DEVELOPMENT OF NOVEL SEMI-CONDUCTING ORTHO-CARBORANE BASED POLYMER FILMS: ENHANCED ELECTRONIC AND CHEMICAL PROPERTIES

Pasquale, Frank L. Development of novel semi-conducting ortho-carborane based polymer films: Enhanced electronic and chemical properties. Doctor of Philosophy (Chemistry-Analytical Chemistry), August 2013, 118 pp., 5 tables, 31 illustrations, references, 110 titles. A novel class of semi-conducting ortho-carborane (B10C2H12) based polymer films with enhanced electronic and chemical properties has been developed. The novel films are formed from electron-beam cross-linking of condensed B10C2H12 and B10C2H12 co-condensed with aromatic linking units (Y) (Y=1,4-diaminobenzene (DAB), benzene (BNZ) and pyridine (PY)) at 110 K. The bonding and electronic properties of the novel films were investigated using X-ray photoelectron spectroscopy (XPS), UV photoelectron spectroscopy (UPS) and Mulliken charge analysis using density functional theory (DFT). These films exhibit site-specific cross-linking with bonding, in the pure B10C2HX films, occurring at B sites non-adjacent to C in the B10C2H12 icosahedra. The B10C2H12:Y films exhibit the same phenomena, with cross-linking that creates bonds primarily between B sites non-adjacent to C in the B10C2H12 icosahedra to C sites in the Y linking units. These novel B10C2HX: Y linked films exhibit significantly different electron structure when compared to pure B10C2HX films as seen in the UPS spectra. The valence ban