Understanding and controlling the flow of heat is a major challenge in nanoelectronics. When a junction is driven out of equilibrium by light or the flow of electric charge, the vibrational and electronic degrees of freedom are, in general, no longer described by a single temperature1,2,3,4,5,6. Moreover, characterizing the steady-state vibrational and electronic distributions in situ is extremely challenging. Here, we show that surface-enhanced Raman emission may be used to determine the effective temperatures for both the vibrational modes and the electrons in the current in a biased metallic nanoscale junction decorated with molecules7. Molecular vibrations show mode-specific pumping by both optical excitation8 and d.c. current9, with effective temperatures exceeding several hundred kelvin. Anti-Stokes electronic Raman emission10,11 indicates that the effective electronic temperature at bias voltages of a few hundred millivolts can reach values up to three times the values measured when there is no current. The precise effective temperatures are model-dependent, but the trends as a function of bias conditions are robust, and allow direct comparisons with theories of nanoscale heating.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Scientific Reports Open Access 18 May 2018
Plasmonic photoluminescence for recovering native chemical information from surface-enhanced Raman scattering
Nature Communications Open Access 28 March 2017
Tunable Ultra-high Aspect Ratio Nanorod Architectures grown on Porous Substrate via Electromigration
Scientific Reports Open Access 29 February 2016
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Chen, Y.-C., Zwolak, M. & Di Ventra, M. Local heating in nanoscale conductors. Nano Lett. 3, 1691–1694 (2003).
Galperin, M. & Nitzan, A. Current-induced light emission and light-induced current in molecular-tunneling junctions. Phys. Rev. Lett. 95, 206802 (2005).
D'Agosta, R., Sai, N. & Di Ventra, M. Local electron heating in nanoscale conductors. Nano Lett. 6, 2935–2938 (2006).
Pecchia, A., Romano, G. & Di Carlo, A. Theory of heat dissipation in molecular electronics. Phys. Rev. B 75, 035401 (2007).
Huang, Z. et al. Local ionic and electron heating in single-molecule junctions. Nature Nanotech. 2, 698–703 (2007).
Galperin, M., Nitzan, A. & Ratner, M. R. Heat conduction in molecular transport junctions. Phys. Rev. B 75, 155312 (2007).
Ward, D. R. et al. Simultaneous measurements of electronic conduction and Raman response in molecular junctions. Nano Lett. 8, 919–924 (2008).
Galloway, C. M., Le Ru, E. C. & Etchegoin, P. G. Single-molecule vibrational pumping in SERS. Phys. Chem. Chem. Phys. 11, 7372–7380 (2009).
Ioffe, Z. et al. Detection of heating in current-carrying molecular junctions by Raman scattering. Nature Nanotech. 3, 727–732 (2008).
Moskovits, M. Surface-enhanced Raman spectroscopy: a brief retrospective. J. Raman Spect. 36, 485–496 (2005).
Otto, A., Akemann, W. & Pucci, A. Normal bands in surface-enhanced Raman scattering (SERS) and their relation to the electron–hole pair excitation background in SERS. Isr. J. Chem. 46, 307–315 (2006).
Datta, S. Electronic Transport in Mesoscopic Systems (Cambridge Univ. Press, 1995).
Stipe, B. C., Rezaei, M. A. & Ho, W. Single-molecule vibrational spectroscopy and microscopy. Science 280, 1732–1735 (1998).
Park, H. et al. Nanomechanical oscillations in a single C60 transistor. Nature 407, 57–60 (2000).
Galperin, M., Ratner, M. A. & Nitzan, A. Raman scattering from nonequilibrium molecular conduction junctions. Nano Lett. 9, 758–762 (2009).
Smit, R. H. M., Untiedt, C. & van Ruitenbeek, J. M. The high-bias stability of monatomic chains. Nanotechnology 15, S472–S478 (2004).
Tsutsui, M., Taniguchi, M. & Kawai, T. Local heating in metal–molecule–metal junctions. Nano Lett. 8, 3293–3297 (2008).
Oron-Carl, M. & Krupke, R. Raman spectroscopic evidence for hot-phonon generation in electrically biased carbon nanotubes. Phys. Rev. Lett. 100, 127401 (2008).
Berciaud, S. et al. Electron and optical phonon temperatures in electrically biased graphene. Phys. Rev. Lett. 104, 227401 (2010).
Zawadowski, A. & Cardona, M. Theory of Raman scattering on normal metals with impurities. Phys. Rev. B 42, 10732–10734 (1990).
Jiang, J., Bosnick, K., Maillard, M. & Brus, L. Single molecule Raman spectroscopy at the junctions of large Ag nanocrystals. J. Phys. Chem. B 107, 9964–9972 (2003).
Mahajan, S. et al. Understanding the surface-enhanced Raman spectroscopy ‘background’. J. Phys. Chem. C 114, 7242–7250 (2010).
Park, H. et al. Fabrication of metallic electrodes with nanometer separation by electromigration. Appl. Phys. Lett. 75, 301–303 (1999).
Ward, D. R. et al. Electromigrated nanoscale gaps for surface-enhanced Raman spectroscopy. Nano Lett. 7, 1396–1400 (2007).
Natelson, D., Yu, L. H., Ciszek, J. W., Keane, Z. K. & Tour, J. M. Single-molecule transistors: electron transfer in the solid state. Chem. Phys. 324, 267–275 (2006).
Ward, D. R., Scott, G. D., Keane, Z. K., Halas, N. J. & Natelson, D. Electronic and optical properties of electromigrated molecular junctions. J. Phys. Condens. Matter 20, 374118 (2008).
Venkataraman, L. et al. Single-molecule circuits with well-defined molecular conductance. Nano Lett. 6, 458–462 (2006).
Galperin, M., Nitzan, A., Ratner, M. A. & Stewart, D. R. Molecular transport junctions: asymmetry in inelastic tunneling processes. J. Phys. Chem B 109, 8519–8522 (2005).
Lambert, D. K. Stark effect of adsorbate vibrations. Solid State Commun. 51, 297–300 (1984).
Galperin, M., Nitzan, A. & Ratner, M. A. Heat conduction in molecular transport junctions. Phys. Rev. B 75, 155312 (2008).
D.N. and D.R.W. acknowledge support by the Robert A. Welch Foundation (grant C-1636) and the Lockheed Martin Advanced Nanotechnology Center of Excellence at Rice (LANCER). D.N. and D.R.W. acknowledge valuable conversations with M. Di Ventra, M.A. Ratner and A. Nitzan.
The authors declare no competing financial interests.
About this article
Cite this article
Ward, D., Corley, D., Tour, J. et al. Vibrational and electronic heating in nanoscale junctions. Nature Nanotech 6, 33–38 (2011). https://doi.org/10.1038/nnano.2010.240
Nature Materials (2022)
Nature Reviews Physics (2020)
Scientific Reports (2018)
Nature Nanotechnology (2018)