Article(id=1320097969538454249, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320097951234502959, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230920, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1701187200000, receivedDateStr=2023-11-29, revisedDate=1704038400000, revisedDateStr=2024-01-01, acceptedDate=null, acceptedDateStr=null, onlineDate=1792665482172, onlineDateStr=2026-10-22, pubDate=1724083200000, pubDateStr=2024-08-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792665482172, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792665482172, creator=13701087609, updateTime=1792665482172, updator=13701087609, issue=Issue{id=1320097951234502959, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='8', pageStart='2453', pageEnd='2754', issueExtLink='null', onlineDate='null', pubDate='1724083200000', pubDateStr='2024-08-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792665477808, creator='13701087609', updateTime=1792666336581, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320101553256640512, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320097951234502959, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320101553256640513, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320097951234502959, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=2463, endPage=2473, ext={EN=ArticleExt(id=1320097969764946666, articleId=1320097969538454249, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Design of Ln3+/Cr3+ Doped Polyphase Glass-Ceramics and Multi-mode Self-calibration Temperature Measurement, columnId=1321894672176362135, journalTitle=Journal of the Chinese Ceramic Society, columnName=Special Issue on Glass Ceramic—Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

The energy transfer between lanthanide ions (Ln3+) and transition metal ions (Cr3+) typically leads to luminescence attenuation, which hinders their application in temperature measurement. However, this issue can be effectively addressed by synthesizing polyphase glass-ceramics that separate the Ln3+ and Cr3+ into different nano-crystals.

In this study, we designed polyhedral glass-ceramics (40SiO2-20Al2O3-15LiF-10Ga2O3-0.1TmF3-0.1ErF3-0.05Cr2O3-1YbF3-0.5SnO) doped with Ln3+/Cr3+ (Ln3+=Er3+/Tm3+/Yb3+). The up-conversion spectra of Tm3+ and Er3+ in the temperature range of 313-573 K, as well as the temperature-dependent properties of the emission intensity ratio of 2E and 4T2 and fluorescence lifetime decay of Cr3+ were systematically investigated. The results demonstrate that Ln3+/Cr3+-doped polyphase glass-ceramics exhibit excellent performance as a four-mode fluorescence temperature measurement material.

Methods

Ln3+/Cr3+-doped glass samples were prepared using melt quenching technology, where the raw materials were melted in a lifting furnace at 1 500 ℃ for 1 h. The sample was then poured onto a preheated copper plate to 300 ℃ and shaped by pressing it with another copper plate. Subsequently, the sample was annealed in a Muffle furnace at 450 ℃ for 6 h to obtain precursor glass (PG). Finally, the PG sample underwent heat treatment at 780 ℃ for 2 h to produce glass-ceramics (GC780).

X-ray diffraction apparatus was employed to measure the XRD spectra of these samples. FS-5 fluorescence spectrometer was used to measure various spectra including up-conversion and down-conversion spectra at room temperature, power-dependent up-conversion spectra, temperature-dependent up-conversion and down-conversion spectra, as well as temperature-dependent fluorescence lifetime decay curves. Transmission electron microscopy techniques such as selective electron diffraction and high-power transmission electron microscopy were utilized to examine GC780 samples.

Results and discussion

The diffraction peaks observed in the XRD pattern of GC780 exhibit excellent agreement with the standard cards of γ-Ga2O3 and β-YF3 respectively, indicating the successful synthesis of polyphase glass-ceramics containing γ-Ga2O3 and β-YF3 grains. The excitation and emission spectra of Cr3+ as well as the up-conversion spectra of Er3+ and Tm3+ indicate no energy transfer between Cr3+ and Er3+ or Tm3+.

