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A new type of a positive tone chemically amplified photoresist based on well‐defined, sequence‐controlled polypeptoids with ten repeat‐units are synthesized and their potential for extreme‐UV lithography (EUVL) is demonstrated, resulting in line‐space patterns of 70 nm pitch. The synthesized samples contain 4‐(ethyl) phenol (Eph) and propyne (Ppy) side chains, while their change in solubility upon exposure is induced by the deprotection of 4‐(ethyl) phenol side groups. The resist performance is evaluated using deep UV and extreme‐UV lithography. While all samples are developable in isopropyl alcohol, the content, and the sequence of hydrophobic alkyne side chains lead to a detectable change in solubility, dissolution rate, and resist performance. [ABSTRACT FROM AUTHOR]

The interactions between counterions and electronic carriers in electrically doped semiconducting polymers are important for delocalization of charge carriers, electronic conductivity, and thermal stability. The introduction of a dianions in semiconducting polymers leads to double doping where there is one counterion for two charge carriers. Double doping minimizes structural distortions, but changes the electrostatic interactions between the carriers and counterions. Polymeric ionic liquids (PIL) with croconate dianions are helpful to investigate the role of the counterion in p‐type semiconducting polymers. PILs prevent diffusion of the cation into the semiconducting polymers during ion exchange. The redox‐active croconate dianions undergo ion exchange with doped semiconducting polymers depending on their ionization energy. Croconate dianions are found to reduce doped films of poly(3‐hexyl thiophene), but undergo ion exchange with a polythiophene with tetraethylene glycol side chains, P(g42T‐T), that has a lower ionization energy. The croconate dianion maintains crystalline order in P(g42T‐T) and leads to a lower activation energy for the electrical conductivity than PF6− counterions. The control of the doping level with croconate allows optimization of the thermoelectric performance of the semiconducting polymer. The thermal stability of the doped films of P(g42T‐T) is found to depend strongly on the nature of the counterion. [ABSTRACT FROM AUTHOR]

Block copolymer (BCP) self‐assembly‐assisted doping for semiconductors is used to achieve discrete doping with nanometer‐scale junction depth, high throughput, and large area coverage. As devices become smaller and more sophisticated, spatial control of dopants becomes more critical. A variety of doping methods, such as monolayer doping and δ‐doping, have been developed to replace the conventional doping method, ion‐implantation; however, lateral patterning of dopants relies on photo‐ or e‐beam lithography. To address these challenges, a self‐assembling dopant (boron)‐containing BCP is designed to directly pattern dopants on the nanometer scale. This method skips the lithography step and is compatible with directed self‐assembly approaches. The effect of the boron concentration in the BCP on the doping performance is systematically studied by changing the volume fraction of the boron‐containing block while keeping the domain spacing and the mesoscale morphology constant. Successful self‐assembly of the BCP into a hexagonally packed cylindrical morphology is confirmed by small‐angle X‐ray scattering and resonant soft X‐ray scattering with a 26 nm cylinder‐to‐cylinder distance. Doping silicon using these BCPs enables discrete doped areas with shallow (7–13 nm) junction depth as demonstrated by the depth profile of boron, and supported by a sheet resistance study. [ABSTRACT FROM AUTHOR]

In organic mixed ionic–electronic conductors (OMIECs), it is critical to understand the motion of ions in the electrolyte and OMIEC. Generally, the focus is on the movement of net charge during gating, and the motion of neutral anion–cation pairs is seldom considered. Uptake of mobile ion pairs by the semiconductor before electrochemical gating (passive uptake) can be advantageous as this can improve device speed, and both ions can participate in charge compensation during gating. Here, such passive ion pair uptake in high‐speed solid‐state devices is demonstrated using an ion gel electrolyte. This is compared to a polymerized ionic liquid (PIL) electrolyte to understand how ion pair uptake affects device characteristics. Using X‐ray photoelectron spectroscopy, the passive uptake of ion pairs from the ion gel into the OMIEC is detected, whereas no uptake is observed with a PIL electrolyte. This is corroborated by X‐ray scattering, which reveals morphological changes to the OMIEC from the uptake of ion pairs. With in situ Raman, a reorganization of both anions and cations is then observed during gating. Finally, the speed and retention of OMIEC‐based neuromorphic devices are tuned by controlling the freedom of charge motion in the electrolyte. [ABSTRACT FROM AUTHOR]

Since doped polymers require a charge‐neutralizing counter‐ion to maintain charge neutrality, tailored and high degrees of doping in organic semiconductors requires an understanding of the coupling between ionic and electronic carrier motion. A method of counter‐ion exchange is utilized using the polymeric semiconductor poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] ‐C14 to deconvolute the effects of ionic/polaronic interactions with the electrical properties of doped semiconducting polymers. In particular, exchanging the counter‐ions of the dopant nitrosonium hexafluorophosphate enables investigation into the role of counter‐ion size from 5.2 to 8.2 Å in diameter. The orientational order of the polymeric crystallites is not affected with this exchange process while effectively modifying the counter‐ion distance to the charge carrier. Doped films have electrical conductivities of 320 S cm−1 and are not sensitive to an increased ion‐polaron distance. It is posited that other factors dominate the electrical properties at a device scale, such as the morphology and presence of domain boundaries. Interestingly, the temperature stability of the doped film can be drastically improved with the use of counter‐ions containing less labile bonds. This platform serves as a unique way to retain the morphology of polymeric thin films while studying charge interactions at the local scale. [ABSTRACT FROM AUTHOR]

