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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Banerjee S., Saikia S., Molokeev M. S., Nag A.
Заглавие : Unveiling temperature-induced structural phase transition and luminescence in Mn2+-doped Cs2NaBiCl6 double perovskite
Колич.характеристики :8 с
Место публикации : Chem. Mater. - 2024. - Vol. 36, Is. 9. - P.4750-4757. - ISSN 08974756 (ISSN), DOI 10.1021/acs.chemmater.4c00514. - ISSN 15205002 (eISSN)
Примечания : Cited References: 49. - Authors acknowledge Dr. Arup Rath’s lab NCL Pune and SAIF-IIT Bombay for diffuse reflectance spectroscopy and ICP-AES measurements, respectively. A.N. acknowledges Science & Engineering Research Board, India, for Swarnajayanti Fellowship (SB/SJF/2020-21/02), and BRICS grant (e-27558) of the Department of Science and Technology, India. Authors acknowledge the Department of Science and Technology India (FIST program, SR/FST/CS-II/2019/105) for temperature-dependent powder XRD and EPR data. S.B. is grateful to IISER Pune for a research fellowship. S.S. acknowledges Prime Minister’s Research Fellowship (PMRF), Ministry of Education, India. M.M. acknowledges the Russian Science Foundation, grant 24-43-00006
Аннотация: Halide double perovskites like Cs2NaBiCl6 are good host materials for luminescent dopants like Mn2+. The nature of photoluminescence (PL) depends on the local structure around the dopant ion, and doping may sometimes influence the global structure of the host. Here, we unveil the correlation between the temperature-induced (global) structural phase transition of Mn2+-doped Cs2NaBiCl6 with the local structure and PL of the Mn2+ dopant. X-ray diffraction analysis shows Mn2+-doped Cs2NaBiCl6 is in a cubic (Fm3m) phase between 300 and 110 K, below which the phase changes to tetragonal (I4/mmm), which persists at least until 15 K. The small (∼1%) doping amount does not alter the phase transition behavior of Cs2NaBiCl6. Importantly, the phase transition does not influence the Mn2+ d-electron PL. The PL peak energy, intensity, spectral width, and lifetime do not show any signature of the phase transition between 300–6 K. The hyperfine splitting in temperature-dependent electron paramagnetic spectra of Mn2+ ions also remain unchanged across the phase transition. These results suggest that the global structural phase transition of the host does not influence the local structure and emission property of the dopant Mn2+ ion. This structure–property insight might be explored for other transition-metal- and lanthanide-doped halide double perovskites as well. The stability of dopant emission regardless of the structural phase transition bodes well for their potential applications in phosphor-converted light emitting diodes.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Denisenko Yu. G., Molokeev M. S., Jiang X., Sedykh A. E., Aleksandrovsky A. S., Oreshonkov A. S., Roginskii E. M., Zhernakov M. A., Heuler D., Seuffert M., Lin Zh., Andreev O. V., Muller-Buschbaum K.
Заглавие : Negative thermal expansion in the polymorphic modification of double sulfate β-AEu(SO4)2 (A–Rb+, Cs+)
Колич.характеристики :11 с
Место публикации : Inorg. Chem. - 2023. - Vol. 62, Is. 31. - P.12423-12433. - ISSN 00201669 (ISSN), DOI 10.1021/acs.inorgchem.3c01624. - ISSN 1520510X (eISSN)
Примечания : Cited References: 71. - The work was partly carried out within the framework of the Strategic Academic Leadership Program ″Priority-2030″ for the Siberian Federal University, Tyumen State University, Kazan Federal University and the state assignment of Kirensky Institute of Physics. The calculations were performed in part using facilities of JSCC supercomputer center of RAS
