Energy transfer in Eu3+-Yb3+ and Tb3+-Yb3+ system in glasses

The behavior of the phonon-assisted energy transfer between trivalent rare-earth ions in glasses was investigated. The ions Eu³⁺ and Tb³⁺ as energy donors and Yb³⁺ as acceptor were selected. The energy gap between the levels of the donor and acceptor was estimated on the basis of the energy diagram of each ion determined from absorption and emission spectra. The probability for the transfers of (Eu, ⁵D₀-⁷F₆): (Yb, ${}^2\text{F}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{-}{}^2\text{F}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$) and (Tb, ⁵D₄-⁷F₀): (Yb, ${}^2\text{F}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{-}{}^2\text{F}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$) in silicate, borosilicate, phosphate and germanate glasses was measured in the temperature range of liquid-nitrogen temperature - 650K. The probability of transfer was the smallest in phosphate glass and B₂O₃ had the effect of increasing it. In germanate glass the dependence of the probability of the energy gap was relatively weak. These results were correlated to the difference in the phonon energy and the strength of the electron-lattice coupling in each glass.     

大尺寸无机闪烁晶体Ce^3＋：YAG的生长和光谱研究

本文研究了大尺寸、高光学质量无机闪烁晶体Ce^3 :YAG的生长,并对它的吸收光谱和荧光光谱进行了测量和分析。在克服了晶体易列裂和出现宏观缺陷的情况下,采用提拉法成功生长出直径达45mm的Ce^3 ：YAG单晶。光谱测量表明晶体具有优良的光学性能。并已经在大规模集成电路的检测上得到应用。     

State of Fe3+ ion and Fe3+ −F− interaction in calcium fluorosilicate glasses

The state of Fe³⁺ ions and Fe³⁺ ?F^? interaction in calcium fluorosilicate glasses xCaF₂·(1- x)CaO·SiO₂) (0 ≤ x ≤ 0.3) containing a small amount of iron were investigated by ESR spectroscopy. Two resonances observed near g = 2.0 and g = 4.3 were assigned to dipole-dipole interacted Fe³⁺ ions and Fe³⁺ ions in a rhombic crystal field, respectively. The fraction of Fe³⁺ ions in a rhombic crystal field decreased and that of dipole-dipole interacted Fe³⁺ ions increased with increasing Fe₂O₃ content. It was found that the quantity of dipole-dipole interacted Fe³⁺ ions depends on the negative partial charge of fluorine ions and shows a maximum at 10 mol% CaF₂ (x = 0.2). The maximum is attributed to the largest difference between absolute values of the ionic potentials of ferric and fluorine ions which is caused by the smallest negative partial charge of flourine at 10 mol% CaF₂.     

EPR of Mo5+ in amorphous MoO3 thin films

Mo⁵⁺ centres in amorphous thin films of MoO₃ have been studied as a function of optical density using EPR techniques. Measurements were made for over an order of magnitude change in optical density and down to helium temperatures. A direct correlation between the optical density and the number of Mo⁵⁺ centres is found for low optical densities but further colouration does not continue to increase the number of Mo⁵⁺ centres. A model is proposed to explain the results.     

白光LED用红色荧光粉SrMoO4: Eu3+,Gd3+的制备与表征

采用共沉淀法合成了红色荧光粉Sr1-x-yMoO4∶ Eu3+x,Gd3+y,分别对样品进行了X射线衍射(XRD)分析、扫面电镜(SEM)和荧光光谱(PL)的测定.结果表明:所合成的样品均为单一纯相四方晶系结构,添加Gd3+(为0.35mol时)使主衍射峰的位置右移了0.35°;SEM照片显示:SrMoO4∶ Eu3+和SrMoO4∶Eu3+,Gd3+颗粒尺寸分布相对均匀,为类方块状,颗粒大小约为1～3μm;Gd3+和Eu3+的共掺得到的SrMoO4∶ Eu3+,Gd3+在616 nm处主发射峰的发光强度约是SrMoO4∶Eu3+的2.09倍;当掺杂x=0.25 mol和y=0.35 mol时,在近紫外光(395 nm)激发下,SrMoO4Eu3+,Gd3+得到616 nm处红光发射极峰.     

