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As the features of microprocessors are miniaturized, low-dielectric-constant (low-k) materials are necessary to limit electronic crosstalk, charge build-up, and signal propagation delay. However, all known low-k dielectrics exhibit low thermal conductivities, which complicate heat dissipation in high-power-density chips. Two-dimensional (2D) covalent organic frameworks (COFs) combine immense permanent porosities, which lead to low dielectric permittivities, and periodic layered structures, which grant relatively high thermal conductivities. However, conventional synthetic routes produce 2D COFs that are unsuitable for the evaluation of these properties and integration into devices. Here, we report the fabrication of high-quality COF thin films, which enable thermoreflectance and impedance spectroscopy measurements. These measurements reveal that 2D COFs have high thermal conductivities (1 W m-1 K-1) with ultra-low dielectric permittivities (k = 1.6). These results show that oriented, layered 2D polymers are promising next-generation dielectric layers and that these molecularly precise materials offer tunable combinations of useful properties.

Emergent quantum phenomena in electronically coupled two-dimensional heterostructures are central to next-generation optical, electronic, and quantum information applications. Tailoring electronic band gaps in coupled heterostructures would permit control of such phenomena and is the subject of significant research interest. Two-dimensional polymers (2DPs) offer a compelling route to tailored band structures through the selection of molecular constituents. However, despite the promise of synthetic flexibility and electronic design, fabrication of 2DPs that form electronically coupled 2D heterostructures remains an outstanding challenge. Here, we report the rational design and optimized synthesis of electronically coupled semiconducting 2DP/2D transition metal dichalcogenide van der Waals heterostructures, demonstrate direct exfoliation of the highly crystalline and oriented 2DP films down to a few nanometers, and present the first thickness-dependent study of 2DP/MoS2 heterostructures. Control over the 2DP layers reveals enhancement of the 2DP photoluminescence by two orders of magnitude in ultrathin sheets and an unexpected thickness-dependent modulation of the ultrafast excited state dynamics in the 2DP/MoS2 heterostructure. These results provide fundamental insight into the electronic structure of 2DPs and present a route to tune emergent quantum phenomena in 2DP hybrid van der Waals heterostructures.

Perovskite solar cells (PSCs) based on 2D/3D heterostructures show great potential to combine the advantages of the high efficiency of 3D perovskites and the high stability of 2D perovskites. However, an in‐depth understanding of the organic‐spacer effects on the 2D quantum well (QW) structures and electronic properties at the 2D/3D interfaces is yet to be fully achieved, especially in the case of 2D perovskites based on diammonium spacers/ligands. Here, a series of diammonium spacers is considered for the construct ion 2D/3D perovskite heterostructures. It is found that the chemical structure and concentration of the spacers can dramatically affect the characteristics of the 2D capping layers, including their phase purity and orientation. Density functional theory calculations indicate that the spacer modifications can induce shifts in the energy‐level alignments at the 2D/3D interfaces and therefore influence the charge‐transfer characteristics. The strong intermolecular interactions between the 2,2‐(ethylenedioxy)bis(ethylammonium) (EDBE) cations and inorganic [PbI6]4− slabs facilitate a controlled deposition of a phase‐pure QW structure (n = 1) with a horizontal orientation, which leads to better surface passivation and carrier extraction. These benefits endow the EDBE‐based 2D/3D devices with a high power conversion efficiency of 22.6% and remarkable environmental stability, highlighting the promise of spacer‐chemistry design for high‐performance 2D/3D PSCs. [ABSTRACT FROM AUTHOR]

