Doped zinc oxide layers are widely used in thin-film solar cells for several purposes,
for instance as transparent contacts, as a source of light scattering and as part of the
back reflector. Magnetron sputtered, aluminum-doped zinc oxide thin films provide
very high transparency and conductivity, and are usually flat in the as-deposited
state. To introduce light scattering, a surface texture is conventionally introduced by
post-deposition etching in diluted hydrochloric acid. However, the ability to obtain
suitable surface morphologies by chemical dissolution is strongly dependent on the
deposition process. Thus, optimization of zinc oxide thin films requires a careful
trade-off between optical, electric, and morphological properties. This markedly limits
the process window and excludes layers with excellent optical and electric properties
due to a lack of suitable texturing processes. Electrochemical methods can help to
overcome these limitations by making novel zinc oxide structures accessible. Both
deposition and dissolution can be achieved using electrochemical methods. In this
context, an advanced understanding of the stability of polycrystalline zinc oxide thin
films in aqueous solutions is crucial. This work investigates the zinc oxide/electrolyte
interface under various conditions in order to further the understanding of the
interfacial reactions and the zinc oxide itself.
Cathodic electrochemical deposition was used for the growth of zinc oxide films
and nano-structures from aqueous solutions. This method utilizes specific manipulation
of the interfacial pH at the substrate surface by reduction of a suitable precursor
such as nitrate or molecular oxygen. The dependence of the zinc oxide precipitation
and crystallization on several parameters such as the deposition potential, the bath
temperature, the substrate, and the composition of the electrolyte were investigated.
Temperatures above 50 ?C were found to be necessary for the crystallization of well
defined hexagonal crystals. The comparison of electrochemical deposition on indium
tin oxide and zinc oxide substrates revealed the fundamental influence of the substrate
on the nucleation. While the growth on zinc oxide seed layers seemed to proceed
epitaxially, conserving the preferential c-axis orientation and crystallite size of the
substrate, the nucleation on indium tin oxide substrates depended largely on the
applied potential. With increasing cathodic potential the density of nucleation sites
increased.
Jan-Philipp Becker