Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics

Basheer Al-Anesi; G. Krishnamurthy Grandhi; Adriana Pecoraro; Vipinraj Sugathan; Noolu Srinivasa Manikanta Viswanath; Harri Ali-Löytty; Maning Liu; Tero-Petri Ruoko; Kimmo Lahtonen; Debjit Manna; Sami Toikkonen; Ana Belén Muñoz-García; Michele Pavone; Paola Vivo

doi:10.26434/CHEMRXIV-2023-NB5JJ

Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics

Basheer Al-Anesi
, G. Krishnamurthy Grandhi^*
, Adriana Pecoraro
, Vipinraj Sugathan
, Noolu Srinivasa Manikanta Viswanath
, Harri Ali-Löytty
, Maning Liu
, Tero-Petri Ruoko
, Kimmo Lahtonen
, Debjit Manna
, Sami Toikkonen
, Ana Belén Muñoz-García
, Michele Pavone
, Paola Vivo^*

^*Corresponding author for this work

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

46 Citations (Scopus)

31 Downloads (Pure)

Abstract

The perovskite-inspired Cu₂AgBiI₆ (CABI) material has been gaining increasing momentum as photovoltaic (PV) absorber due to its low toxicity, intrinsic air stability, direct bandgap, and a high absorption coefficient in the range of 10⁵ cm⁻¹. However, the power conversion efficiency (PCE) of existing CABI-based PVs is still seriously constrained by the presence of both intrinsic and surface defects. Herein, antimony (III) (Sb³⁺) is introduced into the octahedral lattice sites of the CABI structure, leading to CABI-Sb with larger crystalline domains than CABI. The alloying of Sb³⁺ with bismuth (III) (Bi³⁺) induces changes in the local structural symmetry that dramatically increase the formation energy of intrinsic defects. Light-intensity dependence and electron impedance spectroscopic studies show reduced trap-assisted recombination in the CABI-Sb PV devices. CABI-Sb solar cells feature a nearly 40% PCE enhancement (from 1.31% to 1.82%) with respect to the CABI devices mainly due to improvement in short-circuit current density. This work will promote future compositional design studies to enhance the intrinsic defect tolerance of next-generation wide-bandgap absorbers for high-performance and stable PVs.

Original language	English
Article number	2303575
Journal	Small
Volume	19
Issue number	46
DOIs	https://doi.org/10.26434/CHEMRXIV-2023-NB5JJ https://doi.org/10.1002/smll.202303575
Publication status	Published - 15 Nov 2023
Publication type	A1 Journal article-refereed

Funding

B.A.‐A. thanks Vilho, Yrjö and Kalle Väisälä Fund of the Finnish Academy of Science and Letters for the financial support. G.K.G. thanks Tampere Institute for Advanced Study for the postdoctoral funding. P.V. acknowledges the financial support of Jane and Aatos Erkko Foundation within the SOL‐TECH project and Academy of Finland, Decision No. 347772. M.L. thanks the Finnish Cultural Foundation (No. 00220107) for funding. T.P. R acknowledges funding from the Academy of Finland Postdoctoral Researcher Project No. 340103 and the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska‐Curie grant agreement No. 101022777. This work was part of the Academy of Finland Flagship Programme, Photonics Research, and Innovation (PREIN), Decision No. 320165. This work made use of Tampere Microscopy Center facilities at Tampere University.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

defects
low-toxicity
perovskite-inspired material
photovoltaics
wide-bandgap

Publication forum classification

Publication forum level 3

ASJC Scopus subject areas

Biotechnology
General Chemistry
Biomaterials
General Materials Science
Engineering (miscellaneous)

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10.1002/smll.202303575Licence: CC BY

Antimony-Bismuth AlloyingFinal published version, 2.97 MBLicence: CC BY

https://urn.fi/URN:NBN:fi:tuni-202308227728Licence: CC BY

Chemistry Labs for optical spectroscopy, analysis, and synthesis
Ruoko, T.-P. (Contact) & Efimov, A. (Contact)
Materials Science and Environmental Engineering
Facility/equipment: Research infrastructure
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Vippola, M. (Manager), Honkanen, M. (Operator) & Salminen, T. (Operator)
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Facility/equipment: Research infrastructure

