铒掺杂锗酸盐玻璃的颜色可调上转换发光性质研究

研究了铒掺杂80GeO2-20R2O(R=Li,Na,K)玻璃在980nm激光器激发下的上转换发光性质.结果表明:玻璃发射出中心波长为525,546nm绿光和657 nm红光,分别对应Er3+的2H11/2→4I15/2,4S3/2→4I15/2和4F9/2→4I15/2的跃迁;红光和绿光的强度比例随着碱金属离子半径的...     

Yb3+/Er3+共掺碲钨酸盐玻璃的能量传递与频率上转换发光

在970nm LD激发和Er^3 离子浓度几乎不变情况下，研究了Yb^3 ／Er^3 共掺碲钨酸盐玻璃中的能量传递和其上转换发光特性。结果表明：随掺Yb^3 浓度的增加，Yb^3 ／Er^3 间能量传递效率也增加，其值在0．52到0．60之间。在Yb^3 ／Er^3 共掺碲钨酸盐玻璃中观察到峰值分别位于533，547nm和668nm的上转换绿光和红光，它们分别来源于Er^3 离子^2H11/2→^4I15／2(533nm)，^4S3／2→^4I15／2(547nm)和^4F9/2→^4I15／2(668nm)辐射跃迁。上转换红光和绿光均为双光子过程，且随Yb^3 离子掺杂浓度的增加，上转换红绿光强度和其强度比值Ic／Ig也增加，这被认为是与激发态Er^3 与激发态Yb^3 之间的能量传递过程有关。     

In:Yb:Nd:LiNbO3晶体的生长和光谱性能

采用提拉法生长了0.4%(摩尔分数)Yb_2O_3,0.4%Nd_2O_3和(0.5%、1.0%、2.0%)In_2O_3的3种同成分In:Yb:Nd:LiNbO_3晶体。测试了掺杂晶体的紫外-可见吸收光谱和上转换发射光谱,探究了最优掺杂晶体的上转换发光强度与激发功率的关系。结果表明:随着In:Yb:Nd:LiNbO_3晶体中In3+浓度的增加,晶体的紫外吸收边分别位于349、340、和338 nm处。采用980 nm二极管激光器激发获得的上转换发射光谱表明,上转换绿光的发射光强度最强,其次为上转换红光的发射强度,中心波段分别位于562、726 nm处,对应于Nd3+的4G9/2→4I11/2跃迁及4G9/2→4I15/2跃迁。2%In:Yb:Nd:LN晶体上转换荧光发射性能最优。根据不同激发功率测试,Nd~(3+)的近红外发光属于单光子过程,上转换红光及上转换绿光发光属于双光子过程。     

Tm~(3+)/Ho~(3+)/Yb~(3+)掺杂Ga_2O_3-GeO_2-Li_2O玻璃的上转换发光性能研究

采用熔融淬冷法制备了Tm~(3+)/Ho~(3+)/Yb~(3+)掺杂的Ga_2O_3-GeO_2-Li_2O玻璃。测试了样品的拉曼光谱、吸收光谱、980 nm和808 nm泵浦下的上转换发射光谱。详细调查了在980 nm和808 nm激发下不同的Yb2O3掺杂含量对Tm~(3+)/Ho~(3+)掺杂的镓锗锂玻璃的上转换发射光谱的影响,分析了稀土离子间的能量传递。研究发现:980 nm泵浦下样品观察到明显的545 nm和657 nm发射和微弱的476 nm发射峰。随着Yb~(3+)浓度的增大,由于Yb~(3+)对Tm~(3+)和Ho~(3+)的有效的能量传递增强了红光和绿光发射强度,红光的增长率是快于绿光的,Yb_2O_3的掺杂量为0.7 mol%时I657/I545强度比率达到最高。808 nm激发下可以观察到弱的476 nm的蓝光和545 nm的绿光及强烈693 nm发射。     

