Layer-by-layer growth of single crystalline Si was examined with a doping method that applied a low-temperature process. Si2H6 (99.99%) and dopant precursor, PH3 (or B2H6), were injected intermittently on the Si(100) surface, and an atomically smooth surface was obtained with atomic-scale layer controllability of the growth thickness. At a process temperature of 525degreesC, an n-type layer doped with phosphorus was obtained up to the carrier concentration of 2.8 x 10(19) cm(-3), and a smooth surface of the film was obtained under 2 x 10(19) cm(-3). The carrier concentration of the p-type layer doped with boron reached 5 x 10(20) cm(-3) while maintaining an atomically smooth surface at a growth temperature of 510degreesC. Nanometer-scale multilayer structures using doping were fabricated, and the doping profile was sufficiently sharp and on the order of nanometers. (C) 2003 The Electrochemical Society.