卤化铅调整Tm3+/Yb3+共掺碲酸盐玻璃上转换发光研究

研究了卤化铅调整Tm³⁺/Yb³⁺共掺碲酸盐玻璃的热稳定性能、Raman 光谱和上转 换发光光谱，分析了Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光 机理.结果发 现：混合卤化铅调整Tm³⁺/Yb³⁺共掺碲酸盐玻璃具有好的热稳定性 能、低的声 子能量、强的上转换蓝光.这表明混合卤化铅调整Tm³⁺/Yb³⁺共掺碲 酸盐玻璃是一种上转换蓝光激光器的潜在基质材料. 关键词： 氧卤碲酸盐玻璃 上转换光谱 发光机理 上转换蓝光激光器     

Tm3+/Yb3+共掺氧卤碲酸盐玻璃上转换发光研究

研究了Tm3+/Yb3+共掺氧卤碲酸盐玻璃的上转换发光光谱,分析了TmO3量对Tm3+/Yb3+共掺氧卤碲酸盐玻璃上转换发光的影响机理.结果表明:在Tm3+/Yb3+共掺氧卤碲酸盐玻璃的上转换发光中,Tm3+存在较强的浓度猝灭效应.随Tm2O3含量增加,Tm3+的上转换蓝光和红光强度先增加,后降低,在0.1 mol% Tm2O3达到最大.该结果有助于进一步提高Tm3+的上转换发光效率.     

970nm抽运下Er3+/Yb3+/Tm3+共掺碲酸盐玻璃的发光特性

研究了Er3+/Yb3+共掺、Tm3+/Yb3+共掺、Er3+/Yb3+/Tm3+共掺碲酸盐玻璃在970nm抽运下的荧光光谱和上转换光谱性质，测试了Er3+离子的4I11/2和4I13/2能级荧光寿命变化情况.结果发现Er3+/Yb3+/Tm3+共掺碲酸盐玻璃的常规荧光谱线在1450—1700nm区域明显加宽，并在1630nm有一荧光峰，可能是Tm3+：1G4→3F2跃迁产生.上转换发光研究表明，由于碲酸盐玻璃声子能量低的缘故，三种共掺系统下都存在上转换发光现象.在Er3+/Yb3+/Tm3+共掺中，上转 关键词： Er3+/Yb3+/ Tm3+共掺 碲酸盐玻璃 荧光 上转换光谱     

Tm~(3+)/Ho~(3+)/Yb~(3+)掺杂铋碲酸盐玻璃上转换白光

制备了具有多彩上转换荧光Tm3+/Yb3+,Ho3+/Yb3+和Tm3+/Ho3+/Yb3+掺杂铋碲酸盐玻璃,并研究了974 nm激光激发下的上转换荧光光谱。在Tm3+/Ho3+/Yb3+三掺杂体系中,由于Tm3+的上转换蓝光发射属三光子过程,蓝光发光强度随激发功率增加而增长的速率大于绿光和红光。计算了Tm3+/Ho3+/Yb3+三掺样品上转换荧光的色坐标,定性阐述了荧光色坐标与激发功率的关系,揭示出随着激发功率的增大,色坐标在1931-CIE色品图中向左下方移动趋势。研究结果表明,在Tm3+/Ho3+/Yb3+三掺铋碲酸盐玻璃中,通过功率调谐可以调整样品的上转换蓝光、绿光和红光强度比例,实现上转换白光发射,证实了Tm3+/Ho3+/Yb3+三掺铋碲酸盐玻璃是一种高效上转换材料,在多彩显示和白光照明领域具有潜在的应用前景。     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO2-ZnO-Na2O的Tm3+离子单掺和Tm3+/Yb3+共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ωt(t=2,4,6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τrad等光谱参量,测量得到了不同Yb3+离子掺杂浓度下玻璃样品的Tm3+离子上转换发光谱.结果显示,在980nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm3+离子上转换发光分析表明,强烈的Tm3+离子近红外上转换发光主要来自于Yb3+/Yb3+离子间的共振能量传递以及基于单声子和双声子辅助的Yb3+/Tm3+离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm3+∶3 F4→3 H6能级间跃迁的1.8μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb3+/Tm3+共掺TeO2-ZnO-Na2O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

