Hot Carrier Cooling and Recombination Dynamics of Chlorine-Doped Hybrid Perovskite Single Crystals

Mix, L. Tyler; Ghosh, Dibyajyoti; Tisdale, Jeremy; Lee, Min-Cheol; O’Neal, Kenneth; Sirica, Nicholas; Neukirch, Amanda; Nie, Wanyi; Taylor, Antoinette J.; Prasankumar, R. P.; Tretiak, Sergei; Yarotski, D. A.

doi:10.1021/acs.jpclett.0c02243

Cited by 13 publications

(26 citation statements)

References 38 publications

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“…The lattice connectivity can affect the relaxation of hot carriers because of the number of relaxation paths and interaction between the octahedrons, which needs further experimental verification. Through this work, we envision new strategies to control hot carrier relaxation by changing the carrier concentration and tuning electron–phonon coupling, thereby controlling the photovoltaic efficiency in these eco-friendly materials. ,, …”

Section: Resultsmentioning

confidence: 99%

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Cation-Dependent Hot Carrier Cooling in the Lead-Free Bismuth Halide A₃Bi₂I₉ (A = FA, MA, and Cs) Perovskite

et al. 2021

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Lead-free halide perovskites, as environment-friendly materials, have received critical interest in photovoltaic applications. In this regard, the bismuth halide perovskites demonstrate better stability under ambient conditions than lead halide perovskites and consequently remain one of the critical areas for the development of lead-free absorber materials. The steady-state optical properties are widely investigated in these bismuth halide perovskites, but excited-state charge carrier dynamics such as hot carrier relaxation remain elusive. However, it is crucial to investigate the rapid relaxation of above band gap “hot” carriers as it restricts the fundamental efficiency limit in the perovskite solar cells. Here, we demonstrate the cation-dependent hot carrier cooling in the lead-free A3Bi2I9 [A = FA (formamidinium), MA (methylammonium), and Cs (cesium)] perovskite by using femtosecond transient absorption spectroscopy. These lead-free perovskites were fabricated from gamma-butyrolactone (γ-GBL) solvent to ensure uniformity and continuity of the as-grown film and were well characterized by XRD, SEM, and steady-state absorption and photoluminescence spectroscopy. With varying A-cations, we observe that the hot-hole relaxation is slowest in the all-inorganic perovskite Cs3Bi2I9 (12.83 ps) and hot electron relaxation is slowest in the hybrid MA3Bi2I9 perovskite (6.42 ps) at the same excitation energy. The observed strong dependence of carrier cooling on cation composition is explained by the interaction between the different organic cations (A = FA, MA, and Cs) with the Pb–Br frameworks. Our study provides an opportunity to understand the effect of cations on the excited-state carrier dynamics, especially the hot carrier relaxation in the bismuth halide perovskites. This will pave the way for designing hot carrier-based high-efficient lead-free perovskite photovoltaic devices.

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Section: Resultsmentioning

confidence: 99%

“…Through this work, we envision new strategies to control hot carrier relaxation by changing the carrier concentration and tuning electron− phonon coupling, thereby controlling the photovoltaic efficiency in these eco-friendly materials. 13,63,64…”

Section: Resultsmentioning

confidence: 99%

Cation-Dependent Hot Carrier Cooling in the Lead-Free Bismuth Halide A₃Bi₂I₉ (A = FA, MA, and Cs) Perovskite

et al. 2021

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“…[5] However, harvesting HCs in the sub-ps time regime can still be challenging, and a further slowing down of the cooling is necessary. While compositional engineering, defect passivation, and nanostructuring have proven useful for slowing down HC cooling in 3D perovskites, [6][7][8][9][10] these strategies face the same limitation where the losses are dominated by phonon emission. [11] Inorganic semiconductor multi-quantum well (MQW) structures (e.g., InAs/AlAsSb and GaAs/AlAs) have also demonstrated prolonged HC lifetimes.…”

Section: Introductionmentioning

confidence: 99%

Tailoring the Energy Manifold of Quasi‐Two‐Dimensional Perovskites for Efficient Carrier Extraction

Ramesh

Giovanni

Righetto

et al. 2022

Advanced Energy Materials

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Harvesting the excess energy from absorbed above bandgap photons is a promising approach to overcome the detailed balance limit for higher solar cell efficiencies. However, this remains very challenging for 2D layered halide perovskites as the fast excess energy loss competes effectively with charge extraction. Herein, the authors engineer the energy cascade manifold of quantum well (QW) states in quasi‐2D Ruddlesden–Popper perovskites by facile tuning of the organic spacer to decelerate the energy loss. The resulting excess energy loss rate is up to two orders slower compared to 3D perovskites, thus enabling efficient carrier extraction. 2D electronic spectroscopy reveals further insights into the structural and energetic disorder of these layered systems. Importantly, a judicious choice of the organic spacer holds the key to tailoring the coherent coupling between QWs that strongly influences the competition between the energy cascade and charge extraction.

