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Autoperforation of 2D materials for generating two-terminal memristive Janus particles

Nature Materials volume 17, pages 1005–1012 (2018)Cite this article

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Abstract

Graphene and other two-dimensional materials possess desirable mechanical, electrical and chemical properties for incorporation into or onto colloidal particles, potentially granting them unique electronic functions. However, this application has not yet been realized, because conventional top-down lithography scales poorly for producing colloidal solutions. Here, we develop an ‘autoperforation’ technique that provides a means of spontaneous assembly for surfaces composed of two-dimensional molecular scaffolds. Chemical vapour deposited two-dimensional sheets can autoperforate into circular envelopes when sandwiching a microprinted polymer composite disk of nanoparticle ink, allowing liftoff into solution and simultaneous assembly. The resulting colloidal microparticles have two independently addressable, external Janus faces that we show can function as an intraparticle array of vertically aligned, two-terminal electronic devices. Such particles demonstrate remarkable chemical and mechanical stability and form the basis of particulate electronic devices capable of collecting and storing information about their surroundings, extending nanoelectronics into previously inaccessible environments.

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Fig. 1: Autoperforation of 2D materials to generate colloidal microparticles with 2D surfaces.
Fig. 2: Characterization of microparticles after liftoff.
Fig. 3: Electrical properties and memristive characteristics of the graphene (bilayer) microparticles.
Fig. 4: G-PS-G microparticles as a platform to sense and record environmental information.

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Data availability

All relevant data and computer codes are available from the authors and most of them are included within the Supplementary Information, including sections on modelling and simulations, Supplementary Figs 1–60 and Supplementary Videos 1–12. Correspondence and requests for materials should be addressed to M.S.S.

References

  1. Griffith, A. A. The phenomena of rupture and flow in solids. Philos. Trans. Roy. Soc. London Ser. A 221, 163–198 (1921).

    Article  Google Scholar 

  2. Nam, K. H., Park, I. H. & Ko, S. H. Patterning by controlled cracking. Nature 485, 221–224 (2012).

    Article  CAS  Google Scholar 

  3. Kim, B. C., Moraes, C., Huang, J., Thouless, M. D. & Takayama, S. Fracture-based micro- and nanofabrication for biological applications. Biomater. Sci. 2, 288–296 (2014).

    Article  CAS  Google Scholar 

  4. Kim, M., Kim, D.-J., Ha, D. & Kim, T. Cracking-assisted fabrication of nanoscale patterns for micro/nanotechnological applications. Nanoscale 8, 9461–9479 (2016).

    Article  CAS  Google Scholar 

  5. Zhang, P. et al. Fracture toughness of graphene. Nat. Commun. 5, 3782 (2014).

    Article  CAS  Google Scholar 

  6. Yin, H. et al. Griffith criterion for brittle fracture in graphene. Nano Lett. 15, 1918–1924 (2015).

    Article  CAS  Google Scholar 

  7. Reina, A. et al. Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett. 9, 30–35 (2009).

    Article  CAS  Google Scholar 

  8. Kim, K. S. et al. Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457, 706–710 (2009).

    Article  CAS  Google Scholar 

  9. Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009).

    Article  CAS  Google Scholar 

  10. Lee, G.-H. et al. High-strength chemical-vapor-deposited graphene and grain boundaries. Science 340, 1073–1076 (2013).

    Article  CAS  Google Scholar 

  11. Mitchell, N. P., Koning, V., Vitelli, V. & Irvine, W. T. M. Fracture in sheets draped on curved surfaces. Nat. Mater. 16, 89–93 (2017).

    Article  CAS  Google Scholar 

  12. Zhang, T., Li, X. & Gao, H. Fracture of graphene: a review. Int. J. Fracture 196, 1–31 (2015).

    Article  Google Scholar 

  13. Hsu, P. I. et al. Spherical deformation of compliant substrates with semiconductor device islands. J. Appl. Phys. 95, 705–712 (2004).

    Article  CAS  Google Scholar 

  14. Sun, J.-Y. et al. Debonding and fracture of ceramic islands on polymer substrates. J. Appl. Phys. 111, 013517 (2012).

