Investigation into aggregation types in a benzodithiophene-isoindigo copolymer.

The type of aggregation in conjugated polymers determines their use in electronic devices. H-type aggregates are most suitable for solar cell applications, while J-type aggregates are recommended for light-emitting diodes. In this work, we used three methods to determine the type of aggregates in a benzodithiophene-isoindigo-based (PBDTI-DT) copolymer, namely, Huang-Rhys factor evolution with temperature, Franck-Condon analysis, and relative quantum yield (QY) calculation. All three methods indicate that both aggregation types are present, and the QY calculation clearly indicates that H-aggregates are more dominant. Time-dependent density functional theory was used to identify the two absorption bands of PBDTI-DT as local π - π* and intramolecular charge-transfer transitions.

Antimalarial Activity of Acetylenic Thiophenes from Echinops hoehnelii Schweinf.

Malaria is one of the world's most severe endemic diseases and due to the emergence of resistance to the currently available medicines, the need for new targets and relevant antimalarial drugs remains acute. The crude extract, four solvent fractions and two isolated compounds from the roots of Echinops hoehnelii were tested for their antimalarial activity using the standard four-day suppressive method in Plasmodium berghei-infected mice. The 80% methanol extract exhibited suppression of 4.6%, 27.8%, 68.5% and 78.7% at dose of 50, 100, 200 and 400 mg/kg respectively. The dichloromethane fraction displayed chemosuppression of 24.9, 33.5 and 43.0% dose of 100, 200 and 400 mg/kg of body weight. Five acetylenicthiophenes were isolated from the dichloromethane fraction of which 5-(penta-1,3-diynyl)-2-(3,4-dihydroxybut-1-ynyl)-thiophene decreased the level of parasitaemia by 43.2% and 50.2% while 5-(penta-1,3-diynyl)-2-(3-chloro-4-acetoxy-but-1-yn)-thiophene suppressed by 18.8% and 32.7% at 50 and 100 mg/kg, respectively. The study confirmed the traditional claim of the plant to treat malaria and could be used as a new lead for the development of antimalarial drugs.

Enhancing the Performance of Wide-Bandgap Polymer-Based Organic Solar Cells through Silver Nanorod Integration.

Light trapping induced by the introduction of metallic nanoparticles has been shown to improve photo absorption in organic solar cells (OSCs). Researchers in the fields of plasmonics and organic photovoltaics work together to boost sunlight absorption and photon-electron interactions in order to improve device performance. In this contribution, an inverted OSC was fabricated by using indacenodithieno[3,2-b]thiophene-alt-2,2'-bithiazole (PIDTT-BTz) as a wide-band gap donor copolymer and (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) as an acceptor. Silver nanorods (Ag-NRs), synthesized by precipitation method, were embedded in the active layer of the solar cell. The device fabricated with 1 wt % Ag-NRs in the active layer showed a 26% improvement in power conversion efficiency (PCE) when exposed to 100 mW/cm2 simulated solar illumination. The role of Ag-NRs in the performance improvement of the OSCs was analyzed systematically using morphological, electrical, and optical characterization methods. The light trapping and exciton generation were improved due to the localized surface plasmon resonance (LSPR) activated in Ag-NRs in the form of longitudinal and transverse modes. The photoactive layers (PIDTT-BTz:PC71BM) with the incorporation of 0.5 and 1 wt % Ag-NR showed increased absorption, while the absorption with 1.5 wt % Ag-NRs appeared to be reduced in the wavelength range from 400 to 580 nm. Ag-NRs play a favorable role in exciton photogeneration and dissociation due to the two LSPR modes generated by the Ag-NRs. In the optimized device, the short-circuit current density (JSC) increased from 11.92 to 14.25 mA/cm2, resulting in an increase in the PCE from 3.94 to 4.93%, which is attributed to the improved light-trapping by LSPR using Ag-NRs.

