Enhanced Phase Stability of Compressive Strain-Induced Perovskite Crystals

Control of strain in perovskite crystals has been considered as an effective strategy to ensure the phase stability of perovskite films where a compressive strain is particularly preferred over a tensile strain due to a lowered Gibbs free energy by the unit cell contraction effect. Here we adapt the strategy of strain control into perovskite solar cells in which the compressive strain is applied by utilizing a thermal expansion difference between the perovskite film and an adjacent layer. Poly(4-butylphenyldiphenylamine), with a higher thermal expansion coefficient compared to that of perovskite, is employed as a substrate for perovskite crystal growth at 100 °C, followed by cooling to room temperature. The applied compressive strain at the interface, as a result of a greater contraction of the polymer compared to the perovskite film, is confirmed by grazing incidence X-ray diffraction showing a red peak shift with increasing secondary angle. The compressive strain-induced perovskite film shows relatively constant absorbance spectra as a function of time. In the meantime, the absorbance spectra of a film without strain control exhibit a gradual decay with developing an Urbach tail. Importantly, the effect of strain engineering is remarkably prominent in the long-term photovoltaic performance. The photocurrent drops by 41% over 911 h without controlling strain, which is significantly improved by employing compressive strain, showing only a 6% drop in photocurrent from a shelf-stability test without encapsulation. It is also noted that an S-shaped kink appears in the current-voltage curves since 579-h-long storage for the device without strain control, leading to unreliable and overestimated fill factor and conversion efficiency. On the other hand, a 16% increase in fill factor with a stable performance is derived over 911 h from the compressive strain-induced device.