Skip to main content

Thank you for visiting nature.com. 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.

Elastically driven cooperative response of a molecular material impacted by a laser pulse

Nature Materials volume 15, pages 606–610 (2016)Cite this article

Subjects

Abstract

Photoinduced phase transformations1,2 occur when a laser pulse impacts a material, thereby transforming its electronic and/or structural orders, consequently affecting the functionalities3,4,5,6,7. The transient nature of photoinduced states has thus far severely limited the scope of applications. It is of paramount importance to explore whether structural feedback during the solid deformation has the capacity to amplify and stabilize photoinduced transformations. Contrary to coherent optical phonons, which have long been under scrutiny8,9,10, coherently propagating cell deformations over acoustic timescales11,12,13,14 have not been explored to a similar degree, particularly with respect to cooperative elastic interactions. Herein we demonstrate, experimentally and theoretically, a self-amplified responsiveness in a spin-crossover material15 during its delayed volume expansion. The cooperative response at the material scale prevails above a threshold excitation, significantly extending the lifetime of photoinduced states. Such elastically driven cooperativity triggered by a light pulse offers an efficient route towards the generation and stabilization of photoinduced phases in many volume-changing materials.

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

$39.95

Learn more

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

Figure 1: Response to femtosecond laser excitation of LS crystals of different sizes.
Figure 2: Photoresponse of nanocrystals to excitation density.
Figure 3: Monte Carlo simulations with the mechanoelastic model.
Figure 4: Schematics of the mechanism.

References

  1. Nasu, K. Photoinduced Phase Transitions (World Scientific, 2004).

    Book  Google Scholar 

  2. Cailleau, H. et al. Impacting materials by light and seeing their structural dynamics. Eur. Phys. J. 222, 1077–1092 (2013).

    Google Scholar 

  3. Ichikawa, H. et al. Transient photoinduced ‘hidden’ phase in a manganite. Nature Mater. 10, 101–105 (2011).

    Article  CAS  Google Scholar 

  4. Gao, M. et al. Mapping molecular motions leading to charge delocalization with ultrabright electrons. Nature 496, 343–346 (2013).

    Article  CAS  Google Scholar 

  5. Porer, M. et al. Non-thermal separation of electronic and structural orders in a persisting charge density wave. Nature Mater. 13, 857–861 (2014).

    Article  CAS  Google Scholar 

  6. Beaud, P. et al. A time-dependent order parameter for ultrafast photoinduced phase transitions. Nature Mater. 13, 923–927 (2014).

    Article  CAS  Google Scholar 

  7. Collet, E. et al. Laser-induced ferroelectric structural order in an organic charge-transfer crystal. Science 300, 612–615 (2003).

    Article  CAS  Google Scholar 

  8. Sokolowski-Tinten, K. et al. Femtosecond X-ray measurement of coherent lattice vibrations near the Lindemann stability limit. Nature 422, 287–289 (2003).

    Article  CAS  Google Scholar 

  9. Wall, S. et al. Ultrafast changes in lattice symmetry probed by coherent phonons. Nature Commun. 3, 721 (2012).

    Article  CAS  Google Scholar 

  10. Cammarata, M. et al. Sequential activation of molecular breathing and bending during spin-crossover photoswitching revealed by femtosecond optical and X-ray absorption spectroscopy. Phys. Rev. Lett. 113, 227402 (2014).

    Article  Google Scholar 

  11. Feurer, T., Vaughan, J. C. & Nelson, K. A. Spatiotemporal coherent control of lattice vibrational waves. Science 299, 374–377 (2003).

    Article  CAS  Google Scholar 

  12. Lejman, M. et al. Giant ultrafast photo-induced shear strain in ferroelectric BiFeO3 . Nature Commun. 5, 4301 (2014).

    Article  CAS  Google Scholar 

  13. Lorenc, M. et al. Cascading photoinduced, elastic, and thermal switching of spin states triggered by a femtosecond laser pulse in an Fe(III) molecular crystal. Phys. Rev. B 85, 054302 (2012).

    Article  Google Scholar 

  14. Collet, E. et al. Ultrafast spin-state photoswitching in a crystal and slower consecutive processes investigated by femtosecond optical spectroscopy and picosecond X-ray diffraction. Phys. Chem. Chem. Phys. 14, 6192–6199 (2012).

    Article  Google Scholar 

  15. Halcrow, M. (ed.) Spin-Crossover Materials (Wiley, 2013).

  16. Willenbacher, N. & Spiering, H. The elastic interaction of high-spin and low-spin complex molecules in spin-crossover compounds. J. Phys. C 21, 1423–1439 (1988).

    Article  Google Scholar 

  17. Bertoni, R., Lorenc, M., Tissot, A., Boillot, M.-L. & Collet, E. Femtosecond photoswitching dynamics and microsecond thermal conversion driven by laser heating in FeIII spin-crossover solids. Coord. Chem. Rev. 282–283, 66–76 (2015).

    Article  Google Scholar 

  18. Zhang, W. et al. Tracking excited-state charge and spin dynamics in iron coordination complexes. Nature 509, 345–348 (2014).

    Article  CAS  Google Scholar 

  19. Lorenc, M. et al. Successive dynamical steps of photoinduced switching of a molecular Fe(III) spin-crossover material by time-resolved x-ray diffraction. Phys. Rev. Lett. 103, 028301 (2009).

    Article  CAS  Google Scholar 

  20. Tissot, A., Bertoni, R., Collet, E., Toupet, L. & Boillot, M.-L. The cooperative spin-state transition of an iron(III) compound [FeIII(3-MeO-SalEen)2]PF6: thermal- vs ultra-fast photo-switching. J. Mat. Chem. 35, 2333–2340 (2011).

