Effect of Halide ion migration on current-voltage hysteresis in CH3NH3PbI3-xClx based perovskite solar cells
Bernard Geffroy a, Heejae Lee b, Sofia Gaiaschi c, Patrick Chapon c, Arthur Marronnier b, Denis Tondelier b, Yvan Bonnassieux b, Jean-Eric Bourée b
a LICSEN, NIMBE, CEA, CNRS, Université Paris-Saclay, CEA Saclay, F-91191 Gif-sur-Yvette, France
b LPICM, CNRS, Ecole Polytechnique, Université Paris-Saclay, F-91128 Palaiseau, France
c Horiba France S.A.S., CS 45002, 91120 Palaiseau, France
nanoGe Perovskite Conferences
Proceedings of International Conference on Perovskite Thin Film Photovoltaics, Photonics and Optoelectronics (ABXPV18PEROPTO)
Perovskite Thin Film Photovoltaics (ABXPV18). 27-28 Feb
Rennes, France, 2018 February 27th - March 1st
Organizer: Jacky Even
Oral, Bernard Geffroy, presentation 068
DOI: https://doi.org/10.29363/nanoge.abxpvperopto.2018.068
Publication date: 11th December 2017

Hybride perovskite solar cells (PSCs) have rapidly emerged as a promising candidate for the next generation photovoltaics with power conversion efficiencies (PCE) attaining 22.7%. Low temperature solution processing, low cost raw material and relative insensitivity to intrinsic point defects are some of the attractive qualities of this emerging class of devices. But one of the major obstacles for the commercialization of PSCs lies in the long-term stability of the perovskite films subjected to different environmental conditions such as temperature, humidity and illumination.

In this work, we focused on experimental evidence of halide ion migration in CH3NH3PbI3-xClx based solar cells and its effect on current-voltage hysteresis for which various mechanisms have been proposed.

The inverted planar structure adopted for the PSCs was: glass/ITO/PEDOT:PSS/perovskite/PCBM/Ag. The perovskite thin films were deposited by 1-step spin-casting process and the PEDOT:PSS (hole-transporting layer) and PCBM (electron-transporting layer) layers were deposited by spin-coating process. The PCE under 1 sun equivalent illumination reached 12.7% for the best cell of a series of 10 samples with an active area of 0.28 cm2. By using glow discharge optical emission spectrometry (GD-OES) we have shown that halide ions (I- and Cl-) migrate inside the perovskite films under an applied bias in both directions, the time of migration being typically 2 min. Furthermore no migration of lead and nitrogen ions was observed in the same time scale.

Under dark conditions, thus without any photo-generated carriers, we observed a current-voltage hysteresis versus voltage scanning rate and temperature. The activation energy value of 0.253 eV derived from the Nernst-Einstein relation above 264 K, for which the perovskite phase is tetragonal, indicates that the conduction is dominated by the ions. The conduction is ascribed to the migration of anion vacancies, which is well known in the perovskite-type halides such as CsPbCl3 or CsPbBr3. These experiments prove that there is a direct link between halide ion migrations in CH3NH3PbI3-xClx based perovskite thin films and current-voltage hysteresis.

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