Halogen-Bonded Hole-Transport Material Enhances Open-Circuit Voltage of Inverted Perovskite Solar Cells.

Interfacial properties of a hole-transport material (HTM) and a perovskite layer are of high importance, which can influence the interfacial charge transfer dynamics as well as the growth of perovskite bulk crystals particularly in inverted structure. The halogen bonding (XB) has been recognized as a powerful functional group to be integrated with new small molecule HTMs. Herein, a carbazole-based halo (iodine)-functional HTM (O1), is synthesized for the first time, demonstrating a high hole mobility and suitable energy levels that align well with those of perovskites.

GaSI: A Wide-Gap Non-centrosymmetric Helical Crystal.

The complex non-centrosymmetric and chiral nature of helical structures endow materials that possess such motifs with unusual properties. However, despite their ubiquity in biological and organic systems, there is a severe lack of inorganic crystals that display helicity in extended lattices, where these unusual properties are expected to be most pronounced. Here, we report a new inorganic helical structure, gallium sulfur iodide (GaSI), within the exfoliable class of III-VI-VII (1:1:1) one-dimensional (1D) van der Waals (vdW) crystals.

Encapsulation of crystalline and amorphous SbS within carbon and boron nitride nanotubes.

The recent rediscovery of 1D and quasi-1D (q-1D) van der Waals (vdW) crystals has laid foundation for the realization of emergent electronic, optical, and quantum-confined physical phenomena in both bulk and at the nanoscale. Of these, the highly anisotropic q-1D vdW crystal structure and the visible-light optical/optoelectronic properties of antimony trisulfide (SbS) have led to its widespread consideration as a promising building block for photovoltaic and non-volatile phase change devices. However, while these applications will greatly benefit from well-defined and sub-nanometer-thick q-1D structures, little has been known about feasible synthetic routes that can access single covalent chains of SbS.

Lattice-guided assembly of optoelectronically active π-conjugated peptides on 1D van der Waals single crystals.

The deployment of organic molecules in high-performance devices strongly relies on the formation of well-ordered domains, which is often complicated by the dynamic and sensitive nature of supramolecular interactions. Here, we engineered the assembly of water-processable, optoelectronic π-conjugated peptides into well-defined organic-inorganic heterointerfaced assemblies by leveraging the long-range anisotropic ordering of 1D van der Waals (vdW) crystals composed of subnanometer-thick transition metal sulfide chains (MS; M = Nb, Ta) as assembly templates. We found that the monomers can readily form 1D supramolecular assemblies onto the underlying crystal surface, owing to the structural correspondence between the π-π interactions of the quaterthiophene (4T)-based peptide units (DDD-4T) and sulfur atom ordering along the NbS (100) surface.

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals.

Interfacing organic molecular groups with well-defined inorganic lattices, especially in low dimensions, enables synthetic routes for the rational manipulation of both their local or extended lattice structures and physical properties. While appreciably studied in two-dimensional systems, the influence of surface organic substituents on many known and emergent one-dimensional (1D) and quasi-1D (q-1D) crystals has remained underexplored. Herein, we demonstrate the surface functionalization of bulk and nanoscale Chevrel-like q-1D ionic crystals using InMoTe, a predicted q-1D Dirac semimetal, as the model phase.

Buffer Chain Model for Understanding Crystallization Competition in Conjugated Polymers.

It remains challenging to comprehensively understand the packing models of conjugated polymers, in which side chains play extremely critical roles. The side chains are typically flexible and non-conductive and are widely used to improve the polymer solubility in organic solutions. Herein, a buffer chain model is proposed to describe link between conjugated backbone and side chains for understanding the relationship of crystallization competition of conductive conjugated backbones and non-conductive side chains.

Selective Induction of Molecular Assembly to Tissue-Level Anisotropy on Peptide-Based Optoelectronic Cardiac Biointerfaces.

The conduction efficiency of ions in excitable tissues and of charged species in organic conjugated materials both benefit from having ordered domains and anisotropic pathways. In this study, a photocurrent-generating cardiac biointerface is presented, particularly for investigating the sensitivity of cardiomyocytes to geometrically comply to biomacromolecular cues differentially assembled on a conductive nanogrooved substrate. Through a polymeric surface-templated approach, photoconductive substrates with symmetric peptide-quaterthiophene (4T)-peptide units assembled as 1D nanostructures on nanoimprinted polyalkylthiophene (P3HT) surface are developed.

Non-Fully Conjugated Dimerized Giant Acceptors with Different Alkyl-Linked Sites for Stable and 19.13 % Efficiency Organic Solar Cells.

Achieving both high power conversion efficiency (PCE) and device stability is a major challenge for the practical development of organic solar cells (OSCs). Herein, three non-fully conjugated dimerized giant acceptors (named 2Y-sites, including wing-site-linked 2Y-wing, core-site-linked 2Y-core, and end-site-linked 2Y-end) are developed. They share the similar monomer precursors but have different alkyl-linked sites, offering the fine-tuned molecular absorption, packing, glass transition temperature, and carrier mobility.

Single Quasi-1D Chains of SbSe Encapsulated within Carbon Nanotubes.

The realization of stable monolayers from 2D van der Waals (vdW) solids has fueled the search for exfoliable crystals with even lower dimensionalities. To this end, 1D and quasi-1D (q-1D) vdW crystals comprising weakly bound subnanometer-thick chains have been discovered and demonstrated to exhibit nascent physics in the bulk. Although established micromechanical and liquid-phase exfoliation methods have been applied to access single isolated chains from bulk crystals, interchain vdW interactions with nonequivalent strengths have greatly hindered the ability to achieve uniform single isolated chains.

Assessing the Role of BN-Embedding Position in BN-Perylenes.

Incorporating heteroatoms can effectively modulate the molecular optoelectronic properties. However, the fundamental understanding of BN doping effects in BN-embedded polycyclic aromatic hydrocarbons (PAHs) is underexplored, lacking rational guidelines to modulate the electronic structures through BN units for advanced materials. Herein, a concise synthesis of novel BN-perylenes with BN doped at the bay area is achieved to systematically explore the doping effect of BN position on the photophysical properties of PAHs.

Unravelling the Superiority of Nonbenzenoid Acepleiadylene as a Building Block for Organic Semiconducting Materials.

Acepleiadylene (APD), a nonbenzenoid isomer of pyrene, exhibits a unique charge-separated character with a large molecular dipole and a small optical gap. However, APD has never been explored in optoelectronic materials to take advantage of these appealing properties. Here, we employ APD as a building block in organic semiconducting materials for the first time, and unravel the superiority of nonbenzenoid APD in electronic applications.

Biomimetic Sequence-Templating Approach toward a Multiscale Modulation of Chromogenic Polymer Properties.

Precision control via molecular structure over adaptive conjugated polymer properties in aqueous environments is critical for realizing their biomedical applications. Here, we unravel the dependence of amphiphilic peptide-polydiacetylene (PDA) conjugate properties on the characteristic steric and hydrophobic contributions within peptide segments that serve as a biomimetic template for diacetylene polymerization in water. We investigated the functional impacts of molecular volume and polarity changes brought by dipeptide substitution domains on the following peptide-PDA material properties at multiple length scales: supramolecular assembly behavior, chain conformation-dependent photophysical properties, cell-material interfacing, and for the first time, bulk electrical properties of their films processed in water.

Visualizing the multi-level assembly structures of conjugated molecular systems with chain-length dependent behavior.

It remains challenging to understand the structural evolution of conjugated polymers from single chains to solvated aggregates and film microstructures, although it underpins the performance of optoelectrical devices fabricated via the mainstream solution processing method. With several ensemble visual measurements, here we unravel the morphological evolution process of a model system of isoindigo-based conjugated molecules, including the hidden molecular assembly pathways, the mesoscale network formation, and their unorthodox chain dependence. Short chains show rigid chain conformations forming discrete aggregates in solution, which further grow to form a highly ordered film that exhibits poor electrical performance.

Polymer Semiconductors: Synthesis, Processing, and Applications.

Polymer semiconductors composed of a carbon-based π conjugated backbone have been studied for several decades as active layers of multifarious organic electronic devices. They combine the advantages of the electrical conductivity of metals and semiconductors and the mechanical behavior of plastics, which are going to become one of the futures of modulable electronic materials. The performance of conjugated materials depends both on their chemical structures and the multilevel microstructures in solid states.

High n-type and p-type conductivities and power factors achieved in a single conjugated polymer.

The charge transport properties of conjugated polymers are commonly limited by the energetic disorder. Recently, several amorphous conjugated polymers with planar backbone conformations and low energetic disorder have been investigated for applications in field-effect transistors and thermoelectrics. However, there is a lack of strategy to finely tune the interchain π-π contacts of these polymers that severely restricts the energetic disorder of interchain charge transport.

