Crystal growth and optical properties of Cr3+, Er3+, RE3+: Gd3Ga5O12 (RE=Tm,Ho, Eu) for mid-IR laser applications

In this paper we report on the optical properties of triply Cr³⁺, Er³⁺, and RE³⁺ (RE=Tm, Ho, Eu) doped Gd₃Ga₅O₁₂ crystals that were grown by the Czochralski method. Optical absorption, near-infrared (NIR), and mid-infrared (mid-IR) fluorescence spectra were characterized for the fabricated crystals and corresponding luminescence decay measurements under 654 nm excitation were also carried out. Based on the analysis of energy transfer process between Er and RE (RE=Tm, Ho, Eu) ions, the energy transfer efficiency (ETE) values were evaluated, correspondingly. From the spectral data of all the studied crystals, it is observed that the co-doped Cr³⁺ ion highly increases the absorption pump power and the three kinds of co-doped RE³⁺ ions depopulate the Er:⁴I_13/2 energy level effectively. The spectral analysis shows that titled rare earth doped crystals are promising materials for ～3.0 μm mid-IR laser applications and among them Cr,Er,Eu:GGG is relatively more suitable due to its excellent optical properties compared with others.     

Tm~(3+)/Er~(3+)/Yb~(3+)掺杂的镓锗酸盐玻璃光谱性能及能量传递

采用熔融淬冷法制备得到透明的Tm~(3+)/Er~(3+)/Yb~(3+)掺杂镓锗钠玻璃。对比研究了808 nm和980 nm激发下Tm_2O_3含量对样品可见-红外光学光谱特性的影响。结合稀土离子能级结构,分析了Tm~(3+)、Er~(3+)和Yb~(3+)离子之间的能量传递机制。结果表明:在808 nm和980 nm的激发下,Tm~(3+)/Er~(3+)/Yb~(3+)掺杂样品中均观察到了473,655,521,544 nm的蓝、红和绿光。在808 nm激发下,随着Tm~(3+)浓度的增加,Tm~(3+):1 800 nm和Er~(3+):1 530 nm发射强度的比率I1.8/I1.53逐渐增大。由于在Tm~(3+)和Er~(3+)间的能量传递有效地改变了红光和绿光的发射强度,473,521,655 nm的发光强度呈现先升高再降低的趋势,在Tm_2O_3掺杂摩尔分数为0.3%时达到最大值。而在980 nm激发下,由于Yb~(3+)对Er~(3+)和Tm~(3+)的能量传递起主要作用,使得其上转换红光(655 nm)、绿光(521 nm和544 nm)和蓝光(473 nm)的发光强度高于808 nm激发下的上转换发光。     

Sr3Gd(PO4)3:Tm3+的真空紫外光谱特性

研究了Sr3Gd(PO4)3 : Tm3 和GdPO4 : Tm3 样品的结构特性、光谱特性.GdPO4 : Tm3 为单斜晶系,基质掺入铥离子后结构没有明显变化.GdPO4:Tm3 在164和210 nm附近有强烈的吸收峰.位于164 nm附近的强烈的吸收峰是归因于基质的吸收引起,210 nm附近的吸收峰则归因于Gd 的8S7/2-6GJ的能级跃迁.在164 nm真空紫外光激发下,样品于453及363 nm处有较强的发射峰,发射主峰位于453nm,属于Tm3 的1D2→3H4(22,123 cm-1)跃迁的典型发射.由于阳离子质量的不同,Sr3Gd(PO4)3:Tm3 在166 nm附近的激发峰高于GdPO4: Tm3 的同位置的激发峰,其在363 nm处的发射有明显减弱,而在453 nm处的蓝色发射有显著的增强.     

Eu/Tm/Tb掺杂硼硅酸盐玻璃的发光性能

采用熔融淬冷法制备了性能优越的Eu/Tm/Tb单掺、双掺和三掺的硼硅酸盐玻璃。测试了样品的激发和发射光谱,计算了CIE色坐标,研究了紫外激发下Eu/Tm/Tb掺杂的硼硅酸盐玻璃的发光性能。结果表明:在361 nm激发下,随着Tm~(3+)加入到Eu_2O_3掺杂的硼硅酸盐样品中,观察到Tm~(3+)的459 nm(1D_2→3F_4)锐线特征发射峰,同时由于Eu~(3+),Eu2+→Tm~(3+)的能量传递的存在降低了Eu2+的437 nm宽带峰及Eu~(3+)的589nm(5D0→7F1)和612 nm(5D_0→7F_2)的特征发射峰强度。在377 nm激发下,Eu/Tm/Tb三掺样品能够同时出现红、绿和蓝光。调节Eu2O3的含量能有效改变发光玻璃的发光强度和颜色,最终得到色坐标为(0.33,0.386 7)的发光玻璃。     

