Precise control over dopant dose and distribution at the nanoscale is required to support further evolution in microelectronics, photovoltaics, solar fuel conversion, sensors, and quantum computation. In this contribution, an effective bottom-up technology is proposed as a promising solution to overcome the limitations of conventional doping approaches. Precise control of the amount of dopant atoms tethered on silicon substrates is presented, based on polystyrene and poly(methyl methacrylate) polymers, with controlled molar mass and featuring a narrow molar mass distribution, end-terminated with a P-containing moiety. These polymers are spin coated and subsequently end-grafted onto nondeglazed silicon substrates. P atoms were bonded to the surface during the grafting reaction, and their surface density is set by the polymer molar mass, according to the self-limiting nature of the …