Monitoring the vegetation start of season (SOS) across the island of Ireland using the MERIS global vegetation index

The aim of this study was to develop a methodology, based on satellite remote sensing, to estimate the vegetation Start of Season (SOS) across the whole island of Ireland on an annual basis. This growing body of research is known as Land Surface Phenology (LSP) monitoring. The SOS was estimated for each year from a 7-year time series of 10-day composited, 1.2 km reduced resolution MERIS Global Vegetation Index (MGVI) data from 2003 to 2009, using the time series analysis software, TIMESAT. The selection of a 10-day composite period was guided by in-situ observations of leaf unfolding and cloud cover at representative point locations on the island. The MGVI time series was smoothed and the SOS metric extracted at a point corresponding to 20% of the seasonal MGVI amplitude. The SOS metric was extracted on a per pixel basis and gridded for national scale coverage. There were consistent spatial patterns in the SOS grids which were replicated on an annual basis and were qualitatively linked to variation in landcover. Analysis revealed that three statistically separable groups of CORINE Land Cover (CLC) classes could be derived from differences in the SOS, namely agricultural and forest land cover types, peat bogs, and natural and semi-natural vegetation types. These groups demonstrated that managed vegetation, e.g. pastures has a significantly earlier SOS than in unmanaged vegetation e.g. natural grasslands. There was also interannual spatio-temporal variability in the SOS. Such variability was highlighted in a series of anomaly grids showing variation from the 7-year mean SOS. An initial climate analysis indicated that an anomalously cold winter and spring in 2005/2006, linked to a negative North Atlantic Oscillation index value, delayed the 2006 SOS countrywide, while in other years the SOS anomalies showed more complex variation. A correlation study using air temperature as a climate variable revealed the spatial complexity of the air temperature-SOS relationship across the Republic of Ireland as the timing of maximum correlation varied from November to April depending on location. The SOS was found to occur earlier due to warmer winters in the Southeast while it was later with warmer winters in the Northwest. The inverse pattern emerged in the spatial patterns of the spring correlates. This contrasting pattern would appear to be linked to vegetation management as arable cropping is typically practiced in the southeast while there is mixed agriculture and mostly pastures to the west. Therefore, land use as well as air temperature appears to be an important determinant of national scale patterns in the SOS. The TIMESAT tool formed a crucial component of the estimation of SOS across the country in all seven years as it minimised the negative impact of noise and data dropouts in the MGVI time series by applying a smoothing algorithm. The extracted SOS metric was sensitive to temporal and spatial variation in land surface vegetation seasonality while the spatial patterns in the gridded SOS estimates aligned with those in landcover type. The methodology can be extended for a longer time series of FAPAR as MERIS will be replaced by the ESA Sentinel mission in 2013, while the availability of full resolution (300m) MERIS FAPAR and equivalent sensor products holds the possibility of monitoring finer scale seasonality variation. This study has shown the utility of the SOS metric as an indicator of spatiotemporal variability in vegetation phenology, as well as a correlate of other environmental variables such as air temperature. However, the satellite-based method is not seen as a replacement of ground-based observations, but rather as a complementary approach to studying vegetation phenology at the national scale. In future, the method can be extended to extract other metrics of the seasonal cycle in order to gain a more comprehensive view of seasonal vegetation development.

Tudor ‘reform’ treatises and government policy in sixteenth century Ireland

During the sixteenth century hundreds of treatises, position papers and memoranda were composed on the political state of Ireland and how best to ‘reform’, ‘conquer’ or otherwise incorporate that island into the wider Tudor kingdom. These ‘reform’ treatises attempted to identify and analyse the prevailing political, social, cultural and economic problems found in the Irish polity before positing how government policy could be altered to ameliorate these same problems. Written by a broad array of New English, Old English and Gaelic Irish authors, often serving within Irish officialdom, the military, or the Church of Ireland, these papers were generally circulated amongst senior ministers and political figures throughout the Tudor dominions. As such they were written with the express purpose of influencing the direction of government policy for Ireland. Collectively these documents are one of the most significant body of sources, not just for the study of government activity in the second Tudor kingdom, but indeed for the broader history of sixteenth century Ireland. This thesis offers the first systematic study of these texts. It does so by exploring the content of the hundreds of such works and the ‘reform’ treatise as a type of text, while the interrelationship of these documents with government policy in Tudor Ireland, and their effect thereon, is also explored. In so doing it charts the developments from origin to implementation of the principal strategies employed by Tudor Englishmen to enforce English control over the whole of Ireland. Finally, it clearly demonstrates that the ‘reform’ treatises were both central to government activity in sixteenth century Ireland and to the historical developments which occurred in that time and place.

