Activation of Self‐Trapped Emission in Stable Bismuth‐Halide Perovskite by Suppressing Strong Exciton–Phonon Coupling

Zhou, Lei; Liao, Jinfeng; Qin, Youcheng; Wang, Xudong; Wei, Junhua; Li, Ming; Kuang, Dai‐Bin; He, Rongxing

doi:10.1002/adfm.202102654

Cited by 95 publications

(134 citation statements)

References 72 publications

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“…As the temperature increases, a fraction of STEs undergoes either thermal‐activated nonradiative decay or a detrapping process back to the ES. [ 6a,19,20 ] Meanwhile, the ET from excited Mn 2+ to FEs are thermally activated as previously reported. [ 1a,21 ] The transferred energy is readily available to facilitate the formation of extra STEs.…”

Section: Resultssupporting

confidence: 53%

“…[1f,17-18] The obvious suppression of STE emission thermal quenching in (BTPP) 2 MnCl 4 :2.0%Sb indicates that the [MnCl 4 ] 2− host plays a key role in enhancing the thermal stability of STE emission of Sb-Cl. Furthermore, the thermal activation energy (E a ) that manifests the energy required for exciton dissociation, can be estimated by the following Arrhenius equation as shown in Figure 3e and S19 (Supporting Information): [19] 1 300…”

Section: Resultsmentioning

confidence: 99%

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Self‐Trapped Exciton Emission with High Thermal Stability in Antimony‐Doped Hybrid Manganese Chloride

Luo

Liu

et al. 2022

Advanced Optical Materials

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Self‐trapped exciton (STE) emission in some metal halides has acquired great interest in recent years due to their broadband emission, large Stokes shift, and high photoluminescence quantum yield (PLQY). However, severe thermal quenching of STE emission is still a critical bottleneck that impedes their application in light‐emitting field. Herein, a novel zero‐dimensional hybrid metal halide, Sb3+‐doped (BTPP)2MnCl4 (BTPP = Benzyltriphenylphosphonium), is accordingly synthesized to address this issue. This compound exhibits excitation‐dependent dual emissions including STE emission of antimony chloride tetrahedron and 4T1‐6A1 transition of Mn2+ ions, resulting in a tunable emission color from green to orange. More importantly, the PL intensity of STE emission at 420 K in (BTPP)2MnCl4:2.0%Sb can maintain 72.5% of its ambient value, which is superior to current organic–inorganic hybrid metal halides. Temperature‐dependent and time‐resolved spectroscopy results suggest that the high thermal stability of STE emission originates from the efficient energy transfer from (BTPP)2MnCl4 host to antimony chloride tetrahedron, which promotes the formation of STEs. The white light‐emitting diode based on this (BTPP)2MnCl4:2.0%Sb phosphor exhibits high‐performance warm white light with a correlated color temperature of 4827 K and a color rendering index of 88.7, which demonstrates its potential in solid‐state lighting applications.

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Section: Resultssupporting

confidence: 53%

Section: Resultsmentioning

confidence: 99%

Self‐Trapped Exciton Emission with High Thermal Stability in Antimony‐Doped Hybrid Manganese Chloride

Luo

Liu

et al. 2022

Advanced Optical Materials

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“…The higher photon frequency in Cs 3 Cu 2 Cl 5 :2%K + demonstrates that the more compact crystal structure will lead to stronger exciton-photon coupling and is more conducive to the formation of STEs 7. Besides, a lower Huang-Rhys factor S indicates that the phonon-electron coupling strength is reduced, [43] so the radiation-free relaxation is reduced and the luminescence is enhanced eventually. The luminescence dynamics can be intuitively described by the configuration coordinate diagram in Figure 3e.…”

Section: Resultsmentioning

confidence: 99%

Photophysics in Zero‐Dimensional Potassium‐Doped Cesium Copper Chloride Cs₃Cu₂Cl₅ Nanosheets and Its Application for High‐Performance Flexible X‐Ray Detection

