Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Thermochemical nanopatterning of organic semiconductors


Patterning of semiconducting polymers on surfaces is important for various applications in nanoelectronics and nanophotonics. However, many of the approaches to nanolithography that are used to pattern inorganic materials are too harsh for organic semiconductors, so research has focused on optical patterning1,2,3 and various soft lithographies4. Surprisingly little attention has been paid to thermal5, thermomechanical6,7 and thermochemical8,9,10,11,12,13 patterning. Here, we demonstrate thermochemical nanopatterning of poly(p-phenylene vinylene), a widely used electroluminescent polymer14, by a scanning probe. We produce patterned structures with dimensions below 28 nm, although the tip of the probe has a diameter of 5 µm, and achieve write speeds of 100 µm s−1. Experiments show that a resolution of 28 nm is possible when the tip–sample contact region has dimensions of 100 nm and, on the basis of finite-element modelling, we predict that the resolution could be improved by using a thinner resist layer and an optimized probe. Thermochemical lithography offers a versatile, reliable and general nanopatterning technique because a large number of optical materials, including many commercial crosslinker additives and photoresists, rely on chemical mechanisms that can also be thermally activated8,15,16.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it


Prices may be subject to local taxes which are calculated during checkout

Figure 1: Thermochemical nanopatterning.
Figure 2: Nanopatterning of organic semiconductors.
Figure 3: Thermal analysis and cross-sections.
Figure 4: Finite-element simulation of thermal profiles and ultimate resolutions.


  1. Service, R. F. Optical lithography goes to extremes—and beyond. Science 293, 785–786 (2001).

    Article  CAS  Google Scholar 

  2. Riehn, R. & Cacialli, F. A two-dimensional photonic structure made from a conjugated, fluorescent polymer. J. Opt. A 7, S207–S212 (2005).

    Article  Google Scholar 

  3. Sun, S. & Leggett, G. J. Matching the resolution of electron beam lithography by scanning near-field photolithography. Nano Lett. 4, 1381–1384 (2004).

    Article  CAS  Google Scholar 

  4. Granlund, T., Nyberg, T., Roman, L. S., Svensson, M. & Inganäs, O. Patterning of polymer light-emitting diodes with soft lithography. Adv. Mater. 12, 269–273 (2000).

    Article  CAS  Google Scholar 

  5. Schäffer, E., Harkema, S., Roerdink, M., Blossey, R. & Steiner, U. Thermomechanical lithography: pattern replication using a temperature gradient driven instability. Adv. Mater. 15, 514–517 (2003).

    Article  Google Scholar 

  6. Durig, U. et al. ‘Millipede’—an AFM data storage system at the frontier of nanotribology. Tribol. Lett. 9, 25–32 (2000).

    Article  CAS  Google Scholar 

  7. Gotsmann, B., Duerig, U., Frommer, J. & Hawker, C. J. Exploiting chemical switching in a Diels–Alder polymer for nanoscale probe lithography and data storage. Adv. Funct. Mater. 16, 1499–1505 (2006).

    Article  CAS  Google Scholar 

  8. Basu, A. S., McNamara, S. & Gianchandani, Y. B. Scanning thermal lithography: maskless, submicron thermochemical patterning of photoresist by ultracompliant probes. J. Vac. Sci. Technol. B. 22, 3217–3220 (2004).

    Article  CAS  Google Scholar 

  9. Szoszkiewicz, R. et al. High-speed, sub-15 nm feature size thermochemical nanolithography. Nano Lett. 7, 1064–1069 (2007).

    Article  CAS  Google Scholar 

  10. Wang, D. B. et al. Local wettability modification by thermochemical nanolithography with write-read-overwrite capability. Appl. Phys. Lett. 91, 243104 (2007).

    Article  Google Scholar 

  11. Reading, M. Nano-construction processes and analytical processes. International patent WO 2006/120424 A2 (9 May 2005).

  12. King, W. P., Saxena, S., Nelson, B. A., Weeks, B. L. & Pitchimani, R. Nanoscale thermal analysis of an energetic material. Nano Lett. 6, 2145–2149 (2006).

    Article  CAS  Google Scholar 

  13. Duvigneau, J., Schonherr, H. & Vancso, G. J. Atomic force microscopy based thermal lithography of poly(tert-butyl acrylate) block copolymer films for bioconjugation. Langmuir 24, 10825–10832 (2008).

    Article  CAS  Google Scholar 

  14. Burroughes, J. H. et al. Light-emitting-diodes based on conjugated polymers. Nature 347, 539–541 (1990).

    Article  CAS  Google Scholar 

  15. Hung, M. T., Kim, J. & Ju, Y. S. Exploration of thermolithography for micro- and nanomanufacturing. Appl. Phys. Lett. 88, 123110 (2006).

    Article  Google Scholar 

  16. Meyers, G. F., Dineen, M. T., Shaffer, E. O., Stokich, T. & Im, J. Characterization of the surface structural, mechanical and thermal properties of benzocyclobutene dielectric polymers using scanning probe microscopy. Polym. Preprints 41, 1419–1420 (2000).

    CAS  Google Scholar 

  17. Sirringhaus, H. et al. High-resolution inkjet printing of all-polymer transistor circuits. Science 290, 2123–2126 (2000).

    Article  CAS  Google Scholar 

  18. Halls, J. J. M. et al. Efficient photodiodes from interpenetrating polymer networks. Nature 376, 498–500 (1995).

    Article  CAS  Google Scholar 

  19. Sariciftci, N. S., Smilowitz, L., Heeger, A. J. & Wudl, F. Photoinduced electron-transfer from a conducting polymer to buckminsterfullerene. Science 258, 1474–1476 (1992).

    Article  CAS  Google Scholar 

  20. Spreitzer, H. et al. Soluble phenyl-substituted PPVs—new materials for highly efficient polymer LEDs. Adv. Mater. 10, 1340–1343 (1998).

    Article  CAS  Google Scholar 

  21. Morgado, J., Cacialli, F., Gruner, J., Greenham, N. C. & Friend, R. H. Luminescence properties of poly(p-phenylenevinylene): role of the conversion temperature on the photoluminescence and electroluminescence efficiencies. J. Appl. Phys. 85, 1784–1791 (1999).

    Article  CAS  Google Scholar 

  22. Reading, M. et al. Micro-thermal analysis of polymers: current capabilities and future prospects. Macromol. Symp. 167, 45–62 (2001).

    Article  CAS  Google Scholar 

  23. Boroumand, F. A., Voigt, M., Lidzey, D. G., Hammiche, A. & Hill, G. Imaging Joule heating in a conjugated-polymer light-emitting diode using a scanning thermal microscope. Appl. Phys. Lett. 84, 4890–4892 (2004).

    Article  CAS  Google Scholar 

  24. Lee, C. K., Hua, C. C. & Chen, S. A. Single-chain and aggregation properties of semiconducting polymer solutions investigated by coarse-grained Langevin dynamics simulation. J. Phys. Chem. B 112, 11479–11489 (2008).

    Article  CAS  Google Scholar 

  25. Wery, J. et al. Thermal conversion of PPV precursor: characterization at different stages of the process. Synth. Met. 101, 194–195 (1999).

    Article  CAS  Google Scholar 

  26. Gorbunov, V. V., Fuchigami, N., Hazel, J. L. & Tsukruk, V. V. Probing surface microthermal properties by scanning thermal microscopy. Langmuir 15, 8340–8343 (1999).

    Article  CAS  Google Scholar 

  27. Lefevre, S., Volz, S., Saulnier, J. B., Fuentes, C. & Trannoy, N. Thermal conductivity calibration for hot wire based d.c. scanning thermal microscopy. Rev. Sci. Instrum. 74, 2418–2423 (2003).

    Article  CAS  Google Scholar 

  28. Smallwood, R. et al. Tomographic imaging and scanning thermal microscopy: thermal impedance tomography. Thermochim. Acta 385, 19–32 (2002).

    Article  CAS  Google Scholar 

  29. Riehn, R., Charas, A., Morgado, J. & Cacialli, F. Near-field optical lithography of a conjugated polymer. Appl. Phys. Lett. 82, 526–528 (2003).

    Article  CAS  Google Scholar 

  30. Boroumand, F. A., Fry, P. W. & Lidzey, D. G. Nanoscale conjugated-polymer light-emitting diodes. Nano Lett. 5, 67–71 (2005).

    Article  CAS  Google Scholar 

Download references


The authors dedicate this paper to Dr Azzedine Hammiche, who passed away in May 2008, after contributing to this work. L.B. was funded from a Wellcome Trust Programme grant to M.A. Horton (UCL). This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC) and the EU Sixth Framework Programme (ERAS-CT-2003-980409) as part of the European Science Foundation EUROCORES Programme on Self-Organized NanoStructures (SONS). Thanks also go to the EPSRC (DTA studentship to D.C.) and the Royal Society for financial support. The authors thank S. Nesbitt for assistance with the fluorescence imaging and M. Stoneham for useful discussions.

Author information

Authors and Affiliations



F.C. conceived the lithographic experiments, which were performed by O.F., L.B., D.C. and A.H. Atomic force microscopy of lithographic structures and micro-thermal analysis of the precursor material were conducted by O.F., and the confocal microscopy was performed jointly between Y.S. and O.F. O.F. and G.M.L. built the finite element model. The paper was written by O.F. and F.C. in consultation with all authors.

Corresponding author

Correspondence to Franco Cacialli.

Supplementary information

Supplementary information

Supplementary information (PDF 618 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Fenwick, O., Bozec, L., Credgington, D. et al. Thermochemical nanopatterning of organic semiconductors. Nature Nanotech 4, 664–668 (2009).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research