Le but de cette étude est de mieux appréhender les phénomènes régissant l’épitaxie du diamant élaboré par MPCVD assisté pas polarisation sur silicium. Elle s’articule en deux grands axes : une première approche qualitative sur la réactivité du substrat et une seconde approche plus quantitative relative à l’influence des étapes de prétraitement sur le dépôt. L’importance de la mise en œuvre d’un protocole rigoureux est mise en exergue dans ce travail. Le rôle des différentes étapes de préparation des substrats de silicium allant du nettoyage ex situ jusqu’à la croissance du diamant en passant par le nettoyage in situ par plasma H2 et la polarisation a été étudiée grâce à des techniques d’investigations telles que la microscopie électronique à balayage et à transmission, la spectroscopie de photoélectrons X, la microscopie à force atomique et la diffraction en faisceau rasant d’électrons haute énergie. Ces analyses ont mis en évidence l’apparition de structures de type « voids » associées à la formation de carbure de silicium dès l’étape de décapage hydrogène. La formation de carbone amorphe dans les premiers instants de la germination du diamant semble être corrélée à la quantité de diamant constatée après croissance, l’importance du flux d’ions pendant l’étape de polarisation sur les densités a été démontrée en parallèle. Des taux d’épitaxie jusqu'à près de 30% ont été atteints grâce à l’optimisation du couple temps/tension de polarisation ou à une carburation du substrat précédant la polarisation. La technique d’analyse de diffraction d’électrons en faisceau convergent sur des films de diamant s’est révélée adaptée à l’étude statistique de l’orientation des cristaux / The goal of this study is to better apprehend the phenomena governing bias assisted MPCVD diamond epitaxy on silicon. It is organized into two main parts: a first qualitative approach on the reactivity of the substrate and a second approach more quantitative related to the pretreatment stages influence on the deposit. The importance of a rigorous protocol is put forward in this work. The role of the various stages of silicon substrates preparation going from ex situ cleaning, in situ cleaning (plasma H2), bias until diamond growth was studied thanks to investigations techniques such as transmission and scanning electron microscopies, X-ray photoelectrons spectroscopy, atomic force microscopy, reflexion high energy electrons diffraction. These analyses highlighted the appearance of structures of the type “voids” associated with the silicon carbide formation from the hydrogen etching stage. The amorphous carbon formation in the first moments of diamond nucleation seems to be correlated with the diamond quantity measured after growth, the importance of ions flow during nucleation stage on the densities was shown in parallel. Epitaxy ratio up to 30% were reached thanks to the optimization of the couple time/biasing or carburation of the substrate preceding bias. The convergent beam electron diffraction analysis of diamond films appeared well adapted to the statistical study of crystals orientation

The aim of this thesis is a study of NV centres in crystalline and nanocrystalline diamond by laser spectroscopy methods. In the theoretical part we discuss the laser spectroscopy methods, the studied material - diamond and the NV colour centres. In the experimental part we discuss the influence of nanoparticle size on luminescence spectra. We measure the luminescence of samples at room and also at low temperatures depending on the intensity and wavelength of the excitation. We study the photo-conversion of negatively charged state of NV centres to the neutral in detail. We make the time resolved measurements of the luminescence on streak camera for characterization the dynamical properties of the studied samples. The result is the comparison of lifetimes of the states in NV centres in selected samples.

Syftet med denna uppsats var att undersöka hur musikbolagen skapar ett varumärke kring deras artister. Frågeställningarna kretsar kring varumärkesskapande, hur samarbetet mellan kvinnliga artister och musikbolagen de tillhör ser ut i de olika stadierna av artisternas karriärer. Jag ställde mig också frågan hur mycket artisternas karriärer påverkas av att de är kvinnor och hur relationen mellan sociala medier, artister och musikbolagen ser ut.    Uppsatens fokus ligger till största del på den svenska musikindustrin men eftersom båda musikbolagen rör sig utanför Sverige, fanns den internationella marknaden i bakgrunden under studiens gång.    Den metod som valts för denna uppsats var den kvalitativa forsknings intervjun. Det skedde tre stycken intervjuer med fyra kvinnor inom musikbranschen och som jobbar på den musikbolag som är fokuset för denna studie. De musikbolag som besöktes var Playground Music, Universal Music Group och MTA Production. Intervjuerna var uppbyggda kring varumärkesskapandet kring en artist, hur man skapar en långsiktig karriär, sociala mediers betydelse för artister idag och hur kvinnliga artisters karriärer ser ut.    Resultatet blev en tydligare bild kring hur musikbolagen jobbar med artister i stort samt vad de tyckte var viktigt att tänka på som musikbolag och artist. Playground Music och Universal Music skiljer sig i storlek men i grunden vill de båda samma sak: att ge en röst och en plattform för kreativa artister.