Han

Sun

Guo

et al. 2022

Advanced Optical Materials

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X-ray detectors with high performance, durability, and flexibility detectors are required for a wide range of applications in several fields, such as medical treatment (imaging, diagnostic radiology, etc.), nondestructive testing (radioscopic inspections, radiography testing, etc.), security and defense (luggage/body scanning systems, paper mail, etc.), nuclear and radiation industries (nuclear power plants, research reactors, users of nuclear gauges, etc.), and scientific research and development. [1]-[9] Thereof, indirect X-ray detectors are widely used for ordinary flat panel X-ray detection, among which scintillator is the most important factor affecting the detection performance. [10][11][12][13][14] Currently, the ideal scintillator should meet the following basic conditions: (i) good stopping power and excellent radiation absorption, [15]-[18] (ii) high photoluminescence (PL) with large Stokes shift and radioluminescence (RL) intensity, (iii) nontoxicity with environmentally stable, [19] (iv) easily manufactured and extendable to large-area flexible applications. [20,21] Among all, inorganic copper (I)-based metal halide semiconductors meeting all the above requirements are considered as promising candidates. In particular, zero-dimensional (0D) cesium copper chloride, Cs 3 Cu 2 Cl 5 , shows excellent photoelectric performance in ultraviolet photodetectors. [22] With isolated [Cu 2 Cl 5 ] 3dimers and Cs + ions, Cs 3 Cu 2 Cl 5 is expected to exhibit intriguing optical properties mainly derived from self-trapped excitons (STEs). Different from the narrow and rapid emission of free excitons and inter-band recombination, the emission of STEs is featured with broad spectra and large Stokes shifts. Generally, the STEs emission that occurs in Cs 3 Cu 2 Cl 5 originates from structural deformation of [Cu 2 Cl 5 ] 3− dimers. [23] At the time of photoexcitation, the Cu-Cl bonds elongate (shrink) on the equatorial plane but shrink (elongate) in the axial direction, which in turn causes the local structure change from a high symmetry to a low symmetry configuration.To further improve its photophysical characteristics, the diversified structural optimization in Cs 3 Cu 2 Cl 5 could offer deeper insights and more controlling knobs on STEs emission. Zero-dimensionalCs 3 Cu 2 Cl 5 exhibits intriguing optical properties, which can meet the basic requirements of ideal scintillator application. Here, green emitter Cs 3 Cu 2 Cl 5 nanosheets are successfully synthesized, and by doping with 2% potassium (K + ), their photoluminescence quantum yield (70.23% to 81.39%), radioluminescence intensity, and stability are improved. Further experimental and theoretical studies point out that: (1) K + brings the neighboring [Cu 2 Cl 5 ] 3− dimers groups closer, leading to lattice shrinkage and lower lattice constants; (2) such compact crystal structure results in stronger exciton-photon coupling and reduced phonon-electron coupling strength, which is beneficial to form self-trapped excitons and enhanced luminescence; (3) lower lattice ...

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“…[31] However, it must be noted that an extremely strong electron-phonon coupling leads to a dissipation of the excited-state energy into phonons. [11,17,32] In order to gain further insights into the electron-phonon coupling, an independent boson model was employed to study the dynamics of electron excitations, starting from the following equation [33] T k T ( )…”

Section: Resultsmentioning

confidence: 99%

“…[ 31 ] However, it must be noted that an extremely strong electron–phonon coupling leads to a dissipation of the excited‐state energy into phonons. [ 11,17,32 ]…”

Section: Resultsmentioning

confidence: 99%

Wide‐Bandgap Double Perovskites with Multiple Longitudinal‐Optical Phonon Scattering

Wang

Zheng

Vitale

et al. 2022

Adv Funct Materials

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Alloyed lead-free double perovskites display intense photoluminescence, are environmentally friendly, and their devices show long-term operation. Thanks to these properties, which make them excellent warm white-emitting materials, they have recently received great attention in lighting applications. An important factor to tune the optical properties of alloyed lead-free double perovskites is the presence of self-trapped excitons. Here, it is demonstrated that in leadfree double perovskites, the strong electron-phonon coupling plays a crucial role in the generation of self-trapped excitons. The strong electron-phonon coupling is confirmed by a large Huang-Rhys factor and by the presence of multiphonon transitions. In particular, sharp emission lines superimposed on the broad photoluminescence emission band of one of these samples (Cs 2 Ag 0.6 Na 0.4 InCl 6 0.5%Bi) are observed; these are due to the strong coupling of longitudinal-optical phonons with excited electronic states caused by the tetragonally distorted AgCl 6 octahedrons. Such a strong coupling of longitudinal-optical phonons to electrons can effectively modulate the photophysical properties of alloyed double perovskites, and its understanding is, thus, of paramount importance for the design of future optoelectronic devices.

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Activation of Self‐Trapped Emission in Stable Bismuth‐Halide Perovskite by Suppressing Strong Exciton–Phonon Coupling

Cited by 95 publications

References 72 publications

Self‐Trapped Exciton Emission with High Thermal Stability in Antimony‐Doped Hybrid Manganese Chloride

Self‐Trapped Exciton Emission with High Thermal Stability in Antimony‐Doped Hybrid Manganese Chloride

Photophysics in Zero‐Dimensional Potassium‐Doped Cesium Copper Chloride Cs₃Cu₂Cl₅ Nanosheets and Its Application for High‐Performance Flexible X‐Ray Detection

Wide‐Bandgap Double Perovskites with Multiple Longitudinal‐Optical Phonon Scattering

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Activation of Self‐Trapped Emission in Stable Bismuth‐Halide Perovskite by Suppressing Strong Exciton–Phonon Coupling

Cited by 95 publications

References 72 publications

Self‐Trapped Exciton Emission with High Thermal Stability in Antimony‐Doped Hybrid Manganese Chloride

Self‐Trapped Exciton Emission with High Thermal Stability in Antimony‐Doped Hybrid Manganese Chloride

Photophysics in Zero‐Dimensional Potassium‐Doped Cesium Copper Chloride Cs3Cu2Cl5 Nanosheets and Its Application for High‐Performance Flexible X‐Ray Detection

Wide‐Bandgap Double Perovskites with Multiple Longitudinal‐Optical Phonon Scattering

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Product

Resources

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Photophysics in Zero‐Dimensional Potassium‐Doped Cesium Copper Chloride Cs₃Cu₂Cl₅ Nanosheets and Its Application for High‐Performance Flexible X‐Ray Detection