The structure and the energy band gap of hydrogenated amorphous silicon carbide are theoretically revised. In the light of defect pool model, density of states distribution is investigated for various regions of mobility gap. The films are deposited by plasma enhanced chemical vapor deposition system with various gas concentrations at two different, lower (30 mW/cm2) and higher (90 mW/cm2), radio frequency power densities. The elemental composition of hydrogenated amorphous silicon carbide films and relative composition of existing bond types are analyzed by x-ray photoelectron spectroscopy measurements. The thicknesses, deposition rates, refractive indices and optical band gaps of the films are determined by ultraviolet visible transmittance measurements. Uniformity of the deposited films is analyzed along the radial direction of the bottom electrode of the plasma enhanced chemical vapor deposition reactor. The molecular vibration characteristics of the films are reviewed and analyzed by Fourier transform infrared spectroscopy measurements. Electrical characteristics of the films are analyzed by dc conductivity measurements. Conduction mechanisms, such as extended state, nearest neighbor and variable range hopping in tail states are revised. The hopping conductivities are analyzed by considering the density of states distribution in various regions of mobility gap. The experimentally measured activation energies for the films of high carbon content are too low to be interpreted as the difference between Fermi level and relevant band edge. This anomaly has been successfully removed by introducing hopping conduction across localized tail states of the relevant band. In other words, the second contribution lowers the mobility edge towards the Fermi level.

Trapping centres and their distributions in as-grown TlGaSeS layered single crystals were studied using thermally stimulated current (TSC) measurements. The investigations were performed in the temperature range of 10&ndash / 160 K with various heating rates between 0.6&ndash / 1.2 K/s. Experimental evidence has been found for the presence of three electrons trapping centres with activation energies 12, 20, and 49 meV and one hole trapping centre located at 12 meV. Their capture cross-sections and concentrations were also determined. It is concluded that in these centres retrapping is negligible as confirmed by the good agreement between the experimental results and the theoretical predictions of the model that assumes slow retrapping. The optical properties of TlGaSeS layered single crystals have been investigated by measuring the transmission and the reflection in the wavelength region between 400 and 1100 nm. The optical indirect transitions with a band gap energy of 2.27 eV and direct transitions with a band gap energy of 2.58 eV were found by analyzing the absorption data at room temperature. The rate of change v of the indirect band gap with temperature was determined from the transmission measurements in the temperature range of 10&ndash / 300 K. The oscillator and the dispersion energies, the oscillator strength, and the zero-frequency refractive index were also reported. The parameters of monoclinic unit cell and the chemical composition of TlGaSes crystals were found by X-ray powder diffraction and energy dispersive spectroscopic analysis, respectively.

<p>The fascinating optical properties of metallic nanostructures, dominated by collective oscillations of free electrons known as plasmons, open new opportunities for the development of devices fabrication based on noble metal nanoparticle composite materials. This thesis demonstrates a low-cost and versatile technique to produce stimuli-responsive ultrafast plasmonic nanostructures with reversible tunable optical properties. Albeit challenging, further control using thermal external stimuli to tune the local environment of gold nanoparticles embedded in VO2 host matrix would be ideal for the design of responsive functional nanocomposites. We prepared Au-VO2 nanocomposite thin films by the inverted cylindrical reactive magnetron sputtering (ICMS) known as hollow cathode magnetron sputtering for the first time and report the reversible tuning of surface plasmon resonance of Au nanoparticles by only adjusting the external temperature stimuli. The structural, morphological, interfacial analysis and optical properties of the optimized nanostructures have been studied. ICMS has been attracting much attention for its enclosed geometry and its ability to deposit on large area, uniform coating of smart nanocomposites at high deposition rate. Before achieving the aforementioned goals, a systematic study and optimization process of VO2 host matrix has been done by studying the influence of deposition parameters on the structural, morphological and optical switching properties of VO2 thin films. A reversible thermal tunability of the optical/dielectric constants of VO2 thin films by spectroscopic ellipsometry has been intensively also studied in order to bring more insights about the shift of the plasmon of gold nanoparticles imbedded in VO2 host matrix.</p>

