Synthesis and characterization of tridecameric Group 13 hydroxide clusters

• Main Author: Mensinger, Zachary Lee, 1982-
• Language: en_US
• Published: University of Oregon 2011
• Subjects: Tridecameric group 13; Hydroxide clusters; Gallium; Aluminum; Indium; Thin-film transistors; Single-source precursors; Inorganic chemistry; Materials science
• Online Access: http://hdl.handle.net/1794/11300

xx, 153 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. === In the research area of Group 13 hydroxide clusters, progress is often hampered by difficult and inefficient synthetic procedures. This has greatly limited the numerous potential applications of Group 13 hydroxide compounds, many of which require large amounts of material. Most relevant to this dissertation is their application as precursors for high quality amorphous metal oxide thin films. Addressing this issue, this dissertation presents a series of Group 13 containing hydroxide compounds of general formula [M 13 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 which are generated through an efficient, scalable synthetic procedure. Throughout this dissertation, the compounds are generally referred to by their metal content, i.e. [Ga 13 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 is designated as Ga 13 . Chapter I reviews the literature of inorganic and ligand-supported Group 13 hydroxide compounds with the aim of identifying common structural trends in metal composition and coordinating ligands. This summary is limited to clusters of aluminum, gallium, and indium. Chapter II describes in detail the synthesis and characterization of one such cluster, Al 13 . Following this in Chapter III is the description of the first heterometallic Group 13 hydroxide compound, Ga 7 In 6 , which along with Ga 13 was used as a precursor material for metal oxide thin films in collaboration with Professor Doug Keszler at Oregon State University. Chapter IV describes a series of six Ga/In compounds, as well as two Al/In compounds. Included in this chapter is an analysis of the heat-induced decomposition properties of the Ga/In clusters. Understanding such thermal decomposition is particularly relevant for the use of these compounds as precursor materials, as an annealing step is used to condense the films. Chapter V addresses the potential for post-synthetic modification of the compounds through metal and ligand exchange reactions, an area that also addresses the issue of solution stability of the structures Chapter VI describes the synthesis and characterization of related Group 13 compounds, including two infinite chain structures and additional heterometallic compounds. Lastly, Chapter VII concludes this dissertation and discusses potential areas of future research. This dissertation includes co-authored material and previously published results. === Committee in charge: Victoria DeRose, Chairperson, Chemistry; Darren Johnson, Member, Chemistry; James Hutchison, Member, Chemistry; Michael Haley, Member, Chemistry; Raghuveer Parthasarathy, Outside Member, Physics