Tracing the origin of near-infrared emissions emanating from manganese (Ⅱ)

Yu Xiao; Xun Yang; Hao-Ran Zhao; Dan Wu; Ming-Xing Chen; Tianxiang Zheng; Rui Zhang; Ling-Dong Sun; Chun-Hua Yan

doi:10.1038/s41377-025-01816-y

Your Location：

Home >

Browse articles >

Tracing the origin of near-infrared emissions emanating from manganese (Ⅱ)

Original Articles

- Tracing the origin of near-infrared emissions emanating from manganese (Ⅱ)
- Light: Science & Applications Vol. 14, Issue 7, Pages: 1989-2000(2025)
- Affiliations：
  
  1.Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
  2.College of Science, Nanjing Forestry University, Nanjing 210037, China
  3.College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China
  4.School of Physical Science and Technology, Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021, China
  5.Analytical Instrumentation Center of Peking University, Beijing 100871, China
  6.School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China
- Author bio：
  
  Ling-Dong Sun (sun@pku.edu.cn)
  Chun-Hua Yan (yan@pku.edu.cn)
- Funds：
- DOI：10.1038/s41377-025-01816-y
  CLC：
- Received：04 November 2024，
  
  Revised：28 February 2025，
  
  Accepted：06 March 2025，
  
  Published Online：13 May 2025，
  
  Published：31 July 2025
- Accepted：
Scan QR Code
Xiao, Y. et al. Tracing the origin of near-infrared emissions emanating from manganese (Ⅱ). Light: Science & Applications, 14, 1989-2000 (2025).
DOI：

Xiao, Y. et al. Tracing the origin of near-infrared emissions emanating from manganese (Ⅱ). Light: Science & Applications, 14, 1989-2000 (2025). DOI： 10.1038/s41377-025-01816-y.

摘要

Abstract

The enduring enigma surrounding the near-infrared (NIR) emiss

ion of Mn

continues to ignite intense academic discussions. Numerous hypotheses have emerged from extensive research endeavors to explain this phenomenon

such as the formation of Mn

–Mn

ion pairs

occupying cubically coordinated sites

as well as conjectures positing the involvement of Mn

oxidized from Mn

or defects. Despite these diverse and valuable insights

none of the hypotheses have yet achieved broad consensus. In this study

we have observed prolonged fluorescence lifetimes (~10 ms) for the NIR emissions of Mn

ions

hinting at these ions occupying the high-symmetry octahedral sites inherent to the garnet lattice. This inference is supported by the corroborating results from X-ray absorption fine structure analysis and first-principles calculations. The intense crystal field of octahedral sites

similar to that of AlO

facilitates the splitting of

–

energy levels

thereby inducing a red-shift in the emission spectrum to the NIR region due to the transition

(

G) →

(

S) of isolated Mn

. Our findings not only offer a plausible rationale for the NIR emission exhibited by other Mn

-activated garnet phosphors but also pave a definitive route towards understanding the fundamental mechanisms responsible for the NIR emission of Mn

ions.

关键词

Keywords

references

Jia, Z. W. et al. Strategies to approach high performance in Cr 3+ -doped phosphors for high-power NIR-LED light sources. Light Sci. Appl. 9 , 86 (2020)..

Xiao, W. G. et al. Suppressed concentration quenching brightens short-wave infrared emitters. Adv. Mater. 35 , 2306517 (2023)..

Ming, J. et al. High-brightness transition metal-sensitized lanthanide near-infrared luminescent nanoparticles. Nat. Photonics 18 , 1254–1262 (2024)..

Dou, C. et al. Self-recoverable and NIR-Ⅰ to NIR-Ⅱ tunable broadband mechanoluminescence of Cr 3+ -doped antimonate double perovskites. Adv. Funct. Mater. 2419716 https://doi.org/10.1002/adfm.202419716 (2024)..

Zhang, L. L. et al. Recent progress on Cr 3+ doped broad band NIR phosphors. Chin. J. Lumin. 40 , 1449–1459 (2019)..

Zhang, Y. et al. Blue LED-pumped intense short-wave infrared luminescence based on Cr 3+ -Yb 3+ -co-doped pho sphors. Light Sci. Appl. 11 , 136 (2022)..