Orientador: Lucila Helena Deliesposte Cescato / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-15T19:36:27Z (GMT). No. of bitstreams: 1 Avila_LuisFernandode_D.pdf: 1824665 bytes, checksum: 6cab44933ac386ebd3097bd193d85e0f (MD5) Previous issue date: 2010 / Resumo: Materiais fotossensíveis são materiais que sofrem alterações físico-químicas quando expostos à luz de comprimento de onda apropriado. A gama de aplicações para estes materiais é enorme, entre elas as que apresentam maiores exigências em termos do próprio material são as aplicações em armazenagem de informação e imagens. Para avaliar o potencial de um material para uma dada aplicação é necessário entender os mecanismos fotossensíveis envolvidos assim como caracterizar suas propriedades, tais como: sensibilidade espectral, modulação óptica máxima, reversibilidade, estabilidade térmica, etc. Nesta tese de doutorado foi proposto e demonstrado um método para processar os sinais de auto-difração que, além de permitir a medida simultânea e independente das modulações de índice de refração e de coeficiente de absorção, nos permite medir a evolução temporal das modulações e a constante cinética das reações fotossensíveis. Esta técnica foi utilizada para estudar três tipos de materiais fotossensíveis: fotorresinas positivas (SC 1827 da Shipley), fotorresinas negativas (SU-8 da Microchem) e vidros calcogenetos (em particular composições com Sulfeto de Antimônio). As medidas foram realizadas utilizando-se dois interferômetros diferentes: um com óptica para o visível e outro para o ultravioleta. Além disso, foi observada uma modulação de elétrons secundários nas imagens de microscopia eletrônica de amostras de fotorresinas negativas SU8 expostas holograficamente / Abstract: Photosensitive materials are materials that change their optical properties when exposed to light of appropriate wavelength. The range of applications of such materials is very wide. Among these applications the storage of images and information is that present higher requirements in terms of the material itself. To evaluate the potential of a material for a given application it is necessary to understand the mechanisms involved as well as to characterize their photosensitive properties such as spectral sensitivity, maximum optical modulation, reversibility, thermal stability, etc. In this thesis we propose and demonstrate a method for processing the selfdiffraction the signals that allows the simultaneous and independent measurement of the modulations of refractive index and absorption coefficient as well as to measure the temporal evolution of such modulations and their corresponding kinetic constant of the photo-reactions. This technique was employed to study three types of photosensitive materials: positive photoresist (SC 1827 from Shipley), negative photoresist (Microchem SU-8) and chalcogenide glasses (in particular compositions with Antimony Sulfide). Measurements were performed using two different interferometers, one with optics for the visible and one for the ultra-violet. Moreover, a modulation of secondary electrons was observed in the electronic microscopy images of the SU8 negative photoresist samples exposed holographically / Doutorado / Ótica / Doutor em Ciências

Philosophiae Doctor - PhD / The fascinating optical properties of metallic nanostructures, dominated by collective oscillations of free electrons known as plasmons, open new opportunities for the development of devices fabrication based on noble metal nanoparticle composite materials. This thesis demonstrates a low-cost and versatile technique to produce stimuli-responsive ultrafast plasmonic nanostructures with reversible tunable optical properties. Albeit challenging, further control using thermal external stimuli to tune the local environment of gold nanoparticles embedded in VO2 host matrix would be ideal for the design of responsive functional nanocomposites. We prepared Au-VO2 nanocomposite thin films by the inverted cylindrical reactive magnetron sputtering (ICMS) known as hollow cathode magnetron sputtering for the first time and report the reversible tuning of surface plasmon resonance of Au nanoparticles by only adjusting the external temperature stimuli. The structural, morphological, interfacial analysis and optical properties of the optimized nanostructures have been studied. ICMS has been attracting much attention for its enclosed geometry and its ability to deposit on large area, uniform coating of smart nanocomposites at high deposition rate. Before achieving the aforementioned goals, a systematic study and optimization process of VO2 host matrix has been done by studying the influence of deposition parameters on the structural, morphological and optical switching properties of VO2 thin films. A reversible thermal tunability of the optical/dielectric constants of VO2 thin films by spectroscopic ellipsometry has been intensively also studied in order to bring more insights about the shift of the plasmon of gold nanoparticles imbedded in VO2 host matrix. / South Africa

