Heteroepitaxial fluoride structures are candidates of material systems for quantum well devices such as resonant tunneling devices on Si substrates. Resonant tunneling diodes composed of CaF2/CdF2/CaF2 on Si(111) have been demonstrated and they exhibited large potential for high performance quantum effect devices based on high energy barrier and abrupt hetero-interface. However, this material system has significant problem of the pin-hole defects in CaF2 and strong chemical reaction of CdF2 with Si. Fluoride alloys such as CaxCd1-xF2 and CaxMg1-xF2, as well as the post oxidation technique, are effective to overcome these problems.