Orientador: Edison Zacarias da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-12T21:28:51Z (GMT). No. of bitstreams: 1 Pereira_ZennerSilva_M.pdf: 20162945 bytes, checksum: d21814c79148ec7f736ed05982bdddfc (MD5) Previous issue date: 2009 / Resumo: Nós apresentamos nesse trabalho dois assuntos relevantes na atualidade:Crescimento de filmes finos metálicos e nanoindentação.Estudamos esses sistemas utilizando dinâmica molecular com potenciais empíricos. Nós mostramos que é possível modelar o crescimento epitaxial utilizando potenciais adequados e uma específica metodologia de deposição. No crescimento de filmes finos estudamos três sistemas utilizando o potencial EAM:Cu/Ag(001),Cu/Au(001) e Pd/Au(001). Para Cu sobre Au e Cu sobre Ag obtivemos resultados de acordo com experimentos anteriores. Enfatizamos que a temperatura e a espessura do filme depositado estão relacionadas com as estruturas apresentadas durante o crescimento. Mostramos que a princípio o filme cresce sob stress numa fase instável bcc, porém ao atingir uma espessura crítica relaxa numa estrutura bct. Então, após a relaxação o filme apresenta um padrão de deformação (stripes). A Relação entre temperatura espessura e porcentagem de átomos nucleados bcc foi quantificada num gráfico. Para o caso Pd sobre Au mostramos que o crescimento resultou num padrão de deformação após atingir 11 camadas. Analisamos as estruturas e indentificamos defeitos tipo "falhas de empilhamento ". Para a modelagem de sistemas semicondutores nós utilizamos o potencial de Terso ..Com um indentador esférico de diamante indentamos uma superfície de silício.Um gráfico de deslocamento do indentador em função da pressão é apresentado. Analisamos o número de coordenação dos átomos de silício quando o indentador atingiu certos valores de pressão. / Abstract: In this work we present two important and current subjects:Metalic thin .lms and nanoindentation. We studied these systems using molecular dynamics with empirical potentials. We showed that it is possible to model the epitaxial growth using a suitable potential and a specific methodology for deposition.Concerning the growth of thin films,we studied three systems using EAM potential:Cu/Ag(001),Cu/Au(001)and Pd/Au(001).For Cu on Au and Cu on Ag,our results are in agreement with previous experiments. We stress that the existence of a bcc and bcc/bct are related to temperature and thickness of the deposited film. We showed that during the deposition of the first few layers,the film grows under stress to form an unstable bcc phase,but after a critical thickness it relaxes in a bct structure.Then,when the film is relaxed it presentes a deformation pattern (stripes). The relationships between temperature,thickness and formed structures are presented. For the case of Pd on Au the growth resulted in a deformation pattern after we deposited 11 mono-layers. We analysed the structures and found defect types known as stacking faults. To model semiconductors systems we used the Tersoff potential. We indented a surface of silicon with a spheric indenter of diamond.A graph of dislocation as function of pressure for the indenter is presented. We analysed the coordination number of silicon atoms when the indenter reached specific values of pressure. / Mestrado / Física da Matéria Condensada / Mestre em Física

Deep ultraviolet (UV) light sources are useful in a number of applications that include sterilization, medical diagnostics, as well as chemical and biological identification. However, state-of-the-art deep UV light-emitting diodes and lasers made from semiconductors still suffer from low external quantum efficiency and low output powers. These limitations make them costly and ineffective in a wide range of applications. Deep UV sources such as lasers that currently exist are prohibitively bulky, complicated, and expensive. This is typically because they are constituted of an assemblage of two to three other lasers in tandem to facilitate sequential harmonic generation that ultimately results in the desired deep UV wavelength. For semiconductor-based deep UV sources, the most challenging difficulty has been finding ways to optimally dope the (Al,Ga)N/GaN heterostructures essential for UV-C light sources. It has proven to be very difficult to achieve high free carrier concentrations and low resistivities in high-aluminum-containing III-nitrides. As a result, p-type doped aluminum-free III-nitrides are employed as the p-type contact layers in UV light-emitting diode structures. However, because of impedance-mismatch issues, light extraction from the device and consequently the overall external quantum efficiency is drastically reduced. This problem is compounded with high losses and low gain when one tries to make