Tb3+掺杂硅酸盐闪烁玻璃发光特性

对Tb³⁺掺杂的硅酸盐闪烁玻璃进行了研究。对玻璃基质、敏化剂、发光激活剂组分进行了优化,改进了熔制温度、保温时间、气氛等工艺条件。根据氟化物具有较好的稀土可溶性,具有相对较低的声子能量,调整了闪烁玻璃中的氟化物含量。讨论了Tb³⁺离子和Gd³⁺,Dy³⁺离子对闪烁玻璃发光性能的影响。闪烁玻璃样品的激发和发射光谱、光衰减时间谱等结果显示:闪烁玻璃基质中由Gd³⁺和Dy³⁺离子向发光中心Tb³⁺离子的无辐射能量共振转移以及在一定浓度范围内Tb³⁺离子之间的交叉弛豫过程对玻璃的发光性能有重要影响。Tb³⁺离子在一定浓度范围内具有自敏化效应,随着Tb³⁺离子浓度的增加,绿色荧光得到增强,蓝紫色荧光减弱,Tb³⁺掺杂硅酸盐闪烁玻璃的发光性能有明显的提高。     

(La,Ce,Tb)BO3的合成及光谱性质

采用高温固相法合成了(La,Ce,Tb)BO₃绿色发光粉,并对该发光粉进行了XRD和SEM分析。结果表明:(La,Ce,Tb)BO₃的晶体结构和LaBO₃相同,Ce³⁺、Tb³⁺的掺入并没有改变晶体的结构,发光粉颗粒大小均匀,形貌规则,粒度在5 μm左右。研究了(La,Ce,Tb)BO₃的光谱性质,在(La,Ce,Tb)BO₃的发射和激发光谱中除了有Tb³⁺的特征发射和激发峰外,还有Ce³⁺的特征发射和激发峰。比较了(La,Ce)BO₃发射光谱和(La,Tb)BO₃的激发光谱,两者存在重叠,这为Ce³⁺→Tb³⁺的能量传递提供了条件。将(La,Ce,Tb)BO₃的发射光谱与商品粉(La,Ce,Tb)PO₄进行比较,两者的发射主峰都在541 nm处, (La,Ce,Tb)BO₃在489 nm处的峰位稍有红移,通过计算表明,(La,Ce,Tb)BO₃的发光亮度达到商品粉(La,Ce,Tb)PO₄的94.7%。因此,(La,Ce,Tb)BO₃是一种很有应用前景的绿色发光粉。     

RE(POA)3phen配合物的合成、表征及荧光性能

合成了以稀土离子Sm³⁺、Eu³⁺、Tb³⁺、Dy³⁺及Tb³⁺为发光中心,以苯氧乙酸(HPOA)和邻菲罗啉(phen)为配体,掺杂La³⁺、Gd³⁺、 Y³⁺的7种稀土配合物, 对配合物进行了C、H、N元素分析、稀土络合滴定、红外光谱、紫外光谱和发光光谱的研究。结果表明配合物的组成分别为SmL₃L'·1/2H₂O,EuL₃L'·1/2H₂O,TbL₃L'· 1/2H₂O,DyL₃L'·1/2H₂O,掺杂配合物组成分别为Tb_0.5Gd_0.5L₃L'·1/2H₂O,Tb_0.5Y_0.5L₃L'·1/2H₂O,Tb_0.5La_0.5L₃L'·1/2H₂O(L=C₆H₅OCH₂COO^-, L'=phen)。配合物中的稀土离子与苯氧乙酸中羧基的一个氧原子和苯氧基的氧原子配位,与邻菲罗啉中的两个氮原子配位成键;荧光光谱表明,铽三元配合物的发射强度要远大于其它三元配合物的发光强度,掺杂发光惰性稀土离子La³⁺、Gd³⁺、Y³⁺的铽配合物中,Y³⁺掺杂配合物的发光强度有所增强。     