OBJECTIVE: The purpose of this in vitro study was to evaluate the cutting performance and accuracy of CAD/CAM diamond burs in different chemo-mechanical conditions when machining yttria-stabilized zirconia (YTZ), lithium-disilicate, feldspathic porcelain, and double network hybrid ceramic material. The study also examined bur wear mechanisms. MATERIALS AND METHODS: Two experiments were performed. Experiment 1: 45 samples of each material were milled, and four criteria were tested: milling time; surface roughness; change in bur weight after machining, and total cement space. Experiment 2: Four different coolant liquids were used while machining 15 samples of lithium-disilicate, feldspathic porcelain, and double network hybrid ceramic material. The four criteria in Experiment 1, plus marginal adaptation, were measured. Burs and ceramic materials used were examined with SEM before and after machining. RESULTS: Experiment 1: All burs milled 15 crowns of each material successfully, with a general increase in milling time and decrease in weight. Four wear patterns were identified: grit cracks, micro-fractures, dislodgement, and matrix abrasion. Sequential milling time increased for all of the ceramic materials. Surface roughness (Ra) decreased in general for all materials used in the study except YTZ, which showed an increase in Ra by the end of the machining series. Experiment 2: Additives used in this study had no significant effect on IPS e.max CAD milling efficiency or Ra. Boric acid reduced Vita MarkII machining time significantly and Ra. CONCLUSIONS: The cutting rate of diamond burs differed when machining different ceramic materials. In sequential machining, every consecutive milling demonstrated lower cutting efficacy. The surface roughness of consecutive machined samples differed. Some cooling liquids affected the quality of the machined surface. The bur wear mechanism was the same when different ceramic materials were machined, and their microstructure affected their machinability. / 2019-09-26T00:00:00Z

Among several hundred impurities and defects that can occur in diamond, the nitrogenvacancy (NV) center is one of the most interesting for quantum technologies at room temperature. Several properties make it an excellent platform for many applications, from nanosensor to quantum information processing. This thesis presents the first explorations of NV-based technologies in our laboratory, investigating three sets of studies aimed at learning the know-how of this field of research and developing the necessary infrastructure to explore them in future quantum technologies. The first set of studies focus on magnetometry and how to improve NV-based magnetic sensing. We show that, using engineered ensembles of NV centers in ultrapure synthetic diamonds, one can build a relatively simple apparatus to do magnetic imaging of relatively large areas while determining the full vector field with high spatial resolution and very good sensitivity. We also show that these measurements can be used to reconstruct the current density distribution of nearby sources, opening exciting possibilities to study two-dimensional materials. Another set of studies involve spin coherence of an ensemble of NV centers. For that, we developed a method based on a CCD camera and an imaging protocol that allows implementing pulse sequences like Rabi, Ramsey and Hahn echo, performing Electron Spin Resonance (ESR) spectroscopy over extended areas. Using this method we extract parameters from our sample, including measurements for T1, T2 and T*2. The method was also used to observe Electron Spin Echo Envelope Modulation (ESEEM), due to hyperfine interaction with nearby 15N nucleus, resulting in improved frequency sensitivity. The third set of studies explore how to use femtosecond lasers to produce NV centers in diamond and investigated the nonlinear index of refraction (n2) of the diamond (type IIa) in a broad spectral region, from the infrared (1500 nm) to the ultraviolet (260 nm). / Entre várias centenas de impurezas e defeitos que podem ocorrer no diamante, o centro Nitrogênio-Vacância (NV) é um dos mais interessantes para tecnologias quânticas em temperatura ambiente. Diversas propriedades fazem dele uma excelente plataforma para muitas aplicações, desde nanosensores até o processamento de informações quânticas. Esta tese apresenta a primeira exploração de tecnologias baseadas em NV no nosso laboratório, investigando três conjuntos de estudos com objetivo de aprender o know-how desta área de pesquisa e desenvolver a infra-estrutura necessária para explorá-los em futuras tecnologias quânticas. O primeiro conjunto de estudos enfoca a magnetometria e como melhorar o sensores magnético baseado em centros