Quantitative Dedoping of Conductive Polymers

Ian E. Jacobs, Faustine Wang, Nema Hafezi, Cristina Medina-Plaza, Thomas F. Harrelson, Jun Li, Matthew P. Augustine, Mark Mascal, Adam J. Moulé

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Although doping is a cornerstone of the inorganic semiconductor industry, most devices using organic semiconductors (OSCs) make use of intrinsic (undoped) materials. Recent work on OSC doping has focused on the use of dopants to modify a material's physical properties, such as solubility, in addition to electronic and optical properties. However, if these effects are to be exploited in device manufacturing, a method for dedoping organic semiconductors is required. Here, we outline two chemical strategies for dedoping OSC films. In the first strategy, we use an electron donor (a tertiary amine) to act as competitive donor. This process is based on a thermodynamic equilibrium between ionization of the donor and OSC and results in only partial dedoping. In the second strategy, we use an electron donor that subsequently reacts with the p-type dopant to create a nondoping product molecule. Primary and secondary amines undergo a rapid addition reaction with the dopant molecule 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyanoquinodimethane (F4TCNQ), with primary amines undergoing a further reaction eliminating HCN. Under optimized conditions, films of semiconducting polymer poly(3-hexylthiophene) (P3HT) dedoped with 1-propylamine (PA) reach as-cast fluorescence intensities within 5 s of exposure to the amine, eventually reaching 140% of the as-cast values. Field-effect mobilities similarly recover after dedoping. Quantitative fluorescence recovery is possible even in highly fluorescent polymers such as PFB, which are expected to be much more sensitive to residual dopants. Interestingly, treatment of undoped films with PA also yields increased fluorescence intensity and a reduction in conductivity of at least 2 orders of magnitude. These results indicate that the process quantitatively removes not only F4TCNQ but also intrinsic p-type impurities present in as-cast films. The dedoping strategies outlined in this article are generally applicable to other p- and n-type molecular dopants in OSC films.

Original languageEnglish (US)
Pages (from-to)832-841
Number of pages10
JournalChemistry of Materials
Volume29
Issue number2
DOIs
StatePublished - Jan 24 2017

Fingerprint

Semiconducting organic compounds
Polymers
Doping (additives)
Amines
Propylamines
Fluorescence
Semiconductor doping
Semiconducting polymers
Addition reactions
Molecules
Electrons
Electronic properties
Ionization
Optical properties
Solubility
Physical properties
Thermodynamics
Impurities
Semiconductor materials
Recovery

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Jacobs, I. E., Wang, F., Hafezi, N., Medina-Plaza, C., Harrelson, T. F., Li, J., ... Moulé, A. J. (2017). Quantitative Dedoping of Conductive Polymers. Chemistry of Materials, 29(2), 832-841. https://doi.org/10.1021/acs.chemmater.6b04880

Quantitative Dedoping of Conductive Polymers. / Jacobs, Ian E.; Wang, Faustine; Hafezi, Nema; Medina-Plaza, Cristina; Harrelson, Thomas F.; Li, Jun; Augustine, Matthew P.; Mascal, Mark; Moulé, Adam J.

In: Chemistry of Materials, Vol. 29, No. 2, 24.01.2017, p. 832-841.

Research output: Contribution to journalArticle

Jacobs, IE, Wang, F, Hafezi, N, Medina-Plaza, C, Harrelson, TF, Li, J, Augustine, MP, Mascal, M & Moulé, AJ 2017, 'Quantitative Dedoping of Conductive Polymers', Chemistry of Materials, vol. 29, no. 2, pp. 832-841. https://doi.org/10.1021/acs.chemmater.6b04880
Jacobs IE, Wang F, Hafezi N, Medina-Plaza C, Harrelson TF, Li J et al. Quantitative Dedoping of Conductive Polymers. Chemistry of Materials. 2017 Jan 24;29(2):832-841. https://doi.org/10.1021/acs.chemmater.6b04880
Jacobs, Ian E. ; Wang, Faustine ; Hafezi, Nema ; Medina-Plaza, Cristina ; Harrelson, Thomas F. ; Li, Jun ; Augustine, Matthew P. ; Mascal, Mark ; Moulé, Adam J. / Quantitative Dedoping of Conductive Polymers. In: Chemistry of Materials. 2017 ; Vol. 29, No. 2. pp. 832-841.
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