Optimizing Alkyl Side Chains in Difluorobenzene-Rhodanine Small-Molecule Acceptors for Organic Solar Cells.

A series of small molecules, T-2FB-T-ORH, T-2FB-T-BORH, and T-2FB-T-HDRH, were synthesized to have a thiophene-flanked difluorobenzene (T-2FB-T) core and alkyl-substituted rhodanine (RH) end groups for their use as nonfullerene acceptors (NFAs) in organic solar cells (OSCs). Octyl, 2-butyloctyl (BO), and 2-hexyldecyl (HD) alkyl side chains were introduced into RHs to control the material's physical properties based on the length and size of the alkyl chains. The optical properties of the three NFAs were found to be almost the same, irrespective of the alkyl chain length, whereas the molecular crystallinity and material solubility significantly differed depending on the alkyl side chains. Owing to the sufficient solubility of T-2FB-T-HDRH, OSCs based on PTB7-Th and T-2FB-T-HDRH were fabricated. A power conversion efficiency of up to 4.49% was obtained by solvent vapor annealing (SVA). The AFM study revealed that improved charge mobility and a smooth and homogeneous film morphology without excessive aggregation could be obtained in the SVA-treated film.

Neuromuscular complications of the lower extremity after thrombectomy in a patient with superficial femoral artery occlusion: Case series.

BACKGROUND: Ischemia reperfusion (IR) injury may result in rhabdomyolysis and compartment syndrome when blood supply returns after thrombectomy for patients with acute limb ischemia. OBJECTIVE: We highlight the value of early diagnosis and treatment in post-thrombectomy patients with IR injuries in their lower legs. CASE DESCRIPTION: Two patients received thrombectomy due to left superficial femoral artery occlusion. Both patients complained of left calf pain during ambulation at the 1- and 3-day follow up post-thrombectomy, as well as a heating sensation, swelling, weakness, and sensory changes in the affected leg. For early diagnosis musculoskeletal ultrasounds were performed and in both cases revealed swelling and change of echogenicity in the left calf. To further diagnosis, magnetic resonance imaging of the left leg revealed limb IR-induced muscular injury and rhabdomyolysis, respectively. In both cases, an electrodiagnostic study revealed peripheral nerve injury in the left leg. Medications were provided for neuropathic pain control and early rehabilitation was performed to improve function. In both cases, patients reported during their follow-up that their pain and muscle weakness had improved. CONCLUSION: When post-thrombectomy calf pain occurs early evaluation and treatment should be performed to identify any potential IR injury.

Importance of proper ventilator support and pulmonary rehabilitation in obese patients with heart failure: Two case reports.

BACKGROUND: The optimal treatment for heart failure (HF) is a combination of appropriate medications. Controlling the disease using only medical therapy is difficult in patients with HF, severe hypercapnia, and desaturation. These patients should first receive ventilator support followed by pulmonary rehabilitation (PR). CASE SUMMARY: We report two cases in which arterial blood gas (ABG) improved and PR was possible with appropriate ventilator support. Two patients with extreme obesity complaining of worsening dyspnea-a 47-year-old woman and a 36-year-old man both diagnosed with HF-were hospitalized because of severe hypercapnia and hypoxia. Despite proper medical treatment, hypercapnia and desaturation resolved in neither case, and both patients were transferred to the rehabilitation department for PR. At the time of the first consultation, the patients were bedridden because of dyspnea. Oxygen demand was successfully reduced once noninvasive ventilation was initiated. As the patients' dyspnea gradually improved to the point where they could be weaned off the ventilator during the daytime, they started engaging in functional training and aerobic exercise. After 4 mo of follow-up, both patients were able to perform activities of daily living and maintain their lower body weight and normalized ABG levels. CONCLUSION: Symptoms of patients with obesity and HF may improve once ABG levels are normalized through ventilator support and implementation of PR.

Enhanced Static and Dynamic Properties of Highly Miscible Fullerene-Free Green-Selective Organic Photodetectors.