Philosophiae Doctor - PhD / The limited supply of fossil hydrocarbon resources and the negative impact of CO2 emission on the global environment dictate the increasing usage of renewable energy sources. Concentrating solar power (CSP) systems are the most likely candidate for providing the majority of the renewable energy. For efficient photo-thermal conversion, these systems require spectrally selective solar absorber surfaces with high solar absorbance in the solar spectrum region and low thermal emittance in the infrared region. In this thesis, a spectrally selective AlxOy/Pt/AlxOy multilayer solar absorber was designed and deposited onto copper substrate using electron beam evaporation at room temperature. The employment of ellipsometric measurements and optical simulation was proposed as an effective method to optimize and deposit the multilayer solar absorber coatings. The optical constants measured using spectroscopic ellipsometry, showed that both AlxOy layers, which used in the coatings, were dielectric in nature and the Pt layer was semi-transparent. The optimized multilayer coatings exhibited high solar absorptance ~ 0.94±0.01 and low thermal emittance ~ 0.06 ± 0.01 at 82oC.The structural and optical properties of the coatings were investigated. It was found that the stratification of the coatings consists of a semitransparent middle Pt layer sandwiched between two layers of AlxOy. The top and bottom AlxOy layers were nonstoichiometric with no crystalline phases present. The Pt layer is in the fcc crystalline phase with a broad size distribution and spheroidal shape in and between the rims of AlxOy. The surface roughness of the stack was found to be comparable to the inter-particle distance. To study the thermal stability of the multilayer solar absorber coatings, the samples were annealed at different temperatures for different duration in air. The results showed changes in morphology, structure, composition, and optical properties depend on both temperature and duration of annealing. The XRD pattern showed that the intensity of Pt decreased with increasing annealing temperature and therefore, disappeared at high temperature. With increasing annealing temperature, an increase in the size of Pt particles was observed from SEM. The AlxOy/Pt/AlxOy multilayer solar absorber coatings deposited onto Cu substrate were found to be thermally stable up to 500oC in air for 2 h with good spectral selectivity of 0.951/0.09. At 600oC and 700oC, the spectral selectivity decreased to 0.92/0.10 and 0.846/0.11 respectively, which is attributed to the diffusion of Cu and formation of CuO and Cu2O phases. Long term thermal stability study showed that the coatings were thermally stable in air up to 450oC for 24 h. To elucidate the degradation mechanism beyond 500oC, HI-ERDA has been used to study depth-dependent atomic concentration profiles. These measurements revealed outward diffusion of the copper substrate towards the surface and therefore, the decrease in the constituents of the coating. Hence, to prevent copper from diffusing towards the coatings, a thin Tantalum (Ta) layer was deposited between the base AlxOy layer and the copper substrate.The effect of a thin Ta layer on the thermal stability of AlxOy/Pt/AlxOy multilayer solar absorber coatings was investigated. The Cu/Ta/AlxOy/Pt/AlxOy multilayer solar absorber coatings were found to be thermally stable up to 700oC in air for 2 h with good spectral selectivity of 0.937/0.10. At 800oC, the spectral selectivity decreased to 0.870/0.12, which is attributed to the diffusion of Cu and formation of CuO phase. The formation of CuO phase was confirmed by XRD, EDS and Raman spectroscopy. Long term thermal stability study showed that the coatings were thermally stable in air up to 550oC for 24 h. Therefore, the Cu/Ta/AlxOy/Pt/AlxOy spectrally selective solar absorber coatings can be used for high temperature solar-thermal applications.

