Title: Interplay between Perovskite Magic-Sized Clusters and Amino Lead Halide Molecular Clusters

Abstract

Recent progress has been made on the synthesis and characterization of metal halide perovskite magic-sized clusters (PMSCs) with ABX ₃ composition ( $A=\text{C}{\text{H}}_3\text{N}{{\text{H}}_3}^{+}$ or Cs ⁺ , $B=\text{P}{\text{b}}^{2+}$ , and $X=\text{C}{\text{l}}^{-}$ , Br ^- , or I ^- ). However, their mechanism of growth and structure is still not well understood. In our effort to understand their structure and growth, we discovered that a new species can be formed without the CH ₃ NH ₃ ⁺ component, which we name as molecular clusters (MCs). Specifically, CH ₃ NH ₃ PbBr ₃ PMSCs, with a characteristic absorption peak at 424 nm, are synthesized using PbBr ₂ and CH ₃ NH ₃ Br as precursors and butylamine (BTYA) and valeric acid (VA) as ligands, while MCs, with an absorption peak at 402 nm, are synthesized using solely PbBr ₂ and BTYA, without CH ₃ NH ₃ Br. Interestingly, PMSCs are converted spontaneously overtime into MCs. An isosbestic point in their electronic absorption spectra indicates a direct interplay between the PMSCs and MCs. Therefore, we suggest that the MCs are precursors to the PMSCs. From spectroscopic and extended X-ray absorption fine structure (EXAFS) results, we propose some tentative structural models for the MCs. The discovery of the MCs is critical to understanding the growth of PMSCs as well as larger perovskite quantum dots (PQDs) or nanocrystals (PNCs).

Authors:

Vickers, Evan T. ^[1]; Chen, Ziyi ^[2]; Cherrette, Vivien ^[1]; Smart, Tyler ^[3]; Zhang, Peng  ^[2];

• Search DOE PAGES for author "Zhang, Peng"
• Search DOE PAGES for ORCID "0000-0003-3603-0175"

Ping, Yuan  ^[1];

• Search DOE PAGES for author "Ping, Yuan"
• Search DOE PAGES for ORCID "0000-0002-0123-3389"

Zhang, Jin Z.  ^[1]

• Search DOE PAGES for author "Zhang, Jin Z."
• Search DOE PAGES for ORCID "0000-0003-3437-912X"

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+ Show Author Affiliations

1. Department of Chemistry and Biochemistry, University of California, Santa Cruz, CA 95064, USA
2. Department of Chemistry, Dalhousie University, Halifax, NS, Canada, B3H 4R2
3. Department of Physics, University of California, Santa Cruz, CA 95064, USA

Publication Date:

Thu Jan 07 00:00:00 EST 2021

Research Org.:

Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

OSTI Identifier:

1756138

Alternate Identifier(s):

OSTI ID: 1816346

Grant/Contract Number:  

AC02-06CH11357

Resource Type:

Published Article

Journal Name:

Research

Additional Journal Information:

Journal Name: Research Journal Volume: 2021; Journal ID: ISSN 2639-5274

Publisher:

American Association for the Advancement of Science (AAAS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY