Using Bulky Dodecaborane-Based Dopants to Produce Mobile Charge Carriers in Amorphous Semiconducting Polymers
| Author(s) | Wu, Yutong | |
| Author(s) | Salamat, Charlene Z. | |
| Author(s) | Ruiz, Alex León | |
| Author(s) | Simafranca, Alexander F. | |
| Author(s) | Akmanşen-Kalayci, Nesibe | |
| Author(s) | Wu, Eric C. | |
| Author(s) | Doud, Evan | |
| Author(s) | Mehmedović, Zerina | |
| Author(s) | Lindemuth, Jeffrey R. | |
| Author(s) | Phan, Minh D. | |
| Author(s) | Spokoyny, Alexander M. | |
| Author(s) | Schwartz, Benjamin J. | |
| Author(s) | Tolbert, Sarah H. | |
| Date Accessioned | 2024-05-28T17:50:45Z | |
| Date Available | 2024-05-28T17:50:45Z | |
| Publication Date | 2024-05-17 | |
| Description | This article was originally published in Chemistry of Materials. The version of record is available at: https://doi.org/10.1021/acs.chemmater.4c00502. © The Authors. Published by American Chemical Society | |
| Abstract | Conjugated polymers are a versatile class of electronic materials featured in a variety of next-generation electronic devices. The utility of such polymers is contingent in large part on their electrical conductivity, which depends both on the density of charge carriers (polarons) and on the carrier mobility. Carrier mobility, in turn, is largely controlled by the separation between the polarons and dopant counterions, as counterions can produce Coulombic traps. In previous work, we showed that large dopants based on dodecaborane (DDB) clusters were able to reduce Coulombic binding and thus increase carrier mobility in regioregular (RR) poly(3-hexylthiophene-2,5-diyl) (P3HT). Here, we use a DDB-based dopant to study the effects of polaron–counterion separation in chemically doped regiorandom (RRa) P3HT, which is highly amorphous. X-ray scattering shows that the DDB dopants, despite their large size, can partially order the RRa P3HT during doping and produce a doped polymer crystal structure similar to that of DDB-doped RR P3HT; Alternating Field (AC) Hall measurements also confirm a similar hole mobility. We also show that use of the large DDB dopants successfully reduces Coulombic binding of polarons and counterions in amorphous polymer regions, resulting in a 77% doping efficiency in RRa P3HT films. The DDB dopants are able to produce RRa P3HT films with a 4.92 S/cm conductivity, a value that is ∼200× higher than that achieved with 3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), the traditional dopant molecule. These results show that tailoring dopants to produce mobile carriers in both the amorphous and semicrystalline regions of conjugated polymers is an effective strategy for increasing achievable polymer conductivities, particularly in low-cost polymers with random regiochemistry. The results also emphasize the importance of dopant size and shape for producing Coulombically unbound, mobile polarons capable of electrical conduction in less-ordered materials. | |
| Sponsor | This work was supported by the National Science Foundation under awards NSF DMR-2105896 and NSF CHE-2305152. Synthetic work on redox-active boron clusters at UCLA led by A.M.S. was supported as part of the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under award DE-SC0019381. A.M.S. thanks NSF (CHE-1846849) for partial support of this work. This research used resources at the Advanced Photon Source (APS), a U.S. DOE Office of Science User Facility operated by Argonne National Laboratory (ANL) under contract No. DE-AC02-06CH11357. The authors thank Dr. Joseph Strzalka at Sector 8-ID for meaningful conversations and user support. Beamline 8-ID-E was used for GIWAXS. The liquids reflectometer at BL-4B at the Spallation Neutron Source contributed to the data. Research at the Spallation Neutron Source, a U.S. DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (ORNL), was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, DOE. Beamline 1–5 at Stanford Synchrotron Radiation Lightsource contributed to the data. The authors thank Dr. Christopher J. Tassone for discussions about GISAXS and data workup and Dr. Sarah A. Hesse for user support. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Laboratory, is supported by the U.S. DOE Office of Science, Office of Basic Energy Sciences under contract No. DE-AC02-76SF00515. The authors also thank Lake Shore Cryotronics for use of their Lake Shore model 8400 series AC Hall probe system. | |
| Citation | Wu, Yutong, Charlene Z. Salamat, Alex León Ruiz, Alexander F. Simafranca, Nesibe Akmanşen-Kalayci, Eric C. Wu, Evan Doud, et al. “Using Bulky Dodecaborane-Based Dopants to Produce Mobile Charge Carriers in Amorphous Semiconducting Polymers.” Chemistry of Materials, May 17, 2024, acs.chemmater.4c00502. https://doi.org/10.1021/acs.chemmater.4c00502. | |
| ISSN | 1520-5002 | |
| URL | https://udspace.udel.edu/handle/19716/34426 | |
| Language | en_US | |
| Publisher | Chemistry of Materials | |
| dc.rights | Attribution 4.0 International | en |
| dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | |
| Keywords | doping | |
| Keywords | electrical conductivity | |
| Keywords | impurities | |
| Keywords | organic polymers | |
| Keywords | polymers | |
| Title | Using Bulky Dodecaborane-Based Dopants to Produce Mobile Charge Carriers in Amorphous Semiconducting Polymers | |
| Type | Article |
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