Spectroscopic properties of the rubidium and cesium aluminum double molybdate crystals

Infrared, Raman, electron absorption, excitation and emission spectra were measured for RbCr_xAl_1−x(MoO₄)₂ and CsCr_xAl_1−x(MoO₄)₂ crystals (x=0-2%) at the temperatures ranging from 7 to 300 K. A very rich vibronic structure of the emission band was explained and assigned to the respective vibrational modes. One Cr³⁺ center characterized by 2.35 ms lifetimes for rubidium derivative and 1.3 ms for cesium one at 7 K for the ²E→⁴A₂ transition was identified for both crystals. The local structure of the Cr³⁺ surrounding is discussed in terms of the spectroscopic results and the crystal field parameters are derived for both materials.     

Studies on some mixed pyrido-phenol donor ligands as sensitisers for terbium (III)

Incorporation of the 2-(2-hydroxyphenyl)-pyridine system into aza-crown systems produces novel ligands for lanthanide ions and can act as sensitising antennae for terbium (III) ions.     

Optical properties and site distribution of Cr ions in alkali-disilicate glasses

The optical properties of the low-field sites of Cr³⁺-doped alkali (Li, Na, K) disilicate glasses have been investigated using the single configurational coordinate model. The assumption of a Gaussian site distribution for the Cr³⁺ ions taking as parameter the zero-phonon energy has been considered. For alkali disilicate glasses the inhomogeneous contribution to the broadening of the bands, associated to the site distribution, is lower than the homogeneous one. The electron-lattice coupling S and the mean phonon energy ?ω₀ have been obtained with results around 4 and 500 cm⁻¹, respectively, similar to those obtained by other authors in oxide glasses. The site-resolved study of the emission and excitation spectra and the luminescence decay curves have been carried out as a function of temperature. On the one hand, there is evidence of a non-radiative de-excitation process that becomes important over 140 K. On the other hand, and related to the site dependence of the radiative and non-radiative probabilities, different results involving low values for the quantum efficiencies and blue shifts of the emission bands as temperature increases have been explained. Besides, the non-exponential luminescence decay curves have been fitted to an expression proposed by the authors, which takes into account non-coupled distributions for the radiative and non-radiative de-excitation probabilities for the range of temperature covering from 13 to 300 K. From the fits, the temperature dependence of the non-radiative de-excitation probability is obtained for each disilicate glass, the results are in good agreement with the expression obtained assuming the harmonic approximation in the single configurational coordinate model.     

Fluorescence enhancement effect for the determination of curcumin with yttrium(III)—curcumin—sodium dodecyl benzene sulfonate system

It is found that the fluorescence of curcumin is greatly enhanced by yttrium(III) (Y³⁺) in the presence of sodium dodecyl benzene sulfonate. Based on this, a sensitive fluorimetric method for the determination of curcumin in aqueous solution is proposed. In the potassium hydrogen phthalate (KHP) buffer, the fluorescence intensity of curcumin is proportional to the concentration of curcumin in the range of 7.37×10⁻⁴-0.18, 0.18-2.95 μg mL⁻¹ and the detection limit is 0.1583 ng mL⁻¹. The actual samples are satisfactorily determined. In addition, the interaction mechanism is also studied.     

Optical characterization of fourfold (Td)- and sixfold (Oh)-transition-metal species in MgAl2O4:Co by time-resolved spectroscopy

This work investigates the origin of novel visible photoluminescence (PL) bands observed in the spinel MgAl₂O₄:Co²⁺. Besides the well-known fourfold-coordinated Co²⁺(T_d) PL at 670 nm [N.V. Kuleshov, V.P. Mikhailov, V.G. Scherbitsky, P.V. Prokoshin and K.V. Yumashev, J. Lumin. 55 (1993) 265.], a rich structured PL band at 686 nm was also observed that we associate with uncontrolled impurities of sixfold coordinated Cr³⁺(O_h) by time-resolved spectroscopy and lifetime measurements and their variation with temperature. We also show that the lifetime of the Co²⁺(T_d) emission at 670 nm varies from τ=6.7 μs to 780 ns on passing from T=10 to 290 K. This unexpected behaviour for T_d systems is related to the excited-state crossover (⁴T₁↔²E), making the emission band to transform from a narrow-like emission from ²E at low temperature to a broad structureless band from ⁴T₁ at room temperature.     