Er,Yb:(LaGd)_2O_3纳米粉体的制备与发光性质

以碳酸氢铵为沉淀剂,采用共沉淀法制备了Er,Yb:(La Gd)2O3纳米粉体。经1 000℃煅烧2 h得到的粉体颗粒呈规则球形,平均粒径约为90 nm,团聚低,分布均匀。研究了Er3+,Yb3+的掺杂量对样品发光强度的影响。结果表明:掺杂Er3+和Yb3+的摩尔分数分别为4%和5%时,所得样品的发光性能最优。样品的激发和发射光谱显示:在379 nm处激发峰最强,对应Er3+的4I15/2→4G11/2能级跃迁;最强发射峰位于562 nm处,对应于4S3/2/2H11/2→4I15/2能级跃迁。样品的上转换光谱表明:样品在548和662 nm有较强的发射峰,对应Er3+的4S3/2/2H11/2→4I15/2跃迁和4F9/2→4I15/2跃迁。并讨论了发光跃迁机制。     

Nd3+/Yb3+/Tm3+共掺杂NaY（WO4）2纳米晶的制备及其上转换发光性能EI北大核心CSCD

采用水热法合成出Nd^3＋/Yb^3＋/Tm^3＋共掺杂NaY（WO4）2纳米晶。通过X射线衍射、扫描电子显微镜、红外光谱、荧光光谱等,对合成样品的晶体结构、形貌和上转换发光性能进行表征。结果表明：合成的样品均为纯四方相的NaY（WO4）2,粒径在50～55 nm之间。利用聚乙二醇（PEG-2000）作为表面活性剂制得的上转换纳米粒子,尺寸小、分散性好并且具有一定的水溶性。在808 nm近红外光激发下,观察到469 nm处的蓝光发射峰以及539 nm处的绿光发射峰,其中蓝光来自Tm^3＋的^1G4→^3H6能级跃迁,绿光由Tm^3＋的^1D2→^3H5跃迁产生。并研究了共掺杂体系中Nd^3＋→Yb^3＋→Tm^3＋的能量传递过程及其上转换发光机理。     

共沉淀法制备Tm:YbSAG纳米粉体及其发光性能

以聚乙二醇为分散剂,采用共沉淀法制备Tm:Yb3Sc Al4O12纳米粉体。最佳工艺条件为:煅烧温度1 000℃,煅烧时间2 h。通过对样品的扫描电子显微镜分析,得到纳米粉体平均粒径约为90 nm。测试了样品的激发和发射光谱,结果表明:在360 nm处激发峰最强,对应Tm3+的1D2→3H6能级跃迁;最强发射峰位于456 nm处,对应于1G4→3H6能级跃迁。测试了样品的上转换光谱,得到掺杂Tm3+的摩尔分数为2%时样品的发光强度较好,讨论了上转换发光机理,红光和绿光的发射是双光子吸收过程,蓝光发射源于1个三光子吸收过程。     

Yb~(3+)/Ho~(3+)/Tm~(3+)三掺杂ZnO微晶玻璃中的上转换白光（英文）

通过熔融淬冷及热处理方法制备出Yb~(3+)/Tm~(3+)、Yb~(3+)/Ho~(3+)共掺杂和Yb~(3+)/Tm~(3+)/Ho~(3+)共掺杂ZnO微晶玻璃,利用X射线衍射和透射电子显微镜表征了ZnO微晶在玻璃基质中析出。在980 nm激发下,该玻璃体系中可以清晰观察到分别源于Tm~(3+):1G4→3H6、Ho~(3+):5S2、5F4→5I8及5F5→5I8辐射跃迁产生的高效蓝光(477 nm)、绿光(545 nm)和红光(660 nm)上转换发光。上转换发射强度与激发功率依赖关系的数据表明,蓝光发射是三光子过程,而绿光和红光发射是双光子过程。通过优化Yb~(3+)/Ho~(3+)/Tm~(3+)共掺杂微晶玻璃中离子掺杂浓度可获得白光发射。980nm激发下2Yb~(3+)/0.1Ho~(3+)/0.01Tm~(3+)共掺杂和2Yb~(3+)/0.2Ho~(3+)/0.03Tm~(3+)共掺杂微晶玻璃上转换发光的CIE坐标分别为(X=0.32, Y=0.34)和(X=0.33, Y=0.32),非常接近标准白的CIE色坐标(X=0.33, Y=0.33),表明该材料在白光发射领域具有良好的应用前景。     

