Hole Transfer in Dye-Sensitized Cesium Lead Halide Perovskite Photovoltaics: Effect of Interfacial Bonding
Lead halide perovskites have gained attention as an active material in solid-state dye-sensitized photovoltaics due to their high absorption of visible light and long charge-transport lengths. In perovskite-based dye-sensitized photovoltaic architectures the perovskite material is typically paired w...
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ftosti:oai:osti.gov:1480498 2023-07-30T04:03:11+02:00 Hole Transfer in Dye-Sensitized Cesium Lead Halide Perovskite Photovoltaics: Effect of Interfacial Bonding Forde, Aaron Kilin, Dmitri 2021-07-28 application/pdf http://www.osti.gov/servlets/purl/1480498 https://www.osti.gov/biblio/1480498 https://doi.org/10.1021/acs.jpcc.7b04961 unknown http://www.osti.gov/servlets/purl/1480498 https://www.osti.gov/biblio/1480498 https://doi.org/10.1021/acs.jpcc.7b04961 doi:10.1021/acs.jpcc.7b04961 14 SOLAR ENERGY 37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY 36 MATERIALS SCIENCE 2021 ftosti https://doi.org/10.1021/acs.jpcc.7b04961 2023-07-11T09:29:50Z Lead halide perovskites have gained attention as an active material in solid-state dye-sensitized photovoltaics due to their high absorption of visible light and long charge-transport lengths. In perovskite-based dye-sensitized photovoltaic architectures the perovskite material is typically paired with a hole-transport material, such as spiro-OMeTAD, which extracts a hole from the photoexcited perovskite to generate free charge carriers. In this study, we explored two competing charge-transfer pathways at the interface between lead halide perovskite and spiro-OMeTAD: “through-bond” and “through-space”. For the through-bond pathway we use a segment of spiro-OMeTAD that contains methoxy linker groups, which will be referred to as “dye with methoxy linker groups” (DML). For the through-space pathway we use a segment of spiro-OMeTAD with removed linker groups, triphenylamine, which will be referred to as “dye”. Four atomistic models were studied: (I) a periodic cesium lead iodide (CsPbI3) perovskite nanowire (NW) that is paired with the dye molecule, (II) a periodic CsPbI3 perovskite NW paired with the DML molecule where the linker groups form coordination bond to the surface of the nanowire, (III) a CsPbI 3 perovskite thin film (TF) paired with the dye molecule, and (IV) a CsPbI 3 perovskite TF paired with the DML molecule. Charge-transfer dynamics, providing rates of electron/hole relaxation and relaxation pathways, are calculated using reduced density matrix formalism using Redfield theory. Finally, it was found that the terminal surface of the perovskite (Pb–I vs Cs–I) has important implications for energetic alignment at the perovskite–dye interface due to band bending. Finally, computed charge-transfer rates match well with upper and lower bounds of reported experimental results where “fast” picosecond rates correspond to through-bond pathway and “slow” nanosecond rates correspond to through-space. Other/Unknown Material DML SciTec Connect (Office of Scientific and Technical Information - OSTI, U.S. Department of Energy) Spiro ENVELOPE(-59.000,-59.000,-62.267,-62.267) The Journal of Physical Chemistry C 121 37 20113 20125 |
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Open Polar |
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SciTec Connect (Office of Scientific and Technical Information - OSTI, U.S. Department of Energy) |
op_collection_id |
ftosti |
language |
unknown |
topic |
14 SOLAR ENERGY 37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY 36 MATERIALS SCIENCE |
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14 SOLAR ENERGY 37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY 36 MATERIALS SCIENCE Forde, Aaron Kilin, Dmitri Hole Transfer in Dye-Sensitized Cesium Lead Halide Perovskite Photovoltaics: Effect of Interfacial Bonding |
topic_facet |
14 SOLAR ENERGY 37 INORGANIC ORGANIC PHYSICAL AND ANALYTICAL CHEMISTRY 36 MATERIALS SCIENCE |
description |
Lead halide perovskites have gained attention as an active material in solid-state dye-sensitized photovoltaics due to their high absorption of visible light and long charge-transport lengths. In perovskite-based dye-sensitized photovoltaic architectures the perovskite material is typically paired with a hole-transport material, such as spiro-OMeTAD, which extracts a hole from the photoexcited perovskite to generate free charge carriers. In this study, we explored two competing charge-transfer pathways at the interface between lead halide perovskite and spiro-OMeTAD: “through-bond” and “through-space”. For the through-bond pathway we use a segment of spiro-OMeTAD that contains methoxy linker groups, which will be referred to as “dye with methoxy linker groups” (DML). For the through-space pathway we use a segment of spiro-OMeTAD with removed linker groups, triphenylamine, which will be referred to as “dye”. Four atomistic models were studied: (I) a periodic cesium lead iodide (CsPbI3) perovskite nanowire (NW) that is paired with the dye molecule, (II) a periodic CsPbI3 perovskite NW paired with the DML molecule where the linker groups form coordination bond to the surface of the nanowire, (III) a CsPbI 3 perovskite thin film (TF) paired with the dye molecule, and (IV) a CsPbI 3 perovskite TF paired with the DML molecule. Charge-transfer dynamics, providing rates of electron/hole relaxation and relaxation pathways, are calculated using reduced density matrix formalism using Redfield theory. Finally, it was found that the terminal surface of the perovskite (Pb–I vs Cs–I) has important implications for energetic alignment at the perovskite–dye interface due to band bending. Finally, computed charge-transfer rates match well with upper and lower bounds of reported experimental results where “fast” picosecond rates correspond to through-bond pathway and “slow” nanosecond rates correspond to through-space. |
author |
Forde, Aaron Kilin, Dmitri |
author_facet |
Forde, Aaron Kilin, Dmitri |
author_sort |
Forde, Aaron |
title |
Hole Transfer in Dye-Sensitized Cesium Lead Halide Perovskite Photovoltaics: Effect of Interfacial Bonding |
title_short |
Hole Transfer in Dye-Sensitized Cesium Lead Halide Perovskite Photovoltaics: Effect of Interfacial Bonding |
title_full |
Hole Transfer in Dye-Sensitized Cesium Lead Halide Perovskite Photovoltaics: Effect of Interfacial Bonding |
title_fullStr |
Hole Transfer in Dye-Sensitized Cesium Lead Halide Perovskite Photovoltaics: Effect of Interfacial Bonding |
title_full_unstemmed |
Hole Transfer in Dye-Sensitized Cesium Lead Halide Perovskite Photovoltaics: Effect of Interfacial Bonding |
title_sort |
hole transfer in dye-sensitized cesium lead halide perovskite photovoltaics: effect of interfacial bonding |
publishDate |
2021 |
url |
http://www.osti.gov/servlets/purl/1480498 https://www.osti.gov/biblio/1480498 https://doi.org/10.1021/acs.jpcc.7b04961 |
long_lat |
ENVELOPE(-59.000,-59.000,-62.267,-62.267) |
geographic |
Spiro |
geographic_facet |
Spiro |
genre |
DML |
genre_facet |
DML |
op_relation |
http://www.osti.gov/servlets/purl/1480498 https://www.osti.gov/biblio/1480498 https://doi.org/10.1021/acs.jpcc.7b04961 doi:10.1021/acs.jpcc.7b04961 |
op_doi |
https://doi.org/10.1021/acs.jpcc.7b04961 |
container_title |
The Journal of Physical Chemistry C |
container_volume |
121 |
container_issue |
37 |
container_start_page |
20113 |
op_container_end_page |
20125 |
_version_ |
1772814132636024832 |