Naphthalene diimide (NDI) copolymers are attractive n-type materials for use in organic electronic devices. Four highly soluble NDI polymers are presentedeach differing only in the thiophene content ...comprising the material. Electron mobilities as high as 0.076 cm2 V−1 s−1 for the novel material PNDI-3Th are reported. Polymer crystallinity and general macromolecular order are shown to effectively improve by increasing the number of thiophene units within the polymer backbone. The structure−property relationship of NDI−thiophene copolymers is presented and discussed as it pertains to organic field effect transistor (OFET) performance.
The dimensional reduction of solids into smaller fragments provides a route to achieve new physical properties and gain deeper insight into the extended parent structures. Here, we report the ...synthesis of CuTOTP-OR (TOTP n– = 2,3,6,7-tetraoxidotriphenylene), a family of copper-based macrocycles that resemble truncated fragments of the conductive two-dimensional (2D) metal–organic framework Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). The planar metal–organic macrocycles self-assemble into ordered nanotubes with internal diameters of ∼2 nm and short interlayer distances of ∼3.20 Å. Strong π–π stacking interactions between macrocycles facilitate out-of-plane charge transport, and pressed pellet conductivities as high as 2(1) × 10–3 S cm–1 are observed. Peripheral alkyl functionalization enhances solution processability and enables the fabrication of thin-film field-effect transistor devices. Ambipolar charge transport is observed, suggesting that similar behavior may be operative in Cu3(HHTP)2. By coupling the attractive features of metal–organic frameworks with greater processability, these macrocycles enable facile device integration and a more nuanced understanding of out-of-plane charge transport in 2D conductive metal–organic frameworks.
The ability of chemists to design and synthesize π-conjugated organic polymers with precise control remains the key to technological breakthroughs for using polymer materials in electronic and ...photonic devices. In this communication, the controlled chain-growth polymerization of regioregular poly(3-hexylthiophene) (P3HT) from an external initiator using 1,3-bis(diphenylphosphino)propane (dppp) as a catalyst ligand is reported. The complexes cis-chloro(phenyl)(dppp)nickel(II) and cis-chloro(o-tolyl)(dppp)nickel(II) were synthesized and characterized by 31P NMR spectroscopy. These complexes served as initiators in the polymerization of 2-bromo-5-chloromagnesio-3-hexylthiophene in THF at room temperature, affording fully regioregular P3HT with controlled molecular weights and narrow molecular weight distributions, as demonstrated by gel-permeation chromatography and 1H NMR spectroscopy. MALDI-TOF mass spectrometry revealed that the polymers had almost complete incorporation of the initiating aryl group, and when the aryl group was o-tolyl, only Tol/H end groups were observed. Although external initiators have been used previously with a PPh3 ligand, that methodology led to polymers with broad molecular weight distributions. This is the first example in which complete control over the externally initiated P3HT polymerization has been achieved.
A robust method of room temperature direct arylation for benzofuran is reported. This discovery allows for mild arylation by commercially available aryl iodides with complete C-2 regioselectivity and ...tolerates a range of functional groups, including heat sensitive groups. Mechanistically, a Heck-type oxyarylation product from a direct arylation process is reported as a key piece of evidence for a carbopalladation intermediate.
This study explores the role of very small changes in poly(3-hexylthiophene-2,5-diyl) (P3HT) regioregularity on the physical and electronic properties of P3HT nanowires. Due to a high level of ...synthetic control, we are able to isolate the effects of regioregularity from those of polymer molecular weight and dispersity for the first time. A series of P3HTs with regioregularities from 96 to 99%, similar molecular weights, and low dispersities are synthesized. The charge transport properties of these polymers, along with a Soxhlet extracted 93% regioregular P3HT purchased from Rieke metals, are investigated in both thin film and nanowire transistors. The resulting structural characteristics are examined by atomic force microscopy and X-ray diffraction, and the optical characteristics are explored by UV–vis absorption. It is found that increasing the P3HT regioregularity results in improved charge transport characteristics, with an increase in mobility by a factor of 4 for the regioregularities examined. The increased mobility is shown to reflect increasing structural coherence lengths in the (010) direction, as well as improved J-aggregate characteristics due to greater planarity and reduced numbers of defect sites along the polymer nanowires. Overall, this study serves to emphasize the importance of determining and reporting even small changes in polymer regioregularity.
Luminescent solar concentrators (LSCs) can concentrate direct and diffuse solar radiation spatially and energetically to help reduce the overall area of solar cells needed to meet current energy ...demands. LSCs require luminophores that absorb large fractions of the solar spectrum, emit photons into a light-capture medium with high photoluminescence quantum yields (PLQYs), and do not absorb their own photoluminescence. Luminescent nanocrystals (NCs) with near or above unity PLQYs and Stokes shifts large enough to avoid self-absorption losses are well-suited to meet these needs. In this work, we describe LSCs based on quantum-cutting Yb3+:CsPb(Cl1−xBrx)3 NCs that have documented PLQYs as high as ∼200%. Through a combination of solution-phase 1D LSC measurements and modeling, we demonstrate that Yb3+:CsPbCl3 NC LSCs show negligible intrinsic reabsorption losses, and we use these data to model the performance of large-scale 2D LSCs based on these NCs. We further propose a new and unique monolithic bilayer LSC device architecture that contains a Yb3+:CsPb(Cl1−xBrx)3 NC top layer above a second narrower-gap LSC bottom layer (e.g., based on CuInS2 NCs), both within the same waveguide and interfaced with the same Si PV for conversion. We extend the modeling to predict the flux gains of such bilayer devices. Because of the exceptionally high PLQYs of Yb3+:CsPb(Cl1−xBrx)3 NCs, the optimized bilayer device has a projected flux gain of 63 for dimensions of 70 × 70 × 0.1 cm3, representing performance enhancement of at least 19% over the optimized CuInS2 LSC alone.