Eu2+, Cr3+共掺杂的MAl12O19 (M=Ca, Sr, Ba) 的发光性质及能量传递

三基色荧光粉中, 红色荧光粉性能较差, 为获得性能优良的红色荧光粉, 本文采用高温固相法合成了Eu²⁺, Cr³⁺单掺杂及共掺杂的碱土金属多铝酸盐MAl₁₂O₁₉ (M =Ca, Sr, Ba) 发光体. 实验表明, 在以上三种基质中均存在Eu²⁺→Cr³⁺的能量传递, 利用能量传递可以有效将Eu²⁺的蓝光或绿光转换为红光. 三种碱土金属多铝酸盐基质的晶体结构相似,但Eu²⁺, Cr³⁺发光受晶体场影响,导致在不同的基质中Eu²⁺, Cr³⁺间能量传递效率不同.通过光谱分析及能量传递效率计算发现, 相同掺杂浓度下,CaAl₁₂O₁₉中Eu²⁺→Cr³⁺的能量传递效率最高,SrAl₁₂O₁₉次之, BaAl₁₂O₁₉最低.红光转换率在CaAl₁₂O₁₉中最高.     

Relationship between charge transfer energies of Yb and Sm and crystal environmental factor

Relationship between charge transfer energies E_CT of Yb³⁺ and Sm³⁺ and environmental factors h_e in various crystals was investigated using a dielectric chemical bond method. Both results show that they have an exponential relation E_CT=A+B exp(−kh_e), but the exponential factors are different, which indicates that the interaction between the rare earth ions and environment is connected with the kind of rare earth ion. This result provides a method of determining charge transfer energies of Yb³⁺ and Sm³⁺ from a crystal structure.     

Luminescent properties of (Y,Gd)BO3:Bi,RE (RE=Eu, Tb) phosphor under VUV/UV excitation

Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors were prepared and their luminescent properties under vacuum ultraviolet (VUV)/UV excitation were investigated. Strong red emission for (Y,Gd)BO₃:Bi³⁺,Eu³⁺ and strong green emission for (Y,Gd)BO₃:Bi³⁺,Tb³⁺ are observed under VUV excitation from 147 to 200 nm with a much broader excitation region than that of single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃ phosphor. Strong emissions are also observed under UV excitation around 265 nm where as nearly no luminescence is observed for single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃. The luminescence enhancement of Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors is due to energy transfer from Bi³⁺ ion to Eu³⁺ or Tb³⁺ ion not only in the VUV region but also in the UV region. Besides, host sensitization competition between Bi³⁺ and Eu³⁺ or Tb³⁺ is also observed. The investigated phosphors may be preferable for devices with a VUV light 147-200 nm as an excitation source such as PDP or mercury-free fluorescent lamp.     

Pressure induced effects in forsixrite monitored by ESR

Summary

Chromium doped single crystals of Forsterite where investigated directly under the influence of uniaxial pressure in situ by ESR. The two Cr³⁺ centres M₁ and M₂ exhibit distinct response to the action of pressure on the crystal as a whole. The pressure effects are manifested in remarkable changes of the line width of the fine structure transitions. Uniaxial pressure in the MPa range induces nearly symmetrical distribution of distortions of the coordination polyhedra of the Cr³⁺ centres accompanied by reorientation effects.     

Energy transfer between Sm and Er in orthophosphate YPO4

The energy transfer between Sm³⁺ and Er³⁺ ions in yttrium orthophosphate is studied. This choice of ions is based on the possibility of quantum cutting processes and the host material is selected according to the position of the 5d bands of the Sm³⁺ ion. The Sm³⁺ and Er³⁺ doped and Sm³⁺, Er³⁺ co-doped YPO₄ have been synthesized. Spectroscopic studies were done in the ultraviolet and vacuum ultraviolet ranges. The energy transfer between Sm³⁺ and Er³⁺ is very efficient but it does not lead to Er³⁺ visible emission. Whatever the excitation wavelength, the emission of co-doped samples mainly occurs in the infrared range.     

