Unnatural Hygroscopic Property of Nicotinic Acid by Restructuring Molecular Density: Self-Healing Halide Perovskites.

An unnatural hygroscopic property of nonhygroscopic nicotinic acid (NA) is demonstrated by tuning the intermolecular distance. After addition of NA into methylammonium lead iodide, (MAPbI3) NA molecules are preferentially aligned on the interface of the three-dimensional (3D) MAPbI3 crystal structure by a hydrogen bond. This unique behavior allows NA to be used as a versatile additive to improve the water durability of MAPbI3. After exposure under a high humidity atmosphere (RH 100%, 35 °C), MAPbI3 films with NA exhibited self-healing phenomena against moisture while bare MAPbI3 rapidly lost its own intrinsic property. Density functional theory (DFT) calculations were conducted to reveal how H2O molecules can effectively be absorbed by NA according to its planar molecular density. Also, further optimization of photovoltaic device performances was carried out by investigating the relationship between NA concentration and additive alignment.

Polarization-Dependent Photoluminescence of a Highly (100)-Oriented Perovskite Film.

Lead halide perovskite is one of the attractive functional materials owing to its outstanding opto-electronic properties, which have been addressed in numerous studies. This study aims to clarify the link between the growth pattern and the charge carrier related properties for the highly oriented perovskite film along the [100] direction. For this purpose, a CH3 NH3 PbI3 thin film mainly grown along the [100] direction was fabricated and subjected to spectroscopic analysis to understand the basic optoelectronic features of the oriented film. A perovskite film with random growth was also fabricated for comparison. In particular, results from excitation polarization photoluminescence spectroscopy (ExPPS) revealed that the orientation of transition dipole moment, which is relevant to the anisotropic property of the film, is attributed to the growth direction of the perovskite film. This study suggests that the absorption anisotropy can affect the anisotropy in properties of the perovskite device. Furthermore, photodetectors with the perovskite films were fabricated to investigate the effect of growth direction on the photodetector performances, revealing that a photodetector with the oriented perovskite film showed larger photoresponses. In order to provide an explanation for such result, we performed a PL lifetime imaging study of the oriented and randomly grown perovskite films.

Surface-2D/Bulk-3D Heterophased Perovskite Nanograins for Long-Term-Stable Light-Emitting Diodes.

Although metal halide perovskite (MHP) light-emitting diodes (LEDs) have demonstrated great potential in terms of electroluminescence efficiency, the operational stability of MHP LEDs currently remains the biggest bottleneck toward their practical usage. Well-confined excitons/charge carriers in a dielectric/quantum well based on conventional spatial or potential confinement approaches substantially enhance radiative recombination in MHPs, but an increased surface-to-volume ratio and multiphase interfaces likely result in a high degree of surface or interface defect states, which brings about a critical environmentally/operationally vulnerable point on LED stability. Here, an effective solution is suggested to mitigate such drawbacks using strategically designed surface-2D/bulk-3D heterophased MHP nanograins for long-term-stable LEDs. The 2D surface-functionalized MHP renders significantly reduced trap density, environmental stability, and an ion-migration-immune surface in addition to a fast radiative recombination owing to its spatially and potentially confined charge carriers, simultaneously. As a result, heterophased MHP LEDs show substantial improvement in operational lifetime (T50 : >200 h) compared to conventional pure 3D or quasi-2D counterparts (T50 : < 0.2 h) as well as electroluminescence efficiency (surface-2D/bulk-3D: ≈7.70 ph per el% and pure 3D: ≈0.46 ph per el%).

Light Emission Enhancement by Tuning the Structural Phase of APbBr3 (A = CH3NH3, Cs) Perovskites.

Lead halide perovskite (APbX3) has recently emerged as a promising active layer in light-emitting diodes (LEDs) as well as an absorber for photovoltaic devices. For better LED properties, it is important to understand the fundamental mechanism of the optoelectronic behaviors, e.g., how the nanostructure of the APbX3 thin film correlates with its emitting properties. We investigated the effect of APbBr3 (A = CH3NH3, Cs) crystallite size on the photophysical properties regarding its crystallographic changes and spin-orbit coupling. Photoluminescence lifetime measurements, X-ray and electron diffraction analyses, and density functional theory calculations were performed. We demonstrate that the emitting properties of mesoscale APbBr3 crystallites are improved due to the formation of a pure cubic phase that leads to the spin- and momentum-allowed carrier recombination. Our findings provide fundamental insights into the emitting behavior of APbBr3, which suggests a control of its optoelectronic properties by means of modulating the crystal morphology and resultant electronic band structures.

Halide Perovskite Nanopillar Photodetector.

Numerous studies have reported the use of halide perovskites as highly functional light-harvesting materials. The development of optimized compositions and deposition approaches has led to impressive improvements; however, no noticeable breakthrough in performance has been observed for these materials recently. Here, a breakthrough that enables the fabrication of vertically grown halide perovskite (VGHP) nanopillar photodetectors via a nanoimprinting crystallization technique is demonstrated. We used engraved nanopatterned polymer stamps to form VGHP nanopillars during the pressurized crystallization of the softly baked gel state of a methylammonium lead iodide (CH3NH3PbI3, denoted MAPI) film. The VGHP films exhibit much lower defect density and higher conductivity, as supported by current-voltage characteristic measurements and conductive atomic force microscopy measurements. Ultimately, two-terminal lateral photodetectors based on the VGHP nanopillar films show a greatly enhanced photoresponse compared with flat film-based photodetectors. We expect that the deposition method presented here will help surpass the technical limits and contribute to further improvements in various halide-perovskite-based devices.

Unveiling the Crystal Formation of Cesium Lead Mixed-Halide Perovskites for Efficient and Stable Solar Cells.

Thermal instability of organic-inorganic hybrid perovskites will be an inevitable hurdle for commercialization. Recently, all-inorganic cesium lead halide perovskites, in particular, CsPbI2Br, have emerged as thermally stable and efficient photovoltaic light absorbers. However, the fundamental properties of this material have not been studied in detail. The crystal formation behavior of CsPbI2Br is investigated by examining the surface morphology, crystal structure, and chemical state of the perovskite films. We discover a previously uncharacterized feature that the formation of black polymorph through optimal annealing temperature proves to be critical to both solar cell efficiency and phase stability. Our optimized planar heterojunction solar cell exhibits a J-V scan efficiency of 10.7% and open-circuit voltage of 1.23 V, which far outperforms the preceding literature.

In-Situ Formed Type I Nanocrystalline Perovskite Film for Highly Efficient Light-Emitting Diode.

Excellent color purity with a tunable band gap renders organic-inorganic halide perovskite highly capable of performing as light-emitting diodes (LEDs). Perovskite nanocrystals show a photoluminescence quantum yield exceeding 90%, which, however, decreases to lower than 20% upon formation of a thin film. The limited photoluminescence quantum yield of a perovskite thin film has been a formidable obstacle for development of highly efficient perovskite LEDs. Here, we report a method for highly luminescent MAPbBr3 (MA = CH3NH3) nanocrystals formed in situ in a thin film based on nonstoichiometric adduct and solvent-vacuum drying approaches. Excess MABr with respect to PbBr2 in precursor solution plays a critical role in inhibiting crystal growth of MAPbBr3, thereby forming nanocrystals and creating type I band alignment with core MAPbBr3 by embedding MAPbBr3 nanocrystals in the unreacted wider band gap MABr. A solvent-vacuum drying process was developed to preserve nanocrystals in the film, which realizes a fast photoluminescence lifetime of 3.9 ns along with negligible trapping processes. Based on a highly luminescent nanocrystalline MAPbBr3 thin film, a highly efficient green LED with a maximum external quantum efficiency of 8.21% and a current efficiency of 34.46 cd/A was demonstrated.

Potassium Incorporation for Enhanced Performance and Stability of Fully Inorganic Cesium Lead Halide Perovskite Solar Cells.

Thermally unstable nature of hybrid organic-inorganic perovskites has been a major obstacle to fabricating the long-term operational device. A cesium lead halide perovskite has been suggested as an alternative light absorber, due to its superb thermal stability. However, the phase instability and poor performance are hindering the further progress. Here, cesium lead halide perovskite solar cells with enhanced performance and stability are demonstrated via incorporating potassium cations. Based on Cs0.925K0.075PbI2Br, the planar-architecture device achieves a power conversion efficiency of 10.0%, which is a remarkable record in the field of inorganic perovskite solar cells. In addition, the device shows an extended operational lifetime against air. Our research will stimulate the development of cesium lead halide perovskite materials for next-generation photovoltaics.

ß-Functionalized Push-Pull Porphyrin Sensitizers in Dye-Sensitized Solar Cells: Effect of π-Conjugated Spacers.

A series of new ß-functionalized push-pull-structured porphyrin dyes were synthesized so as to investigate the effect of the π-conjugated spacer on the performance of dye-sensitized solar cells (DSSCs). Suzuki- and Heck-type palladium-catalyzed coupling methodologies were used to obtain various ß-functionalized porphyrins and ß-benzoic acid (ZnPHn) and ß-vinylbenzoic acid (ZnPVn) derivatives from ß-borylated porphyrin precursors. Photophysical studies of the resulting porphyrins revealed a clear dependence on the nature of the ß linker. In particular, it was found that a ß-vinylene linkage perturbs the electronic structure of the porphyrin core; this is less true for a ß-phenyl linkage. Theoretical analyses provided support for the intrinsic intramolecular charge-transfer character of the ß-functionalized, push-pull porphyrins of this study. The extent of charge transfer depends on the nature of the ß-conjugated linkage. The photovoltaic performances of the cells sensitized with ß-phenylenevinylene ZnPVn exhibited higher power conversion efficiency values than those bearing ß-phenyl linkages (ZnPHn). This was ascribed to differences in light-harvesting efficiency. Furthermore, compared to the use of a standard iodine-based electrolyte, the DSSC performance of cells made from the present porphyrins was improved by more than 1 % upon using a cobalt(II/III)-based electrolyte. Under standard AM 1.5 illumination, the highest efficiency, 8.2 %, was obtained by using cells made from the doubly ß-butadiene-linked porphyrin.