Mn<sup>2+</sup>‐Based Luminescent Metal Halides: Syntheses, Properties, and Applications

Liang, Dehai; Xiao, Hongbin; Cai, Wensi; Lu, Shirong; Zhao, Shuangyi; Zang, Zhigang; Xie, Lei

doi:10.1002/adom.202202997

Cited by 45 publications

(11 citation statements)

References 168 publications

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“…Sufficiently long Mn–Mn distances in 0D metal halides enable spontaneous emission from all Mn 2+ centers, resulting in near-unity PLQY. , For manganese halide emitters, their photoluminescence (PL) strongly depends on the crystal field environment. Tetrahedrally coordinated Mn 2+ emits narrow-band green emission, while octahedrally coordinated Mn 2+ emits broad-band orange or red emission. ,− Figure a displays the PL and PL excitation (PLE) spectra of (BPTP) 2 MnBr 4 (the inset shows a photograph of the powders under a 365 nm UV lamp) at room temperature (RT). The PLE spectrum consists of five bands corresponding to the electron transitions 6 A 1 → 4 T 1 ( 4 F) (287 nm), 6 A 1 → 4 E( 4 D) (364 nm), 6 A 1 → 4 T 2 ( 4 D) (378 nm), 6 A 1 → 4 A 1 ( 4 G) (439 nm), 4 E( 4 G) (453 nm), and 6 A 1 → 4 T 2 (G) (468 nm) of Mn 2+ .…”

Section: Resultsmentioning

confidence: 99%

High-Efficiency Narrow-Band Green-Emitting Manganese(II) Halide for Multifunctional Applications

Zhang,

Xie,

Liu

et al. 2023

ACS Appl. Mater. Interfaces

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Zero-dimensional (0D) Mn2+-based metal halides used as luminescent materials and scintillators have become a research hotspot in the field of photoelectric materials and devices due to their unique composition, structure, and fluorescence properties. It is of great value to explore new Mn2+-based metal halides to achieve multifunctional applications. Herein, the novel 0D Mn2+-based metal halide single crystal (BPTP)2MnBr4 is synthesized by a simple solvent–antisolvent recrystallization method. Under excitation at 468 nm, the (BPTP)2MnBr4 single crystal shows a pronounced narrow-band green luminescence centered at 515 nm derived from the d–d transition of the Mn2+ ion. This emission has a relatively narrow full width at half maximum of 43 nm and a high photoluminescence quantum yield (PLQY) of 82%. In addition, (BPTP)2MnBr4 exhibits good thermal stability at 393 K with a retention of 79% of the initial photoluminescence intensity at 298 K. Benefiting from its strong blue light excitation, high PLQY, and good thermal stability, we manufacture an ideal white light-emitting diode (LED) device using a 460 nm blue LED chip, green-emitting (BPTP)2MnBr4, and commercial K2SiF6:Mn4+ red phosphor. Under 20 mA drive current, the LED shows a high luminous efficiency of 112 lm/W and a wide color gamut of 110.8%, according to the National Television System Committee standard. In addition, (BPTP)2MnBr4 crystals show a strong X-ray absorption. Based on the commercial Lu3Al5O12:Ce3+ scintillator, the calculated light yield of (BPTP)2MnBr4 reaches up to about 136,000 photons/MeV and the detection limit reaches 0.282 μGyair s–1. Additionally, a melt quenching approach is used to construct a (BPTP)2MnBr4 clear glass scintillation screen, realizing a spatial resolution of 10.1 lp/mm. The proper performances of (BPTP)2MnBr4 as phosphor-converted LED materials and the X-ray scintillator with the addition of eco-friendly, low-cost solution processability make 0D Mn2+-based metal halides potential luminescent materials for multifunctional applications.