    Google Scholar 

  21. Félix, G. et al. Lattice dynamics in spin-crossover nanoparticles through nuclear inelastic scattering. Phys. Rev. B 91, 024422 (2015).

    Article  Google Scholar 

  22. Enachescu, C., Stoleriu, L., Stancu, A. & Hauser, A. Model for elastic relaxation phenomena in finite 2D hexagonal molecular lattices. Phys. Rev. Lett. 102, 257204 (2009).

    Article  Google Scholar 

  23. Tissot, A., Enachescu, C. & Boillot, M.-L. Control of the thermal hysteresis of the prototypal spin-transition FeII(phen)2(NCS)2 compound via the microcrystallites environment: experiments and mechanoelastic model. J. Mater. Chem. 22, 20451–20457 (2012).

    Article  CAS  Google Scholar 

  24. Stoleriu, L., Chakraborty, P., Hauser, A., Stancu, A. & Enachescu, C. Thermal hysteresis in spin-crossover compounds studied within the mechanoelastic model and its potential application to nanoparticles. Phys. Rev. B 84, 134102 (2011).

    Article  Google Scholar 

  25. Varret, F. et al. The propagation of the thermal spin transition of [Fe(btr)2(NCS)2]H2O single crystals, observed by optical microscopy. New J. Chem. 35, 2333–2340 (2011).

    Article  CAS  Google Scholar 

  26. Cobo, S. et al. Single-laser-shot-induced complete bidirectional spin transition at room temperature in single crystals of (FeII(pyrazine)(Pt(CN)4)). J. Am. Chem. Soc. 130, 9019–9024 (2008).

    Article  CAS  Google Scholar 

  27. Hauser, A., Gütlich, P. & Spiering, H. High-spin → low-spin relaxation kinetics and cooperative effects in the [Fe(ptz)6(BF4)2[Zn1−xFex(ptz)6](BF4)2 (ptz = 1-Propyltetrazole) spin-crossover systems. Inorg. Chem. 25, 4245–4248 (1986).

    Article  CAS  Google Scholar 

  28. Gütlich, P., Hauser, A. & Spiering, H. Thermal and optical switching of Iron (II) complexes. Angew. Chem. Int. Ed. 33, 2024–2054 (1994).

    Article  Google Scholar 

  29. Kobatake, S., Takami, S., Muto, H., Ishikawa, T. & Irie, M. Rapid and reversible shape changes of molecular crystals on photoirradiation. Nature 446, 778–781 (2007).

    Article  CAS  Google Scholar 

  30. Ohkoshi, S. et al. Synthesis of a metal oxide with a room-temperature photoreversible phase transition. Nature Chem. 2, 539–545 (2010).

    Article  CAS  Google Scholar 

  31. Camjayi, A. et al. First-order insulator-to-metal Mott transition in the paramagnetic 3D System GaTa4Se8 . Phys. Rev. Lett. 113, 086404 (2014).

    Article  CAS  Google Scholar 

  32. Veber, S. L. et al. High-field EPR reveals the strongly temperature-dependent exchange interaction in “breathing” crystals Cu(hfac)2LR. J. Am. Chem. Soc. 130, 2444–2445 (2008).

    Article  CAS  Google Scholar 

  33. Okamoto, H. et al. Photoinduced phase transition in tetrathiafulvalene-p-chloranil observed in femtosecond reflection spectroscopy. Phys. Rev. B 70, 165202 (2004).

    Article  Google Scholar 

  34. Okimoto, Y. et al. Ultrasonic propagation of a metallic domain in Pr0.5Ca0.5CoO3 undergoing a photoinduced insulator–metal transition. Phys. Rev. Lett. 103, 027402 (2009).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Institut Universitaire de France, Rennes Métropole, Région Bretagne (CREATE 4146), ANR (ANR-13-BS04-0002) and Europe (FEDER). C.E. thanks CNCS-UEFISCDI Romania (grant number PN-II-RU-TE-2014-4-0987).

Author information

Author notes

  1. Antoine Tissot

    Present address: Present address: Institut Lavoisier de Versailles, UMR 8180, Université de Versailles, Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France.,

Authors and Affiliations

  1. Université de Rennes 1, Institut de Physique de Rennes, UMR UR1-CNRS 6251, F-35000 Rennes, France

    Roman Bertoni, Maciej Lorenc, Hervé Cailleau & Eric Collet

  2. Institut de Chimie Moléculaire et des Matériaux d’Orsay, Université Paris Sud, Université Paris-Saclay, CNRS, 91405 Orsay, France

    Antoine Tissot, Jérôme Laisney & Marie-Laure Boillot

  3. Faculty of Physics, Alexandru Ioan Cuza University, 700506 Iasi, Romania

    Laurentiu Stoleriu, Alexandru Stancu & Cristian Enachescu

Authors
  1. Roman Bertoni
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Maciej Lorenc
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hervé Cailleau
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Antoine Tissot
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jérôme Laisney
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Marie-Laure Boillot
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Laurentiu Stoleriu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Alexandru Stancu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Cristian Enachescu
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Eric Collet
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

E.C. and M.L. conceived and coordinated the project. R.B. performed time-resolved optical measurements and analysed the data. A.T., J.L. and M.-L.B. grew and prepared the samples. L.S., A.S. and C.E. extended the mechanoelastic model and performed Monte Carlo simulations. E.C., H.C., M.L., R.B. and C.E. proposed the physical picture and wrote the paper. All authors contributed to discussions and gave comments on the manuscript.

Corresponding authors

Correspondence to Maciej Lorenc or Eric Collet.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 928 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Bertoni, R., Lorenc, M., Cailleau, H. et al. Elastically driven cooperative response of a molecular material impacted by a laser pulse. Nature Mater 15, 606–610 (2016). https://doi.org/10.1038/nmat4606

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat4606

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing