Photoinduced Current Transient Spectroscopy on Metal Halide Perovskites: Electron Trapping and Ion Drift.

Metal halide perovskites (MHPs) are disruptive materials for a vast class of optoelectronic devices. The presence of electronic trap states has been a tough challenge in terms of characterization and thus mitigation. Many attempts based on electronic spectroscopies have been tested, but due to the mixed electronic-ionic nature of MHP conductivity, many experimental results retain a large ambiguity in resolving electronic and ionic charge contributions. Here we adapt a method, previously used in highly resistive inorganic semiconductors, called photoinduced current transient spectroscopy (PICTS) on lead bromide 2D-like ((PEA)2PbBr4) and standard "3D" (MAPbBr3) MHP single crystals. We present two conceptually different outcomes of the PICTS measurements, distinguishing the different electronic and ionic contributions to the photocurrents based on the different ion drift of the two materials. Our experiments unveil deep level trap states on the 2D, "ion-frozen" (PEA)2PbBr4 and set new boundaries for the applicability of PICTS on 3D MHPs.

Ionic Field Screening in MAPbBr3 Crystals Revealed from Remnant Sensitivity in X-ray Detection.

Research on metal halide perovskites as absorbers for X-ray detection is an attractive subject due to the optimal optoelectronic properties of these materials for high-sensitivity applications. However, the contact degradation and the long-term instability of the current limit the performance of the devices, in close causality with the dual electronic-ionic conductivity of these perovskites. Herein, millimeter-thick methylammonium-lead bromide (MAPbBr3) single and polycrystalline samples are approached by characterizing their long-term dark current and photocurrent under X-ray incidence. It is shown how both the dark current and the sensitivity of the detectors follow similar trends at short-circuit (V = 0 V) after biasing. By performing drift-diffusion numerical simulations, it is revealed how large ionic-related built-in fields not only produce relaxations to equilibrium lasting up to tens of hours but also continue to affect the charge kinetics under homogeneous low photogeneration rates. Furthermore, a method is suggested for estimating the ionic mobility and concentration by analyzing the initial current at short-circuit and the characteristic diffusion times.