Surface versus Bulk Currents and Ionic Space-Charge Effects in CsPbBr3 Single Crystals

CsPbBr3 single crystals have potential for application in ionizing-radiation detection devices due to their optimal optoelectronic properties. Yet, their mixed ionic–electronic conductivity produces instability and hysteretic artifacts hindering the long-term device operation. Herein, we report an electrical characterization of CsPbBr3 single crystals operating up to the time scale of hours. Our fast time-of-flight measurements reveal bulk mobilities of 13–26 cm2 V–1 s–1 with a negative voltage bias dependency. By means of a guard ring (GR) configuration, we separate bulk and surface mobilities showing significant qualitative and quantitative transport differences. Our experiments of current transients and impedance spectroscopy indicate the formation of several regimes of space-charge-limited current (SCLC) associated with mechanisms similar to the Poole–Frenkel ionized-trap-assisted transport. We show that the ionic-SCLC seems to be an operational mode in this lead halide perovskite, despite the fact that experiments can be designed where the contribution of mobile ions to transport is negligible.

[1]  G. Garcia‐Belmonte,et al.  Coupling between Ion Drift and Kinetics of Electronic Current Transients in MAPbBr3 Single Crystals , 2022, ACS energy letters.

[2]  Device Performance of Emerging Photovoltaic Materials (Version 2) , 2021, Advanced Energy Materials.

[3]  G. Garcia‐Belmonte,et al.  Ballistic-like space-charge-limited currents in halide perovskites at room temperature , 2021, Applied Physics Letters.

[4]  R. D. De Souza,et al.  Nonlinear ion mobility at high electric field strengths in the perovskites SrTiO3 and CH3NH3PbI3 , 2021, Physical Review Materials.

[5]  M. Kanatzidis,et al.  On the Origin of Room-Temperature Amplified Spontaneous Emission in CsPbBr3 Single Crystals , 2021, Chemistry of Materials.

[6]  M. Johnston,et al.  Crystallization of CsPbBr3 single crystals in water for X-ray detection , 2021, Nature Communications.

[7]  Jianxu Ding,et al.  Highly In-Plane Polarization-Sensitive Photodetection in CsPbBr3 Single Crystal. , 2021, The journal of physical chemistry letters.

[8]  C. Brabec,et al.  Characterization of Aerosol Deposited Cesium Lead Tribromide Perovskite Films on Interdigited ITO Electrodes , 2021, Advanced Electronic Materials.

[9]  H. Akiyama,et al.  Exciton Localization and Enhancement of the Exciton–LO Phonon Interaction in a CsPbBr3 Single Crystal , 2020 .

[10]  Joshua W. Kleppinger,et al.  Growth of Large-Area Cd₀.₉Zn₀.₁Te Single Crystals and Fabrication of Pixelated Guard-Ring Detector for Room-Temperature γ-Ray Detection , 2020, IEEE Transactions on Nuclear Science.

[11]  Jiaoxian Yu,et al.  Perovskite CsPbBr3 crystals: growth and applications , 2020 .

[12]  Xiaoyan Liang,et al.  Study on the Performance of a Planar CdZnTe Detector with Guard-Ring , 2020, Journal of Electronic Materials.

[13]  C. Brabec,et al.  Sensitive Direct Converting X‐Ray Detectors Utilizing Crystalline CsPbBr3 Perovskite Films Fabricated via Scalable Melt Processing , 2020, Advanced Materials Interfaces.

[14]  Vincent M. Le Corre,et al.  Toward Understanding Space-Charge Limited Current Measurements on Metal Halide Perovskites , 2020, ACS Energy Letters.

[15]  Guangda Niu,et al.  Rubidium Doping to Enhance Carrier Transport in CsPbBr3 Single Crystals for High-Performance X-Ray Detection. , 2019, ACS applied materials & interfaces.

[16]  Zhiping Zheng,et al.  Ionic transport characteristics of large-size CsPbBr3 single crystals , 2019, Materials Research Express.

[17]  X. Miao,et al.  Hot‐Pressed CsPbBr3 Quasi‐Monocrystalline Film for Sensitive Direct X‐ray Detection , 2019, Advanced materials.

[18]  C. Brabec,et al.  Ionic dipolar switching hinders charge collection in perovskite solar cells with normal and inverted hysteresis , 2019, Solar Energy Materials and Solar Cells.

[19]  G. Garcia‐Belmonte,et al.  On the Utilization of Temperature-Sweeping Capacitive Techniques to Evaluate Band-Gap Defect Densities in Photovoltaic Perovskites. , 2019, The journal of physical chemistry letters.

[20]  Chong Qu,et al.  Growth and optoelectronic application of CsPbBr3 thin films deposited by pulsed-laser deposition. , 2019, Optics letters.

[21]  H. Jung,et al.  Efficient and stable green-emitting CsPbBr3 perovskite nanocrystals in a microcapsule for light emitting diodes , 2018, Chemical Engineering Journal.

[22]  L. Quan,et al.  Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent , 2018, Nature.

[23]  X. Tao,et al.  Anisotropic Optoelectronic Properties of Melt-Grown Bulk CsPbBr3 Single Crystal. , 2018, The journal of physical chemistry letters.

