Lead-free scintillators based on pyridine manganese halide for X-ray imaging

Li, Chen; Lai, Junan; Wu, Daofu; Wang, Qiang; Bai, Yanjun; He, Peng; An, Kang; Tang, Xiaosheng

doi:10.1016/j.jlumin.2022.119130

Cited by 12 publications

(17 citation statements)

References 28 publications

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“…The excitation spectrum has multiple excitation peaks at 253, 333, 360, 423, 446, and 525 nm, which are attributed to the transitions of octahedrally coordinated Mn 2+ from ground state 6 A 1 to excited states 4 4 T 2 ( 4 G), and 4 T 1 ( 4 G), respectively. [42][43][44][45] Under 360 nm excitation, (Gua) 2 MnCl 4 shows a bright red emission peaking at 650 nm with a full width at half maximum (FWHM) of 123 nm. It is related to the de-excitation of Mn 2+ 4 T 1 ( 4 G) to 6 76%, which is higher than that of other reported 0D Mn(II)-based hybrid scintillators, such as 59.4% for (C 5 H 6 N) 2 MnBr 4 [42] and 60.3% for TEA 2 MnI 4 .…”

Section: Resultsmentioning

confidence: 99%

Red‐Emitting Organic–Inorganic Hybrid Manganese(II) Halides for X‐Ray Imaging

Zhou

Wang

et al. 2023

Advanced Sensor Research

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Low‐dimensional organic–inorganic hybrid manganese(II) halides are emerging as a highly promising class of candidate materials for X‐ray imaging due to their excellent radioluminescence performance. Here, a red‐emitting (Gua)2MnCl4 (Gua = guanidine, CH6N3+) single crystal scintillator grown by a simple solution‐processing method is reported. (Gua)2MnCl4 crystallizes into a zero‐dimensional (0D) crystal structure consisting of trimeric [Mn3Cl12]6− units. It has a high PLQY of 76% and a large Stokes shift of 125 nm. (Gua)2MnCl4 flexible scintillation screen demonstrates a decent X‐ray detection limit of 145.3 nGyair s−1 and a superior imaging resolution of 8 lp mm−1. These results highlight the potential of low‐dimensional red‐emitting Mn‐based hybrids for X‐ray imaging applications.

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Section: Resultsmentioning

confidence: 99%

Red‐Emitting Organic–Inorganic Hybrid Manganese(II) Halides for X‐Ray Imaging

Zhou

Wang

et al. 2023

Advanced Sensor Research

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“…The difference of binding energy and peak intensity may be due to relatively lower amount of nitrogen in (TBA) 2 MnCl 4 . Due to the effect of spin–orbit split (SOS), the 2p orbital exhibits double peaks . This is why the Cl 2p orbitals of (TEA) 2 MnCl 4 and (TBA) 2 MnCl 4 have double peaks which are located at 197.5 eV (Cl 2p 3/2 of (TEA) 2 MnCl 4 ), 199.1 eV (Cl 2p 1/2 of (TEA) 2 MnCl 4 ), 197.23 eV (Cl 2p 3/2 of (TEA) 2 MnCl 4 ), and 198.9 eV (Cl 2p 1/2 of (TBA) 2 MnCl 4 ), respectively.…”

Section: Resultsmentioning

confidence: 99%

“…This is why the Cl 2p orbitals of (TEA) 2 MnCl 4 and (TBA) 2 MnCl 4 have double peaks which are located at 197.5 eV (Cl 2p 3/2 of (TEA) 2 MnCl 4 ), 199.1 eV (Cl 2p 1/2 of (TEA) 2 MnCl 4 ), 197.23 eV (Cl 2p 3/2 of (TEA) 2 MnCl 4 ), and 198.9 eV (Cl 2p 1/2 of (TBA) 2 MnCl 4 ), respectively. For the manganese element which has unpaired electrons, the peaks of 2p orbitals are split . Therefore, the 2p orbital of Mn shows four peaks, which are 641 eV (Mn 2p 3/2 of (TEA) 2 MnCl 4 ), 645.96 eV (Mn 2p 3/2 of (TEA) 2 MnCl 4 ), 652.8 eV (Mn 2p 1/2 of (TEA) 2 MnCl 4 ), 657.94 eV (Mn 2p 1/2 of (TEA) 2 MnCl 4 ), 641.28 eV (Mn 2p 3/2 of (TBA) 2 MnCl 4 ), 646.41 eV (Mn 2p 3/2 of (TBA) 2 MnCl 4 ), 653.03 eV (Mn 2p 1/2 of (TBA) 2 MnCl 4 ), and 658.17 eV (Mn 2p 1/2 of (TBA) 2 MnCl 4 ).…”

