上转换激光晶体研究进展

本文综述近年来晶体材料的上转换过程研究进展，介绍了上转换发光晶体材料研究中的一些新动向以及在室温环境下，掺杂稀土离子的晶体上转换激光运转的成功经验，列举了几种室温上转换激光器的泵浦条件、发射波长、以及转换效率等参数，说明晶体材料的上转换激光技术已趋于实用化。     

戊二醛法修饰上转换发光材料Na[Y0.57Yb0.39Er0.04]F4的研究

本文利用表面接枝改性法对上转换发光材料Na[Y0.57Yb0.39Er0.04]F4进行表面修饰醛基的研究,通过一系列的实验,确定了较好的修饰醛基的实验条件。在0.05 mol.L-1Na2CO3-NaHCO3缓冲液为溶剂的条件下,修饰醛基的反应时间1.5h,缓冲溶液的pH值控制在9.5,修饰剂戊二醛的加入量5.0ml。通过此种实验条件对上转换发光材料的表面的醛基修饰,在上转换发光材料的表面形成活化的醛基,与蛋白质的氨基发生缩合反应,形成共价键,为其在生物芯片上的应用提供了可行条件。     

溶剂对磷光上转换纳米材料性能的影响

采用水热法,并在EDTA加入前后,分别以去离子水、乙醇为反应溶剂的体系中,合成了掺杂18;Yb3+、2;Er3+的NaYF4磷光上转换纳米材料.实验表明,当EDTA∶ Ln3+(Ln=Y,Yb,和Er)的比例为1.6∶ 1时,在以乙醇为反应溶剂的体系中所得的材料在无需高温处理的情况下,得到了六角晶相较纯、颗粒分散较好、粒度大小均匀的上转换发光材料.且材料在可见光区具有较高的发射强度,适于应用到太阳能电池上.     

793nm光激发下GdVO4∶Eu3+上转换发光性能的研究

用水热法制备出GdVO4:Eu3上转换发光材料.对合成样品的发光性能进行研究,探讨了Eu3+掺杂量、pH值及乙二胺四乙酸二钠掺杂量对样品上转换发光性能的影响.结果表明:样品的结构为四方晶系,在793 nm近红外光的激发下,Eu3浓度为12;、pH值为3、乙二胺四乙酸二钠与稀土离子Eu3+掺杂比例为1:1时,GdVO4:Eu3+样品的上转换发光性能最好;且样品的发射光谱由四个发射峰组成,分别位于596 nm、619 nm、650 nm和698 nm处,归属于Eu3的5D0→7(J=1,2,3,4)电子跃迁.     

飞秒激光激发的β-Ga2O3粉体的上转换发光研究

采用水热法制备了β-Ga2O3粉体,利用X射线衍射(XRD)、扫描电子显微镜(SEM)、拉曼光谱和光致发光谱等测试手段对合成样品的结构、形貌和发光性能进行了表征.结果表明:所得样品为单斜晶系的β-Ga2O3粉体;在800 nm飞秒激光下,β-Ga2O3粉体产生上转换发光现象,出现了394 nm,430 nm,448 nm,458 nm,470 nm,476nm,525 nm,552 nm和652 nm上转换发射峰,实现了紫、蓝、绿和红上转换发光.     

980nm红外激发下氟氧化物中Er3+的上转换可见发光

制备了掺杂Er3+的氟氧化物(10ZrF4-10PbF2-10NaF-5Na2O-60SiO2)材料,测量了样品的吸收谱、上转换荧光发射谱和上转换发光强度与激光泵浦功率的对数关系.分析了Er3+的上转换可见发光机制,证实了在980nmLD的激发下,Er3+在402nm、449nm蓝光波段和520nm、551nm绿光波段的上转换荧光发射来自于4f电子的2H9/2、4F5/2、4S3/2、2H11/2激发态到基态4I15/2的跃迁,给出了2H9/2→4I15/2、4F5/2→4I15/2蓝光三光子激发态吸收(ESA)和4S3/2→4I15/2、2H11/2→4I15/2绿光双光子激发态吸收(ESA)的上转换发光机制.     

