Hot-Hole cooling controls the initial ultrafast relaxation in methylammonium lead iodide perovskite

Gordon James Hedley; C Quarti; Jonathon Robert Harwell; O Prezhdo; D Beljonne; Ifor David William Samuel

doi:10.1038/s41598-018-26207-9

Hot-Hole cooling controls the initial ultrafast relaxation in methylammonium lead iodide perovskite

Gordon James Hedley, C Quarti, Jonathon Robert Harwell, O Prezhdo, D Beljonne, Ifor David William Samuel

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Abstract

Understanding the initial ultrafast excited state dynamics of methylammonium lead iodide (MAPI) perovskite is of vital importance to enable its fullest utilisation in optoelectronic devices and the design of improved materials. Here we have combined advanced measurements of the ultrafast photoluminescence from MAPI films up to 0.6 eV above the relaxed excited state with cutting-edge advanced non-adiabatic quantum dynamics simulations, to provide a powerful unique insight into the earliest time behaviour in MAPI. Our joint experimental-theoretical approach highlights that the cooling of holes from deep in the valence band to the valence band edge is fast, occurring on a 100-500 fs timescale. Cooling of electrons from high in the conduction band to the conduction band edge, however, is much slower, on the order of 1-10 ps. Density of states calculations indicate that excited states with holes deep in the valence band are greatly favoured upon photoexcitation, and this matches well with the fast (100-500 fs) formation time for the relaxed excited state observed in our ultrafast PL measurements. Consequently we are able to provide a complete observation of the initial excited state evolution in this important prototypical material.

Original language	English
Article number	8115
Number of pages	9
Journal	Scientific Reports
Volume	8
DOIs	https://doi.org/10.1038/s41598-018-26207-9
Publication status	Published - 25 May 2018

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Equipment Account: Characterisation and Manipulation of Advanced Functional Materials and their Interfaces at the Nanoscale
Samuel, I. D. W. (PI)
EPSRC
1/10/13 → 30/09/23
Project: Standard
ERC Advanced Grant EXCITON: EU FP7 ERC Advanced Grant 2012 EXCITON
Samuel, I. D. W. (PI)
European Research Council
1/04/13 → 30/03/19
Project: Standard
The Influence of Excited State Physics: The influence of Excited State Physics in Conjugated Polymer Devices
Samuel, I. D. W. (PI)
EPSRC
1/10/12 → 30/09/15
Project: Standard

Optoelectronic Applications of Lead Halide Perovskites (thesis data)
Harwell, J. R. (Creator) & Samuel, I. D. W. (Supervisor), University of St Andrews, 2019
DOI: 10.17630/fa576f47-27ef-4610-baf5-56893d646329, http://hdl.handle.net/10023/16943
Dataset: Thesis dataset

File
Hot-Hole Cooling Controls the Initial Ultrafast Relaxation in Methyl Ammonium Lead Iodide Perovskite (dataset)
Hedley, G. J. (Creator), Quarti, C. (Creator), Harwell, J. R. (Creator), Prezhdo, O. (Creator), Beljonne, D. (Creator) & Samuel, I. D. W. (Creator), University of St Andrews, 25 May 2018
DOI: 10.17630/6f533425-f4b6-49c9-aa69-ea02692c6af0
Dataset

File

Cite this

@article{927c150b4b514a438222750fa3b3016e,

title = "Hot-Hole cooling controls the initial ultrafast relaxation in methylammonium lead iodide perovskite",

abstract = "Understanding the initial ultrafast excited state dynamics of methylammonium lead iodide (MAPI) perovskite is of vital importance to enable its fullest utilisation in optoelectronic devices and the design of improved materials. Here we have combined advanced measurements of the ultrafast photoluminescence from MAPI films up to 0.6 eV above the relaxed excited state with cutting-edge advanced non-adiabatic quantum dynamics simulations, to provide a powerful unique insight into the earliest time behaviour in MAPI. Our joint experimental-theoretical approach highlights that the cooling of holes from deep in the valence band to the valence band edge is fast, occurring on a 100-500 fs timescale. Cooling of electrons from high in the conduction band to the conduction band edge, however, is much slower, on the order of 1-10 ps. Density of states calculations indicate that excited states with holes deep in the valence band are greatly favoured upon photoexcitation, and this matches well with the fast (100-500 fs) formation time for the relaxed excited state observed in our ultrafast PL measurements. Consequently we are able to provide a complete observation of the initial excited state evolution in this important prototypical material.",

