Применение активных методов обучения

Материалы II науч.-метод. конф., Гомель, 10–11 нояб. 2011 г

Experimental evidence that short-range intermolecular aggregation is sufficient for efficient charge transport in conjugated polymers Experimental evidence that short-range intermolecular aggregation is sufficient for efficient charge transport in conjuga

properties. In these conditions, the semiconducting polymer chains are inhibited from attaining long range order in the -stacking or alkyl stacking directions, as demonstrated from the absence of significant X-ray diffraction intensity corresponding to these crystallographic directions, yet still remain extended along the backbone direction and aggregate on a local length scale. As a result, the polymer films maintain high mobility even at very low concentrations. Our findings provide a simple picture that clarifies the role of local order and connectivity of domains. 3 Significance Statement Understanding the nature of charge transport and its limitations has guided the rational design of organic semiconductors. Research has mainly focused on increasing the crystallinity of conjugated polymers as a strategy to improve the long-range charge transport properties. Here, we demonstrate that local aggregation over very few chains is a sufficient mesoscopic structure to ensure high mobility, with charge transport mainly occurring along the polymer backbones, and that extended crystallinity is not necessary. These results provide an explanation for the high mobilities observed in seemingly disordered polymers and set molecular-design guidelines for next generation conjugated polymers

Experimental evidence that short-range intermolecular aggregation is sufficient for efficient charge transport in conjugated polymers

Efficiency, current throughput, and speed of electronic devices are to a great extent dictated by charge carrier mobility. The classic approach to impart high carrier mobility to polymeric semiconductors has often relied on the assumption that extensive order and crystallinity are needed. Recently, however, this assumption has been challenged, because high mobility has been reported for semiconducting polymers that exhibit a surprisingly low degree of order. Here, we show that semiconducting polymers can be confined into weakly ordered fibers within an inert polymer matrix without affecting their charge transport properties. In these conditions, the semiconducting polymer chains are inhibited from attaining long-range order in the p-stacking or alkyl-stacking directions, as demonstrated from the absence of significant X-ray diffraction intensity corresponding to these crystallographic directions, yet still remain extended along the backbone direction and aggregate on a local length scale. As a result, the polymer films maintain high mobility even at very low concentrations. Our findings provide a simple picture that clarifies the role of local order and connectivity of domains.Funding Agencies|Advanced Functional Materials Center at Linkoping University; Onnesjo Foundation; Knut and Alice Wallenberg Foundation; Swedish Foundation for Strategic Research; Swedish Governmental Agency for Innovation Systems (VINNOVA); National Science Foundation [DMR 1205752]; US Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-76SF00515]</p

Role of Molecular Weight Distribution on Charge Transport in Semiconducting Polymers

Model semiconducting polymer blends of well-controlled molecular weight distributions are fabricated and demonstrated to be a simple method to control intermolecular disorder without affecting intramolecular order or degree of aggregation. Mobility measurements exhibit that even small amounts of low molecular weight material are detrimental to charge transport. Trends in charge carrier mobility can be reproduced by a simple analytical model which indicates that carriers have no preference for high or low molecular weight chains and that charge transport is limited by interchain hopping. These results quantify the role of long polymer tie-chains and demonstrate the need for controlled polydispersity for achieving high carrier mobilities

Enhanced Photovoltaic Performance of Indacenodithiophene-Quinoxaline Copolymers by Side- Chain Modulation

Two pairs of indacenodithiophene (IDT) and quinoxaline-based copolymers with meta- or para-hexyl-phenyl side chains on the IDT unit are synthesized. The meta-substituted polymers offer better solubility, higher molecular weight for both fluorinated and non-fluorinated copolymers, and a superior photovoltaic performance with a power conversion efficiency of 7.8%. The side-chain design strategy presented is an efficient way to produce high performance conjugated polymers for organic electronics

The Effect of Processing Additives on Energetic Disorder in Highly Efficient Organic Photovoltaics : A Case Study on PBDTTT-C-T:PC71BM

Energetic disorder, an important parameter affecting the performance of organic photovoltaics, is significantly decreased upon the addition of processing additives in a highly efficient benzodithiophene-based copolymer blend (PBDTTT-C-T:PC71BM). Wide-angle and small-angle X-ray scattering measurements suggest that the origin of this reduced energetic disorder is due to increased aggregation and a larger average fullerene domain size together with purer phases.Funding Agencies|Swedish Research Council (VR); European Commission Marie Sklodowska-Curie actions; Swedish Energy Agency; Knut and Alice Wallenberg foundation (KAW)</p

The Role of Regioregularity, Crystallinity, and Chain Orientation on Electron Transport in a High-Mobility n-Type Copolymer

We investigated the correlation between the polymer backbone structural regularity and the charge transport properties of poly{[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} [P(NDI2OD-T2)], a widely studied semiconducting polymer exhibiting high electron mobility and an unconventional micromorphology. To understand the influence of the chemical structure and crystal packing of conventional regioregular P(NDI2OD-T2) [RR-P(NDI2OD-T2)] on the charge transport, the corresponding regioirregular polymer RI-P(NDI2OD-T2) was synthesized. By combining optical, X-ray, and transmission electron microscopy data, we quantitatively characterized the aggregation, crystallization, and backbone orientation of all of the polymer films, which were then correlated to the electron mobilities in electron-only diodes. By carefully selecting the preparation conditions, we were able to obtain RR-P(NDI2OD-T2) films with similar crystalline structure along the three crystallographic axes but with different orientations of the polymer chains with respect to the substrate surface. RI-P(NDI2OD-T2), though exhibiting a rather similar LUMO structure and energy compared with the regioregular counterpart, displayed a very different packing structure characterized by the formation of ordered stacks along the lamellar direction without detectible π-stacking. Vertical electron mobilities were extracted from the space-charge-limited currents in unipolar devices. We demonstrate the anisotropy of the charge transport along the different crystallographic directions and how the mobility depends on π-stacking but is insensitive to the degree or coherence of lamellar stacking. The comparison between the regioregular and regioirregular polymers also shows how the use of large planar functional groups leads to improved charge transport, with mobilities that are less affected by chemical and structural disorder with respect to classic semicrystalline polymers such as poly(3-hexylthiophene)

Conformational Disorder Enhances Solubility and Photovoltaic Performance of a Thiophene–Quinoxaline Copolymer

The side-chain architecture of alternating copolymers based on thiophene and quinoxaline (TQ) is found to strongly influence the solubility and photovoltaic performance. In particular, TQ polymers with different linear or branched alkyloxy-phenyl side chains on the quinoxaline unit are compared. Attaching the linear alkyloxy side-chain segment at the meta- instead of the para-position of the phenyl ring reduces the planarity of the backbone as well as the ability to order. However, the delocalisation across the backbone is not affected, which permits the design of high-performance TQ polymers that do not aggregate in solution. The use of branched meta-(2-ethylhexyl)oxy-phenyl side-chains results in a TQ polymer with an intermediate degree of order. The reduced tendency for aggregation of TQ polymers with linear meta-alkyloxy-phenyl persists in the solid state. As a result, it is possible to avoid the decrease in charge-transfer state energy that is observed for bulk-heterojunction blends of more ordered TQ polymers and fullerenes. The associated gain in open-circuit voltage of disordered TQ:fullerene solar cells, accompanied by a higher short-circuit current density, leads to a higher power conversion efficiency overall. Thus, in contrast to other donor polymers, for TQ polymers there is no need to compromise between solubility and photovoltaic performance

The role of regioregularity, crystallinity, and chain orientation on electron transport in a high-mobility n-type copolymer

We investigated the correlation between the polymer backbone structural regularity and the charge transport properties of poly{[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} [P(NDI2OD-T2)], a widely studied semiconducting polymer exhibiting high electron mobility and an unconventional micromorphology. To understand the influence of the chemical structure and crystal packing of conventional regioregular P(NDI2OD-T2) [RR-P(NDI2OD-T2)] on the charge transport, the corresponding regioirregular polymer RI-P(NDI2OD-T2) was synthesized. By combining optical, X-ray, and transmission electron microscopy data, we quantitatively characterized the aggregation, crystallization, and backbone orientation of all of the polymer films, which were then correlated to the electron mobilities in electron-only diodes. By carefully selecting the preparation conditions, we were able to obtain RR-P(NDI2OD-T2) films with similar crystalline structure along the three crystallographic axes but with different orientations of the polymer chains with respect to the substrate surface. RI-P(NDI2OD-T2), though exhibiting a rather similar LUMO structure and energy compared with the regioregular counterpart, displayed a very different packing structure characterized by the formation of ordered stacks along the lamellar direction without detectible π-stacking. Vertical electron mobilities were extracted from the space-charge-limited currents in unipolar devices. We demonstrate the anisotropy of the charge transport along the different crystallographic directions and how the mobility depends on π-stacking but is insensitive to the degree or coherence of lamellar stacking. The comparison between the regioregular and regioirregular polymers also shows how the use of large planar functional groups leads to improved charge transport, with mobilities that are less affected by chemical and structural disorder with respect to classic semicrystalline polymers such as poly(3-hexylthiophene)