Anchored Ligands Facilitate Efficient B-Site doping in metal halide perovskites

Zhenyu Yang; Mingyang Wei; Oleksandr Voznyy; Petar Todorovic; Mengxia Liu; Rafael Quintero-Bermudez; Peining Chen; James Z. Fan; Andrew H. Proppe; Li Na Quan; Grant Walters; Hairen Tan; Je Wei Chang; U. Ser Jeng; Shana O. Kelley; Edward H. Sargent

doi:10.1021/jacs.9b02565

Anchored Ligands Facilitate Efficient B-Site doping in metal halide perovskites

Zhenyu Yang, Mingyang Wei, Oleksandr Voznyy, Petar Todorovic, Mengxia Liu, Rafael Quintero-Bermudez, Peining Chen, James Z. Fan, Andrew H. Proppe, Li Na Quan, Grant Walters, Hairen Tan, Je Wei Chang, U. Ser Jeng, Shana O. Kelley, Edward H. Sargent^*

^*Corresponding author for this work

Chemistry

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

55 Scopus citations

Abstract

Metal halide perovskites exhibit outstanding optoelectronic properties: Superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX3, where A is a monovalent cation (e.g., methylammonium (MA+), Cs+), B is the divalent metal ion(s) (e.g., Pb²⁺, Sn²⁺), and X is the halide group (e.g., Cl-, Br-, or I-), the isovalent exchange of A- A nd X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancymediated diffusion of B-site cations are much higher than those for A- A nd X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn²⁺, Zn²⁺, Bi3+) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in threedimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.

Original language	English (US)
Pages (from-to)	8296-8305
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	141
Issue number	20
DOIs	https://doi.org/10.1021/jacs.9b02565
State	Published - 2020

Funding

This publication is based in part on work supported by the Ontario Research Fund - Research Excellence Program, by the Natural Sciences and Engineering Research Council of Canada (NSERC), and by the US Department of the Navy, Office of Naval Research (Grant Award No.: N00014-17-1-2524). H.T. acknowledges The Netherlands Organisation for Scientific Research (NWO) for a Rubicon grant (680-50-1511) to support his postdoctoral research at University of Toronto. The authors thank Mr. P. Li and Prof. Z. H. Lu (MSE, University of Toronto) for UPS measurement and analysis. Dr. D. S. Robinson (Argonne National Laboratory) is thanked for the assistance with high-energy XRD measurements. Mr. C.-Y. Lin (CE, National Tsing Hua University) and Dr. C. S. Tan (ECE, University of Toronto) are thanked for the assistance with GIWAXS measurements. Dr. Y. Wang (University of Toronto) is thanked for the figure design and optimization. Mr. R. Wolowiec, Mr. D. Kopilovic, and Ms. E. Palmiano (University of Toronto) are thanked for their help in laboratory maintenance.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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Yang, Z., Wei, M., Voznyy, O., Todorovic, P., Liu, M., Quintero-Bermudez, R., Chen, P., Fan, J. Z., Proppe, A. H., Quan, L. N., Walters, G., Tan, H., Chang, J. W., Jeng, U. S., Kelley, S. O., & Sargent, E. H. (2020). Anchored Ligands Facilitate Efficient B-Site doping in metal halide perovskites. Journal of the American Chemical Society, 141(20), 8296-8305. https://doi.org/10.1021/jacs.9b02565

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title = "Anchored Ligands Facilitate Efficient B-Site doping in metal halide perovskites",

abstract = "Metal halide perovskites exhibit outstanding optoelectronic properties: Superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX3, where A is a monovalent cation (e.g., methylammonium (MA+), Cs+), B is the divalent metal ion(s) (e.g., Pb2+, Sn2+), and X is the halide group (e.g., Cl-, Br-, or I-), the isovalent exchange of A- A nd X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancymediated diffusion of B-site cations are much higher than those for A- A nd X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn2+, Zn2+, Bi3+) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in threedimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.",

author = "Zhenyu Yang and Mingyang Wei and Oleksandr Voznyy and Petar Todorovic and Mengxia Liu and Rafael Quintero-Bermudez and Peining Chen and Fan, {James Z.} and Proppe, {Andrew H.} and Quan, {Li Na} and Grant Walters and Hairen Tan and Chang, {Je Wei} and Jeng, {U. Ser} and Kelley, {Shana O.} and Sargent, {Edward H.}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.{\textcopyright} 2019 American Chemical Society.",

year = "2020",

doi = "10.1021/jacs.9b02565",

language = "English (US)",

volume = "141",

pages = "8296--8305",

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Yang, Z, Wei, M, Voznyy, O, Todorovic, P, Liu, M, Quintero-Bermudez, R, Chen, P, Fan, JZ, Proppe, AH, Quan, LN, Walters, G, Tan, H, Chang, JW, Jeng, US, Kelley, SO & Sargent, EH 2020, 'Anchored Ligands Facilitate Efficient B-Site doping in metal halide perovskites', Journal of the American Chemical Society, vol. 141, no. 20, pp. 8296-8305. https://doi.org/10.1021/jacs.9b02565

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T1 - Anchored Ligands Facilitate Efficient B-Site doping in metal halide perovskites

AU - Yang, Zhenyu

AU - Wei, Mingyang

AU - Voznyy, Oleksandr

AU - Todorovic, Petar

AU - Liu, Mengxia

AU - Quintero-Bermudez, Rafael

AU - Chen, Peining

AU - Fan, James Z.

AU - Proppe, Andrew H.

AU - Quan, Li Na

AU - Walters, Grant

AU - Tan, Hairen

AU - Chang, Je Wei

AU - Jeng, U. Ser

AU - Kelley, Shana O.

AU - Sargent, Edward H.

PY - 2020

Y1 - 2020

N2 - Metal halide perovskites exhibit outstanding optoelectronic properties: Superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX3, where A is a monovalent cation (e.g., methylammonium (MA+), Cs+), B is the divalent metal ion(s) (e.g., Pb2+, Sn2+), and X is the halide group (e.g., Cl-, Br-, or I-), the isovalent exchange of A- A nd X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancymediated diffusion of B-site cations are much higher than those for A- A nd X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn2+, Zn2+, Bi3+) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in threedimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.

AB - Metal halide perovskites exhibit outstanding optoelectronic properties: Superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX3, where A is a monovalent cation (e.g., methylammonium (MA+), Cs+), B is the divalent metal ion(s) (e.g., Pb2+, Sn2+), and X is the halide group (e.g., Cl-, Br-, or I-), the isovalent exchange of A- A nd X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancymediated diffusion of B-site cations are much higher than those for A- A nd X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn2+, Zn2+, Bi3+) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in threedimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.

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ER -

Anchored Ligands Facilitate Efficient B-Site doping in metal halide perovskites

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