abstract: Silicon (Si) solar cells are the dominant technology used in the Photovoltaics industry. Field-effect passivation by means of electrostatic charges stored in an overlying insulator on a silicon solar cell has been proven to be a significantly efficient way to reduce effective surface recombination velocity and increase minority carrier lifetime. Silicon nitride (SiNx) films have been extensively used as passivation layers. The capability to store charges makes SiNx a promising material for excellent feild effect passivation. In this work, symmetrical Si/SiO2/SiNx stacks are developed to study the effect of charges in SiNx films. SiO2 films work as barrier layers. Corona charging technique showed the ability to inject charges into the SiNx films in a short time. Minority carrier lifetimes of the Czochralski (CZ) Si wafers increased significantly after either positive or negative charging. A fast and contactless method to characterize the charged overlying insulators on Si wafer through lifetime measurements is proposed and studied in this work, to overcome the drawbacks of capacitance-voltage (CV) measurements such as time consuming, induction of contanmination and hysteresis effect, etc. Analytical simulations showed behaviors of inverse lifetime (Auger corrected) vs. minority carrier density curves depend on insulator charge densities (Nf). From the curve behavior, the Si surface condition and region of Nf can be estimated. When the silicon surface is at high strong inversion or high accumulation, insulator charge density (Nf) or surface recombination velocity parameters (Sn0 and Sp0) can be determined from the slope of inverse lifetime curves, if the other variable is known. If Sn0 and Sp0 are unknown, Nf values of different samples can be compared as long as all have similar Sn0 and Sp0 values. Using the saturation current density (J0) and intercept fit extracted from the lifetime measurement, the bulk lifetime can be calculated. Therefore, this method is feasible and promising for charged insulator characterization. / Dissertation/Thesis / M.S. Electrical Engineering 2014

Orientador: Jose Alexandre Diniz / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-10T02:20:44Z (GMT). No. of bitstreams: 1 Zoccal_LeonardoBreseghello_D.pdf: 6734188 bytes, checksum: 05f6c64d923bafb5e071d89514d0fa43 (MD5) Previous issue date: 2007 / Resumo: Este trabalho apresenta um método simples de passivação de superfícies semicondutoras III-V de substratos de arseneto de gálio (GaAs) e de heteroestruturas de fosfeto de gálio-índio sobre arseneto de gálio (InGaP/GaAs), que são utilizados em transist res de efeito de campo, MESFET (Metal-Semiconductor Field Effect Transistor) e MISFET Metal-Insulator-Semiconductor Field Effect Transistor), e transistores bipolares de heterojunção (HBT), respectivamente. O processo de passivação visa à máxima redução da densidade de estados de superfícies semicondutoras para níveis menores que 1012 cm-2. A alta densidade de estados na superfície do GaAs provoca corrente de fuga nas regiões ativas dos transistores MESFET e HBT, reduzindo o desempenho destes dispositivos. Além disso, impossibilita a formação de dispositivos MISFET sobre os substratos de GaAs, devido à alta densidade de estados na região da interface isolante-semicondutor. Para o estudo da passivação de superfícies, filmes de nitreto de silício (SiNX) são depositados diretam nte por plasma ECR-CVD (Electron Cyclotron Resonance - Chemical Vapor Deposition) sobre substratos de GaAs e heteroestruturas do tipo InGaP/GaAs. Os plasmas ECR foram analisados por espectroscopia de emissão óptica (OES), e identificou-se baixa formação de espécies H e NH na fase gasosa para pressão de processo de 2,5 mTorr. Os filmes de SiNX foram caracterizados estruturalmente por espectroscopia de absorção do infravermelho (FTIR) e por elipsometria, que indicaram, respectivamente, a formação de ligações Si-N e valores de índice de refração es de nitreto de silício. Capacitores MIS e transisto T foram fabricados para avaliar os efeitos da passivação sobre os dispositivos. Os excelentes resultados obtidos, tais como transist o e em torno de 2,0 nos filmres