Polymorphism in the 1:1 Charge-Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Katelyn P. Goetz; Jun’ya Tsutsumi; Sujitra Pookpanratana; Jihua Chen; Nathan S. Corbin; Rakesh K. Behera; Veaceslav Coropceanu; Curt A. Richter; Christina A. Hacker; Tatsuo Hasegawa; Oana D. Jurchescu

doi:10.1002/aelm.201600203

Polymorphism in the 1:1 Charge-Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Katelyn P. Goetz, Jun’ya Tsutsumi, Sujitra Pookpanratana, Jihua Chen, Nathan S. Corbin, Rakesh K. Behera, Veaceslav Coropceanu, Curt A. Richter, Christina A. Hacker, Tatsuo Hasegawa, Oana D. Jurchescu

Macromolecular Nanomaterials

Research output: Contribution to journal › Article › peer-review

78 Scopus citations

Abstract

The organic charge-transfer complex dibenzotetrathiafulvalene–7,7,8,8-tetracyanoquinodimethane is found to crystallize in two polymorphs when grown by physical vapor transport: the known α-polymorph and a new structure, the β-polymorph. Structural and elemental analysis via selected area electron diffraction, X-ray photoelectron spectroscopy, and polarized IR spectroscopy reveal that the complexes have the same stoichiometry with a 1:1 donor: acceptor ratio, but exhibit unique unit cells. The structural variations result in significant differences in the optoelectronic properties of the crystals, as observed in the experiments and electronic-structure calculations. Raman spectroscopy shows that the α-polymorph has a degree of charge transfer of about 0.5e, while the β-polymorph is nearly neutral. Organic field-effect transistors fabricated on these crystals reveal that in the same device structure both polymorphs show ambipolar charge transport, but the α-polymorph exhibits electron-dominant transport while the β-polymorph is hole-dominant. Together, these measurements imply that the transport features result from differing donor–acceptor overlap and consequential varying in frontier molecular orbital mixing, as suggested theoretically for charge-transfer complexes.

Original language	English
Article number	1600203
Journal	Advanced Electronic Materials
Volume	2
Issue number	10
DOIs	https://doi.org/10.1002/aelm.201600203
State	Published - Oct 1 2016

Funding

The authors acknowledge Dr. Rachel Williamson of the Australian Synchrotron in her efforts to discern the structure for the β-DBTTF–TCNQ. The authors would also like to thank Prof. Alejandro Briseno and Dr. Marcos Reyes-Martinez at the University of Massachusetts at Amherst for their advice and training in preparing the parylene deposition system. This research was partially supported by the National Science Foundation under grants DMR-1105147 and ECCS-1254757 and by the U.S. Army Research Laboratory and U.S. Army Research Office under contract/grant number W911NF-13-1-0387. KPG acknowledges the NSF Graduate Research Fellowship Program (GRFP) and Graduate Research Opportunities Worldwide (GROW) under grant DGE-0907738. TEM (J.C.) experiments were conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

Keywords

charge-transfer complexes
organic semiconductors
polymorphism
single crystals

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10.1002/aelm.201600203

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Goetz, K. P., Tsutsumi, J., Pookpanratana, S., Chen, J., Corbin, N. S., Behera, R. K., Coropceanu, V., Richter, C. A., Hacker, C. A., Hasegawa, T., & Jurchescu, O. D. (2016). Polymorphism in the 1:1 Charge-Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties. Advanced Electronic Materials, 2(10), Article 1600203. https://doi.org/10.1002/aelm.201600203

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abstract = "The organic charge-transfer complex dibenzotetrathiafulvalene–7,7,8,8-tetracyanoquinodimethane is found to crystallize in two polymorphs when grown by physical vapor transport: the known α-polymorph and a new structure, the β-polymorph. Structural and elemental analysis via selected area electron diffraction, X-ray photoelectron spectroscopy, and polarized IR spectroscopy reveal that the complexes have the same stoichiometry with a 1:1 donor: acceptor ratio, but exhibit unique unit cells. The structural variations result in significant differences in the optoelectronic properties of the crystals, as observed in the experiments and electronic-structure calculations. Raman spectroscopy shows that the α-polymorph has a degree of charge transfer of about 0.5e, while the β-polymorph is nearly neutral. Organic field-effect transistors fabricated on these crystals reveal that in the same device structure both polymorphs show ambipolar charge transport, but the α-polymorph exhibits electron-dominant transport while the β-polymorph is hole-dominant. Together, these measurements imply that the transport features result from differing donor–acceptor overlap and consequential varying in frontier molecular orbital mixing, as suggested theoretically for charge-transfer complexes.",

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Polymorphism in the 1:1 Charge-Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

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