铋离子掺杂RO-Al2O3-SiO2玻璃近红外超宽带发光性质

研究了碱土金属氧化物对Bi离子掺杂RO-Al₂O₃-SiO₂ (R=Ca, Sr, Ba)玻璃近红外超宽带发光性质的影响. 结果表明: 玻璃样品在不同抽运源激发下都可检测到较强的近红外超宽带发光. 在808 nm激光激发下, 随着碱土金属离子半径的增加, Bi离子在1 300 nm附近的近红外发光强度显著增加, 荧光半高宽逐渐增加, 其荧光寿命最长可超过600 μms; 而在690 nm激光激发下, 随着碱土金属离子半径的增加, Bi离子在1 100 nm附近的近红外发光呈减弱趋势, 荧光半高宽逐渐增大, 半高宽最大可超过400 nm. 近红外发光可能源于两种不同形式铋的发光中心. 针对上述结果探讨了该玻璃体系中Bi离子近红外发光的机理.     

Au/Bi共掺二氧化硅薄膜的制备及近红外光谱调控

根据X射线光电子能谱分析和选择性光致发光谱测试结果,探讨了Bi离子掺杂非晶二氧化硅薄膜的近红外发光来源。我们认为非晶二氧化硅薄膜中Bi离子的近红外发光来源于低价态Bi~+离子从轨道~3P_1层到~3P_0层的辐射复合跃迁和Bi~0从轨道~2D_(3/2)层到~4S_(3/2)层的辐射复合跃迁。此外,本文利用限制性晶化原理,通过在掺Bi二氧化硅薄膜中引入Au离子,实现了Bi离子相关的近红外发光峰位可调,荧光强度增大了300%。高分辨透射电子显微镜截面图片证实了非晶二氧化硅薄膜厚度约为90 nm以及不同尺寸、数密度Au量子点的形成。变温光致发光谱测试结果表明,部分Au离子可有效降低Bi离子掺杂非晶二氧化硅薄膜中羟基集团等非辐射复合中心密度。Bi离子掺杂非晶二氧化硅薄膜近红外发光来源的探讨以及通过Au量子点调控Bi离子近红外发光性质的讨论将有助于未来掺Bi发光材料的相关研究。     

电子束辐照诱导Bi:α-BaB2O4 单晶近红外宽带发光的研究

用提拉法技术生长出了Bi:α-BaB₂O₄单晶,并进行电子束辐照.测定了电子束辐照前后的吸收谱和荧光发射谱.在808 nm波长激光二极管的激发下,电子束辐照后的Bi:α-BaB₂O₄单晶中观测到了中心波长在1135 nm附近、半高宽为52 nm左右的近红外宽带发光现象.近红外宽带发光的发光中心是Bi⁺离子.电子束射线起到了将Bi³⁺和Bi²⁺还原至一价态 关键词： 近红外宽带发光 2O₄单晶')" href="#">α-BaB₂O₄单晶 电子束辐照     

结构自还原效应对铋掺碱土金属硅磷铝硼玻璃超宽带近红外发光的影响

本文报道了结构自还原对铋掺杂碱土金属硅磷铝硼玻璃超宽带近红外发光性质的影响. 以Eu作为对比, 在空气气氛中采用高温熔融法分别制备了Eu₂O₃和Bi₂O₃掺杂的35SiO₂-25AlPO₄-12.5Al₂O₃-12.5B₂O₃-15RO(R=Ca,Sr,Ba) 玻璃. 结果证实该玻璃中可发生Eu³⁺→Eu²⁺的高温自还原现象, 且随着碱土金属离子半径增大Eu²⁺ 的自还原性减弱; 同样条件下Bi位于1300 nm波段的近红外发光却随之增强, 而位于1100 nm波段近红外发光和源于Bi²⁺的红光则减弱. 根据结构自还原机理及碱土离子半径变化对玻璃近红外超宽带发光性质的影响, 讨论了Bi离子的近红外发光中心的归属. 上述研究表明玻璃结构自还原特性可以为Bi近红外发光机理研究以及高效Bi掺杂超宽带近红外发光玻璃的设计提供一种有效的思路和方法. 关键词： 玻璃 铋掺杂 近红外发光 自还原效应     

