Peter V. Pikhitsa

Mn2+ ion doping is used as an electron paramagnetic resonance (EPR) probe to investigate the influence of low-coordination structural defects such as step edges at the surface of terraced (001) MgO nanoparticles on the electronic properties. Beside the well-known hyperfine sextet of Mn2+ ions in the cubic crystal field of MgO, an additional EPR feature with a striking non-monotonous temperature dependent shift of the g-factor is observed in terraced nanoparticles in the temperature range from 4K to room temperature. By linking the difference in the temperature dependence of the Mn2+ sextet intensity in cubic and terraced nanoparticles with the possible s-d exchange shift and enhanced Zeeman splitting we conclude that the novel EPR feature originates from the loosely trapped charge-compensating carriers at the abundant structural defects at the surface of terraced nanoparticles due to their exchange interaction with neighboring Mn2+ ions.

Perovskite solar cells have shown fast deterioration during actual operation even with encapsulation, but its mechanism has been elusive. We found the fundamental mechanism for irreversible degradation of perovskite materials in which trapped charges regardless of the polarity play a decisive role. A novel experimental setup utilizing different polarity ions revealed that the moisture induced irreversible dissociation of perovskite materials is triggered by charges trapped along grain boundaries. Our finding clearly explained the intriguing observations why light soaking induces irreversible degradation while in the dark, moisture only causes reversible hydration, and why degradation begins from different side of interface for different charge extraction layers. The deprotonation of organic cations by trapped charge induced local electric field is attributed to the initiation of irreversible decomposition.