NV. Mostramos que um aparato relativamente simples pode ser usado para produzir imagens magnéticas do campo vetorial, usando ensembles de centros NV em diamantes sintéticos ultrapuros. Também mostramos que essas medidas podem ser usadas para reconstruir a distribuição de densidade de corrente de fontes próximas, abrindo possibilidades interessantes para o estudo de materiais bidimensionais. Outro conjunto de estudos envolve a coerência de spin de um ensemble de centros NV. Para isso, desenvolvemos um método baseado em uma câmera CCD e um protocolo de imagem que permite implementar sequências de pulsos como Rabi, Ramsey e eco Hahn, realizando espectroscopia de ressonância de spin eletrônico (ESR) sobre áreas estendidas. Usando esse método, extraímos parâmetros de nossa amostra, incluindo medidas para T1, T2 e T*2. O método também foi usado para observar o efeito ESEEM (Envelope de Modulação de Eco de Spin Eletrônico), devido à interação hiperfina com o núcleo próximo de 15N, resultando numa melhor sensibilidade de freqüência. Finalmente, o terceiro conjunto de estudos explorou como usar lasers de femtossegundos para produzir centros NV em diamante e investigou o índice de refração não-linear (n2) do diamante (tipo IIa) em uma ampla região espectral, desde o infravermelho (1500 nm) até o ultravioleta (260 nm).

Abstract A range of di®erent high-quality single crystal diamonds synthesized under high pressure and high temperature (HPHT) conditions have been studied in view of their potential as candidates for specialized electronic devices with emphasis on particle detectors. The studies incorporated a long range of spectroscopic and electronic characterization techniques. Special attention was given to electronic properties and device performance re- lated to the electrical contacts applied, the type and the concentration of impur- ities and the crystallographic defects present. The electronic response of a dia- mond detector as far as impurities are concerned is predominantly determined by the single substitutional nitrogen (SSN) and boron acceptors. Di®erent tech- niques were used to assess the role of such impurities in the diamond crystals stud- ied, as well as to study the dynamics due to the interaction of such impurities with each other (compensation). Hence, the electron spin resonance (ESR) and the current-deep level transient spectroscopy (I-DLTS) techniques were used in this re- spect to extract the information concerning activation energies, nitrogen-boron dy- namics, and the nitrogen and boron concentrations. ii iii It was found that the SSN content was below 1013 cm¡3 with this result giving the approximate concentration of boron acceptors, being the same value as of that of the SSN, or slightly above. Maximum activation energies of boron acceptors were extracted from three di®erent regions in the bulk of the diamond. The values were approximately 0.311 eV § 0.0027 eV in the center region, 0.308 eV § 0.007 eV in the intermediate region and 0.29 eV § 0.007 eV at the edge region, respectively. The maximum activation energy when boron is fully compensated is about 0.37 eV. Properties of ohmic and Schottky contacts as a function of concentration of SSN and boron acceptors were investigated using Current-Voltage characteristic and photo- current measurements. Di®erent surface treatment conditions and di®erent types of diamonds (IIa, IIb and Ib) were used. Electronic properties as a function of contacts were assessed for high purity synthetic type IIa diamond detector, incorporating a time of °ight (TOF) UV laser set-up. The maximum hole collection distance at room temperature was found to be 91.00 cm, the maximum transient time for holes was about 1.00 ms and the e±ciency was approximately 41%, with contacts made of Ti/Pt/Au-Ru. When Ru-Ru contacts are applied, the maximum hole mobility and the velocity were extracted at room temperature to be about 17963.44 cm2V¡1s¡1 and 5.02 £107 cms¡1, respectively, and the e±ciency of the device is about 30%. The maximum applied external electric ¯elds with Ru-Ru contacts were increased to about 1.32 times that at low temperature and to about 1.84 times that at room temperature. iv Large signals generated by ®-particles from 228Th were obtained without using amp- li¯cation. However, a full analysis of the pulse was not possible due to the narrow bandwidth of the electronic probes used. In a detector made of type Ib diamond, with SSN concentrations of about 50 ppm, it was found that regions in the bulk exhibiting better charge collection properties contained small concentrations of uncompensated boron impurity. On the other hand, the di®erence in the concentrations of SSN between the two type Ib diamonds, with about 50 ppm and about 200 ppm of SSN concentrations, respectively, resulted in approximately 70 ps di®erence in the transit time between two detectors made of these diamonds. Keywords: Synthetic diamond, detector, HPHT, type Ib, type IIa, single substitutional ni- trogen, SSN, ESR, ARP, I-DLTS, metallization, uncompensated boron impurity, crystallographic defects, rise and decay times, charge carrier life time, charge carrier mobility, carrier mean free path , charge collection distance, carrier Schubweg.