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At least 1,027 records · Page 57

Optimized active layer morphology toward efficient and polymer batch insensitive organic solar cells

Abstract Morphology control in laboratory and industry setting remains as a major challenge for organic solar cells (OSCs) due to the difference in film-drying kinetics between spin coating and the printing process. A two-step sequential deposition method is developed to control the active layer morphology. A conjugated polymer that self-assembles into a well-defined fibril structure is used as the first layer, and then a non-fullerene acceptor is introduced into the fibril mesh as the second layer to form an optimal morphology. A benefit of the combined fibril network morphology and non-fullerene acceptor properties was that a high efficiency of 16.5% (certified as 16.1%) was achieved. The preformed fibril network layer and the sequentially deposited non-fullerene acceptor form a robust morphology that is insensitive to the polymer batches, solving a notorious issue in OSCs. Such progress demonstrates that the utilization of polymer fibril networks in a sequential deposition process is a promising approach towards the fabrication of high-efficiency OSCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulated space environmental effects on some experimental high performance polymers

High performance polymers for potential space applications were evaluated under simulated space environmental conditions. Experimental resins from blends of acetylene terminated materials, poly(arylene ether)s and low color polyimides were exposed to high energy electron and ultraviolet radiation in an attempt to simulate space environmental effects. Thin films, neat resin moldings, and carbon fiber reinforced composites were exposed, and the effect on certain polymer properties were determined. Recent research involving the effects of various radiation exposures on the physical, optical, and mechanical properties of several experimental polymer systems is reviewed.

Connell, John W.↗

Discovery and adaptation of microbes that degrade oxidized low-density polyethylene films

There is a growing interest in developing a methodology for effectively cleaving carbon–carbon (C–C) bonds in polymer backbones through bioconversion processes that utilize microorganisms and their enzymes. This upsurge of interest is driven by the goal of achieving a circular economy. Polyolefin post-consumer plastics are a substantial source of carbon, but the recycling potential is severely limited. Upcycling routes are needed for converting polyolefin post-consumer plastics into value-added products while concurrently mitigating adverse environmental effects. These materials contain carbon-based chemicals that can, in principle, serve as the feedstock for microbial metabolism. Some microbes have been reported to grow on polyolefin plastics, but the rate of biodegradation is insufficient for industrial processes. In this study, low-density polyethylene (LDPE) films were subjected to two mild ozone-based oxidation treatments, which facilitated biodegradation. The degree of oxidation was determined by Fourier transform infrared spectroscopy via analysis of the carbonyl index (1,710/1,460 cm −1 ), which ranged from 0.3 to 2.0, and also via analysis of the carboxylic acid content. Following oxidation of the films, studies were conducted to investigate the ability of a panel of polyvinyl alcohol-degrading microbes to degrade the oxidized films. A defined minimal medium was used to cultivate and assess microbial growth on the oxidized films. Following 45 days of cultivation, the most effective strains were further cultivated up to three additional generations on the oxidized film substrates to improve their ability to degrade the oxidized LDPE films. After these enrichments, we identified a strain from the third generation of Pseudomonas sp. Rh926 that exhibited significant cell growth and reduced the oxidized LDPE film mass by 25% in 30 days, demonstrating an enhanced capacity for degrading the oxidized LDPE films.

Adaptation↗

Dielectric Coating For Hot-Film Flow Sensors

Very-thin-film dielectric coating stable over range of temperatures developed. This dielectric coating, combination of fused silica and thermoplastic polymer, has sufficient stability to withstand stresses placed upon it by cycling to and from cryogenic temperatures. Coating tailored to meet almost any criterion of roughness height. Useful for research in application of hot-film sensors to airfoils.

Hopson, Purnell, Jr.↗

New secondary batteries utilizing electronically conductive polymer cathodes

The objectives of this project are to optimize the transport rates in electronically conductive polypyrrole films by controlling the morphology of the film and to assess the utility of these films as cathodes in a lithium/polypyrrole secondary battery. During this research period, progress has been made in improving the charge transport rate of the supermolecular-engineered polypyrrole electrode by eliminating the polypyrrole baselayer that hampered earlier work. Also, the fibril density of the polypyrrole electrode was increased, providing more electroactive sites per unit area.

