Anomalous NIR Luminescence in Mn<sup>2+</sup>‐Doped Fluoride Perovskite Nanocrystals

Song, Enhai; Ding, Sha; Wu, Ming; Ye, Shi; Xiao, Fang; Zhou, Shifeng; Zhang, Qinyuan

doi:10.1002/adom.201400066

Cited by 88 publications

(55 citation statements)

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“…6a, while those samples ( x = 0, 0.2, 0.4, 0.6) exhibit no apparent UC emissions. Since there is a large gap between the first excited state of 4 T 1 and ground state of 6 A 1 for Mn 2+ (normally > 17,000 cm −1 ) and there is no metastable excited state above 10,000 cm −1 for Yb 3+ ion2627282930, it normally requires the vicinity of Mn 2+ -Yb 3+ ions in the lattice for super exchange-interaction or cooperative sensitization based UC process. Therefore, when Mn 2+ content is high enough ( x ≥ 0.8), the Mn 2+ ions tend to show up at the neighbor of Yb 3+ ions.…”

Section: Resultsmentioning

confidence: 99%

“…The emission color of Mn 2+ can be tuned from green to deep red2425, depending on its coordinated chemical environment. It is recently reported by our group that two emission peaks at ~585 nm (visible) and ~770 nm (near infrared) in Mn 2+ doped perovskite fluorides26, which are ascribed to the emission of isolated Mn 2+ and the antiferromagnetic coupling within Mn 2+ -Mn 2+ dimers, respectively. The latter could be controlled by concentration of Mn 2+ dopant (i.e.…”

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confidence: 78%

“…Meanwhile, upconversion (UC) emission of Mn 2+ could be realized by codoping Yb 3+ in the Mn 2+ doped materials27. It generally requires the vicinity of Mn 2+ -Yb 3+ ions in the lattice for superexchange-interaction or cooperative sensitization based UC process, because there is a large gap between the first excited (emissive) state 4 T 1 and the ground state 6 A 1 for Mn 2+ (normally >17,000 cm −1 ) while there is no metastable excited state above 10,000 cm −1 for Yb 3+ ion2627282930. Therefore, Mn 2+ -Yb 3+ codopants may be an option in the zeolite-Y host to check their interaction and energy transfer involved.…”

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Interaction between the exchanged Mn2+ and Yb3+ ions confined in zeolite-Y and their luminescence behaviours

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Xiong

et al. 2017

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Luminescent zeolites exchanged with two distinct and interacted emissive ions are vital but less-studied for the potential applications in white light emitting diodes, solar cells, optical codes, biomedicine and so on. Typical transition metal ion Mn2+ and lanthanide ion Yb3+ are adopted as a case study via their characteristic transitions and the interaction between them. The option is considered with that the former with d-d transition has a large gap between the first excited state 4T1 and the ground state 6A1 (normally >17,000 cm−1) while the latter with f-f transition has no metastable excited state above 10,000 cm−1, which requires the vicinity of these two ions for energy transfer. The results of various characterizations, including BET measurement, photoluminescence spectroscopy, solid-state NMR, and X-ray absorption spectroscopy, etc., show that Yb3+ would preferably enter into the zeolite-Y pores and introduction of Mn2+ would cause aggregation of each other. Herein, cation-cation repulsion may play a significant role for the high valence of Mn2+ and Yb3+ when exchanging the original cations with +1 valence. Energy transfer phenomena between Mn2+ and Yb3+ occur only at elevated contents in the confined pores of zeolite. The research would benefit the design of zeolite composite opto-functional materials.

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Interaction between the exchanged Mn2+ and Yb3+ ions confined in zeolite-Y and their luminescence behaviours

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et al. 2017

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“…Great attention have been paid for UC luminescent materials due to their potential applications in various areas such as color displays, medical, biological labels, anti-counterfeiting, solar cells and so on [2][3][4][5] . 11,12 Besides the Mn 2+ , Cr 3+ is another known NIR emitting TM ion and Yb 3+ -Cr 3+ is a potential efficient NIR UC system. [6][7][8] Tm 3+ is the most commonly used NIR emitting ion in the Yb 3+ codoped UC materials.…”

Section: ⅰ ⅰ ⅰ ⅰIntroductionmentioning

confidence: 99%

Multifunctionalities of near-infrared upconversion luminescence, optical temperature sensing and long persistent luminescence in La₃Ga₅GeO₁₄:Cr³⁺,Yb³⁺,Er³⁺and their potential coupling

