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.

  • Article
  • Published:

Local symmetry breaking drives picosecond spin domain formation in polycrystalline halide perovskite films

Nature Materials volume 22, pages 977–984 (2023)Cite this article

Subjects

Abstract

Photoinduced spin–charge interconversion in semiconductors with spin–orbit coupling could provide a route to optically addressable spintronics without the use of external magnetic fields. However, in structurally disordered polycrystalline semiconductors, which are being widely explored for device applications, the presence and role of spin-associated charge currents remains unclear. Here, using femtosecond circular-polarization-resolved pump–probe microscopy on polycrystalline halide perovskite thin films, we observe the photoinduced ultrafast formation of spin domains on the micrometre scale formed through lateral spin currents. Micrometre-scale variations in the intensity of optical second-harmonic generation and vertical piezoresponse suggest that the spin-domain formation is driven by the presence of strong local inversion symmetry breaking via structural disorder. We propose that this leads to spatially varying Rashba-like spin textures that drive spin-momentum-locked currents, leading to local spin accumulation. Ultrafast spin-domain formation in polycrystalline halide perovskite films provides an optically addressable platform for nanoscale spin-device physics.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Picosecond spin-domain formation.
Fig. 2: Local lateral spin-current formation.
Fig. 3: Inversion of spin-domain formation by inverting pump helicity.
Fig. 4: Signatures of local inversion symmetry breaking.
Fig. 5: Toy model of spin currents in a polycrystalline local inversion asymmetric environment.

Similar content being viewed by others

Data availability

The data that support the plots within this paper and other findings of this study are available at the University of Cambridge Repository at https://doi.org/10.17863/CAM.95175.

References

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

    CAS  Google Scholar 

  2. Fert, A. Nobel lecture: origin, development, and future of spintronics. Rev. Mod. Phys. 80, 1517–1530 (2008).

    CAS  Google Scholar 

  3. Baibich, M. N. et al. Giant magnetoresistance of (001)Fe/(001)Cr magnetic superlattices. Phys. Rev. Lett. 61, 2472–2475 (1988).

    CAS  Google Scholar 

  4. Bychkov, Y. A. & Rashba, E. I. Properties of a 2D electron gas with lifted spectral degeneracy. JETP Lett. 39, 78–81 (1984).

    Google Scholar 

  5. Dresselhaus, G. Spin-orbit coupling effects in zinc blende structures. Phys. Rev. 100, 580–586 (1955).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  7. Ganichev, S. D. Spin photocurrents in quantum wells. Inst. Phys. Conf. Ser. 171, 277–285 (2003).

    CAS  Google Scholar 

  8. Ganichev, S. D. et al. Conversion of spin into directed electric current in quantum wells. Phys. Rev. Lett. 86, 4358–4361 (2001).

    CAS  Google Scholar 

  9. Gambardella, P. & Miron, I. M. Current-induced spin–orbit torques. Philos. Trans. R. Soc. A Math. Phys. Eng. Sci. 369, 3175–3197 (2011).

    CAS  Google Scholar 

  10. Liu, X. et al. Circular photogalvanic spectroscopy of Rashba splitting in 2D hybrid organic–inorganic perovskite multiple quantum wells. Nat. Commun. 11, 323 (2020).

    CAS  Google Scholar 

  11. Golub, L. E., Ivchenko, E. L. & Spivak, B. Semiclassical theory of the circular photogalvanic effect in gyrotropic systems. Phys. Rev. B 102, 85202 (2020).

    CAS  Google Scholar 

  12. Rojas-Sánchez, J. C. et al. Spin to charge conversion at room temperature by spin pumping into a new type of topological insulator: α-Sn films. Phys. Rev. Lett. 116, 096602 (2016).

    Google Scholar 

  13. Shen, K., Vignale, G. & Raimondi, R. Microscopic theory of the inverse Edelstein effect. Phys. Rev. Lett. 112, 096601 (2014).

    Google Scholar 

  14. Ganichev, S. D. et al. Spin-galvanic effect. Nature 417, 153–156 (2002).

    CAS  Google Scholar 

  15. Huang, Z. et al. Observation of spatially resolved Rashba states on the surface of CH3NH3PbBr3 single crystals. Appl. Phys. Rev. 8, 031408 (2021).

    CAS  Google Scholar 

  16. Saitoh, E., Ueda, M., Miyajima, H. & Tatara, G. Conversion of spin current into charge current at room temperature: inverse spin-Hall effect. Appl. Phys. Lett. 88, 15–18 (2006).

    Google Scholar 

  17. He, X. W. et al. Anomalous photogalvanic effect of circularly polarized light incident on the two-dimensional electron gas in AlxGa1–xN/GaN heterostructures at room temperature. Phys. Rev. Lett. 101, 147402 (2008).

    CAS  Google Scholar 

  18. Wang, J. et al. Spin-optoelectronic devices based on hybrid organic-inorganic trihalide perovskites. Nat. Commun. 10, 129 (2019).

  19. Li, J. & Haney, P. M. Circular photogalvanic effect in organometal halide perovskite CH3NH3PbI3. Appl. Phys. Lett. 109, 193903 (2016).

  20. Bourelle, S. A. et al. How exciton interactions control spin-depolarization in layered hybrid perovskites. Nano Lett. 20, 5678–5685 (2020).

    CAS  Google Scholar 

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

  22. Stranks, S. D. & Plochocka, P. The influence of the Rashba effect. Nat. Mater. 17, 381–382 (2018).

    CAS  Google Scholar 

  23. Lafalce, E. et al. Rashba splitting in organic–inorganic lead–halide perovskites revealed through two-photon absorption spectroscopy. Nat. Commun. 13, 483 (2022).

  24. Sajedi, M. et al. Absence of a giant Rashba effect in the valence band of lead halide perovskites. Phys. Rev. B 102, 081116(R) (2020).

  25. Zheng, F., Tan, L. Z., Liu, S. & Rappe, A. M. Rashba spin–orbit coupling enhanced carrier lifetime in CH3NH3PbI3. Nano Lett. 15, 7794–7800 (2015).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  27. Feldmann, S. et al. Photodoping through local charge carrier accumulation in alloyed hybrid perovskites for highly efficient luminescence. Nat. Photon. 14, 123–128 (2020).

    CAS  Google Scholar 

  28. Saliba, M. et al. Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency. Energy Environ. Sci. 9, 1989–1997 (2016).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  30. Schellman, J. & Jensen, H. P. Optical spectroscopy of oriented molecules. Chem. Rev. 87, 1359–1399 (1987).

    CAS  Google Scholar 

  31. Shindo, Y. & Ohmi, Y. Critical liquid circular. J. Am. Chem. Soc. 107, 91–97 (1985).

    CAS  Google Scholar 

  32. Yang, S., Vetter, E., Wang, T., Amassian, A. & Sun, D. Observation of long spin lifetime in MAPbBr3 single crystals at room temperature. J. Phys. Mater. 3, 015012 (2020).

    CAS  Google Scholar 

  33. Yang, J. et al. Acoustic-optical phonon up-conversion and hot-phonon bottleneck in lead-halide perovskites. Nat. Commun. 8, 14120 (2017).

    CAS  Google Scholar 

  34. Price, M. B. et al. Hot-carrier cooling and photoinduced refractive index changes in organic-inorganic lead halide perovskites. Nat. Commun. 6, 8420 (2015).

  35. Ashoka, A. et al. Direct observation of ultrafast singlet exciton fission in three dimensions. Nat. Commun. 13, 5963 (2022).

  36. Sung, J. et al. Long-range ballistic propagation of carriers in methylammonium lead iodide perovskite thin films. Nat. Phys. 16, 171–176 (2020).

    CAS  Google Scholar 

  37. Sánchez, J. C. R. et al. Spin-to-charge conversion using Rashba coupling at the interface between non-magnetic materials. Nat. Commun. 4, 2944 (2013).

  38. Hermes, I. M. et al. Ferroelastic fingerprints in methylammonium lead iodide perovskite. J. Phys. Chem. C 120, 5724–5731 (2016).

    CAS  Google Scholar 

  39. Vorpahl, S. M. et al. Orientation of ferroelectric domains and disappearance upon heating methylammonium lead triiodide perovskite from tetragonal to cubic phase. ACS Appl. Energy Mater. 1, 1534–1539 (2018).

    CAS  Google Scholar 

  40. Frohna, K. et al. Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals. Nat. Commun. 9, 1829 (2018).

    Google Scholar 

  41. Wang, J. S. et al. Direct evidence of correlation between the second harmonic generation anisotropy patterns and the polarization orientation of perovskite ferroelectric. Sci. Rep. 7, 9051 (2017).

  42. Doherty, T. A. S. et al. Stabilized tilted-octahedra halide perovskites inhibit local formation of performance-limiting phases. Science 374, 1598–1605 (2021).

    CAS  Google Scholar 

  43. Ghosh, D., Walsh Atkins, P., Islam, M. S., Walker, A. B. & Eames, C. Good vibrations: locking of octahedral tilting in mixed-cation iodide perovskites for solar cells. ACS Energy Lett. 2, 2424–2429 (2017).

    CAS  Google Scholar 

  44. Weber, O. J. et al. Phase behavior and polymorphism of formamidinium lead iodide. Chem. Mater. 30, 3768–3778 (2018).

    CAS  Google Scholar 

  45. Leppert, L., Reyes-Lillo, S. E. & Neaton, J. B. Electric field- and strain-induced Rashba effect in hybrid halide perovskites. J. Phys. Chem. Lett. 7, 3683–3689 (2016).

    CAS  Google Scholar 

  46. Frohna, K. et al. Nanoscale chemical heterogeneity dominates the optoelectronic response of alloyed perovskite solar cells. Nat. Nanotechnol. 17, 190–196 (2022).

    CAS  Google Scholar 

  47. Young-Hoon, K. et al. Chiral-induced spin selectivity enables a room-temperature spin light-emitting diode. Science 371, 1129–1133 (2021).

    Google Scholar 

  48. Allwood, D. A. et al. Magnetic domain-wall logic. Science 309, 1688–1692 (2005).

    CAS  Google Scholar 

  49. Lozovoy, V. V., Pastirk, I. & Dantus, M. Multiphoton intrapulse interference. IV. Ultrashort laser pulse spectral phase characterization and compensation. Opt. Lett. 29, 775–777 (2004).

    Google Scholar 

  50. Trebino, R. et al. Measuring ultrashort laser pulses in the time-frequency domain using frequency-resolved optical gating. Rev. Sci. Instrum. 68, 3277–3295 (1997).

    CAS  Google Scholar 

Download references

Acknowledgements

We thank E. Gottlob and R. Friend for helpful discussions and A. Giudici for help with figure preparation. We acknowledge funding support from the Engineering and Physical Sciences Research Council (EPSRC, UK) via grants EP/M006360/1 and EP/S030638/1. We acknowledge financial support from the Winton Programme for the Physics of Sustainability. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 758826). A.A. acknowledges funding from the Gates Cambridge Trust and as well as support from the Winton Programme for the Physics of Sustainability. S.N. acknowledges EPSRC (EP/012932/1) for funding. J.L.M.-D. and N.S. acknowledge funding from a Royal Academy of Engineering Chair in Emerging Technologies grant (CIET1819_24), a Swiss National Science Foundation grant (P2EZP2-199913) and an ERC grant (EU-H2020-ERC-ADG 882929 EROS). J.S. acknowledges support from a National Research Foundation of Korea grant funded by the Korean government (Ministry of Science and ICT; no. 2022R1C1C1005970). S.F. acknowledges support from the Rowland Fellowship at the Rowland Institute at Harvard University. S.D.S. acknowledges the EPSRC (EP/R023980/1, EP/012932/1 and EP/S030638/1) for funding. This work was funded by the UKRI. For the purpose of open access, the author has applied a Creative Commons Attribution (CC BY) license to any Author Accepted Manuscript version arising.

Author information

Authors and Affiliations

  1. Cavendish Laboratory, University of Cambridge, Cambridge, UK

    Arjun Ashoka, Ashish Sharma, Alexander J. Sneyd & Akshay Rao

  2. Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, UK

    Satyawan Nagane, Bart Roose & Samuel D. Stranks

  3. Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK

    Nives Strkalj & Judith L. MacManus-Driscoll

  4. Department of Emerging Materials Science, DGIST, Daegu, Republic of Korea

    Jooyoung Sung

  5. Rowland Institute, Harvard University, Cambridge, MA, USA

    Sascha Feldmann

Authors
  1. Arjun Ashoka
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Satyawan Nagane
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Nives Strkalj
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ashish Sharma
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bart Roose
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Alexander J. Sneyd
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jooyoung Sung
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Judith L. MacManus-Driscoll
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Samuel D. Stranks
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Sascha Feldmann
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Akshay Rao
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

A.A., S.F. and A.R. conceived the project. A.A. performed all the optical experiments and built and programmed the pulse shaper for pulse compression. S.N. and B.R. fabricated the halide perovskite films. N.S. performed the PFM measurements. A.S. contributed to the analysis of possible optical artefacts in the signal. A.A. and A.J.S. built the pump–probe microscope set-up. J.S. supervised the building of the pump–probe microscope set-up. J.L.M.-D. supervised the PFM measurements. S.D.S. supervised the work of S.N. and B.R.; S.F. and A.R. supervised the project. A.A. wrote the manuscript with input from all authors.

Corresponding authors

Correspondence to Sascha Feldmann or Akshay Rao.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Materials thanks Michel Viret and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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 Figs. 1–32, captions for Videos 1 and 2 and text.

Supplementary Video 1

A video showing the photoinduced wide-field spin polarization underlying the data presented in Fig. 1 of the main text. Here the spin-polarized wide-field images display a flat background before the arrival of the pump pulse at 0 fs. Upon arrival of the pump pulse, the domains are immediately formed, as we are probing well below the photoexcitation, and spin scattering effects have already taken place before the charge carriers arrive at the band edge (750 nm), where we image. The video shows that at later time delays, the negative regions have grown in magnitude as compared to the positive regions, which have an ultrafast rise and remain constant thereafter.

Supplementary Video 2

A video of the time-resolved propagation of the spin-polarized local currents in the micrometre-scale disordered landscape shown in Fig. 4 of the main text using a Monte Carlo toy model. Here the time step between each frame is 100 fs, and the total simulation time is 10 ps. The orange circles represent the co-polarized spins, and we initialize a uniform grid of these at time zero. Upon scattering to the other branch of the Rashba-like bands, the spin-polarized local currents change their colour to blue and also reverse direction due to spin-momentum locking in any given region. The black lines demarcate the local boundaries shown in Fig. 5 of the main text. The spin accumulation of the blue and orange spin currents with time can be seen by eye.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ashoka, A., Nagane, S., Strkalj, N. et al. Local symmetry breaking drives picosecond spin domain formation in polycrystalline halide perovskite films. Nat. Mater. 22, 977–984 (2023). https://doi.org/10.1038/s41563-023-01550-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-023-01550-z

This article is cited by

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