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Approaching disorder-free transport in high-mobility conjugated polymers

Nature volume 515, pages 384–388 (2014)Cite this article

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Abstract

Conjugated polymers enable the production of flexible semiconductor devices that can be processed from solution at low temperatures. Over the past 25 years, device performance has improved greatly as a wide variety of molecular structures have been studied1. However, one major limitation has not been overcome; transport properties in polymer films are still limited by pervasive conformational and energetic disorder2,3,4,5. This not only limits the rational design of materials with higher performance, but also prevents the study of physical phenomena associated with an extended π-electron delocalization along the polymer backbone. Here we report a comparative transport study of several high-mobility conjugated polymers by field-effect-modulated Seebeck, transistor and sub-bandgap optical absorption measurements. We show that in several of these polymers, most notably in a recently reported, indacenodithiophene-based donor–acceptor copolymer with a near-amorphous microstructure6, the charge transport properties approach intrinsic disorder-free limits at which all molecular sites are thermally accessible. Molecular dynamics simulations identify the origin of this long sought-after regime as a planar, torsion-free backbone conformation that is surprisingly resilient to side-chain disorder. Our results provide molecular-design guidelines for ‘disorder-free’ conjugated polymers.

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Figure 1: Transistor characteristics of IDTBT-based FETs compared with other polymer FETs.
Figure 2: Field-effect-modulated Seebeck coefficients in high-mobility polymer devices.
Figure 3: Energetic disorder probed using photothermal deflection spectroscopy.
Figure 4: Resilience of torsion-free polymer backbone conformation to side-chain disorder.

References

  1. Bruetting, W. Physics of Organic Semiconductors (Wiley-VCH, 2005)

    Book  Google Scholar 

  2. Bässler, H. Localized states and electronic transport in single component organic solids with diagonal disorder. Phys. Stat. Solidi B 107, 9–54 (1981)

    Article  ADS  Google Scholar 

  3. Sirringhaus, H. Device physics of solution-processed organic field-effect transistors. Adv. Mater. 17, 2411–2425 (2005)

    Article  CAS  Google Scholar 

  4. Rivnay, J. et al. Structural origin of gap states in semicrystalline polymers and the implications for charge transport. Phys. Rev. B 83, 121306 (2011)

    Article  ADS  Google Scholar 

  5. Noriega, R. et al. A general relationship between disorder, aggregation and charge transport in conjugated polymers. Nature Mater. 12, 1038–1044 (2013)

    Article  ADS  CAS  Google Scholar 

  6. Zhang, W. M. et al. Indacenodithiophene semiconducting polymers for high performance air-stable transistors. J. Am. Chem. Soc. 132, 11437–11439 (2010)

    Article  CAS  Google Scholar 

  7. Nielsen, C. B., Turbiez, M. & McCulloch, I. Recent advances in the development of semiconducting DPP-containing polymers for transistor applications. Adv. Mater. 25, 1859–1880 (2013)

    Article  CAS  Google Scholar 

  8. Kim, N.-K. et al. Solution-processed barium salts as charge injection layers for high performance N-channel organic field-effect transistors. ACS Appl. Mater. Interfaces 6, 9614–9621 (2014)

    Article  CAS  Google Scholar 

  9. Kim, G. et al. A thienoisoindigo-naphthalene polymer with ultrahigh mobility of 14.4 cm2/V s that substantially exceeds benchmark values for amorphous silicon semiconductors. J. Am. Chem. Soc. 136, 9477–9483 (2014)

    Article  CAS  Google Scholar 

  10. Tseng, H.-R. et al. High-mobility field-effect transistors fabricated with macroscopic aligned semiconducting polymers. Adv. Mater. 26, 2993–2998 (2014)

    Article  CAS  Google Scholar 

  11. Callen, H. B. Thermodynamics Ch. 17 (Wiley, 1960)

    MATH  Google Scholar 

  12. Emin, D. Seebeck effect. In Wiley Encyclopedia of Electrical and Electronics Engineering Online (ed. Webster, J. G. ) (Wiley, 2013)

