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.

  • Letter
  • Published:

Optically excited structural transition in atomic wires on surfaces at the quantum limit

Abstract

Transient control over the atomic potential-energy landscapes of solids could lead to new states of matter and to quantum control of nuclear motion on the timescale of lattice vibrations. Recently developed ultrafast time-resolved diffraction techniques1 combine ultrafast temporal manipulation with atomic-scale spatial resolution and femtosecond temporal resolution. These advances have enabled investigations of photo-induced structural changes in bulk solids that often occur on timescales as short as a few hundred femtoseconds2,3,4,5,6. In contrast, experiments at surfaces and on single atomic layers such as graphene report timescales of structural changes that are orders of magnitude longer7,8,9. This raises the question of whether the structural response of low-dimensional materials to femtosecond laser excitation is, in general, limited. Here we show that a photo-induced transition from the low- to high-symmetry state of a charge density wave in atomic indium (In) wires supported by a silicon (Si) surface takes place within 350 femtoseconds. The optical excitation breaks and creates In–In bonds, leading to the non-thermal excitation of soft phonon modes, and drives the structural transition in the limit of critically damped nuclear motion through coupling of these soft phonon modes to a manifold of surface and interface phonons that arise from the symmetry breaking at the silicon surface. This finding demonstrates that carefully tuned electronic excitations can create non-equilibrium potential energy surfaces that drive structural dynamics at interfaces in the quantum limit (that is, in a regime in which the nuclear motion is directed and deterministic)8. This technique could potentially be used to tune the dynamic response of a solid to optical excitation, and has widespread potential application, for example in ultrafast detectors10,11.

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

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

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

Figure 1: Electron diffraction patterns and surface structures.
Figure 2: Time evolution of the diffraction intensities following photo-excitation.
Figure 3: Potential energy surfaces, electronic surface states, molecular dynamics, damping of vibrational modes and variation of bond strength.
Figure 4: Electron population decay in unoccupied states probed by trARPES.

Similar content being viewed by others

References

  1. Thomas, J. M. Ultrafast electron crystallography: the dawn of a new era. Angew. Chem. Int. Ed. 43, 2606–2610 (2004)

    Article  CAS  Google Scholar 

  2. Baum, P., Yang, D. S. & Zewail, A. H. 4D visualization of transitional structures in phase transformations by electron diffraction. Science 318, 788–792 (2007)

    Article  ADS  CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  4. Sciaini, G. et al. Electronic acceleration of atomic motions and disordering in bismuth. Nature 458, 56–59 (2009)

    Article  ADS  CAS  Google Scholar 

  5. Eichberger, M. et al. Snapshots of cooperative atomic motions in the optical suppression of charge density waves. Nature 468, 799–802 (2010)

    Article  ADS  CAS  Google Scholar 

  6. Morrison, V. R. et al. A photoinduced metal-like phase of monoclinic VO2 revealed by ultrafast electron diffraction. Science 346, 445–448 (2014)

    Article  ADS  CAS  Google Scholar 

  7. Ruan, C. Y., Lobastov, V. A., Vigliotti, F., Chen, S. & Zewail, A. H. Ultrafast electron crystallography of interfacial water. Science 304, 80–84 (2004)

    Article  ADS  CAS  Google Scholar 

  8. Ruan, C. Y ., Vigliotti, F ., Lobastov, V. A ., Chen, S . & Zewail, A. H. Ultrafast electron crystallography: transient structures of molecules, surfaces, and phase transitions. Proc. Natl Acad. Sci. USA 101, 1123–1128 (2004)

  9. Gulde, M. et al. Imaging techniques. Ultrafast low-energy electron diffraction in transmission resolves polymer/graphene superstructure dynamics. Science 345, 200–204 (2014)

    Article  ADS  CAS  Google Scholar 

  10. Fleming, G. R. & Ratner, M. A. Grand challenges in basic energy sciences. Phys. Today 61, 28–33 (2008)

    Article  Google Scholar 

  11. Thomas, J. M. Concluding remarks. Time-resolved chemistry: from structure to function. A summary. Faraday Discuss. 122, 395–399 (2003)