MISFET e HB ores HBT passivados apresentando maiores ganhos de corrente do que os não-passivados, e os transistores MISFET apresentando maiores valores de transcondutância do que os MESFET (que foram usados como dispositivos de controle), indicam que o nosso processo de passivação é muito eficiente, sendo completamente compatível com a tecnologia de fabricação de circuitos integrados monolíticos de microondas (MMIC) / Abstract: This work presents a simple passivation method for III-V semiconductor surfaces of gallium arsenide (GaAs) substrates and indium-gallium phosphide on gallium arsenide (InGaP/GaAs) heterostructures, which are us in field effect transistors MESFET (Metal-Semiconductor Field Effect Transistor) and MISFET (Metal-Insulator-Semiconductor Field Effect Transistor) and heterojunction bip lar transistors (HBT), respectively. The passivation process aims the maximum reduction of semiconductor surface state density at levels lower than 1012 states/cm2. The high surface state density on GaAs surface produces current leakage in active regions of MESFET and HBT transistors, reducing the device performance. Furthermore, the MISFET device formation on GaAs substrate is not allowed, passivation study, silicon nitride films (SiNX) are deposited by ECR-CVD (Electron Cyclotron Resonance - Chemical Deposition Vapor) plasma directly over GaAs substrate and InGaP/GaAs heterostructures. The ECR plasmas were analyzed by optical emission spectroscopy, (OES), and low formation of H and NH molecules in the gas phase was detected at process pressure of 2.5 mTorr. The SiNX film structural characterization was obtained by infra-red absorption spectrometry (FTIR) and ellipsometry, which, respectively, indicate the Si-N bo tive index values of about 2.0 at the silicon nitride films. MIS cap BT transistors were fabricated to verify the passivation process effect on devices. The excellent results obtained, such as higher and formation and refracacitors, MISFET and H current gain of passivated device compared to unpassivated HBTs and higher transconductances of MISFET devices compared to MESFET (which were used as control devices), indicate that our simple passivation process is very efficient, being fully compatible with monolithic microwave integrated circuits (MMIC) / Doutorado / Eletrônica, Microeletrônica e Optoeletrônica / Doutor em Engenharia Elétrica

Orientadores: Peter Jurgen Tatsch, Stanislav A. Moshkalyov / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-05T15:04:36Z (GMT). No. of bitstreams: 1 Nunes_AlcineiMoura_M.pdf: 4164375 bytes, checksum: 7cc7a3a84a2aa99efc455551e270bc57 (MD5) Previous issue date: 2005 / Resumo: Este trabalho apresenta os resultados e as discussões dos mecanismos de corrosão por plasma de filmes de silício policristalino e nitreto de silício para aplicações em dispositivos MEMS e CMOS. A corrosão foi feita em um reator convencional de corrosão por plasma em modo RIE (Reactive Ion Etching). Para aplicação em MEMS, corrosões de silício policristalino com perfis anisotrópicos e seletividade maior que 10 para óxido de silício foram obtidos. As misturas gasosas utilizadas na corrosão foram: SF6/CF4/CHF3 e SF6/CF4/N2. Processos híbridos, utilizando duas etapas de corrosão em condições diferentes, num mesmo processo, foram feitos para possibilitar a obtenção de perfis altamente anisotrópicos, com seletividade elevada. Para avaliar melhor a evolução do perfil de corrosão, foram utilizadas amostras com filmes espessos de silício policristalino (>3mm). Para aplicação em eletrodo de transistores CMOS, afinamento de linhas de 5mm para 1mm de largura foram obtidos com perfil anisotrópico (A~0,95) em processos híbridos, utilizando uma primeira etapa de corrosão com condições de maior bombardeio iônico e menor seletividade, e uma segunda etapa com menor bombardeio iônico e maiores seletividades para o óxido e fotorresiste. Corrosões de nitreto de silício (SiNx), com seletividade elevada são imprescindíveis para aplicação em tecnologia LOCOS. Resultados de corrosões e filmes de nitreto de silício para esta aplicação foram feitas utilizando as seguintes misturas gasosas: CF4/O2/N2, CF4/H2, SF6/CF4/N2 e