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.

Peltier cooling in molecular junctions

Abstract

The study of thermoelectricity in molecular junctions is of fundamental interest for the development of various technologies including cooling (refrigeration) and heat-to-electricity conversion1,2,3,4. Recent experimental progress in probing the thermopower (Seebeck effect) of molecular junctions5,6,7,8,9 has enabled studies of the relationship between thermoelectricity and molecular structure10,11. However, observations of Peltier cooling in molecular junctions—a critical step for establishing molecular-based refrigeration—have remained inaccessible. Here, we report direct experimental observations of Peltier cooling in molecular junctions. By integrating conducting-probe atomic force microscopy12,13 with custom-fabricated picowatt-resolution calorimetric microdevices, we created an experimental platform that enables the unified characterization of electrical, thermoelectric and energy dissipation characteristics of molecular junctions. Using this platform, we studied gold junctions with prototypical molecules (Au–biphenyl-4,4′-dithiol–Au, Au–terphenyl-4,4′′-dithiol–Au and Au–4,4′-bipyridine–Au) and revealed the relationship between heating or cooling and charge transmission characteristics. Our experimental conclusions are supported by self-energy-corrected density functional theory calculations. We expect these advances to stimulate studies of both thermal and thermoelectric transport in molecular junctions where the possibility of extraordinarily efficient energy conversion has been theoretically predicted2,3,4,14.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Probing cooling in molecular junctions.
Fig. 2: Observation of Peltier cooling in Au–BPDT–Au junctions.
Fig. 3: Measured Peltier effect in Au–TPDT–Au, Au–Au and Au–BP–Au junctions.
Fig. 4: Computed heating/cooling effect in the molecular junctions used in this experiment.

References

  1. 1.

    Dubi, Y. & Di Ventra, M. Colloquium: Heat flow and thermoelectricity in atomic and molecular junctions. Rev. Mod. Phys. 83, 131–155 (2011).

    Article  Google Scholar 

  2. 2.

    Finch, C. M., García-Suárez, V. M. & Lambert, C. J. Giant thermopower and figure of merit in single-molecule devices. Phys. Rev. B 79, 033405 (2009).

    Article  Google Scholar 

  3. 3.

    Bergfield, J. P., Solis, M. A. & Stafford, C. A. Giant thermoelectric effect from transmission supernodes. ACS Nano 4, 5314–5320 (2010).

    Article  Google Scholar 

  4. 4.

    Karlström, O., Linke, H., Karlström, G. & Wacker, A. Increasing thermoelectric performance using coherent transport. Phys. Rev. B 84, 113415 (2011).

    Article  Google Scholar 

  5. 5.

    Kim, Y., Jeong, W., Kim, K., Lee, W. & Reddy, P. Electrostatic control of thermoelectricity in molecular junctions. Nat. Nanotech. 9, 881–885 (2014).

    Article  Google Scholar 

  6. 6.

    Li, Y., Xiang, L., Palma, J., Asai, Y. & Tao, N. J. Thermoelectric effect and its dependence on molecular length and sequence in single DNA molecules. Nat. Commun. 7, 11294 (2016).

    Article  Google Scholar 

  7. 7.

    Reddy, P., Jang, S. Y., Segalman, R. A. & Majumdar, A. Thermoelectricity in molecular junctions. Science 315, 1568–1571 (2007).

    Article  Google Scholar 

  8. 8.

    Rincón-García, L. et al. Molecular design and control of fullerene-based bi-thermoelectric materials. Nat. Mater. 15, 289–293 (2016).

    Article  Google Scholar 

  9. 9.

    Widawsky, J. R., Darancet, P., Neaton, J. B. & Venkataraman, L. Simultaneous determination of conductance and thermopower of single molecule junctions. Nano Lett. 12, 354–358 (2012).

    Article  Google Scholar 

  10. 10.

    Aradhya, S. V. & Venkataraman, L. Single-molecule junctions beyond electronic transport. Nat. Nanotech. 8, 399–410 (2013).

    Article  Google Scholar 

  11. 11.

    Cui, L., Miao, R., Jiang, C., Meyhofer, E. & Reddy, P. Perspective: thermal and thermoelectric transport in molecular junctions. J. Chem. Phys. 146, 092201 (2017).

    Article  Google Scholar 

  12. 12.

    Tan, A. et al. Effect of length and contact chemistry on the electronic structure and thermoelectric properties of molecular junctions. J. Am. Chem. Soc. 133, 8838–8841 (2011).

    Article  Google Scholar 

  13. 13.

    Tan, A., Sadat, S. & Reddy, P. Measurement of thermopower and current-voltage characteristics of molecular junctions to identify orbital alignment. Appl. Phys. Lett. 96, 013110 (2010).

    Article  Google Scholar 

  14. 14.

    Sadeghi, H., Sangtarash, S. & Lambert, C. J. Oligoyne molecular junctions for efficient room temperature thermoelectric power generation. Nano Lett. 15, 7467–7472 (2015).

    Article  Google Scholar 

  15. 15.

    Callen, H. B. Thermodynamics: An Introduction to the Physical Theories of Equilibrium Thermostatics and Irreversible Thermodynamics (Wiley, New York, 1960).

  16. 16.