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“…Similarly, Yarotski and group performed Nonadiabatic Molecular Dynamics (NAMD) simulations as well as transient studies on MAPbBr 3 and Chlorine (Cl) doped MAPbBr 3 to understand the impact of Cl doping on the HC cooling processes. [83] The transient studies conducted in reflectance mode show that not only the early time signal growth (Figure 12 B) is sluggish in the pristine system as compared to that of the doped system but also similar trend is discerned in the signal decay (Figure 12 A). Herein, the initial growth has been attributed to the HC cooling process and the decay is ascribed to the surface recombination of the photo excited electrons in the conduction band minima with the holes in the valence band and later followed by the diffusion of these carriers in the bulk.…”

Section: The Lattice Temperaturementioning

confidence: 70%

“…(C) Hot electron lifetimes calculated for MAPbBr 3-x Cl x . "Reprinted (adapted) with permission from ref [83]. Copyright (2020) American Chemical Society.…”

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confidence: 99%

Chemically Engineered Avenues: Opportunities for Attaining Desired Carrier Cooling in Perovskites

Kaur

Shukla

Babu

et al. 2022

The Chemical Record

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Hot carrier extraction‐based devices are presently being persuaded as the most revolutionary means of surpassing the theoretical thermodynamic conversion efficiency limit (∼67 % for a model hot carrier solar cell). However, for practical realisation, there stand various hurdles that need to be surmounted, a major among all being the rapid hot carrier cooling rate. Though, the perovskite family has already demonstrated itself to exhibit slower cooling in contrast to the prototypical semiconductors. Decelerating this entire process of cooling further can prove to be a crucial stride in this regard. Quite contrarily, for the optoelectronic applications the situation is entirely conflicting where quick rate of cooling is a chief prerequisite. In the recent times, there have been various key developments that have targeted altering this cooling rate by various chemically engineered strategies. This review highlights such blueprints that can be utilized towards the advantageous alteration of the carrier cooling in accordance with the device requirements.

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Hot Carrier Cooling and Recombination Dynamics of Chlorine-Doped Hybrid Perovskite Single Crystals

Cited by 13 publications

References 38 publications

Cation-Dependent Hot Carrier Cooling in the Lead-Free Bismuth Halide A₃Bi₂I₉ (A = FA, MA, and Cs) Perovskite

Cation-Dependent Hot Carrier Cooling in the Lead-Free Bismuth Halide A₃Bi₂I₉ (A = FA, MA, and Cs) Perovskite

Tailoring the Energy Manifold of Quasi‐Two‐Dimensional Perovskites for Efficient Carrier Extraction

Chemically Engineered Avenues: Opportunities for Attaining Desired Carrier Cooling in Perovskites

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Hot Carrier Cooling and Recombination Dynamics of Chlorine-Doped Hybrid Perovskite Single Crystals

Cited by 13 publications

References 38 publications

Cation-Dependent Hot Carrier Cooling in the Lead-Free Bismuth Halide A3Bi2I9 (A = FA, MA, and Cs) Perovskite

Cation-Dependent Hot Carrier Cooling in the Lead-Free Bismuth Halide A3Bi2I9 (A = FA, MA, and Cs) Perovskite

Tailoring the Energy Manifold of Quasi‐Two‐Dimensional Perovskites for Efficient Carrier Extraction

Chemically Engineered Avenues: Opportunities for Attaining Desired Carrier Cooling in Perovskites

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Product

Resources

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Cation-Dependent Hot Carrier Cooling in the Lead-Free Bismuth Halide A₃Bi₂I₉ (A = FA, MA, and Cs) Perovskite

Cation-Dependent Hot Carrier Cooling in the Lead-Free Bismuth Halide A₃Bi₂I₉ (A = FA, MA, and Cs) Perovskite