Yb3+和Er3+共掺杂的NaY（WO4）2纳米晶的制备与发光性能

采用水热法制备出NaY(WO4):Yb3+,Er3+纳米发光粉。通过X射线衍射、扫描电子显微镜表征了制备的发光粉样品;研究了不同Yb/Er摩尔比对发光强度的影响。结果表明:Yb3+和Er3+共掺杂的NaY(WO4)2属于四方晶系,其粒径在30 nm左右,且分散均匀。当Yb/Er摩尔比为4:1时,NaY(WO4):Yb3+,Er3+发光粉样品的发射峰强度达到了最大值。用980nm激光对其进行激发,在室温下观察到了410、524、553和656nm的发射峰,分别对应于2H9/2→4I15/2,2H11/2→4I15/2,4S3/2→4I15/2和4F9/2→4I15/2的跃迁。根据激发功率与发光强度的关系得出410、524、553和656 nm发射峰均为双光子过程。     

Er~(3+)-Yb~(3+)共掺杂ZrO_2-TiO_2粉末的上转换发光性质

通过共沉淀方法制备了Er3+和Yb3+共掺的ZrO2-TiO2上转换发光材料。用X射线衍射(XRD)对合成的物相结构进行了检测,并对样品在980 nm激光激发下的上转换发光性质进行了研究。观察到了位于528、550和662 nm附近的绿色和红色发光,分别对应于Er3+离子的2H11/2,4S2/3→4I15/2and4F9/2→4I15/2跃迁。样品的红光和绿光强度随着ZrO2和TiO2配比的变化而变化。随着烧结温度的升高,样品整体发光强度增加。讨论了上转换发光可能的机理:激发态吸收(ESA)和能量传递上转换(ET)过程。     

烧结温度对Er~(3+)/Yb~(3+)共掺氟氧化物粉末上转换发光的影响

采用高温固相法在600～1100 ℃范围内选择6个不同烧结温度制备了系列相同配方的Er~(3+)/Yb~(3+)共掺氟氧化物上转换发光粉末.在室温下对各样品采用波长为980 nm泵浦光激发,肉眼均可观察到峰值位于658 nm、539 nm和523 nm处的上转换红光和绿光,分别对应于Er~(3+)的~4F_(9/2)→~4I_(15/2)和~4S_(3/2)/~2H_(11/2)→~4I_(15/2)能级跃迁,且红光强度大于绿光强度.通过比较,各样品的上转换图谱形状完全相同,而红绿上转换发光强度明显不同,800 ℃烧结制得样品的红绿荧光强度最强.样品的绿色荧光强度与红色荧光强度的比值随烧结温度升高而增加.通过各样品的X射线粉末衍射图谱(XRD)分析其成分结构,发现烧结温度对样品的成分含量有较大影响.通过测量不同烧结温度下制得样品的上转换发光强度与激发功率的变化关系,发现不同烧结温度可改变样品的上转换发光机理.     

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.     

掺铒铋酸盐玻璃和掺铒碲酸盐玻璃的荧光俘获和浓度猝灭效应

用高温熔融法制备了系列掺铒铋酸盐和碲酸盐玻璃,用分光光度计测试吸收光谱,并用荧光光谱仪测试了不同铒离子掺杂浓度时玻璃样品的荧光光谱和荧光寿命.结果显示:掺铒后,铋酸盐玻璃和碲酸盐玻璃中存在着强烈的荧光俘获和浓度猝灭效应.随着玻璃中铒离子掺杂浓度的增加,1.53 μm波段荧光谱展宽,1 560 m波长处荧光次峰增强,但相对于铋酸盐玻璃,碲酸盐玻璃具有更为强烈的荧光俘获效应.同时,随着铒离子掺杂浓度的增加,4I13/2能级荧光寿命和1.53 μm波段荧光强度呈先增加后减小趋势.根据Dexter能量转移理论,计算并分析比较了这2种宽带玻璃系统中铒离子发生浓度猝火的临界距离R0及相互作用参数Cer-Er.     

钨酸钆镉单晶的光致发光性能

采用提拉法生长了钨酸钆镉[CdGd2(WO4)4, CGW]单晶.在室温下测试和研究了CGW单晶的光致发光谱和X射线能量色散谱.结果表明:样品中有Gd,Cd,W和O元素,未见其他杂质元素;样品的发光性质随激发波长的不同而有所变化.在313 nm波长光激发下,有3个发光带,分别为447 nm蓝光,487 nm蓝绿光和545 nm绿光;在353 nm波长光激发下,不仅有蓝光、蓝绿光和绿光出现,另外出现了575 nm黄光发光峰;在367 nm波长的光激发下,出现775 nm红光发光峰.对发光机制分析认为:蓝光和蓝绿光为本征发射,起源于WO42-离子团的内部电子跃迁;绿光起源于"WO42- Oi";黄光和红光起源于WO3内部跃迁.     

