Characterization of order-disorder transition in MgAl2O4:Cr3+ spinel using photoluminescence

Wang, Chengsi; Shen, Andy H.; Liu, Yungui

doi:10.1016/j.jlumin.2020.117552

Cited by 12 publications

(8 citation statements)

References 30 publications

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“…Cationic ordering–disordering is a long-lasting topic and is also essential in the study of spinel-type materials because it is coupled strongly to the physical properties. − For instance, only reversibility of 12% Mg 2+ insertion can be achieved in MgCrMnO 4 and excessive Mg 2+ insertion would destabilize the crystal structure due to Mg 2+ /Mn 2+ antisite disordering caused by the irreversible migration of the Mn 2+ from the octahedral site to the tetrahedral site . The A/B-antisite disordering of spinel can be quantified by an inversion parameter ( i ).…”

Section: Introductionmentioning

confidence: 99%

Mg₄InSbO₈ Spinel: Double 2:1 Ordering in Tetrahedral and Octahedral Sublattices and Perspective Application as an Optical Thermometer via Mn^2+/4+ Doping

Cheng,

Huang,

et al. 2023

Chem. Mater.

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AB2O4-type spinel oxides were extensively investigated as prospective magnetic, photocatalytic, cathode, and host materials. Herein, a new Mg4InSbO8 spinel was rationally designed and structurally characterized by high-resolution X-ray powder diffraction (XRPD) in combination with neutron powder diffraction. Mg4InSbO8 crystallizes in the Imma-superstructure with lattice dimensions of a = √2/2·a C, b = 3√2/2·a C, and c = a C, where a C is the lattice parameter of the cubic (Fd3̅m) archetype spinel. The formation of this hitherto unreported Imma-spinel superstructure is a result of 2:1 Mg2+/Sb5+ ordering in the octahedral sublattice, which further creates two crystallographically independent tetrahedral sites with distinctive sizes and thereby resulting in a site-selective 2:1 occupation for the Mg2+ and In3+ cations. Mg4InSbO8 is the first spinel superstructure exhibiting double 2:1 cationic ordering in both octahedral and tetrahedral sublattices. Compared with other ordered spinel structures, we found that the ionic radius and charge differences, coordination geometry preference, and chemical bonding character are all responsible for the formation of this unique doubly ordered spinel superstructure of Mg4InSbO8. Theoretical calculations, together with diffuse reflectance spectroscopy, revealed that Mg4InSbO8 is an indirect semiconductor. Moreover, the multiple tetrahedral and octahedral sites in Mg4InSbO8 are appropriate for green- and deep-red-emitting Mn2+ and Mn4+ activators, respectively. Tunable color emission from green to white and then to deep red can be achieved for Mg4InSbO8/Mn2+/4+ phosphors by adjusting the excitation energy. More importantly, Mn2+ and Mn4+ activators experience distinctive thermal quenching responses, thereby resulting in a vivid color change from green to red for Mg4InSbO8/Mn2+/4+ upon heating. The highest sensitivity for color change is S r = 2.10% at 453 K, manifesting potential applications in temperature sensing. Our findings pave the way to designing cation-ordered spinel superstructures and exploring and expanding their prospective applications.

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Section: Introductionmentioning

confidence: 99%

Mg₄InSbO₈ Spinel: Double 2:1 Ordering in Tetrahedral and Octahedral Sublattices and Perspective Application as an Optical Thermometer via Mn^2+/4+ Doping

Cheng,

Huang,

et al. 2023

Chem. Mater.

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“…For example, Mn 2+ is the most popular luminescence agent in nature, and Fe 3+ is a commonly known quenchant [20]. The red fluorescence in minerals, such as ruby and spinel, is mainly caused by Cr 3+ [21,22]. Therefore, in this study, the contents of the common transition metal elements (Cr, Ti, V, Mn, and Fe) are compared with the fluorescence color and intensity of taaffeites to analyze their correlation.…”

