The Effects of Crystallinity on Charge Transport and the Structure of Sequentially Processed F 4 TCNQ‐Doped Conjugated Polymer Films

Abstract The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution sequential processing (SqP) was used to introduce 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F 4 TCNQ) into poly(3‐hexylthiophene‐2...

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Published inAdvanced functional materials Vol. 27; no. 44
Main Authors Scholes, D. Tyler, Yee, Patrick Y., Lindemuth, Jeffrey R., Kang, Hyeyeon, Onorato, Jonathan, Ghosh, Raja, Luscombe, Christine K., Spano, Frank C., Tolbert, Sarah H., Schwartz, Benjamin J.
Format Journal Article
LanguageEnglish
Published Germany Wiley Blackwell (John Wiley & Sons) 01.11.2017
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Abstract Abstract The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution sequential processing (SqP) was used to introduce 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F 4 TCNQ) into poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) while preserving the pristine polymer's degree of crystallinity. X‐ray data suggest that F 4 TCNQ anions reside primarily in the amorphous regions of the film as well as in the P3HT lamellae between the side chains, but do not π‐stack within the polymer crystallites. Optical spectroscopy shows that the polaron absorption redshifts with increasing polymer crystallinity and increases in cross section. Theoretical modeling suggests that the polaron spectrum is inhomogeneously broadened by the presence of the anions, which reside on average 6–8 Å from the polymer backbone. Electrical measurements show that the conductivity of P3HT films doped by F 4 TCNQ via SqP can be improved by increasing the polymer crystallinity. AC magnetic field Hall measurements show that the increased conductivity results from improved mobility of the carriers with increasing crystallinity, reaching over 0.1 cm 2 V −1 s −1 in the most crystalline P3HT samples. Temperature‐dependent conductivity measurements show that polaron mobility in SqP‐doped P3HT is still dominated by hopping transport, but that more crystalline samples are on the edge of a transition to diffusive transport at room temperature.
AbstractList Abstract The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution sequential processing (SqP) was used to introduce 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F 4 TCNQ) into poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) while preserving the pristine polymer's degree of crystallinity. X‐ray data suggest that F 4 TCNQ anions reside primarily in the amorphous regions of the film as well as in the P3HT lamellae between the side chains, but do not π‐stack within the polymer crystallites. Optical spectroscopy shows that the polaron absorption redshifts with increasing polymer crystallinity and increases in cross section. Theoretical modeling suggests that the polaron spectrum is inhomogeneously broadened by the presence of the anions, which reside on average 6–8 Å from the polymer backbone. Electrical measurements show that the conductivity of P3HT films doped by F 4 TCNQ via SqP can be improved by increasing the polymer crystallinity. AC magnetic field Hall measurements show that the increased conductivity results from improved mobility of the carriers with increasing crystallinity, reaching over 0.1 cm 2 V −1 s −1 in the most crystalline P3HT samples. Temperature‐dependent conductivity measurements show that polaron mobility in SqP‐doped P3HT is still dominated by hopping transport, but that more crystalline samples are on the edge of a transition to diffusive transport at room temperature.
Author Onorato, Jonathan
Ghosh, Raja
Luscombe, Christine K.
Schwartz, Benjamin J.
Kang, Hyeyeon
Scholes, D. Tyler
Spano, Frank C.
Tolbert, Sarah H.
Yee, Patrick Y.
Lindemuth, Jeffrey R.
Author_xml – sequence: 1
  givenname: D. Tyler
  surname: Scholes
  fullname: Scholes, D. Tyler
  organization: Department of Chemistry and Biochemistry University of California, Los Angeles Los Angeles CA 90095‐1569 USA
– sequence: 2
  givenname: Patrick Y.
  surname: Yee
  fullname: Yee, Patrick Y.
  organization: Department of Chemistry and Biochemistry University of California, Los Angeles Los Angeles CA 90095‐1569 USA
– sequence: 3
  givenname: Jeffrey R.
  surname: Lindemuth
  fullname: Lindemuth, Jeffrey R.
  organization: Lake Shore Cryotronics Westerville OH 43082 USA
– sequence: 4
  givenname: Hyeyeon
  surname: Kang
  fullname: Kang, Hyeyeon
  organization: Department of Chemistry and Biochemistry University of California, Los Angeles Los Angeles CA 90095‐1569 USA
– sequence: 5
  givenname: Jonathan
  surname: Onorato
  fullname: Onorato, Jonathan
  organization: Materials Science and Engineering Department University of Washington Seattle WA 98195‐2120 USA
– sequence: 6
  givenname: Raja
  surname: Ghosh
  fullname: Ghosh, Raja
  organization: Department of Chemistry Temple University Philadelphia PA 19122 USA
– sequence: 7
  givenname: Christine K.
  surname: Luscombe
  fullname: Luscombe, Christine K.
  organization: Materials Science and Engineering Department University of Washington Seattle WA 98195‐2120 USA
– sequence: 8
  givenname: Frank C.
  surname: Spano
  fullname: Spano, Frank C.
  organization: Department of Chemistry Temple University Philadelphia PA 19122 USA
– sequence: 9
  givenname: Sarah H.
  surname: Tolbert
  fullname: Tolbert, Sarah H.
  organization: Department of Chemistry and Biochemistry University of California, Los Angeles Los Angeles CA 90095‐1569 USA, Department of Materials Science and Engineering University of California, Los Angeles Los Angeles CA 90095 USA, California NanoSystems Institute University of California, Los Angeles Los Angeles CA 90095 USA
– sequence: 10
  givenname: Benjamin J.
  orcidid: 0000-0003-3257-9152
  surname: Schwartz
  fullname: Schwartz, Benjamin J.
  organization: Department of Chemistry and Biochemistry University of California, Los Angeles Los Angeles CA 90095‐1569 USA, California NanoSystems Institute University of California, Los Angeles Los Angeles CA 90095 USA
BackLink https://www.osti.gov/biblio/1395403$$D View this record in Osti.gov
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Snippet Abstract The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution...
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Title The Effects of Crystallinity on Charge Transport and the Structure of Sequentially Processed F 4 TCNQ‐Doped Conjugated Polymer Films
URI https://www.osti.gov/biblio/1395403
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