Liquid‐phase epitaxy allows SiGe alloys of good quality to be grown on Si substrates. We deposit single crystalline,n‐type Si1−xGexfilms with 0.7<x<1 from Bi solutions on (111)‐oriented Si. The films are up to several &mgr;m thick and are uniform in thickness and in composition. The analysis by x‐ray diffraction indicates good crystallinity and a dislocation density below 5×107cm−2. Photoluminescence measurements show well‐resolved peaks with the smallest linewidths reported so far for epitaxial SiGe. Hall‐effect measurements yield electron concentrations around 1×1016cm−3and room‐temperature electron mobilities of up to 340 cm2/V s.