Control of Crystallite Orientation in Diketopyrrolopyrrole-Based Semiconducting Polymers via Tuning of Intermolecular Interactions.

Numerous previous studies have focused on the notion that semiconducting polymers with an edge-on dominant orientation are advantageous for horizontal charge transport, whereas polymers with a face-on dominant orientation are advantageous for vertical charge transport, since the crystallite orientation determines the π-π stacking direction, which in turn affects the interchain charge transport direction. Here, we report that the crystallite orientation is dependent on the intermolecular interactions in the semiconducting polymer. In this study, we control the intermolecular interactions in a donor-acceptor (D-A) semiconducting polymer via side chain engineering. To perform side chain engineering, we use two different polymers: one with side chains on only A units (PDPP-B) and the other with side chains on both D and A units (PDPP-C8). We observe that PDPP-C8 is characterized by weaker intermolecular interactions due to the additional side chains on D units. A morphological analysis reveals that PDPP-B and PDPP-C8 films have microstructures that are characterized by edge-on and face-on dominant orientations, respectively. Therefore, we demonstrate that our strategies effectively control intermolecular interactions and, consequently, the crystallite orientation. Finally, we compare the vertical and horizontal mobilities of both polymer films. These results show that the crystallite orientation has significant influence on charge transport behaviors.

Clinical and Laboratory Findings of Middle East Respiratory Syndrome Coronavirus Infection.

There is a paucity of data regarding the differentiating characteristics of patients with laboratory-confirmed and those negative for Middle East respiratory syndrome coronavirus (MERS-CoV) in South Korea. This hospital-based retrospective study compared MERS-CoV-positive and MERS-CoV-negative patients. A total of seven positive patients and 55 negative patients with a median age of 43 years (P = 0.845) were included. No statistical differences were observed with respect to their sex and the presence of comorbidities. At the time of admission, headache (28.6% vs. 3.6%; odds ratio [OR], 10.60; 95% confidence interval [CI], 1.22-92.27), myalgia (57.1% vs. 9.1%; OR, 13.33; 95% CI, 2.30-77.24), and diarrhea (57.1% vs. 14.5%; OR, 7.83; 95% CI, 1.47-41.79) were common among MERS-CoV-positive patients. MERS-CoV-positive patients were more likely to have a low platelet count (164 ± 76.57 vs. 240 ± 79.87) and eosinophil (0.27 ± 0.43 vs. 2.13 ± 2.01; P = 0.003). Chest radiography with diffuse bronchopneumonia was more frequent in MERS-CoV-positive patients than in negative patients (100% vs. 62.5%; P = 0.491). The symptoms of headache, myalgia, and diarrhea, as well as laboratory characteristics, including low platelet counts and eosinophil, and chest X-ray showing diffuse bronchopneumonia might enhance the ability to detect patients in South Korea infected with MERS-CoV.

Gradated Mixed Hole Transport Layer in a Perovskite Solar Cell: Improving Moisture Stability and Efficiency.

We demonstrate a simple and facile way to improve the efficiency and moisture stability of perovskite solar cells using commercially available hole transport materials, 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD) and poly(3-hexylthiophene) (P3HT). The hole transport layer (HTL) composed of mixed spiro-OMeTAD and P3HT exhibited favorable vertical phase separation. The hydrophobic P3HT was more distributed near the surface (the air atmosphere), whereas the hydrophilic spiro-OMeTAD was more distributed near the perovskite layer. This vertical separation resulted in improved moisture stability by effectively blocking moisture in air. In addition, the optimized composition of spiro-OMeTAD and P3HT improved the efficiency of the solar cells by enabling fast intramolecular charge transport. In addition, a suitable energy level alignment facilitated charge transfer. A device fabricated using the mixed HTL exhibited enhanced performance, demonstrating 18.9% power conversion efficiency and improved moisture stability.

Amine-Functionalized Covalent Organic Framework for Efficient SO2 Capture with High Reversibility.

Removing sulfur dioxide (SO2) from exhaust flue gases of fossil fuel power plants is an important issue given the toxicity of SO2 and subsequent environmental problems. To address this issue, we successfully developed a new series of imide-linked covalent organic frameworks (COFs) that have high mesoporosity with large surface areas to support gas flowing through channels; furthermore, we incorporated 4-[(dimethylamino)methyl]aniline (DMMA) as the modulator to the imide-linked COF. We observed that the functionalized COFs serving as SO2 adsorbents exhibit outstanding molar SO2 sorption capacity, i.e., PI-COF-m10 record 6.30 mmol SO2 g-1 (40 wt%). To our knowledge, it is firstly reported COF as SO2 sorbent to date. We also observed that the adsorbed SO2 is completely desorbed in a short time period with remarkable reversibility. These results suggest that channel-wall functional engineering could be a facile and powerful strategy for developing mesoporous COFs for high-performance reproducible gas storage and separation.

High-Field-Effect Mobility of Low-Crystallinity Conjugated Polymers with Localized Aggregates.

Charge carriers typically move faster in crystalline regions than in amorphous regions in conjugated polymers because polymer chains adopt a regular arrangement resulting in a high degree of π-π stacking in crystalline regions. In contrast, the random polymer chain orientation in amorphous regions hinders connectivity between conjugated backbones; thus, it hinders charge carrier delocalization. Various studies have attempted to enhance charge carrier transport by increasing crystallinity. However, these approaches are inevitably limited by the semicrystalline nature of conjugated polymers. Moreover, high-crystallinity conjugated polymers have proven inadequate for soft electronics applications because of their poor mechanical resilience. Increasing the polymer chain connectivity by forming localized aggregates via π-orbital overlap among several conjugated backbones in amorphous regions provides a more effective approach to efficient charge carrier transport. A simple strategy relying on the density of random copolymer alkyl side chains was developed to generate these localized aggregates. In this strategy, steric hindrance caused by these side chains was modulated to change their density. Interestingly, a random polymer exhibiting low alkyl side chain density and crystallinity displayed greatly enhanced field-effect mobility (1.37 cm(2)/(V·s)) compared with highly crystalline poly(3-hexylthiophene).

Requirements for Forming Efficient 3-D Charge Transport Pathway in Diketopyrrolopyrrole-Based Copolymers: Film Morphology vs Molecular Packing.

To achieve extremely high planarity and processability simultaneously, we have newly designed and synthesized copolymers composed of donor units of 2,2'-(2,5-dialkoxy-1,4-phenylene)dithieno[3,2-b]thiophene (TT-P-TT) and acceptor units of diketopyrrolopyrrole (DPP). These copolymers consist of a highly planar backbone due to intramolecular interactions. We have systematically investigated the effects of intermolecular interactions by controlling the side chain bulkiness on the polymer thin-film morphologies, packing structures, and charge transport. The thin-film microstructures of the copolymers are found to be critically dependent upon subtle changes in the intermolecular interactions, and charge transport dynamics of the copolymer based field-effect transistors (FETs) has been investigated by in-depth structure-property relationship study. Although the size of the fibrillar structures increases as the bulkiness of the side chains in the copolymer increases, the copolymer with the smallest side chain shows remarkably high charge carrier mobility. Our findings reveal the requirement for forming efficient 3-D charge transport pathway and highlight the importance of the molecular packing and interdomain connectivity, rather than the crystalline domain size. The results obtained herein demonstrate the importance of tailoring the side chain bulkiness and provide new insights into the molecular design for high-performance polymer semiconductors.

In situ modulation of the vertical distribution in a blend of P3HT and PC(60)BM via the addition of a composition gradient inducer.

2,2,3,3,4,4,4-Heptafluoro-N-phenyl-butyr-amide (F-ADD) was synthesized and shown to induce a composition gradient in a blend of P3HT and PC60BM. The addition of small amounts (ca. 0.5 wt%) of F-ADD modulated the chemical distribution in the blend along the vertical direction by controlling the blend component interface energy through selective interactions between F-ADD and PC60BM. A homogeneous compositional distribution along the vertical direction in the nanostructured bulk heterojunction (BHJ) increased the interfacial area, which shortened the exciton path length to the donor-acceptor interface and improved the photovoltaic performance.