Cr4+掺杂Li1.14Zn1.43SiO4透明微晶玻璃近红外宽带光谱特性

采用高温熔融法和热处理制备了Cr⁴⁺掺杂Li_1.14Zn_1.43SiO₄微晶玻璃, 探讨了不同热处理温度下样品的物相、微观形貌及发光性能. 结果表明: 580℃热处理2h得到的微晶玻璃, Li_1.14Zn_1.43SiO₄微晶的粒径约为5nm, 在808nm的二极管激发下, 可观察到中心波长位于1226nm, 半高宽为230nm的近红外宽带发射峰, 荧光寿命约为200.73±1.71μs. 随着热处理温度的升高, Cr⁴⁺离子所处的晶体场环境发生了变化, 且可以观察到样品吸收光谱发生微弱的蓝移, 而荧光光谱发生少量的红移, 分析了晶体场环境变化对样品发光性能的影响. 关键词： 铬离子 微晶玻璃 超宽带发光 晶体场     

γ射线辐照诱导Bi:α-BaB2O4单晶近红外宽带发光的研究

用提拉法技术生长出了掺Bi的α-BaB₂O₄单晶并经过γ射线辐照.测定了样品在室温下的吸收光谱、发射光谱及荧光衰减曲线.在808 nm波长光的激发下,经γ射线辐照后的α-BaB₂O₄单晶中发现了中心波长为1139 nm、半高宽为113 nm的近红外宽带发光现象.讨论了辐照条件和退火处理对Bi离子发光的影响.对于其发光机理进行了初步的探讨. 关键词： 近红外宽带发光 2O₄单晶')" href="#">α-BaB₂O₄单晶 辐照 退火处理     

Dy3+掺杂NaYF4纳米粒子的制备及其上转换发光性质

制备了Dy³⁺掺杂 NaYF₄上转换发光纳米晶体,通过X射线衍射(XRD)、扫描电子显微镜(SEM)、荧光(FL)光谱、红外光谱仪(FT-IR)对合成样品的结构、形貌和发光性能进行表征。探讨了稀土离子掺杂浓度和焙烧温度对NaYF₄∶Dy³⁺纳米晶的结构、形貌和发光的影响。在776 nm红外光下激发样品,出现479,574 nm上转换发射峰,实现了蓝、绿上转换发光。绿光来自于Dy³⁺的⁴F_9/2→⁶H_13/2跃迁,蓝光是由Dy³⁺的⁴F_9/2→ ⁶H_15/2跃迁产生的。     

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。     

掺铋BaF2晶体的制备及其近红外发光研究

通过温度梯度法制备了Bi₂O₃:BaF₂以及BiF₃:BaF₂晶体.在Bi₂O₃:BaF₂晶体中观察到了发光峰位于961 nm,半高宽202 nm的超宽带红外发光.在BiF₃:BaF₂晶体中检测到Bi²⁺和Bi³⁺可见区的发光,但是没有观察到红外发光.通过γ射线辐照实现了BiF₃:BaF₂晶体的近红外发光, 发光峰位于1135 nm,半高宽192 nm.讨论了Bi₂O₃和BiF₃掺杂BaF₂晶体的红外发光的机理. 关键词： 近红外发光 铋 氟化钡晶体 γ辐照     

双掺Eu3+ 和Tb3+ 的下转换β-NaYF4的合成与发光性能

采用高温溶剂热法合成了下转换发光材料NaYF₄∶Eu³⁺ 和NaYF₄∶Eu³⁺,Tb³⁺ ,采用X射线衍射(XRD)、场发射扫描电镜(FESEM)、激发(PLE)谱和光致发光(PL)谱对材料的物相结构、形貌特征和发光性质进行了表征和研究,并分析了其发光原理。结果表明:所合成的NaYF₄∶Eu³⁺ 和NaYF₄∶Eu³⁺,Tb³⁺ 为纯六方相晶体,尺寸在100 nm左右;改变Eu³⁺ 和Tb³⁺ 的掺杂浓度后晶格结构没有发生明显变化,说明Eu³⁺ 和Tb³⁺ 取代的是Y³⁺的晶格位置;在394 nm光的激发下,检测到Eu³⁺ 在⁵D₀→⁷F₁ 和⁵D₀→⁷F₂跃迁处的特征发射光,并且可见光强度随着Eu³⁺ 离子掺杂浓度的变化而变化。另外Tb³⁺ 离子浓度对NaYF₄∶Eu³⁺ 晶体结构产生了一定的影响,说明掺杂Tb³⁺ 离子改变了Eu³⁺ 离子所处的配位环境,导致红色发光带增强,而这主要源于电偶极子跃迁的贡献。     

