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.

Ironworking in late medieval Ireland, c. AD. 1200 to 1600

The landscape of late medieval Ireland, like most places in Europe, was characterized by intensified agricultural exploitation, the growth and founding of towns and cities and the construction of large stone edifices, such as castles and monasteries. None of these could have taken place without iron. Axes were needed for clearing woodland, ploughs for turning the soil, saws for wooden buildings and hammers and chisels for the stone ones, all of which could not realistically have been made from any other material. The many battles, waged with ever increasingly sophisticated weaponry, needed a steady supply of iron and steel. During the same period, the European iron industry itself underwent its most fundamental transformation since its inception; at the beginning of the period it was almost exclusively based on small furnaces producing solid blooms and by the turn of the seventeenth century it was largely based on liquid-iron production in blast-furnaces the size of a house. One of the great advantages of studying the archaeology of ironworking is that its main residue, slag, is often produced in copious amounts both during smelting and smithing, is virtually indestructible and has very little secondary use. This means that most sites where ironworking was carried out are readily recognizable as such by the occurrence of this slag. Moreover, visual examination can distinguish between various types of slag, which are often characteristic for the activity from which they derive. The ubiquity of ironworking in the period under study further means that we have large amounts of residues available for study, allowing us to distinguish patterns both inside assemblages and between sites. Disadvantages of the nature of the remains related to ironworking include the poor preservation of the installations used, especially the furnaces, which were often built out of clay and located above ground. Added to this are the many parameters contributing to the formation of the above-mentioned slag, making its composition difficult to connect to a certain technology or activity. Ironworking technology in late medieval Ireland has thus far not been studied in detail. Much of the archaeological literature on the subject is still tainted by the erroneous attribution of the main type of slag, bun-shaped cakes, to smelting activities. The large-scale infrastructure works of the first decade of the twenty-first century have led to an exponential increase in the amount of sites available for study. At the same time, much of the material related to metalworking recovered during these boom-years was subjected to specialist analysis. This has led to a near-complete overhaul of our knowledge of early ironworking in Ireland. Although many of these new insights are quickly seeping into the general literature, no concise overviews on the current understanding of the early Irish ironworking technology have been published to date. The above then presented a unique opportunity to apply these new insights to the extensive body of archaeological data we now possess. The resulting archaeological information was supplemented with, and compared to, that contained in the historical sources relating to Ireland for the same period. This added insights into aspects of the industry often difficult to grasp solely through the archaeological sources, such as the people involved and the trade in iron. Additionally, overviews on several other topics, such as a new distribution map of Irish iron ores and a first analysis of the information on iron smelting and smithing in late medieval western Europe, were compiled to allow this new knowledge on late medieval Irish ironworking to be put into a wider context. Contrary to current views, it appears that it is not smelting technology which differentiates Irish ironworking from the rest of Europe in the late medieval period, but its smithing technology and organisation. The Irish iron-smelting furnaces are generally of the slag-tapping variety, like their other European counterparts. Smithing, on the other hand, is carried out at ground-level until at least the sixteenth century in Ireland, whereas waist-level hearths become the norm further afield from the fourteenth century onwards. Ceramic tuyeres continue to be used as bellows protectors, whereas these are unknown elsewhere on the continent. Moreover, the lack of market centres at different times in late medieval Ireland, led to the appearance of isolated rural forges, a type of site unencountered in other European countries during that period. When these market centres are present, they appear to be the settings where bloom smithing is carried out. In summary, the research below not only offered us the opportunity to give late medieval ironworking the place it deserves in the broader knowledge of Ireland's past, but it also provided both a base for future research within the discipline, as well as a research model applicable to different time periods, geographical areas and, perhaps, different industries..