Mn2+掺杂NaScF4:Yb3+,Er3+上转换发光材料制备及性能研究

采用三氟乙酸盐高温热分解法,以稀土氧化物(RE2O3,RE=Sc,Yb,Er)、三氟乙酸(CF3COOH)、一氧化锰(MnO)和氢氧化钠(NaOH)为原料,以油胺和十八烯为混合溶剂,制备Mn2+掺杂NaScF4:18;Yb3+/2;Er3+上转换发光材料.研究了Mn2+掺杂浓度对NaScF4:18;Yb3+/2;Er3+上转换发光材料的晶相结构、微观形貌及发光性能的影响.实验结果表明:Mn2+掺杂浓度在0～5mol;范围内,所制得的产物为纯六方相NaScF4:Yb3+,Er3+晶体.当Mn2+掺杂浓度增大到10～30mol;时,样品的晶相结构并未改变,但衍射峰的强度有所降低,所制得产物的形貌由球状转变为片状.当Mn2+掺杂浓度在0～20mol;范围内,所制得的产物在980 nm激光激发下共产生3个发射峰,中心波长分别位于525 nm,555 nm和660 nm.当Mn2+掺杂浓度达到30mol;时,所制备产物的绿光发射峰几乎全部转变为波长为650～670 nm的红光发射峰.     

InGaAlP/InGaP多量子阱中的红外向可见光的上转换

利用808nm激光二极管泵浦的Nd:YAG晶体发出的1064nm皮秒激光器实现了InGaAlP多量子阱材料的红外1064nm向可见光波长660nm、625nm、580nm的上转换,并且通过条纹相机收集的时间分辨表征了此材料的上转换激发态的寿命.波长1064nm向625nm的上转换激发态寿命约为5ns,而1064nm向660nm的上转换激发态寿命约为7ns.通过双光子原理解释了此现象.     

稀土Tm3+/Yb3+共掺杂氟氧化物上转换可见发光

制备了稀土Tm3+/Yb3+共掺杂氟氧化物上转换发光材料(60TeO2-10AlF3-10PbF2-10NaF-2Tm2O3-8Yb2O3),在980nm红外光泵浦激发下,测量了样品的吸收谱、上转换荧光发射谱和上转换发光强度与激光泵浦功率的对数关系.观察到峰值为477nm蓝光和651nm红光可见发射,分别是稀土Tm3+的激发态1G4→3H6,1G4→3F4跃迁;在806nm附近,观察到较强的红外发射(3H4→3H6),分析了稀土Tm3+/Yb3+共掺杂氟氧化物上转换可见发射机制,证实了稀土Tm3+上转换发射是在稀土Yb3+的敏化作用下,通过能量传递(ET)和激发态吸收(ESA),实现了激发态1G4向基态3H6、激发态3F4跃迁的三光子吸收过程和激发态3H4→3H6的双光子吸收过程.     

空心结构NaYF4∶Yb,Er上转换材料的制备

以稀土三氟乙酸盐、氟化钠和三氟乙酸钠为原料通过溶剂热法成功制备出了空心结构的Na YF4∶Yb,Er上转换材料,探索了反应温度、钠离子浓度对产物形貌、晶相及发光性能的影响。利用扫描电镜,透射电镜,X射线衍射和发光光谱对产物的形貌、物相结构及荧光性能进行表征。结果表明,当Na F和Y3+的摩尔比为2.5,220℃溶剂热反应12 h时,可得到空心结构的上转换材料,该结构兼具上转换荧光、载药双重功能。     

Surface plasmon excited infrared-to-visible upconversion in Er-doped transparent glass ceramics

The surface plasmon (SP) excited infrared-to-visible upconversion luminescence has been studied in the oxyfluoride glass ceramics containing Er³⁺-doped fluoride nano-crystals. Upconversion luminescence was observed at glass ceramics. Quantum yield of upconversion luminescence increased with increasing heat-treatment temperature. The transparent glass ceramics heat-treated at 700 °C was covered with a 50 nm gold film, and then attached to an SF10 prism with index-matching oil to make an attenuated total reflection (ATR) illumination. The intense upconversion luminescence bands at 540 and 660 nm were observed at the SP resonance angle by using p-polarized laser beam. The apparent dependences of the upconversion efficiency on laser polarization and on incident angle demonstrated the SP excited upconversion of Er³⁺.     

