journal article·2025-06

Temperature-independent emission in a [(CH3)3NPh]2MnBr4 single crystal analogous to thermally activated delayed fluorescence

Mutibah Alanazi, Atanu Jana, Won Woong Choi, D. ChangMo Yang, Robert A. Taylor, Chang Woo Myung, Youngsin Park

Publisher page

Abstract

We demonstrate a novel defect-mediated, thermally-activated emission mechanism in [(CH3)3NPh]2MnBr4 single crystals, driven by the coexistence of temperature-sensitive shallow traps and temperature-independent deep traps introduced by Br vacancies. Through comprehensive temperature-dependent photoluminescence (PL) and time-resolved PL measurements, combined with first-principles calculations, we reveal that the material exhibits exceptional thermal stability, retaining 67 % of its relative PL quantum yield at room temperature and achieving an absolute quantum yield of ∼38.9 % under optimal excitation conditions. The dual-component PL decay dynamics consist of a fast decay (∼hundreds of ps) governed by shallow traps and a long decay (∼350 μs) dominated by deep traps, creating an energy cascade that efficiently promotes radiative recombination while minimizing non-radiative losses. Our findings provide critical insights into defect-mediated, thermally-sensitive delayed emission mechanisms and establish [(CH3)3NPh]2MnBr4 as a lead-free, thermally stable material with high efficiency, making it an excellent candidate for next-generation optoelectronic applications, including solid-state lighting and temperature-sensitive devices.
Source: openaire · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Perovskite Materials and Applications · Organic and Molecular Conductors Research · Luminescence and Fluorescent Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (51)