Magister Philosophiae - MPhil / The fascinating optical properties of metallic nanostructures, dominated by collective oscillations of free electrons known as plasmons, open new opportunities for the development of devices fabrication based on noble metal nanoparticle composite materials. This thesis demonstrates a low-cost and versatile technique to produce stimuli-responsive ultrafast plasmonic nanostructures with reversible tunable optical properties. Albeit challenging, further control using thermal external stimuli to tune the local environment of gold nanoparticles embedded in V02 host matrix would be ideal for the design of responsive functional nanocomposites. We prepared Au-V02 nanocomposite thin films by the inverted cylindrical reactive magnetron sputtering (ICMS) known as hollow cathode magnetron sputtering for the first time and report the reversible tuning of surface plasmon resonance of Au nanoparticles by only adjusting the external temperature stimuli. The structural, morphological, interfacial analysis and optical properties of the optimized nanostructures have been studied. ICMS has been attracting much attention for its enclosed geometry and its ability to deposit on large area, uniform coating of smart nanocomposites at high deposition rate. Before achieving the aforementioned goals, a systematic study and optimization process of V02 host matrix has been done by studying the influence of deposition parameters on the structural, morphological and optical switching properties of V02 thin films. A reversible thermal tunability of the optical/dielectric constants of V02 thin films by spectroscopic ellipsometry has been intensively also studied in order to bring more insights about the shift of the plasmon of gold nanoparticles imbedded in V02 host matrix.

The incredible technological advancements over the last century have been possible due to tiny trinkets designed using semiconducting crystalline materials, especially Silicon and III-V compounds. Silicon, a group IV element has become the first choice in developing microchips serving an ever-growing set of applications including, computation, RF communications, solar cells, power electronics, quantum computing and its periphery, optoelectronics, IOT sensors, and lately artificial intelligence. Billions of Si-based complementary transistors (CMOS) are present at the center of most computing devices used today such as HPC servers, compute farms, laptops, and smartphones. The astonishing rise in transistor count, performance, and functionality as well as the exponential reduction in cost has been possible over the past decades due to a singular idea: shrinking the device. However, this rule, also called Moore's Law has been slowing over the past two decades and has eventually come to a standstill in its traditional definition. Moore's law has since been sustained by ingenious innovations such as high-k gate dielectrics, vertical scaling, lattice strain engineering, novel material developments and, lately chiplets as well as multi-die vertical packaging. As conventional Si CMOS approaches a roadblock, this work presents research on Germanium-based multi-gate devices providing promise for faster and low-power operation. This work discusses how Ge grown on a GaAs substrate can be tuned and utilized to form a virtually defect-free channel for ultra-scaled multi-gate transistors. Calibrated solvers informed using in-house materials and devices as well as literature are used to predict device performance for advanced structures. Further, a hybrid CMOS system with the high hole mobility p-channel device formed using tensile strained Ge, and the high electron mobility n-channel device formed using the underlying InGaAs layer is proposed and simulated. As scaling approaches Gate-all-around Nanosheet FETs in 2024 and complementary-FETs (CFETs) around 2034, Ge-on-AlAs based transistors can offer unique process simplifications, defect reduction, yield improvement, and high-performance advantages showing promise for future IRDS nodes. The process design, material stack, device, and circuit performance for this novel Ge-based NSFET is presented in this work. The lack of large strain or strain relaxation in the NS multilayer starting stack is seen to be a great process advantage for the Ge-AlAs NSFET system. To a certain extent, Si seems omnipotent for all things electronics. However, one exception is on-chip light generation. A coherent electrically controllable on-chip light source is a central component critical for optoelectronics, quantum technologies, fiber communications, and sensing. Due to the indirect bandgap, Si cannot produce light hence direct bandgap materials such as GaAs and GaN have been the primary choice for off-chip light sources integrable on the platform. Interestingly, Ge has a pseudo-direct bandgap, i.e., unlike Silicon, it can be manipulated to produce light using heavy doping, tensile strain, and Sn alloying. Similar to conventional III-V light sources, reduction in the dimensionality of the gain medium, i.e., Ge can enable a drastic reduction in the current required to produce light, among other performance considerations. This reduced dimensionality can be achieved by forming quantum wells and quantum dots. In this work, two new types of Ge-based quantum well lasers are introduced and analyzed along with qualitative and quantitive benchmarking. The first QW laser uses a small epitaxial biaxial tensile strain to improve the direct-ness of the Ge gain medium. The internal quantum efficiency, net gain, and threshold current can be improved drastically by choosing the right tensile strain while staying within a certain critical thickness value. For the first time, the impact of biaxial tensile strain on the optical properties of Ge is analyzed and reported through a systematic study of the dielectric spectra and optical constant using VASE. The changes in the band structure due to tensile strain are correlated with the critical points to uncover various optical transitions. An even better QW laser architecture is possible by utilizing a GeSn QW. This QW laser uses Sn-alloying to form a GeSn active region which is further lattice matched to the waveguide (InGaAs) and the optical confinement layers (InAlAs) around it. This completely lattice-matched laser structure can offer unique advantages such as virtually defect-free active region, tunability as well as improved efficiency and threshold current density. The absence of strain and consequently strain relaxation in the laser stack enables one to steer away from the critical thickness limitation while opening doors to designing multiple quantum well lasers among other complex architectures. The impact of Sn alloying on the atomic structure, lattice coherence, and relaxation is analyzed through XRD reciprocal space maps and rocking curves as a function of Sn concentration. Further, this lattice-matched system, GeSn-InGaAs-InAlAs has the potential to mirror the benefits of the mature GaAs-AlGaAs system which led to many great technological innovations over the past decades such as lasers and LEDs. / Doctor of Philosophy / This thesis introduces two transistor technologies to extend the scaling beyond conventional Si devices into the next decade, and two QW laser technologies for integrated photonics. Through calibrated numerical solvers, a high mobility Ge and InGaAs cointegrated CMOS system for 0.5 V is introduced, analyzed and benchmarked with literature. A lattice matched Ge-on-AlAs multilayer stack is shown to have great potential to form a novel CMOS system which uses Ge Nanosheets, providing process advantage and superior performance. The next part of the thesis introduces two types of Ge based quantum well lasers, one based on tensile strained Ge and the other based on lattice matched Ge. Both show large performance improvements over previous attempts in literature. Lasing from an indirect bandgap material such as Ge, the associated challenges and performance metrics are discussed. Lastly, the optical, dielectrics and CP properties of tensile strained are presented for the first time uncovering interesting trends. Ge samples with increasing tensile strain are grown using MBE and measured using VASE to elucidate the physical phenomenon.

