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Carrier-resolved photo-Hall effect

Nature volume 575, pages 151–155 (2019)Cite this article

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Abstract

The fundamental parameters of majority and minority charge carriers—including their type, density and mobility—govern the performance of semiconductor devices yet can be difficult to measure. Although the Hall measurement technique is currently the standard for extracting the properties of majority carriers, those of minority carriers have typically only been accessible through the application of separate techniques. Here we demonstrate an extension to the classic Hall measurement—a carrier-resolved photo-Hall technique—that enables us to simultaneously obtain the mobility and concentration of both majority and minority carriers, as well as the recombination lifetime, diffusion length and recombination coefficient. This is enabled by advances in a.c.-field Hall measurement using a rotating parallel dipole line system and an equation, ΔμH = d(σ2H)/dσ, which relates the hole–electron Hall mobility difference (ΔμH), the conductivity (σ) and the Hall coefficient (H). We apply this technique to various solar absorbers—including high-performance lead-iodide-based perovskites—and demonstrate simultaneous access to majority and minority carrier parameters and map the results against varying light intensities. This information, which is buried within the photo-Hall measurement1,2, had remained inaccessible since the original discovery of the Hall effect in 18793. The simultaneous measurement of majority and minority carriers should have broad applications, including in photovoltaics and other optoelectronic devices.

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Fig. 1: The carrier-resolved photo-Hall measurement.
Fig. 2: Carrier-resolved photo-Hall analysis in a high-performance perovskite film.
Fig. 3: Carrier-resolved photo-Hall analysis in a single-crystal p-silicon sample.

Data availability

The datasets generated and analysed during the current study are available from the corresponding author on reasonable request.

References

  1. Fowler, A. Photo-Hall effect in CdSe sintered photoconductors. J. Phys. Chem. Solids 22, 181–188 (1961).

    Article  CAS  ADS  Google Scholar 

  2. Dresner, J. The photo-Hall effect in vitreous selenium. J. Phys. Chem. Solids 25, 505–511 (1964).

    Article  CAS  ADS  Google Scholar 

  3. Hall, E. H. On a new action of the magnet on electric currents. Am. J. Math. 2, 287–292 (1879).

    Article  MathSciNet  Google Scholar 

  4. Klitzing, K. v., Dorda, G. & Pepper, M. New method for high-accuracy determination of the fine-structure constant based on quantized Hall resistance. Phys. Rev. Lett. 45, 494–497 (1980).

    Article  ADS  Google Scholar 

  5. Tsui, D. C., Stormer, H. L. & Gossard, A. C. Two-dimensional magnetotransport in the extreme quantum limit. Phys. Rev. Lett. 48, 1559–1562 (1982).

    Article  CAS  ADS  Google Scholar 

  6. Ponseca, C. S., Jr et al. Organometal halide perovskite solar cell materials rationalized: ultrafast charge generation, high and microsecond-long balanced mobilities, and slow recombination. J. Am. Chem. Soc. 136, 5189–5192 (2014).

    Article  CAS  Google Scholar 

  7. Leijtens, T. et al. Electronic properties of meso-superstructured and planar organometal halide perovskite films: charge trapping, photodoping, and carrier mobility. ACS Nano 8, 7147–7155 (2014).

    Article  CAS  Google Scholar 

  8. Xing, G. et al. Long-range balanced electron-and hole-transport lengths in organic-inorganic CH3NH3PbI3. Science 342, 344–347 (2013).

    Article  CAS  ADS  Google Scholar 

  9. Stranks, S. D. et al. Electron–hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013).

    Article  CAS  ADS  Google Scholar 

  10. Wehrenfennig, C., Liu, M., Snaith, H. J., Johnston, M. B. & Herz, L. M. Charge-carrier dynamics in vapour-deposited films of the organolead halide perovskite CH3NH3PbI3−xClx. Energy Environ. Sci. 7, 2269–2275 (2014).

    Article  CAS  Google Scholar 

  11. Shi, D. et al. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 347, 519–522 (2015).

    Article  CAS  ADS  Google Scholar 

  12. Dong, Q. et al. Electron–hole diffusion lengths >175 μm in solution-grown CH3NH3PbI3 single crystals. Science 347, 967–970 (2015).