Eu3+掺杂BaO-TiO2-3SiO2发光材料的制备与发光性质

采用溶胶-凝胶法在室温下制备了以BaO-TiO₂-3SiO₂为基质的稀土Eu³⁺掺杂的发光材料,各材料的量比为 n(Ba):n(Ti):n(Si):n(Eu)=1:1:3:x。 通过DTA-TG、IR、XRD、激发和发射光谱对材料的结构和发光性能进行了分析。DTA-TG测试表明,样品在50~400 ℃之间出现明显失重现象,说明在此过程中凝胶中的吸附水、乙醇、醋酸等物质发生了脱附释放。IR光谱显示,制备的样品中主要存在Ti-O-Si和O-Si-O键。XRD测试证明,材料属于非晶态。激发和发射光谱图显示,材料制备的最佳退火温度为800 ℃,Eu³⁺的最佳掺杂比例为x(Eu)=5.75×10^-3。在612 nm监测波长下,测得的最佳激发波长为紫外光395 nm 和可见光465 nm,即在395 nm和465 nm光激发下,材料发射的红光单色性好且强度基本相同。     

稀土离子掺杂LaAlO3:RE3+(RE=Eu,Tb,Sm,Tm)荧光粉的发光性能

采用溶胶凝胶法合成La_1-xAlO₃：xRE³⁺（RE=Eu,Tb,Sm,Tm）荧光粉,对样品进行热重差热（TGA-DTA）、X射线粉末衍射（XRD）、透射电镜（TEM）以及荧光光谱（PL）等表征,探讨样品的合成温度及稀土离子掺杂浓度对样品发光性能的影响。研究结果表明,当煅烧温度为800~1 200℃时,所合成样品为三方晶体结构。在紫外光激发下,掺杂离子均表现出特征的f-f电子跃迁发射,在一定掺杂浓度范围内,当Eu³⁺、Tb³⁺、Sm³⁺和Tm³⁺的掺杂浓度x值分别为0.02,0.04,0.005和0.005时,样品发光强度最大,在一定波长激发下,样品分别发射出红光、绿光、橙黄光和蓝光,Eu³⁺-Tb³⁺、Eu³⁺-Sm³⁺和Eu³⁺-Tm³⁺共掺杂有可能获得白光。     

晶态四硼酸锶中二价镝的发射

在室温下测量了在空气中灼烧掺杂Dy2O3的SrB3O7的发射光谱。观测到了由Dy^3 到Dy^2 氧化态的变化。经优化,当在空气中灼烧温度为650℃时为产生Dy^2 的最佳温度。在457．9nm的激发下测出了两个峰位分别位于550和660nm的宽发射带。我们认为这两个宽发射带是由Dy^2 离子由5d态向4f基态能级（^5I8）跃迁产生的。讨论了几个有益于在这种基质中还原Dy^3 离子的条件。为了实现Dy^3 离子的还原,我们还在Ar/H2(4%)气氛中制备了Dy2O3掺杂的SrB4O7比较了这种样品和在空气中所制备的样品的光学特性。本文还对标专SrB4O7还原性和稳定性的g－因子由Tm^2 的[E0(Tm^3 /Tm^2 =-2.3V]推导出Dy^2 的[E0(Dy^3 /Dy^2 )=-2.6V],但对这种还原过程的局限性尚未确定。     

Sensitized thulium ultraviolet upconversion luminescence in Tm3+/Yb3+/Nd3+ triply doped nanoglass ceramics

Intense four- and five-photon ultraviolet upconversion processes through sensitization of Tm3+ ions in transparent SiO2-Al2O3-NaF-YF3 glass ceramics triply doped with Tm3+/Yb3+/Nd3+ under 796 nm excitation were investigated. Judd-Ofelt analyses evidenced the incorporation of rare-earth ions into the precipitated beta-YF3 nanocrystals. In contrast with the triply doped one, no ultraviolet upconversion luminescence was observed in the Tm3+/Nd3+ codoped glass ceramic, indicating that Yb3+ acts as bridging ions to enhance the energy transfer efficiency between Nd3+ and Tm3+. Based on the pumping power dependence of luminescence, upconversion mechanisms were proposed.     