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy / Raman and photoluminescence (PL) spectroscopy techniques were used to investigate the mechanical properties of diamond and cubic boron nitride (cBN) by optical means. Both these materials have extreme mechanical properties that make them the material of choice for many industrial applications, ranging from cutting and grinding to wire-drawing dies. The results obtained on single crystal diamond, polycrystalline diamond (PCD) and cBN are summarised below. Micro-Raman and photoluminescence (PL) spectroscopy were used to map the threedimensional (3D) stress and deformation distributions surrounding a plastic impression made in a synthetic, type Ib single crystal diamond. Using data from the Raman peak position, a 3D map of the stress contours surrounding the impression was generated, while the Raman width data yielded a map of the plastic deformation volume. The stress contours compare favorably with the resolved shear stress contours calculated for diamond. PL intensity maps of the zero phonon line (ZPL) associated with the [N-V]– defect centre at 1.945eV provide images of the extent of vacancy formation and movement during the impression process. Data concerning the position and width of the ZPL correspond well with the Raman results. Polycrystalline diamond (PCD) tools commonly consist of a PCD layer sintered onto a cobalt-tungsten carbide (Co-WC) substrate. These tools are used in diverse applications and both the magnitude and distribution of the stresses in the PCD layer affect tool behavior. These stresses in sample drillbits were investigated by means of micro-Raman spectroscopy. Cyclic annealing of a sample drillbit to 600 oC shows that the tool properties are retained after 5 cycles, while similar cycling to 800 oC resulted in a permanent decrease of the average surface compressive stress. This implies a reduction in the drillbit’s ability to resist crack formation and propagation and is thus a degradation of the tool properties. The method of Raman mapping of stress and deformation in diamond was also applied to single crystals of cBN. Indentations on cubic boron nitride (cBN) crystals and polycrystalline cubic boron nitride (PcBN) composites were mapped and the shifts of the cBN Raman lines from their unstressed positions used to quantify the residual stresses in the boron nitride due to the deformation brought about by the indentation. These were found to be of the order of 1 GPa. vi These measurements illustrated for the first time the use of Raman spectroscopy to study residual stresses in boron nitride. Defects in cBN were studied using photoluminescence spectroscopy at low temperature (< 10 K) of two types of cBN irradiated at ambient temperature with 1.9 MeV electrons. All the samples were small (<1 mm diameter) single crystals of cBN. Three defect centres (with narrow lines at 2.28 eV, 2.15 eV and 1.98 eV) were introduced in both the amber-coloured and blackbrown coloured samples by the irradiation. The amber coloured sample also showed a defect centre (at 1.65 eV) that is present before and after irradiation. Line shape analysis of the zero phonon lines of all three irradiation-induced centres showed that the lines are predominantly Gaussian in character, suggesting that linetype defects such as dislocations are a prevalent characteristic of these crystals. Raman spectroscopy of cBN single crystals as a function of temperature was performed over a wide temperature range from 4 K to 1373 K. The low temperature measurements extended the data previously reported in literature, as this data ranged from room temperature upwards. It was concluded from the shift of Raman peak position with temperature that both linear expansion and anharmonic effects were required to adequately account for the observed data. This is in agreement with previously published findings. Both 3- and 4-phonon processes were required to account for the observed linewidths as a function of temperature, again in agreement with literature. The results presented here and in the associated journal publications illustrate clearly how optical spectroscopy techniques can serve as non-destructive characterisation tools for the mechanical properties of ultra-hard materials.