Polymeric ionic liquids (PILs) have attracted considerable attention as electrolytes with high stability and mechanical durability. Light‐responsive materials are enabling for a variety of future technologies owing to their remote and noninvasive manipulation, spatiotemporal control, and low environmental impact. To address this potential, responsive PIL materials based on diarylethene units were designed to undergo light‐mediated conductivity changes. Key to this modulation is tuning of the cationic character of the imidazolium bridging unit upon photoswitching. Irradiation of these materials with UV light triggers a circa 70 % drop in conductivity in the solid state that can be recovered upon subsequent irradiation with visible light. This light‐responsive ionic conductivity enables spatiotemporal and reversible patterning of PIL films using light. This modulation of ionic conductivity allows for the development of light‐controlled electrical circuits and wearable photodetectors. [ABSTRACT FROM AUTHOR]

ABSTRACT Organic materials are promising candidates for thermoelectric applications owing to their tunable structure and therefore, properties, low cost, earth abundance, and solution processability. Conventional thermoelectric module architecture that relies on relatively thick (∼ mm) 'legs' has limited the incorporation of organics into scalable modules. Herein, we report the fabrication of thermoelectric modules based on organic thermoelectric materials consisting of 100 or more p- and n-legs. This approach utilizes an innovative rolled module design that is shown to easily maintain a temperature gradient above 50 K in the axial direction. Rolled modules comprising PEDOT:PSS ( p-type) and nickel ( n-type) material system with 288 legs were shown to produce an open circuit voltage and a power output of 260 mV and 46 μW, respectively at a temperature difference of 65 K. We note that the thermoelectric power generated by such modules is sufficient to simultaneously light up nine blue LEDs after boosting the output voltage with a voltage step up converter. We also demonstrate the versatility of this approach by fabricating corrugated modules, which enables facile module assembly onto rigid (polylactic acid, PLA) or flexible (polydimethylsiloxane, PDMS) substrates, without significant loss in the power output compared to the rolled modules. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44208. [ABSTRACT FROM AUTHOR]

ABSTRACT Charge transport in poly(3-alkylthiophene)s (P3AT)s is closely linked to the nanoscale organization of crystallites. Block copolymer morphologies provide an ideal platform to study crystallization as the chain ends are tethered at a known interface in a well-defined geometry. The impact of soft versus hard confinement on P3EHT crystallization was studied using poly(3-(2′-ethyl)hexylthiophene) (P3EHT) containing diblocks with both rubbery poly(methyl acrylate) (PMA) and glassy polystyrene (PS) blocks. Here, P3EHT's lower melting point relative to the commonly studied poly(3-hexylthiophene) (P3HT) facilitated its confined crystallization and makes it an ideal model system. While transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) revealed well-ordered lamellar morphologies both in the melt and post-crystallization for both sets of diblocks, the glassy blocks inhibit confined crystallization of P3EHT relative to rubbery matrix blocks. Analysis of aligned diblocks by both SAXS and wide angle X-ray scattering (WAXS) revealed that the P3EHT chain axis aligns perpendicular to domain interfaces, allowing preferential growth of the alkyl-chain and π-π stacking directions parallel to lamellae. Finally, it was shown that following diblock self-assembly in the melt, crystallite growth drives expansion of microdomains to match the P3EHT contour length. It was concluded that P3EHT chains adopted an extended conformation within confined crystallites due to the rigid nature of polythiophenes relative to flexible chain crystalline polymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 205-215 [ABSTRACT FROM AUTHOR]

The article discusses study on large-area, nanometer-scale discrete doping of semiconductors via block copolymer self-assembly. Topics discussed include boron concentration profiles determined using secondary ion mass spectrometry (SIMS), investigation of transmission electron micrographs of as-doped silicon (Si) substrates and surface morphology of spun-coated films studied using tapping mode atomic force microscopy (AFM) reveals a quasi-hexagonal array of spherical micelles.

Side-chain engineering is increasingly being utilized as a technique to impact the structural order and enhance the electronic properties of semiconducting polymers. However, the correlations drawn between structural changes and the resulting charge transport properties are typically indirect and qualitative in nature. In the present work, a combination of grazing incidence X-ray diffraction and crystallographic refinement calculations is used to determine the precise molecular packing structure of two thiophene-based semiconducting polymers to study the impact of side-chain modifications. The optimized structures provide high-quality fits to the experimental data and demonstrate that in addition to a large difference in interchain spacing between the two materials, there exists a significant disparity in backbone orientation as well. The calculated structures are utilized in density functional theory calculations to determine the band structure of the two materials and are shown to exhibit a dramatic disparity in interchain dispersion which accounts for the large observed difference in charge carrier mobility. The techniques presented here are meant to be general and are therefore applicable to many other highly diffracting semicrystalline polymers. [ABSTRACT FROM AUTHOR]

A study of the scope and limitations of varying the ligand framework around the dinuclear core of FvRu2 in its function as a molecular solar thermal energy storage framework is presented. It includes DFT calculations probing the effect of substituents, other metals, and CO exchange for other ligands on Δ Hstorage. Experimentally, the system is shown to be robust in as much as it tolerates a number of variations, except for the identity of the metal and certain substitution patterns. Failures include 1,1′,3,3′-tetra- tert-butyl ( 4), 1,2,2′,3′-tetraphenyl ( 9), diiron ( 28), diosmium ( 24), mixed iron-ruthenium ( 27), dimolybdenum ( 29), and ditungsten ( 30) derivatives. An extensive screen of potential catalysts for the thermal reversal identified AgNO3-SiO2 as a good candidate, although catalyst decomposition remains a challenge. [ABSTRACT FROM AUTHOR]

In this work, crystallization kinetics and aggregate growth of poly(3-ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X-ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time-dependent, field-effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2-3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter-aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics. [ABSTRACT FROM AUTHOR]

A fluctuation X-ray scattering experiment has been carried out on platinum-coated gold nanoparticles randomly oriented on a substrate. A complete algorithm for determining the electron density of an individual particle from diffraction patterns of many particles randomly oriented about a single axis is demonstrated. This algorithm operates on angular correlations among the measured intensity distributions and recovers the angular correlation functions of a single particle from measured diffraction patterns. Taking advantage of the cylindrical symmetry of the nanoparticles, a cylindrical slice model is proposed to reconstruct the structure of the nanoparticles by fitting the experimental ring angular auto-correlation and small-angle scattering data obtained from many scattering patterns. The physical meaning of the refined structure is discussed in terms of their statistical distributions of the shape and electron density profile. [ABSTRACT FROM AUTHOR]

The heterogeneous microstructure of semicrystalline polymers complicates the relationship between their electrical conductivity and carrier concentration. Charge transport models typically describe conductivity with an assumption of uniform doping throughout the material. Here, the evolution in morphology and optoelectronic properties of poly(3‐hexylthiophene) (P3HT) is reported as a function of carrier concentration in an organic electrochemical transistor using a polymeric ionic liquid (PIL) as the gate insulator. Operando grazing incidence X‐ray scattering reveals that negatively charged ions from the dielectric first infiltrate the amorphous regions of the semiconductor, and then penetrate the crystalline regions at a critical carrier density of 4 × 1020 cm−3. Upon infiltration, the crystallites expand by 12% in the alkyl stacking direction and compress by 4% in the π–π stacking direction. The change in crystal structure of P3HT correlates with a sharply increasing effective carrier mobility. UV–visible spectroscopy reveals that holes induced in P3HT first reside in the crystalline regions of the polymer, which verifies that a charge carrier need not be in the same physical domain as its associated counterion. The dopant‐induced morphological changes of P3HT rationalize the dependence of mobility on carrier concentration, suggesting a phase transition of crystalline regions at high carrier concentration. Operando grazing incidence X‐ray scattering reveals structural changes during electrochemical gating of poly(3‐hexylthiophene) transistors using a polymeric ionic liquid gate dielectric. [ABSTRACT FROM AUTHOR]

Charge transport in semiconducting polymers is inextricably linked to their microstructure, making the characterization of polymer morphology at all length‐scales essential for understanding the factors that limit mobility in these materials. Indeed, charge transport depends both on the ability of polarons to delocalize at the approximately nanometer length‐scale and navigate a complex energetic and morphological mesoscale landscape. While characterization of the mesoscale morphology of polymers is well‐established, studies of the local chain packing and nanoscale disorder, which affect delocalization, can be significantly more difficult to carry out. Through infrared charge modulation spectroscopy and theoretical modeling, the effect of the local chain environment on polaron delocalization is directly measured and quantified. Using a series of polymers based on the model system, poly(3‐hexylthiophene), the link between disorder and polaron localization is systematically explored. Polaron delocalization is correlated with known trends in mobility, revealing that while charge delocalization is always beneficial, the formation of tie‐chains is necessary to reach the highest mobilities in semicrystalline polymers. The results provide direct evidence for the importance of both nanoscale (charge carrier delocalization) and mesoscale (tie‐chains) orders, demonstrating the need to distinguish the key length‐scale limiting charge transport in the design of new, high mobility polymers. Quantitative infrared studies of polaron absorption combined with a vigorous and complete theoretical model reveal rich information about the local, nanoscale packing of a series of polymers based on poly(3‐hexylthiophene). Correlating these insights to independent studies of carrier mobility, direct evidence for the effect of charge localization and crystallite connectivity on charge transport is shown. [ABSTRACT FROM AUTHOR]

An obituary for professor Edward J. Kramer, of Department of Materials Science and Engineering at Cornell University is presented.

Review: 151 refs. [ABSTRACT FROM AUTHOR]