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.
Original language | English (US) |
---|---|
Pages (from-to) | 329-337 |
Number of pages | 9 |
Journal | Nature Materials |
Volume | 22 |
Issue number | 3 |
DOIs | |
State | Published - Mar 2023 |
All Science Journal Classification (ASJC) codes
- Chemistry(all)
- Materials Science(all)
- Condensed Matter Physics
- Mechanics of Materials
- Mechanical Engineering
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In: Nature Materials, Vol. 22, No. 3, 03.2023, p. 329-337.
Research output: Contribution to journal › Article › peer-review
TY - JOUR
T1 - A multiscale ion diffusion framework sheds light on the diffusion–stability–hysteresis nexus in metal halide perovskites
AU - Ghasemi, Masoud
AU - Guo, Boyu
AU - Darabi, Kasra
AU - Wang, Tonghui
AU - Wang, Kai
AU - Huang, Chiung Wei
AU - Lefler, Benjamin M.
AU - Taussig, Laine
AU - Chauhan, Mihirsinh
AU - Baucom, Garrett
AU - Kim, Taesoo
AU - Gomez, Enrique D.
AU - Atkin, Joanna M.
AU - Priya, Shashank
AU - Amassian, Aram
N1 - Funding Information: 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. Funding Information: 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. Publisher Copyright: © 2023, The Author(s), under exclusive licence to Springer Nature Limited.
PY - 2023/3
Y1 - 2023/3
N2 - 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.
AB - 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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UR - http://www.scopus.com/inward/citedby.url?scp=85149051774&partnerID=8YFLogxK
U2 - 10.1038/s41563-023-01488-2
DO - 10.1038/s41563-023-01488-2
M3 - Article
C2 - 36849816
AN - SCOPUS:85149051774
SN - 1476-1122
VL - 22
SP - 329
EP - 337
JO - Nature Materials
JF - Nature Materials
IS - 3
ER -