Semiconductor quantum-well structures and superlattices are key building blocks in modern optoelectronics, but it is difficult to simultaneously realize defect-free epitaxial growth while fine tuning ...the chemical composition, layer thickness and band structure of each layer to achieve the desired performance. Here we demonstrate the modulation of the electronic structure-and consequently the optical properties-of organic semiconducting building blocks that are incorporated between the layers of perovskites through a facile solution processing step. Self-aggregation of the conjugated organic molecules is suppressed by functionalization with sterically demanding groups and single crystalline organic-perovskite hybrid quantum wells (down to one-unit-cell thick) are obtained. The energy and charge transfers between adjacent organic and inorganic layers are shown to be fast and efficient, owing to the atomically flat interface and ultrasmall interlayer distance of the perovskite materials. The resulting two-dimensional hybrid perovskites are very stable due to protection given by the bulky hydrophobic organic groups.
Organic polymers that exhibit both ionic and electronic conduction are of interest for energy storage devices and emerging bioelectronic applications. Nevertheless, organic mixed conductors are at an ...early stage of development with nascent design rules and relatively few material chemistries having been experimentally characterized. Here, we report a coarse-grained modeling framework that is sufficiently flexible to represent a range of mixed conducting chemistries while retaining the molecular physics necessary to interrogate structure–function relationships. A detailed overview of the framework is presented, accompanied by an applied study of the effect of hydration and oxidation levels on a representative mixed conductor. The model recapitulates experimental trends related to the macroscopic ionic and electronic conductivities, including the nonlinear suppression of the electronic mobility with respect to the oxidation level and the direct relationship between the ionic mobility and the hydration level, while revealing the complex interplay of polymer morphology, ionic–electronic coupling, and electrolyte distribution that govern these relationships. These results provide a validation of this framework for future applications in establishing structure–function relationships in this important material class and suggest several near-term opportunities for tailoring mixed conduction via a side-chain design.
Algorithmic reaction exploration based on transition state searches has already made inroads into many niche applications, but its potential as a general‐purpose tool is still largely unrealized. ...Computational cost and the absence of benchmark problems involving larger molecules remain obstacles to further progress. Here an ultra‐low cost exploration algorithm is implemented and used to explore the reactivity of unimolecular and bimolecular reactants, comprising a total of 581 reactions involving 51 distinct reactants. The algorithm discovers all established reaction pathways, where such comparisons are possible, while also revealing a much richer reactivity landscape, including lower barrier reaction pathways and a strong dependence of reaction conformation in the apparent barriers of the reported reactions. The diversity of these benchmarks illustrate that reaction exploration algorithms are approaching general‐purpose capability.
An ultra‐low cost reaction exploration algorithm (Yet Another Reaction Program, v2.0) is used to predict reaction outcomes and characterize multiple unimolecular and bimolecular reaction networks. The diversity of these benchmarks illustrate that reaction exploration algorithms are approaching general‐purpose capability.
Resolving the reaction networks associated with biomass pyrolysis is central to understanding product selectivity and aiding catalyst design to produce more valuable products. However, even the ...pyrolysis network of relatively simple Formula: see text-D-glucose remains unresolved due to its significant complexity in terms of the depth of the network and the number of major products. Here, a transition-state-guided reaction exploration has been performed that provides complete pathways to most significant experimental pyrolysis products of Formula: see text-D-glucose. The resulting reaction network involves over 31,000 reactions and transition states computed at the semiempirical quantum chemistry level and approximately 7,000 kinetically relevant reactions and transition states characterized with density function theory, comprising the largest reaction network reported for biomass pyrolysis. The exploration was conducted using graph-based rules to explore the reactivities of intermediates and an adaption of the Dijkstra algorithm to identify kinetically relevant intermediates. This simple exploration policy surprisingly (re)identified pathways to most major experimental pyrolysis products, many intermediates proposed by previous computational studies, and also identified new low-barrier reaction mechanisms that resolve outstanding discrepancies between reaction pathways and yields in isotope labeling experiments. This network also provides explanatory pathways for the high yield of hydroxymethylfurfural and the reaction pathway that contributes most to the formation of hydroxyacetaldehyde during glucose pyrolysis. Due to the limited domain knowledge required to generate this network, this approach should also be transferable to other complex reaction network prediction problems in biomass pyrolysis.
