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Metal halide perovskites exhibit intriguing properties for optoelectronic and electronic applications. Understanding their intrinsic photoexcitation and band‐tail dynamics is essential for exploring novel functionality and improving device performance. This report addresses the band‐tail luminescence of lead bromide perovskite (APbBr3) single crystals, where A is methylammonium, formamidinium, and cesium. Using time‐resolved photoluminescence (PL) spectroscopy, the dynamics of well‐defined dual emission peaks are unambiguously resolved from the picosecond to the microsecond scale. Whereas the long‐lived states exhibit similar recombination dynamics at high temperatures, a clear, fast transition occurs between the high and low energy states at low temperatures, indicating direct communication between these two states. These time‐resolved PL spectra shed light on the intrinsic optical properties of metal halide perovskites. [ABSTRACT FROM AUTHOR]

Low‐dimensional halide perovskites with broad emission are a hot topic for their promising application as white light sources. However, the physical origin of this broadband emission in the sub‐bandgap region is still controversial. This work investigates the broad Stokes‐shifted emission bands in mixed lead‐tin 2D perovskite films prepared by mixing precursor solutions of phenethylammonium lead iodide (PEA2PbI4, PEA = phenethylammonium) and phenethylammonium tin iodide (PEA2SnI4). The bandgap can be tuned by the lead‐tin ratio, whereas the photoluminescence is broad and significantly Stokes‐shifted and appears to be fairly insensitive to the relative amount of Pb and Sn. It is experimentally observed that these low‐dimensional systems show substantially less bandgap bowing than their 3D counterpart. Theoretically, this can be attributed to the smaller spin–orbit coupling effect on the 2D perovskites compared to that of 3D ones. The time‐resolved photoluminescence shows an ultrafast decay in the high‐energy range of the spectra that coincides with the emission range of PEA2SnI4, while the broadband emission decay is slower, up to the microsecond range. Sub‐gap photoexcitation experiments exclude exciton self‐trapping as the origin of the broadband emission, pointing to defects as the origin of the broadband emission in 2D Sn/Pb perovskite alloys. [ABSTRACT FROM AUTHOR]

2D perovskites offers a rich playing field to explore exciton physics and they possess a great potential for a variety of opto‐electronic applications. Whilst their photophysics shows intricate interactions of excitons with the lattice, most reports have so far relied on single compound studies. With the exception of variations of the organic spacer cations, the effect of constituent substitution on the photophysics and the nature of emitting species, in particular, have remained largely under‐explored. Here PEA2PbBr4, PEA2PbI4, and PEA2SnI4 (where PEA stands for phenylethylammonoium) are studied through a variety of optical spectroscopy techniques to reveal a complex set of excitonic transitions at low temperature. Weak high‐energy features are attributed to vibronic transitions breaking Kasha's, for which the responsible phonons cannot be accessed through simple Raman spectroscopy. Bright peaks at lower energy are due to two distinct electronic states, of which the upper is a convolution of the free exciton and a localized dark state and the lower is attributed to recombination involving shallow defects. This study offers deeper insights into the photophysics of 2D perovskites through compositional substitution and highlights critical limits to the communities' current understanding of processes in these compounds. [ABSTRACT FROM AUTHOR]

The stability of the active layer is an underinvestigated aspect of metal halide perovskite solar cells. Furthermore, the few articles on the subject are typically focused on thin films, which are complicated by the presence of defects and grain boundaries. Herein, a different approach is taken: a perovskite composition that is known to be stable in single crystal form is used, and its (photo‐)physical properties are studied in the form of spin‐coated thin films. The perovskites are lead‐based with cesium and formamidinium as the A‐site cations and iodide and bromide as the halide anions, with the formula Cs0.1FA0.9PbI3−xBrx. These compounds show high potential in terms of stability in single crystal form and closely resemble the compounds that have successfully been used in highly efficient perovskite–silicon tandem solar cells. It is found that a small difference in bromine content (x = 0.45 vs 0.6) has a significant impact in terms of the phase purity and charge carrier lifetimes, and conclude that the thin films of Cs0.1FA0.9PbI2.55Br0.45 have good potential for the use in optoelectronic devices. [ABSTRACT FROM AUTHOR]

