Atomistic modeling of Ge damage accumulation, amorphization and solid phase epitaxial regrowth

En los últimos años, el Ge ha ganado de nuevo atención con la finalidad de ser integrado en el seno de las existentes tecnologías de microelectrónica. Aunque no se le considera como un canddato capaz de reemplazar completamente al Si en el futuro próximo, probalemente servirá como un excelente complemento para aumentar las propiedades eléctricas en dispositivos futuros, especialmente debido a su alta movilidad de portadores. Esta integración requiere de un avance significativo del estado del arte en los procesos de fabricado. Técnicas de simulación, como los algoritmos de Monte Carlo cinético (KMC), proporcionan un ambiente atractivo para llevar a cabo investigación y desarrollo en este campo, especialmente en términos de costes en tiempo y financiación. En este estudio se han usado, por primera vez, técnicas de KMC con el fin entender el procesado “front-end” de Ge en su fabricación, específicamente la acumulación de dañado y amorfización producidas por implantación iónica y el crecimiento epitaxial en fase sólida (SPER) de las capas amorfizadas. Primero, simulaciones de aproximación de clisiones binarias (BCA) son usadas para calcular el dañado causado por cada ión. La evolución de este dañado en el tiempo se simula usando KMC sin red, o de objetos (OKMC) en el que sólamente se consideran los defectos. El SPER se simula a través de una aproximación KMC de red (LKMC), siendo capaz de seguir la evolución de los átomos de la red que forman la intercara amorfo/cristalina. Con el modelo de amorfización desarrollado a lo largo de este trabajo, implementado en un simulador multi-material, se pueden simular todos estos procesos. Ha sido posible entender la acumulación de dañado, desde la generación de defectos puntuales hasta la formación completa de capas amorfas. Esta acumulación ocurre en tres regímenes bien diferenciados, empezando con un ritmo lento de formación de regiones de dañado, seguido por una rápida relajación local de ciertas áreas en la fase amorfa donde ambas fases, amorfa y cristalina, coexisten, para terminar en la amorfización completa de capas extensas, donde satura el ritmo de acumulación. Dicha transición ocurre cuando la concentración de dañado supera cierto valor límite, el cual es independiente de las condiciones de implantación. Cuando se implantan los iones a temperaturas relativamente altas, el recocido dinámico cura el dañado previamente introducido y se establece una competición entre la generación de dañado y su disolución. Estos efectos se vuelven especialmente importantes para iones ligeros, como el B, el cual crea dañado más diluido, pequeño y distribuido de manera diferente que el causado por la implantación de iones más pesados, como el Ge. Esta descripción reproduce satisfactoriamente la cantidad de dañado y la extensión de las capas amorfas causadas por implantación iónica reportadas en la bibliografía. La velocidad de recristalización de la muestra previamente amorfizada depende fuertemente de la orientación del sustrato. El modelo LKMC presentado ha sido capaz de explicar estas diferencias entre orientaciones a través de un simple modelo, dominado por una única energía de activación y diferentes prefactores en las frecuencias de SPER dependiendo de las configuraciones de vecinos de los átomos que recristalizan. La formación de maclas aparece como una consecuencia de esta descripción, y es predominante en sustratos crecidos en la orientación (111)Ge. Este modelo es capaz de reproducir resultados experimentales para diferentes orientaciones, temperaturas y tiempos de evolución de la intercara amorfo/cristalina reportados por diferentes autores. Las parametrizaciones preliminares realizadas de los tensores de activación de tensiones son también capaces de proveer una buena correlación entre las simulaciones y los resultados experimentales de velocidad de SPER a diferentes temperaturas bajo una presión hidrostática aplicada. Los estudios presentados en esta tesis han ayudado a alcanzar un mejor entendimiento de los mecanismos de producción de dañado, su evolución, amorfización y SPER para Ge, además de servir como una útil herramienta para continuar el trabajo en este campo. In the recent years, Ge has regained attention to be integrated into existing microelectronic technologies. Even though it is not thought to be a feasible full replacement to Si in the near future, it will likely serve as an excellent complement to enhance electrical properties in future devices, specially due to its high carrier mobilities. This integration requires a significant upgrade of the state-of-the-art of regular manufacturing processes. Simulation techniques, such as kinetic Monte Carlo (KMC) algorithms, provide an appealing environment to research and innovation in the field, specially in terms of time and funding costs. In the present study, KMC techniques are used, for the first time, to understand Ge front-end processing, specifically damage accumulation and amorphization produced by ion implantation and Solid Phase Epitaxial Regrowth (SPER) of the amorphized layers. First, Binary Collision Approximation (BCA) simulations are used to calculate the damage caused by every ion. The evolution of this damage over time is simulated using non-lattice, or Object, KMC (OKMC) in which only defects are considered. SPER is simulated through a Lattice KMC (LKMC) approach, being able to follow the evolution of the lattice atoms forming the amorphous/crystalline interface. With the amorphization model developed in this work, implemented into a multi-material process simulator, all these processes can be simulated. It has been possible to understand damage accumulation, from point defect generation up to full amorphous layers formation. This accumulation occurs in three differentiated regimes, starting at a slow formation rate of the damage regions, followed by a fast local relaxation of areas into the amorphous phase where both crystalline and amorphous phases coexist, ending in full amorphization of extended layers, where the accumulation rate saturates. This transition occurs when the damage concentration overcomes a certain threshold value, which is independent of the implantation conditions. When implanting ions at relatively high temperatures, dynamic annealing takes place, healing the previously induced damage and establishing a competition between damage generation and its dissolution. These effects become specially important for light ions, as B, for which the created damage is more diluted, smaller and differently distributed than that caused by implanting heavier ions, as Ge. This description successfully reproduces damage quantity and extension of amorphous layers caused by means of ion implantation reported in the literature. Recrystallization velocity of the previously amorphized sample strongly depends on the substrate orientation. The presented LKMC model has been able to explain these differences between orientations through a simple model, dominated by one only activation energy and different prefactors for the SPER rates depending on the neighboring configuration of the recrystallizing atoms. Twin defects formation appears as a consequence of this description, and are predominant for (111)Ge oriented grown substrates. This model is able to reproduce experimental results for different orientations, temperatures and times of evolution of the amorphous/crystalline interface reported by different authors. Preliminary parameterizations for the activation strain tensors are able to also provide a good match between simulations and reported experimental results for SPER velocities at different temperatures under the appliance of hydrostatic pressure. The studies presented in this thesis have helped to achieve a greater understanding of damage generation, evolution, amorphization and SPER mechanisms in Ge, and also provide a useful tool to continue research in this field.

