How additives for tin halide perovskites influence the Sn4+ concentration

Joy, Syed; Atapattu, Harindi R.; Sorensen, Stephanie; Pruett, Henry; Olivelli, Alexander B.; Huckaba, Aron J.; Miller, Anne-Frances; Graham, Kenneth R.

doi:10.1039/d2ta01429g

Title: How additives for tin halide perovskites influence the Sn⁴⁺ concentration

Journal Article · 06 June 2022 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/d2ta01429g · OSTI ID:1978916

^[1]; Atapattu, Harindi R. ^[1]; Sorensen, Stephanie ^[1]; Pruett, Henry ^[1]; Olivelli, Alexander B. ^[1];

^[1];

^[1]

Univ. of Kentucky, Lexington, KY (United States)

Tin halide perovskite (Sn-HPs) photovoltaics could potentially equal or exceed the performance of their more toxic Pb-based analogues if defect state densities, particularly originating from the presence of Sn⁴⁺, can be significantly decreased. Numerous additives are incorporated into Sn-HPs to minimize the amount of Sn⁴⁺, including SnF₂, reducing agents such as hydrazine derivatives, and various antioxidants. However, despite the frequent use of additives to reduce Sn⁴⁺ content, there is limited understanding of how they function and consequently limited guidance for the development of new additives. Herein, we use cyclic voltammetry to probe the redox behavior of SnI₂, SnI₄, Sn-HP precursor solutions, and 18 different additives. Through ¹¹⁹Sn NMR measurements we show that hydrochloride containing additives undergo halide exchange with SnI₄ to form SnI_xCl_y, which results in decreased Sn⁴⁺ concentrations and less p-type character in the Sn-HP films. We find that the most effective additive at lowering the Sn⁴⁺ content in FASnI₃ is not capable of reducing SnI₄ or forming SnI_xCl_y, but rather it acts as a sacrificial and coordinating antioxidant. In general, when selecting additives for Sn-HPs it is important to account for the redox potential, coordination with Sn species, ability to react with oxygen, and the potential for halide exchange.

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Research Organization:: Univ. of Kentucky, Lexington, KY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USDOE

Grant/Contract Number:: SC0018208; SC0021283; DMR 2102257; CHE 2108134

OSTI ID:: 1978916

Alternate ID(s):: OSTI ID: 1872271; OSTI ID: 2478002

Journal Information:: Journal of Materials Chemistry. A, Vol. 10, Issue 25; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Energy & Fuels
Materials Science
36 MATERIALS SCIENCE
perovskite
Sn NMR
photovoltaics

Title: How additives for tin halide perovskites influence the Sn4+ concentration

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References (41)

Figures / Tables (7)

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Title: How additives for tin halide perovskites influence the Sn⁴⁺ concentration