表面活性剂辅助合成Y2O2S:Eu3+,Mg2+,Ti4+红色长余辉材料

以表面活性剂十二烷基硫酸钠为均匀分散剂,通过液相与固相相结合的方法制备了Y2O2S∶Eu3+,Mg2,Ti4+红色长余辉材料.采用X射线衍射(XRD)、扫描电镜(SEM)、激发与发射光谱、热释光谱等手段对材料进行了表征.研究结果表明,与高温固相法相比,样品的最低合成温度与最佳合成温度均降低了200～300℃,其发光特性没有改变,表面活性剂的添加影响了样品的形貌.同时,对表面活性剂引入后,Y2O2S∶Eu3+,Mg2+,Ti4+的生长机制和发光机理进行了讨论.     

柠檬酸燃烧法制备Gd3Ga5O12:Eu3+纳米晶及发光性质

以柠檬酸为燃烧剂,乙二醇为分散剂,采用燃烧法制备了Gd3Ga5O12∶Eu3+纳米晶.利用X射线衍射仪、扫描电镜和荧光光谱对样品的结构、形貌和发光性能进行了研究.XRD研究结果表明:合成的样品均为单一的Gd3Ga5O12晶相,纳米晶的一次性粒径分布在16～ 30nm.发射光谱和激发光谱的研究表明:主发射峰来自于Eu3+的5D0→7F1的跃迁;宽激发带主要来自于Eu-O电荷迁移带.讨论了柠檬酸和乙二醇用量对晶粒尺寸、品格常数、发射和激发强度的影响.结果表明:过量的柠檬酸和适量的乙二醇有利于晶体发育和发光强度的提高.     

Crystal structure of R[UO2(CH3COO)3] (R = NH 4+ , K+, or Cs+)

The single crystal structure of NH₄[UO₂(CH₃COO)₃] (I), K[UO₂(CH₃COO)₃] (II), and Cs[UO₂(CH₃COO)₃] (III) is studied by X-ray diffraction. I and II crystallize in the tetragonal crystal system. The crystal data are as follows: a = 13.6985(3) and c = 27.5678(14) ?, V = 5173.1(3) ?³, space group I4₁/a, Z = 16, and R = 0.023 for I; a = 13.8890(5) and c = 26.0839(18) ?, V = 5031.7(4) ?³, space group I4₁/a, Z = 16, and R = 0.037 for II. Crystals III are orthorhombic, a = 18.176(2), b = 13.119(2), and c = 22.088(4) ?, V = 5267(1)?³, space group Pbca, Z = 16, and R = 0.0424. In structures I–III, the uranium-containing structural units are represented by discrete mononuclear [UO₂(CH₃COO)₃]⁻ groups, which belong to the AB ₃⁰¹ (A = UO₂²⁺, B ⁰¹=CH₃COO⁻) crystal chemical group of uranyl complexes.     

SrCeO3:Sm3+红色发光粉的制备及发光性能

采用溶胶-凝胶法合成了SrCeO3∶Sm3+红色荧光粉,用XRD、SEM、FL分析表征了样品的结构、形貌及发光性能。研究了助熔剂H3BO3对其发光性能的影响。结果表明:样品为具有正交晶系结构的SrCeO3晶型,呈椭球型结构。荧光光谱测试结果表明:Sm3+掺杂的SrCeO3在紫外波段有两个吸收带,一是峰值位于320 nm左右的宽吸收带,归属于Ce4+→O2-的电荷迁移带,另一个为峰值位于408 nm的锐线吸收带,对应于Sm3+的6H5/2→4L13/2跃迁吸收;在波长408 nm的激发下,样品发红光,发射主峰位于601 nm,对应于Sm3+的4G5/2→6H7/2跃迁。样品的发光强度随着Sm3+和助熔剂H3BO3加入量的增加先增强,后减弱。当Sm3+的掺杂量为3mol%,H3BO3加入量为0.5 mol%时,发光强度最大。     

Some examples of H to g transformations as applied to Fe3+ EPR in glass

In this paper we show some examples of transforming an Fe³⁺ EPR line shape in H into a probability density in g. We find that the classical g = 4.3 line in glass, though quite pronounced in the derivative spectra in H, is less striking in g. We also find that there are substantial contributions at g = 2 and g = 1 to the total g density distribution.     

