abstract: High-k dielectrics have been employed in the metal-oxide semiconductor field effect transistors (MOSFETs) since 45 nm technology node. In this MOSFET industry, Moore’s law projects the feature size of MOSFET scales half within every 18 months. Such scaling down theory has not only led to the physical limit of manufacturing but also raised the reliability issues in MOSFETs. After the incorporation of HfO2 based high-k dielectrics, the stacked oxides based gate insulator is facing rather challenging reliability issues due to the vulnerable HfO2 layer, ultra-thin interfacial SiO2 layer, and even messy interface between SiO2 and HfO2. Bias temperature instabilities (BTI), hot channel electrons injections (HCI), stress-induced leakage current (SILC), and time dependent dielectric breakdown (TDDB) are the four most prominent reliability challenges impacting the lifetime of the chips under use. In order to fully understand the origins that could potentially challenge the reliability of the MOSFETs the defects induced aging and breakdown of the high-k dielectrics have been profoundly investigated here. BTI aging has been investigated to be related to charging effects from the bulk oxide traps and generations of Si-H bonds related interface traps. CVS and RVS induced dielectric breakdown studies have been performed and investigated. The breakdown process is regarded to be related to oxygen vacancies generations triggered by hot hole injections from anode. Post breakdown conduction study in the RRAM devices have shown irreversible characteristics of the dielectrics, although the resistance could be switched into high resistance state. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2018

CAPES / Com o avanço da miniaturização de componentes e dispositivos eletrônicos ocorrida nos últimos anos, a utilização de materiais dielétricos e a necessidade de informações precisas sobre o comportamento dielétrico apresentado por estes materiais aumentou consideravelmente. Neste trabalho é apresentado inicialmente as motivações para o estudo do comportamento dielétrico e da modelagem da função resposta dielétrica. A partir da teoria proposta por Debye e identificando suas peculiaridades, são exploradas algumas extensões deste modelo e analisada a interpretação da função resposta proposta por estes. Muitos modelos assumiam a existência de múltiplas interações envolvendo os dipolos com o meio dielétrico, as quais contribuíam para a dinâmica do comportamento dielétrico, somente mais tarde é que estas múltiplas interações ganharam uma conexão entre a resposta dielétrica observada com as propriedades intrínsecas do material. Por meio do modelo proposto por Dissado e Hill e assumindo dados experimentais disponíveis na literatura para alguns materiais, foi testada a validade da função resposta resultante do modelo, na qual veri cou-se a capacidade da mesma em ajustar as curvas para as componentes real e imaginária da permissividade para uma grande variedade de materiais dielétricos. A partir das simulações e análises realizadas, ficou evidente a dependência do comportamento dielétrico com a temperatura, fato este que deverá ser abordado em trabalhos futuros. / With the improvement of miniaturization of electronic components and devices occurred in recent years, the use of dielectric materials and the need for accurate information about the dielectric behavior displayed by these materials has increased considerably. In this work is initially presented the motivations for the study of dielectric behavior and the modeling of the dielectric response function. From the theory proposed by Debye and identifying its peculiarities, are exploited some extensions of this model and analyzed the interpretation of response function proposed by these. Many models used to assume the existence of multiple interactions involving the dipoles with the dielectric medium, which contributed to the dynamics of the dielectric behavior, only later the multiple interactions won a connection between the dielectric response observed with the intrinsic properties of the materials. Through the model proposed by Dissado and Hill and assuming experimental data available in bibliography for some materials, was tested the validity of the response function resulting from the model, in which was veri ed the ability of the same to adjust the curves for the real and imaginary components of permittivity to a wide variety of dielectric materials. From the simulations and analyzes performed, was evident the dependence of dielectric behavior with temperature, a fact that should be discussed in future works.