氟锆酸盐玻璃中Tm^3＋和（Tm^3＋＋Ho^3＋）离子的光谱研究

给出氟锆酸（ＺＢＬＡＮ）玻璃中＾Ｔｍ＾３＋和Ｈｏ＾３＋离子的Ｑｔ参量，并与氧化物玻璃中Ｔｍ＾３＋和Ｈｏ＾３＋的Ｑｔ参量进行了比较，用３７５ｎｍ和４６８ｎｍ波长激发单掺ＺＢＬＡＮ中Ｔｍ＾３＋离子，获得来自Ｄ，２，＾３Ｈ４，Ｇ４能级不同发射波长的发光强度随掺杂浓度的变化，而用小于１μｍ的激发波长激发发单掺Ｔｍ＾３＋或Ｈｏ＾３＋样品，获得近红外区发射光谱。文中给出掺杂浓度对于Ｔｍ＾３＋和Ｈｏ＾＋近红外区     

Co-doped Y2O3:Tb3+/Tm3+ multicolor emitting phosphors for thermometry

In this study, the new temperature-dependent phosphor, Y2O3:Tb3+/Tm3+, was investigated for high-temperature thermometry. The photoluminescence intensity at 456?nm emitted from Tm3+ was strong at temperatures higher than 1100?K, whereas the peak intensities emitted from Tb3+ decreased due to the thermal quenching effect. Thus, the intensity ratio between those emissions showed an appropriate variation for thermometry over a wide temperature range. In addition, the phosphors showed a distinct change of visible emission colors from green to blue with increasing temperature. These findings suggest the applicability of these phosphors in visual thermo-sensors.     

Critical separation for efficient Tm3+ -Tm3+ energy transfer evidenced in nanostructured Tm3+: Al2O3 thin films

Nanostructured amorphous Al oxide (a-Al2O3) thin films doped with Tm3+ were synthesized by alternate pulsed laser deposition. The Tm3+ ions have been deposited in layers with in-depth separation ranging from 0.75 to 6 nm. The films show two broad emission bands originated from the Tm3+ 3H4-->3F4 and 3F4-->3H6 transitions. Their intensity increases at a similar rate and the lifetimes are not modified as the layer separation decreases down to 1.5 nm, suggesting that there is no concentration quenching. At the critical value of 1.5 nm the onset of Tm3+ -Tm3+ energy transfer is evidenced by a sharp decrease of the emission intensity and lifetime. Below this critical value, the rate at which the intensity increases for the 3F4-->3H6 transition is much higher than that for the 3H4-->3F4 transition, evidencing quenching of the 3H4-->3F4 transition through a cross-relaxation mechanism. The control of the Tm3+ ions in the nanometer scale allows evidencing the onset of energy transfer processes among ions and offers a route to optimize compact photonic gain integrated devices.     

绿色荧光粉Gd2Ba3B3O12:Tb3+的发光性能研究

采用高温同相法制备了一系列Gd<,2>Ba<,3>B<,3>O<,12>:Tb<'3+>绿色荧光粉,借助X射线粉末衍射仪(XRD)、真空紫外光谱和荧光光谱仪(VUV-UV)对样品的物相、发光性能进行了表征.结果表明,Tb<'3+>作为发光中心全部进入到基质Gd<,2>Ba<,3>B<,3>O<,12>的品格中并占据Gd...     