    Article  CAS  ADS  Google Scholar 

  13. Chen, Y. et al. Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements. Nat. Commun. 7, 12253 (2016).

    Article  CAS  ADS  Google Scholar 

  14. Gokmen, T., Gunawan, O. & Mitzi, D. B. Minority carrier diffusion length extraction in Cu2ZnSn(Se,S)4 solar cells. J. Appl. Phys. 114, 114511 (2013).

    Article  ADS  Google Scholar 

  15. National Renewable Energy Laboratories. Best research-cell efficiencies https://www.nrel.gov/pv/cell-efficiency.html (2019).

  16. Tan, Z.-K. et al. Bright light-emitting diodes based on organometal halide perovskite. Nat. Nanotech. 9, 687–692 (2014).

    Article  CAS  ADS  Google Scholar 

  17. Dou, L. et al. Solution-processed hybrid perovskite photodetectors with high detectivity. Nat. Commun. 5, 5404 (2014).

    Article  CAS  ADS  Google Scholar 

  18. Gunawan, O., Virgus, Y. & Tai, K. F. A parallel dipole line system. Appl. Phys. Lett. 106, 062407 (2015).

    Article  ADS  Google Scholar 

  19. Sze, S. M. & Ng, K. K. Physics of Semiconductor Devices 3rd edn (John Wiley & Sons, 2006).

  20. Schroder, D. K. Semiconductor Material and Device Characterization 3rd edn (John Wiley & Sons, 2006).

  21. Gunawan, O. & Gokmen, T. Hall measurement system with rotary magnet. US patent 9,041,389 (2015).

    Google Scholar 

  22. Gunawan, O. & Pereira, M. Rotating magnetic field Hall measurement system. US patent 9,772,385 (2017).

    Google Scholar 

  23. Gunawan, O. & Virgus, Y. The one-dimensional camelback potential in the parallel dipole line trap: Stability conditions and finite size effect. J. Appl. Phys. 121, 133902 (2017).

    Article  ADS  Google Scholar 

  24. Jeon, N. J. et al. Compositional engineering of perovskite materials for high-performance solar cells. Nature 517, 476–480 (2015).

    Article  CAS  ADS  Google Scholar 

  25. Zhang, C. et al. Magnetic field effects in hybrid perovskite devices. Nat. Phys. 11, 427–434 (2015).

    Article  CAS  Google Scholar 

  26. Levine, I. et al. Can we use time-resolved measurements to get steady-state transport data for halide perovskites? J. Appl. Phys. 124, 103103 (2018).

    Article  ADS  Google Scholar 

  27. Wehrenfennig, C., Eperon, G. E., Johnston, M. B., Snaith, H. J. & Herz, L. M. High charge carrier mobilities and lifetimes in organolead trihalide perovskites. Adv. Mater. 26, 1584–1589 (2014).

    Article  CAS  Google Scholar 

  28. Sum, T. C. et al. Spectral features and charge dynamics of lead halide perovskites: origins and interpretations. Acc. Chem. Res. 49, 294–302 (2016).

    Article  CAS  Google Scholar 

  29. Rosling, M., Bleichner, H., Jonsson, P. & Nordlander, E. The ambipolar diffusion coefficient in silicon: dependence on excess-carrier concentration and temperature. J. Appl. Phys. 76, 2855–2859 (1994).

    Article  CAS  ADS  Google Scholar 

  30. Sinton, R. A. & Cuevas, A. Contactless determination of current–voltage characteristics and minority carrier lifetimes in semiconductors from quasi steady state photoconductance data. Appl. Phys. Lett. 69, 2510–2512 (1996).

    Article  CAS  ADS  Google Scholar 

Download references

Acknowledgements

S.R.P. and B.S. acknowledge financial support from the Technology Development Program to Solve Climate Changes of the National Research Foundation (NRF) funded by the Ministry of Science, ICT & Future Planning (no. 2016M1A2A2936757), and from the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea (no. 20173010012980). J.H.N. acknowledges financial support from NRF grants funded by the Korea government (MSIP) (2017R1A2B2009676, 2017R1A4A1015022). D.B.M. and O.G. thank the National Science Foundation for support under grant no. DMR-1709294. We thank S. Guha for managing the IBM photovoltaics program; H. Hamann for support; M. Pereira and K. F. Tai for PDL Hall system development; B. Hekmatshoartabari for the silicon sample; and J. Kim for Supplementary Table 4.