A medida do teor de umidade de materiais resulta em ganhos econômicos e ambientais ao possibilitar o controle preciso da secagem de produtos agrícolas, de processos de cura e armazenagem, e reduzir perdas de material e consumo de energia. Tal medida pode ser feita através da interação de ondas eletromagnéticas nas frequências de micro-ondas. Apresenta-se o desenvolvimento histórico e o estado da arte dessa área da metrologia que é conhecida por aquametria por micro-ondas. Detalha-se o comportamento das ondas eletromagnéticas em dielétricos, o modelo de espalhamento nas interfaces das amostras, a relação entre a permissividade complexa e a umidade, métodos para a determinação da permissividade, instrumentos, sistemas e aspectos metrológicos da cadeia de medição para espectroscopia dielétrica. Dois novos métodos, com equações explícitas originais para a determinação da permissividade são obtidos. As novas equações resultam em incerteza menor que os métodos clássicos. Uma nova metodologia, através do método de Monte Carlo, é empregada para a avaliação das mesmas. Conclui-se que o desenvolvimento da aquametria passa, necessariamente, pelo aperfeiçoamento dos instrumentos e métodos para determinação da permissividade dos materiais. / The measurement of moisture content of materials results in economic and environmental gains. Monitoring drying and curing of materials prevents loss of products and waste of energy. This can be done through the interaction of electromagnetic waves at microwave frequencies. This dissertation presents the historical development and the state-of-the-art in aquametry, the behavior of electromagnetic waves in dielectrics, sample interface scattering model, the relationship between the complex permittivity and moisture, methods for determining permittivity, instruments and metrological aspects of the measurement chain, and some instruments for dielectric spectroscopy. Two new methods, capable of providing explicit equation for the permittivity, are obtained and the Monte Carlo method is applied to determine their uncertainty. The new equations have lower uncertainty than the classic methods. The general conclusion is that the development of instrumentation and techniques in aquametry must be based in improvements in permittivity measurement.

abstract: In this dissertation, remote plasma interactions with the surfaces of low-k interlayer dielectric (ILD), Cu and Cu adhesion layers are investigated. The first part of the study focuses on the simultaneous plasma treatment of ILD and chemical mechanical polishing (CMP) Cu surfaces using N2/H2 plasma processes. H atoms and radicals in the plasma react with the carbon groups leading to carbon removal for the ILD films. Results indicate that an N2 plasma forms an amide-like layer on the surface which apparently leads to reduced carbon abstraction from an H2 plasma process. In addition, FTIR spectra indicate the formation of hydroxyl (Si-OH) groups following the plasma exposure. Increased temperature (380 °C) processing leads to a reduction of the hydroxyl group formation compared to ambient temperature processes, resulting in reduced changes of the dielectric constant. For CMP Cu surfaces, the carbonate contamination was removed by an H2 plasma process at elevated temperature while the C-C and C-H contamination was removed by an N2 plasma process at elevated temperature. The second part of this study examined oxide stability and cleaning of Ru surfaces as well as consequent Cu film thermal stability with the Ru layers. The ~2 monolayer native Ru oxide was reduced after H-plasma processing. The thermal stability or islanding of the Cu film on the Ru substrate was characterized by in-situ XPS. After plasma cleaning of the Ru adhesion layer, the deposited Cu exhibited full coverage. In contrast, for Cu deposition on the Ru native oxide substrate, Cu islanding was detected and was described in terms of grain boundary grooving and surface and interface energies. The thermal stability of 7 nm Ti, Pt and Ru ii interfacial adhesion layers between a Cu film (10 nm) and a Ta barrier layer (4 nm) have been investigated in the third part. The barrier properties and interfacial stability have been evaluated by Rutherford backscattering spectrometry (RBS). Atomic force microscopy (AFM) was used to measure the surfaces before and after annealing, and all the surfaces are relatively smooth excluding islanding or de-wetting phenomena as a cause of the instability. The RBS showed no discernible diffusion across the adhesion layer/Ta and Ta/Si interfaces which provides a stable underlying layer. For a Ti interfacial layer RBS indicates that during 400 °C annealing Ti interdiffuses through the Cu film and accumulates at the surface. For the Pt/Cu system Pt interdiffuion is detected which is less evident than Ti. Among the three adhesion layer candidates, Ru shows negligible diffusion into the Cu film indicating thermal stability at 400 °C. / Dissertation/Thesis / Ph.D. Physics 2012