[24]  C. Brabec,et al.  Assessing Temperature Dependence of Drift Mobility in Methylammonium Lead Iodide Perovskite Single Crystals , 2018 .

[25]  A. Nenashev,et al.  Field dependence of hopping mobility: Lattice models against spatial disorder , 2017 .

[26]  Ce Zhou,et al.  Centimeter-Sized Inorganic Lead Halide Perovskite CsPbBr3 Crystals Grown by an Improved Solution Method , 2017 .

[27]  Darien J. Morrow,et al.  Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO3). , 2017, Journal of the American Chemical Society.

[28]  Jinsong Huang,et al.  Dopant compensation in alloyed CH3NH3PbBr3-xClx perovskite single crystals for gamma-ray spectroscopy. , 2017, Nature materials.

[29]  Thilo Michel,et al.  High-performance direct conversion X-ray detectors based on sintered hybrid lead triiodide perovskite wafers , 2017, Nature Photonics.

[30]  H. Zeng,et al.  Ultralarge All‐Inorganic Perovskite Bulk Single Crystal for High‐Performance Visible–Infrared Dual‐Modal Photodetectors , 2017 .

[31]  H. Cui,et al.  High Detectivity and Rapid Response in Perovskite CsPbBr3 Single-Crystal Photodetector , 2017 .

[32]  Namchul Cho,et al.  Inorganic Lead Halide Perovskite Single Crystals: Phase‐Selective Low‐Temperature Growth, Carrier Transport Properties, and Self‐Powered Photodetection , 2017 .

[33]  G. Garcia‐Belmonte,et al.  On Mott-Schottky analysis interpretation of capacitance measurements in organometal perovskite solar cells , 2016 .

[34]  Marcus L. Böhm,et al.  Low-Temperature Solution-Grown CsPbBr3 Single Crystals and Their Characterization , 2016 .

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

[36]  M. Kanatzidis,et al.  Excitonic emissions and above-band-gap luminescence in the single-crystal perovskite semiconductors CsPbB r 3 and CsPbC l 3 , 2015 .

[37]  Ming Liu,et al.  Charge carrier hopping transport based on Marcus theory and variable-range hopping theory in organic semiconductors , 2015 .

[38]  Juan Bisquert,et al.  Capacitive Dark Currents, Hysteresis, and Electrode Polarization in Lead Halide Perovskite Solar Cells. , 2015, The journal of physical chemistry letters.

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

[40]  Zhifu Liu,et al.  Crystal Growth of the Perovskite Semiconductor CsPbBr3: A New Material for High-Energy Radiation Detection , 2013 .

[41]  Jin Young Kim,et al.  Diffusion studies on Si-PIN x-ray detectors with guard-rings for single photon counting sensors , 2010, Optical Engineering + Applications.

[42]  R. Coehoorn,et al.  Carrier-density and field-dependent charge-carrier mobility in organic semiconductors with correlated Gaussian disorder , 2009 .

[43]  Jin-Young Kim,et al.  Effect of a Guard-Ring on the Leakage Current in a Si-PIN X-Ray Detector for a Single Photon Counting Sensor , 2008, IEICE Trans. Electron..

[44]  H. Khoury,et al.  Evaluation of a multi-guard ring (MGR) structure diode as diagnostic X-ray dosimeter , 2007 .

[45]  S. K. Kataria,et al.  Role of guard rings in improving the performance of silicon detectors , 2005 .

[46]  K. Yasuda,et al.  Study of multi-electrodes structure in CdTe nuclear radiation detectors , 2004, IEEE Symposium Conference Record Nuclear Science 2004..

[47]  G. Sato,et al.  Improvement of the CdTe diode detectors using a guard-ring electrode , 2004, IEEE Transactions on Nuclear Science.

[48]  G. Bertuccio,et al.  Silicon carbide for high resolution X-ray detectors operating up to 100°C☆ , 2004 .

[49]  K. Wyllie.  Floating guard rings as high-voltage termination structures for radiation-tolerant silicon detectors , 1998 .

[50]  E. Conwell,et al.  High-field hopping mobility of polarons in disordered molecular solids. A Monte Carlo study , 1994 .

[51]  Ranko Richert,et al.  Poole-Frenkel behavior of charge transport in organic solids with off-diagonal disorder studied by Monte Carlo simulation , 1990 .

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

[53]  P. Murgatroyd,et al.  Theory of space-charge-limited current enhanced by Frenkel effect , 1970 .

[54]  H. Fröhlich.  Electronic Processes in Ionic Crystals , 1949, Nature.

[55]  D. C. Stockbarger.  Artificial fluorite. , 1949, Journal of the Optical Society of America.

[56]  J. Frenkel,et al.  On Pre-Breakdown Phenomena in Insulators and Electronic Semi-Conductors , 1938 .

[57]  P. W. Bridgman.  Certain Physical Properties of Single Crystals of Tungsten, Antimony, Bismuth, Tellurium, Cadmium, Zinc, and Tin , 1925 .

[58]  Irving Langmuir,et al.  The Effect of Space Charge and Residual Gases on Thermionic Currents in High Vacuum , 1913 .

[59]  C. D. Child,et al.  Discharge From Hot Cao , 1911 .