Luminescence behavior of Er ions in glass-ceramics containing CaF2 nanocrystals

The upconversion luminescence and near infrared luminescence of the Er³⁺ ions in transparent oxyfluoride glass-ceramics containing CaF₂ nanocrystals have been investigated. The formation of CaF₂ nanocrystals in the glass-ceramics was confirmed by XRD. The oscillator strengths for several transitions of the Er³⁺ ions in the glass and glass-ceramics have been obtained and then the Judd-Ofelt parameters were calculated. The split near infrared emission peaks of the Er³⁺ ions in the glass-ceramics can be observed because the Er³⁺ ions have been incorporated into crystalline environment of the CaF₂ nanocrystals. The upconversion luminescence intensity of Er³⁺ ions in the glass-ceramics increased significantly with increasing heat treated time. The transition mechanism of the upconversion luminescence has been ascribed to a two-photon absorption process.     

Short-wavelength upconversion luminescence of Yb/Tm co-doped glass ceramic containing SrF2 nanocrystals

The preparation process and upconversion luminescence properties of the Yb³⁺ and Tm³⁺ co-doped glass ceramic containing SrF₂ nanocrystals were investigated. In the glass ceramic, the SrF₂ nanocrystals were embedded uniformly in the glass matrix. The Yb³⁺ and Tm³⁺ ions could be enriched into the precipitated SrF₂ nanocrystalline phase, which provide much lower phonon energy than the glass matrix. The glass ceramic exhibited much stronger upconversion luminescence from ultraviolet to visible than the precursor glass. The upconversion luminescence mechanisms were mainly attributed to Yb³⁺-Yb³⁺ cooperative upconversion, Yb³⁺-Tm³⁺ energy transfer and Tm³⁺-Tm³⁺ cross relaxation.     

飞秒激光辐照Tm:YAG晶体的紫外发光研究(英文)

本文报道了室温下飞秒激光辐照Tm∶YAG晶体的紫外光上转换荧光。Tm3+荧光的强度与泵浦光的功率之间的依赖关系揭示了晶体的上转换过程由三光子吸收过程所主导。研究表明上能级粒子的增加来自于Tm3+吸收一个泵浦光子跃迁到3H4能级后再吸收两个泵浦光子,然后离子跃迁至下能级产生上转换荧光。     

掺铒PLZT电光陶瓷发光特性

测量并分析了Er3+∶PLZT电光陶瓷的吸收光谱和上转换光谱,利用Dexter理论和速率方程理论研究了该材料的发光特性.通过Dexter理论计算得到4I13/2+4I13/2→4I9/2+4I15/2( ET1)和4I11/2+4I11/2→ 4I15/2+4F7/2(ET2)能量传递过程的交叉驰豫几率分别为2.06×105 s-1和1.61 ×105 s-1.以此为基础,结合Er3+跃迁的动力学模型,利用速率方程讨论了交叉驰豫过程对4 I13/2,4I11/2,4I9/2能级上离子数的影响.通过分析可知,ET1和ET2交叉驰豫过程将会使4I13/2能级粒子数大幅度减少,不利于1550hm发光,而对800 nm的发光起到较大的促进作用.     

Spectroscopic properties of Er-Yb co-doped glass ceramics containing BaF2 nanocrystals

A Er³⁺ and Yb³⁺ co-doped transparent oxyfluoride glass ceramic containing BaF₂ nanocrystals has been prepared. The formation of BaF₂ nanocrystals in the glass ceramic was confirmed by X-ray diffraction. Intense upconversion luminescence in the Er³⁺ and Yb³⁺ co-doped glass ceramic could be observed. Stark splitting of the Er³⁺ upconversion luminescence peaks in the glass ceramic indicated that Er³⁺ and Yb³⁺ had been incorporated into the BaF₂ nanocrystals. Near infrared luminescence decay curves showed that the Er³⁺ and Yb³⁺ co-doped glass ceramic had higher luminescence efficiency than the precursor glass.     

