一种简单的电压/时间转换器及其在模拟/数字转换中的应用

本文介绍一种已用于控制机作模拟/数字转换用的电压/时间转换器。它用一支硅三极管作恒流源,用一支 MOS 型场效应晶体管作温度补偿,其线性度和稳定性可达±0.1%。

Qualidade da matéria orgânica do solo de sistema agroflorestal: uma abordagem de avaliação termogravimétrica.

2010

Ab initio calculations of group 4 metallocene reaction mechanisms: atomic layer deposition and bond activation catalysis

Thin film dielectrics based on titanium, zirconium or hafnium oxides are being introduced to increase the permittivity of insulating layers in transistors for micro/nanoelectronics and memory devices. Atomic layer deposition (ALD) is the process of choice for fabricating these films, as it allows for high control of composition and thickness in thin, conformal films which can be deposited on substrates with high aspect-ratio features. The success of this method depends crucially on the chemical properties of the precursor molecules. A successful ALD precursor should be volatile, stable in the gas-phase, but reactive on the substrate and growing surface, leading to inert by-products. In recent years, many different ALD precursors for metal oxides have been developed, but many of them suffer from low thermal stability. Much promise is shown by group 4 metal precursors that contain cyclopentadienyl (Cp = C5H5-xRx) ligands. One of the main advantages of Cp precursors is their thermal stability. In this work ab initio calculations were carried out at the level of density functional theory (DFT) on a range of heteroleptic metallocenes [M(Cp)4-n(L)n], M = Hf/Zr/Ti, L = Me and OMe, in order to find mechanistic reasons for their observed behaviour during ALD. Based on optimized monomer structures, reactivity is analyzed with respect to ligand elimination. The order in which different ligands are eliminated during ALD follows their energetics which was in agreement with experimental measurements. Titanocene-derived precursors, TiCp*(OMe)3, do not yield TiO2 films in atomic layer deposition (ALD) with water, while Ti(OMe)4 does. DFT was used to model the ALD reaction sequence and find the reason for the difference in growth behaviour. Both precursors adsorb initially via hydrogen-bonding. The simulations reveal that the Cp* ligand of TiCp*(OMe)3 lowers the Lewis acidity of the Ti centre and prevents its coordination to surface O (densification) during both of the ALD pulses. Blocking this step hindered further ALD reactions and for that reason no ALD growth is observed from TiCp*(OMe)3 and water. The thermal stability in the gas phase of Ti, Zr and Hf precursors that contain cyclopentadienyl ligands was also considered. The reaction that was found using DFT is an intramolecular α-H transfer that produces an alkylidene complex. The analysis shows that thermal stabilities of complexes of the type MCp2(CH3)2 increase down group 4 (M = Ti, Zr and Hf) due to an increase in the HOMO-LUMO band gap of the reactants, which itself increases with the electrophilicity of the metal. The reverse reaction of α-hydrogen abstraction in ZrCp2Me2 is 1,2-addition reaction of a C-H bond to a Zr=C bond. The same mechanism is investigated to determine if it operates for 1,2 addition of the tBu C-H across Hf=N in a corresponding Hf dimer complex. The aim of this work is to understand orbital interactions, how bonds break and how new bonds form, and in what state hydrogen is transferred during the reaction. Calculations reveal two synchronous and concerted electron transfers within a four-membered cyclic transition state in the plane between the cyclopentadienyl rings, one π(M=X)-to-σ(M-C) involving metal d orbitals and the other σ(C-H)-to-σ(X-H) mediating the transfer of neutral H, where X = C or N. The reaction of the hafnium dimer complex with CO that was studied for the purpose of understanding C-H bond activation has another interesting application, namely the cleavage of an N-N bond and resulting N-C bond formation. Analysis of the orbital plots reveals repulsion between the occupied orbitals on CO and the N-N unit where CO approaches along the N-N axis. The repulsions along the N-N axis are minimized by instead forming an asymmetrical intermediate in which CO first coordinates to one Hf and then to N. This breaks the symmetry of the N-N unit and the resultant mixing of MOs allows σ(NN) to be polarized, localizing electrons on the more distant N. This allowed σ(CO) and π(CO) donation to N and back-donation of π*(Hf2N2) to CO. Improved understanding of the chemistry of metal complexes can be gained from atomic-scale modelling and this provides valuable information for the design of new ALD precursors. The information gained from the model decomposition pathway can be additionally used to understand the chemistry of molecules in the ALD process as well as in catalytic systems.

