Ions Matter: Description of the Anomalous Electronic Behavior in Methylammonium Lead Halide Perovskite Devices

Carrier transport in methylammonium lead iodide (MAPbI3)-based hybrid organic–inorganic perovskites (HOIPs) is obscured by vacancy-mediated ion migration. Thus, the nature of migrating species (cation/anion) and their effect on electronic transport in MAPbI3 has remained controversial. Temperature-dependent pulsed voltage–current measurements of MAPbI3 thin films are performed under dark conditions, designed to decouple ion-migration/accumulation and electronic transport. Measurement conditions (electric-field history and scan rate) are shown to affect the electronic transport in MAPbI3 thin films, through a mechanism involving ion migration and accumulation at the electrode interfaces. The presence of thermally activated processes with distinct activation energies (Ea) of 0.1 ± 0.001 and 0.41 ± 0.02 eV is established, and are assigned to electromigration of iodine vacancies and methylammonium vacancies, respectively. Analysis of activation energies obtained from electronic conduction versus capacitive discharge shows that the electromigration of these ionic species is responsible for the modification of interfacial electronic properties of MAPbI3, and elaborates previously unaddressed issues of “fast” and “slow” ion migration. The results demonstrate that the intrinsic behavior of MAPbI3 material is responsible for the hysteresis of the solar cells, but also have implications for other HOIP-based devices, such as memristors, detectors, and energy storage devices.

[1]  Hiroshi Suga,et al.  Dielectric study of CH3NH3PbX3 (X = Cl, Br, I) , 1992 .

[2]  Nakita K. Noel,et al.  Anomalous Hysteresis in Perovskite Solar Cells. , 2014, The journal of physical chemistry letters.

[3]  Aron Walsh,et al.  Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells , 2014, 1405.5810.

[4]  Zhengguo Xiao,et al.  Energy‐Efficient Hybrid Perovskite Memristors and Synaptic Devices , 2016 .

[5]  Zheng-Hong Lu,et al.  Work function of fluorine doped tin oxide , 2011 .

[6]  S. Meloni,et al.  Ionic polarization-induced current–voltage hysteresis in CH3NH3PbX3 perovskite solar cells , 2016, Nature Communications.

[7]  R. Waser,et al.  Nanoionics-based resistive switching memories. , 2007, Nature materials.

[8]  Aron Walsh,et al.  Ionic transport in hybrid lead iodide perovskite solar cells , 2015, Nature Communications.

[9]  Yongbo Yuan,et al.  Photovoltaic Switching Mechanism in Lateral Structure Hybrid Perovskite Solar Cells , 2015 .

[10]  E. Tsymbal,et al.  Surface Electronic Structure of Hybrid Organo Lead Bromide Perovskite Single Crystals , 2016 .

[11]  N. Zhao,et al.  Native Defect‐Induced Hysteresis Behavior in Organolead Iodide Perovskite Solar Cells , 2016 .

[12]  Eric T. Hoke,et al.  Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics† †Electronic supplementary information (ESI) available: Experimental details, PL, PDS spectra and XRD patterns. See DOI: 10.1039/c4sc03141e Click here for additional data file. , 2014, Chemical science.

[13]  T. N. Guru Row,et al.  Is CH3NH3PbI3 Polar? , 2016, The journal of physical chemistry letters.

[14]  Wolfgang Kowalsky,et al.  Water Infiltration in Methylammonium Lead Iodide Perovskite : Fast and Inconspicuous , 2015 .

[15]  Yongbo Yuan,et al.  Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability. , 2016, Accounts of chemical research.

[16]  Wei Zhang,et al.  Metal halide perovskites for energy applications , 2016, Nature Energy.

[17]  Yanfa Yan,et al.  Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber , 2014 .

[18]  Wei Zhang,et al.  Photo-induced halide redistribution in organic–inorganic perovskite films , 2016, Nature Communications.

[19]  David Cahen,et al.  Hybrid organic—inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties , 2016 .

