A Strategy for Revealing the Packing in Semicrystalline π‐Conjugated Polymers: Crystal Structure of Bulk Poly‐3‐hexyl‐thiophene (P3HT)

Dudenko, Dmytro; Kiersnowski, Adam; Shu, Jie; Pisula, Wojciech; Sebastiani, Daniel; Spiess, Hans Wolfgang; Hansen, Michael Ryan

doi:10.1002/anie.201205075

Cited by 164 publications

(218 citation statements)

References 51 publications

Supporting

Mentioning

183

Contrasting

Order By: Relevance

“…59 However, a key requirement for the 2D The broad 1 H line width of the thiophene proton is a result of restricted molecular mobility of several P3TMAHT chains sticking together in addition to the spatial overlap between the π-conjugated chains, leading to a shift to lower frequency (or equivalently a high-field shift). 60 This is in agreement with the neutron and light scattering studies on aqueous solutions of P3TMAHT suggesting that the chains aggregate with interparticle order. 40,61 Mixing P3TMAHT with CLP in D 2 O gives the 1 H NMR spectrum in Figure 4b.…”

Section: ■ Experimental Methodssupporting

confidence: 85%

Temperature-Regulated Fluorescence and Association of an Oligo(ethyleneglycol)methacrylate-Based Copolymer with a Conjugated Polyelectrolyte—The Effect of Solution Ionic Strength

et al. 2013

Self Cite

View full text Add to dashboard Cite

Aqueous mixtures of a dye-labeled non-ionic thermoresponsive copolymer and a conjugated cationic polyelectrolyte are shown to exhibit characteristic changes in fluorescence properties in response to temperature and to the presence of salts, enabling a double-stimuli responsiveness. In such mixtures at room temperature, i.e., well below the lower critical solution temperature (LCST), the emission of the dye is strongly quenched due to energy transfer to the polycation, pointing to supramolecular interactions between the two macromolecules. Increasing the concentration of salts weakens the interpolymer interactions, the extent of which is simultaneously monitored from the change in the relative emission intensity of the components. When the mixture is heated above its LCST, the transfer efficiency is significantly reduced, signaling a structural reorganization process, however, surprisingly only if the mixture contains salt ions. To elucidate the reasons behind such thermo- and ion-sensitive fluorescence characteristics, we investigate the effect of salts of alkali chlorides, in particular of NaCl, on the association behavior of these macromolecules before and after the polymer phase transition by a combination of UV-vis, fluorescence, and (1)H NMR spectroscopy with light scattering and small-angle neutron scattering measurements.

show abstract

Section: ■ Experimental Methodssupporting

confidence: 85%

Temperature-Regulated Fluorescence and Association of an Oligo(ethyleneglycol)methacrylate-Based Copolymer with a Conjugated Polyelectrolyte—The Effect of Solution Ionic Strength

et al. 2013

Self Cite

View full text Add to dashboard Cite

show abstract

“…These 13 C aggregation shifts could provide valuable constraints for the determination of the P3HT crystal lattice geometry, supplementing information provided by the well-studied 1 H aggregation shifts. 17,38 The assignment of crystalline 13 C peaks could also be used to determine crystallinity. Nieuwendaal et al reported that the signals from ordered domains exhibit longer T 1ρ than those from the disordered region.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Measuring the Degree of Crystallinity in Semicrystalline Regioregular Poly(3-hexylthiophene)

2016

View full text Add to dashboard Cite

By using a combination of wide-angle X-ray diffraction (WAXD), mass density, and 13 C solid-state nuclear magnetic resonance (NMR) measurements, a quantification of the absolute degree of crystallinity in regioregular poly(3-hexylthiophene) (rr-P3HT) is presented. A regiorandom P3HT (rra-P3HT), lacking long-range order, was used to separate the crystalline contribution from the total scattering in WAXD, thus yielding degrees of crystallinity in the range of 47−56% at room temperature for three different rrP3HTs. For the same rr-P3HT with identical processing history, NMR yields degrees of crystallinity that are consistently ∼10% greater than that obtained by WAXD, which can only be explained by ordered chain segments in the amorphous phase. NMR results also suggest that rra-P3HT contains weakly ordered chain segments, which likely contribute to an underestimation of degree of crystallinity when determined from mass density measurements, if rra-P3HT is used to approximate a fully amorphous P3HT. The results shown in this study provide direct proof of three different types of P3HT chain segments: crystallites (i.e., longrange ordered chain packing), amorphous phase (i.e., disordered chain packing), and shortrange ordered chain packing embedded in the amorphous phase. The presence of the short-range ordered chain packing is particularly important when correlating the morphology to macroscopic charge transport properties in P3HT-based devices. In general, those locally ordered chain segments, though not constituting a distinct phase, are believed to be of critical importance in determining the transport characteristics of conjugated semiconducting polymers with or without a distinct crystalline phase present. ■ INTRODUCTIONDuring the rapid development of organic photovoltaics (OPV) in the past two decades, regioregular poly(3-hexylthiophene) (rr-P3HT) has been recognized as a prototypical semicrystalline photoactive semiconducting polymer, providing critical insights into key aspects of OPVs and leading to designs of more advanced materials, better morphologies, and more efficient devices. 1−3 From a morphological perspective, one of the most important structural parameters for P3HT is the degree of order, which influences the UV−vis absorption, the miscibility with n-type [6,6]-phenyl-C61-butyric-acid methyl ester (PCBM) in the OPV active layer, charge transport properties, and therefore the ultimate device performance. 4,5 For instance, it has been shown in the literature that for both benchmark rr-P3HT and the new low band gap conjugated copolymer based on benzodithiophene and asymmetric thienothiophene monomers, higher regioregularity of semiconducting polymers leads to enhanced molecular ordering and higher crystallinity, which, in turn, contributes to markedly improved optical absorption, hole mobility, and OPV device power conversion efficiency. 6,7 Quantifying the degree of crystallinity in the semiconducting polymers is expected to deepen our understanding of the semicrystalline morphology, which is of criti...

show abstract

“…This technique offers access to these molecular scale properties via the proton ( 1 H) and carbon ( 13 C) chemical shis as reected in their isotropic chemical shis and resonance line widths. 16 Here, we further exploit the different T 2 -relaxation properties of the crystalline and amorphous regions of the polymers by applying the refocused 18 or the through space dipole-dipole coupling, respectively, allowing us to differentiate between rigid and exible regions of the polyesters. Fig.…”

mentioning

confidence: 99%

Topological behavior mimicking ethylene–hexene copolymers using branched lactones and macrolactones

et al. 2014

Self Cite

View full text Add to dashboard Cite

show abstract

A Strategy for Revealing the Packing in Semicrystalline π‐Conjugated Polymers: Crystal Structure of Bulk Poly‐3‐hexyl‐thiophene (P3HT)

Cited by 164 publications

References 51 publications

Temperature-Regulated Fluorescence and Association of an Oligo(ethyleneglycol)methacrylate-Based Copolymer with a Conjugated Polyelectrolyte—The Effect of Solution Ionic Strength

Temperature-Regulated Fluorescence and Association of an Oligo(ethyleneglycol)methacrylate-Based Copolymer with a Conjugated Polyelectrolyte—The Effect of Solution Ionic Strength

Measuring the Degree of Crystallinity in Semicrystalline Regioregular Poly(3-hexylthiophene)

Topological behavior mimicking ethylene–hexene copolymers using branched lactones and macrolactones

Contact Info

Product

Resources

About