Rare Earth Photoluminescence in Bismuth-Germanate Crystals

In the present work, the photoluminescence (PL) spectra of bismuth germanate (BGO) doped with trivalent rare earth element (REE) ions with different doping concentrations (0.03 wt% Eu, 0.4 wt% Tm, and 1.1 wt% Nd) are reported in the temperature range from 10 to 300 K using different detectors, namely, photomultiplier tube (PMT), InGaAs (IGA), and Si. The luminescence in the NIR region was also measured at room temperature. Two broad emission bands attributed to undoped BGO were found at circa 1350 and 1800 nm, respectively. The broad-band emissions are replaced by narrow-band line emissions defined by the trivalent rare earth dopants. The emission spectra from rare earth ion–doped BGO extend from 500 to 2000 nm. Rare earth ions act as the dominant recombination centers and define the emission spectra. This is interpreted as resulting from direct charge transfer from intrinsic defect traps to rare earth recombination centers. The temperature-dependent luminescence of BGO doped with 0.4 wt% Tm is also presented.     

Near-infrared luminescence of OH and Cl doped Bi4Ge3O12 crystals

OH⁻ and Cl⁻ doped Bi₄Ge₃O₁₂ (BGO) single crystals had been grown by Vertical Bridgman (VB) method. The structure of these crystals was determined by XRD, the transmittance and emission spectra in near infrared region (NIR) were measured at room temperature. 5% OH⁻ doped BGO shows a significant emission band peaking around 1181 nm under 808 nm laser diodes (LDs) excitation, and the 5% Cl⁻ doped BGO exhibits a relatively weak emission band as well. 100% and 5% OH⁻ doped BGO show noticeable emission band centered at about 1346 nm under 980 nm LDs excitation.     

Spectroscopic properties of OH doped and Bi-rich Bi4Ge3O12 crystals by vertical Bridgman method

OH⁻ doped and Bi-rich Bi₄Ge₃O₁₂ (BGO) single crystals were grown by Vertical Bridgman (VB) method. The structure of these crystals was determined by XRD, and the emission spectra in visible and near infrared region (NIR) were measured at room temperature. The emission spectrum of Bi-rich BGO has extra peaks at 385, 367 and 357 nm, Bi-rich BGO after annealing in Ar at 500 °C for 5 h shows a significant emission band peaking around 1170 nm under 808 nm laser diodes (LDs) excitation, and OH⁻ doped BGO shows a noticeable emission band centered at about 1346 nm under 980 nm LDs excitation. A brief discussion is presented.     

Ce~(3+)和Tb~(3+)掺杂钆-钡-硅酸盐闪烁玻璃的发光性能

采用高温熔融法制备Ce~(3+)或Tb~(3+)单掺和Ce~(3+)/Tb~(3+)共掺钆-钡-硅酸盐闪烁玻璃。通过透射光谱、光致激发和发射光谱、X射线激发发射光谱及荧光衰减曲线等手段对其发光性能进行研究。实验结果表明:在紫外光的激发下,Tb~(3+)掺杂闪烁玻璃发出明亮的绿光(544 nm),而Ce~(3+)掺杂闪烁玻璃发出蓝紫光。对于Ce~(3+)/Tb~(3+)共掺闪烁玻璃,在紫外光和X射线激发下均观察到Ce~(3+)离子敏化Tb~(3+)离子发光的现象,这是由于存在Ce~(3+)→Tb~(3+)的能量转移。Ce~(3+)/Tb~(3+)共掺闪烁玻璃的最佳Ce2O3掺杂摩尔分数为0.2%,此时Ce~(3+)离子向Tb~(3+)离子的能量传递效率为45.7%。在X射线激发下,Ce_2O_3摩尔分数为0.2%的Ce~(3+)/Tb~(3+)共掺闪烁玻璃在544 nm处的发光强度是Bi_4Ge_3O_(12)(BGO)闪烁晶体在500 nm处发光强度的4.2倍,积分闪烁效率达到BGO晶体的55.6%,这有利于在高分辨率医学成像中降低辐射剂量。     

