Optical properties and local structure of MnCl4-6in ABCl3:Mn2+

Lucas, M.C. Marco de; Rodríguez, F.; Prieto, C.; Moreno, M.; Güdel, Hans‐Ulrich

doi:10.1080/10420159508229814

Cited by 8 publications

(10 citation statements)

References 8 publications

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“…This goes in line with examples of octahedrally coordinated Mn 2 + ions in inorganic host compounds such as KMgF 3 : 0.5 % Mn 2 + (τ = 100 ms at room temperature) or selected perovskite-derived chlorides AMCl 3 : Mn 2 + (A = K, Rb, Cs; M = Mg, Ca, Sr) (τ � 20 ms at room temperature) with slightly distorted octahedral doping sites for the Mn 2 + ions. [66,67] In contrast, the FWHM of Mn 2 + -related emission band in Zn[B 2 (SO 4 ) 4 ] : Mn 2 + is comparably small and in a similar order of magnitude compared to reported values for the FWHMs of emission bands for tetrahedrally coordinated Mn 2 + (in halides: 1400 cm À 1 -2000 cm À 1 at room temperature). [64] Moreover, the emission wavelength is comparably short for octahedrally coordinated Mn 2 + , which usually extends beyond 600 nm (e.g.…”

Section: Methodssupporting

confidence: 60%

“…[64] Moreover, the emission wavelength is comparably short for octahedrally coordinated Mn 2 + , which usually extends beyond 600 nm (e.g. MgSiO 3 : Mn 2 + : λ em = 661 nm, [32] CsMnBr 3 : λ em = 680 nm, [68] Ba 2 Ca(BO 3 ) 2 : Mn 2 + : λ em = 630 nm [33] ) and only becomes orange in weak octahedral ligand fields (AMCl 3 : Mn 2 + : λ em � 560 nm, [67] CsPbCl 3 : Mn 2 + : λ em = 586 nm, [69] MgF 2 : Mn 2 + : λ em = 586 nm [70] ). Altogether, these properties demonstrate that the Mn 2 + ions are octahedrally coordinated in Zn[B 2 (SO 4 ) 4 ] : Mn 2 + but with only weakly coordinating ligands.…”

Section: Methodsmentioning

confidence: 99%

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Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands

Träger,

Pasqualini,

Huppertz

et al. 2023

Angew Chem Int Ed

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The impact of the surrounding ligand field is successfully exploited in the case of Eu2+ to tune the emission characteristics of inorganic photoactive materials with potential application in e.g., phosphor‐converted white light‐emitting diodes (pc‐wLEDs). However, the photoluminescence of Mn2+ related to intraconfigurational 3d5‐3d5 transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal‐ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer‐like borosulfate ligand in the Mn(II)‐containing solid solutions Zn1‐xMnx[B2(SO4)4] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B2(SO4)4]:Mn2+ shows orange narrow‐band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn2+ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn‐O bonds with values close to the Racah parameters of the free Mn2+ ion. Overall, this strategy demonstrates that electronic control of the metal‐ligand bond can be a tool to make Mn2+ a potent alternative emitter to Eu2+ for inorganic phosphors.

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Section: Methodssupporting

confidence: 60%

Section: Methodsmentioning

confidence: 99%

Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands

Träger,

Pasqualini,

Huppertz

et al. 2023

Angew Chem Int Ed

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“…54 In contrast, the Mn 2+ :CsPb(Cl 1−x Br x ) 3 NCs show biexponential PL decay with components of 859 μs and 2.3 ms. We note that the Mn 2+ PLQY increases after this anion exchange, possibly due to reduced exciton trapping prior to energy capture by Mn 2+ . Shorter Mn 2+ PL lifetimes are typically observed in bromide compared to chloride lattices (e.g., 54.9 ms in CsCaCl 3 vs 23 ms in CsMgBr 3 , respectively, at 10 K 66,67 ), attributable to the increased spin−orbit coupling of the heavier halides, but this effect cannot explain the biexponential decay or the short time constant observed in Figure 5. Moreover, the hyperfine splittings in the EPR spectra of these NCs (Figure 3) indicate that Mn 2+ remains essentially exclusively coordinated by chloride anions, also ruling out an effect from bromide spin−orbit coupling.…”

Section: ■ Results and Analysismentioning

confidence: 86%

Spinodal Decomposition During Anion Exchange in Colloidal Mn²⁺-Doped CsPbX₃ (X = Cl, Br) Perovskite Nanocrystals

et al. 2019

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Manganese(II)-doped cesium–lead–chloride (Mn2+:CsPbCl3) perovskite nanocrystals have recently been developed as promising luminescent materials and attractive candidates for white-light generation. One approach to tuning the luminescence of these materials has involved anion exchange to incorporate Br–, but the effects of anion exchange on Mn2+ speciation in doped metal-halide perovskites is not well understood at a microscopic level. Here, we use a combination of X-band electron paramagnetic resonance (EPR) and photoluminescence spectroscopies to monitor the Mn2+ dopants in Mn2+:CsPbCl3 nanocrystals during Cl– → Br– anion exchange. Analytical measurements show that the nanocrystals retain their Mn2+ over the course of Cl– → Br– anion exchange and they continue to show strong Mn2+ d–d luminescence but, surprisingly, the Mn2+ EPR intensities all but vanish. Further results suggest that Mn2+ ions migrate during anion exchange to form clusters that are still luminescent but show no EPR signal due to antiferromagnetic superexchange coupling. Monte Carlo simulation and analysis of the Mn2+:CsPb(Cl1–x Br x )3 lattice at various halide compositions (x) bolsters this interpretation by indicating a propensity for Mn2+–Cl– units to cluster as the Br– content increases, increasing the probability of the nearest-neighbor Mn2+–Mn2+ interactions. The driving force for this clustering is retention of the stronger Mn–Cl bonds compared to Mn–Br bonds. In addition, modeling predicts spinodal decomposition to form Mn2+-enriched domains even at the end point compositions of x = 0 and 1, with Mn2+ ordering in next-nearest-neighbor positions driven by Coulomb interactions and lattice-strain minimization. These results have important implications for both fundamental studies and applications of doped and alloyed metal-halide perovskites.