Absorption and emission of Ho3+ in germanate glasses

Absorption spectra of Ho³⁺ in germanate glasses were measured in the range 300–2500 nm and the intensity parameters were calculated by the Judd-Ofelt theory. Excitation and emission spectra were measured in the visible at a temperature range of 80–573 K. The radiative transition probabilities from the excited states [⁵F₄, ⁵S₂], ⁵F₅, ⁵I₄, ⁵I₅ and ⁵I₆, branching ratios and integrated emission cross-sections were calculated. The non-radiative relaxation rate from the (⁵F₄, ⁵S₂) levels is estimated to be about 2 × 10⁵ s^?1.     

Sr2+和F-对Ca7Si2O8Cl6:Eu2+荧光粉发光性能的影响

采用高温固相法制备了系列蓝绿色Ca7Si2O8Cl6∶Eu2+荧光粉,并对样品进行了XRD分析、发光性能和色参数的测试。结果表明,合成的样品为单相Ca7Si2O8Cl6;在紫外光激发下,样品呈现一个不对称宽峰结构;分别监测这个发射峰,得到一个较宽的激发谱。同时研究了在样品中分别加入Sr2+和F-后荧光粉的激发和发射光谱,得到了这些离子的加入量与样品发光性能的关系,并探究了发生该现象的原因。结果表明,加入Sr2+或F-后可以得到较好的蓝绿色发光材料。     

Enhanced luminescent properties of Tb3+ ions in transparent glass ceramics containing BaGdF5 nanocrystals

Tb³⁺ doped transparent oxyfluoride glass ceramics containing BaGdF₅ nanocrystals were prepared. The transmission spectra, photoluminescence spectra, decay time and X-ray excited luminescence spectra of the Tb³⁺-doped glass and glass ceramics were investigated. Energy transfer from Gd³⁺ to Tb³⁺ has been observed in the glass and glass ceramics. The emission intensity of green band (⁵D₄ → ⁷F_J) of the Tb³⁺-doped glass ceramics is enhanced compared with that of the glass under ultraviolet and X-rays, which could be attributed to that the generation of BaGdF₅ nanocrystals with low phonon energy reduces the non-radiative transitions.     

Single crystals of the fluorite nonstoichiometric phase Eu 0.9162+ Eu 0.0843+ F2.084 (conductivity, transmission, and hardness)

The nonstoichiometric phase EuF_2+x has been obtained via the partial reduction of EuF₃ by elementary Si at 900–1100°C. Eu_0.916²⁺Eu_0.084³⁺F_2.084 (EuF_2.084) single crystals have been grown from melt by the Bridgman method in a fluorinating atmosphere. These crystals belong to the CaF₂ structure type (sp. gr. Fm $ \bar 3 $ \bar 3 m) with the cubic lattice parameter a = 5.8287(2) ?, are transparent in the spectral range of 0.5–11.3 μm, and have microhardness H _μ = 3.12 ± 0.13 GPa and ionic conductivity σ = 1.4 × 10⁻⁵ S/cm at 400°C with the ion transport activation energy E _a = 1.10 ± 0.05 eV. The physicochemical characteristics of the fluorite phases in the EuF₂ − EuF₃ systems are similar to those of the phases in the SrF₂ − EuF₃ and SrF₂ − GdF₃ systems due to the similar lattice parameters of the EuF₂ and SrF₂ components. Europium difluoride supplements the list of fluorite components MF₂ (M = Ca, Sr, Ba, Cd, Pb), which are crystal matrices for nonstoichiometric (nanostructured) fluoride materials M _{1 − x} R _x F_{2 + x} (R are rare earth elements).     

