Trap-Free Hot Carrier Relaxation in Lead–Halide Perovskite Films
Item Type Article
Authors Bretschneider, Simon A.;Laquai, Frédéric;Bonn, Mischa Citation Bretschneider SA, Laquai F, Bonn M (2017) Trap-Free Hot
Carrier Relaxation in Lead–Halide Perovskite Films. The Journal of Physical Chemistry C 121: 11201–11206. Available: http://
dx.doi.org/10.1021/acs.jpcc.7b03992.
Eprint version Post-print
DOI 10.1021/acs.jpcc.7b03992
Publisher American Chemical Society (ACS) Journal The Journal of Physical Chemistry C
Rights This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/
full/10.1021/acs.jpcc.7b03992.
Download date 2023-11-01 08:52:12
Link to Item http://hdl.handle.net/10754/625586
Supplementary information on
Trap-Free Hot Carrier Relaxation in Lead-Halide Perovskite Films
Simon A. Bretschneider1, Frédéric Laquai2 and Mischa Bonn1*
1Department of Molecular Spectroscopy, Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
2 King Abdullah University of Science and Technology (KAUST), KAUST Solar Center (KSC), Physical Sciences and Engineering Division (PSE), Material Science and Engineering Program (MSE), Thuwal, 23955-6900, Kingdom of Saudi Arabia
Corresponding Author
Mischa Bonn, [email protected], +49 6131 379 161
Content:
Optical characterization and SEM of MAPbI3(Cl), additional transient absorption and photoluminescence measurements.
Figure S1: Optical characterization of the MAPbI3(Cl) sample for the measurement: absorbance shown in black, integrated emission shown in red.
Figure S2: Scanning-electron microscopy of the MAPbI3(Cl) sample for the measurement. The scale bar is 2 µm.
Figure S3: Population of the ground state, the band edges and the hot state obtained from the fitting of the three-level rate equation.
The parameters of the fit shown in Fig. 1C are
relax = 3085 ± 44 ps
cool = 40.1 ± 1.8 ps
= 0.012 ± 9.6×10-5
= 0.0058 ± 1.1×10-4
Figure S4: Ultrafast transient absorption measurements MAPbI3(Cl) after excitation with a ~150 fs pulse at 3.1 eV for a fluence of 12.5 µJ/cm2. The bleach probed at 1.62 eV shows the delayed rise with a peak at ~ 60 ps. The decay was fitted with a single exponential function; the lifetime
is 1147 ± 28 ps for the signal at 1.62 eV.
Figure S5: Ultrafast transient absorption measurements of MAPbI3(Cl) after excitation with a
~150 fs pulse at 3.1 eV for a fluence of 39µJ/cm2. (A) shows the false color two-dimensional
transient absorption data for a pump fluence. It shows the same sub-ps feature as in Fig. 2a, but a much broader high-energy tail extending towards 1.9 eV and the ground-state bleach with stronger red-shift (0.02 eV between 1 ps and 1 ns). Both features have been associated with the hot-phonon bottleneck.1 (B) shows the comparison of the kinetics of the ground-state bleach (black) and of the hot carriers, probed at 1.73 eV; indicated by the dashed boxes in (A). The hot carriers decay exponentially with a time constant of τ = 15.57 ± 0.55 ps, on a similar timescale to the ingrowth of the peak of the ground-state bleach.
For the high fluence measurement, similar timescales were extracted for the delayed rise of the GSB signal (23 ± 3 ps) and the decay of the hot carriers (probed at 1.7 eV: τ = 15.6 ± 0.6 ps).
Compared to the low-fluence measurement, the high-energy tail (see Fig. S4, A) becomes much more prominent. The similar timescale of the decay of hot carriers and the rise of the GSB, in combination with the spectral narrowing over time and the substantial redshift, indicates a hot- phonon bottleneck. This interpretation is in line with that by Yang et al. and Price et al..1-2 They attributed the delayed rise of the GSB to spectral narrowing of the bleach signal, which, for a slowly decaying population, will result in an increase of the bleach signal.1 The increased carrier density enhances bimolecular- and Auger recombination, and accordingly, the overall lifetime of the GSB is significantly reduced, evident also from the kinetics shown in above.3
Figure S6: Time-resolved photoluminescence measurements of MAPbI3(Cl) measured at a fluence of 2.5µJ/cm2 after excitation with a 100 fs pulse at 400 nm. (A) shows the temporal evolution of the emission peak between 0 and 1500 ns and the associated global fits based on the model proposed by Zhu.4 (B) shows the normalized emission spectra between 0 and 1 ns. The
high-energy tail is still observable in normalized intensity. (C) shows the fraction of the spectrally integrated fraction of the high-energy photoluminescence above 1.7 eV and the photoluminescence originating from band-to-band transition. The signal fraction rises with the emission signal up to 0.42 before it decays within 400 ps. A fit of the decay with a single exponential function reveals a lifetime of 94 ± 13 ps. The background of the signal (0.25) is substantial; we attribute the background to the relatively low signal-to-noise ratio obtained above 1.7 eV, which is why we use 1.7 eV as limit of the hot emission. (D) shows the linear kinetics and a single-exponential fit for the hot photoluminescence at 1.7 eV (τ = 117 ± 10 ps) measured in a time-window of 2 ns and an instrument response function of 16 ps. (E) shows the linear kinetics for band-edge and hot photoluminescence. In comparison to Chang et al., the amplitude of the sub-100 ps emission is much smaller than the 50% mentioned.5 (F) shows the normalized spectrum at t = 0, 10 and 90 ns. We do not observe a significant red-shift (≤ 6 meV), suggestion limited effects of vertical carrier diffusion affecting our conclusions.4, 6-7
Figure S7: Intensity-dependent time-resolved photoluminescence spectra of MAPbI3(Cl). The fluence was increased from 2.5 µJ/cm2 to 39 µJ/cm2, resulting in a reduction of the high-energy tail of the photoluminescence4, 8.
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