Interpretation of inverted photocurrent transients in organic lead halide perovskite solar cells: proof of the field screening by mobile ions and determination of the space charge layer widths

Belisle, Rebecca A.; Nguyen, William H.; Bowring, Andrea R.; Calado, Philip; Li, Xiaoe; Irvine, Stuart J.  C.; McGehee, Michael D.; Barnes, Piers R.  F.; O'Regan, Brian C.

doi:10.1039/c6ee02914k

Title: Interpretation of inverted photocurrent transients in organic lead halide perovskite solar cells: proof of the field screening by mobile ions and determination of the space charge layer widths

Journal Article · Sun Jan 01 00:00:00 EST 2017 · Energy & Environmental Science

DOI:https://doi.org/10.1039/c6ee02914k· OSTI ID:1425387

Belisle, Rebecca A. ^[1]; Nguyen, William H. ^[1]; Bowring, Andrea R. ^[1]; Calado, Philip ^[2]; Li, Xiaoe ^[2]; Irvine, Stuart J. C. ^[3]; McGehee, Michael D. ^[1]; Barnes, Piers R. F. ^[2];

^[4]

Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
Imperial College, London (United Kingdom). Dept. of Physics
Swansea Univ., Swansea (United Kingdom). Centre for Solar Energy Research
Sunlight Scientific, Berkeley, CA (United States)

In Methyl Ammonium Lead Iodide (MAPI) perovskite solar cells, screening of the built-in field by mobile ions has been proposed as part of the cause of the large hysteresis observed in the current/voltage scans in many cells. Here, we show that photocurrent transients measured immediately (e.g. 100 μs) after a voltage step can provide direct evidence that this field screening exists. Just after a step to forward bias, the photocurrent transients are reversed in sign (i.e. inverted), and the magnitude of the inverted transients can be used to find an upper bound on the width of the space charge layers adjacent to the electrodes. This in turn provides a lower bound on the mobile charge concentration, which we find to be ≳1 x 10¹⁷ cm^-3. Using a new photocurrent transient experiment, we show that the space charge layer thickness remains approximately constant as a function of bias, as expected for mobile ions in a solid electrolyte. We also discuss additional characteristics of the inverted photocurrent transients that imply either an unusually stable deep trapping, or a photo effect on the mobile ion conductivity.

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Research Organization:: Stanford Univ., CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); Engineering and Physical Sciences Research Council (EPSRC)

Grant/Contract Number:: EE0006707; EP/J002305/1; EP/M023532/1; EP/I019278/1; EP/M025020/1; EP/G037515/1; EP/M014797/1).

OSTI ID:: 1425387

Journal Information:: Energy & Environmental Science, Vol. 10, Issue 1; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 125 works

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References (47)