PEI/CeF3 : Tb3+纳米晶体的简易合成及荧光特性

用水热法制备了PEI/CeF₃ : Tb³⁺纳米晶体,运用透射电子显微镜,X射线衍射,傅立叶变换近红外光谱,对样品进行了表征。结果表明:所得纳米晶体平均粒径为10 nm,呈比较规则的立方体形;纳米晶体表面包覆有PEI,因而具有较好的水溶性和潜在的生物应用价值。我们给出了该纳米晶体的荧光激发谱与发射谱,详细说明了各发光峰对应能级的跃迁及其发光机理,分析了不同掺杂浓度对其荧光强度的影响。结果表明:所制备的纳米晶体在紫外光激发下,显示出明亮的绿色荧光。当Tb³⁺离子掺杂摩尔分数20%左右时,样品的荧光强度达到最大值。     

LiMBO3 : Dy3+材料的发光特性

采用固相法制备了LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料,并研究了材料的发光特性。LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料的发射光谱均呈多峰发射,对应于Ca,Sr,Ba,其主发射峰分别是Dy³⁺的⁴F_9/2→⁶H_15/2(484,486,486 nm),⁶H_13/2(577,578,578 nm)和⁶H_11/2(668,668,666 nm)跃迁。监测黄色发射峰时,所得激发光 谱峰值位置相同,主激发峰分别为331,368, 397,433,462,478 nm,对应Dy³⁺的⁶H_15/2→ ⁴D_7/2,⁶P_7/2,⁶M_21/2,⁴G_11/2,⁴I_15/2和⁶F_9/2跃迁。研究了敏化剂Ce³⁺及电荷补偿剂Li⁺、Na⁺和K⁺对LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料发光强度的影响。结果显示:加入敏化剂Ce³⁺提高了材料的发光强度,发光强度最大处对应的Ce³⁺浓度为3%;加入电荷补偿剂Li⁺、Na⁺和K⁺后,材料的发光强度也得到了明显提高,但发光强度最大处对应的Li⁺、Na⁺和K⁺浓度不同,依次为4%、4%和3%。     

双酰胺稀土配合物的合成及荧光性能

为寻求发光性能良好的配合物,设计合成了一种新的双酰胺配体1,4-二 苯(L),并在氯仿和乙酸乙酯溶液中合成了其与硝酸钐、硝酸铕和硝酸铽的发光稀土配合物。元素分析数据表明稀土硝酸盐与配体形成的是 1 : 1 型的配合物;红外光谱显示配合物具有相似的配位结构。对配体及其配合物的荧光进行了详细的研究,结果表明:钐、铕和铽配合物分别呈现出Sm³⁺、Eu³⁺、Tb³⁺的特征发射,铕离子处于不对称中心格位,硝酸铽配合物荧光相对强度最大。     

共沉淀法制备NaYF4 : Tm3+,Yb3+的上转换发光

通过共沉淀法制备Tm³⁺和Yb³⁺掺杂的NaYF₄上转换发光材料。其中Tm³⁺和Yb³⁺的摩尔分数分别为0.01%,0.1%。在室温下测试了NaYF₄ : Tm³⁺,Yb³⁺材料在300~1 100 nm的吸收光谱。利用X射线衍射(XRD),扫描电镜(SEM)测试了合成材料的物相结构和微观形貌。结果表明:NaYF₄ : Tm³⁺,Yb³⁺材料为六方相晶体,其颗粒大小约为50~60 nm,产物结晶良好,含有少量杂相。在798 nm近红外光激发下,测试了样品的上转换发光光谱。观察到了蓝、绿色上转换发光。讨论了上转换发光的可能机理,蓝光主要来源于Tm³⁺的激发态¹G₄到基态³H₆的跃迁,绿光来源于Tm³⁺的¹D₂→³H₅跃迁。     