abstract: The mechanism of loss in high performance microwave dielectrics with complex perovskite structure, including Ba(Zn1/3Ta2/3)O3, Ba(Cd1/3Ta2/3)O3, ZrTiO4-ZnNb2O6, Ba(Zn1/3Nb2/3)O3, and BaTi4O9-BaZn2Ti4O11, has been investigated. We studied materials synthesized in our own lab and from commercial vendors. Then the measured loss tangent was correlated to the optical, structural, and electrical properties of the material. To accurately and quantitatively determine the microwave loss and Electron Paramagnetic Resonance (EPR) spectra as a function of temperature and magnetic field, we developed parallel plate resonator (PPR) and dielectric resonator (DR) techniques. Our studies found a marked increase in the loss at low temperatures is found in materials containing transition metal with unpaired d-electrons as a result of resonant spin excitations in isolated atoms (light doping) or exchange coupled clusters (moderate to high doping) ; a mechanism that differs from the usual suspects. The loss tangent can be drastically reduced by applying static magnetic fields. Our measurements also show that this mechanism significantly contributes to room temperature loss, but does not dominate. In order to study the electronic structure of these materials, we grew single crystal thin film dielectrics for spectroscopic studies, including angular resolved photoemission spectroscopy (ARPES) experiment. We have synthesized stoichiometric Ba(Cd1/3Ta2/3)O3 [BCT] (100) dielectric thin films on MgO (100) substrates using Pulsed Laser Deposition. Over 99% of the BCT film was found to be epitaxial when grown with an elevated substrate temperature of 635 C, an enhanced oxygen pressures of 53 Pa and a Cd-enriched BCT target with a 1 mol BCT: 1.5 mol CdO composition. Analysis of ultra violet optical absorption results indicate that BCT has a bandgap of 4.9 eV. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2013

A evolução do potencial de superfície de amostras dielétricas é calculada através da resolução de modelos teóricos pelo método numérico de diferenças finitas. São considerados os fenômenos de polarização elétrica, condutividade intrínseca, injeção de carga espacial, dissociação iônica no volume da amostra e difusão de moléculas, através da superfície da amostra, as quais podem se dissociar no volume. A subida do potencial de superfície é calculada para cada caso e também são discutidas as situações nas quais se consideram a ocorrência de dois fenômenos. Procura-se, com a ajuda dos modelos desenvolvidos, interpretar o comportamento geral da subida do potencial em função do tempo para amostras ferroelétricas (polímero PVDF-beta e copolímero P(VDF-TrFE)) e amostras não ferroelétricas (polímero PVDF-alfa). / The finite-difference method has been employed for the determination of the surface potencial buildup of dielectric samples. In the models several processes have been considered such as the electric polarization, intrinsic conductivity, space charge injection, ionic dissociation and diffusion of molecules which dissociates in the sample bulk. The surface potential has been determined for each case considering two different phenomena. The models developed throughout the work are used for interpreting surface potential buildup curves of ferroelectric materials (PVDF-beta and P(VDF-TrFE) copolymers) and also of non-ferroelectric PVDF-alfa samples.

Construímos um acelerador de elétrons de baixa energia (opera na faixa de 0,4 - 20 keV) que dispõe dos recursos necessários para ser utilizado como instrumento de pesquisa em áreas relacionadas com os isolantes. Neste trabalho, ele foi empregado para estudar a emissão secundária em polímeros ou, mais especificamente, para mostrar que um novo método de medida de emissão secundária, que designamos \"Método de Medida Dinâmica\", descrito por H. Von Seggern [IEEE Trans. Nucl. Sei. NS-32, p.1503 (1985)] não permite, ao contrário do que se esperava, obter a verdadeira curva de emissão secundária devido à influência exercida pela carga positiva acumulada sobre a emissão. Contudo, no decorrer do trabalho, mostramos que a montagem descrita por ele ainda pode ser utilizada com vantagem para: i) medir precisamente a energia do 2&#176 ponto de cruzamento e ii) para levantar a verdadeira curva de emissão se, ao invés irradiarmos o alvo continuamente, usarmos pulsos de corrente. Além disso, pudemos, analisando o modo como a carga positiva age sobre a emissão nas mais diversas situações. I) estimar a profundidade de escape máxima e média dos secundários; II) mostrar que a carga positiva líquida numa amostra carregada positivamente fica próxima da superfície e III) mostrar que em amostras carregadas negativamente as cargas positivas ficam próximas da superfície e as negativas, em maior número, no volume do material. / We have constructed an accelerator for the generation of low energy e1ectrons (in the 0.4 to 20 keV range). The accelerator is equipped with some devices especially designed for the investigation of the e1ectrical properties of electron-irradiated dielectrics. In this work we have employed it for the study of the secondary electron emission of irradiated polymers. Reference is made to a method proposed bt H. von Seggern [IEEE Trans. Nucl. Sci. NS-32, p.1503 (1985)] which was intended for the determination of the electron emission yield especially between the two cross-over points in a single run, here called the dynamical method. We have been able to prove that, contrary to expectation, this method does not give correct results over the entire emission curve. Rather it gives yield values which are too low by 25% in the region where the emission exhibits a maximum, due to the interaction between the electron emission process and the positive surface charge of the dielectric. However the method needs not to be dismissed entirely. As it is, it can be used advantageously for the precise determination of the energy of the second cross-over point. In addition, with the same set up, the method could be improved by replacing the continuous irradiation of the sample by a pulsed irradiation, leading to results essentially the same as those shown in the literature. Finally, analyzing the process of interaction between the positive charge of the dielectric and the mechanism of electron emission in several situations, we were able: I) to determine the maximum value and the average value of the escape depth of the emitted electrons; II) for a sample with a net positive charge, to show that the positive charge resides very near the surface of incidence; III) for a sample with a net negative charge, to show that the positive charge also resides near the surface while the (prevalent) negative charge resides in the bulk of the material

Orientador: Fernando Galembeck / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-13T18:39:32Z (GMT). No. of bitstreams: 1 Burgo_ThiagoAugustodeLima_M.pdf: 5433149 bytes, checksum: 072a8a59c85a99f30a12ff303fcdb4e1 (MD5) Previous issue date: 2009 / Resumo: Neste trabalho estudou-se o comportamento de potenciais induzidos em celulose pela aproximação de um corpo eletrificado e também a dissipação de cargas (positivas e negativas) em polietileno de baixa densidade (PEBD) geradas por descarga corona. As medidas de determinação do potencial eletrostático foram feitas utilizando eletrodos de Kelvin acoplados a voltímetros eletrostáticos. Os resultados mostraram que a umidade relativa (UR) tem papel decisivo tanto sobre a indução e dissipação de cargas em celulose quanto sobre a dissipação de cargas em polietileno. Nos experimentos de dissipação de carga em PEBD (virgem e oxidado) os potenciais são mais rapidamente dissipados em umidade elevada. O polietileno sempre apresenta um potencial negativo no equilíbrio (¿4,6 ±0,7V), independente do sinal do potencial medido após a eletrização inicial, positivo ou negativo. A atmosfera se mostrou decisiva tanto para a aquisição quanto para a dissipação de cargas nos materiais e os resultados foram interpretados de acordo com um modelo no qual a atmosfera atua como reservatório de cargas uma vez que o equilíbrio da água sob um potencial eletrostático V mostra excesso de concentração de íons H(H2O)n se V < 0 e excesso de concentração de OH(H2O)m se V > 0, de acordo com a definição de potencial eletroquímico. De acordo com este modelo, a atmosfera é um importante e provavelmente decisivo reservatório de íons na eletrização e dissipação de cargas de dielétricos / Abstract: The objective of this study is the verification of a model for electrostatic charge induction and dissipation in dielectrics. Experiments aimed at 1) the determination of electrostatic potential induced and dissipated in cellulose by the approximation of a charged body and 2) the determination of electrostatic potential dissipation by low-density polyethylene (LDPE) charged with corona pulses. Measurements were made using Kelvin electrodes coupled to electrostatic voltmeters with spatial resolution at the macroscopic and nanometric scales. In cellulose, positive and negative charge induction follow the same kinetics with similar time constants but positive corona-induced potentials in LDPE are dissipated faster than negative corona potentials. LDPE surface oxidation causes an increase in the rate of corona potential decay that increases with the degree of oxidation. Relative humidity (RH) is decisive for both charge acquisition and dissipation and the present results cannot be explained by the usual assumption of surface conductivity as the main charge/discharge mechanism. On the other hand, experimental results are interpreted assuming that the atmospheric water is a charge reservoir for dielectrics and charge acquisition and dissipation is the result of adsorption and desorption of H and OH ions from adsorbed water, under the effect of external or internal fields. LDPE in equilibrium under a moist nitrogen atmosphere is not electroneutral, showing an equilibrium potential equal to ¿4.6±0.7 V / Mestrado / Físico-Química / Mestre em Química

Guias de onda de luz foram fabricados por difusão térmica de Titânio em substratos de LiNbO3. Os índices efetivos dos modos guiados foram medidos usando o método de acoplamento por prismas e a equação de onda resolvida numericamente usando a aproximação WKB. Profundidade de difusão, variação máxima do índice de refração e o perfil da concentração de Titânio são calculados para um guia que suporta três modos TE / Optical waveguides have been fabricated by thermal diffusion of Titanium into LiNO3 substrate. The effective indices of guided modes have been measured using a prism coupling method and the wave equation has been solute numerically using the WKB approximation. The diffusion depth, maximum refractive index change and titanium concentration profited was calculated for one waveguide that support three TE modes