UV nitride lasers. In this thesis, we provide a robust and reproducible approach to resolving most of these challenges. By using a liquid-metal-enabled growth mode in a plasma-assisted molecular beam epitaxy process, we show that highly-doped aluminum containing III-nitride films can be achieved. This growth mode is driven by kinetics. Using this approach, we have been able to achieve extremely high p-type and n-type doping in (Al,Ga)N films with high aluminum content. By incorporating a very high density of Mg atoms in (Al,Ga)N films, we have been able to show, by temperature-dependent photoluminescence, that the activation energy of the acceptors is substantially lower, thus allowing a higher hole concentration than usual to be available for conduction. It is believed that the lower activation energy is a result of an impurity band tail induced by the high Mg concentration. The successful p-type doping of high aluminum-content (Al,Ga)N has allowed us to demonstrate operation of deep ultraviolet LEDs emitting at 274 nm. This achievement paves the way for making lasers that emit in the UV-C region of the spectrum. In this thesis, we performed preliminary work on using our structures to make UV-C lasers based on photonic crystal nanocavity structures. The nanocavity laser structures show that the threshold optical pumping power necessary to reach lasing is much lower than in conventional edge-emitting lasers. Furthermore, the photonic crystal nanocavity structure has a small mode volume and does not need mirrors for optical feedback. These advantages significantly reduce material loss and eliminate mirror loss. This structure therefore potentially opens the door to achieving efficient and compact lasers in the UV-C region of the spectrum.

This study focuses on the growth and characterization of epitaxial InAs and InAs1-xSbx. Layers are grown on InAs, GaAs and GaSb substrates by metalorganic vapour phase epitaxy, using trimethylindium, trimethylantimony and arsine as precursors. The growth parameters (V/III ratio, Sb vapour phase compositions) are varied in the temperature range from 500 ºC to 700 ºC, in order to study the influence of these parameters on the structural, optical and electrical properties of the materials. The layers were assessed by X-ray diffraction, electron and optical microscopy, photoluminescence and Hall measurements. Furthermore, the influence of hydrogenation and annealing on the electrical and optical properties of GaSb was investigated. It is shown that the growth temperature and the V/III ratio play a vital role in the resulting surface morphology of homoepitaxial and heteroepitaxial InAs layers. Growth at low temperatures is found to promote three-dimensional growth in both cases, with improvements in the surface morphologies observed for higher growth temperatures. All the investigated epilayers are n-type. It is shown that the electrical properties of heteroepitaxial InAs epilayers are complicated by a competition between bulk conduction and conduction due to a surface accumulation and an interface layer. The low temperature photoluminescence spectra of homoepitaxial InAs are dominated by two transitions. These are identified as band-to-band/excitonic and donor-acceptor recombination. The incorporation efficiency of antimony (Sb) into InAs1-xSbx is dependent on the growth temperature and the V/III ratio. Under the growth conditions used in this study, the incorporation efficiency of Sb is controlled by the thermal stability of the two constituent binaries (i.e. InAs and InSb). Changes in the low temperature photoluminescence spectra are detected with increasing x. From temperature and laser power dependent measurements, the highest energy line is attributed to band-to-band/excitonic recombination, while the peak appearing approximately 15 meV below this line is assigned to donor-acceptor recombination. The origin of an additional “moving” peak observed for higher Sb mole fraction x is tentatively attributed to quasi-donor-acceptor-recombination, arising from increased impurity/defect concentrations and a higher compensation ratio in the material. However, the unusual behaviour of this peak may also be ascribed to the presence of some degree of ordering in InAsSb. The exposure of a semiconductor to a hydrogen plasma usually leads to the passivation of shallow and deep centres, thereby removing their electrical and optical activity. In this study, the passivation and thermal stability of the native acceptor in p-type GaSb is also investigated. It is shown that this acceptor can be passivated, where after improvements in the electrical and optical properties of GaSb are observed. Upon annealing the passivated samples above 300 °C, the acceptor is reactivated.