et al. 2015

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The multifunctionalities of La 3 Ga 5 GeO 14 :Cr 3+ ,Yb 3+ ,Er 3+ (LGG:Cr 3+ ,Yb 3+ ,Er 3+ ) with respective functions of near-infrared (NIR) upconversion (UC) luminescence, optical temperature sensing (OTS) and long persistent luminescence (LPL) were carried out and investigated in detail, which makes the materials attractive for bioapplications.The NIR UC luminescence at ~830 nm with deep penetration in tissues is ascribed to the 4 T 2 → 4 A 2 transition of Cr 3+ . OTS function based on the intensity ratio variation of 2 H 11/2 → 4 I 15/2 to 4 S 3/2 → 4 I 15/2 transitions of Er 3+ ion detected that the thermal effects of the UC material caused by the laser irradiation ranges from 307 to 332 K for pumping power of 60 to 86 mW mm -2 . It also showed LPL of Cr 3+ with defects trap depth of ~0.77 eV below the conduction band, benefiting excitation-free and noise-free imaging in tissues. Additionally, anomalous temperature dependant UC emission behaviours of Cr 3+ and Er 3+ in this material were also characterized and discussed, which can be understood by the configurational coordinate (CC) model and the complex foreward and backward energy transfer processes among the dopants, respectively. The potential coupling of these functions was further discussed, such as UC induced NIR LPL, which would repetitively restrengthen the fading LPL signals and alerting the operators to thermal damage of the biosystems by NIR laser in the tissue imaging.LGG has a space group of P321, its 2d site is disorderly occupied by 50% of Ga (2) and 50% of Ge. Layers formed by (Ga/Ge)O 4 tetrahedrons and GaO 4 tetrahedrons sharing the corner are connected by GaO 6 octahedra along c axis, with La 3+ ions in the forming cages of the framework (as seen in Fig. 3). Some typical cation-cation distances are also listed in Table 1. It should be noted that the distance between La-Ga is shorter than that of La-La.

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“…[1][2][3][4][5][6][7] With the development of manufacturing technology for nanometer materials, UCL labelling has gathered great attention. [8][9][10][11] The study on UCL was derived from the detection of IR light; however, it has a great number of potential applications in the elds of solid-state lasers, 3D displays, IR quantum counters, optical probes in uorescent imaging techniques, anti-counterfeiting, NIR photocatalysis, and temperature sensors. 6,7,9,10,[12][13][14][15] Most of UC materials are rareearth doped solid compounds; in which, a lanthanide ion absorbs more than one photon with lower energy and converts them to one photon with higher energy by using its metastable energy levels.…”

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Ultraviolet upconversion emission of Pb²⁺ ions sensitized by Yb³⁺-trimers in CaF₂

et al. 2017

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Under 978 nm near infrared (NIR) excitation, ultraviolet (UV) upconversion (UC) emissions from Pb 2+ ions in With the development of manufacturing technology for nanometer materials, UCL labelling has gathered great attention.8-11 The study on UCL was derived from the detection of IR light; however, it has a great number of potential applications in the elds of solid-state lasers, 3D displays, IR quantum counters, optical probes in uorescent imaging techniques, anti-counterfeiting, NIR photocatalysis, and temperature sensors. 6,7,9,10,[12][13][14][15] Most of UC materials are rareearth doped solid compounds; in which, a lanthanide ion absorbs more than one photon with lower energy and converts them to one photon with higher energy by using its metastable energy levels. Yb 3+ ion has been extensively adopted as a sensitizer in UC processes because it has a long excited state lifetime and a relatively large absorption cross-section in the NIR region. ion from the view of energy. Cooperative transition usually means the physical processes in which identical ions or atoms simultaneously make transitions by absorbing (or emitting) one photon with the sum of all transition energies, or transferring their energies to another ion or atom. Cooperative transition includes cooperative luminescence (CL), cooperative absorption (CA), and cooperative energy transfer (CET) and is closely relative to clustered lanthanide ions in solid hosts. Clusters made of lanthanide ions can easily form in many materials, especially in alkaline-earth uoride crystal AF 2 (A ¼ Ca, Sr, Ba). When a lanthanide ion with +3 oxidation state is doped in an alkaline-earth uoride, nonequilibrium of charge arises in the lattice due to the lanthanide ion usually occupy the position of an alkaline-earth ion with +2 oxidation state. The non-equilibrium of charge produces crystal defects such as the interstitials of F À ions and cation vacancies in order to compensate excess plus charges, which gives non-uniform distribution of lanthanide ions.

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Anomalous NIR Luminescence in Mn²⁺‐Doped Fluoride Perovskite Nanocrystals

Cited by 88 publications

References 37 publications

Interaction between the exchanged Mn2+ and Yb3+ ions confined in zeolite-Y and their luminescence behaviours

Interaction between the exchanged Mn2+ and Yb3+ ions confined in zeolite-Y and their luminescence behaviours

Multifunctionalities of near-infrared upconversion luminescence, optical temperature sensing and long persistent luminescence in La₃Ga₅GeO₁₄:Cr³⁺,Yb³⁺,Er³⁺and their potential coupling

Ultraviolet upconversion emission of Pb²⁺ ions sensitized by Yb³⁺-trimers in CaF₂

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Anomalous NIR Luminescence in Mn2+‐Doped Fluoride Perovskite Nanocrystals

Cited by 88 publications

References 37 publications

Interaction between the exchanged Mn2+ and Yb3+ ions confined in zeolite-Y and their luminescence behaviours

Interaction between the exchanged Mn2+ and Yb3+ ions confined in zeolite-Y and their luminescence behaviours

Multifunctionalities of near-infrared upconversion luminescence, optical temperature sensing and long persistent luminescence in La3Ga5GeO14:Cr3+,Yb3+,Er3+and their potential coupling

Ultraviolet upconversion emission of Pb2+ ions sensitized by Yb3+-trimers in CaF2

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Anomalous NIR Luminescence in Mn²⁺‐Doped Fluoride Perovskite Nanocrystals

Multifunctionalities of near-infrared upconversion luminescence, optical temperature sensing and long persistent luminescence in La₃Ga₅GeO₁₄:Cr³⁺,Yb³⁺,Er³⁺and their potential coupling

Ultraviolet upconversion emission of Pb²⁺ ions sensitized by Yb³⁺-trimers in CaF₂