Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

State of the Art and Prospects for Halide Perovskite Nanocrystals.

The large specific surface area of perovskite nanocrystals (NCs) increases the likelihood of surface defects compared to that of bulk single crystals and polycrystalline thin films. It is thus crucial to comprehend and control their defect population in order to exploit the potential of perovskite NCs. This Perspective describes and classifies recent advances in understanding defect chemistry and avenues toward defect density reduction in perovskite NCs, and it does so in the context of the promise perceived in light-emitting devices. Several pathways for decreasing the defect density are explored, including advanced NC syntheses, new surface-capping strategies, doping with metal ions and rare earths, engineering elemental compensation, and the translation of core-shell heterostructures into the perovskite materials family. We close with challenges that remain in perovskite NC defect research.

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Reducing Defects in Halide Perovskite Nanocrystals for Light-Emitting Applications

The surface of a semiconductor often has a key role in determining its properties. For metal halide perovskites, understanding the surface features and their impact on the materials and devices is becoming increasingly important. At length scales down to the nanoscale regime, surface features become dominant in regulating the properties of perovskite materials, owing to the high surface-to-volume ratio. For perovskite bulk films in the micrometre range, defects and structural disorder readily form at the surface and affect device performance. Through concerted efforts to optimize processing techniques, high-quality perovskite thin films can now be fabricated with monolayer-like polycrystalline grains or even single crystals. Surface defects therefore remain the major obstacle to progress, pushing surface studies to the forefront of perovskite research. In this Review, we summarize and assess recent advances in the understanding of perovskite surfaces and surface strategies towards improving perovskite materials and the efficiency and stability of perovskite devices. The surface features of metal halide perovskites have a crucial role in determining their properties. This Review introduces the recent advances in the understanding of perovskite surfaces and surveys the surface strategies towards improving the properties of perovskite materials and the performance of perovskite optoelectronic devices.

The surface of halide perovskites from nano to bulk

Inorganic CsPbI3 perovskite quantum dot (PQD) receives increasing attention for the application in the new generation solar cells, but the defects on the surface of PQDs significantly affect the photovoltaic performance and stability of solar cells. Herein, the amino acids are used as dual-passivation ligands to passivate the surface defects of CsPbI3 PQDs using a facile single-step ligand exchange strategy. The PQD surface properties are investigated in depth by combining experimental studies and theoretical calculation approaches. The PQD solid films with amino acids as dual-passivation ligands on the PQD surface are thoroughly characterized using extensive techniques, which reveal that the glycine ligand can significantly improve defect passivation of PQDs and therefore diminish charge carrier recombination in the PQD solid. The power conversion efficiency (PCE) of the glycine-based PQD solar cell (PQDSC) is improved by 16.9% compared with that of the traditional PQDSC fabricated with Pb(NO3 )2 treating the PQD surface, owning to improved charge carrier extraction. Theoretical calculations are carried out to comprehensively understand the thermodynamic feasibility and favorable charge density distribution on the PQD surface with a dual-passivation ligand.

Dual Passivation of CsPbI3 Perovskite Nanocrystals with Amino Acid Ligands for Efficient Quantum Dot Solar Cells.

Tailored PEDOT:PSS hole transport layer for higher performance in perovskite solar cells: Enhancement of electrical and optical properties with improved morphology

Long-chain saturated hydrocarbons and alkoxysilanes are ligands that are commonly used to passivate perovskite quantum dots (PQDs) to enhance their stability and optical properties. However, the insulating nature of these capping ligands creates an electronic energy barrier and impedes interparticle electronic coupling, thereby limiting device applications. One strategy to solve this problem is the use of short conductive aromatic ligands that allow delocalization of the electronic wave function from the PQDs, which, in turn, facilitates charge transport between PQDs by lowering the energy barrier. This is demonstrated with methylammonium lead bromide (MAPbBr3) QDs prepared using benzylamine (BZA) and benzoic acid (BA) capping ligands. Optimized BZA-BA-MAPbBr3 QDs are highly stable and show very high photoluminescence (PL) quantum yield (QY) (86%). More importantly, the BZA-BA-MAPbBr3 QD film exhibits higher conductivity and carrier lifetime and more efficient charge extraction compared to PQDs with insul...

Improving Charge Carrier Delocalization in Perovskite Quantum Dots by Surface Passivation with Conductive Aromatic Ligands

Compared to bulk perovskites, charge transport in perovskite quantum dot (PQD) solids is limited. To address this issue, energetically aligned capping ligands were used to prepare methylammonium le...

Enhancing Charge Carrier Delocalization in Perovskite Quantum Dot Solids with Energetically Aligned Conjugated Capping Ligands

Magic sized clusters (MSCs), small nanoparticles with a single size or narrow size distribution, possess unique chemical and physical properties. CH3NH3PbBr3 perovskite MSCs (PMSCs) were synthesize...

Ligand Dependent Growth and Optical Properties of Hybrid Organo-metal Halide Perovskite Magic Sized Clusters


 
 
 Biologics targeting TNF are the mainstay of therapy for children with Crohn’s Disease (CD). However, a subset of patients do not respond, progressing to intestinal fibrosis requiring surgical resection. Prior studies have defined an ileal gene expression module linked to future strictures, and identified small molecules which may reverse this gene signature and suppress fibroblast activation. In the current study we developed a pre-clinical model system and tested a lead candidate, eicosatetraynoic acid (ETYA), a Peroxisome Proliferator-Activated Receptor (PPAR) agonist and arachidonic acid metabolism inhibitor.
 
 
 
 Peripheral blood samples were collected from pediatric CD patients and induced pluripotent stem cell (iPSC) lines were generated. iPSC were differentiated into human intestinal organoids (HIOs) and macrophage-like cells. Macrophage:HIO co-cultures were exposed to lipopolysaccharide (LPS) with and without eicosatetraynoic acid (ETYA) pre-treatment. Flow cytometry and cytospin characterized macrophage activation markers and morphology. Co-culture populations were harvested, and RNA and conditioned media were isolated for downstream analysis. TaqMan Low Density Array, Luminex multiplex assay, immunohistologic staining, and sirius red polarized light microscopy were performed to quantify measures of inflammation and fibrosis, and to test whether introduction of ETYA abated any of these inflammatory or fibrotic changes.
 
 
 
 iPSC-derived macrophages exhibited morphology similar to primary macrophages, and expressed inflammatory macrophage cell surface markers including CD68 (Fig. 1A). LPS-stimulated iPSC-derived macrophages expressed a global pattern of gene expression by RNA sequencing enriched in CD ileal inflammatory macrophages (ToppCell Atlas, p=4.397E-117), and produced cytokines and chemokines implicated in refractory disease (Fig. 1B). Co-culture of LPS-primed macrophages with HIO led to up-regulation of the fibroblast activation genes ACTA2 and COL1A1 (Fig. 2). Under these conditions, HIO collagen content measured by sirius red staining and polarized light microscopy was increased (Fig. 2). ETYA pre-treatment prevented these pro-fibrotic effects of LPS-primed macrophages upon HIO gene expression and collagen content. However, LPS induction of macrophage IL1B, TNF, and OSM production was not suppressed by ETYA, suggesting an alternative mechanism of action upon HIO fibroblast activation and collagen content in the co-culture system.
 
 
 
 ETYA inhibits effects of LPS-primed macrophages upon HIO pro-fibrotic gene expression and collagen production. This was not associated with an effect of ETYA upon macrophage inflammatory cytokine production. Future studies will test alternate pathways including PPAR activation and arachidonic acid metabolism which may mediate this response.


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Eicosatetraynoic acid regulates pro-fibrotic pathways in an induced pluripotent stem cell derived macrophage:human intestinal organoid model of ileal crohn’s disease

675 eicosatetraynoic acid regulates pro-fibrotic pathways in an induced pluripotent stem cell derived macrophage:human intestinal organoid model of ileal crohn's disease

Benjamin W. Dreskin

Papers

Improving Charge Carrier Delocalization in Perovskite Quantum Dots by Surface Passivation with Conductive Aromatic Ligands

Enhancing Charge Carrier Delocalization in Perovskite Quantum Dot Solids with Energetically Aligned Conjugated Capping Ligands

Ligand Dependent Growth and Optical Properties of Hybrid Organo-metal Halide Perovskite Magic Sized Clusters

Eicosatetraynoic acid regulates pro-fibrotic pathways in an induced pluripotent stem cell derived macrophage:human intestinal organoid model of ileal crohn’s disease

675 eicosatetraynoic acid regulates pro-fibrotic pathways in an induced pluripotent stem cell derived macrophage:human intestinal organoid model of ileal crohn's disease