A study of low temperature crystallization of amorphous thin film indium–tin–oxide

Deposition of tin-doped–indium-oxide (ITO) on unheated substrates via low energy processes such as electron-beam deposition can result in the formation of amorphous films. The amorphous-to-crystalline transformation was studied in this system using in situ resistivity, time resolved reflectivity, glancing incidence angle x-ray diffraction, and transmission electron microscopy. The resistivity of 180 nm thick $In2O3(9.9 wt. %SnO2)$ was monitored during isothermal anneals at 125, 135, 145, and 165 °C. The dependence of the resistance on the volume fraction of crystalline phase was established using glancing incidence angle x-ray diffraction and a general two phase resistivity model for this system was developed. These studies show that, upon annealing, as-deposited amorphous ITO undergoes both a structural relaxation and crystallization. Structural relaxation of the amorphous material includes local ordering that increases the ionized vacancy concentration which, in turn, increases the carrier density in the material. Kinetic growth parameters were extracted from the data, which reveal that the relaxation of the amorphous structure occurs via a process that obeys a first order reaction rate law, while crystallization occurs via classical nucleation and growth with a growth mode parameter that is consistent with two- to three-dimensional transformation geometry. Both the relaxation and crystallization processes have an activation energy of approximately $1.3±0.2 eV.$ Time resolved reflectivity analysis of the electron beam deposited ITO reveals that there is a sharp and monotonic decrease in reflectivity during the anneal of the sample which is associated with the amorphous relaxation process.