Eu3+扩散钨酸铅晶体(PbWO4)光学性能研究

利用离子扩散法对下降法生长PbWO4晶体进行Eu3+扩散,通过透射光谱、荧光光谱、光产额和衰减时间的测试,研究了Eu3+扩散对PbWO4晶体的光学性能的影响.结果表明:Eu3+扩散PbWO4晶体可明显改善在350 nm波段的透过率,荧光光谱主峰为430 nm,且发光强度得到增强,在1000 ns的积分时间门宽内光产额为46 pe/MeV,衰减时间为6.5 ns.     

The investigation of the magnetic interaction between Cu2+ and V4+ ions in x(CuO·2V2O5)(1 − x)[2B2O3·K2O] glasses

EPR and magnetic susceptibility measurements have been performed on (CuO·2V₂O₅)(1?x)[2B₂O₃·K_2O] glasses with 0 ? x ? 40 mol. %.For x < 10 mol.%, both Cu²⁺ and V⁴⁺ ions are present mostly as the isolated species. The values of MO coefficients indicate a high covalent degree of the transition metal (TM)-oxygen bonds. Also, the EPR parameters suggest the presence of strong (TM)-oxygen bonds along the 0_z axis, which lead to an octahedral (Oh) symmetry component at TM ions sites.In the case of 10 ? x ? 40 mol.%, the dipole-dipole and superexchange interactions occur between transition metal ions, which determine a broad resonance line at $\text{g ? 2}$. The strong interactions between Cu²⁺ and V⁴⁺ ions give rise to the exchange coupled Cu²⁺ V⁴⁺ pairs in the studied glasses with x > 10 mol.% (y > 3.9 mol.%).     

An EXAFS study of Ag3AsS3 glass

The local structures of Ag₃AsS₃ glass at 80 and 300 K have been investigated by extended X-ray absorption fine structure analysis. By comparing the glass structure with that of Ag₃AsS₃ crystal (proustite), the possibility of ionic conduction by this glass is discussed. The local structure around an As atom in the glass is similar to that in the crystal. This fact suggest that, even in the glass structure, the As atoms from AsS₃ trigonal pyramids of shape similar to that in the crystal. The Ag---S distance (2.449 Å at 300 K) and the large root mean square displacement, σ, for the Ag---S atomic pairs in the glass, groups with a by the parameter fitting method, show that the Ag atoms are quite randomly distributed around the AsS₃ groups with a similar Ag---S distance to that in the crystal. Further, it is possible that the large thermal contribution to σ_Ag---S² for the glass may indicate the involvement of the Ag atoms in ionic conduction.     

Structure type of hexagonal tantalum bronzes with variable composition K6Ta6 + ZO15F6(F, O)y: Ta(5 ? δ)+ bronzes and Ta5+ compounds

The structure type of hexagonal compounds with the variable composition K₆Ta_{6 + z} O₁₅F₆ (F, O)_y, where Z ≤ 1 and y ≤ 3 (sp. gr. P6/m, a ∼ 13.12 Å, c ∼ 3.86 Å) has been studied. Based on the structural data for a crystal of the Ta⁵⁺-containing compound and two crystals of Ta^{(5 − δ)+}-containing bronzes formed at the cathode during electrolysis of salt melts containing Ta⁺ cations, it was established that the bronze formation is associated with the interstitial defects of intercalated Ta cations. The scheme of reduction of Ta cations at the cathode is suggested, and the formulas of the compounds are obtained with due regard for partial Ta reduction to various integral oxidation degrees. The crystals of the colorless transparent Ta⁵⁺-containing compound of the composition K₆Ta _6.27 ⁵⁺ O₁₅F_7.4, brown semitransparent partly reduced Ta⁺-containing bronze of the composition K₆Ta _6.33 ⁵⁺ Ta _0.55 ⁺ O₁₅F_8.2, and dark gray metal-like completely reduced Ta⁺-containing bronze of the composition K₆Ta ₆ ⁵⁺ Ta⁺O₁₅F₇ are studied experimentally. __________ Translated from Kristallografiya, Vol. 49, No. 1, 2004, pp. 75–91. Original Russian Text Copyright ? 2004 by Arakcheeva, Chapuis, Grinevich, Shamrai. Dedicated to the 80th Birthday of L.A. Shuvalov