Graduation date: 2007
The critical contribution of this dissertation is to provide a better
understanding of the fundamental Chemical Bath Deposition (CBD) growth
kinetic and mechanism for the well known II-VI semiconductor CdS using the
newly developed continuous flow microreactor. This continuous flow microreactor
provides the temporal resolution to control the homogeneous reaction of the
chemical solution before it impinges on the substrate surface. This capability was
used to decouple the homogeneous particle formation and deposition from the
molecular level heterogeneous surface reaction to overcome the drawbacks
associated with a conventional batch process. Transmission electron microscopy
(TEM) analysis indicated an impinging flux without the formation of nanoparticles
which could be obtained from this reactor in a short residence time. In addition,
the reactor could be operated in a homogeneous particle formation regime. Size
increasing CdS nanoparticles grown by homogeneous reaction were clearly
observed from TEM and SEM micrographs by increasing the residence time from
1 to 280 sec using pre-heated precursor solutions. The formation of CdS nanorod
and arrayed nanorod bundle structures using the CBD recipe were also observed in
some areas and reported here for the first time. The growth kinetics were studied
using a particle-free flux. The deposition results suggest that HS− ions formed
through the thiourea hydrolysis reaction are the dominant sulfide ion source
responsible for the CdS deposition rather than thioura itself that had been widely
discussed in almost all of the previous literature. This finding could not be
observed previously by a conventional CBD batch setup because all the reactant
solutions were sequentially pulled into the reaction beaker and mixed all at once.
An impinging flux without the formation of nanoparticles enables us to deposit
extremely smooth and highly oriented nanocrystalline CdS semiconductor thin
films at low temperature (80°C). Enhancement-mode functional thin film
transistors with an effective mobility of μ[subscript eff] =1.46 cm²/V s, drain current on-to-off
ratio of approximately 10⁵ and turn-on voltage at 0 V were fabricated from the asdeposited
films without any post annealing process. This microreactor could be
adapted for the deposition of other compound semiconductor thin films such as
highly transparent amorphous Indium Oxide (In₂O₃) thin films at low temperature
(70°C) using chemical solution deposition and opens a low-cost avenue to
fabricate thin film flexible electronics on polymeric substrates.