    Google Scholar 

  13. Emin, D. Enhanced Seebeck coefficient from carrier-induced vibrational softening. Phys. Rev. B 59, 6205–6210 (1999)

    Article  ADS  CAS  Google Scholar 

  14. Emin, D. Polarons (Cambridge Univ. Press, 2013)

    Google Scholar 

  15. Pernstich, K. P., Roessner, B. & Batlogg, B. Field-effect-modulated Seebeck coefficient in organic semiconductors. Nature Mater. 7, 321–325 (2008)

    Article  ADS  CAS  Google Scholar 

  16. Kronemeijer, A. J. et al. A selenophene-based low-bandgap donor–acceptor polymer leading to fast ambipolar logic. Adv. Mater. 24, 1558–1565 (2012)

    Article  CAS  Google Scholar 

  17. Kronemeijer, A. J. et al. Two-dimensional carrier distribution in top-gate polymer field-effect transistors: correlation between width of density of localized states and Urbach energy. Adv. Mater. 26, 728–733 (2014)

    Article  CAS  Google Scholar 

  18. Chen, Z. et al. High performance ambipolar diketopyrrolopyrrole-thieno[3,2-b]thiophene copolymer field-effect transistors with balanced electron and hole mobilities. Adv. Mater. 24, 647–652 (2012)

    Article  CAS  Google Scholar 

  19. Li, J. et al. A stable solution-processed polymer semiconductor with record high mobility for printed transistors. Sci. Rep. 2, 754 (2012)

    Article  Google Scholar 

  20. Zhang, X. et al. Molecular origin of high field-effect mobility in an indacenodithiophene–benzothiadiazole copolymer. Nature Commun. 4, 2238 (2013)

    Article  ADS  Google Scholar 

  21. Sirringhaus, H. Organic field-effect transistors — the path beyond amorphous silicon. Adv. Mater. 26, 1319–1335 (2014)

    Article  CAS  Google Scholar 

  22. Brondijk, J. J. et al. Two-dimensional charge transport in disordered organic semiconductors. Phys. Rev. Lett. 109, 056601 (2012)

    Article  ADS  CAS  Google Scholar 

  23. Venkateshvaran, D., Kronemeijer, A. J., Moriarty, J., Emin, D. & Sirringhaus, H. Field-effect modulated Seebeck coefficient measurements in an organic polymer using a microfabricated on-chip architecture. APL Mater. 2, 032102 (2014)

    Article  ADS  Google Scholar 

  24. Germs, W. C., Guo, K., Janssen, R. A. J. & Kemerink, M. Unusual thermoelectric behavior indicating hopping to bandlike transition in pentacene. Phys. Rev. Lett. 109, 016601 (2012)

    Article  ADS  Google Scholar 

  25. Overhof, H. & Beyer, W. A model for the electronic transport in hydrogenated amorphous silicon. Philos. Mag. B 43, 433–450 (1981)

    Article  ADS  CAS  Google Scholar 

  26. DeLongchamp, D. M. et al. High carrier mobility polythiophene thin films: structure determination by experiment and theory. Adv. Mater. 19, 833–837 (2007)

    Article  CAS  Google Scholar 

  27. von Mühlenen, A., Errien, N., Schaer, M., Bussac, M.-N. & Zuppiroli, L. Thermopower measurements on pentacene transistors. Phys. Rev. B 75, 115338 (2007)

    Article  ADS  Google Scholar 

  28. Aselage, T. L., Emin, D., McCready, S. S. & Duncan, R. V. Large enhancement of boron carbides’ Seebeck coefficients through vibrational softening. Phys. Rev. Lett. 81, 2316–2319 (1998)

    Article  ADS  CAS  Google Scholar 

  29. Yan, H. et al. A high-mobility electron-transporting polymer for printed transistors. Nature 457, 679–686 (2009)

    Article  ADS  CAS  Google Scholar 

  30. Olivier, Y. et al. High-mobility hole and electron transport conjugated polymers: how structure defines function. Adv. Mater. 26, 2119–2136 (2014)

    Article  CAS  Google Scholar 

  31. Cho, E. et al. Three-dimensional packing structure and electronic properties of biaxially oriented poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) films. J. Am. Chem. Soc. 134, 6177–6190 (2012)

