Progressive polytypism and bandgap tuning in azetidinium lead halide perovskites

Jiyu Tian; David B. Cordes; Alexandra M. Z. Slawin; Eli Zysman-Colman; Finlay D. Morrison

doi:10.1021/acs.inorgchem.1c01425

Progressive polytypism and bandgap tuning in azetidinium lead halide perovskites

Jiyu Tian, David B. Cordes, Alexandra M. Z. Slawin, Eli Zysman-Colman, Finlay D. Morrison

Research output: Contribution to journal › Article › peer-review

Abstract

Mixed halide azetidinium lead perovskites AzPbBr₃–_xX_x (X = Cl or I) were obtained by mechanosynthesis. With varying halide composition from Cl^– to Br^– to I^–, the chloride and bromide analogues both form in the hexagonal 6H polytype while the iodide adopts the 9R polytype. An intermediate 4H polytype is observed for mixed Br/I compositions. Overall, the structure progresses from 6H to 4H to 9R perovskite polytype with varying halide composition. Rietveld refinement of the powder X-ray diffraction patterns revealed a linear variation in unit cell volume as a function of the average radius of the anion, which not only is observed within the solid solution of each polytype (according to Vegard’s law) but also extends uniformly across all three polytypes. This is correlated to a progressive (linear) tuning of the bandgap from 3.43 to 2.00 eV. Regardless of halide, the family of azetidinium halide perovskite polytypes are highly stable, with no discernible change in properties over more than 6 months under ambient conditions.

Original language	English
Pages (from-to)	12247–12254
Number of pages	8
Journal	Inorganic Chemistry
Volume	60
Issue number	16
Early online date	28 Jul 2021
DOIs	https://doi.org/10.1021/acs.inorgchem.1c01425
Publication status	Published - 16 Aug 2021

Keywords

Anions
Diffraction
Inorganic compounds
Perovskites
Halogens

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10.1021/acs.inorgchem.1c01425

Tian_InorgChem_AzPbHalide
Copyright © 2021 American Chemical Society. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/acs.inorgchem.1c01425
Accepted author manuscript, 1.77 MB

https://doi.org/10.26434/chemrxiv.14502372.v1Licence: CC BY-NC-ND

Progressive Polytypism and Bandgap Tuning in Azetidinium Lead Halide Perovskites (dataset)
Tian, J. (Contributor), Cordes, D. B. (Contributor), Slawin, A. M. Z. (Contributor), Zysman-Colman, E. (Creator) & Morrison, F. D. (Creator), University of St Andrews, 21 Dec 2021
DOI: 10.17630/50fde8ad-d6a8-4365-a484-c40e72a3816e
Dataset

File
CCDC 2079681 & 2079682: Experimental Crystal Structure Determination
Tian, J. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator), Zysman-Colman, E. (Creator) & Morrison, F. D. (Creator), Cambridge Crystallographic Data Centre, 2021
DOI: 10.5517/ccdc.csd.cc27t2hn, https://dx.doi.org/10.5517/ccdc.csd.cc27t2jp
Dataset

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@article{b3d873ef7b53478c93674f097dbab359,

title = "Progressive polytypism and bandgap tuning in azetidinium lead halide perovskites",

abstract = "Mixed halide azetidinium lead perovskites AzPbBr3–xXx (X = Cl or I) were obtained by mechanosynthesis. With varying halide composition from Cl– to Br– to I–, the chloride and bromide analogues both form in the hexagonal 6H polytype while the iodide adopts the 9R polytype. An intermediate 4H polytype is observed for mixed Br/I compositions. Overall, the structure progresses from 6H to 4H to 9R perovskite polytype with varying halide composition. Rietveld refinement of the powder X-ray diffraction patterns revealed a linear variation in unit cell volume as a function of the average radius of the anion, which not only is observed within the solid solution of each polytype (according to Vegard{\textquoteright}s law) but also extends uniformly across all three polytypes. This is correlated to a progressive (linear) tuning of the bandgap from 3.43 to 2.00 eV. Regardless of halide, the family of azetidinium halide perovskite polytypes are highly stable, with no discernible change in properties over more than 6 months under ambient conditions.",

keywords = "Anions, Diffraction, Inorganic compounds, Perovskites, Halogens",

author = "Jiyu Tian and Cordes, {David B.} and Slawin, {Alexandra M. Z.} and Eli Zysman-Colman and Morrison, {Finlay D.}",

note = "We thank the Chinese Scholarship Council for Ph.D. Studentship support (to J.T., CSC No. 201603780020).",

year = "2021",

month = aug,

day = "16",

doi = "10.1021/acs.inorgchem.1c01425",

language = "English",

volume = "60",

pages = "12247–12254",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society (ACS)",

number = "16",

}

TY - JOUR

T1 - Progressive polytypism and bandgap tuning in azetidinium lead halide perovskites

AU - Tian, Jiyu

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Zysman-Colman, Eli

AU - Morrison, Finlay D.

N1 - We thank the Chinese Scholarship Council for Ph.D. Studentship support (to J.T., CSC No. 201603780020).

PY - 2021/8/16

Y1 - 2021/8/16

N2 - Mixed halide azetidinium lead perovskites AzPbBr3–xXx (X = Cl or I) were obtained by mechanosynthesis. With varying halide composition from Cl– to Br– to I–, the chloride and bromide analogues both form in the hexagonal 6H polytype while the iodide adopts the 9R polytype. An intermediate 4H polytype is observed for mixed Br/I compositions. Overall, the structure progresses from 6H to 4H to 9R perovskite polytype with varying halide composition. Rietveld refinement of the powder X-ray diffraction patterns revealed a linear variation in unit cell volume as a function of the average radius of the anion, which not only is observed within the solid solution of each polytype (according to Vegard’s law) but also extends uniformly across all three polytypes. This is correlated to a progressive (linear) tuning of the bandgap from 3.43 to 2.00 eV. Regardless of halide, the family of azetidinium halide perovskite polytypes are highly stable, with no discernible change in properties over more than 6 months under ambient conditions.

AB - Mixed halide azetidinium lead perovskites AzPbBr3–xXx (X = Cl or I) were obtained by mechanosynthesis. With varying halide composition from Cl– to Br– to I–, the chloride and bromide analogues both form in the hexagonal 6H polytype while the iodide adopts the 9R polytype. An intermediate 4H polytype is observed for mixed Br/I compositions. Overall, the structure progresses from 6H to 4H to 9R perovskite polytype with varying halide composition. Rietveld refinement of the powder X-ray diffraction patterns revealed a linear variation in unit cell volume as a function of the average radius of the anion, which not only is observed within the solid solution of each polytype (according to Vegard’s law) but also extends uniformly across all three polytypes. This is correlated to a progressive (linear) tuning of the bandgap from 3.43 to 2.00 eV. Regardless of halide, the family of azetidinium halide perovskite polytypes are highly stable, with no discernible change in properties over more than 6 months under ambient conditions.

KW - Anions

KW - Diffraction

KW - Inorganic compounds

KW - Perovskites

KW - Halogens

U2 - 10.1021/acs.inorgchem.1c01425

DO - 10.1021/acs.inorgchem.1c01425

M3 - Article

SN - 0020-1669

VL - 60

SP - 12247

EP - 12254

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 16

ER -

Progressive polytypism and bandgap tuning in azetidinium lead halide perovskites

Abstract

Keywords

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Datasets

Progressive Polytypism and Bandgap Tuning in Azetidinium Lead Halide Perovskites (dataset)

CCDC 2079681 & 2079682: Experimental Crystal Structure Determination

Cite this