Section: Fluorescence Spectroscopymentioning

confidence: 99%

Gemological and Luminescence Characteristics of Taaffeites from Mogok, Myanmar

Lin

Zhang

et al. 2023

Minerals

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Taaffeite is a rare gem that has been found in different localities such as Tanzania, Sri Lanka, China, and Mogok, Myanmar. In this study, thirty-two taaffeite samples from Mogok, Myanmar, were investigated by conventional gemological testing, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Raman spectrometry, and fluorescence spectrometry. Through microscopic observations, various types of inclusions were observed in these taaffeites, including irregular inclusions, orange and brown intrusions, black dotted and flake inclusions, healed fissures, tubular inclusions, fingerprint inclusions, and multi-phase inclusions. The Raman spectra demonstrated that the inclusions were mainly calcite, forsterite, celestite, graphite, dolomite, and transparent tubular or columnar inclusions filled with CO2. In previous studies, taaffeite showed inert or chalky fluorescence under long-wave ultraviolet (LWUV) light and inert fluorescence under short-wave ultraviolet (SWUV) light. In this study, the taaffeite samples revealed different fluorescence phenomena under ultraviolet light. Thirty-two taaffeite samples were classified into four categories according to their fluorescence under LWUV: orange-red, pink, green, and blue-white fluorescence. Under SWUV, all samples presented inert to bright pink fluorescence. Two-dimensional fluorescence spectra were obtained through a fluorescence spectrometer. For the samples with orange-red and pink fluorescence under LWUV, two-dimensional fluorescence spectra showed that peaks at 686 nm and 690 nm (in the red region) were strong. For the samples with green and blue-white fluorescence under LWUV, peaks at 439 nm and 464 nm (in the blue region) were strong, peaks at 507–515 nm (in the green region) were relatively weak, and peaks at 686 and 690 nm (in the red region) were very weak. Combined with the data from LA-ICP-MS, it is speculated that Cr3+ was responsible for samples having orange-red and pink fluorescence, that Mn2+ was responsible for samples having green fluorescence, and that Fe inhibited the generation of fluorescence.

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“…The emission spectra from Cr 3+ has been shown to be useful in identifying the order-disorder in the Cr 3+ -doped spinel structures. [35][36][37] The normal spinel structure of ZnAl 2 O 4 or ZnGa 2 O 4 having all Zn is in 8a tetrahedral sites, while Al/Ga is in all octahedral positions. The ratio of peaks at B690 nm to 700 nm (R/N ratio) in the 2 E( 4 F) -4 A 2 ( 4 F) band can be treated as a relative quantity in understanding the degree of inversion in the studies spinel structures.…”

Section: Photoluminescence Measurementsmentioning

confidence: 99%

Design of need-based phosphors and scintillators by compositional modulation in the ZnGa_2−xAl_xO₄:Cr³⁺ spinel: pure compound versus solid solutions

Gupta

Sudarshan

Modak

et al. 2022

Phys. Chem. Chem. Phys.

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Characterization of order-disorder transition in MgAl2O4:Cr3+ spinel using photoluminescence

Cited by 12 publications

References 30 publications

Mg₄InSbO₈ Spinel: Double 2:1 Ordering in Tetrahedral and Octahedral Sublattices and Perspective Application as an Optical Thermometer via Mn^2+/4+ Doping

Mg₄InSbO₈ Spinel: Double 2:1 Ordering in Tetrahedral and Octahedral Sublattices and Perspective Application as an Optical Thermometer via Mn^2+/4+ Doping

Gemological and Luminescence Characteristics of Taaffeites from Mogok, Myanmar

Design of need-based phosphors and scintillators by compositional modulation in the ZnGa_2−xAl_xO₄:Cr³⁺ spinel: pure compound versus solid solutions

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Characterization of order-disorder transition in MgAl2O4:Cr3+ spinel using photoluminescence

Cited by 12 publications

References 30 publications

Mg4InSbO8 Spinel: Double 2:1 Ordering in Tetrahedral and Octahedral Sublattices and Perspective Application as an Optical Thermometer via Mn2+/4+ Doping

Mg4InSbO8 Spinel: Double 2:1 Ordering in Tetrahedral and Octahedral Sublattices and Perspective Application as an Optical Thermometer via Mn2+/4+ Doping

Gemological and Luminescence Characteristics of Taaffeites from Mogok, Myanmar

Design of need-based phosphors and scintillators by compositional modulation in the ZnGa2−xAlxO4:Cr3+ spinel: pure compound versus solid solutions

Contact Info

Product

Resources

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Mg₄InSbO₈ Spinel: Double 2:1 Ordering in Tetrahedral and Octahedral Sublattices and Perspective Application as an Optical Thermometer via Mn^2+/4+ Doping

Mg₄InSbO₈ Spinel: Double 2:1 Ordering in Tetrahedral and Octahedral Sublattices and Perspective Application as an Optical Thermometer via Mn^2+/4+ Doping

Design of need-based phosphors and scintillators by compositional modulation in the ZnGa_2−xAl_xO₄:Cr³⁺ spinel: pure compound versus solid solutions