Effect of cations substitution in lead-free double perovskite Cs2AgBiBr6 solar cells

Cationic substitution can be exploited as strategy to modulate the structural, electronic, and optical properties of perovskite materials. This work investigates the effect of doping Cs2AgBiBr6 double perovskite compounds as 10 at% Rb, Zn, and Sb-substituted formulations, further incorporated in wet...

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Main Authors: Nathan Daem, Anthony Maho, Pierre Colson, Gilles Spronck, Cédric Malherbe, Thi Hieu Hoang, Mohamed-Nawfal Ghazzal, Guorui He, Felix Lang, Rudi Cloots, Jennifer Dewalque
Format: Article
Language:English
Published: Elsevier 2025-07-01
Series:Next Materials
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Online Access:http://www.sciencedirect.com/science/article/pii/S294982282500173X
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author Nathan Daem
Anthony Maho
Pierre Colson
Gilles Spronck
Cédric Malherbe
Thi Hieu Hoang
Mohamed-Nawfal Ghazzal
Guorui He
Felix Lang
Rudi Cloots
Jennifer Dewalque
author_facet Nathan Daem
Anthony Maho
Pierre Colson
Gilles Spronck
Cédric Malherbe
Thi Hieu Hoang
Mohamed-Nawfal Ghazzal
Guorui He
Felix Lang
Rudi Cloots
Jennifer Dewalque
author_sort Nathan Daem
collection DOAJ
description Cationic substitution can be exploited as strategy to modulate the structural, electronic, and optical properties of perovskite materials. This work investigates the effect of doping Cs2AgBiBr6 double perovskite compounds as 10 at% Rb, Zn, and Sb-substituted formulations, further incorporated in wet-processed solar cells. Impacts on crystal structure, light harvesting, and charge generation mechanisms are highlighted, especially in terms of photoconversion metrics and efficiency. Regardless of the doping atom, the morphology of the spin-coated photoactive layers presents high homogeneity and coverage rate as well as uniform thickness, matching the characteristics of the undoped benchmark. Advantageously, a significant enhancement of the harvested light is established from UV–VIS spectrometry analyses, with the layers optical band gap notably decreasing from 2.32 to 2.20–2.28 eV following substitution. However, photovoltaic efficiencies calculated from J-V measurements drop from 1.6 % with undoped Cs2AgBiBr6, to 1.1, 0.3, and 0.4 % with Rb, Zn, and Sb- substituted formulations. Structural analyses of XRD and tolerance factor calculations, combined with Raman and XPS, rationalize these drops by a crystal lattice being too destabilized from the atomic substitutions, especially in Sb- and Zn-substituted samples, with the latest being further undermined by the occurrence of cationic vacancies. Joined UPS, PL and EIS studies also highlight differences of charge transfer properties in the different configurations of solar cells, notably owing to the materials energy levels (mis)alignment. All in all, the present contribution allows for an in-depth understanding of how such cationic substitutions affect Cs2AgBiBr6 intrinsic behavior and functionality as photovoltaic material, filling a key knowledge gap.
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spelling doaj-art-942a529bb92b4c16b4e3e7b0da09c5a92025-08-20T02:24:57ZengElsevierNext Materials2949-82282025-07-01810065510.1016/j.nxmate.2025.100655Effect of cations substitution in lead-free double perovskite Cs2AgBiBr6 solar cellsNathan Daem0Anthony Maho1Pierre Colson2Gilles Spronck3Cédric Malherbe4Thi Hieu Hoang5Mohamed-Nawfal Ghazzal6Guorui He7Felix Lang8Rudi Cloots9Jennifer Dewalque10Group of Research in Energy and Environment from Materials (GREEnMat), CESAM Research Unit, Chemistry Department, University of Liège, Allée du Six-Août 13, Liège 4000, BelgiumUniversité de Bordeaux, CNRS, Bordeaux INP, ICMCB, UMR 5026, 87 Avenue du Docteur Schweitzer, Pessac 33600, FranceGroup of Research in Energy and Environment from Materials (GREEnMat), CESAM Research Unit, Chemistry Department, University of Liège, Allée du Six-Août 13, Liège 4000, BelgiumGroup of Research in Energy and Environment from Materials (GREEnMat), CESAM Research Unit, Chemistry Department, University of Liège, Allée du Six-Août 13, Liège 4000, BelgiumMass Spectrometry Laboratory (MSLab), MolSys Research Unit, Chemistry Department, University of Liège, Allée du Six-Août 11, Liège 4000, BelgiumUniversité Paris-Saclay, UMR8000 CNRS, Institut de Chimie Physique, Orsay 91405, FranceUniversité Paris-Saclay, UMR8000 CNRS, Institut de Chimie Physique, Orsay 91405, FranceROSI Freigeist Juniorgroup, Physics of Soft Matter, University of Potsdam, Potsdam 14476, GermanyROSI Freigeist Juniorgroup, Physics of Soft Matter, University of Potsdam, Potsdam 14476, GermanyGroup of Research in Energy and Environment from Materials (GREEnMat), CESAM Research Unit, Chemistry Department, University of Liège, Allée du Six-Août 13, Liège 4000, BelgiumGroup of Research in Energy and Environment from Materials (GREEnMat), CESAM Research Unit, Chemistry Department, University of Liège, Allée du Six-Août 13, Liège 4000, Belgium; Corresponding author.Cationic substitution can be exploited as strategy to modulate the structural, electronic, and optical properties of perovskite materials. This work investigates the effect of doping Cs2AgBiBr6 double perovskite compounds as 10 at% Rb, Zn, and Sb-substituted formulations, further incorporated in wet-processed solar cells. Impacts on crystal structure, light harvesting, and charge generation mechanisms are highlighted, especially in terms of photoconversion metrics and efficiency. Regardless of the doping atom, the morphology of the spin-coated photoactive layers presents high homogeneity and coverage rate as well as uniform thickness, matching the characteristics of the undoped benchmark. Advantageously, a significant enhancement of the harvested light is established from UV–VIS spectrometry analyses, with the layers optical band gap notably decreasing from 2.32 to 2.20–2.28 eV following substitution. However, photovoltaic efficiencies calculated from J-V measurements drop from 1.6 % with undoped Cs2AgBiBr6, to 1.1, 0.3, and 0.4 % with Rb, Zn, and Sb- substituted formulations. Structural analyses of XRD and tolerance factor calculations, combined with Raman and XPS, rationalize these drops by a crystal lattice being too destabilized from the atomic substitutions, especially in Sb- and Zn-substituted samples, with the latest being further undermined by the occurrence of cationic vacancies. Joined UPS, PL and EIS studies also highlight differences of charge transfer properties in the different configurations of solar cells, notably owing to the materials energy levels (mis)alignment. All in all, the present contribution allows for an in-depth understanding of how such cationic substitutions affect Cs2AgBiBr6 intrinsic behavior and functionality as photovoltaic material, filling a key knowledge gap.http://www.sciencedirect.com/science/article/pii/S294982282500173XCs2AgBiBr6 double perovskiteLead-freeCations substitutionRubidiumZincAntimony
spellingShingle Nathan Daem
Anthony Maho
Pierre Colson
Gilles Spronck
Cédric Malherbe
Thi Hieu Hoang
Mohamed-Nawfal Ghazzal
Guorui He
Felix Lang
Rudi Cloots
Jennifer Dewalque
Effect of cations substitution in lead-free double perovskite Cs2AgBiBr6 solar cells
Next Materials
Cs2AgBiBr6 double perovskite
Lead-free
Cations substitution
Rubidium
Zinc
Antimony
title Effect of cations substitution in lead-free double perovskite Cs2AgBiBr6 solar cells
title_full Effect of cations substitution in lead-free double perovskite Cs2AgBiBr6 solar cells
title_fullStr Effect of cations substitution in lead-free double perovskite Cs2AgBiBr6 solar cells
title_full_unstemmed Effect of cations substitution in lead-free double perovskite Cs2AgBiBr6 solar cells
title_short Effect of cations substitution in lead-free double perovskite Cs2AgBiBr6 solar cells
title_sort effect of cations substitution in lead free double perovskite cs2agbibr6 solar cells
topic Cs2AgBiBr6 double perovskite
Lead-free
Cations substitution
Rubidium
Zinc
Antimony
url http://www.sciencedirect.com/science/article/pii/S294982282500173X
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