Novel Red Phosphor of Gd<sup>3+</sup>, Sm<sup>3+</sup> co-Activated Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.30</sub>☐<sub>(1−2<i>x</i>−2<i>y</i>)/3</sub>WO<sub>4</sub> Scheelites for LED Lighting
Gd<sup>3+</sup> and Sm<sup>3+</sup> co-activation, the effect of cation substitutions and the creation of cation vacancies in the scheelite-type framework are investigated as factors influencing luminescence properties. Ag<i><sub>x</sub></i>Gd<sub&g...
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2023-06-01
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| Online Access: | https://www.mdpi.com/1996-1944/16/12/4350 |
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| author | Vladimir A. Morozov Bogdan I. Lazoryak Aleksandra A. Savina Elena G. Khaikina Ivan I. Leonidov Alexey V. Ishchenko Dina V. Deyneko |
| author_facet | Vladimir A. Morozov Bogdan I. Lazoryak Aleksandra A. Savina Elena G. Khaikina Ivan I. Leonidov Alexey V. Ishchenko Dina V. Deyneko |
| author_sort | Vladimir A. Morozov |
| collection | DOAJ |
| description | Gd<sup>3+</sup> and Sm<sup>3+</sup> co-activation, the effect of cation substitutions and the creation of cation vacancies in the scheelite-type framework are investigated as factors influencing luminescence properties. Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.3</sub>☐<sub>(1−2<i>x</i>)/3</sub>WO<sub>4</sub> (<i>x</i> = 0.50, 0.286, 0.20; <i>y</i> = 0.01, 0.02, 0.03, 0.3) scheelite-type phases (A<i><sub>x</sub></i>GS<i><sub>y</sub></i>E) have been synthesized by a solid-state method. A powder X-ray diffraction study of A<i><sub>x</sub></i>GS<i><sub>y</sub></i>E (<i>x</i> = 0.286, 0.2; <i>y</i> = 0.01, 0.02, 0.03) shows that the crystal structures have an incommensurately modulated character similar to other cation-deficient scheelite-related phases. Luminescence properties have been evaluated under near-ultraviolet (n–UV) light. The photoluminescence excitation spectra of A<i><sub>x</sub></i>GS<i><sub>y</sub></i>E demonstrate the strongest absorption at 395 nm, which matches well with commercially available UV-emitting GaN-based LED chips. Gd<sup>3+</sup> and Sm<sup>3+</sup> co-activation leads to a notable decreasing intensity of the charge transfer band in comparison with Gd<sup>3+</sup> single-doped phases. The main absorption is the <sup>7</sup>F<sub>0</sub> → <sup>5</sup>L<sub>6</sub> transition of Eu<sup>3+</sup> at 395 nm and the <sup>6</sup>H<sub>5/2</sub> → <sup>4</sup>F<sub>7/2</sub> transition of Sm<sup>3+</sup> at 405 nm. The photoluminescence emission spectra of all the samples indicate intense red emission due to the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> transition of Eu<sup>3+</sup>. The intensity of the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> emission increases from ~2 times (<i>x</i> = 0.2, <i>y</i> = 0.01 and <i>x</i> = 0.286, <i>y</i> = 0.02) to ~4 times (<i>x</i> = 0.5, <i>y</i> = 0.01) in the Gd<sup>3+</sup> and Sm<sup>3+</sup> co-doped samples. The integral emission intensity of Ag<sub>0.20</sub>Gd<sub>0.29</sub>Sm<sub>0.01</sub>Eu<sub>0.30</sub>WO<sub>4</sub> in the red visible spectral range (the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> transition) is higher by ~20% than that of the commercially used red phosphor of Gd<sub>2</sub>O<sub>2</sub>S:Eu<sup>3+</sup>. A thermal quenching study of the luminescence of the Eu<sup>3+</sup> emission reveals the influence of the structure of compounds and the Sm<sup>3+</sup> concentration on the temperature dependence and behavior of the synthesized crystals. Ag<sub>0.286</sub>Gd<sub>0.252</sub>Sm<sub>0.02</sub>Eu<sub>0.30</sub>WO<sub>4</sub> and Ag<sub>0.20</sub>Gd<sub>0.29</sub>Sm<sub>0.01</sub>Eu<sub>0.30</sub>WO<sub>4</sub>, with the incommensurately modulated (3 + 1)D monoclinic structure, are very attractive as near-UV converting phosphors applied as red-emitting phosphors for LEDs. |