Tm3+/Yb3+共掺铋碲酸盐玻璃中的高效蓝色上转换荧光

制备了高折射率Tm3+/Yb3+共掺杂铋碲酸盐玻璃,利用棱镜耦合法测量出玻璃在632.8和1550 nm波长处的折射率分别为2.0365和1.9795. 对玻璃的吸收、荧光和红外透过光谱展开了测试与分析,根据Judd-Ofelt理论对吸收光谱进行拟合,求得Tm3+的振子强度参数Ωt(t=2,4,6)分别为3.90×10-20, 2.03×10-20和9.03×10-21 cm2,并进一步计算了Tm3+在玻璃中各能级跃迁的振子强度、自发辐射跃迁概率、辐射寿命和荧光分支比等光谱参数. 在980 nm激光激发下测得强的蓝色三光子上转换和近红外双光子上转换荧光. 宽的红外透过窗口、高的折射率和强的蓝色上转换荧光表明,Tm3+/Yb3+共掺铋碲酸盐玻璃有希望成为高效的上转换发光和激光材料.     

Yb3+/Ho3+/Tm3+共掺碲酸盐玻璃的上转换白光发射及其机理研究

采用高温熔融法分别制备了Yb3+/Ho3+,Yb3+/Tm3+和Yb3+/Ho3+/Tm3+共掺的碲酸盐玻璃。在980nm红外激光激发下,Yb3+/Ho3+/Tm3+共掺的玻璃样品显示了强的蓝光、绿光和红光发射,分别对应于Tm3+的1 G4→3 H6跃迁、Ho3+的5 F4(5 S2)→5I 8跃迁以及Ho3+的5 F5→5I 8和Tm3+的1 G4→3 F4跃迁。通过对比发现,Yb3+/Ho3+/Tm3+共掺样品中的红、绿光积分发射强度比值(3.95)明显大于Yb3+/Ho3+共掺样品(1.69),这是由于Ho3+和Tm3+间存在交叉弛豫过程3 H4(Tm3+)+5I 6(Ho3+)→3 F4(Tm3+)+5 F5(Ho3+)和3 F4(Tm3+)+5I 8(Ho3+)→3 H6(Tm3+)+5I 7(Ho3+)所致。在激发功率密度为8.2 W.cm-2时,Yb3+/Ho3+/Tm3+共掺样品的上转换发光色坐标值为x=0.345,y=0.338,非常接近于等能白光(x=0.333,y=0.333)。     

Tm3+/Yb3+共掺碲铅锌镧玻璃的能量传递和上转换发光

制备了Tm3+/Yb3+共掺TeO2-PbO-ZnO-La2O3玻璃,研究了玻璃红外吸收光谱和980 nm激光抽运下上转换发光光谱,分析了上转换发光机制.基于Tm3+和Yb3+的能级图及上转换机制建立了速率方程,得出了稀土离子各能级的粒子数分布密度以及Tm3+与Yb3+之间的能量转移系数Cbi(i=0,1,3).结果表明,随着PbO加入,Yb3+:2F5/2与Tm3+:3H4间的能量转移不断增加,上转换蓝光的发光强度明显增强.     

