Real-time monitoring of ITO film structure during annealing: effect of film thickness

The amorphous indium tin oxide (ITO) films were grown by reactive pulsed middle frequency dual magnetron sputtering on the Si substrates covered with SiO₂. The real-time evolution of the ITO film structure during annealing was continuously investigated by synchrotron X-ray diffraction at ROssendorf Beam Line (ROBL), which is located at the European Synchrotron Radiation Facility in Grenoble, France. The annealing experiments were carried out in UHV annealing chamber equipped with beryllium dome at constant temperature of 310 C. In situ four-point probe technique was applied to characterize film resistivity. Three series of samples with thicknesses of ~50, 170 – 180, and 310-320 nm have been investigated.
The time dependence of the integral intensity exhibits an s-like shape, which is typical of the crystallization process. The XRD data were analyzed in a frame of the Kolmogorov – Johnson – Mehl – Avrami (KJMA) model. The kinetic parameters of crystallization process were determined. The range of KJMA exponent of approximately 2 obtained for all ITO films points to two-dimensional grain growth in the site saturated mode. However, detailed TEM studies of partly crystallized ITO samples display two-dimensional grain growth only during crystallization of 50 nm ITO films. In contrast, the thicker films show two stages of crystallization process. During the first stage, the single grains grew from a film surface to interface, after that, lateral growth of the grain was observed. The KJMA model can not predict the difference in the crystallization kinetics for the films with diverse thicknesses. The essential anisotropy and limited thickness of the films are discussed as the main reasons for the change of the crystallization kinetics.