Ce travail de thèse porte sur la croissance et sur la caractérisation optique de nanostructures à base d’antimoine sur substrats InP, en vue d’applications dans le domaine des télécommunications optiques. La transition inter-sous-bande est un processus ultrarapide qui permet la modulation de la lumière dans les réseaux de télécommunication optique. Durant cette thèse, une absorption inter-sous-bande dans le proche-infrarouge provenant de puits quantiques Ga0.47In0.53As/AlAs0.56Sb0.44 a été observée pour la première fois au laboratoire. Les analyses par microscopie électronique à effet tunnel sur la face clivée montrent cependant de nombreux déviations à l’idéalité de nos structures : mélange à l’échelle atomique aux interfaces entre GaInAs et AlAsSb, inhomogénéité de l’alliage GaInAs, incorporation non-intentionnel d’antimoine dans le GaInAs. Les puits quantiques InAs/AlAs0.56Sb0.44 sont potentiellement des objets de choix pour la réalisation de composants intersous- bande travaillant à 1,55 μm. Des puits quantiques InAs/AlAs0.56Sb0.44 contraint, exempt de défauts ont été obtenus par croissance assistée par effet surfactant de Sb. En symétrisant la contrainte induite par le dépôt d’InAs par l’insertion de couches nanométriques de AlAs dans les barrières, des multi-puits InAs/AlAs0.56Sb0.44 sans contrainte macroscopique ont été réalisés. L’effet de l’antimoine en surface sur la croissance de structure InAs/GaAs0.51Sb0.49 a également été étudié. En présence d’antimoine sur substrats InP d’orientation (001), le dépôt d’InAs conduit à la formation de puits quantiques. Par contre sur ceux orientés suivant (113)B des boites quantiques sont formées suivant le mode de croissance Volmer-Weber. Ces résultats sont discutés en termes d’effets cinétiques ou énergétiques de l’antimoine en surface. La modification de l’anisotropie de l’énergie de surface induite par l’antimoine permet d’interpréter nos résultats sur substrats (100) et (113) B. / This PhD work presents molecular beam epitaxy growth and optical studies on several Sb-nanostructures on InP substrate, for their potential use in optical telecommunication. Inter-subband transition in Ga0.47In0.53As/AlAs0.56Sb0.44 quantum well is a useful physical process for implementing ultrafast fulloptical modulations. Near-infrared inter-subband transition in this material was achieved and microscopic studies on this structure has revealed that the intermixing at GaInAs/AlAsSb interface, unintentional Sb incorporation in GaInAs layer and the inhomogeneity within GaInAs layer could prevent Ga0.47In0.53As/ AlAs0.56Sb0.44 multiple quantum wells from achieving intersubband transition in 1.55 μm optical telecommunication band. The strained InAs/AlAs0.56Sb0.44 quantum well is another material that has potential use in 1.55 μm full-optical modulation. 2 nm-thick defect-free InAs/AlAs0.56Sb0.44 was obtained under Sb surfactant-mediated growth, and by using strain compensation techniques, InAs/AlAs0.56Sb0.44 multiple quantum wells with zero net-strain were realized. The study of Sb-mediated growth is also carried on to InAs/GaAs0.51Sb0.49 nanostructures. The growths of such structures on InP (001) substrate has led to the formation of flat InAs layer, while high-density InAs/GaAs0.51Sb0.49 quantum dots were obtained on InP (113)B substrates under Volmer-Weber growth mode. We attribute such phenomena to the surfaceorientation dependent surfactant effect of Sb. Emission wavelength close to 2 μm was achieved with only 5 ML of InAs deposition, which makes these quantum dots attractive to InPbased mid-wave applications.