Atomic layer deposition of copper for CMOS interconnects

This work concerns the atomic layer deposition (ALD) of copper. ALD is a technique that allows conformal coating of difficult topographies such as narrow trenches and holes or even shadowed regions. However, the deposition of pure metals has so far been less successful than the deposition of oxides except for a few exceptions. Challenges include difficulties associated with the reduction of the metal centre of the precursor at reasonable temperatures and the tendency of metals to agglomerate during the growth process. Cu is a metal of special technical interest as it is widely used for interconnects on CMOS devices. These interconnects are usually fabricated by electroplating, which requires the deposition of thin Cu seed layers onto the trenches and vias. Here, ALD is regarded as potential candidate for replacing the current PVD technique, which is expected to reach its limitations as the critical dimensions continue to shrink. This work is separated into two parts. In the first part, a laboratory-scale ALD reactor was constructed and used for the thermal ALD of Cu. In the second part, the potentials of the application of Cu ALD on industry scale fabrication were examined in a joint project with Applied Materials and Intel. Within this project precursors developed by industrial partners were evaluated on a 300 mm Applied Materials metal-ALD chamber modified with a direct RF-plasma source. A feature that makes ALD a popular technique among researchers is the possibility to produce high- level thin film coatings for micro-electronics and nano-technology with relatively simple laboratory- scale reactors. The advanced materials and surfaces group (AMSG) at Tyndall National Institute operates a range of home-built ALD reactors. In order to carry out Cu ALD experiments, modifications to the normal reactor design had to be made. For example a carrier gas mechanism was necessary to facilitate the transport of the low-volatile Cu precursors. Precursors evaluated included the readily available Cu(II)-diketonates Cu-bis(acetylacetonate), Cu-bis(2,2,6,6-tetramethyl-hepta-3,5-dionate) and Cu-bis(1,1,1,5,5,5-hexafluoacetylacetonate) as well as the Cu-ketoiminate Cu-bis(4N-ethylamino- pent-3-en-2-onate), which is also known under the trade name AbaCus (Air Liquide), and the Cu(I)- silylamide 1,3-diisopropyl-imidazolin-2-ylidene Cu(I) hexamethyldisilazide ([NHC]Cu(hmds)), which was developed at Carleton University Ottawa. Forming gas (10 % H2 in Ar) was used as reducing agent except in early experiments where formalin was used. With all precursors an extreme surface selectivity of the deposition process was observed and significant growth was only achieved on platinum-group metals. Improvements in the Cu deposition process were obtained with [NHC]Cu(hmds) compared with the Cu(II) complexes. A possible reason is the reduced oxidation state of the metal centre. Continuous Cu films were obtained on Pd and indications for saturated growth with a rate of about 0.4 Å/cycle were found for deposition at 220 °C. Deposits obtained on Ru consisted of separated islands. Although no continuous films could be obtained in this work the relatively high density of Cu islands obtained was a clear improvement as compared to the deposits grown with Cu(II) complexes. When ultra-thin Pd films were used as substrates, island growth was also observed. A likely reason for this extreme difference to the Cu films obtained on thicker Pd films is the lack of stress compensation within the thin films. The most likely source of stress compensation in the thicker Pd films is the formation of a graded interlayer between Pd and Cu by inter-diffusion. To obtain continuous Cu films on more materials, reduction of the growth temperature was required. This was achieved in the plasma assisted ALD experiments discussed in the second part of this work. The precursors evaluated included the AbaCus compound and CTA-1, an aliphatic Cu-bis(aminoalkoxide), which was supplied by Adeka Corp.. Depositions could be carried out at very low temperatures (60 °C Abacus, 30 °C CTA-1). Metallic Cu could be obtained on all substrate materials investigated, but the shape of the deposits varied significantly between the substrate materials. On most materials (Si, TaN, Al2O3, CDO) Cu grew in isolated nearly spherical islands even at temperatures as low as 30 °C. It was observed that the reason for the island formation is the coalescence of the initial islands to larger, spherical islands instead of forming a continuous film. On the other hand, the formation of nearly two-dimensional islands was observed on Ru. These islands grew together forming a conductive film after a reasonably small number of cycles. The resulting Cu films were of excellent crystal quality and had good electrical properties; e.g. a resistivity of 2.39 µΩ cm was measured for a 47 nm thick film. Moreover, conformal coating of narrow trenches (1 µm deep 100/1 aspect ratio) was demonstrated showing the feasibility of the ALD process.

Uncle Tom's Cabin and the Irish National Tale

Accepted Version