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Photoactive Organic/Inorganic Hybrid Materials with Nanosegregated Donor–Acceptor Arrays
Fabrice Mathevet,Xiaolei Zhu,Cheriehan Hessin,Aude Salam,Lydia Sosa-Vargas,David Kreher,Chihaya Adachi,Anna Proust,Pierre Mialane,Jerome Marrot,Aude Bouchet,Michel Sliwa,Stephane Mery,Benoit Heinrich 한국고분자학회 2021 한국고분자학회 학술대회 연구논문 초록집 Vol.46 No.2
We designed and synthesized a first example of mesogenic donor-acceptor polyoxometalate (POM)-based hybrid. 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 subunit organizations in the composite are similar to that observed for the individual POM and organic donor precursors. Photophysical studies showed 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.
Madathil, Pramod Kandoth,Heinrich, Benoî,t,Donnio, Bertrand,Mathevet, Fabrice,Fave, Jean-Louis,Guillon, Daniel,Attias, Andre-Jean,Lee, Changjin,Kim, Tae-Dong,Lee, Kwang-Sup American Scientific Publishers 2010 Journal of Nanoscience and Nanotechnology Vol.10 No.10
<P>We report here the synthesis and characterization of novel diethynylbenzene-based liquid crystalline semiconductor (P1) for organic thin-film transistors (OTFTs). Compound P1 was synthesized by the Sonogashira coupling reaction between 2-bromo-5-(4-hexylthiophen-2-yl)thieno[3,2-b]thiophene and 1,4-bis(dodecyloxy)-2,5-diethynylbenzene. Top contact OTFTs were fabricated by spin casting with 2 wt% solution of P1 in chloroform and their best performance, which exhibited a hole mobility of 4.5 x 10(-5) cm2/Vs, was showed after annealing of the films at liquid crystalline temperature. Time-of-flight (TOF) mobility measured at liquid crystalline phase was observed to be 1.5 x 10(-6) cm2/Vs for both positive and negative carriers. These results indicate that the liquid crystallinity helps to improve the molecular packing and enhance charge mobility for P1. These advantages can be applicable to design and construct solution-processable OTFT materials for electronic applications.</P>
Vincent Balaya,Fabrice Lécuru,Laurent Magaud,Charlotte Ngô,Cyrille Huchon,Anne-Sophie Bats,Patrice Mathevet 대한부인종양학회 2019 Journal of Gynecologic Oncology Vol.30 No.3
Objective: The aim of this study was to determine the predictive factors of postoperative morbidity of patients who have undergone a radical trachelectomy (RT) for early-stage cervical cancer and to assess the oncologic outcomes. Methods: We retrospectively analysed the data of 2 prospective trials on sentinel node biopsy for cervical cancer (SENTICOL I and II). Patients having a RT for early-stage cervical cancer with negative sentinel lymph node and safe margins, were included. Results: Forty-nine patients met the inclusion criteria. Forty-five patients had a laparoscopicassisted vaginal technique and 4 patients a total laparoscopic technique. The median age was 32 years (range, 22–46 years). 83.7% of patients had a stage IB1 disease. There were 63.3% squamous cell carcinomas and 34.7% adenocarcinomas. The median follow-up was 46 months (range, 1–85 months). Two patients (3.3%) had a severe postoperative complication (Clavien-Dindo ≥III and/or CTCAE ≥3). The main postoperative complications were urinary (28.6%), lymphovascular (26.5%) and neurologic (14.3%). On a multivariate analysis, postoperative complications were significantly associated with history of pelvic surgery and IB1 International Federation of Gynecology and Obstetrics stage. Inclusion in high surgical skills centers decrease the risk of postoperative complications. During the follow-up, 3 patients (6.1%) had a local recurrence and one patient died from a breast cancer. Between group with complications and group without any complications, overall survival and recurrence-free survival did not significantly differ at 5-year of follow-up. Conclusion: RT has few severe postoperative complications and appears as a safe alternative to spare fertility of young patients. To guarantee best surgical outcomes, patients should be referred to expert center.
Bae, Insung,Kang, Seok Ju,Shin, Yu Jin,Park, Youn Jung,Kim, Richard Hahnkee,Mathevet, Fabrice,Park, Cheolmin WILEY‐VCH Verlag 2011 Advanced Materials Vol.23 No.30
<P><B>Single crystalline triisopropylsilylethynyl pentacene (TIPS‐PEN) arrays</B> are fabricated with both size and shape of each patterned domain precisely tailored by selective contact evaporation printing (SCEP), which exhibit sufficient ON/OFF current ratio as well as high field effect mobility.</P>
Lee, Kwang Jin,Xiao, Yiming,Woo, Jae Heun,Kim, Eunsun,Kreher, David,Attias, André,-Jean,Mathevet, Fabrice,Ribierre, Jean-Charles,Wu, Jeong Weon,André,, Pascal Nature Publishing Group, a division of Macmillan P 2017 NATURE MATERIALS Vol.16 No.7
<P>Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene: perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7-that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal-dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.</P>
Yoon, Seong‐,Jun,Kim, Jong H.,Kim, Kil Suk,Chung, Jong Won,Heinrich, Benoî,t,Mathevet, Fabrice,Kim, Pyosang,Donnio, Bertrand,Attias, André,‐,Jean,Kim, Dongho,Park, Soo Young WILEY‐VCH Verlag 2012 Advanced Functional Materials Vol.22 No.1
<P><B>Abstract</B></P><P>A new dicyanodistyrylbenzene‐based phasmidic molecule, (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(3,4,5‐tris(dodecyloxy)phenyl)acrylonitrile), GDCS, is reported, which forms a hexagonal columnar liquid crystal (LC) phase at room temperature (RT). GDCS molecules self‐assemble into supramolecular disks consisting of a pair of molecules in a side‐by‐side disposition assisted by secondary bonding interactions of the lateral polar cyano group, which, in turn, constitute the hexagonal columnar LC structure. GDCS shows very intense green/yellow fluorescence in liquid/solid crystalline states, respectively, in contrast to the total absence of fluorescence emission in the isotropic melt state according to the characteristic aggregation‐induced enhanced emission (AIEE) behavior. The AIEE and two‐color luminescence thermochromism of GDCS are attributed to the peculiar intra‐ and intermolecular interactions of dipolar cyanostilbene units. It was found that the intramolecular planarization and restricted molecular motion associated with a specific stacking situation in the liquid/solid crystalline phases are responsible for the AIEE phenomenon. The origin of the two‐color luminescence was elucidated to be due to the interdisk stacking alteration in a given column driven by the specific local dipole coupling between molecular disks. These stacking changes, in turn, resulted in the different degree of excited‐state dimeric coupling to give different emission colors. To understand the complicated photophysical properties of GDCS, temperature‐dependent steady‐state and time‐resolved PL measurements have been comprehensively carried out. Uniaxially aligned and highly fluorescent LC and crystalline microwires of GDCS are fabricated by using the micromolding in capillaries (MIMIC) method. Significantly enhanced electrical conductivity (0.8 × 10<SUP>−5</SUP> S•cm<SUP>−1</SUP>/3.9 × 10<SUP>−5</SUP> S•cm<SUP>−1</SUP>) of the aligned LC/crystal microwires were obtained over that of multi‐domain LC sample, because of the almost perfect shear alignment of the LC material achieved in the MIMIC mold.</P>
Lee, K. J.,Woo, J. H.,Kim, E.,Xiao, Y.,Su, X.,Mazur, L. M.,Attias, A.-J.,Fages, F.,Cregut, O.,Barsella, A.,Mathevet, F.,Mager, L.,Wu, J. W.,D'Alé,o, A.,Ribierre, J.-C. The Royal Society of Chemistry 2016 Physical chemistry chemical physics Vol.18 No.11
<P>We investigate the photophysical properties of organic donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units linked by a non-conjugated flexible bridge in solution using complementary optical spectroscopy techniques. When these molecules are diluted in dichloromethane solution, energy transfer from the triphenylene to the perylene diimide excited moieties is evidenced by time-resolved fluorescence measurements resulting in a quenching of the emission from the triphenylene moieties. Simultaneously, another quenching process that affects the emission from both donor and acceptor units is observed. Solution ultrafast transient absorption measurements provide evidence of photo-induced charge transfer from either the donor or the acceptor depending upon the excitation. Overall, the analysis of the detailed time-resolved spectroscopic measurements carried out in the dyad and triad systems as well as in the triphenylene and perylene diimide units alone provides useful information both to better understand the relations between energy and charge transfer processes with molecular structures, and for the design of future functional dyad and triad architectures based on donor and acceptor moieties for organic optoelectronic applications.</P>
Howells, Calvyn T.,Marbou, Khalid,Kim, Haeri,Lee, Kwang Jin,Heinrich, Benoî,t,Kim, Sang Jun,Nakao, Aiko,Aoyama, Tetsua,Furukawa, Seiichi,Kim, Ju-Hyung,Kim, Eunsun,Mathevet, Fabrice,Mery, St&eacut The Royal Society of Chemistry 2016 Journal of Materials Chemistry A Vol.4 No.11
<P>We demonstrate that blending fluorinated molecules in PEDOT:PSS hole transport layers (HTL) induces charge transfers which impact on both charge extraction and photogeneration within organic photovoltaic (OPV) devices. OPVs fabricated with modified HTL and two photoactive polymer blends led systematically to power conversion efficiencies (PCE) increases, with PTB7:PC70BM blend exhibiting PCE of ∼8.3%,<I>i.e.</I>∼15% increase compared to pristine HTL devices. A reduced device-to-device characteristics variations was also noticed when fluorinated additives were used to modify the PEDOT:PSS. Shading lights onto the effect of HTL fluorination, we show that the morphology of the polymer:PCBM blends remains surprisingly unaffected by the fluorinated HTL surface energy but that, instead, the OPVs are impacted not only by the HTL electronic properties (work function, dipole layer, open circuit voltage, charge transfer dynamic) but also by alteration of the complex refractive indices (photogeneration, short circuit current density, external quantum efficiencies, electro-optic modelling). Both mechanisms find their origin in fluorination induced charge transfers. This work points towards fluorination as a promising strategy toward combining both external quantum efficiency modulation and power conversion efficiency enhancement in OPVs. Charge transfers could also be used more broadly to tune the optical constants and electric field distribution, as well as to reduce interfacial charge recombinations within OPVs.</P>