Molecular-Level Insight into Impact of Additives on Film Formation and Molecular Packing in Y6-based Organic Solar Cells.

Additive engineering is widely utilized to optimize film morphology in active layers of organic solar cells (OSCs). However, the role of additive in film formation and adjustment of film morphology remains unclear at the molecular level. Here, taking high-efficiency Y6-based OSC films as an example, this work thus employs all-atom molecular-dynamics simulations to investigate how introduction of additives with different π-conjugation degree thermodynamically and dynamically impacts nanoscale molecular packings. These results demonstrate that the van der Waals (vdW) interactions of the Y6 end groups with the studied additives are strongest. The larger the π-conjugation degree of the additive molecules, the stronger the vdW interactions between additive and Y6 molecules. Due to such vdW interactions, the π-conjugated additive molecules insert into the neighboring Y6 molecules, thus opening more space for relaxation of Y6 molecules to trigger more ordered packing. Increasing the interactions between the Y6 end groups and the additive molecules not only accelerates formation of the Y6 ordered packing, but also induces shorter Y6-intermolecular distances. This work reveals the fundamental molecular-level mechanism behind film formation and adjustment of film morphology via additive engineering, providing an insight into molecular design of additives toward optimizing morphologies of organic semiconductor films.

What is the Limit Size of 2D Conjugated Extension on Central Units of Small Molecular Acceptors in Organic Solar Cells?

2D conjugated extension on central units of small molecular acceptors (SMAs) has gained great successes in reaching the state-of-the-art organic photovoltaics. Whereas the limit size of 2D central planes and their dominant role in constructing 3D intermolecular packing networks are still elusive. Thus, by exploring a series of SMAs with gradually enlarged central planes, it is demonstrated that, at both single molecular and aggerated levels, there is an unexpected blue-shift for their film absorption but preferable reorganization energies, exciton lifetimes and binding energies with central planes enlarging, especially when comparing to their Y6 counterpart. More importantly, the significance of well-balanced molecular packing modes involving both central and end units is first disclosed through a systematic single crystal analysis, indicating that when the ratio of central planes area/end terminals area is no more than 3 likely provides a preferred 3D intermolecular packing network of SMAs. By exploring the limit size of 2D central planes, This work indicates that the structural profiles of ideal SMAs may require suitable central unit size together with proper heteroatom replacement instead of directly overextending 2D central planes to the maximum. These results will likely provide some guidelines for future better molecular design.

Trifluoromethylation Enables Compact 2D Linear Stacking and Improves the Efficiency and Stability of Q-PHJ Organic Solar Cells.

Compared to the bulk heterojunction (BHJ) devices, the quasiplanar heterojunction (Q-PHJ) exhibits a more stable morphology and superior charge transfer performance. To achieve both high efficiency and long-term stability, it is necessary to design new materials for Q-PHJ devices. In this study, QxIC-CF3 and QxIC-CH3 are designed and synthesized for the first time. The trifluoromethylation of the central core exerts a modulatory effect on the molecular stacking pattern, leveraging the strong electrostatic potential and intermolecular interactions. Compared with QxIC-CH3, the single crystal structure reveals that QxIC-CF3 exhibits a more compact 2D linear stacking behavior. These benefits, combined with the separated electron and hole transport channels in Q-PHJ device, lead to increased charge mobility and reduced energy loss. The devices based on D18/QxIC-CF3 exhibit an efficiency of 18.1%, which is the highest power conversion efficiency (PCE) for Q-PHJ to date. Additionally, the thermodynamic stability of the active layer morphology enhances the lifespan of the aforementioned devices under illumination conditions. Specifically, the T80 is 420 h, which is nearly twice that of the renowned Y6-based BHJ device (T80 = 220 h). By combining the advantages of the trifluoromethylation and Q-PHJ device, efficient and stable organic solar cell devices can be constructed.

Linear, Planar, Orbicular, and Macrocyclic Multinuclear Zinc (Meth)acrylate Complexes.