Ionic transport in hybrid lead iodide perovskite solar cells Eames, Christopher; Frost, Jarvist M.; Barnes, Piers R. F. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8497	journal	June 2015
Spatial Localization of Excitons and Charge Carriers in Hybrid Perovskite Thin Films Simpson, Mary Jane; Doughty, Benjamin; Yang, Bin The Journal of Physical Chemistry Letters, Vol. 6, Issue 15 https://doi.org/10.1021/acs.jpclett.5b01050	journal	July 2015
6.5% efficient perovskite quantum-dot-sensitized solar cell Im, Jeong-Hyeok; Lee, Chang-Ryul; Lee, Jin-Wook Nanoscale, Vol. 3, Issue 10, p. 4088-4093 https://doi.org/10.1039/c1nr10867k	journal	January 2011
Hysteresis and transient behavior in current–voltage measurements of hybrid-perovskite absorber solar cells Unger, E. L.; Hoke, E. T.; Bailie, C. D. Energy Environ. Sci., Vol. 7, Issue 11 https://doi.org/10.1039/C4EE02465F	journal	January 2014
Photo-induced halide redistribution in organic–inorganic perovskite films deQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11683	journal	May 2016
Inorganic caesium lead iodide perovskite solar cells Eperon, Giles E.; Paternò, Giuseppe M.; Sutton, Rebecca J. Journal of Materials Chemistry A, Vol. 3, Issue 39 https://doi.org/10.1039/C5TA06398A	journal	January 2015
Modulating the Electron–Hole Interaction in a Hybrid Lead Halide Perovskite with an Electric Field Leijtens, Tomas; Srimath Kandada, Ajay Ram; Eperon, Giles E. Journal of the American Chemical Society, Vol. 137, Issue 49 https://doi.org/10.1021/jacs.5b09085	journal	December 2015
Can slow-moving ions explain hysteresis in the current–voltage curves of perovskite solar cells? Richardson, Giles; O'Kane, Simon E. J.; Niemann, Ralf G. Energy & Environmental Science, Vol. 9, Issue 4 https://doi.org/10.1039/C5EE02740C	journal	January 2016
Unusual defect physics in CH ₃ NH ₃ PbI ₃ perovskite solar cell absorber Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Applied Physics Letters, Vol. 104, Issue 6 https://doi.org/10.1063/1.4864778	journal	February 2014
Extremely Slow Photoconductivity Response of CH ₃ NH ₃ PbI ₃ Perovskites Suggesting Structural Changes under Working Conditions Gottesman, Ronen; Haltzi, Eynav; Gouda, Laxman The Journal of Physical Chemistry Letters, Vol. 5, Issue 15 https://doi.org/10.1021/jz501373f	journal	July 2014
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051 https://doi.org/10.1021/ja809598r	journal	May 2009
Iodine Migration and its Effect on Hysteresis in Perovskite Solar Cells Li, Cheng; Tscheuschner, Steffen; Paulus, Fabian Advanced Materials, Vol. 28, Issue 12 https://doi.org/10.1002/adma.201503832	journal	January 2016
Anomalously large interface charge in polarity-switchable photovoltaic devices: an indication of mobile ions in organic–inorganic halide perovskites Zhao, Yong; Liang, Chunjun; Zhang, Huimin Energy & Environmental Science, Vol. 8, Issue 4 https://doi.org/10.1039/C4EE04064C	journal	January 2015
Understanding the rate-dependent J–V hysteresis, slow time component, and aging in CH ₃ NH ₃ PbI ₃ perovskite solar cells: the role of a compensated electric field Tress, W.; Marinova, N.; Moehl, T. Energy & Environmental Science, Vol. 8, Issue 3 https://doi.org/10.1039/C4EE03664F	journal	January 2015
Efficient and stable large-area perovskite solar cells with inorganic charge extraction layers Chen, W.; Wu, Y.; Yue, Y. Science, Vol. 350, Issue 6263 https://doi.org/10.1126/science.aad1015	journal	October 2015
Ionic polarization-induced current–voltage hysteresis in CH3NH3PbX3 perovskite solar cells Meloni, Simone; Moehl, Thomas; Tress, Wolfgang Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10334	journal	February 2016
High-performance photovoltaic perovskite layers fabricated through intramolecular exchange Yang, W. S.; Noh, J. H.; Jeon, N. J. Science, Vol. 348, Issue 6240 https://doi.org/10.1126/science.aaa9272	journal	May 2015
Modeling Anomalous Hysteresis in Perovskite Solar Cells van Reenen, Stephan; Kemerink, Martijn; Snaith, Henry J. The Journal of Physical Chemistry Letters, Vol. 6, Issue 19 https://doi.org/10.1021/acs.jpclett.5b01645	journal	September 2015
Drift mobility techniques for the study of electrical transport properties in insulating solids Spear, W. E. Journal of Non-Crystalline Solids, Vol. 1, Issue 3 https://doi.org/10.1016/0022-3093(69)90001-5	journal	April 1969
Heterojunction Modification for Highly Efficient Organic–Inorganic Perovskite Solar Cells Wojciechowski, Konrad; Stranks, Samuel D.; Abate, Antonio ACS Nano, Vol. 8, Issue 12 https://doi.org/10.1021/nn505723h	journal	November 2014
Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells Shao, Yuchuan; Xiao, Zhengguo; Bi, Cheng Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6784	journal	December 2014
Charge selective contacts, mobile ions and anomalous hysteresis in organic–inorganic perovskite solar cells Zhang, Ye; Liu, Mingzhen; Eperon, Giles E. Materials Horizons, Vol. 2, Issue 3 https://doi.org/10.1039/C4MH00238E	journal	January 2015
Photovoltaic Switching Mechanism in Lateral Structure Hybrid Perovskite Solar Cells Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan Advanced Energy Materials, Vol. 5, Issue 15 https://doi.org/10.1002/aenm.201500615	journal	June 2015
Ionic charging by local imbalance at interfaces in hybrid lead halide perovskites Almora, Osbel; Guerrero, Antonio; Garcia-Belmonte, Germà Applied Physics Letters, Vol. 108, Issue 4 https://doi.org/10.1063/1.4941033	journal	January 2016