    Article  ADS  CAS  Google Scholar 

  12. Perfetti, L. et al. Time evolution of the electronic structure of 1T-TaS2 through the insulator-metal transition. Phys. Rev. Lett. 97, 067402 (2006)

    Article  ADS  CAS  Google Scholar 

  13. Faure, J. et al. Direct observation of electron thermalization and electron-phonon coupling in photoexcited bismuth. Phys. Rev. B 88, 075120 (2013)

    Article  ADS  Google Scholar 

  14. Sokolowski-Tinten, K. et al. Thickness-dependent electron-lattice equilibration in laser-excited thin bismuth films. New J. Phys. 17, 113047 (2015)

    Article  ADS  Google Scholar 

  15. Streubühr, C. et al. Comparing ultrafast surface and bulk heating using time-resolved electron diffraction. Appl. Phys. Lett. 104, 161611 (2014)

    Article  ADS  Google Scholar 

  16. Schäfer, H., Kabanov, V. V., Beyer, M., Biljakovic, K. & Demsar, J. Disentanglement of the electronic and lattice parts of the order parameter in a 1D charge density wave system probed by femtosecond spectroscopy. Phys. Rev. Lett. 105, 066402 (2010)

    Article  ADS  Google Scholar 

  17. Rettig, L. et al. Persistent order due to transiently enhanced nesting in an electronically excited charge density wave. Nat. Commun. 7, 10459 (2016)

    Article  ADS  CAS  Google Scholar 

  18. Hellmann, S. et al. Time-domain classification of charge-density-wave insulators. Nat. Commun. 3, 1069 (2012)

    Article  ADS  CAS  Google Scholar 

  19. Schmitt, F. et al. Transient electronic structure and melting of a charge density wave in TbTe3 . Science 321, 1649–1652 (2008)

    Article  ADS  CAS  Google Scholar 

  20. Rohwer, T. et al. Collapse of long-range charge order tracked by time-resolved photoemission at high momenta. Nature 471, 490–493 (2011)

    Article  ADS  CAS  Google Scholar 

  21. Petersen, J. C. et al. Clocking the melting transition of charge and lattice order in 1T-TaS2 with ultrafast extreme-ultraviolet angle-resolved photoemission spectroscopy. Phys. Rev. Lett. 107, 177402 (2011)

    Article  ADS  CAS  Google Scholar 

  22. Sohrt, C., Stange, A., Bauer, M. & Rossnagel, K. How fast can a Peierls–Mott insulator be melted? Faraday Discuss. 171, 243–257 (2014)

    Article  ADS  CAS  Google Scholar 

  23. Yeom, H. W. et al. Instability and charge density wave of metallic quantum chains on a silicon surface. Phys. Rev. Lett. 82, 4898–4901 (1999)

    Article  ADS  CAS  Google Scholar 

  24. Snijders, P. C. & Weitering, H. H. Colloquium: electronic instabilities in self-assembled atom wires. Rev. Mod. Phys. 82, 307–329 (2010)

    Article  ADS  CAS  Google Scholar 

  25. González, C., Flores, F. & Ortega, J. Soft phonon, dynamical fluctuations, and a reversible phase transition: indium chains on silicon. Phys. Rev. Lett. 96, 136101 (2006)

    Article  ADS  Google Scholar 

  26. Wippermann, S. & Schmidt, W. G. Entropy explains metal-insulator transition of the Si(111)-In nanowire array. Phys. Rev. Lett. 105, 126102 (2010)

    Article  ADS  CAS  Google Scholar 

  27. Klasing, F. et al. Hysteresis proves that the In/Si(111) (8 × 2) to (4 × 1) phase transition is first-order. Phys. Rev. B 89, 121107 (2014)

    Article  ADS  Google Scholar 

  28. Wall, S. et al. Atomistic picture of charge density wave formation at surfaces. Phys. Rev. Lett. 109, 186101 (2012)

    Article  ADS  Google Scholar 

  29. Riikonen, S., Ayuela, A. & Sanchez-Portal, D. Metal-insulator transition in the In/Si(111) surface. Surf. Sci. 600, 3821–3824 (2006)

    Article  ADS  CAS  Google Scholar 

  30. Fleischer, K., Chandola, S., Esser, N., Richter, W. & McGilp, J. F. Surface phonons of the Si(111):In-(4 × 1) and (8 × 2) phases. Phys. Rev. B 76, 205406 (2007)

