Temperature-activated dielectric relaxation in lead-free halide perovskite single crystals

Abstract

Lead-free metal-halide perovskites have recently appeared as a promising candidate in optoelectronics and photovoltaics because of their non-toxicity, stability, and unique photophysical properties. Much scientific research has been done on optoelectronic characteristics and photovoltaic applications of lead-free perovskites, but the dielectric characteristics and insight into the relaxation phenomenon remain elusive. Here, we study the dielectric relaxation and conduction mechanism in the single crystalline (SC) A3Bi2X9 (A = MA+/FA+) perovskite using temperature-dependent electrochemical impedance spectroscopy in correlation with the modulus spectroscopy. With increasing temperature, the peak of −Z″(ω) shifts toward a high-frequency regime which specifies the thermally dependent relaxation mechanism in both crystals. The activation energy was estimated as 381 meV for MA3Bi2I9 (MBI) crystal and 410 meV for the FA3Bi2I9 (FBI) crystal suggesting hopping of mobile ions between lattice sites. The connected orientational polarization with the thermal motion of molecules leads to the enhancement in the dielectric constant (ϵ′) with temperature. The ϵ″(ω) in these crystals shows the significant ionic conductivity with a typical 1/fγ type characteristics (in the low-frequency regime) where γ is found to be in the range of 0.93–1.0 for MBI crystal and 0.88–0.98 for FBI crystal. The correlated imaginary part of impedance (−Z″) and modulus (M″) demonstrate the temperature-activated delocalized relaxation (non-Debye toward the Debye type) in these crystals. Stevels model suggests that the contribution of traps reduces with temperature rise and therefore conductivity enhances. Our study provides a comprehensive analysis and in-depth knowledge about the dielectric and conductivity relaxation mechanism in these lead-free perovskite SCs, which will help to implement efficient energy storage devices using these materials.