STEM and ELS Observation of Early Oxide Formation on the Surface of Cr Thin Films

STEM coupled with the optical system was used for the investigation of the early oxidation on the surface of Cr. Cr thin films (30 – 1000Å) were prepared by evaporation onto the polished or air-cleaved NaCl substrates at room temperature and 45°C in a vacuum of 10−6 Torr with an evaporation speed 0.3Å/sec. Rather thick specimens (200 – 1000Å) with various preferred orientations were used for the investigation of the oxidation at moderately high temperature (600 − 1100°C). Selected area diffraction patterns in these specimens are usually very much complicated by the existence of the different kinds of oxides and their multiple twinning. The determination of the epitaxial orientation relationship of the oxides formed on the Cr surface was made possible by intensive use of the optical system and microdiffraction techniques. Prior to the formation of the known rhombohedral Cr2O3, a thin spinel oxide, probably analogous to γ -Al203 or γ -Fe203, was formed. Fig. 1a shows the distinct epitaxial growth of the spinel (001) as well as the rhombohedral (125) on the well-oriented Cr(001) surface. In the case of the Cr specimen with the (001) preferred orientation (Fig. 1b), the rings explainable by spinel structure appeared as well as the well defined epitaxial spots of the spinel (001). The microdif fraction from 20A areas (Fig. 2a) clearly shows the same pattern as Fig. Ia with the weaker oxide spots among the more intense Cr spots, indicating that the thickness of the oxide is much less than that of Cr. The rhombohedral Cr2O3 was nucleated preferably at the Cr(011) sites provided by the polycrystalline nature of the present specimens with the relation Cr2O3 (001)//Cr(011), and by further oxidation it grew into full coverage of the rest of the Cr surface with the orientation determined by the initial nucleation.