaterials to understand their relation. In this work, we will use a unique instrument to perform real time atomic force microscopy (AFM) and scanning tunneling microscopy (STM) of nanomaterials inside a transmission electron microscopy (TEM) system. This AFM/STM-TEM system is used to investigate the mechanical, electrical, and electrochemical properties of boron nitride nanotubes (BNNTs) and Silicon nanorods (SiNRs). BNNTs are one of the subjects of this PhD research due to their comparable, and in some cases superior, properties compared to carbon nanotubes. Therefore, to further develop their applications, it is required to investigate these characteristics in atomic level. In this research, the mechanical properties of multi-walled BNNTs were first studied. Several tests were designed to study and characterize their real-time deformation behavior to the applied force. Observations revealed that BNNTs possess highly flexible structures under applied force. Detailed studies were then conducted to understand the bending mechanism of the BNNTs. Formations of reversible ripples were observed and described in terms of thermodynamic energy of the system. Fracture failure of BNNTs were initiated at the outermost walls and characterized to be brittle. Second, the electrical properties of individual BNNTs were studied. Results showed that the bandgap and electronic properties of BNNTs can be engineered by means of applied strain. It was found that the conductivity, electron concentration and carrier mobility of BNNTs can be tuned as a function of applied stress. Although, BNNTs are considered to be candidate for field emission applications, observations revealed that their properties degrade upon cycles of emissions. Results showed that due to the high emission current density, the temperature of the sample was increased and reached to the decomposition temperature at which the B-N bonds start to break. In addition to BNNTs, we have also performed in-situ study on the electrochemical properties of silicon nanorods (SiNRs). Specifically, lithiation and delithiation of SiNRs were studied by our STM-TEM system. Our observations showed the direct formation of Li22Si5 phases as a result of lithium intercalation. Radial expansion of the anode materials were observed and characterized in terms of size-scale. Later, the formation and growth of the lithium fibers on the surface of the anode materials were observed and studied. Results revealed the formation of lithium islands inside the ionic liquid electrolyte which then grew as Li dendrite toward the cathode material.

Study of ammonia borane and its derivatives: Influence of nanoconfinements and pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. ^ The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. ^ The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ∼140 degree Celcius and ∼0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. ^ The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ∼125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ∼13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. ^ In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.^

High Frequency Class DE Converter Using a Multilayer Coreless PCB Transformer

In modern power electronics equipment, it is desirable to design a low profile, high power density, and fast dynamic response converter. Increases in switching frequency reduce the size of the passive components such as transformers, inductors, and capacitors which results in compact size and less requirement for the energy storage. In addition, the fast dynamic response can be achieved by operating at high frequency. However, achieving high frequency operation while keeping the efficiency high, requires new advanced devices, higher performance magnetic components, and new circuit topology. These are required to absorb and utilize the parasitic components and also to mitigate the frequency dependent losses including switching loss, gating loss, and magnetic loss. Required performance improvements can be achieved through the use of Radio Frequency (RF) design techniques. To reduce switching losses, resonant converter topologies like resonant RF amplifiers (inverters) combined with a rectifier are the effective solution to maintain high efficiency at high switching frequencies through using the techniques such as device parasitic absorption, Zero Voltage Switching (ZVS), Zero Current Switching (ZCS), and a resonant gating. Gallium Nitride (GaN) device technologies are being broadly used in RF amplifiers due to their lower on- resistance and device capacitances compared with silicon (Si) devices. Therefore, this kind of semiconductor is well suited for high frequency power converters. The major problems involved with high frequency magnetics are skin and proximity effects, increased core and copper losses, unbalanced magnetic flux distribution generating localized hot spots, and reduced coupling coefficient. In order to eliminate the magnetic core losses which play a crucial role at higher operating frequencies, a coreless PCB transformer can be used. Compared to the conventional wire-wound transformer, a planar PCB transformer in which the windings are laid on the Printed Board Circuit (PCB) has a low profile structure, excellent thermal characteristics, and ease of manufacturing. Therefore, the work in this thesis demonstrates the design and analysis of an isolated low profile class DE resonant converter operating at 10 MHz switching frequency with a nominal output of 150 W. The power stage consists of a class DE inverter using GaN devices along with a sinusoidal gate drive circuit on the primary side and a class DE rectifier on the secondary side. For obtaining the stringent height converter, isolation is provided by a 10-layered coreless PCB transformer of 1:20 turn’s ratio. It is designed and optimized using 3D Finite Element Method (FEM) tools and radio frequency (RF) circuit design software. Simulation and experimental results are presented for a 10-layered coreless PCB transformer operating in 10 MHz.

Theory and optimisation of 1.3 and 1.55 μm (Al)InGaAs metamorphic quantum well lasers

The use of InGaAs metamorphic buffer layers (MBLs) to facilitate the growth of lattice-mismatched heterostructures constitutes an attractive approach to developing long-wavelength semiconductor lasers on GaAs substrates, since they offer the improved carrier and optical confinement associated with GaAs-based materials. We present a theoretical study of GaAs-based 1.3 and 1.55 μm (Al)InGaAs quantum well (QW) lasers grown on InGaAs MBLs. We demonstrate that optimised 1.3 μm metamorphic devices offer low threshold current densities and high differential gain, which compare favourably with InP-based devices. Overall, our analysis highlights and quantifies the potential of metamorphic QWs for the development of GaAs-based long-wavelength semiconductor lasers, and also provides guidelines for the design of optimised devices.

Design, production and testing of innovative key components of HEV/BEV powertrains

Through modelling activity, experimental campaigns, test bench and on-field validation, a complete powertrain for a BEV has been designed, assembled and used in a motorsport competition. The activity can be split in three main subjects, representing the three key components of an BEV vehicle. First of all a model of the entire powertrain has been developed in order to understand how the various design choices will influence the race lap-time. The data obtained was then used to design, build and test a first battery pack. After bench tests and track tests, it was understood that by using all the cell charac-teristics, without breaking the rules limitations, higher energy and power densities could have been achieved. An updated battery pack was then designed, produced and raced with at Motostudent 2018 re-sulting in a third place at debut. The second topic of this PhD was the design of novel inverter topologies. Three inverters have been de-signed, two of them using Gallium Nitride devices, a promising semiconductor technology that can achieve high switching speeds while maintaining low switching losses. High switching frequency is crucial to reduce the DC-Bus capacitor and then increase the power density of 3 phase inverters. The third in-verter uses classic Silicon devices but employs a ZVS (Zero Voltage Switching) topology. Despite the in-creased complexity of both the hardware and the control software, it can offer reduced switching losses by using conventional and established silicon mosfet technology. Finally, the mechanical parts of a three phase permanent magnet motor have been designed with the aim to employ it in UniBo Motorsport’s 2020 Formula Student car.

Rotational and ro-vibrational spectroscopy of small nitrogen-containing species and their astrophysical applications

This thesis presents the study of small nitrogen-bearing molecules, from diatomic radicals to complex organic molecules, by means of rotational and ro-vibrational spectroscopy. Besides their theoretical relevance, which spans from anharmonic force field analyses to energetic and structural properties, I have chosen this family of species because of their astrochemical importance. After some basic knowledge of molecular spectroscopy and astrochemistry is introduced, the instrumentation used during the course of my PhD school is described. Then, the most relevant studies I conducted during the last three years are presented. Generally speaking, a number of molecules of astrophysical relevance have been characterized by means of rotational and ro-vibrational spectroscopy. The sample of studied species is constituted by small radicals (imidogen, amidogen, and titanium nitride), cyanopolyynes (cyanoacetylene) and pre-biotic molecules (aminoacetonitrile): these studies are presented in great detail. Among the results, the first astronomical detection of two deuterated radicals (NHD and ND2) is presented in this thesis.Thanks to our studies, it was possible to clearly identify molecular absorptions of these species towards the pre-stellar core IRAS16293-2422, as recorded by the Herschel Space Observatory mission. These observations confirm the strong deuterium enhancement generally observed in this cloud but they reveal that models underestimate the abundances of NHD and ND2. I also report the detection of vibrationally excited aminoacetonitrile (NH2CH2CN) in Sagittarius B2, as observed in the ReMoCa survey. This is the second detection of aminoacetonitrile in the interstellar medium and the first astronomical observation of its vibrationally hot lines. This represents a small step toward the comprehension on how complex organic molecules are formed and which processes can lead to the formation of glycine. Finally, few general remarks are discussed and the importance of future laboratory studies is pointed out, along with possible perspectives.

Long-term reliability of power GaN HEMTS

The world is quickly changing, and the field of power electronics assumes a pivotal role in addressing the challenges posed by climate change, global warming, and energy management. The introduction of wide-bandgap semiconductors, particularly gallium nitride (GaN), in contrast to the traditional silicon technology, is leading to lightweight, compact and evermore efficient circuitry. However, GaN technology is not mature yet and still presents reliability issues which constrain its widespread adoption. Therefore, GaN reliability is a hotspot for the research community. Extensive efforts have been directed toward understanding the physical mechanisms underlying the performance and reliability of GaN power devices. The goal of this thesis is to propose a novel in-circuit degradation analysis in order to evaluate the long-term reliability of GaN-based power devices accurately. The in-circuit setup is based on measure-stress-measure methodology where a high-speed synchronous buck converter ensures the stress while the measure is performed by means of full I-V characterizations. The switch from stress mode to characterization mode and vice versa is automatic thanks to electromechanical and solid-state relays controlled by external unit control. Because these relays are located in critical paths of the converter layout, the design has required a comprehensive study of electrical and thermal problems originated by the use of GaN technology. In addition, during the validation phase of the converter, electromagnetic-lumped-element circuit simulations are carried out to monitor the signal integrity and junction temperature of the devices under test. However, the core of this work is the in-circuit reliability analysis conducted with 80 V GaN HEMTs under several operating conditions of the converter in order to figure out the main stressors which contribute to the device's degradation.

Determination of local density of states in amorphous oxide semiconductors with Kelvin Probe Force Microscopy

Amorphous semiconductors are important materials as they can be deposited by physical deposition techniques on large areas and even on plastic substrates. Therefore, they are crucial for transistors in large active matrices for imaging and transparent wearable electronics. The most widely applied candidate for amorphous thin film transistors production is Indium Gallium Zinc Oxide (IGZO). It is attracting much interest because of its optical transparency, facile processing by sputtering deposition and notable improved charge carrier mobility with respect to hydrogenated amorphous silicon a-Si:H. Degradation of the device and long-term performance issues have been observed if IGZO thin film transistors are subjected to electrical stress, leading to a modification of IGZO channel properties and subthreshold slope. Therefore, it is of great interest to have a reliable and precise method to study the conduction band tail, and the density of states in amorphous semiconductors. The aim of this thesis is to develop a local technique using Kelvin Probe Force Microscopy to study the evolution of IGZO DOS properties. The work is divided into three main parts. First, solutions to the non-linear Poisson-Boltzmann equation of a metal-insulator-semiconductor junction describing the charge accumulation and its relation to DOS properties are elaborated. Second macroscopic techniques such as capacitance voltage (CV) measurements and photocurrent spectroscopy are applied to obtain a non-local estimate of band-tail DOS properties in thin film transistor samples. The third part of my my thesis is dedicated to the KPFM measurements. By fitting the data to the developed numerical model, important parameters describing the amorphous conduction band tail are obtained. The results are in excellent agreement with the macroscopic characterizations. KPFM result is comparable also with non-local optoelectronic characterizations, such as photocurrent spectroscopy.