Oligothiophene-Bridged Conjugated Covalent Organic Frameworks.

Two-dimensional covalent organic frameworks (2D-COFs) are crystalline, porous materials comprising aligned columns of π-stacked building blocks. With a view toward the application of these materials in organic electronics and optoelectronics, the construction of oligothiophene-based COFs would be highly desirable. The realization of such materials, however, has remained a challenge, in particular with respect to laterally conjugated imine-linked COFs. We have developed a new building block design employing an asymmetric modification on an otherwise symmetric backbone that allows us to construct a series of highly crystalline quaterthiophene-derived COFs with tunable electronic properties. Studying the optical response of these materials, we have observed for the first time the formation of a charge transfer state between the COF subunits across the imine bond. We believe that our new building block design provides a general strategy for the construction of well-ordered COFs from various extended building blocks, thus greatly expanding the range of applicable molecules.

Synchronized Offset Stacking: A Concept for Growing Large-Domain and Highly Crystalline 2D Covalent Organic Frameworks.

Covalent organic frameworks (COFs), formed by reversible condensation of rigid organic building blocks, are crystalline and porous materials of great potential for catalysis and organic electronics. Particularly with a view of organic electronics, achieving a maximum degree of crystallinity and large domain sizes while allowing for a tightly π-stacked topology would be highly desirable. We present a design concept that uses the 3D geometry of the building blocks to generate a lattice of uniquely defined docking sites for the attachment of consecutive layers, thus allowing us to achieve a greatly improved degree of order within a given average number of attachment and detachment cycles during COF growth. Synchronization of the molecular geometry across several hundred nanometers promotes the growth of highly crystalline frameworks with unprecedented domain sizes. Spectroscopic data indicate considerable delocalization of excitations along the π-stacked columns and the feasibility of donor-acceptor excitations across the imine bonds. The frameworks developed in this study can serve as a blueprint for the design of a broad range of tailor-made 2D COFs with extended π-conjugated building blocks for applications in photocatalysis and optoelectronics.

Synthesis and Reactivity of Triazaphenanthrenes.

Pyridonaphthyridines (triazaphenanthrenes) were prepared in 4 steps and in 13-52% overall yield using Negishi cross-couplings between iodopicolines and 2-chloro-pyridylzinc derivatives. After chlorination, Gabriel amination and spontaneous ring-closure, the final aromatization leading to the triazaphenanthrenes was achieved with chloranil. This heterocyclic scaffold underwent a nucleophilic addition at position 6 leading to further functionalized pyridonaphthyridines. The influence of these chemical modifications on the optical properties was studied by steady-state and time-resolved optical spectroscopy. While the thiophene-substituted heterocycles exhibited the most extended absorption, the phenyl- and furan-substituted compounds showed a stronger photoluminescence, reaching above 20% quantum yield and lifetimes of several nanoseconds.

Stabilization of the Trigonal High-Temperature Phase of Formamidinium Lead Iodide.

Formamidinium lead iodide (FAPbI3) has the potential to achieve higher performance than established perovskite solar cells like methylammonium lead iodide (MAPbI3), while maintaining a higher stability. The major drawback for the latter material is that it can crystallize at room temperature in a wide bandgap hexagonal symmetry (P63mc) instead of the desired trigonal (P3m1) black phase formed at a higher temperature (130 °C). Our results show that employing a mixture of MAI and FAI in films deposited via a two-step approach, where the MAI content is <20%, results in the exchange of FA molecules with MA without any significant lattice shrinkage. Additionally, we show with temperature-dependent X-ray diffraction that the trigonal phase exhibits no phase changes in the temperature range studied (25 to 250 °C). We attribute the stabilization of the structure to stronger interactions between the MA cation and the inorganic cage. Finally, we show that the inclusion of this small amount of MA also has a positive effect on the lifetime of the photoexcited species and results in more efficient devices.

A highly-ordered 3D covalent fullerene framework.

A highly-ordered 3D covalent fullerene framework is presented with a structure based on octahedrally functionalized fullerene building blocks in which every fullerene is separated from the next by six functional groups and whose mesoporosity is controlled by cooperative self-assembly with a liquid-crystalline block copolymer. The new fullerene-framework material was obtained in the form of supported films by spin coating the synthesis solution directly on glass or silicon substrates, followed by a heat treatment. The fullerene building blocks coassemble with a liquid-crystalline block copolymer to produce a highly ordered covalent fullerene framework with orthorhombic Fmmm symmetry, accessible 7.5 nm pores, and high surface area, as revealed by gas adsorption, NMR spectroscopy, small-angle X-ray scattering (SAXS), and TEM. We also note that the 3D covalent fullerene framework exhibits a dielectric constant significantly lower than that of the nonporous precursor material.

Preparation of Single-Phase Films of CH3NH3Pb(I1-xBrx)3 with Sharp Optical Band Edges.

Organometallic lead-halide perovskite-based solar cells now approach 18% efficiency. Introducing a mixture of bromide and iodide in the halide composition allows tuning of the optical bandgap. We prepare mixed bromide-iodide lead perovskite films CH3NH3Pb(I1-xBrx)3 (0 ≤ x ≤ 1) by spin-coating from solution and obtain films with monotonically varying bandgaps across the full composition range. Photothermal deflection spectroscopy, photoluminescence, and X-ray diffraction show that following suitable fabrication protocols these mixed lead-halide perovskite films form a single phase. The optical absorption edge of the pure triiodide and tribromide perovskites is sharp with Urbach energies of 15 and 23 meV, respectively, and reaches a maximum of 90 meV for CH3NH3PbI1.2Br1.8. We demonstrate a bromide-iodide lead perovskite film (CH3NH3PbI1.2Br1.8) with an optical bandgap of 1.94 eV, which is optimal for tandem cells of these materials with crystalline silicon devices.

Efficient Planar Heterojunction Perovskite Solar Cells Based on Formamidinium Lead Bromide.

The development of medium-bandgap solar cell absorber materials is of interest for the design of devices such as tandem solar cells and building-integrated photovoltaics. The recently developed perovskite solar cells can be suitable candidates for these applications. At present, wide bandgap alkylammonium lead bromide perovskite absorbers require a high-temperature sintered mesoporous TiO2 photoanode in order to function efficiently, which makes them unsuitable for some of the above applications. Here, we present for the first time highly efficient wide bandgap planar heterojunction solar cells based on the structurally related formamidinium lead bromide. We show that this material exhibits much longer diffusion lengths of the photoexcited species than its methylammonium counterpart. This results in planar heterojunction solar cells exhibiting power conversion efficiencies approaching 7%. Hence, formamidinium lead bromide is a strong candidate as a wide bandgap absorber in perovskite solar cells.