Yb3+-Tm3+共掺钨钼酸盐纳米晶体的发光特性

以聚乙二醇为络合剂,采用水热法制备了发光性能优越的Yb3+-Tm3+共掺BaGd2(WO4)0.5(MoO4)0.5纳米晶体。改变稀土掺杂量并生产不同掺杂量的BaGd2(WO4)0.5(MoO4)0.5∶Yb3+/Tm3+。以X射线衍射仪(XRD)、扫描电子显微镜(SEM)及透射电子显微镜(TEM)对样品进行表征。结果表明,BaGd2(WO4)0.5-(MoO4)0.5∶Yb3+/Tm3+纳米晶属四方晶系,粒径在25~40nm之间,使用Hitachif-4500分光光度计分析样品,发现当Yb3+/Tm3+为4∶1、Yb3+离子浓度为6.0%时,BaGd2(WO4)0.5(MoO4)0.5∶Yb3+/Tm3+的发光效率最高。当Tm3+离子发生1G4→3H6跃迁时会产生可见光发射,对应于光谱图中475nm处的蓝光;当Tm3+离子发生1G4→3F4跃迁时产生的可见光发射,对应于光谱图中650nm处的红光。光谱图像及泵浦功率的双对数曲线表明,其中蓝光发射是三光子发射过程,红光发射是双光子发射过程。样品的量子产率接近0.9%。Yb3+-Tm3+共掺BaGd2(WO4)0.5(MoO4)0.5纳米晶体的发光性能优异,具有很高的应用价值。     

VUV-UV excited luminescent properties of LnCa4O(BO3)3:RE (Ln=Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa₄O(BO₃)₃:RE³⁺ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E_ct were calculated and compared with their excitation spectra.Eu³⁺ and Tb³⁺ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce³⁺ ions do not show efficient luminescence and quench the luminescence of Tb³⁺ ions when Tb³⁺ and Ce³⁺ ions are co-doped into LnCOB. GdCOB doped with Dy³⁺ shows yellowish white light under irradiation of 254 nm light for the reason that Gd³⁺ ions transfer the energy from itself to Dy³⁺. Because of the existence of Gd³⁺, the samples of GdCOB:RE³⁺ show higher excitation efficiency than LaCOB:RE³⁺ and YCOB:RE³⁺, around 188 nm, which indicates that the Gd³⁺ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb³⁺, Dy³⁺ and Eu³⁺.     

Tm3+掺杂SiO2-Al2O3-PbF2-AlF3玻璃的光谱特性

用高温熔融法制备了不同Tm3 摩尔分数掺杂的摩尔分数比为0.3(SiO2)…0.1(Al2O3)…0.1(AlF3)…0.5(PbF2)…x(Tm2O3)(摩尔分数x=0.5%,1.0%,2.0%,3.0%)玻璃。从吸收光谱特性出发,应用Judd-Ofelt理论,计算得到了Tm3 的J-O强度参量(Ω2,Ω4,Ω6)及Tm3 各激发能级的自发辐射跃迁概率、荧光分支比以及辐射寿命等光谱参量。在808nm波长的激光二极管激发下,研究了不同Tm3 掺杂摩尔分数下玻璃在约1.47μm与约1.8μm处的荧光特性,在掺杂摩尔分数约达到2.0%时,在1.8μm处的荧光强度达最大,然后随着掺杂摩尔分数的增大,其荧光强度反而降低。作者从Tm3 的交叉弛豫与摩尔分数猝灭效应解释了这一荧光强度变化的规律,同时,根据McCumber理论计算了Tm3 跃迁3H6→3F4的吸收截面和跃迁3F4→3H6的受激发射截面。     

970 nm抽运下Tm3+/Yb3+共掺氧氟玻璃的频率上转换发光

稀土离子掺杂的氧氟玻璃是一种新型上转换发光材料。制备了Tm^3／Yb^3＋单掺、共掺的摩尔分数为n（SiO2）-0．30,n（PbF2）-0．50,n=（Al2O3）=0．15,n（AlF3）=（0．049-x）,n（TmF3）=y,n（YbF3）=x（x=0,0．001,0．010,0．015,0．020,y=0,0．001）系统氧氟玻璃,研究了其上转换发光特性、分析了其上转换发光机理。研究发现,在970nm抽运光源激发下,Tm^3＋单掺时没有可见光上转换发射;而加入Yb^3＋后产生了强的蓝光（452nm,476nm）、红光（647nm）及近红外光（791nm）发射,分别对应如下辐射跃迁：^1D2→^3F4、^1G4→^3H6、^1G4→^3F4和^3H4→^3H6;且随着Yb^3＋离子浓度的增加上转换发光增强。在970nm光源抽运下用Yb^3＋敏化Tm^3＋可以显著提高其上转换发光强度,且随着Yb^3＋离子浓度的增加,增强了对抽运光源的吸收并提高了Yb^3＋到T^3＋”的能量转移几率,从而增强了上转换发光强度。     

