Effect of Chalcogen Atom Substitution on the Optoelectronic Properties in Cyclopentadithiophene Polymers

We report the synthesis and characterization of a series of cyclopentadithiophene polymers containing thiophene, selenophene, and tellurophene as comonomers. The effect of the chalcogen atom has been studied by a range of techniques, including thermal, optical, electrochemical, and computational. The results showed that by increasing the size of the chalcogen atom, the optical band gap is reduced mainly due to a downshift in the LUMO energy level. In addition, the larger size also increases the intermolecular heteroatom–heteroatom interactions facilitating the formation of polymer aggregates. This led to not only a stronger red-shifted band in the UV–vis absorption spectrum as well as raise in the HOMO energy level but also a potential solubility issue for higher molecular weight polymers containing particularly tellurophene units

Dithienosilolothiophene: A New Polyfused Donor for Organic Electronics

We report the synthesis of a novel pentacyclic donor moiety, dithienosilolothiophene, and its incorporation into low bandgap semiconducting polymers. The unique geometry of this new donor allowed attaching four solubilizing side chains on the same side of the fused ring system, thus ensuring sufficient solubility when incorporated into conjugated polymers while simultaneously reducing the steric hindrance between adjacent polymer chains. The optoelectronic properties of three new polymers comprising the novel pentacyclic donor were investigated and compared to structurally similar thieno­[3,2-<i>b</i>]­thienobis­(silolothiophene) polymers. Organic solar cells were fabricated in order to evaluate the new materials’ potential as donor polymers in bulk heterojunction solar cells and gain further insight into how the single-sided side-chain arrangement affects the active layer blend morphology

Organic/inorganic epitaxy: commensurate epitaxial growth of truxenone on Cu (111)

<p>The growth of monolayers of truxenone on Cu (111) is investigated using scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). Two distinct molecular packing motifs are observed which exist individually at low and high coverage, and coexist at intermediate states. In each case a commensurate epitaxial relationship between the molecular surface mesh and the substrate is observed.  </p

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

The conjugated polymer poly­(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefully engineer the solid-state microstructure of these “singlet fission polymers” to produce the long-lived triplets needed to realize efficient photovoltaic devices

Fluorinated Alcohol-Processed N‑Type Organic Electrochemical Transistor with High Performance and Enhanced Stability

Tuning the film morphology and aggregated structure is a vital means to improve the performance of the mixed ionic–electronic conductors in organic electrochemical transistors (OECTs). Herein, three fluorinated alcohols (FAs), including 2,2,2-trifluoroethanol (TFE), 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), and perfluoro-tert-butanol (PFTB), were employed as the alternative solvents for engineering the n-type small-molecule active layer gNR. Remarkedly, an impressive μC* of 5.12 F V–1 cm–1 s–1 and a normalized transconductance of 1.216 S cm–1 are achieved from the HFIP-fabricated gNR OECTs, which is three times higher than that of chloroform. The operational stability has been significantly enhanced by the FA-fabricated devices. Such enhancements can be ascribed to the aggregation-induced structural ordering by FAs during spin coating, which optimizes the microstructure of the films for a better mixed ion and electron transport. These results prove the huge research potential of FAs to improve OECT materials’ processability, device performance, and stability, therefore promoting practical bio-applications

Efficient Charge Photogeneration by the Dissociation of PC₇₀BM Excitons in Polymer/Fullerene Solar Cells

The role of PC₇₀BM excitons in driving charge photogeneration in low bandgap polymer/fullerene bulk heterojunction solar cells has been studied. Both transient absorption spectroscopy of charge generation yields in blend films as a function of excitation energies and photocurrent quantum efficiency spectra of the corresponding devices indicate that charge generation in this system results primarily from direct optical excitation of PC₇₀BM. Blend composition studies of photocurrent density and photoluminescence quenching indicate that the efficiency of photocurrent generation is primarily determined by the limited efficiency of PC₇₀BM exciton diffusion to the polymer due to the formation of PC₇₀BM domains (≥5 nm). This limitation becomes more severe as the PC₇₀BM content is increased above 50%. Despite this limitation and despite the poor charge photogeneration from polymer excitons, organic solar cells fabricated using this photoactive blend layer yielded device photocurrents of 7.1 mA/cm², maximal EQEs of 41%, and a device efficiency of 3.1%

Benzotrithiophene Copolymers: Influence of Molecular Packing and Energy Levels on Charge Carrier Mobility

The planar benzotrithiophene unit (<b>BTT</b>) was incorporated into four different donor polymers, and by systematically changing the nature and positioning of the solubilizing alkyl side chains along the conjugated backbone, the polymers’ frontier energy levels and optoelectronic properties were controlled. Reducing the steric hindrance along the polymer backbone lead to strong interchain aggregation and highly ordered thin films, achieving hole mobilities of 0.04 cm²/(V s) in organic thin film transistors. In an attempt to increase the polymer’s processability and reduce chain aggregation, steric hindrance between alkyl side chains was exploited. As a result of the increased solubility, the film forming properties of the polymer could be improved, but at the cost of reduced hole mobilities in OFET devices, due to the lack of long-range order in the polymer films

Chalcogenophene Comonomer Comparison in Small Band Gap Diketopyrrolopyrrole-Based Conjugated Polymers for High-Performing Field-Effect Transistors and Organic Solar Cells

The design, synthesis, and characterization of a series of diketopyrrolopyrrole-based copolymers with different chalcogenophene comonomers (thiophene, selenophene, and tellurophene) for use in field-effect transistors and organic photovoltaic devices are reported. The effect of the heteroatom substitution on the optical, electrochemical, and photovoltaic properties and charge carrier mobilities of these polymers is discussed. The results indicate that by increasing the size of the chalcogen atom (S < Se < Te), polymer band gaps are narrowed mainly due to LUMO energy level stabilization. In addition, the larger heteroatomic size also increases intermolecular heteroatom–heteroatom interactions facilitating the formation of polymer aggregates leading to enhanced field-effect mobilities of 1.6 cm²/(V s). Bulk heterojunction solar cells based on the chalcogenophene polymer series blended with fullerene derivatives show good photovoltaic properties, with power conversion efficiencies ranging from 7.1–8.8%. A high photoresponse in the near-infrared (NIR) region with excellent photocurrents above 20 mA cm^–2 was achieved for all polymers, making these highly efficient low band gap polymers promising candidates for use in tandem solar cells

Photocurrent Enhancement from Diketopyrrolopyrrole Polymer Solar Cells through Alkyl-Chain Branching Point Manipulation

Systematically moving the alkyl-chain branching position away from the polymer backbone afforded two new thieno­[3,2-<i>b</i>]­thiophene–diketopyrrolopyrrole (DPPTT-T) polymers. When used as donor materials in polymer:fullerene solar cells, efficiencies exceeding 7% were achieved without the use of processing additives. The effect of the position of the alkyl-chain branching point on the thin-film morphology was investigated using X-ray scattering techniques and the effects on the photovoltaic and charge-transport properties were also studied. For both solar cell and transistor devices, moving the branching point further from the backbone was beneficial. This is the first time that this effect has been shown to improve solar cell performance. Strong evidence is presented for changes in microstructure across the series, which is most likely the cause for the photocurrent enhancement