Article(id=1320099057368941546, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320099031116792469, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20240190, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1709827200000, receivedDateStr=2024-03-08, revisedDate=1715788800000, revisedDateStr=2024-05-16, acceptedDate=null, acceptedDateStr=null, onlineDate=1792665741531, onlineDateStr=2026-10-22, pubDate=1734624000000, pubDateStr=2024-12-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792665741531, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792665741531, creator=13701087609, updateTime=1792665741531, updator=13701087609, issue=Issue{id=1320099031116792469, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='12', pageStart='3663', pageEnd='3904', issueExtLink='null', onlineDate='null', pubDate='1734624000000', pubDateStr='2024-12-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792665735272, creator='13701087609', updateTime=1792666214857, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320101042704994698, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320099031116792469, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320101042704994699, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320099031116792469, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=3718, endPage=3727, ext={EN=ArticleExt(id=1320099057574462443, articleId=1320099057368941546, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Full Spectrum Emission Performance of Eu
2+/Eu
3+ Co-doped Cs
3Cu
2I
5/CsCu
2I
3 Dual-Phase Quantum Dots Glass, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction Lead halide perovskites have attracted much attention in optoelectronic research due to their exceptional properties, such as long carrier diffusion lengths, low exciton binding energies, and cost-effective production. However, their inherent lead toxicity and poor environmental stability have challenges, restricting their wider adoption. It is thus important to search for safer, lead-free alternatives. Cesium copper halides emerge as promising candidates, offering the similar photoluminescent properties and potential for full-spectrum emission. Nevertheless, these materials still suffer from degradation under harsh conditions, which limits their practical use. Embedding cesium copper halides in glass matrices can enhance the stability via protecting the quantum dots from environmental factors like moisture and oxygen. However, challenges such as low transparency and limited tunability remain. To overcome these issues, the introduction of rare-earth ions like europium (Eu2+/Eu3+) into the glass matrix is proposed. In this work, transparent Eu2+/Eu3+ doped Cs3Cu2I5/CsCu2I3 dual-phase quantum dot glass was synthesized by an one-step melt-quenching method. The resulting glass exhibits a full-spectrum cold white light emission with a correlated color temperature (C) of 7 421 K, a general color rendering index (R) of 82, and a photoluminescence quantum yield of 75.1%.
Methods In this study, a transparent Eu2+/Eu3+ doped Cs3Cu2I5/CsCu2I3 biphasic quantum dot glass was synthesized by an one-step melt-quenching method. The glass composition designed was 20% SiO2, 50% B2O3, 5% ZnO, 3% Al2O3, 10% Cs2CO3, and 12% NaI, all in molar percentages. To induce the precipitation of biphasic quantum dots within the glass matrix, additional components were introduced, i.e., 1% CuI to promote the formation of cesium copper iodide, 0.04% SnO to prevent the oxidation of Cu+, 1% CaO to facilitate the precipitation process, and 1% MnO to reduce the viscosity of the glass. Various concentrations of Eu2O3 (i.e., 0%, 0.02%, 0.05%, and 0.10%) were added to enhance the glass emission properties.
The crystalline phases in the glass were determined by X-ray diffraction (XRD). The glass transition temperature and crystallization temperature were determined by differential scanning calorimetry (DSC) as indicatives of the thermal stability of the glass. The photoluminescence (PL) spectra were employed to evaluate the optical properties of the glass (i.e., the emission spectrum, quantum yield, and R). The oxidation states of the elements within the glass were analyzed by X-ray photoelectron spectroscopy, providing an insight into the distribution of Eu2+/Eu3+. The absorption spectra of the glass were characterized by UV-visible spectrophotometry.
Results and Discussion The results demonstrate that the Eu2+/Eu3+ doped Cs3Cu2I5/CsCu2I3 biphasic quantum dot glass exhibits enhanced photoluminescent properties, compared to the undoped samples. The introduction of Eu2O3 can increase the overall emission intensity and broaden the emission spectrum, resulting in a full-spectrum cold white light emission. Specifically, the glass doped with 0.05% Eu2O3 achieves a photoluminescence quantum yield of 75.1%, with a C of 7421 K and a general R of 82. These results indicate that the Eu2+/Eu3+ co-doping effectively improves the glass emission characteristics via providing additional emission centers in the blue and red regions of the spectrum, attributed to Eu2+ and Eu3+, respectively. The structural analysis shows the effective incorporation of Eu2+/Eu3+ ions into the Cs3Cu2I5/CsCu2I3 matrix without disrupting the existing crystal structures. The XRD patterns indicate that the doped glass maintains the characteristic diffraction peaks of Cs3Cu2I5 and CsCu2I3, indicating that the addition of Eu2O3 does not alter the fundamental crystal structure of the biphasic quantum dots. Moreover, the DSC analysis reveal a high glass transition temperature of 652 K and a crystallization temperature of 717 K, indicating that the doped glass has an excellent thermal stability. The glass samples are also subjected to long-term stability tests, showing a minimal degradation in their optical properties after three months of storage. The photoluminescence spectra of the stored samples exhibit only minor shifts in emission peak positions and intensity, indicating that the glass retains its luminescent properties. In addition, the Eu2+/Eu3+ doping also improves the glass transparency and color rendering capabilities. The doped glass samples have a higher degree of transparency, compared to the undoped samples, which is attributed to the clarifying effect of Eu2O3. The Eu2+/Eu3+ ions provide complementary blue and red emission, thus enhancing the overall color rendering and allowing for the production of cold white light with a high color quality. The improved transparency and color rendering make the doped glass suitable for use in lighting and display applications in which high brightness and accurate color representation are required.
Conclusions Eu2+/Eu3+ doped Cs3Cu2I5/CsCu2I3 biphasic quantum dot glass was synthesized as a stable, lead-free photoluminescent material. The synthesized glass demonstrated an excellent full-spectrum cold white light emission, making it a promising candidate for various optoelectronic applications (i.e., lighting, displays, and sensors). The one-step melt-quenching method was effective in producing a material with a high thermal stability, a robust structural integrity and an enhanced optical performance. The introduction of Eu2O3 provided additional emission centers, improved transparency, and enhanced color rendering, addressing the limitations of previous cesium copper halide quantum dot glasses. This study could provide a viable strategy for the design and fabrication of advanced quantum dot glasses that meet the stringent demands of modern optoelectronic devices, offering a safer and more stable alternative to lead-based perovskites.
, authors=Zhaoqi LIU, Changfu XU, Pengbo LV, Lizhong SUN, authorsList=Zhaoqi LIU, Changfu XU, Pengbo LV, Lizhong SUN, authorCompany=null, correspAuthors=Pengbo LV, authorNote=
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2+/Eu
3+共掺Cs
3Cu
2I
5/CsCu
2I
3复相量子点玻璃的全光谱发射特性, columnId=1263922770220560512, journalTitle=硅酸盐学报, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=
相较于铅卤钙钛矿材料，无铅金属卤化物因其优异的发光特性和无毒属性而受到关注。基于铯铜卤化物制备的无铅量子点玻璃，因玻璃基质的致密性可以将铯铜卤化物与水、氧气等侵蚀性环境隔离开，从而适应各种复杂的使用场景。本工作研究了在玻璃中原位析出的Eu3+/Eu2+共掺Cs3Cu2I5/CsCu2I3双相量子点透明玻璃，并通过改变Eu2O3的掺杂量和激发波长调控光谱发射，实现了不同色温的全光谱照明。结果表明，Eu3+/Eu2+的共掺杂可以实现Cs3Cu2I5/CsCu2I3双相量子点玻璃色温为7 421 K、一般显色指数为82、光致发光量子产率为75.1%的高效单基质冷白光发射。
, authors=刘朝奇, 徐昌富, 吕蓬勃, 孙立忠, authorsList=刘朝奇, 徐昌富, 吕蓬勃, 孙立忠, authorCompany=null, correspAuthors=吕蓬勃, authorNote=
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吕蓬勃（1988—），男，博士，副教授。
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刘朝奇（2000—），男，博士研究生。
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