Theoretical Calculations Meet Experiment to Explain the Luminescence Properties and the Presence of Defects in <i>m</i>-ZrO<sub>2</sub>

Lafargue‐Dit‐Hauret, William; Schira, Romain; Latouche, Camille; Jobic, Stéphane

doi:10.1021/acs.chemmater.1c00590

Cited by 11 publications

(22 citation statements)

References 83 publications

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“…Typically, the synthesized ZrO 2 sample exhibits 5–10% of the tetragonal phase along with the monoclinic phase. − According to the literature, a prominent PL peak appears in the range 390–425 nm for a pure tetragonal structure , with a lifetime decay smaller than 10 ns. ,, A PL peak is reported between 475 and 500 nm for monoclinic ZrO 2 ,− with a corresponding lifetime decay of up to a few μs (<20 μs). , As far as monoclinic ZrO 2 is concerned, the origin of the prominent emission band (expected in the range 475–500 nm) is still a matter of debate. Several reports attribute this band to the inherent presence of impurity titanium ions (Ti 3+ ) ,,, and this hypothesis is supported by density functional theory (DFT) calculations . However, the presence of Ti 3+ ions in monoclinic ZrO 2 is not seen in EPR measurements or no experimental evidence is provided for the presence of Ti 3+ ions. ,, Another model suggested that the PL emission peak at 475–500 nm is related to oxygen vacancies, ,,, as observed through EPR analysis, confirming the presence of F + centers, which are ascribed to singly charged oxygen vacancies .…”

Section: Introductionmentioning

confidence: 92%

Unraveling the Charge State of Oxygen Vacancies in Monoclinic ZrO₂ and Spectroscopic Properties of ZrO₂:Sm³⁺ Phosphor

et al. 2021

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Ion beam analysis methods are very sensitive to analyze the defects and impurities in insulators and semiconductors. The present study focuses on an investigation of the nature of defects in monoclinic ZrO 2 and spectroscopic properties of ZrO 2 :Sm 3+ (1 mol %) phosphor using ionoluminescence (IL) under the excitation of 100 MeV Si 7+ ions. The structures of the combustion-synthesized ZrO 2 and ZrO 2 :Sm 3+ samples were revealed to be monoclinic as analyzed through X-ray diffraction, Raman spectroscopy, and selected area electron diffraction methods. Structural parameters were assessed utilizing Rietveld refinement of the obtained XRD data using GSAS II software. The average particle size of ZrO 2 and ZrO 2 :Sm 3+ samples was found to be 77 ± 2 and 72 ± 3 nm, respectively, as determined from transmission electron microscopy images. The electronic structure and the oxygen vacancy defect population were analyzed using experimental measurements [viz ionoluminescence (IL), photoluminescence (PL), PL lifetime decay, electron paramagnetic resonance (EPR), and diffuse reflectance spectroscopy (DRS)]. The prominent IL and PL emission peaks seen at 499 nm in monoclinic ZrO 2 are attributed to the F + type center that was assigned to the F 2 + centeran aggregate of the singly ionized oxygen vacancies. ZrO 2 :Sm 3+ (1 mol %) samples display Sm 3+ characteristic IL emission peaks between 562−582, 600−620, 635−673, and 719 nm, corresponding to ( 4 G 5/2 → 6 H 5/2 ), ( 4 G 5/2 → 6 H 7/2 ), ( 4 G 5/2 → 6 H 9/2 ), and ( 4 G 5/2 → 6 H 11/2 ) transitions under 100 MeV Si 7+ ion excitation for various fluences. The 100 MeV Si 7+ ion-induced ion track radius (damaged cross section) and local temperature were estimated through the thermal spike model to be 0.53 nm and 700 K (the duration is about 10 −13 second), respectively. CIE coordinates fall near the yellow color region and then slightly shift toward the green color region with an increase of fluence because of the lattice distortion and change of the Sm 3+ symmetry site.

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Section: Introductionmentioning

confidence: 92%

Unraveling the Charge State of Oxygen Vacancies in Monoclinic ZrO₂ and Spectroscopic Properties of ZrO₂:Sm³⁺ Phosphor

et al. 2021

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“…It is already known that the green emission of ZrO 2 :Ti originates from the charge transfer of Ti. 50 After fluorination, the d−d transition of Ti 3+ may lead to the yellow emission. Surprisingly, the excitation and emission spectra of ZrO 0.46 F 3.08 :Ti and ZrO 0.33 F 3.33 :Ti are sufficiently similar, the emission peaks of both are located in the UV range, appearing at 343 and 340 nm.…”

Section: Resultsmentioning

confidence: 99%

“…Both ZrO 2 :Ti and Zr 7 O 9 F 10 :Ti emit in the visible light range, with a green emission at 470 nm and a yellow emission at 512 nm, respectively. It is already known that the green emission of ZrO 2 :Ti originates from the charge transfer of Ti . After fluorination, the d–d transition of Ti 3+ may lead to the yellow emission.…”

Section: Resultsmentioning

confidence: 99%

Controllable Syntheses, Crystal Structure Evolution, and Photoluminescence of Polymorphic Zirconium Oxyfluorides

Wen

Liu

et al. 2021

Inorg. Chem.