Exotic aspects of quantum mechanics, such as quantum entanglement, can be exploited to solve computational problems that are impractical to solve with conventional computers. With the realization of robust solid-state qubits, such as Nitrogen Vacancy (NV) centers in diamond, an outstanding challenge is to develop experimental approaches that can control the interactions between individual qubits. This dissertation develops a diamond-based experimental system that exploits acoustic waves or mechanical vibrations to mediate interactions between spin qubits. This spin-mechanical system features three essential elements: robust qubits, high quality-factor diamond nanomechanical resonator, and strong spin- mechanical coupling, thus enabling a new and promising platform for pursuing solid- state quantum computer. For the spin-mechanical system, NV centers are created near the surface of a bulk diamond through nitrogen ion implantation followed by stepwise high temperature annealing. We successfully suppress environmental fluctuations and achieve NV centers with stable and spectrally narrow (< 50 MHz) fluorescence at low temperature, which is crucial for the spin-mechanical system. Diamond nanomechanical resonators with a fundamental frequency near 1 GHz have been successfully fabricated with a diamond-on-insulator approach. The resonators are suspended from a silicon substrate and are supported with long and thin tethers, decoupling the mechanical modes from the surrounding environment. Diamond nanofabrication is still in its infancy. Numerous fabrication problems occurring during etching, mask transfer, and wafer bonding have been painstakingly resolved. Strong spin-mechanical coupling is demonstrated via the strain coupling of the NV excited-states. The spin-mechanical coupling takes place through a 𝚲-type three- level system, where two ground-spin-states couple to an excited-state through a phonon-assisted as well as a direct dipole optical transition. Both coherent population trapping and optically-driven spin transitions have been realized. The coherent population trapping demonstrates the coupling between an acoustic wave and an electron spin coherence through a dark state, thus avoiding the short lifetime of the excited state. The optically-driven spin transitions can enable the quantum control of both spin and mechanical degrees of freedom. This dissertation includes previously published co-authored material.

Uma das técnicas para fabricar microestruturas em diamante é usar moldes em silício microfabricados. Assim, microestruturas são produzidas em laminas de silício, um filme de diamante é depositado sobre essa lamina e o silício é corroído. Dessa forma é possível se obter réplicas de diamante das microestruturas que estavam presentes na superfície do molde de silício. Nesta técnica é muito importante a fidelidade morfológica da réplica de diamante, quando comparada ao molde de silício, previamente microfabricado. Um dos objetivos deste trabalho é analisar quantitativamente a fidelidade de reprodução de microestruturas em filmes de diamante, utilizando moldes de silício microfabricados. Nossos resultados mostram que a rugosidade das réplicas de diamante é sistematicamente maior que a rugosidade dos moldes de silício. Medindo degraus em escala de centenas de nanômetros, o erro na reprodução morfológica está entre 6 e 11 %. No caso de medidas de degraus em escala de dezenas de nanômetros, o erro na reprodução é de aproximadamente 18 %. O segundo objetivo deste trabalho consiste em comparar a variação da rugosidade de uma superfície devido ao recobrimento com filmes de DLC. Os resultados sugerem que, para substratos com rugosidade original de centenas de nanômetros, a variação da rugosidade tende a aumentar com a espessura do filme de DLC até um valor máximo, a partir do qual ela tende a diminuir. Para substratos com rugosidade original de alguns poucos nanômetros, a variação da rugosidade oscila aleatoriamente, não apresentando tendências de aumentar ou diminuir com a espessura do filme de DLC. Finalmente, a última parte desta Tese foi fabricar um microbocal de diamante utilizando a técnica de moldes microfabricados em silício. / One of the techniques to fabricate microstructures in