Date of Award

Spring 1-1-2013

Document Type


Degree Name

Doctor of Philosophy (PhD)


Chemistry & Biochemistry

First Advisor

Steven M. George

Second Advisor

Douglas L. Gin

Third Advisor

Yung-Cheng Lee

Fourth Advisor

Wei Zhang

Fifth Advisor

Daniel L. Feldheim


Atomic Layer Deposition (ALD) and its subset, Molecular layer deposition (MLD), is a thin film deposition technique using alternating self-limiting precursors to grow thin films on a substrates. Recent research has expanded MLD to use reactive metal alkyls/halides and organic fragments containing alcohol groups such as ethylene glycol for use in protective barriers. Unfortunately using ethylene glycol as a precursor causes film stability issues and does not provide adequate mechanical properties for projected uses. The current research looks into the investigation of using different metal alkyls and metal halides with the trifunctional precursor glycerol.

The three main films investigated were the AlGL using trimethylaluminum and glycerol, ZnGL using diethyl zinc and glycerol and TIGL using titanium (IV) chloride and glycerol. The films were investigated using quartz crystal microbalance, X-ray reflectivity, and spectroscopic ellipsometry for characterization of their film growth. All films exhibited linear growth at a range of temperatures above 130° C with AlGL, ZnGL and TiGL displaying a growth rate at 150° C of ~ 2.34 Å/cycle, ~ 1.29 Å/cycle, and ~ 2.2 Å/cycle respectfully. Initially film growth was investigated in situ using quartz crystal microbalance and then the growth rates confirmed ex situ using X-ray reflectivity.

Once the film growth and mechanism were investigated, the mechanical properties were investigated to determine if there was an improvement in cross-linking in the films. The mechanical properties of these MLD films were also investigated using a mechanical testing system and nanoindenter. The mechanical properties for AlGL and ZnGL showed a large improvement from 0.69% to 1.2% for their critical tensile strain compared to previous MLD films. The films also showed an increase in mechanical properties from their nanoindentation results consistent with an increase in cross-linking.