Using Eu3+ as an atomic probe to investigate the local environment in LaPO4–GdPO4 monazite end-members

Huittinen, Nina; Arinicheva, Yulia; Schmidt, Moritz; Neumeier, Stefan; Stumpf, Thorsten

doi:10.1016/j.jcis.2016.08.027

Cited by 23 publications

(33 citation statements)

References 54 publications

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“…In either case, it is clear that the dopant Eu 3+ site suffers a significant local structural distortion that perturbs the site symmetry from the crystallographic D 2 d to C 1 . This splitting pattern is similar to that of monazite‐based LnPO 4 (Ln=La–Gd), in which Eu 3+ exhibits C 1 dopant site symmetry for all members. The luminescence spectra in both cases exhibit the same splitting patterns but different intensity distributions, both with respect to the relative intensities of J sublevels and F 1 /F 2 intensity ratio.…”

Section: Resultssupporting

confidence: 71%

“…However, the details of the incorporation behavior are rather different. For monazite ceramics, systematic trends in both excitation peak position and FWHM have been observed throughout the solid solution series . In contrast, for the xenotime ceramics no such trend is discernable.…”

Section: Resultssupporting

confidence: 67%

“…Based on the crystal structure of xenotime, we can assume species A represents Eu 3+ incorporation on the Ln 3+ lattice site. The same substitution has been observed in monazite LnPO 4 . However, the details of the incorporation behavior are rather different.…”

Section: Resultsmentioning

confidence: 99%

“…Rare‐earth orthophosphates LnPO 4 (Ln=La–Lu, Y) with xenotime or monazite structures contain only one crystallographically unique Ln site each, having the simplest chemical and structural configuration among rare‐earth phosphates. However, the spectroscopic data presented here for xenotime combined with previous research on monazite demonstrate that the incorporation of Eu 3+ proceeds rather differently in these two materials. In the case of monazite, a homogeneous solid solution series was found with systematic linear trends in the spectroscopic features.…”

Section: Resultsmentioning

confidence: 99%

“…However, owing to the very low symmetry of the Ln 3+ lattice site in the monazite structure, TRLFS is not sensitive to any additional reduction in crystal field symmetry. In this respect, doping‐induced local structural distortions could not be studied in the monazite system . Accordingly, it is still not clear how the local environment around guest and host ions is affected in the rare‐earth orthophosphates family.…”

Section: Introductionmentioning

confidence: 99%

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Local Structural Effects of Eu³⁺ Incorporation into Xenotime‐type Solid Solutions with Different Host Cations

Xiao

Lösch

Huittinen

et al. 2018

Chemistry A European J

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In this study, the effect of host cations on the local structure around the dopant site of materials from the xenotime family is systematically studied on the molecular level. A series of six Eu -doped xenotime-type single crystals (Tb, Y, Ho, Er, Yb, and LuPO ) have been grown and spectroscopically analyzed by using polarization-dependent laser-induced luminescence spectroscopy (p-TRLFS). Our results demonstrate that the structural disorder changes in a non-linear manner with a structural break between Yb and Lu . Despite adopting identical crystal structures, the solid solutions of these materials vary significantly, and differ from monazite solid solutions. Similar Eu incorporation behavior with a strongly distorted dopant site is found for the early members of the xenotime family, whereas LuPO with the largest host versus dopant radii mismatch is anomalous in that it contains the most symmetrical lattice site. This goes along with a significantly stronger crystal field, indicating a shorter Eu-O bond length, as well as a strong vibronic coupling to external translational lattice vibrations. The p-TRLFS analysis confirms the breakdown of the crystallographic site symmetry from D to C in YPO , whereas a small distortion of the crystallographic site in LuPO results in an S point symmetry for the Eu cation. The lattice with the smallest cation host site is no longer sufficiently flexible to make room for Eu and instead "forces" the guest ion to occupy a less distorted Lu site.