Many efforts are currently devoted to improving the stability and crystallinity of imine‐based two‐dimensional (2D) covalent organic frameworks (COFs) given their wide range of potential applications. The variation in the relative orientations of the imine bonds has been found to be a critical factor that impacts the stacking of the 2D COF layers, leads to the formation of isomer structures, and influences the crystallinity of the final product. Most investigations to date have focused only on the structural properties, while the role of the imine orientations on the electronic properties has not been studied systematically. Here, we explore this effect by examining how the electronic band structures, electronic couplings, and effective masses evolve when considering four isomeric structures of an imine‐linked tetraphenyl‐pyrene naphthalene‐diimide COF. Our results provide an understanding of the impact of the imine orientations and how they need to be controlled to realize COF inter‐layer stackings that can lead to efficient cross‐plane electron transport. They can be used to guide the design and synthesis of imine‐based COFs for applications where charge transport needs to be optimized. [ABSTRACT FROM AUTHOR]

Reduced dimensionality forms of perovskites with alternating layers of organic ligands are a promising class of materials for achieving stable perovskite solar cells. Most work until now has focused on phases utilizing two ammonium terminated ligands per formula unit. However, phases utilizing a single diammonium ligand per formula unit are advantageous in that they can potentially have a thinner insulating organic layer between Pb‐halide layers, yet the structural effects on their optoelectronic properties are not yet well understood. In this study two organic ligands, butane 1,4‐diammonium (BDA) and N,N‐dimethylpropane diammonium (DMPD), are investigated as spacers in n = 1, 2D perovskites. Using ultraviolet and inverse photoelectron spectroscopies, BDAPbI4 is shown to have a larger transport gap by 350 meV and a larger exciton binding energy by 140 meV than DMPDPbI4. Through density functional theory calculations, the cause of this difference is traced to the out‐of‐plane tilting of the Pb‐halide octahedra provoked by the asymmetric ligand in DMPDPbI4. Parallel channels of nearly straight PbIPb bonds are formed in one direction, leading to enhanced electronic coupling and higher band dispersion in that direction. In BDAPbI4, no such channels exist, resulting in greater electronic confinement and a larger bandgap and exciton binding energy. [ABSTRACT FROM AUTHOR]

Emergent quantum phenomena in electronically coupled two-dimensional heterostructures are central to next-generation optical, electronic, and quantum information applications. Tailoring electronic band gaps in coupled heterostructures would permit control of such phenomena and is the subject of significant research interest. Two-dimensional polymers (2DPs) offer a compelling route to tailored band structures through the selection of molecular constituents. However, despite the promise of synthetic flexibility and electronic design, fabrication of 2DPs that form electronically coupled 2D heterostructures remains an outstanding challenge. Here, we report the rational design and optimized synthesis of electronically coupled semiconducting 2DP/2D transition metal dichalcogenide van der Waals heterostructures, demonstrate direct exfoliation of the highly crystalline and oriented 2DP films down to a few nanometers, and present the first thickness-dependent study of 2DP/MoS 2 heterostructures. Control over the 2DP layers reveals enhancement of the 2DP photoluminescence by two orders of magnitude in ultrathin sheets and an unexpected thickness-dependent modulation of the ultrafast excited state dynamics in the 2DP/MoS 2 heterostructure. These results provide fundamental insight into the electronic structure of 2DPs and present a route to tune emergent quantum phenomena in 2DP hybrid van der Waals heterostructures.

An important application of all-atom explicit-solvent molecular dynamics (MD) simulations is the refinement of protein structures from low-resolution experiments or template-based modeling. A critical requirement is that the native structure is stable with the force field. We have applied a recently developed residue-specific force field, RSFF1, to a set of 30 refinement targets from recent CASP experiments. Starting from their experimental structures, 1.0 μs unrestrained simulations at 298 K retain most of the native structures quite well except for a few flexible terminals and long internal loops. Starting from each homology model, a 150 ns MD simulation at 380 K generates the best RMSD improvement of 0.85 Å on average. The structural improvements roughly correlate with the RMSD of the initial homology models, indicating possible consistent structure refinement. Finally, targets TR614 and TR624 have been subjected to long-time replica-exchange MD simulations. Significant structural improvements are generated, with RMSD of 1.91 and 1.36 Å with respect to their crystal structures. Thus, it is possible to achieve realistic refinement of protein structure models to near-experimental accuracy, using accurate force field with sufficient conformational sampling.