Ever since the introduction of the metal-oxide-silicon field-effect-transistor (MOSFET), the nature of mobile and trapped charge in the oxide layer has been studied in great detail. For example, contamination with alkali ions such as sodium, causing instability of the flat-band voltage, was a major concern in the early days of MOS fabrication. Another SiO2 impurity of particular interest is hydrogen, because of its beneficial property of passivating charge traps. In this work we show that annealing of Si/SiO2/Si structures in forming gas (Ar:H2; 95:5) above 400 °C can introduce mobile H+ ions into the SiO2 layer. These mobile protons are confined within the oxide layer, and their space-charge distribution is well controllable and easily rearrangeable by applying a gate bias, making them potentially useful for application in a reliable nonvolatile MOSFET memory device. We present speed, retention, endurance, and radiation tolerance data showing that this non-volatile memory technology can be competitive with existing Si-based non-volatile memory technologies such as Flash.
The chemical kinetics of mobile-proton reactions in the SiO2 film are also analyzed in greater detail. Our data show that the initial buildup of mobile protons during hydrogen annealing is limited by the rate of lateral hydrogen diffusion into the buried SiO2 films. The final density of mobile protons is determined by the cooling rate which terminates the annealing process and, in the case of subsequent anneals, by the temperature of the final anneal. To explain the observations, we propose a dynamical equilibrium model. Based on these insights, the incorporation of the proton generation process into standard semiconductor process flows is discussed.