Enhanced near-infrared to green upconversion from Er3+-doped oxyfluoride glass and glass ceramics containing BaGdF5 nanocrystals

In this work, effect of glass composition as well as ceramization on visible and near-infrared (NIR) luminescence properties along with their decay dynamics of Er³⁺ ions has been compared considering two different oxyfluoride glasses yielding BaF₂ and BaGdF₅ nanocrystals. Both the glass systems have exhibited an intense normal and upconversion green emission under ultraviolet (378 nm) and NIR (978 nm) excitations, respectively. A remarkable enhancement of these emission intensities is observed for gadolinium-(Gd) containing glasses. Interestingly, NIR fluorescence intensity from Er³⁺ ions at 1540 nm has showed marginal decrease in gadolinium-containing glass which is attributed to occurrence of strong excited-state absorption (ESA) due to higher fluorine content ensuing an augmentation of upconversion green emission with a concomitant decrease in NIR emission. The quadratic dependence of upconversion green emission intensity on its pump power for all the samples revealed biphotonic absorption process from ground-state ⁴I_15/2 to the excited-state ⁴I_11/2 followed by ESA of second photon to the ⁴F_7/2 level. The intense green upconversion emission as well as enhanced NIR fluorescence lifetimes indicate the suitability of these glass/glass ceramics for upconversion lasers and amplification in the third telecom window.     

Enhancement of photoluminescence intensity of sintered CaAlSiN3:Eu2+ red phosphor-bismuthate glass composites

Wavelength converters in white light-emitting diodes are usually made by sintering of phosphor-glass powder compacts. An issue is that the sintering process usually results in the reduction of phosphor amount. In the present study, composites containing CaAlSiN₃:Eu²⁺ red phosphor and Bi₂O₃-B₂O₃-ZnO-Sb₂O₅ glass were fabricated by sintering method. Influences of CaAlSiN₃:Eu²⁺ phosphor content (10 vol%–30 vol%) and sintering temperature (410–430°C) on the residual amount of the phosphor phase and the resulting luminescence intensity of the composites were investigated. The change of CaAlSiN₃:Eu²⁺ content due to sintering was analyzed by X-ray diffraction. The interdiffusion between the CaAlSiN₃:Eu²⁺ and glass matrix was examine by scanning electron microscope equipped with energy dispersive X-ray spectrometry. This paper focuses on the change of luminescence intensity after sintering. It was found that although the content of phosphor CaAlSiN₃:Eu²⁺ reduces after sintering; the luminescent intensity of the composites anomalously increases. The optimum luminescence intensity is 14% higher than that of the as-mixed, unfired powder. It is proposed that the incorporation of Bi³⁺ ions from the glass matrix into the phosphor CaAlSiN₃:Eu²⁺ during sintering improves the luminescence ability of the phosphor particles.     

Investigation of optical properties: Eu with Al codoping in aluminum silicate glasses and glass‐ceramics

Eu‐doped transparent oxyfluoride aluminosilicate glass was prepared by controlling with Al codoping of melt‐quenched glass fabricated under air atmosphere. In the presence of Al input, the photoluminescence emission spectra under 393 nm excitation shows a blue shift by adjusting the ratio of Eu³⁺ and Eu²⁺. After heat treatment of glass, the ratio of Eu³⁺ and Eu²⁺ of luminescence emission were changed by controlling treatment temperature. The PL intensity of Eu³⁺ and Eu²⁺ ions in the glass‐ceramics (GC) was much stronger than in the precursor glass (PG). The possible mechanism responsible for color tuneability of the ratio of Eu³⁺ and Eu²⁺ doped was discussed.     

