Achieving low-power, high-mobility organic thin-film transistors requires control over the buried interface between the semiconductor and the dielectric layers. Here, we demonstrate that siloxane-based molecular design provides a powerful means of engineering interfacial compatibility and charge transport. By integrating siloxane-functionalized diketopyrrolopyrrole (DPP) semiconductors with a PDMS-based polyionic liquid (PIL) dielectric, we show that siloxane-siloxane interactions promote enhanced molecular ordering, increased crystal coherence, and improved charge-carrier mobility of the semiconductor. Grazing-incidence wide-angle X-ray scattering and Raman morphological analyses indicate that interfacial interactions drive coherent stacking and reduce the level of disorder at the interface. This interfacial design strategy offers a general approach to tuning interfaces through conjugated polymer/dielectric systems, offering insight into strategies for the development of low-voltage, high-performance organic electronics.

Resolving the nanoscale morphology of donor-acceptor heterojunction systems remains a challenge for conventional characterization techniques which often lack either chemical sensitivity or sufficient spatial resolution. Here we present the characterization of organic semiconducting nanoparticles by combining scanning transmission X-ray microscopy (STXM) and soft X-ray ptychography (SXP). STXM provides chemically specific composition maps while SXP provides high resolution amplitude and phase images. This approach when applied to P3HT/PC61BM and PTQ10/ITIC-4F nanoparticles, synthesized by different fabrication routes, namely miniemulsion and nanoprecipitation, show radially segregated core-shell morphology and intermixed morphology. These results establish STXM and SXP as complementary techniques for morphological study especially in radiation-sensitive organic semiconductor nanoparticles.

In this contribution, doping of oriented thin films is investigated for three PBTTT polymers bearing different side chains including linear alkyl & horbar;(CH2)12 & horbar;H, single ether & horbar;(CH2)7 & horbar;O & horbar;(CH2)4 & horbar;H and alkyl-siloxane & horbar;(CH2)5 & horbar;(Si(CH3)2O)2 & horbar;Si(CH3)3 A combination of transmission electron microscopy, polarized UV-vis-NIR spectroscopy and transport measurements helps uncover the essential role of the chemical nature of side chains on the efficacy of the doping and on the resulting thermoelectric performances in oriented PBTTT films. Siloxane side chains help to reach record alignment level of PBTTT with dichroic ratio beyond 50 for an optimized rubbing temperature but they impede effective doping of PBTTT crystals with F6TCNNQ, resulting in very poor TE properties. By contrast, doping the amorphous phase of all three PBTTTs with magic blue (MB) results in excellent TE performances. Both, chemical nature of side chains and semi-crystalline structure of the polymer determine the efficacy of doping. The use of siloxane side chains further impacts the scaling laws S proportional to sigma-1/s between the Seebeck coefficient S and the charge conductivity sigma. An unexpected s = 2 exponent is observed and tentatively attributed to the dimensionality of charge transport in the highly oriented mesophase of PBTTT.

The development of high-performance, fully non-fused ring electron acceptors (NFREAs) for organic solar cells (OSCs) is often hindered by multistep synthesis, use of hazardous reagents, and high synthetic complexity (SC), ultimately limiting their figure-of-merit (FOM). In this study, we report three simple and cost-effective NFREAs, SN-1, SN-2, and SN-3, featuring a dialkoxybenzene central core and hexyldicyanorhodanine terminal acceptor groups linked via distinct pi-bridging units: furan, thiophene, and ethylenedioxythiophene (EDOT), respectively. These NFREAs were synthesized in just four steps using a direct C-H arylation reaction, without any hazardous reagents, with very high overall yields of up to 49%. To enhance the molecular planarity and charge transport, an intramolecular noncovalent interaction strategy was employed to restrict the C-C bond rotation between the pi-conjugated units. Notably, SN-3 exhibited multiple OS and OH interactions between core and end groups, effectively rigidifying the backbone and promoting J-aggregation. As a result, PM-6:SN-3-based OSCs achieved a power conversion efficiency (PCE) of 11.56%, a high FOM of 67.09, and a low SC value of 17.26. In comparison, devices based on SN-1 and SN-2 delivered PCEs of 10.26% and 6.97%, respectively. These findings underscore the critical role of noncovalent interactions in conformationally stabilizing simple NFREAs and highlight their potential for high FOM OSCs.

Scanning transmission X-ray microscopy (STXM) and soft X-ray ptychography (SXP) are powerful techniques for nanoscale imaging, offering high spatial resolution with chemical sensitivity. However, the interplay between spatial resolution and X-ray radiation damage remains a critical consideration for sensitive samples, such as organic materials. In this study, we quantitatively compared spatial resolution and radiation damage between the two techniques. Spatial resolution is assessed using Fourier ring correlation (FRC), applying both the 1/2-bit threshold and a signal-to-noise ratio (SNR) threshold mathematically computed for each spatial frequency. SXP achieves superior spatial resolution due to its phase-retrieval capabilities and enhanced coherent imaging properties. In this paper, a resolution of 20-25 nm with SXP at the nitrogen K-edge (similar to 400 eV) was achieved for the first time, while STXM is limited by zone plate used, outermost zone width as 25 nm giving a theoretical resolution of 30.5 nm (1.22 x outermost zone width). Moreover, in our measurements, we find that the X-ray radiation dose required for SXP is approximately 6 times lower than for STXM, leading to a remarkably low damage level, highlighting its potential for damage-sensitive studies. These findings establish SXP as a highly efficient and minimally invasive imaging technique for the nanoscale characterization of organic material.

The thorough characterization of polymer chains grafted through a “grafting-from” process onto substrates based on the determination of number (Mn) and weight (Mw) average molar masses, as well as dispersity (Ɖ), is quite challenging. It requires the cleavage of grafted chains selectively at the polymer–substrate bond without polymer degradation to allow their analysis in solution with steric exclusion chromatography, in particular. The study herein describes a technique for the selective cleavage of PMMA grafted onto titanium substrate (Ti-PMMA) using an anchoring molecule that combines an atom transfer radical polymerization (ATRP) initiator and a UV-cleavable moiety. This technique allows the demonstration of the efficiency of the ATRP of PMMA on titanium substrates and verification that the chains were grown homogeneously.

We show that through the introduction of short dimethylsiloxane chains, it was possible to suppress the crystalline state of CBP in favor of various types of organization, transitioning from a soft crystal to a fluid liquid crystal mesophase, then to a liquid state. Characterized by X-ray scattering, all organizations reveal a similar layered configuration in which layers of edge-on lying CBP cores alternate with siloxane. The difference between all CBP organizations essentially lay on the regularity of the molecular packing that modulates the interactions of neighboring conjugated cores. As a result, the materials show quite different thin film absorption and emission properties, which could be correlated to the features of the chemical architectures and the molecular organizations.

Electron-hole separation in self-assembled mesomorphic nanostructures composed of donor-acceptor (DA) co-oligomers is investigated by combined microelectrostatics and kinetic Monte Carlo simulations. The relevant DA dyads are based on perylene diimide (PDI) acceptor moieties covalently bound to fluorene-thiophene-benzothiadiazole donor moieties, which form highly ordered, stacked structural motifs upon self-assembly. These are characterized by efficient electron transport along PDI stacks, whereas hole transport is almost three orders of magnitude slower. On the basis of an atomistic structure obtained by electron diffraction, the energetics of charge separation is characterized by a microelectrostatics analysis. This information is subsequently employed to compute electron-hole (e-h) separation rates and dissociation yields by kinetic Monte Carlo simulations. The latter have been calibrated against recent quantum dynamical studies for a reduced one-dimensional representation of the DA system. It is shown that charge separation of "cold" e-h pairs is characterized by dissociation rates around 10(9) s(-1), which are associated with two-dimensional transport features, where the predominant electron transport in the PDI stacking direction is assisted by a secondary mechanism that involves neighboring stacks.

We report herein the synthesis of siloxane-functionalized CBP molecules (4,4′-bis(carbazole)-1,1′-biphenyl) for liquid optoelectronic applications. The room-temperature liquid state is obtained through a convenient functionalization of the molecules with heptamethyltrisiloxane chains via hydrosilylation of alkenyl spacers. The synthesis comprises screening of metal-catalyzed methodologies to introduce alkenyl linkers into carbazoles (Stille and Suzuki Miyaura cross-couplings), incorporate the alkenylcarbazoles to dihalobiphenyls (Ullmann coupling), and finally introduce the siloxane chains. The used conditions allowed the synthesis of the target compounds, despite the high reactivity of the alkenyl moieties bound to π-conjugated systems toward undesired side reactions such as polymerization, isomerization, and hydrogenation. The features of these solvent-free liquid CBP derivatives make them potentially interesting for fluidic optoelectronic applications.

La dermatite atopique (DA) est une dermatose inflammatoire chronique fréquente ayant un retentissement important sur la qualité de vie des patients concernés. Le pharmacien, en tant que dernier professionnel de santé interagissant avec le patient avant la dispensation des soins, joue un rôle clé dans l’éducation thérapeutique. Cependant, plusieurs études soulignent les lacunes des pharmaciens en matière de connaissances des pathologies cutanées et des traitements topiques, et notamment les dermocorticoïdes. Le but de notre étude était d’évaluer l’impact d’un programme de e-learning appelé POP-training (Pour Parcours Officinal du Patient) sur la prise en charge de la DA par les pharmaciens d’officine. Le programme était composé de 6 modules abordant des thèmes différents : la physiopathologie, la corticophobie, les traitements locaux, la motivation pour le maintien des traitements dans la durée, et l’approche éducative. Chaque module était précédé et suivi d’une évaluation et un questionnaire envoyé 9 mois après la formation permettait de déterminer la rémanence des connaissances. Le score moyen des évaluations était de 13,4 (12,7–14,1) avant le e-learning, de 16,7 (16,2–17,3) juste après le e-learning et de 16,0 (15,4–16,6) 9 mois après. Les notes augmentaient quel que soit le thème abordé mais la progression était la plus grande pour les thèmes de la physiopathologie et de la corticophobie. L’originalité de ce projet réside dans la conception d’un e-learning, qui a permis une transmission facilitée des connaissances. Par ailleurs, les modules et évaluations ont été conçus par 6 équipes appartenant à des centres de référence de l’ETP dans la DA, assurant ainsi une formation d’une grande qualité. Notre étude a été limitée par un faible taux de participation (23 %) et un désinvestissement progressif au cours du e-learning, qui peuvent être expliqués par la gratuité de la formation, mais aussi peut-être par la longueur de la formation ou la redondance de certains sujets. À l’avenir, une version synthétique de ce programme pourrait être élaborée, prenant en compte le retour d’expérience du patient.

Over the past decade, halogenated semiconducting polymers have attracted considerable interest due to their outstanding optoelectronic properties. Thus, in most of today's organic photovoltaic devices benchmark organic semiconductors are halogenated materials, either electron donor polymers or non‐fullerene acceptor (NFA) small molecules. However, the nature and position of the substituted halogen atoms in halogenated semiconducting polymers impact, through self‐assembly modification, their optoelectronic properties in a way that is difficult to predict. Yet, the solid‐state self‐assembling of these materials has been shown to be a key parameter toward high charge transport properties and photovoltaic efficiencies. In this context, there is still a need to develop analytical methods that will enable an atomic‐scale structural characterization of these materials as a function of the halogenation. In this study, the solid‐state nuclear magnetic resonance (NMR) under magic angle spinning (MAS) is explored as a tool to investigate the local structure and supramolecular organization of a series of conjugated polymers, specially designed for this study. Through a comprehensive study using complementary techniques, including MAS–NMR, small and wide‐angle X‐ray scattering, and molecular modeling investigations, the molecular conformation of these polymers in relation to their chemical composition, is successfully determined.

The use of Non-Fullerene Acceptors (NFAs) in the active layer of organic solar cells (OSCs) has made it possible to exceed 18% conversion efficiency. However, OSCs still present stability issues under operational conditions that need to be surpassed for their industrialization. In this work, we investigated binary and ternary blends to examine their efficiency and their stability as active layers of OSCs. We used a fluorinated polymer (PF2) as an electron donor and two different electron acceptors, a fullerene derivative (PC71BM) and a NFA (EH-IDTBR). We demonstrated that using EH-IDTBR instead of PC71BM leads to a decrease in efficiency attributed to the low out-of-plane electron mobility measured in the blend. However, using EH-IDTBR as single electron-acceptor significantly enhanced the OSCs stability under continuous illumination. Ternary blends were tested to reach simultaneously a high efficiency and a long-term stability. The best efficiency/stability compromise appeared to be when using EH-IDTBR only as electron-acceptor. We identified changes in the main charge-carrier recombination mechanism in photo-degraded devices from bimolecular in low EH-IDTBR content blends to trap-assisted in high EH-IDTBR ones. Finally, the blend morphology at a nanometer scale appeared as stable in high EH-IDTBR content blends while photo-degradation impacted significantly the morphology of the low EH-IDTBR content blend.

Journal of the European Academy of Dermatology and VenereologyVolume 35, Issue 10 p. e656-e659 Letter To The EditorToken Access Impact of an e-learning programme on pharmacists’ management of atopic dermatitis A.-C. Garreau, Corresponding Author anne-camille.garreau@chu-lyon.fr orcid.org/0000-0002-0042-7034 Univ Lyon, Lyon Sud University Hospital, Allergy and Clinical Immunology Department, Pierre-Benite, France *Correspondence: A.-C. Garreau. E-mail: anne-camille.garreau@chu-lyon.frSearch for more papers by this authorJ.-F. Stalder, Dermatology Department, University Hospital of Nantes, Nantes, FranceSearch for more papers by this authorS. Méry, Eczema Foundation, Pierre Fabre Laboratories, Toulouse, FranceSearch for more papers by this authorP. Bunouf, Eczema Foundation, Pierre Fabre Laboratories, Toulouse, FranceSearch for more papers by this authorC. Jean-Decoster, orcid.org/0000-0002-8185-6198 Eczema Foundation, Pierre Fabre Laboratories, Toulouse, FranceSearch for more papers by this authorA. Nosbaum, Univ Lyon, Lyon Sud University Hospital, Allergy and Clinical Immunology Department, Pierre-Benite, France CIRI, Centre International de Recherche en Infectiologie, Univ Lyon, Inserm, U1111, Université Claude Bernard Lyon 1, CNRS, UMR5308, ENS de Lyon, Lyon, FranceSearch for more papers by this author on behalf of the Eczema Foundation, the French Group on Therapeutic Education in Dermatology (GET), Search for more papers by this author A.-C. Garreau, Corresponding Author anne-camille.garreau@chu-lyon.fr orcid.org/0000-0002-0042-7034 Univ Lyon, Lyon Sud University Hospital, Allergy and Clinical Immunology Department, Pierre-Benite, France *Correspondence: A.-C. Garreau. E-mail: anne-camille.garreau@chu-lyon.frSearch for more papers by this authorJ.-F. Stalder, Dermatology Department, University Hospital of Nantes, Nantes, FranceSearch for more papers by this authorS. Méry, Eczema Foundation, Pierre Fabre Laboratories, Toulouse, FranceSearch for more papers by this authorP. Bunouf, Eczema Foundation, Pierre Fabre Laboratories, Toulouse, FranceSearch for more papers by this authorC. Jean-Decoster, orcid.org/0000-0002-8185-6198 Eczema Foundation, Pierre Fabre Laboratories, Toulouse, FranceSearch for more papers by this authorA. Nosbaum, Univ Lyon, Lyon Sud University Hospital, Allergy and Clinical Immunology Department, Pierre-Benite, France CIRI, Centre International de Recherche en Infectiologie, Univ Lyon, Inserm, U1111, Université Claude Bernard Lyon 1, CNRS, UMR5308, ENS de Lyon, Lyon, FranceSearch for more papers by this author on behalf of the Eczema Foundation, the French Group on Therapeutic Education in Dermatology (GET), Search for more papers by this author First published: 29 April 2021 https://doi.org/10.1111/jdv.17326Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat Volume35, Issue10October 2021Pages e656-e659 RelatedInformation

Two new dumbbell-shaped molecules based on two solubilizing and structuring triazatruxene (TAT) units linked by a central chromophore were synthesized and studied. The central chromophore was an electro-deficient fluorene-malononitrile (FM) unit, that can be functionalized symmetrically on two different positions, giving rise to two positional isomers, called TAT-pFM and TAT-mFM, when the TATs are connected to the 2,7- and 3,6-positions, respectively. The two isomers exhibited different electronic conjugation pathways that drastically affect their absorption properties and energy levels. Moreover, while TAT-pFM was organized in a stable 3D mesomorphic structure from room-temperature to the melting point, TAT-mFM remained crystalline and decomposed before melting. Finally, despite a lower hole mobility, the TAT-mFM exhibited the highest Power Conversion Efficiency (PCE) of about 2 % in organic solar cells. This higher PCE was attributed essentially to the pronounced internal charge transfer band contribution to the charge photogeneration observed in TAT-mFM solar cells.

The synthesis of the first mesogenic donor-acceptor polyoxometalate (POM)-based hybrid is herein described. The structural and electronic properties of the hybrid compound were evaluated through combination of small- and wide-angle X-ray scattering, optical microscopy, electrochemistry and photoluminescence. In the solid state, the compound behaves as a birefringent solid, displaying a lamellar organization in which double-layers of POMs and bis(thiophene)thienothiophene organic donors alternate regularly. Noticeably, the sub-unit organizations in the composite are similar to that observed for the individual POM and organic donor precursors. Photophysical studies show that in the hybrid, the fluorescence of the organic donor unit is considerably quenched both in solution and in the solid state, which is attributed to occurrence of intramolecular charge-separated state.

Triazatruxene-based dumbbell-shaped molecules self-assemble into a novel bridged columnar phase, where conducting segments connect adjacent columns of triazatruxene units across the insulating aliphatic domains, resulting in efficient hole transport in 3D.

Herein reported is the impact of the functionalization of four different semiconducting polymer structures by a linear siloxane‐terminated side‐chains. The latter is tetrasiloxane (Si 4 ) or trisiloxane (Si 3 ) chains, substituted at their extremity to a pentylene linker. The polymer structure is based on 5,6‐difluorobenzothiadiazole comonomer (PF2), a diketopyrrolopyrrole unit (PDPP‐TT), a naphtalediimide unit (PNDI‐T 2 ), and a poly[bis(thiophen‐2‐yl)thieno[3,2,b]thiophene (PBTTT). The properties of these siloxane‐functionalized polymers are scrutinized and compared with the ones of their alkyl‐substituted polymer analogues. The impact of the alkyl‐to‐siloxane chain substitution clearly depends on the molecular section of the side chains. When a branched 2‐octyldodecyl chain (C 20 ) is replaced by a Si 4 chain of same molecular section, the greatest impact is the strong increase of the π‐stacking overlap of the polymer backbones. This effect leads to a significative enhancement of the charge mobility values of the polymers. As in‐plane and out‐of‐plane mobility are increased simultaneously, this π‐overlap enhancement effect happens to be preponderant over the polymer orientation variations. When a linear tetradecyl chain (C 14 ) is replaced by a linear Si 3 chain of twice larger molecular section, the polymer structure is profoundly affected. While PBTTT‐C 14 is crystalline and purely edge‐on, PBTTT‐Si 3 is mesomorphic and shows a mixed face‐on/edge‐on orientation.

Introduction Les conseils discordants des professionnels de santé pendant le parcours de soin des patients souffrant d’eczéma atopique génèrent de la confusion et diminuent l’adhésion au traitement. Les pharmaciens sont le dernier maillon de la chaîne de soins avant le domicile. Le Groupe d’éducation thérapeutique de la SFD (GET) en partenariat avec la Fondation Eczéma a mis en place le programme de formation POP Training (pour « Parcours Officinal du Patient »), reposant sur du e-learning dédié aux pharmaciens d’officine. L’objectif de ce travail était d’évaluer l’impact de ce programme de formation sur les connaissances des pharmaciens d’officine et leur personnel. Matériel et méthodes Les pharmaciens s’inscrivaient pour suivre 6 modules d’une heure et demie sur une plateforme pédagogique en ligne, développée par la Fondation Eczéma. Le programme couvrait la physiopathologie, la corticophobie, les traitements locaux, la motivation pour un maintien des traitements dans la durée et l’approche éducative. Le résultat des quiz évaluant les connaissances avant et après chaque module a été évalué statistiquement. Résultats Sur les 1630 inscrits, 336 pharmaciens ont suivi le module 1 et 195 ont terminé l’ensemble des 6 modules. Les notes obtenues aux quiz ont montré une amélioration des connaissances d’environ 2,5 points/20, sur l’ensemble des modules. Néanmoins, les pharmaciens, les préparateurs et les étudiants n’avaient pas les mêmes niveaux de progression. Discussion Chaque module de POP TRAINING a ciblé des thématiques spécifiques. Les équipes officinales avaient une bonne connaissance des traitements locaux (module 3), qui sont de leur domaine d’expertise. Cependant, la formation a apporté des connaissances supplémentaires, puisque la moyenne après le module était augmentée. Le niveau de connaissance en éducation thérapeutique du patient (ETP) était également élevé avant le module 5, 40h de formation d’ETP étant intégrées au cursus universitaire des pharmaciens. Toutefois, on note une amélioration à l’issue du module. L’état des connaissances sur la corticophobie et l’approche psychologique pour garder les patients motivés, ont montré des niveaux de connaissance plus faibles en début des modules 2 et 4. Ces résultats soulignent les points forts et les points faibles des connaissances des pharmaciens sur le terrain. Le programme POP Training a permis une amélioration des connaissances des pharmaciens pour la prise en charge des patients souffrant d’eczéma atopique. Il permet d’asseoir leur rôle dans ce parcours de soin, avec un alignement des discours entres les différents acteurs de soins.