ABSTRACT
The coupled ionic and electronic transport in halide perovskites opens up new possibilities for semiconductor iontronic devices beyond solar cells. Nevertheless, the fundamental understanding of ionic behavior at the microscale remains vague, largely because of the inhomogeneity in polycrystalline thin films. Here, we show that the ion dynamics in single-crystalline perovskite nanoplates (NPs) are significantly different and that an external bias may induce highly anisotropic ionic transport in the NPs, thereby leading to a greatly enhanced local electric field. Using modified scanning photocurrent microscopy (SPCM), the origin of the photocurrent is pinpointed to the cathode region of the NP device, where subsequent energy dispersive spectroscopy (EDS) characterization confirms a large accumulation of halogen vacancies. In addition, the Kelvin probe force microscopy (KPFM) measurement demonstrates a strong built-in electric field within a submicron length near the cathode, which alters the local electronic structure for efficient photo carrier separation. Such field-induced ionic behavior deepens the understanding of ion dynamics in perovskites and promotes scale-down of perovskite micro- and nanoiontronic and ion-optoelectronic devices.
ABSTRACT
Heterostructures play an irreplaceable role in high-performance optoelectronic devices. However, the preparation of robust perovskite heterostructures is challenging due to spontaneous interdiffusion of halogen anions. Herein, a vapor-phase anion exchange method universally suitable for the preparation of robust 2D Ruddlesden-Popper perovskite (RPP) heterostructures is developed. A variety of heterostructures are fabricated based on exfoliated RPP microplates (MPs). Depending on the specific organic cations, the heterostructures can be either sharp and uniform, or broad and gradient, suggesting a new anion diffusion behavior different from that in 3D perovskites. Further experimental studies reveal that the lateral transport of anions follows a threshold-dominating mechanism, while the vertical transport can be partially or completely suppressed by organic cations. Subsequently, quantitative investigation of anion diffusion in 2D perovskites is conducted. The lateral diffusion coefficient of halogen anions is calculated to be 6 to 7 orders of magnitude larger than the vertical coefficient, consistent with the observed highly anisotropic anion diffusion. In addition, it is shown that the anion exchange threshold can also enhance the thermodynamic stability of the heterostructures at elevated temperature. These results provide a general method to fabricate robust lateral RPP heterostructures, and offer important insights into anion behavior in low-dimensional perovskites.
ABSTRACT
Anion-exchange in halide perovskites provides a unique pathway of bandgap engineering for fabricating heterojunctions in low-cost photovoltaics and optoelectronics. However, it remains challenging to achieve robust and sharp perovskite heterojunctions, due to the spontaneous anion interdiffusion across the heterojunction in 3D perovskites. Here, it is shown that the anionic behavior in 1D perovskites is fundamentally different, that the anion exchange can readily drive an indirect-to-direct bandgap phase transition in CsPbI3 nanowires (NWs) and greatly lower the phase transition temperature. In addition, the heterojunction created by phase transition is epitaxial in nature, and its chemical composition can be precisely controlled upon postannealing. Further study of the phase transition dynamics reveals a threshold-dominating anion exchange mechanism in these 1D NWs rather than the gradient-dominating mechanism in 3D systems. The results provide important insights into the ionic behavior in halide perovskites, which is beneficial for applications in solar cells, light-emitting diodes (LEDs), and other semiconductor devices.
