High‐Resolution In‐Situ Synchrotron X‐Ray Studies of Inorganic Perovskite CsPbBr3: New Symmetry Assignments and Structural Phase Transitions
Year: 2021
Type: article
Abstract: Perovskite photovoltaic ABX3 systems are being studied due to their high energy‐conversion efficiencies with current emphasis placed on pure inorganic systems. In this work, synchrotron single‐crystal diffraction measurements combined with second harmonic generation measurements reveal the absence of inversion symmetry below room temperature in CsPbBr3. Local structural analysis by pair distribution function and X‐ray absorption fine structure methods are performed to ascertain the local ordering, atomic pair correlations, and phase evolution in a broad range of temperatures. The currently accepted space group assignments for CsPbBr3 are found to be incorrect in a manner that profoundly impacts physical properties. New assignments are obtained for the bulk structure: (above ≈410 K), P21/m (between ≈300 K and ≈410 K), and the polar group Pm (below ≈300 K), respectively. The newly observed structural distortions exist in the bulk structure consistent with the expectation of previous photoluminescence and Raman measurements. High‐pressure measurements reveal multiple low‐pressure phases, one of which exists as a metastable phase at ambient pressure. This work should help guide research in the perovskite photovoltaic community to better control the structure under operational conditions and further improve transport and optical properties.
Source: Advanced Science
Language: English
Subfield: Electrical and Electronic Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $5,000
Funders: National Science Foundation, U.S. Department of Energy, National Energy Research Scientific Computing Center, Nanjing Institute of Technology, Office of Science, Division of Materials Research, Division of Chemistry, Basic Energy Sciences, Air Force Materiel Command, Air Force Office of Scientific Research, Brookhaven National Laboratory
Awards: G102163711, THE CHICAGO/DOE ALLIANCE CENTER (CDAC)IS DEDICATED TO BASIC RESEARCH, TRAINING, AND TECHNIQUE DEVELOPMENT IN THE STUDY OF MATERIALS IN EXTREME CONDITIONS. THE CENTER HAS ENABLED NUMEROUS ADVANCES IN HIGH P-T SCIENCE, TECHNOLOGY, AND TRAINING SINCE ITS INCEPTION 16 YEARS AGO AS THE CARNEGIE/DOE ALLIANCE CENTER. THESE ADVANCES INCLUDE STUDENT AND POSTDOC-LED SCIENTIFIC DISCOVERIES AND A SUCCESSFUL TRACK RECORD IN TRAINING EARLY CAREER SCIENTISTS FOR WORK IN THE NNSA COMPLEX.
MATERIALS OF INTEREST ENCOMPASS CRYSTALLINE SOLIDS, FLUIDS AND GLASSES, NANOSTRUCTURED TO MESOSTRUCTURED MATERIALS, AND COMPLEX COMPOSITES. CHEMICALLY THESE MATERIALS INCLUDE D- AND F-ELECTRON ELEMENTS AND ALLOYS, LOW-Z MOLECULAR COMPOUNDS, ENERGETIC MATERIALS AND DETONATION PRODUCTS, DENSE GASES, METAL OXIDES AND HYDRIDES, AND CHEMICALLY HETEROGENEOUS SUBSTANCES. CDAC WILL ADVANCE UNDERSTANDING OF THESE STEWARDSHIP-RELATED CLASSES OF MATERIALS IN EXTREME CONDITIONS IN THE FOLLOWING SIX MATERIAL PROPERTY THRUSTS (1) HIGH P-T STRUCTURES AND PHASE RELATIONS; (2) P-V-T EQUATIONS OF STATE; (3) PHONONS, VIBRATIONAL THERMODYNAMICS, AND ELASTICITY; (4) PLASTICITY, YIELD STRENGTH, AND DEFORMATION; (5) ELECTRONIC AND MAGNETIC STRUCTURE AND DYNAMICS; AND (6) HIGH P-T CHEMISTRY. FOR EACH OF THESE ABOVE MATERIALS AND PROPERTIES THRUSTS, CDAC WILL ADDRESS NEW QUESTIONS, INCLUDING THE FOLLOWING:
• HOW CAN WE UNDERSTAND, PREDICT, AND CONTROL MATTER AND MATERIALS TO VERY HIGH COMPRESSIONS?
• WHAT NEW PHYSICS MAY EMERGE IN ‘COLD’ TO ‘WARM’ DENSE MATTER?
• HOW CAN WE ACCURATELY DETERMINE FUNDAMENTAL THERMODYNAMIC PROPERTIES TO VERY HIGH P AND T?
• HOW DO DEFECTS, GRAIN BOUNDARIES, AND INTERFACES RESPOND TO HIGH P-T CONDITIONS AND STRAIN RATES?
• HOW CAN WE BETTER MEASURE TIME-DEPENDENT TRANSFORMATIONS, AND BRIDGE STRAIN-RATE GAPS BETWEEN STATIC, QUASI-STATIC, AND DYNAMIC COMPRESSION?
• CAN WE BETTER DETERMINE STRENGTH, PLASTICITY, AND RHEOLOGY AT VERY HIGH P-T CONDITIONS?