Neste trabalho foram fabricados e caracterizados eletricamente capacitores MOS com óxido de silício ultrafino (2,6 nm) com porta de silício policristalino (Si-poli) P+ e N+. Os capacitores MOS com porta de Si-poli dopados com boro tiveram a estrutura Si-poli/SiO2/Si previamente implantada com nitrogênio nas doses de 1.10\'POT.13\', 1.10\'POT.14\', 1.10\'POT.15\' e 5.10\'POT.15\' at.cm-², com o pico da concentração de nitrogênio próximo à interface SiO2/Si. Os capacitores MOS foram fabricados sobre lâminas de silício do tipo p que passaram por uma limpeza química préoxidação tipo RCA mais imersão final em solução diluída em HF. Na seqüência, as lâminas foram oxidadas em um ambiente de O2 (1,5 l/min) + N2/H2 (2l/min; 10 %) que proporcionou óxidos de silício com excelentes características elétricas. Para a fabricação dos capacitores MOS com porta de Si-poli P+, utilizou-se SOG de boro seguido por difusão térmica sobre camada de Si-poli (340 nm). Após testes com receitas de difusão a 950, 1000, 1050 e 1100 °C todas padronizadas por um tempo de 30 min optamos por realizar a difusão a 1050 °C por 30 min, pois essa receita proporcionou concentração de boro superior a 1.10\'POT.20\' at.cm-³ e segregação desprezível do boro em direção ao substrato de Si. A dopagem dos capacitores MOS com porta de Si-poli N+ foi realizada por aplicação do SOG de fósforo seguido por difusão a 1050 °C por 30 min. Os resultados indicaram segregação do boro desprezível para o Si, baixa densidade de estados de interface (< 1.10\'POT.11\' eV-¹ cm-²) e no aumento do campo elétrico de ruptura (de 14 MV/cm para 21 MV/cm) com o aumento da dose de nitrogênio (de 1.10\'POT.13\' a 5.10\'POT.15\' at/cm²). Embora ocorresse uma maior dispersão e um aumento desfavorável da tensão de banda plana com o aumento da dose de nitrogênio, os valores 1.10\'POT.15\' e 5.10\'POT.15\' at.cm-² resultaram em capacitores MOS com tensão de faixa plana próxima ao parâmetro diferença de função trabalho (\'fi\' MS) significando densidade efetiva de cargas no dielétrico de porta inferior à cerca de 1.10\'POT.11\' cm-². / In this work we manufactured and electrically characterized MOS capacitors with ultrathin silicon oxides (2,6 nm) and polysilicon gate (Si-poli), P+ or N+. P+ - doped polysilicon gate MOS capacitors (Si-poli/SiO2/Si structure) were previously implanted with nitrogen using doses of 1.10\'POT.13\', 1.10\'POT.14\', 1.10\'POT.15\' and 5.10\'POT.15\' at.cm-², and implantation peak centered close to the SiO2/Si interface before boron doping. The MOS capacitors were fabricated on p-type silicon wafers, which were submitted to RCA - based cleaning procedure and a final dip in diluted HF solution. Following, the wafers were oxidize in ultrapure O2 (1,5 l/min) + N2/H2 (2l/min; 10 %) having, as a result, silicon gate oxides with excellent electrical characteristics. To obtain P+ polysilicon, it Spin On Glass (SOG) of boron the wafers was annealed at 950, 1000, 1050 or 1100 °C during 30 min. We have chosen a diffusion recipe of 1050 °C during 30 min to obtain volumetric concentration of boron higher than 1.10\'POT.20\' cm-³ and no boron segregation to the silicon. N+ polysilicon was also obtained using phosphorus SOG and diffusion at 1050 °C during 30 min. As a result, besides no boron segregation to Si, the interface states density was low (< 1.10\'POT.11\' eV-¹cm-²) and the breakdown field of the gate oxides increased (from 14 MV/cm to 21 MV/cm) by increasing the nitrogen doses (from 1.10\'POT.13\' to 5.10\'POT.15\' at/cm²). Although a larger dispersion and increasing of the flat-band voltage have occurred as the nitrogen dose was increased, values of 1.10\'POT.15\' and 5.10\'POT.15\' at.cm-² induced flat band voltage close to the parameter workfunction difference (\'fi\'MS) which meant effective charge density in the gate dielectrics lower than about 1.10\'POT.11\' cm-².