Er3+掺杂氧氟锗硅酸盐玻璃的频率上转换研究

研究了基质玻璃成分对Er^3 掺杂氧氟锗硅酸盐玻璃上转换光谱和Raman光谱的影响,分析了氧氟锗硅酸盐玻璃中Er^3 的上转换发光机理。结果表明：通过975nm的激光二极管激发,在室温下同时观察到强烈的绿光(529,545nm)和红光(657nm)发射,分别是由于Er^3 的。H11/2→^4I15/2,^4S3/2→^4I15/2,和^4F9/2→^4I15/2跃迁,且均为双光子吸收过程。与545nm的绿光发射相比,657nm的红光发光强度比较微弱。随GeO2浓度的增加,基质玻璃的最大声子能量下降,导致无辐射跃迁几率降低,因此绿光和红光的发光强度都增强,但是其对绿光的影响大于红光。     

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。     

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。     

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。     

Tb~(3+)/Yb~(3+)共掺α-NaYF_4单晶近红外到可见光的合作上转换发光（英文）

用980 nm的近红外激光泵浦Bridgman方法生长的Tb~(3+)/Yb~(3+)共掺的α-NaYF_4单晶,研究了其上转换荧光以及荧光强度与泵浦功率的关系。结果表明:2个或者3个激发态的Yb~(3+)离子传递能量给1个Tb~(3+)离子并引发了双光子或三光子上转换。高效的三光子上转换的381、414、435和462 nm光和双光子上转换的481、541、587、651、659和668 nm光分别产生于Tb~(3+)离子的~5D_3→~7F_J(J=6,5,4,3)和~5D_4→~7F_J(J=6,5,4,3,2,1)辐射跃迁。现有实验下,当Tb~(3+)的掺杂量为0.52%(摩尔分数)时,Yb~(3+)的最佳掺杂量为7.98%,并可以进一步增加。以上结果表明了Tb~(3+)/Yb~(3+)共掺的α-NaYF_4单晶在上转换绿光固体激光材料方面的潜在应用。     

Ho^3＋：ZnW04的光谱和上转换发光

用提拉法生长出光学质量的Ho^3 ：ZnWO4单晶，研究了晶体在可见和近红外区的吸收光谱和发射光谱，分析了Ho^3 离子在钨酸锌晶体结构中能级位置和晶体场能级分裂。研究表明：在波长488nm激光激发时，550，665nm和758nm3个波段有较强荧光，荧光分支比分别为84．18％，0．68％，15．14％，对应于^5S2→^5I8，^5Fs→^5I8和^5S2→^5I7跃迁。在633nm激光激发时观测到了来自^5S2→^5I8跃迁的540～556nm宽带上转换荧光，上转换过程主要是单离子步进吸收。     

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。     

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...     

一种新的微型激光器材料--稀土掺杂玻璃

制得了具有双包层结构的掺Nd^3 和Yb^3 单模磷酸盐玻璃光纤,用中心波长为800nm的半导体激光器件钕光纤的光泵源,在室温下获得了波长为1．053um,输出功率为8．36mW的连续激光输出,用930nm的钛宝石激光泵浦掺镱光纤,也获得了1．067um的激光,研究了Nd^3 ,Yb^3 ,Er^3 离子掺杂四磷酸盐玻璃和氟化物玻璃的发光性能与浓度的关系,以及Yb^3 /Er^3 双掺杂玻璃的发光性能,得到了掺钕四磷酸盐玻璃,Yb^3 /Er^3 双掺四磷酸盐玻璃和掺氟铝酸盐玻璃等几种在微片激光器有应用前景的材料。     

Synthesis and Optical Properties of Er^3＋-Doped CaF2 Nanopowder

采用直接沉淀法制备掺铒氟化钙（Er3＋：CaF2）纳米粉体,通过 X 射线衍射仪、场发射扫描电子显微镜、透射电镜、分光光度计和电感耦合等离子发射光谱仪等分析手段研究了不同反应溶液浓度对 Er3＋：CaF2纳米粉体结构、形貌、粒径和 Er3＋真实掺入量的影响。结果表明：随着反应溶液浓度的增大,粉体颗粒尺寸逐渐减小,团聚程度加剧,Er3＋的真实掺入量逐渐减少。反应溶液浓度为 0.5mol/L 时合成粉体分散性最好,颗粒平均尺寸约为32 nm,有利于制备性能优异的 Er3＋：CaF2透明陶瓷。在 978 nm 激光二极管激发下,该粉体实现了绿色（530～550 nm）和红色（650～660 nm）两种上转换发光,与之对应的 Er3＋辐射跃迁分别属于2H11/2、4S3/2→4I15/2和4F9/2→4I15/2,相对绿光而言红光发射强度较强     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

