Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals

Methylammonium lead iodide perovskite (MAPbI_3) exhibits long charge carrier lifetimes that are linked to its high efficiency in solar cells. Yet, the mechanisms governing these unusual carrier dynamics are not completely understood. A leading hypothesis—disproved in this work—is that a large, static bulk Rashba effect slows down carrier recombination. Here, using second harmonic generation rotational anisotropy measurements on MAPbI_3 crystals, we demonstrate that the bulk structure of tetragonal MAPbI_3 is centrosymmetric with I4/mcmspace group. Our calculations show that a significant Rashba splitting in the bandstructure requires a non-centrosymmetric lead iodide framework, and that incorrect structural relaxations are responsible for the previously predicted large Rashba effect. The small Rashba splitting allows us to compute effective masses in excellent agreement with experiment. Our findings rule out the presence of a large static Rashba effect in bulk MAPbI_3, and our measurements find no evidence of dynamic Rashba effects

Solvent-dependent dual fluorescence of the push–pull system 2-diethylamino-7-nitrofluorene

The solvent-dependent excited state behavior of the molecular push-pull system 2-diethylamino-7-nitrofluorene has been explored using femtosecond transient absorption spectroscopy in combination with density functional theory calculations. Several excited state minima have been identified computationally, all possessing significant intramolecular charge transfer character. The experimentally observed dual fluorescence is suggested to arise from a planar excited state minimum and another minimum reached by twisting of the aryl-nitrogen bond of the amino group. The majority of the excited state population, however, undergo non-radiative transitions and potential excited deactivation pathways are assessed in the computational investigation. A third excited state conformer, characterized by twisting around the aryl-nitrogen bond of the nitro group, is reasoned to be responsible for the majority of the non-radiative decays and a crossing between the excited state and ground state is localized. Additionally, ultrafast intersystem crossing is observed in the apolar solvent cyclohexane and rationalized to occur via an El-Sayed assisted transition from one of the identified excited state minima. The solvent thus determines more than just the fluorescence lifetime and shapes the potential energy landscape, thereby dictating the available excited state pathways

Temperature-induced lattice relaxation of perovskite crystal enhances optoelectronic properties and solar cell performance

Hybrid organic-inorganic perovskite crystals have recently become one of the most important classes of photoactive materials in the solar cell and optoelectronic communities. Albeit improvements focused on state-of-the-art technology including various fabrication methods, device architectures, and surface passivation, progress is yet to be made in understanding the actual operational temperature on the electronic properties and the device performances. The substantial effect of temperature on the optoelectronic properties, charge separation, charge recombination dynamics and photoconversion efficiency (PCE) are explored. The results clearly demonstrated a significant enhancement in the carrier mobility, photocurrent, charge carrier lifetime and solar cell performance in the 60±5 °C temperature range. In this temperature range, perovskite crystal exhibits a highly symmetrical relaxed cubic structure with well-aligned domains that are perpendicular to a principal axis, thereby remarkably improving the device operation. This finding provides a new key variable component and paves the way towards using perovskite crystals in highly efficient photovoltaic cells

Giant Photoluminescence Enhancement in CsPbCl<inf>3</inf> Perovskite Nanocrystals by Simultaneous Dual-Surface Passivation

The presence of localized trap states on the surface of CsPbCl3 perovskite nanocrystals (NCs) is one of the greatest challenges precluding the development of optoelectronic applications of these NCs. Passivation of these defect sites provides a promising pathway to remediating their electronic and optical properties, such as the photoluminescence quantum yield (PLQY). Herein, we demonstrate a postsynthetic dual-surface treatment using trivalent metal ion salts, i.e., YCl3, as a new passivation approach that enhances the PLQY up to 60% while preserving the NC size and crystal structure. Such remarkable enhancement of the PLQY along with prolongation of the average PL lifetimes of treated NCs samples indicates effective passivation of the surface defects and subsequent suppression of the formation of surface nonradiative recombination centers. As a segue toward optoelectronic applications, we probed the photoelectric performance of the NCs using ultraflexible devices; we found that YCl3-treated CsPbCl3 NC films exhibit an order of magnitude larger photocurrent compared to their nontreated counterparts. Our experimental and theoretical results provide an insightful understanding of the effective passivating roles of Y3+ and Cl- ions on the surface of CsPbCl3 NCs, as well as offering a new path to synthesize high-quality NCs for UV light conversion applications

How Humidity and Light Exposure Change the Photophysics of Metal Halide Perovskite Solar Cells

Metal halide perovskites exhibit outstanding optical and electronic properties, but are very sensitive to humidity and light-soaking. In this work, the photophysics of perovskites that have been exposed to such conditions are studied and, in this context, the impact of excess lead iodide (PbI2) is revealed. For exposed samples, the formation of subbandgap states and increased trap-assisted recombination is observed, using highly sensitive absorption and time-resolved photoluminescence (TRPL) measurements, respectively. It appears that such exposure primarily affects the perovskite surface. Consequently, on n–i–p device level, the spiro-OMeTAD/perovskite interface is more rapidly affected than its buried electron-collecting interface. Moreover, both stoichiometric and nonstoichiometric MAPbI3-based solar cells show reduced device performance mainly due to voltage losses. Overall, this study brings forward key points to consider in engineering perovskite solar cells with improved performance and material stability

Ultralow Self-Doping in Two-dimensional Hybrid Perovskite Single Crystals

Unintentional self-doping in semiconductors through shallow defects is detrimental to optoelectronic device performance. It adversely affects junction properties and it introduces electronic noise. This is especially acute for solution-processed semiconductors, including hybrid perovskites, which are usually high in defects due to rapid crystallization. Here, we uncover extremely low self-doping concentrations in single crystals of the two-dimensional perovskites (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1 (n = 1, 2, and 3), over three orders of magnitude lower than those of typical three-dimensional hybrid perovskites, by analyzing their conductivity behavior. We propose that crystallization of hybrid perovskites containing large organic cations suppresses defect formation and thus favors a low self-doping level. To exemplify the benefits of this effect, we demonstrate extraordinarily high light-detectivity (1013 Jones) in (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1 photoconductors due to the reduced electronic noise, which makes them particularly attractive for the detection of weak light signals. Furthermore, the low self-doping concentration reduces the equilibrium charge carrier concentration in (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1, advantageous in the design of p-i-n heterojunction solar cells by optimizing band alignment and promoting carrier depletion in the intrinsic perovskite layer, thereby enhancing charge extraction

Double charged surface layers in lead halide perovskite crystals

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrate that the surface layers of the perovskite crystals may acquire a high concentration of positively charged halide vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near to the surface generate an electric field that can induce a shift in the optical band gap of the surface layers to higher energy compared to the bulk counterpart. We found that the charge separation, electric field and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskites crystals. Our findings reveal the peculiarity of surface effects that is currently limiting the application of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them