Epitaxial heterostructures based on oxide perovskites and III-V, II-VI and transition metal dichalcogenide semiconductors form the foundation of modern electronics and optoelectronics
. Halide ...perovskites-an emerging family of tunable semiconductors with desirable properties-are attractive for applications such as solution-processed solar cells, light-emitting diodes, detectors and lasers
. Their inherently soft crystal lattice allows greater tolerance to lattice mismatch, making them promising for heterostructure formation and semiconductor integration
. Atomically sharp epitaxial interfaces are necessary to improve performance and for device miniaturization. However, epitaxial growth of atomically sharp heterostructures of halide perovskites has not yet been achieved, owing to their high intrinsic ion mobility, which leads to interdiffusion and large junction widths
, and owing to their poor chemical stability, which leads to decomposition of prior layers during the fabrication of subsequent layers. Therefore, understanding the origins of this instability and identifying effective approaches to suppress ion diffusion are of great importance
. Here we report an effective strategy to substantially inhibit in-plane ion diffusion in two-dimensional halide perovskites by incorporating rigid π-conjugated organic ligands. We demonstrate highly stable and tunable lateral epitaxial heterostructures, multiheterostructures and superlattices. Near-atomically sharp interfaces and epitaxial growth are revealed by low-dose aberration-corrected high-resolution transmission electron microscopy. Molecular dynamics simulations confirm the reduced heterostructure disorder and larger vacancy formation energies of the two-dimensional perovskites in the presence of conjugated ligands. These findings provide insights into the immobilization and stabilization of halide perovskite semiconductors and demonstrate a materials platform for complex and molecularly thin superlattices, devices and integrated circuits.
Open-shell macromolecules (i.e., polymers containing radical sites either along their backbones or at the pendant sites of repeat units) have attracted significant attention owing to their intriguing ...chemical and physical (e.g., redox, optoelectronic, and magnetic) properties, and they have been proposed and/or implemented in a wide range of potential applications (e.g., energy storage devices, electronic systems, and spintronic modules). These successes span multiple disciplines that range from advanced macromolecular chemistry through nanoscale structural characterization and on to next-generation solid-state physics and the associated devices. In turn, this has allowed different scientific communities to expand the palette of radical-containing polymers relatively quickly. However, critical gaps remain on many fronts, especially regarding the elucidation of key structure–property–function relationships that govern the underlying electrochemical, optoelectronic, and spin phenomena in these materials systems. Here, we highlight vital developments in the history of open-shell macromolecules to explain the current state of the art in the field. Moreover, we provide a critical review of the successes and bring forward open opportunities that, if solved, could propel this class of materials in a meaningful manner. Finally, we provide an outlook to address where it seems most likely that open-shell macromolecules will go in the coming years. Our considered view is that the future of radical-containing polymers is extremely bright and the addition of talented researchers with diverse skills to the field will allow these materials and their end-use devices to have a positive impact on the global science and technology enterprise in a relatively rapid manner.
Solid-state conducting polymers usually have highly conjugated macromolecular backbones and require intentional doping in order to achieve high electrical conductivities. Conversely, ...single-component, charge-neutral macromolecules could be synthetically simpler and have improved processibility and ambient stability. We show that poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl), a nonconjugated radical polymer with a subambient glass transition temperature, underwent rapid solid-state charge transfer reactions and had an electrical conductivity of up to 28 siemens per meter over channel lengths up to 0.6 micrometers. The charge transport through the radical polymer film was enabled with thermal annealing at 80°C, which allowed for the formation of a percolating network of open-shell sites in electronic communication with one another. The electrical conductivity was not enhanced by intentional doping, and thin films of this material showed high optical transparency.
Solid polymer electrolytes (SPEs) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li+ conductivity remains a barrier to technological ...viability. SPEs are designed to maximize Li+ diffusivity relative to the anion while maintaining sufficient salt solubility. It is thus remarkable that poly(ethylene oxide) (PEO), the most widely used SPE, exhibits Li+ diffusivity that is an order of magnitude smaller than that of typical counterions at moderate salt concentrations. We show that Lewis-basic polymers like PEO favor slow cation and rapid anion diffusion, while this relationship can be reversed in Lewis-acidic polymers. Using molecular dynamics, polyboranes are identified that achieve up to 10-fold increases in Li+ diffusivities and significant decreases in anion diffusivities, relative to PEO in the dilute-ion regime. These results illustrate a general principle for increasing Li+ diffusivity and transference number with chemistries that exhibit weaker cation and stronger anion coordination.
Anionic diffusion in a soft crystal lattice of hybrid halide perovskites affects their stability, optoelectronic properties and the resulting device performance. The use of two-dimensional (2D) ...halide perovskites improves the chemical stability of perovskites and suppresses the intrinsic anionic diffusion in solid-state devices. Based on this strategy, devices with an enhanced stability and reduced hysteresis have been achieved. However, a fundamental understanding of the role of organic cations in inhibiting anionic diffusion across the perovskite-ligand interface is missing. Here we demonstrate the first quantitative investigation of the anionic interdiffusion across atomically flat 2D vertical heterojunctions. Interestingly, the halide diffusion does not follow the classical diffusion process. Instead, a 'quantized' layer-by-layer diffusion model is proposed to describe the behaviour of the anionic migration in 2D halide perovskites. Our results provide important insights into the mechanism of anionic diffusion in 2D perovskites and provide a new materials platform with an enhanced stability for heterostructure integration.
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