Hybrid organic-inorganic perovskites are semiconductors that have great potential for optoelectronic applications such as light-emitting diodes, photodetectors, and solar cells. In such devices, the surface plays a crucial role in the performance and stability, as it strongly influences the recombination rate of excited charge carriers. It is reported that molecular ligands such as benzylamine are capable of reducing the surface trap state density in thin films. In this work, we aim to clarify the mechanisms that govern the surface passivation of hybrid perovskites by benzylamine. We developed a versatile approach to investigate the influence of benzylamine passivation on the well-defined surface of freshly cleaved hybrid perovskite crystals. We show that benzylamine permanently passivates surface trap states in these single crystals, resulting in enhanced photoluminescence and charge carrier lifetimes. Additionally, we show that exposure to benzylamine leads to the replacement of the methylammonium cations by benzylammonium, thereby creating a thermodynamically more stable two-dimensional (2D) perovskite (BA)2PbBr4 on the surface of the three-dimensional crystal. This conversion to a 2D perovskite drives an anisotropic etching of the crystal surface, with the {100} planes being most prone to etching. Initially, square etching pits appear spread over the surface. As time elapses, these etching pits broaden and merge to yield large flat terraces that are oriented normally to the cleaving plane when they form. A thorough understanding of the mechanisms governing the surface passivation is crucially important to optimize and design novel passivation schemes, with the ultimate goal of further advancing the efficiency of optoelectronic devices based on hybrid perovskites. [ABSTRACT FROM AUTHOR]

Abstract: Wide bandgap (WB) organic–inorganic hybrid perovskites (OIHPs) with a bandgap ranging between 1.7 and 2.0 eV have shown great potential to improve the efficiency of single‐junction silicon or thin‐film solar cells by forming a tandem structure with one of these cells or with a narrow bandgap perovskite cell. However, WB‐OIHPs suffer from a large open‐circuit voltage (Voc) deficit in photovoltaic devices, which is associated with the phase segregation of the materials under light illumination. In this work the photoinstability is demonstrated and Voc loss can be addressed by combining grain crystallization and grain boundary passivation, achieved simultaneously through tuning of perovskite precursor composition. Using FA0.17Cs0.83PbI3–xBrx (x = 0.8, 1.2 1.5, and 1.8), with a varied bandgap from 1.72 to 1.93 eV, as the model system it is illustrated how precursor additive Pb(SCN)2 should be matched with a proper ratio of FAX (I and Br) to realize large grains with defect‐healed grain boundaries. The optimized WB‐OIHPs show good photostability at both room‐temperature and elevated temperature. Moreover, the corresponding solar cells exhibit excellent photovoltaic performances with the champion Voc/stabilized power output efficiency reaching 1.244 V/18.60%, 1.284 V/16.51%, 1.296 V/15.01%, and 1.312 V/14.35% for WB‐OIHPs with x = 0.8, 1.2, 1.5, and 1.8, respectively. [ABSTRACT FROM AUTHOR]

Abstract: The low power conversion efficiency (PCE) of tin‐based hybrid perovskite solar cells (HPSCs) is mainly attributed to the high background carrier density due to a high density of intrinsic defects such as Sn vacancies and oxidized species (Sn4+) that characterize Sn‐based HPSCs. Herein, this study reports on the successful reduction of the background carrier density by more than one order of magnitude by depositing near‐single‐crystalline formamidinium tin iodide (FASnI3) films with the orthorhombic a‐axis in the out‐of‐plane direction. Using these highly crystalline films, obtained by mixing a very small amount (0.08 m) of layered (2D) Sn perovskite with 0.92 m (3D) FASnI3, for the first time a PCE as high as 9.0% in a planar p–i–n device structure is achieved. These devices display negligible hysteresis and light soaking, as they benefit from very low trap‐assisted recombination, low shunt losses, and more efficient charge collection. This represents a 50% improvement in PCE compared to the best reference cell based on a pure FASnI3 film using SnF2 as a reducing agent. Moreover, the 2D/3D‐based HPSCs show considerable improved stability due to the enhanced robustness of the perovskite film compared to the reference cell. [ABSTRACT FROM AUTHOR]

