Bulk assembly of a 0D organic antimony chloride hybrid with highly efficient orange dual emission by self-trapped states

Peng, Hui; Tian, Yan; Wang, Xinxin; Huang, Tao; Xiao, Yonghao; Dong, Ting; Hu, Jinming; Wang, Jianping; Zou, B. S.

doi:10.1039/d1tc02906a

Cited by 59 publications

(57 citation statements)

References 39 publications

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“…4d. It can be seen that the average lifetime of the carriers is 3.82 ns, which is similar to the (TPA)2SbCl5 single crystal which is also the STE luminescence mechanism 32 . In addition, we characterize the PL of (4-HBA)SbCl5•H2O single crystal at different excitation wavelengths as shown in Fig.…”

Section: Optical Propertiessupporting

confidence: 60%

Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA) SbX5∙H2O Perovskite-Like Single Crystals

Zhuang¹,

Jin²,

Tian³

et al. 2022

Acta Physico Chimica Sinica

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Luminescent materials have attracted considerable attention because of their extensive applications, for example, in lighting, display, and imaging. As one of the emerging luminescent materials, perovskites have been widely studied and reported. Among them, Pb-based perovskites have shown great promise as their photoluminescence quantum yield (PLQY) is almost 100%. However, the high chemical toxicity and low stability of Pb-based perovskites increase their production costs and limit their practical applications. Sn-based perovskites are also widely studied and their PLQY can reach approximately 90%; however, Sn 2+ easily oxidizes to Sn 4+ especially upon air exposure. When compared with Pband Sn-based perovskites, Sb-based perovskites have the advantages of low chemical toxicity and high thermal stability. Furthermore, the optical properties of Sb-based perovskites have been improved in recent years and are expected to surpass those of Pb-and Sn-based perovskites. Herein, we report a novel series of (4-HBA)SbX5•H2O single crystals (where 4-HBA is short for 4-hydroxybenzylamine, and X is Cl or Br). High quality single crystals of (4-HBA)SbBr5•H2O, (4-HBA)SbBr3Cl2•H2O, and (4-HBA)SbCl5•H2O with Sb 5+ can be prepared via the solvothermal method. The abovementioned three materials belong to the P-1 space group. The halide and hydroxyl ions surrounded by Sb 5+ ions in 4-hydroxybenzylamine formed distorted octahedral structures. Based on the results of steadystate fluorescence spectroscopy, excitation spectroscopy, transient fluorescence spectroscopy, fluorescence lifetime imaging, and density functional theory, it was found that the (4-HBA)SbBr5•H2O single crystal has a direct band gap, whereas the single crystals of (4-HBA)SbBr3Cl2•H2O and (4-HBA)SbCl5•H2O have an indirect band gap. When the concentration of Cl − in (4-HBA)SbX5•H2O increased, the band gap increased from 2.99 to 3.58 eV and the photoluminescence wavelength decreased from 618 to 595 nm. The obtained results also showed that the emission of the (4-HBA)SbX5•H2O single crystal originated from the self-trapping exciton effect. With the introduction of Cl − , the size of the [SbX5O] 2− octahedron decreased, the exciton shielding reduced, and the exciton absorption was enhanced. Additionally, after replacing Br − with Cl − , the radiation recombination process of the excited electrons from the Sb 5+ ions surrounding the halide ions gradually replaced the electron recombination of the hydroxyl ions, which extended the fluorescence lifetime from 12 to 22 ns and improved the PLQY by a factor of approximately 40.

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Section: Optical Propertiessupporting

confidence: 60%

Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA) SbX5∙H2O Perovskite-Like Single Crystals

Zhuang¹,

Jin²,

Tian³

et al. 2022

Acta Physico Chimica Sinica

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“…Antimony-based metal halides with a stable oxidation state possess excellent luminescence properties. Several antimony-based luminescent metal halides have been reported in recent years. − Ma and coauthors synthesized antimony-based organic–inorganic hybrid metal halide (Ph 4 P) 2 SbCl 5 (Ph 4 P = tetraphenylphosphonium) with up to 87% quantum efficiency and excellent air stability . Employing antimony as an ionic dopant or alloying with other metal centers can also significantly enhance PL. − For example, our group recently reported a series of indium–antimony alloyed halide single crystals.…”

Section: Introductionmentioning

confidence: 99%

Water-Molecule-Induced Emission Transformation of Zero-Dimension Antimony-Based Metal Halide

2021

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Low-dimensional organic–inorganic metal halides have recently emerged as a class of promising luminescent materials. However, the intrinsic toxicity of lead would strongly hamper future application. Herein, we synthesized a new type of lead-free zero-dimensional (0D) antimony-based organic–inorganic metal halide single crystals, (PPZ)2SbCl7·5H2O (PPZ = 1-phenylpiperazine), which features a broadband emission at 720 nm. Ultrafast transient absorption and temperature-dependent photoluminescence (PL) spectra are combined to investigate the PL mechanism, revealing that self-trapped exciton recombination was involved. Furthermore, it is interesting that (PPZ)2SbCl7·5H2O material shows reversible PL emission transformation between red light (720 nm) and yellow light (590 nm) as water molecules are inserted or removed from the lattice. Such reversible emission transformation phenomenon renders the (PPZ)2SbCl7·5H2O as a potential low-cost water sensing material.

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“…Therefore, 0D perovskites incline to display intrinsic lower-energy broadband light emissions with large Stokesshifts, which are different from the narrow emission bands of 3D APbX 3 PQDs. [18][19][20][21][22] As a result, lower-energy green, yellow, and red light emissions are easily realized in 0D halide perovskites, but higher-energy blue light emission remains extremely challenging, especially in pure-blue spectral region (460-480 nm). [23][24][25][26] Simultaneously considering the biological toxicity of Pb 2+ ion and lower PLQY of blue emitting perovskite, it is greatly significant and stringent to design lead-free 0D perovskites comprising environment-friendly metals as highly efficient blue emitters to achieve balanced development of three primary-color in high-definition display and lighting devices.Another critical bottleneck that restricts the practical applications of perovskites is the poor stability toward various chemical and physical factors including water, humid air, polar solvents, light, etc., due to the ionic nature of material itself.…”

mentioning

confidence: 99%

Ultrastable 0D Organic Zinc Halides with Highly Efficient Blue Light Emissions

Sun

et al. 2022

Advanced Optical Materials

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functional luminescent materials due to diversified photoluminescence (PL) performance and ultrahigh emission efficiency with unique applications in solid-state light emitting diodes, X-ray scintillation, remote thermography, etc. [7][8][9][10][11] Especially, the 0D organic-inorganic hybrid perovskites deliver highly adjustable structural architectures and PL properties derived from the synergistic effect of versatile organic species and anionic blocks. [12][13][14] In these 0D hybrid perovskites, the spatially discrete metal halide units are wrapped by bulk organic components with perfect core-shell structures from molecular level, which mean that the semiconducting halide species periodically embed in the insulated organic matrix as light emitting centers. Benefiting from the strong spatial and quantum confinement effect from organic walls, the photoinduced carriers are highly localized in the discrete metal halide species, which leads to firmly confined bound excitons with large exciton binding energy and high photoluminescence quantum yield (PLQY) at room temperature. [15][16][17] At the same time, the strong electron-quantum coupling transiently localizes the excitons along with large excited-state structural deformation, which produces self-trapped excitons (STEs) with lower excited state energy. Therefore, 0D perovskites incline to display intrinsic lower-energy broadband light emissions with large Stokesshifts, which are different from the narrow emission bands of 3D APbX 3 PQDs. [18][19][20][21][22] As a result, lower-energy green, yellow, and red light emissions are easily realized in 0D halide perovskites, but higher-energy blue light emission remains extremely challenging, especially in pure-blue spectral region (460-480 nm). [23][24][25][26] Simultaneously considering the biological toxicity of Pb 2+ ion and lower PLQY of blue emitting perovskite, it is greatly significant and stringent to design lead-free 0D perovskites comprising environment-friendly metals as highly efficient blue emitters to achieve balanced development of three primary-color in high-definition display and lighting devices.Another critical bottleneck that restricts the practical applications of perovskites is the poor stability toward various chemical and physical factors including water, humid air, polar solvents, light, etc., due to the ionic nature of material itself. [27] As a result, the PL emission is easily quenched by these external stimuli along with the structural decomposition or phase transitions, especially perovskites without additional protection Despite remarkable luminescent performance of 0D lead halide perovskites, achieving highly efficient blue light emission is extremely challenging and crucial for this domain. Considering the high toxicity of Pb 2+ ion, it is significant to explore water-stable lead-free 0D halides as highly efficient and stable blue emitting materials. To address these issues, a family of 0D hybrid zinc halides of AZnBr 4 (A = EP, BP, and TMPDA) based on discrete [ZnBr 4 ] 2− tetrahedrons...

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Bulk assembly of a 0D organic antimony chloride hybrid with highly efficient orange dual emission by self-trapped states

Abstract: Low-dimensional organic-inorganic hybrid metal halides have drawn intense attention due to its flexibility structure and outstanding optical properties. However, the toxicity of lead halide hinders its future application in optoelectronic...

Cited by 59 publications

References 39 publications

Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA) SbX<sub>5</sub>∙H<sub>2</sub>O Perovskite-Like Single Crystals

Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA) SbX<sub>5</sub>∙H<sub>2</sub>O Perovskite-Like Single Crystals

Water-Molecule-Induced Emission Transformation of Zero-Dimension Antimony-Based Metal Halide

Ultrastable 0D Organic Zinc Halides with Highly Efficient Blue Light Emissions

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Bulk assembly of a 0D organic antimony chloride hybrid with highly efficient orange dual emission by self-trapped states

Abstract: Low-dimensional organic-inorganic hybrid metal halides have drawn intense attention due to its flexibility structure and outstanding optical properties. However, the toxicity of lead halide hinders its future application in optoelectronic...

Cited by 59 publications

References 39 publications

Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA) SbX<sub>5</sub>&#8729;H<sub>2</sub>O Perovskite-Like Single Crystals

Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA) SbX<sub>5</sub>&#8729;H<sub>2</sub>O Perovskite-Like Single Crystals

Water-Molecule-Induced Emission Transformation of Zero-Dimension Antimony-Based Metal Halide

Ultrastable 0D Organic Zinc Halides with Highly Efficient Blue Light Emissions

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Product

Resources

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Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA) SbX<sub>5</sub>∙H<sub>2</sub>O Perovskite-Like Single Crystals

Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA) SbX<sub>5</sub>∙H<sub>2</sub>O Perovskite-Like Single Crystals