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“…It must be noted that while the thermal shift undergone by the OA or excitation bands is quite similar [7,9], the PL band shift is different at low temperatures. In Mn 2+ -doped systems such as KMgCl 3 :Mn 2+ [8], the PL band experiences a continuous blueshift of 56 meV with increasing temperature in the 10-300 K range. A blue-shift of 14 meV is The experimental energies were taken from the OA spectra at T = 290 K (figure 1) and 10 K (not shown).…”

Section: Optical Absorption and Pl Spectra; Crystal-field Analysismentioning

confidence: 99%

“…In isolated Mn 2+ -doped systems, both the excitation or the optical absorption (OA) and the associated PL rely to a great extent on the crystal field (CF) at the Mn 2+ site, i.e. the number and nature of the ligands, the local symmetry, and the corresponding bond lengths [4][5][6][7][8][9]. In concentrated materials, however, the proximity of Mn 2+ 2+ ion, as in isolated impurities, but can be either in a different Mn 2+ ion (intrinsic PL), in a perturbed Mn 2+ trap (extrinsic PL), or in another impurity, which can be either PL (activator) or non-PL (killer).…”

Section: Introductionmentioning

confidence: 99%

Intrinsic and extrinsic photoluminescence in the NH₄MnCl₃cubic perovskite: a spectroscopic study

Hernández¹,

Rodrı́guez

2003

J. Phys.: Condens. Matter

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This work investigates the photoluminescence (PL) properties of the cubic chloroperovskite NH 4 MnCl 3 . Like in most concentrated materials, the Mn 2+ PL which is located at 2.10 eV at T = 10 K strongly depends on the temperature. Optical absorption (OA), emission, and excitation spectroscopy, as well as lifetime measurements, performed on NH 4 MnCl 3 indicate that the PL is mainly intrinsic at T = 10 K and consists of a broad band located at 2.10 eV. Above this temperature, the PL gradually transforms to extrinsic PL due to exciton migration and subsequent trapping. Further temperature increase above 100 K yields transfer to killers of excitation which are responsible for the PL quenching, and hence the absence of PL at ambient conditions. The exciton traps are identified with perturbed Mn 2+ sites with the effective activation energy of 52 meV, whilst the activation energy for energy transfer is 47 meV. The existence of these traps has been directly revealed by time-resolved spectroscopy. The detected intrinsic and extrinsic PL bands are displaced by 6 meV, which coincides with the activation energy difference between pure Mn 2+ and trap Mn 2+ , as derived from temperature dependence studies of the lifetime τ (T ). Interestingly, a PL band at 1.82 eV is observed above 60 K. This band, which was initially associated with deeper excitation traps, actually corresponds to precipitates of MnCl 2 inside NH 4 MnCl 3 . The correlation analysis performed on NH 4 MnCl 3 using OA, PL, and lifetime data provides an estimate of the precipitate concentration of 0.3 mol %. The presence of two separated Mn 2+ PL bands at different temperatures is a rather common phenomenon in concentrated materials such as AMnX 3 (A = NH 4 , Rb; X = Cl, F), and has been interpreted in terms of exciton transfer to deeper traps. The present finding stresses the relevance of an adequate structural characterization in dealing with PL in concentrated materials.

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Optical properties and local structure of MnCl^4-₆in ABCl₃:Mn²⁺

Cited by 8 publications

References 8 publications

Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands

Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands

Spinodal Decomposition During Anion Exchange in Colloidal Mn²⁺-Doped CsPbX₃ (X = Cl, Br) Perovskite Nanocrystals

Intrinsic and extrinsic photoluminescence in the NH₄MnCl₃cubic perovskite: a spectroscopic study

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Optical properties and local structure of MnCl4-6in ABCl3:Mn2+

Cited by 8 publications

References 8 publications

Photoluminescence of Mn2+ in the Borosulfate Zn[B2(SO4)4] : Mn2+—A Tool to Detect Weak Coordination Behavior of Ligands

Photoluminescence of Mn2+ in the Borosulfate Zn[B2(SO4)4] : Mn2+—A Tool to Detect Weak Coordination Behavior of Ligands

Spinodal Decomposition During Anion Exchange in Colloidal Mn2+-Doped CsPbX3 (X = Cl, Br) Perovskite Nanocrystals

Intrinsic and extrinsic photoluminescence in the NH4MnCl3cubic perovskite: a spectroscopic study

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Optical properties and local structure of MnCl^4-₆in ABCl₃:Mn²⁺

Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands

Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands

Spinodal Decomposition During Anion Exchange in Colloidal Mn²⁺-Doped CsPbX₃ (X = Cl, Br) Perovskite Nanocrystals

Intrinsic and extrinsic photoluminescence in the NH₄MnCl₃cubic perovskite: a spectroscopic study