CHF3/O2. As Maiores seletividades obtidas foram de aproximadamente 10 para óxido e aproximadamente 7 para o substrato de silício. Os filmes foram caracterizados com vários equipamentos. Um Perfilômetro foi utilizado para medir a profundidade das corrosões, e por conseguinte, calcular a taxa de corrosão através da divisão pelo tempo. Um Elipsômetro foi utilizado para medir as espessuras e índices de refração dos filmes utilizados. O FTIR (Fourier Transform Infrared Spectrocopy) foi utilizado para caracterizar a composição do filme de nitreto de silício após o tratamento térmico. Imagens SEM (Scanning Electron Microscopy) dos filmes corroídos foram feitas para analisar o perfil e mecanismo de corrosão para cada mistura / Abstract: This work presents the results and the discussion about mechanisms of plasma etching of polysilicon and silicon nitride films for applications in MEMS and CMOS devices. The etching was performed in a conventional reactor of plasma etching in a RIE mode (Reactive Ion Etching). For application in MEMS, polysilicon etching with anisotropic profile and high selectivity (>10) for silicon oxide was obtained. The mixtures used in etching were SF6/CF4/CHF3 and SF6/CF4/N2. Hybrid processes, using two etching stages in different conditions, in the same etching process, were done as possible solutions for highly anisotropic profiles with elevated selectivity. The evolution of the etching profile is better evaluated using polysilicon thick films (>3mm). For application in CMOS transistors electrode, 5mm to 1mm thinning was obtained with anisotropic profile (A~0,95) in hybrids processes, using the first stage in conditions with elevated ionic bombardment and reduction selectivity, and the second stage with reduction ionic bombardment and elevated selectivity to the oxide and photorresist. Highly selective silicon nitride etching (SiNx) is necessary for application in LOCOS technology. Results of the etching and silicon nitride films for this application was performed using the following mixtures: CF4/O2/N2, CF4/H2, SF6/CF4/N2 and CHF3/O2. High selectivity was obtained for silicon oxide (>10) and silicon substrate (~7). The films were characterized by various equipment. The Profiler was used to measure the etching depth, and herewith, the etching rate was evaluated. The Elipsometer was used to measure the refractive index and width of the films. FTIR (Fourier Transform Infrared Spectroscopy) was used to characterize the composition of the nitride film after the thermal treatment. SEM (Scanning Electron Microscopy) images of the etched films were done to analyse the profile and the etching mechanism for each mixture / Mestrado / Microeletronica / Mestre em Engenharia Elétrica

The effects of direct plasma chemistries on carbon removal from silicon nitride (SiNx) and oxynitride (SiOxNy ) surfaces and Cu have been studied by x-photoelectron spectroscopy (XPS) and ex-situ contact angle measurements. The data indicate that O2,NH3 and He capacitively coupled plasmas are effective at removing adventitious carbon from silicon nitride (SiNx) and Silicon oxynitride (SiOxNy ) surfaces. O2plasma and He plasma treatment results in the formation of silica overlayer. In contrast, the exposure to NH3 plasma results in negligible additional oxidation of the SiNx and SiOxNy surface. Ex-situ contact angle measurements show that SiNx and SiOxNy surfaces when exposed to oxygen plasma are initially more hydrophilic than surfaces exposed to NH3 plasma and He plasma, indicating that the O2 plasma-induced SiO2 overlayer is highly reactive towards ambient corresponding to increased roughness measured by AFM. At longer ambient exposures (>~10 hours), however surfaces treated by either O2, He or NH3 plasma exhibit similar steady state contact angles, correlated with rapid uptake of adventitious carbon, as determined by XPS. Surface passivation by exposure to molecular hydrogen prior to ambient exposure significantly retards the increase in the contact angle upon the exposure to ambient. The results suggest a practical route to enhancing the time available for effective bonding to surfaces in microelectronics packaging applications.

