Although silicon (Si) nanostructures exhibit size dependent light emission, which can be attributed to quantum confinement, the role of surface passivation is not yet fully understood. This understanding is central to the development of nanocrystal-based detectors. This study investigated the growth, surface chemistry, passivation with deuterium (D2), ammonia (ND3) and diborane (B2D6) and the resulting optical properties of Si nanostructures. Si nanocrystals less than 6 nm in diameter are grown on SiO2 surfaces in an ultra high vacuum chamber using hot-wire chemical vapor deposition and the as grown surfaces are exposed to atomic deuterium. Temperature programmed desorption (TPD) spectra show that that the nanocrystals surfaces are covered by a mix of monodeuteride, dideuteride and trideuteride species. The manner of filling of the deuteride states on nanocrystals differs from that for extended surfaces as the formation of the dideuteride and trideuteride species is facilitated by the curvature of the nanocrystal. No photoluminescence (PL) is observed from the as grown unpassivated nanocrystals. As the deuterium dose is increased, the PL intensity also begins to increase. This can be associated with increasing amounts of mono-, di- and trideuteride species on the nanocrystal surface, which results in better passivation of the dangling bonds and relaxing of the reconstructed surface. At high deuterium doses, the surface structure breaks down and amorphization of the top layer of the nanocrystal takes place. Amorphization reduces the PL intensity. Finally, as the nanocrystal size is varied, the PL peak shifts, which is characteristic of quantum confinement. The dangling bonds and the reconstructed bonds at the NC surface are also passivated and transformed with D and NDx by using deuterated ammonia (ND3), which is predissociated over a hot tungsten filament prior to adsorption. At low hot wire ND3 doses PL emission is observed at 1000 nm corresponding to reconstructed surface bonds capped by predominantly monodeuteride and Si-ND2 species. As the hot wire ND3 dose is increased, di- and trideuteride species form and intense PL is observed around 800 nm that does not shift with NC size and is associated with defect levels resulting from NDx insertion into the strained Si-Si bonds forming Si2=ND. The PL intensity at 800 nm increases as the ND3 dose is increased and the intensity increase is correlated to increasing concentrations of deuterides. At extremely high ND3 doses PL intensity decreases due to amorphization of the NC surface. In separate experiments, Si NCs were subjected to dissociative (thermal) exposures of ammonia followed by exposures to atomic deuterium. These NCs exhibited size dependent PL and this can be attributed to the prevention of the formation of Si2=ND species. Finally, deuterium-passivated Si NCs are exposed to BDx radicals formed by dissociating deuterated diborane (B2D6) over a hot tungsten filament and photoluminescence quenching is observed. Temperature programmed desorption spectra reveal the presence of low temperature peaks, which can be attributed to deuterium desorption from surface Si atoms bonded to subsurface boron atoms. The subsurface boron likely enhances nonradiative Auger recombination. / text

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Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-07-11T19:05:22Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE Renato Barbosa da Silva.pdf: 6315157 bytes, checksum: 2b3ac093113d303d28b902d531315c52 (MD5) / Made available in DSpace on 2016-07-11T19:05:22Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE Renato Barbosa da Silva.pdf: 6315157 bytes, checksum: 2b3ac093113d303d28b902d531315c52 (MD5) Previous issue date: 2015-08-27 / CAPES / Diferentes tipos de materiais foram abordados nesta tese visando sua possível aplicação na fotônica. Por isso, o texto foi dividido em duas partes. A Parte 1 trata da preparação de materiais para a aplicação em laser aleatório. O primeiro material sintetizado foram as nanocascas metálicas, cuja estrutura é formada por um caroço de sílica com uma casca metálica ao seu redor. Assim, foi descrito um procedimento experimental melhorado com o intuito de se obter nanocascas de ouro e de prata de maneira mais reprodutível no menor tempo possível. Neste experimento, foi demostrado que a taxa de agitação no final da síntese tem importante influência na formação ou não das nanocascas metálicas. O crescimento de nanocascas de ouro e prata ocorria para taxas de 190 rpm e 1500 rpm respectivamente. O segundo material consistiu de partículas sub-micrométricas de sílica com corante rodamina 640 encapsulado. O encapsulamento ocorreu pela simples adição de uma solução do corante durante a síntese das partículas de sílica. Assim, para uma concentração de corante de 10-2 M, foi descrito um experimento de laser aleatório bicromático. Ao contrário de outros trabalhos na literatura foi possível controlar a emissão do laser aleatório apenas mudando a intensidade de excitação. Durante estes experimentos também foi verificada a existência de frequency-pulling entre dímeros e monômeros