Section: Resultsmentioning

confidence: 99%

“…The absorption and excitation peaks correspond to the electronic transitions from the ground state 6 A 1 of Mn 2+ to different excited states. The excitation spectrum shows energy states of a tetrahedrally coordinated Mn 2+ ion split into three distinct groups of bands with a homologous electronic transition (Figure b,e). , Due to the tetrahedral coordination of the Mn 2+ ion, (TBA) 2 MnCl 4 and (TEA) 2 MnCl 4 exhibit bright green emissions (Figure b,e) from d–d transitions ( 6 A 1 → 4 T 1 ), which are located at 512 nm with a full width at half-maximum of 45 nm ((TBA) 2 MnCl 4 ) and 524 nm ((TEA) 2 MnCl 4 ) with a full width at half-maximum of 55 nm, respectively. The main factor determining the wavelength of the emission peak is the anion, while the length of the organic cation within the same group has little effect on the emission peak .…”

Section: Resultsmentioning

confidence: 99%

“…Flexible films have good foldability, high crack resistance, favorable compatibility, and potential application in portable and wearable devices. 29 Here, flexible scintillators with a large size (5 × 5 cm 2 ) were demonstrated by blending (TBA) 2 MnCl 4 and (TEA) 2 MnCl 4 fine powders with PDMS. As shown in Figure 5b,e, the films reveal great flexibility and uniform green emission under UV irradiation.…”

Section: Density Functional Theory (Dft) Calculationsmentioning

confidence: 99%

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Ultrahigh Photoluminescence Quantum Yield Organic Manganese Halide Scintillator for X-ray Imaging

Cao

et al. 2023

ACS Appl. Opt. Mater.

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X-ray indirect detection based on metal halide scintillators has great potential in various applications, such as medical diagnosis, computerized tomography, and quality inspection. However, there are still many limitations in metal halide scintillation materials, such as toxicity, high production costs, and strong self-absorption caused by a band-edge transition limiting the photoluminescence quantum yield (PLQY). Here, (TEA)2MnCl4 and (TBA)2MnCl4 single crystals as scintillators with advanced properties were synthesized from TEAC (tetraethylammonium chloride), TBAC (tetrabutylammonium chloride), and manganese chloride by an antisolvent method at room temperature. These two zero-dimensional organometallic halides exhibit green emission peaking at 512 nm ((TBA)2MnCl4) and 524 nm ((TEA)2MnCl4) with high PLQYs of 99.96% and 65.07%, respectively. The ultrahigh PLQY of (TBA)2MnCl4 benefits from the long Mn–Mn distance in (TBA)2MnCl4. (TBA)2MnCl4 shows an outstanding scintillation performance with a high light yield of 21000 photons/MeV, a low detection limit of 381 nGy/s, and a spatial resolution of 5.6 lp/mm. X-ray imaging experiments demonstrate that the flexible scintillators based on (TEA)2MnCl4 and (TBA)2MnCl4 could be used in high-resolution X-ray imaging.

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Highly Emissive Chiral Mn(II) Bromide Hybrids for UV‐Pumped Circularly Polarized LEDs and Scintillator Image Applications

Davydova

Meng

Рахманова

et al. 2023

Advanced Optical Materials

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Organic–inorganic hybrid metal halides are a promising platform for the design of materials for circularly polarized luminescence (CPL) and X‐ray detection applications. Meanwhile, despite the recent progress in this hot field, hybrid metal halides, simultaneously endowed with efficient CPL and high photoluminescence quantum yield (PLQY), are still limited to a few examples. Herein, the efficient, stable, and low‐cost CPL‐active Mn(II) hybrids are developed via blending of luminogenic [MnBr4]2− anions with N/OH‐bond free R/S‐[MBA‐Me3]+ cations in a single ionic structure. The synthesized R/S‐[MBA‐Me3]MnBr4 hybrids display brightly green Mn2+‐centered circularly polarized phosphorescence with near‐unity PLQY and a high glum factor of 0.0045. Single crystals of R/S‐[MBA‐Me3]MnBr4 are used to fabricate UV‐pumped circularly polarized light‐emitting diodes (LEDs) displaying a high optical selectivity upon exposure to right‐handed and left‐handed circular polarization conditions. Moreover, the titled compounds are found to emit strong X‐ray radioluminescence with excellent linear response to X‐ray dose rate that is used for X‐ray imaging demonstration. These findings reveal a great potential of R/S‐[MBA‐Me3]MnBr4 as low‐cost materials for CPL‐LEDs, scintillators, and X‐ray imaging applications.

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Lead-free scintillators based on pyridine manganese halide for X-ray imaging

Cited by 12 publications

References 28 publications

Red‐Emitting Organic–Inorganic Hybrid Manganese(II) Halides for X‐Ray Imaging

Red‐Emitting Organic–Inorganic Hybrid Manganese(II) Halides for X‐Ray Imaging

Ultrahigh Photoluminescence Quantum Yield Organic Manganese Halide Scintillator for X-ray Imaging

Highly Emissive Chiral Mn(II) Bromide Hybrids for UV‐Pumped Circularly Polarized LEDs and Scintillator Image Applications

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