稀土配合物RE(TPTZ)Cl_3的合成、表征及荧光性能研究

首次以2,4,6-三吡啶基三嗪（TPTZ）与Sm, Eu, Tb和Dy氯化物反应,合成四种单一稀土配合物以及Tb分别1∶1掺Gd, Y, La的三种异核配合物。经元素分析、稀土络合滴定、摩尔电导率、红外光谱、紫外光谱和差热-热重测定表明,配合物的组成分别为RE（TPTZ）Cl3&#183;3H2O（RE=Sm, Eu, Tb, Dy）和Tb0.5Ln0.5（TPTZ）Cl3&#183;3H2O（Ln=Gd, Y, La）;TPTZ作为三齿配体与稀土离子配位,即中心环提供一个N原子,两个吡啶环分别提供一个N原子;配合物中3个水分子与稀土离子配位,1个Cl-在外界,2个在内界,为1∶1型电解质;配合物内外界可能为[RE（TPTZ）（H2O）3Cl2] Cl,稀土离子的配位数为8。配合物的荧光光谱测试表明,四种单一稀土配合物中,Tb配合物发光最强;三种1∶1掺杂异核Tb配合物荧光强度大于纯Tb配合物,表明Y3＋, La3＋和Gd3＋都可以敏化Tb3＋的发光,其中Gd3＋的敏化作用最强,Y3＋次之,La3＋最差。     

Tm3+/Yb3+共掺杂玻璃和玻璃陶瓷中蓝色 上转换发光中的能量传递过程

利用高温固相法制备了Tm³⁺/Yb³⁺共掺杂的氟氧化物玻璃和玻璃陶瓷材料,在980 nm的激光激发下,样品发射出明亮的蓝色上转换荧光。通过对玻璃和玻璃陶瓷样品的对比,发现Tm³⁺离子和Yb³⁺离子之间存在着Tm³⁺(³H₄)→Yb³⁺(²F_5/2)的反向能量传输通道,并且与晶场有较强的依赖关系。分析了在玻璃和玻璃陶瓷中蓝色上转换发光过程,随着敏化剂Yb³⁺浓度的增加,在玻璃中正向和反向能量传递的竞争作用使得Tm³⁺离子在Yb³⁺离子的最佳浓度时上转换发光最强;而在玻璃陶瓷中, Tm³⁺离子的上转换发光始终随着Yb³⁺离子的浓度增加而增强。     

热解法制备KY3F10: Yb, RE(RE=Er, Ho, Tm)纳米晶及其特性研究

有机染料和量子点等荧光标记材料存在发射光谱宽、 光热稳定性差和细胞毒性等缺陷, 限制了其在生物学研究中的应用. 镧系掺杂上转换发光材料不存在"自发荧光"和"光漂白"现象, 灵敏度高, 长期稳定性好, 利于活体检测. 论文首次采用热解法, 以油酸和十八烯为表面活性剂和溶剂, 制备了KY₃F₁₀: Yb, RE(RE=Er, Ho, Tm) 纳米晶. 研究了油酸含量对产物形貌和粒径尺寸的影响, 当油酸与十八烯的比例为3:1时, 为制备类球形单分散纳米晶体的最佳工艺条件, 在980 nm半导体激光器激发下, 样品KY₃F₁₀: Yb, RE(RE=Er, Ho, Tm) 分别发射出较强的黄绿、 绿色和蓝色光, 这些结果显示KY₃F₁₀: Yb, RE(RE=Er, Ho, Tm) 纳米粒子作为生物探针在多重荧光标记方面具有优异的特性.     

纳米晶Gd2O3：Eu^3＋的制备及发光性能

采用低温燃烧合成法制备了Gd2O3：Eu^3＋纳米晶。用X射线衍射仪（XRD）、高分辨透射电子显微镜（HRTEM）和荧光光谱仪分别对样品的结构、形貌和发光性能进行了研究。结果表明，改变甘氨酸与稀土离子的比例（G／M）、退火温度可以制备出不同结构和晶粒尺寸的Gd2O3：Eu^3＋纳米晶。在退火温度为800℃，G／M等于0．83和1．0时，均得到了纯立方相的Gd2O3：Eu^3＋纳米晶，随着G／M的增加，Gd2O3：Eu^3＋从立方相逐渐向单斜相转变。粉末的晶粒尺寸随着退火温度的增高而增大，晶粒尺寸在10-30nm之间。立方相的Gd2O3：Eu^3＋纳米晶主发射峰位置在612nm（^5D^0→^7F2跃迁），激发光谱中电荷迁移态发生了红移。