nos experimentos. Finalmente na Parte 2 é discutida a síntese e caracterização de nanocristais de silício (ncSi). Os ncSi apresentam luminescência cujo comprimento de onda pode ser controlado variando o tamanho dos nanocristais. A síntese foi baseada no processamento termal em altas temperaturas do hidrossilicato HSiO1.5, derivado do triclorossilano (HSiCl3). Em seguida, os vidros são finamente macerados num almofariz e pistilo de ágata antes dos ncSi serem extraídos via extração ácida. Neste experimento o objetivo foi obter nanocristais de silício monodispersos sem a utilização de etapas pós-síntese como a ultracentrifugação. O objetivo foi alcançado adicionando cloreto de sódio (NaCl) durante a etapa maceração, com o intuito de diminuir o tamanho dos grãos e garantir uma extração uniforme dos mesmos / Different materials were reported in this thesis aiming their possible photonic applications. Therefore the content of this thesis was distributed in two parts. Part 1 is related to the synthesis of materials for applications in random laser. The first material synthesized were the metallic nanoshells, which structure is based in a silica core and a metallic shell around it. An improved experimental method was reported for synthesize gold and silver nanoshells in order to guarantee the reproducibility and decrease the time necessary for synthesis. It was shown that the stirring rate at the end of synthesis plays an important role on the growth of metallic nanoshells. The growth of gold nanoshells was performed using a stirring rate of 190 rpm, on the other hand, the growth of silver nanoshells was performed using a stirring rate of 1500 rpm. The second material consisted of sub-micrometer silica particles whith encapsulated rhodamine 640. The encapsulation was made by the simple addition of a dye solution to do during a Synthesis of silica particles. An bichromatic random laser was operated using a concentration of 10-2 M of laser dye. Unlike other works in the literature it was possible to control the emission of the random laser only changing the intensity of the excitation source. These experiments were also revealed the possibility of frequency-pulling between dimers and monomers of rhodamine through the shift of the laser emission. Finally, in Part 2 it is discussed the synthesis and characterization of silicon nanocrystals (ncSi). The ncSi present luminescence that can be tunable by changing the ncSi sizes The synthesis was based on the thermal processing at high temperatures of HSiO1.5 hydrosilicate derivative of trichlorosilane (HSiCl3). Then, the glasses are finely grounded in a agate mortar and pestle before been extracted via an acid etching. In this experiment the objective was to obtain monodisperse nanocrystals of silicon without the use of post-synthesis steps such as ultracentrifugation. The objective was reached added sodium chloride (NaCl) during the ground step in order to decrease the size of grain for to obtain a uniform etching.

Down-conversion (DC) and down-shifting (DS) layers are optical layers mounted on the top surface of a solar cell that can potentially increase the solar cell efficiency. The effect of DC and DS layers to enhance the performance of single-junction solar cells has been studied by means of simulation and experimental work. In this thesis a model is developed to study the effects of DC and DS layers by modifying the incident spectrum. The effect of the layers on ideal cells as well as commercial grade silicon and CIGS solar cells that are modeled in a device simulator is examined. Silicon nanocrystals (Si-nC) embedded in a silicon dioxide matrix to act as a DS layer were fabricated and characterized at McMaster University as part of this project. The measured optical properties as well as the photoluminescence measurements are used as input parameters to the optical model. The enhancement due to the Si-nC when coupled to silicon and CIGS solar cells is explored. Beside the DC and DS effects, there is also disturbance to the surface reflections due to the addition of a new layer to the top surface and is referred to as antireflection coating (ARC) effect. For the simulated silicon solar cell under the standard AM1.5G spectrum (1000W/m2), a maximum increase in Jsc of 8.4% is achieved for a perfect DS layer as compared to a reference cell, where 7.2% is due to ARC effect and only 1.2% is due to DS effect. On the other hand, there is an increase in Jsc of 19.5% for the CIGS solar cell when coupled to a perfect DS layer. The DS effect is dominant with 18%, while the ARC effect contributes only 1.5% to the total Jsc enhancement. Accurately characterizing DS layers coupled to solar cell requires knowledge of optical properties of the complete structure. Internal quantum efficiency is an important tool for characterizing DS systems, nevertheless, it is rarely reported. In addition, the ARC effect is not experimentally decoupled from the DS effect. In this work, a straightforward method for calculating the active layer contribution that minimizes error by subtracting optically-modeled electrode absorption from experimentally measured total absorption.