Aqueous Processed All-Polymer Solar Cells with High Open-Circuit Voltage Based on Low-Cost Thiophene-Quinoxaline Polymers.

Eco-friendly solution processing and the low-cost synthesis of photoactive materials are important requirements for the commercialization of organic solar cells (OSCs). Although varieties of aqueous-soluble acceptors have been developed, the availability of aqueous-processable polymer donors remains quite limited. In particular, the generally shallow highest occupied molecular orbital (HOMO) energy levels of existing polymer donors limit further increases in the power conversion efficiency (PCE). Here, we design and synthesize two water/alcohol-processable polymer donors, poly[(thiophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-T)) and poly[(selenophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-Se)) with oligo(ethylene glycol) (OEG) side chains, having deep HOMO energy levels (∼-5.4 eV). The synthesis of the polymers is achieved in a few synthetic and purification steps at reduced cost. The theoretical calculations uncover that the dielectric environmental variations are responsible for the observed band gap lowering in OEG-based polymers compared to their alkylated counterparts. Notably, the aqueous-processed all-polymer solar cells (aq-APSCs) based on P(Qx8O-T) and poly[(N,N'-bis(3-(2-(2-(2-methoxyethoxy)-ethoxy)ethoxy)-2-((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-methyl)propyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-(2,5-thiophene)] (P(NDIDEG-T)) active layer exhibit a PCE of 2.27% and high open-circuit voltage (VOC) approaching 0.8 V, which are among the highest values for aq-APSCs reported to date. This study provides important clues for the design of low-cost, aqueous-processable polymer donors and the fabrication of aqueous-processable OSCs with high VOC.

Embedding plasmonic gold nanoparticles in a ZnO layer enhanced the performance of inverted organic solar cells based on an indacenodithieno[3,2-b]thiophene-alt-5,5'-di(thiophen-2-yl)-2,2'-bithiazole-based push-pull polymer.

Recently, plasmonic nanoparticles (NPs) have attracted considerable attention as good candidates for enhancing the power conversion efficiency (PCE) of organic solar cells (OSCs) owing to their localized surface plasmon resonance (LSPR). In this study, the effect of embedding colloidal gold nanoparticles (cAu NPs) in the ZnO electron transport layer (ETL) on the PCEs of wide band gap polymer-based inverted OSCs was investigated. The active layer was composed of a bulk heterojunction of conjugated polymer based on indacenodithieno[3,2-b]thiophene and 5,5'-di(thiophen-2-yl)-2,2'-bithiazole PIDTT-DTBTz as a donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as an acceptor. The PCE of the reference device was improved by 22% when 10 wt% cAu NPs were embedded in the ZnO ETL. The short circuit current density (JSC) and fill factor (FF) were the main photovoltaic parameters contributing to the PCE enhancement. An improved absorption in the active layer due to the LSPR of cAu NPs as well as efficient exciton dissociation and charge collection were found to be the reasons for the enhanced JSC while the increase in FF was mainly due to the suppressed traps and improved conductivity of the ZnO layer by the NPs.

Photophysical, Thermal and Structural Properties of Thiophene and Benzodithiophene-Based Copolymers Synthesized by Direct Arylation Polycondensation Method.

Three low-band-gap copolymers based on isoindigo acceptor units were designed and successfully synthesized by direct arylation polycondensation method. Two of them were benzodithiophene (BDT)-isoindigo copolymers (PBDTI-OD and PBDTI-DT) with 2-octlydodecyl (OD) and 2-decyltetradecyl (DT) substituted isoindigo units, respectively. Thiophene donor and DT-substituted isoindigo acceptor units were copolymerized to synthesize PTI-DT. The copolymers have a broad absorption range that extends to over 760 nm with a band gap ≈1.5 eV. The photophysical property studies showed that the BDT-based copolymers have non-polar ground states. Their emission exhibited the population of the intramolecular charge transfer (ICT) state in polar solvents and tightly bound excitonic state in non-polar solvents due to self-aggregation. On the contrary, the emission from the thiophene-based copolymers was only from the tightly bound excitonic state. The thermal decomposition temperature of the copolymers was above 380 °C. The X-ray diffraction pattern of the three copolymers showed a halo due to π-π stacking. A second, sharper peak was observed in the BDT-based copolymer with a longer side chain on the isoindigo unit (PBDTI-DT), and the thiophene-based copolymers with PTI-DT, exhibiting a better structural order.