Zheng, T. X. et al. CaY 2 ZrScAl 3 O 12 : Cr 3+ —an efficient and thermally stable garnet phosphor for high-performance NIR LEDs. J. Mater. Chem. C 12 , 11340–11346 (2024)..

Tamboli, S. et al. Blue-light pumped NIR emission of LaOF: Pr 3+ nanorods for highly sensitive nanothermometry. Ceram. Int. 49 , 23579–23590 (2023)..

Kuwik,M. et al. Experimental and theoretical studies on NIR luminescence of titanate‐germanate glasses doped with Pr 3+ and Tm 3+ ions. J. Am. Ceram. Soc. 106 , 7460–7472 (2023)..

Zhuang, Y. F. et al. Investigation of a novel long persistent NIR emitting phosphor Ca 2 GeO 4 : Yb 3+ . J. Lumin. 258 , 119792 (2023)..

Zhao, Y. J. et al. Enhanced broadband NIR emission in glass–ceramic fibers containing Nd 3+ /Yb 3+ co‐doped YCa 4 O(BO 3 ) 3 disordered nanocrystal. J. Am. Ceram. Soc. 106 , 4634–4642 (2023)..

Zhan g, J. & Jiang, C. Near-infrared quantum cutting of Dy 3+ , Ho 3+ -Yb 3+ and Er 3+ -Yb 3+ -doped Ca 10 K(PO 4 ) 7 phosphors. Funct. Mater. Lett. 7 , 1450047 (2014)..

Tang, Z. B. et al. Single‐site occupancy of Eu 2+ in multiple cations enables efficient ultra‐broadband visible to near‐infrared luminescence. Laser Photonics Rev. 17 , 2200911 (2023)..

Li, S. X. et al. Efficient near-infrared phosphors discovered by parametrizing the Eu(Ⅱ) 5 d -to-4 f energy gap. Matter 5 , 1924–1936 (2022)..

Zhu, F. M. et al. Ni 2+ -doped MgTa 2 O 6 phosphors capable of near-infrared Ⅱ and Ⅲ emission under blue-light excitation. Chem. Eng. J. 479 , 147568 (2024)..

Song, E. H. et al. Heavy Mn 2+ doped MgAl 2 O 4 phosphor for high-efficient near-infrared light-emitting diode and the night-vision application. Adv. Opt. Mater. 7 , 1901105 (2019)..

Wang, J. Environmentally friendly Fe 3+ -activated near-infrared-emitting phosphors for spectroscopic analysis. Light Sci. Appl. 11 , 178 (2022) ..

Liu, D. J. et al. Highly efficient Fe 3+ -doped A 2 BB ′O 6 ( A = Sr 2+ , Ca 2+ ; B , B ′= In 3+ , Sb 5+ , Sn 4+ ) broadband near-infrared-emitting phosphors for spectroscopic analysis. Light Sci. Appl. 11 , 112 (2022)..

Liu, S. Q. et al. Intervalence charge transfer of Cr 3+ −Cr 3+ aggregation for NIR-Ⅱ luminescence. Light Sci. Appl. 12 , 181 (2023)..

Chen, G. et al. Boosting broadband short-wave infrared emission to achieve near-unity quantum efficiency via bridging Cr 3+ −Ni 2+ in spinel solid-solutions towards light-emitting diode applications. Dalton Trans. 53 , 4214–4221 (2024)..

Wang, X. et al. Ultra-broadband red to NIR photoemission from multiple bismuth centers in Sr 2 B 5 O 9 Cl: Bi crystal. Opt. Lett. 44 , 4821–4824 (2019)..

Wang, S. W. et al. Achieving high quantum efficiency broadband NIR Mg 4 Ta 2 O 9 : Cr 3+ phosphor through lithium-ion compensation. Adv. Mater. 35 , 2300124 (2023)..

Jiang, L. P. et al. Broadband near-infrared luminescence in garnet Y 3 Ga 3 MgSiO 12 : Cr 3+ phosphors. Inorg. Chem. 62 , 4220–4226 (2023)..

Li, R. Y. et al. Boosting applications with high-performance near-infrared phosphor-converted light-emitting diodes. Laser Photonics Rev. 18 , 2300608 (2024)..

Tang, W. Q. et al. An efficient perovskite-like phosphor with peak emission wavelength at 850 nm for high-performance NIR LEDs. Adv. Opt. Mater. 11 , 2202237 (2023)..

Dang, P. P. et al. Recent advances in chromium-doped near-infrared luminescent materials: fundamentals, optimization strategies, and applications. Adv. Opt. Mater. 11 , 2201739 (2023)..

Xiao, Y. et al. An extra‐broadband VIS‐NIR emitting phosphor toward multifunctional LED applications. Adv. Funct. Mater. 32 , 2109618 (2022)..

Zhao, C. et al. Performance optimization of Ce: YAG sapphire films for high power density white laser-driven lighting applications. Ceram. Int. 49 , 18638–18644 (2023)..

Chen, X. Y. & Huang, X. Y. Ce 3+ -Activated SrLu 2 Al 3 ScSiO 12 cyan-green-emitting garnet-structured inorganic phosphor materials toward application in blue-chip-based phosphor-converted solid-state white lighting. Inorg. Chem. 63 , 5743–5752 (2024)..

Xu, J. et al. Near-infrared multi-wavelengths long persistent luminescence of Nd 3+ ion through persistent energy transfer in Ce 3+ , Cr 3+ co-doped Y 3 Al 2 Ga 3 O 12 for the first andsecond bio-imaging windows. Appl. Phys. Lett. 107 , 081903 (2015)..

Wen, H. Y. et al. Luminescence properties of Ce 3+ −Cr 3+ co-doped Ba 3 Sc 4 O 9 phosphors. Chin. J. Lumin. 44 , 2149–2157 (2023)..

Li, H. R. et al. Highly efficient green-emitting phosphor BaZnAl 10 O 17 : Mn 2+ with ultra-narrow band and extremely low thermal quenching for wide color gamut LCD backlights. Adv. Opt. Mater. 9 , 2100799 (2021)..

Zhu, Y. L. et al. Narrow-band green-emitting Sr 2 MgAl 22 O 36 : Mn 2+ phosphors with superior thermal stability and wide color gamut for backlighting display applic ations. Adv. Opt. Mater. 7 , 1801419 (2019)..

Zhu, X. M., Yao, Y. L. & Zhou, Z. F. Synthesis, crystal structure, and luminescence properties of a novel green emitting phosphor Na 2 Mg 1-x SiO 4 : Mn x 2+ . Opt. Mater. 62 , 104–109 (2016)..

Xia, Z. G. et al. Structural and luminescence properties of yellow-emitting NaScSi 2 O 6 : Eu 2+ phosphors: Eu 2+ site preference analysis and generation of red emission by codoping Mn 2+ for white-light-emitting diode applications. J. Phys. Chem. C 117 , 20847–20854 (2013)..

Deng, M. L. et al. Thermally stable red-emitting Ca 18 K 3 Sc(PO 4 ) 14 : Mn 2+ phosphor and enhanced luminescence by energy transfer between Ce 3+ –Eu 2+ –Mn 2+ . Inorg. Chem. 63 , 3901–3912 (2024)..

Gong, W. J. et al. Thermal-stable blue-red dual-emitting Na 2 Mg 2 Si 6 O 15 : Eu 2+ , Mn 2+ phosphor for plant growth lighting. J. Lumin. 239 , 118372 (2021)..

Benecke, C. et al. On the excitation and emission of the infrared luminescence of wid e band gap Mn Ⅱ–Ⅵ semimagnetic semiconductors. Phys. Status Solidi B 153 , 391–402 (1989)..

Shcherbakov, V. D. Instability of the local environment of Mn 2+ in BaF 2 . Crystallogr. Rep. 62 , 430–436 (2017)..

Zhan, C. Y. et al. Mn 2+ –Mn 2+ dimers induced robust light absorption in heavy Mn 2+ doped ZnAl 2 O 4 near-infrared phosphor with an excellent photoluminescence quantum yield and thermal stability. Adv. Opt. Mater. 12 , 2400574 (2024)..