Аннотация: New polymorphic modifications of double sulfates β-AEu(SO4)2 (A–Rb+, Cs+) were obtained by the hydrothermal method, the structure of which differs significantly from the monoclinic modifications obtained earlier by solid-state methods. According to single-crystal diffraction data, it was found that the compounds crystallize in the orthorhombic system, space group Pnna, with parameters β-RbEu(SO4)2: a = 9.4667(4) Å, b = 13.0786(5) Å, c = 5.3760(2) Å, V = 665.61(5) Å3; β-CsEu(SO4)2: a = 9.5278(5) Å, b = 13.8385(7) Å, c = 5.3783(3) Å, V = 709.13(7) Å3. The asymmetric part of the unit cell contains one-half Rb+/Cs+ ion, one-half Eu3+ ion, both in special sites, and one SO42– ion. Both compounds exhibit nonlinear negative thermal expansion. According to the X-ray structural analysis and theoretical calculations, the polarizing effect of the alkali metal ion has a decisive influence on the demonstration of this phenomenon. Experimental indirect band gaps of β-Rb and β-Cs are 4.05 and 4.11 eV, respectively, while the direct band gaps are 4.48 and 4.54 eV, respectively. The best agreement with theoretical calculations is obtained using the ABINIT package employing PAW pseudopotentials with hybrid PBE0 functional, while norm-conserving pseudopotentials used in the frame of CASTEP code and LCAO approach in the Crystal package gave worse agreement. The properties of alkali ions also significantly affect the luminescent properties of the compounds, which leads to a strong temperature dependence of the intensity of the 5D0 → 7F4 transition in β-CsEu(SO4)2 in contrast to much weaker dependence of this kind in β-RbEu(SO4)2.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Chen Y., Liu F., Zhang Z., Hong J., Molokeev M. S., Bobrikov I. A., Shi J., Zhou J., Wu M.
Заглавие : A novel Mn4+-activated fluoride red phosphor Cs30(Nb2O2F9)9(OH)3·H2O:Mn4+ with good waterproof stability for WLEDs
Место публикации : J. Mater. Chem. C. - 2022. - Vol. 10, Is. 18. - P.7049-7057. - ISSN 20507534 (ISSN), DOI 10.1039/d2tc00132b
Примечания : Cited References: 56. - This work was financially supported by grants from the National Natural Science Foundation of China (NSFC) (No. 51802359), the Joint Funds of NSFC and Yunnan Province (No. U1702254), and Guangdong Basic and Applied Basic Research Foundation (No. 2020A1515010556)
Аннотация: Red-light-emitting materials, as pivotal components of warm white light-emitting diodes (WLEDs), have drawn increasing public focus. Among these, Mn4+-doped red light-emitting fluorides have drawn considerable attention when combined with an InGaN chip; however, they suffer from poor water stability under humid conditions. In this work, a novel fluoride red phosphor, Cs30(Nb2O2F9)9(OH)3·H2O:xMn4+ (CNOFM), with good water resistance was synthesized for the first time using a facile co-precipitation method at ambient temperature. Experiments were implemented for the precise analysis of its crystal structure, optical properties, micro-morphology, thermal behavior, and waterproof properties. 6.66% Mn4+-doped CNOFM maintained a stable crystal structure and possessed strong PL intensity located at 633 nm with high color purity of 96%. CNOFM showed better thermal and waterproof stability compared with the commercial K2SiF6:Mn4+ red phosphor. Without any surface modifications, the PL intensity remained at about 83% of the initial value after immersion in water for 60 min, and the mechanism was investigated. Finally, a warm WLED with a CRI of 92.3 and CCT of 3271 K was fabricated using the CNOFM red phosphor.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Zhou J., Chen Y., Jiang C., Milicevic B., Molokeev M. S., Brik M. G., Bobrikov I. A., Yan J., Li J., Wu M.
Заглавие : High moisture resistance of an efficient Mn4+-activated red phosphor Cs2NbOF5:Mn4+ for WLEDs
Место публикации : Chem. Eng. J. - 2021. - Vol. 405. - Ст.126678. - ISSN 13858947 (ISSN), DOI 10.1016/j.cej.2020.126678
Примечания : Cited References: 43. - This work was financially supported by grants from the National Natural Science Foundation of China (No. 51802359, 21801254, 51902354) and its Joint Funds of Yunnan and Guangdong Province (No. U1702254 and No. U1801253), Special Fund of Guangdong Province Project for Applied Science and Technology Research and Development (No. 2017B090917001), Guangdong Basic and Applied Basic Research Foundation (No. 2020A1515010556), the Fundamental Research Funds for the Central Universities (No. 19lgpy123), and China Postdoctoral Science Foundation (No. 2019M663230). M. G. Brik thanks the supports from the National Recruitment Program of High-end Foreign Experts (No. GDT20185200479 and GDW20145200225), the Programme for the Foreign Experts (No. W2017011) and Wenfeng High-end Talents Project (No. W2016-01) offered by Chongqing University of Posts and Telecommunications (CQUPT) , Estonian Research Council grant PUT PRG111, and European Regional Development Fund (TK141)
Аннотация: Mn4+-activated fluoride red phosphors, the most important red phosphors for warm white light emitting diodes (LEDs), usually suffer from inherent poor moisture resistance which is a major obstacle to their long-lasting outdoor applications in a high humidity environment. Surface modification of phosphors by coating with either organic or inorganic shells is an effective way to improve waterproof stability. However, the coating procedure usually has a negative impact on the luminous efficacy due to the increased passivation shell thickness. In this work, Mn4+-activated oxyfluoroniobate (Cs2NbOF5), a highly efficient phosphor with internal quantum efficiency of ca. 82%, has been successfully synthesized and it is interesting to note that Cs2NbOF5:Mn4+ can exhibit remarkably improved waterproof stability even without surface coating compared to well-accepted commercial fluoride red-emitting phosphor, K2SiF6:Mn4+. The results obtained indicate that Nb5+ ions inside red phosphor play a crucial role in improving the water-resistant performance of Mn4+, which provides a new concept for overcoming the downside of their waterproof in humid conditions and maintaining the luminescence efficiency. In the final phase white LEDs with a high luminous efficacy of 174 lm/W (higher than commercial fluoride red phosphors), low correlated color temperature (3164 K) and high color rendering index (Ra = 90 and R9 = 85) have been fabricated using Cs2NbOF5:Mn4+.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Zhou, Jun, Rong, Ximing, Molokeev M. S., Wang, Yulong, Yun, Xiangyan, Xu, Denghui, Li, Xiong
Заглавие : Alloying Cs+ into Rb2ZrCl6:Te4+ toward highly efficient and stable perovskite variants
Коллективы : Beijing Natural Science FoundationBeijing Natural Science Foundation [2214068]; National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [61705003]; Beijing Technology and Business University Research Team Construction Project [PXM2019_014213_000007, PXM2020_014213_000017]
Место публикации : Mat. Chem. Front. - 2021. - Vol. 5, Is. 13. - P.4997-5003. - ISSN 2052-1537(eISSN), DOI 10.1039/d1qm00302j
Примечания : Cited References: 37. - This work is supported by Beijing Natural Science Foundation (No. 2214068), the National Natural Science Foundation of China (No. 61705003), and the Beijing Technology and Business University Research Team Construction Project (No. PXM2019_014213_000007 and PXM2020_014213_000017)
Предметные рубрики: TELLER
PHOTOLUMINESCENCE
TELLURIUM(IV)
COMPLEXES
PHOSPHORS
Аннотация: Doping or alloying in perovskites and perovskite variants provides a promising way for modulating the electronic and photoluminescence properties and the structural stability. In this work, a series of yellow-emitting Rb2−xCsxZrCl6:Te4+ solid solution phosphors were prepared by a hydrothermal method, and their broad emission is assigned to the triplet 3P1–1S0 self-trapped excitons (STEs). Upon increasing the alloying ion Cs+, the yellow emission can be greatly enhanced by a stronger Jahn–Teller distortion. Moreover, Cs2ZrCl6:Te4+ shows a high photoluminescence quantum yield (PLQY), and impressive thermal and anti-water stability. This doping–alloying strategy presents a new direction towards designing lead-free, high-performance and stable perovskite derivatives.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Liu, Ying, Molokeev M. S., Xia, Zhiguo