Structural and luminescence properties of silica powders and transparent glass‐ceramics containing LaF3:Eu3+ nanocrystals

In this work, silica powders and transparent glass‐ceramic materials containing LaF₃:Eu³⁺ nanocrystals were synthesized using the low‐temperature sol‐gel technique. Prepared samples were characterized by TG/DSC analysis as well as X‐ray diffraction and IR spectroscopy. The transformation from liquid sols toward bulk powders and xerogels was also examined and analyzed. The optical behavior of prepared Eu³⁺‐doped sol‐gel samples were evaluated based on photoluminescence excitation (PLE: λ_em = 611 nm) and emission (PL: λ_exc = 393 nm, λ_exc = 397 nm) spectra as well as luminescence decay analysis. The series of luminescence lines located within reddish‐orange spectral scope were registered and identified as the intra‐configurational 4f⁶‐4f⁶ transitions originated from Eu³⁺ optically active ions (⁵D₀ → ⁷F_J, J = 0‐4). Moreover, the R/O‐ratio was also calculated to estimate the symmetry in local framework around Eu³⁺ ions. The luminescence spectra and double‐exponential character of decay curves recorded for fabricated nanocrystalline sol‐gel samples (τ₁(⁵D₀) = 2.07 ms, τ₂(⁵D₀) = 8.07 ms and τ₁(⁵D₀) = 0.79 ms, τ₂(⁵D₀) = 9.76 ms for powders and glass‐ceramics, respectively) indicated the successful migration of optically active Eu³⁺ ions from amorphous silica framework to low phonon energy LaF₃ nanocrystal phase.     

Enhanced luminescence in Tb3+-doped germanate glass ceramic scintillators containing CaF2 nanocrystals

Tb³⁺-doped germanate glass ceramics containing CaF₂ nanocrystals were prepared by melt quenching method with subsequent heat treatment. Their microstructures were investigated by XRD and TEM techniques. Their optical properties were studied by the transmittance, the photoluminescence, and the X-ray excited luminescence (XEL). The luminescence intensity in the glass ceramics under 377 nm light and X-ray excitations is significantly enhanced. The maximum integrated XEL intensity of the glass ceramics is about 50% of that of the commercial Bi₄Ge₃O₁₂ (BGO) scintillating crystal. The results indicate that Tb³⁺-doped germanate glass ceramic could be a promising scintillating material used in X-ray detection for slow event.     

Preparation,optical, and thermal stability of Tb3+-doped glass ceramics containing Al4Ti2SiO12

The Tb³⁺-doped transparent glass ceramics containing Al₄Ti₂SiO₁₂ crystal are synthesized by the melt-solid-crystallization method. The optimal heat treatment conditions for the glass ceramic samples are determined to be 750°C, 1.5 h based on differential scanning calorimeter, X-ray diffractometer, scanning electron microscope, and light transmittance curve. The luminescence properties of the glass ceramics samples are characterized by a fluorescence spectrometer. The emission spectrum revealed that the dominant emission is green attributed to Tb³⁺, the optimal doping concentration is 0.3%. And the thermal quenching activation energy of 0.3% Tb³⁺-doped glass ceramics is 0.2554 eV, while the relative sensitivity is 1.50% K⁻¹ at 298 K and the absolute sensitivity is 2.27×10⁻² K⁻¹ at 418 K through variable temperature fluorescence spectroscopy test and a series of calculations. These findings demonstrate the excellent stability and temperature sensitivity of glass ceramics, thereby highlighting their potential for use in green lighting and temperature sensing applications.     

草酸沉淀法制备纳米晶Y2O3:Eu3+及粉体评价

报道了草酸作为沉淀剂并添加表面活性剂合成了纳米晶Y2O3：Eu^3 的方法,其一次粒径为20-30nm,团聚尺寸D50=0.53μm。粉体细且分布均匀。与微米晶比较,该纳米晶的发射光谱发生明显蓝移,色座标合荧光粉要求。     

Transparent ultrafine Yb3+:Y2O3 laser ceramics fabricated by spark plasma sintering