Cite this

Al-Anesi, B., Grandhi, G. K., Pecoraro, A., Sugathan, V., Viswanath, N. S. M., Ali-Löytty, H., Liu, M., Ruoko, T.-P., Lahtonen, K., Manna, D., Toikkonen, S., Muñoz-García, A. B., Pavone, M., & Vivo, P. (2023). Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics. Small, 19(46), Article 2303575. https://doi.org/10.26434/CHEMRXIV-2023-NB5JJ, https://doi.org/10.1002/smll.202303575

@article{0fdbbe4c8871468e962bc30f12229df3,

title = "Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics",

abstract = "The perovskite-inspired Cu2AgBiI6 (CABI) material has been gaining increasing momentum as photovoltaic (PV) absorber due to its low toxicity, intrinsic air stability, direct bandgap, and a high absorption coefficient in the range of 105 cm−1. However, the power conversion efficiency (PCE) of existing CABI-based PVs is still seriously constrained by the presence of both intrinsic and surface defects. Herein, antimony (III) (Sb3+) is introduced into the octahedral lattice sites of the CABI structure, leading to CABI-Sb with larger crystalline domains than CABI. The alloying of Sb3+ with bismuth (III) (Bi3+) induces changes in the local structural symmetry that dramatically increase the formation energy of intrinsic defects. Light-intensity dependence and electron impedance spectroscopic studies show reduced trap-assisted recombination in the CABI-Sb PV devices. CABI-Sb solar cells feature a nearly 40\% PCE enhancement (from 1.31\% to 1.82\%) with respect to the CABI devices mainly due to improvement in short-circuit current density. This work will promote future compositional design studies to enhance the intrinsic defect tolerance of next-generation wide-bandgap absorbers for high-performance and stable PVs.",

keywords = "defects, low-toxicity, perovskite-inspired material, photovoltaics, wide-bandgap",

author = "Basheer Al-Anesi and Grandhi, \{G. Krishnamurthy\} and Adriana Pecoraro and Vipinraj Sugathan and Viswanath, \{Noolu Srinivasa Manikanta\} and Harri Ali-L{\"o}ytty and Maning Liu and Tero-Petri Ruoko and Kimmo Lahtonen and Debjit Manna and Sami Toikkonen and Mu{\~n}oz-Garc{\'i}a, \{Ana Bel{\'e}n\} and Michele Pavone and Paola Vivo",

note = "Funding Information: B.A.‐A. thanks Vilho, Yrj{\"o} and Kalle V{\"a}is{\"a}l{\"a} Fund of the Finnish Academy of Science and Letters for the financial support. G.K.G. thanks Tampere Institute for Advanced Study for the postdoctoral funding. P.V. acknowledges the financial support of Jane and Aatos Erkko Foundation within the SOL‐TECH project and Academy of Finland, Decision No. 347772. M.L. thanks the Finnish Cultural Foundation (No. 00220107) for funding. T.P. R acknowledges funding from the Academy of Finland Postdoctoral Researcher Project No. 340103 and the European Union's Horizon 2020 research and innovation programme under the Marie Sk{\l}odowska‐Curie grant agreement No. 101022777. This work was part of the Academy of Finland Flagship Programme, Photonics Research, and Innovation (PREIN), Decision No. 320165. This work made use of Tampere Microscopy Center facilities at Tampere University. Publisher Copyright: {\textcopyright} 2023 The Authors. Small published by Wiley-VCH GmbH.",

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Al-Anesi, B, Grandhi, GK, Pecoraro, A, Sugathan, V, Viswanath, NSM, Ali-Löytty, H, Liu, M, Ruoko, T-P , Lahtonen, K, Manna, D, Toikkonen, S, Muñoz-García, AB, Pavone, M & Vivo, P 2023, 'Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics', Small, vol. 19, no. 46, 2303575. https://doi.org/10.26434/CHEMRXIV-2023-NB5JJ, https://doi.org/10.1002/smll.202303575

