X-ray study of anisotropically shaped metal halide perovskite nanoparticles in tubular pores

Recently, we have reported that metal halide perovskite nanoparticles formed in nanoporous alumina and silicon thin films exhibit blue shifted photoluminescence due to spatial confinement, thus allowing for color tuning of the emission by varying the pore size. While perovskite nanoparticles grown in nanoporous alumina films have been integrated into LEDs, similar approaches have failed with silicon. Here, we report the results of investigating the structure of the alumina pore system and the perovskite crystallites forming within. We use two x-ray diffraction techniques, namely, small-angle x-ray scattering (SAXS) and high-energy microbeam wide-angle x-ray scattering (WAXS). SAXS reveals that the alumina pore system diffracts like regularly arranged tubes with the average diameter and nearest neighbor distance of 12 nm and 20 nm, respectively. High-energy microbeam WAXS shows that perovskite nanoparticles within the nanoporous alumina have a distinctly anisotropic shape with the average particle length along and perpendicular to the pore axis of 26 nm and 13 nm, respectively. In contrast, no shape anisotropy has been detected for nanoparticles inside the silicon pores in a previous study. This suggests that utilizing nanoporous alumina has a twofold advantage. First, the tubular alumina pores, spanning the entire insulating film, offer percolated paths for the perovskite to fill. Second, the elongation of the nanoparticles in the tubular alumina pores can be expected to aid device performance as the length of the nanoparticles approaches the active layer thickness (ca. 40 nm) of LEDs, while the small diameter of the crystallites accounts for the observed blue shifted emission.Recently, we have reported that metal halide perovskite nanoparticles formed in nanoporous alumina and silicon thin films exhibit blue shifted photoluminescence due to spatial confinement, thus allowing for color tuning of the emission by varying the pore size. While perovskite nanoparticles grown in nanoporous alumina films have been integrated into LEDs, similar approaches have failed with silicon. Here, we report the results of investigating the structure of the alumina pore system and the perovskite crystallites forming within. We use two x-ray diffraction techniques, namely, small-angle x-ray scattering (SAXS) and high-energy microbeam wide-angle x-ray scattering (WAXS). SAXS reveals that the alumina pore system diffracts like regularly arranged tubes with the average diameter and nearest neighbor distance of 12 nm and 20 nm, respectively. High-energy microbeam WAXS shows that perovskite nanoparticles within the nanoporous alumina have a distinctly anisotropic shape with the average particle length a...

[1]  Victor Malgras,et al.  Stable Blue Luminescent CsPbBr3 Perovskite Nanocrystals Confined in Mesoporous Thin Films. , 2018, Angewandte Chemie.

[2]  E. Kymakis,et al.  Perovskite nanostructures for photovoltaic and energy storage devices , 2018 .

[3]  G. Rainò,et al.  Superfluorescence from lead halide perovskite quantum dot superlattices , 2018, Nature.

[4]  C. Brabec,et al.  Revealing Trap States in Lead Sulphide Colloidal Quantum Dots by Photoinduced Absorption Spectroscopy , 2018 .

[5]  Song Jin,et al.  Continuous‐Wave Lasing in Cesium Lead Bromide Perovskite Nanowires , 2018 .

[6]  J. Galisteo‐López,et al.  Strong Quantum Confinement and Fast Photoemission Activation in CH3NH3PbI3 Perovskite Nanocrystals Grown within Periodically Mesostructured Films , 2017 .

[7]  P. Kim,et al.  Unbalanced Hole and Electron Diffusion in Lead Bromide Perovskites. , 2017, Nano letters.

[8]  M. Kaltenbrunner,et al.  Confining metal-halide perovskites in nanoporous thin films , 2016, Science Advances.

[9]  Jasmina A. Sichert,et al.  Colloidal lead halide perovskite nanocrystals: synthesis, optical properties and applications , 2016 .

[10]  Victor Malgras,et al.  Observation of Quantum Confinement in Monodisperse Methylammonium Lead Halide Perovskite Nanocrystals Embedded in Mesoporous Silica. , 2016, Journal of the American Chemical Society.

[11]  Sunho Jeong,et al.  Parallelized Nanopillar Perovskites for Semitransparent Solar Cells Using an Anodized Aluminum Oxide Scaffold , 2016 .

[12]  M. Kovalenko,et al.  Harnessing Defect-Tolerance at the Nanoscale: Highly Luminescent Lead Halide Perovskite Nanocrystals in Mesoporous Silica Matrixes , 2016, Nano letters.

[13]  Oleksandr Voznyy,et al.  Highly Efficient Perovskite‐Quantum‐Dot Light‐Emitting Diodes by Surface Engineering , 2016, Advanced materials.

[14]  Matthew N. O’Brien,et al.  Templated Synthesis of Uniform Perovskite Nanowire Arrays. , 2016, Journal of the American Chemical Society.

[15]  Feng Gao,et al.  Colloidal metal halide perovskite nanocrystals: synthesis, characterization, and applications , 2016 .

[16]  Oleksandr Voznyy,et al.  Efficient Luminescence from Perovskite Quantum Dot Solids. , 2015, ACS applied materials & interfaces.

[17]  Yu Tong,et al.  Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets. , 2015, Nano letters.

[18]  Christopher H. Hendon,et al.  Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut , 2015, Nano letters.

[19]  Christopher J. Tassone,et al.  Chloride in lead chloride-derived organo-metal halides for perovskite-absorber solar cells , 2014 .

[20]  W. Lee,et al.  Porous anodic aluminum oxide: anodization and templated synthesis of functional nanostructures. , 2014, Chemical reviews.

[21]  Olga Malinkiewicz,et al.  Nontemplate synthesis of CH3NH3PbBr3 perovskite nanoparticles. , 2014, Journal of the American Chemical Society.

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

[23]  R. Feidenhans'l,et al.  Angle calculations for a (2+3)-type diffractometer: focus on area detectors , 2011 .

[24]  Norbert Schell,et al.  The High Energy Materials Science Beamline (HEMS) at PETRA III , 2010 .

[25]  Maik Naumann,et al.  Small-angle X-ray scattering (SAXS) off parallel, cylindrical, well-defined nanopores: from random pore distribution to highly ordered samples , 2009 .

[26]  J. Hedrick,et al.  Pore size distributions in nanoporous methyl silsesquioxane films as determined by small angle x-ray scattering , 2002 .

[27]  Ralf B. Wehrspohn,et al.  Self-ordering Regimes of Porous Alumina: The 10% Porosity Rule , 2002 .

[28]  Kenji Fukuda,et al.  Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb Structures of Anodic Alumina , 1995, Science.