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.

Multiple exciton generation for photoelectrochemical hydrogen evolution reactions with quantum yields exceeding 100%

Abstract

Multiple exciton generation (MEG) in quantum dots (QDs) has the potential to greatly increase the power conversion efficiency in solar cells and in solar-fuel production. During the MEG process, two electron–hole pairs (excitons) are created from the absorption of one high-energy photon, bypassing hot-carrier cooling via phonon emission. Here we demonstrate that extra carriers produced via MEG can be used to drive a chemical reaction with quantum efficiency above 100%. We developed a lead sulfide (PbS) QD photoelectrochemical cell that is able to drive hydrogen evolution from aqueous Na2S solution with a peak external quantum efficiency exceeding 100%. QD photoelectrodes that were measured all demonstrated MEG when the incident photon energy was larger than 2.7 times the bandgap energy. Our results demonstrate a new direction in exploring high-efficiency approaches to solar fuels.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: MEG PEC cell illustration.
Figure 2: PEC performance characteristics.
Figure 3: IPCE front and back illumination.
Figure 4: Absorbed photon-to-current efficiency measurements.

References

  1. 1

    Lewis, N. S. Research opportunities to advance solar energy utilization. Science 351, aad1920 (2016).

    Article  Google Scholar 

  2. 2

    Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).

    Article  Google Scholar 

  3. 3

    Ross, R. T. & Nozik, A. J. Efficiency of hot-carrier solar energy converters. J. Appl. Phys. 53, 3813–3818 (1982).

    Article  Google Scholar 

  4. 4

    Klimov, V. I. Multicarrier interactions in semiconductor nanocrystals in relation to the phenomena of Auger recombination and carrier multiplication. Annu. Rev. Condens. Matter Phys. 5, 285–316 (2014).

    Article  Google Scholar 

  5. 5

    Sambur, J. B., Novet, T. & Parkinson, B. A. Multiple exciton collection in a sensitized photovoltaic system. Science 330, 63–66 (2010).

    Article  Google Scholar 

  6. 6

    Semonin, O. E. et al. Peak external photocurrent quantum efficiency exceeding 100% via MEG in a quantum dot solar cell. Science 334, 1530–1533 (2011).

    Article  Google Scholar 

  7. 7

    Davis, N. J. L. K. et al. Multiple-exciton generation in lead selenide nanorod solar cells with external quantum efficiencies exceeding 120%. Nat. Commun. 6, 8259 (2015).

    Article  Google Scholar 

  8. 8

    Böhm, M. L. et al. Lead telluride quantum dot solar cells displaying external quantum efficiencies exceeding 120%. Nano Lett. 15, 7987–7993 (2015).

    Article  Google Scholar 

  9. 9

    Han, Z., Qiu, F., Eisenberg, R., Holland, P. L. & Krauss, T. D. Robust photogeneration of H2 in water using semiconductor nanocrystals and a nickel catalyst. Science 338, 1321–1324 (2012).

    Article  Google Scholar 

  10. 10

    Seol, M., Jang, J.-W., Cho, S., Lee, J. S. & Yong, K. Highly efficient and stable cadmium chalcogenide quantum dot/ZnO nanowires for photoelectrochemical hydrogen generation. Chem. Mater. 25, 184–189 (2012).

    Article  Google Scholar 

  11. 11

    Kim, H., Seol, M., Lee, J. & Yong, K. Highly efficient photoelectrochemical hydrogen generation using hierarchical ZnO/WOx nanowires cosensitized with CdSe/CdS. J. Phys. Chem. C 115, 25429–25436 (2011).

    Article  Google Scholar 

  12. 12

    Trevisan, R. et al. Harnessing infrared photons for photoelectrochemical hydrogen generation. A PbS quantum dot based “quasi-artificial leaf”. J. Phys. Chem. Lett. 4, 141–146 (2012).

    Article  Google Scholar 

  13. 13

    Yan, H. et al. Visible-light-driven hydrogen production with extremely high quantum efficiency on Pt–PdS/CdS photocatalyst. J. Catalys. 266, 165–168 (2009).

    Article  Google Scholar 

  14. 14

    Lai, L.-H., Gomulya, W., Protesescu, L., Kovalenko, M. V. & Loi, M. A. High performance photoelectrochemical hydrogen generation and solar cells with a double type II heterojunction. Phys. Chem. Chem. Phys. 16, 7531–7537 (2014).