YAB晶体中Yb3+到Er3+的能量传递

1.55 μm波段是光通讯的一个重要波段,而且对人眼安全,有高的大气透过率,因此可以广泛应用于通讯和遥感测距等领域。由于Er³⁺离子对商品化的InGaAs激光二极管的抽运波长不能有效吸收,因此一般通过在基质中共掺杂Yb³⁺和Er³⁺离子来获得1.55 μm波段激光输出。采用助熔剂法生长了不同Yb³⁺和Er³⁺掺杂浓度的YAl₃(BO₃)₄(YAB)晶体。运用速率方程模型研究了晶体中Yb³⁺到Er³⁺能量传递过程,得到了根据Yb³⁺离子的荧光寿命计算能量传递系数的简单计算公式。计算了不同掺杂离子浓度的YAB晶体中的能量传递系数等相关参数。结果表明,在YAB晶体中,Yb³⁺到Er³⁺能量传递非常有效,YAB晶体可以作为一种能获得1.55 μm激光输出的良好介质材料。     

红色LiMBO3 : Re3+(Re=Eu,Sm) 发光材料的特性

采用固相法制备了红色LiM(M=Ca, Sr, Ba)BO₃ : Re³⁺(Re=Eu, Sm)发光材料,研究了材料的发光性能。研究发现LiM(M=Ca, Sr, Ba)BO₃ : Eu³⁺材料呈现多峰发射,最强发射分别位于610,615,613 nm处,分别监测这三个最强峰,所得激发光谱峰值位于369,400,470 nm。LiM(M=Ca, Sr, Ba)BO₃ : Sm³⁺材料也呈多峰发射,分别对应Sm³⁺的⁴G_5/2→⁶H_5/2、⁴G_5/2→⁶H_7/2和⁴G_5/2→⁶H_9/2跃迁发射;分别监测602,599,597 nm三个最强发射峰,所得激发光谱峰值位于374,405 nm。研究了激活剂浓度对材料发射强度的影响,结果随激活剂浓度的增大,发射强度先增强后减弱,即,存在浓度猝灭效应。实验表明,加入电荷补偿剂Li⁺、Na⁺或K⁺均可提高LiM(M=Ca, Sr, Ba)BO₃ : Re³⁺(Re=Eu, Sm)材料的发射强度。     

Er3+/Tm3+共掺碲酸盐玻璃光谱特性及能量传递

采用高温熔融法制备了两系列不同掺杂比的Er³⁺/Tm³⁺共掺的碲酸盐玻璃,测试了样品的吸收光谱和在980 nm LD激发下的发光光谱、上转换发光光谱及发光寿命。讨论了Er³⁺与Tm³⁺掺杂浓度对样品光谱性质的影响,Tm³⁺离子的掺入会减弱Er³⁺的1.53 μm发光强度,但通过共振能量传递可以获得Tm³⁺的1.8 μm发光,并随着Tm³⁺离子浓度的增加而增强。同时表明Tm³⁺离子的增加会减弱Er³⁺离子在528 nm和545 nm附近的上转换绿光强度,而上转换红光出现了先增强后减弱的现象。研究了Er³⁺/Tm³⁺共掺杂碲酸盐玻璃的能量传递机制与传递效率,分析了Tm³⁺/Er³⁺离子掺杂浓度比对上转换发光的影响。     

Luminescent Hybrid Materials Based on Polymers of Poly(Alpha-Fluoroacrylates) Doped with Tb(III) Complex

This study is devoted to the development of efficient luminescent hybrid materials excited by UV radiation and featuring narrow luminescence lines as well as light, humidity, and temperature resistance. As a luminescent material, a terbium ion coordination compound introduced into the matrix of an organofluorine polymer is used. It has been shown that efficient excitation transfer to electronic levels of the terbium ion can be achieved by proper ligand selection. The polymer matrix material does not affect the luminescence properties of the Tb(III) coordination compound.     

