Directional charge separation in isolated organic semiconductor crystalline nanowires

Labastide, J. A.; Thompson, H. B.; Marques, S. R.; Colella, N. S.; Briseno, A. L.; Barnes, M. D.

doi:10.1038/ncomms10629

Directional charge separation in isolated organic semiconductor crystalline nanowires

Journal Article · Thu Feb 25 00:00:00 EST 2016 · Nature Communications

DOI:https://doi.org/10.1038/ncomms10629· OSTI ID:1361622

Labastide, J. A. ^[1]; Thompson, H. B. ^[2]; Marques, S. R. ^[2]; Colella, N. S. ^[2]; Briseno, A. L. ^[2]; Barnes, M. D. ^[2]

Univ. of Massachusetts, Amherst, MA (United States); Department of Chemistry, University of Massachusetts, Amherst Massachusetts
Univ. of Massachusetts, Amherst, MA (United States)

One of the fundamental design paradigms in organic photovoltaic device engineering is based on the idea that charge separation is an extrinsically driven process requiring an interface for exciton fission. This idea has driven an enormous materials science engineering effort focused on construction of domain sizes commensurate with a nominal exciton diffusion length of order 10 nm. Here, we show that polarized optical excitation of isolated pristine crystalline nanowires of a small molecule n-type organic semiconductor, 7,8,15,16-tetraazaterrylene, generates a significant population of charge-separated polaron pairs along the π-stacking direction. Charge separation was signalled by pronounced power-law photoluminescence decay polarized along the same axis. In the transverse direction, we observed exponential decay associated with excitons localized on individual monomers. We propose that this effect derives from an intrinsic directional charge-transfer interaction that can ultimately be programmed by molecular packing geometry.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Massachusetts, Amherst, MA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-05ER15695

OSTI ID:: 1361622

Journal Information:: Nature Communications, Journal Name: Nature Communications Vol. 7; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (28)

