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Abstract Semiconducting polymers are of interest due to their solution processibility and broad electronic applications. Electrochemistry allows these wide bandgap semiconductors to be converted to conducting polymers by doping such polymers at various potentials. When polymers arep‐doped to improve their conductivity via electrochemical oxidation, various positively‐charged carriers are created, including polarons (singly‐charged) and bipolarons (doubly‐charged). Carrier creation is accompanied by anion intercalation from the electrolyte for charge balance, and this insertion requires ion mobility. In this work, poly(3‐hexylthiophene) (P3HT) with different regioregularities is used to understand the relationship between solvent swelling, which affects anion intercalation, and electrochemical doping. Cyclic voltammetry, optical absorption spectroscopy, and grazing incidence wide‐angle X‐ray scattering (GIWAXS) measurements are used to correlate the doping level with structural changes. In situ electrochemical quartz crystal microbalance (EQCM) measurements are used to quantify the swelling of the polymers dynamically during electrochemical cycling. Lastly, in situ conductivity measurements are done to measure the effect of swelling on the ionic and electronic conductivity. The results indicate that solvent swelling is required for bipolaron formation, and that swelling facilitates both the small structural changes need for polaron formation and the disordering required for bipolaron formation.
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Swelling as a stabilizing mechanism in irradiated thin films: II. Effect of swelling rate
Abstract It has long been observed experimentally that energetic ion-beam irradiation of semiconductor surfaces may lead to spontaneous nanopattern formation. For most ion/target/energy combinations, the patterns appear when the angle of incidence exceeds a critical angle, and the models commonly employed to understand this phenomenon exhibit the same behavioral transition. However, under certain conditions, patterns do not appear for any angle of incidence, suggesting an important mismatch between experiment and theory. Previous work by our group (Swenson and Norris 2018 J. Phys.: Condens. Matter 30 304003) proposed a model incorporating radiation-induced swelling, which is known to occur experimentally, and found that in the analytically-tractable limit of small swelling rates, this effect is stabilizing at all angles of incidence, which may explain the observed suppression of ripples. However, at that time, it was not clear how the proposed model would scale with increased swelling rate. In the present work, we generalize that analysis to the case of arbitrary swelling rates. Using a numerical approach, we find that the stabilization effect persists for arbitrarily large swelling rates, and maintains a stability profile largely similar to that of the small swelling case. Our findings strongly support the inclusion of a swelling mechanism in models of pattern formation under ion beam irradiation, and suggest that the simpler small-swelling limit is an adequate approximation for the full mechanism. They also highlight the need for more—and more detailed—experimental measurements of material stresses during pattern formation.
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- Award ID(s):
- 1840260
- PAR ID:
- 10343167
- Date Published:
- Journal Name:
- Journal of Physics: Condensed Matter
- Volume:
- 34
- Issue:
- 32
- ISSN:
- 0953-8984
- Page Range / eLocation ID:
- 325302
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1088/1361-648X/ac75a3
