Chemical vapor deposition (CVD) and atomic layer deposition (ALD) are corner-stone techniques for depositing thin films in semi-conductor manufacturing. To deposit semiconductor grade materials, these techniques rely on high-performance precursors. This thesis covers synthesis, characterization, and evaluation of 1,3-dialkyltriazenides of group 11–14 metals as precursors for CVD and ALD.  

Triazenides had previously not been used as precursors for ALD, nor any other CVD process. The gallium and indium triazenides were used for ALD of indium- and gallium nitride and yielded materials of superior quality over other precursors. The success of these precursors sparked subsequent investigation into triazenides of zinc, and the group 11- and 14 metals. These triazenides showed high volatility and thermal stability making them highly interesting as CVD and ALD precursors. 

Group 11 thin films are desirable as interconnects in microelectronics. Although many M-N-bonded Cu precursors have been explored for vapor deposition, there is currently a lack of suitable Ag and Au derivatives. Herein, we present monovalent Cu, Ag, and Au 1,3-di-tert-butyltriazenides that have potential for use in vapor deposition. Their thermal stability and volatility rival that of current state-of-the-art group 11 precursors with bidentate M-N-bonded ligands. Solution-state thermolysis of these triazenides yielded polycrystalline films of elemental Cu, Ag, and Au. The compounds are therefore highly promising as single-source precursors for vapor deposition of coinage metal films.

Indium and gallium nitride are important semi-conductor materials with desirable properties for high-frequency and power electronics. We have previously demonstrated high-quality ALD grown InN and GaN using the hexacoordinated 1,3-diisopropyltriazenide In(III) and Ga(III) precursors. Herein we report the structural and thermal properties their analogues employing combinations of isopropyl, sec-butyl and tert-butyltriazenide alkyl groups on the exocyclic nitrogen of the triazenide ligand. The new triazenide compounds were all found to be volatile (80-120 degrees C, 0.5 mbar) and showed very good thermal stability (200 and 300 degrees C). These new triazenide analogues provide a set of precursors whose thermal properties are determined and can be accordingly tailored by strategic choice of exocyclic nitrogen alkyl substituents.