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Anomalous thickness dependence of photoluminescence quantum yield in black phosphorous

Nature Nanotechnology volume 18, pages 507–513 (2023)Cite this article

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Abstract

Black phosphorus has emerged as a unique optoelectronic material, exhibiting tunable and high device performance from mid-infrared to visible wavelengths. Understanding the photophysics of this system is of interest to further advance device technologies based on it. Here we report the thickness dependence of the photoluminescence quantum yield at room temperature in black phosphorus while measuring the various radiative and non-radiative recombination rates. As the thickness decreases from bulk to ~4 nm, a drop in the photoluminescence quantum yield is initially observed due to enhanced surface carrier recombination, followed by an unexpectedly sharp increase in photoluminescence quantum yield with further thickness scaling, with an average value of ~30% for monolayers. This trend arises from the free-carrier to excitonic transition in black phosphorus thin films, and differs from the behaviour of conventional semiconductors, where photoluminescence quantum yield monotonically deteriorates with decreasing thickness. Furthermore, we find that the surface carrier recombination velocity of black phosphorus is two orders of magnitude lower than the lowest value reported in the literature for any semiconductor with or without passivation; this is due to the presence of self-terminated surface bonds in black phosphorus.

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Fig. 1: Excitonic to free-carrier transition in BP.
Fig. 2: Excitonic recombination in thin BP.
Fig. 3: Free-carrier recombination in BP.
Fig. 4: Comparison of SRV.
Fig. 5: Enhanced PL QY by optical cavity.

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Data availability

All data generated or analysed during this study are included in this published Article. Source data are provided with this paper.

Code availability

All codes to analyse the band structures, densities of states and optical properties are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Contract No. DE-AC02-05-CH11231 (EMAT program KC1201). N.H. acknowledges support from the Postdoctoral Fellowships for Research Abroad of the Japan Society for the Promotion of Science. E.R. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05-CH11231 within the Fundamentals of Semiconductor Nanowire Program (KCPY23). The optical incoupling/outcoupling simulation performed in Australia was supported by the Australian Research Council Centre of Excellence for Transformative Meta-Optical Systems (project no. CE200100010) and by the Discovery Projects Program (DP210103428). We thank E. Yablonovitch for his help with carrier recombination modelling and S. Balendhran, H. Kim and N. Gupta for their help with optical measurements and simulations.

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Author notes

  1. Shiekh Zia Uddin

    Present address: Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, MA, USA

  2. These authors contributed equally: Naoki Higashitarumizu, Shiekh Zia Uddin.

Authors and Affiliations

  1. Electrical Engineering and Computer Sciences, University of California, Berkeley, Berkeley, CA, USA

    Naoki Higashitarumizu, Shiekh Zia Uddin, I. K. M. Reaz Rahman, Vivian Wang & Ali Javey

  2. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Naoki Higashitarumizu, Shiekh Zia Uddin, I. K. M. Reaz Rahman, Vivian Wang, Eran Rabani & Ali Javey

  3. Department of Chemistry, University of California, Berkeley, Berkeley, CA, USA

    Daniel Weinberg & Eran Rabani

  4. School of Physics, University of Melbourne, Melbourne, Victoria, Australia

    Nima Sefidmooye Azar & Kenneth B. Crozier

  5. Department of Electrical and Electronic Engineering, University of Melbourne, Parkville, Victoria, Australia

    Kenneth B. Crozier

  6. Australian Research Council (ARC) Centre of Excellence for Transformative Meta-Optical Systems (TMOS), University of Melbourne, Parkville, Victoria, Australia

    Kenneth B. Crozier

  7. The Raymond and Beverly Sackler Center of Computational Molecular and Materials Science, Tel Aviv University, Tel Aviv, Israel

    Eran Rabani

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Contributions

N.H., S.Z.U. and A.J. conceived the idea for the project and designed the experiments. N.H., S.Z.U., I.K.M.R.R. and V.W. prepared samples and performed optical measurements. N.H., S.Z.U. and A.J. analysed the data. S.Z.U. performed analytical modelling. D.W. and E.R. performed electronic band structure calculations. N.H., S.Z.U., N.S.A., V.W. and K.B.C. performed optical simulations. N.H., S.Z.U. and A.J. wrote the paper. All authors discussed the results and commented on the paper.

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Correspondence to Ali Javey.

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Higashitarumizu, N., Uddin, S.Z., Weinberg, D. et al. Anomalous thickness dependence of photoluminescence quantum yield in black phosphorous. Nat. Nanotechnol. 18, 507–513 (2023). https://doi.org/10.1038/s41565-023-01335-0

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