Er3+离子掺杂钡镓锗玻璃上转换发光机理研究

研究了Er³⁺离子掺杂钡镓锗玻璃的吸收光谱、拉曼光谱和上转换光谱.分析了Er³⁺离子在钡镓锗玻璃中的上转换发光机理.结果表明：玻璃的最大声子能量为828cm^-1，紫外截止波长为275nm.采用800nm和980nmLD激发玻璃样品，在室温下观察到强烈的上转换绿光和红光发射.随着Er³⁺离子浓度的增加，绿光发光强度先增加后减小，而红光发光强度呈单调递增趋势.能量分析表明：800nmLD激发产生的绿光主要源于Er³⁺离子4I_13/2能级的激发态吸收过程；红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程.980nmLD激发产生的绿光主要源于Er³⁺离子4I_11/2能级之间的能量转移过程；而红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程和4I_13/2能级的激发态吸收过程.通过量子效率分析，发现采用800nmLD激发Er³⁺离子掺杂浓度为1mol% 的样品时，上转换绿光发光效率最高. 关键词： 上转换发光机理 3+离子掺杂')" href="#">Er³⁺离子掺杂 钡镓锗玻璃     

Upconversion luminescence in Er-doped germanate-oxyfluoride and tellurium-germanate-oxyfluoride transparent glass-ceramics

Upconversion luminescence has been studied for Er³⁺ in a germanate-oxyfluoride and a tellurium-germanate-oxyfluoride transparent glass-ceramic using 800 nm excitation. Significantly increased upconversion luminescence was observed from transparent glass-ceramics compared with that from their corresponding as-prepared glasses. In addition to a strong green emission centered at 545 nm from ⁴S_3/2 state and a weaker red emission centered at 662 nm from ⁴F_9/2 state generally seen from Er³⁺-doped glasses, a violet emission centered at 410 nm from ²H_9/2 state and a near-ultra-violet emission centered at 379 nm from ⁴G_11/2 state were also observed from transparent glass-ceramics. The upconversion luminescence of Er³⁺ ions in transparent glass-ceramics revealed sharp Stark-splitting peaks generally seen in a crystal host. The increased upconversion efficiency is attributed to the decreased effective phonon energy and the increased energy transfer between excited ions when Er³⁺ ions were incorporated into the precipitated β-PbF₂ nanocrystals.     

Optical thermometry through green and red upconversion emissions in Er/Yb/Li:ZrO2 nanocrystals

Variations of fluorescence intensity ratio of green (generated from Er^{3+ 2}H_11/2 and ⁴S_3/2 levels) and red (generated from the sublevels of Er^{3+ 4}F_9/2 level) upconversion emissions in Er³⁺/Yb³⁺/Li⁺:ZrO₂ nanocrystals have been studied as a function of temperature under 976 nm laser diode excitation. In the temperature range of 323-673 K, the maximum sensitivities of about 0.0134 K^− 1 and 0.0104 K^− 1 are obtained by using green and red emission, respectively. Er³⁺/Yb³⁺/Li⁺:ZrO₂ nanocrystals show potential application value in nanoscale thermal sensor.     

Host dependent thermal stability and frequency upconversion of Er^3＋-doped heavy metal oxyfluoride germanate glasses

The upconversion properties of Er^3＋-doped heavy metal oxyfluoride germanate glasses under 975 nm excitation have been investigated. The intense green （551 and 529 nm） and relatively weak red （657 nm） emissions corresponding to the transitions ^4S3/2→^4I15/2, ^2H11/2→^4 I15/2 and ^4F9/2 →^4I15/2, respectively, were simultaneously observed at room temperature. The content of PbF2 has an important influence on the upconversion luminescence emission. With increasing content of PbF2, the intensities of green （529 nm） and red （657 nm） emissions increase slightly, while the green emission （551 nm） increases markedly. These results suggest that PbF2 has an influence on the green （551 nm） emission more than on the green （529 nm） and red （657 nm） emissions.     