Engineering Multi-Scale Organization for Biotic and Organic Abiotic Electroactive Systems.

Multi-scale organization of molecular and living components is one of the most critical parameters that regulate charge transport in electroactive systems-whether abiotic, biotic, or hybrid interfaces. In this article, an overview of the current state-of-the-art for controlling molecular order, nanoscale assembly, microstructure domains, and macroscale architectures of electroactive organic interfaces used for biomedical applications is provided. Discussed herein are the leading strategies and challenges to date for engineering the multi-scale organization of electroactive organic materials, including biomolecule-based materials, synthetic conjugated molecules, polymers, and their biohybrid analogs.

Conjugated Polymers in Solution: A Physical Perspective.

Excellent progress has been made in the optoelectronic properties of conjugated polymers by controlling solution-state aggregation. However, due to the wide variety and complex structures of conjugated polymers, it is still challenging to fully understand the complex aggregation process and microstructures both in solution and in the solid state. This Perspective focuses on the chain conformations and the aggregation of conjugated polymers in solution.

Controlling Solution-State Aggregation and Solid-State Microstructures of Conjugated Polymers by Tuning Backbone Conformation.

Molecular ordering of conjugated polymers both in solution-state aggregates and in solid-state microstructures is a determining factor of the charge transport properties in optoelectronic devices. However, the effect of backbone conformation in conjugated polymers on assembly structures is still unclear. Herein, to understand such backbone conformation effect, three novel chlorinated benzodifurandionge-based oligo(p-phenylene vinylene) (BDOPV) polymers are systematically developed.

BN-Anthracene for High-Mobility Organic Optoelectronic Materials through Periphery Engineering.

Despite the remarkable synthetic accomplishments in creating diverse polycyclic aromatic hydrocarbons with B-N bonds (BN-PAHs), their optoelectronic applications have been less exploited. Herein, we report the achievement of high-mobility organic semiconductors based on existing BN-PAHs through a "periphery engineering" strategy. Tetraphenyl- and diphenyl-substituted BN-anthracenes (TPBNA and DPBNA, respectively) are designed and synthesized.

"Spine Surgery" of Perylene Diimides with Covalent B-N Bonds toward Electron-Deficient BN-Embedded Polycyclic Aromatic Hydrocarbons.

BN-embedded polycyclic aromatic hydrocarbons (PAHs) with unique optoelectronic properties are underdeveloped relative to their carbonaceous counterparts due to the lack of suitable and facile synthetic methods. Moreover, the dearth of electron-deficient BN-embedded PAHs further hinders their application in organic electronics. Here we present the first facile synthesis of novel perylene diimide derivatives (BN-PDIs) featuring n-type B-N covalent bonds.

Regulation of High Miscibility for Efficient Charge-Transport in n-Doped Conjugated Polymers.

Strong interchain interactions of conjugated polymers usually result in poor miscibility with molecular dopants, limiting the doping efficiency because of uncontrolled phase separation. We have developed a strategy to achieve efficient charge-transport and high doping miscibility in n-doped conjugated polymers. We solve the miscibility issue through disorder side-chains containing dopants better.

Parent B N -Perylenes with Different BN Orientations.

Introducing BN units into polycyclic aromatic hydrocarbons expands the chemical space of conjugated materials with novel properties. However, it is challenging to achieve accurate synthesis of BN-PAHs with specific BN positions and orientations. Here, three new parent B N -perylenes with different BN orientations are synthesized with BN-naphthalene as the building block, providing systematic insight into the effects of BN incorporation with different orientations on the structure, (anti)aromaticity, crystal packing and photophysical properties.

Correlating Charge Transport Properties of Conjugated Polymers in Solution Aggregates and Thin-Film Aggregates.

The role of solution aggregates on the charge transport process of conjugated polymers in electronic devices has gained increasing attention; however, the correlation of the charge carrier mobilities between the solution aggregates and the solid-state films remains elusive. Herein, three polymers, FBDOPV-2T, FBDOPV-2F2T, and FBDOPV-4F2T, are designed and synthesized with distinct aggregation behavior in solution. By combining contact-free ultrafast terahertz (THz) spectroscopy and field-effect transistor measurements, we track the charge carrier mobility of the aggregates of these polymers from the solution to the thin-film state.