Author information

Authors and Affiliations

  1. IBM T. J. Watson Research Center, Yorktown Heights, NY, USA

    Oki Gunawan, Douglas M. Bishop, Yudistira Virgus, Yun Seog Lee, Xiaoyan Shao & Teodor Todorov

  2. Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon, South Korea

    Seong Ryul Pae & Byungha Shin

  3. Division of Advanced Materials, Korea Research Institute of Chemical Technology, Daejeon, South Korea

    Jun Hong Noh & Nam Joong Jeon

  4. School of Civil, Environmental and Architectural Engineering and Green School, Korea University, Seoul, South Korea

    Jun Hong Noh

  5. Department of Mechanical and Aerospace Engineering, Seoul National University, Seoul, South Korea

    Yun Seog Lee

  6. Department of Mechanical Engineering and Material Science, Duke University, Durham, NC, USA

    David B. Mitzi

  7. Department of Chemistry, Duke University, Durham, NC, USA

    David B. Mitzi

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  1. Oki Gunawan
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Contributions

O.G. and B.S. conceived the project. O.G. led the project, built the experimental setup, programmed the analysis software, derived equation (1) and other formulas, and performed measurement and analyses. S.R.P. prepared samples, and performed optical and Hall measurements and analysis. O.G., S.R.P., B.S. and D.M.B. developed data analysis, interpretation and participated in manuscript writing. Y.V. helped with the development of the PDL system and derivation of the formulae. Y.S.L. and D.M.B. helped with the optical study. N.J.J. and J.H.N. prepared the perovskite samples and solar cells. D.B.M., T.T. and X.S. developed the champion CZTSSe process. D.B.M. managed the IBM photovoltaics program and participated in manuscript writing.

Corresponding authors

Correspondence to Oki Gunawan or Byungha Shin.

Ethics declarations

Competing interests

The PDL Hall system was developed at IBM Research and documented in the following patent families: (1) O. Gunawan & T. Gokmen, US 9,041,389 (ref. 21); (2) O. Gunawan & M. Pereira, US 9,772,385 (ref. 22), US 9,678,040, US 15/581183 and related patent applications (WO 2016162772A1, UK 1717263.6, Japan 2017-552496, Germany 112016000875.9); (3) O. Gunawan, US 15/281,968; (4) O. Gunawan & W. Zhou, US 16/382,937. Patent families (1) and (2) cover the basic a.c. field/PDL Hall system, and (3) and (4) cover the related photo-Hall setup and method.

Additional information

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

Peer review information Nature thanks Henry Snaith and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Extended data figures and tables

Extended Data Fig. 1 Performance of the (FAPbI3)0.88(MAPbBr3)0.12 solar cell device.

a, Current density–voltage (J–V) curves measured by reverse (black) and forward (red) scans. The photovoltaic performance values are summarized in the table. b, The external quantum efficiency spectrum. c, Histogram of the power conversion efficiencies obtained from J–V curves measured by reverse scan (grey) and forward scan (blue), and the average for 80 cells (red).

Supplementary information

Supplementary Information

This file contains Supplementary Text, sections A–H; Supplementary Figures S1–S8; Supplementary Tables 1–4, Supplementary Equations 4–38; and Supplementary References 31–83.

Supplementary Video 1

| Animation of the rotating parallel dipole line (PDL) Hall system and its field evolution The master magnet generates a counterclockwise field rotation (red) while the slave magnet follows synchronously but in the opposite direction, generating a clockwise field rotation (green). This results in a total field (blue) that is unidirectional (always pointing normal to the sample) and single harmonic at the centre where the sample resides.

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Gunawan, O., Pae, S.R., Bishop, D.M. et al. Carrier-resolved photo-Hall effect. Nature 575, 151–155 (2019). https://doi.org/10.1038/s41586-019-1632-2

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