La fonctionnalisation de la surface du verre par des molécules organiques permet de modifier son énergie de surface ou d’améliorer l’adhésion d’un revêtement. La méthode classique de fonctionnalisation directe du verre repose sur une réaction de silanisation, via la formation de ponts siloxanes Si O Si. Ces ponts ont tendance à s’hydrolyser en milieu salin ou alcalin, entrainant la perte de la fonctionnalité du verre. Une solution envisagée consiste à déposer une couche de nitrure de silicium (SixN4) sur le verre, permettant de greffer des molécules organiques via des liaisons covalentes robustes : Si C ou N C. Le nitrure de silicium présente l’avantage d’être un matériau très souvent utilisé dans l’industrie verrière en raison de sa capacité à bloquer la diffusion des ions sodium et de protéger ainsi le verre de la corrosion.L’objectif de ce travail de thèse est de caractériser et contrôler la surface du nitrure de silicium, puis d’optimiser et de comprendre la modification de sa surface par le greffage covalent de molécules organiques.Lorsque le nitrure de silicium est exposé à l’air, une couche d’oxynitrure est formée en surface. L’optimisation et la compréhension du décapage de cette couche d’oxynitrure natif en milieu liquide est l’objet de la première phase de ce travail. La composition chimique de la surface est finement caractérisée et quantifiée en combinant des mesures de spectroscopie infrarouge en mode de réflexion totale atténuée (IR-ATR), de spectroscopie de photoélectrons X (XPS) et des dosages chimiques de surface. Le décapage dans des solutions fluorées (HF et NH4F) permet de retirer efficacement la couche d’oxynitrure et laisse majoritairement en surface des liaisons Si-F et dans une moindre mesure des liaisons N H et Si OH. La composition chimique de la surface peut toutefois être modifiée pour former des groupements Si H, soit en enrichissant la couche du SixN4 en silicium, soit en soumettant la surface à un traitement par plasma d’hydrogène à l’issue du décapage. A partir des observations expérimentales, une proposition décrivant les mécanismes mis en jeu lors du décapage est présentée.Dans la seconde partie de la thèse, la surface du nitrure de silicium est modifiée par l’immobilisation de molécules organiques, plus spécifiquement par la réaction d’un 1 alcène sous activation thermique ou photochimique. La composition chimique de la surface et les conditions d’activation de la réaction modifient la réaction de greffage et la densité des couches organiques. En particulier, la présence de liaisons Si-H et l’enrichissement de la couche en silicium sont étudiés en détail. Dans une dernière partie, dans une visée plus applicative, des couches denses fluorées présentant un caractère hydrophobe naturel sont greffées sur la surface du nitrure de silicium. / Covalent grafting of organic molecules on glass can modify its surface physico-chemical properties or improve the adhesion of a coating. Such a functionalization usually relies on a silanisation reaction, bonding molecules to the surface through Si-O-Si bonds. Unfortunately, the resulting molecular layers do not exhibit long-term stability due to the hydrolysis of siloxane groups. One solution would consist in depositing a silicon nitride layer on glass, allowing the glass surface to be functionalized through more stable bonds N-C or Si-C. Silicon nitride layers are frequently used in glass industry. They are well-known for their durability properties and are often used as a protective layer against glass corrosion.The aim of this project is to characterize and control the non-oxidized silicon nitride surface, then to optimize and understand the surface modification by covalent grafting of organic molecules.When silicon nitride is exposed to atmosphere, an oxynitride layer is formed on its surface. Several efficient ways to remove this native oxynitride are first studied and optimized. The quantitative characterization and control of the surface chemical composition provide a reliable starting point for the functionalization step. The surface chemical composition is quantitatively investigated by combining Attenuated Total Reflection InfraRed spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and chemical dosing. The etching in HF-based solutions efficiently removes the oxynitride layer and leads to a surface mainly covered with Si-F bonds and smaller amounts of Si-OH and N-H bonds. The surface composition can be modified by a H2 plasma treatment performed after the wet etching or by changing the silicon nitride layer composition (silicon enrichment), leading in either case to the formation of Si-H bonds on surface. An etching mechanism is suggested from these experimental observations.The second part of this work is focused on the grafting of the alkyl chains on the silicon nitride surface. The surface is reacted with a 1-alkene, using photochemical or thermal activation. The grafting efficiency depends on the surface composition and the activation conditions. The presence of surface Si-H bonds and the effect of Si enrichment are considered in details. In a final part, in an applicative view, functional hydrophobic molecules are grafted on the silicon nitride surface.