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Section: Resultssupporting

confidence: 71%

Section: Resultssupporting

confidence: 67%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Local Structural Effects of Eu³⁺ Incorporation into Xenotime‐type Solid Solutions with Different Host Cations

Xiao

Lösch

Huittinen

et al. 2018

Chemistry A European J

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Molten‐Salt‐Assisted Synthesis of Na₃Bi(PO₄)₂:Eu³⁺ Nanoparticles with Strong Red Emission

Boyi

Yao

Liu

2019

Physica Status Solidi (a)

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Single phase Eu 3þ -doped Na 3 Bi(PO 4 ) 2 (NBPO) nanoparticles with different Eu 3þ concentrations are successfully synthesized by a molten-salten method using Na 3 PO 4 Á 12H 2 O both as reaction medium and as reactant. The influence of synthesis conditions such as the Na 3 PO 4 Á 12H 2 O content, heating temperature, and time on the crystal structure of the final products is investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It reveals that pure phase Na 3 Bi(PO 4 ) 2 nanoparticles with size about 100 nm are successfully achieved when the mixture (molar ratio of 1:4 between Bi(NO 3 ) 3 Á 5H 2 O and Na 3 PO 4 Á 12H 2 O) is heated at 180 C for 12 h. After Eu 3þ -doping, NBPO:Eu 3þ nanoparticles exhibit bright red emission peaking at 620 nm under the excitation of the near ultraviolet (NUV) light. The luminescence is attributed to the electric dipole transition 5 D 0 ! 7 F 2 of Eu 3þ ions. The luminescent intensity of the NBPO:Eu 3þ phosphors is strongly dependent on the Eu 3þ content and concentration quenching occurred when the Eu 3þ concentration is larger than 8 mol%, which is attributed to dipole-dipole interaction. This work provides a green way for the synthesis of phosphate-based nanomaterials and suggests that Eu 3þdoped Na 3 Bi(PO 4 ) 2 has a great potential application in the lighting and display fields.

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Understanding the local structure of Eu3+- and Y3+-stabilized zirconia: insights from luminescence and X-ray absorption spectroscopic investigations

et al. 2020

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This study combines bulk structural and spectroscopic investigations of Eu3+- or Y3+/Eu3+ co-doped tetragonal and cubic zirconia polymorphs to gain an in-depth understanding of the solid solution formation process. Our bulk structural characterizations show that the dopant is homogenously distributed in the ZrO2 host structure resulting in an increase of the bulk symmetry with increasing dopant substitution (from 8 to 26 mol%). The local site symmetry around the Eu3+ dopant, however, determined with luminescence spectroscopy (TRLFS), remains low in all samples. Results obtained with X-ray pair distribution function and X-ray absorption spectroscopy show that the average coordination environment in the stabilized zirconia structures remains practically unchanged. Despite this very constant average dopant environment, site-selective TRLFS data show the presence of three nonequivalent Eu3+ environments in the ZrO2 solid structures. These Eu3+ environments are assumed to arise from Eu3+ incorporation at superficial sites, which increase in abundance as the size of the crystallites decrease, and incorporation on two bulk sites differing in the location of the oxygen vacancies with respect to the dopant cation.

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Using Eu3+ as an atomic probe to investigate the local environment in LaPO4–GdPO4 monazite end-members

Cited by 23 publications

References 54 publications

Local Structural Effects of Eu³⁺ Incorporation into Xenotime‐type Solid Solutions with Different Host Cations

Local Structural Effects of Eu³⁺ Incorporation into Xenotime‐type Solid Solutions with Different Host Cations

Molten‐Salt‐Assisted Synthesis of Na₃Bi(PO₄)₂:Eu³⁺ Nanoparticles with Strong Red Emission

Understanding the local structure of Eu3+- and Y3+-stabilized zirconia: insights from luminescence and X-ray absorption spectroscopic investigations

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Using Eu3+ as an atomic probe to investigate the local environment in LaPO4–GdPO4 monazite end-members

Cited by 23 publications

References 54 publications

Local Structural Effects of Eu3+ Incorporation into Xenotime‐type Solid Solutions with Different Host Cations

Local Structural Effects of Eu3+ Incorporation into Xenotime‐type Solid Solutions with Different Host Cations

Molten‐Salt‐Assisted Synthesis of Na3Bi(PO4)2:Eu3+ Nanoparticles with Strong Red Emission

Understanding the local structure of Eu3+- and Y3+-stabilized zirconia: insights from luminescence and X-ray absorption spectroscopic investigations

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Product

Resources

About

Local Structural Effects of Eu³⁺ Incorporation into Xenotime‐type Solid Solutions with Different Host Cations

Local Structural Effects of Eu³⁺ Incorporation into Xenotime‐type Solid Solutions with Different Host Cations

Molten‐Salt‐Assisted Synthesis of Na₃Bi(PO₄)₂:Eu³⁺ Nanoparticles with Strong Red Emission