Conventional ceramic processing techniques do not produce ultrafine‐grained materials. However, since the mechanical and optical properties are highly dependent on the grain size, advanced processing techniques are needed to obtain ceramics with a grain size smaller than the wavelength of visible light for new laser sources. As an empirical study for lasing from an ultrafine‐grained ceramics, transparent Yb³⁺:Y₂O₃ ceramics with several doping concentrations were fabricated by spark plasma sintering (SPS) and their microstructures were analyzed, along with optical and spectroscopic properties. Laser oscillation was verified for 10 at.% Yb³⁺:Y₂O₃ ceramics. The laser ceramics in our study were sintered without sintering additives, and the SPS produced an ultrafine microstructure with an average grain size of 261 nm, which is about one order of magnitude smaller than that of ceramics sintered by conventional techniques. A load was applied during heating to enhance densification, and an in‐line transmittance near the theoretical value was obtained. An analysis of the crystal structure confirmed that the Yb³⁺:Y₂O₃ ceramics were in a solid solution. To the best of our knowledge, this study is the first report verifying the lasing properties of not only ultrafine‐grained but also Yb‐doped ceramics obtained by SPS.     

红色荧光粉YAl3(BO3)4:Eu3+的制备及发光性能研究

以稀土氧化物、硝酸铝和硼酸为原料,高温固相反应制备了单相红色荧光粉YAl3(BO3)4:Eu3+,用X射线衍射和发射光谱对荧光粉末的结构和发光性能进行了分析.研究了煅烧温度、Eu3+掺杂量对其发光性能的影响.结果表明,反应物在1 250 ℃下煅烧可制得单相YAl3(BO3)4:Eu3+晶体,在YAl3(BO3)4:Eu3+晶体中,Eu3+取代了YAl3(BO3)4晶体中Y3+,占据了非对称中心格位.在394 nm的紫外光激发下,YAl3(BO3)4:Eu3+荧光粉具有很强的发光性能,与(Y,Gd)BO3:Eu3+荧光粉相比,最强发射线波长由596 nm变为618 nm,由橙红色光变为红色光,色纯度有了很大提高.Eu3+的最佳掺杂量为8%(物质的量分数).     

Red emission from Eu3+: PVA polymer film

Bright red luminescent Eu³⁺ doped polyvinyl alcohol (PVA) films were made by solution casting technique. The emission performance of these films was studied from the measurement of excitation, emission, and lifetimes. On irradiation with an UV source, the doped films emitted bright red light. Such luminescent polymer films are expected to find potential applications as new optical materials. Emission process in the system was explained by an energy level scheme. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3273–3276, 2006     

Distribution of Tm3+ and Ni2+ in chalcogenide glass ceramics containing Ga2S3 nanocrystals: Influence on photoluminescence properties

The distribution of Tm³⁺ and Ni²⁺ ions is unambiguously exhibited in 80GeS₂-20Ga₂S₃ chalcogenide glass ceramics (GCs) containing Ga₂S₃ nanocrystals (NCs) by using advanced analytical transmission electron microscopy. Distinctively different distribution patterns of Tm³⁺ and Ni²⁺ ions are observed in the GCs obtained by controlled crystallization. The distribution of the dopants imposes strong influence on their optical properties which are revealed by absorption and photoluminescence (PL) spectra. Detailed discussions are given of the mechanisms of the crystallization-induced PL enhancement and quenching of the Tm³⁺ mid-infrared and Ni²⁺ near-infrared emissions, respectively.     

水热法合成SrAl2O4:Eu2+,Dy3+长余辉材料

研究了SrAl2O4：Eu^2 ，Dy^3 长余辉材料的一种新合成方法。首先利用水热法制备出该发光材料的前驱体，然后将此前驱体粉体在还原气氛下高温烧结，得亮度高，余辉时间长的洲SrAl2O4：Eu^2 ，Dy^3 超细长余辉材料，并对其发光性能进行了研究。并对水热法和复合沉淀法合成的此种材料进行了比较。     

Comprehensive study of tellurium based glass ceramics for thermoelectric application

