Spectroscopic ellipsometry of tin-doped indium oxide at elevated temperatures: properties evolution during film growth and annealing

Thin films of indium tin oxide (ITO) are widely used in optoelectronic devices due to the materials transparency in the visible range of the spectrum and its low electrical resistivity. The ITO film formation and evolution at elevated temperatures is not properly addressed because the phase diagram of this material is not known. The amorphous-to-crystalline transition is often assumed as the reason for decrease of ITO resistivity at enhanced temperatures due to a Sn donor activation, but the physical mechanisms behind the experimental observations are not clear.
This study is focused on in situ spectroscopic ellipsometry (SE) monitoring of the film properties during growth at elevated temperatures (Ts=RT-500 °C) as well as during postdeposition annealing (Ta=200-300 °C). In addition, during annealing, the SE results are contrasted with data of in situ four point probe resistivity measurement technique, the in situ X-ray diffraction (XRD) and elastic recoil detection analysis (ERDA). The atomic force microscopy and cross-sectional transmission electron microscopy were used to study the film morphology ex situ.
The free electron parameters were determined from parameterization of the film optical constants in Drude-Lorentz approach. The applicability of spectroscopic ellipsometry as a non-contact and in situ tool for monitoring of the film resistivity is shown. However, quantitative characterization of the resistivity by SE requires further improvement of the optical model for the growing film. The existence of the resistivity grading through the film thickness was indicated by this method for the growth without heating. ITO film resistivity rapidly deteriorates at thickness below 40 nm if the substrate temperature is less or equal 270 °C due to decrease of the free electron density and mobility. It can be explained by formation of an amorphous layer or layer with chaotically oriented crystallites on initial stages of the film growth, depending on the film temperature. There is no such layer observed at deposition temperatures higher than 400°C that denotes change in the film growth mode.
Spectroscopic ellipsometry provides valuable information both on the properties and the morphology modification during isothermal annealing of ITO films. Isothermal heating modifies the film properties in two stages which are attributed to: (i) relaxation of In-O bonds in the amorphous phase, (ii) Sn-donor activation by removal of interstitial oxygen. Different crystallization modes at 210 and 240 °C are suggested both by the real-time roughness behavior from SE and in situ XRD analysis.