Zinc carboxylate complexes are widely utilized as artificial models of metalloenzymes and as secondary building units of PCPs/MOFs. However, the relationship between the structure of the monodentate carboxylato ligand and the molecular arrangement of multinuclear zinc carboxylate complexes is not fully understood because of the coordination flexibility of the Zn ion and carboxylato ligands. Herein, we report the structural analysis of a series of complexes derived from zinc (meth)acrylate which has a linear infinite chain structure. The molecular structure of µ4-oxido-bridged tetranuclear complexes [Zn4(µ4-O)(OCOR)6] revealed a distorted Zn4O core. Crystallization of zinc acrylate under aqueous conditions afforded a µ3-hydroxido-containing pentanuclear complex [Zn5(µ3-OH)2(OCOR)8] as the repeating unit of an infinite sheet-like structure in the solid state. It was also obtained by the hydrolysis of the µ4-oxido-bridged tetranuclear complex. In sharp contrast, the methacrylate analog retained the methacrylato ligands under aqueous crystallization conditions to form a macrocyclic dodecanuclear complex with methacrylato as the sole ligand.

Molecular Packing Topology and Interactions to Decipher Mechanical Compliances in Dicyano-Distyrylbenzene Derivatives.

Flexible optoelectronics is the need of the hour as the market moves toward wearable and conformable devices. Crystalline π-conjugated materials offer high performance as active materials compared to their amorphous counterpart, but they are typically brittle. This poses a significant challenge that needs to be overcome to unfold their potential in optoelectronic devices. Unveiling the molecular packing topology and identifying interaction descriptors that can accommodate strain offers essential guiding principles for developing conjugated materials as active components in flexible optoelectronics. The molecular packing and interaction topology of eight crystal systems of dicyano-distyrylbenzene derivatives are investigated. Face-to-face π-stacks in an inclined orientation relative to the bending surface can accommodate expansion and compression with minimal molecular motion from their equilibrium positions. This configuration exhibits good compliance towards mechanical strain, while a similar structure with a criss-cross arrangement capable of distributing applied strain equally in opposite directions enhances the flexibility. Molecular arrangements that cannot reversibly undergo expansion and compression exhibit brittleness. In the isometric CT crystals, the disproportionate strength of the interactions along the bending plane and orthogonal directions makes these materials sustain a moderate bending strain. These results provide an updated explanation for the elastic bending in semiconducting π-conjugated crystals.

Recent Progress in Solid-State Room Temperature Afterglow Based on Pure Organic Small Molecules.

Organic room temperature afterglow (ORTA) can be categorized into two key mechanisms: continuous thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP), both of which involve a triplet excited state. However, triplet excited states are easily quenched by non-radiative transitions due to oxygen and molecular vibrations. Solid-phase systems provide a conducive environment for triplet excitons due to constrained molecular motion and limited oxygen permeation within closely packed molecules. The stimulated triplet state tends to release energy through radiative transitions. Despite numerous reports on RTP in solid-phase systems in recent years, the complexity of these systems precludes the formulation of a universal theory to elucidate the underlying principles. Several strategies for achieving ORTA luminescence in the solid phase have been developed, encompassing crystallization, polymer host-guest doping, and small molecule host-guest doping. Many of these systems exhibit luminescent responses to various physical stimuli, including light stimulation, mechanical stimuli, and solvent vapor exposure. The appearance of these intriguing luminescent phenomena in solid-phase systems underscores their significant potential applications in areas such as light sensing, biological imaging, and information security.

Non-ionic Perylene-Diimide Polymer as Universal Cathode Interlayer for Conventional, Inverted, and Blade-Coated Organic Solar Cells.

