This paper presents the results of surface energy measurements performed in situ during annealing of silicon wafers. The method allows conclusions to be drawn about the progress of silanol condensation while surface energy increases. The effects of wafer conditioning by atmospheric pressure plasmas, chemical post-treatments after plasma exposure but before bonding, and annealing temperatures on silanol condensation is investigated. Using nitrogen or nitrogen/oxygen gas mixtures for plasma activation, higher fracture surface energies γ are obtained at room temperature compared with oxygen plasma activation. Upon annealing, an increase in surface energies starts below
100°C
. Possible reasons responsible for the effects of nitrogen plasma treatment and post-treatments with ammonia are discussed. Upward bent
γ(t)
curves are obtained during annealing at
200°C
, independently of the type of wafer preconditioning, in contrast with the implications of existing chemical-kinetic models of the bonding process. Aside from a self-enhancement of the process due to facilitated water removal from the interface, the hypothesis of the nucleation and growth of covalently bonded microareas is able to explain the observed behavior qualitatively.