Article(id=1319971972298166562, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319971875086783028, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230668, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1693411200000, receivedDateStr=2023-08-31, revisedDate=1695484800000, revisedDateStr=2023-09-24, acceptedDate=null, acceptedDateStr=null, onlineDate=1792635442089, onlineDateStr=2026-10-22, pubDate=1710864000000, pubDateStr=2024-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792635442089, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792635442089, creator=13701087609, updateTime=1792635442089, updator=13701087609, issue=Issue{id=1319971875086783028, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='3', pageStart='737', pageEnd='1170', issueExtLink='null', onlineDate='null', pubDate='1710864000000', pubDateStr='2024-03-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792635418912, creator='13701087609', updateTime=1792641878851, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1319998970110264006, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319971875086783028, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1319998970110264007, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319971875086783028, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1128, endPage=1148, ext={EN=ArticleExt(id=1319971972491104547, articleId=1319971972298166562, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Development on Spectral Regulation of Ce3+-Doped Garnet-Based Fluorescent Materials, columnId=1263922772401635899, journalTitle=Journal of the Chinese Ceramic Society, columnName=Review, runingTitle=null, highlight=null, articleAbstract=

For the favorable physicochemical properties, high fluorescence conversion efficiencies, a relatively short fluorescence lifetime, and an efficient spectral congruence between excitation and ultraviolet/blue LED emission spectra, Ce3+-doped garnet-based fluorescent materials can be used in encompassing lighting, displays, medical imaging, etc.. For leveraging the diverse cation sites within a garnet structure, the emission wavelength of Ce3+ can be continuously adjusted from 460 nm to 610 nm via the incorporation of varied matrix chemical constituents. This versatile tunability broadens the horizons of their potential applications and augments the repertoire of materials available for advancing Ce3+ luminescence theory. However, recent work on Ce3+-doped garnet-based fluorescent materials has unveiled certain anomalies and even contradictions within the characteristics and the emission wavelength modulation theory, becoming one of the prominent bottlenecks hindering the development of this material. To address this issue, this review represented the relative theories of substrate chemical component substitution and the modulation of Ce3+ emission wavelengths. The review also summarized recent advancements in Ce3+-doped garnet-based fluorescent materials, and the influence of ion substitution on Ce3+ luminescence performance with the distortion factor of [CeO8].

This review discussed the Ce3+-doped yttrium aluminum garnet structure as a prototype and comprehensively analyzed the impacts of commonly used doping ions that occupy the [AO8], [BO6], and [CO4] sites on the emission wavelength, thermal quenching resistance, and the [CeO8] distortion factor of Ce3+.

The ion substitution of a single lattice generally necessitates that the substituting ion and the substituted ion have the same valence state and exhibit a minimal disparity in atomic radius. In the case of [AO8] lattice substitution, Y3+ can be replaced with rare-earth ions, i.e., Lu3+, Tb3+, Gd3+, and La3+. When the radius of the doped rare-earth ions is greater that that of Y3+, the emission wavelength of Ce3+ shifts towards the red end of the spectrum. Conversely, when the radius is smaller, the shift occurs in the opposite direction.

The ion substitution of octahedral lattice sites mainly involves the replacement of Al3+ by Ga3+, Sc3+, and In3+. With an escalation in the concentration of doped ions like Ga3+, Sc3+, and In3+, the peak wavelength of the Ce3+ emission spectrum has a blue shift. In addition, the incorporation of Sc3+ effectively enhances the thermal quenching resistance of Ce3+, while the inclusion of Ga3+ diminishes the thermal quenching resistance of Ce3+.

The main substitutions of dodecahedral-octahedral lattice ion pairs include Ca2+-Hf4+ and Ca2+-Zr4+ replacing Y3+-Al3+. The emission and excitation peak wavelengths of Ce3+ gradually blueshifts as Ca2+-Hf4+ and Ca2+-Zr4+ doping contents increase.

The substitution of dodecahedral-tetrahedral lattice ions is mainly achieved by M2+-Si4+ (M=Mg, Ca, Sr, Ba) replacing Y3+-Al3+, with alkaline earth metals occupying the dodecahedral lattice and Si4+ occupying the tetrahedral lattice. In the garnet system, when M2+-Si4+ replaces Y3+-Al3+, the emission wavelength of Ce3+ undergoes a blue shift with the increase of M2+ ion radius, resulting in improving the thermal stability.

The substitution of octahedral-tetrahedral lattice ions mainly involves Mg2+-Si4+/Ge4+ replacing Al3+-Al3+, where Mg2+ occupies the octahedral lattice and Si4+/Ge4+ occupies the tetrahedral lattice. Among them, Mg2+-Si4+ replacing Al3+-Al3+ is an effective method to achieve a large redshift of Ce3+ emission wavelength. The introduction of Mg2+-Ge4+ also leads to the redshift of Ce3+ emission wavelength, but the extent of this redshift is considerably less than that achieved by Mg2+-Si4+.

The chemical components in dodecahedral-octahedral-tetrahedral lattice co-substitutions are more intricate, with Ca2+ and Mg2+ occupying the dodecahedral lattice, Mg2+, Sc3+, and Hf4+ occupying the octahedral lattice, and Si4+ and Ge4+ in the tetrahedral lattice. Different lattice ions on the co-substitution affect the luminescence performance of Ce3+.

Summary and prospects

The effect of ion substitution on the luminescence performance of Ce3+ is analyzed via utilizing Ce3+-doped yttrium aluminum garnet fluorescent material as a prototype. The comparative study reveals that the most effective redshift of Ce3+ emission wavelength appears when Mg2+-Si4+ occupies the octahedral-tetrahedral lattice configuration. This results in a possibility of red shifting the emission wavelength of Ce3+ at 610 nm, thereby significantly enhancing the color rendering capabilities of white LED/LD lighting systems.

Conversely, an effective blue shift in Ce3+ emission wavelength appears in Ca2+-Zr4+ located in the dodecahedral-octahedral lattice, with a potential shifting at 460 nm. Furthermore, the inclusion of Sc3+ in the octahedral lattice and Ba2+-Si4+ in the dodecahedral-tetrahedral lattice markedly improves the thermal quenching resistance of Ce3+. Hence, this combination exhibits substantial advantages for high-power LED and LD lighting applications. In contrast, the introduction of Ca2+-Mg2+-Si4+/Ge4+ into the dodecahedral-octahedral-tetrahedral lattice configuration leads to a poor thermal quenching resistance for Ce3+, indicating a unsuitability for white light LED/LD illumination.

Furthermore, the d88/d81 ratio is related to the Ce3+ emission wavelength and thermal stability, based on the degree of [CeO8] distortion. It is indicated that at an equivalent Ce3+ doping concentration, an increase in the d88/d81 ratio corresponds to a redshift in emission wavelength and a decrease in thermal stability. Among the research results available, little work on the impact of d88/d81 value on the luminescence performance has been done yet. A future research on the in-depth physical models and subsequent experimental validation for Ce3+-doped garnet-based fluorescent materials is needed.

, authors=Yanna TIAN, Jintai FAN, Benxue JIANG, Jie CHEN, Shengming ZHOU, authorsList=Yanna TIAN, Jintai FAN, Benxue JIANG, Jie CHEN, Shengming ZHOU, authorCompany=null, correspAuthors=Shengming ZHOU, authorNote=

TIAN Yanna (1994-), female, Ph.D., Postdoctoral. E-mail:

, correspAuthorsNote=
ZHOU Shengming (1964-), male, Ph.D., Professor. E-mail:
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Ce3+掺杂石榴石基荧光材料凭借其良好的物化特性、高荧光转换效率、较短的荧光寿命、激发光谱与紫外/蓝光发光二极管发射谱的高效匹配等特点,被广泛用于照明、显示、医学成像等领域。得益于石榴石结构丰富的阳离子格位,通过多种类基质化学组分取代可实现Ce3+发射波长从460~610 nm范围内的连续可调,不仅大大拓宽了其潜在应用场景,也为Ce3+发光理论的建立和完善提供了广泛的素材。然而随着近年来相关实验探索的大幅增加,种类较为庞杂的Ce3+掺杂石榴石基荧光材料特性与发射波长调控理论常常出现无法解释甚至矛盾之处,成为阻碍Ce3+掺杂石榴石基荧光材料发展的重要瓶颈之一。针对这一问题,本文简要介绍了基质化学组分取代调控Ce3+发射波长的几种主要理论,综述了近年来Ce3+掺杂石榴石基荧光材料的研究进展,并结合理论与实验,主要从[CeO8]畸变因子角度出发,讨论了离子取代对Ce3+发光性能的影响。

, authors=田燕娜, 范金太, 姜本学, 陈杰, 周圣明, authorsList=田燕娜, 范金太, 姜本学, 陈杰, 周圣明, authorCompany=null, correspAuthors=周圣明, authorNote=

田燕娜(1994—),女,博士,博士后。

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周圣明(1964—),男,博士,研究员。
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Ce3+掺杂石榴石基荧光材料的光谱调控研究进展
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田燕娜 , 范金太 , 姜本学 , 陈杰 , 周圣明
硅酸盐学报 | 综合评述 2024,52(3): 1128-1148
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硅酸盐学报 |综合评述 2024 , 52 (3) : 1128 -1148
Ce3+掺杂石榴石基荧光材料的光谱调控研究进展
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田燕娜 , 范金太, 姜本学, 陈杰, 周圣明
作者信息
  • 中国科学院上海光学精密机械研究所,中国科学院强激光材料重点实验室,上海 201800
通讯作者:
周圣明(1964—),男,博士,研究员。
作者简介:

田燕娜(1994—),女,博士,博士后。

Development on Spectral Regulation of Ce3+-Doped Garnet-Based Fluorescent Materials
Yanna TIAN , Jintai FAN, Benxue JIANG, Jie CHEN, Shengming ZHOU
Affiliations
  • Key Laboratory of Materials for High Power Lasers, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, China
  • Corresponding Author:
    ZHOU Shengming (1964-), male, Ph.D., Professor. E-mail:

    TIAN Yanna (1994-), female, Ph.D., Postdoctoral. E-mail:

出版时间: 2024-03-20 doi: 10.14062/j.issn.0454-5648.20230668
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Ce3+掺杂石榴石基荧光材料凭借其良好的物化特性、高荧光转换效率、较短的荧光寿命、激发光谱与紫外/蓝光发光二极管发射谱的高效匹配等特点,被广泛用于照明、显示、医学成像等领域。得益于石榴石结构丰富的阳离子格位,通过多种类基质化学组分取代可实现Ce3+发射波长从460~610 nm范围内的连续可调,不仅大大拓宽了其潜在应用场景,也为Ce3+发光理论的建立和完善提供了广泛的素材。然而随着近年来相关实验探索的大幅增加,种类较为庞杂的Ce3+掺杂石榴石基荧光材料特性与发射波长调控理论常常出现无法解释甚至矛盾之处,成为阻碍Ce3+掺杂石榴石基荧光材料发展的重要瓶颈之一。针对这一问题,本文简要介绍了基质化学组分取代调控Ce3+发射波长的几种主要理论,综述了近年来Ce3+掺杂石榴石基荧光材料的研究进展,并结合理论与实验,主要从[CeO8]畸变因子角度出发,讨论了离子取代对Ce3+发光性能的影响。

石榴石  /  荧光材料  /  铈氧十二面体  /  热稳定性

For the favorable physicochemical properties, high fluorescence conversion efficiencies, a relatively short fluorescence lifetime, and an efficient spectral congruence between excitation and ultraviolet/blue LED emission spectra, Ce3+-doped garnet-based fluorescent materials can be used in encompassing lighting, displays, medical imaging, etc.. For leveraging the diverse cation sites within a garnet structure, the emission wavelength of Ce3+ can be continuously adjusted from 460 nm to 610 nm via the incorporation of varied matrix chemical constituents. This versatile tunability broadens the horizons of their potential applications and augments the repertoire of materials available for advancing Ce3+ luminescence theory. However, recent work on Ce3+-doped garnet-based fluorescent materials has unveiled certain anomalies and even contradictions within the characteristics and the emission wavelength modulation theory, becoming one of the prominent bottlenecks hindering the development of this material. To address this issue, this review represented the relative theories of substrate chemical component substitution and the modulation of Ce3+ emission wavelengths. The review also summarized recent advancements in Ce3+-doped garnet-based fluorescent materials, and the influence of ion substitution on Ce3+ luminescence performance with the distortion factor of [CeO8].

This review discussed the Ce3+-doped yttrium aluminum garnet structure as a prototype and comprehensively analyzed the impacts of commonly used doping ions that occupy the [AO8], [BO6], and [CO4] sites on the emission wavelength, thermal quenching resistance, and the [CeO8] distortion factor of Ce3+.

The ion substitution of a single lattice generally necessitates that the substituting ion and the substituted ion have the same valence state and exhibit a minimal disparity in atomic radius. In the case of [AO8] lattice substitution, Y3+ can be replaced with rare-earth ions, i.e., Lu3+, Tb3+, Gd3+, and La3+. When the radius of the doped rare-earth ions is greater that that of Y3+, the emission wavelength of Ce3+ shifts towards the red end of the spectrum. Conversely, when the radius is smaller, the shift occurs in the opposite direction.

The ion substitution of octahedral lattice sites mainly involves the replacement of Al3+ by Ga3+, Sc3+, and In3+. With an escalation in the concentration of doped ions like Ga3+, Sc3+, and In3+, the peak wavelength of the Ce3+ emission spectrum has a blue shift. In addition, the incorporation of Sc3+ effectively enhances the thermal quenching resistance of Ce3+, while the inclusion of Ga3+ diminishes the thermal quenching resistance of Ce3+.

