Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors

Journal name:
Nature Materials
Volume:
14,
Pages:
636–642
Year published:
DOI:
doi:10.1038/nmat4271
Received
Accepted
Published online

Abstract

The remarkable performance of lead halide perovskites in solar cells can be attributed to the long carrier lifetimes and low non-radiative recombination rates, the same physical properties that are ideal for semiconductor lasers. Here, we show room-temperature and wavelength-tunable lasing from single-crystal lead halide perovskite nanowires with very low lasing thresholds (220 nJ cm−2) and high quality factors (Q ~ 3,600). The lasing threshold corresponds to a charge carrier density as low as 1.5 × 1016 cm−3. Kinetic analysis based on time-resolved fluorescence reveals little charge carrier trapping in these single-crystal nanowires and gives estimated lasing quantum yields approaching 100%. Such lasing performance, coupled with the facile solution growth of single-crystal nanowires and the broad stoichiometry-dependent tunability of emission colour, makes lead halide perovskites ideal materials for the development of nanophotonics, in parallel with the rapid development in photovoltaics from the same materials.

At a glance

Figures

  1. Structural characterization of single-crystal CH3NH3PbX3 NWs.
    Figure 1: Structural characterization of single-crystal CH3NH3PbX3 NWs.

    a,b, Optical (a) and SEM (b) images of CH3NH3PbI3 nanostructures grown from PbAc2 thin film in a 40 mg ml−1 CH3NH3I/isopropanol solution with a reaction time of 24 h. c, Low-resolution TEM image and its selected-area electron diffraction pattern along the [110] zone axis (ZA). d,e, Magnified SEM images of NWs (top view), showing a square or rectangular cross-section and flat end facets perpendicular to the long NW axis. f, High-resolution TEM image and its corresponding fast Fourier transform. g, PXRD patterns of as-grown CH3NH3PbX3 (X = I, Br, Cl) NWs, confirming the tetragonal phase (for X = I) and cubic phase (for X = Br, Cl) of the perovskites, without any impurity phases.

  2. Near-infrared lasing from CH3NH3PbI3 NWs.
    Figure 2: Near-infrared lasing from CH3NH3PbI3 NWs.

    a, Schematic of a NW on SiO2 substrate pumped by 402 nm laser excitation (~150 fs, 250 kHz). b, 2D pseudo-colour plot of NW emission spectra under different pump fluences (P) showing a broad SPE peak below the threshold (PTh) of ~600 nJ cm−2 and a narrow lasing peak above the threshold. Note the logarithmic colour scale. c, NW emission spectra around the lasing threshold. Inset: Integrated emission intensity and FWHM as a function of P showing the lasing threshold at ~600 nJ cm−2. The FWHM of the lasing peak (δλ) at 630 nJ cm−2 is 0.22 nm, corresponding to a Q factor ~3,600. d, Optical image (left) of single NW with a length of 8.5 μm. The middle and right images show the NW emission below and above PTh (scale bar, 10 μm). The emission is uniform below PTh but mostly comes from the two end facets with coherent interference under lasing operation. e, TRPL decay kinetics after photoexcitation with fluence below (P ~ 0.85PTh, blue) and above (P ~ 1.1PTh, red) the threshold, showing a ~5.5 ns SPE decay process below PTh and a ≤20 ps lasing process above PTh. Also shown (black) is the TRPL decay kinetics with a lifetime ~150 ns at a very low photoexcited carrier density (1.5 × 1014 cm−3).

  3. Visible lasing from CH3NH3PbBr3 NWs.
    Figure 3: Visible lasing from CH3NH3PbBr3 NWs.

    a, 2D pseudo-colour plots of NW emission spectra as a function of pump fluences for CH3NH3PbBr3 NWs of different lengths: top 7.5 μm; middle 13.6 μm; and bottom 23.6 μm. Note the logarithmic colour scale for emission intensity. Inset: Emission images of NWs of different lengths above the lasing threshold (scale bars, 10 μm). b, TRPL decay kinetics after photoexcitation with fluence below (P ~ 0.82PTh, blue) and above (P ~ 1.13PTh, red) the threshold, showing a ~2 ns spontaneous decay process below PTh and a ≤20 ps (instrument limited; see grey dashed curve for instrument response function) lasing process above PTh for the 7.5-μm-long NW. The dots are data points and solid lines are multi-exponential decay fitting. Inset: Emission spectrum above the threshold with a Gaussian fitting. The FWHM is ~0.23 nm, corresponding to a Q factor of ~2,400. c, Mode spacing of the lasing peaks as a function of reciprocal NW length (black triangles). The experimental data are well described by a linear function (green) with intercept at zero.

  4. Tunable lasing from mixed perovskite NWs.
    Figure 4: Tunable lasing from mixed perovskite NWs.

    a,b, Optical (a) and SEM (b) images of CH3NH3PbCl1.24Br1.76 nanostructures. The inset in b shows a magnified SEM image of NWs, showing rectangular cross-sections and flat end facets. c, Typical SEM image (top) of an individual CH3NH3PbCl1.24Br1.76 NW and the corresponding EDS mapping showing the uniform elemental distribution of Pb, Cl and Br. d, Widely tunable lasing emission wavelength at room temperature from single-crystal NW lasers of mixed lead halide perovskites.

