Stabilization of Lead-Reduced Metal Halide Perovskite Nanocrystals by High-Entropy Alloying.

Colloidal metal halide perovskite (MHP) nanocrystals (NCs) are an emerging class of fluorescent quantum dots (QDs) for next-generation optoelectronics. A great hurdle hindering practical applications, however, is their high lead content, where most attempts addressing the challenge in the literature compromised the material's optical performance or colloidal stability. Here, we present a postsynthetic approach that stabilizes the lead-reduced MHP NCs through high-entropy alloying. Upon doping the NCs with multiple elements in considerably high concentrations, the resulting high-entropy perovskite (HEP) NCs remain to possess excellent colloidal stability and narrowband emission, with even higher photoluminescence (PL) quantum yields, ηPL, and shorter fluorescence lifetimes, τPL. The formation of multiple phases containing mixed interstitial and doping phases is suggested by X-ray crystallography. Importantly, the crystalline phases with higher degrees of lattice expansion and lattice contraction can be stabilized upon high-entropy alloying. We show that the lead content can be approximately reduced by up to 55% upon high-entropy alloying. The findings reported here make one big step closer to the commercialization of perovskite NCs.

Ligand-assisted solid phase synthesis of mixed-halide perovskite nanocrystals for color-pure and efficient electroluminescence.

Colloidal nanocrystals (NCs) of lead halide perovskites have generated considerable interest in the fabrication of optoelectronic devices, such as light emitting-diodes (LEDs), because of their tunable optical bandgap, narrow spectral width, and high defect tolerance. However, the inhomogeneous halide distribution within individual NCs remains a critical challenge in order to obtain color-stable electroluminescence in mixed-halide systems. Here, we demonstrate a new post-synthetic approach, ligand-assisted solid phase synthesis (LASPS), for the preparation of electroluminescent colloidal NCs of methylammonium (MA) lead halide perovskites, at room temperature. The slow reaction kinetics preserves the morphology, size, and shape in the resulting NCs whose emission covers the entire visible spectral region with photoluminescence (PL) quantum yields (QYs) of up to >90% and colloidal stability up to several months. The LEDs fabricated using the prepared mixed-halide NCs display narrowband electroluminescence (EL) ranging from 476 to 720 nm. The optimized red LEDs exhibit an external quantum efficiency, η ext, of up to 2.65%, with the CIE 1931 color coordinates of (0.705, 0.290), nearly identical to those of the red primary in the recommendation (rec.) 2020 standard (0.708, 0.292).

Unraveling the Growth Mechanism of Magic-Sized Semiconductor Nanocrystals.

Magic-sized clusters (MSCs) of semiconductor are typically defined as specific molecular-scale arrangements of atoms that exhibit enhanced stability. They often grow in discrete jumps, creating a series of crystallites, without the appearance of intermediate sizes. However, despite their long history, the mechanism behind their special stability and growth remains poorly understood. It is particularly difficult to explain experiments that have shown discrete evolution of MSCs to larger sizes well beyond the "cluster" regime and into the size range of colloidal quantum dots. Here, we study the growth of MSCs, including these larger magic-sized CdSe nanocrystals, to unravel the underlying growth mechanism. We first introduce a synthetic protocol that yields a series of nine magic-sized nanocrystals of increasing size. By investigating these crystallites, we obtain important clues about the mechanism. We then develop a microscopic model that uses classical nucleation theory to determine kinetic barriers and simulate the growth. We show that magic-sized nanocrystals are consistent with a series of zinc-blende crystallites that grow layer by layer under surface-reaction-limited conditions. They have a tetrahedral shape, which is preserved when a monolayer is added to any of its four identical facets, leading to a series of discrete nanocrystals with special stability. Our analysis also identifies strong similarities with the growth of semiconductor nanoplatelets, which we then exploit to further increase the size range of our magic-sized nanocrystals. Although we focus here on CdSe, these results reveal a fundamental growth mechanism that can provide a different approach to nearly monodisperse nanocrystals.

Scalable photonic sources using two-dimensional lead halide perovskite superlattices.

Miniaturized photonic sources based on semiconducting two-dimensional (2D) materials offer new technological opportunities beyond the modern III-V platforms. For example, the quantum-confined 2D electronic structure aligns the exciton transition dipole moment parallel to the surface plane, thereby outcoupling more light to air which gives rise to high-efficiency quantum optics and electroluminescent devices. It requires scalable materials and processes to create the decoupled multi-quantum-well superlattices, in which individual 2D material layers are isolated by atomically thin quantum barriers. Here, we report decoupled multi-quantum-well superlattices comprised of the colloidal quantum wells of lead halide perovskites, with unprecedentedly ultrathin quantum barriers that screen interlayer interactions within the range of 6.5 Å. Crystallographic and 2D k-space spectroscopic analysis reveals that the transition dipole moment orientation of bright excitons in the superlattices is predominantly in-plane and independent of stacking layer and quantum barrier thickness, confirming interlayer decoupling.

Understanding the Ligand Effects on Photophysical, Optical, and Electroluminescent Characteristics of Hybrid Lead Halide Perovskite Nanocrystal Solids.

There has been a tremendous amount of interest in developing high-efficiency light-emitting diodes (LEDs) based on colloidal nanocrystals (NCs) of hybrid lead halide perovskites. Here, we systematically investigate the ligand effects on EL characteristics by tuning the hydrophobicity of primary alkylamine ligands used in NC synthesis. By increasing the ligand hydrophobicity, we find (i) a reduced NC size that induces a higher degree of quantum confinement, (ii) a shortened exciton lifetime that increases the photoluminescence quantum yield, (iii) a lowering of refractive index that increases the light outcoupling efficiency, and (iv) an increased thin-film resistivity. Accordingly, ligand engineering allows us to demonstrate high-performance green LEDs exhibiting a maximum external quantum efficiency up to 16.2%. The device operational lifetime, defined by the time lasted when the device luminance reduces to 85% of its initial value, LT85, reaches 243 min at an initial luminance of 516 cd m-2.