A Generalized Packing Model for Bulk Crystalline Regioregular Poly(3‐alkylthiophenes) with Extended Side Chains

Bohle, Anne; Dudenko, Dmytro; Koenen, Nils; Sebastiani, Daniel; Allard, Sybille; Scherf, Ullrich; Spieß, Hans Wolfgang

doi:10.1002/macp.201700266

Cited by 13 publications

(26 citation statements)

References 87 publications

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“…The peaks at 1.5 and 3.8 ppm in the 1D 1 H spectra were assigned to the protons on the alkyl side chains and the methoxy group of the DMBDT unit, respectively. The peaks at 5.9 and 7 ppm were assigned to the protons on the π‐conjugated main chain in crystalline and amorphous domains, respectively . 1D 13 C spectra showed a major peak at 143.3 ppm and a minor peak at 143.9 ppm (Figure S11b), both of which were assigned to the carbon atoms in C 60 because of the 13 C enrichment in C 60 (90 %) and the large C 60 content (polymer:C 60 =1:2).…”

Section: Methodssupporting

confidence: 80%

Intermolecular Arrangement of Fullerene Acceptors Proximal to Semiconducting Polymers in Mixed Bulk Heterojunctions

et al. 2018

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Precise control of the molecular arrangements at the interface between the electron donor and acceptor in mixed bulk heterojunctions (BHJs) remains challenging,d espite the correlation between structural characteristics and efficiency in organic photovoltaics (OPVs). This study reveals that the substitution patterns of linear and branched alkyls ide chains on electron-donating/-accepting alternating copolymers can control the positions of an acceptor molecule (C 60 )around the p-conjugated main chains in mixed BHJs.T wo-dimensional solid-state NMR demonstrates am arked difference in the location of C 60 in the blend films.Acopolymer with an electron-accepting unit positioned in close proximityt oC 60 demonstrated higher OPV performance in combination with various fullerene derivatives.T his molecular design offers precise control over the interfacial molecular structure,thereby paving the way for overcoming the current limitations of OPVs comprising mixed BHJs.This decade has witnessed the remarkable development of organic photovoltaics (OPVs) as ap romising renewable energy source owing to their potential use in lightweight, flexible,a nd large-area devices. [1][2][3] This progress has been driven by the synthesis of novel semiconducting polymers with optical and electronic properties that are carefully tuned by the design of p-conjugated structures.D onor-acceptor (D-A) alternating copolymers consisting of electron-donating and -accepting units have been widely used as ak ey method for tuning electronic properties. [4][5][6][7][8][9] Thep hotoactive layers of highly efficient OPVs are mixed bulk heterojunction (BHJ) structures typically composed of ab lend of as emiconducting copolymer as the electron donor and fullerene derivatives as the electron acceptor. [10,11] Recently,the power conversion efficiency (PCE) of OPVs comprising BHJs of polymers and fullerene derivatives reached over 11 %PCE. [12] There have been substantial advances in understanding the mechanism of OPVs.I th as been shown that the properties of the organic interfaces strongly affect the charge separation and recombination processes. [13] Thec hargetransfer (CT) state at the interface has as trong correlation with the OPV performance. [14][15][16][17][18][19] Therefore,t he spatial arrangement of the donor and acceptor can strongly affect the photophysical and electronic processes in OPVs,a s suggested by theoretical calculations [20][21][22] and experimental studies using planar heterojunctions as model systems. [23][24][25][26] Taken together,t hese studies suggest that precise control of the BHJ structure at the molecular level could be crucial to improving the performance of OPVs further.T he interfacial structures of mixed BHJs,however,are difficult to analyze at the molecular scale because of the limitations of analytical methods. [27] Controlling the interfacial structures is even more challenging in BHJs.Systematic studies of polymer synthesis suggest that the structures of the p-conjugated main chains are not the only factor that af...

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Section: Methodssupporting

confidence: 80%

Intermolecular Arrangement of Fullerene Acceptors Proximal to Semiconducting Polymers in Mixed Bulk Heterojunctions

et al. 2018

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“…Previous studies on the crystalline structure of undoped P3HT revealed unit cells comprised of two P3HT chains. [41][42][43] Structural studies on F4TCNQ doped re-P3HT have shown that the p-p packing distance decreases in a mixed crystalline phase. 16,44 Jacobs et al recently reported that the lamellar packing distance also decreases along with the p-p packing distance upon doping under certain processing conditions, in unit cells containing two doped P3HT chains.…”

Section: Resultsmentioning

confidence: 99%

The optical signatures of molecular-doping induced polarons in poly(3-hexylthiophene-2,5-diyl): individual polymer chainsversusaggregates

et al. 2020

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“…Poly(3-hexylthiophene-2,5-diyl) (P3HT) is the prototypical polymer used in polymer-based optoelectronic devices. For example, it was physically blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) to yield bulk heterojunction (BHJ) mixing that serves as an active layer in polymer solar cells. − There have been many experimental studies to reveal polymer packing configurations under different processing conditions with X-ray scattering and absorption, − electron microscopy and diffraction, solid-state NMR, optical spectroscopy, − neutron scattering, and Raman spectroscopy with their respective advantages.…”

Section: Introductionmentioning

confidence: 99%

Deciphering Anomalous Raman Features of Regioregular Poly(3-hexylthiophene) in Ordered Aggregation Form

et al. 2018

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Poly(3-hexylthiophene) (P3HT), being a prototypic conjugated polymer, bears a high charge mobility that is sensitive to its packing configuration in the condensed phase. Despite its extensive experimental study with X-ray diffraction, its specified packing structure still remains stymied. This study searched for possible structures of crystalline P3HT and identified the one that holds a simulated Raman spectrum most approximate to the experimental one of ordered P3HT aggregates in the frozen solvent. The spectral correspondence shows that the Raman-active C–C stretch peak exhibits a red shift in frequency, while the CC stretch peak displays a blue shift as the layer planarity of P3HT is relaxed. Moreover, the CC peak splits into two when adjacent thiophene rings in the P3HT chain hold a dihedral angle of 22° with respect to each other. This study demonstrates that Raman spectroscopy plus first-principles simulations can serve as a powerful tool to resolve fine structures of molecular crystals.

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A Generalized Packing Model for Bulk Crystalline Regioregular Poly(3‐alkylthiophenes) with Extended Side Chains

Cited by 13 publications

References 87 publications

Intermolecular Arrangement of Fullerene Acceptors Proximal to Semiconducting Polymers in Mixed Bulk Heterojunctions

Intermolecular Arrangement of Fullerene Acceptors Proximal to Semiconducting Polymers in Mixed Bulk Heterojunctions

The optical signatures of molecular-doping induced polarons in poly(3-hexylthiophene-2,5-diyl): individual polymer chainsversusaggregates

Deciphering Anomalous Raman Features of Regioregular Poly(3-hexylthiophene) in Ordered Aggregation Form

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