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Title: Size-Dependent Lattice Structure and Confinement Properties in CsPbI3 Perovskite Nanocrystals: Negative Surface Energy for Stabilization

Abstract

CsPbI3 nanocrystals with narrow size distributions were readied to study the size-dependent properties. The nanocrystals adopt the perovskite (over the nonperovskite orthorhombic) structure with improved stability over thin-film materials. Among the perovskite phases (cubic α, tetragonal β, and orthorhombic γ), the samples are characterized by the γ phase, rather than α, but may have a size-dependent average tilting between adjacent octahedra. Size-dependent lattice constants systematically vary 3% across the size range, with unit cell volume increasing linearly with the inverse of size to 2.1% for the smallest size. We estimate the surface energy to be from -3.0 to -5.1 eV nm-2 for ligated CsPbI3 nanocrystals. Moreover, the size-dependent bandgap is best described using a nonparabolic intermediate confinement model. We experimentally determine the bulk bandgap, effective mass, and exciton binding energy, concluding with variations from the bulk a-phase values. This provides a robust route to understanding ..gamma..-phase properties of CsPbI3.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2];  [2]; ORCiD logo [4];  [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [2]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Nankai Univ., Tianjin (China)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
  4. Nankai Univ., Tianjin (China)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  6. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE); National Renewable Energy Lab. (NREL), Golden, CO (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); China Scholarship Council (CSC); Natural Science Foundation of Tianjin; National Natural Science Foundation of China (NNSFC); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office
OSTI Identifier:
1595568
Alternate Identifier(s):
OSTI ID: 1634005
Report Number(s):
NREL/JA-5900-74571
Journal ID: ISSN 2380-8195
Grant/Contract Number:  
AC36-08GO28308; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 5; Journal Issue: 1; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 77 NANOSCIENCE AND NANOTECHNOLOGY; nanocrystals; perovskites; thin film materials

Citation Formats

Zhao, Qian, Hazarika, Abhijit, Schelhas, Laura T., Liu, Jun, Gaulding, E. Ashley, Li, Guoran, Zhang, Minghui, Toney, Michael F., Sercel, Peter C., and Luther, Joseph M. Size-Dependent Lattice Structure and Confinement Properties in CsPbI3 Perovskite Nanocrystals: Negative Surface Energy for Stabilization. United States: N. p., 2019. Web. https://doi.org/10.1021/acsenergylett.9b02395.
Zhao, Qian, Hazarika, Abhijit, Schelhas, Laura T., Liu, Jun, Gaulding, E. Ashley, Li, Guoran, Zhang, Minghui, Toney, Michael F., Sercel, Peter C., & Luther, Joseph M. Size-Dependent Lattice Structure and Confinement Properties in CsPbI3 Perovskite Nanocrystals: Negative Surface Energy for Stabilization. United States. https://doi.org/10.1021/acsenergylett.9b02395
Zhao, Qian, Hazarika, Abhijit, Schelhas, Laura T., Liu, Jun, Gaulding, E. Ashley, Li, Guoran, Zhang, Minghui, Toney, Michael F., Sercel, Peter C., and Luther, Joseph M. Wed . "Size-Dependent Lattice Structure and Confinement Properties in CsPbI3 Perovskite Nanocrystals: Negative Surface Energy for Stabilization". United States. https://doi.org/10.1021/acsenergylett.9b02395. https://www.osti.gov/servlets/purl/1595568.
@article{osti_1595568,
title = {Size-Dependent Lattice Structure and Confinement Properties in CsPbI3 Perovskite Nanocrystals: Negative Surface Energy for Stabilization},
author = {Zhao, Qian and Hazarika, Abhijit and Schelhas, Laura T. and Liu, Jun and Gaulding, E. Ashley and Li, Guoran and Zhang, Minghui and Toney, Michael F. and Sercel, Peter C. and Luther, Joseph M.},
abstractNote = {CsPbI3 nanocrystals with narrow size distributions were readied to study the size-dependent properties. The nanocrystals adopt the perovskite (over the nonperovskite orthorhombic) structure with improved stability over thin-film materials. Among the perovskite phases (cubic α, tetragonal β, and orthorhombic γ), the samples are characterized by the γ phase, rather than α, but may have a size-dependent average tilting between adjacent octahedra. Size-dependent lattice constants systematically vary 3% across the size range, with unit cell volume increasing linearly with the inverse of size to 2.1% for the smallest size. We estimate the surface energy to be from -3.0 to -5.1 eV nm-2 for ligated CsPbI3 nanocrystals. Moreover, the size-dependent bandgap is best described using a nonparabolic intermediate confinement model. We experimentally determine the bulk bandgap, effective mass, and exciton binding energy, concluding with variations from the bulk a-phase values. This provides a robust route to understanding ..gamma..-phase properties of CsPbI3.},
doi = {10.1021/acsenergylett.9b02395},
journal = {ACS Energy Letters},
number = 1,
volume = 5,
place = {United States},
year = {2019},
month = {12}
}

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