Benzyl Alcohol-Treated CH3NH3PbBr3 Nanocrystals Exhibiting High Luminescence, Stability, and Ultralow Amplified Spontaneous Emission Thresholds.

We report the high yield synthesis of about 11 nm sized CH3NH3PbBr3 nanocrystals with near-unity photoluminescence quantum yield. The nanocrystals are formed in the presence of surface-binding ligands through their direct precipitation in a benzyl alcohol/toluene phase. The benzyl alcohol plays a pivotal role in steering the surface ligands binding motifs on the NC surface, resulting in enhanced surface-trap passivation and near-unity PLQY values. We further demonstrate that thin films from purified CH3NH3PbBr3 nanocrystals are stable >4 months in air, exhibit high optical gain (about 520 cm-1), and display stable, ultralow amplified spontaneous emission thresholds of 13.9 ± 1.3 and 569.7 ± 6 µJ cm-2 at one-photon (400 nm) and two-photon (800 nm) absorption, respectively. To the best of our knowledge, the latter signifies a 5-fold reduction of the lowest reported threshold value for halide perovskite nanocrystals to date, which makes them ideal candidates for light-emitting and low-threshold lasing applications.

Understanding the Origins of Nucleophilic Hydride Reactivity of a Sodium Hydride-Iodide Composite.

Sodium hydride (NaH) has been commonly used as a Brønsted base in chemical syntheses, while it has rarely been employed to add hydride (H(-) ) to unsaturated electrophiles. We previously developed a procedure to activate NaH through the addition of a soluble iodide source and found that the new NaH-NaI composite can effect even stereoselective nucleophilic hydride reductions of nitriles, imines, and carbonyl compounds. In this work, we report that mixing NaH with NaI or LiI in tetrahydrofuran (THF) as a solvent provides a new inorganic composite, which consists of NaI interspersed with activated NaH, as revealed by powder X-ray diffraction, and both solid-state NMR and X-ray photoelectron spectroscopies. DFT calculations imply that this remarkably simple inorganic composite, which is comprised of NaH and NaI, gains nucleophilic hydridic character similar to covalent hydrides, resulting in unprecedented and unique hydride donor chemical reactivity.

Inducing Isotropic Growth in Multidimensional Cesium Lead Halide Perovskite Nanocrystals.

A new two-step synthetic protocol to yield monodisperse spherical zero-dimensional (0D) Cs4 PbX6 nanocrystals (NCs) and three-dimensional (3D) CsPbX3 NCs is described. The first step of the reaction involves the colloidal synthesis of spherical PbX2 seed NCs, which are subsequently converted to Cs4 PbX6 and CsPbX3 NCs through hot injection of a Cs precursor at the desired reaction temperatures. By employing less reactive Pb and halide precursors, the reaction time was extended from several seconds to about five minutes, thereby allowing greater control during the crystallization and growth stages. The adjustment of halide ratios allows color tuning over a wide spectral range (411-669 nm) for CsPbX3 NCs, with high photoluminescence quantum yields (6-65 %) and narrow emission line widths (ca. 13-30 nm). We envisage our spherical NCs to become a starting point for shell growth (e.g., ZnS, CdS, PbS) by overcoming the difficulty of shell growth around thermodynamically unfavorable (i.e., high surface free energy) cuboid-shaped NCs.

Enhanced Exciton and Photon Confinement in Ruddlesden-Popper Perovskite Microplatelets for Highly Stable Low-Threshold Polarized Lasing.

At the heart of electrically driven semiconductors lasers lies their gain medium that typically comprises epitaxially grown double heterostuctures or multiple quantum wells. The simultaneous spatial confinement of charge carriers and photons afforded by the smaller bandgaps and higher refractive index of the active layers as compared to the cladding layers in these structures is essential for the optical-gain enhancement favorable for device operation. Emulating these inorganic gain media, superb properties of highly stable low-threshold (as low as ≈8 µJ cm-2 ) linearly polarized lasing from solution-processed Ruddlesden-Popper (RP) perovskite microplatelets are realized. Detailed investigations using microarea transient spectroscopies together with finite-difference time-domain simulations validate that the mixed lower-dimensional RP perovskites (functioning as cladding layers) within the microplatelets provide both enhanced exciton and photon confinement for the higher-dimensional RP perovskites (functioning as the active gain media). Furthermore, structure-lasing-threshold relationship (i.e., correlating the content of lower-dimensional RP perovskites in a single microplatelet) vital for design and performance optimization is established. Dual-wavelength lasing from these quasi-2D RP perovskite microplatelets can also be achieved. These unique properties distinguish RP perovskite microplatelets as a new family of self-assembled multilayer planar waveguide gain media favorable for developing efficient lasers.

Highly stable, luminescent core-shell type methylammonium-octylammonium lead bromide layered perovskite nanoparticles.

A new protocol for the synthesis of a highly stable (over 2 months under ambient conditions) solution-processed core-shell type structure of mixed methylammonium-octylammonium lead bromide perovskite nanoparticles (5-12 nm), having spherical shape, color tunability in the blue to green spectral region (438-521 nm) and a high photoluminescence quantum yield (PLQY) of up to 92% is described. The color tunability, high PLQY and stability are due to the quantum confinement imparted by the crystal engineering associated with core-shell nanoparticle formation during growth.