The use of ion implantation doping instead of the standard gaseous diffusion is a promising way to simplify the fabrication process of silicon solar cells. However, difficulties to form high-quality boron (B) implanted emitters are encountered when implantation doses suitable for the emitter formation are used. This is due to a more or less complete activation of Boron after thermal annealing. To have a better insight into the actual state of the B distributions, we analyze three different B emitters prepared on textured Si wafers: (1) a BCl3 diffused emitter and two B implanted emitters (fixed dose) annealed at (2) 950°C and at (3) 1050°C (less than an hour). Our investigations are in particular based on atom probe tomography, a technique able to explore 3D atomic distribution inside a material at nanometer scale. Atom probe tomography is employed here to characterize B atomic distribution inside textured Si solar cell emitters and to quantify clustering of B atoms. Here, we show that implanted emitters annealed at 950 °C present maximum clusters due to poor solubility at lower temperature and also highest emitter saturation current density (J0e = 1000 fA/cm2). Increasing the annealing temperature results in greatly improved J0e (131 fA/cm2) due to higher solubility and a consequently lower number of clusters. BCl3 diffused emitters do not contain any B clusters and presented the best emitter quality. From our results, we conclude that clustering of B atoms is the main reason behind higher J0e in the implanted boron emitters and hence degraded emitter quality.