Triplet transfer from PbS quantum dots to tetracene ligands: is faster always better?

Victor Gray; William Drake; Jesse R. Allardice; Zhilong Zhang; James Xiao; Daniel G. Congrave; Jeroen Royakkers; Weixuan Zeng; Simon Dowland; Neil C. Greenham; Hugo Bronstein; John E. Anthony; Akshay Rao

doi:10.1039/d2tc03470k

Triplet transfer from PbS quantum dots to tetracene ligands: is faster always better?

Victor Gray, William Drake, Jesse R. Allardice, Zhilong Zhang, James Xiao, Daniel G. Congrave, Jeroen Royakkers, Weixuan Zeng, Simon Dowland, Neil C. Greenham, Hugo Bronstein, John E. Anthony, Akshay Rao

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

Abstract

Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro-cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications.

Original language	English
Pages (from-to)	16321-16329
Number of pages	9
Journal	Journal of Materials Chemistry C
Volume	10
Issue number	43
DOIs	https://doi.org/10.1039/d2tc03470k
State	Published - Oct 11 2022

Bibliographical note

Funding Information:
We thank the Winton Programme for the Physics of Sustainability and the Engineering and Physical Sciences Research Council (Grant EP/P027741/1) for funding. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement no. 758826). VG acknowledges funding from the Swedish research council, Vetenskapsrådet 2018-00238. J. R. A. acknowledges Cambridge Commonwealth European and International Trust for financial support. Z. Z. acknowledges funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Actions grant (no. 842271 – TRITON project). J. X. acknowledges EPSRC Cambridge NanoDTC, EP/L015978/1 for financial support. D. G. C. acknowledges the Herchel Smith fund for a postdoctoral fellowship. JEA acknowledge the US National Science Foundation under cooperative agreement no. 1849213, for support of organic semiconductor synthesis.

Publisher Copyright:
© 2022 The Royal Society of Chemistry.

ASJC Scopus subject areas

Chemistry (all)
Materials Chemistry

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10.1039/d2tc03470k

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@article{aba170488d554ff581c456bd2847a9f3,

title = "Triplet transfer from PbS quantum dots to tetracene ligands: is faster always better?",

abstract = "Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro-cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications.",

author = "Victor Gray and William Drake and Allardice, {Jesse R.} and Zhilong Zhang and James Xiao and Congrave, {Daniel G.} and Jeroen Royakkers and Weixuan Zeng and Simon Dowland and Greenham, {Neil C.} and Hugo Bronstein and Anthony, {John E.} and Akshay Rao",

note = "Funding Information: We thank the Winton Programme for the Physics of Sustainability and the Engineering and Physical Sciences Research Council (Grant EP/P027741/1) for funding. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement no. 758826). VG acknowledges funding from the Swedish research council, Vetenskapsr{\aa}det 2018-00238. J. R. A. acknowledges Cambridge Commonwealth European and International Trust for financial support. Z. Z. acknowledges funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sk{\l}odowska-Curie Actions grant (no. 842271 – TRITON project). J. X. acknowledges EPSRC Cambridge NanoDTC, EP/L015978/1 for financial support. D. G. C. acknowledges the Herchel Smith fund for a postdoctoral fellowship. JEA acknowledge the US National Science Foundation under cooperative agreement no. 1849213, for support of organic semiconductor synthesis. Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = oct,

day = "11",

doi = "10.1039/d2tc03470k",

language = "English",

volume = "10",

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AU - Gray, Victor

AU - Drake, William

AU - Allardice, Jesse R.

AU - Zhang, Zhilong

AU - Xiao, James

AU - Congrave, Daniel G.

AU - Royakkers, Jeroen

AU - Zeng, Weixuan

AU - Dowland, Simon

AU - Greenham, Neil C.

AU - Bronstein, Hugo

AU - Anthony, John E.

AU - Rao, Akshay

N1 - Funding Information: We thank the Winton Programme for the Physics of Sustainability and the Engineering and Physical Sciences Research Council (Grant EP/P027741/1) for funding. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement no. 758826). VG acknowledges funding from the Swedish research council, Vetenskapsrådet 2018-00238. J. R. A. acknowledges Cambridge Commonwealth European and International Trust for financial support. Z. Z. acknowledges funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Actions grant (no. 842271 – TRITON project). J. X. acknowledges EPSRC Cambridge NanoDTC, EP/L015978/1 for financial support. D. G. C. acknowledges the Herchel Smith fund for a postdoctoral fellowship. JEA acknowledge the US National Science Foundation under cooperative agreement no. 1849213, for support of organic semiconductor synthesis. Publisher Copyright: © 2022 The Royal Society of Chemistry.

PY - 2022/10/11

Y1 - 2022/10/11

N2 - Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro-cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications.

AB - Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro-cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications.

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Triplet transfer from PbS quantum dots to tetracene ligands: is faster always better?

Abstract

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