The material properties of low stress silicon nitride make it a possible replacement material for beryllium in X-ray windows. In this study, X-ray windows made of LPCVD deposited low stress silicon nitride are fabricated and characterized. The Young's modulus of the LPCVD low stress silicon nitride are characterized and found to be 226±23 GPa. The residual stress is characterized using two different methods and is found to be 127±25 MPa and 141±0.28 MPa. Two support structure geometries for the low stress silicon nitride X-ray windows are used. X-ray windows with thicknesses of 100 nm and 200 nm are suspended on a silicon rib support structure. A freestanding circular geometry is used for a 600 nm thick X-ray window. The 100 nm and 200 nm thick low stress silicon nitride X-ray windows with a silicon support structure are burst tested, cycling tested and leak rate tested. The average burst pressure for the 100 and 200 nm films on a silicon support structure are 1.4 atm and 2.2 atm respectively. Both 100 nm and 200 nm windows are able to withstand a difference in pressure of 1 atm for over 100 cycles with a leak rate of less than 10-10 mbar-L/s.The low stress silicon nitride with 100 nm and 200 nm thicknesses, the 600 nm freestanding low stress silicon nitride windows and freestanding 8 micron thick beryllium windows are mechanical shock resistance tested. The support structure low stress silicon nitride and beryllium windows are tested with an applied vacuum. The freestanding 600 nm thick low stress silicon nitride windows burst at 0.4 atm and are therefore mechanical shock wave tested without an applied vacuum. The support structure low stress silicon nitride windows fractured when subjected to an acceleration of roughly 5,000 g. The 8 micron thick beryllium windows are subjected to accelerations of over 30,000 g without fracturing. A quasistatic model is used to show that for low stress silicon nitride with a freestanding circular geometry, an acceleration of 106 g is required to have the same order of magnitude of stress caused by a pressure differential of 1 atm. Low stress silicon nitride can act as a replacement for beryllium in X-ray windows, but the support geometry, residual stress, and strength of the material need to be optimized.

The resonance frequency of a silicon nitride (SiN) nano-electromechanical systems (MEMS/NEMS) can be measured precisely due to their large quality factor that is associated to low thermomechanical fluctuations. While these properties enable the fabrication of high performance sensors, their use will eventually raise questions regarding their long-term stability, notably for calibration purposes. The long-term frequency stability and aging of SiN are less studied than the short-term fluctuations such as thermomechanical noise. Long-term aging studies exist for quartz clocks as well as MEMS silicon clocks and accelerometers, but not for SiN resonators with high quality factors. Thus, in this work we conduct the aging study of SiN membranes fabricated by our lab, by constantly tracking changes of the resonance frequency of the device over a long period. The evolution of the frequency drift is tracked, by optical interrogation, continuously for 135 days with a digital phase locked loop (PLL). Our device is placed in a cell under high vacuum to suppress air damping on our resonating membrane. Furthermore, due to its high sensitivity to temperature changes, our silicon nitride resonator and vacuum chamber are placed in an air bath providing a stable temperature (within 0.5 K over 135 days in the present case). To compensate further the frequency drifts induced by temperature changes, a multimeter measures the resistance of a calibrated thermistor placed inside the vacuum environment. The measured frequency drift for the aging periods of 135 days was of 300 parts per million (ppm) and was consistent with previously reported double logarithmic models for quartz oscillators. The initial stage of negative frequency drift, in our aging data, is consistent with the behaviour expected from the desorption of water due to the transition from ambient air environment to high vacuum. We review models explaining how water adsorption/desorption impacts our membrane's frequency by (1) inducing chemical reaction stresses (most important effect), (2) through the contribution of the water surface tension stress (non-negligible effect), and (3) through mass loading from water molecules (weakest effect). After this initial negative trend, the membrane frequency drift inverts and increases almost linearly, in a fashion consistent with loss of mass from desorption of other chemical species. To identify these chemical species, X-ray photoelectron spectroscopy measurements were conducted on a reference membrane stored in an ambient setting and on our membrane placed under vacuum during our aging studies. The aged membrane, compared to its reference counterpart, contained substantially less alkaline ion contaminants (i.e., sodium, calcium and potassium), most likely due to desorption of these species during the aging measurement, and to the increase in adsorption occurring on the reference membrane concurrently. We therefore hypothesize that trapped negative charges, which is a typical phenomenon within dielectric materials such as SiN, might progressively attract positive ion contaminants over time when the device is exposed to ambient air.

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