Dynamic Disorder Dominates Delocalization, Transport, and Recombination in Halide Perovskites

Munson, Kyle T.; Kennehan, Eric R.; Doucette, Grayson S.; Asbury, John B.

doi:10.1016/j.chempr.2018.09.001

Cited by 118 publications

(210 citation statements)

References 92 publications

Supporting

Mentioning

192

Contrasting

Order By: Relevance

“…Interestingly, this predicted behavior is consistent with previous reports of radiative recombination rates as a function of temperature but, 87 we note, also consistent with the temperature dependence of Rrad,0 (c.f. Eq.…”

Section: Thz For Perovskites)supporting

confidence: 93%

“…22,76,95 Recently, Asbury and coworkers have shown optical signatures of large polarons in the mid-IR decaying slower at elevated temperatures. 87 They have attributed this to a reduction in the charge carrier mobility and a localization of polaron states at higher temperatures. Other studies have attempted to indirectly probe polaron recombination by investigating different perovskite compositions, APbBr3, with A + = CH3NH3 + (MA), NH2CHNH2 + (FA), and Cs + , which all exhibit similar recombination kinetics.…”

Section: Thz For Perovskites)mentioning

confidence: 99%

See 1 more Smart Citation

Charge-Carrier Recombination in Halide Perovskites

et al. 2019

View full text Add to dashboard Cite

In 1983 he was in the very small inaugural group promoted by Sandia National Laboratories to be a Distinguished Member of Technical Staff. He retired from Sandia but continues his research while an Adjunct Professor in the Department of Physics and Astronomy of the University of New Mexico. In 2008 David Emin was named an "outstanding referee" by the American Physical Society in its first round of selectees. Thomas Kirchartz received his PhD from the RWTH Aachen in 2009 and subsequently moved to Imperial College London working on organic solar cells with Prof. Jenny Nelson. In 2013, he was appointed Professor at the University of Duisburg-Essen (Electrical Engineering) and became head of a group working on characterization and simulation of solution-processable solar cells at the Research Centre Jülich. Since 2017, he is deputy head of the IEK-5 Photovoltaics, the institute dealing with all photovoltaics-related research at the Research Centre Jülich.

show abstract

Section: Thz For Perovskites)supporting

confidence: 93%

Section: Thz For Perovskites)mentioning

confidence: 99%

Charge-Carrier Recombination in Halide Perovskites

et al. 2019

View full text Add to dashboard Cite

show abstract

“…The PL spectra are nearly invariant in width but have an increased Stokes shift as the cation becomes larger, 6 indicating that excitons find energetic minima before recombining, consistent with disorder and/or polaron formation. 5,9,13,[17][18][19][20][21] As the temperature is decreased from 300 K to 10 K, the excitonic absorption and PL resonances for 2-F, 2-Cl, and 2-Br linearly red-shift ( Figure S5 reports by us and others for Pb-based hybrid perovskites 6,22,23 as well as lead chalcogenides. [24][25][26] α is much smaller than that we observed for (PEA)2PbI4 and its derivatives which have longer cations with unchanged cross-sectional area, where α ranged from -0.14 to -0.16 meV/K, 27 indicative of a weaker temperature dependence of the electronic properties of 2DHPs as the Pb-I-Pb bond angle decreases and the band gap increases.…”

Section: Resultsmentioning

confidence: 82%

Tailoring Hot Exciton Dynamics in 2D Hybrid Perovskites through Cation Modification

et al. 2020

View full text Add to dashboard Cite

We report a family of two-dimensional hybrid perovskites (2DHPs) based on phenethylammonium lead iodide ((PEA)2PbI4) that show complex structure in their lowtemperature excitonic absorption and photoluminescence (PL) spectra as well as hot exciton PL.We replace the 2-position (ortho) H on the phenyl group of the PEA cation with F, Cl, or Br to systematically increase the cation's cross-sectional area and mass and study changes in the excitonic structure. These single atom substitutions substantially change the observable number of and spacing between discrete resonances in the excitonic absorption and PL spectra and drastically increase the amount of hot exciton PL that violates Kasha's rule by over an order of magnitude. To fit the progressively larger cations, the inorganic framework distorts and is strained, reducing the Pb-I-Pb bond angles and increasing the 2DHP band gap. Correlation between the 2DHP structure and steady-state and time-resolved spectra suggests the complex structure of resonances arises from one or two manifolds of states, depending on the 2DHP Pb-I-Pb bond angle (as)symmetry, and the resonances within a manifold are regularly spaced with an energy separation that decreases as the mass of the cation increases. The uniform separation between resonances and the dynamics that show excitons can only relax to the next-lowest state are consistent with a vibronic progression caused by a vibrational mode on the cation. These

show abstract

“…Indeed, the recently discovered high-efficiency perovskite-based solar cells seem to exemplify this situation. 37 These metallic-and organometallic-halide perovskite materials have 1) extremely large values of 0/, [6][7][8][9] 2) moderate rrier mobilities that are comparable to those of alkali halides' large polarons, [38][39][40][41][42] 3) large-polaron-like absorption bands, 43 and 4) suppressed recombination. 44 Remarkably, the efficiencies of these novel perovskite solar cells, > 20%, are much larger than those of conventional silicon-based solar cells, 10%.…”

Section: Interactions Between Polaronsmentioning

confidence: 99%

Large (bi)Polarons for Novel Energy Conversion and Superconductivity

Emin

2019

J Supercond Nov Magn

View full text Add to dashboard Cite

The last fifty years produced fundamental advances in understanding the formation, motion and interactions among (bi)polarons. Interference between the atomic displacement patterns of oppositely charged (bi)polarons generates a short-range repulsion which impedes their reconalmbination, significantly enhancing efficiencies of energy-conversion devices, e.g. perovskite solar cells. A large-(bi)polaron's atomic vibrations are softened by the relaxation of its self-trapped electronic carriers. Scattering of impinging ambient phonons by large-bipolarons' softened vibrations generates distinctive transport. Coherence between the softened atomic vibrations of large-bipolarons generates a phonon-assisted mutual attraction which facilitates their condensation into a liquid. A large-bipolaron liquid's superconducting Bose condensate is characterized by coherent zero-point atomic vibrations which decrease positron annihilation and increase ion channeling. Disorder can trigger electronic charge carriers' collapse into small polarons. The back-and-forth Arrhenius hopping of a small-polaron softens the associated atoms' vibrations thereby increasing their entropy. This effect explains the empirically observed Meyer-Neldel compensation effect. In particular, the temperature-independent factor of the jump-rate increases exponentially in proportion to its activation energy.

show abstract

Dynamic Disorder Dominates Delocalization, Transport, and Recombination in Halide Perovskites

Cited by 118 publications

References 92 publications

Charge-Carrier Recombination in Halide Perovskites

Charge-Carrier Recombination in Halide Perovskites

Tailoring Hot Exciton Dynamics in 2D Hybrid Perovskites through Cation Modification

Large (bi)Polarons for Novel Energy Conversion and Superconductivity

Contact Info

Product

Resources

About