Total synthesis, antiprotozoal and cytotoxicity activities of rhuschalcone VI and analogs.

The total synthesis of a potent antiplasmodial natural bichalcone, rhuschalcone VI, is described starting from simple and available resorcinol and 4-hydroxybenzaldehyde. Key steps include the solvent-free Aldol syntheses of chalcones, and the successful application of the Suzuki-Miyaura coupling reaction in the synthesis of bichalcones. The present work constitutes a general method for the rapid syntheses of a number of bichalcones related to rhuschalcone VI. Some of the bichalcones showed moderate antiprotozoal activities against Bodo caudatus, a preliminary screening system for antitrypanosomal activities, most of them with little or no cytotoxicity.

Reduced Nonradiative Voltage Loss in Terpolymer Solar Cells.

The dissociation of hybrid local exciton and charge transfer excitons (LE-CT) in efficient bulk-heterojunction nonfullerene solar cells contributes to reduced nonradiative photovoltage loss, a mechanism that still remains unclear. Herein we studied the energetic and entropic contribution in the hybrid LE-CT exciton dissociation in devices based on a conjugated terpolymer. Compared with reference devices based on ternary blends, the terpolymer devices demonstrated a significant reduction in the nonradiative photovoltage loss, regardless of the acceptor molecule, be it fullerene or nonfullerene. Fourier transform photocurrent spectroscopy revealed a significant LE-CT character in the terpolymer-based solar cells. Temperature-dependent hole mobility and photovoltage confirm that entropic and energetic effects contribute to the efficient LE-CT dissociation. The energetic disorder value measured in the fullerene- or nonfullerene-based terpolymer devices suggested that this entropic contribution came from the terpolymer, a signature of higher disorder in copolymers with multiple aromatic groups. This gives new insight into the fundamental physics of efficient LE-CT exciton dissociation with smaller nonradiative recombination loss.

Recent Advances in n-Type Polymers for All-Polymer Solar Cells.

All-polymer solar cells (all-PSCs) based on n- and p-type polymers have emerged as promising alternatives to fullerene-based solar cells due to their unique advantages such as good chemical and electronic adjustability, and better thermal and photochemical stabilities. Rapid advances have been made in the development of n-type polymers consisting of various electron acceptor units for all-PSCs. So far, more than 200 n-type polymer acceptors have been reported. In the last seven years, the power conversion efficiency (PCE) of all-PSCs rapidly increased and has now surpassed 10%, meaning they are approaching the performance of state-of-the-art solar cells using fullerene derivatives as acceptors. This review discusses the design criteria, synthesis, and structure-property relationships of n-type polymers that have been used in all-PSCs. Additionally, it highlights the recent progress toward photovoltaic performance enhancement of binary, ternary, and tandem all-PSCs. Finally, the challenges and prospects for further development of all-PSCs are briefly considered.

Efficient Near-Infrared Electroluminescence at 840 nm with "Metal-Free" Small-Molecule:Polymer Blends.

Due to the so-called energy-gap law and aggregation quenching, the efficiency of organic light-emitting diodes (OLEDs) emitting above 800 nm is significantly lower than that of visible ones. Successful exploitation of triplet emission in phosphorescent materials containing heavy metals has been reported, with OLEDs achieving remarkable external quantum efficiencies (EQEs) up to 3.8% (peak wavelength > 800 nm). For OLEDs incorporating fluorescent materials free from heavy or toxic metals, however, we are not aware of any report of EQEs over 1% (again for emission peaking at wavelengths > 800 nm), even for devices leveraging thermally activated delayed fluorescence (TADF). Here, the development of polymer light-emitting diodes (PLEDs) peaking at 840 nm and exhibiting unprecedented EQEs (in excess of 1.15%) and turn-on voltages as low as 1.7 V is reported. These incorporate a novel triazolobenzothiadiazole-based emitter and a novel indacenodithiophene-based transport polymer matrix, affording excellent spectral and transport properties. To the best of knowledge, such values are the best ever reported for electroluminescence at 840 nm with a purely organic and solution-processed active layer, not leveraging triplet-assisted emission.

High Performance All-Polymer Photodetector Comprising a Donor-Acceptor-Acceptor Structured Indacenodithiophene-Bithieno[3,4-c]Pyrroletetrone Copolymer.

The synthesis of an acceptor polymer PIDT-2TPD, comprising indacenodithiophene (IDT) as the electron-rich unit and an interconnected bithieno[3,4-c]pyrrole-4,4',6,6'-tetrone (2TPD) as the electron-deficient unit, and its application for all-polymer photodetectors is reported. The optical, electrochemical, charge transport, and device properties of a blend of poly(3-hexylthiophene) and PIDT-2TPD are studied. The blend shows strong complementary absorption and balanced electron and hole mobility, which are desired properties for a photoactive layer. The device exhibits dark current density in the order of 10-5 mA/cm2, external quantum efficiency broadly above 30%, and nearly planar detectivity over the entire visible spectral range (maximum of 1.1 × 1012 Jones at 610 nm) under -5 V bias. These results indicate that PIDT-2TPD is a highly functional new type of acceptor and further motivate the use of 2TPD as a building block for other n-type materials.

25th anniversary article: isoindigo-based polymers and small molecules for bulk heterojunction solar cells and field effect transistors.

Driven by the potential advantages and promising applications of organic solar cells, donor-acceptor (D-A) polymers have been intensively investigated in the past years. One of the strong electron-withdrawing groups that were widely used as acceptors for the construction of D-A polymers for applications in polymer solar cells and FETs is isoindigo. The isoindigo-based polymer solar cells have reached efficiencies up to ∼7% and hole mobilities as high as 3.62 cm(2) V(-1) s(-1) have been realized by FETs based on isoindigo polymers. Over one hundred isoindigo-based small molecules and polymers have been developed in only three years. This review is an attempt to summarize the structures and properties of the isoindigo-based polymers and small molecules that have been reported in the literature since their inception in 2010. Focus has been given only to the syntheses and device performances of those polymers and small molecules that were designed for use in solar cells and FETs. Attempt has been made to deduce structure-property relationships that would guide the design of isoindigo-based materials. It is expected that this review will present useful guidelines for the design of efficient isoindigo-based materials for applications in solar cells and FETs.

Fluorine substitution enhanced photovoltaic performance of a D-A(1)-D-A(2) copolymer.

A new alternating donor-acceptor (D-A1-D-A2) copolymer containing two electron-deficient moieties, isoindigo and quinoxaline, was synthesized. The photovoltaic performance of this polymer could be improved by incorporating fluorine atoms into the quinoxaline units, resulting in an efficiency of 6.32%. This result highlights the attractive promise of D-A1-D-A2 copolymers for high-performance bulk heterojunction solar cells.

Small band gap polymers synthesized via a modified nitration of 4,7-dibromo-2,1,3-benzothiadiazole.

The nitration of 4,7-dibromo-2,1,3-benzothiadiazole was modified by using CF(3)SO(3)H and HNO(3) as the nitrating agent, and the related yield was improved greatly. On the basis of this improvement, two new small band gap polymers, P1TPQ and P3TPQ, were developed. Bulk heterojunction solar cells based on P3TPQ and [6,6]-phenyl-C(71)-butyric acid methyl ester exhibit interesting results with a power conversion efficiency of 2.1% and photoresponse up to 1.1 µm.