Martin, Charles R.↗

Subpiosecond Third Order Nonlinear Response in Polythiophene and Thiopene Based Thin Films

Ultrafast relaxation kinetics of the third order nonlinear susceptibility of polythiophene and polycondensed thiophene-based polymer was determined by the forward degenerate four-wave mixing technique. Deep into the absorption band the nonlinear response shows only a fast component (less than 900 fs at 587 nm) while at the edge of the absorption band at 642 nm a much slower and complex decay was measured.

Harris, D.↗

Conformal Membrane Reflectors for Deployable Optics

This presentation reports the Phase I results on NASA's Gossamer Spacecraft Exploratory Research and Technology Program. Cornerstone Research Group, Inc., the University of Rochester, and International Photonics Consultants collaborated to investigate the feasibility of free-standing, liquid-crystal-polymer (LCP) reflectors for integration into space-based optical systems. The goal of the program was to achieve large-diameter, broadband. reflective membranes that are resistant to the effects of space, specifically cryogenic environments and gamma-ray irradiation. Additionally, we assessed the applicability of utilizing the technology as tight sails, since, by their very nature, these films offer high-reflectivity at specified wavelengths. Previous research programs have demonstrated all-polymer, narrow-band Specular reflectors and diffuse membrane reflectors. The feasibility of fabricating an all-polymer broadband specular reflector and a narrow-band specular membrane reflector was assessed in the Phase I Gossamer program. In addition, preliminary gamma irradiation studies were conducted to determine the stability of the polymer reflectors to radiation. Materials and process technology were developed to fabricate coupon-scale reflectors of both broad- and narrow-band specular reflectors in Phase 1. This presentation will report the results of these studies, including, the performance of a narrow-band specular membrane. Gamma irradiation exposures indicate limited impact on the optical performance although additional exposure studies are warranted. Plans to scale up the membrane fabrication process will be presented.

Hood, Patrick J.↗

Radical Polymer-Based Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are an emerging platform for bioelectronic applications. Significant effort has been placed in designing advanced polymers that simultaneously transport both charge and ions (i.e., macromolecules that are mixed conductors). Furthermore, the considerations for mixed organic conductors are often different from the established principles that are well-known in the solid-state organic electronics field; thus, the discovery of new OECT macromolecular systems is highly desired. Here, we demonstrate a new materials system by blending a radical polymer (i.e., a macromolecule with a nonconjugated backbone and with stable open-shell sites at its pendant group) with a frequently used conjugated polymer. Specifically, poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl) (PTEO) was blended with poly(3-hexylthiophene) (P 3 HT) to create thin films with distinct closed-shell and open-shell domains. Importantly, the sharp and unique oxidation–reduction (redox) potential associated with the radical moieties of the PTEO chain provided a distinct actuation feature to the blended films that modulated the ionic transport of the OECT devices. In turn, this led to controlled regulation of the doping of the P 3 HT phase in the composite film. By decoupling the ionic and electronic transport into two distinct phases and by using an ion transport phase with well-controlled redox activity, never-before-seen performance for a P3HT-based OECT was observed. That is, at loadings as low as 5% PTEO (by weight) OECTs achieved figure-of-merit (i.e., μC*) values >150 F V –1 cm –1 s –1 , which place the performance on the same order as state-of-the-art conjugated polymers despite the relatively common conjugated macromolecular moiety implemented. As such, this effort presents a design platform by which to readily create a tailored OECT response through strategic macromolecular selection and polymer processing.