Excitons in Conjugated Oligomer Aggregates, Films, and Crystals Spano, Frank C. ChemInform, Vol. 37, Issue 51 https://doi.org/10.1002/chin.200651265	journal	December 2006
Exciton dynamics in pentacene thin films studied by pump-probe spectroscopy Jundt, C.; Klein, G.; Sipp, B. Chemical Physics Letters, Vol. 241, Issue 1-2 https://doi.org/10.1016/0009-2614(95)00603-2	journal	July 1995
Synthesis and Characterization of 7,8,15,16-Tetraazaterrylene Fan, Jian; Zhang, Lei; Briseno, Alejandro L. Organic Letters, Vol. 14, Issue 4 https://doi.org/10.1021/ol203285n	journal	January 2012
Singlet exciton fission in solution Walker, Brian J.; Musser, Andrew J.; Beljonne, David Nature Chemistry, Vol. 5, Issue 12 https://doi.org/10.1038/nchem.1801	journal	November 2013
Excitons in nanoscale systems Scholes, Gregory D.; Rumbles, Garry Nature Materials, Vol. 5, Issue 9 https://doi.org/10.1038/nmat1710	journal	September 2006
Spectroscopy of discrete vertically oriented single-crystals of n-type tetraazaterrylene: understanding the role of defects in molecular semiconductor photovoltaics Wise, A. J.; Zhang, Y.; Fan, J. Phys. Chem. Chem. Phys., Vol. 16, Issue 30 https://doi.org/10.1039/c4cp00113c	journal	January 2014
Interplay between intrachain and interchain interactions in semiconducting polymer assemblies: The HJ-aggregate model Yamagata, H.; Spano, F. C. The Journal of Chemical Physics, Vol. 136, Issue 18 https://doi.org/10.1063/1.4705272	journal	May 2012
Charge Separation in Semicrystalline Polymeric Semiconductors by Photoexcitation: Is the Mechanism Intrinsic or Extrinsic? Paquin, Francis; Latini, Gianluca; Sakowicz, Maciej Physical Review Letters, Vol. 106, Issue 19 https://doi.org/10.1103/physrevlett.106.197401	journal	May 2011
Charge-Transfer Excitations Steer the Davydov Splitting and Mediate Singlet Exciton Fission in Pentacene Beljonne, D.; Yamagata, H.; Brédas, J. L. Physical Review Letters, Vol. 110, Issue 22 https://doi.org/10.1103/physrevlett.110.226402	journal	May 2013
Ultrafast Transient Spectroscopy of Polymer/Fullerene Blends for Organic Photovoltaic Applications Singh, Sanjeev; Vardeny, Zeev Materials, Vol. 6, Issue 3 https://doi.org/10.3390/ma6030897	journal	March 2013
Charge Formation, Recombination, and Sweep-Out Dynamics in Organic Solar Cells Cowan, Sarah R.; Banerji, Natalie; Leong, Wei Lin Advanced Functional Materials, Vol. 22, Issue 6 https://doi.org/10.1002/adfm.201101632	journal	January 2012
Design Rules for Donors in Bulk-Heterojunction Solar Cells—Towards 10 % Energy-Conversion Efficiency Scharber, M. C.; Mühlbacher, D.; Koppe, M. Advanced Materials, Vol. 18, Issue 6, p. 789-794 https://doi.org/10.1002/adma.200501717	journal	March 2006
Optical probes of chain packing structure and exciton dynamics in polythiophene films, composites, and nanostructures Barnes, Michael D.; Baghar, Mina Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 15 https://doi.org/10.1002/polb.23105	journal	June 2012
Statistical approaches for probing single-molecule dynamics photon-by-photon Yang, Haw; Xie, X. Sunney Chemical Physics, Vol. 284, Issue 1-2 https://doi.org/10.1016/S0301-0104(02)00672-9	journal	November 2002
The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates Spano, Frank C. Accounts of Chemical Research, Vol. 43, Issue 3 https://doi.org/10.1021/ar900233v	journal	March 2010
Near-IR Femtosecond Transient Absorption Spectroscopy of Ultrafast Polaron and Triplet Exciton Formation in Polythiophene Films with Different Regioregularities Guo, Jiamo; Ohkita, Hideo; Benten, Hiroaki Journal of the American Chemical Society, Vol. 131, Issue 46 https://doi.org/10.1021/ja906621a	journal	November 2009
Time- and Polarization-Resolved Photoluminescence Decay from Isolated Polythiophene (P3HT) Nanofibers Labastide, Joelle A.; Baghgar, Mina; McKenna, Aidan The Journal of Physical Chemistry C, Vol. 116, Issue 44 https://doi.org/10.1021/jp308503u	journal	October 2012
Designing J- and H-Aggregates through Wave Function Overlap Engineering: Applications to Poly(3-hexylthiophene) Yamagata, Hajime; Pochas, Chris M.; Spano, Frank C. The Journal of Physical Chemistry B, Vol. 116, Issue 49 https://doi.org/10.1021/jp309407r	journal	November 2012
HJ-Aggregate Behavior of Crystalline 7,8,15,16-Tetraazaterrylene: Introducing a New Design Paradigm for Organic Materials Yamagata, H.; Maxwell, D. S.; Fan, J. The Journal of Physical Chemistry C, Vol. 118, Issue 49 https://doi.org/10.1021/jp509011u	journal	November 2014
Time- and Polarization-Resolved Photoluminescence of Individual Semicrystalline Polythiophene (P3HT) Nanoparticles Labastide, Joelle A.; Baghgar, Mina; Dujovne, Irene The Journal of Physical Chemistry Letters, Vol. 2, Issue 17 https://doi.org/10.1021/jz200958x	journal	August 2011
Direct observation of ultrafast long-range charge separation at polymer–fullerene heterojunctions Provencher, Françoise; Bérubé, Nicolas; Parker, Anthony W. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5288	journal	July 2014
Spectroscopy of discrete vertically oriented single-crystals of n-type tetraazaterrylene: understanding the role of defects in molecular semiconductor photovoltaics Wise, A. J.; Zhang, Y.; Fan, J. Phys. Chem. Chem. Phys., Vol. 16, Issue 30 https://doi.org/10.1039/C4CP00113C	journal	January 2014
The effect of phase morphology on the nature of long-lived charges in semiconductor polymer:fullerene systems Dou, Fei; Buchaca-Domingo, Ester; Sakowicz, Maciej Journal of Materials Chemistry C, Vol. 3, Issue 15 https://doi.org/10.1039/C4TC02637C	journal	January 2015
Theoretical investigation on electronic, optical, and charge transport properties of 7,8,15,16-tetraazaterrylene and its derivatives with electron-attracting substituents Zhao, Caibin; Wang, Wenliang; Yin, Shiwei New Journal of Chemistry, Vol. 37, Issue 9 https://doi.org/10.1039/c3nj00561e	journal	January 2013
Exciton mobility control through sub − Å packing modifications in molecular crystals Hestand, Nicholas J.; Tempelaar, Roel; Knoester, Jasper Physical Review B, Vol. 91, Issue 19 https://doi.org/10.1103/PhysRevB.91.195315	journal	May 2015
Charge Separation in Semicrystalline Polymeric Semiconductors by Photoexcitation: Is the Mechanism Intrinsic or Extrinsic? Paquin, Francis; Latini, Gianluca; Sakowicz, Maciej Physical Review Letters, Vol. 106, Issue 19 https://doi.org/10.1103/PhysRevLett.106.197401	journal	May 2011
Charge-Transfer Excitations Steer the Davydov Splitting and Mediate Singlet Exciton Fission in Pentacene Beljonne, D.; Yamagata, H.; Brédas, J. L. Physical Review Letters, Vol. 110, Issue 22 https://doi.org/10.1103/PhysRevLett.110.226402	journal	May 2013
Excitons in Conjugated Oligomer Aggregates, Films, and Crystals Spano, Frank C. Annual Review of Physical Chemistry, Vol. 57, Issue 1 https://doi.org/10.1146/annurev.physchem.57.032905.104557	journal	May 2006

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