Enhancing Interlayer Charge Transport of Two-Dimensional Perovskites by Structural Stabilization via Fluorine Substitution.

Two-dimensional lead-halide perovskites provide a more robust alternative to three-dimensional perovskites in solar energy and optoelectronic applications due to increased chemical stability afforded by interlayer ligands. At the same time, the ligands create barriers for interlayer charge transport, reducing device performance. Using a recently developed ab initio simulation methodology, we demonstrate that ligand fluorination can enhance both hole and electron mobility by 1-2 orders of magnitude.

Efficient near-infrared organic light-emitting diodes with emission from spin doublet excitons.

The development of luminescent organic radicals has resulted in materials with excellent optical properties for near-infrared emission. Applications of light generation in this range span from bioimaging to surveillance. Although the unpaired electron arrangements of radicals enable efficient radiative transitions within the doublet-spin manifold in organic light-emitting diodes, their performance is limited by non-radiative pathways introduced in electroluminescence.

Non-equilibrium transport in polymer mixed ionic-electronic conductors at ultrahigh charge densities.

Conducting polymers are mixed ionic-electronic conductors that are emerging candidates for neuromorphic computing, bioelectronics and thermoelectrics. However, fundamental aspects of their many-body correlated electron-ion transport physics remain poorly understood. Here we show that in p-type organic electrochemical transistors it is possible to remove all of the electrons from the valence band and even access deeper bands without degradation.

Optical Properties of H-Bonded Heterotriangulene Supramolecular Polymers: Charge-Transfer Excitations Matter.

H-bonded -heterotriangulene (NHT) supramolecular polymers offer a nice playground to explore the nature and dynamics of electronic excitations in low-dimensional organic nanostructures. Here, we report on a comprehensive molecular modeling of the excited-state electronic structure and optical properties of model NHT stacks, highlighting the important role of intermolecular charge-transfer (CT) excitations in shaping their optical absorption and emission lineshapes. Most importantly, we show that the coupling between the local and CT excitations, modulated by the electric fields induced by the presence of polar amide groups forming H-bonded arrays along the stacks, significantly increases the resulting hybrid exciton bandwidth.

Cation-Dependent Mixed Ionic-Electronic Transport in a Perylenediimide Small-Molecule Semiconductor.

A rapidly growing interest in organic bioelectronic applications has spurred the development of a wide variety of organic mixed ionic-electronic conductors. While these new mixed conductors have enabled the community to interface organic electronics with biological systems and efficiently transduce biological signals (ions) into electronic signals, the current materials selection does not offer sufficient selectivity towards specific ions of biological relevance without the use of auxiliary components such as ion-selective membranes. Here, we present the molecular design of an n-type (electron-transporting) perylene diimide semiconductor material decorated with pendant oligoether groups to facilitate interactions with cations such as Na and K.

MXenes with ordered triatomic-layer borate polyanion terminations.

Surface terminations profoundly influence the intrinsic properties of MXenes, but existing terminations are limited to monoatomic layers or simple groups, showing disordered arrangements and inferior stability. Here we present the synthesis of MXenes with triatomic-layer borate polyanion terminations (OBO terminations) through a flux-assisted eutectic molten etching approach. During the synthesis, Lewis acidic salts act as the etching agent to obtain the MXene backbone, while borax generates BO species, which cap the MXene surface with an O-B-O configuration.

Nanoscale doping of polymeric semiconductors with confined electrochemical ion implantation.

Nanoresolved doping of polymeric semiconductors can overcome scaling limitations to create highly integrated flexible electronics, but remains a fundamental challenge due to isotropic diffusion of the dopants. Here we report a general methodology for achieving nanoscale ion-implantation-like electrochemical doping of polymeric semiconductors. This approach involves confining counterion electromigration within a glassy electrolyte composed of room-temperature ionic liquids and high-glass-transition-temperature insulating polymers.

Elucidating the Non-Covalent Interactions that Trigger Interdigitation in Lead-Halide Layered Hybrid Perovskites.

Two-dimensional (2D) hybrid organic-inorganic perovskites constitute a versatile class of materials applied to a variety of optoelectronic devices. These materials are composed of alternating layers of inorganic lead halide octahedra and organic ammonium cations. Most perovskite research studies so far have focused on organic sublattices based on phenethylammonium and alkylammonium cations, which are packed by van der Waals cohesive forces.