In the variable temperature up-conversion emission spectra of GC780 sample within a temperature range of 313 to 573 K, the emission peak intensity ratio (FIR) I522/I543 and I694/I474, which change with temperature, were selected for temperature detection. As the temperature increases from 313 K to 573 K, there is a decrease in relative sensitive (SR) for I522/I543 with increasing temperature, reaching a maximum value of 1.03%·K-1 at 313 K. On the other hand, SR for I694/I474 initially increases and then decreases with rising temperature, peaking at a maximum value of 1.45%·K-1 at 473 K. In the down-conversion temperature-changing spectra (303-543 K) of Cr3+ excited at 397 nm, the intensity of the luminescence peaks at 615 nm and 720 nm is used to detect the temperature dependence of FIR(I615/I720). When the temperature is from 303 K to 543 K, SR gradually decreases with increasing temperature, and the maximum value of 1.74%·K-1 appears at 303 K. The relative sensitivity is 0.51%·K-1 at 496 K when Cr3+ down-conversion attenuation curve is used to measure temperature dependence.

Conclusions

Polyphase glass-ceramics doped with β-YF3 and γ-Ga2O3 nano-crystals in Ln3+/Cr3+ (Ln3+=Er3+/Tm3+/Yb3+) have been successfully synthesized by melt quenching method in this work. The up-conversion spectra of GC780 were measured in the temperature range of 313-573 K. The maximum relative sensitivities were 1.03%·K-1 and 1.45%·K-1, respectively, by selecting I522/I543 and I694/I474 intensity ratios. The 2E→4A2 and 4T2→4A2 emission2 peaks of Cr3+ were used for temperature detection, and the maximum relative sensitivity was 1.74%·K-1 at 303 K. In addition, the Cr3+ down-conversion attenuation curve is used to measure the temperature dependence, and the maximum relative sensitivity is 0.51%·K-1 at 496 K. The Ln3+/Cr3+ (Ln3+=Er3+/Tm3+/Yb3+) co-doped β-YF3 and γ-Ga2O3 nano-crystals polyphase glass-ceramic is thus indicated to be a highly promising competitive four-mode self-calibration temperature measurement material.

, authors=Fangfang HU, Yuhao MA, Falin ZHANG, Hai GUO, authorsList=Fangfang HU, Yuhao MA, Falin ZHANG, Hai GUO, authorCompany=null, correspAuthors=Fangfang HU, Hai GUO, authorNote=

HU Fangfang (1989-), female, Ph.D., Associate Professor. E-mail:

, correspAuthorsNote=
GUO Hai (1980-), male, Ph.D., Professor. E-mail: ;
HU Fangfang (1989-), female, Ph.D., Associate Professor.
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采用熔融淬冷法合成了Ln3+/Cr3+(Ln3+=Er3+/Tm3+/Yb3+)掺杂的含β-YF3和γ-Ga2O3纳米晶的多相微晶玻璃(40SiO2-20Al2O3-15LiF-10Ga2O3-0.1TmF3-0.1ErF3-0.05Cr2O3-1YbF3-0.5SnO)。利用Ln3+在β-YF3纳米晶和Cr3+在γ-Ga2O3纳米晶中的富集,有效抑制了Ln3+与Cr3+之间的能量传递,从而实现多色、多模式的高效发光。分别利用Er3+和Tm3+的发光强度比I522/I543和I694/I474进行温度监测,得到的最大相对灵敏度分别为1.03%·K-1(313 K)、1.45%·K-1(473 K)。此外,基于Cr3+的2E和4T2的发光强度比I615/I720和寿命进行温度探测,得到最大相对灵敏度分别为1.74%·K-1(303 K)、0.51%·K-1(496 K)。Ln3+/Cr3+共掺的多相微晶玻璃是一种极富竞争力的四模自校准测温材料。

, authors=胡芳芳, 马昱昊, 张发林, 郭海, authorsList=胡芳芳, 马昱昊, 张发林, 郭海, authorCompany=null, correspAuthors=胡芳芳, 郭海, authorNote=

胡芳芳(1989—),女,博士,副教授。

, correspAuthorsNote=
郭海(1980—),男,博士,教授;
胡芳芳(1989—),女,博士,副教授。
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Ln3+/Cr3+掺杂多晶相微晶玻璃的设计及多模自校准测温
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胡芳芳 , 马昱昊 , 张发林 , 郭海
硅酸盐学报 | 微晶玻璃专题—研究论文 2024,52(8): 2463-2473
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硅酸盐学报 |微晶玻璃专题—研究论文 2024 , 52 (8) : 2463 -2473
Ln3+/Cr3+掺杂多晶相微晶玻璃的设计及多模自校准测温
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胡芳芳 , 马昱昊, 张发林, 郭海
作者信息
  • 浙江师范大学物理与电子信息工程学院,浙江 金华 321004
通讯作者:
郭海(1980—),男,博士,教授;
胡芳芳(1989—),女,博士,副教授。
作者简介:

胡芳芳(1989—),女,博士,副教授。

Design of Ln3+/Cr3+ Doped Polyphase Glass-Ceramics and Multi-mode Self-calibration Temperature Measurement
Fangfang HU , Yuhao MA, Falin ZHANG, Hai GUO
Affiliations
  • College of Physics and Electronic Information Engineering, Zhejiang Normal University, Jinhua 321004, Zhejiang, China
  • Corresponding Author:
    GUO Hai (1980-), male, Ph.D., Professor. E-mail: ;
    HU Fangfang (1989-), female, Ph.D., Associate Professor.

    HU Fangfang (1989-), female, Ph.D., Associate Professor. E-mail:

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20230920
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采用熔融淬冷法合成了Ln3+/Cr3+(Ln3+=Er3+/Tm3+/Yb3+)掺杂的含β-YF3和γ-Ga2O3纳米晶的多相微晶玻璃(40SiO2-20Al2O3-15LiF-10Ga2O3-0.1TmF3-0.1ErF3-0.05Cr2O3-1YbF3-0.5SnO)。利用Ln3+在β-YF3纳米晶和Cr3+在γ-Ga2O3纳米晶中的富集,有效抑制了Ln3+与Cr3+之间的能量传递,从而实现多色、多模式的高效发光。分别利用Er3+和Tm3+的发光强度比I522/I543和I694/I474进行温度监测,得到的最大相对灵敏度分别为1.03%·K-1(313 K)、1.45%·K-1(473 K)。此外,基于Cr3+的2E和4T2的发光强度比I615/I720和寿命进行温度探测,得到最大相对灵敏度分别为1.74%·K-1(303 K)、0.51%·K-1(496 K)。Ln3+/Cr3+共掺的多相微晶玻璃是一种极富竞争力的四模自校准测温材料。

微晶玻璃  /  氟化钇  /  氧化镓  /  荧光温度探测
Introduction

The energy transfer between lanthanide ions (Ln3+) and transition metal ions (Cr3+) typically leads to luminescence attenuation, which hinders their application in temperature measurement. However, this issue can be effectively addressed by synthesizing polyphase glass-ceramics that separate the Ln3+ and Cr3+ into different nano-crystals.

In this study, we designed polyhedral glass-ceramics (40SiO2-20Al2O3-15LiF-10Ga2O3-0.1TmF3-0.1ErF3-0.05Cr2O3-1YbF3-0.5SnO) doped with Ln3+/Cr3+ (Ln3+=Er3+/Tm3+/Yb3+). The up-conversion spectra of Tm3+ and Er3+ in the temperature range of 313-573 K, as well as the temperature-dependent properties of the emission intensity ratio of 2E and 4T2 and fluorescence lifetime decay of Cr3+ were systematically investigated. The results demonstrate that Ln3+/Cr3+-doped polyphase glass-ceramics exhibit excellent performance as a four-mode fluorescence temperature measurement material.

Methods

Ln3+/Cr3+-doped glass samples were prepared using melt quenching technology, where the raw materials were melted in a lifting furnace at 1 500 ℃ for 1 h. The sample was then poured onto a preheated copper plate to 300 ℃ and shaped by pressing it with another copper plate. Subsequently, the sample was annealed in a Muffle furnace at 450 ℃ for 6 h to obtain precursor glass (PG). Finally, the PG sample underwent heat treatment at 780 ℃ for 2 h to produce glass-ceramics (GC780).

X-ray diffraction apparatus was employed to measure the XRD spectra of these samples. FS-5 fluorescence spectrometer was used to measure various spectra including up-conversion and down-conversion spectra at room temperature, power-dependent up-conversion spectra, temperature-dependent up-conversion and down-conversion spectra, as well as temperature-dependent fluorescence lifetime decay curves. Transmission electron microscopy techniques such as selective electron diffraction and high-power transmission electron microscopy were utilized to examine GC780 samples.

