Lead-free/rare earth-free Green-light-emitting crystal based on organic-inorganic hybrid [(C10H16N)2][MnBr4] with high emissive quantum yields and large crystal size

Cai, Xichen; Zhao, Yingying; Li, Hong; Huang, Cuiping; Zhou, Zhen

doi:10.1016/j.molstruc.2018.01.093

Cited by 49 publications

(26 citation statements)

References 44 publications

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“…The excitation spectrum of 4 shows three dominant peaks, which correspond to the electronic transitions of Mn 2+ in MnBr 4 2− tetrahedron from the 6 A 1 ground state to Td excited states, as labeled in Figure d. Due to the change of crystal structure, the emission peak of 4 greatly blue shifts to 525 nm, which is consistent well with the emission characteristics of tetrahedrally coordinated Mn 2+ . The measured PL QY of 4 is 16.04%.…”

Section: Resultssupporting

confidence: 65%

Tuning the Crystal Structure and Luminescence of Pyrrolidinium Manganese Halides via Halide Ions

Jiang

Han

et al. 2019

Crystal Research and Technology

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Luminescent and lead-free organic-transition metal halides (OTMHs) are greatly interesting for optical applications. In this work, six single crystals of pyrrolidinium manganese halides are prepared (crystal configurations). The analysis of crystal structures illustrates that halide ions play an important role in the crystal structure and further affect the luminescent properties of pyrrolidinium manganese halides. It is only for Cl − and Br − that produce perovskite-type crystals which exhibit red emission. Other crystals with MnX 4 2− tetrahedron unit emit green or yellow lights. It is interesting that the obtained crystals only contain one kind of halide ion with higher atomic number if there are two kinds of halide ions existing in the crystal growth solution. This study illustrates that the luminescent properties of OTMHs can be tuned by halide ions through deliberately designing experiments.

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Section: Resultssupporting

confidence: 65%

Tuning the Crystal Structure and Luminescence of Pyrrolidinium Manganese Halides via Halide Ions

Jiang

Han

et al. 2019

Crystal Research and Technology

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“…(BTMA)2MnBr4 was previously reported by Cai et al, with a high PLQY of 72%. 41 In these two examples, there is no Hbonding. The steric effect of the rigid aromatic ring also helps to push the [MnBr4] 2tetrahedra further apart, resulting in longer Mn … Mn distances (8.64 Å and 9.58 Å for (TMPEA)2MnBr4; 8.97 Å and 9.58 Å for (BTMA)2MnBr4).…”

Section: Resultsmentioning

confidence: 97%

Design Principles for Enhancing Photoluminescence Quantum Yield in Hybrid Manganese Bromides

et al. 2020

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Hybrid manganese halides have attracted widespread attention on account of their highly emissive optical properties. To understand the underlying structural factors that dictate the photoluminescence quantum yield (PLQY) of these materials, we report five new hybrid manganese bromides with the general formula AmMnBr4 [m = 1 or 2, A = dimethylammonium (DMA), 3methylpiperidinium (3-MP), 3-aminometylpiperidinium (3AMP), heptamethylenimine (HEP) and trimethylphenylammonium (TMPEA)]. By studying the crystal structures and optical properties of these materials and combining our results with the findings from previously reported analogs, we have found a direct correlation between Mn … Mn distance and the PLQY, where high PLQYs are associated with long Mn … Mn distances. This effect can be viewed as a manifestation of the concentration-quenching effect, except these are in stoichiometric compounds with precise interatomic distances, rather than random alloys. To gain better separation of the Mn centers and prevent energy transfer, a bulky singly-protonated cation that avoids H-bonding is ideal. We have demonstrated this principle in one of our newly reported material, (TMPEA)2MnBr4, where a PLQYs of 70.8 % for a powder sample and 98 % for a large single crystal sample is achieved. Our study reveals a generalized method for improving PLQYs in hybrid manganese bromides and is readily extended to designing all varieties of highly emissive hybrid materials.

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“…Mn 2+ ‐based 0D metal halides act as a kind of special system due to their unique optical properties, such as the narrow full width at half maximum (fwhm), high thermal stability, and abnormal PLQY. [ 191–205 ] As discussed above, the Mn 2+ PL characteristics are closely related to the crystal field environment; as a result, Mn 2+ ‐based metal halides generally show the green emission with tetrahedrally coordinated Mn 2+ ions as well as the red emission with octahedral coordinated Mn 2+ ions. Recently, some Mn 2+ ‐based metal halides are reported to show excellent luminescent and ferroelectric performances.…”

Section: Mn2+‐doped Luminescent Halide Perovskites With Different Strmentioning

confidence: 96%

Mn²⁺‐Doped Metal Halide Perovskites: Structure, Photoluminescence, and Application

Zhou

Huang

et al. 2020

Laser & Photonics Reviews

197

146

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Doping impurity ions into semiconductor luminescent materials offers a unique pathway for inducing new emission centers and enabling photoluminescence (PL) tuning. Among various luminescence materials, doping Mn2+ into metal halide perovskites becomes a hot topic since Mn2+ ions demonstrate an energy transfer route from host to dopants, resulting in interesting photophysical properties. This review aims to discuss the PL properties of Mn2+ ions in halide perovskites nanocrystals or bulk crystals with different structural dimensions and local environments (MnX42– tetrahedron, MnX62– octahedron, or shortest Mn─Mn distance). In this regard, the effects of Mn2+ doping on the PL properties and their modifications are summarized. Variable ion exchange dynamics, increased emission intensity, and enhanced stability induced by Mn2+ doping are analyzed. These results also provide beneficial insights into applications of the doped luminescent halide perovskites. Finally, the present challenges in Mn2+‐doped luminescent halide perovskites are elaborated.

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Lead-free/rare earth-free Green-light-emitting crystal based on organic-inorganic hybrid [(C10H16N)2][MnBr4] with high emissive quantum yields and large crystal size

Cited by 49 publications

References 44 publications

Tuning the Crystal Structure and Luminescence of Pyrrolidinium Manganese Halides via Halide Ions

Tuning the Crystal Structure and Luminescence of Pyrrolidinium Manganese Halides via Halide Ions

Design Principles for Enhancing Photoluminescence Quantum Yield in Hybrid Manganese Bromides

Mn²⁺‐Doped Metal Halide Perovskites: Structure, Photoluminescence, and Application

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Lead-free/rare earth-free Green-light-emitting crystal based on organic-inorganic hybrid [(C10H16N)2][MnBr4] with high emissive quantum yields and large crystal size

Cited by 49 publications

References 44 publications

Tuning the Crystal Structure and Luminescence of Pyrrolidinium Manganese Halides via Halide Ions

Tuning the Crystal Structure and Luminescence of Pyrrolidinium Manganese Halides via Halide Ions

Design Principles for Enhancing Photoluminescence Quantum Yield in Hybrid Manganese Bromides

Mn2+‐Doped Metal Halide Perovskites: Structure, Photoluminescence, and Application

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Mn²⁺‐Doped Metal Halide Perovskites: Structure, Photoluminescence, and Application