Luminescent europium(III) and terbium(III) nicotinate complexes covalently linked to a 1,10-phenanthroline functionalised sol-gel glass

Sol-gel glasses with covalently linked lanthanide complexes are luminescent materials which can be processed at ambient temperatures, which have a good solubility and uniform distribution of the complexes in the host matrix. In this study, a luminescent terbium(III) complex was covalently coupled to an organic-inorganic hybrid material prepared by the sol-gel process. This was realised by use of nicotinate groups as the ligands for the terbium(III) ion. The [Tb(C₅H₄NCO₂)₃(phen)(H₂O)₂] complex was immobilised on the sol-gel glass matrix and showed a green photoluminescence upon irradiation with ultraviolet light. The nicotinate groups act as an antenna to absorb the incident light and channel the excitation energy to the terbium(III) ion. The sol-gel glass was also prepared for the corresponding europium(III) complex. In this case, excitation of the europium(III) ion was possible via both the nicotinate ligands and the 1,10-phenanthroline ligands. High-resolution luminescence and excitation spectra were recorded and the radiative lifetimes were measured.     

铽-聚N-乙烯基乙酰胺体系中镧钆掺杂稀土配合物谱学研究

在乙醇溶液中合成了掺杂镧和钆的铽-聚N-乙烯基乙酰胺(PNVA)的掺杂稀土配合物, 并通过红外光谱、紫外光谱、 XPS光电子能谱和荧光光谱研究了该配合物的光谱性质. 结果表明: 掺杂稀土配合物中的稀土离子都与高分子配体PNVA产生配位作用. 配合物的最佳激发波长为303 nm;在此波长激发下, 配合物发出较强铽的特征荧光, 说明非荧光稀土离子(La3 和Gd3 )对Tb3 离子的发光有显著的增强作用, 而对Tb3 的发射峰位影响不大.     

Photophysical Properties of Luminescent Quaternary Lanthanide Molecular Hybrid Systems with Chemical Bonds from the Cooperative Design and Assembly of Structure and Function

Two long chain aliphatic acyl chlorides (dodecanoyl chloride (C₁₀H₁₉OCl, abbreviated as DC) and stearoyl chloride (C₁₈H₃₅Ocl, abbreviated as SC)) were modified by means of the amidation reaction with crosslinking molecules (N-aminopropyl-triethoxylsiliane, (APES, H₂N(CH₂)₃Si(OC₂H₅)₃)) and afford two kinds of structural molecular bridge DC (SC)− APES with double reactivity. Subsequently, according to the principle of coordination chemistry, ternary lanthanide (terbium and europium) molecular complex systems with two molecular bridges DC (SC)− APES and 1,10-phenanthroline (phen) of were successfully assembled. Then the modified molecular bridges behave as structural ligands to form the covalent bond Si− O network with matrix precursor (tetraethoxysilane, TEOS) through a sol-gel process (cohydrolysis and copolycondensation process), resulting in a novel quaternary molecular hybrid material (so called as phen-Tb(Eu)−DC(SC)− APES) with strong chemical bonds (N− Tb(Eu)− O coordination bonds and Si− O covalent bonds). And phen behaves as functional ligand to sensitize the luminescence of terbium or europium ions through the effective intramolecular energy transfer process, which gives rise to the characteristic emission of metal ion.     

Preparation, Characterization and Photophysical Properties of Highly Luminescent Terbium Complexes Incorporated Into SiO2/Polymer Hybrid Material

Two new highly luminescent Tb(III) coordination complexes of beta-diketone ligands, [TbL(capital I, Ukrainian)(NO(3))(3)(H(2)O)] 1 [L(capital I, Ukrainian)=N-(2-pyridinyl)ketoacetamide] and [TbL(capital I, Ukrainiancapital I, Ukrainian) (2)(NO(3))(2)(C(3)H(6)O)][TbL(capital I, Ukrainiancapital I, Ukrainian)(NO(3))(4)] 2 [L(capital I, Ukrainiancapital I, Ukrainian)=N-(6-(4-methylpyridinyl))ketoacetamide], were synthesized and characterized by single crystal X-ray diffraction, and incorporated into SiO(2)/polymer hybrid material by sol-gel method resulting in a novel ternary molecular hybrid material. The Tb(III) complexes display characteristic metal-centered luminescence while the ligands emission are completely quenched, showing that efficient ligand-to-metal energy transfer (antenna effect) occurs. The gels can exhibit the characteristic emission bands of terbium ion. In addition, terbium ions present longer fluorescence lifetime in gels than in the corresponding pure complexes powders. Compared with the complexes, the unit mass luminescence intensities of the gels are enhanced. And the increase extent of luminescence intensity of the gel is influenced by the substituent of the ligands. At the same time, concentration effects on the luminescence intensity were investigated. The photo stabilities of the gels under UV radiation are much better than those of the pure terbium complexes.     

