Hasan Yilmaz, Gülsüm Kinik, Masahiko Isobe, Pascal Puphal, Markus Suta, Oliver Clemens
{"title":"单晶荧光粉Gd3In2Ga3O12:RE3+ (RE = Nd3+和Ho3+)的合成及光学性能","authors":"Hasan Yilmaz, Gülsüm Kinik, Masahiko Isobe, Pascal Puphal, Markus Suta, Oliver Clemens","doi":"10.1002/adpr.202500074","DOIUrl":null,"url":null,"abstract":"<p>The continuous development of innovative optical materials with lanthanoid ions as activators has emerged as a modern sector of materials chemistry. The experience with the fabrication of single crystals with the optical float zone has motivated one to investigate the luminescence of Nd<sup>3+</sup> and Ho<sup>3+</sup> ions in the garnets (Gd<sub>3−<i>x</i></sub>RE<sub><i>x</i></sub>)In<sub>2</sub>Ga<sub>3</sub>O<sub>12</sub> (RE = Nd and Ho, <i>x</i> = 0; 0.15–0.30). Upon usage of an Ar/O<sub>2</sub> (80:20 ratio) atmosphere and application of an auxiliary pressure (6 bar) to suppress In<sub>2</sub>O<sub>3</sub> evaporation, single-crystalline domain sizes in the order of ≈6 × 6 × 1 mm<sup>3</sup> are obtained. Structural analysis confirms the formation of a cubic garnet phase with space group <span></span><math>\n <semantics>\n <mrow>\n <mi>I</mi>\n <mi>a</mi>\n <mover>\n <mn>3</mn>\n <mo>¯</mo>\n </mover>\n <mi>d</mi>\n </mrow>\n <annotation>$I a \\bar{3} d$</annotation>\n </semantics></math>, with the substituents incorporated in accordance with Vegard's law. Backscattered electron imaging and energy-dispersive X-ray spectroscopy are conducted, demonstrating a homogeneous elemental distribution within the crystals. Photoluminescence studies are carried out, revealing the characteristic narrow-line 4<i>f</i> <sup><i>n</i></sup> → 4<i>f</i> <sup><i>n</i></sup> transitions of Nd<sup>3+</sup> and Ho<sup>3+</sup>, with decay times in the submillisecond range, suggesting non-negligible cross-relaxation effects are present. Despite this, the large nearest-neighbor Gd–Gd distance (3.88 Å) in Gd<sub>3</sub>In<sub>2</sub>Ga<sub>3</sub>O<sub>12</sub> and the low phonon cutoff energy (≈700 cm<sup>−1</sup>) are found to limit cross-relaxation pathways, preserving significant photoluminescence brightness. These results highlight the potential of Gd<sub>3</sub>In<sub>2</sub>Ga<sub>3</sub>O<sub>12</sub>:RE<sup>3+</sup> single crystals as promising candidates for advanced optical applications.</p>","PeriodicalId":7263,"journal":{"name":"Advanced Photonics Research","volume":"6 8","pages":""},"PeriodicalIF":3.9000,"publicationDate":"2025-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/adpr.202500074","citationCount":"0","resultStr":"{\"title\":\"Synthesis and Optical Properties of Single-Crystalline Phosphors Gd3In2Ga3O12:RE3+ (RE = Nd3+ and Ho3+) Grown via the Optical Float Zone Method\",\"authors\":\"Hasan Yilmaz, Gülsüm Kinik, Masahiko Isobe, Pascal Puphal, Markus Suta, Oliver Clemens\",\"doi\":\"10.1002/adpr.202500074\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The continuous development of innovative optical materials with lanthanoid ions as activators has emerged as a modern sector of materials chemistry. The experience with the fabrication of single crystals with the optical float zone has motivated one to investigate the luminescence of Nd<sup>3+</sup> and Ho<sup>3+</sup> ions in the garnets (Gd<sub>3−<i>x</i></sub>RE<sub><i>x</i></sub>)In<sub>2</sub>Ga<sub>3</sub>O<sub>12</sub> (RE = Nd and Ho, <i>x</i> = 0; 0.15–0.30). Upon usage of an Ar/O<sub>2</sub> (80:20 ratio) atmosphere and application of an auxiliary pressure (6 bar) to suppress In<sub>2</sub>O<sub>3</sub> evaporation, single-crystalline domain sizes in the order of ≈6 × 6 × 1 mm<sup>3</sup> are obtained. Structural analysis confirms the formation of a cubic garnet phase with space group <span></span><math>\\n <semantics>\\n <mrow>\\n <mi>I</mi>\\n <mi>a</mi>\\n <mover>\\n <mn>3</mn>\\n <mo>¯</mo>\\n </mover>\\n <mi>d</mi>\\n </mrow>\\n <annotation>$I a \\\\bar{3} d$</annotation>\\n </semantics></math>, with the substituents incorporated in accordance with Vegard's law. Backscattered electron imaging and energy-dispersive X-ray spectroscopy are conducted, demonstrating a homogeneous elemental distribution within the crystals. Photoluminescence studies are carried out, revealing the characteristic narrow-line 4<i>f</i> <sup><i>n</i></sup> → 4<i>f</i> <sup><i>n</i></sup> transitions of Nd<sup>3+</sup> and Ho<sup>3+</sup>, with decay times in the submillisecond range, suggesting non-negligible cross-relaxation effects are present. Despite this, the large nearest-neighbor Gd–Gd distance (3.88 Å) in Gd<sub>3</sub>In<sub>2</sub>Ga<sub>3</sub>O<sub>12</sub> and the low phonon cutoff energy (≈700 cm<sup>−1</sup>) are found to limit cross-relaxation pathways, preserving significant photoluminescence brightness. These results highlight the potential of Gd<sub>3</sub>In<sub>2</sub>Ga<sub>3</sub>O<sub>12</sub>:RE<sup>3+</sup> single crystals as promising candidates for advanced optical applications.</p>\",\"PeriodicalId\":7263,\"journal\":{\"name\":\"Advanced Photonics Research\",\"volume\":\"6 8\",\"pages\":\"\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-05-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/adpr.202500074\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advanced Photonics Research\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://advanced.onlinelibrary.wiley.com/doi/10.1002/adpr.202500074\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Photonics Research","FirstCategoryId":"1085","ListUrlMain":"https://advanced.onlinelibrary.wiley.com/doi/10.1002/adpr.202500074","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
以镧系离子为活化剂的新型光学材料的不断发展已成为材料化学的一个现代分支。利用光学浮子区制备单晶的经验,激发了人们对石榴石(Gd3−xREx)In2Ga3O12 (RE = Nd and Ho, x = 0;0.15 - -0.30)。在Ar/O2(80:20)气氛和辅助压力(6 bar)抑制In2O3蒸发的条件下,获得了≈6 × 6 × 1 mm3大小的单晶畴。结构分析证实形成了具有空间群I为3¯d$ I a \bar{3} d$的立方石榴石相,取代基的加入符合维加德定律。进行了背散射电子成像和能量色散x射线光谱分析,表明晶体内元素分布均匀。光致发光研究揭示了Nd3+和Ho3+的特征窄线4f n→4f n跃迁,衰变时间在亚毫秒范围内,表明存在不可忽略的交叉弛豫效应。尽管如此,发现Gd3In2Ga3O12中较大的近邻Gd-Gd距离(3.88 Å)和低声子截止能量(≈700 cm−1)限制了交叉弛豫途径,保持了显著的光致发光亮度。这些结果突出了Gd3In2Ga3O12:RE3+单晶作为先进光学应用的有前途的候选者的潜力。
Synthesis and Optical Properties of Single-Crystalline Phosphors Gd3In2Ga3O12:RE3+ (RE = Nd3+ and Ho3+) Grown via the Optical Float Zone Method
The continuous development of innovative optical materials with lanthanoid ions as activators has emerged as a modern sector of materials chemistry. The experience with the fabrication of single crystals with the optical float zone has motivated one to investigate the luminescence of Nd3+ and Ho3+ ions in the garnets (Gd3−xREx)In2Ga3O12 (RE = Nd and Ho, x = 0; 0.15–0.30). Upon usage of an Ar/O2 (80:20 ratio) atmosphere and application of an auxiliary pressure (6 bar) to suppress In2O3 evaporation, single-crystalline domain sizes in the order of ≈6 × 6 × 1 mm3 are obtained. Structural analysis confirms the formation of a cubic garnet phase with space group , with the substituents incorporated in accordance with Vegard's law. Backscattered electron imaging and energy-dispersive X-ray spectroscopy are conducted, demonstrating a homogeneous elemental distribution within the crystals. Photoluminescence studies are carried out, revealing the characteristic narrow-line 4fn → 4fn transitions of Nd3+ and Ho3+, with decay times in the submillisecond range, suggesting non-negligible cross-relaxation effects are present. Despite this, the large nearest-neighbor Gd–Gd distance (3.88 Å) in Gd3In2Ga3O12 and the low phonon cutoff energy (≈700 cm−1) are found to limit cross-relaxation pathways, preserving significant photoluminescence brightness. These results highlight the potential of Gd3In2Ga3O12:RE3+ single crystals as promising candidates for advanced optical applications.