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A multiscale ion diffusion framework sheds light on the diffusion–stability–hysteresis nexus in metal halide perovskites

Nature Materials volume 22, pages 329–337 (2023)Cite this article

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Abstract

Stability and current–voltage hysteresis stand as major obstacles to the commercialization of metal halide perovskites. Both phenomena have been associated with ion migration, with anecdotal evidence that stable devices yield low hysteresis. However, the underlying mechanisms of the complex stability–hysteresis link remain elusive. Here we present a multiscale diffusion framework that describes vacancy-mediated halide diffusion in polycrystalline metal halide perovskites, differentiating fast grain boundary diffusivity from volume diffusivity that is two to four orders of magnitude slower. Our results reveal an inverse relationship between the activation energies of grain boundary and volume diffusions, such that stable metal halide perovskites exhibiting smaller volume diffusivities are associated with larger grain boundary diffusivities and reduced hysteresis. The elucidation of multiscale halide diffusion in metal halide perovskites reveals complex inner couplings between ion migration in the volume of grains versus grain boundaries, which in turn can predict the stability and hysteresis of metal halide perovskites, providing a clearer path to addressing the outstanding challenges of the field.

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Fig. 1: Schematic representation of multiscale diffusion in polycrystalline solids, and lateral diffusion profile quantification and modelling.
Fig. 2: Volume diffusion in metal halide perovskites.
Fig. 3: GB diffusion as a function of temperature, halide type and composition.
Fig. 4: Aerobic photodegradation.
Fig. 5: Current density versus voltage curves of MHP PVs, halide exchange in MHPs and GB ‘strength’ model.

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Data availability

Source data are provided with this paper. All other datasets generated and/or analysed during the current study are available from the corresponding authors upon request.

Code availability

The code used for the conversion of a 2D SIMS image to a matrix and subsequent integration for 2D-to-1D conversion is available from the corresponding authors upon request.

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Acknowledgements

M.G. and A.A. acknowledge helpful discussions with D. Irving at North Carolina State University (NCSU) in relation to the GB strength model. M.G., B.G. and A.A. acknowledge support from Office of Naval Research grant N00014-20-1-2573. C.-W.H. and J.M.A. acknowledge support from the National Science Foundation Chemical Measurement and Imaging programme under grant no. CHE-1848278. A.A., L.T., G.B., K.D. and M.G. also acknowledge the support of NCSU and the Carbon Electronics cluster for start-up funding (to A.A.). K.W. acknowledges support from the US Department of Energy’s Office of Energy Efficiency and Renewable Energy under the Solar Energy Technologies Office, award no. DE-EE0009364. S.P. acknowledges support through the US Department of Energy’s Small Business Technology Transfer programme (Prime – NanoSonic Inc.), no. DE-SC0019844. NanoSonic Inc. is lead on a Small Business Innovation Research project (“prime” is commonly used for indicating “lead”). Penn State has received a subcontract on this project. SIMS measurements were performed at the Analytical Instrumentation Facility at NCSU, which is partially supported by the State of North Carolina and the National Science Foundation, and the Materials Characterization Lab at Pennsylvania State University. We acknowledge C. Zhou for providing support for SIMS measurements. M.G. and E.D.G. acknowledge financial support from the Penn State Institutes of Energy and the Environment and Office of Naval Research grant no. N00014-19-1-2453 for X-ray photoemission spectroscopy and SIMS experiments. We acknowledge the support of B. Hengstebeck for SIMS and X-ray photoemission spectroscopy measurements at Pennsylvania State University and S. Koohfar for supporting the analysis of X-ray photoemission spectroscopy results. We also acknowledge F. Castellano for providing a PL facility for superoxide measurements. This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. Abridged legal disclaimer: The views expressed herein do not necessarily represent the views of the US Department of Energy or the United States Government.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, and Organic and Carbon Electronics Laboratories (ORaCEL), North Carolina State University, Raleigh, NC, USA

    Masoud Ghasemi, Boyu Guo, Kasra Darabi, Tonghui Wang, Benjamin M. Lefler, Laine Taussig, Mihirsinh Chauhan, Garrett Baucom, Taesoo Kim & Aram Amassian

  2. Department of Chemical Engineering, Pennsylvania State University, University Park, PA, USA

    Masoud Ghasemi & Enrique D. Gomez

  3. Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA, USA

    Kai Wang, Enrique D. Gomez & Shashank Priya

  4. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC, USA

    Chiung-Wei Huang & Joanna M. Atkin

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  1. Masoud Ghasemi
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Contributions

A.A. and M.G. conceived the scientific framework and designed all experiments. M.G. designed and executed experimental protocols, coordinated the experimental work, performed SIMS and halide exchange measurements and analysed SIMS results. M.G., B.G., G.B., B.M.L. and L.T. prepared the MHP samples used for different measurements. B.M.L. performed additional SIMS measurements. B.G. and K.D. performed the UV–visible absorbance measurements and degradation studies. T.W. prepared the perovskite single crystals and carried out the single-crystal mechanical polishing. M.C., B.G. and K.D. performed the superoxide measurements. K.D. performed the X-ray diffraction measurements. K.W. prepared PV devices and PV stability tests, and performed time-resolved PL measurements with the supervision of S.P.; M.G. prepared the X-ray photoemission spectroscopy samples and the samples used for SIMS using the PHI nanoTOF instrument, with the supervision of E.D.G.; and C.-W.H. and J.M.A. performed the µPL measurements and analysed the data.

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Correspondence to Masoud Ghasemi or Aram Amassian.

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Nature Materials thanks Juan-Pablo Correa-Baena and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–32, Equations 1–4 and Tables 1–4.

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Source data

Source Data Fig. 1

The 2D SIMS map matrix and 1D SIMS profile.

Source Data Fig. 2

The 2D SIMS map matrix and 1D SIMS profile; µPL plots; temperature-dependent 1D diffusion profiles; and volume diffusion coefficients of halide in different MHP compositions.

Source Data Fig. 3

The 1D SIMS profiles and temperature-dependent GB diffusion coefficients of halide in different MHP systems, as well as extrapolated values of DGB and DV at room temperature and EV and Eg.

Source Data Fig. 4

Absorbance values for MAPbI3 and FACsRbI as a function of time at 750 nm.

Source Data Fig. 5

J–V data for MAPbI3 and FACsI PVs in forward and reverse bias, and the bandgap changes in MAPbI3/MAPbBr3 and FACsRbI/FAPbBr3 heterostructures as a function of annealing time.

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Ghasemi, M., Guo, B., Darabi, K. et al. A multiscale ion diffusion framework sheds light on the diffusion–stability–hysteresis nexus in metal halide perovskites. Nat. Mater. 22, 329–337 (2023). https://doi.org/10.1038/s41563-023-01488-2

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