Computational modeling of defects in nanoscale device materials

This PhD thesis concerns the computational modeling of the electronic and atomic structure of point defects in technologically relevant materials. Identifying the atomistic origin of defects observed in the electrical characteristics of electronic devices has been a long-term goal of first-principles methods. First principles simulations are performed in this thesis, consisting of density functional theory (DFT) supplemented with many body perturbation theory (MBPT) methods, of native defects in bulk and slab models of In0.53Ga0.47As. The latter consist of (100) - oriented surfaces passivated with A12O3. Our results indicate that the experimentally extracted midgap interface state density (Dit) peaks are not the result of defects directly at the semiconductor/oxide interface, but originate from defects in a more bulk-like chemical environment. This conclusion is reached by considering the energy of charge transition levels for defects at the interface as a function of distance from the oxide. Our work provides insight into the types of defects responsible for the observed departure from ideal electrical behaviour in III-V metal-oxidesemiconductor (MOS) capacitors. In addition, the formation energetics and electron scattering properties of point defects in carbon nanotubes (CNTs) are studied using DFT in conjunction with Green’s function based techniques. The latter are applied to evaluate the low-temperature, low-bias Landauer conductance spectrum from which mesoscopic transport properties such as the elastic mean free path and localization length of technologically relevant CNT sizes can be estimated from computationally tractable CNT models. Our calculations show that at CNT diameters pertinent to interconnect applications, the 555777 divacancy defect results in increased scattering and hence higher electrical resistance for electron transport near the Fermi level.

Reformulating time-dependent density functional theory with non-orthogonal localized molecular orbitals.

Time-dependent density functional theory (TDDFT) has broad application in the study of electronic response, excitation and transport. To extend such application to large and complex systems, we develop a reformulation of TDDFT equations in terms of non-orthogonal localized molecular orbitals (NOLMOs). NOLMO is the most localized representation of electronic degrees of freedom and has been used in ground state calculations. In atomic orbital (AO) representation, the sparsity of NOLMO is transferred to the coefficient matrix of molecular orbitals (MOs). Its novel use in TDDFT here leads to a very simple form of time propagation equations which can be solved with linear-scaling effort. We have tested the method for several long-chain saturated and conjugated molecular systems within the self-consistent charge density-functional tight-binding method (SCC-DFTB) and demonstrated its accuracy. This opens up pathways for TDDFT applications to large bio- and nano-systems.

Cambios en las reservas de materia orgánica del suelo y sus fracciones granulométricas : efecto de la secuencia de cultivo, del sistema de labranza y de la fertilización nitrogenada

Los cambios producidos en los sistemas de cultivo de la Pampa Ondulada en las últimas décadas fueron masivamente adoptados sin una evaluación previa de su posible impacto sobre las reservas de materia orgánica del suelo (MOS) en el largo plazo. Por este motivo se propuso como objetivos evaluar el efecto de ocho sistemas de cultivo luego de 25 años (25 años de maíz-trigo/soja (M-T/S) bajo siembra directa (SD) y bajo labranza con arado de cincel (LV), 4 años de soja laboreada convencionalmente (LC) + 21 años de trigo/soja (T/S) bajo SD y LV, 8 años de soja LC + 17 años de monocultivo de maíz (M) bajo SD y LV y 8 años de soja LC + 17 años de monocultivo de soja (S) bajo SD y bajo LV) y estimar el impacto de la fertilización nitrogenada bajo SD en las secuencias M-T/S, T/S y M sobre las reservas de carbono (C) y nitrógeno (N) orgánico del suelo y sus fracciones granulométricas, utilizando ensayos de larga duración ubicados en un Argiudol típico. Se adoptó la metodología de fraccionamiento granulométrico para evaluar el efecto de las prácticas de manejo sobre las fracciones de la MOS, luego de su comparación con la de fraccionamiento densimétrico, a pesar de que los resultados mostraron que ambas metodologías midieron aproximadamente la misma cantidad de fracciones lábiles de C y que podrían utilizarse indistintamente. Además, se estudió la evolución del C en cuatro secuencias de cultivo (M-T/S, T/S, M y S) bajo SD y LV desde el inicio de cada secuencia hasta 2004 en los mismos experimentos. Luego de 25 años, solamente las secuencias de cultivo más intensificadas bajo SD (25 años de M-T/S y 4 años de soja bajo LC + 21 años de T/S) presentaron reservas de MOS superiores a las logradas con LV. El efecto de largo plazo de la intensificación de la secuencia de cultivo sobre las reservas de C y N fue más importante que el efecto del sistema de labranza. La fertilización nitrogenada bajo SD no produjo cambios en las reservas de MOS. Las pérdidas de C dependieron de la cantidad de C inicialmente presente en cada secuencia de cultivo, de los aportes diferenciales de C de cada secuencia y de las entradas diferentes de N. Un aporte de 4 Mg C ha-1 año-1 puede mantener las reservas de COS en 41 Mg ha-1 para una masa de suelo de 2500 Mg ha-1.