Mixed iodide-bromide organolead perovskites with a bandgap of 1.70-1.80 eV have great potential to boost the efficiency of current silicon solar cells by forming a perovskite-silicon tandem structure. Yet, the stability of the perovskites under various application conditions, and in particular combined light and heat stress, is not well studied. Here, FA0.15Cs0.85Pb(I0.73Br0.27)3, with an optical bandgap of ≈1.72 eV, is used as a model system to investigate the thermal-photostability of wide-bandgap mixed halide perovskites. It is found that the concerted effect of heat and light can induce both phase segregation and decomposition in a pristine perovskite film. On the other hand, through a postdeposition film treatment with benzylamine (BA) molecules, the highly defective regions (e.g., film surface and grain boundaries) of the film can be well passivated, thus preventing the progression of decomposition or phase segregation in the film. Besides the stability improvement, the BA-modified perovskite solar cells also exhibit excellent photovoltaic performance, with the champion device reaching a power conversion efficiency of 18.1%, a stabilized power output efficiency of 17.1% and an open-circuit voltage ( Voc) of 1.24 V. [ABSTRACT FROM AUTHOR]

The mechanism behind the temperature dependence of the device performance in hybrid perovskite solar cells (HPSCs) is investigated systematically. The power conversion efficiency (PCE) of the reference cell using [60]PCBM as electron extraction layer (EEL) drops significantly from 11.9% at 295 K to 7% at 180 K. The deteriorated charge carrier extraction is found as the dominant factor causing this degradation. Temperature dependent spectroscopy and charge transport studies demonstrate that the poor electron transport in the [60]PCBM EEL at low temperature leads to inefficient charge carrier extraction. It is further demonstrated that the n-type doping of [60]PCBM EEL or the use of an EEL (fulleropyrrolidine with a triethylene glycol monoethyl ether side chain) with higher electron transport capability is an effective strategy to achieve HPSCs working efficiently over a broad temperature range. The devices fabricated with these highly performing EELs have PCEs at 180 K of 16.7% and 18.2%, respectively. These results support the idea that the temperature dependence of the electron transport in the EELs limits the device performance in HPSCs, especially at lower temperatures and they also give directions toward further improvement of the PCE of HPSCs at realistic operating temperatures. [ABSTRACT FROM AUTHOR]

The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as broad tunability of bandgap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity (narrow full-width at half maximum). In this review, the photophysical properties of hybrid perovskites, which relates with light-emission, such as broad tunability, nature of the recombination processes and quantum efficiency are examined. The prospects of hybrid perovskite light-emitting diodes and lasers, and their key challenges are also discussed. [ABSTRACT FROM AUTHOR]

Despite the rich experience gained in controlling the microstructure of perovskite films over the past several years, little is known about how the microstructure affects the device properties of perovskite solar cells (HPSCs). In this work, the effects of the perovskite film microstructure on the charge recombination and light-soaking phenomenon in mixed halide HPSCs are investigated. Devices with noncompact perovskite morphology show a severe light soaking effect, with the power conversion efficiency (PCE) improved from 3.7% to 11.6% after light soaking. Devices with compact perovskite morphology show a negligible light soaking effect, with PCE slightly increased from 11.4% to 11.9% after light soaking. From device investigations, photoluminescence, and impedance spectroscopy measurements, it is demonstrated that interface electron traps at the grain boundaries as well as at the crystal surface dominate the light soaking effect. Severe trap-assisted recombination takes place in HPSCs using noncompact films, while it is effectively eliminated in devices with compact films. Moreover, how the grain size of the perovskite film affects the light soaking phenomenon is investigated. In the case of compact perovskite films, the size of the grains has a limited effect on the light soaking. In these compact films, grains are fused and trap states are effectively reduced. [ABSTRACT FROM AUTHOR]

