Local Strain Heterogeneity Influences the Optoelectronic Properties of Halide Perovskites

Halide perovskites are promising semiconductors for optoelectronics, yet thin films show substantial microscale heterogeneity. Understanding the origins of these variations is essential for mitigating parasitic losses such as non-radiative decay. Here, we probe the structural and chemical origins of the heterogeneity by utilizing scanning X-ray diffraction beamlines at two different synchrotrons combined with high-resolution transmission electron microscopy to spatially characterize the crystallographic properties of individual micrometer-sized perovskite grains in high-quality films. We reveal new levels of heterogeneity on the ten-micrometer scale (super-grains) and even ten-nanometer scale (sub-grain domains). By directly correlating these properties with their corresponding local time-resolved photoluminescence properties, we find that regions showing the greatest luminescence losses correspond to strained regions, which arise from enhanced defect concentrations. Our work reveals remarkably complex heterogeneity across multiple length scales, shedding new light on the defect tolerance of perovskites.

[1]  Olivier Durand,et al.  Light-induced lattice expansion leads to high-efficiency perovskite solar cells , 2018, Science.

[2]  Edward P. Booker,et al.  Maximizing and stabilizing luminescence from halide perovskites with potassium passivation , 2018, Nature.

[3]  James E. Bishop,et al.  In situ simultaneous photovoltaic and structural evolution of perovskite solar cells during film formation , 2018 .

[4]  J. Etheridge,et al.  Microstructural Characterisations of Perovskite Solar Cells – From Grains to Interfaces: Techniques, Features, and Challenges , 2017 .

[5]  Dane W. deQuilettes,et al.  Tracking Photoexcited Carriers in Hybrid Perovskite Semiconductors: Trap-Dominated Spatial Heterogeneity and Diffusion. , 2017, ACS nano.

[6]  Jinsong Huang,et al.  Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells , 2017, Science Advances.

[7]  Sandeep Kumar Pathak,et al.  Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals , 2017 .

[8]  Dong Uk Lee,et al.  Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells , 2017, Science.

[9]  S. Stranks Nonradiative Losses in Metal Halide Perovskites , 2017 .

[10]  Jay B. Patel,et al.  Crystallization Kinetics and Morphology Control of Formamidinium–Cesium Mixed‐Cation Lead Mixed‐Halide Perovskite via Tunability of the Colloidal Precursor Solution , 2017, Advanced materials.

[11]  Miao Hu,et al.  Real-Time Nanoscale Open-Circuit Voltage Dynamics of Perovskite Solar Cells. , 2017, Nano letters.

[12]  Rachel C. Kurchin,et al.  Perovskite-Inspired Photovoltaic Materials: Toward Best Practices in Materials Characterization and Calculations , 2017 .

[13]  Wei Li,et al.  Direct observation of intrinsic twin domains in tetragonal CH3NH3PbI3 , 2017, Nature Communications.

[14]  Henk J. Bolink,et al.  Efficient vacuum deposited p-i-n and n-i-p perovskite solar cells employing doped charge transport layers , 2016 .

[15]  Anders Hagfeldt,et al.  Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance , 2016, Science.

[16]  Jay B. Patel,et al.  Efficient perovskite solar cells by metal ion doping , 2016 .

[17]  David S. Ginger,et al.  Photoluminescence Lifetimes Exceeding 8 μs and Quantum Yields Exceeding 30% in Hybrid Perovskite Thin Films by Ligand Passivation , 2016 .

[18]  D. F. Ogletree,et al.  Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite , 2016, Nature Energy.

[19]  Brookhaven National Laboratory,et al.  Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite , 2016, 1606.09267.

[20]  R. Friend,et al.  Mapping Morphological and Structural Properties of Lead Halide Perovskites by Scanning Nanofocus XRD , 2016, 1606.04096.

[21]  James J. Steffes,et al.  Mapping the Photoresponse of CH3NH3PbI3 Hybrid Perovskite Thin Films at the Nanoscale. , 2016, Nano letters.

[22]  Edward H. Sargent,et al.  Perovskite photonic sources , 2016, Nature Photonics.

[23]  Anders Hagfeldt,et al.  Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5ee03874j Click here for additional data file. , 2016, Energy & environmental science.

[24]  M. Green,et al.  Energy conversion approaches and materials for high-efficiency photovoltaics. , 2016, Nature materials.

[25]  Wei Zhang,et al.  Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells , 2015, Nature Communications.

[26]  G. Eperon,et al.  Charge Carriers in Planar and Meso-Structured Organic-Inorganic Perovskites: Mobilities, Lifetimes, and Concentrations of Trap States. , 2015, The journal of physical chemistry letters.

[27]  Libai Huang,et al.  Spatial and temporal imaging of long-range charge transport in perovskite thin films by ultrafast microscopy , 2015, Nature Communications.

[28]  D. Ginger,et al.  Impact of microstructure on local carrier lifetime in perovskite solar cells , 2015, Science.

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

[30]  Y. Kanemitsu,et al.  Spontaneous Defect Annihilation in CH3NH3PbI3 Thin Films at Room Temperature Revealed by Time-Resolved Photoluminescence Spectroscopy. , 2015, The journal of physical chemistry letters.

[31]  Alain Goriely,et al.  Recombination Kinetics in Organic-Inorganic Perovskites: Excitons, Free Charge, and Subgap States , 2014 .

[32]  Jing Feng Mechanical properties of hybrid organic-inorganic CH3NH3BX3 (B = Sn, Pb; X = Br, I) perovskites for solar cell absorbers , 2014 .

[33]  G. Ice,et al.  Strain and Dislocation Gradients from Diffraction:Spatially-Resolved Local Structure and Defects , 2014 .

[34]  S. Kurtz,et al.  Strong Internal and External Luminescence as Solar Cells Approach the Shockley–Queisser Limit , 2011, IEEE Journal of Photovoltaics.

[35]  J. Aizenberg,et al.  Mechanism of calcite co-orientation in the sea urchin tooth. , 2009, Journal of the American Chemical Society.

[36]  Gregory Y. Morrison,et al.  A dedicated superbend x-ray microdiffraction beamline for materials, geo-, and environmental sciences at the advanced light source. , 2009, The Review of scientific instruments.

[37]  Ning Gu,et al.  Facile synthesis of micrometer-sized gold nanoplates through an aniline-assisted route in ethylene glycol solution , 2006 .

[38]  A. Stoneham,et al.  Non-radiative transitions in semiconductors , 1981 .

[39]  John Ziman,et al.  A theory of the electrical properties of liquid metals , 1965 .

[40]  J. R. Haynes,et al.  Trapping of Minority Carriers in Silicon. I. P -Type Silicon , 1955 .