Upconversion Luminescence Dynamics in Er^3＋/Yb^3＋ Codoped Nanocrystalline Yttria

The upconversion luminescence and dynamics in Er^3＋ /Yb^3＋ codoped nanocrystalline yttria （7-65 nm） are studied under 980-nm pulsed laser excitation, It is found that the red emission of ^4F9/2-^4I15/2 and the green emission of ^2H11/2/^4S3/2 in nanoparticles with lower concentration of Yb^3＋ result from a two-photon excitation, In nanocrystals with higher Yb^3＋ concentration, the red emissions from a two-photon excitation, while the green emissions from a three-photon excitation, The luminescence dynamics indicates that as the particle size decreases, both the rise and the decay time constants become shorter, As the size decreases to several nanometres, the rise process nearly disappears, suggesting that the upconversion luminescence originates mainly from self-excitation of Er^3＋, instead of the energy transfer of Yb^3＋→ Er^3＋.     

Intense Green Upconversion Luminescence in Er^3＋：Yb^3＋ Codoped Fluorophosphate Glass Ceramic Containing SrTe5O11 Nanocrystals

Er^3＋ ：Yb^3＋ codoped tellurite-fluorophosphate （TFP） glass ceramic exhibits much stronger upconversion luminescence. The intensity of the 540nm green light and 651 nm red light of the TFP glass ceramic is 120 times and 44 times stronger than that of the fluorophospahte （FP） glass, respectively. XRD analysis shows that the nanocrystal in TFP glass ceramic is SrTe5O11. TFP glass ceramic also displays much higher upconversion fluorescence lifetime and crystallization stability. The narrow and strong peak at 540nm is very ideal for practical upconversion luminescence realization. This work is a new trial for exploring non-PbF2 involved nanocrystal upconversion glass ceramics.     

Research on upconversion codoped oxyfluoride luminescence in new Er^3＋/Yb^3＋ borosilicate glass ceramics

The upconversion luminescence of Er^3＋/Yb^3＋ ions is researched in a novel transparent oxyfluoride borosil- icate glass and glass ceramics under 980-nm excitation. Fluoride nanocrystals Ba2YF7 are successfully precipitated in glass matrix, which is affirmed by the X-ray diffraction results. Compared with the parent glasses, significant enhancement of upconversion luminescence is observed in the Er^3＋/Yb^3＋ codoped transparent glass-ceramics, which may be due to the variation of coordination environment around Er^3＋ and Yb^3＋ ions after crystallization. The possible upconversion mechanism is also discussed.     

High Efficiency Infrared-to-Visible Upconversion Emission in Er^3＋,Yb^3＋, and Ho^3＋ Codoped Tellurite Glasses

A novel method of codoping the Er^3＋, Yb^3＋, and Ho^3＋ ions in tellurite glasses is demonstrated to obtain a high efficiency of infrared-to-visible upconversion. Three intense emission bands observed in Er^3＋, Yb^3＋, and Ho^3＋ codoped tellurite glasses centred at 525, 547, and 657nm correspond to Er^3＋： ^2H11/2 -4 ^4I15/2, Er^3＋： ^4S3/2 →^4I15/2＋Ho^3＋： ^5S2（^5F4） → ^5Is, and Er^3＋： ^4Sa/2 → ^4I15/2＋Ho^3＋： ^5F5 → ^5Is transitions, respectively. No visible upconversion quenching phenomenon is observed when three rare-earth ions are codoped together in tellurite glasses. In contrast, the upconversion intensity of red and green emissions in Er^3＋, Yb^3＋, and Ho^3＋ codoped glasses is enhanced largely when compared with Er^3＋ /Yb^3＋-codoped glasses. The dependence of upconversion intensities on excitation power and the possible upconversion mechanisms are evaluated. The three emissions are based on two-photon absorption processes.     

Abnormal Visible Luminescence Mechanism of Tb^3＋-Yb^3＋ Codoped SiOu-Al2O3-CaF2 Glass Studied by Time-Resolved Spectra

The upconversion energy transfer mechanism in Tb^3＋-Yb^3＋ co-doped SiO2-Al2O3-CaF2 glass is investigated by time-resolved spectra. The effect of donor ion Yb^3＋ is involved in the dynamic decay behavior of acceptor ion Tb^3＋, which provides direct proof for the energy transfer from Yb^3＋ to Tb^3＋. The pump power dependence curves show that the upconversion luminescence is a two-photon process. The measured decay curves of the 5D4 state （Tb^3＋） contain two parts： a slow decay process corresponding to its radiation, and a fast one with a decay parameter approximately twice the lifetime of the ^2F5/2 state （Yb^3＋ ）. The fast decay process is contradictory to the generally accepted cooperative sensitization upconversion rate equation model. Since the effect of the host environmental is excluded by comparative experiments, we believe that there should be another energy transfer mechanism in Tb^3＋-Yb^3＋ co-doped SiO2-Al2O3-CaF2 glass in addition to the cooperative sensitization process.     

