Stark Effect and Environment-Induced Modulation of Emission in Single Halide Perovskite Nanocrystals

Organic-inorganic halide perovskites have emerged as promising materials for next-generation solar cells. In nanostructured form also, these materials are excellent candidates for optoelectronic applications such as lasers and light-emitting diodes for displays and lighting. While great progress has been achieved so far in optimizing the intrinsic photophysical properties of perovskite nanocrystals (NCs), in working optoelectronic devices, external factors, such as the effects of conducting environment and the applied electric field on exciton generation and photon emission, have been largely unexplored. Here, we use NCs of the all-inorganic perovskite CsPbBr₃ dispersed polyvinyl carbazole, a hole-conductor, and in poly(methyl methacrylate), an insulator, to examine the effects of applied electric field and conductivity of the matrix on the perovskite photophysics at the single-particle level. We found that the conducting environment causes a significant decrease of photoluminescence (PL) brightness of individual NCs due the appearance of intermediate-intensity emitting states with significantly shortened lifetime. Applied electric field has a similar effect and, in addition, causes a nonlinear spectral shift of the PL maxima, a combination of linear and quadratic Stark effects caused by environment-induced polarity and field-related polarizability. The environment and electric-field effects are explained by ionization of the NCs through hole transfer and emission of the resulting negatively charged excitons.