diamond is to use microfabricated silicon molds. Microstructures are produced on silicon wafer; diamond film is deposited on it and the silicon is etched. In this way, it is possible to obtain diamond replicas of the microstructures that were present in the silicon surface. In this technique it is very important the morphological fidelity of the diamond replica, when compared with the silicon mold previously microfabricated. One of our objectives in this work is to analyze quantitatively the reproduction fidelity of microstructures in diamond films, using microfabricated silicon molds. The results show that, roughnesses of the diamond replicas are systematically higher than the roughness of the silicon molds. Measuring steps in scales of hundreds of nanometers, the reproduction error is between 6 and 11 %. In the case of steps measured in scales of tenth of nanometers, the reproduction error is about 18 %. A second objective of this work is to compare the roughness change of rough surfaces coated with DLC films. The results suggest that, for substrates with original roughness of hundreds of nanometers, the roughness shift tends to increase with the DLC film thickness until a maximum value and then it tends to decrease. For substrates with original roughness of few nanometers, the roughness shift oscillates erratically and it does not tend to increase or decrease with the DLC film thickness. Finally, the last part of this Thesis was to fabricate a diamond micronozzle, using the technique of silicon molds microfabricated.

O desenvolvimento de metodologias eletroanalíticas altamente eficientes para a determinação de resíduos de pesticidas em amostras de alimentos usando a radiação de ultra-som (US) e o eletrodo de diamante dopado com boro (DDB) é reportado neste trabalho.Também são apresentadas tentativas para melhorar a degradação eletroquímica de pesticidas e de seus metabólitos no ambiente usando estas novas ferramentas (US e DDB) para minimizar o bloqueio da superfície eletródica que, usualmente, impede tais processos.A primeira parte do trabalho apresenta a determinação do metilparation (MP), do seu produto de degradação 4-nitrofenol (4-NF) e do carbaril em água pura e em amostras de alimentos, por voltametria de onda quadrada (SWV) na ausência e na presença do ultra-som usando o eletrodo de DDB. Os resultados obtidos em água pura foram comparados com os dados obtidos por cromatografia líquida de alta eficiência.As metodologias sonoeletroanalíticas para todos os analitos em água pura e nas matrizes de alimentos apresentaram maior sensibilidade e precisão e menores limites de detecção (LD) e de quantificação (LQ) em relação às medidas silenciosas. Para a redução do MP e do 4-NF e para a oxidação do carbaril em água pura, o LD diminuiu de 10,8 para 4,86 &mu;g L-1, de 6,38 para 2,57 &mu;g L-1 e de 2,96 para 2,08 &mu;g L-1, respectivamente. Para a detecção do MP em extrato de batata e do 4-NF em suco de limão, o valor do LD diminuiu de 36,6 para 10,1 &mu;g L-1 e de 13,8 para 8,32 &mu;g L-1, respectivamente.Em todos os casos, foi observado que os valores de LD e LQ estão dentro da concentração máxima permitida para os compostos em amostras de alimentos (50 e 500 &mu;g kg-1 para amostras de batata e de milho, respectivamente, de 1000 &mu;g kg-1 para frutas cítricas e de 500 &mu;g kg-1 para amostras de abacaxi). Satisfatórios valores de recuperação dos analitos nas amostras indicam a possibilidade da determinação direta do MP em extratos de batata e de milho (83 a 96 %) e do 4-NF em sucos de laranja e de limão (84 a 94 %) e também para a detecção do carbaril em suco de abacaxi após o procedimento de extração líquido-líquido (89 a 92 %). Inicialmente, não foram encontrados resíduos detectáveis dos compostos em todas essas amostras de alimentos.As vantagens observadas para os estudos na presença do ultra-som são devidas ao aumento do transporte de espécies até a superfície eletródica e também à limpeza da superfície, visto que a limpeza intermediária não é necessária, resultando em análises mais rápidas e reprodutíveis.Na segunda parte do trabalho, os efeitos benéficos do ultra-som, particularmente a limpeza da superfície eletródica, foram avaliados em associação às eletrólises potenciostáticas