author = "Hedley, {Gordon James} and C Quarti and Harwell, {Jonathon Robert} and O Prezhdo and D Beljonne and Samuel, {Ifor David William}",

note = "Funding: EPSRC (grants EP/J009016 and EP/L017008) and the European Research Council (grant 321305). IDWS acknowledges a Royal Society Wolfson Research Merit Award.",

year = "2018",

month = may,

day = "25",

doi = "10.1038/s41598-018-26207-9",

language = "English",

volume = "8",

journal = "Scientific Reports",

issn = "2045-2322",

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TY - JOUR

T1 - Hot-Hole cooling controls the initial ultrafast relaxation in methylammonium lead iodide perovskite

AU - Hedley, Gordon James

AU - Quarti, C

AU - Harwell, Jonathon Robert

AU - Prezhdo, O

AU - Beljonne, D

AU - Samuel, Ifor David William

N1 - Funding: EPSRC (grants EP/J009016 and EP/L017008) and the European Research Council (grant 321305). IDWS acknowledges a Royal Society Wolfson Research Merit Award.

PY - 2018/5/25

Y1 - 2018/5/25

N2 - Understanding the initial ultrafast excited state dynamics of methylammonium lead iodide (MAPI) perovskite is of vital importance to enable its fullest utilisation in optoelectronic devices and the design of improved materials. Here we have combined advanced measurements of the ultrafast photoluminescence from MAPI films up to 0.6 eV above the relaxed excited state with cutting-edge advanced non-adiabatic quantum dynamics simulations, to provide a powerful unique insight into the earliest time behaviour in MAPI. Our joint experimental-theoretical approach highlights that the cooling of holes from deep in the valence band to the valence band edge is fast, occurring on a 100-500 fs timescale. Cooling of electrons from high in the conduction band to the conduction band edge, however, is much slower, on the order of 1-10 ps. Density of states calculations indicate that excited states with holes deep in the valence band are greatly favoured upon photoexcitation, and this matches well with the fast (100-500 fs) formation time for the relaxed excited state observed in our ultrafast PL measurements. Consequently we are able to provide a complete observation of the initial excited state evolution in this important prototypical material.

AB - Understanding the initial ultrafast excited state dynamics of methylammonium lead iodide (MAPI) perovskite is of vital importance to enable its fullest utilisation in optoelectronic devices and the design of improved materials. Here we have combined advanced measurements of the ultrafast photoluminescence from MAPI films up to 0.6 eV above the relaxed excited state with cutting-edge advanced non-adiabatic quantum dynamics simulations, to provide a powerful unique insight into the earliest time behaviour in MAPI. Our joint experimental-theoretical approach highlights that the cooling of holes from deep in the valence band to the valence band edge is fast, occurring on a 100-500 fs timescale. Cooling of electrons from high in the conduction band to the conduction band edge, however, is much slower, on the order of 1-10 ps. Density of states calculations indicate that excited states with holes deep in the valence band are greatly favoured upon photoexcitation, and this matches well with the fast (100-500 fs) formation time for the relaxed excited state observed in our ultrafast PL measurements. Consequently we are able to provide a complete observation of the initial excited state evolution in this important prototypical material.

U2 - 10.1038/s41598-018-26207-9

DO - 10.1038/s41598-018-26207-9

M3 - Article

SN - 2045-2322

VL - 8

JO - Scientific Reports

JF - Scientific Reports

M1 - 8115

ER -

Hot-Hole cooling controls the initial ultrafast relaxation in methylammonium lead iodide perovskite

Abstract

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Projects

Equipment Account: Characterisation and Manipulation of Advanced Functional Materials and their Interfaces at the Nanoscale

ERC Advanced Grant EXCITON: EU FP7 ERC Advanced Grant 2012 EXCITON

The Influence of Excited State Physics: The influence of Excited State Physics in Conjugated Polymer Devices

Datasets

Optoelectronic Applications of Lead Halide Perovskites (thesis data)

Hot-Hole Cooling Controls the Initial Ultrafast Relaxation in Methyl Ammonium Lead Iodide Perovskite (dataset)

Cite this