Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites

The remarkable performance of hybrid perovskite photovoltaics is attributed to their long carrier lifetimes and high photoluminescence (PL) efficiencies. High-quality films are associated with slower PL decays, and it has been claimed that grain boundaries have a negligible impact on performance. We used confocal fluorescence microscopy correlated with scanning electron microscopy to spatially resolve the PL decay dynamics from films of nonstoichiometric organic-inorganic perovskites, CH3NH3PbI3(Cl). The PL intensities and lifetimes varied between different grains in the same film, even for films that exhibited long bulk lifetimes. The grain boundaries were dimmer and exhibited faster nonradiative decay. Energy-dispersive x-ray spectroscopy showed a positive correlation between chlorine concentration and regions of brighter PL, whereas PL imaging revealed that chemical treatment with pyridine could activate previously dark grains. Copyright © 2015, American Association for the Advancement of Science.

Organic-inorganic hybrid materials promise both the superior carrier mobility of inorganic semiconductors and the processability of organic materials. A thin-film field-effect transistor having an organic-inorganic hybrid material as the semiconducting channel was demonstrated. Hybrids based on the perovskite structure crystallize from solution to form oriented molecular-scale composites of alternating organic and inorganic sheets. Spin-coated thin films of the semiconducting perovskite (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4) form the conducting channel, with field-effect mobilities of 0.6 square centimeters per volt-second and current modulation greater than 10(4). Molecular engineering of the organic and inorganic components of the hybrids is expected to further improve device performance for low-cost thin-film transistors.

Recent discoveries of highly efficient solar cells based on lead iodide perovskites have led to a surge in research activity on understanding photo carrier generation in these materials, but little is known about trap states that may be detrimental to solar cell performance. Here we provide direct evidence for hole traps on the surfaces of three-dimensional (3D) CH3NH3PbI3 perovskite thin films and excitonic traps below the optical gaps in these materials. The excitonic traps possess weak optical transition strengths, can be populated from the relaxation of above gap excitations, and become more significant as dimensionality decreases from 3D CH3NH3PbI3 to two-dimensional (2D) (C4H9NH3I)2(CH3NH3I)(n-1)(PbI2)(n) (n = 1, 2, 3) perovskites and, within the 2D family, as n decreases from 3 to 1. We also show that the density of excitonic traps in CH3NH3PbI3 perovskite thin films grown in the presence of chloride is at least one-order of magnitude lower than that grown in the absence of chloride, thus explaining a widely known mystery on the much better solar cell performance of the former. The trap states are likely caused by electron-phonon coupling and are enhanced at surfaces/interfaces where the perovskite crystal structure is most susceptible to deformation.