The presence of the Aragonese language in the magazine "El Ebro" (1917-1936)

El Ebro (1917-1936) was a magazine published in Barcelona by Aragonese emigrants at the beginning of the 20th century. It was the first experience of coexistence of different dialectal varieties of the Aragonese language in the same media. El Ebro was an experience that has gone virtually unnoticed in the recent history of one of the most minority languages, and with minor media presence, of Western Europe. In its pages El Ebro mixed dialects spoken in different regions of linguistic Aragonese area together with transcripts of medieval documents. At the same time, this newspaper raised debates about the language issue that they were truncated due to disappearance of the publication and the lack of theoretical realization

Electrical Characterisation of SOI Substrates Incorporating WSix Ground Planes

Silicon-on-insulator (SOI) substrates incorporating tungsten silicide ground planes (GPs) have been shown to offer the lowest reported crosstalk figure of merit for application in mixed signal integrated circuits. The inclusion of the silicide layer in the structure may lead to stress or defects in the overlying SOI layers and resultant degradation of device performance. It is therefore essential to establish the quality of the silicon on the GPSOI substrate. MOS capacitor structures have been employed in this paper to characterize these GPSOI substrates for the first time. High quality MOS capacitor characteristics have been achieved with minority carrier lifetime of similar to 0.8 ms. These results show that the substrate is suitable for device manufacture with no degradation in the silicon due to stress or metallic contamination resulting from the inclusion of the underlying silicide layer.

Low temperature surface nitridation processes for dielectric-Ge interfaces

Germanium MOS capacitors have been fabricated with a high-? HfO dielectric using ALD. An in-situ low temperature (250°C) nitrogen plasma treatment on the germanium surface prior to the deposition of HfO was found to be beneficial to the electrical properties of the devices. Germanium MOS capacitors have also been fabricated with a SiO dielectric deposited by an atmospheric pressure CVD 'silox' process. The same low temperature plasma nitridation was found to degrade the electrical properties of the silox devices. The effect of a post-metal anneal in H and N on both types of capacitor structure was also found to degrade device electrical properties. copyright The Electrochemical Society.

Atomic layer deposition of hafnium oxide dielectrics on silicon and germanium substrates

Hafnium oxide films have been deposited at 250 °C on silicon and germanium substrates by atomic layer deposition (ALD), using tetrakis-ethylmethylamino hafnium (TEMAH) and water vapour as precursors in a modified Oxford Instruments PECVD system. Self-limiting monolayer growth has been verified, characterised by a growth rate of 0.082 nm/ cycle. Layer uniformity is approximately within ±1% of the mean value. MOS capacitors have been fabricated by evaporating aluminium electrodes. CV analysis has been used to determine the bulk and interface properties of the HfO 2, and their dependence on pre-clean schedule, deposition conditions and post-deposition annealing. The dielectric constant of the HfO 2 is typically 18. On silicon, best results are obtained when the HfO 2 is deposited on a chemically oxidised hydrophilic surface. On germanium, best results are obtained when the substrate is nitrided before HfO 2 deposition, using an in-situ nitrogen plasma treatment. © Springer Science+Business Media, LLC 2007.

Germanium on sapphire

This paper explores the potential of germanium on sapphire (GeOS) wafers as a universal substrate for System on a Chip (SOC), mm wave integrated circuits (MMICs) and optical imagers. Ge has a lattice constant close to that of GaAs enabling epitaxial growth. Ge, GaAs and sapphire have relatively close temperature coefficients of expansion (TCE), enabling them to be combined without stress problems. Sapphire is transparent over the range 0.17 to 5.5 µm and has a very low loss tangent (a) for frequencies up to 72 GHz. Ge bonding to sapphire substrates has been investigated with regard to micro-voids and electrical quality of the Ge back interface. The advantages of a sapphire substrate for integrated inductors, coplanar waveguides and crosstalk suppression are also highlighted. MOS transistors have been fabricated on GeOS substrates, produced by the Smart-cut process, to illustrate the compatibility of the substrate with device processing. © 2008 World Scientific Publishing Company.

