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.

Coupling between Ion Drift and Kinetics of Electronic Current Transients in MAPbBr3 Single Crystals.

The optoelectronic properties of halide perovskite materials have fostered their utilization in many applications. Unravelling their working mechanisms remains challenging because of their mixed ionic-electronic conductive nature. By registering, with high reproducibility, the long-time current transients of a set of single-crystal methylammonium lead tribromide samples, the ion migration process was proved. Sample biasing experiments (ionic drift), with characteristic times exhibiting voltage dependence as ∝ V -3/2, is interpreted with an ionic migration model obeying a ballistic-like voltage-dependent mobility (BVM) regime of space-charge-limited current. Ionic kinetics effectively modify the long-time electronic current, while the steady-state electronic currents' behavior is nearly ohmic. Using the ionic dynamic doping model (IDD) for the recovering current at zero bias (ion diffusion), the ionic mobility is estimated to be ∼10-6 cm2 V-1 s-1. Our findings suggest that ionic currents are negligible in comparison to the electronic currents; however, they influence them via changes in the charge density profile.

Mobile Ion-Driven Modulation of Electronic Conductivity Explains Long-Timescale Electrical Response in Lead Iodide Perovskite Thick Pellets.

The favorable optoelectronic properties of metal halide perovskites have been used for X- and γ-ray detection, solar energy, and optoelectronics. Large electronic mobility, reduced recombination losses of the electron-hole pairs, and high sensitivity upon ionizing irradiation have fostered great attention on technological realizations. Nevertheless, the recognized mixed ionic-electronic transport properties of hybrid perovskites possess severe limitations as far as long-timescale instabilities and degradation issues are faced. Several effects are attributed to the presence of mobile ions such as shielding of the internal electrical field upon biasing and chemical interaction between intrinsic moving defects and electrode materials. Ion-originated modulations of electronic properties constitute an essential peace of knowledge to further progress into the halide perovskite device physics and operating modes. Here, ionic current and electronic impedance of lead methylammonium iodide perovskite thick pellets are independently monitored, showing self-consistent patterns. Our findings point to a coupling of ionic and electronic properties as a dynamic doping effect caused by moving ions that act as mobile dopants. The electronic doping profile changes within the bulk as a function of the actual ion inner distribution, then producing a specific time dependence in the electronic conductivity that reproduces time patterns of the type ∝t, a clear fingerprint of diffusive transport. Values for the iodine-related defect diffusivity in the range of Dion ∼ 10-8 cm2 s-1, which corresponds to ionic mobilities of about µion ∼ 10-6 cm2 V-1 s-1, are encountered. Technological realizations based on thick perovskite layers would benefit from this fundamental information, as far as long-timescale current stabilization is concerned.

Utilization of Temperature-Sweeping Capacitive Techniques to Evaluate Band Gap Defect Densities in Photovoltaic Perovskites.

Capacitive techniques, routinely used for solar cell parameter extraction, probe the voltage-modulation of the depletion layer capacitance isothermally as well as under varying temperature. In addition, defect states within the semiconductor band gap respond to such stimuli. Although extensively used, capacitive methods have found difficulties when applied to elucidating bulk defect bands in photovoltaic perovskites. This is because perovskite solar cells (PSCs) actually exhibit some intriguing capacitive features hardly connected to electronic defect dynamics. The commonly reported excess capacitance observed at low frequencies is originated by outer interface mechanisms and has a direct repercussion on the evaluation of band gap defect levels. Starting by updating previous observations on Mott-Schottky analysis in PSCs, it is discussed how the thermal admittance spectroscopy and the deep level transient spectroscopy characterization techniques present spectra with overlapping or even "fake" peaks caused by the mobile ion-related, interfacial excess capacitance. These capacitive techniques, when used uncritically, may be misleading and produce wrong outcomes.