Many recent studies of the highlighted problem of visible-range photoluminescence of porous silicon (po-Si) indicate the presence of hydrogen in this material. However, its actual role is not clear with the discussed possibilities ranging from passivation of the surface defects to some form of active participation in the photoluminescence (PL) mechanism itself. At the same time, in several magnetic resonance studies of po-Si the so-called Pb center, originally identified with the <111>-directed silicon broken bond stabilized at Si/SiO2 interfaces, has been reported.
Very recently the paramagnetic state of molecular hydrogen in bulk silicon has been identified. The spin-Hamiltonian parameters of the related Si-NL52 EPR spectrum appear to be identical to those of the Pb center. This observation casts severe doubts on the original interpretation of the Pb center while, on the other hand, offering new evidence of a prominent presence of hydrogen molecules both in po-Si and at the Si/SiO2 interface. In this paper the similarities of Si-NL52 and Pb centers are examined in detail, and it is argued that the centers are the same. It is concluded that many features of the Pb center which could not be explained within the broken-bond model can be understood with the interstitial hydrogen molecule model.