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.

Colloidal-quantum-dot photovoltaics using atomic-ligand passivation

Nature Materials volume 10, pages 765–771 (2011)Cite this article

Subjects

Abstract

Colloidal-quantum-dot (CQD) optoelectronics offer a compelling combination of solution processing and spectral tunability through quantum size effects. So far, CQD solar cells have relied on the use of organic ligands to passivate the surface of the semiconductor nanoparticles. Although inorganic metal chalcogenide ligands have led to record electronic transport parameters in CQD films, no photovoltaic device has been reported based on such compounds. Here we establish an atomic ligand strategy that makes use of monovalent halide anions to enhance electronic transport and successfully passivate surface defects in PbS CQD films. Both time-resolved infrared spectroscopy and transient device characterization indicate that the scheme leads to a shallower trap state distribution than the best organic ligands. Solar cells fabricated following this strategy show up to 6% solar AM1.5G power-conversion efficiency. The CQD films are deposited at room temperature and under ambient atmosphere, rendering the process amenable to low-cost, roll-by-roll fabrication.

Your institute does not have access to this article

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

Buy

All prices are NET prices.

Figure 1: Organic and atomic passivation strategies.
Figure 2: Materials characterization following halide anion treatment.
Figure 3: Photovoltaic device physics and performance.
Figure 4: TRIR characterization of Br−-capped PbS CQD film.
Figure 5: Light-intensity-dependent photovoltaic performance and frequency dependent photodiode performance.

References

  1. Konstantatos, G. et al. Ultrasensitive solution-cast quantum dot photodetectors. Nature 442, 180–183 (2006).

    CAS  Article  Google Scholar 

  2. Konstantatos, G., Clifford, J., Levina, L. & Sargent, E. H. Sensitive solution-processed visible-wavelength photodetectors. Nature Photon. 1, 531–534 (2007).

    CAS  Article  Google Scholar 

  3. Sukhovatkin, V., Hinds, S., Brzozowski, L. & Sargent, E. H. Colloidal quantum-dot photodetectors exploiting multiexciton generation. Science 324, 1542–1544 (2009).

    CAS  Article  Google Scholar 

  4. Coe, S., Woo, W. K., Bawendi, M. & Bulovic, V. Electroluminescence from single monolayers of nanocrystals in molecular organic devices. Nature 420, 800–803 (2002).

    CAS  Article  Google Scholar 

  5. Klimov, V. I. et al. Optical gain and stimulated emission in nanocrystal quantum dots. Science 290, 314–317 (2000).

    CAS  Article  Google Scholar 

  6. Tang, J. A. & Sargent, E. H. Infrared colloidal quantum dots for photovoltaics: Fundamentals and recent progress. Adv. Mater. 23, 12–29 (2011).

    CAS  Article  Google Scholar 

  7. Henry, C. H. Limiting efficiencies of ideal single and multiple energy-gap terrestrial solar-cells. J. Appl. Phys. 51, 4494–4500 (1980).

    CAS  Article  Google Scholar 

  8. King, R. R. Multijunction cells—record breakers. Nature Photon. 2, 284–286 (2008).

    CAS  Article  Google Scholar 

  9. Murray, C. B., Kagan, C. R. & Bawendi, M. G. Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu. Rev. Mater. Sci. 30, 545–610 (2000).

    CAS  Article  Google Scholar 

  10. Klem, E. J. D. et al. Impact of dithiol treatment and air annealing on the conductivity, mobility, and hole density in PbS colloidal quantum dot solids. Appl. Phys. Lett. 92, 212105 (2008).

    Article  Google Scholar 

  11. Luther, J. M. et al. Schottky solar cells based on colloidal nanocrystal films. Nano Lett. 8, 3488–3492 (2008).

    CAS  Article  Google Scholar 

  12. Koleilat, G. I. et al. Efficient, stable infrared photovoltaics based on solution-cast colloidal quantum dots. ACS Nano 2, 833–840 (2008).

    CAS  Article  Google Scholar 

  13. Talapin, D. V. & Murray, C. B. PbSe nanocrystal solids for n- and p-channel thin film field-effect transistors. Science 310, 86–89 (2005).

    CAS  Article  Google Scholar 

  14. Pattantyus-Abraham, A. G. et al. Depleted-heterojunction colloidal quantum dot solar cells. ACS Nano 4, 3374–3380 (2010).

    CAS  Article  Google Scholar 

  15. Kovalenko, M. V., Scheele, M. & Talapin, D. V. Colloidal nanocrystals with molecular metal chalcogenide surface ligands. Science 324, 1417–1420 (2009).

