Optical properties of the MnCl 4- 6 complex formed in ABCl 3 : Mn 2+ pseudoperovskite crystals: Influence of the chemical pressure

Lucas, M.C. Marco de; ́guez, F. Rodri; ̈del, H.U. Gu; Furer, N.

doi:10.1016/0022-2313(94)90222-4

Cited by 24 publications

(12 citation statements)

References 9 publications

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“…Mn 2+ can emit in the green to deep red spectral region depending on the local coordination. The Tanabe‒Sugano diagram for ions with the 3d5 configuration shows that the position of the emitting lowest energy excited state 4 T 1 shifts to lower energies as the crystal field splitting increases3637. In CsPbCl 3 the Mn 2+ will substitute on the octahedrally coordinated Pb 2+ site (the Cs + ‒site is too large).…”

Section: Resultsmentioning

confidence: 99%

“…However, octahedral coordination gives rise to a large crystal field splitting and even for weak ligands orange‒red emission is typically observed for Mn 2+ . For example, in CdCl 2 and a variety of chloride perovskites where Mn 2+ is in an octahedral Cl - coordination, the emission maximum of the 4 T 1 ‒ 6 A 1 emission of Mn 2+ has been observed at wavelengths varying between 570 nm and 630 nm3637. The presently observed emission maximum at 600 nm is in excellent agreement with this range and provides further support for the assignment of the orange emission to 4 T 1 ‒ 6 A 1 emission of Mn 2+ in an octahedral Cl - coordination.…”

Section: Resultsmentioning

confidence: 99%

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Luminescent manganese-doped CsPbCl3 perovskite quantum dots

Lin

Wang

et al. 2017

Sci Rep

102

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Nanocrystalline cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I) form an exciting new class of semiconductor materials showing quantum confinement. The emission color can be tuned over the full visible spectral region making them promising for light‒emitting applications. Further control over the optical and magnetic properties of quantum dots (QDs) can be achieved through doping of transition metal (TM) ions such as Mn2+ or Co2+. Here we demonstrate how, following QD synthesis in the presence of a Mn‒precursor, dropwise addition of silicon tetrachloride (SiCl4) to the QDs in toluene results in the formation of Mn‒doped CsPbCl3 QDs showing bright orange Mn2+ emission around 600 nm. Evidence for successful doping is provided by excitation spectra of the Mn2+ emission, with all features of the CsPbCl3 QD absorption spectrum and a decrease of the 410 nm excitonic emission life time with increasing Mn‒concentration, giving evidence for enhanced exciton to Mn2+ energy transfer. As a doping mechanism we propose a combination of surface etching and reconstruction and diffusion doping. The presently reported approach provides a promising avenue for doping TM ions into perovskites QDs enabling a wider control over optical and magnetic properties for this new class of QDs.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Luminescent manganese-doped CsPbCl3 perovskite quantum dots

Lin

Wang

et al. 2017

Sci Rep

102

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“…This is noteworthy, since no evidence of any increase of the Stokes shift with increasing pressure has been reported so far. In contrast, a decrease of the Stokes shift was observed upon volume reduction in MnF 4− 6 through the ABF 3 :Mn 2+ perovskite compound series [30,31], and in MnCl 4− 6 through the ABCl 3 :Mn 2+ series [32,33], whose chemical pressure effect provides metal-ligand distance variations of 0.27 Å (from CsCaF 3 to KMgF 3 ) and 0.33 Å (from SrCaCl 3 to KMgCl 3 ) through the series, respectively [31,33]. A similar behaviour has also been observed in Cr 3+ -doped chloroelpasolites [34][35][36].…”

Section: Discussionmentioning

confidence: 97%

Optical spectroscopy of Al₂O₃:Ti³⁺single crystal under hydrostatic pressure. The influence on the Jahn-Teller coupling

Garcı́a-Revilla

Rodrı́guez

Valiente

et al. 2001

J. Phys.: Condens. Matter

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This work investigates the effect of hydrostatic pressure on the excitation and emission spectra, as well as on the lifetime, of Al 2 O 3 :Ti 3+ at room temperature. The aim is to establish correlations between the pressure-induced band shifts and the corresponding local structural changes undergone by the TiO 6 complex. A blue-shift of 8.52 and 6.86 cm −1 kbar −1 was found for the lower (E 1) and upper (E 2) energy components of the excitation band at 17 760 and 20 500 cm −1 , respectively, and blue-shifts of 5.93 and 5.40 cm −1 kbar −1 for the two overlapping bands of the emission spectrum located at 12 680 and 14 210 cm −1. We explain these results on the basis of a reduction of the TiO 6 Jahn-Teller distortion upon increasing the pressure. In contrast, the increase of the overall Stokes shift, which is mainly associated with electron-vibration coupling to the totally symmetric a 1g vibration, is explained by the increase of the excited-state stabilization energy, S a 1gh ω a 1g , with increasing pressure. The luminescence lifetime is also found to be pressure dependent, varying from 2.6 µs at ambient conditions to 3.2 µs at 80 kbar. This increase is caused by a diminution of the transition oscillator strength that is related to the oddvibration assistance mechanism. The softening of the transition mechanism is interpreted in terms of the blue-shift experienced by the O 2− → Ti 3+ chargetransfer transition energy upon increasing the pressure.