• CAN WE EXPAND THE HIGH P-T SYNTHETIC CHEMISTRY FRONTIER TO PRODUCE NEW, OPTIMIZED MATERIALS?
CDAC WILL ADDRESS THESE QUESTIONS WITH BOTH STATIC AND DYNAMIC COMPRESSION EXPERIMENTS TOGETHER WITH THEORY, MODELING, AND SIMULATION IN CDAC UNIVERSITY LABORATORIES AS WELL AS DOE/SC AND DOE/NNSA FACILITIES. THE WORK WILL BE ENABLED BY CONTINUED ACCESS TO CDAC’S PARTNER SYNCHROTRON RADIATION FACILITIES, HIGH PRESSURE COLLABORATIVE ACCESS TEAM (HPCAT) AT THE ADVANCED PHOTON SOURCE, ARGONNE NATIONAL LABORATORY (ANL) AND THE FRONTIER INFRARED SPECTROSCOPY (FIS) BEAMLINE AT THE NATIONAL SYNCHROTRON LIGHT SOURCE II, BROOKHAVEN NATIONAL LABORATORY (BNL), AS WELL AS OTHER FACILITIES. THE OVERARCHING SCIENTIFIC OUTCOME IS ADVANCING FUNDAMENTAL UNDERSTANDING OF MATERIALS BEHAVIOR IN EXTREME CONDITIONS, WHICH IN TURN WILL LEAD TO IMPROVED UNDERSTANDING OF MATERIALS AGING, PERFORMANCE OF NEWLY MANUFACTURED MATERIALS, MATERIALS IN MULTIPLE EXTREME ENVIRONMENTS, AND THE CREATION OF NEW MATERIALS.
CDAC ENGAGEMENT WITH NNSA PROGRAMS AT ANL AND WITH ITS PARTNER GROUPS IN ILLINOIS WILL BE SIGNIFICANTLY ENHANCED BY ITS MOVE TO THE UNIVERSITY OF ILLINOIS (UIC). CDAC WILL CONTINUE ITS ACTIVE PROGRAM IN EDUCATION AND TRAINING OF NEXT-GENERATION RESEARCHERS FOR STEWARDSHIP SCIENCE. IN SO DOING, CDAC WILL HOST STUDENT WORKSHOPS AND SPONSOR MEETINGS AND SYMPOSIA FOR THE BROADER COMMUNITY. THE CENTER WILL FACILITATE STUDENT ENGAGEMENT WITH NNSA LABORATORIES AND BE A VEHICLE FOR INTRODUCING EARLY CAREER SCIENTISTS TO NNSA LABORATORY PROGRAMS. THE CENTER WILL CONTINUE TO CLOSELY COLLABORATE WITH OTHER ACADEMIC GROUPS, OTHER SSAA AWARDEES, AND NATIONAL LABORATORY SCIENTISTS. CDAC WILL CONTINUE TO LEVERAGE THE SSAA COOPERATIVE AGREEMENT WITH ADDITIONAL GRANTS, WHICH SO FAR HAVE MULTIPLIED BY SEVERAL TIMES THE IMPACT AND INVESTMENT OF NNSA IN THE CENTER. FINALLY, CDAC WILL CONTINUE TO SUPPORT USE OF NNSA FACILITIES, INCLUDING NIF, Z, AND LANSCE, AND FEASIBILITY STUDIES FOR NEXT-GENERATION NNSA FACILITIES., G1210759672, G122673668, G1285306620, G1286236842, G1286251239, G1287846976, G1414775356, G1445641779, G1505794299, G1523888516, G1643559597, G1677143136, G1769256354, G1816284028, NSF's ChemMatCARS: A synchrotron X-ray national facility for chemistry and materials research at the Advanced Photon Source, G1847291448, G1863003419, G1868695577, G2101401529, G2287611682, G2406398159, G241279073, G262962599, G2829608538, G2959462655, Impact of Nanoscale Structure on Properties of Multiferroic Complex Oxides, G302599308, G3031701862, G30714459, G3083819904, Consortium for Materials Properties Research in Earth Sciences (COMPRES): National Facilities and Infrastructure Development for High-Pressure Geosciences Research, G3262563802, G3310577945, G357145406, G3589692066, G365575497, G3850097093, ChemMatCARS: A synchrotron X-ray national facility for chemistry and materials research at the Advanced Photon Source, G4038517476, G419881185, G426311843, G4279724742, G42916606, G4501827968, G4516736450, G4662383146, G4713042109, G4972998915, G498139845, G5076365615, G5094606986, G5106849484, G513797252, G5296923526, G5387317844, G5417557083, G5535608740, G5632581352, G5633341255, G5765906131, G5849692847, G5910536577, G5986892838, G6330817128, G6343337543, G650090426, G6671297155, G6733788163, G6836203857, G6848031779, G6918803902, G6965541988, G7047700447, G7098706596, G7368700025, G741291543, G7463374569, G7583137537, G7990639328, G805243471, Hybrid Halide Perovskite Materials for Photocatalytic Carbon-Carbon Bond Formation, G872144517, G8978062500, G969889393, G993149817
OpenAlex ID: W3178630009