    Article  Google Scholar 

  15. Brandrup, J. & Immergut, E. H. (Eds) Polymer Handbook 2nd edn, Ch. IV (John Wiley & Sons, New York, USA).

  16. Zhang, L. et al. Janus graphene from asymmetric two-dimensional chemistry. Nat. Commun. 4, 1443 (2013).

    Article  Google Scholar 

  17. Dendukuri, D., Pregibon, D. C., Collins, J., Hatton, T. A. & Doyle, P. S. Continuous-flow lithography for high-throughput microparticle synthesis. Nat. Mater. 5, 365–369 (2006).

    Article  CAS  Google Scholar 

  18. Walther, A. & Müller, A. H. E. Janus particles: synthesis, self-assembly, physical properties, and applications. Chem. Rev. 113, 5194–5261 (2013).

    Article  CAS  Google Scholar 

  19. Splendiani, A. et al. Emerging photoluminescence in monolayer MoS2. Nano Lett. 10, 1271–1275 (2010).

    Article  CAS  Google Scholar 

  20. Lee, S., Lee, K., Liu, C.-H. & Zhong, Z. Homogeneous bilayer graphene film based flexible transparent conductor. Nanoscale 4, 639–644 (2012).

    Article  CAS  Google Scholar 

  21. Yang, J. J. et al. Memristive switching mechanism for metal//oxide//metal nanodevices. Nat. Nanotech. 3, 429–433 (2008).

    Article  CAS  Google Scholar 

  22. Brent, J. R. et al. Production of few-layer phosphorene by liquid exfoliation of black phosphorus. Chem. Commun. 50, 13338–13341 (2014).

    Article  CAS  Google Scholar 

  23. Hanlon, D. et al. Liquid exfoliation of solvent-stabilized few-layer black phosphorus for applications beyond electronics. Nat. Commun. 6, 8563 (2015).

    Article  CAS  Google Scholar 

  24. Hao, C. et al. Liquid-exfoliated black phosphorous nanosheet thin films for flexible resistive random access memory applications. Adv. Funct. Mater. 26, 2016–2024 (2016).

    Article  CAS  Google Scholar 

  25. Grunlan, J. C., Mehrabi, A. R., Bannon, M. V. & Bahr, J. L. Water-based single-walled-nanotube-filled polymer composite with an exceptionally low percolation threshold. Adv. Mater. 16, 150–153 (2004).

    Article  CAS  Google Scholar 

  26. Island, J. O., Steele, G. A., van der Zant, H. S. J. & Castellanos-Gomez, A. Environmental instability of few-layer black phosphorus. 2D Mater. 2, 6 (2015).

    Article  Google Scholar 

  27. Huang, Y. et al. Interaction of black phosphorus with oxygen and water. Chem. Mater. 28, 8330–8339 (2016).

    Article  CAS  Google Scholar 

  28. Youngwoo, S. et al. A study of bilayer phosphorene stability under MoS2 passivation. 2D Mater. 4, 025091 (2017).

    Article  Google Scholar 

  29. O’Hern, S. C. et al. Selective molecular transport through intrinsic defects in a single layer of CVD graphene. ACS Nano. 6, 10130–10138 (2012).

    Article  Google Scholar 

  30. Koman, V. B. et al. Colloidal nanoelectronic state machines based on 2D materials for aerosolizable electronics. Nat. Nanotech. 13, 819–827 (2018).

    Article  CAS  Google Scholar 

  31. Liu, P. et al. Emerging trends in 2D nanotechnology that are redefining our understanding of ‘nanocomposites’. Nano Today 21, 18–40 (2018).

    Article  CAS  Google Scholar 

  32. Mahajan, S. G. et al. Sustainable power sources based on high efficiency thermopower wave devices. Energy Environ. Sci. 9, 1290–1298 (2016).

    Article  CAS  Google Scholar 

  33. Liu, A. T. et al. Electrical energy generation via reversible chemical doping on carbon nanotube fibers. Adv. Mater. 28, 9752–9757 (2016).

    Article  CAS  Google Scholar 

  34. Kunai, Y. et al. Observation of the Marcus inverted region of electron transfer from asymmetric chemical doping of pristine (n,m) single-walled carbon nanotubes. J. Am. Chem. Soc. 139, 15328–15336 (2017).

    Article  CAS  Google Scholar 

  35. Cottrill, A. L. et al. Ultra-high thermal effusivity materials for resonant ambient thermal energy harvesting. Nat. Commun. 9, 664 (2018).

    Article  Google Scholar 

  36. Liu, P. et al. Layered and scrolled nanocomposites with aligned semi-infinite graphene inclusions at the plateletlimit. Science 353, 364–367 (2016).