Tellurium based glasses have interesting thermoelectric characteristics. However, their high electrical resistivity is still an obstacle to considering them for thermoelectric applications. In this work, the (Te₈₅Se₁₅)_60???0.6xAs_40???0.4xCu_x glass system was studied. This revealed that Cu can act as glass former and increase both glass thermal stability and electrical conductivity. The best candidate, (Te₈₅Se₁₅)₄₅As₃₀Cu₂₅, was chosen to prepare composites with Bi_0.5Sb_1.5Te₃ using spark plasma sintering. These glass ceramic samples exhibited a much better thermoelectric performance. Glass ceramics with 50?mol. % of Bi_0.5Sb_1.5Te₃ show a maximum ZT value equal to 0.37 at 413?K. Meanwhile, the advantages of glass including low sintering temperature and high formability are well maintained.     

Phase evolution and photoluminescence in Er3+ doped glass ceramics containing lutetium oxyfluoride nanocrystals

Crystalline phase evolution through merely adjusting composition was achieved in silicate glass ceramics containing Lu_nO_n-1F_n+2 (n = 5–10) nanocrystals. Orthorhombic or cubic phase nanocrystals were precipitated in the aluminosilicate glass matrix after thermal treatment together with varying the Na₂O/NaF ratio. Oxyfluoride nanocrystals with quasi-spherical shape show homogenous and dense distribution in glass matrix by transmission electron microscopy measurement. Intense upconversion and mid-infrared emissions were realized in these glass ceramics compared to the precursor glass, and the emission spectral shapes, relative emission intensity and fluorescence decay curves of Er³⁺ in cubic LuOF embedded samples exhibit remarkable differences due to the crystal phase dependent effect in glass ceramics. These results indicate that the crystallization and luminescence properties of oxyfluoride glass ceramics could be modified through the alteration of glass composition, which could be used for the development of novel glass ceramics and design of luminescent properties.     

YVO4:Eu3+,Bi3+荧光粉的制备及荧光性能研究

用溶胶凝胶法在较低温度下制备了YVO4:Eu3+,Bi3+荧光粉,采用X射线衍射仪(XRD),扫描电子显微镜(SEM)及荧光分光光度计测试,研究了合成产物的结构、表面形貌,分析了在Eu3+含量一定的情况下掺杂Bi3+的浓度的变化对发光性能的影响.结果表明,溶胶凝胶法合成的YVO4:Eu3+,Bi3荧光粉为单相结构、粒径在1 μm左右、无团聚现象;Bi3+对Eu3+离子有敏化作用,在一定浓度下使荧光粉的发射强度增加.     

Eu~(3+)掺杂浓度对NaYF_4:Eu~(3+)晶体荧光强度的影响

在乙醇和乙二醇的混合溶剂中,用溶剂热法,150℃,反应12 h,成功合成了NaYF4:Eu3+晶体。室温下,用X射线衍射对材料的组成进行了表征,JCPDS号为16-0334。荧光光谱分析表明,在395 nm(7F0→5L4)紫外光激发下,其发射峰在476 nm、540~578 nm、718 nm分别对应着Eu3+的5DJ(J=0,1,2,3)→7FJ(J=1,2,3,4)能级跃迁。并讨论了离子Y3+:Eu3+不同浓度掺杂比对荧光性质的影响。结果表明,Eu3+的最佳掺杂浓度比为5%,当掺杂浓度为10%时,出现荧光猝灭。     