We developed p-n junction organic photodetectors (OPDs) composed of a polymer donor and a nonfullerene acceptor (NFA) to increase both the responsivity (R) and detectivity (D*) while maintaining a narrow wavelength selectivity. The selection of the polymer donor and NFA with similar green (G) absorption is important for achieving G-wavelength selectivity in these OPDs, which differentiates them from current fullerene-based OPDs and NFA-based panchromatic absorption OPDs. In addition, mixing the polymer donor and asymmetric NFA was efficient toward increasing the miscibility and decreasing the interfacial energy difference of the blended films, resulting in the formation of a uniform and well-mixed nanomorphology in the photoconductive layer. Two-dimensional (2D) grazing incidence X-ray diffraction and Fourier-transform infrared spectroscopy revealed that the lamellar ordering of the polymer donor was enhanced in the blend film prepared with an asymmetric NFA, whereas the aggregation of a symmetric NFA in the blend films did not increase the lamellar ordering of the polymer donor. Consequently, we achieved an R value of 0.31 A/W and D* value of 2.0 × 1013 Jones with a full width at half-maximum value of 230 nm at -2 V and fast response time of 27 µs without any external bias in the asymmetric NFA-based OPDs. The enhancement in the lamellar ordering and miscibility of the blended films are crucial toward increasing the static and dynamic properties of OPDs.

Alkyl-Side-Chain Engineering of Nonfused Nonfullerene Acceptors with Simultaneously Improved Material Solubility and Device Performance for Organic Solar Cells.

Two nonfullerene small molecules, TBTT-BORH and TBTT-ORH, which have the same thiophene-benzothiadiazole-thiophene (TBTT) core flanked with butyloctyl (BO)- and octyl (O)-substituted rhodanines (RHs) at both ends, respectively, are developed as electron acceptors for organic solar cells (OSCs). The difference between the alkyl groups introduced into TBTT-BORH and TBTT-ORH strongly influence the intermolecular aggregation in the film state. Differential scanning calorimetry and UV-vis absorption studies reveal that TBTT-ORH exhibited stronger molecular aggregation behavior than TBTT-BORH. On the contrary, the material solubility is greatly improved by the introduction of a BO group in TBTT-BORH, and the inevitably low molecular interaction and packing ability of the as-cast TBTT-BORH film can be effectively increased by a solvent-vapor annealing (SVA) treatment. OSCs based on the two acceptors and PTB7-Th as a polymer donor are fabricated owing to their complementary absorption and sufficient energy-level offsets. The best power conversion efficiency of 8.33% is obtained with the SVA-treated TBTT-BORH device, where, together with a high open-circuit voltage of 1.02 V, the charge-carrier mobility and the short-circuit current density were greatly improved by the SVA treatment to levels comparable to those of the TBTT-ORH device because of the suppressed charge recombination and improved film morphology. In this work, the simultaneous improvement of both material solubility and device performance is achieved through alkyl side-chain engineering to balance the trade-offs among material solubility/crystallinity/device performance.

Simple and Versatile Non-Fullerene Acceptor Based on Benzothiadiazole and Rhodanine for Organic Solar Cells.

Most non-fullerene acceptors (NFAs) are designed in a complex planar molecular conformation containing fused aromatic rings in high-efficiency organic solar cells (OSCs). To obtain the final molecules, however, numerous synthetic steps are necessary. In this work, a novel simple-structured NFA containing alkoxy-substituted benzothiadiazole and a rhodanine end group (BTDT2R) is designed and synthesized. We also investigate the photovoltaic properties of BTDT2R-based OSCs employing representative polymer donors (wide band gap and high-crystalline P3HT, medium band gap and semicrystalline PPDT2FBT, and narrow band gap and low-crystalline PTB7-Th) to compare the performance capabilities of fullerene acceptor-based OSCs, which are well matched with various polymer donors. OSCs based on P3HT:BTDT2R, PPDT2FBT:BTDT2R, and PTB7-Th:BTDT2R achieved efficiency as high as 5.09, 6.90, and 8.19%, respectively. Importantly, photoactive films incorporating different forms of optical and molecular ordering characteristics exhibit favorable morphologies by means of solvent vapor annealing. This work suggests that the new n-type organic semiconductor developed here is highly promising as a universal NFA that can be paired with various polymer donors with different optical and crystalline properties.

