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- Anselmo, Ana Sofia, 1980-, et al.
(författare)
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Characterisation of vertical phase separation in polymer : fullerene blend films for photovoltaics by dSIMS and NEXAFS
- 2011
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Ingår i: E-MRS 2011 Spring Meeting. - Malden, MA : John Wiley & Sons. ; , s. 62-63
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Konferensbidrag (refereegranskat)abstract
- Morphological control and characterization of blend films is key in the development of viable polymer solar cells. Spontaneous formation of vertical compositional gradients during solution processing has been shown for polyfluorene:PCBM blends and rationalized with thermodynamic and kinetic models of nucleation and spinodal decomposition.[1, 2] The extent of vertical stratification is affected by polymer side-chain modification aimed at controlling polymer:fullerene miscibility.[3] Here we present high-resolution film morphology results for several polymer:fullerene systems as obtained from near-edge X-ray fine structure spectroscopy (NEXAFS) in partial and in total electron yield modes. Blend films were found to be polymer- enriched at the surface. Dynamic secondary ion mass spectrometry (dSIMS) and NEXAFS give compositional information at different depths, resulting in a more complete picture of the film morphology.
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- Anselmo, Ana Sofia, 1980-, et al.
(författare)
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Tuning the Vertical Phase Separation in Polyfluorene: Fullerene Blend Films by Polymer Functionalization
- 2011
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Ingår i: Chemistry of Materials. - Washington : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 23:9, s. 2295-2302
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Tidskriftsartikel (refereegranskat)abstract
- Achieving control over the nanomorphology of blend films of the fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester, PCBM, with light-absorbing conjugated polymers is an important challenge in the development of efficient solution-processed photovoltaics. Here, three new polyfluorene copolymers are presented, tailored for enhanced miscibility with the fullerene through the introduction of polymer segments with modified side chains, which enhance the polymer's polar character. The composition of the spincoated polymer:PCBM films is analyzed with dynamic secondary ion mass spectrometry (dSIMS). The dSIMS depth profiles demonstrate compositional variations perpendicular to the surface plane, as a result of vertical phase separation, directed by the substrate. These variations propagate to a higher degree through the film for the polymers with a larger fraction of modified side chains. The surface composition of the films is studied by Near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Quantitative analysis of the NEXAFS spectra through a linear combination fit with the spectra of the pure components yields the surface composition. The resulting blend ratios reveal polymer-enrichment of the film surface for all three blends, which also becomes stronger as the polar character of the polymer increases. Comparison of the NEXAFS spectra collected with two different sampling depths shows that the vertical composition gradient builds up already in the first nanometers underneath the surface of the films. The results obtained with this new series of polymers shed light on the onset of formation of lamellar structures in thin polymer:PCBM films prepared from highly volatile solvents.
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- Armstrong, Emily J., et al.
(författare)
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A ground-state complex between methyl viologen and the fluorescent whitening agent 4,4 '-bis(2-sulfostyryl)-biphenyl disodium salt : a fluorescence spectroscopy study
- 2021
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Ingår i: Canadian journal of chemistry (Print). - : Canadian science publishing. - 0008-4042 .- 1480-3291. ; 99:7, s. 563-569
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Tidskriftsartikel (refereegranskat)abstract
- This study explores the quenching of the dianionic fluorescent whitening agent, NFW, by various substances, including methyl viologen (MV), in water and in the presence of beta-cyclodextrin (beta-CD). Results of a fluorescence spectro-scopic examination of the beta-CD-NFW system are presented. It was found that NFW forms a 1:1 inclusion complex with b-CD with an association constant of 2540 +/- 380 M-1. The included NFW fluorescent state is protected by the beta-CD cavity from a range of water-based quenchers (neutral, anionic, and cationic). Quenching proceeds near the diffusion-controlled limit in water for the quenchers tested with the exception of the dicationic MV. Methyl viologen is an extremely efficient quencher of NFW fluorescence with a nominal K-SV similar to 5.0 x 10(3) M-1 in water alone, corresponding to a nominal k(q) of similar to 4 x 10(12) M-1 s(-1), which exceeds the diffusion-controlled limit in this solvent. The quenching efficiency of MV is strongly suppressed in the presence of 10 mM beta-CD (K-SV = 105 +/- 12 M-1) and in the presence of NaCl (K-SV = 106 +/- 9 M-1 at 0.5 M salt). In the absence of CD or salt, there is a strong contribution from static quenching in the MV system; the presence of these additives suppresses the static quenching. Various results suggest the static quenching is due to formation of a ground-state complex between the dianion NFW and the dication MV.
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