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Wayne State University Dissertations

2021

Inorganic Chemistry

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Thermal Atomic Layer Deposition Of Titanium Nitride Films: Synthesis And Characterization Of Novel Titanium Precursors, Anuththara Chalani Upeksha Abesinghe Arachchige Jan 2021

Thermal Atomic Layer Deposition Of Titanium Nitride Films: Synthesis And Characterization Of Novel Titanium Precursors, Anuththara Chalani Upeksha Abesinghe Arachchige

Wayne State University Dissertations

Due to the continuous miniaturization of microelectronic devices, robust deposition techniques are required which can provide continuous and conformal thin films even in high aspect ratio structures. Atomic Layer Deposition (ALD) is an excellent choice of deposition technique as it is capable of providing perfect film coverage. Because of its self-limited growth mechanism, ALD can afford sub-nanometer thickness control. Precursors used in ALD should be volatile, thermally stable at the deposition temperature, and highly reactive towards the co-regent. Traditionally, ALD has been used to grow metal oxide films. However, the microelectronics industry now demands ALD for metals and metal nitrides. …


Synthesis And Reactivity Of Metal Bis(Alkoxide) Complexes In Nitrene Coupling And Polymerization Of Polar Monomers, Duleeka Chamini Wannipurage Jan 2021

Synthesis And Reactivity Of Metal Bis(Alkoxide) Complexes In Nitrene Coupling And Polymerization Of Polar Monomers, Duleeka Chamini Wannipurage

Wayne State University Dissertations

The nitrene homocoupling to produce azoarenes was done using two different iron (II) alkoxide complexes, Fe(OCtBu2(3,5-Ph2C6H3)2(THF)2 and Fe[OO]Ph(THF)2. Due to the steric bulkiness of HOCtBu2(3,5-Ph2C6H3 ligand, this complex exhibited selectivity for the bis(alkoxide) ligation; no tris(alkoxide) complexes were observed. As a result, both bulky and non-bulky aryl nitrenes are coupled with Fe(OCtBu2(3,5-Ph2Ph)2(THF)2, albeit the coupling of the less bulky substrates requires higher temperatures and longer reaction times. Stoichiometric reactions of Fe(OCtBu2(3,5-Ph2C6H3)2(THF)2 with non-bulky aryl azides led to the observation of the iron(III) tetrazene radical anion complexes, that can produce azoarene products after heating. Tetrazene complexes likely serve as a “masked …