Заглавие : Lattice doping of lanthanide ions in Cs2AgInCl6 nanocrystals enabling tunable photoluminescence
Место публикации : Energy Mater. Adv. - 2021. - Vol. 2021. - Ст.2585274. - ISSN 2692-7640 (eISSN), DOI 10.34133/2021/2585274
Примечания : Cited References: 42. - This work was supported by the National Natural Science Foundation of China (grant numbers 51961145101 and 51972118), the Fundamental Research Funds for the Central Universities (grant number FRFTP-18-002C1), the Guangzhou Science & Technology Project (202007020005), and the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (grant number 2017BT01X137). This work was also funded by RFBR according to the research project no. 19-52-80003
Аннотация: Lead-free halide double perovskite Cs2AgInCl6 has become the research hotspot in the optoelectronic fields. It is a challenge to utilize the lattice doping by different lanthanide ions with rich and unique photoluminescence (PL) emissions for emerging photonic applications. Here, we successfully incorporated Dy3+, Sm3+, and Tb3+ ions into Cs2AgInCl6 nanocrystals (NCs) by the hot-injection method, bringing diverse PL emissions of yellowish, orange, and green light in Cs2AgInCl6:Ln3+ (Ln3+ = Dy3+, Sm3+, Tb3+). Moreover, benefiting from the energy transfer process, Sm3+ and Tb3+ ion-codoped Cs2AgInCl6 NCs achieved tunable emission from green to yellow orange and a fluorescent pattern from the as-prepared NC-hexane inks by spray coating was made to show its potential application in fluorescent signs and anticounterfeiting technology. This work indicates that lanthanide ions could endow Cs2AgInCl6 NCs the unique and tunable PL properties and stimulate the development of lead-free halide perovskite materials for new optoelectronic applications.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Liu, Ying, Rong, Ximing, Li, Mingze, Molokeev M. S., Zhao, Jing, Xia, Zhiguo
Заглавие : Incorporating rare-earth terbium(III) Ions into Cs2AgInCl6:Bi nanocrystals toward tunable photoluminescence
Место публикации : Angew. Chem. - Int. Edit. - 2020. - Vol. 59, Is. 28. - P.11634-11640. - ISSN 1433-7851, DOI 10.1002/anie.202004562. - ISSN 1521-3773(eISSN)
Примечания : Cited References: 43. - This work is supported by the National Natural Science Foundation of China (51961145101, 51972118 and 51722202), Fundamental Research Funds for the Central Universities (FRFTP-18-002C1), Guangdong Provincial Science & Technology Project (2018A050506004) and the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01X137). This work is also funded by RFBR according to the research project No. 19-52-80003.
Предметные рубрики: HALIDE DOUBLE PEROVSKITE
LEAD-FREE
LANTHANIDE
STABILITY
EMISSION
Аннотация: The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare‐earth ions doping and intrinsic emission of lead‐free double perovskite Cs2AgInCl6 NCs to impart and tune the optical performances in the visible light region. Tb3+ ions were incorporated into Cs2AgInCl6 NCs and occupied In3+ sites as verified by both crystallographic analyses and first‐principles calculations. Trace amounts of Bi doping endowed the characteristic emission (5D4→7F6‐3) of Tb3+ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb3+. By controlling Tb3+ ions concentration, the emission colors of Bi‐doped Cs2Ag(In1−x Tbx )Cl6 NCs could be continuously tuned from green to orange, through the efficient energy‐transfer channel from self‐trapped excitons to Tb3+ ions. Our study provides the salient features of the material design of lead‐free perovskite NCs and to expand their luminescence applications.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Zhou, Jun, Li, Mingze, Molokeev M. S., Sun, Jiayue, Xu, Denghui, Xia, Zhiguo
Заглавие : Tunable photoluminescence in Sb3+-doped zero-dimensional hybrid metal halides with intrinsic and extrinsic self-trapped excitons
Место публикации : J. Mater. Chem. C. - 2020. - Vol. 8, Is. 15. - P.5058-5063. - ISSN 2050-7526, DOI 10.1039/d0tc00391c. - ISSN 2050-7534(eISSN)
Примечания : Cited References: 33. - This work is supported by the National Natural Science Foundation of China (No. 51722202, 51961145101, 51972118, 21576002 and 61705003), Fundamental Research Funds for the Central Universities (D2190980), the Guangdong Provincial Science & Technology Project (2018A050506004), and Beijing Technology and Business University Research Team Construction Project (No. PXM2019_014213_000007). This work was also funded by RFBR according to the Research Project No. 19-52-80003.
