In contrast to inorganic quantum wells, hybrid quantum wells (HQWs) based on metal-organic semiconductors are characterized by relatively soft lattices, in which excitonic states can strongly couple to lattice phonons. Therefore, understanding the lattice's impact on exciton dynamics is essential for harnessing the optoelectronic potential of HQWs. Beyond 2D metal halide perovskites, layered metal-organic chalcogenides (MOCs), which are an air-stable, underexplored material class hosting room-temperature excitons, can be exploited as photodetectors, light emitting devices, and ultrafast photoswitches. Here, the role of phonons in the optical transitions of the prototypical MOC [AgSePh]∞ is elucidated. Impulsive stimulated Raman scattering (ISRS) allows the detection of coherent exciton oscillations driven by Fröhlich interaction with low-energy optical phonons. Steady state absorption and Raman spectroscopies reveal a strong exciton-phonon coupling (Huang-Rhys parameter ≈1.7) and its anharmonicity, manifested as a nontrivial temperature-dependent Stokes shift. The ab initio calculations support these observations, hinting at an anharmonic behavior of the low-energy phonons <200 cm−1. These results untangle complex exciton-phonon interactions in MOCs, establishing an ideal testbed for room-temperature many-body phenomena.

Metal-organic species can be designed to self-assemble in large-scale, atomically defined, supramolecular architectures. A particular example is hybrid quantum wells, where inorganic two-dimensional (2D) planes are separated by organic ligands. The ligands effectively form an intralayer confinement for charge carriers resulting in a 2D electronic structure, even in multilayered assemblies. Air-stable layered transition metal organic chalcogenides have recently been found to host tightly bound 2D excitons with strong optical anisotropy in a bulk matrix. Here, we investigate the excited carrier dynamics in the prototypical metal-organic chalcogenide [AgSePh]_∞, disentangling three excitonic resonances by low temperature transient absorption spectroscopy. Our analysis suggests a complex relaxation cascade comprising ultrafast screening and renormalization, interexciton relaxation, and self-trapping of excitons within a few picoseconds (ps). The ps-decay provided by the self-trapping mechanism may be leveraged to unlock the material's potential for ultrafast optoelectronic applications.

Metal-organic species can be designed to self-assemble in large-scale, atomically defined, supramolecular architectures. Hybrid quantum wells, where inorganic two-dimensional (2D) planes are separated by organic ligands, are a particular example. The ligands effectively provide an intralayer confinement for charge carriers resulting in a 2D electronic structure, even in multilayered assemblies. Air-stable metal organic chalcogenides hybrid quantum wells have recently been found to host tightly bound 2D excitons with strong optical anisotropy in a bulk matrix. Here, we investigate the excited carrier dynamics in the prototypical metal organic chalcogenide [AgSePh], disentangling three excitonic resonances by low temperature transient absorption spectroscopy. Our analysis suggests a complex relaxation cascade comprising ultrafast screening and renormalization, inter-exciton relaxation, and self-trapping of excitons within few picoseconds. The ps-decay provided by the self-trapping mechanism may be leveraged to unlock the material's potential for ultrafast optoelectronic applications.

The material demands for metal-organic frameworks (MOFs) for next-generation energy-efficient CO2 capture technologies necessitate advances in their expedient and scalable synthesis. Toward that end, the recently discovered expanded MOF-74, or M2(dobpdc), where M = divalent metal cation and dobpdc = 4,4′-dioxido-3,3′-biphenyldicarboxylate, can now be prepared in minutes via a controlled dissolution-crystallization route from divalent metal oxides as precursors. We show that the available surface area of the metal oxide plays a critical role in the precursor dissolution, which was found to be rate-limiting. Based on this understanding of the reaction trajectory, we pushed the chemical transformation to its fringe kinetic limit by configuring the metal oxide precursors as ligand-free colloidal metal oxide nanocrystals, which allowed MOF formation in less than 1 min. MOFs prepared by this strategy were highly crystalline, with BET surface areas on par with conventional multihour syntheses from metal halide salts. This method was also applied successfully in the synthesis of M2(dobdc) MOFs, highlighting its generality. Our work challenges the conventional wisdom that plurality of steps in MOF formation is inherently time-intensive.

