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Title: Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy

Abstract

The Shockley-Queisser limit for solar cell efficiency can be overcome if hot carriers can be harvested before they thermalize. Recently, carrier cooling time up to 100 picoseconds was observed in hybrid perovskites, but it is unclear whether these long-lived hot carriers can migrate long distance for efficient collection. Here, we report direct visualization of hot-carrier migration in methylammonium lead iodide (CH 3NH 3PbI 3) thin films by ultrafast transient absorption microscopy, demonstrating three distinct transport regimes. Quasiballistic transport was observed to correlate with excess kinetic energy, resulting in up to 230 nanometers transport distance that could overcome grain boundaries. The nonequilibrium transport persisted over tens of picoseconds and ~600 nanometers before reaching the diffusive transport limit. Lastly, these results suggest potential applications of hot-carrier devices based on hybrid perovskites.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Solar Energy Technologies Office (EE-4S); National Science Foundation (NSF)
OSTI Identifier:
1351584
Report Number(s):
NREL/JA-5900-68003
Journal ID: ISSN 0036-8075
Grant/Contract Number:
AC36-08GO28308; NSF-DMR-1507803
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Science
Additional Journal Information:
Journal Volume: 356; Journal Issue: 6333; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; hot-carrier devices; hybrid perovskites; efficiency; transport

Citation Formats

Guo, Zhi, Wan, Yan, Yang, Mengjin, Snaider, Jordan, Zhu, Kai, and Huang, Libai. Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy. United States: N. p., 2017. Web. doi:10.1126/science.aam7744.
Guo, Zhi, Wan, Yan, Yang, Mengjin, Snaider, Jordan, Zhu, Kai, & Huang, Libai. Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy. United States. doi:10.1126/science.aam7744.
Guo, Zhi, Wan, Yan, Yang, Mengjin, Snaider, Jordan, Zhu, Kai, and Huang, Libai. Fri . "Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy". United States. doi:10.1126/science.aam7744. https://www.osti.gov/servlets/purl/1351584.
@article{osti_1351584,
title = {Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy},
author = {Guo, Zhi and Wan, Yan and Yang, Mengjin and Snaider, Jordan and Zhu, Kai and Huang, Libai},
abstractNote = {The Shockley-Queisser limit for solar cell efficiency can be overcome if hot carriers can be harvested before they thermalize. Recently, carrier cooling time up to 100 picoseconds was observed in hybrid perovskites, but it is unclear whether these long-lived hot carriers can migrate long distance for efficient collection. Here, we report direct visualization of hot-carrier migration in methylammonium lead iodide (CH3NH3PbI3) thin films by ultrafast transient absorption microscopy, demonstrating three distinct transport regimes. Quasiballistic transport was observed to correlate with excess kinetic energy, resulting in up to 230 nanometers transport distance that could overcome grain boundaries. The nonequilibrium transport persisted over tens of picoseconds and ~600 nanometers before reaching the diffusive transport limit. Lastly, these results suggest potential applications of hot-carrier devices based on hybrid perovskites.},
doi = {10.1126/science.aam7744},
journal = {Science},
number = 6333,
volume = 356,
place = {United States},
year = {Fri Apr 07 00:00:00 EDT 2017},
month = {Fri Apr 07 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 28works
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  • High-bandgap mixed-halide hybrid perovskites have higher open-circuit voltage deficits and lower carrier diffusion lengths than their lower-bandgap counterparts. We have developed a ligand-assisted crystallization (LAC) technique that introduces additives in situ during the solvent wash and developed a new method to dynamically measure the absolute intensity steady-state photoluminescence and the mean carrier diffusion length simultaneously. The measurements reveal four distinct regimes of material changes and show that photoluminescence brightening often coincides with losses in carrier transport, such as in degradation or phase segregation. Further, the measurements enabled optimization of LAC on the 1.75 eV bandgap FA 0.83Cs 0.17Pb(I 0.66Br 0.34)more » 3, resulting in an enhancement of the photoluminescence quantum yield (PLQY) of over an order of magnitude, an increase of 80 meV in the quasi-Fermi level splitting (to 1.29 eV), an increase in diffusion length by a factor of 3.5 (to over 1 μm), and enhanced open-circuit voltage and short-circuit current from photovoltaics fabricated from the LAC-treated films.« less
    Cited by 5
  • High-bandgap mixed-halide hybrid perovskites have higher open-circuit voltage deficits and lower carrier diffusion lengths than their lower-bandgap counterparts. We have developed a ligand-assisted crystallization (LAC) technique that introduces additives in situ during the solvent wash and developed a new method to dynamically measure the absolute intensity steady-state photoluminescence and the mean carrier diffusion length simultaneously. The measurements reveal four distinct regimes of material changes and show that photoluminescence brightening often coincides with losses in carrier transport, such as in degradation or phase segregation. Further, the measurements enabled optimization of LAC on the 1.75 eV bandgap FA 0.83Cs 0.17Pb(I 0.66Br 0.34)more » 3, resulting in an enhancement of the photoluminescence quantum yield (PLQY) of over an order of magnitude, an increase of 80 meV in the quasi-Fermi level splitting (to 1.29 eV), an increase in diffusion length by a factor of 3.5 (to over 1 μm), and enhanced open-circuit voltage and short-circuit current from photovoltaics fabricated from the LAC-treated films.« less
  • High-bandgap mixed-halide hybrid perovskites have higher open-circuit voltage deficits and lower carrier diffusion lengths than their lower-bandgap counterparts. We have developed a ligand-assisted crystallization (LAC) technique that introduces additives in situ during the solvent wash and developed a new method to dynamically measure the absolute intensity steady-state photoluminescence and the mean carrier diffusion length simultaneously. The measurements reveal four distinct regimes of material changes and show that photoluminescence brightening often coincides with losses in carrier transport, such as in degradation or phase segregation. Further, the measurements enabled optimization of LAC on the 1.75 eV bandgap FA 0.83Cs 0.17Pb(I 0.66Br 0.34)more » 3, resulting in an enhancement of the photoluminescence quantum yield (PLQY) of over an order of magnitude, an increase of 80 meV in the quasi-Fermi level splitting (to 1.29 eV), an increase in diffusion length by a factor of 3.5 (to over 1 μm), and enhanced open-circuit voltage and short-circuit current from photovoltaics fabricated from the LAC-treated films.« less
  • Singlet fission presents an attractive solution to overcome the Shockley–Queisser limit by generating two triplet excitons from one singlet exciton. Although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. We report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. Moreover, these measurements revealmore » a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.« less