Spectroscopic properties and mechanism of Tm^3＋/Er^3＋/Yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals

Transparent Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals are prepared. Under excitation of a 980-nm laser diode （LD）, compared with the glass before heat treatment, the Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics can emit intense blue, green and red up-conversion luminescence and Stark- split peaks; X-ray diffraction （XRD） and transmission electron microscope （TEM） results show that BaF2 nanocrystals with an average diameter of 20 nm are precipitated from the glass matrix. Stark splitting of the up-conversion luminescence peaks in the glass ceramics indicates that Tm^3＋, Er^3＋ and （or） Yb^3＋ ions are incorporated into the BaF2 nanocrystals. The up-conversion luminescence intensities of Tm^3＋, Er^3＋ and the splitting degree of luminescence peaks in the glass ceramics increase significantly with the increase of heat treat temperature and heat treat time extension. In addition, the possible energy transfer process between rare earth ions and the up-conversion luminescence mechanism are also proposed.     

Infrared-to-green upconversion luminescence and mechanism of Ho3+, Nd3+ and Yb3+ ions in oxyfluoride glass ceramics

New oxyfluoride glasses and glass ceramics co-doped with Nd^{3+}, Yb^{3+} and Ho^{3+} were prepared. The upconversion of infrared radiation into green fluorescence has been studied for Nd^{3+}, Yb^{3+} and Ho^{3+} in the transparent oxyfluoride glass ceramics. At room temperature very strong green upconversion luminescence due to the Ho^{3+}: ({}^5F_4, {}^5S_2)→{}^5I_8 transition under 800 nm excitation was observed in the glass ceramics. The intensity of the green upconversion luminescence in a 1mol% YbF_3-containing glass ceramic was found to be about 120 times stronger than that in the precursor oxyfluoride glass. The reason for the highly efficient Ho^{3+} upconversion luminescence in the oxyfluoride glass ceramics is discussed. The upconversion mechanism is also investigated.     

Upconversion luminescence of Tm^3＋/Yb^3＋ codoped oxyfluoride glasses

Novel oxyfluoride glasses are developed with the composition of 30SiO2-15Al2O3-28PbF2-22CdF2-0.1TmF3 - xYbF3 - （4.9 - x） AlF3（x=0, 0.5, 1.0, 1.5, 2.0） in tool fraction, Furthermore, the upconversion luminescence characteristics under a 970nm excitation are investigated. Intense blue, red and near infrared luminescences peaked at 453nm, 476nm, 647nm and 789nm, which correspond to the transitions of Tm^3＋： ^1D2 →^3F4, ^1G4 →^3H6, ^1G4 →^3F4, and ^3H4 →^3H6, respectively, are observed. Due to the sensitization of Yb^3＋ ions, all the upconversion luminescence intensities are enhanced considerably with Yb^3＋ concentration increasing. The upconversion mechanisms are discussed based on the energy matching rule and quadratic dependence on excitation power. The results indicate that the dominant mechanism is the excited state absorption for those upconversion emissions.     

Er^3＋/Tm^3＋/Yb^3＋ tridoped oxyfluoride glass ceramics with efficient upconversion white-light emission

A novel Tm^3＋/Yb^3＋ triply-doped glass ceramics containing BaF2 nano-crystals are successfully prepared. Fluoride nanocrystals BaF2 are successfully precipitated in glass matrix, which is affirmed by the X-ray diffraction results. The intense blue （476 nm）, green （543 nm）, and red （656 nm） emissions of the glass ceramics are simultaneously observed at room temperature under 980-am excitation, and the emission luminescence intensity increases significantly compared with the precursor glass, which is attributed to the low phonon energy of fluoride nanocrystals when rare-earth ions are incorporated into the precipitated BaF2 nanocrystals. Under 980-nm excitation at 400 mW, the international commission on illumination （CIE） chromaticity coordinate （X = 0.278, Y = 0.358） of the tridoped oxyfluoride glass ceramics＇ upconversion emissions is close to the standard white-light illumination （X = 0.333, Y= 0.333）. The results indicate that Tm^3＋/Yb^3＋ triply doped glass ceramics can act as suitable materials for potential three-dimensional displays applications.     

Influences of Mg^2＋ ion on dopant occupancy and upconversion luminescence of Ho^3＋ ion in LiNbO3 crystal

The effects of a Mg^2＋ ion on the dopant occupancy and upconversion luminescence of a Ho^3＋ ion in LiNbO3 crystal are reported. The birefringence gradient of the crystal is measured to investigate the optical homogeneity. The X-ray powder diffraction spectrum and the upconversion luminescence are used to investigate defect structure and spectroscopic properties of Mg,Ho：LiNbO3. Under 808-nm excitation, blue, red, and very intense yellow-green bands are observed. Based on the energy levels of Ho^3＋ in LiNbO3, and the pump intensity dependence of the observed emission, an excitation scheme is presented. The upconversion emission spectra reveal an enhancement of upconversion intensity when the Mg^2＋ ions are introduced into Ho：LiNbO3. The main upconversion mechanism is discussed in this work.     

Yb3+敏化的Er3+/Ho3+共掺碲酸盐玻璃的上转换发光研究

用高温熔融法制备了系列Er³⁺/Yb³⁺共掺，Ho³⁺/Yb³⁺共掺，和Er³⁺/Yb³⁺/Ho³⁺三掺碲酸盐玻璃，在975nm激光抽运下三种掺杂玻璃中都出现了较强的绿光和红光上转换.研究了Yb³⁺离子对Er³⁺和Ho³⁺离子上转换发光强度的影响以及Yb³⁺→Er关键词： 3+/Yb³⁺/Ho³⁺共掺')" href="#">Er³⁺/Yb³⁺/Ho³⁺共掺 碲酸盐玻璃 光谱性质 上转换     

980 nm激发下Er3+/Yb3+共掺杂ZrO2-Al2O3粉末的上转换发光特性

通过固相反应法制备了Er³⁺/Yb³⁺共掺杂ZrO₂-Al₂O₃粉末的样品，并对样品在980nm激光激发下的上转换发光特性进行了研究.从发射光谱可以发现，在可见光范围内有3个强的发光带，一个位于654nm附近的红光带和两个分别位于545nm、525nm附近的绿光带，分别对应于Er³⁺离子的以下辐射跃迁：⁴F_9/2→⁴I_15/2、⁴S_3/2→⁴I_15/2、 ²H_11/2→⁴I_15/2.其中又以Er³⁺离子的⁴F_9/2→⁴I_15/2跃迁产生的红色荧光辐射最强.对其上转换发光机制进行了分析，发现这三个发光过程都是双光子过程.对样品粉末进行了XRD检测，发现ZrO₂主要以立方相为主，并且计算得到了这种立方结构的晶格常数.Al₂O₃固溶于ZrO₂中，Al³⁺嵌入ZrO₂后产生氧空位，导致ZrO₂晶体的对称性降低，这种结构变化更有利于提高上转换效率，即上转换发光强度增强. 关键词： 3+/Yb³⁺')" href="#">Er³⁺/Yb³⁺ 上转换 2-Al₂O₃')" href="#">ZrO₂-Al₂O₃ 荧光 稀土     

Er3+，Er3+/Yb3+掺杂氟化镧超微材料的光谱特性与上转换发光

采用共沉淀法制备了Er³⁺掺杂和Er³⁺/Yb³⁺共掺杂LaF₃超微材料,所制备的样品的颗粒呈球形,尺寸为250nm左右.计算得到Er³⁺单掺杂样品中对应着⁴S_3/2和⁴F_9/2能级的发光量子效率分别为67.0%和71.9%.研究发现,随着Yb³⁺离子浓度的增加 关键词： 3+')" href="#">Er³⁺ 3+')" href="#">Yb³⁺ 发光 能量传递     

Er3+及Er3+/Yb3+掺杂ZrO2-Al2O3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO₂-Al₂O₃∶Er³⁺发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547 nm、560 nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO₂-Al₂O₃∶Er³⁺/Yb³⁺的上转换发光,并分析了上转换的跃迁机制.发现ZrO₂-Al₂O₃∶Er³⁺的绿光为双光子过程,而ZrO₂-Al₂O₃∶Er³⁺、Yb³⁺的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er³⁺的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%（Er³⁺/Zr⁴⁺）.     

Ce3+对Er3+/Yb3+共掺氟磷酸盐玻璃光谱性质的影响

研究了能量接受离子Ce³⁺对Er³⁺上转换发光强度以及Er³⁺在1.5μm附近波段发光性能参数的影响，并从能量匹配及能级结构角度出发对Er³⁺/Ce³⁺间的能量转移机制进行了分析.分析认为，⁴I_11/2能级的Er³⁺通过无辐射能量转移把能量传递给²F_5/2能级的Ce³⁺关键词： 氟磷酸盐玻璃 光谱性质 光纤放大器 3+和Ce³⁺')" href="#">Er³⁺和Ce³⁺     

Preparation and upconversion properties of Ba2ErF7 and Ba2ErF7:Yb powders

Novel Ba₂ErF₇ and Yb³⁺-doped Ba₂ErF₇ powders were synthesized by a coprecipitation method. In Ba₂ErF₇ sample, abundant upconverted emission bands from violet to infrared region are observed under 980 nm excitation, whereas only green and red emissions are observed under 812 nm excitation. Under the two excitations, the luminescence decay curves of the green and red emissions are measured and the quenching behaviors of Yb³⁺ doping are also explored. It is found that a suitable Yb³⁺ concentration can efficiently enhance the intensity ratio of the blue and violet emissions to the green and red ones, which may be due to the competition between the energy transfer process from Er³⁺ to Yb³⁺ and the sensitizing process from Yb³⁺ to Er³⁺ in Ba₂ErF₇:Yb³⁺. This indicates that the Yb³⁺-doped Ba₂ErF₇ might be a good candidate for blue and violet upconversion phosphor.     

Yb3+/Er3+共掺锗碲酸盐玻璃上转换发光增强机理的研究

玻璃的最大声子能量决定稀土离子的上转换发光强度，但本研究发现：Yb³⁺/Er ³⁺共掺锗碲酸盐玻璃在980nm LD抽运下，上转换荧光强度随着Bi₂O ₃对PbO的取代和碱 金属离子半径的增大而明显增强.而Raman光谱显示基质玻璃的最大声子能量并不随Bi ₂O₃对PbO的取代和碱金属离子半径的增大而变化，但玻璃的最大声子密 度随着Bi₂O₃对PbO 取代和碱金属离子半径的增大而降低.从玻璃无辐射跃迁概率的角度，通过分析表明，最大 声子密度的降低是玻璃上转换发光强度增强的主要原因.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO₂-ZnO-Na₂O的Tm³⁺离子单掺和Tm³⁺/Yb³⁺共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ω_t(t=2, 4, 6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τ_rad等光谱参量,测量得到了不同Yb³⁺离子掺杂浓度下玻璃样品的Tm³⁺离子上转换发光谱.结果显示,在980 nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm³⁺离子上转换发光分析表明,强烈的Tm³⁺离子近红外上转换发光主要来自于Yb³⁺/Yb³⁺离子间的共振能量传递以及基于单声子和双声子辅助的Yb³⁺/Tm³⁺离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm³⁺:³F₄→³H₆能级间跃迁的1.8 μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb³⁺/Tm³⁺共掺TeO₂-ZnO-Na₂O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

Ce3+对Er3+/Yb3+共掺TeO2-WO3-ZnO玻璃发光性能的影响

在Er³⁺/Yb³⁺共掺TeO₂-WO₃-ZnO玻璃中引入Ce³⁺，研究了Ce³⁺对Er³⁺1.5μm发射性能及其上转换发光性能的影响。结果表明，随Ce³⁺浓度的增加Er³⁺1.5μm波段的荧光强度先增强后降低，优化的Ce³⁺掺杂浓度在2.07×10²⁰/cm³左右；1.5μm波段的荧光寿命则随Ce³⁺浓度的增加有轻微降低，从3.4ms降到3.0ms，但Ce³⁺浓度的增加对1.5μm波段的荧光半高宽基本无影响；Er³⁺/Ce³⁺间的交叉弛豫Er³⁺(⁴I_11/2)+Ce³⁺(²F_5/2)→Er³⁺(⁴I_13/2)+Ce³⁺(²F_7/2)使玻璃的上转换发光强度大大降低，但在过高的Ce³⁺浓度下，Er³⁺/Ce³⁺间的另一交叉弛豫Er³⁺(⁴I_13/2)+Ce³⁺(²F_5/2)→Er³⁺(⁴I_15/2)+Ce³⁺(²F_7/2)则使Er³⁺⁴I_13/2能级粒子数减少，导致1.5μm波段荧光强度和荧光寿命降低. 关键词： 碲钨酸盐玻璃 发光性能 3+离子')" href="#">Er³⁺离子 3+离子')" href="#">Ce³⁺离子 交叉弛豫     

LD抽运Er3+，Yb3+共掺磷酸盐玻璃被动调Q激光器的理论分析和数值计算

研究了以Co²⁺:MgAl₂O₄晶体为饱和吸收体的LD抽运Er³⁺,Yb³⁺共掺磷酸盐玻璃激光器.针对双掺离子之间的能量传递和Er³⁺的多种跃迁过程，结合Co²⁺:MgAl₂O₄晶体中Co²⁺离子的饱和吸收特性，给出了详尽的速率方程，在其基础上进行了数值分析，分析了输出镜透过率、激光介质长度、谐振腔长度、腔内往返损耗、饱和吸收体长度对激光阈值、峰值功率、单脉冲能量以及脉冲宽度的影响.