The Significance of Ion Conduction in a Hybrid Organic-Inorganic Lead-Iodide-Based Perovskite Photosensitizer.

The success of perovskite solar cells has sparked enormous excitement in the photovoltaic community not only because of unexpectedly high efficiencies but also because of the future potential ascribed to such crystalline absorber materials. Far from being exhaustively studied in terms of solid-state properties, these materials surprised by anomalies such as a huge apparent low-frequency dielectric constant and pronounced hysteretic current-voltage behavior. Here we show that methylammonium (but also formamidinium) iodoplumbates are mixed conductors with a large fraction of ion conduction because of iodine ions. In particular, we measure and model the stoichiometric polarization caused by the mixed conduction and demonstrate that the above anomalies can be explained by the build-up of stoichiometric gradients as a consequence of ion blocking interfaces. These findings provide insight into electrical charge transport in the hybrid organic-inorganic lead halide solar cells as well as into new possibilities of improving the photovoltaic performance by controlling the ionic disorder.

[1]  I. Yokota On the Electrical Conductivity of Cuprous Sulfide: A Diffusion Theory , 1953 .

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

[3]  Yoshihiro Furukawa,et al.  Chloride ion conductor CH3NH3GeCl3 studied by Rietveld analysis of X-ray diffraction and 35Cl NMR , 1995 .

[4]  J. Jamnik,et al.  Treatment of the Impedance of Mixed Conductors Equivalent Circuit Model and Explicit Approximate Solutions , 1999 .

[5]  Takashi Kondo,et al.  Comparative study on the excitons in lead-halide-based perovskite-type crystals CH3NH3PbBr3 CH3NH3PbI3 , 2003 .

[6]  Joachim Maier,et al.  Generalised equivalent circuits for mass and charge transport: chemical capacitance and its implications , 2001 .

[7]  Mercouri G Kanatzidis,et al.  Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. , 2013, Inorganic chemistry.

[8]  Rainer Waser,et al.  dc Electrical Degradation of Perovskite‐Type Titanates: III, A Model of the Mechanism , 1990 .

[9]  Qi Chen,et al.  The identification and characterization of defect states in hybrid organic-inorganic perovskite photovoltaics. , 2015, Physical chemistry chemical physics : PCCP.

[10]  Peng Gao,et al.  Mixed-organic-cation perovskite photovoltaics for enhanced solar-light harvesting. , 2014, Angewandte Chemie.

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

[12]  Yoshihiro Furukawa,et al.  Phase Transition and Electric Conductivity of ASnCl3 (A = Cs and CH3NH3). , 1998 .

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

[14]  Juan Bisquert,et al.  Chemical capacitance of nanostructured semiconductors: its origin and significance for nanocomposite solar cells , 2003 .

[15]  Ruhul Amin,et al.  Defect Chemistry of LiFePO4 , 2008 .

[16]  J. Maier Mass Transport in the Presence of Internal Defect Reactions—Concept of Conservative Ensembles: I, Chemical Diffusion in Pure Compounds , 1993 .

[17]  Aron Walsh,et al.  Self-Regulation Mechanism for Charged Point Defects in Hybrid Halide Perovskites** , 2015, Angewandte Chemie.

[18]  Andrew R. Kitahara,et al.  Defect density and dielectric constant in perovskite solar cells , 2014 .

[19]  H. Snaith,et al.  Low-temperature processed meso-superstructured to thin-film perovskite solar cells , 2013 .

[20]  M. H. Hebb Electrical Conductivity of Silver Sulfide , 1952 .

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

[22]  J. Noh,et al.  Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells. , 2013, Nano letters.

[23]  J. Maier Evaluation of Electrochemical Methods in Solid State Research and Their Generalization for Defects with Variable Charges , 1984 .

[24]  Albrecht Poglitsch,et al.  Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy , 1987 .

[25]  Sergei Tretiak,et al.  High-efficiency solution-processed perovskite solar cells with millimeter-scale grains , 2015, Science.

[26]  Mao-Hua Du,et al.  Efficient carrier transport in halide perovskites: theoretical perspectives , 2014 .

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

[28]  N. Park,et al.  Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9% , 2012, Scientific Reports.

[29]  Aron Walsh,et al.  Structural and electronic properties of hybrid perovskites for high-efficiency thin-film photovoltaics from first-principles , 2013, 1309.4215.

[30]  G. Cantele,et al.  Ab initio investigation of hybrid organic-inorganic perovskites based on tin halides , 2008 .

[31]  I. Yokota On the Theory of Mixed Conduction with Special Reference to Conduction in Silver Sulfide Group Semiconductors , 1961 .

[32]  David B. Mitzi,et al.  Templating and structural engineering in organic–inorganic perovskites , 2001 .

[33]  M. White,et al.  Alkylammonium lead halides. Part 2. CH3NH3PbX3 (X = Cl, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation , 1990 .

[34]  J. Jamnik,et al.  Transport across Boundary Layers in Ionic Crystals Part I: General Formalism and Conception , 1997 .

[35]  J. Maier Electrochemical Investigation Methods of Ionic Transport Properties in Solids , 1994 .

[36]  M. Grätzel,et al.  Sequential deposition as a route to high-performance perovskite-sensitized solar cells , 2013, Nature.

[37]  Juan Bisquert,et al.  Slow Dynamic Processes in Lead Halide Perovskite Solar Cells. Characteristic Times and Hysteresis. , 2014, The journal of physical chemistry letters.

[38]  Laura M Herz,et al.  High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites , 2013, Advanced materials.

[39]  M. Grätzel,et al.  Title: Long-Range Balanced Electron and Hole Transport Lengths in Organic-Inorganic CH3NH3PbI3 , 2017 .

[40]  Sang Il Seok,et al.  Solvent engineering for high-performance inorganic-organic hybrid perovskite solar cells. , 2014, Nature materials.

[41]  Peng Gao,et al.  Impedance spectroscopic analysis of lead iodide perovskite-sensitized solid-state solar cells. , 2014, ACS nano.

[42]  Kazuo Fueki,et al.  Ionic conduction of the perovskite-type halides , 1983 .

[43]  D. L. Staebler,et al.  Electrocoloration in SrTiO3: Vacancy Drift and Oxidation-Reduction of Transition Metals , 1971 .

[44]  G. Papavassiliou,et al.  Some new organic-inorganic hybrid semiconductors based on metal halide units: Structural, optical and related properties , 1999 .

[45]  Laura M. Herz,et al.  Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber , 2013, Science.

[46]  Aron Walsh,et al.  Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells , 2014, Nano letters.

[47]  Tsutomu Miyasaka,et al.  Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. , 2009, Journal of the American Chemical Society.

[48]  Sang Il Seok,et al.  Voltage output of efficient perovskite solar cells with high open-circuit voltage and fill factor , 2014 .