Intense Upconversion Luminescence of Yb<Superscript>3+</Superscript>-Er<Superscript>3+</Superscript> in Li<Subscript>2</Subscript>O Content Tungsten-tellurite Glasses

The Er³⁺ -Yb³⁺ codoped in Li₂O content tungsten -tellurite (TWL) transparent glasses are synthesized and measured the absorption, Raman and upconversion luminescence (UPL) spectra. At room temperature intense green emission peak at 560 nm ( ⁴S_3/2→⁴I_15/2) and red emission peak at 670 nm ( ⁴F_9/2→⁴I_15/2) of Er³⁺ observed even at minimum 86 mW pumping power of infrared 980 nm excitation. For structure of the TWL glass, Raman spectrum result revealed that an important role of WO₃ in the formation of glass network linkage with Li₂O. Under this influence estimated lifetime of the ⁴I_11/2 of Er³⁺ was 1.89 μs and due to lower phonon energy of the glass produce strong upconversion signal. The effect of Er₂O₃ concentration on emission intensity result indicated that green emission intensity initially increase in compare to red emission. Under the 980 nm pump power variation measured the relatively increases the red emission to the green emission intensity and analyze the possible upconversion mechanism and process.     

Structural and upconversion fluorescence properties of Er/Yb-codoped oxychloride lead-germanium-bismuth glass

Structural and infrared-to-visible upconversion fluorescence properties of Er³⁺/Yb³⁺-codoped oxychloride lead-germanium-bismuth glass have been studied. The Raman spectrum investigation indicates that PbCl₂ plays an important role in the formation of glass network, and has an important influence on the upconversion luminescence owing to lower phonon energy. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. The quadratic dependence of the 525, 546, and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs under 975 nm excitation.     

Upconversion luminescence and kinetics in Er:YAlO3 under 652.2 nm excitation

Ultraviolet and visible upconversion properties of Er³⁺ in YAlO₃ were investigated following 652.2 nm excitation of the multiples ⁴F_9/2. The luminescence and excitation spectra were recorded. Ultraviolet (326-342 and 354-359 nm), violet (405-420 nm), blue (436-442 nm) and green (525-575 nm) upconversion and infrared downconversion luminescence were simultaneously observed. The intense green luminescence corresponds to the emissions from the thermal coupled ⁴S_3/2 and ²H_11/2 bands and ²G_9/2 level. Energy transfer upconversion processes were proposed to explain the upconversion phenomena. The luminescence kinetics was discussed in detail by the analyses of fluorescence decay curves.     

Upconversion fluorescence property of Er/Yb-codoped novel bismuth-germanium glass

Infrared-to-visible upconversion fluorescence property of Er³⁺/Yb³⁺-codoped novel bismuth-germanium glass under 975 nm LD excitation has been studied. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. The structure of the bismuth-germanium glass has been investigated by peak-deconvolution of FT-Raman spectrum, and the structural information was obtained from the peak wavenumbers. This novel bismuth-germanium glass with low maximum phonon energy (∼750 cm⁻¹) can be used as potential host material for upconversion lasers.     

掺铒矾酸钇晶体上转换荧光研究

使用波长为808和658nm的半导体激光器和染料激光器作为激发源，测量了Er³⁺：YVO₄晶体的波长在553和410nm附近的上转换荧光.对激发过程的分析表明，贡献于上转换荧光的主要激发机制为激发态吸收.在不同浓度下对上转换荧光的寿命测量结果显示，随Er³⁺浓度的提高，553nm绿光的荧光寿命随浓度的增加而减小，但410nm的荧光寿命随Er³⁺浓度无明显变化.结合绿光强度随掺杂浓度增加而减小的结果，认为在所测浓度范围内 关键词：     

Near infrared to visible upconversion of Er in CaZrO3/CaSZ eutectic crystals with ordered lamellar microstructure

In this work we report the near infrared to visible upconversion luminescence of Er³⁺ ions in CaZrO₃/CaSZ eutectic crystals with ordered lamellar microstructure. The microstructure consists of alternating 2-μm-thick lamellae of calcia-stabilized zirconia (CaSZ) and calcium zirconate (CaZrO₃) single crystals. Er³⁺ ions enter both phases but at a higher concentration in CaSZ. Wavelength selective excitation along the ⁴I_15/2→⁴I_9/2 absorption band allows to distinguish the upconverted emission from Er³⁺ sites in the two eutectic phases. In the CaZrO₃ phase the upconversion emission spectrum is dominated by an intense green emission characterized by sharp (²H_11/2,⁴S_3/2) levels together with a more weak red emission from ⁴F_9/2 level. In the CaSZ phase, a broad green and red emissions occur with an enhancement of the red emission from level ⁴F_9/2. These upconverted emissions are attributed to a two photon process. The excitation wavelength dependence of the upconverted luminescence together with its time evolution after infrared pulsed excitation suggest that energy transfer upconversion processes are responsible for the upconversion luminescence.     

Tunable upconversion in Er-doped orthorhombic lead fluoride compound

Near infrared-visible upconversion in Er³⁺ doped orthorhombic PbF₂ compound is investigated. It is experimentally observed that the red emission intensity increases monotonously with Er³⁺ concentration increase, while the green emission intensity first increases and then decreases. Based on the rate-equation, the energy transfers involved in the upconversion processes have been explored. It is shown that due to the different multipolar nature for the energy transfer processes of ²H_11/2 (⁴S_3/2)+⁴I_15/2→⁴I_9/2+⁴I_13/2 and ⁴I_11/2+⁴I_11/2→⁴F_7/2+⁴I_15/2, the green and red upconversion emissions depend on Er³⁺ concentration in different ways. The theoretical results are in good agreement with the experimental observation. It is shown that the upconverted emission bands can be tuned by controlling Er³⁺ concentration in orthorhombic PbF₂ compound, which has many photonic applications under NIR excitation.     

Er3+掺杂新型GeS2-In2S3-CsI玻璃上转换光谱性质研究

用熔融淬冷法制备了掺Er³⁺的80GeS₂-10In2S₃-10CsI(mol%)硫卤玻璃样品,测试了样品的热学稳定性、喇曼光谱、吸收光谱以及上转换光谱,分析了Er³⁺离子在该玻璃中的上转换发光机理.应用Judd-Ofelt理论计算分析了Er3+离子在该样品中的强度参量Ωt(t=2,4,6)、自发辐射跃迁几率A、荧光分支比β以及辐射寿命τrad等光谱参量.在980 nm LD泵浦激发下,首次在该种玻璃中观察到强烈的绿光(526 nm、549 nm),分别对应于2H11/2→4I15/2和4S3/2→4I15/2的跃迁,其中549 nm处绿光较强.549 nm处上转换荧光寿命为0.34 ms,量子效率为69%.同时研究了绿光(526 nm、549 nm)上转换发光强度随泵浦激发功率的变化,其发光曲线拟合斜率分别为1.71和2.03,表明绿光是双光子吸收过程.研究结果表明：掺Er³⁺的80GeS₂-10In2S₃-10CsI硫卤玻璃是一种上转换绿光激光器的潜在基质材料.     

方波激发下Er3+上转换绿光发光动力学过程的研究

用方波电源驱动808 nm,980 nm激光二极管（LD）激发Er³⁺掺杂的亚碲酸盐氟氧化物玻璃,测量²H_11/2,⁴S_3/2能级上转换发光的上升和衰减,不同波长激发下的上升时间常数不同,说明808 nm LD和980 nm LD激发下²H_11/2,⁴S_3/2能级上转换激发途径不同.通过建立速率方程模型分析了⁴S_3/2能级的上升特性与中间能级寿命的关系,从而确定了两种波长激发下上转换绿光的激发机理. 关键词： 上转换 激发过程 3+')" href="#">Er³⁺ 方波激发     

Crystalline-structure-dependent green and red upconversion emissions of Er-Yb-Li codoped TiO2

Crystalline structures and infrared-to-visible upconversion luminescence spectra have been investigated in 1 mol% Er³⁺, 10 mol% Yb³⁺ and 0-20 mol% Li⁺ codoped TiO₂ [1Er10Yb(0-20)Li:TiO₂] nanocrystals. The crystalline structures of 1Er10Yb(0-20)Li:TiO₂ were divided into three parts by the addition of Yb³⁺ and Li⁺. Both green and red upconversion emissions were observed from the ²H_11/2/⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ in Er³⁺-Yb³⁺-Li⁺ codoped TiO₂, respectively. The green and red upconversion emissions of 1Er:TiO₂ were enhanced significantly by Yb³⁺ and Li⁺ codoping, in which the intensities of green and red emissions and the intensity ratio of green to red emissions (I_green/I_red) were highly dependent on the crystalline structures. The significant enhanced upconversion emissions resulted from the energy migration between Er³⁺ and Yb³⁺ as well as the distortion of crystal field symmetry of Er³⁺ caused by the dissolving of Li⁺ at lower Li⁺ codoping concentration and the phase transformation at higher Li⁺ concentration. It is concluded that codoping with ions of smaller ionic radius like Li⁺ can efficiently improve the upconversion emissions of Er³⁺ or other rare-earth ions doped luminsecence materials.     

Spectral performance and intensive green upconversion luminescence in Er/Yb-codoped NaY(WO4)2 crystal

Using Czochralski (CZ) pulling method, an Er³⁺/Yb³⁺-codoped NaY(WO₄)₂ crystal was prepared. Absorption spectra, emission spectra and excitation spectra of this crystal were measured at room temperature. Some optical parameters, such as intensity parameters, spontaneous emission probabilities and lifetimes, were calculated from absorption spectra with Judd-Ofelt (J-O) theory. Upconversion luminescence excited by a 970 nm diode laser was studied. In this crystal, green upconversion luminescence is particularly intensive. Energy transfer mechanisms that play an important role in upconversion processes were analyzed. Two cross-relaxation processes: ⁴G_11/2 + ⁴I_9/2 → ²H_11/2 (or ⁴S_3/2) + ²H_11/2 (or ⁴S_3/2), and ⁴G_11/2 + ⁴I_15/2 → ²H_11/2 (or ⁴S_3/2) + ²I_13/2, which contribute to the intensive green luminescence under 378 nm excitation, were put forward. Background energy transfer ⁴G_11/2(Er³⁺) + ²F_7/2(Yb³⁺) → ⁴F_9/2(Er³⁺) + ²F_5/2(Yb³⁺) was also demonstrated.     

Energy transfer and infrared-to-visible upconversion luminescence of Er/Yb-codoped halide modified tellurite glasses

We report on the energy transfer and frequency upconversion spectroscopic properties of Er³⁺-doped and Er³⁺/Yb³⁺-codoped TeO₂-ZnO-Na₂O-PbCl₂ halide modified tellurite glasses upon excitation with 808 and 978 nm laser diode. Three intense emissions centered at around 529, 546 and 657 nm, alongwith a very weak blue emission at 410 nm have clearly been observed for the Er³⁺/Yb³⁺-codoped halide modified tellurite glasses upon excitation at 978 nm and the involved mechanisms are explained. The quadratic dependence of fluorescence on excitation laser power confirms the fact that the two-photon contribute to the infrared to green-red upconversion emissions. And the blue upconversion at 410 nm involved a sequential three-photon absorption process.     

Thermal stability and spectroscopic properties of Er-doped lead fluorogermanate glasses

The thermal characterization and spectroscopic properties of Er³⁺-doped 0.6GeO₂-(0.4-x)PbO-xPbF₂ glasses were investigated experimentally. With the replacement of PbO by PbF₂ the thermal stability of glasses is improved and the infrared fluorescence intensity at 1530 nm is increased. The Judd-Ofelt intensity parameters, radiative transition rates, and fluorescence lifetimes of the excited ⁴I_13/2 level of Er³⁺ ions were calculated from Judd-Ofelt theory. The asymmetric ligand field around Er³⁺ ions resulted from the incorporation of PbF₂ into germanate glasses, broadens the infrared emission spectra at 1530 nm. Upconversion luminescence in the investigated glasses was observed at room temperature under the excitation of 976 nm laser diode. The glass 0.6GeO₂-0.3PbO-0.1PbF₂ exhibits the maximum upconversion emission intensity, while no frequency upconversion luminescence was observed in the 0.6GeO₂-0.4PbO glass. The quadratic dependence of the green and red emissions on excitation power indicates that two-photon absorption contributes to the visible emission under the 976-nm excitation.     

Enhancement of upconversion intensity in Er3+ doped tellurite glass in presence of Yb3+

TeO₂–PbO glasses doped/codoped with Er³⁺/Er³⁺-Yb³⁺ ions have been fabricated by melting and quenching method. Efficient frequency upconversion emissions spanning from blue to red regions corresponding to the ²H_11/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions, respectively, upon excitation with 976 nm diode laser radiation have been observed. The variations observed in the intensity of whole upconversion emission spectra due to the presence of the Yb³⁺ ions are reported and discussed in detail.     

Composition dependent frequency upconversion luminescence in Er-doped oxychloride germanate glasses

Er³⁺-doped oxychloride germanate glasses have been synthesized by conventional melting and quenching method. Structural and thermal stability properties were obtained based on the Raman spectra and differential thermal analysis, indicating that PbCl₂ plays an important role in the formation of glass network and has an important influence on the maximum phonon energy and thermal stability of host glasses. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. With increasing PbCl₂ content, the intensity of green (525 and 546 nm) emissions increases significantly, while the red (657 nm) emission increases slowly. The results indicate that PbCl₂ has more influence on the green emissions than the red emission in oxychloride germanate glasses. The possible upconversion luminescence mechanisms has also been estimated and discussed.     

Synthesis and luminescence properties of Gd6MoO12:Yb3+, Er3+ phosphor with enhanced photoluminescence by Li+ doping

Yb³⁺/Er³⁺ co-doped Gd₆MoO₁₂ and Yb³⁺/Er³⁺/Li⁺ tri-doped Gd₆MoO₁₂ phosphors were prepared by adjusting the annealing temperature via the high temperature solid-state method. Under the excitation of 980 nm semiconductor, the upconversion luminescence properties were investigated and discussed. In the experimental process, we get the optimum Yb³⁺ concentration and the concentration quench effect will happen while the concentration extends the given region. According to the Yb³⁺ concentration quenching effects, the critical distance between Yb³⁺ ions had been calculated. The measured UC luminescence exhibited a strong red emission near 660 nm and green emission at 530 nm and 550 nm, which are due to the transitions of Er³⁺(⁴F_9/2, ²H_11/2, ⁴S_3/2) → Er³⁺(⁴I_15/2). Then the effect of excitation power density in different regions on the upconversion mechanisms was investigated and the calculated results demonstrate that the green and red upconversion is a two-photon process. A possible mechanism was discussed. After Li⁺ ions mixing, the upconversion emission enhanced largely, and the optimum Li⁺ concentration was obtained while fixed the Yb³⁺ and Er³⁺ on the above optimum concentration. This enhancement owns to the decrease of the local symmetry around Er³⁺ after Li⁺ ions doping into the system. This result indicates that Li⁺ is a promising candidate for improving luminescence in some case.