铽掺钇配合物[(TbxY1-x)(HL)L'Cl·1/2H2O]的合成及荧光性质研究

以1,3,5-苯三甲酸根(BTC3-)为阴离子配体,1,10邻菲啰啉(phen)为中性配体,以不同摩尔比铽、钇离子为中心体,合成了系列铽掺钇配合物.经C,N,H元素分析,稀土总量络合滴定和铽、钇分量的测定推测配合物的组成为(TbxY1-x)(HL)L'C1·1/2H2O(x=0.10,0.30,0.50,0.70,0....     

新型三元配合物Tb(DPAB)_3IP的制备与发光性能

合成了邻菲罗啉的衍生物咪唑并[5,6-f]邻菲罗啉(IP),并以其为第二配体,二苯胺羰基邻苯甲酸(HDPAB)为第一配体,制备出新型稀土铽三元有机配合物Tb(DPAB)3IP。采用元素分析、红外光谱和紫外光谱对合成的配体及配合物进行了表征。通过荧光光谱研究了配合物的荧光性质,结果表明第二配体IP有较大的共轭体系,在紫外光激发下,配合物中的配体可将吸收的能量传递给稀土Tb3+离子,表现出较强的Tb3+离子的特征发射,且配体Tb(DPAB)3IP的荧光强度明显大于Tb(DPAB)3phen的荧光强度。这说明适宜的第二配体对配合物有很好的敏化发光作用,合成的Tb(DPAB)3IP是一种良好的绿光材料。     

Observation of localized modes in TbOx and TbAl2 by resonance absorption of γ-quanta

In order to investigate excitations in TbO_x and TbAl₂, the nuclear resonant absorption of the 58 keV Mössbauer line supplied by¹⁵⁹Dy sources was studied.Localized states observed in both compounds are partly attributed to excitations of the terbium ion within theJ=6 state multiplet. In the case of TbO_x, this is confirmed by an investigation of the Schottky anomalies in the specific heat. In TbAl₂, the observed excitation states agree with values calculated by using parameters from magnetization data. Other localized states appearing in TbO_x are assigned to vibrations of the terbium ion. The cut off frequencies of the terbium oscillations are determined to be 18 meV (TbO_x) and 15 meV (TbAl₂) in agreement with conclusions from Debye Waller factors also investigated in the present experiments.     

表面活性剂敏化稀土荧光探针对环丙沙星药物的测定研究

稀土铽离子能与环丙沙星形成络合物,并发射铽离子的特征荧光,加入表面活性剂SDBS能大大增强体系的荧光强度,由此建立了表面活性剂敏化的铽离子荧光探针测定环丙沙星的方法。用1 cm 石英比色池在激发波长为300 nm, 发射波长为545 nm处测定其荧光强度。在最佳测试条件为pH=8.0～8.5, Tb3+ 浓度为5.0×10-5 mol·L-1, SDBS浓度为8.0×10-4 mol·L-1时,环丙沙星的浓度与体系的荧光强度呈线性关系,线性范围为2.0×10-8 mol·L-1～2.5×10-6 mol·L-1, 相关系数为0.999 6,检出限为4.0×10-9 mol·L-1。该法可用于不同剂型环丙沙星药物的测定。     

Ion implantation doping of zinc sulphide thin films

This letter reports on the ion implantation doping of zinc sulphide thin films with terbium, erbium and manganese and shows that the resultant cathode-excited emission is characteristic of the implanted ion.