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“…Δ plays a key role in relevant physical phenomena like color, magnetism, or conductivity. Examples of this behavior are spin crossover phenomena involving either excited states , or the ground state, − which affect the photoluminescence properties or the TM-ion magnetic moment, respectively, or metallization processes in TM oxides. − The Δ( R ) value results crucial to predict critical phenomena associated with the spin state of iron in magnesiowüstite (Mg,Fe)O, and other Fe 2+ /Fe 3+ containing silicates, under the pressure and temperature conditions of the Earth’s interior, , pressure-induced Mott-type insulator–metal transition in TM-oxides, − or high-spin to low-spin transitions induced by pressure or temperature. , In addition, Δ can be an efficient probe to determine impurity-ligand distance in diluted systems through optical spectroscopy, once the relation between Δ and R is established. − Due to the lack of experimental studies, such models frequently assume a R– (or V −) dependence of Δ as R –5 (or V –5/3 ) as given by crystal-field theory (CFT). ,− The situation is even more challenging if different TM coordination geometries are involved, i.e., tetrahedral, octahedral, hexahedral, or dodecahedral coordinations . Our study solves out this problem as it provides precise Δ( R ) data in two cobalt fluoride archetypes, enabling verification of CFT predictions in two different Co 2+ coordinations.…”

Section: Introductionmentioning

confidence: 99%

Crystal-Field Theory Validity Through Local (and Bulk) Compressibilities in CoF₂ and KCoF₃

et al. 2016

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Crystal field theory (CFT) predicts that crystal field acting on an transition-metal (TM) ion complex of cubic symmetry varies as R –5, where R is the TM-ligand distance. Yet simple and old-fashioned, CFT is used extensively since it provides excellent results in most TM ion-bearing systems, although no direct and thorough validation has been provided so far. Here we investigate the evolution of the electronic and crystal structures of two archetypal Co2+ compounds by optical absorption and X-ray diffraction under high pressure. Both the electronic excited states and crystal-field splitting, Δ = 10Dq, between 3d(e g + t 2g) orbitals of Co2+ as a function of volume, V, and Co–F bond length, R, in 6-fold octahedral (oct) and 8-fold hexahedral (cub) coordination in compressed CoF2 have been analyzed. We demonstrated that Δ scales with R in both coordinations as R –n , with n close to 5 in agreement with CFT predictions. The pressure-induced rutile to fluorite structural phase transition at 15 GPa in CoF2 is associated with an increase of R due to the 6 → 8 coordination change. The experimental Δ(oct)/ Δ(cub) = −1.10 for the same R-values is close to −9/8, in agreement with CFT. A similar R-dependence is observed in KCoF3 in which the CoF6 O h coordination is maintained in the 0–80 GPa pressure range.

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Optical properties of the MnCl 4- 6 complex formed in ABCl 3 : Mn 2+ pseudoperovskite crystals: Influence of the chemical pressure

Cited by 24 publications

References 9 publications

Luminescent manganese-doped CsPbCl3 perovskite quantum dots

Luminescent manganese-doped CsPbCl3 perovskite quantum dots

Optical spectroscopy of Al₂O₃:Ti³⁺single crystal under hydrostatic pressure. The influence on the Jahn-Teller coupling

Crystal-Field Theory Validity Through Local (and Bulk) Compressibilities in CoF₂ and KCoF₃

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Optical properties of the MnCl 4- 6 complex formed in ABCl 3 : Mn 2+ pseudoperovskite crystals: Influence of the chemical pressure

Cited by 24 publications

References 9 publications

Luminescent manganese-doped CsPbCl3 perovskite quantum dots

Luminescent manganese-doped CsPbCl3 perovskite quantum dots

Optical spectroscopy of Al2O3:Ti3+single crystal under hydrostatic pressure. The influence on the Jahn-Teller coupling

Crystal-Field Theory Validity Through Local (and Bulk) Compressibilities in CoF2 and KCoF3

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Optical spectroscopy of Al₂O₃:Ti³⁺single crystal under hydrostatic pressure. The influence on the Jahn-Teller coupling

Crystal-Field Theory Validity Through Local (and Bulk) Compressibilities in CoF₂ and KCoF₃