Tm3+/Ho3+掺杂碲酸盐玻璃的上转换发光性能与能量转换机制

采用高温熔融法制备了单掺Tm3+和Tm3+/Ho3+共掺碲酸盐玻璃,测试了808 nm激光泵浦下玻璃的红外和上转换荧光光谱。Tm3+/Ho3+共掺碲酸盐玻璃上转换荧光光谱主要由695 nm红光、544 nm绿光、474 nm蓝光和740 nm红光四个发光带组成。通过分析样品的光谱性能和能量转换机制,发现很少报道的740 nm红光可能是由Tm3+：1D₂ →3F_{2, 3}能级跃迁产生的。在掺杂0.5 mol％ Tm₂O₃的样品中添加0.3 mol％ Ho₂O₃,695 nm红光、740 nm红光和474 nm蓝光等上转换发光强度明显增大,大约分别是单掺0.5 mol％ Tm₂O₃样品中发光强度的3倍,2.5倍和14倍。这些情况说明存在着强烈的Ho3+→Tm3+反向能量传递。单掺Tm3+碲酸盐玻璃中1D₂能级(发射740 nm红光)上的粒子集居主要来源于合作上转换(CU)过程,而3F_{2, 3}能级(发射695 nm红光)上的粒子集居除了来源于CU过程之外,还有740 nm红光的发射和1G₄能级上部分粒子的无辐射跃迁(1G₄→3F_{2, 3})两条途径,因此样品中695 nm红光强度明显要大于740 nm红光强度。通过交叉驰豫作用CR2和CR3以及反向共振能量转移RET2,Tm3+/Ho3+共掺碲酸盐玻璃中Tm3+的1G₄能级(发射474 nm蓝光)上的粒子集居数比单掺Tm3+时出现了净增加。Tm3+的1G₄能级上粒子集居数的增加可能进一步强化了该能级的无辐射跃迁、740 nm红光的发射以及CU过程,并进而促使Tm3+的3F_{2, 3}能级上的粒子集居。所以,当Tm3+/Ho3+共掺碲酸盐玻璃与单掺Tm3+碲酸盐玻璃中掺杂相同浓度的Tm3+时,前者的红光和蓝光等上转换荧光强度均比后者要大。本文还研究了Tm3+之间以及Tm3+与 Ho3+之间的交叉弛豫和能量传递等效应,并进一步探讨了Tm3+与 Ho3+之间的能量转换机制。     

Yb3+敏化的Er3+/Ho3+共掺碲酸盐玻璃的上转换发光研究

用高温熔融法制备了系列Er3+/Yb3+共掺,Ho3+/Yb3+共掺,和Er3+/Yb3+/Ho3+三掺碲酸盐玻璃,在975 nm激光抽运下三种掺杂玻璃中都出现了较强的绿光和红光上转换.研究了Yb3+离子对Er3+和Ho3+离子上转换发光强度的影响以及Yb3+→Er3+,Yb3+→Ho3+能量传递效率.分析了碲酸盐玻璃中Yb3+直接敏化Er3+,Ho3+上转换发光机理.当Er3+和Ho3+浓度较低时,Er3+/Yb3+/Ho3+三掺玻璃的上转换强度随着Yb3+离子浓度的增加而增强,出现的548 nm绿光和660 nm红光主要是由于Er3+:4S3/2→4I15/2,Ho3+:5F4(5S2)→5I8和Er3+:4F9/2→4I15/2,Ho3+:5F5→5I8跃迁共同作用的结果.Er3+/Yb3+/Ho3+三掺碲酸盐玻璃的上转换机理受Er3+/Yb3+之间,Ho3+/Yb3+之间,Er3+/Ho3+之间三者共同相互作用影响,Er3+/Ho3+离子间存在的交叉弛豫过程可增加Ho3+离子在可见光范围的上转换强度.     

Fine structure and isotope shift of the 3s4d 3 D-3s3p 3 P, 3s5d 3 D-3s3p 3 P and 3p 2 3 P-3s3p 3 P Transitions of MgI

Summary We report the measurements of the³ D(3s4d)-³ P(3s3p)³ D(3s5d)-³ P(3s3p), and³ P(3p ²)-³ P(3s3p) transition frequency of MgI, the fine-structure separation and isotope shift between²⁴Mg and²⁶Mg. The measurements have been performed in a metastable atomic beam; a good agreement is found for data already existing in the literature. The accuracy of the measurements reported in this paper is mainly limited by the Doppler broadening of theI ₂ transitions used as a reference and by the precision in the knowledge of the related wavelengths.     