2(3)-四-(2-异丙基-5-甲基苯氧基)钛氧酞菁的合成及其近红外发光特性

通过分步合成的方法,在钛氧酞菁的外围引入了四个苯氧基团,合成了一种2(3)-四-(2-异丙基-5-甲基苯氧基)钛氧酞菁.通过质谱、核磁、元素分析、紫外可见吸收光谱、近红外光荧光谱和循环伏安法对其结构和性质进行了表征,并利用旋涂加真空热蒸发的方法制得了该材料的电致发光器件(ITO/PVK:TiOPc/BCP/LiF/Al).结果表明,四取代的钛氧酞菁固态的近红外光荧光峰值在1080nm左右;其近红外电致发光的峰值波长落在1050nm左右.在PVK掺杂的器件中,钛氧酞菁的质量分数为30%时有较强的发光强度.     

Noninvasive Temperature Measurement in Dental Materials Using Nd3+, Yb3+ Doped Nanoparticles Emitting in the Near Infrared Region

In this work, the application of near infrared (NIR)-emitting NaYbF₄:1%Tm³⁺@NaLuF₄:30%Nd³⁺ core–shell nanoparticles is reported for noninvasive probing and monitoring the temperature during photopolymerization of dental materials. When excited at 808 nm, the synthesized nanoparticles emit NIR photoluminescence (PL) with two distinctive peaks at 865 and 980 nm which correspond to radiative transitions from the doped Nd³⁺ and Yb³⁺ ions, respectively. Luminescence intensity ratio between these two bands is found to vary with temperature due to temperature-dependent electronic excitation energy transfer between Nd³⁺ and Yb³⁺ ions at the core/shell interface. This finding allows luminescence ratiometric evaluation of the in situ temperature during photopolymerization of resin cement (doped with nanoparticles) in a veneer placement procedure. In addition, the NIR emission also enables PL imaging of the distribution of the adhesive under the veneer. The results highlight that rare-earth ions–doped nanoparticles with both excitation and emission in the NIR spectral range are advantageous for both PL-based nanothermometry and imaging due to the reduced attenuation of NIR light by dental ceramics.     

红色Bi4 Ge3 O12晶体在低温下的发光性能

用下降法制备了Bi₄Ge₃O₁₂晶体,发现生长出来的圆柱状晶体外侧呈现淡红色。对红色Bi₄Ge₃O₁₂晶体进行了低温(至8 K)下的近红外发射光谱及衰减寿命等测试分析。发现低温时(200 K以下)红色Bi₄Ge₃O₁₂在1 150 nm等波长处有较强的发射峰,强度随温度降低而增强,衰减时间为几百μs。     

Fe掺杂对CdS光学特性的影响

采用低压金属有机化学气相沉积技术,在固定源流量的条件下,通过调节衬底温度(270~360℃)生长了不同Fe掺杂浓度的CdS薄膜。光谱测量表明低铁掺杂对CdS晶格振动的影响较小,但对光致发光性质影响较为明显。样品的光致发光谱包括两部分:2.5eV附近带-带跃迁的发光以及2.0~2.4eV之间与缺陷相关的发光。随着铁含量的增加,带-带跃迁逐渐被抑制,发光光谱被缺陷相关的发光主导,同时薄膜的电导也由n型转为p型,说明Fe离子掺入在薄膜引入了受主杂质。通过不同激发密度下的光致发光光谱测量,我们将2.0~2.4eV的发光归结为铁受主相关的D-A对发射,并根据掺杂浓度和发光峰位置估算了Fe受主的能级位置。     

Electron–hole recombination luminescence in LiYF4:U single crystal

Photoluminescence (PL), photostimulated luminescence (PSL), thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) studies were carried out on LiYF₄:U⁴⁺ and pure LiYF₄ crystals. The PL and EPR investigations have identified the presence of Eu³⁺, Tb³⁺ and Gd³⁺ ions in both of these crystals possibly due to their existence in the starting materials. The luminescence observed during afterglow, PSL and TSL revealed that emission occurs at wavelength positions 382, 413, 437 and 544 nm, which are characteristic of Tb³⁺ ions. The present investigations using PSL and TSL in combination with PL studies before and after gamma irradiation have revealed that selective energy transfer to Tb³⁺ ions occurs during electron–hole recombination processes like PSL and TSL. Even though other luminescent ions (U⁴⁺ and Eu³⁺) are present in the system and U⁴⁺/U³⁺ ions are participating in electron capture/release processes, the selective energy transfer results in Tb³⁺ ions acting as luminescence centers.