Light intensity modulated impedance spectroscopy (LIMIS) in all-solid-state solar cells at open-circuit

Potentiostatic impedance spectroscopy (IS) is a well-established characterization technique for elucidating the electric resistivity and capacitive features of materials and devices. For solar cells, by applying a small voltage perturbation the current signal is recorded and the recombination processes and defect distributions can be accessed. In this work, a photo-impedance approach, named “light intensity modulated impedance spectroscopy” (LIMIS), is first time tested in all-solid-state photovoltaics by individually recording photocurrent (IMPS) and photovoltage (IMVS) responsivity signals due to a small light perturbation at open-circuit (OC), and combining them: LIMIS = IMVS/IMPS. The experimental LIMIS spectra from silicon, organic, and perovskite solar cells are presented and compared with IS. Our theoretical analyses, including equivalent circuit models, show a correction to the lifetimes values by obtaining the total differential resistances and capacitances combining IS and LIMIS. This correction addresses some discrepancies among different techniques, as also shown with photo-induced transient photovoltage. The experimental differences between IS and LIMIS proves the unsuitability of the superposition principle and suggest a bias-dependent photo-current correction to the empirical Shockley equation of the steady-state current at different illumination intensities around OC. In addition, new features are reported for the low-frequency capacitance of perovskite solar cells

Surface versus Bulk Currents and Ionic Space-Charge Effects in CsPbBr3 Single Crystals

CsPbBr3 single crystals have potential for application in ionizing-radiation detection devices due to their optimal optoelectronic properties. Yet, their mixed ionic–electronic conductivity produces instability and hysteretic artifacts hindering the long-term device operation. Herein, we report an electrical characterization of CsPbBr3 single crystals operating up to the time scale of hours. Our fast time-of-flight measurements reveal bulk mobilities of 13–26 cm2 V–1 s–1 with a negative voltage bias dependency. By means of a guard ring (GR) configuration, we separate bulk and surface mobilities showing significant qualitative and quantitative transport differences. Our experiments of current transients and impedance spectroscopy indicate the formation of several regimes of space-charge-limited current (SCLC) associated with mechanisms similar to the Poole–Frenkel ionized-trap-assisted transport. We show that the ionic-SCLC seems to be an operational mode in this lead halide perovskite, despite the fact that experiments can be designed where the contribution of mobile ions to transport is negligible.Funding for open access charge: CRUE-Universitat Jaume