An n-Type Open-Shell Conjugated Polymer with High-Spin Ground-State and High Intrinsic Electrical Conductivity.

Open-shell conjugated polymers with a high intrinsic conductivity and high-spin ground state hold considerable promise for applications in organic electronics and spintronics. Herein, two novel acceptor-acceptor (A-A) conjugated polymers based on a highly electron-deficient quinoidal benzodifurandione unit have been developed, namely DPP-BFDO-Th and DPP-BFDO. The incorporation of the quinoidal moiety into the polymers backbones enables deeply aligned lower-lying lowest unoccupied molecular orbital (LUMO) levels of below -4.0 eV. Notably, DPP-BFDO exhibits an exceptionally low LUMO (-4.63 eV) and a high-spin ground state characterized by strong diradical characters. Moreover, a self-doping through intermolecular charge-transfer is observed for DPP-BFDO, as evidenced by X-ray photoelectron spectroscopy (XPS) studies. The high carrier concentration in combination with a planar and linear conjugated backbone yields a remarkable electrical conductivity (σ) of 1.04 S cm-1 in the "undoped" native form, ranking among the highest values reported for n-type radical-based conjugated polymers. When employed as an n-type thermoelectric material, DPP-BFDO achieves a power factor of 12.59 µW m-1 K-2. Furthermore, upon n-doping, the σ could be improved to 65.68 S cm-1. This study underscores the great potential of electron-deficient quinoidal units in constructing dopant-free n-type conductive polymers with a high-spin ground state and exceptional intrinsic conductivity.

B─N Covalent Bond-Based Nonfullerene Electron Acceptors for Efficient Organic Solar Cells.

The optoelectronic properties and photovoltaic performance of nonfullerene electron acceptors (NFEAs) in organic solar cells (OSCs) are greatly influenced by the rational structure regulation of the central core unit. This study introduces a novel type of six-membered fused electron-donating core containing B─N covalent bonds to construct acceptor-donor-acceptor (A-D-A)-type NFEAs. By modulating the branching alkyl chains on the nitrogen atom, two NFEAs, BN910 and BN1014, are synthesized and characterized. Both molecules exhibit strong near-infrared absorption, narrow bandgaps (≈1.45 eV), appropriate energy levels, and tunable molecular packing behaviors, positioning them as promising candidates for efficient NFEAs in OSCs. The investigation reveals that BN1014, with longer and C2-branched alkyl chains, demonstrates superior intermolecular packing and morphology within active layers, leading to enhanced exciton dissociation, improved charge transfer, and reduced charge recombination in OSCs. As a result, a power conversion efficiency (PCE) of 10.02% is achieved for D18:BN1014-based binary OSCs. Notably, BN1014 can be utilized as the third component in the D18:DT-Y6 binary system to fabricate the ternary OSCs, and a PCE of 17.65% is achieved, outperforming 17.05% of D18:DT-Y6-based binary OSCs. These findings highlight the potential of heteroarenes featuring B─N covalent bonds for constructing high-efficiency NFEAs in OSCs.

Conductivity and Stability Enhancement of PEDOT:PSS Electrodes via Facile Doping of Sodium 3-Methylsalicylate for Highly Efficient Flexible Organic Light-Emitting Diodes.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most prospering transparent conductive materials for flexible optoelectronic devices, which arises from its nonpareil features of low-cost solution processability, tunable conductivity, high transparency, and superior mechanical flexibility. However, acidity and hygroscopicity of PSS chains cause a decrease in conductivity, substrate corrosion, and device degradation. This work proposes a facile and effective direct doping strategy of sodium 3-methylsalicylate to enhance the conductivity, alleviate the acidity, and improve the stability of PEDOT:PSS electrodes, simultaneously. Owing to the formation of weaker acid and PSS-Na, PSS chains are disentangled from the coiled PEDOT:PSS complexes, leading to the phase separation of PEDOT:PSS and the formation of fibril-like PEDOT domains. Eventually, the sodium 3-methylsalicylate-modified PEDOT:PSS electrode is employed in flexible organic light-emitting diodes with an outstanding external quantum efficiency of up to 25%. The improved performance is attributed to the more matched work function and the as-formed interfacial dipole. The sodium 3-methylsalicylate-modified PEDOT:PSS electrode with high conductivity and transmittance, superior stability in the air as well as good mechanical flexibility has the potential to be the most promising transparent conductive material for flexible optoelectronic device applications.

Inkjet-Printed Highly Conductive Poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate) Electrode for Organic Light-Emitting Diodes.

Recently, inkjet printing technology has attracted much attention due to the advantages of drop-on-demand deposition, low-cost and large-area production for organic light-emitting diode (OLED) displays. However, there are still some problems in industrial production and practical application, such as the complexity of ink modulation, high-quality films with homogeneous morphology, and the re-dissolution phenomenon at interfaces. In this work, a printable poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) ink is developed and obtains an adjustable viscosity. Finally, a patterned PEDOT:PSS electrode is fabricated by inkjet printing, and achieves a high conductivity of 1213 S/cm, a transparency of 86.8% and a uniform morphology without coffee-ring effect. Furthermore, the vacuum-evaporated and solution-processed OLEDs are fabricated based on this electrode and demonstrate a current efficiency of 61 cd/A, which is comparable to that of the indium tin oxide counterpart. This work confirms the feasibility of inkjet printing technology to prepare patterned electrodes and expects that it can be used to fabricate highly efficient optoelectronic devices.