Electrical characterization of ALD Al2O3 and HfO2 films on germanium

Al2O3 and HfO2 films were deposited on germanium substrates by atomic layer deposition (ALD) and analyzed by MOS capacitor electrical characterization. In-situ plasma nitridation performed prior to ALD was found to improve the stability of the interface. For Al 2O3/GeON/Ge capacitors, a 450°C anneal in nitrogen ambient reduced hysteresis and oxide fixed charge to 90 mV and 1012 cm-2 respectively, with low leakage current density. On the contrary, degradation was observed for un-nitrided Al2O3/Ge capacitors after 300 and 400°C post-metal anneals. HfO2/GeON/Ge capacitors benefitted from a 400°C densification anneal but exhibited degradation after post-metal anneals at temperatures greater than 300°C. This degradation is attributed to the influence of Al electrodes on the HfO 2 gate stack. HfO2 is considered to be a suitable material for the gate stack and Al2O3 for the buried dielectric in a GeOI structure. ©The Electrochemical Society.

A experiência barroca e a identidade local na Semana Santa de Campanha, Minas Gerais

Este trabalho analisa a formação de uma sensibilidade barroca em Minas Gerais a partir da orientação participativa e altamente emotiva das festas coloniais, cujo legado se mantem presente nas festas religiosas de muitas antigas cidades mineradoras do estado. Enfocando as celebrações da Semana Santa na cidade sul-mineira de Campanha, o texto mostra como este evento anual era organizado pela Irmandade do Santíssimo Sacramento, passando então às mãos de uma comissão local após a extinção da irmandade. Se até meados do século XIX, havia músicos semi-profissionais contratados para tocar e cantar nas celebrações, a música foi assumida progressivamente por grupos de amadores. Assim, a festa passou a ser entendida como uma produção local e a cada ano a população renova o seu orgulho campanhense, ao contemplar sua capacidade de produzir um evento tão ‘maravilhoso’.

This paper analyses the formation of a baroque sensibility in the State of Minas Gerais (Brazil) that derives from the participatory and highly emotive orientation of the colonial festivals, the legacy of which is still present in many former mining towns in the region. By focusing upon the Holy Week celebrations in Campanha, a small town in southern Minas Gerais, the text shows how this annual event was organized by the Confraternity of the Holy Sacrament, but was then transferred to a local committee after the confraternity was made extinct. If up to the mid 19th century there were semi-professional musicians to perform for the celebrations, responsibility for the music was slowly taken over by amateur groups. In this way the festival came to be understood as a local affair, and each year the population renews its pride in itself for its capacity to stage such a ‘marvelous’ event.

Fabrication and characterisation of high resistivity SOI substrates for monolithic high energy physics detectors

Silicon on Insulator (SOI) substrates offer a promising platform for monolithic high energy physics detectors with integrated read-out electronics and pixel diodes. This paper describes the fabrication and characterisation of specially-configured SOI substrates using improved bonded wafer ion split and grind/polish technologies. The crucial interface between the high resistivity handle silicon and the SOI buried oxide has been characterised using both pixel diodes and circular geometry MOS transistors. Pixel diode breakdown voltages were typically greater than 100V and average leakage current densities at 70 V were only 55 nA/ sq cm. MOS transistors subjected to 24 GeV proton irradiation showed an increased SOI buried oxide trapped charge of only 3.45x1011cn-2 for a dose of 2.7Mrad

Gemini observations of Wolf-Rayet stars in the Local Group starburst galaxy IC 10

We present Gemini-N GMOS and CFHT MOS spectroscopy of Wolf-Rayet candidates in the Local Group dwarf galaxy IC 10 that were previously identified by Massey et al. and Royer et al. From the present spectroscopic survey, the WC/WN ratio for IC 10 remains unusually high, given its low metallicity, although none of the WC9 stars suspected from narrow-band imaging are confirmed. Our spectroscopy confirms 9 newly discovered Wolf-Rayet candidates from Royer et al., whilst spectral types of 14 Wolf-Rayet stars previously observed by Massey & Armandroff are refined here. In total, there are 26 spectroscopically confirmed Wolf-Rayet stars in IC 10. All but one of the fourteen WC stars are WC4-6 stars, the exception being # 10 from Massey et al., a broad-lined, apparently single WC7 star. There are a total of eleven WN stars, which are predominantly early WN3-4 stars, but include a rare WN10 star, # 8 from Royer et al. # 5 from Massey et al. is newly identified as a transition WN/C star. Consequently, the WC/WN ratio for IC10 is 14/11similar to1.3, unusually high for a metal-poor galaxy. Re-evaluating recent photometric data of Massey & Holmes, we suggest that the true WC/WN ratio may not be as low as similar to0.3. Finally, we present ground-based finding charts for all confirmed WR stars, plus HST/WFPC2 charts for twelve cases.