The origin of the mid-infrared (IR) spectral features for hole absorption in doped poly(3-hexylthiophene) (P3HT) films is investigated theoretically and experimentally. Using a Holstein-style ...Hamiltonian to treat vibronic coupling involving the prominent vinyl stretching mode, the low-energy peak (A) occurring in the spectral interval 0.1–0.15 eV is found to contain a substantial (sometimes dominant) intrachain-polarized component, in contrast to the predictions of the more conventional treatments based on self-trapped, mid-gap polaron states where peak A is entirely interchain in origin. A higher-energy peak (B) located between 0.35 and 0.7 eV and largely intrachain-polarized is also obtained and associated with the conventional P1 polaron transition. Spectral signatures for polaron coherence based on peaks A and B are identified and used to analyze the molecular weight dependence of the IR spectral line shapes of P3HT doped with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. Generally, the polaron coherence lengths along the chain and stacking axes increase with molecular weight, which is consistent with similar studies conducted on hole absorption in undoped P3HT.
Chemical identification of microplastics is a crucial step in understanding the sources of microplastics and studying the effects of microplastic pollution. A major challenge to microplastics ...identification is that weathered microplastics undergo surface chemical changes that differ from their unweathered counterparts which hinders spectroscopic matching and thus identification. While IR spectroscopy is a common technique used for microplastics identification, Raman spectroscopy is a complementary technique and its higher spatial resolution capabilities (capable of analyzing particles as small as 1 μm) make it a popular tool to identify smaller microplastics that can otherwise go undetected by IR techniques. Currently, there is limited Raman spectroscopic information on weathered microplastics. Herein, we investigate the effects of artificial weathering on polyethylene and polypropylene microplastics for 0–26 weeks in four different weathering conditions (air, DI water, artificial seawater, and Puget Sound seawater) using Raman and IR spectroscopy. Microplastics weathering in different environments reveal that they can lead to different IR spectra, suggestive of varying degradation pathways for plastics, but relatively similar Raman spectra. Raman spectra, however, do show variations in peaks associated with the crystallinity and amorphous regions in the polymers which indicate morphological changes in the weathered microplastics. Overall, Raman spectroscopy acts as a practical interrelated method that can be used in lieu of IR spectroscopy in cases where weathering can complicate plastics identification by spectroscopic matching. This work aims to provide spectral information to facilitate marine microplastic chemical identification and encourage more investigations on the conditions that influence microplastic weathering.
•Weathering of polyethylene and polypropylene microplastics was monitored for 26 weeks in four weathering conditions.•Microplastic weathering in different environments show varying IR spectra, suggestive of different degradation pathways.•Raman spectral analysis show variation of crystallinity and amorphous region changes in weathered microplastics.•IR analysis indicates Puget Sound seawater weathered microplastics show the most degradation compared to other conditions.
Intercrystallite molecular connections are widely recognized to tremendously impact the macroscopic properties of semicrystalline polymers. Because it is challenging to directly probe such ...connections, theoretical frameworks have been developed to quantify their concentrations and predict the mechanical properties that result from these connections. Tie-chain connectivity similarly impacts the electrical properties in semicrystalline conjugated polymers. Yet, its quantitative impact has eluded the community. Here, we assess the Huang–Brown model, a framework commonly used to describe the structural origins of mechanical properties in polyolefins, to quantitatively elucidate the effect of tie chains on the electrical properties of a model conjugated polymer. We found that a critical tie-chain fraction of 10–3 is needed to support macroscopic charge transport, below which intercrystallite connectivity limits charge transport, and above which intracrystallite disorder is the bottleneck. Extending the Huang–Brown framework to conjugated polymers enables the prediction of macroscopic electrical properties based on experimentally accessible morphological parameters. Our study implicates the importance of long and rigid polymer chains for efficient charge transport over device length scales.
All-printed electronics is the key technology to ultra-low-cost, large-area electronics. As a critical step in this direction, we demonstrate that laser sintering of inkjet-printed metal ...nanoparticles enables low-temperature metal deposition as well as high-resolution patterning to overcome the resolution limitation of the current inkjet direct writing processes. To demonstrate this process combined with the implementation of air-stable carboxylate-functionalized polythiophenes, high-resolution organic transistors were fabricated in ambient pressure and room temperature without utilizing any photolithographic steps or requiring a vacuum deposition process. Local thermal control of the laser sintering process could minimize the heat-affected zone and the thermal damage to the substrate and further enhance the resolution of the process. This local nanoparticle deposition and energy coupling enable an environmentally friendly and cost-effective process as well as a low-temperature manufacturing sequence to realize large-area, flexible electronics on polymer substrates.