Polar Polymorphism: A New Intermediate Structure toward the Thin-Film Phase in Asymmetric Benzothieno[3,2-][1]-benzothiophene Derivatives.

Understanding structure and polymorphism is relevant for any organic device optimization, and it is of particular relevance in 7-decyl-2-phenyl[1]benzothieno[3,2-][1]benzothiophene (Ph-BTBT-10) since high carrier mobility in Ph-BTBT-10 thin films has been linked to the structural transformation from the metastable thin-film phase to the thermodynamically stable bilayer structure via thermal annealing. We combine here a systematic nanoscale morphological analysis with local Kelvin probe force microcopy (KPFM) that demonstrates the formation of a polar polymorph in thin films as an intermediate structure for thicknesses lower than 20 nm. The polar structure develops with thickness a variable amount of structural defects in the form of individual flipped molecules (point defects) or sizable polar domains, and evolves toward the reported nonpolar thin-film phase.

Interlayer Charge Transport in 2D Lead Halide Perovskites from First Principles.

We report on the implementation of a versatile projection-operator diabatization approach to calculate electronic coupling integrals in layered periodic systems. The approach is applied to model charge transport across the saturated organic spacers in two-dimensional (2D) lead halide perovskites. The calculations yield out-of-plane charge transfer rates that decay exponentially with the increasing length of the alkyl chain, range from a few nanoseconds to milliseconds, and are supportive of a hopping mechanism.

Integrating Benzoxazine-PDMS 3D Networks with Carbon Nanotubes for flexible Pressure Sensors.

Shapeable and flexible pressure sensors with superior mechanical and electrical properties are of major interest as they can be employed in a wide range of applications. In this regard, elastomer-based composites incorporating carbon nanomaterials in the insulating matrix embody an appealing solution for designing flexible pressure sensors with specific properties. In this study, PDMS chains of different molecular weight were successfully functionalized with benzoxazine moieties in order to thermally cure them without adding a second component, nor a catalyst or an initiator.

Controlling Charge Transport in 2D Conductive MOFs─The Role of Nitrogen-Rich Ligands and Chemical Functionality.

Two-dimensional electrically conducting metal-organic frameworks (2D-e-MOFs) have emerged as a class of highly promising functional materials for a wide range of applications. However, despite the significant recent advances in 2D-e-MOFs, developing systems that can be postsynthetically chemically functionalized, while also allowing fine-tuning of the transport properties, remains challenging. Herein, we report two isostructural 2D-e-MOFs: Ni(HITAT) and Ni(HITBim) based on two new 3-fold symmetric ligands: 2,3,7,8,12,13-hexaaminotriazatruxene (HATAT) and 2,3,8,9,14,15-hexaaminotribenzimidazole (HATBim), respectively, with reactive sites for postfunctionalization.

Molecularly induced order promotes charge separation through delocalized charge-transfer states at donor-acceptor heterojunctions.

The energetic landscape at the interface between electron donating and accepting molecular materials favors efficient conversion of intermolecular charge-transfer (CT) states into free charge carriers (FCC) in high-performance organic solar cells. Here, we elucidate how interfacial energetics, charge generation and radiative recombination are affected by molecular arrangement. We experimentally determine the CT dissociation properties of a series of model, small molecule donor-acceptor blends, where the used acceptors (B2PYMPM, B3PYMPM and B4PYMPM) differ only in the nitrogen position of their lateral pyridine rings.

Transiently delocalized states enhance hole mobility in organic molecular semiconductors.

Evidence shows that charge carriers in organic semiconductors self-localize because of dynamic disorder. Nevertheless, some organic semiconductors feature reduced mobility at increasing temperature, a hallmark for delocalized band transport. Here we present the temperature-dependent mobility in two record-mobility organic semiconductors: dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]-thiophene (DNTT) and its alkylated derivative, C8-DNTT-C8.

Isomer Discrimination via Defect Engineering in Monolayer MoS.

The all-surface nature of two-dimensional (2D) materials renders them highly sensitive to environmental changes, enabling the on-demand tailoring of their physical properties. Transition metal dichalcogenides, such as 2H molybdenum disulfide (MoS), can be used as a sensory material capable of discriminating molecules possessing a similar structure with a high sensitivity. Among them, the identification of isomers represents an unexplored and challenging case.