As a class of predominantly used cathode interlayers (CILs) in organic solar cells (OSCs), perylene-diimide (PDI)-based polymers exhibit intriguing characteristics of excellent charge transporting capacity and suitable energy levels. Despite that, PDI-based CILs with satisfied film-forming ability and adequate solvent resistance are rather rare, which not only limits the further advance of OSC performances but also hinders the practical use of PDI CILs. Herein, we designed and synthesized two non-conjugated PDI polymers for achieving high power conversion efficiency (PCE) in diverse types of OSCs. The utilization of oligo (ethylene glycol) (OEG) linkage enhanced the n-doping effect of PDI polymers, leading to an improved ability of the CIL to reduce work function and improve electron transporting capability. Moreover, the introduction of the non-ionic OEG chain effectively improve the wetting property and solvent resistance of PDI polymers, so the PPDINN CIL can withstand diverse processing conditions in fabricating different OSCs, including conventional, inverted and blade-coated devices. The binary OSC with conventional structure using PPDINN CIL showed a PCE of 18.6%, along with an improved device stability. Besides, PPDINN is compatible with the large-area blade-coating technique, and a PCE of 16.6% was achieved in the 1-cm2 OSC where a blade-coated PPDINN was used.

Precisely Manipulating Molecular Packing via Tuning Alkyl Side-Chain Topology Enabling High-Performance Nonfused-Ring Electron Acceptors.

In the development of high-performance organic solar cells (OSCs), the self-organization of organic semiconductors plays a crucial role. This study focuses on the precisely manipulation of molecular assemble via tuning alkyl side-chain topology in a series of low-cost nonfused-ring electron acceptors (NFREAs). Among the three NFREAs investigated, DPA-4, which possesses an asymmetric alkyl side-chain length, exhibits a tight packing in the crystal and high crystallinity in the film, contributing to improved electron mobility and favorable film morphology for DPA-4. As a result, the OSC device based on DPA-4 achieves an excellent power conversion efficiency of 16.67 %, ranking among the highest efficiencies for NFREA-based OSCs.

NIR-II Fluorescence Sensor Based on Steric Hindrance Regulated Molecular Packing for In Vivo Epilepsy Visualization.

Fluorescence sensing is crucial to studying biological processes and diagnosing diseases, especially in the second near-infrared (NIR-II) window with reduced background signals. However, it's still a great challenge to construct "off-on" sensors when the sensing wavelength extends into the NIR-II region to obtain higher imaging contrast, mainly due to the difficult synthesis of spectral overlapped quencher. Here, we present a new fluorescence quenching strategy, which utilizes steric hindrance quencher (SHQ) to tune the molecular packing state of fluorophores and suppress the emission signal. Density functional theory (DFT) calculations further reveal that large SHQs can competitively pack with fluorophores and prevent their self-aggregation. Based on this quenching mechanism, a novel activatable "off-on" sensing method is achieved via bio-analyte responsive invalidation of SHQ, namely the Steric Hindrance Invalidation geNerated Emission (SHINE) strategy. As a proof of concept, the ClO--sensitive SHQ lead to the bright NIR-II signal release in epileptic mouse hippocampus under the skull and high photon scattering brain tissue, providing the real-time visualization of ClO- generation process in living epileptic mice.

Regulating Electron-Phonon Coupling by Solid Additive for Efficient Organic Solar Cells.

Strong electron-phonon coupling can hinder exciton transport and induce undesirable non-radiative recombination, resulting in a shortened exciton diffusion distance and constrained exciton dissociation in organic solar cells (OSCs). Therefore, suppressing electron-phonon coupling is crucially important for achieve high-performance OSCs. Here, we employ the solid additive to regulating electron-phonon coupling in OSCs. The planar configuration of SA1 confers a significant advantage in suppressing lattice vibrations in the active layers, reducing the scattering of excitons by phonons caused by lattice vibrations. Consequently, a slow but sustained hole transfer process is identified in the SA1-assisted film, indicating an enhancement in hole transfer efficiency. Prolonged exciton diffusion length and exciton lifetime are achieved in the blend film processed with SA1, attributed to a low non-radiative recombination rate and low energetic disorder for charge carrier transport. As a result, a high efficiency of 20% was achieved for ternary device with a remarkable short-circuit current. This work highlights the important role of suppressing electron-phonon coupling in improving the photovoltaic performance of OSCs.