Highly oriented films of the semiconducting transition metal silicide, CrSi2, were grown on (111) silicon substrates, with the matching crystallographic faces being CrSi_2(001)/Si(111). Reflection high‐energy electron diffraction (RHEED) yielded symmetric patterns of sharp streaks. The expected streak spacings for different incident RHEED beam directions were calculated from the reciprocal net of the CrSi_2(001) face and shown to match the observed spacings. The predominant azimuthal orientation of the films was thus determined to be CrSi_2〈210〉∥Si〈110〉. This highly desirable heteroepitaxial relationship may be described with a common unit mesh of 51 Å^2 and a mismatch of −0.3%. RHEED also revealed the presence of limited film regions of a competing azimuthal orientation, CrSi_2〈110〉∥Si〈110〉. A new common unit mesh for this competing orientation is suggested; it possesses an area of 612 Å^2 and a mismatch of −1.2%