Show source-provided references
1. Reverse intersystem crossing from upper triplet levels to excited singlet: a “hot excition” path for organic light-emitting diodes10.1098/rsta.2014.0318 ↗
2. Metal-halide perovskites for photovoltaic and light-emitting devices10.1038/nnano.2015.90 ↗
3. Properties and potential optoelectronic applications of lead halide perovskite nanocrystals10.1126/science.aam7093 ↗
4. Perovskite photonic sources10.1038/nphoton.2016.62 ↗
5. Low-temperature solution-processed wavelength-tunable perovskites for lasing10.1038/nmat3911 ↗
6. Dynamic ultralong phosphorescence and optical waveguiding switches in silver-organic complex via reversible single-crystal-to-single-crystal conversion10.1002/anie.202502782 ↗
7. Solid-State photochemical cascade process boosting smart ultralong room-temperature phosphorescence in bismuth halides10.1002/anie.202402634 ↗
8. Dynamic photoresponsive ultralong phosphorescence from one-dimensional halide microrods toward multilevel information storage10.31635/ccschem.023.202202605 ↗
9. Unlocking full-spectrum brilliance: dimensional regulation in lead-free metal halides for superior photoluminescence10.1021/acs.nanolett.4c03843 ↗
10. Double perovskite Cs2AgInCl6:cr3+: broadband and near-infrared luminescent materials10.1039/C9QI00905A ↗
11. Revealing the nature of photoluminescence emission in the metal-halide double perovskite Cs2AgBiBr610.1039/C9TC02402F ↗
12. Highly efficient phosphorescent emission from organic electroluminescent devices10.1038/25954 ↗
13. Nearly 100% internal phosphorescence efficiency in an organic light-emitting device10.1063/1.1409582 ↗
14. Triplet–triplet annihilation based upconversion- from triplet sensitizers and triplet acceptors to upconversion quantum yields10.1039/c1ra00469g ↗
15. Ultralow-loss optical waveguides through balancing deep-blue TADF and orange room temperature phosphorescence in hybrid antimony halide microstructures10.1002/anie.202309913 ↗
16. Full-color, time-valve controllable and Janus-type long-persistent luminescence from all-inorganic halide perovskites10.1038/s41467-024-49654-7 ↗
17. Upconversion and multiexciton generation in organic Mn(ii) complex boost the quantum yield to >100%10.1039/D2QM00447J ↗
18. Improving the light-harvesting of amorphous silicon solar cells with photochemical upconversion10.1039/c2ee21136j ↗
19. Indirect tail states formation by thermal-induced polar fluctuations in halide perovskites10.1038/s41467-019-08326-7 ↗
20. Efficient charge generation by relaxed charge-transfer states at organic interfaces koen10.1038/nmat3807 ↗
21. Electron-phonon coupling in hybrid lead halide perovskites10.1038/ncomms11755 ↗
22. Charge-carrier dynamics in organic-inorganic metal halide perovskites10.1146/annurev-physchem-040215-112222 ↗
23. Origin of unusual bandgap shift and dual emission in organic-inorganic lead halide perovskites10.1126/sciadv.1601156 ↗
24. Simultaneous long-persistent blue luminescence and high quantum yield within 2D organic–Metal halide perovskite micro/nanosheets10.1002/anie.201909760 ↗
25. Efficient thermally activated delayed fluorescence from all-inorganic cesium zirconium halide perovskite nanocrystals10.1002/anie.202009101 ↗
26. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set10.1103/PhysRevB.54.11169 ↗
27. Generalized gradient approximation made simple10.1103/PhysRevLett.77.3865 ↗
28. Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data10.1103/PhysRevLett.102.073005 ↗
29. High photoluminescence quantum yield in band gap tunable bromide containing mixed halide perovskites10.1021/acs.nanolett.5b04884 ↗
30. Excitation-power dependence ofthe near-band-edge photoluminescence of semiconductors10.1103/PhysRevB.45.8989 ↗
31. Equal footing of thermal expansion and electron−phonon interaction in the temperature dependence of lead halide perovskite band gaps10.1021/acs.jpclett.9b00876 ↗
32. Intrinsic white-light emission from layered hybrid perovskites10.1021/ja507086b ↗
33. Structural phase transition causing anomalous photoluminescence behavior in perovskite (C6H11NH3)2[PbI4]10.1063/1.4936776 ↗
34. Formation of long-lived color centers for broadband visible light emission in low-dimensional layered perovskites10.1021/jacs.7b10223 ↗
35. Broadband extrinsic self-trapped exciton emission in Sn-doped 2D lead-halide perovskites10.1002/adma.201806385 ↗
36. Temperature-dependent photoluminescence of PbS quantum dots in glass: evidence of exciton state splitting and carrier trapping10.1103/PhysRevB.82.125320 ↗
37. Direct–indirect character of the bandgap inmethylammounium lead iodide perovskite10.1038/nmat4765 ↗
38. Defects in perovskite-halides and their effects in solar cells10.1038/nenergy.2016.149 ↗
39. Giant bandgap renormalization and exciton–phononScattering in perovskite nanocrystals10.1002/adom.201700231 ↗
40. Multi-excitonic complexes in single InGaN quantum dots10.1063/1.1751214 ↗
41. Luminescence linewidths of excitons in GaAs quantum wells below 150 K10.1103/PhysRevB.33.5512 ↗
42. High-efficiency luminescence and robust thermal quenching resistance in organic–Inorganic hybrid indium-based metal halides10.1002/adom.202402409 ↗
43. High photoluminescence efficiency and optically pumped lasing in solution-processed mixed halide perovskite semiconductors10.1021/jz5005285 ↗
44. Interpreting time-resolved photoluminescence of perovskite materials10.1039/D0CP04950F ↗
45. Temperature-dependent photoluminescence spectra and decay dynamics of MAPbBr3 and MAPbI3 thin films
46. Exciton localization in solution-processed organolead trihalide perovskites10.1038/ncomms10896 ↗
47. Long-lived dark exciton emission in Mn-doped CsPbCl3 perovskite nanocrystals10.1021/acs.jpcc.8b12035 ↗
48. Electron‑hole excitations and optical spectra from first principles10.1103/PhysRevB.62.4927 ↗
49. Anharmonicity-driven Rashba cohelical excitons break quantum efficiency limitation10.1002/adma.202005400 ↗
50. Electron‑energy‑loss spectra and the structural stability of nickel oxide: an LSDA+ U study10.1103/PhysRevB.57.1505 ↗
51. Impacts of carrier capture processes in the thermal quenching of photoluminescence in Al–N co-doped SiC10.1007/s00340-019-7279-8 ↗