  5. Emission polarization of the CH3NH3PbI3 NW laser.
    Figure 5: Emission polarization of the CH3NH3PbI3 NW laser.

    a, Lasing spectra of a single CH3NH3PbI3 NW pumped at P ~ 1.3PTh with orthogonal detection polarizations (red, detection polarization perpendicular to NW axis, denoted φ = 90°; blue, detection polarization parallel to NW axis, denoted φ = 0°). Upper inset: Normalized emission intensities (symbols) as a function of detection polarization angle (φ) for lasing (green) and SPE (maroon); solid curves are fits to cos2φ. The lasing and SPE regions are anti-correlated, indicating orthogonal polarization preference. Lower inset: Optical image of the NW (L = 7.5μm). b, Cross-sectional view of the simulated electric field intensity profiles at 790 nm for fundamental waveguide modes in a CH3NH3PbI3 NW (width = 600 nm, height = 300 nm) on a SiO2/Si substrate. The white rectangular region is the CH3NH3PbI3 NW and the area below the white line is the SiO2/Si substrate. |Ex|2: along the substrate, perpendicular to the NW; |Ey|2: perpendicular to the substrate and NW; |Ez|2: along the NW. The fundamental mode is mostly transverse-electric-like with dominant x polarization and a weak longitudinal component.

