AbstractCathodoluminescence measurements at cryogenic temperatures are reported on boron- and phosphorus-doped CVD-diamond films grown on silicon substrates. Boron and phosphorus concentrations were determined by SIMS measurements; for boron, they reached from unintentional background doping levels up to 3500 ppm. At increasing boron concentrations, the radiative recombination of boron bound excitons (BEto) at 5.22 eV photon energy systematically broadens and shifts down to 4.99 eV whereas the free exciton emission (FEto) disappears for 40 ppm and higher. In the phosphorus-doped films we observe new lines at 5.16 eV and 4.99 eV which we ascribe to TO- and (TO+Or)-phonon assisted transitions of an exciton bound to a shallow impurity other than boron, possibly phosphorus or a phosphorus-related shallow complex.