(Invited) From Bulk to Nanostructured Perovskites

Abstract

The dimensionality of semiconductors has a crucial role in determining their properties. Recently, metal halide perovskites have been demonstrated with many exciting applications, attracting wide attention to further their development for advanced optoelectronics, such as photovoltaics, photodetectors, light-emitting diodes, and lasers. At length scales down to nanoscale regimes, surface features as well as quantum confinement effects become dominant in regulating the material properties of perovskite materials. In past years, our group focus on the synthesis and characterization of metal halide perovskites with different configurations, ranging from bulk films, microplates, nanosheets, to nanowires. The corresponding physical properties and device applications were also systematically studied based on their widely tunable dimensionality, morphologies, and compositions.Specifically, for perovskite bulk films, surface defects and bulk structural order significantly affect their device performance. Through optimizing processing techniques, self-assembled quasi-2D perovskite films with graded phase distribution were successfully prepared. Gradient type-II band alignments along the out-of-plane direction of perovskites with spontaneous separation of photo-generated electrons and holes are obtained, which is later employed to construct self-powered vertical-structure photodetectors for the first time. Without any driving voltage, the device exhibited impressive performance with the responsivity up to 444 mA/W and ultrashort response time down to 52 µs. In addition, to assess the intrinsic material properties of crystalline perovskites, freestanding MAPbI3 nanosheets and lead-free Cs3Sb2I9 microplates were fabricated by two-step chemical vapor deposition method, in which excellent optoelectronic performance (e.g., responsively of MAPbI3 nanosheet is measured to be 40 A/W) together with ultra-fast response speed (down to 58 µs) and superior thermal stability were obtained.For nanostructured perovskites, understanding the dimensional features and their impact on the materials and devices is becoming increasingly important. Lately, we reported the direct vapor-liquid-solid growth of single-crystalline all-inorganic lead halide perovskite (i.e., CsPbX3; X = Cl, Br, or I) NWs. These NWs exhibited high-performance photodetection with the responsivity exceeding 4489 A/W and detectivity over 7.9 × 1012 Jones toward the visible light regime. Field-effect transistors based on individual CsPbX3 NWs were also fabricated to show the impressive carrier mobility of 3.05 cm2/Vs, being higher than other all-inorganic perovskite devices. Besides, the realization of high-mobility CsPbBr3 NW devices is reported via a simple surface charge transfer doping strategy. After MoO3 decoration and device fabrication, the hole mobility of CsPbBr3/MoO3 core-shell NW device is significantly enhanced to 23.3 cm2/Vs. All these results provide important guidelines for the further improvement of these perovskite nanostructures for practical utilization.