3,3'-Bicarbazole-Based Host Molecules for Solution-Processed Phosphorescent OLEDs.

Solution-processed organic light-emitting diodes (OLEDs) are attractive due to their low-cost, large area displays, and lighting features. Small molecules as well as polymers can be used as host materials within the solution-processed emitting layer. Herein, we report two 3,3'-bicarbazole-based host small molecules, which possess a structural isomer relationship. 9,9'-Di-4-n-butylphenyl-9H,9'H-3,3'-bicarbazole (BCz-nBuPh) and 9,9'-di-4-t-butylphenyl-9H,9'H-3,3'-bicarbazole (BCz-tBuPh) exhibited similar optical properties within solutions but different photoluminescence within films. A solution-processed green phosphorescent OLED with the BCz-tBuPh host exhibited a high maximum current efficiency and power efficiency of 43.1 cd/A and 40.0 lm/W, respectively, compared to the device with the BCz-nBuPh host.

Morphology controls the thermoelectric power factor of a doped semiconducting polymer.

The electrical performance of doped semiconducting polymers is strongly governed by processing methods and underlying thin-film microstructure. We report on the influence of different doping methods (solution versus vapor) on the thermoelectric power factor (PF) of PBTTT molecularly p-doped with F n TCNQ (n = 2 or 4). The vapor-doped films have more than two orders of magnitude higher electronic conductivity (σ) relative to solution-doped films. On the basis of resonant soft x-ray scattering, vapor-doped samples are shown to have a large orientational correlation length (OCL) (that is, length scale of aligned backbones) that correlates to a high apparent charge carrier mobility (µ). The Seebeck coefficient (α) is largely independent of OCL. This reveals that, unlike σ, leveraging strategies to improve µ have a smaller impact on α. Our best-performing sample with the largest OCL, vapor-doped PBTTT:F4TCNQ thin film, has a σ of 670 S/cm and an α of 42 µV/K, which translates to a large PF of 120 µW m-1 K-2. In addition, despite the unfavorable offset for charge transfer, doping by F2TCNQ also leads to a large PF of 70 µW m-1 K-2, which reveals the potential utility of weak molecular dopants. Overall, our work introduces important general processing guidelines for the continued development of doped semiconducting polymers for thermoelectrics.

Increased Photovoltaic Performance in Polymer-Oligothiophene-[6,6]-Phenyl-C61 -Butyric Acid Methylester Ternary Blend Films.

The introduction of oligothiophenes (b-5T and b-5TB) improved the performance of F85TB:PCBM bulk heterojunction OPV cells due to improved UV-vis absorption and the well-matched cascade energy levels between components.

Rhodanine dye-based small molecule acceptors for organic photovoltaic cells.

The solution-processable small molecules based on carbazole or fluorene containing rhodanine dyes at both ends were synthesized and introduced as acceptors in organic photovoltaic cells. The high energy levels of their lowest unoccupied molecular orbitals resulted in a power conversion efficiency of 3.08% and an open circuit voltage of up to 1.03 V.

Enhancing the performance of solution-processed n-type organic field-effect transistors by blending with molecular "aligners".

A novel approach to enhancing the performance of solution-processed n-type organic field-effect transistors by using trace amounts of molecular "aligners" to manipulate the assembly of "matrix" molecules in thin films is demonstrated. The device performance is one order of magnitude higher in 1wt% blended thin films than that in neat films, which correlates to an induced change of preferred orientation of the in-plane π-stacking molecules upon blending.

Polymer Side Chain Modification Alters Phase Separation in Ferroelectric-Semiconductor Polymer Blends for Organic Memory.

