Dual Emission Bands of a 2D Perovskite Single Crystal with Charge Transfer State Characteristics

Several hybrid halide 2D-perovskite species emit light with an emergent and controversial broadband emission Stokes-shifted down from the narrow band emission. This paper uncovers the sub- and above-bandgap emission and absorption characteristics of PEA2PbI4 prepared with gap states introduced durin...

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Veröffentlicht in:ACS nano 2023-07, Vol.17 (13), p.12200-12207
Hauptverfasser: Dryzhakov, Bogdan, Lawrie, Benjamin J., Celio, Jakob Zosa, Wang, Miaosheng, Koehler, Michael, Hu, Bin
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container_end_page 12207
container_issue 13
container_start_page 12200
container_title ACS nano
container_volume 17
creator Dryzhakov, Bogdan
Lawrie, Benjamin J.
Celio, Jakob Zosa
Wang, Miaosheng
Koehler, Michael
Hu, Bin
description Several hybrid halide 2D-perovskite species emit light with an emergent and controversial broadband emission Stokes-shifted down from the narrow band emission. This paper uncovers the sub- and above-bandgap emission and absorption characteristics of PEA2PbI4 prepared with gap states introduced during single crystal growth. Here, gap states led to coexistent intrinsic and heterostructured electronic frameworks that are selectively accessible with ultraviolet (UV) and infrared (IR) light, respectively, resulting in the phenomenon of photoluminescence (PL) switching from narrowband green to broadband red. Electron-energy dependent cathodoluminescence shows a relative increase in the broadband red PL intensity as the electron penetration depth increases from 30 nm to 2 μm, confirming the heterostructured framework is formed in the bulk of the crystal. Excitation–emission power slope of 2.5 and up-conversion pump transient absorption (TA) spectra suggest that the IR up-conversion excitation with red photoluminescence, peaked at 655 nm, is a multiphoton process occurring in the heterostructured framework through a nonlinear optical response. The energetic pathways toward the dual emission bands are revealed by pump–probe transient absorption spectroscopy, showing energetically broad gap states with high sensitivity to an IR pump are upconverted and subsequently quickly relax from high to low energy levels within 4 ps. Furthermore, the up-conversion red PL demonstrates a linear polarization with magnetic field effects, thus affirming that the band-like heterostructured framework is crystallographically aligned with characteristics of spatially extended charge-transfer states.
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source American Chemical Society Journals
subjects broadband emission
charge-transfer state
defects
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
perovskite
single crystal
up-conversion
title Dual Emission Bands of a 2D Perovskite Single Crystal with Charge Transfer State Characteristics
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