Luminescence properties of Mn2+ in KMgF3 and KZnF3 perovskite crystals

Rodrı́guez, F.; Riesen, Hans; Güdel, Hans U.

doi:10.1016/0022-2313(91)90024-p

Cited by 43 publications

(44 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Due to the localized character of active electrons in both ground and excited states such modes involve basically the distortion of ligands. Experimental evidence on these modes can sometimes be obtained from low-temperature emission or absorption spectra [28,8]. In the non-radiative decay process it has been shown that energy is transferred in a first step to local modes and later to lattice modes [29].…”

Section: Introductionmentioning

confidence: 99%

“…The present work is aimed at exploring the local structure and optical and vibrational properties associated with Mn 2+ impurities in cubic AMF 3 fluoroperovskites [4][5][6][7][8][9][10][11][12][13][14] by means of a recent method for improving the embedding in the realm of the density functional theory (DFT) [15][16][17]. In this method the electronic density of a finite cluster is divided into two regions.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Optical and vibrational properties of MnF₆⁴⁻complexes in cubic fluoroperovskites: insight through embedding calculations using Kohn–Sham equations with constrained electron density

Garcı́a-Lastra

Wesołowski

Barriuso

et al. 2006

J. Phys.: Condens. Matter

View full text Add to dashboard Cite

The local structure and optical and vibrational properties associated with Mn 2+ -doped cubic AMF 3 (A = K, Rb; M = Mg, Zn, Cd) fluoroperovskites are studied by means of embedding calculations using Kohn-Sham equations with constrained electron density. It is shown that while an electronic parameter like 10Dq essentially depends on the Mn 2+ -F − distance, the local vibration frequencies ω i (i = a 1g , e g modes) are dominated by the interaction between F − ligands and nearest M 2+ ions lying along bonding directions. The high ω a values observed for KMgF 3 :Mn 2+ and KZnF 3 :Mn 2+ , the huge variations of ω e and ω a frequencies when the host lattice is changed, as well as the increase of Huang-Rhys factors and the Stokes shift following the host lattice parameter, are shown to be related to this elastic coupling of the MnF 4− 6 complex to the rest of the host lattice. The present results support the conclusion that the Stokes shift is determined by the interaction of the excited 4 T 1g state with a 1g and e g local modes while the coupling with the t 2g shear mode is not relevant. The variations of local vibrational frequencies and the Stokes shift induced by a hydrostatic pressure on a given system are shown to be rather different to those produced by the chemical pressure associated with distinct host lattices.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Optical and vibrational properties of MnF₆⁴⁻complexes in cubic fluoroperovskites: insight through embedding calculations using Kohn–Sham equations with constrained electron density

Garcı́a-Lastra

Wesołowski

Barriuso

et al. 2006

J. Phys.: Condens. Matter

View full text Add to dashboard Cite

show abstract

“…Experimental (calculated) energy (eV) Experimental (calculated) energy (eV) 6 also observed for the corresponding first excitation transition 6 A 1g (S) → 4 T 1g (G) in the same temperature range according to expectations from the Tanabe-Sugano diagram for a d 5 ion on the basis of a 10Dq reduction. However, an opposite behaviour is observed in concentrated systems such as NH 4 MnCl 3 (figures 2 and 3).…”

Section: Cf Band Assignmentmentioning

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%

See 1 more Smart Citation

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

Hernández¹,

Rodrı́guez

2003

J. Phys.: Condens. Matter

View full text Add to dashboard Cite

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.

show abstract

Photolumineszenz von Mn²⁺ in dem Borosulfat Zn[B₂(SO₄)₄] : Mn²⁺ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden

Träger,

Pasqualini,

Huppertz

et al. 2023

Angewandte Chemie

View full text Add to dashboard Cite

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.

show abstract

Luminescence properties of Mn2+ in KMgF3 and KZnF3 perovskite crystals

Cited by 43 publications

References 35 publications

Optical and vibrational properties of MnF₆⁴⁻complexes in cubic fluoroperovskites: insight through embedding calculations using Kohn–Sham equations with constrained electron density

Optical and vibrational properties of MnF₆⁴⁻complexes in cubic fluoroperovskites: insight through embedding calculations using Kohn–Sham equations with constrained electron density

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

Photolumineszenz von Mn²⁺ in dem Borosulfat Zn[B₂(SO₄)₄] : Mn²⁺ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden

Contact Info

Product

Resources

About

Luminescence properties of Mn2+ in KMgF3 and KZnF3 perovskite crystals

Cited by 43 publications

References 35 publications

Optical and vibrational properties of MnF64−complexes in cubic fluoroperovskites: insight through embedding calculations using Kohn–Sham equations with constrained electron density

Optical and vibrational properties of MnF64−complexes in cubic fluoroperovskites: insight through embedding calculations using Kohn–Sham equations with constrained electron density

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

Photolumineszenz von Mn2+ in dem Borosulfat Zn[B2(SO4)4] : Mn2+ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden

Contact Info

Product

Resources

About

Optical and vibrational properties of MnF₆⁴⁻complexes in cubic fluoroperovskites: insight through embedding calculations using Kohn–Sham equations with constrained electron density

Optical and vibrational properties of MnF₆⁴⁻complexes in cubic fluoroperovskites: insight through embedding calculations using Kohn–Sham equations with constrained electron density

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

Photolumineszenz von Mn²⁺ in dem Borosulfat Zn[B₂(SO₄)₄] : Mn²⁺ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden