We present an extended model for B clustering in crystalline or in preamorphized Si and with validity under conditions below and above the equilibrium solid solubility limit of B in Si. This model includes boron-interstitial clusters (BICs) with BnIm configurations—complexes with n B atoms and m Si interstitials—larger (n > 4), and eventually more stable, than those included in previous models. In crystalline Si, the formation and dissolution pathways into large BICs configurations require high B concentration and depend on the flux of Si interstitials. In the presence of high Si interstitial flux, large BICs with a relatively large number of interstitials (m ≥ n) are formed, dissolving under relatively low thermal budgets. On the contrary, for low Si interstitial flux large BICs with few interstitials (m ≪ n) can form, which are more stable than small BICs, and whose complete dissolution requires very intense thermal budgets. We …