    Article  CAS  Google Scholar 

  32. Schmidtke, J. P., Kim, J.-S., Gierschner, J., Silva, C. & Friend, R. H. Optical spectroscopy of a polyfluorene copolymer at high pressure: intra- and intermolecular interactions. Phys. Rev. Lett. 99, 167401 (2007)

    Article  ADS  Google Scholar 

  33. Jacobson, M. A., Konstantinov, O. V., Nelson, D. K., Romanovskii, S. O. & Hatzopoulos, Z. Absorption spectra of GaN: film characterization by Urbach spectral tail and the effect of electric field. J. Cryst. Growth 230, 459–461 (2001)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge financial support from the Engineering and Physical Sciences Research Council through a programme grant (EP/G060738/1) and the Technology Strategy Board (PORSCHED project). D.V. acknowledges financial support from the Cambridge Commonwealth Trust through a Cambridge International Scholarship. K.B. acknowledges post-doctoral fellowship support from the German Research Foundation. M.Z. acknowledges funding from NanoDTC in Cambridge. The work in Mons was supported by the European Commission/Région Wallonne (FEDER – Smartfilm RF project), the Interuniversity Attraction Pole programme of the Belgian Federal Science Policy Office (PAI 7/05), Programme d’Excellence de la Région Wallonne (OPTI2MAT project) and FNRS-FRFC. D.B. and J.C. are FNRS Research Fellows.

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Author notes

  1. Deepak Venkateshvaran and Mark Nikolka: These authors contributed equally to this work.

Authors and Affiliations

  1. Optoelectronics Group, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, UK ,

    Deepak Venkateshvaran, Mark Nikolka, Aditya Sadhanala, Mateusz Zelazny, Auke Jisk Kronemeijer, Vincenzo Pecunia, Iyad Nasrallah, Igor Romanov, Katharina Broch & Henning Sirringhaus

  2. Laboratory for Chemistry of Novel Materials, Université de Mons, 20 Place du Parc, 7000 Mons, Belgium ,

    Vincent Lemaur, Yoann Olivier, Jerome Cornil & David Beljonne

  3. Centre for Science at Extreme Conditions, University of Edinburgh, Mayfield Road, Edinburgh EH9 3JZ, UK ,

    Michal Kepa

  4. Department of Chemistry and Centre for Plastic Electronics, Imperial College London, London SW7 2AZ, UK,

    Michael Hurhangee & Iain McCulloch

  5. Department of Physics and Astronomy, University of New Mexico, 1919 Lomas Boulevard Northeast, Albuquerque, New Mexico 87131, USA,

    David Emin

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  1. Deepak Venkateshvaran
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Contributions

D.V. designed and fabricated the devices and performed field-effect modulated Seebeck measurements on them. M.N. and A.J.K. optimized the fabrication of IDTBT-based organic FETs and performed transistor measurements. A.S. and M.N. performed photothermal deflection spectroscopy measurements. V.P. optimized the patterning procedure for organic devices. V.L., M.Z., Y.O., J.C. and D.B. performed quantum chemical and molecular dynamic simulations. M.Z. and M.K. acquired the high-pressure induced Raman spectra. K.B. performed measurements on DPPTTT-based devices. I.N. and I.R. performed charge accumulation spectroscopy measurements (Supplementary Information). I.M. and M.H. synthesized IDTBT. D.E. explained the Seebeck measurements on the basis of a narrow-band model. H.S. directed and coordinated the research. D.V., M.N., V.L., Y.O., J.C., D.B., D.E. and H.S. wrote the manuscript.

Corresponding author

Correspondence to Henning Sirringhaus.

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The authors declare no competing financial interests.

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Supplementary Information

This file contains Supplementary Text and Data, Supplementary Figures 1-20, Supplementary Tables 1-2 and Supplementary references. (PDF 8680 kb)

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Venkateshvaran, D., Nikolka, M., Sadhanala, A. et al. Approaching disorder-free transport in high-mobility conjugated polymers. Nature 515, 384–388 (2014). https://doi.org/10.1038/nature13854

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