Chen, Z. T. et al. Exchange coupled Mn–Mn pair: an approach for super-broadband 1380 nm emission in α-MnS. Appl. Phys. Lett. 109 , 191907 (2016)..

Song, E. H. et al. Tailored near‐infrared photoemission in fluoride perovskites through activator aggregation and super‐exchange between divalent manganese ions. Adv. Sci. 2 , 1500089 (2015)..

Li, X. S. et al. Highly efficient Mn–Mn dimer activated phosphors for high-power near-infrared LED application. J. Mater. Chem. C 11 , 712–721 (2023)..

van Bunni ngen, A. J., Keizer, S. T. & Meijerink, A. Understanding enormous redshifts in highly concentrated Mn 2+ phosphors. J. Mater. Chem. C 11 , 8961–8970 (2023)..

Zhou, Q. et al. Mn 2+ and Mn 4+ red phosphors: synthesis, luminescence and applications in WLEDs. A review. J. Mater. Chem. C 6 , 2652–2671 (2018)..

Zong, Q. et al. High-temperature preparation of a new Mn 2+ phosphor in the open air with red emitting properties. J. Lumin. 266 , 120298 (2024)..

Madkhli, A. Y. Simultaneous oxidation of Mn 2+ to Mn 4+ by devitrification of transparent glassy Na 2 Ge 4 O 9 : Mn. Ceram. Int. 50 , 24913–24920 (2024)..

Xiao, Y., Yan, D. C. & Wu, D. Comment on "Bandshift luminescence thermometry using Mn 4+ : Na 4 Mg(WO 4 ) 3 phosphors". Chem. Mater. 32 , 9813–9816 (2020)..

Ma, C. G. et al. A novel borate phosphor Lu 5 Ba 6 B 9 O 27 : Ce 3+ codoped with Sr 2+ /Tb 3+ for NUV-white light emitting diode application. Dalton Trans. 53 , 14153–14162 (2024)..

Xiao, Y. et al. Highly efficient green-emitting phosphors Ba 2 Y 5 B 5 O 17 with low thermal quenching due to fast energy transfer from Ce 3+ to Tb 3+ . Inorg. Chem. 56 , 4538–4544 (2017)..

Xia, Z. G. & Meijerink, A. Ce 3+ -doped garnet phosphors: composition modification, luminescence properties and applications. Chem. Soc. Rev. 46 , 275–299 (2017)..

Dexter, D. L. A theory of sensitized luminescence in solids. J. Chem. Phys. 21 , 836–850 (1953)..

Kück, S. et al. Emission of octahedrally coordinated Mn 3+ in garnets. Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 54 , 1741–1749 (1998)..

Lin, H. H. et al. Luminescence of Ba 2 Ca(BO 3 ) 2 : Ce 3+ —influence of charge compensator, energy transfer and LED application. J. Phys. D Appl. Phys. 42 , 165409 (2009)..

Ji, H. P. Analysis of site-occupation of activator in phosphors. Chin. J. Lumin. 43 , 26–41 (2022)..

Vink, A. P. et al. Luminescence of exchange coupled pairs of transition metal ions. J. Electrochem. Soc. 148 , E313–E320 (2001)..

Chen, Q. L. et al. Elucidating the multisite and multivalence nature of Mn ions in solids and predicting their optical transition properties: a case study on a series of garnet hosts. Inorg. Chem. 61 , 18690–18700 (2022)..

Ferguson, J., Guggenheim, H. J. & Tanabe, Y. Absorption of light by pairs of like and unlike transition-metal ions. Phys. Rev. Lett. 14 , 737–738 (1965)..

Zabinsky, S. I. et al. Multiple-scattering calculations of x-ray-absorption spectra. Phys. Rev. B 52 , 2995–3009 (1995)..

Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59 , 1758–1775 (1999)..

Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77 , 3865–3868 (1996)..

Gali, A. e t al. Theory of spin-conserving excitation of the N - V - center in diamond. Phys. Rev. Lett. 103 , 186404 (2009)..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

No data

Related Author

No data

Related Institution

No data

⁰