References

  1. Yan, R. X., Gargas, D. & Yang, P. D. Nanowire photonics. Nature Photon. 3, 569576 (2009).
  2. Huang, M. H. et al. Room-temperature ultraviolet nanowire nanolasers. Science 292, 18971899 (2001).
  3. Johnson, J. C. et al. Single gallium nitride nanowire lasers. Nature Mater. 1, 106110 (2002).
  4. Qian, F. et al. Multi-quantum-well nanowire heterostructures for wavelength-controlled lasers. Nature Mater. 7, 701706 (2008).
  5. Agarwal, R., Barrelet, C. J. & Lieber, C. M. Lasing in single cadmium sulfide nanowire optical cavities. Nano Lett. 5, 917920 (2005).
  6. Pan, A. et al. Continuous alloy-composition spatial grading and superbroad wavelength-tunable nanowire lasers on a single chip. Nano Lett. 9, 784788 (2009).
  7. Saxena, D. et al. Optically pumped room-temperature GaAs nanowire lasers. Nature Photon. 7, 963968 (2013).
  8. Hua, B., Motohisa, J., Kobayashi, Y., Hara, S. & Fukui, T. Single GaAs/GaAsP coaxial core-shell nanowire lasers. Nano Lett. 9, 112116 (2009).
  9. Chen, R. et al. Nanolasers grown on silicon. Nature Photon. 5, 170175 (2011).
  10. Wang, Z. et al. Polytypic InP nanolaser monolithically integrated on (001) silicon. Nano Lett. 13, 50635069 (2013).
  11. Mayer, B. et al. Lasing from individual GaAs–AlGaAs core–shell nanowires up to room temperature. Nature Commun. 4, 2931 (2013).
  12. Duan, X., Huang, Y., Agarwal, R. & Lieber, C. M. Single-nanowire electrically driven lasers. Nature 421, 241245 (2003).
  13. Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 60506051 (2009).
  14. Lee, M. M., Teuscher, J., Miyasaka, T., Murakami, T. N. & Snaith, H. J. Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 338, 643647 (2012).
  15. Liu, M., Johnston, M. B. & Snaith, H. J. Efficient planar heterojunction perovskite solar cells by vapour deposition. Nature 501, 395398 (2013).
  16. Burschka, J. et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499, 316319 (2013).
  17. Zhou, H. et al. Interface engineering of highly efficient perovskite solar cells. Science 345, 542546 (2014).
  18. Stranks, S. D. et al. Electron–hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341344 (2013).
  19. Xing, G. et al. Long-range balanced electron- and hole-transport lengths in organic–inorganic CH3NH3PbI3. Science 342, 344347 (2013).
  20. Deschler, F. et al. High photoluminescence efficiency and optically pumped lasing in solution-processed mixed halide perovskite semiconductors. J. Phys. Chem. Lett. 5, 14211426 (2014).
  21. Tan, Z. K. et al. Bright light-emitting diodes based on organometal halide perovskite. Nature Nanotech. 9, 687692 (2014).
  22. Xing, G. et al. Low-temperature solution-processed wavelength-tunable perovskites for lasing. Nature Mater. 13, 476480 (2014).
  23. Sutherland, B. R., Hoogland, S., Adachi, M. M., Wong, C. T. & Sargent, E. H. Conformal organohalide perovskites enable lasing on spherical resonators. ACS Nano 8, 1094710952 (2014).
  24. Zhang, Q., Ha, S. T., Liu, X., Sum, T. C. & Xiong, Q. Room-temperature near-infrared high-q perovskite whispering-gallery planar nanolasers. Nano Lett. 14, 59956001 (2014).
  25. Meng, F., Morin, S. A., Forticaux, A. & Jin, S. Screw dislocation driven growth of nanomaterials. Acc. Chem. Res. 46, 16161626 (2013).
  26. Poglitsch, A. & Weber, D. Dynamic disorder in methylammonium-trihalogeno-plumbates (II) observed by millimeter-wave spectroscopy. J. Chem. Phys. 87, 63736378 (1987).
  27. Liang, K., Mitzi, D. B. & Prikas, M. T. Synthesis and characterization of organic–inorganic perovskite thin films prepared using a versatile two-step dipping technique. Chem. Mater. 10, 403411 (1998).
  28. Morin, S. A., Bierman, M. J., Tong, J. & Jin, S. Mechanism and kinetics of spontaneous nanotube growth driven by screw dislocations. Science 328, 476480 (2010).
  29. Bierman, M. J., Lau, Y. K. A., Kvit, A. V., Schmitt, A. L. & Jin, S. Dislocation-driven nanowire growth and Eshelby Twist. Science 320, 10601063 (2008).
  30. Li, L. et al. Facile solution synthesis of α-FeF3 ⋅ 3H2O nanowires and their conversion to α-Fe2O3 nanowires for photoelectrochemical application. Nano Lett. 12, 724731 (2012).
  31. Casperson, L. W. Threshold characteristics of multimode laser oscillators. J. Appl. Phys. 46, 51945201 (1975).
  32. van Vugt, L. K., Ruhle, S. & Vanmaekelbergh, D. Phase-correlated nondirectional laser emission from the end facets of a ZnO nanowire. Nano Lett. 6, 27072711 (2006).
  33. Johnson, J. C., Yan, H. Q., Yang, P. D. & Saykally, R. J. Optical cavity effects in ZnO nanowire lasers and waveguides. J. Phys. Chem. B 107, 88168828 (2003).
  34. Eliseev, P. G. & Shuikin, N. N. Single-mode and single-frequency injection lasers (review). Sov. J. Quant. Electron. 3, 181192 (1973).
  35. Ning, C. Z. in Semiconductors and Semimetals Vol. 86 (eds Coleman, J. J., Bryce, A. C. & Jagadish, C.) 455486 (Academic Press, 2012).
  36. Snaith, H. J. et al. Anomalous hysteresis in perovskite solar cells. J. Phys. Chem. Lett. 5, 15111515 (2014).
  37. Wu, X. et al. Trap States in lead iodide perovskites. J. Am. Chem. Soc. 137, 20892096 (2015).
  38. Haruyama, J., Sodeyama, K., Han, L. & Tateyama, Y. Termination dependence of tetragonal CH3NH3PbI3 surfaces for perovskite solar cells. J. Phys. Chem. Lett. 5, 29032909 (2014).
  39. Saba, M. et al. Correlated electron–hole plasma in organometal perovskites. Nature Commun. 5, 5049 (2014).
  40. Svelto, O. Principles of Lasers 4th edn (Springer, 1998).
  41. Li, H. Y., Ruhle, S., Khedoe, R., Koenderink, A. F. & Vanmaekelbergh, D. Polarization, microscopic origin, and mode structure of luminescence and lasing from single ZnO nanowires. Nano Lett. 9, 35153520 (2009).
  42. Wang, J., Gudiksen, M. S., Duan, X., Cui, Y. & Lieber, C. M. Highly polarized photoluminescence and photodetection from single indium phosphide nanowires. Science 293, 14551457 (2001).
  43. Shan, C. X., Liu, Z. & Hark, S. K. Photoluminescence polarization in individual CdSe nanowires. Phys. Rev. B 74, 153402 (2006).
  44. Collin, R. E. Field Theory of Guided Waves (Wiley-IEEE Press, 1991).

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Author information

  1. These authors contributed equally to this work.

    • Haiming Zhu &
    • Yongping Fu

Affiliations

  1. Department of Chemistry, Columbia University, New York, New York 10027, USA

    • Haiming Zhu,
    • Xiaoxi Wu,
    • Zizhou Gong,
    • Martin V. Gustafsson,
    • M. Tuan Trinh &
    • X-Y. Zhu
  2. Department of Chemistry, University of Wisconsin—Madison, Madison, Wisconsin 53706, USA

    • Yongping Fu,
    • Fei Meng,
    • Qi Ding &
    • Song Jin

Contributions

H.Z., Y.F., S.J. and X-Y.Z. conceived the idea and designed the experiments. Y.F., F.M. and Q.D. synthesized and characterized the samples. H.Z., X.W. and Z.G. conducted the optical measurements. M.V.G. helped with metal-coated sample preparation and M.T.T. with experimental set-up for lasing measurement. H.Z. analysed the data and performed the simulation. H.Z., Y.F., S.J. and X-Y.Z. wrote the manuscript. All authors discussed the results, interpreted the findings, and reviewed the manuscript.

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The authors declare no competing financial interests.

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