Despite the availability of chemistries to tailor the pore architectures of microporous polymer membranes for chemical separations, trade-offs in permeability and selectivity with functional group manipulations nevertheless persist, which ultimately places an upper bound on membrane performance. Here we introduce a new design strategy to uncouple these attributes of the membrane. Key to our success is the incorporation of phase-change metal-organic frameworks (MOFs) into the polymer matrix, which can be used to increase the solubility of a specific gas in the membrane, and thereby its permeability. We further show that it is necessary to scale the size of the phase-change MOF to nanoscopic dimensions, in order to take advantage of this effect in a gas separation. Our observation of an increase in solubility and permeability of only one of the gases during steady-state permeability measurements suggests fast exchange between free and chemisorbed gas molecules within the MOF pores. While the kinetics of this exchange in phase-change MOFs are not yet fully understood, their role in enhancing the efficacy and efficiency of the separation is clearly a compelling new direction for membrane technology.

X-ray detection for personal dosimetry requires sensitive, stable and non-toxic materials. At the same time, scalability onto large-area and flexible substrates is emerging as a desirable property. To satisfy these requirements, novel materials to be employed as the active layer of direct X-ray detectors are needed. In this search for easy-processability, large area, efficient and non-toxic materials for direct X-ray detection, we assess the performance of a layered metal-organic chalcogenide [AgSePh]∞, recently proposed as representative of a novel excitonic semiconductors platform. Here we demonstrate that [AgSePh]∞ can be successfully applied as direct ionizing radiation detecting layer, reaching sensitivities up to (180 ± 10) μC Gy−1 cm−2 and competitive limit of detection down to (100 ± 30) nGy s−1. Moreover, it offers good stability and reproducibility of detection after 100 Gy of irradiation and upon bending to a curvature radius of 5 mm.

Metal halide perovskites (MHPs) are low-temperature processable hybrid semiconductor materials with exceptional performances that are revolutionizing the field of optoelectronic devices. Despite their great potential, commercial deployment is hindered by MHPs lack of stability and durability, mainly attributed to ion migration and chemical interactions with the electrodes. To address these issues, 2D layered MHPs are investigated as possible device interlayers or active material substitutes. Here, the 2D perovskite (PEA)2PbBr4 is considered that is recently discussed as promising candidate for X-ray direct detection. While the increased resilience of (PEA)2PbBr4 radiation detectors has already been reported, the physical mechanisms responsible for such improvement compared to 3D perovskites are not still fully understood. To unravel the charge transport process in (PEA)2PbBr4 crystals thought to underly the device better performance, an investigation technique is adapted previously used on highly resistive inorganic semiconductors, called photo induced current transient spectroscopy (PICTS). It is demonstrated that PICTS can reliably detect three trap states (T1, T2, and T3), and that their evolution upon X-ray exposure can explain (PEA)2PbBr4 superior radiation tolerance and reduced aging effects. Overall, the results provide essential insights into the electrical characteristics of 2D perovskites and their potential application as reliable direct X-ray detectors.

Many forward-looking clean-energy technologies hinge on the development of scalable and efficient membrane-based separations. Ongoing investment in the basic research of microporous materials is beginning to pay dividends in membrane technology maturation. Specifically, improvements in membrane selectivity, permeability, and durability are being leveraged for more efficient carbon capture, desalination, and energy storage, and the market adoption of membranes in those areas appears to be on the horizon. Herein, an overview of the microporous materials chemistry driving advanced membrane development, the clean-energy separations employing them, and the theoretical underpinnings tying membrane performance to membrane structure across multiple length scales is provided. The interplay of pore architecture and chemistry for a given set of analytes emerges as a critical design consideration dictating mass transport outcomes. Opportunities and outstanding challenges in the field are also discussed, including high-flux 2D molecular-sieving membranes, phase-change adsorbents as performance-enhancing components in composite membranes, and the need for quantitative metrologies for understanding mass transport in heterophasic materials and in micropores with unusual chemical interactions with analytes of interest.

[This corrects the article DOI: 10.1039/C7SC05217K.].

[This corrects the article DOI: 10.1039/C7SC05217K.].