The main substitutions of dodecahedral-octahedral lattice ion pairs include Ca2+-Hf4+ and Ca2+-Zr4+ replacing Y3+-Al3+. The emission and excitation peak wavelengths of Ce3+ gradually blueshifts as Ca2+-Hf4+ and Ca2+-Zr4+ doping contents increase.

The substitution of dodecahedral-tetrahedral lattice ions is mainly achieved by M2+-Si4+ (M=Mg, Ca, Sr, Ba) replacing Y3+-Al3+, with alkaline earth metals occupying the dodecahedral lattice and Si4+ occupying the tetrahedral lattice. In the garnet system, when M2+-Si4+ replaces Y3+-Al3+, the emission wavelength of Ce3+ undergoes a blue shift with the increase of M2+ ion radius, resulting in improving the thermal stability.

The substitution of octahedral-tetrahedral lattice ions mainly involves Mg2+-Si4+/Ge4+ replacing Al3+-Al3+, where Mg2+ occupies the octahedral lattice and Si4+/Ge4+ occupies the tetrahedral lattice. Among them, Mg2+-Si4+ replacing Al3+-Al3+ is an effective method to achieve a large redshift of Ce3+ emission wavelength. The introduction of Mg2+-Ge4+ also leads to the redshift of Ce3+ emission wavelength, but the extent of this redshift is considerably less than that achieved by Mg2+-Si4+.

The chemical components in dodecahedral-octahedral-tetrahedral lattice co-substitutions are more intricate, with Ca2+ and Mg2+ occupying the dodecahedral lattice, Mg2+, Sc3+, and Hf4+ occupying the octahedral lattice, and Si4+ and Ge4+ in the tetrahedral lattice. Different lattice ions on the co-substitution affect the luminescence performance of Ce3+.

Summary and prospects

The effect of ion substitution on the luminescence performance of Ce3+ is analyzed via utilizing Ce3+-doped yttrium aluminum garnet fluorescent material as a prototype. The comparative study reveals that the most effective redshift of Ce3+ emission wavelength appears when Mg2+-Si4+ occupies the octahedral-tetrahedral lattice configuration. This results in a possibility of red shifting the emission wavelength of Ce3+ at 610 nm, thereby significantly enhancing the color rendering capabilities of white LED/LD lighting systems.

Conversely, an effective blue shift in Ce3+ emission wavelength appears in Ca2+-Zr4+ located in the dodecahedral-octahedral lattice, with a potential shifting at 460 nm. Furthermore, the inclusion of Sc3+ in the octahedral lattice and Ba2+-Si4+ in the dodecahedral-tetrahedral lattice markedly improves the thermal quenching resistance of Ce3+. Hence, this combination exhibits substantial advantages for high-power LED and LD lighting applications. In contrast, the introduction of Ca2+-Mg2+-Si4+/Ge4+ into the dodecahedral-octahedral-tetrahedral lattice configuration leads to a poor thermal quenching resistance for Ce3+, indicating a unsuitability for white light LED/LD illumination.

Furthermore, the d88/d81 ratio is related to the Ce3+ emission wavelength and thermal stability, based on the degree of [CeO8] distortion. It is indicated that at an equivalent Ce3+ doping concentration, an increase in the d88/d81 ratio corresponds to a redshift in emission wavelength and a decrease in thermal stability. Among the research results available, little work on the impact of d88/d81 value on the luminescence performance has been done yet. A future research on the in-depth physical models and subsequent experimental validation for Ce3+-doped garnet-based fluorescent materials is needed.

garnet  /  fluorescent materials  /  cerium oxide dodecahedron  /  thermal stability
田燕娜, 范金太, 姜本学, 陈杰, 周圣明. Ce3+掺杂石榴石基荧光材料的光谱调控研究进展. 硅酸盐学报, 2024 , 52 (3) : 1128 -1148 . DOI: 10.14062/j.issn.0454-5648.20230668
Yanna TIAN, Jintai FAN, Benxue JIANG, Jie CHEN, Shengming ZHOU. Development on Spectral Regulation of Ce3+-Doped Garnet-Based Fluorescent Materials[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (3) : 1128 -1148 . DOI: 10.14062/j.issn.0454-5648.20230668
  • 上海市自然科学基金面上项目(22ZR1470800)
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doi: 10.14062/j.issn.0454-5648.20230668
  • 接收时间:2023-08-31
  • 首发时间:2026-10-22
  • 出版时间:2024-03-20
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  • 收稿日期:2023-08-31
  • 修回日期:2023-09-24
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上海市自然科学基金面上项目(22ZR1470800)
作者信息
    中国科学院上海光学精密机械研究所,中国科学院强激光材料重点实验室,上海 201800

通讯作者:

周圣明(1964—),男,博士,研究员。
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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