Physical properties and bulk organic geochemical results for sediments from DSDP Hole 96-619

The concentration and carbon isotopic composition (d13C) of sedimentary organic carbon (C_org), N/C ratios, and terrigenous and marine d13C_org endmembers form a basis from which to address problems of Late Quaternary glacial-interglacial climatic variability in a 208.7 m hydraulic piston core (DSDP 619) from the Pigmy Basin in the northern Gulf of Mexico. While interpretations of sedimentary d13C_org time series records are often not unique, paired analyses of d13C_org and N/C are consistent with the hypothesis that the C_org in the Pigmy Basin is a climatically determined mixture of C3-photosynthetic terrigenous and marine organic matter, confirming the earlier d13C_org model of Sackett (1964). A high resolution (~1.4-2.9 Ka/sample) d13C_org record shows that sedimentary organic carbon in interglacial oxygen isotope (sub)stages 1 and 5a-b are enriched in 13C (average +/-1 sigma values are -24.2+/-1.2? and -22.9+/-0.7? relative to PDB, respectively) while glacial isotope stage values 2 are relatively depleted (-25.6+/-0.5?). Concentrations of terrigenous and marine sedimentary organic carbon are calculated for the first time using d13C_org and C_org measurements, and empirically determined terrigenous and marine d13C_org endmembers. The net accumulation rate of terrigenous organic carbon is 4.3+/-2.6 times higher in isotope stages 2-4 than in (sub)stages 1 and 5a-b, recording higher erosion rates of terrigenous organic material in glacial times. The concentration and net accumulation rates of marine and terrigenous C_org suggest that the nutrient-bearing plume of the Mississippi River may have advanced and retreated across the Pigmy Basin as sea level fell and rose in response to glacial-interglacial sea level change.

Benthic foraminiferal assemblages and paleoproductivity reconstructions for the last 550 kyr of the Ontong Java Plateau, western equatorial Pacific

We analyzed foraminiferal and nannofossil assemblages and stable isotopes in samples from ODP Hole 807A on the Ontong Java Plateau in order to evaluate productivity and carbonate dissolution cycles over the last 550 kyr (kilo year) in the western equatorial Pacific. Our results indicate that productivity was generally higher in glacials than during interglacials, and gradually increased since MIS 13. Carbonate dissolution was weak in deglacial intervals, but often reached a maximum during interglacial to glacial transitions. Carbonate cycles in the western equatorial Pacific were mainly influenced by changes of deep-water properties rather than by local primary productivity. Fluctuations of the estimated thermocline depth were not related to glacial to interglacial alternations, but changed distinctly at ~280 kyr. Before that time the thermocline was relatively shallow and its depth fluctuated at a comparatively high amplitude and low frequency. After 280 kyr, the thermocline was deeper, and its fluctuations were at lower amplitude and higher frequency. These different patterns in productivity and thermocline variability suggest that thermocline dynamics probably were not a controlling factor of biological productivity in the western equatorial Pacific Ocean. In this region, upwelling, the influx of cool, nutrient-rich waters from the eastern equatorial Pacific or of fresh waters from rivers have probably never been important, and their influence on productivity has been negligible over the studied period. Variations in the inferred productivity in general are well correlated with fluctuations in the eolian flux as recorded in the northwestern Pacific, a proxy for the late Quaternary history of the central East Asian dust flux into the Pacific. Therefore, we suggest that the dust flux from the central East Asian continent may have been an important driver of productivity in the western Pacific.

