Article

Spin-polarized exciton quantum beating in hybrid organic–inorganic perovskites

  • Nature Physics volume 13, pages 894899 (2017)
  • doi:10.1038/nphys4145
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Abstract

Hybrid organic–inorganic perovskites have emerged as a new class of semiconductors that exhibit excellent performance as active layers in photovoltaic solar cells. These compounds are also highly promising materials for the field of spintronics due to their large and tunable spin–orbit coupling, spin-dependent optical selection rules, and their predicted electrically tunable Rashba spin splitting. Here we demonstrate the optical orientation of excitons and optical detection of spin-polarized exciton quantum beating in polycrystalline films of the hybrid perovskite CH3NH3PbClxI3−x. Time-resolved Faraday rotation measurement in zero magnetic field reveals unexpectedly long spin lifetimes exceeding 1 ns at 4 K, despite the large spin–orbit couplings of the heavy lead and iodine atoms. The quantum beating of exciton states in transverse magnetic fields shows two distinct frequencies, corresponding to two g-factors of 2.63 and −0.33, which we assign to electrons and holes, respectively. These results provide a basic picture of the exciton states in hybrid perovskites, and suggest they hold potential for spintronic applications.

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References

  1. 1.

    & Electronic analog of the eletro-optic modulator. App. Phys. Lett. 56, 665–667 (1990).

  2. 2.

    et al. Spintronics: a spin-based electronics vision for the future. Science 294, 1488–1495 (2001).

  3. 3.

    , & Spintronics: fundamentals and applications. Rev. Mod. Phys. 76, 323–410 (2004).

  4. 4.

    & Challenges for semiconductor spintronics. Nat. Phys. 3, 153–159 (2007).

  5. 5.

    & Lateral drag of spin coherence in gallium arsenide. Nature 397, 139–141 (1999).

  6. 6.

    Theory of electrical spin injection: tunnel contacts as a solution of the conductivity mismatch problem. Phys. Rev. B 62, R16267–R16270 (2000).

  7. 7.

    , , , & Efficient electrical spin injection from a magnetic metal/tunnel barrier contact into a semiconductor. App. Phys. Lett. 80, 1240–1242 (2002).

  8. 8.

    & Spin diffusion and injection in semiconductor structures: electric field effects. Phys. Rev. B 66, 235302 (2002).

  9. 9.

    et al. Electrical detection of spin transport in lateral ferromagnet-semiconductor devices. Nat. Phys. 3, 197–202 (2007).

  10. 10.

    & Performance of a spin-based insulated gate field effect transistor. App. Phys. Lett. 88, 162503 (2006).

  11. 11.

    et al. Control of spin precession in a spin-injected field effect transistor. Science 325, 1515–1518 (2009).

  12. 12.

    et al. Spin-transistor action via tunable Landau–Zener transitions. Science 337, 324–327 (2012).

  13. 13.

    et al. All-electric all-semiconductor spin field-effect transistors. Nat. Nanotech. 10, 35–39 (2015).

  14. 14.

    Silicon spintronics. Nat. Mater. 11, 400–408 (2012).

  15. 15.

    , , & Graphene spintronics. Nat. Nanotech. 9, 794–807 (2014).

  16. 16.

    , , , & Quantum control over single spins in diamond. Annu. Rev. Condens. Matter Phys. 4, 23–50 (2013).

  17. 17.

    , , & Observation of the spin Hall effect in semiconductors. Science 306, 1910–1913 (2004).

  18. 18.

    et al. Fast spin-orbit qubit in an indium antimonide nanowire. Phys. Rev. Lett. 110, 066806 (2013).

  19. 19.

    , , , & Room-temperature reversible spin Hall effect. Phys. Rev. Lett. 98, 156601 (2007).

  20. 20.

    , , & Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 6050–6051 (2009).

  21. 21.

    National renewable energy labs (NREL) efficiency chart (2017);

  22. 22.

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

  23. 23.

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

  24. 24.

    et al. Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors. Nat. Mater. 14, 636–642 (2015).

  25. 25.

    & Metal-halide perovskites for photovoltaic and light-emitting devices. Nat. Nanotech. 10, 391–402 (2015).

  26. 26.

    , , , & Switchable S = 1/2 and J = 1/2 Rashba bands in ferroelectric halide perovskites. Proc. Natl Acad. Sci. USA 111, 6900–6904 (2014).

  27. 27.

    et al. Highly spin-polarized carrier dynamics and ultralarge photoinduced magnetization in CH3NH3PbI3 perovskite thin films. Nano Lett. 15, 1553–1558 (2015).

  28. 28.

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

  29. 29.

    et al. Giant Rashba splitting in CH3NH3PbBr3 organic–inorganic perovskite. Phys. Rev. Lett. 117, 126401 (2016).

  30. 30.

    et al. Spintronics of organometal trihalide perovskites. Preprint at (2016).

  31. 31.

    et al. Rashba and Dresselhaus effects in hybrid organic–inorganic perovskites: from basics to devices. ACS Nano 9, 11557–11567 (2015).

  32. 32.

    et al. The role of chlorine in the formation process of CH3NH3PbI3−xClx perovskite. Adv. Funct. Mater. 24, 7102–7108 (2014).

  33. 33.

    , , & Ultrafast spectroscopy of photoexcitations in organometal trihalide perovskites. Adv. Funct. Mater. 26, 1617–1627 (2016).

  34. 34.

    et al. Qualifying composition dependent p and n self-doping in CH3NH3PbI3. App. Phys. Lett. 105, 163508 (2014).

  35. 35.

    , , , & Charge carrier recombination channels in the low-temperature phase of organic–inorganic lead halide perovskite thin films. APL Mater. 2, 081513 (2014).

  36. 36.

    et al. Excitons versus free charges in organo-lead tri-halide perovskites. Nat. Commun. 5, 3586 (2014).

  37. 37.

    et al. Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites. Nat. Phys. 11, 582–587 (2015).

  38. 38.

    , , & Importance of spin–orbit coupling in hybrid organic/inorganic perovskites for photovoltaic applications. J. Phys. Chem. Lett. 4, 2999–3005 (2013).

  39. 39.

    , , & Spin dynamics in semiconductor nanocrystals. Phys. Rev. B 66, 125307 (2002).

  40. 40.

    et al. Synthesis and crystal chemistry of the hybrid perovskite CH3NH3PbI3 for solid-state sensitised solar cell applications. J. Mater. Chem. A 1, 5628–5641 (2013).

  41. 41.

    Effective-mass model and magneto-optical properties in hybrid perovskites. Sci. Rep. 6, 28576 (2016).

  42. 42.

    , & Excitonic exchange splitting in bulk semiconductors. Phys. Rev. B 59, 5568–5574 (1999).

  43. 43.

    , , & Fine structure of excitons in type-II GaAs/AlAs quantum wells. Phys. Rev. B 41, 5283–5292 (1990).

  44. 44.

    & Nanoscale charge localization induced by random orientations of organic molecules in hybrid perovskite CH3NH3PbI3. Nano Lett. 15, 248–253 (2015).

  45. 45.

    et al. Four-wave mixing in perovskite photovoltaic materials reveals long dephasing times and weaker many-body interactions than GaAs. Preprint at (2016).

  46. 46.

    et al. Exciton fine structure in InGaAs/GaAs quantum dots revisited by pump–probe Faraday rotation. Phys. Rev. B 75, 195325 (2007).

  47. 47.

    & Resonant spin amplification in n-type GaAs. Phys. Rev. Lett. 80, 4313–4316 (1998).

  48. 48.

    , & Spin noise of conduction electrons in n-type bulk GaAs. Phys. Rev. B 79, 035208 (2009).

  49. 49.

    et al. Are mobilities in hybrid organic–inorganic halide perovskites actually “high”? J. Phys. Chem. Lett. 6, 4754–4757 (2015).

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Acknowledgements

We acknowledge M. Raikh and E. Ehrenfreund for helpful discussions. This work is mainly supported by a start-up grant from University of Utah (Low temperature ultrafast and CW optics measurement systems), and in part by the DOE, Office of Science, grant DE-SC0014579 (ultrafast laser, perovskite film synthesis and evaluation). We also acknowledge the NSF Material Science and Engineering Center at the University of Utah (DMR-1121252) for supporting the perovskite growth and device preparation facilities.

Author information

Author notes

    • Patrick Odenthal
    •  & William Talmadge

    These authors contributed equally to this work.

    • Ruizhi Wang

    Present address: School of Electronic and Optical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, China.

Affiliations

  1. Department of Physics and Astronomy, University of Utah, Utah 84112, USA

    • Patrick Odenthal
    • , William Talmadge
    • , Nathan Gundlach
    • , Ruizhi Wang
    • , Chuang Zhang
    • , Dali Sun
    • , Z. Valy Vardeny
    •  & Yan S. Li
  2. ISP/Applied Sciences Laboratory, Washington State University, Spokane, Washington 99210, USA

    • Zhi-Gang Yu

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Contributions

Y.S.L. conceived and supervised the experiments. P.O., W.T., N.G. and R.W. performed the optical measurements and analysed the data. R.W., C.Z. and D.S. prepared the samples, and characterized the crystal structure and morphology of the samples. Z.-G.Y. provided theoretical description of the exciton states. P.O., N.G. and Y.S.L. wrote the paper in consultation with Z.-G.Y. and Z.V.V. All authors commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Yan S. Li.

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