Letter | Published:

Tuning charge transport in solution-sheared organic semiconductors using lattice strain

Nature volume 480, pages 504508 (22 December 2011) | Download Citation

Abstract

Circuits based on organic semiconductors are being actively explored for flexible, transparent and low-cost electronic applications1,2,3,4,5. But to realize such applications, the charge carrier mobilities of solution-processed organic semiconductors must be improved. For inorganic semiconductors, a general method of increasing charge carrier mobility is to introduce strain within the crystal lattice6. Here we describe a solution-processing technique for organic semiconductors in which lattice strain is used to increase charge carrier mobilities by introducing greater electron orbital overlap between the component molecules. For organic semiconductors, the spacing between cofacially stacked, conjugated backbones (the π–π stacking distance) greatly influences electron orbital overlap and therefore mobility7. Using our method to incrementally introduce lattice strain, we alter the π–π stacking distance of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) from 3.33 Å to 3.08 Å. We believe that 3.08 Å is the shortest π–π stacking distance that has been achieved in an organic semiconductor crystal lattice (although a π–π distance of 3.04 Å has been achieved through intramolecular bonding8,9,10). The positive charge carrier (hole) mobility in TIPS-pentacene transistors increased from 0.8 cm2 V−1 s−1 for unstrained films to a high mobility of 4.6 cm2 V−1 s−1 for a strained film. Using solution processing to modify molecular packing through lattice strain should aid the development of high-performance, low-cost organic semiconducting devices.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    & Organic thin film transistors for large area electronics. Adv. Mater. 14, 99–117 (2002)

  2. 2.

    et al. High-mobility air-stable n-type semiconductors with processing versatility: dicyanoperylene-3,4:9,10-bis(dicarboximides). Angew. Chem. 116, 6523–6526 (2004)

  3. 3.

    et al. Paper-like electronic displays: large-area rubber-stamped plastic sheets of electronics and microencapsulated electrophoretic inks. Proc. Natl Acad. Sci. USA 98, 4835–4840 (2001)

  4. 4.

    et al. Dithieno[2,3-d;2′,3′-d′]benzo[1,2-b;4,5-b′]dithiophene (DTBDT) as semiconductor for high-performance, solution-processed organic field-effect transistors. Adv. Mater. 21, 213–216 (2009)

  5. 5.

    et al. Field-effect transistors based on a benzothiadiazole−cyclopentadithiophene copolymer. J. Am. Chem. Soc. 129, 3472–3473 (2007)

  6. 6.

    , , , & Strained Si, SiGe, and Ge channels for high-mobility metal-oxide-semiconductor field-effect transistors. J. Appl. Phys. 97, 011101 (2005)

  7. 7.

    , , & Organic semiconductors: a theoretical characterization of the basic parameters governing charge transport. Proc. Natl Acad. Sci. USA 99, 5804–5809 (2002)

  8. 8.

    et al. Single microcrystals of organoplatinum(II) complexes with high charge-carrier mobility. Chem. Sci. 2, 216–220 (2011)

  9. 9.

    et al. Homoleptic platinum(II) and palladium(II) organothiolates and phenylselenolates: solvothermal synthesis, structural determination, optical properties, and single-source precursors for PdSe and PdS nanocrystals. Chem. Asian J. 5, 2062–2074 (2010)

  10. 10.

    Molecular Co-crystals: Semiconductors, Photoactive Solids, and Catalysts PhD thesis, Univ. Iowa. (2007)

  11. 11.

    et al. Uniaxial strain on graphene: Raman spectroscopy study and band-gap opening. ACS Nano 2, 2301–2305 (2008)

  12. 12.

    , & A road map to stable, soluble, easily crystallized pentacene derivatives. Org. Lett. 4, 15–18 (2002)

  13. 13.

    , , & Chlorination: a general route toward electron transport in organic semiconductors. J. Am. Chem. Soc. 131, 3733–3740 (2009)

  14. 14.

    et al. Synthesis, characterization, and field-effect transistor performance of pentacene derivatives. Adv. Mater. 19, 3381–3384 (2007)

  15. 15.

    et al. Towards high charge-carrier mobilities by rational design of the shape and periphery of discotics. Nature Mater. 8, 421–426 (2009)

  16. 16.

    et al. A crystal-engineered hydrogen-bonded octachloroperylene diimide with a twisted core: an n-channel organic semiconductor. Angew. Chem. 122, 752–755 (2010)

  17. 17.

    , & Thermally induced solid-state phase transition of bis(triisopropylsilylethynyl) pentacene crystals. J. Phys. Chem. B 110, 16397–16403 (2006)

  18. 18.

    et al. Thin film structure of tetraceno[2,3-b]thiophene characterized by grazing incidence X-ray scattering and near-edge X-ray absorption fine structure analysis. J. Am. Chem. Soc. 130, 3502–3508 (2008)

  19. 19.

    , & Thin film structure of triisopropylsilylethynyl-functionalized pentacene and tetraceno[2,3-b]thiophene from grazing incidence X-ray diffraction. Adv. Mater. 23, 127–131 (2011)

  20. 20.

    & Band-like temperature dependence of mobility in a solution-processed organic semiconductor. Nature Mater. 9, 736–740 (2010)

  21. 21.

    et al. Solution-processable pentacene microcrystal arrays for high performance organic field-effect transistors. Appl. Phys. Lett. 90, 132106 (2007)

  22. 22.

    , , , & High-performance organic thin-film transistors through solution-sheared deposition of small-molecule organic semiconductors. Adv. Mater. 20, 2588–2594 (2008)

  23. 23.

    & Investigation of the properties of directionally solidified poly(vinylidene fluoride). Polymer 20, 725–732 (1979)

  24. 24.

    & Crystal growth near moving contact lines on homogeneous and chemically patterned surfaces. Langmuir 26, 11485–11493 (2010)

  25. 25.

    et al. Controlled deposition of highly ordered soluble acene thin films: effect of morphology and crystal orientation on transistor performance. Adv. Mater. 21, 4926–4931 (2009)

  26. 26.

    et al. Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films. Nature Mater. 8, 952–958 (2009)

  27. 27.

    , , & High mobility solution processed 6,13-bis(triisopropyl-silylethynyl) pentacene organic thin film transistors. Appl. Phys. Lett. 91, 063514 (2007)

  28. 28.

    , , , & Grain-boundary-limited charge transport in solution-processed 6,13 bis(tri-isopropylsilylethynyl) pentacene thin film transistors. J. Appl. Phys. 103, 114512–114513 (2008)

  29. 29.

    et al. Controlling nucleation and crystallization in solution-processed organic semiconductors for thin-film transistors. Adv. Mater. 21, 3605–3609 (2009)

  30. 30.

    et al. Crystalline ultrasmooth self-assembled monolayers of alkylsilanes for organic field-effect transistors. J. Am. Chem. Soc. 131, 9396–9404 (2009)

Download references

Acknowledgements

We thank A. Salleo, J. E. Anthony, H. Li, A. Sokolov and J. Rivnay for discussions. We thank J. E. Anthony and M. M. Nelson of 3M Corp. for providing high-purity TIPS-pentacene. This publication was partially supported by the National Science Foundation DMR-Solid State Chemistry (DMR-0705687-002), the Samsung Advanced Institute of Technology, the Global Climate and Energy Project at Stanford University (SPO 25591130-45282-A) and the Air Force Office of Scientific Research (award number FA9550-09--0256). E.V. thanks the Eastman Kodak Corporation Kodak Fellows Program for support. Z.B. acknowledges support from the David Filo and Jerry Yang Faculty Fellowship from Stanford University. Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a national user facility operated by Stanford University on behalf of the US Department of Energy, Office of Basic Energy Sciences. Any opinions, findings, and conclusions or recommendations expressed in this publication are those of the authors and do not necessarily reflect the views of Stanford University, the Sponsors of the Global Climate and Energy Project, or others involved with the Global Climate and Energy Project.

Author information

Affiliations

  1. Department of Chemical Engineering, Stanford University, Stanford, California 94305, USA

    • Gaurav Giri
    • , Eric Verploegen
    • , Do Hwan Kim
    •  & Zhenan Bao
  2. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

    • Eric Verploegen
    • , Stefan C. B. Mannsfeld
    •  & Michael F. Toney
  3. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA

    • Sule Atahan-Evrenk
    •  & Alán Aspuru-Guzik
  4. Display Device Laboratory, Samsung Advanced Institute of Technology, Mt 14-1, Nongseo-dong, Giheung-gu, Yongin-Si, Kyunggi-Do 449-712, South Korea

    • Sang Yoon Lee
  5. Department of Chemistry, Brigham Young University—Idaho, Rexburg, Idaho 83460, USA

    • Hector A. Becerril

Authors

  1. Search for Gaurav Giri in:

  2. Search for Eric Verploegen in:

  3. Search for Stefan C. B. Mannsfeld in:

  4. Search for Sule Atahan-Evrenk in:

  5. Search for Do Hwan Kim in:

  6. Search for Sang Yoon Lee in:

  7. Search for Hector A. Becerril in:

  8. Search for Alán Aspuru-Guzik in:

  9. Search for Michael F. Toney in:

  10. Search for Zhenan Bao in:

Contributions

G.G. and H.A.B. built the current version of the solution-shearing set-up. G.G. and E.V. performed X-ray and transistor measurements. S.C.B.M. performed unit cell and molecular packing calculations. G.G., E.V., S.C.B.M., D.H.K., M.F.T. and Z.B. analysed the X-ray data. S.A.-E. and A.A.-G. performed transfer integral calculations. G.G., E.V. and Z.B. wrote the manuscript, and all other authors had input. Z.B. and S.Y.L. directed the project.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Zhenan Bao.

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    This file contains Supplementary Methods and a Discussion, Supplementary Figures 1-13 with legends, Supplementary Tables 1-4, legends for Supplementary Movies 1-2 and additional references.

Videos

  1. 1.

    Supplementary Movie 1

    This movie shows in-situ strain relief of GIXD peaks during toluene vapor annealing.

  2. 2.

    Supplementary Movie 2

    This movie shows in-situ heating TIPS-pentacene thin films, showing no strain relief of the (010) GIXD peak.

Text files

  1. 1.

    Supplementary Data 1

    This file shows the structure of thin film unstrained TIPS-pentacene.

  2. 2.

    Supplementary Data 2

    This file shows the structure of thin film strained TIPS-pentacene solution sheared at 8mm/s

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nature10683

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.