Asymmetric Bipolar Resistive Switching of Halide Perovskite Film in Contact with TiO2 Layer.

Halide perovskite materials such as methylammonium lead iodide (CH3NH3PbI3) have attracted considerable interest for the resistive random-access memory applications, which exploit a dramatic change in the resistance by an external electric bias. In many semiconductor films, the drift, accumulation, and chain formation of defects explain the change in the resistance by an external bias. This study demonstrates that the interface of CH3NH3PbI3 with TiO2 has a significant impact on the formation and rupture of defect chains and causes the asymmetric bipolar resistive switching in the Au/CH3NH3PbI3/TiO2/FTO device (FTO = fluorine-doped tin oxide). When a negative bias is applied to the Au electrode, iodine interstitials with the lowest migration activation energy move toward TiO2 in the CH3NH3PbI3 layer and pile up at the CH3NH3PbI3-TiO2 interface. Under the same condition, oxygen vacancies in the TiO2 layer also travel to the CH3NH3PbI3-TiO2 interface and strongly attract iodine interstitials. As a result, a Schottky barrier appears at the CH3NH3PbI3-TiO2 interface, and the resistance of Au/CH3NH3PbI3/TiO2/FTO becomes much larger than that of Au/CH3NH3PbI3/FTO in the high resistance state. The frequency dependence of the capacitance confirms the asymmetric appearance of a large space charge polarization at the CH3NH3PbI3-TiO2 interface, which causes the unique bipolar resistive switching behavior with the on/off ratio (103) and retention time (>104 seconds) at -0.85 V in Au/CH3NH3PbI3/TiO2/FTO film.

Highly Bendable Flexible Perovskite Solar Cells on a Nanoscale Surface Oxide Layer of Titanium Metal Plates.

We report highly bendable and efficient perovskite solar cells (PSCs) that use thermally oxidized layer of Ti metal plate as an electron transport layer (ETL). The power conversion efficiency (PCE) of flexible PSCs reaches 14.9% with a short-circuit current density (Jsc) of 17.9 mA/cm2, open-circuit voltage (Voc) of 1.09, and fill factor (ff) of 0.74. Moreover, the Ti metal-based PSCs exhibit a superior fatigue resistance over indium tin oxide/poly(ethylene terephthalate) substrate. Flexible PSCs maintain 100% of their initial PCE even after PSCs are bent 1000 times at a bending radius of 4 mm. This excellent performance of flexible PSCs is due to high crystalline quality and low oxygen vacancy concentration of TiO2 layer. The concentration of oxygen vacancies in the oxidized Ti metal surface controls the electric function of TiO2 as ETL of PSCs. A decrease in the oxygen vacancy concentration of the TiO2 layer is critical to improving the electron collection efficiency of the ETL. Our results suggest that Ti metal-based PSCs possess excellent mechanical properties, which can be applied to the renewable energy source for flexible electronics.

Low-Temperature Modification of ZnO Nanoparticles Film for Electron-Transport Layers in Perovskite Solar Cells.

An electron-transport layer (ETL) that selectively collects photogenerated electrons is an important constituent of halide perovskite solar cells (PSCs). Although TiO2 films are widely used as ETL of PSCs, the processing of TiO2 films with high electron mobility requires high-temperature annealing and TiO2 dissociates the perovskite layer through a photocatalytic reaction. Here, we report an effective surface-modification method of a room-temperature processed ZnO nanoparticles (NPs) layer as an alternative to the TiO2 ETL. A combination of simple UV exposure and nitric acid treatment effectively removes the hydroxyl group and passivates surface defects in ZnO NPs. The surface modification of ZnO NPs increases the power conversion efficiency (PCE) of PSCs to 14 % and decreases the aging of PSCs under light soaking. These results suggest that the surface-modified ZnO film can be a good ETL of PSCs and provide a path toward low-temperature processing of efficient and stable PSCs that are compatible with flexible electronics.