    Rowe, D. M. Thermoelectrics Handbook: Macro to Nano (CRC/Taylor & Francis, Boca Raton, 2006).

  17. 17.

    Huang, Z. et al. Local ionic and electron heating in single-molecule junctions. Nat. Nanotech. 2, 698–703 (2007).

    Article  Google Scholar 

  18. 18.

    Ioffe, Z. et al. Detection of heating in current-carrying molecular junctions by Raman scattering. Nat. Nanotech. 3, 727–732 (2008).

    Article  Google Scholar 

  19. 19.

    Ward, D. R., Corley, D. A., Tour, J. M. & Natelson, D. Vibrational and electronic heating in nanoscale junctions. Nat. Nanotech. 6, 33–38 (2011).

    Article  Google Scholar 

  20. 20.

    Lee, W. et al. Heat dissipation in atomic-scale junctions. Nature 498, 209–212 (2013).

    Article  Google Scholar 

  21. 21.

    Zotti, L. A. et al. Heat dissipation and its relation to thermopower in single-molecule junctions. New. J. Phys. 16, 015004 (2014).

    Article  Google Scholar 

  22. 22.

    Galperin, M., Saito, K., Balatsky, A. V. & Nitzan, A. Cooling mechanisms in molecular conduction junctions. Phys. Rev. B 80, 115427 (2009).

    Article  Google Scholar 

  23. 23.

    Wold, D. J. & Frisbie, C. D. Fabrication and characterization of metal–molecule–metal junctions by conducting probe atomic force microscopy. J. Am. Chem. Soc. 123, 5549–5556 (2001).

    Article  Google Scholar 

  24. 24.

    Choi, S. H., Kim, B. & Frisbie, C. D. Electrical resistance of long conjugated molecular wires. Science 320, 1482–1486 (2008).

    Article  Google Scholar 

  25. 25.

    Pauly, F. et al. Cluster-based density-functional approach to quantum transport through molecular and atomic contacts. New. J. Phys. 10, 125019 (2008).

    Article  Google Scholar 

  26. 26.

    Quek, S. Y. et al. Amine–gold linked single-molecule circuits: experiment and theory. Nano Lett. 7, 3477–3482 (2007).

    Article  Google Scholar 

  27. 27.

    Segal, D. & Agarwalla, B. K. Vibrational heat transport in molecular junctions. Annu. Rev. Phys. Chem. 67, 185–209 (2016).

    Article  Google Scholar 

  28. 28.

    Cui, L. et al. Quantized thermal transport in single-atom junctions. Science 355, 1192–1195 (2017).

    Article  Google Scholar 

  29. 29.

    Klöckner, J. C., Siebler, R., Cuevas, J. C. & Pauly, F. Thermal conductance and thermoelectric figure of merit of C60-based single-molecule junctions: electrons, phonons, and photons. Phys. Rev. B 95, 245404 (2017).

    Article  Google Scholar 

  30. 30.

    Lin, S. F. & Leonard, W. F. Thermoelectric power of thin gold films. J. Appl. Phys. 42, 3634–3639 (1971).

    Article  Google Scholar 

  31. 31.

    Ahlrichs, R., Bar, M., Haser, M., Horn, H. & Kolmel, C. Electronic-structure calculations on workstation computers — the program system TURBOMOLE. Chem. Phys. Lett. 162, 165–169 (1989).

    Article  Google Scholar 

  32. 32.

    Perdew, J. P. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys. Rev. B 33, 8822–8824 (1986).

    Article  Google Scholar 

  33. 33.

    Schafer, A., Horn, H. & Ahlrichs, R. Fully optimized contracted Gaussian-basis sets for atoms Li to Kr. J. Chem. Phys. 97, 2571–2577 (1992).

    Article  Google Scholar 

Download references

Acknowledgements

P.R. and E.M. acknowledge funding from the Office of Naval Research (N00014-16-1-2672, instrumentation), the Department of Energy (DE-SC0004871, scanning probe microscopy), and the National Science Foundation (CBET 1509691, ECCS 1407967, calorimetry). L.A.Z. and J.C.C. acknowledge funding from the Spanish MINECO (projects MAT2014-58982-JIN and FIS2014-53488-P, and FIS2017-84057-P). J.C.C. also thanks the Deutsche Forschungsgemeinschaft, the research programme SFB767 for sponsoring his stay at the University of Konstanz as Mercator Fellow. We acknowledge the Lurie Nanofabrication Facility and Michigan Center for Materials Characterization for facilitating the fabrication and calibration of devices.

Author information

Affiliations

Authors

Contributions

P.R., E.M. and J.C.C. conceived the work. L.C., R.M. and K.W. performed the experiments. D.T. designed and fabricated the devices. L.A.Z. performed the calculations. The manuscript was written by L.C., P.R., E.M. and J.C.C. with comments and inputs from all authors.

Corresponding authors

Correspondence to Juan Carlos Cuevas or Edgar Meyhofer or Pramod Reddy.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary information

Supplementary Figures 1–10 and Supplementary Table 1.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Cui, L., Miao, R., Wang, K. et al. Peltier cooling in molecular junctions. Nature Nanotech 13, 122–127 (2018). https://doi.org/10.1038/s41565-017-0020-z

Download citation

Further reading

Search

Quick links

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