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Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films

Nature Materials volume 8, pages 952958 (2009) | Download Citation

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Abstract

Solution-processable organic semiconductors are central to developing viable printed electronics, and performance comparable to that of amorphous silicon has been reported for films grown from soluble semiconductors. However, the seemingly desirable formation of large crystalline domains introduces grain boundaries, resulting in substantial device-to-device performance variations. Indeed, for films where the grain-boundary structure is random, a few unfavourable grain boundaries may dominate device performance. Here we isolate the effects of molecular-level structure at grain boundaries by engineering the microstructure of the high-performance n-type perylenediimide semiconductor PDI8–CN2 and analyse their consequences for charge transport. A combination of advanced X-ray scattering, first-principles computation and transistor characterization applied to PDI8–CN2 films reveals that grain-boundary orientation modulates carrier mobility by approximately two orders of magnitude. For PDI8–CN2 we show that the molecular packing motif (that is, herringbone versus slip-stacked) plays a decisive part in grain-boundary-induced transport anisotropy. The results of this study provide important guidelines for designing device-optimized molecular semiconductors.

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References

  1. 1.

    Organic Electronics: Materials, Manufacturing and Applications (Wiley, 2006).

  2. 2.

    Semiconductors for organic transistors. Mater. Today 10, 28–37 (2007).

  3. 3.

    A bright future for organic field-effect transistors. Nature Mater. 5, 605–613 (2006).

  4. 4.

    , , & Organic heterostructure field-effect transistors. Science 269, 1560–1562 (1995).

  5. 5.

    et al. Tunable Frohlich polarons in organic single-crystal transistors. Nature Mater. 5, 982–986 (2006).

  6. 6.

    , & Improving organic thin-film transistor performance through solvent-vapor annealing of solution-processable triethylsilylethynyl anthradithiophene. Adv. Mater. 18, 1721–1726 (2006).

  7. 7.

    et al. Contact-induced crystallinity for high-performance soluble acene-based transistors and circuits. Nature Mater. 7, 216–221 (2008).

  8. 8.

    & Sequential lateral solidification of thin silicon films on SiO2. Appl. Phys. Lett. 69, 2864–2866 (1996).

  9. 9.

    et al. Manifestation of intrinsic defects in optical properties of self-organized opal photonic crystals. Phys. Rev. E 61, 5784–5793 (2000).

  10. 10.

    , , & Self-assembling three-dimensional colloidal photonic crystal structure with high crystalline quality. Appl. Phys. Lett. 78, 52–54 (2001).

  11. 11.

    , & Transport in polycrystalline polymer thin-film transistors. Phys. Rev. B 71, 165202 (2005).

  12. 12.

    , , , & Scanning tunneling microscopy investigations of self-organized poly(3-hexylthiophene) two-dimensional polycrystals. Adv. Mater. 15, 881–884 (2003).

  13. 13.

    , , , & Charge-transport anisotropy due to grain boundaries in directionally crystallized thin films of regioregular poly(3-hexylthiophene). Adv. Mater. 21, 1568–1572 (2009).

  14. 14.

    & Temperature and gate voltage dependent transport across a single organic semiconductor grain boundary. J. Appl. Phys. 90, 1342–1349 (2001).

  15. 15.

    , , & Grain orientation mapping of polycrystalline organic semiconductor films by transverse shear microscopy. Adv. Mater. 20, 4033–4039 (2008).

  16. 16.

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

  17. 17.

    et al. Humidity effect on electrical performance of organic thin-film transistors. Appl. Phys. Lett. 86, 042105 (2005).

  18. 18.

    et al. Two-dimensional charge transport in self-organized, high-mobility conjugated polymers. Nature 401, 685–688 (1999).

  19. 19.

    et al. Effect of rubbed polyimide layer on the field-effect mobility in pentacene thin-film transistors. Appl. Phys. Lett. 92, 052107 (2008).

  20. 20.

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

  21. 21.

    , , & Anisotropic mobility in large grain size solution processed organic semiconductor thin films. Appl. Phys. Lett. 92, 063302 (2008).

  22. 22.

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

  23. 23.

    , , , & Long-range ordering of diblock copolymers induced by droplet pinning. Langmuir 19, 9910–9913 (2003).

  24. 24.

    et al. p-channel organic semiconductors based on hybrid acene–thiophene molecules for thin-film transistor applications. J. Am. Chem. Soc. 127, 3997–4009 (2005).

  25. 25.

    , & Surface energetics and growth of pentacene. Phys. Rev. B 66, 121404 (2002).

  26. 26.

    et al. High-mobility air-stable n-type semiconductors with processing versatility: Dicyanoperylene-3,4:9,10-bis(dicarboximides). Angew. Chem. Int. Ed. 43, 6363–6366 (2004).

  27. 27.

    et al. Thermal and mechanical cracking in bis(triisopropylsilylethnyl) pentacene thin films. J. Polym. Sci. 44, 3631–3641 (2006).

  28. 28.

    et al. Solution processed top-gate n-channel transistors and complementary circuits on plastics operating in ambient conditions. Adv. Mater. 20, 3393–3398 (2008).

  29. 29.

    et al. Anisotropy of transient photoconductivity in functionalized pentacene single crystals. Appl. Phys. Lett. 89, 192113 (2006).

  30. 30.

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

  31. 31.

    et al. Charge transport in organic semiconductors. Chem. Rev. 107, 926–952 (2007).

  32. 32.

    , , , & Structural characterization of a pentacene monolayer on an amorphous SiO2 substrate with grazing incidence X-ray diffraction. J. Am. Chem. Soc. 126, 4084–4085 (2004).

  33. 33.

    et al. Molecular ordering in bis(phenylenyl)bithiophenes. J. Mater. Chem. 17, 3427–3432 (2007).

  34. 34.

    , , , & Structure of pentacene monolayers on amorphous silicon oxide and relation to charge transport. Adv. Mater. 21, 2294–2298 (2009).

  35. 35.

    et al. High-performance organic integrated circuits based on solution processable polymer–small molecule blends. Appl. Phys. Lett. 93, 253301 (2008).

  36. 36.

    et al. High-performance polymer–small molecule blend organic transistors. Adv. Mater. 21, 1166–1171 (2009).

  37. 37.

    , , & Tuning orbital energetics in arylene diimide semiconductors. Materials design for ambient stability of n-type charge transport. J. Am. Chem. Soc. 129, 15259–15278 (2007).

  38. 38.

    & Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).

  39. 39.

    , , & Density-functional theory calculations for poly-atomic systems: Electronic structure, static and elastic properties and ab initio molecular dynamics. Comput. Phys. Commun. 107, 187–222 (1997).

  40. 40.

    & Efficient pseudopotentials for plane-wave calculations. II. Operators for fast iterative diagonalization. Phys. Rev. B 43, 8861–8869 (1991).

  41. 41.

    & Ground state of the electron gas by a stochastic method. Phys. Rev. Lett. 45, 566–569 (1980).

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Acknowledgements

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 DOE, Office of Basic Energy Sciences. J.R. gratefully acknowledges financial support from ONR in the form of an NDSEG Fellowship, and A.S. and L.H.J. gratefully acknowledge financial support from NSF in the form of, respectively, a Career Award and a Graduate Student Fellowship. This publication was partially based on work supported by the Center for Advanced Molecular Photovoltaics (Award No KUS-C1-015-21, made by King Abdullah University of Science and Technology, KAUST). J.E.N. thanks AFOSR (FA9550-09-1-0436), and T.J.M. and A.F. thank AFOSR (FA9550-08-1-0331) for support of this research.

Author information

Affiliations

  1. Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, USA

    • Jonathan Rivnay
    • , Leslie H. Jimison
    •  & Alberto Salleo
  2. Palo Alto Research Center (PARC), Palo Alto, California 94304, USA

    • John E. Northrup
  3. Stanford Synchrotron Radiation Lightsource, Menlo Park, California 94025, USA

    • Michael F. Toney
  4. Department of Applied Physics, Stanford University, Stanford, California 94305, USA

    • Rodrigo Noriega
  5. Polyera Corporation, Skokie, Illinois 60077, USA

    • Shaofeng Lu
    •  & Antonio Facchetti
  6. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA

    • Tobin J. Marks
    •  & Antonio Facchetti

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Contributions

J.R. and A.S. conceived and designed the research. J.R. fabricated films/devices, and carried out electrical testing. J.R., L.H.J., R.N. and M.F.T. carried out X-ray-scattering experiments and unit-cell determination. J.E.N. carried out first-principles calculations. T.J.M. and A.F. oversaw materials design, synthesis and processing. S.L. synthesized the material. J.R., J.E.N. and A.S. prepared the manuscript. All authors revised and approved the manuscript.

Corresponding author

Correspondence to Alberto Salleo.

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DOI

https://doi.org/10.1038/nmat2570

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