Publications by authors named "Dean M DeLongchamp"

The distribution of counterions and dopants within electrically doped semicrystalline conjugated polymers, such as poly(3-hexylthiophene-2,5-diyl) (P3HT), plays a pivotal role in charge transport. The distribution of counterions in doped films of P3HT with controlled crystallinity was examined using polarized resonant soft X-ray scattering (P-RSoXS). The changes in scattering of doped P3HT films containing trifluoromethanesulfonimide (TFSI) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (FTCNQ) as counterions to the charge carriers revealed distinct differences in their nanostructure.

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Hierarchical structure-within-structure assemblies offer a route toward increasingly complex and multifunctional materials while pushing the limits of block copolymer self-assembly. We present a detailed study of the self-assembly of a series of fluorinated high-χ block copolymers (BCPs) prepared via postmodification of a single poly(styrene)--poly(glycidyl methacrylate) (S--G) parent polymer with the fluorinated alkylthiol pendent groups containing 1, 6, or 8 fluorinated carbons (termed trifluoro-ethanethiol (TFET), perfluoro-octylthiol (PFOT), and perfluoro-decylthiol (PFDT), respectively). Bulk X-ray scattering of thermally annealed samples demonstrates hierarchical molecular assembly with phase separation between the two blocks and within the fluorinated block.

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Article Synopsis
  • Physical vapor deposition (PVD) can create organic glasses with specific molecular orientations, but the effects of the interface on structure and stability are not well understood, presenting a knowledge gap in the field.
  • Polarized resonant soft X-ray reflectivity (P-RSoXR) is used to analyze the molecular orientation and composition of a bilayer film made from DSA-Ph on Alq3, revealing that the DSA-Ph molecules align parallel to the Alq3 interface before transitioning to their bulk orientation.
  • The study shows a correlation between the interface orientation and the bulk behavior of similar composite glasses, providing a method for predicting molecular orientation at interfaces, which is vital for advancing
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Article Synopsis
  • - Polarized resonant soft X-ray scattering (P-RSoXS) is a cutting-edge technique that helps analyze the molecular orientation and chemical makeup of soft materials like polymers and biomaterials through X-ray scattering and spectroscopy.
  • - A new open-source virtual instrument has been developed to simulate P-RSoXS patterns using powerful GPUs, significantly speeding up the process and handling complex sample properties at nanoscale levels.
  • - This new framework dramatically enhances simulation speed (over 1000 times faster than existing software) and simplifies user interaction by integrating with Python, making it easier for researchers to explore, analyze, and apply the data in various scientific applications.
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The ability to control structure in molecular glasses has enabled them to play a key role in modern technology; in particular, they are ubiquitous in organic light-emitting diodes. While the interplay between bulk structure and optoelectronic properties has been extensively investigated, few studies have examined molecular orientation near buried interfaces despite its critical role in emergent functionality. Direct, quantitative measurements of buried molecular orientation are inherently challenging, and many methods are insensitive to orientation in amorphous soft matter or lack the necessary spatial resolution.

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The use of polymer-polymer blends to tailor mechanical properties and improve electrical performance is becoming widespread in the field of printed electronics. Similarly, meniscus-guided coating can be used to tailor electrical properties through alignment of the semiconducting material. We report on a long-wavelength instability during blade coating of a semiconducting polymer/elastomer blend for organic transistor applications that results in significant variation of the semiconducting polymer nanofibril alignment across the instability period.

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Polymer chains are attached to nanoparticle surfaces for many purposes, including altering solubility, influencing aggregation, dispersion, and even tailoring immune responses in drug delivery. The most unique structural motif of polymer-grafted nanoparticles (PGNs) is the high-density region in the corona where polymer chains are stretched under significant confinement, but orientation of these chains has never been measured because conventional nanoscale-resolved measurements lack sensitivity to polymer orientation in amorphous regions. Here, we directly measure local chain orientation in polystyrene grafted gold nanoparticles using polarized resonant soft X-ray scattering (P-RSoXS).

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The end-capping group (EG) is the essential electron-withdrawing component of nonfullerene acceptors (NFAs) in bulk heterojunction (BHJ) organic solar cells (OSCs). To systematically probe the impact of two frequent EG functionalization strategies, π-extension and halogenation, in A-DAD-A type NFAs, we synthesized and characterized four such NFAs: , , , and . To assess the relative importance of these strategies, we contrast these NFAs with the baseline acceptors, and .

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We present the design and performance of a polarized resonant soft x-ray scattering (RSoXS) station for soft matter characterization built by the national institute of standards and technology at the national synchrotron light source-II (NSLS-II). The RSoXS station is located within the spectroscopy soft and tender beamline suite at NSLS-II located in Brookhaven national laboratory, New York. Numerous elements of the RSoXS station were designed for optimal performance for measurements on soft matter systems, where it is of critical importance to minimize beam damage and maximize collection efficiency of polarized x-rays.

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The temperature dependent aggregation behavior of PffBT4T polymers used in organic solar cells plays a critical role in the formation of a favorable morphology in fullerene-based devices. However, there has been little investigation into the impact of donor/acceptor ratio on morphology tuning, especially for non-fullerene acceptors (NFAs). Herein, the influence of composition on morphology is reported for blends of PffBT4T-2DT with two NFAs, O-IDTBR and O-IDFBR.

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The field-effect electron mobility of aqueous solution-processed indium gallium oxide (IGO) thin-film transistors (TFTs) is significantly enhanced by polyvinyl alcohol (PVA) addition to the precursor solution, a >70-fold increase to 7.9 cm/Vs. To understand the origin of this remarkable phenomenon, microstructure, electronic structure, and charge transport of IGO:PVA film are investigated by a battery of experimental and theoretical techniques, including In K-edge and Ga K-edge extended X-ray absorption fine structure (EXAFS); resonant soft X-ray scattering (R-SoXS); ultraviolet photoelectron spectroscopy (UPS); Fourier transform-infrared (FT-IR) spectroscopy; time-of-flight secondary-ion mass spectrometry (ToF-SIMS); composition-/processing-dependent TFT properties; high-resolution solid-state H, Ga, and In NMR spectroscopy; and discrete Fourier transform (DFT) analysis with ab initio molecular dynamics (MD) liquid-quench simulations.

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Emerging nonfullerene acceptors (NFAs) with crystalline domains enable high-performance bulk heterojunction (BHJ) solar cells. Thermal annealing is known to enhance the BHJ photoactive layer morphology and performance. However, the microscopic mechanism of annealing-induced performance enhancement is poorly understood in emerging NFAs, especially regarding competing factors.

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The rational creation of two-component conjugated polymer systems with high levels of phase purity in each component is challenging but crucial for realizing printed soft-matter electronics. Here, we report a mixed-flow microfluidic printing (MFMP) approach for two-component -polymer systems that significantly elevates phase purity in bulk-heterojunction solar cells and thin-film transistors. MFMP integrates laminar and extensional flows using a specially microstructured shear blade, designed with fluid flow simulation tools to tune the flow patterns and induce shear, stretch, and pushout effects.

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Organic photovoltaics based on non-fullerene acceptors (NFAs) show record efficiency of 16 to 17% and increased photovoltage owing to the low driving force for interfacial charge-transfer. However, the low driving force potentially slows down charge generation, leading to a tradeoff between voltage and current. Here, we disentangle the intrinsic charge-transfer rates from morphology-dependent exciton diffusion for a series of polymer:NFA systems.