Phosphorus components, trace metals and Ba excess of ODP Site 202-1237 sediments

We determined the sedimentary concentrations of phosphorus (P), barium (Ba), manganese (Mn), titanium (Ti), aluminum (Al), and uranium (U) for sediment samples from the southeast Pacific Nazca Ridge, Ocean Drilling Program Site 1237. This unique record extends to 31 Ma over 360 meters composite depth (mcd), recording depositional history as the site progressed eastward over its paleohistory. We sampled with a temporal resolution of ~0.2 m.y. throughout the sequence, equivalent to an average spacing of 1.63 m/sample. Concentrations of sequentially extracted components of P (oxide-associated, authigenic, organic, and detrital) increase toward the modern. Al/Ti ratios indicate that the background detrital source material is consistent with upper continental crust. U enrichment factors (U EFs) generally exceed crustal values and indicate slightly reducing environments. However, authigenic U precipitation can also be influenced by the organic carbon rain rate and may not be solely an indicator of redox conditions. Dramatic changes in Mn EFs at ~162 mcd, from values between 12 and 93 to values <12 after this depth, and a sharp color contact boundary lead us to believe that a paleoredox boundary from an oxygenated to a more reducing depositional environment occurred near this depth. Estimates of biogenic barite concentrations from a total sediment digestion technique (Ba excess) are greater than those from a barite extraction (Ba barite) for selected samples across the entire depth range. Applying a range of Ba/Ti ratios from different source materials to correct for detrital inputs does not change the lack of agreement with Ba barite concentrations. Reactive P (P reactive) concentrations (the sum of oxide-associated, authigenic, and organic P concentrations) increase toward the modern with values typically <12 µmol P/g from the base of our record through ~100 mcd, with a gradual increase to concentrations >15 µmol P/g. Ba excess follows the same general trends as Preactive, with concentrations <14 µmol Ba/g in the lower portion of the record to values >15 µmol Ba/g. Accumulation rate records of these proxies will be needed to infer paleoproductivity. P reactive/Ba excess ratios, an indicator of the relative burial of the nutrient P to organic carbon export, exhibit higher values, similar to modern, from the base of our record through ~180 mcd. The remainder of the record exhibits values lower than modern, indicating that organic carbon export to the sediments was higher relative to nutrient burial.

Geochemistry of Eocene/Oligocene sediments of ODP Hole 154-925A

Paleoproductivity, nutrient burial, and carbon cycling were investigated across the Eocene/Oligocene (E/O) boundary (begin to end; 36.9-32.7 Ma at ~40 kyr resolution, timescale of Shackleton et al. (1999, doi:10.1098/rsta.1999.0407) at Ocean Drilling Program Site 925 on the Ceara Rise in the western equatorial Atlantic (3040 m present water depth; 748.26-850.70 mbsf). Downcore bulk sediment records of biogenic barium, total reactive phosphorus, biogenic silica, and calcium carbonate are interpreted to represent export production, net nutrient burial, biogenic opal production, and inorganic carbon burial, respectively. The global positive excursion in d13C subsequent to the E/O boundary is recorded at Site 925. Export production appears to have been externally forced by orbital parameters at eccentricity frequencies during the study interval, based on spectral analysis of the biogenic barium and reactive phosphorus records. Biogenic silica production or preservation increased after the Eocene/Oligocene boundary to a higher baseline, although overall productivity and nutrient burial did not increase, based on barium and reactive phosphorus records. Thus, although absolute production did not increase at this site, a shift in relative abundance of siliceous versus carbonate productivity may have resulted in a change in relative organic carbon burial. This may have contributed to the positive excursion in global oceanic d13C subsequent to the Eocene/Oligocene boundary, although the silica maximum persists after the carbon isotope excursion ends.