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Precise synthesis of polymorphic phases with similar components but distinct crystal structures is one of the key problems in inorganic chemistry. In this work, we report a fluorination method adopting ZrO2 as the starting material and NH4F as the fluoridation agent that can afford multiphases in the Zr–O–F system, including Zr7O9F10, Zr3O2F8, ZrO0.46F3.08, ZrO0.33F3.33, β-ZrF4, NH4Zr2F9, and NH4ZrF5. A preliminary phase formation diagram was established as a function of the fluorination temperature (T), reaction time (t), and F/Zr ratio after systematic optimization of the preparation conditions. Among the as-obtained phases, the detailed crystal structures of Zr7O9F10 and ZrO0.33F3.33 were refined based on the powder X-ray diffraction patterns. As the F/O ratio increases, the crystal structures of Zr–O–F phases transform gradually from an anion-deficient α-UO3-related structure of Zr7O9F10 to an anion-excess ReO3-related structure of ZrO0.33F3.33. At last, we also prepared Ti-doped ZrO2, Zr7O9F10, ZrO0.46F3.08, and ZrO0.33F3.33 to study the host-lattice-dependent photoluminescence properties of zirconium oxyfluorides. The four materials show distinct photoluminescence in the UV and visible regions due to different local coordination environments of Zr/Ti. This work demonstrates the low-temperature fluorination method as an efficient route to phase-selective polymorphic metal oxyfluorides, which can be employed in further structure–property relationship studies.

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“…3d levels of Ti lie between VBM and CBM, close to conduction band (CB) levels of Zr. These orbitals are sufficiently far from the CBM that electrons in the CB are easily captured by Ti states, as already demonstrated by some of us for the ZrO 2 material …”

Section: Methodsmentioning

confidence: 99%

Modeling Luminescence Spectrum of BaZrO₃:Ti Including Vibronic Coupling from First Principles Calculations

Cavignac

Jobic

Latouche

2022

J. Chem. Theory Comput.

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Herein, we present a methodology based on constrained density functional theory and vibrational mode computations to simulate and interpret the luminescence spectra of periodic solids. A multi-dimension harmonic model is used to combine electronic and vibrational contributions into an overall vibrationally resolved emission spectrum. We applied it to Ti-doped BaZrO3 to accurately reproduce its blue luminescence and unambiguously assign the observed luminescence to a Ti3+ + O– → Ti4+ + O2– charge transfer.

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Theoretical Calculations Meet Experiment to Explain the Luminescence Properties and the Presence of Defects in m-ZrO₂

Cited by 11 publications

References 83 publications

Unraveling the Charge State of Oxygen Vacancies in Monoclinic ZrO₂ and Spectroscopic Properties of ZrO₂:Sm³⁺ Phosphor

Unraveling the Charge State of Oxygen Vacancies in Monoclinic ZrO₂ and Spectroscopic Properties of ZrO₂:Sm³⁺ Phosphor

Controllable Syntheses, Crystal Structure Evolution, and Photoluminescence of Polymorphic Zirconium Oxyfluorides

Modeling Luminescence Spectrum of BaZrO₃:Ti Including Vibronic Coupling from First Principles Calculations

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Theoretical Calculations Meet Experiment to Explain the Luminescence Properties and the Presence of Defects in m-ZrO2

Cited by 11 publications

References 83 publications

Unraveling the Charge State of Oxygen Vacancies in Monoclinic ZrO2 and Spectroscopic Properties of ZrO2:Sm3+ Phosphor

Unraveling the Charge State of Oxygen Vacancies in Monoclinic ZrO2 and Spectroscopic Properties of ZrO2:Sm3+ Phosphor

Controllable Syntheses, Crystal Structure Evolution, and Photoluminescence of Polymorphic Zirconium Oxyfluorides

Modeling Luminescence Spectrum of BaZrO3:Ti Including Vibronic Coupling from First Principles Calculations

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Resources

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Theoretical Calculations Meet Experiment to Explain the Luminescence Properties and the Presence of Defects in m-ZrO₂

Unraveling the Charge State of Oxygen Vacancies in Monoclinic ZrO₂ and Spectroscopic Properties of ZrO₂:Sm³⁺ Phosphor

Unraveling the Charge State of Oxygen Vacancies in Monoclinic ZrO₂ and Spectroscopic Properties of ZrO₂:Sm³⁺ Phosphor

Modeling Luminescence Spectrum of BaZrO₃:Ti Including Vibronic Coupling from First Principles Calculations