Spectroscopic investigations and configuration-interaction-assisted crystal field analysis of Pr in YPO4 single crystal

An optical study of a Y_0.99Pr_0.01PO₄ single crystal is presented. Measurements of optical absorption, excitation, and emission by selective excitation into ¹D₂, ³P₀ and ³P₁, at different temperatures between 20 and 295 K, are described. A detailed account of the line assignments is given for absorption in the 4300-23 000 cm⁻¹ spectral range, and for emission in the 6400-23 000 cm⁻¹ range. The lifetimes of the emitting levels are determined. Vibronic sidebands accompanying absorption, emission and excitation spectra are reported. The decay processes of the ³P₁, ³P₀ and ¹D₂ levels are discussed. The aim of this study is a test of the configuration-interaction-assisted crystal field analysis as well as the accurate experimental determination of the energy level scheme. It was reported previously that the introduction of configuration interaction between the ground 4f² configuration with the excited 4f6p configuration always resulted in a decrease (≈50-60%) in the standard deviations between the observed and calculated energy levels. In the present work the 4f5d configuration is included as well. The crystal field is analysed in the theoretical D_2d site symmetry with and without configuration interaction. The results with 4f², 4f²+4f5d, 4f²+4f6p and 4f²+4f5d+4f6p are given. The calculation on the basis of the 315 (4f²+4f5d+4f6p) levels gives the best overall standard deviation lowering it by 75% with regard to the calculation on the 91 4f² levels only.     

Cr4+在八面体格位中的光谱特性研究

采用提拉法生长了Cr单掺和Cr，Mg共掺Al₂O₃晶体，后者具有900—1600nm的宽带吸收.研究了该吸收带在不同气氛、不同温度退火下的变化规律.通过建立合理的晶格缺陷模型，成功地解释了所有的实验结果，并确定Cr，Mg共掺Al₂O₃晶体红外波段宽吸收带属于八面体格位中的Cr⁴⁺离子. 关键词： 4+离子')" href="#">Cr⁴⁺离子 八面体格位 晶格缺陷     

Mn, Cr-co-doped MgAl2O4 phosphors for white LEDs

The Mn-, Cr-doped and Mn, Cr-co-doped MgAl₂O₄ powders have been synthesized via a gel-solid reaction method. Energy transfer from Mn²⁺ to Cr³⁺ has been observed for the first time in the co-doped MgAl₂O₄ phosphors. When excited with blue light with a wavelength of 450 nm at room temperature, both green emission from Mn²⁺ around 520 nm and red emission from Cr³⁺ around 675and 693 nm were generated. Moreover, the color of the emission can be modified by controlling the doping concentrations of Mn²⁺ and Cr³⁺. Therefore, MgAl₂O₄: Mn²⁺, Cr³⁺ could be used as a single-phased phosphor for white LED with a blue LED chip. The energy transfer in terms of Mn²⁺ to Cr³⁺ is determined by means of radiation and reabsorption.     

High energy and high stability Cr:YAG passively Q-switched laser with convex-ARR unstable resonator

A convex-ARR (Anti-resonant Ring) unstable resonator was introduced in a Cr⁴⁺:YAG passively Q-switched Nd:YAG pulsed laser. There are two novel features in this cavity, one is the unstable resonator increasing output energy and improving laser mode; the other is the ARR structure efficiently enhancing the laser stability. A high energy and high stability Q-switched pulse with a single pulse energy of 85.6 mJ, a pulse width of 38 ns and an energy stability of 99.6% was obtained. The experimental results were analyzed well by using the mechanism of transient grating and the properties of the unstable resonator.     

Tetragonal distortions of the octahedral environments of Cr3+, Fe3+ and Gd3+ ions in A2CdF4 (A = Rb,Cs) and ACdF3 crystals

Abstract

The tetragonal distortions of local octahedral environments of Cr³⁺, Fe³⁺ and Gd³⁺ ions in Rb₂CdF₄, Cs₂CdF₄, RbCdF₃ and CsCdF₃ crystals have been studied by analyzing their EPR spectra. From the studies, it is found that the tetragonal distortions for Cr³⁺ and Fe³⁺ impurity ions, which substitute Cd²⁺ and have nearly the same ionic radius, are close to each other, whereas that for Gd³⁺ impurity ion, having a larger ionic radius, is larger than those for Cr³⁺ and Fe³⁺ ions in the same crystal. It appears that not only the impurity-ligand distance, but also the tetragonal distortions of impurity centres in crystals are closely related to the size of impurity.     