Poly(benzimidazobenzophenanthroline)-Ladder-Type Two-Dimensional Conjugated Covalent Organic Framework for Fast Proton Storage.

Electrochemical proton storage plays an essential role in designing next-generation high-rate energy storage devices, e.g., aqueous batteries.

Curved graphene nanoribbons derived from tetrahydropyrene-based polyphenylenes one-pot K-region oxidation and Scholl cyclization.

Precise synthesis of graphene nanoribbons (GNRs) is of great interest to chemists and materials scientists because of their unique opto-electronic properties and potential applications in carbon-based nanoelectronics and spintronics. In addition to the tunable edge structure and width, introducing curvature in GNRs is a powerful structural feature for their chemi-physical property modification. Here, we report an efficient solution synthesis of the first pyrene-based GNR (PyGNR) with curved geometry one-pot K-region oxidation and Scholl cyclization of its corresponding well-soluble tetrahydropyrene-based polyphenylene precursor.

Reversible spin-optical interface in luminescent organic radicals.

Molecules present a versatile platform for quantum information science and are candidates for sensing and computation applications. Robust spin-optical interfaces are key to harnessing the quantum resources of materials. To date, carbon-based candidates have been non-luminescent, which prevents optical readout via emission.

Interplay of structure and photophysics of individualized rod-shaped graphene quantum dots with up to 132 sp² carbon atoms.

Nanographene materials are promising building blocks for the growing field of low-dimensional materials for optics, electronics and biophotonics applications. In particular, bottom-up synthesized 0D graphene quantum dots show great potential as single quantum emitters. To fully exploit their exciting properties, the graphene quantum dots must be of high purity; the key parameter for efficient purification being the solubility of the starting materials.

Enantiopure Dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophenes: Reaching High Magnetoresistance Effect in OFETs.

Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented.

Carbon Vacancies Steer the Activity in Dual Ni Carbon Nitride Photocatalysis.

The manipulation of carbon nitride (CN) structures is one main avenue to enhance the activity of CN-based photocatalysts. Increasing the efficiency of photocatalytic heterogeneous materials is a critical step toward the realistic implementation of sustainable schemes for organic synthesis. However, limited knowledge of the structure/activity relationship in relation to subtle structural variations prevents a fully rational design of new photocatalytic materials, limiting practical applications.

Vacuum-Deposited Donors for Low-Voltage-Loss Nonfullerene Organic Solar Cells.

The advent of nonfullerene acceptors (NFAs) enabled records of organic photovoltaics (OPVs) exceeding 19% power conversion efficiency in the laboratory. However, high-efficiency NFAs have so far only been realized in solution-processed blends. Due to its proven track record in upscaled industrial production, vacuum thermal evaporation (VTE) is of prime interest for real-world OPV commercialization.

Exceptionally high charge mobility in phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type two-dimensional conjugated polymers.

Two-dimensional conjugated polymers (2DCPs), composed of multiple strands of linear conjugated polymers with extended in-plane π-conjugation, are emerging crystalline semiconducting polymers for organic (opto)electronics. They are represented by two-dimensional π-conjugated covalent organic frameworks, which typically suffer from poor π-conjugation and thus low charge carrier mobilities. Here we overcome this limitation by demonstrating two semiconducting phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type 2DCPs (2DCP-MPc, with M = Cu or Ni), which are constructed from octaaminophthalocyaninato metal(II) and naphthalenetetracarboxylic dianhydride by polycondensation under solvothermal conditions.

Benchmarking DFT Functionals for Excited-State Calculations of Donor-Acceptor TADF Emitters: Insights on the Key Parameters Determining Reverse Inter-System Crossing.

The importance of intermediate triplet states and the nature of excited states has gained interest in recent years for the thermally activated delayed fluorescence (TADF) mechanism. It is widely accepted that simple conversion between charge transfer (CT) triplet and singlet excited states is too crude, and a more complex route involving higher-lying locally excited triplet excited states has to be invoked to witness the magnitude of the rate of reverse inter-system crossing (RISC) rates. The increased complexity has challenged the reliability of computational methods to accurately predict the relative energy between excited states as well as their nature.