    CAS  Article  Google Scholar 

  16. Kovalenko, M. V., Bodnarchuk, M. I., Zaumseil, J., Lee, J. S. & Talapin, D. V. Expanding the chemical versatility of colloidal nanocrystals capped with molecular metal chalcogenide ligands. J. Am. Chem. Soc. 132, 10085–10092 (2010).

    CAS  Article  Google Scholar 

  17. Lee, J. S., Kovalenko, M. V., Huang, J., Chung, D. S. & Talapin, D. V. Band-like transport, high electron mobility and high photoconductivity in all-inorganic nanocrystal arrays. Nature Nanotech. 6, 348–352 (2011).

    CAS  Article  Google Scholar 

  18. Bryant, G. W. & Jaskolski, W. Surface effects on capped and uncapped nanocrystals. J. Phys. Chem. B 109, 19650–19656 (2005).

    CAS  Article  Google Scholar 

  19. Gai, Y. Q., Peng, H. W. & Li, J. B. Electronic properties of nonstoichiometric PbSe quantum dots from first principles. J. Phys. Chem. C 113, 21506–21511 (2009).

    CAS  Article  Google Scholar 

  20. Owen, J. S., Park, J., Trudeau, P. E. & Alivisatos, A. P. Reaction chemistry and ligand exchange at cadmium–selenide nanocrystal surfaces. J. Am. Chem. Soc. 130, 12279–12280 (2008).

    CAS  Article  Google Scholar 

  21. Tang, J. et al. Quantum dot photovoltaics in the extreme quantum confinement regime: The surface-chemical origins of exceptional air- and light-stability. ACS Nano 4, 869–878 (2010).

    CAS  Article  Google Scholar 

  22. Fernee, M. J. et al. Inorganic surface passivation of PbS nanocrystals resulting in strong photoluminescent emission. Nanotechnology 14, 991–997 (2003).

    CAS  Article  Google Scholar 

  23. Pietryga, J. M. et al. Utilizing the lability of lead selenide to produce heterostructured nanocrystals with bright, stable infrared emission. J. Am. Chem. Soc. 130, 4879–4885 (2008).

    CAS  Article  Google Scholar 

  24. Robinson, R. D. et al. Spontaneous superlattice formation in nanorods through partial cation exchange. Science 317, 355–358 (2007).

    CAS  Article  Google Scholar 

  25. Schapotschnikow, P., Hommersom, B. & Vlugt, T. J. H. Adsorption and binding of ligands to CdSe nanocrystals. J. Phys. Chem. C 113, 12690–12698 (2009).

    CAS  Article  Google Scholar 

  26. Fritzinger, B., Capek, R. K., Lambert, K., Martins, J. C. & Hens, Z. Utilizing self-exchange to address the binding of carboxylic acid ligands to CdSe quantum dots. J. Am. Chem. Soc. 132, 10195–10201 (2010).

    CAS  Article  Google Scholar 

  27. Luther, J. M. et al. Structural, optical and electrical properties of self-assembled films of PbSe nanocrystals treated with 1,2-ethanedithiol. ACS Nano 2, 271–280 (2008).

    CAS  Article  Google Scholar 

  28. Zhao, N. et al. Colloidal PbS quantum dot solar cells with high fill factor. ACS Nano 4, 3743–3752 (2010).

    CAS  Article  Google Scholar 

  29. Hanrath, T., Choi, J. J. & Smilgies, D. M. Structure/processing relationships of highly ordered lead salt nanocrystal superlattices. ACS Nano 3, 2975–2988 (2009).

    CAS  Article  Google Scholar 

  30. Moreels, I., Fritzinger, B., Martins, J. C. & Hens, Z. Surface chemistry of colloidal PbSe nanocrystals. J. Am. Chem. Soc. 130, 15081–15086 (2008).

    CAS  Article  Google Scholar 

  31. Nefedov, V. I. A comparison of results of an ESCA study of nonconducting solids using spectrometers of different constructions. J. Electron Spectrosc. Relat. Phenom. 25, 29–47 (1982).

    CAS  Article  Google Scholar 

  32. Kang, M. S., Lee, J., Norris, D. J. & Frisbie, C. D. High carrier densities achieved at low voltages in ambipolar PbSe nanocrystal thin-film transistors. Nano Lett. 9, 3848–3852 (2009).

    CAS  Article  Google Scholar 

  33. Liu, Y. et al. Dependence of carrier mobility on nanocrystal size and ligand length in PbSe nanocrystal solids. Nano Lett. 10, 1960–1969 (2010).

    CAS  Article  Google Scholar 

  34. Luther, J. M. et al. Stability assessment on a 3% bilayer PbS/ZnO quantum dot heterojunction solar cell. Adv. Mater. 22, 3704–3707 (2010).