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Section: Resultsmentioning

confidence: 99%

High-Efficiency Narrow-Band Green-Emitting Manganese(II) Halide for Multifunctional Applications

Zhang,

Xie,

Liu

et al. 2023

ACS Appl. Mater. Interfaces

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“…In addition, the electronic transition of protonated DMAP (i.e., DMAPH) is also observed below 300 nm, particularly at 295 and 265 nm . The photoluminescence (PL) spectra of the three Mn(II) halide samples are depicted in Figure c, and the green PL from tetrahedral Mn(II) halides is well-known in the literature . The halide has only minor influence on the position of the PL peak as the emission arises from the d–d ( 4 T 1 → 6 A 1 ) transition of Mn(II) (Figures b and c).…”

mentioning

confidence: 87%

“…35 The photoluminescence (PL) spectra of the three Mn(II) halide samples are depicted in Figure 3c, and the green PL from tetrahedral Mn(II) halides is well-known in the literature. 36 The halide has only minor influence on the position of the PL peak as the emission arises from the d−d ( 4 T 1 → 6 A 1 ) transition of Mn(II) (Figures 3b and 3c). The Cl-, Br-, and I-based samples exhibit PL peaks at ∼550, 525, and 545 nm, respectively.…”

mentioning

confidence: 99%

Zn(II) Alloying Improves the Luminescence Efficiency of Hybrid Tetrahedral Mn(II) Halides ((DMAPH)₂MnX₄; X = Cl, Br, and I) to Near-Unity

Babu

Samanta

Prasanthkumar

et al. 2023

ACS Materials Lett.

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Zero-dimensional (0D) tetrahedral Mn(II) halides (MnX4 2– (X = Cl, Br, I)) have emerged as solid-state green emitters with high photoluminescence quantum yield (PLQY). However, their PLQYs are significantly dependent on the environment surrounding the Mn(II), i.e., the organic cation and the halide. Although the tetrahedral Mn(II) bromide is highly emissive, Mn(II) iodide exhibits relatively low PLQY. Herein, we report the preparation of organic–inorganic hybrid tetrahedral Mn(II) halides (Cl, Br, and I) using the organic cation protonated 4-dimethylaminopyridine ((DMAPH)+), and they all exhibit bright green luminescence with high PLQY (∼76%–80%), regardless of the halide ion. Surprisingly, DMAPH undergoes N-demethylation exclusively in the case of tetrahedral Mn(II) iodide. Furthermore, we find that the controlled Zn2+-doping/alloying in the Mn(II) halide lattice improves the PLQY to near-unity (∼88%–94%) and is stable for more than 60 days. The increase of the excited state decay time in time-resolved PL lifetime measurements revealed that the improved luminescence is due to reduced Mn(II)–Mn(II) interactions of the lattice upon replacing some of the Mn(II) with Zn(II). This is further supported by the Zn-alloying-induced hyperfine splitting of Mn(II) ions observed in the electron paramagnetic resonance (EPR) measurements. However, excess alloying reduces PLQY due to the decrease in the tetrahedral Mn(II) concentration in the lattice. These results demonstrate the fabrication of hybrid Mn(II) halide (Cl, Br, and I) single crystals with near-unity PLQY and provide design strategies to improve their PLQY by selective organic cations and doping/alloying.

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“…Therefore, it is important and necessary to develop economical and environmentally friendly synthetic methods and simplify the synthetic process pathway. 13,14 In this work, manganese ion-doped M 2 CdCl 4 layered hybrid pervoskite materials were synthesized by a facile mechanochemical method, focusing on the optical properties of manganese ion-doped MA 2 showed orange emission (605 nm) under 254 nm excitation, which originated from the Mn 2+ transition of 4 T 1 -6 A 1 , with a quantum efficiency as high as 87% in the case of 20% Mn doping. In addition, MA 2 CdCl 4 :20%Mn 2+ @PVA flexible films were prepared, which also emitted bright orange-red light under a 254 UV lamp.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Meanwhile, as efficient luminescent dopants, Mn 2+ ions are widely used to modulate the optical and magnetic properties of doped semiconductors. Of these, Mn 2+ -doped metal halide perovskites have additional photoluminescence properties, enhanced stability, tunable band gap, and improved optoelectronic device performance. , For example, the Mn 2+ -doped 2D perovskite (But) 2 PbBr 4 (But = C 4 H 9 NH 3 ) shows enhanced energy transfer efficiency from the strongly bound excitons of the host material to the d electrons of Mn 2+ ions, which is due to a spin-forbidden internal transition ( 4 T 1 - 6 A 1 ) with a high quantum yield of 37%. The material can be used as a color-converting phosphor material and energy downshift coating for perovskite solar cells .…”

Section: Introductionmentioning

confidence: 99%

Mn-Doped M₂CdCl₄ (M = CH₃NH₃⁺, C₂H₈N⁺, and C₃H₁₀N⁺) Layered Hybrid Perovskite and Its Flexible Film Based on Simple Mechanochemical Synthesis

Xu,

Dong,

et al. 2024

Inorg. Chem.

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Layered hybrid perovskites show significant advantages in the field of optoelectronics. However, the low quantum efficiency and complex preparation methods limit their applications. In this work, we developed a series of perovskite powders with a twodimensional (2D) layered structure of organic−inorganic hybrid metal halides M 2 CdCl 4 :x%Mn (M = CH 3 NH 3 + , C 2 H 8 N + , C 3 H 10 N + ) via facile mechanochemical methods. The prepared manganese Mn-doped MA 2 CdCl 4 produces orange emission at 605 nm under both 254 and 420 nm excitation, which originates from a dual excitation channel competition mechanism, and its excitation channel could be changed with the increase of Mn 2+ ion concentration. Typically, MA 2 CdCl 4 :20%Mn powder exhibits high photoluminescence quantum yield (PLQY) close to 90% at 605 nm due to the organic amine ions enlarging the Mn−Mn interlayer distances. In addition, we prepared MA 2 CdCl 4 :x%Mn@PVA flexible films, which also exhibit good luminescence at 254 nm excitation and were unexpectedly found to have a better response to Cs + , which could be a candidate for anticounterfeiting applications.

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Mn²⁺‐Based Luminescent Metal Halides: Syntheses, Properties, and Applications

Cited by 45 publications

References 168 publications

High-Efficiency Narrow-Band Green-Emitting Manganese(II) Halide for Multifunctional Applications

High-Efficiency Narrow-Band Green-Emitting Manganese(II) Halide for Multifunctional Applications

Zn(II) Alloying Improves the Luminescence Efficiency of Hybrid Tetrahedral Mn(II) Halides ((DMAPH)₂MnX₄; X = Cl, Br, and I) to Near-Unity

Mn-Doped M₂CdCl₄ (M = CH₃NH₃⁺, C₂H₈N⁺, and C₃H₁₀N⁺) Layered Hybrid Perovskite and Its Flexible Film Based on Simple Mechanochemical Synthesis

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Mn2+‐Based Luminescent Metal Halides: Syntheses, Properties, and Applications

Cited by 45 publications

References 168 publications

High-Efficiency Narrow-Band Green-Emitting Manganese(II) Halide for Multifunctional Applications

High-Efficiency Narrow-Band Green-Emitting Manganese(II) Halide for Multifunctional Applications

Zn(II) Alloying Improves the Luminescence Efficiency of Hybrid Tetrahedral Mn(II) Halides ((DMAPH)2MnX4; X = Cl, Br, and I) to Near-Unity

Mn-Doped M2CdCl4 (M = CH3NH3+, C2H8N+, and C3H10N+) Layered Hybrid Perovskite and Its Flexible Film Based on Simple Mechanochemical Synthesis

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Product

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Mn²⁺‐Based Luminescent Metal Halides: Syntheses, Properties, and Applications

Zn(II) Alloying Improves the Luminescence Efficiency of Hybrid Tetrahedral Mn(II) Halides ((DMAPH)₂MnX₄; X = Cl, Br, and I) to Near-Unity

Mn-Doped M₂CdCl₄ (M = CH₃NH₃⁺, C₂H₈N⁺, and C₃H₁₀N⁺) Layered Hybrid Perovskite and Its Flexible Film Based on Simple Mechanochemical Synthesis