Nano-crystals precipitation and upconversion luminescence properties in Er3+/Yb3+ co-doped fluoride phosphate glass-ceramics

Er³⁺/Yb³⁺ co-doped transparent glass-ceramics containing Ca₅(PO₄)₃F nano-crystals were prepared and their upconversion properties were investigated. Transparent glass-ceramics were obtained after heat treatment at the first crystallization temperature, TEM images showed that Ca₅(PO₄)₃F nano-crystals of 10–20 nm in diameter precipitated uniformly in the glass matrix, which is similar to the result of those calculated by Scherrer equation. Comparing with the samples before heat treatment, high efficiency upconversion luminescence of Er³⁺ at 547 nm and 667 nm was observed in the glass-ceramics under 980 nm excitation, and the intensity of red emission showed different tendency to that of green emission after nano-crystals precipitation. The reasons for the highly efficient upconversion luminescence in glass-ceramics were discussed.     

The effect of PbF2 content on the microstructure and upconversion luminescence of Er-doped SiO2-PbF2-PbO glass ceramics

The Er³⁺ doped transparent oxyfluoride glass ceramics were obtained by appropriate heat treatment of the precursor glasses with composition (mol%) 50SiO₂-xPbF₂-(50 − x)PbO-0.5ErF₃. The microstructure and optical properties of the glasses and glass ceramics were determined by differential scanning calorimetry (DSC), X-ray diffraction (XRD), absorption spectra and luminescence spectra. The intensity of upconversion luminescence significantly increased in glass ceramics compared to that in precursor glass. The emission bands centered around 660 nm (⁴F_9/2 → ⁴I_15/2) and 410 nm (²H_9/2 → ⁴I_15/2) were simultaneously observed in glass ceramics but cannot be seen in the corresponding precursor glass. The influence of different PbF₂ content on the microstructure and upconversion luminescence of the samples was analyzed in detail. The results indicated that with the increase of PbF₂ content, the Ω₂ was almost the same and the ratios of red to green upconversion luminescence decreased in glass ceramics.     

Preparation and upconversion luminescence characterization of 12CaO·7Al2O3:Ho3+/Yb3+ polycrystals

The effect of Yb³⁺ concentration on the fluorescence of 12CaO·7 Al₂O₃:Ho³⁺/Yb³⁺ polycrystals is investigated. The Raman spectra of pure C12A7 under 633‐nm excitation show that the highest photon energy is 787.267 cm⁻¹, which is not much bigger than general fluorides, so it can realize high efficiency upconversion. The upconversion emission spectra suggest that the green upconversion emission centered at 548 nm and the red upconversion emission at 662 nm correspond to the ⁵F₄/⁵S₂→⁵I₈ and ⁵F₅→⁵I₈ transition of Ho³⁺ ions, respectively. The intensity of the upconversion luminescence and the ratio of red to green are changed with Yb³⁺ ion concentration. The pump dependence and luminescence decay dynamics spectra show the green and red upconversion emissions are populated by a two‐photon process, and the upconversion mechanisms are analyzed. The relative luminous efficiencies of green and red emissions are 2.035% and 0.7%, respectively. The normalized efficiency obtained for green emission of Ho³⁺ at RT when the sample is excited by 980‐nm light with an absorbed intensity of 7.5 W/cm² is 0.27 cm²/W. This result is comparable to the values obtained in YF₃ for the Yb³⁺, Er³⁺ green emission. The C12A7 with upconversion red and green light will be a promising luminous material.     

Optical properties of Er3+-singly doped and Er3+/Yb3+-codoped novel oxyfluoride glasses

Novel oxyfluoride glasses SiO₂–Al₂O₃–Na₂O–ZnF₂ doped with Er³⁺ and Er³⁺/Yb³⁺ were fabricated. The optical properties of the synthesized glasses were experimentally and theoretically investigated in detail. The experimental and calculated oscillator strengths of Er³⁺ were determined by measurement of the absorption spectrum of Er³⁺-singly doped glass. According to the Judd–Ofelt theory, the experimental intensity parameters were calculated, from which the radiative transition probabilities, fluorescence branching ratios and radiative lifetimes were obtained. The fluorescence lifetime and quantum efficiency for the near-infrared emission of Er³⁺-singly doped glass were determined to be 3.0 ms, and 42%, respectively. Visible upconversion luminescence was observed under 980 nm diode laser excitation. The dependence of the upconversion emission intensity upon the excitation power was examined, and the upconversion mechanisms are discussed.