    CAS  Article  Google Scholar 

  35. Zaban, A., Meier, A. & Gregg, B. A. Electric potential distribution and short-range screening in nanoporous TiO2 electrodes. J. Phys. Chem. B 101, 7985–7990 (1997).

    CAS  Article  Google Scholar 

  36. Zhong, H. Z. et al. Noninjection gram-scale synthesis of monodisperse pyramidal CuInS2 nanocrystals and their size-dependent properties. ACS Nano 4, 5253–5262 (2010).

    CAS  Article  Google Scholar 

  37. Zhang, J. & Jiang, X. M. Confinement-dependent below-gap state in PbS quantum dot films probed by continuous-wave photoinduced absorption. J. Phys. Chem. B 112, 9557–9560 (2008).

    CAS  Article  Google Scholar 

  38. Guyot-Sionnest, P., Shim, M., Matranga, C. & Hines, M. Intraband relaxation in CdSe quantum dots. Phys. Rev. B 60, R2181–R2184 (1999).

    CAS  Article  Google Scholar 

  39. Riedel, I. et al. Effect of temperature and illumination on the electrical characteristics of polymer-fullerene bulk-heterojunction solar cells. Adv. Funct. Mater. 14, 38–44 (2004).

    CAS  Article  Google Scholar 

  40. Clifford, J. P. et al. Fast, sensitive and spectrally tuneable colloidal quantum-dot photodetectors. Nature Nanotech. 4, 40–44 (2009).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This publication is based in part on work supported by Award No. KUS–11–009-21, made by King Abdullah University of Science and Technology (KAUST). We thank Angstrom Engineering and Innovative Technologies for useful discussions concerning material deposition methods and control of the glovebox environment, respectively. The authors thank H. Zhong, R. Li, L. Brzozowski, V. Sukhovatkin, A. Barkhouse, I. Kramer, G. Koleilat, E. Palmiano and R. Wolowiec for their help during the course of study. R.D. acknowledges the financial support of e8 scholarship. K.S.J. and J.B.A. gratefully acknowledge partial support from the Petroleum Research Fund (PRF #49639-ND6), the National Science Foundation (CHE 0846241), and the Office of Naval Research (N00014-11-1-0239).

Author information

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, 10 King’s College Road, Toronto, Ontario, M5S 3G4, Canada

    Jiang Tang, Kyle W. Kemp, Sjoerd Hoogland, Huan Liu, Larissa Levina, Melissa Furukawa, Xihua Wang, Ratan Debnath, Armin Fischer & Edward H. Sargent

  2. Department of Chemistry, The Pennsylvania State University, 104 Chemistry Building, University Park, Pennsylvania 16802, USA

    Kwang S. Jeong & John B. Asbury

  3. Department of Electronic Science & Technology, Huazhong University of Science & Technology, Wuhan, 430074, China

    Huan Liu

  4. Advanced Nanofabrication, Imaging and Characterization Laboratory, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia

    Dongkyu Cha

  5. Division of Physical Sciences and Engineering, Materials Science and Engineering Program, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia

    Kang Wei Chou & Aram Amassian

Authors
  1. Jiang Tang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kyle W. Kemp
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sjoerd Hoogland
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kwang S. Jeong
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Huan Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Larissa Levina
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Melissa Furukawa
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Xihua Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Ratan Debnath
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Dongkyu Cha
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Kang Wei Chou
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Armin Fischer
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Aram Amassian
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. John B. Asbury
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Edward H. Sargent
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.T. and E.H.S. designed and directed this study and analysed the experimental results. J.T. contributed to all the experimental work. K.W.K. and S.H. carried out the photodiode work and K.W.K. assisted in all the experimental work. K.S.J. and J.B.A. carried out the TRIR experiments and analysed the data. H.L. fabricated the TiO2 electrodes. L.L. synthesized the PbS CQDs. K.W.K., L.L. and R.D. contributed to the solution Cd treatment experiment. D.C, K.W.C. and A.A. carried out the GISAXS and TEM measurements and analysed the data. S.H., M.F., X.W., H.L., A.F. and R.D. assisted in device fabrication and characterization. J.T., J.B.A. and E.H.S. wrote the manuscript. All authors commented on the paper.

Corresponding author

Correspondence to Edward H. Sargent.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 3343 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Tang, J., Kemp, K., Hoogland, S. et al. Colloidal-quantum-dot photovoltaics using atomic-ligand passivation. Nature Mater 10, 765–771 (2011). https://doi.org/10.1038/nmat3118

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat3118

Further reading

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