The original work presented in this thesis describes research into Si-based luminescent materials, prepared specifically by ion implantation and rapid thermal processing of thermal oxide films. An in-depth optical characterisation, employing photoluminescence (PL) and Raman spectroscopy was complimented with electron microscopy, revealing the source of efficient room temperature PL as nano-scale silicon inclusions (Si-NCs). The evolution of the Si-NC size and density with isothermal and isochronal annealing may be described using classical thermodynamics according to a diffusion limited, Ostwald ripening process. Values for the coarsening rate and activation energy, extracted from the evolution of the Si-NC size with annealing indicate that the transport of Si atoms and precipitate formation are enhanced in ion implanted films, attributable to the presence of vacancy and interstitial defects generated during ion irradiation. The PL and Raman spectra are well correlated with the evolving Si-NC size and density according to the quantum confinement (QC) model in which samples containing larger clusters emit at longer wavelengths. However, the formation of bound exciton states within the band gap of small clusters (< 2nm), as a result of specific surface chemistries, suppresses higher energy emissions. The increase in PL intensity with annealing was exactly correlated with the increase in PL lifetime, characteristic of the removal of non-radiative defects. A dependence of the PL dynamics on emission energy, with higher energies exhibiting shorter lifetimes, further evidences the QC effect. Blue shifted emission at high excitation flux and/or low temperature is correspondent with the slower PL dynamics and preferential saturation at longer wavelengths. Raman spectra were fit using a phonon confinement model, from which Si-NC size distributions were extracted and found to compare favourably with those obtained from TEM images. Stresses in the films, determined from the Raman peak position, were used as an independent method for calculating the Si surface energy, which is very close to the literature values. A single, high temperature anneal of Si and erbium (Er) co-doped films revealed a preferential aggregation of Er at the Si-NC formation site, which is of particular importance for the photo-sensitization of Er PL around 1.5μm. The Er PL was enhanced in the presence of Si-NCs by several orders of magnitude compared with a reference SiO2:Er. Whilst broadband pumping of the Er via Si-NCs evidences a non-resonant energy transfer mechanism with an efficiency which depends on the Si-NC size, the process is limited at high excitation flux by a combination of low sensitizer (Si-NC) density and non-radiative losses. Finally the Si-NC PL intensity in phosphorus (P) co-doped films was studied and found to depend strongly on the annealing conditions and P concentration. For lower temperature treatments, a factor 2 PL enhancement, relative to an un-doped reference was obtained, attributed to the passivation of Si-NC surface defects. Higher temperature treatments resulted in the monotonic quenching of the PL with increasing P concentration, attributed to the introduction of an efficient Augerre combination channel as a result of the ionization of P-donors inside large Si-NCs. A simple statistical model predicts this behaviour and provides an incidental estimate of the Si-NC size.

