Dual Species Emission from Single Polyfluorene Molecules:  Signatures of Stress-Induced Planarization of Single Polymer Chains

Becker, K. W.; Lupton, John M.

doi:10.1021/ja051583l

Cited by 96 publications

(117 citation statements)

References 25 publications

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“…This has been particularly true in the pursuit of efficient organic photovoltaic devices, where polymer composites of nominally electron accepting and donating materials are blended together, forming percolation networks, such as with C 60 and P3HT (poly[3-hexylthiophene-2,5-diyl]) [13][14][15][16]. One polymer system where structural order is known to lead to dramatic changes in electronic processes is PFO, which exhibits the above mentioned glassy phase and the rigid, molecular wire-like β-phase [17][18][19][20]. These two intramolecular conformation phases are sketched in the insets of Fig.…”

Section: Pacsmentioning

confidence: 99%

Morphology effects on spin-dependent transport and recombination in polyfluorene thin films

et al. 2016

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We have studied the role of spin-dependent processes on conductivity in polyfluorene (PFO) thin films by conducting continuous wave (c.w.) electrically detected magnetic resonance (EDMR) spectroscopy at temperatures between 10 K and 293 K using microwave frequencies between about 100 MHz and 20 GHz as well as pulsed EDMR at X-band (10 GHz). Variable frequency EDMR allows us to establish the role of spin-orbit coupling in spin-dependent processes whereas pulsed EDMR allows for the observation of coherent spin motion effects. We used PFO for this study in order to allow for the investigation of the effects of microscopic morphological ordering since this material can adopt two distinct intrachain morphologies: an amorphous (glassy) phase, in which monomer units are twisted with respect to each other, and an ordered (β) phase, where all monomers lie within one plane. In thin films of organic light-emitting diodes (OLEDs) the appearance of a particular phase can be controlled by deposition parameters and solvent vapor annealing, and is verified by electroluminescence spectroscopy. Under bipolar charge carrier 2 injection conditions we conducted multi-frequency c.w. EDMR, electrically detected Rabi spinbeat experiments, Hahn-echo and inversion-recovery measurements. Coherent echo spectroscopy reveals electrically detected electron spin-echo envelope modulation (ESEEM) due to the coupling of the carrier spins to nearby nuclei spins. Our results demonstrate that while conformational disorder can influence the observed EDMR signals, including the sign of the current changes on resonance as well as the magnitudes of local hyperfine fields and charge carrier spin-orbit interactions, it does not qualitatively affect the nature of spin-dependent transitions in this material. In both morphologies, we observe the presence of at least two different spin-dependent recombination processes. At 293 K and 10 K, polaron-pair recombination through weakly spin-spin coupled intermediate charge carrier pair states is dominant, while at low temperatures, additional signatures of spin-dependent charge transport through the interaction of polarons with triplet excitons are seen in the half-field resonance of a triplet spin-1 species. This additional contribution arises since triplet lifetimes are increased at lower temperatures. We tentatively conclude that spectral broadening induced by hyperfine coupling is slightly weaker in the more ordered β-phase than in the glassy-phase, since protons are more evenly spaced, whereas broadening effects due to spin-orbit coupling, which impacts the distribution of g-factors, appears to be somewhat more significant in the β-phase. PACS

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Section: Pacsmentioning

confidence: 99%

Morphology effects on spin-dependent transport and recombination in polyfluorene thin films

et al. 2016

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“…PFs can be synthesized in increasingly complicated chemical structures [11] but much can be learned already by considering archetypical PFs with linear alkyl side chains [12]. A prime example is poly(9,9-dioctylfluorene) (PF8) [13,14] which shows crystalline α and α phases [15,16], noncrystalline β, nematic, and amorphous phases [17], and as a g phase [18] in the solid state. The β phase [19,20] has a mesomorphic structure [21] associated with narrow linewidths in absorption, prompt, and delayed fluorescence, phosphorescence, and photoinduced triplet absorption spectra [22].…”

Section: Introductionmentioning

confidence: 99%

Network structure of polyfluorene sheets as a function of alkyl side chain length

et al. 2011

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The formation of self-organized structures in poly(9,9-di-n-alkylfluorene)s ∼1 vol % methylcyclohexane (MCH) and deuterated MCH solutions was studied at room temperature using neutron and x-ray scattering (with the overall q range of 0.000 58-4.29Å−1 ) and optical spectroscopy. The number of side chain carbons (N ) ranged from 6 to 10. The phase behavior was rationalized in terms of polymer overlap, cross-link density, and blending rules. For N = 6−9, the system contains isotropic areas and lyotropic areas where sheetlike assemblies (lateral size of >400Å) and free polymer chains form ribbonlike agglomerates (characteristic dimension of >1500Å) leading to a gel-like appearance of the solutions. The ribbons are largely packed together with surface fractal characteristics for N = 6−7 but become open networklike structures with mass fractal characteristics for N = 8−9, until the system goes through a transition to an isotropic phase of overlapping rodlike polymers for N = 10. The polymer order within sheets varies allowing classification for loose membranes and ordered sheets, including the so-called β phase. The polymers within the ordered sheets have restricted motion for N = 6−7 but more freedom to vibrate for N = 8−9. The nodes in the ribbon network are suggested to contain ordered sheets cross-linking the ribbons together, while the nodes in the isotropic phase appear as weak density fluctuations cross-linking individual chains together. The tendencies for macrophase separation and the formation of non beta sheets decrease while the proportion of free chains increases with increasing N. The fraction of β phase varies nonlinearly, reaching its maximum at N = 8.

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“…8 Among PFs, important blue emitting polymers, even small differences in the molecular structure can influence the charge carrier mobility 9 and fluorescence. 10 Poly͓9,9-bis͑2-ethylhexyl͒-9H-fluorene-2,7-diyl͔ ͑or PF2/6͒ ͑Ref. 11͒ is a well-known helical PF polymer functionalized with branched alkyl side chains.…”

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confidence: 99%

Influence of star-like iridium complexes in the graphoepitaxy of polyfluorene thin films

et al. 2006

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We report on the impact on the equatorial and meridional orientation in hairy-rod poly͓9,9-bis͑2-ethylhexyl͒-fluorene-2,7-diyl͔ thin films when blended with tris-cyclometalated oligo-fluorenylpyridine iridium͑III͒ complex. The presence of this transition-metal complex does not alter the underlying helical motif of the polymer chain or the hexagonal unit-cell intermolecular packing. However, systematic changes in the resulting texture patterning of the crystallites are observed. Crystallites with two preferred a-b orientations, so called type I and II and differing by 30 degrees, are superimposed on an isotropic background that is designated as type III. The extent of meridional alignment for all three is found to be similar. DOI: 10.1103/PhysRevB.74.214203 PACS number͑s͒: 61.10.Ϫi, 82.35.Lr, 81.07.Bc, 81.16.Dn Manipulating and controlling the molecular-level structure of functionalized polymers in bulk and at surfaces is central to the science and applications of these materials. Hairy-rod polymers 1 are one important example and, among those with -conjugated backbones 2 ͓e.g., poly͑p-phenylenes͒, 3 polyfluorenes ͑PFs͒, 4 and ladder derivatives 5 ͔, the nature of the main chain conformation and interchain packing are crucial factors in ultimately determining optical and transport properties. The structural characteristics at larger length scales are equally as important, and this has been the main emphasis in a number of recent studies. A classic example is the poly͑3-alkylthiophene͒ family 6 in which the extent of structural isomorphism or regioregularity strongly affects the internal crystallite structure 7 and the subsequent structural evolution when intercalated or doped. 8 Among PFs, important blue emitting polymers, even small differences in the molecular structure can influence the charge carrier mobility 9 and fluorescence. 10 Poly͓9,9-bis͑2-ethylhexyl͒-9H-fluorene-2,7-diyl͔ ͑or PF2/6͒ ͑Ref. 11͒ is a well-known helical PF polymer functionalized with branched alkyl side chains. PF2/6's optical properties 12 are relatively insensitive to either changes in the molecular weight ͑MW͒ or processing history, and so it is an excellent model system for studies of intermolecular self-organization. 13 However, this intermolecular assembly is affected by changes in the MW ͑or number averaged MW, M n ͒. In PF2/6, there is a threshold MW, M n * , at which there is a crossover in the phase behavior. 14 Low MW samples exhibit only a single nematic liquid crystal phase ͑n-LC and M n Ͻ M n * ͒ while high MW samples ͑M n Ͼ M n * ͒ include a distinctive thermotropic transition between this n-LC phase and a hexagonal crystalline phase. This threshold MW also marks sharp changes in both meridional alignment 15 and surface morphology. 16 In aligned films on rubbed polyimide ͑PI͒, the rigid PF2/6 lies on the substrate with the helical axes pointing along the rubbing direction ͑denoted z here͒. Consequently, meridional alignment leads to a large absorption and dispersion of the refractive index in the ͑xy0͒ plane along the z...

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Dual Species Emission from Single Polyfluorene Molecules: Signatures of Stress-Induced Planarization of Single Polymer Chains

Cited by 96 publications

References 25 publications

Morphology effects on spin-dependent transport and recombination in polyfluorene thin films

Morphology effects on spin-dependent transport and recombination in polyfluorene thin films

Network structure of polyfluorene sheets as a function of alkyl side chain length

Influence of star-like iridium complexes in the graphoepitaxy of polyfluorene thin films

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