The gas phase infrared band contours of s-triazine and s-triazine-d3: The fundamentals of C3N3H3 and C3N3D3 and some overtone and combination bands of C3N3H3

The systematic application of band contour techniques to account for most of the observed features of the ir spectra of s-triazine and s-triazine-d₃ have been made as well as a critique as to the limitations of such methods. The experimental and computer methods used to study the gas phase infrared band contours of s-triazine and s-triazine-d₃ are out-lined. Contours of the five E′ fundamentals of s-triazine have been recorded under moderate resolution and analyzed to give the Coriolis constants $\text{ζ}{}_{\mathrm{i}}{}^{\mathrm{z}}$, i = 6–10. The effects of l-resonance are very apparent for ν₈ and ν₉, in the form of holes in the Q branches of these bands. Under the highest resolution available, ν₆ and ν₁₀ also show l-resonance effects. Values of the l-doubling constants $\text{q}{}_{\mathrm{i}}{}^{\mathrm{(+)}}$ were obtained for these four fundamentals. One of the parallel A₂″ fundamentals of C₃H₃N₃ (ν₁₂) has also been studied. It lies close to ν₁₀(E′) and an A × E type of second-order Coriolis resonance may be the cause of the intensity enhancement observed in the inner wings of the ν₁₂ and ν₁₀ bands. Hot bands of the type (ν_i + nν₁₄ ? nν₁₄) have been observed in the contours of ν₈, ν₁₀, and ν₁₂. This is felt to be responsible for the large difference between our observed zeta sum (?1.30) and the theoretical sum (?1.00).The gas phase infrared band contours of the five E′ and 2A₂″ fundamentals of C₃N₃D₃ have also been recorded under moderate resolution. From P-R separations and by computer simulation of the contours, values of the Coriolis constants $\text{ζ}{}_{\mathrm{i}}{}^{\mathrm{z}}$ have been obtained for the E′ modes. The effects of l-resonance have been observed for ν₈(E′) and ν₁₀(E′) and values of the l-doubling constants $\text{q}{}_{\mathrm{i}}{}^{\mathrm{(+)}}$ have been estimated. An extensive series of hot bands of the type (ν₁₂ + nν₁₄ ? nν₁₄) has been observed in the contour of the ν₁₂ (A₂″) fundamental. The mass effect on the Coriolis constants has been discussed.Infrared band contours of the overtone 2ν₇ and seven degenerate E′ combination bands of C₃N₃H₃ have been recorded under moderate resolution. Analysis of these contours using the P-R separation method and computer simulation of the contours has given values of $\text{ζ}{}_{\mathrm{<mtext>eff</mtext>}}{}^{\mathrm{z}}$ for these bands. Fermi resonance between 2ν₇ and ν₆ has been analyzed. The importance of considering both the observed contour as well as the observed frequency when assigning higher tone bands is illustrated.     

LaGaO3:RE3+(RE3+=Eu3+,Ho3+)的光谱

本文用固态反应合成了钙钛矿型的LaGaO3和LaGaO3:RE3+(RE3+=Eu3+,Ho3+)荧光体,并观察了物相随不同的激活离子浓度的变化。测量了化合物在室温下的反射光谱,激发光谱和荧光光谱。研究了Eu3+的D0→7F2和Ho3+的5S2→5I8的荧光强度与激活离子浓度的关系,发现了浓度猝灭,并得到了最大荧光强度的浓度值。     

Infrared spectra of matrix isolated BH3NH3, BD3ND3, and BH3ND3

The infrared spectra of ammonia-borane, BH₃NH₃, and two of its deuterated isotropic species, BD₃ND₃ and BH₃ND₃, isolated in argon matrix at liquid hydrogen temperature have been measured. Well resolved bands for these three isotopic species have been observed for all the fundamentals. A complete frequency assignment based on C₃v molecular symmetry has been made. A set of force constants have been calculated from the data for the two isotopes BH₃NH₃ and BD₃ND₃ using a valence force field. The agreement between experiment and frequencies calculated from these force constants for the mixed isotopic species, BH₃ND₃, substantiates the present assignment.     