    Article  ADS  Google Scholar 

  31. Baum, P . & Zewail, A. H. Breaking resolution limits in ultrafast electron diffraction and microscopy. Proc. Natl Acad. Sci. USA 103, 16105–16110 (2006)

    Article  ADS  CAS  Google Scholar 

  32. Bovensiepen, U. & Kirchmann, P. S. Elementary relaxation processes investigated by femtosecond photoelectron spectroscopy of two-dimensional materials. Laser Photonics Rev. 6, 589–606 (2012)

    Article  ADS  Google Scholar 

  33. Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009)

    Article  Google Scholar 

  34. Dederichs, P. H., Blügel, S., Zeller, R. & Akai, H. Ground-states of constrained systems: application to cerium impurities. Phys. Rev. Lett. 53, 2512–2515 (1984)

    Article  ADS  CAS  Google Scholar 

  35. Maintz, S., Deringer, V. L., Tchougreeff, A. L. & Dronskowski, R. Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids. J. Comput. Chem. 34, 2557–2567 (2013)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Deutsche Forschungsgemeinschaft through SFB616 ‘Energy dissipation at surfaces’, FOR1700 ‘Metallic nanowires on the atomic scale: electronic and vibrational coupling in real world systems’, SFB1242 ‘Non-equilibrium dynamics of condensed matter in the time domain’, FOR1405 ‘Dynamics of electron transfer processes within transition metal sites in biological and bioinorganic systems’ and the High Performance Computing Center Stuttgart and the Paderborn Center for Parallel Computing. We acknowledge discussions with R. Ernstorfer and K. Sokolowski-Tinten.

Author information

Authors and Affiliations

Authors

Contributions

T.F., B.H. and T.W. performed the ultrafast electron diffraction measurements and data analysis. The tilted pulse front scheme was set up by C.S., T.F., P.Z., M.L. and D.v.d.L. The trARPES measurements were performed by A.S.S., M.L., V.M.T. and I.A. and M.L. analysed the data. DFT calculations were performed by A.L., S.W., U.G., S.S. and W.G.S. B.K., M.H.-v.H., M.L. and U.B. conceived the experiments. The manuscript was written by B.K., T.F., M.L., U.B., M.H.-v.H. and W.G.S. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to M. Horn-von Hoegen.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

Reviewer Information Nature thanks J. Freericks, J. Ortega and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Extended data figures and tables

Extended Data Figure 1 Excitation of characteristic phonon modes through the (de-)population of certain electronic states.

Orbital character of indium surface states that are particularly susceptible to photo-induced structural changes in the Si(111)(8 × 2)–In surface; colour coding corresponds to Extended Data Fig. 3. The occupation of the blue and green interchain In–In bond states (empty in the (8 × 2) phase) excites the shear phonon mode of the indium chain. Emptying the yellow and orange intrachain In–In bond states (occupied in the (8 × 2) phase) excites the rotary phonon mode of the indium chain. The nuclear motion of the excited phonon modes is indicated by arrows.

Extended Data Figure 2 Transient heating of the high-temperature phase following photo-excitation.

Transient intensity of the (01) spot of the (4 × 1) phase at a substrate temperature of T0 = 142 K for two different incident fluences: Φ = 1.3 mJ cm−2 (pink) and Φ = 3.1 mJ cm−2 (orange). The decreases in the fits to the intensity (solid lines) can be converted into maximum temperature jumps of ΔT ≈ 19 K and ΔT ≈ 19 30 K, respectively.

Extended Data Figure 3 Electronic surface states of the low- and high-temperature phases.

a, b, Calculated electronic band structure for Si(111)(8 × 2)–In (a) and Si(111)(4 × 1)–In (b) (phases depicted as insets). The grey shaded areas show the projected silicon bulk bands. Excitations with a partially emptied zone-boundary valence state (a, orange and yellow) and partially occupied zone-centre conduction state (a, green and blue) are indicated with red open and filled circles.

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Frigge, T., Hafke, B., Witte, T. et al. Optically excited structural transition in atomic wires on surfaces at the quantum limit. Nature 544, 207–211 (2017). https://doi.org/10.1038/nature21432

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature21432

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

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