36 MATERIALS SCIENCE↗

Thermodynamic Properties and Molecular Packing Explain Performance and Processing Procedures of Three D18:NFA Organic Solar Cells

Abstract Organic solar cells (OSCs) based on D18:Y6 have recently exhibited a record power conversion efficiency of over 18%. The initial work is extended and the device performance of D18‐based OSCs is compared with three non‐fullerene acceptors, Y6, IT‐4F, and IEICO‐4Cl, and their molecular packing characteristics and miscibility are studied. The D18 polymer shows unusually strong chain extension and excellent backbone ordering in all films, which likely contributes to the excellent hole‐transporting properties. Thermodynamic characterization indicates a room‐temperature miscibility for D18:Y6 and D18:IT‐4F near the percolation threshold. This corresponds to an ideal quench depth and explains the use of solvent vapor annealing rather than thermal annealing. In contrast, D18:IEICO‐4Cl is a low‐miscibility system with a deep quench depth during casting and poor morphology control and low performance. A failure of ternary blends with PC 71 BM is likely due to the near‐ideal miscibility of Y6 to begin with and indicates that strategies for developing successful ternary or quaternary solar cells are likely very different for D18 than for other high‐performing donors. This work reveals several unique property–performance relations of D18‐based photovoltaic devices and helps guide design or fabrication of yet higher efficiency OSCs.

Wang, Zhen↗

Photochemical Decomposition of Y‐Series Non‐Fullerene Acceptors Is Responsible for Degradation of High‐Efficiency Organic Solar Cells

Abstract Organic photovoltaic cells that employ Y‐series non‐fullerene acceptors (NFAs) have recently achieved impressive power‐conversion efficiencies (>18%). To fulfill their commercial promise, it is important to quantify their operational lifetimes and understand their degradation mechanisms. In this work, the spectral‐dependent photostability of films and solar cells comprising several Y‐series acceptors and the donor polymer PM6 is investigated systematically. By applying longpass filters during aging, it is shown that UV/near‐UV photons are responsible for the photochemical decomposition of Y‐series acceptors; this degradation is the primary driver of early solar cell performance losses. Using mass spectrometry, the vinylene linkage between the core and electron‐accepting moieties of Y‐series acceptors is identified as the weak point susceptible to cleavage under UV‐illumination. Employing a series of device characterization, along with numerical simulations, the efficiency losses in organic photovoltaic cells are attributed to the formation of traps, which reduces charge extraction efficiency and facilitates non‐radiative recombination as the Y‐series acceptors degrade. This study provides new insights for molecular degradation of organic photovoltaic absorber materials and highlights the importance of future molecular design and strategies for improved solar cell stability.

14 SOLAR ENERGY↗

Chitin- and cellulose-based sustainable barrier materials: a review

Abstract The accumulation of synthetic plastics used in packaging applications in landfills and the environment is a serious problem. This challenge is driving research efforts to develop biodegradable, compostable, or recyclable barrier materials derived from renewable sources. Cellulose, chitin/chitosan, and their combinations are versatile biobased packaging materials because of their diverse biological properties (biocompatibility, biodegradability, antimicrobial properties, antioxidant activity, non-toxicity, and less immunogenic compared to protein), superior physical properties (high surface area, good barrier properties, and mechanical properties), and they can be assembled into different forms and shapes (powders, fibers, films, beads, sponges, gels, and solutions). They can be either assembled into packaging films or used as fillers to improve the properties of other biobased polymers. Methods such as preparation of composites, multilayer coating, and alignment control are used to further improve their barrier, mechanical properties, and ameliorate their moisture sensitivity. With the growing application of cellulose and chitin-based packaging materials, their biodegradability and recyclability are also discussed in this review paper. The future trends of these biobased materials in packaging applications and the possibility of gradually replacing petroleum-based plastics are analyzed in the “Conclusions” section.

36 MATERIALS SCIENCE↗

Hierarchical, Self-Assembled Metasurfaces via Exposure-Controlled Reflow of Block Copolymer-Derived Nanopatterns

Here, nanopatterning for the fabrication of optical metasurfaces entails a need for high-resolution approaches like electron beam lithography that cannot be readily scaled beyond prototyping demonstrations. Block copolymer thin film self-assembly offers an attractive alternative for producing periodic nanopatterns across large areas, yet the pattern feature sizes are fixed by the polymer molecular weight and composition. Here, a general strategy is reported that overcomes the limitation of fixed feature size by treating the copolymer thin film as a hierarchical resist, in which the nanoscale pattern motif is defined by self-assembly. Feature sizes can then be tuned by thermal reflow controlled locally by irradiative crosslinking or chemical alteration using lithographic ultraviolet light or electron beam exposure. Using blends of polystyrene-block-poly(methylmethacrylate) (PS-b-PMMA) with PS and PMMA homopolymer, we demonstrate both self-assembled PS grating and hexagonal hole patterns; exposure-controlled reflow is then used to reduce hole diameter by as much as 50% or increase PS grating linewidth by more than 180%. Transferring these nanopatterns, or their inverse obtained by a lift-off approach, into silicon yields structural colors that may be prescriptively controlled based on nanoscale feature size. Furthermore, patterned exposure enables area-selective feature size control, yielding uniform structural color patterns across centimeter square areas. Electron beam lithography is also used to show that the lithographic resolution of this selective-area control can be extended to the nanoscale dimensions of the self-assembled features. The exposure-controlled reflow approach demonstrated here takes a pivotal step towards fabricating complex, hierarchical optical metasurfaces using scalable self-assembly methods.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

In-house synthesized poly(ether ether ketone) ionenes. I. ToF-SIMS spectra in the positive ion mode

Static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed for acquiring the high-resolution surface spectra of four types of synthesized imidazolium ionene membranes. These novel membranes have aromatic ether–ketone–ether linkages inspired by poly(ether ether ketone) (PEEK). The PEEK-ionenes synthesized for this study have imidazolium cations placed in the polymeric backbone with bistriflimide [Tf 2 N]- counterions. The attention given to synthetically modified PEEK derivatives, such as PEEK-ionenes, is considerable due to their ability to selectively capture CO 2 molecules and other light gases. Therefore, it is important to characterize the surface of these synthesized novel PEEK-ionenes. In this work, characteristic and unique peaks were identified in the positive spectra of each sample. The differences in mass spectra among the samples provide insights for optimizing or fine-tuning the PEEK-ionenes synthesis to achieve a high-performance CO 2 separation membrane with enhanced permeability, selectivity, and mechanical stability. The SIMS spectra and identified characteristic peaks of these synthesized ionenes will serve as a reference in the positive mode, complementing the corresponding spectra reported in the negative ion mode (Paper II).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma generation by household microwave oven for surface modification and other emerging applications

A simple and inexpensive method to generate plasma using a kitchen microwave oven is described in this paper. The microwave-generated plasma is characterized by spectroscopic analysis and compared with the absorption spectra of a gas discharge tube. A Paschen-like curve is observed as the microwave plasma initiation time is plotted as a function of the pressure of the plasma chamber. We have also demonstrated that this microwave-generated air plasma can be used in a multitude of applications such as: (a) surface modification of a substrate to change its wettability; (b) surface modification to change electrical/optical properties of a substrate; and (c) enhancement of adhesive forces for improved bonding of polymeric microfluidic molds, such as bonding polydimethylsiloxane (PDMS) chips to glass covers. These simple techniques of plasma generation and subsequent surface treatment and modification applications may bring new opportunities leading to new innovations not only in advanced labs, but also in undergraduate and even high school research labs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Plasma chemistry and its applications

The relationship between discharge phenomena and plasma chemistry, as well as the equipment and mechanisms of plasma chemical reactions are described. Various areas in which plasma chemistry is applied are surveyed, such as: manufacturing of semiconductor integrated circuits; synthetic fibers; high polymer materials for medical uses; optical lenses; and membrane filters (reverse penetration films).

Hozumi, K.↗

Polyphenylquinoxalines Containing Alkylenedioxy Groups

New polyphenylquinoxalines (PPQ's) prepared from reaction of novel bis(alpha-diketones) with aromatic bis(o-diamines). Contain alkylenedioxy groups in repeating units. Lower glass-transition temperatures and melt viscosities and better processability than all-aromatic PPQ's. Tensile strength, modulus, elongation, adhesive strength, fracture energy, and solvent resistance of new polymers comparable with properties of known PPQ's. Useful as adhesives, coatings, films, and molded products, particularly for aerospace applications.

Hergenrother, Paul M.↗