Deep ultraviolet light emitting diodes (UV LEDs) are an important emerging technology for a number of applications such as water/air/surface disinfection, communications, and epoxy curing. However, as of yet, deep UV LEDs grown on sapphire substrates are neither efficient enough nor powerful enough to fully serve these and other potential applications. The majority of UV LEDs reported so far in the literature are grown on sapphire substrates and their design consists of AlGaN quantum wells (QWs) embedded in an AlGaN p-i-n junction with the n-type layer on the sapphire. These devices suffer from a high concentration of threading defects originating from the large lattice mismatch between the sapphire substrate and AlGaN alloys. Other issues include the poor doping efficiency of the n- and particularly the p-AlGaN alloys, the extraction of light through the sapphire substrate, and the heat dissipation through the thermally insulating sapphire substrate. These problems have historically limited the internal quantum efficiency (IQE), injection efficiency (IE), and light extraction efficiency (EE) of devices. As a means of addressing these efficiency and power challenges, I have contributed to the development of a novel inverted vertical deep UV LED design based on AlGaN grown on p-SiC substrates. Starting with a p-SiC substrate that serves as the p-type side of the p-i-n junction largely eliminates the necessity for the notoriously difficult p-type doping of AlGaN alloys, and allows for efficient heat dissipation through the highly thermally conductive SiC substrate. UV light absorption in the SiC substrate can be addressed by first growing p-type doped distributed Bragg reflectors (DBRs) on top of the substrate prior to the deposition of the active region of the device. A number of n-AlGaN films, AlGaN/AlGaN multiple quantum wells, and p-type doped AlGaN DBRs were grown by molecular beam epitaxy (MBE). These were characterized in situ by reflected high energy electron diffraction (RHEED) and ex situ by x-ray diffraction, scanning electron microscopy, atomic force microscopy, photoluminescence, and reflectivity. Using the primary elements of the proposed design, this research culminated in the MBE growth, fabrication, and characterization of prototype deep UV LED devices emitting below 300 nm.

abstract: The molecular beam epitaxy growth of the III-V semiconductor alloy indium arsenide antimonide bismide (InAsSbBi) is investigated over a range of growth temperatures and V/III flux ratios. Bulk and quantum well structures grown on gallium antimonide (GaSb) substrates are examined. The relationships between Bi incorporation, surface morphology, growth temperature, and group-V flux are explored. A growth model is developed based on the kinetics of atomic desorption, incorporation, surface accumulation, and droplet formation. The model is applied to InAsSbBi, where the various process are fit to the Bi, Sb, and As mole fractions. The model predicts a Bi incorporation limit for lattice matched InAsSbBi grown on GaSb.The optical performance and bandgap energy of InAsSbBi is examined using photoluminescence spectroscopy. Emission is observed from low to room temperature with peaks ranging from 3.7 to 4.6 μm. The bandgap as function of temperature is determined from the first derivative maxima of the spectra fit to an Einstein single oscillator model. The photoluminescence spectra is observed to significantly broaden with Bi content as a result of lateral composition variations and the highly mismatched nature of Bi atoms, pairs, and clusters in the group-V sublattice. A bowing model is developed for the bandgap and band offsets of the quinary alloy GaInAsSbBi and its quaternary constituents InAsSbBi and GaAsSbBi. The band anticrossing interaction due to the highly mismatched Bi atoms is incorporated into the relevant bowing terms. An algorithm is developed for the design of mid infrared GaInAsSbBi quantum wells, with three degrees freedom to independently tune transition energy, in plane strain, and band edge offsets for desired electron and hole confinement. The physical characteristics of the fundamental absorption edge of the relevant III-V binaries GaAs, GaSb, InAs, and InSb are examined using spectroscopic ellipsometry. A five parameter model is developed that describes the key physical characteristics of the absorption edge, including the bandgap energy, the Urbach tail, and the absorption coefficient at the bandgap. The quantum efficiency and recombination lifetimes of bulk InAs0.911Sb0.089 grown by molecular beam epitaxy is investigated using excitation and temperature dependent steady state photoluminescence. The Shockley-Read-Hall, radiative, and Auger recombination lifetimes are determined. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

