Role of Polyhedron Unit in Distinct Photophysics of Zero-Dimensional Organic–Inorganic Hybrid Tin Halide Compounds

Liu, Xiaoyu; Li, Yuanyuan; Liang, Tianyuan; Fan, Jiyang

doi:10.1021/acs.jpclett.1c01540

Cited by 14 publications

(12 citation statements)

References 65 publications

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“…22−24 The zerodimensional (0D) perovskite comprises isolated polyhedra completely separated from each other by the organic cations. 25,26 These 0D metal halides have distinct optical properties compared with 3D perovskites, such as large Stokes shift, broadband emission, and high quantum yield. It is usually supposed that their luminescence arises from self-trapped excitons (STEs) or quasi-self-trapped excitons (such as in Cs 4 PbCl 6 and Cs 4 PbBr 6 quantum dots 27,28 ).…”

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confidence: 99%

“…The optoelectronic properties of the hybrid metal halides depend on the dimensionality determined by the type of connection of the metal–halide polyhedra in that their conduction/valence band minimums/maximums are mainly contributed by the polyhedra. , The 3D hybrid perovskite is composed of corner-shared octahedra, and the cations lie in the voids among them. The 2D perovskite comprises parallel octahedral networks separated by the intermediate organic cations. − The zero-dimensional (0D) perovskite comprises isolated polyhedra completely separated from each other by the organic cations. , These 0D metal halides have distinct optical properties compared with 3D perovskites, such as large Stokes shift, broadband emission, and high quantum yield. It is usually supposed that their luminescence arises from self-trapped excitons (STEs) or quasi-self-trapped excitons (such as in Cs 4 PbCl 6 and Cs 4 PbBr 6 quantum dots , ).…”

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confidence: 99%

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One-Center and Two-Center Self-Trapped Excitons in Zero-Dimensional Hybrid Copper Halides: Tricolor Luminescence with High Quantum Yields

Liu

Liang

et al. 2022

J. Phys. Chem. Lett.

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The organic–inorganic hybrid copper halides exhibit intriguing and complex photophysical properties, and the underlying mechanisms are far from clear. Here, we study the photodynamics of six novel types of low-dimensional hybrid copper halides, which have a maximum quantum yield of 98.6%. They exhibit two origins of photon emission with distinct temperature dependence and quantum transition rates. The experiments in junction with first-principles calculations indicate that they stem from two kinds of self-trapped excitons (STEs): one-center a-STE (localized on Cu+ monomer) and two-center m-STE (localized on Cu2 2+ dimer). There is phase transition between a-STE and m-STE when enough thermal energy is acquired for crossing the potential barrier between them. The degree of softness of the compositional organic cations of the copper halide plays a key role in determining the self-trapping type of the STEs.

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One-Center and Two-Center Self-Trapped Excitons in Zero-Dimensional Hybrid Copper Halides: Tricolor Luminescence with High Quantum Yields

Liu

Liang

et al. 2022

J. Phys. Chem. Lett.

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“…Moreover, an external quantum yield of about 2% was determined. Overall, 0D metal halides are promising materials for broad PL emission, and in some cases, e.g., C 10 H 28 N 4 Cl 2 SnCl 4 ·2H 2 O with isolated [SnCl 4 ] 2– units, their quantum yields exceed 90% . However, in the case of (CH 3 ) 3 SSnCl 3 , the quantum yield is low, and it is similar to bromine-containing tin(II) perovskites, e.g., [NEt 4 ]SnBr 3 with a quantum yield of 0.46% at 603 nm …”

Section: Resultsmentioning

confidence: 99%

Synthesis, Crystal Structure, and Broadband Emission of (CH₃)₃SSnCl₃

et al. 2022

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We report here on the synthesis, crystal structure, optoelectronic and vibrational properties, as well as the DFT calculations of the novel trimethylsulfonium tin trichloride (CH 3 ) 3 SSnCl 3 . The air-stable compound is prepared by reacting the (CH 3 ) 3 SCl and SnCl 2 solid precursors in evacuated silica tubes at 100 °C. According to powder X-ray diffraction and Rietveld refinement, it crystallizes at room temperature in the orthorhombic space group Pbca (No. 61) with isolated pyramids of [SnCl 3 ] − and (CH 3 ) 3 S + units. UV−vis reflectance and photoluminescence spectroscopies reveal a direct energy band gap of 3.85 eV, accompanied by a broad Stokes-shifted luminescence signal. Photoexcitation of the compound at room temperature and at −196 °C results in broadband luminescence with weak magenta emission centered at 400 nm using an excitation at 250 nm. First principal calculations provide insight into the physical properties through the electron and phonon density of states. Multitemperature Raman spectroscopy and differential scanning calorimetry reveal a reversible phase transition at ca. 70 °C that affects the vibrational modes of the [SnCl 3 ] − . By dissolving (CH 3 ) 3 SSnCl 3 in dimethylformamide in ambient air for a week, oxidation of tin occurs in the "defect" perovskite ((CH 3 ) 3 S) 2 SnCl 6 . The crystal structure of ((CH 3 ) 3 S) 2 SnCl 6 is also determined with high accuracy via single-crystal X-ray diffraction (cubic space group Pa-3 (No. 205)) and compared with (CH 3 ) 3 SSnCl 3 via Hirshfeld surface analysis.

