We report the formation of sub-5 nm ultrashallow junctions in 4 in. Si wafers enabled by the molecular monolayer doping of phosphorus and boron atoms and the use of conventional spike annealing. The junctions are characterized by secondary ion mass spectrometry and noncontact sheet resistance measurements. It is found that the majority ( approximately 70%) of the incorporated dopants are electrically active, therefore enabling a low sheet resistance for a given dopant areal dose. The wafer-scale uniformity is investigated and found to be limited by the temperature homogeneity of the spike anneal tool used in the experiments. Notably, minimal junction leakage currents (<1 microA/cm(2)) are observed that highlights the quality of the junctions formed by this process. The results clearly demonstrate the versatility and potency of the monolayer doping approach for enabling controlled, molecular-scale ultrashallow junction formation without introducing defects in the semiconductor.