[20]  Nazifah Islam,et al.  Ionic and Optical Properties of Methylammonium Lead Iodide Perovskite across the Tetragonal-Cubic Structural Phase Transition. , 2016, ChemSusChem.

[21]  Darryl P Almond,et al.  An Explanation of the Photoinduced Giant Dielectric Constant of Lead Halide Perovskite Solar Cells. , 2015, The journal of physical chemistry letters.

[22]  A. Walsh,et al.  What Is Moving in Hybrid Halide Perovskite Solar Cells? , 2016, Accounts of chemical research.

[23]  T. Peltola,et al.  Can slow-moving ions explain hysteresis in the current–voltage curves of perovskite solar cells? , 2016 .

[24]  Patrick Pons,et al.  Voltage and temperature effect on dielectric charging for RF-MEMS capacitive switches reliability investigation , 2008, Microelectron. Reliab..

[25]  Henry J Snaith,et al.  Metal-halide perovskites for photovoltaic and light-emitting devices. , 2015, Nature nanotechnology.

[26]  Christophe Ballif,et al.  Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance. , 2014, The journal of physical chemistry letters.

[27]  Lei Meng,et al.  Recent Advances in the Inverted Planar Structure of Perovskite Solar Cells. , 2016, Accounts of chemical research.

[28]  Sung-Hoon Lee,et al.  The Role of Intrinsic Defects in Methylammonium Lead Iodide Perovskite. , 2014, The journal of physical chemistry letters.

[29]  J. Bisquert,et al.  Defect migration in methylammonium lead iodide and its role in perovskite solar cell operation , 2015 .

[30]  Eric T. Hoke,et al.  Hysteresis and transient behavior in current–voltage measurements of hybrid-perovskite absorber solar cells , 2014 .

[31]  Kai Zhu,et al.  Room-temperature crystallization of hybrid-perovskite thin films via solvent–solvent extraction for high-performance solar cells , 2015 .

[32]  P. Delugas,et al.  Thermally Activated Point Defect Diffusion in Methylammonium Lead Trihalide: Anisotropic and Ultrahigh Mobility of Iodine. , 2016, The journal of physical chemistry letters.

[33]  Qingfeng Dong,et al.  Giant switchable photovoltaic effect in organometal trihalide perovskite devices. , 2015, Nature materials.

[34]  E. Sargent,et al.  Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals , 2015, Science.

[35]  Keitaro Sodeyama,et al.  First-Principles Study of Ion Diffusion in Perovskite Solar Cell Sensitizers. , 2015, Journal of the American Chemical Society.

[36]  Q. Gong,et al.  Inverted Perovskite Solar Cells: Progresses and Perspectives , 2016 .

[37]  Fujun Zhang,et al.  Dynamic interface charge governing the current-voltage hysteresis in perovskite solar cells. , 2015, Physical chemistry chemical physics : PCCP.

[38]  Yuanyuan Zhou,et al.  Direct Observation of Ferroelectric Domains in Solution-Processed CH3NH3PbI3 Perovskite Thin Films. , 2014, The journal of physical chemistry letters.

[39]  A. Köhler,et al.  Iodine Migration and its Effect on Hysteresis in Perovskite Solar Cells , 2016, Advanced materials.

[40]  H. Fan,et al.  Discerning the Surface and Bulk Recombination Kinetics of Organic–Inorganic Halide Perovskite Single Crystals , 2016 .

[41]  Leeor Kronik,et al.  Theory of Hydrogen Migration in Organic–Inorganic Halide Perovskites , 2015, Angewandte Chemie.

[42]  Tingting Shi,et al.  Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance , 2014, Advanced materials.

[43]  Juan Bisquert,et al.  Photoinduced Giant Dielectric Constant in Lead Halide Perovskite Solar Cells. , 2014, The journal of physical chemistry letters.

[44]  Z. Yin,et al.  Enhanced electron extraction using SnO2 for high-efficiency planar-structure HC(NH2)2PbI3-based perovskite solar cells , 2016, Nature Energy.

[45]  Jinsong Huang,et al.  Grain boundary dominated ion migration in polycrystalline organic–inorganic halide perovskite films , 2016 .