Formamidinium lead iodide (FAPbI3) has a broader absorption spectrum and better thermal stability than the most famous methylammonium lead iodide, thus exhibiting great potential for photovoltaic applications. In this report, the light-induced photoluminescence (PL) evolution in FAPbI3 thin films is investigated. The PL intensity evolution is found to be strongly dependent on the atmosphere surrounding the samples. When the film is exposed to air, its photoluminescence intensity is enhanced more than 140 times after continuous ultraviolet laser illumination for 2 h, and the average lifetime is prolonged from 17 to 389 ns. The enhanced photoluminescence implies that the trap density is significantly reduced. The comparative study of the photoluminescence properties in air, nitrogen, and oxygen/helium environment suggests that moisture is important for the PL enhancement. This is explained in terms of moisture-assisted light-healing effect in FAPbI3 thin films. With this study, a new method is demonstrated to increase and control the quality of hybrid perovskite thin films. [ABSTRACT FROM AUTHOR]

Hybrid perovskite solar cells have attracted an unprecedented research attention due to their skyrocketing record power conversion efficiency (PCE), which now exceeds 23% in less than a decade from the initial PCE of 3.8%. Besides the excellent optoelectronic properties of the perovskite absorbers, the high efficiencies are also dependent on preparation methods and advanced device engineering. In this study, the role of the device architecture (planar n‐i‐p vs inverted p‐i‐n structure) and of the charge‐selective interlayer on the photophysical properties of the perovskite absorber and device performance are explored. FA0.85MA0.15PbBr0.45I2.55 (MA = methylammonium, FA = formamidinium) as the perovskite absorber and chloride‐capped TiO2 colloidal nanocrystals (TiO2‐Cl) and poly(3,4‐ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as close‐to‐the‐substrate layers in the conventional and inverted structures are employed, respectively. Extremely different device performances are demonstrated by the two structures. The device where the active layer is deposited on TiO2‐Cl displays a champion PCE of 19.9%, while the one using PEDOT:PSS gives about 15.1% efficiency. The photophysical and electrical investigations indicate that the TiO2‐Cl/perovskite interface has lower number of traps, underlining the importance of interfaces for achieving highly performing perovskite solar cells. This study highlights the importance of device architecture and interfaces in planar hybrid perovskite solar cells on device performance. The device based on the conventional structure gives better power conversion efficiency (PCE) of 19.9% in comparison to the inverted structure with PCE of 15.1%. The extreme difference in performance is due to perovskite film morphology and interface traps. [ABSTRACT FROM AUTHOR]

In article number 1701305, Maria Antonietta Loi and co‐workers show that the electron transport capability of the electron‐extracting layer dominates the temperature dependence of the performance of hybrid perovskite solar cells. The authors further demonstrate efficient hybrid perovskite solar cells over a temperature range from 295 K to 160 K by n‐doping the PCBM electron‐extracting layer or using a fullerene derivative with intrinsically higher electron transport capability. [ABSTRACT FROM AUTHOR]

On page 4653, N. Zhao, M. A. Loi, and co‐workers report a giant light‐induced enhancement of the photoluminescence intensity in formamidinium lead iodide perovskite thin films. They demonstrate that the “brightening” of the perovskite can be attributed to a moisture‐assisted light‐healing effect, which can be potentially used to increase and control the quality of hybrid perovskite thin films. [ABSTRACT FROM AUTHOR]