FAxCs1–xPbI3 Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition

Vigil, Julian A.; Hazarika, Abhijit; Luther, Joseph M.; Toney, Michael F.

doi:10.1021/acsenergylett.0c01069

Title: FA_xCs_1–xPbI₃ Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition

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Abstract

Nanoscale semiconductors show remarkably tunable properties. For metal halide perovskite (MHP) nanocrystals (NCs), surface energy and lattice strain stabilize desirable MHP compositions and crystallographic phases that are unstable in the bulk. We report an X-ray scattering study of the average room-temperature crystal structure of ~15 nm FA_xCs_1–xPbI₃ (FA = formamidinium) NCs. All compositions crystallize in the perovskite structure; however, the average structure lowers in symmetry from the a (cubic) to ß (tetragonal) to γ (orthorhombic) perovskite phases with decreasing x (Cs addition). The corresponding a- to ß- and ß- to γ-phase transitions occur between x = 0.75–0.5 and x = 0.25–0.1, respectively. Furthermore, structural refinements also indicate large octahedral tilt angles (10–30°) in the ß- and γ-phases and an increase in (pseudo)cubic unit cell volume upon FA addition. This work establishes the composition–structure relationship for FA_xCs_1–xPbI₃ NCs and demonstrates the ability to target average crystal symmetry with facile synthetic control.

Authors:

^[1];

^[2];

^[3]

National Renewable Energy Lab. (NREL), Golden, CO (United States). Center for Hybrid Organic Inorganic Semiconductors for Energy; Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
National Renewable Energy Lab. (NREL), Golden, CO (United States). Center for Hybrid Organic Inorganic Semiconductors for Energy
National Renewable Energy Lab. (NREL), Golden, CO (United States). Center for Hybrid Organic Inorganic Semiconductors for Energy; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Publication Date:: Thu Jun 25 00:00:00 EDT 2020

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:: 1660006

Report Number(s):: NREL/JA-5900-76552
Journal ID: ISSN 2380-8195; MainId:7226;UUID:b9e50562-c413-4daa-a29c-e0945d2353b2;MainAdminID:13758

Grant/Contract Number:: AC36-08GO28308; AC02-76SF00515; DGE−1656518

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: ACS Energy Letters

Additional Journal Information:: Journal Volume: 5; Journal Issue: 8; Journal ID: ISSN 2380-8195

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; composition-structure relations; halide perovskites; nanocrystals; quantum dots; x-ray diffraction

Citation Formats


                    Vigil, Julian A., Hazarika, Abhijit, Luther, Joseph M., and Toney, Michael F. FAxCs1–xPbI3 Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition.  United States: N. p., 2020. 
        Web.  doi:10.1021/acsenergylett.0c01069.

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                    Vigil, Julian A., Hazarika, Abhijit, Luther, Joseph M., & Toney, Michael F. FAxCs1–xPbI3 Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition.  United States.  https://doi.org/10.1021/acsenergylett.0c01069

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                    Vigil, Julian A., Hazarika, Abhijit, Luther, Joseph M., and Toney, Michael F. 2020.  
        "FAxCs1–xPbI3 Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition".  United States.  https://doi.org/10.1021/acsenergylett.0c01069.  https://www.osti.gov/servlets/purl/1660006.

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@article{osti_1660006,

  title        = {FAxCs1–xPbI3 Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition},

  author       = {Vigil, Julian A. and Hazarika, Abhijit and Luther, Joseph M. and Toney, Michael F.},

  abstractNote = {Nanoscale semiconductors show remarkably tunable properties. For metal halide perovskite (MHP) nanocrystals (NCs), surface energy and lattice strain stabilize desirable MHP compositions and crystallographic phases that are unstable in the bulk. We report an X-ray scattering study of the average room-temperature crystal structure of ~15 nm FAxCs1–xPbI3 (FA = formamidinium) NCs. All compositions crystallize in the perovskite structure; however, the average structure lowers in symmetry from the a (cubic) to ß (tetragonal) to γ (orthorhombic) perovskite phases with decreasing x (Cs addition). The corresponding a- to ß- and ß- to γ-phase transitions occur between x = 0.75–0.5 and x = 0.25–0.1, respectively. Furthermore, structural refinements also indicate large octahedral tilt angles (10–30°) in the ß- and γ-phases and an increase in (pseudo)cubic unit cell volume upon FA addition. This work establishes the composition–structure relationship for FAxCs1–xPbI3 NCs and demonstrates the ability to target average crystal symmetry with facile synthetic control.},

  doi          = {10.1021/acsenergylett.0c01069},

  url          = {https://www.osti.gov/biblio/1660006},
  journal      = {ACS Energy Letters},

  issn         = {2380-8195},

  number       = 8,

  volume       = 5,

  place        = {United States},

  year         = {Thu Jun 25 00:00:00 EDT 2020},

  month        = {Thu Jun 25 00:00:00 EDT 2020}

}

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Title: FAxCs1–xPbI3 Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition

Abstract

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Title: FA_xCs_1–xPbI₃ Nanocrystals: Tuning Crystal Symmetry by A-Site Cation Composition