Sedimentology, organic geochemistry, and stable isotopes of core PS2138-1

We studied variations in terrigenous (TOM) and marine organic matter (MOM) input in a sediment core on the northern Barents Sea margin over the last 30 ka. Using a multiproxy approach, we reconstructed processes controlling organic carbon deposition and investigated their paleoceanographic significance in the North Atlantic-Arctic Gateways. Variations in paleo-surface-water productivity are not documented in amount and composition of organic carbon. The highest level of MOM was deposited during 25-23 ka as a result of scavenging on fine-grained, reworked, and TOM-rich material released by the retreating Svalbard/Barents Sea ice sheet during the late Weichselian. A second peak of MOM is preserved because of sorptive protection by detrital and terrigenous organic matter, higher surface-water productivity due to permanent intrusion of Atlantic water, and high suspension load release by melting sea ice during 15.9-11.2 ka.

(Table 1) Stable oxygen isotopic ratios and yearly snow accumulation of firn and ice cores from Svalbard

We analyse ice cores from Vestfonna ice cap (Nordaustlandet, Svalbard). Oxygen isotopic measurements were made on three firn cores (6.0, 11.0 and 15.5 m deep) from the two highest summits of the glacier located on the SW-NE and NW-SE central ridges. Sub-annual d18O cycles were preserved and could be counted visually in the uppermost parts of the cores, but deeper layers were affected by post-depositional smoothing. A pronounced d18O minimum was found near the bottom of the three cores. We consider candidates for this d18O signal to be a valuable reference horizon since it is also seen elsewhere in Nordaustlandet. We attribute it to isotopically depleted snow precipitation, which NCEP/NCAR reanalysis shows was unusual for Vestfonna, and came from northerly air during the cold winter of 1994/95. Finding the 1994/95 time marker allows establishment of a precise depth/age scale for the three cores. The derived annual accumulation rates indirectly fill a geographical gap in mass balance measurements and thus provide information on spatial and temporal variability of precipitation over the glacier for the period spanned by the cores (1992-2009). Comparing records at the two locations also reveals that the snow net accumulation at the easternmost part of Vestfonna was only half of that in the western part over the last 17 years.

(Table 1) Concentrations of Os, Ir, Pt and 187Os/188Os ratio in ODP Hole 130-806C samples

New osmium (Os) isotope and platinum group element (PGE) concentration data are used in conjunction with published 3He and Th isotope data to determine the relative proportions of lithogenic, extraterrestrial and hydrogenous iridium (Ir) in a Pacific pelagic carbonate sequence from the Ocean Drilling Program (ODP) Site 806 on the Ontong Java Plateau (OJP). These calculations demonstrate that lithogenic and extraterrestrial contributions to sedimentary Ir budget are minor, while hydrogenous Ir accounts for roughly 85% of the total Ir. Application of analogous partitioning calculations to previously reported data from a North Pacific red clay sequence (LL44-GPC3) yields very similar results. Total Ir burial fluxes at Site 806 and LL44-GPC3 are also similar, 45 and 30 pg/cm**2/kyr, respectively. Average Ir/3He and Ir/xs230Th_initial ratios calculated from the entire Site 806 data set are similar to those reported earlier for Pacific sites. In general, down-core profiles of Ir, 3He and xs230Th_initial, are not well correlated with one another. However, all three data sets show similar variance and yield sediment mass accumulation rate estimates that agree within a factor of two. While these results indicate that Ir concentration has potential as a point-paleoflux tracer in pelagic carbonates, Ir-based paleoflux estimates are likely subject to uncertainties that are similar to those associated with Co-based paleoflux estimates. Consequently, local calibration of Ir flux in space and time will be required to fully assess the potential of Ir as a point paleoflux tracer. Measured 187Os/188Os of the OJP sediments are systematically lower than the inferred 187Os/188Os of contemporaneous seawater and a clear glacial-interglacial 187Os/188Os variation is lacking. Mixing calculations suggest Os contributions from lithogenic sources are insufficient to explain the observed 187Os/188Os variations. The difference between the 187Os/188Os of bulk sediment and that of seawater is interpreted in terms of subtle contributions of unradiogenic Os carried by particulate extraterrestrial material. Down-core variations of 187Os/188Os with Pt/Ir and Os/Ir also point to contributions from extraterrestrial particles. Mixing calculations for each set of several triplicate analyses suggest that the unradiogenic Os end member cannot be characterized by primary extraterrestrial particles of chondritic composition. It is noteworthy that in efforts aimed at determining the effect of extraterrestrial contributions, 187Os/188Os of pelagic carbonates has greater potential compared to abundances of PGE. An attempt has been made for the first time to estimate sediment mass accumulation rates based on amount of extraterrestrial Os in the OJP samples and previously reported extraterrestrial Os flux. Throughout most of the OJP record, Os isotope-based paleoflux estimates are within a factor of two of those derived using other constant flux tracers. Meaningful flux estimates cannot be made during glacial maxima because the OJP sediments do not record the low 187Os/188Os reported previously. We speculate that this discrepancy may be related to focusing of extraterrestrial particles at the OJP, as has been suggested to explain down-core 3He variations.