First principles modelling of nucleation and growth during atomic layer deposition onto III-V substrates

Atomic layer deposition (ALD) is now used in semiconductor fabrication lines to deposit nanometre-thin oxide films, and has thus enabled the introduction of high-permittivity dielectrics into the CMOS gate stack. With interest increasing in transistors based on high mobility substrates, such as GaAs, we are investigating the surface treatments that may improve the interface characteristics. We focus on incubation periods of ALD processes on III-V substrates. We have applied first principles Density Functional Theory (DFT) to investigate detailed chemistry of these early stages of growth, specifically substrate and ALD precursor interaction. We have modelled the ‘clean-up’ effect by which organometallic precursors: trimethylaluminium (TMA) or hafnium and titanium amides clean arsenic oxides off the GaAs surface before ALD growth of dielectric commences and similar effect on Si3N4 substrate. Our simulations show that ‘clean-up’ of an oxide film strongly depends on precursor ligand, its affinity to the oxide and the redox character of the oxide. The predominant pathway for a metalloid oxide such as arsenic oxide is reduction, producing volatile molecules or gettering oxygen from less reducible oxides. An alternative pathway is non-redox ligand exchange, which allows non-reducible oxides (e.g. SiO2) to be cleaned-up. First principles study shows also that alkylamides are more susceptible to decomposition rather than migration on the oxide surface. This improved understanding of the chemical principles underlying ‘clean-up’ allows us to rationalize and predict which precursors will perform the reaction. The comparison is made between selection of metal chlorides, methyls and alkylamides precursors.

The political philosophy of Miki Kiyoshi: A close reading of the philosophical foundations of cooperative communitarianism

The thesis is a historical and philological study of the mature political theory of Miki Kiyoshi (1897-1945) focused on Philosophical Foundations of Cooperative Communitarianism (1939), a full translation of which is included. As the name suggests, it was a methodological and normative communitarianism, which critically built on liberalism, Marxism and Confucianism to realise a regional political community. Some of Miki’s Western readers have wrongly considered him a fascist ideologue, while he has been considered a humanist Marxist in Japan. A closer reading cannot support either view. The thesis argues that the Anglophone study of Japanese philosophy is a degenerating research programme ripe for revolution in the sense of returning full circle to an original point. That means returning to the texts, reading them contextually and philologically, in principle as early modern European political theory is read by intellectual historians, such as the representatives of Cambridge School history of political thought. The resulting reading builds critically on the Japanese scholarship and relates it to contemporary Western and postcolonial political theory and the East Asian tradition, particularly neo-Confucianism. The thesis argues for a Cambridge School perspective radicalised by the critical addendum of geo-cultural context, supplemented by Geertzian intercultural hermeneutics and a Saidian ‘return to philology’. As against those who have seen radical reorientations in Miki’s political thought, the thesis finds gradual progression and continuity between his neo-Kantian, existentialist, Marxian anthropology, Hegelian and finally communitarian phases. The theoretical underpinnings are his philosophical anthropology, a structurationist social theory of praxis, and a critique of liberalism, Marxism, nationalism and idealism emphasising concrete as opposed to abstract theory and the need to build on existing cultural traditions to modernise rather than westernise East Asia. This post-Western fusion was imagined to be the beginning of a true and pluralistic universalism.