3-叠氮甲基-3-甲基氧丁环的合成

以三羟甲基乙烷与碳酸二乙酯为原料,经环化反应合成了3-羟甲基-3-甲基氧丁环(HMM O)。在低温下,HMM O与对甲苯磺酰氯反应生成3-磺酸酯甲基-3-甲基氧丁环(M TM O)。M TM O和叠氮化钠发生叠氮化反应形成叠氮单体3-叠氮甲基-3-甲基氧丁环(AMM O)。三步反应收率分别为76%,96%,85%。用核磁、红外、元素分析和DSC表征了化合物的结构与性能。结构鉴定表明为目标化合物AMM O。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇（BBMP）为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷（BrMMO）。讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响。通过实验确定的最佳工艺条件为：BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4h时,BrMMO产率为65%。最终产品经元素分析、IR和1HNMR检测确定为BrMMO。该试验工艺简单,原料易得,且溶剂便于回收、污染小。     

Tunable color emission in LaScO3:Bi3+,Tb3+,Eu3+ phosphor

LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ (x = 0 − 0.04, y = 0 − 0.05, z = 0 − 0.05) phosphors were prepared via high-temperature solid-state reaction. Phase identification and crystal structures of the LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors were investigated by X-ray diffraction (XRD). Crystal structure of phosphors was analyzed by Rietveld refinement and transmission electron microscopy (TEM). The luminescent performance of these trichromatic phosphors is investigated by diffuse reflection spectra and photoluminescence. The phenomenon of energy transfer from Bi³⁺ and Tb³⁺ to Eu³⁺ in LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors was investigated. By changing the ratio of x, y, and z, trichromatic can be obtained in the LaScO₃ host, including red, green, and blue emission with peak centered at 613, 544, and 428 nm, respectively. Therefore, two kinds of white light-emitting phosphors were obtained, LaScO₃:0.02Bi³⁺,0.05Tb³⁺,zEu³⁺ and LaScO₃:0.02Bi³⁺,0.03Eu³⁺,yTb³⁺. The energy transfer was characterized by decay times of the LaScO₃:xBi³⁺, yTb³⁺, zEu³⁺ phosphors. Moreover absolute internal QY and CIE chromatic coordinates are shown. The potential optical thermometry application of LaScO₃:Bi³⁺,Eu³⁺ was based on the temperature sensitivity of the fluorescence intensity ratio (FIR). The maximum S_a and S_r are 0.118 K⁻¹ (at 473.15 K) and 0.795% K⁻¹ (at 448.15 K), respectively. Hence, the LaScO₃:Bi³⁺,Eu³⁺ phosphor is a good material for optical temperature sensing.     

2,2,3-三氯-3-苯基-3-(3-甲基苯甲酰基)丙腈的合成研究

以苯甲酰氯、四氯化碳、间甲基苯甲酰氰为原料,合成了标题化合物。重点考察了氰化过程中不同原料配比、反应温度、时间、溶剂和催化剂用量对收率的影响。实验结果表明,其最佳反应条件为:n(1,1,2-三氯-2-苯基乙烯)∶n(3-甲基苯甲酰氰)=1∶1.2,二氯甲烷为反应溶剂,3 mmol催化剂三乙胺,室温反应5 h,总收率达80.6%。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇(BBMP)为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷(BrMMO).讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响.通过实验确定的最佳工艺条件为:BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4 h时,BrMMO产率为65%.最终产品经元素分析、IR和1HNMR检测确定为BrMMO.该试验工艺简单,原料易得,且溶剂便于回收、污染小.     

The Preparation and Crystal Structure of TlMnCl3, TlFeCl3, TlCoCl3 and TlNiCl3

The compounds TlMnCl₃, TlFeCl₃, TlCoCl₃ and TlNiCl₃ were prepared by heating T1C1 with the corresponding transition metal dichloride in an evacuated ampoule. Atomic positions were determined from powder photographs. All four compounds were found to be related to the perovskite type structure. TlMnCl₃ has a cubic structure, space group Pm3m, with a_o = 5.025 Å. The other three compounds are hexagonal, probable space group P6₃mc, with cell dimensions (in Å) a₀ = 6.976 and c₀ = 6.008 for the Fe compound, a₀ = 6.907 and c₀ = 5.981 for the Co compound and a₀ = 6.863 and c₀ = 5.881 for the Ni compound. The three hexagonal compounds are isomorphous. A measureable concentration of basal plane stacking faults was found to occur in TlFeCl₃ and also, to a lesser degree, in TlCoCl_3.     

Ba3Tb(BO3)3:Eu3+的制备与发光性质

采用高温固相法合成了Ba3Tb(BO3)3:Eu3+红色荧光粉,并研究了Ba3Tb(BO3)3:Eu3+的发光特性。Ba3Tb(BO3)3:Eu3+的激发光谱包含250nm～330nm和350nm～400nm的2个宽带,最大峰值位于383nm,可以被紫外-近紫外发光二极管(light-emitting diodes,LED)有效激发。Ba3Tb(BO3)3:Eu3+的发射谱显示出4组发射峰,其主发射峰位于620nm,对应Eu3+的5D0→7F2跃迁;Eu3+掺杂摩尔分数为2%时,Ba3Tb(BO3)3:Eu3+发光亮度最高。经分析发现Ba3Tb(BO3)3:Eu3+存在Tb3+→Eu3+的能量传递。     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001