Effective Approach toward Selective Near-Infrared Dyes: Rational Design, Synthesis, and Characterization of Thieno[3,4-b]thiophene-Based Quinoidal Oligomers.

This paper describes syntheses, photophysical properties, and electrochemical characteristics of three thieno[3,4-b]thiophene (TT)-based quinoidal oligomers OnTTO. The rigid planar backbones of these oligomers give the molecules narrow absorption bands, and the main absorption bands were significantly red-shifted when the TT units were extended and demonstrated wide transparent windows. The compound O4TTO was found to possess strong absorption in the near-infrared (NIR) region approaching 1200 nm but remained transparent in the visible region. Electrochemical experiments have shown that the energy band gaps gradually narrow when the TT units are increased. Optical properties predicted by density functional theory calculations are in good agreement with the experimental optical results. These dye molecules could be promising candidates for future NIR photodetectors, filters, and bioimaging technologies.

Synergy between Photoluminescence and Charge Transport Achieved by Finely Tuning Polymeric Backbones for Efficient Light-Emitting Transistor.

The lack of design principle for developing high-performance polymer materials displaying strong fluorescence and high ambipolar charge mobilities limited their performance in organic light-emitting transistors (OLETs), electrically pumped organic laser, and other advanced electronic devices. A series of semiladder polymers by copolymerization of weak acceptors (TPTQ or TPTI) and weak donors (fluorene (F) or carbazole (C)) have been developed for luminescent and charge transporting properties. It was found that enhanced planarity, high crystallinity, and a delicate balance in interchain aggregation obtained in the new copolymer, TPTQ-F, contributed to high ambipolar charge mobilities and photoluminescent quantum yield. TPTQ-F showed excellent performance in solution-processed multilayered OLET devices with an external quantum efficiency (EQE) of 5.3%.

Finely Designed P3HT-Based Fully Conjugated Graft Polymer: Optical Measurements, Morphology, and the Faraday Effect.

In this work, our group synthesized and characterized a fully conjugated graft polymer comprising of a donor-acceptor molecular backbone and regioregular poly(3-hexylthiophene) (RRP3HT) side chains. Here, our macromonomer (MM) was synthesized via Kumada catalyst transfer polycondensation reaction based on ditin-benzodithiophene (BDT) initiator. The tin content of MM was then investigated by inductively coupled plasma-mass spectrometry (ICP-MS), which allowed for accurate control of donor/acceptor monomer ratio of 1:1 for the following Stille coupling polymerization toward our graft polymer (BP). The structures of the polymers were then characterized by gel permeation chromatography (GPC), NMR, and elemental analysis. This was followed by the characterization of optical, electrochemical, and physical properties. The magneto-optical activity of graft polymer BP was then measured. It was found that, despite the presence of the acceptor backbone, the characteristic large Faraday rotation of RRP3HT was maintained in polymer BP, which exhibited a Verdet constant of 2.39 ± 0.57 (104) °/T·m.

Design of High-Performance Organic Light-Emitting Transistors.

Organic light-emitting transistors (OLETs) integrate the light-emitting and gate-modulated electrical switching functions in a single device. Over the past decades, progress has been made in developing new fluorescent semiconductors and device engineering that pushed efficiencies of OLET devices to 8%. However, this efficiency of transistors is still too low to be competitive with organic light-emitting diodes (OLEDs). Currently, there are relatively few suitable organic fluorescent semiconductors suitable for OLETs, and the mechanism of electroluminescence in the devices is still not fully understood. In this mini-review, we discuss the state of highly efficient OLETs and plausible approaches to those unsettled problems. Since this is a mini-review, we will not be able to cover all the excellent work in the literature. Readers are encouraged to read other excellent reviews published earlier.

Foldable semi-ladder polymers: novel aggregation behavior and high-performance solution-processed organic light-emitting transistors.