Eu3+在LiSrPO4中的发光及浓度猝灭机理

采用高温固相法合成了白光发光二极管用LiSrPO4:Eu3+红色荧光粉.测量了LiSrPO4:Eu3+的激发和发射光谱,结果显示材料的发射光谱为一系列尖峰,主峰位于616 nm,具有很强的红光发射;激发光谱中O2-→Eu3+的电荷迁移态CTS (220～310 nm)非常低,Eu3+的f→f (310～500 nm)跃迁吸收很强,主峰位于393 nm,与InGaN(350～410 nm)管芯匹配.比较了LiSrPO4:Eu3+与LiCaPO4:Eu3+、LiBaPO4:Eu3+发射光谱的差异,这三种晶体中Eu3+占据的格位对称性按Ca、Sr、Ba顺序逐渐增加.根据Dexter理论判定Eu3+在LiSrPO4中的浓度猝灭机理为电四极-电四极(q-q)相互作用.加入电荷补偿剂Li+、Na+和Cl 均提高了LiSrPO4:Eu3+材料的发射强度.LiSrPO4: Eu3+是一种适合白光发光二极管激发的红色荧光粉.     

InBO3:Eu3+荧光粉的制备及光谱特性

合成了InBO3:Eu3 红色荧光粉 ,测定了其发光光谱 ,讨论了其发光亮度与稀土离子Eu3 浓度的关系     

Excitation-dependent energy transfer and color tunability in Dy3+/Eu3+ co-doped multi-component borophosphate glasses

Using the melt-quench technique, potassium zinc borophosphate (KZnBP) glasses incorporated with Dy³⁺, Eu³⁺, and Dy³⁺/Eu³⁺ ions individually and combinedly were prepared, and their photoluminescence (PL)-related features were investigated. The KZnBP glass containing an optimized content of Dy³⁺ (0.5 mol%) is co-doped with Eu³⁺ in various contents, and the energy transfer (ET) process between them was studied at λ_exci = 349, 364, 387 (Dy³⁺), and 394 nm (Eu³⁺). The Dy³⁺/Eu³⁺ co-doped system, when excited with Dy³⁺ excitations has resulted in a significant decrease in the intensity of Dy³⁺ peaks observed at 480 nm (⁴F_9/2→⁶H_15/2, blue) and 574 nm (⁴F_9/2→⁶H_13/2, yellow), with simultaneous enhancement of the intensity of Eu³⁺ peaks at 591 nm (⁵D₀→⁷F₁, orange) and 617 nm (⁵D₀→⁷F₂, red). This trend is due to the efficient energy transfer from Dy³⁺ to Eu³⁺, indicating that Eu³⁺ ions were sensitized by Dy³⁺ ions. Dexter's theory and the Inokuti–Hirayama (I–H) model revealed that the dipole–dipole interaction is accountable for the energy transfer from Dy³⁺ to Eu³⁺ through energy-transfer channels [⁴F_9/2(Dy³⁺)+⁷F_1,2(Eu³⁺)→⁶H_15/2(Dy³⁺)+⁵D₂(Eu³⁺)] and [⁴F_9/2(Dy³⁺)+⁷F₀(Eu³⁺)→⁶H_13/2(Dy³⁺)+⁵D₀(Eu³⁺)]. The color coordinates of the Dy³⁺/Eu³⁺ co-doped glasses under various excitations fall within the white light emission spectrum, indicating their potential application in warm white LEDs.     

Luminescence and temperature-sensing properties of Y4GeO8:Bi3+,Eu3+ phosphor

In this paper, Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor with dual emission centers was elaborated via conventional solid-state reaction technology. Thorough research on the structure, morphology, and luminous properties of Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor, the potential applications in optical thermometry were investigated by means of fluorescence intensity ratio and thermochromic techniques. Under 290 and 347 nm excitation, Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor presents broadband emission from ³P₁ → ¹S₀ transition of Bi³⁺ ions and characteristic emission peaks from 4f–4f transition of Eu³⁺ ions. Outstanding temperature-sensing capabilities are acquired from Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor. The maximum relative sensitivity (S_r) can attain 1.51% K⁻¹ (λ_ex = 290 nm). With temperature raising (303–513 K), the emitted color of Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor (λ_ex = 290 nm) shifts from faint yellow to red with a high chromaticity shift (0.180), which can be distinguished by the unaided eye clearly. Our results indicate that Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor has potential applications in optical temperature measurement and high-temperature safety marker.