Side chain modification of a semiconducting polythiophene changes the resulting phase separation length scales when blended with a ferroelectric polymer for use in organic ferroelectric resistive switches. The domain size of the semiconducting portion of blends of poly[3-(ethyl- 5-pentanoate)thiophene-2,5-diyl] (P3EPT) and poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) in thin film blends are smaller than previously reported and easily controllable in size through simple tuning of the weight fraction of the semiconducting polymer. Furthermore, P3EPT has a relatively high degree of crystallinity and bimodal crystallite orientations, as probed by wide-angle X-ray scattering. Resistive switches fabricated from blends of P3EPT and PVDF-TrFE show memristive switching behavior over a wide range of polythiophene content and good ON/OFF ratios.

Synthesis and characterization of poly(vinylpyrrolidone)-capped silicon-nanoparticles.

Polymer-capped silicon nanoparticles (Si NPs) were prepared using poly(vinylpyrrolidone) (PVP) as a protection layer to minimize the surface oxidation of the surface. The wet synthetic procedure were performed at room temperature via a one-pot synthesis. The PVP capped Si-NPs were characterized by thermo gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), high resolution transmission electron microscopy (HR-TEM) and field emission scanning electron microscopy (FE-SEM). HR-TEM micrograms confirm the presence of crystalline Si-NPs. The pattern by Selected Area Electron Diffraction (SAED) reveals (111), (220) lattice planes which are consistent with the cubic-structured crystalline silicon. The mean size of Si-NPs is estimated to be ca. 10 nm, which is larger than those from conventional wet synthetic methods for silicon quantum dots.

Relationship between the energy levels and the photovoltaic properties of oligothiophenes.

A series of linear π-conjugated oligothiophenes, α,α'-dihexylquinquethiophene (DH5T), 2,5-bis(5'-hexyl-2,2'-bithiophene-5-yl)thieno[3,2-b]thiophene (DH5TT), and α,α'-dihexylheptathiophene (DH7T), has been synthesized using the Suzuki coupling reaction. The optical and electrochemical properties of oligothiophenes were easily tuned by controlling the thiophene number. The UV-vis absorption and photoluminescence (PL) spectra are gradually red-shifted on going from DH5T and DH5TT to DH7T due to the increase in α-conjugation length. The energy band gap decreased as the oligothiophene length increased. The optical band gaps of DH5T, DH5TT, and DH7T occur at 2.39, 2.25, and 2.01 eV, respectively. Bulk heterojunction organic photovoltaic cells (OPVs) fabricated from oligomers showed the power conversion efficiency of 0.45-0.8% under AM 1.5 (100 mW/cm2). Among them, DH5T showed the best OPV performance of an open circuit voltage (VOC) of 0.51 V, short-circuit current (JSC) of 4.25 mA/cm2, and fill factor (FF) of 0.37, resulting in the power conversion efficiency of 0.80%. Moreover, the relationship between conjugation length and photovoltaic properties was systematically investigated in terms of the energy band gap and open circuit voltage (VOC).

Structural modification of fluorene-thiophene-based copolymers for OPVs.

A series of fluorene-thiophene-based pi-conjugated copolymers, PFT2, PFT4, and PFT2BP, have been synthesized using the Suzuki coupling reaction. Compared to PFT2 and PFT2BP, PFT4 film showed clearly red-shifted UV-visible absorption and photoluminescence (PL) spectra with maxima at 474 and 597 nm, respectively. The optical and electrochemical properties of copolymers could be tuned by changing conjugation lengths of comonomer units from bithiophene (PFT2) to quaterthiophene (PFT4). Moreover, PFT4 containing quaterthiophene showed relatively lower optical band gap of 2.16 eV. The organic photovoltaic cells (OPVs) were fabricated using the copolymers as donor with a sandwich configuration of ITO/PEDOT:PSS/copolymer:PC71BM/LiF/Al. PFT4 showed the best device performance with the optimized power conversion efficiency (PCE) of 2.26% (J(SC) = 7.67 mA/cm2, V(OC) = 0.81 V, FF = 0.36). The higher OPV performance of PFT4 can be explained by its relatively low energy band gap and improved UV absorption property.

Evolution of ordered metal chalcogenide architectures through chemical transformations.

Metal chalcogenides are important materials for a myriad of devices, but the ability to control their porosity is lacking. We report a method of inducing hierarchically ordered porosity using surface-treated nanocrystals and complementary architecture-directing agents. The resulting mesoporous materials are robust to thermal annealing and chemical transformations.

Synthesis and photovoltaic properties of a new thiophene-cyclopentadiene-based conjugated polymer.

A new low-band gap polymer containing thiophene and cyclopentadiene, poly(5,2,2'-dioctyldithio-phenylcyclopentadiene) (PDTCP), has been synthesized via the FeCl3 oxidative polymerization. PDTCP showed a broad absorption band and a low energy band gap of 1.82 eV. The photoluminescence (PL) of PDTCP is completely quenched upon addition of PCBM indicative of efficient charge transfer. Bulk heterojunction organic photovoltaic cells (OPVs) fabricated from PDTCP as an electron donor showed an open-circuit voltage (V(OC)) of 0.50 V, a short-circuit current (J(SC)) of 1.24 mA/cm2, and the power conversion efficiency of up to 0.20% under AM 1.5 (100 mW/cm2).

Synthesis and photovoltaic properties of new conjugated polymers based on benzo[1,2-b:4,5-b']dithiophene.

New conjugated polymers based on benzo[1,2-b:4,5-b']dithiophene, poly(benzo[1,2-b:4,5-b'] dithiophene-alt-bithiophene) (PBT-2T) and poly(benzo[1,2-b:4,5-b']dithiophene-alt-terthiophene) (PBT-3T), have been synthesized via the Stille coupling reaction and their optical and electrochemical properties were characterized by UV-vis, photoluminescence (PL) and cyclic voltammetry (CV) measurements. Compared to PBT-2T, PBT-3T film showed clearly red-shifted UV-visible absorption and PL spectra with maxima at 511 and 653 nm, respectively. Especially, PBT-3T containing terthiophene showed very small optical band gap of 1.65 eV. The PBT-2T and PBT-3T showed the power conversion efficiencies of 0.25% and 0.34%, respectively, under AM 1.5 (100 m/cm2).

Synthesis and characterization of regioregular alkyl-substituted poly(3,4-ethylenedioxythiophenes).

In order to increase the solubility of PEDOT, we introduced an alkyl chain into polymer backbone. Depending on the position of the alkyl bond, the steric hindrance between the alkyl chains can also leads to regioregularity in the polymer. The regioregular polymers can easily occur self-assembly, both in solution and in the solid state, resulting in highly ordered two- and three-dimensional polymer architectures. A series of soluble regioregular alkyl-substituted PEDOTs were synthesized using the Grignard Metathesis (GRIM) for the purpose of study on regiorandom and regioregular PEDOT. The ethylene proton adjacent to the oxygen atom of regioregular methoxydodecyl-PEDOT appears at 3.51 ppm, whereas the corresponding peak of regiorandom methoxydodecyl-PEDOT appears at 3.42 ppm.

Improved photovoltaic properties of fluorene-thiophene-based copolymers by an electron-transporting triazole unit in the main chain.

An electron-transporting triazole (Tz) unit was introduced into the fluorene-thiophene-based copolymer backbone via a Suzuki coupling reaction. The resulting copolymer, poly[9,9'-dioctyl-fluorene-co-5, 5-(4', 7'-di-2-thienyl-2', 1',3'-benzothiadiazole)-co-(4-(4-butyl-phenyl)-3, 5-diphenyl-4H-1,2,4]triazole)] (PF3TBTz), was soluble in common organic solvents and can be easily used as the active layer in organic photovoltaic cells (OPVs). By the introduction of the triazole unit, the OPV performance was nearly doubled from 0.62% (PF3TB) to 1.25% (PF3TBTz) under the same conditions. The higher performance can be explained by the improved surface morphology, resulting in better charge photogeneration and higher short circuit current (J(sc)) value in PF3TBTz in comparison with PF3TB. The possibility of the use of triazole units in OPV applications are described herein.