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| institution | Directory Open Access Journal |
| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-03-11T02:12:19Z |
| publishDate | 2023-06-01 |
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| record_format | Article |
| series | Materials |
| spelling | doaj.art-5519e5718b74414da1bce1292d9429052023-11-18T11:25:00ZengMDPI AGMaterials1996-19442023-06-011612435010.3390/ma16124350Novel Red Phosphor of Gd<sup>3+</sup>, Sm<sup>3+</sup> co-Activated Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.30</sub>☐<sub>(1−2<i>x</i>−2<i>y</i>)/3</sub>WO<sub>4</sub> Scheelites for LED LightingVladimir A. Morozov0Bogdan I. Lazoryak1Aleksandra A. Savina2Elena G. Khaikina3Ivan I. Leonidov4Alexey V. Ishchenko5Dina V. Deyneko6Chemistry Department, Moscow State University, 119991 Moscow, RussiaChemistry Department, Moscow State University, 119991 Moscow, RussiaSkolkovo Institute of Science and Technology, 121205 Moscow, RussiaBaikal Institute of Nature Management, Siberian Branch, Russian Academy of Science, 670047 Ulan-Ude, RussiaInstitute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences, 620990 Ekaterinburg, RussiaNANOTECH Center, Ural Federal University, 620002 Ekaterinburg, RussiaChemistry Department, Moscow State University, 119991 Moscow, RussiaGd<sup>3+</sup> and Sm<sup>3+</sup> co-activation, the effect of cation substitutions and the creation of cation vacancies in the scheelite-type framework are investigated as factors influencing luminescence properties. Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.3</sub>☐<sub>(1−2<i>x</i>)/3</sub>WO<sub>4</sub> (<i>x</i> = 0.50, 0.286, 0.20; <i>y</i> = 0.01, 0.02, 0.03, 0.3) scheelite-type phases (A<i><sub>x</sub></i>GS<i><sub>y</sub></i>E) have been synthesized by a solid-state method. A powder X-ray diffraction study of A<i><sub>x</sub></i>GS<i><sub>y</sub></i>E (<i>x</i> = 0.286, 0.2; <i>y</i> = 0.01, 0.02, 0.03) shows that the crystal structures have an incommensurately modulated character similar to other cation-deficient scheelite-related phases. Luminescence properties have been evaluated under near-ultraviolet (n–UV) light. The photoluminescence excitation spectra of A<i><sub>x</sub></i>GS<i><sub>y</sub></i>E demonstrate the strongest absorption at 395 nm, which matches well with commercially available UV-emitting GaN-based LED chips. Gd<sup>3+</sup> and Sm<sup>3+</sup> co-activation leads to a notable decreasing intensity of the charge transfer band in comparison with Gd<sup>3+</sup> single-doped phases. The main absorption is the <sup>7</sup>F<sub>0</sub> → <sup>5</sup>L<sub>6</sub> transition of Eu<sup>3+</sup> at 395 nm and the <sup>6</sup>H<sub>5/2</sub> → <sup>4</sup>F<sub>7/2</sub> transition of Sm<sup>3+</sup> at 405 nm. The photoluminescence emission spectra of all the samples indicate intense red emission due to the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> transition of Eu<sup>3+</sup>. The intensity of the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> emission increases from ~2 times (<i>x</i> = 0.2, <i>y</i> = 0.01 and <i>x</i> = 0.286, <i>y</i> = 0.02) to ~4 times (<i>x</i> = 0.5, <i>y</i> = 0.01) in the Gd<sup>3+</sup> and Sm<sup>3+</sup> co-doped samples. The integral emission intensity of Ag<sub>0.20</sub>Gd<sub>0.29</sub>Sm<sub>0.01</sub>Eu<sub>0.30</sub>WO<sub>4</sub> in the red visible spectral range (the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> transition) is higher by ~20% than that of the commercially used red phosphor of Gd<sub>2</sub>O<sub>2</sub>S:Eu<sup>3+</sup>. A thermal quenching study of the luminescence of the Eu<sup>3+</sup> emission reveals the influence of the structure of compounds and the Sm<sup>3+</sup> concentration on the temperature dependence and behavior of the synthesized crystals. Ag<sub>0.286</sub>Gd<sub>0.252</sub>Sm<sub>0.02</sub>Eu<sub>0.30</sub>WO<sub>4</sub> and Ag<sub>0.20</sub>Gd<sub>0.29</sub>Sm<sub>0.01</sub>Eu<sub>0.30</sub>WO<sub>4</sub>, with the incommensurately modulated (3 + 1)D monoclinic structure, are very attractive as near-UV converting phosphors applied as red-emitting phosphors for LEDs.https://www.mdpi.com/1996-1944/16/12/4350incommensurately modulated structureswhite light-emitting diodesscheeliteluminescencephosphorstungstates |
| spellingShingle | Vladimir A. Morozov Bogdan I. Lazoryak Aleksandra A. Savina Elena G. Khaikina Ivan I. Leonidov Alexey V. Ishchenko Dina V. Deyneko Novel Red Phosphor of Gd<sup>3+</sup>, Sm<sup>3+</sup> co-Activated Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.30</sub>☐<sub>(1−2<i>x</i>−2<i>y</i>)/3</sub>WO<sub>4</sub> Scheelites for LED Lighting Materials incommensurately modulated structures white light-emitting diodes scheelite luminescence phosphors tungstates |
| title | Novel Red Phosphor of Gd<sup>3+</sup>, Sm<sup>3+</sup> co-Activated Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.30</sub>☐<sub>(1−2<i>x</i>−2<i>y</i>)/3</sub>WO<sub>4</sub> Scheelites for LED Lighting |
| title_full | Novel Red Phosphor of Gd<sup>3+</sup>, Sm<sup>3+</sup> co-Activated Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.30</sub>☐<sub>(1−2<i>x</i>−2<i>y</i>)/3</sub>WO<sub>4</sub> Scheelites for LED Lighting |
| title_fullStr | Novel Red Phosphor of Gd<sup>3+</sup>, Sm<sup>3+</sup> co-Activated Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.30</sub>☐<sub>(1−2<i>x</i>−2<i>y</i>)/3</sub>WO<sub>4</sub> Scheelites for LED Lighting |
| title_full_unstemmed | Novel Red Phosphor of Gd<sup>3+</sup>, Sm<sup>3+</sup> co-Activated Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.30</sub>☐<sub>(1−2<i>x</i>−2<i>y</i>)/3</sub>WO<sub>4</sub> Scheelites for LED Lighting |
| title_short | Novel Red Phosphor of Gd<sup>3+</sup>, Sm<sup>3+</sup> co-Activated Ag<i><sub>x</sub></i>Gd<sub>((2−<i>x</i>)/3)−0.3−<i>y</i></sub>Sm<i><sub>y</sub></i>Eu<sup>3+</sup><sub>0.30</sub>☐<sub>(1−2<i>x</i>−2<i>y</i>)/3</sub>WO<sub>4</sub> Scheelites for LED Lighting |
| title_sort | novel red phosphor of gd sup 3 sup sm sup 3 sup co activated ag i sub x sub i gd sub 2 i x i 3 0 3 i y i sub sm i sub y sub i eu sup 3 sup sub 0 30 sub ☐ sub 1 2 i x i 2 i y i 3 sub wo sub 4 sub scheelites for led lighting |
| topic | incommensurately modulated structures white light-emitting diodes scheelite luminescence phosphors tungstates |
| url | https://www.mdpi.com/1996-1944/16/12/4350 |
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