    Article  CAS  Google Scholar 

  37. Oomen, A. G. et al. Comparison of five in vitro digestion models to study the bioaccessibility of soil contaminants. Environ. Sci. Technol. 36, 3326–3334 (2002).

    Article  CAS  Google Scholar 

  38. Ruby, M. V. et al. Development of an in vitro screening test to evaluate the in vivo bioaccessibility of ingested mine-waste lead. Environ. Sci. Technol. 27, 2870–2877 (1993).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was primarily funded by a 2015 US Air Force Office of Scientific Research (AFOSR) Multi University Research Initiative (MURI) grant on Foldable and Adaptive Two-Dimensional Electronics (FATE) at MIT, Harvard University and University of Southern California (award no. FA9550-15-1-0514). The authors acknowledge characterization support from The MIT Center for Materials Science and Engineering, and support for graphene synthesis and characterization from the Army Research Office and support via award no. 64655-CH-ISN to the Institute for Soldier Nanotechnologies. P.L. acknowledges the ‘One-hundred Talents Program’ of Zhejiang University. A.T.L. acknowledges the MIT Presidential Fellow programme. D.K. is supported by a Grant-in-Aid for JSPS Fellows (JSPS KAKENHI grant no. 15J07423) and Encouragement of Young Scientists (B) (JSPS KAKENHI grant no. JP16K17485) from the Japan Society for the Promotion of Science. V.B.K. is supported by The Swiss National Science Foundation (project no. P2ELP3_162149).

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  1. These authors contributed equally: Pingwei Liu, Albert Tianxiang Liu

Authors and Affiliations

  1. State Key Lab of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, China

    Pingwei Liu & Song Wang

  2. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Pingwei Liu, Albert Tianxiang Liu, Daichi Kozawa, Juyao Dong, Jing Fan Yang, Volodymyr B. Koman, Max Saccone, Song Wang, Youngwoo Son, Min Hao Wong & Michael S. Strano

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Contributions

P.L., A.T.L. and M.S.S. conceived of the experiments and wrote the paper. P.L., A.T.L. and M.S.S. performed experiments and data analysis. P.L., A.T.L. and M.S.S. designed the physical models to explain the controlled fracture of 2D materials. A.T.L. and M.S. performed the calculations and finite-element simulation. D.K. assisted in fluorescence characterization of the microparticles with MoS2 layers, J.D. assisted with the inkjet printing, and J.F.Y. performed statistical analyses for the memristor data to generate Fig. 3i. V.B.K. assisted with building the memristor function of the microparticles. S.W. and Y.S. assisted in the growth and transfer of 2D materials. M.H.W. set up the flow cell used to track liquid-phase particle translocation. All authors have given their approval to the final version of the manuscript.

Corresponding author

Correspondence to Michael S. Strano.

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Supplementary information

Supplementary Information

Supplementary Figures 1–60, Supplementary Table 1, Supplementary References 1–23.

Supplementary Video 1

Strain guided fracture propagation of graphene with stochastic seed crack formation.

Supplementary Video 2

Finite element coarse grained MD simulation for mould-based graphene folding.

Supplementary Video 3

Autoperforation for G-PS-G microparticles—lift-off process on SiO2-Si substrate—I.

Supplementary Video 4

Autoperforation for G-PS-G microparticles—lift-off process on SiO2-Si substrate—II.

Supplementary Video 5

Autoperforation for G-PS-G microparticles—lift-off process on PDMS substrate.

Supplementary Video 6

Control—lift-off process of PS control microparticles without grapheme.

Supplementary Video 7

Flowing and rotating of G-PS-G microparticles in microfluidic channel.

Supplementary Video 8

Magnetic propulsion of Gr-Fe3O4-PS-Gr microparticles.

Supplementary Video 9

Autoperforation for G-PS microparticles with only one layer of graphene (Graphene A).

Supplementary Video 10

Autoperforation for PS-G microparticles with only one layer of graphene (Graphene B).

Supplementary Video 11

The whole process starting from autoperforation, capturing, information write in, lift-off, recapturing to information readout.

Supplementary Video 12

Aerosolization of G-PS-G microparticles with atomizer.

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Liu, P., Liu, A.T., Kozawa, D. et al. Autoperforation of 2D materials for generating two-terminal memristive Janus particles. Nature Mater 17, 1005–1012 (2018). https://doi.org/10.1038/s41563-018-0197-z

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