Active doping of B was observed in nanometer silicon layers confined in SiO(2) layers by secondary ion mass spectrometry (SIMS) depth profiling analysis and confirmed by Hall effect measurements. The uniformly distributed boron atoms in the B-doped silicon layers of [SiO(2) (8 nm)/B-doped Si(10 nm)](5) films turned out to be segregated into the Si/SiO(2) interfaces and the Si bulk, forming a distinct bimodal distribution by annealing at high temperature. B atoms in the Si layers were found to preferentially substitute inactive three-fold Si atoms in the grain boundaries and then substitute the four-fold Si atoms to achieve electrically active doping. As a result, active doping of B is initiated at high doping concentrations above 1.1 × 10(20) atoms cm( - 3) and high active doping of 3 × 10(20) atoms cm( - 3) could be achieved. The active doping in ultra-thin Si layers was implemented for silicon quantum dots (QDs) to realize a Si QD solar cell. A high energy-conversion efficiency of 13.4% was realized from a p-type Si QD solar cell with B concentration of 4 × 10(20) atoms cm( - 3).