<p>Single junction silicon photovoltaic cells (SJSPVCs) are unable to transform all the energy in the solar spectrum into electricity, due to the broad nature of the solar spectrum and the limits imposed by a single bandgap. Furthermore, high surface recombination velocity reduces the SJSPVC external quantum efficiency response, particularly to ultraviolet photons. It is the goal of spectral engineering to optimize the light that is incident on the cell, by down-shifting high energy photons to lower energies, for example, to improve the performance of photovoltaic cells.</p> <p>This thesis represents a study into the luminescence of ion implanted films, involving silicon nanocrystals (Si-NCs) and rare-earth ions in fused silica or silicon nitride. Quantum efficiency measurements taken with an integrating sphere were used to characterize some of the samples. Other photoluminescence (PL) characterization work was carried out with a single-wavelength laser and a collection lens normal to the sample. Variable angle spectroscopic ellipsometry (VASE) was used to estimate the optical constants of the implanted films. In secondary work, Rutherford backscattering spectrometry, time-dependent PL, infrared-PL measurements, and electrical conductivity measurements were used to characterize select samples.</p> <p>It was found that the conversion efficiency of Si-NCs in fused silica was about 1% – too low to be useful according to modeled results. However, considerable variation in the peak wavelength of the Si-NC PL was obtained, depending on the peak concentration of implanted silicon. Si-NC-type PL was also produced by low-energy implantation of oxygen into a Czochralski silicon wafer.</p> <p>Oxygen was also implanted into films of cerium-doped high-purity silicon nitride, and it was shown that the photoluminescence from these films is largely dependent on the level of oxygen doping. The internal conversion efficiency of a cerium-doped fused silica sample was found to approach 20%, which indicates that this is a promising avenue for future research.</p> <p>Finally, energy transfer was demonstrated between Si-NCs and erbium ions. The lifetime of the erbium PL appears to increase with increasing implanted silicon fluence.</p> / Master of Applied Science (MASc)

<p>The aim of third-generation photovoltaics (PV) is ultimately to achieve low-cost, high-efficiency devices. This work focused on a third-generation PV concept known as down-shifting, which is the conversion of high-energy photons into low-energy photons which are more useful for a typical solar cell. Silicon nanocrystals (Si-NCs) fabricated using electron-cyclotron resonance plasma-enhanced chemical vapour deposition (ECR-PECVD) were studied as a down-shifting material for single-junction silicon cells. A calibration was done to determine optimal deposition parameters for Si-NC formation. An experiment was then done to determine the effect of film thickness on emission, optical properties, and photoluminescence quantum efficiencies.</p> <p>Photoluminescence (PL) peaks varied depending on the stoichiometry of the films, ranging from approximately 790 nm to 850 nm. Variable-angle spectroscopic ellipsometry was used to determine the optical constants of the Si-NC films. The extinction coefficients indicated strong absorption below 500 nm, ideal for a down-shifting material. Transmission Electron Microscopy (TEM) was used to determine the size, density, and distribution of Si-NCs in two of the films. Si-NCs were seen to have an average diameter of approximately 4 nm, with larger nanocrystals more common near the surface of the film. A density of approximately 10⁵ nanocrystals per cubic micron was approximated from one of the TEM samples.</p> <p>The design and implementation of a PL quantum efficiency measurement system was achieved, using an integrating sphere to measure the absolute efficiency of Si-NC emission. Internal quantum efficiencies (IQE) as high as 1.84% and external quantum efficiencies (EQE) of up to 0.19% were measured. The EQE was found to increase with thicker films due to more intense photoluminescence; however the IQE remained relatively independent of film thickness.</p> / Master of Applied Science (MASc)

Le regain d'attention des industriels pour les mémoires non volatiles intégrant des nanocristaux, illustré par l'introduction sur le marché de la Flexmemory de Freescale en technologie 90 nm, incite à poursuivre des études sur ce type de systèmes. Pour cela, nous avons mis au point des cellules mémoires élémentaires, à savoir des transistors MOS dont l'oxyde de grille contient une grille granulaire formée par un plan de nanocristaux de silicium (Si-ncx) stockant la charge électrique.Ce travail présente les principaux résultats issus de ces travaux, ceux-ci allant du procédé de fabrication à la caractérisation fine des dispositifs mémoires. Le parfait contrôle de l'élaboration de la grille granulaire de Si-ncx par implantation ionique à très basse énergie (ULE-IBS) est accompagné de caractéristiques « mémoires » répondant aux normes industrielles d'endurance et d'une discrimination des pièges responsables du chargement. Le stockage majoritaire par les Si-ncx est démontré, ce qui est essentiel pour la rétention de la charge. Nous avons développé une technique électrique permettant d'extraire à la fois la quantité de charge stockée par les Si-ncx mais également leurs principales caractéristiques structurales (taille, densité, position dans l'oxyde). Cette extension de la technique