Repository logo

Infoscience

  • English
  • French
Log In
Logo EPFL, École polytechnique fédérale de Lausanne

Infoscience

  • English
  • French
Log In
  1. Home
  2. Academic and Research Output
  3. Journal articles
  4. Local Structure and Dynamics in Methylammonium, Formamidinium, and Cesium Tin(II) Mixed-Halide Perovskites from Sn-119 Solid-State NMR
 
research article

Local Structure and Dynamics in Methylammonium, Formamidinium, and Cesium Tin(II) Mixed-Halide Perovskites from Sn-119 Solid-State NMR

Kubicki, Dominik J.  
•
Prochowicz, Daniel
•
Salager, Elodie
Show more
April 29, 2020
Journal Of The American Chemical Society

Organic-inorganic tin(II) halide perovskites have emerged as promising alternatives to lead halide perovskites in optoelectronic applications. While they suffer from considerably poorer performance and stability in comparison to their lead analogues, their performance improvements have so far largely been driven by trial and error efforts due to a critical lack of methods to probe their atomic-level microstructure. Here, we identify the challenges and devise a Sn-119 solid-state NMR protocol for the determination of the local structure of mixed-cation and mixed-halide tin(II) halide perovskites as well as their degradation products and related phases. We establish that the longitudinal relaxation of Sn-119 can span 6 orders of magnitude in this class of compounds, which makes judicious choice of experimental NMR parameters essential for the reliable detection of various phases. We show that Cl/Br and I/Br mixed-halide perovskites form solid alloys in any ratio, while only limited mixing is possible for I/CI compositions. We elucidate the degradation pathways of Cs-, MA-, and FA-based tin(II) halides and show that degradation leads to highly disordered, qualitatively similar products, regardless of the A-site cation and halide. We detect the presence of metallic tin among the degradation products, which we suggest could contribute to the previously reported high conductivities in tin(II) halide perovskites. Sn-119 NMR chemical shifts are a sensitive probe of the halide coordination environment as well as of the A-site cation composition. Finally, we use variable-temperature multifield relaxation measurements to quantify ion dynamics in MASnBr(3) and establish activation energies for motion and show that this motion leads to spontaneous halide homogenization at room temperature whenever two different pure-halide perovskites are put in physical contact.

  • Files
  • Details
  • Metrics
Type
research article
DOI
10.1021/jacs.0c00647
Web of Science ID

WOS:000529959000015

Author(s)
Kubicki, Dominik J.  
Prochowicz, Daniel
Salager, Elodie
Rakhmatullin, Aydar
Grey, Clare P.
Emsley, Lyndon  
Stranks, Samuel D.
Date Issued

2020-04-29

Published in
Journal Of The American Chemical Society
Volume

142

Issue

17

Start page

7813

End page

7826

Subjects

Chemistry, Multidisciplinary

•

Chemistry

•

nuclear-magnetic-resonance

•

spin-lattice-relaxation

•

hybrid perovskites

•

phase segregation

•

solar-cells

•

lead iodide

•

tin iodide

•

electrical-conductivity

•

highly efficient

•

cation dynamics

Note

ACS AuthorChoice with CC-BY license. This is an open access article published under a Creative Commons Attribution (CC-BY) License.

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LRM  
FunderGrant Number

FNS

200020_178860

Available on Infoscience
May 24, 2020
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/168923
Logo EPFL, École polytechnique fédérale de Lausanne
  • Contact
  • infoscience@epfl.ch

  • Follow us on Facebook
  • Follow us on Instagram
  • Follow us on LinkedIn
  • Follow us on X
  • Follow us on Youtube
AccessibilityLegal noticePrivacy policyCookie settingsEnd User AgreementGet helpFeedback

Infoscience is a service managed and provided by the Library and IT Services of EPFL. © EPFL, tous droits réservés