Design of luminescent inorganic materials: new photophysical processes studied by optical spectroscopy

Recent spectroscopic results in the emerging area of transition-metal NIR-to-visible upconversion are related. The examples of Ti(2+)-, Re(4+)-, and Os(4+)-doped materials showing upconversion illustrate GSA/ESA, GSA/ETU, and photon avalanche multiphoton excitation mechanisms, respectively. Strategies for manipulation of such upconversion processes using the spectroscopic or magnetic properties of the host material are described. High-resolution low-temperature continuous-wave absorption and emission and time-resolved emission experiments combine to yield information about energy splittings, intensities, and excited-state dynamics, and assist in the design and development of luminescent materials showing novel multiphoton excitation properties.     

Controlled synthesis and optical spectroscopy of lanthanide-doped KLaF₄ nanocrystals

KLaF(4), as a good host matrix for trivalent lanthanide (Ln(3+)) ions to fabricate upconversion (UC) or downconversion (DC) phosphors, has been rarely reported. Herein, monodisperse (～10 nm) cubic-phase Ln(3+)-doped KLaF(4) nanocrystals (NCs) were synthesized via a facile thermal decomposition method. Upon excitation at 980 nm, UC luminescence properties of KLaF(4):Ln(3+)/Yb(3+) (Ln = Tm, Ho, Er) NCs were comprehensively surveyed. Particularly, after coating an inert KLaF(4) shell, the green and red UC luminescence intensity of KLaF(4):Er(3+)/Yb(3+) NCs was enhanced ～35 times, and the corresponding UC lifetimes of (4)S(3/2) and (4)F(9/2) levels of Er(3+) were observed significantly prolonged from 42 and 68 μs in core-only NCs to 87 and 136 μs in core/shell counterparts. Furthermore, intense DC luminescence was also achieved in Ce(3+)/Tb(3+) and Eu(3+) doped KLaF(4) NCs, with absolute quantum yields of 39.8% (Tb(3+)) and 17.3% (Eu(3+)). The luminescence lifetimes of (5)D(0) (Eu(3+)) and (5)D(4) (Tb(3+)) were determined to be 4.2 and 4.7 ms, respectively. Water-soluble Ln(3+)-doped KLaF(4) NCs featuring excellent monodispersion, long luminescence lifetime, and high UC/DC efficiency may have versatile and promising applications as luminescent nano-biolabels.     

Green and red upconversion luminescence of Er-doped K0.5Na0.5NbO3 ceramics

Er³⁺ doped K_0.5Na_0.5NbO₃ (KNN) lead-free piezoelectric ceramics were synthesized by the solid-state reaction method. The upconversion emission properties of Er³⁺ doped KNN ceramics were investigated as a function of Er³⁺ concentration and incident pumping power intensity. Bright green (~555 nm) and red (670 nm) upconversion emission bands were obtained under 980 nm excitation at room temperature, which are attributed to (²H_11/2, ⁴S_3/2)→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions, respectively. The upconversion emission intensity can be adjusted by changing Er³⁺ concentration, and the mechanism of upconversion processes involve not only a two-photon absorption but also a three-photon absorption. In addition to the admirable intrinsic piezoelectric properties of KNN, this kind of material may have potential application as a multifunctional device by integrating its upconversion and piezoelectric property.     

Preparation and Upconversion Properties of Yb3+, Ho3+: Lu2O3 Nanocrystalline Powders

Yb³⁺, Ho³⁺: Lu₂O₃ nanocrystalline powders were synthesized by a reverse-strike co-precipitation method using NH₄HCO₃ and NH₃·H₂O as precipitators. X-ray diffraction analysis and field emission scanning electron microscopy observation showed that the phase composition of the powders was cubic and the particle size was 30–50 nm. Under the excitation of a 980 nm continuous wave diode laser, green and red emissions centered around 548 and 667 nm, respectively, were observed and the green emission dominated the upconversion spectrum. Power studies revealed that a two-photon process was involved in the upconversion emissions and the possible upconversion mechanisms were discussed.