A critical issue in developing high-performance organic light-emitting transistors (OLETs) is to balance the trade-off between charge transport and light emission in a semiconducting material. Although traditional materials for organic light-emitting diodes (OLEDs) or organic field-effect transistors (OFETs) have shown modest performance in OLET devices, design strategies towards high-performance OLET materials and the crucial structure-performance relationship remain unclear. Our research effort in developing cross-conjugated weak acceptor-weak donor copolymers for luminescent properties lead us to an unintentional discovery that these copolymers form coiled foldamers with intramolecular H-aggregation, leading to their exceptional OLET properties. An impressive external quantum efficiency (EQE) of 6.9% in solution-processed multi-layer OLET devices was achieved.

Intra-molecular Charge Transfer and Electron Delocalization in Non-fullerene Organic Solar Cells.

Two types of electron acceptors were synthesized by coupling two kinds of electron-rich cores with four equivalent perylene diimides (PDIs) at the α-position. With fully aromatic cores, TPB and TPSe have π-orbitals spread continuously over the whole aromatic conjugated backbone, unlike TPC and TPSi, which contain isolated PDI units due to the use of a tetrahedron carbon or silicon linker. Density functional theory calculations of the projected density of states showed that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for TPB are localized in separate regions of space. Further, the LUMO of TPB shows a greater contribution from the orbitals belonging to the connective core of the molecules than that of TPC. Overall, the properties of the HOMO and LUMO point at increased intra-molecular delocalization of negative charge carriers for TPB and TPSe than for TPC and TPSi and hence at a more facile intra-molecular charge transfer for the former. The film absorption and emission spectra showed evidences for the inter-molecular electron delocalization in TPB and TPSe, which is consistent with the network structure revealed by X-ray diffraction studies on single crystals of TPB. These features benefit the formation of charge transfer states and/or facilitate charge transport. Thus, higher electron mobility and higher charge dissociation probabilities under Jsc condition were observed in blend films of TPB:PTB7-Th and TPSe:PTB7-Th than those in TPC:PTB7-Th and TPSi:PTB7-Th blend films. As a result, the Jsc and fill factor values of 15.02 mA/cm2, 0.58 and 14.36 mA/cm2, 0.55 for TPB- and TPSe-based solar cell are observed, whereas those for TPC and TPSi are 11.55 mA/cm2, 0.47 and 10.35 mA/cm2, 0.42, respectively.

Enhancement in Open-Circuit Voltage in Organic Solar Cells by Using Ladder-Type Nonfullerene Acceptors.

The open-circuit voltage ( Voc) loss has always been a major factor in lowering power conversion efficiencies (PCEs) in bulk heterojunction organic photovoltaic cells (OPVs). A method to improve the Voc is indispensable to achieve high PCEs. In this paper, we investigated a series of perylene diimide-based ladder-type molecules as electron acceptors in nonfullerene OPVs. The D-A ladder-type structures described here lock our π-systems into a planar structure and eliminate bond twisting associated with linear conjugated systems. This enlarges the interface energy gap (Δ EDA), extends electronic delocalization, and hence improves the Voc. More importantly, these devices showed an increase in Voc without compromising either the Jsc or the FF. C5r exhibited a strong intermolecular interaction and a PCE value of 6.1%. Moreover, grazing-incident wide-angle X-ray scattering analysis and atomic force microscopy images suggested that our fused-ring acceptors showed a suitable domain size and uniform blend films, which were not affected by their rigid molecular structures.

Wide bandgap OPV polymers based on pyridinonedithiophene unit with efficiency >5.

We report the properties of a new series of wide band gap photovoltaic polymers based on the N-alkyl 2-pyridone dithiophene (PDT) unit. These polymers are effective bulk heterojunction solar cell materials when blended with phenyl-C71-butyric acid methyl ester (PC71BM). They achieve power conversion efficiencies (up to 5.33%) high for polymers having such large bandgaps, ca. 2.0 eV (optical) and 2.5 eV (electrochemical). Grazing incidence wide-angle X-ray scattering (GIWAXS) reveals strong correlations between π-π stacking distance and regularity, polymer backbone planarity, optical absorption maximum energy, and photovoltaic efficiency.