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In crystalline silicon, atomic hydrogen released from hydrogen dimers forms acceptor–hydrogen pairs during annealing in the dark at elevated temperatures. In this study, the formation of boron–hydrogen (BH) and gallium–hydrogen (GaH) pairs in 1 Ω cm silicon is investigated at temperatures ranging from 140 to 220 °C. Acceptor–hydrogen concentrations in the low 1014cm−3range are quantified by means of highly sensitive resistance measurements. GaH pairs are generally found to form faster than BH pairs. Arrhenius analysis shows a difference in activation energy (BH: 1.20 eV, GaH: 1.04 eV) while the trial frequency is the same (≈4×108s−1). The formation of boron–hydrogen (BH) and gallium–hydrogen (GaH) pairs in the low 1014 cm−3range in boron‐ or gallium‐doped crystalline silicon during annealing in the dark at temperatures ranging from 140 to 220 °C is investigated by means of highly sensitive resistance measurements. An Arrhenius analysis reveals differences in formation dynamics.

This study deals with the dynamics of the formation and dissociation of boron–hydrogen (BH) pairs in crystalline silicon during a rapid high‐temperature treatment and subsequent dark annealing between 200 and 300 °C. Highly accurate resistivity measurements are used to detect BH pairs in chemically polished B‐doped float‐zone silicon. It is found that an unexpecteded high amount of hydrogen is present in the as‐purchased wafers. Hydrogen is initially mostly paired to boron but can be dissolved by a short high‐temperature firing step. If a firing step (530 °C) is applied to bare, unpassivated Si wafers, most of the initial BH pairs are dissolved, and hydrogen dimers (H2) form. With increasing peak temperature, an increasing amount of hydrogen leaves the H2⇌BHsystem, while the proportion of BH increases. Additional hydrogen can be introduced by firing a wafer passivated with plasma‐enhanced chemical vapor deposition (PECVD) SiNx:H. A three‐state model shows a good agreement with the measured data for both bare and coated samples as well as for different annealing temperatures. With increasing dark annealing temperatures, the BH dynamics accelerates, whereas the maximum BH concentration reached decreases. For temperatures above 280 °C, significant changes in the reaction dynamics are observed. Highly accurate resistivity measurements are used to detect boron–hydrogen (BH) pairs in crystalline silicon. The authors found an unexpectedly high amount of hydrogen present in as‐purchased wafers. Initially bound to boron, the dynamics of the formation and dissociation of these BH pairs under various firing conditions and dark anneal temperatures is studied.