électrique de « pompage de charges », non destructive et in-situ permet de suivre l'état du composant en fonctionnement et de caractériser des pièges (e.g. les Si-ncx) pour la première fois au-delà de 3 nm de profondeur dans l'oxyde. Ces résultats ont été validés par des observations TEM. La résolution du pompage de charge étant le piège unique, nous avons alors couplé l'ULE-IBS avec la lithographie « Stencil » pour réduire latéralement le nombre de Si-ncx synthétisés. Cette technique nous permet pour le moment de contrôler la synthèse locale à la position désirée dans l'oxyde de « poches » de Si-ncx de 400 nm. La synthèse de « quelques » Si-ncx est envisagée à très court terme. Nous serons alors en mesure de fabriquer des mémoires à nombre choisi de nanocristaux (par SM-ULE-IBS), dont les propriétés structurales (taille, densité, position) et électriques (quantité de charge stockée) seront vérifiées par pompage de charge, offrant ainsi des outils puissants pour la fabrication et la caractérisation de mémoires à nombre réduit de nanocristaux, notamment pour des longueurs de grilles inférieures à 90 nm / The aim of this thesis has been to fabricate and electrically characterize elementary memory cells containing silicon nanocrystals (Si-ncs), in other words MOSFET which insulating layer (SiO2) contains a Si-ncs array storing the electrical charge. We have shown that we perfectly control the synthesis of a 2D array of 3-4 nm Si-ncs embedded into the MOSFET oxide by low-energy ion implantation (1-3 keV) Reaching this goal implied two key steps: on the one hand develop a reliable MOSFET fabrication process incorporating the Si-ncs synthesis steps and on the other hand develop tools and methods for both memory window and Si-ncs array itself characterizations. We have developed an in-situ characterization technique based on the well-known charge pumping technique, allowing for the first time the extraction of traps depth (e.g. the Si-ncs array) further than 3 nm into the oxide layer leading to the characterization of both position of these Si-ncs into the SiO2 matrix and their structural properties (diameter, density). These results have been confirmed by EF-TEM measurements. Finally, we have worked on the improvement of controlled local synthesis of Si-ncs pockets by combining low-energy ion implantation and stencil lithography. We reduced the size of these pockets down to about 400 nm using this parallel, low cost and reliable technique and identified the limiting effect for the pockets size reduction. These results pave the way for memory cells containing a few Si-ncs with a well-defined position into the oxide and a well-controlled number of ncs

Title: Bioapplications of novel nanostructured materials Author: Anna Fučíková Department / Institute: Department of Chemical Physics and Optics, Faculty of Mathematics and Physics, Charles University in Prague Supervisor of the doctoral thesis: Doc. RNDr. Jan Valenta, Ph.D., Department of Chemical Physics and Optics, Faculty of Mathematics and Physics, Charles University in Prague Abstract: This work is aimed at development of new fluorescent labels based on silicon nanocrystals. Nanodiamonds and commercial CdSe quantum dots have been used as comparative materials. Silicon nanocrystals are relatively small (1-4 nm) compared to other studied nanomaterials. They are prepared by electro-chemical etching and their surface can be activated by various molecules which strongly influences luminescence properties. Luminescence quantum efficiency can be as high as 30 % and perfectly photostable even in biological environment. Si nanocrystals are biodegradable in a living organism within reasonable time scale and non-toxic. We are able to detect luminescence of single nanocrystals, even inside living cells, with use of our micro-spectroscopy apparatus. Nanodiamonds have weak luminescence; they are toxic at higher dosages and very stable in living bodies (without available technique how to remove them). Studied CdSe...

Les nanocristaux de Silicium (SiNCs) de taille inférieure à 5 nm sont des matériaux qui présentent une intense photoluminescence (PL) et capables d’amplification optique. Cette dernière propriété est un pré-requis à l’obtention d’émission stimulée sous pompage optique. Atteindre l’émission stimulé (et l’effet laser) à partir de nanostructures basées sur Si est d’un intérêt particulier dans le domaine de la photonique à base de silicium. Le but de ce travail était (i) d’étudier les propriétés optiques fondamentales de SiNCs, (ii) de concevoir et de réaliser un cristal photonique présentant une efficacité d’extraction augmentée et (iii) d’explorer la possibilité d’améliorer l’amplification optique des émetteurs de lumière à base de SiNCs en les combinant avec un cristal photonique à deux dimensions. / Silicon nanocrystals (SiNCs) of sizes below approximately 5 nm are a material with an efficient room-temperature photoluminescence (PL) and optical gain. Optical gain is a prerequisite for obtaining stimulated emission from a pumped material, and the achievement of stimulated emission (and lasing) from Si-based nanostructures is of particular interest in the field of silicon photonics. The aim of this work was (i) to investigate fundamental optical properties of SiNCs, (ii) to design and prepare a photonic crystal with enhanced light extraction efficiency and (iii) to explore a possibility of enhancing optical gain of light-emitting SiNCs by combining them with a two-dimensional photonic crystal.