Preparation and optical properties of Ce activated (Ca1 − x,Srx)Al2Si2O8 phosphors

(Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺, M⁺ (M⁺ = Li⁺, Na⁺, K⁺) phosphors have been prepared by conventional solid-state reaction method. The structural and optical properties of the phosphors were characterized by X-ray diffraction (XRD) technique and spectrophotometer, respectively. A regular variation was found among the XRD patterns of (Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺ phosphors based on the changing of Sr content. With the increase of Sr content, the maximum of emission band presented slight blue shifts (~ 15 nm). The luminescence intensity of CaAl₂Si₂O₈:0.06Ce³⁺ and SrAl₂Si₂O₈:0.06Ce³⁺ were significantly enhanced when K⁺ and Li⁺ were incorporated, respectively.     

Structural characterization for the chemically Li ion extracted LiyCoO2, LiyCo0.95Ga0.05O2, and LiyCo0.9Ga0.1O2 compounds

Chemical Li ion extraction processes have been carried out for pristine LiCoO₂, LiCo_0.95Ga_0.05O₂, and LiCo_0.9Ga_0.1O₂ compounds by swirling them in 0.35 M H₂SO₄ solution. It is confirmed from XRD patterns that the compounds maintain the two-dimensional framework with pristine-type structure even after the acid treatment up to 12 h. The Ga-substituted compounds keep Li ions for longer time on the acid treatment rather than the LiCoO₂. The average oxidation state of Co ions increases with the Li⁺ ion extraction time up to 3.45+. The local structure refinements for the chemically Li⁺ ion extracted compounds have been investigated by Co K-edge X-ray absorption spectroscopy. The extraction causes the increase of Debye-Waller (DW) factor or static disorder around the Co ion. The DW factor of the Co-Co bond pair less increases with the extraction time for the Li_yCo_0.95Ga_0.05O₂, and Li_yCo_0.9Ga_0.1O₂ compounds than that for the LiCoO₂. The Ga-substituted compounds are more stable against acid treatments than the LiCoO₂, since more basic Ga³⁺ ion retards the structural distortion of the CoO₆ octahedra against the Li ion extraction.     

On the Coexistence of Chemically Similar Stable and Metastable Phases in the BeO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> System

The joint crystallization of the stable phase (a number of solid solutions of chromium-containing beryllian indialite) and metastable phases (crystalline modifications) of the compound with β-quartz structure (Si_0.64Al_0.28Mg_0.21Be_0.09)^IVO₂ ~ Mg_1.89Be_0.81Al_2.52Si_5.76O₁₈ admixed with Cr₂O₃ phases of khmaralite Mg_1.21Cr_0.01Be_0.46Al_1.78Si_3.38O₂₀ and spinel {(Mg_0.95Be_0.045Si_0.005)^IV(Al_1.31Cr_0.67Mg_0.02)^VI}O₄ is performed using melted chromium–beryllian indialite preliminarily obtained by solid-phase synthesis as a precursor. Simultaneously, the residual X-ray amorphous melt of composition Mg_1.83Cr_0.01Be_1.04Al_2.64Si_5.57O₁₈ is hardened. Thus, a reconstructive transition from the beryllian indialite melt to a phase with the β-quartz structure is implemented, and the chemical similarity of these compounds is demonstrated. The rate of change in the crystallization isotherm of 2°С/h and increased heat outflow through the highly heat-conducting walls of the Pt–Rh crucible (taper) contribute to this process.     

Paramagnetic Ag2+/A1O4 center in α-quartz

EPR of interstitial Ag₂⁺ ions in x-irradiated α-quartz associated as charge compensators with Al³⁺ ions substituted into Si⁴⁺ oxide tetrahedra, is reported and discussed.     

Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Electronic structure and the infrared absorption and Raman spectra of the semiconductor clusters C24, B12N12, