Recent development of dopant induced solubility control (DISC) patterning of polymer semiconductors has enabled direct‐write optical patterning of poly‐3‐hexylthiophene (P3HT) with diffraction limited resolution. Here, the optical DISC patterning technique to the most simple circuit element, a wire, is applied. Optical patterning of P3HT and P3HT doped with the molecular dopant 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) wires with dimensions of 20–70 nm thickness, 200–900 nm width, and 40 μm length is demonstrated. In addition, optical patterning of wire patterns like “L” bends and “T” junctions without changing the diameter or thickness of the wires at the junctions is demonstrated. The wires themselves show up to 0.034 S cm‐1conductance when sequentially doped. It is also demonstrated that a P3HT nanowire can be doped, de‐doped, and re‐doped from solution without changing the dimension of the wire. The combined abilities to optically pattern and reversibly dope a polymer semiconductor represents a full suite of patterning steps equivalent to photolithography for inorganic semiconductors.
- Award ID(s):
- 1636385
- PAR ID:
- 10111934
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- Volume:
- 7
- Issue:
- 2
- ISSN:
- 2050-7526
- Page Range / eLocation ID:
- 302 to 313
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract One of the most effective ways to tune the electronic properties of conjugated polymers is to dope them with small‐molecule oxidizing agents, creating holes on the polymer and molecular anions. Undesirably, strong electrostatic attraction from the anions of most dopants localizes the holes created on the polymer, reducing their mobility. Here, a new strategy utilizing a substituted boron cluster as a molecular dopant for conjugated polymers is employed. By designing the cluster to have a high redox potential and steric protection of the core‐localized electron density, highly delocalized polarons with mobilities equivalent to films doped with no anions present are obtained. AC Hall effect measurements show that P3HT films doped with these boron clusters have conductivities and polaron mobilities roughly an order of magnitude higher than films doped with F4TCNQ, even though the boron‐cluster‐doped films have poor crystallinity. Moreover, the number of free carriers approximately matches the number of boron clusters, yielding a doping efficiency of ≈100%. These results suggest that shielding the polaron from the anion is a critically important aspect for producing high carrier mobility, and that the high polymer crystallinity required with dopants such as F4TCNQ is primarily to keep the counterions far from the polymer backbone.
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The mechanism and the nature of the species formed by molecular doping of the model polymer poly(3-hexylthiophene) (P3HT) in its regioregular (rre-) and regiorandom (rra-) forms in solution are investigated for three different dopants: the prototypical π-electron acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), the strong Lewis acid tris(pentafluorophenyl)borane (BCF), and the strongly oxidizing complex molybdenum tris[1-(methoxycarbonyl)-2-(trifluoromethyl)-ethane-1,2-dithiolene] (Mo(tfd-CO2Me)3). In a combined optical and electron paramagnetic resonance study, we show that the doping of rreP3HT in solution occurs by integer charge transfer, resulting in the formation of P3HT radical cations (polarons) for all the dopants considered here. Remarkably, despite the different chemical nature of the dopants and dopant-polymer interaction, the formed polarons exhibit essentially identical optical absorption spectra. The situation is very different for the doping of rraP3HT, where we observe the formation of a charge-transfer complex with F4TCNQ and formation of a “localized” P3HT polaron on non-aggregated chains upon doping with BCF, while there is no indication of dopant-induced species in case of Mo(tfd-CO2Me)3. We estimate the ionization efficiency of the respective dopants for the two polymers in solution and report the molar extinction coefficient spectra of the three different species. Finally, we observe increased spin delocalization in regioregular compared to regiorandom P3HT by electron nuclear double resonance, suggesting that the ability of the charge to delocalize on aggregates of planarized polymer backbones plays a significant role in determining the doping mechanism.more » « less
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Abstract Carrier mobility in doped conjugated polymers is limited by Coulomb interactions with dopant counterions. This complicates studying the effect of the dopant's oxidation potential on carrier generation because different dopants have different Coulomb interactions with polarons on the polymer backbone. Here, dodecaborane (DDB)‐based dopants are used, which electrostatically shield counterions from carriers and have tunable redox potentials at constant size and shape. DDB dopants produce mobile carriers due to spatial separation of the counterion, and those with greater energetic offsets produce more carriers. Neutron reflectometry indicates that dopant infiltration into conjugated polymer films is redox‐potential‐driven. Remarkably, X‐ray scattering shows that despite their large 2‐nm size, DDBs intercalate into the crystalline polymer lamellae like small molecules, indicating that this is the preferred location for dopants of any size. These findings elucidate why doping conjugated polymers usually produces integer, rather than partial charge transfer: dopant counterions effectively intercalate into the lamellae, far from the polarons on the polymer backbone. Finally, it is shown that the IR spectrum provides a simple way to determine polaron mobility. Overall, higher oxidation potentials lead to higher doping efficiencies, with values reaching 100% for driving forces sufficient to dope poorly crystalline regions of the film.
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c8tc04519d