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Article Synopsis
  • Incorporating a heterojunction between a donor polymer (PTB7-Th) and a non-fullerene acceptor (EH-IDTBR) in organic nanoparticles enhances photocatalytic activity for hydrogen evolution compared to single organic semiconductors.
  • Adjusting the stabilizing surfactant during nanoparticle fabrication allows for control over the nanomorphology, transforming the structure from core-shell to intermixed blend, and significantly increases hydrogen production efficiency.
  • The optimized photocatalysts achieve an impressive hydrogen evolution rate of over 60,000 µmol h g under visible light (350 to 800 nm), with external quantum efficiencies exceeding 6% at peak solar photon flux.
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We show that glasses with aligned smectic liquid crystal-like order can be produced by physical vapor deposition of a molecule without any equilibrium liquid crystal phases. Smectic-like order in vapor-deposited films was characterized by wide-angle X-ray scattering. A surface equilibration mechanism predicts the highly smectic-like vapor-deposited structure to be a result of significant vertical anchoring at the surface of the equilibrium liquid, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy orientation analysis confirms this prediction.

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Achieving efficient polymer solar cells (PSCs) requires a structurally optimal donor-acceptor heterojunction morphology. Here we report the combined experimental and theoretical characterization of a benzodithiophene-benzothiadiazole donor polymer series (PBTZF4-R; R = alkyl substituent) blended with the non-fullerene acceptor ITIC-Th and analyze the effects of substituent dimensions on blend morphology, charge transport, carrier dynamics, and PSC metrics. Varying substituent dimensions has a pronounced effect on the blend morphology with a direct link between domain purity, to some extent domain dimensions, and charge generation and collection.

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Due to the highly directional nature of transport in polymer-based organic field-effect transistors (OFETs), alignment of the polymer backbone can significantly affect device performance. While many methods of alignment have been detailed, the mechanism of alignment is rarely revealed-especially in cases of flow-induced alignment. Polymer aggregates are often observed in highly aligned systems, but their role is similarly unclear.

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Efficient injection of charge carriers from the contacts into the semiconductor layer is crucial for achieving high-performance organic devices. The potential drop necessary to accomplish this process yields a resistance associated with the contacts, namely the contact resistance. A large contact resistance can limit the operation of devices and even lead to inaccuracies in the extraction of the device parameters.

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Organic semiconductors may be processed from fluids using graphical arts printing and patterning techniques to create complex circuitry. Because organic semiconductors are weak van der Waals solids, the creation of glassy phases during processing is quite common. Because structural disorder leads to electronic disorder, it is necessary to understand these phases to optimize and control the electronic properties of these materials.

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Intra- and intermolecular ordering greatly impact the electronic and optoelectronic properties of semiconducting polymers. Despite much prior efforts regarding molecular packing, the interrelationship between ordering of alkyl sidechains and conjugated backbones has not been fully detailed. We report here the discovery of a highly ordered alkyl sidechain phase in six representative semiconducting polymers, determined from distinct spectroscopic and diffraction signatures.

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Bottlebrush block copolymers offer rich opportunities for the design of complex hierarchical materials. As consequences of the densely grafted molecular architecture, bottlebrush polymers can adopt highly extended backbone conformations and exhibit unique physical properties. A recent report has described the unusual phase behavior of ABC bottlebrush triblock terpolymers bearing grafted poly(-lactide) (PLA), polystyrene (PS), and poly(ethylene oxide) (PEO) blocks (LSO).

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To realize the full promise of solution deposited photovoltaic devices requires processes compatible with high-speed manufacturing. We report the performance and morphology of blade-coated bulk heterojunction devices based on the small molecule donor p-DTS(FBTTh) when treated with a post-deposition solvent vapor annealing (SVA) process. SVA with tetrahydrofuran improves the device performance of blade-coated films more than solvent additive processing (SA) with 1,8-diiodooctane.

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Solution-processed organic films are a facile route to high-speed, low cost, large-area deposition of electrically functional components (transistors, solar cells, emitters, etc.) that can enable a diversity of emerging technologies, from Industry 4.0, to the Internet of things, to point-of-use heath care and elder care.

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