Предметные рубрики: WHITE-LIGHT EMISSION
LUMINESCENCE
PEROVSKITES
CS2NASCCL6
CS2NAYCL6
Аннотация: Dopants in luminescent metal halides provide an alternative way for photoluminescence tuning towards versatile optical applications. Here we report a trivalent antimony (Sb3+)-doped single crystalline 0D metal halide with the composition of (C9NH20)9[Pb3Cl11](ZnCl4)2:Sb3+. This compound possessed the coexistence of two emission centers including intrinsic and extrinsic self-trapped excitons (STEs), which are ascribed to [Pb3Cl11]5− clusters and triplet STEs formed by the 3P1–1S0 transition of Sb3+. By regulating the Sb3+ concentration, the emission can be tuned from green to yellow and finally to orange, which would help to develop optically pumped white light-emitting diodes (WLEDs) with different photometric characteristics. Moreover, this dopant-induced extrinsic STE approach presents a new direction towards tuning the luminescence properties of 0D metal halides, and may find application in environmentally-friendly, high-performance metal halide light emitters.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Liu, Ying, Rong, Ximing, Li, Mingze, Molokeev M. S., Zhao, Jing, Xia, Zhiguo
Заглавие : Incorporating rare-earth terbium(III) ions into Cs2AgInCl6:Bi nanocrystals toward tunable photoluminescence
Место публикации : Angew. Chem. - 2020. - Vol. 132, Is. 28. - P.11731-11737. - ISSN 1521-3757(eISSN), DOI 10.1002/ange.202004562
Примечания : Cited References: 43
Предметные рубрики: HALIDE DOUBLE PEROVSKITE
LEAD-FREE
LANTHANIDE
STABILITY
EMISSION
Аннотация: The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare‐earth ions doping and intrinsic emission of lead‐free double perovskite Cs2AgInCl6 NCs to impart and tune the optical performances in the visible light region. Tb3+ ions were incorporated into Cs2AgInCl6 NCs and occupied In3+ sites as verified by both crystallographic analyses and first‐principles calculations. Trace amounts of Bi doping endowed the characteristic emission (5D4→7F6‐3) of Tb3+ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb3+. By controlling Tb3+ ions concentration, the emission colors of Bi‐doped Cs2Ag(In1−xTbx)Cl6 NCs could be continuously tuned from green to orange, through the efficient energy‐transfer channel from self‐trapped excitons to Tb3+ ions. Our study provides the salient features of the material design of lead‐free perovskite NCs and to expand their luminescence applications.
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10.

Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Su, Binbin, Molokeev M. S., Xia, Zhiguo
Заглавие : Mn2+-Based narrow-band green-emitting Cs3MnBr5 phosphor and the performance optimization by Zn2+ alloying
Место публикации : J. Mater. Chem. C. - 2019. - Vol. 7, Is. 36. - P.11220-11226. - ISSN 2050-7526, DOI 10.1039/c9tc04127c. - ISSN 2050-7534(eISSN)
Примечания : Cited References: 24. - The present work was supported by the National Natural Science Foundations of China (Grant No. 51722202, 51972118 and 51572023), Natural Science Foundations of Beijing (2172036) and the Guangdong Provincial Science & Technology Project (no. 2018A050506004).
Предметные рубрики: THERMAL-STABILITY
BACKLIGHT
EMISSION
Аннотация: To discover new narrow-band green-emitting phosphors is a challenge for backlighting light-emitting diodes (LEDs) used in liquid crystal displays (LCDs). The synthesis and optical properties of Cs3MnBr5 are demonstrated herein. The intrinsic Mn2+ luminescence without concentration quenching leads to intense green emission at 520 nm with narrow full width at half maximum of 42 nm and high photoluminescence quantum yield (PLQY) of 49% under the excitation at 460 nm. When a small amount of Zn2+ is introduced into Cs3MnBr5, the luminescence intensity decreases slightly. However, the thermal stability of Cs3MnBr5 is improved from 82% to 87% with the intensity values at 423 K compared to that at 298 K. The white LED device fabricated using Cs3Mn0.96Zn0.04Br5 (green) and K2SiF6:Mn4+ (red) phosphors with a blue LED chip exhibit a high luminous efficiency (107.76 lm W-1) and wide color gamut (101% National Television System Committee standard (NTSC) in Commission Internationale de L'Eclairage (CIE) 1931 color space), demonstrating its potential application in wide color gamut LCD backlights.
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