A copolymerization strategy is developed to utilize porphyrin as a complementary light-harvesting unit (LHU) in D-A polymers. For polymer solar cells (PSCs), the presence of LHUs increases the short-circuit current density (Jsc ) without sacrificing the open-circuit voltage (Voc ) and fill factor (FF). Up to 8.0% power conversion efficiency (PCE) is delivered by PPor-2:PC71 BM single-junction PSCs. A PCE of 8.6% is achieved when a C-PCBSD cathodic interlayer is introduced.

Poly(dimethylsiloxane) (PDMS)-assisted crystallization (PAC) is a facile method to produce oriented C60 crystal arrays. Changing the drying mechanism from evaporation to solvent absorption (by PDMS) widens the solvent selection and facilitates the engineering of both the macroscopic shape and the microscopic lattice structure of the crystal arrays. The method also shows the potential to be applied to other organic semiconductors and large-area production.

Among the polycyclic aromatic hydrocarbons, although perylene is commercially available and possesses higher solubility and stability than the others, its thin-film structures and organic field-effect transistor (OFET) performances have been rarely explored. To understand its potential as an active material in OFETs, the polymorphic behaviors, packing structures, and OFET characteristics of perylene were carefully examined. The well-oriented crystal arrays of perylene prepared via droplet-pinned crystallization delivered the highest hole mobility among the reported perylene OFETs. Fluorescence microscope, electron diffraction, and lattice modeling results confirm the polymorphic behavior of perylene in the solution-processed crystal arrays and its influences on the OFET performances. The concentration-sensitive and temperature-sensitive polymorphic behavior of perylene make processing conditions crucial in the preparation of pure-phase crystal arrays. The results show the great potential of perylene as an active material in low-cost and high-performance OFETs. Moreover, the knowledge regarding the polymorphic behavior of perylene provides opportunity for the further optimization of perylene-based OFETs.

D–A conjugated molecules are complicated in both their molecular and their packing structures. In this perspective, we summarize more than 40 crystal lattices of conjugated oligomers to identify the morphological influence of each building block on the D–A molecules. These lattice structures reveal not only the packing preferences of the conjugated oligomers but also the conformational disorder in the lattices. The presence of this disorder in slowly grown crystals implies that attaining total long-range conformational order is challenging for D–A oligomers, which are structurally complicated and readily distorted and which have building blocks of incommensurate packing dimensions. In optoelectronic applications, a decreased duration of processing can prevent ordering and trap the thin films of D–A oligomers from becoming crystalline phases. Although D–A oligomers conform to packing principles in the formation of a single crystal, their phase behaviors in the formation of active thin films are much more difficult to comprehend. Continuous advances in methods of characterization are still strongly required for the steps of attaining a true structure–property relation of D–A oligomers in active films for optoelectronic applications.

New 3,3'-dithioalkyl-2,2'-bithiophene (SBT)-based small molecular and polymeric semiconductors are synthesized by end-capping or copolymerization with dithienothiophen-2-yl units. Single-crystal, molecular orbital computations, and optical/electrochemical data indicate that the SBT core is completely planar, likely via S(alkyl)⋯S(thiophene) intramolecular locks. Therefore, compared to semiconductors based on the conventional 3,3'-dialkyl-2,2'-bithiophene, the resulting SBT systems are planar (torsional angle <1°) and highly π-conjugated. Charge transport is investigated for solution-sheared films in field-effect transistors demonstrating that SBT can enable good semiconducting materials with hole mobilities ranging from ≈0.03 to 1.7 cm V s . Transport difference within this family is rationalized by film morphology, as accessed by grazing incidence X-ray diffraction experiments.

Stable and laser manipulable iron-carbonyl aqueous vesicles with aggregation-enhanced IR absorption and emission are reported.

Here, two diketopyrrolopyrrole (DPP)-based oligomers, DPP-4T and DPP-6T, are studied to reveal the influences of conjugation length on thin-film morphology and organic field-effect transistor (OFET) performances. PDMS-assisted crystallization in a solvent-annealing chamber is applied to prepare crystal arrays of DPP-4T and DPP-6T to optimize the quality of charge channels for OFET characterizations. To deliver insights into microstructure and morphology of thin films, a characterization procedure for determining molecular packing in thin film and crystallinity of the crystal arrays is presented via grazing incidence wide-angle X-ray scattering, electron diffraction, and lattice simulation software package (Cerius2). With the lattice parameters derived from analyses of grazing incidence wide-angle X-ray scattering (GIWAXS) and electron diffraction (ED), the lattice modeling results indicate that the inferior organic field-effect transistor (OFET) performances of DPP-6T are attributed to longer π-stacking distance. Also, less-ordered molecular arrangement and lower continuity of crystalline domains, both of which are revealed from crystallinity results, lead to lower mobility of DPP-6T. In this case, longer conjugated backbones with more conformational degrees of freedom thus cause inherent crystal defects during the crystal growth process, despite the potential to enhance intermolecular π-orbital overlap. Therefore, to achieve better OFET performance, suitable backbone length makes conjugated oligomers give high intermolecular π-orbital overlap and low density of structural disorder, which are the priorities for constructing good charge channel.

In organic field-effect transistors (OFETs), the quality of chargetransport pathway, controlled by crystal structures of organic semiconductors (OSCs), strongly affects the performance of the device. To achieve higher charge mobility, solution-processed single-crystal (SPSC) techniques have been used to decrease crystal defects by aligning the crystals of OSCs in the in-plane direction. Nonetheless, through SPSC techniques, whether the crystalline lattices are wellaligned in the out-of-plane direction and how the out-of-plane lattice misorientaion affects OFET performances remain unclear. Here, a characterization protocol based on polarized optical microscope, X-ray diffraction, and electron diffraction is established to identify the lattice structure, the in-plane and out-of-plane lattice alignment in the crystal array of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-PEN). Regardless of the solvents used in the PDMS-assisted crystallization, the characterization protocol confirms that all the crystal arrays share the same lattice structure (form I phase), and have similar in-plane lattice alignment. However, TIPS-PEN molecules have sufficient time to unify their out-of-plane orientation and prevent the formation of low angle grain boundary (LAGB) during crystal growth if high boiling temperature solvents are used. The improved out-of-plane lattice alignment increases the hole mobility and decreases the performance fluctuations of devices. The results confirm that the out-of-plane lattice alignment significantly impacts the performance of the devices and the reproducibility of the solution-processed TIPS-PEN OFETs.