para a degradação do pentaclorofenol (PCF) a 0,9, 2,0 e 3,0 V vs. Ag/AgCl e do carbaril a 3,0 V vs. Ag/AgCl.Para o pentaclorofenol, as eletrólises a 0,9 V mostraram que o bloqueio da superfície eletródica foi mais rápido na sonoeletrólise em relação ao processo na ausência do ultra-som, devido à formação de um composto dimérico na superfície eletródica. Eletrólises a 2,0 V e a 3,0 V mostraram maiores níveis de decaimento das bandas do PCF para os estudos na presença do ultra-som em relação àqueles obtidos por medidas silenciosas, devido ao aumento do transporte de massa, minimização da inativação do eletrodo e geração simultânea de radicais hidroxila pelo ultra-som e pela superfície polarizada do DDB. Resultados similares àqueles obtidos para o pentaclorofenol no maior valor de potencial foram também observados para a degradação do carbaril a 3,0 V. / The development of highly efficient electroanalytical methodologies for the determination of pesticide residues in food samples using ultrasound radiation (US) and a boron-doped diamond (BDD) electrode is reported in this work.Also reported are attempts to improve the electrochemical degradation of pesticides and their metabolites in the environment by using those new tools (US and BDD) to minimize the blockage of the electrode surface that usually hinders such processes.The first part of the work presents the determination of methylparathion (MP), their degradation product 4-nitrophenol (4-NP) and carbaryl in pure water and food samples by square wave voltammetry (SWV) in the absence and presence of ultrasound using the BDD electrode. The results obtained in pure water were compared with the high performance liquid chromatography data.The sonoelectroanalytical methodologies for all analytes in pure water and food matrices showed greater sensitivity and precision and lower limits of detection (LOD) and quantification (LOQ) than the silent measurements. For the reduction of MP and 4-NP and oxidation of carbaryl in pure water, the LOD diminished from 10.8 to 4.86 &mu;g L-1, from 6.38 to 2.57 &mu;g L-1 and from 2.96 to 2.08 &mu;g L-1, respectively. For the detection of MP in potato extract and of 4-NP in lemon juice, the LOD value diminished from 36.6 to 10.1 &mu;g L-1 and from 13.8 to 8.32 &mu;g L-1, respectively.In all cases, it was observed that the LOD and LOQ values are inside of the maximum allowed concentration for compounds in food samples (50 and 500 &mu;g kg-1 for potato and corn samples, respectively, 1000 &mu;g kg-1 for citrus fruit and 500 &mu;g kg-1 for pineapple sample). Satisfactory recovery values for the analytes in the samples indicate the possibility of the direct determination of MP in potato and corn extracts (83 to 96 %) and 4-NP in orange and lemon juices (84 to 94 %) and also for the detection of carbaryl in a pineapple juice after a liquid-liquid extraction procedure (89 to 92 %). In all these food samples, no initial detectable residues of the compounds were found.The advantages observed for the insonated studies are due to the increase in the mass transport of species to the electrode surface and also to the cleaning of the surface, since the intermediary cleaning is not necessary thus resulting in a more rapid and reproducible analysis.In the second part of the work, the beneficial effects of the ultrasound, particularly the cleaning of electrode surface, were evaluated in association to potentiostatic electrolyses for the degradation of pentachlorophenol (PCP) at 0.9, 2.0 and 3.0 V vs. Ag/AgCl and for carbaryl at 3.0 V vs. Ag/AgCl.For pentachlorophenol the electrolyses at 0.9 V showed that the blockage of the electrode surface was faster in the sonoelectrolysis than in the absence of ultrasound due to the formation of a dimeric compound on the electrode surface. Electrolyses at 2.0 V and 3.0 V showed greater decay levels of the PCP bands for insonated studies than those obtained for the silent measurements, due the increase of mass transport, minimization of the electrode fouling and to the added generation of hydroxyl radicals by both ultrasound and the polarized BDD surface. Similar results to those for pentachlorophenol at the higher potential were also observed for the degradation of carbaril at 3.0 V.