Preparation and characterization of TiO2 photocatalysts co-doped with iron (III) and lanthanum for the degradation of organic pollutants

Titanium dioxide photocatalysts co-doped with iron (III) and lanthanum were prepared by a facile sol-gel method. The structure of catalysts was characterized by X-ray diffraction (XRD), Raman spectroscopy, UV-vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were evaluated by the degradation of methylene blue in aqueous solutions under visible light (λ > 420 nm) and UV light irradiation. Doping with Fe³⁺ results in a lower anatase to rutile (A-R) phase transformation temperature for TiO₂ particles, while doping with La³⁺ inhibits the A-R phase transformation, and co-doping samples indicate that Fe³⁺ partly counteracts the effect of La³⁺ on the A-R transformation property of TiO₂. Fe-TiO₂ has a long tail extending up the absorption edges to 600 nm, whereas La-TiO₂ results in a red shift of the absorption. However, Fe and La have synergistic effect in the absorption of TiO₂. Compared with Fe³⁺ and La³⁺ singly doped TiO₂, the co-doped simple exhibits excellent visible light and UV light activity and the synergistic effect of Fe³⁺ and La³⁺ is responsible for improving the photocatalytic activity.     

Photographic sensitivity of silver halide emulsions (on the light-intensity factor determining the mechanism of chemical sensitization)

Some evidence which indicates that the role of chemical sensitization is different for exposures to low and to high intensities have been demonstrated with a model emulsion. This paper presents a review of several published reports and offers some new information. The author concludes that the sensitivity specks on the surface of the grains are responsible for sensitivity at high intensities, whereas the silver-ion gelatin complexes and a small group of silver-atoms surrounded by gelatin attached to the grain surface are responsible for sensitivity at low intensities.     

Fluorometric determination of proteins using the yttrium(III)-sodium lauryl sulfate-rutin-protein system

It is found that rutin can react with yttrium(III) (Y³⁺), and emits fluorescence of rutin. The intensity is greatly enhanced by proteins in the presence of sodium lauryl sulfate (SLS). Based on this, a new fluorimetric method of determination of proteins is developed. Under optimum conditions, the enhanced intensity of fluorescence is in proportion to the concentration of proteins in the range of 5.0×10⁻⁹-1.0×10⁻⁵ g/mL for bovine serum albumin (BSA), 3.0×10⁻⁸-1.0×10⁻⁵ g/mL for human serum albumin (HSA) and 1.0×10⁻⁷-2.0×10⁻⁵ g/mL for egg albumin (EA). Their detection limits (S/N=3) are 1.6×10⁻⁹, 9.8×10⁻⁹ and 2.1×10⁻⁸ g/mL, respectively. The interaction mechanism is also studied.     

Red, green and blue (RGB) emission doped Y3Al5O12 (YAG) phosphors prepared by non-hydrolytic sol-gel route

An evolutionary optimization process involving combination chemistry was employed in an attempt to develop Y₃Al₅O₁₂ (YAG). The combination chemistry process utilized here consisted the doping of the YAG host with appropriate amounts of red (R), green (G), and blue (B) dopants in a single layer, for use in tricolor white light. The doped YAG was acieved by means of the non-hydrolytic sol-gel route. Four samples were prepared, three of which were mono-doped samples containing 1.0% of a certain lanthanide (Eu³⁺, Tb³⁺, or Tm³⁺) ion, while the fourth contained the three ions. The samples were characterized by X-ray diffractometry and photoluminescence. The diffraction pattern of the mono-doped samples synthered at 800 °C for 16 h displayed peaks corresponding to the Y₃Al₅O₁₂ (YAG) phase, while the sample doped with the three ions revealed the presence of a mixture of Y₃Al₅O₁₂ (YAG) and Y₄Al₂O₉ (YAM) phases. The emission spectra of the three mono-doped YAG samples displayed the typical bands of the blue, green, and red emission of the corresponding lanthanide ions. As for the sample doped with the three lanthanide ions; it simultaneously emitted R, G and B lights. The green emission (546 nm) was more intense and narrow in relation to the red and blue emissions, which may be due to differences in the size of the three incorporated ions.