Optical properties of Tl4In3GaSe8, Tl4InGa3Se8, Tl4In3GaS8, Tl2InGaS4 and Tl4InGa3S8 chain and layered crystals were studied by means of photoluminescence (PL) and transmission-reflection experiments. Several emission bands were observed in the PL spectra within the 475-800 nm wavelength region. The results of the temperature- and excitation intensity-dependent PL measurements in 15-300 K and 0.13&times / 10-3-110.34 W cm-2 ranges, respectively, suggested that the observed bands were originated from the recombination of electrons with the holes by realization of donor-acceptor or free-to-bound type transitions. Transmission-reflection measurements in the wavelength range of 400-1100 nm revealed the values of indirect and direct band gap energies of the crystals studied. By the temperature-dependent transmission measurements in 10-300 K range, the rates of change of the indirect band gap of the samples with temperature were found to be negative. The oscillator and dispersion energies, and zero-frequency refractive indices were determined by the analysis of the refractive index dispersion data using the Wemple&ndash / DiDomenico single-effective-oscillator model. Furthermore, the structural parameters of all crystals were defined by the analysis of X-ray powder diffraction data. The determination of the compositional parameters of the studied crystals was done by energy dispersive spectral analysis experiments.

Trapping centres in as-grown TlInS2 layered single crystals have been studied by using a thermally stimulated current (TSC) technique. TSC measurements have been performed in the temperature range of 10-300 K with various heating rates. Experimental evidence has been found for the presence of five trapping centres with activation energies 12, 14, 400, 570 and 650 meV. Their capture cross-sections and concentrations were also determined. It is concluded that in these centres retrapping is negligible as confirmed by the good agreement between the experimental results and the theoretical predictions of the model that assumes slow retrapping. An exponential distribution of traps was revealed from the analysis of the TSC data obtained at different light excitation temperatures. The transmission and reflection spectra of TlInS2 crystals were measured over the spectral region of 400-1100 nm to determine the absorption coefficient and refractive index. The analysis of the room temperature absorption data revealed the coexistence of the indirect and direct transitions. The absorption edge was observed to shift toward the lower energy values as temperature increases from 10 to 300 K. The oscillator and the dispersion energies, and the zero-frequency refractive index were also reported. Furthermore, the chemical composition of TlInS2 crystals was determined from energy dispersive spectroscopic analysis. The parameters of monoclinic unit cell were found by studying the x-ray powder diffraction.