TY - JOUR
T1 - Confinement and Exciton Binding Energy Effects on Hot Carrier Cooling in Lead Halide Perovskite Nanomaterials
AU - Carwithen, Ben P.
AU - Hopper, Thomas R.
AU - Ge, Ziyuan
AU - Mondal, Navendu
AU - Wang, Tong
AU - Mazlumian, Rozana
AU - Zheng, Xijia
AU - Krieg, Franziska
AU - Montanarella, Federico
AU - Nedelcu, Georgian
AU - Kroll, Martin
AU - Siguan, Miguel Albaladejo
AU - Frost, Jarvist M.
AU - Leo, Karl
AU - Vaynzof, Yana
AU - Bodnarchuk, Maryna I.
AU - Kovalenko, Maksym V.
AU - Bakulin, Artem A.
N1 - Funding Information:
The authors would like to thank Matthew Beard (NREL), Bernard Wenger (Helio), and Adam Wright (Princeton) for valuable discussions; and Dmitry Dirin (ETH Zurich) for providing SEM/TEM images of the nanomaterials. T.R.H. would like to acknowledge support from an EPSRC Doctoral Prize Fellowship. N.M. and A.A.B. acknowledge support from the European Commission through the Marie Skłodowska-Curie Actions (Project PeroVIB, H2020-MSCA-IF-2020-101018002). F.M. acknowledges support from ETH Zürich via the ETH Postdoctoral Fellowship (FEL-1518-2) and from the Marie Skłodowska-Curie Actions COFUND Program. F.M. also acknowledges financial support from the European Union’s Horizon 2020 program, through a FET-Open research and innovation action under grant agreement No. 899141 (PoLLoC). J.M.F. is supported by a Royal Society University Research Fellowship (URF-R1-191292). M.K. and K.L. thank the Deutsche Forschungsgemeinschaft (DFG) for support through the Phive-X project, “Perovskite Heterostructure Investigations using Vacuum Evaporation and X-ray Diffraction” (LE 747/64-1); and the EFRE project, “Investigation of Lead and Tin Free Perovskites by Vacuum Deposition” (100341673). Y.V. thanks the DFG for funding through the PERFECT PVs project (424216076) within the framework of SPP 2196, and the Fulbright Commission for support (Fulbright-Cottrell Award 2018). M.V.K. acknowledges financial support from Innosuisse─Swiss Innovation Agency under project 32908.1 IP-EE. A.A.B. acknowledges support from the Royal Society and Leverhulme Trust.
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/4/11
Y1 - 2023/4/11
N2 - The relaxation of the above-gap (“hot”) carriers in lead halide perovskites (LHPs) is important for applications in photovoltaics and offers insights into carrier-carrier and carrier-phonon interactions. However, the role of quantum confinement in the hot carrier dynamics of nanosystems is still disputed. Here, we devise a single approach, ultrafast pump-push-probe spectroscopy, to study carrier cooling in six different size-controlled LHP nanomaterials. In cuboidal nanocrystals, we observe only a weak size effect on the cooling dynamics. In contrast, two-dimensional systems show suppression of the hot phonon bottleneck effect common in bulk perovskites. The proposed kinetic model describes the intrinsic and density-dependent cooling times accurately in all studied perovskite systems using only carrier-carrier, carrier-phonon, and excitonic coupling constants. This highlights the impact of exciton formation on carrier cooling and promotes dimensional confinement as a tool for engineering carrier-phonon and carrier-carrier interactions in LHP optoelectronic materials.
AB - The relaxation of the above-gap (“hot”) carriers in lead halide perovskites (LHPs) is important for applications in photovoltaics and offers insights into carrier-carrier and carrier-phonon interactions. However, the role of quantum confinement in the hot carrier dynamics of nanosystems is still disputed. Here, we devise a single approach, ultrafast pump-push-probe spectroscopy, to study carrier cooling in six different size-controlled LHP nanomaterials. In cuboidal nanocrystals, we observe only a weak size effect on the cooling dynamics. In contrast, two-dimensional systems show suppression of the hot phonon bottleneck effect common in bulk perovskites. The proposed kinetic model describes the intrinsic and density-dependent cooling times accurately in all studied perovskite systems using only carrier-carrier, carrier-phonon, and excitonic coupling constants. This highlights the impact of exciton formation on carrier cooling and promotes dimensional confinement as a tool for engineering carrier-phonon and carrier-carrier interactions in LHP optoelectronic materials.
KW - hot carriers
KW - nanocrystals
KW - nanoplatelets
KW - two-dimensional perovskites
KW - ultrafast spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85151241763&partnerID=8YFLogxK
U2 - 10.1021/acsnano.2c12373
DO - 10.1021/acsnano.2c12373
M3 - Article
C2 - 36939330
AN - SCOPUS:85151241763
SN - 1936-0851
VL - 17
SP - 6638
EP - 6648
JO - Acs Nano
JF - Acs Nano
IS - 7
ER -