Charge transport in mixed metal halide perovskite semiconductors – Nature.com

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Nature Materials volume 22, pages 216–224 (2023)Cite this article
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Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm² V^–1 s⁻¹. The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices.
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The data presented in the paper will be made available after acceptance of the paper on the University of Cambridge repository: https://www.data.cam.ac.uk/repository.
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S.P.S. acknowledges funding support from the Royal Society through the Newton Alumni Fellowship (AL211004, AL201019 and AL191021), Science and Engineering Research Board (SERB-SRG/2020/001641 and IPA/2021/000096), Department of Atomic Energy (DAE), Government of India. K.D. acknowledges the support of the Cambridge Trust and SERB (Government of India) in the form of a Cambridge India Ramanujan Scholarship. K.D. thanks F. Lang for useful discussions on PL measurements. This work received funding from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (HYPERION, grant agreement no. 756962). R.H.F. and R.S. acknowledge funding and support from the SUNRISE project (EP/P032591/1). R.S. acknowledges a Newton International Fellowship from the Royal Society. J.L.M.D. and W.L. thank the UK Royal Academy of Engineering, grant CiET1819_24; Engineering and Physical Sciences Research Council (EPSRC) grants EP/N004272/1, EP/P007767/1 and EP/L011700/1; and the Winton Programme for the Physics of Sustainability. W.L. acknowledges B. Welland for useful discussions. B.R. acknowledges EPSRC, grant number EP/T02030X/1. S.J.Z. acknowledges support from the Polish National Agency for Academic Exchange within the Bekker programme (grant no. PPN/BEK/2020/1/00264/U/00001). N.T. acknowledges the use of resources of the Center for Functional Nanomaterials, which is a US Department of Energy Office of Science User Facility, at Brookhaven National Laboratory under contract no. DE-SC0012704. D.G. thanks the Center for Integrated Nanotechnologies, a US Department of Energy and Office of Basic Energy Sciences user facility, at Los Alamos National Laboratory, for providing computational facilities. Y.Z. thanks the Chinese Scholarship Council and the EPSRC Centre for Doctoral Training in Graphene Technology for financial support. H.S. thanks the Royal Society for support through a Royal Society Research Professorship (RPR1201082). S.D.S. acknowledges support from the Royal Society and Tata Group (UF150033).
Ravichandran Shivanna
Present address: Department of Physics, Indian Institute of Technology Madras, Chennai, India
These authors contributed equally: Satyaprasad P. Senanayak, Krishanu Dey.
Nanoelectronics and Device Physics Lab, National Institute of Science Education and Research, School of Physical Sciences, HBNI, Jatni, India
Satyaprasad P. Senanayak
Optoelectronics Group, Department of Physics, Cavendish Laboratory, University of Cambridge, Cambridge, UK
Krishanu Dey, Ravichandran Shivanna, Youcheng Zhang, Szymon J. Zelewski, Zahra Andaji-Garmaroudi, William Wood, Richard H. Friend, Samuel D. Stranks & Henning Sirringhaus
Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK
Weiwei Li & Judith L. MacManus-Driscoll
College of Physics, MIIT Key Laboratory of Aerospace Information Materials and Physics, Nanjing University of Aeronautics and Astronautics, Nanjing, China
Weiwei Li
Department of Materials Science and Engineering, Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, India
Dibyajyoti Ghosh
Cambridge Graphene Centre, Department of Engineering, University of Cambridge, Cambridge, UK
Youcheng Zhang
Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, UK
Bart Roose & Samuel D. Stranks
Department of Semiconductor Materials Engineering, Faculty of Fundamental Problems of Technology, Wrocław University of Science and Technology, Wrocław, Poland
Szymon J. Zelewski
Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA
Nikhil Tiwale
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S.P.S. and K.D. conceived the idea and designed the experimental plan with input from S.D.S. and H.S.; K.D. optimized the perovskite films used for the measurements and performed the spectroscopic and structural measurements. S.P.S. fabricated the FETs and performed all the FET measurements and bias stress stability measurements. R.S. performed the PL mapping measurement and discussed it with S.P.S., K.D. and R.H.F.; W.L. and J.L.M.D. performed and analysed the XPS measurements. D.G. carried out the first-principles density functional theory calculations. S.P.S. and Y.Z. performed the switching measurement, the contact modification and the associated FET measurements. B.R. measured the top-view scanning electron microscopy of the perovskite films. S.J.Z. and Z.A.-G. conducted the PDS measurements. W.W. assisted with the Hall measurements. N.T. performed the grazing incidence wide-angle X-ray scattering measurements. Y.Z. and N.T. fabricated the Hall patterns. S.P.S. and K.D. interpreted all the data related to device measurements and material characterization, with input from all authors. All authors discussed and revised the manuscript.
Correspondence to Satyaprasad P. Senanayak, Samuel D. Stranks or Henning Sirringhaus.
S.D.S. is a cofounder of Swift Solar. The remaining authors declare no competing interests.
Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.
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Senanayak, S.P., Dey, K., Shivanna, R. et al. Charge transport in mixed metal halide perovskite semiconductors. Nat. Mater. 22, 216–224 (2023). https://doi.org/10.1038/s41563-022-01448-2
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Received: 27 January 2022
Accepted: 24 November 2022
Published: 26 January 2023
Issue Date: February 2023
DOI: https://doi.org/10.1038/s41563-022-01448-2
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