Les matériaux III-nitrures sont des excellents semi-conducteurs qui présentent plusieurs propriétés intéressantes pour les applications photovoltaïques et piézoélectriques. Au même temps, la croissance epitaxiale de ces matériaux sous forme de nanofil (NF) est de tant en plus intéressant, car les NFs nitrures binaires et heterostructurés, ont une qualité cristalline supérieure comparés aux homologues 2D et massifs. Dans ces contextes, ce travail est axé sur la croissance par MBE assistée par plasma (PA-MBE) de NFs InGaN/GaN et leur caractérisation. Trois sujets principaux ont été abordés: l'étude de la croissance d’heterostructures InGaN axiales par PA-MBE, leur caractérisation optique, et l'étude de la croissance sélective de NFs GaN sur graphène transféré. Ces études m’ont permis d’obtenir un control rational sur le mode de croissance d’heterostructures InGaN dans une large gamme de teneurs d’In (jusqu'à ~ 40%) et morphologies, de étudier leur structure de bande axiale, utile pour la conception optimale de la structure p-i-n photovoltaïque, et de démontrer pour le première fois dans la littérature, que l’épitaxie sélective de NFs de GaN sur MCG lithographié est une route possible et très promettent pour améliorer leur homogénéité. Ainsi, des tests préliminaires ont montré que la capacité de piézo-conversion des NFs GaN peut être améliorée d'environ 35% lors de l'intégration d’une insertion InGaN riche en In dans leur volume.Tous ces résultats constituent un ’étape décisive dans le contrôle et la comprension des propriétés de ces nanostructures, et donnent des perspectives très encourageantes pour leur intégrations dans des nano-générateurs à haute efficacité. / III-nitride materials are excellent semiconductors presenting several interesting properties for photovoltaic and piezoelectric applications. At the same time, the epitaxial growth of these materials in the form of nanowires (NW) is even more interesting, because binary and heterostructured III-N NWs have a higher crystalline quality compared to the 2D and bulk counterparts. In these contexts, this work focuses on the plasma-assisted MBE (PA-MBE) growth of InGaN / GaN NWs and their characterization. Three main topics are addressed: the growth of axial InGaN heterostructures by PA-MBE, their optical characterization, and the study of the selective area growth (SAG) of GaN NWs on transferred graphene. These studies allowed me to obtain a rational control on the growth mode of InGaN heterostructures in a wide range of In contents (up to ~ 40%) and morphologies, to study their axial band edge profile, useful for the optimal design of the photovoltaic structure, and to demonstrate for the first time in the literature, that the SAG of GaN NWs on patterned mono-layer graphene is a possible and very promising strategy to improve their homogeneity. Also, preliminary tests have shown that the piezoelectric conversion capacity of GaN NWs can be improved by about 35% when integrating an In-rich InGaN insertion into their volume.All these results constitute a decisive step in the control and the comprehension of the properties of these nanostructures, and establish very encouraging perspectives for their integration in novel and efficient photovoltaic and piezoelectric nano-generators.

Tungsten oxide thin films were prepared by vacuum evaporation on surfaces of Pd(111), Cu(111), Cu(110) and Cu(100) single crystals and studied by RHEED, XPS and AFM methods. The tungsten oxide deposition was done at temperatures from 300 řC to 400 řC in UHV or in oxygen atmosphere. The best deposition conditions - substrate temperature of 400 řC and oxygen atmosphere - were found resulting in growth of epitaxial and only partially reduced thin films. Thin films grown on the Pd(111) and Cu(111) surfaces consisted of two phases: a nearly atomically flat phase with (100) epitaxial plane and a phase formed by three dimensional particles with (111) epitaxial plane. Thin film deposited on Cu(100) also consisted of two phases: a flat film with (100) epitaxial plane and self-organised 1D structures parallel to Cu[010] and Cu[001] directions. Thin film prepared on the Cu(110) surface contained solely 1D structures parallel to Cu[1-10] surface direction. Capability of the partially reduced thin films for oxidation was studied. We applied oxidation using RF oxygen plasma, O2 exposure at elevated temperature and exposure to atmosphere. Thermal stability of the WO3/Cu(110) system was also investigated by heating up to 620 řC.

B-Ga2O3 is one of the emerging semiconductor materials with high breakdown field strength (~ 8 MV/cm) and ultrawide-bandgap (UWBG) 4.9 eV. Therefore, B-Ga2O3 and related compound semiconductors are ideal for power electronics and deep/vacuum ultraviolet-wavelength photodetector applications. High-crystal-quality B-Ga2O3 semiconductor materials epitaxially deposited on the various substrate are prerequisites for realizing any practical application. However, it is still challenging to grow high-crystal-quality V-Ga2O3 layer and to integrate B-Ga2O3 with other semiconductor materials by direct epitaxy. Understanding the epitaxial relationship of the integrated oxide heterostructure and the substrate used helps to shed light on the feasibility of heterojunctions formation for photonic applications, such as the ultraviolet-wavelength photodetectors developed in this thesis. By optimizing pulsed laser deposition (PLD) conditions, such as laser energy, ambient gas, pressure, etc., a single-crystalline oxide heterostructure were successfully integrated into a photonic platform. This included p-NiO/n-B-Ga2O3/a-Al2O3, B-Ga2O3/y-In2O3/a-Al2O3, and B-Ga2O3/TiN/MgO structures. The epitaxial thin film crystallographic and chemical properties were investigated by different characterization techniques. The high-resolution X-ray diffraction (HRXRD) was applied to study the heterostructures’ epitaxial orientation relationship by out-of-plane XRD w-2θ-scan and asymmetric skew ɸ-scan. The lattice-mismatch at the heterostructure interfaces were examined and the crystal quality of the epitaxial thin films were measured by means of full-width at half-maximum (FWHM) fitting. Scanning-TEM energy-dispersive X-ray spectroscopy (STEM-EDX) was applied to qualitatively study the chemical elements’ spatial distribution. Rutherford backscattering spectroscopy (RBS) was applied to study the epitaxial thin film chemical composition, material stoichiometry, and inter-diffusion. The X-ray photoelectron spectroscopy (XPS) was applied to study the conduction and valence band offsets which is essential to determine the types of heterostructures formed. Finally, the p-NiO/n-B-Ga2O3/a-Al2O3 B-Ga2O3/y-In2O3/a-Al2O3, and B-Ga2O3/TiN/MgO epitaxial thin-film were fabricated into ultraviolet-wavelength photodetectors. The wavelength-dependent and power-dependent characterizations were applied to measure the cut-off wavelength and the peak responsivity. The time response characterization was applied to measure the photodetectors’ responses to pulse signals, and the rise and decay times were fitted by a double exponential function.

Hexagonal molybdenum nitride (δ-MoN) is one of the hardest superconductors, and its superconducting properties depend on the crystalline structure and the substrate of use. Herein, a versatile growth method has been utilized to grow single-crystalline (SC) δ-MoN thin films on any arbitrary substrate of interest. SC δ-MoN films have been achieved on amorphous substrates via the transfer of MoS2 precursors followed by chemical phase conversion. The transferred SC δ-MoN film on an amorphous SiO2/Si substrate exhibits superconductivity at Tc = 4.75 with an upper critical field Hc2(0) = 8.24 K. The effect of the transfer process was assessed by directly growing SC δ-MoN on an Al2O3 substrate, which showed enhanced superconductivity properties due to the nonuniformity in film thickness that the transfer process induces. The crystalline structure effect on superconductivity was studied by directly growing amorphous δ-MoN film on an amorphous SiO2/Si substrate. The amorphous film showed degraded superconducting behavior and confirmed that disorders in the crystal structure suppress superconductivity. The upper critical fields of the non-transferred δ-MoN films exceeded their Pauli paramagnetic limits, which could give rise to the existence of the Ising pairing effect, but further studies are needed to confirm this behavior.