Dielectric investigations of solid solutions SrTiO3-KTaO3 and SrTiO3-KNbO3

The temperature dependences of the dielectric constant and dielectric hysteresis loops in ceramic samples of (1 ? x)SrTiO_3?x KNbO₃ and (1 ? x)SrTiO_3?x KTaO₃ (0 ≤ x ≤ 0.3) solid solutions prepared using different heat treatments have been investigated. Phase diagrams of the studied solid solutions have been constructed in the T-x coordinates. It has been shown that, after quenching of samples (spontaneous cooling at room temperature after long-term heating at the sintering temperature of the ceramic samples), the temperature of the induced phase transition increases because of the weakening of random electric fields associated with nonisovalent impurities due to their “frozen” nonequilibrium redistribution. For small concentrations x, strong dielectric relaxation is observed in the temperature range of 150–250 K. A model of relaxing centers, which is based on the local charge compensation of heterovalent impurities, has been proposed.     

Terahertz Vibrational Modes in CH3NH3PbI3 and CsPbI3 Perovskite Films

JETP Letters - Films of CH3NH3PbI3 organometallic perovskite, which is currently considered as a promising basic material for new-generation solar cells, as well as films containing CsPbI3...     

Ba3La(BO3)3基质中Tb3+的光致发光

以高温固相法合成了Ba3La(BO3)3∶Tb3 发光材料。在254nm紫外光激发下,研究了Ba3La(BO3)3∶Tb3 的激发光谱、发射光谱、发光强度与Tb3 浓度的关系。确定了Ba3La(BO3)3基质中Tb3 的自身浓度猝灭机理;探讨了助熔剂LiCO、敏化剂Ce3 、Bi3 的加入对荧光粉的发光强度的影响。     

Modulated magnetic structures of ErPb3, HoPb3, ErTl3 and HoTl3

Neutron diffraction experiments have been carried out on the magnetically ordered phases of ErPb₃, HoPb₃, ErTl₃ and HoTl₃. The magnetic moments were found to be sinusoidally modulated with a propagation vector of (0, 0.2, 0.5) for the Pb-compounds and (0.38, 0.38, 0.16) for the Tl-compounds.Work supported by the Bundesministerium für Forschung und Technologie     

O_3 fast and simple treatment-enhanced p-doped in Spiro-MeOTAD for CH_3NH_3I vapor-assisted processed CH_3NH_3PbI_3 perovskite solar cells

We demonstrate a simple and fast post-deposition treatment with high process compatibility on the hole transport material(HTM) Spiro-MeOTAD in vapor-assisted solution processed methylammonium lead triiodide(CH_3NH_3PbI_3)-based solar cells. The prepared Co-doped p-type Spiro-MeOTAD films are treated by O_3 at room temperature for 5 min,10 min, and 20 min, respectively, prior to the deposition of the metal electrodes. Compared with the traditional oxidation of Spiro-MeOTAD films overnight in dry air, our fast O_3 treatment of HTM at room temperature only needs just 10 min,and a relative 40.3% increment in the power conversion efficiency is observed with respect to the result of without-treated perovskite solar cells. This improvement of efficiency is mainly attributed to the obvious increase of the fill factor and short-circuit current density, despite a slight decrease in the open-circuit voltage. Ultraviolet photoelectron spectroscopy(UPS) and Hall effect measurement method are employed in our study to determine the changes of properties after O_3 treatment in HTM. It is found that after the HTM is exposed to O_3, its p-type doping level is enhanced. The enhancement of conductivity and Hall mobility of the film, resulting from the improvement in p-doping level of HTM, leads to better performances of perovskite solar cells. Best power conversion efficiencies(PCEs) of 13.05% and 16.39% are achieved with most properly optimized HTM via CH_3NH_3I vapor-assisted method and traditional single-step method respectively.