Giant switchable photovoltaic effect in organometal trihalide perovskite devices Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan Nature Materials, Vol. 14, Issue 2 https://doi.org/10.1038/nmat4150	journal	December 2014
Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability Yuan, Yongbo; Huang, Jinsong Accounts of Chemical Research, Vol. 49, Issue 2 https://doi.org/10.1021/acs.accounts.5b00420	journal	January 2016
The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8124	journal	May 2015
A vacuum flash–assisted solution process for high-efficiency large-area perovskite solar cells Li, Xiong; Bi, Dongqin; Yi, Chenyi Science, Vol. 353, Issue 6294 https://doi.org/10.1126/science.aaf8060	journal	June 2016
Observable Hysteresis at Low Temperature in “Hysteresis Free” Organic–Inorganic Lead Halide Perovskite Solar Cells Bryant, Daniel; Wheeler, Scot; O’Regan, Brian C. The Journal of Physical Chemistry Letters, Vol. 6, Issue 16 https://doi.org/10.1021/acs.jpclett.5b01381	journal	July 2015
Local Time-Dependent Charging in a Perovskite Solar Cell Bergmann, Victor W.; Guo, Yunlong; Tanaka, Hideyuki ACS Applied Materials & Interfaces, Vol. 8, Issue 30 https://doi.org/10.1021/acsami.6b04104	journal	July 2016
Photoferroelectric and Photopiezoelectric Properties of Organometal Halide Perovskites Liu, Shi; Zheng, Fan; Grinberg, Ilya The Journal of Physical Chemistry Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acs.jpclett.6b00527	journal	April 2016
Native Defect-Induced Hysteresis Behavior in Organolead Iodide Perovskite Solar Cells Yu, Hui; Lu, Haipeng; Xie, Fangyan Advanced Functional Materials, Vol. 26, Issue 9 https://doi.org/10.1002/adfm.201504997	journal	January 2016
Giant photostriction in organic–inorganic lead halide perovskites Zhou, Yang; You, Lu; Wang, Shiwei Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11193	journal	April 2016
Intrinsic slow charge response in the perovskite solar cells: Electron and ion transport Shi, Jiangjian; Xu, Xin; Zhang, Huiyin Applied Physics Letters, Vol. 107, Issue 16 https://doi.org/10.1063/1.4934633	journal	October 2015
Anomalous Hysteresis in Perovskite Solar Cells Snaith, Henry J.; Abate, Antonio; Ball, James M. The Journal of Physical Chemistry Letters, Vol. 5, Issue 9 https://doi.org/10.1021/jz500113x	journal	April 2014
Ion Migration and the Role of Preconditioning Cycles in the Stabilization of the J - V Characteristics of Inverted Hybrid Perovskite Solar Cells De Bastiani, Michele; Dell'Erba, Giorgio; Gandini, Marina Advanced Energy Materials, Vol. 6, Issue 2 https://doi.org/10.1002/aenm.201501453	journal	October 2015
Evidence for ion migration in hybrid perovskite solar cells with minimal hysteresis Calado, Philip; Telford, Andrew M.; Bryant, Daniel Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13831	journal	December 2016
The Interface between FTO and the TiO ₂ Compact Layer Can Be One of the Origins to Hysteresis in Planar Heterojunction Perovskite Solar Cells Jena, Ajay Kumar; Chen, Hsin-Wei; Kogo, Atsushi ACS Applied Materials & Interfaces, Vol. 7, Issue 18 https://doi.org/10.1021/acsami.5b01789	journal	May 2015
Mapping the Photoresponse of CH ₃ NH ₃ PbI ₃ Hybrid Perovskite Thin Films at the Nanoscale Kutes, Yasemin; Zhou, Yuanyuan; Bosse, James L. Nano Letters, Vol. 16, Issue 6 https://doi.org/10.1021/acs.nanolett.5b04157	journal	May 2016
Fabrication of Planar Heterojunction Perovskite Solar Cells by Controlled Low-Pressure Vapor Annealing Li, Yanbo; Cooper, Jason K.; Buonsanti, Raffaella The Journal of Physical Chemistry Letters, Vol. 6, Issue 3 https://doi.org/10.1021/jz502720a	journal	January 2015
Spatially Non-uniform Trap State Densities in Solution-Processed Hybrid Perovskite Thin Films Draguta, Sergiu; Thakur, Siddharatha; Morozov, Yurii V. The Journal of Physical Chemistry Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acs.jpclett.5b02888	journal	February 2016
Optoelectronic Studies of Methylammonium Lead Iodide Perovskite Solar Cells with Mesoporous TiO ₂ : Separation of Electronic and Chemical Charge Storage, Understanding Two Recombination Lifetimes, and the Evolution of Band Offsets during J – V Hysteresis O’Regan, Brian C.; Barnes, Piers R. F.; Li, Xiaoe Journal of the American Chemical Society, Vol. 137, Issue 15 https://doi.org/10.1021/jacs.5b00761	journal	April 2015
Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites Coll, Mariona; Gomez, Andrés; Mas-Marza, Elena The Journal of Physical Chemistry Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acs.jpclett.5b00502	journal	April 2015
Enhancing the Hole-Conductivity of Spiro-OMeTAD without Oxygen or Lithium Salts by Using Spiro(TFSI) ₂ in Perovskite and Dye-Sensitized Solar Cells Nguyen, William H.; Bailie, Colin D.; Unger, Eva L. Journal of the American Chemical Society, Vol. 136, Issue 31 https://doi.org/10.1021/ja504539w	journal	July 2014
Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability Jinsong, Huang,; Yongbo, Yuan, American Chemical Society https://doi.org/10.17615/2vnf-mm34	text	January 2016
Photo-induced halide redistribution in organic-inorganic perovskite films. DeQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M. Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.12475	text	January 2016
Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells Zhengguo, Xio,; Yuchuan, Shao,; Jinsong, Huang, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/kpp6-9914	text	January 2014

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