Results and discussion

The diffraction peaks observed in the XRD pattern of GC780 exhibit excellent agreement with the standard cards of γ-Ga2O3 and β-YF3 respectively, indicating the successful synthesis of polyphase glass-ceramics containing γ-Ga2O3 and β-YF3 grains. The excitation and emission spectra of Cr3+ as well as the up-conversion spectra of Er3+ and Tm3+ indicate no energy transfer between Cr3+ and Er3+ or Tm3+.

In the variable temperature up-conversion emission spectra of GC780 sample within a temperature range of 313 to 573 K, the emission peak intensity ratio (FIR) I522/I543 and I694/I474, which change with temperature, were selected for temperature detection. As the temperature increases from 313 K to 573 K, there is a decrease in relative sensitive (SR) for I522/I543 with increasing temperature, reaching a maximum value of 1.03%·K-1 at 313 K. On the other hand, SR for I694/I474 initially increases and then decreases with rising temperature, peaking at a maximum value of 1.45%·K-1 at 473 K. In the down-conversion temperature-changing spectra (303-543 K) of Cr3+ excited at 397 nm, the intensity of the luminescence peaks at 615 nm and 720 nm is used to detect the temperature dependence of FIR(I615/I720). When the temperature is from 303 K to 543 K, SR gradually decreases with increasing temperature, and the maximum value of 1.74%·K-1 appears at 303 K. The relative sensitivity is 0.51%·K-1 at 496 K when Cr3+ down-conversion attenuation curve is used to measure temperature dependence.

Conclusions

Polyphase glass-ceramics doped with β-YF3 and γ-Ga2O3 nano-crystals in Ln3+/Cr3+ (Ln3+=Er3+/Tm3+/Yb3+) have been successfully synthesized by melt quenching method in this work. The up-conversion spectra of GC780 were measured in the temperature range of 313-573 K. The maximum relative sensitivities were 1.03%·K-1 and 1.45%·K-1, respectively, by selecting I522/I543 and I694/I474 intensity ratios. The 2E→4A2 and 4T2→4A2 emission2 peaks of Cr3+ were used for temperature detection, and the maximum relative sensitivity was 1.74%·K-1 at 303 K. In addition, the Cr3+ down-conversion attenuation curve is used to measure the temperature dependence, and the maximum relative sensitivity is 0.51%·K-1 at 496 K. The Ln3+/Cr3+ (Ln3+=Er3+/Tm3+/Yb3+) co-doped β-YF3 and γ-Ga2O3 nano-crystals polyphase glass-ceramic is thus indicated to be a highly promising competitive four-mode self-calibration temperature measurement material.

glass-ceramics  /  yttrium fluoride  /  gallium oxide  /  fluorescence temperature detection
胡芳芳, 马昱昊, 张发林, 郭海. Ln3+/Cr3+掺杂多晶相微晶玻璃的设计及多模自校准测温. 硅酸盐学报, 2024 , 52 (8) : 2463 -2473 . DOI: 10.14062/j.issn.0454-5648.20230920
Fangfang HU, Yuhao MA, Falin ZHANG, Hai GUO. Design of Ln3+/Cr3+ Doped Polyphase Glass-Ceramics and Multi-mode Self-calibration Temperature Measurement[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2463 -2473 . DOI: 10.14062/j.issn.0454-5648.20230920
  • 国家自然科学基金项目(LY21A040005)
  • 浙江省自然科学基金项目(11804303; 11974315; 51802285)
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2024年第52卷第8期
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doi: 10.14062/j.issn.0454-5648.20230920
  • 接收时间:2023-11-29
  • 首发时间:2026-10-22
  • 出版时间:2024-08-20
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  • 收稿日期:2023-11-29
  • 修回日期:2024-01-01
基金
国家自然科学基金项目(LY21A040005)
浙江省自然科学基金项目(11804303; 11974315; 51802285)
作者信息
    浙江师范大学物理与电子信息工程学院,浙江 金华 321004

通讯作者:

郭海(1980—),男,博士,教授;
胡芳芳(1989—),女,博士,副教授。
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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
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