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“…Metal halides including lead halide perovskites and their derivatives have drawn broad interest in optoelectronic applications, including photovoltaics, light-emitting diodes, and photodetectors. − Particularly, the self-trapped exciton (STE)-based emission is widely observed in low-dimensional (2D to 0D) metal halides that feature a soft lattice and strong electron-phonon coupling. − In contrast to the narrow band photoluminescence (PL) from band-edge emission typically observed in rigid 3D materials, the STE emission associated with a transient local lattice distortion results in a broad PL band with the full width at half-maximum often greater than 60 nm and a large Stokes shift . Besides lead halides, low-dimensional Ge(II), Sn(II), Sb(III), Bi(III), In(III), Ag(I), and Cu(I) halides with high PL quantum yield (PLQY) have also been reported. − Among them, copper halides have attracted particularly great interest in recent years because of the earth abundance and nontoxicity of the copper element, structural diversity, and impressive photophysical properties that are promising for commercial applications. − …”

Section: Introductionmentioning

confidence: 99%

First-Principles Investigation on the Stability, Electronic Structure, and Exciton Self-Trapping Mechanism of 0D and 1D Cs₃Cu₂Cl₅

Xiong

Sun

et al. 2023

J. Phys. Chem. C

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Copper(I) halides with broadband emission from self-trapped excitons (STEs) are promising luminescent materials due to their structural diversities and intriguing photophysical properties. Despite great efforts invested in these materials, an in-depth understanding of their structural variations and the corresponding STE emission mechanisms is still lacking. Here, first-principles calculations reveal two distinct STEs in 0D and 1D polymorphs of Cs3Cu2Cl5, which feature the same chemical composition but different crystal structures. The electronic band structure analysis reveals that the strong Cu–Cl 4s–3p coupling along the 1D [Cu2Cl5]3– chain brings a large band dispersion, resulting in an increase of optical anisotropy in the 1D structure. The STE in 0D Cs3Cu2Cl5 involves the formation of one Cu–Cu bond and the breakage of two Cu–Cl bonds within an isolated [Cu2Cl5]3– unit. In contrast, the exciton self-trapping in the 1D structure is found to be associated with the formation of one Cu–Cu bond accompanied by two Cu–Cl bonds in the [Cu2Cl5]3– chain. Despite significant structural differences in 0D and 1D Cs3Cu2Cl5, quantitative characterizations of the configuration coordinate diagrams in the two polymorphs lead to similar STE emission energies (2.38 and 2.48 eV for 0D and 1D, respectively), which theoretically explains similar green-light emission experimentally observed in both compounds. This study provides important insights for understanding complex relations between the structural dimensionality, building units, and emission properties in low-dimensional metal halides.

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Role of Polyhedron Unit in Distinct Photophysics of Zero-Dimensional Organic–Inorganic Hybrid Tin Halide Compounds

Cited by 14 publications

References 65 publications

One-Center and Two-Center Self-Trapped Excitons in Zero-Dimensional Hybrid Copper Halides: Tricolor Luminescence with High Quantum Yields

One-Center and Two-Center Self-Trapped Excitons in Zero-Dimensional Hybrid Copper Halides: Tricolor Luminescence with High Quantum Yields

Synthesis, Crystal Structure, and Broadband Emission of (CH₃)₃SSnCl₃

First-Principles Investigation on the Stability, Electronic Structure, and Exciton Self-Trapping Mechanism of 0D and 1D Cs₃Cu₂Cl₅

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Role of Polyhedron Unit in Distinct Photophysics of Zero-Dimensional Organic–Inorganic Hybrid Tin Halide Compounds

Cited by 14 publications

References 65 publications

One-Center and Two-Center Self-Trapped Excitons in Zero-Dimensional Hybrid Copper Halides: Tricolor Luminescence with High Quantum Yields

One-Center and Two-Center Self-Trapped Excitons in Zero-Dimensional Hybrid Copper Halides: Tricolor Luminescence with High Quantum Yields

Synthesis, Crystal Structure, and Broadband Emission of (CH3)3SSnCl3

First-Principles Investigation on the Stability, Electronic Structure, and Exciton Self-Trapping Mechanism of 0D and 1D Cs3Cu2Cl5

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Synthesis, Crystal Structure, and Broadband Emission of (CH₃)₃SSnCl₃

First-Principles Investigation on the Stability, Electronic Structure, and Exciton Self-Trapping Mechanism of 0D and 1D Cs₃Cu₂Cl₅