    Article  Google Scholar 

  15. 15

    Ma, G. et al. Direct splitting of H2S into H2 and S on CdS-based photocatalyst under visible light irradiation. J. Catalys. 260, 134–140 (2008).

    Article  Google Scholar 

  16. 16

    Crisp, R. W. et al. Metal halide solid-state surface treatment for high efficiency PbS and PbSe QD solar cells. Sci. Rep. 5, 9945 (2015).

    Article  Google Scholar 

  17. 17

    Zhang, J. et al. Preparation of Cd/Pb chalcogenide heterostructured janus particles via controllable cation exchange. ACS Nano. 9, 8157–8164 (2015).

    Article  Google Scholar 

  18. 18

    Stewart, J. T. et al. Comparison of carrier multiplication yields in PbS and PbSe nanocrystals: the role of competing energy-loss processes. Nano Lett. 12, 622–628 (2012).

    Article  Google Scholar 

  19. 19

    Shockley, W. & Queisser, H. J. Detailed balance limit of efficiency of p–n junction solar cells. J. Appl. Phys. 32, 510–519 (1961).

    Article  Google Scholar 

  20. 20

    Hanna, M. C. & Nozik, A. J. Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers. J. Appl. Phys. 100, 074510 (2006).

  21. 21

    Khaselev, O. & Turner, J. A. A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting. Science 280, 425–427 (1998).

    Article  Google Scholar 

  22. 22

    Gu, J. et al. p-Type CuRhO2 as a self-healing photoelectrode for water reduction under visible light. J. Am. Chem. Soc. 136, 830–833 (2014).

    Article  Google Scholar 

  23. 23

    Gu, J. et al. Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst. Nat. Mater. 15, 456–460 (2015).

    Article  Google Scholar 

  24. 24

    White, J. L. et al. Light-driven heterogeneous reduction of carbon dioxide: photocatalysts and photoelectrodes. Chem. Rev. 115, 12888–12935 (2015).

    Article  Google Scholar 

  25. 25

    Cirloganu, C. M. et al. Enhanced carrier multiplication in engineered quasi-type-II quantum dots. Nat. Commun. 5, 4148 (2014).

    Article  Google Scholar 

  26. 26

    Chernomordik, B. D., Marshall, A. R., Pach, G. F., Luther, J. M. & Beard, M. C. Quantum dot solar cell fabrication protocols. Chem. Mater. 29, 189–198 (2017).

    Article  Google Scholar 

  27. 27

    Gu, J. et al. A graded catalytic-protective layer for an efficient and stable water-splitting photocathode. Nat. Energy 2, 16192 (2017).

    Article  Google Scholar 

Download references

Acknowledgements

We would like to thank B. To and C. Xiao from NREL for the scanning electron micrographs. A. J. Nozik, J. Luther, D. Kroupa and Y. Yang are thanked for their helpful discussions. Y.Y. would like to acknowledge the support from the startup fund at New Jersey Institute of Technology. Y.Y., R.W.C., B.D.C., G.F.P., A.R.M. and M.C.B. acknowledge support from the Center for Advanced Solar Photophysics, an Energy Frontier Research Center funded by the Office of Basic Energy Sciences within the Office of Science. J.G. and J.A.T. acknowledge the solar photochemistry programme within the division of Chemical Sciences,Geosciences, and Biosciences of the Office of Basic Energy Sciences within the Office of Science. All work is supported by the Department of Energy under contract No. DE-AC36-08GO28308 to NREL.

Author information

Affiliations

Authors

Contributions

Y.Y. and M.C.B. conceived the experiments and led the project; Y.Y. and J.G. carried out the photoelectrode synthesis and characterization and photoelectrochemical investigation; R.W.C., B.D.C., G.F.P. and A.R.M. carried out quantum-dot synthesis and film preparation; Y.Y., J.A.T. and M.C.B. analysed the data; Y.Y. and M.C.B. wrote the manuscript with input and discussion from all authors.

Corresponding authors

Correspondence to Yong Yan or Matthew C. Beard.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Figures 1–3, Supplementary Tables 1–3, Supplementary Note 1 (PDF 933 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Yan, Y., Crisp, R., Gu, J. et al. Multiple exciton generation for photoelectrochemical hydrogen evolution reactions with quantum yields exceeding 100%. Nat Energy 2, 17052 (2017). https://doi.org/10.1038/nenergy.2017.52

Download citation

Further reading

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