TY - JOUR

T1 - Antimony-Bismuth Alloying

T2 - The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics

AU - Al-Anesi, Basheer

AU - Grandhi, G. Krishnamurthy

AU - Pecoraro, Adriana

AU - Sugathan, Vipinraj

AU - Viswanath, Noolu Srinivasa Manikanta

AU - Ali-Löytty, Harri

AU - Liu, Maning

AU - Ruoko, Tero-Petri

AU - Lahtonen, Kimmo

AU - Manna, Debjit

AU - Toikkonen, Sami

AU - Muñoz-García, Ana Belén

AU - Pavone, Michele

AU - Vivo, Paola

N1 - Funding Information: B.A.‐A. thanks Vilho, Yrjö and Kalle Väisälä Fund of the Finnish Academy of Science and Letters for the financial support. G.K.G. thanks Tampere Institute for Advanced Study for the postdoctoral funding. P.V. acknowledges the financial support of Jane and Aatos Erkko Foundation within the SOL‐TECH project and Academy of Finland, Decision No. 347772. M.L. thanks the Finnish Cultural Foundation (No. 00220107) for funding. T.P. R acknowledges funding from the Academy of Finland Postdoctoral Researcher Project No. 340103 and the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska‐Curie grant agreement No. 101022777. This work was part of the Academy of Finland Flagship Programme, Photonics Research, and Innovation (PREIN), Decision No. 320165. This work made use of Tampere Microscopy Center facilities at Tampere University. Publisher Copyright: © 2023 The Authors. Small published by Wiley-VCH GmbH.

PY - 2023/11/15

Y1 - 2023/11/15

N2 - The perovskite-inspired Cu2AgBiI6 (CABI) material has been gaining increasing momentum as photovoltaic (PV) absorber due to its low toxicity, intrinsic air stability, direct bandgap, and a high absorption coefficient in the range of 105 cm−1. However, the power conversion efficiency (PCE) of existing CABI-based PVs is still seriously constrained by the presence of both intrinsic and surface defects. Herein, antimony (III) (Sb3+) is introduced into the octahedral lattice sites of the CABI structure, leading to CABI-Sb with larger crystalline domains than CABI. The alloying of Sb3+ with bismuth (III) (Bi3+) induces changes in the local structural symmetry that dramatically increase the formation energy of intrinsic defects. Light-intensity dependence and electron impedance spectroscopic studies show reduced trap-assisted recombination in the CABI-Sb PV devices. CABI-Sb solar cells feature a nearly 40% PCE enhancement (from 1.31% to 1.82%) with respect to the CABI devices mainly due to improvement in short-circuit current density. This work will promote future compositional design studies to enhance the intrinsic defect tolerance of next-generation wide-bandgap absorbers for high-performance and stable PVs.

AB - The perovskite-inspired Cu2AgBiI6 (CABI) material has been gaining increasing momentum as photovoltaic (PV) absorber due to its low toxicity, intrinsic air stability, direct bandgap, and a high absorption coefficient in the range of 105 cm−1. However, the power conversion efficiency (PCE) of existing CABI-based PVs is still seriously constrained by the presence of both intrinsic and surface defects. Herein, antimony (III) (Sb3+) is introduced into the octahedral lattice sites of the CABI structure, leading to CABI-Sb with larger crystalline domains than CABI. The alloying of Sb3+ with bismuth (III) (Bi3+) induces changes in the local structural symmetry that dramatically increase the formation energy of intrinsic defects. Light-intensity dependence and electron impedance spectroscopic studies show reduced trap-assisted recombination in the CABI-Sb PV devices. CABI-Sb solar cells feature a nearly 40% PCE enhancement (from 1.31% to 1.82%) with respect to the CABI devices mainly due to improvement in short-circuit current density. This work will promote future compositional design studies to enhance the intrinsic defect tolerance of next-generation wide-bandgap absorbers for high-performance and stable PVs.

KW - defects

KW - low-toxicity

KW - perovskite-inspired material

KW - photovoltaics

KW - wide-bandgap

U2 - 10.26434/CHEMRXIV-2023-NB5JJ

DO - 10.26434/CHEMRXIV-2023-NB5JJ

M3 - Article

AN - SCOPUS:85164808090

SN - 1613-6810

VL - 19

JO - Small

JF - Small

IS - 46

M1 - 2303575

ER -

Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics

Abstract

Funding

UN SDGs

Keywords

Publication forum classification

ASJC Scopus subject areas

Access to Document

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Equipment

Chemistry Labs for optical spectroscopy, analysis, and synthesis

Tampere Microscopy Center

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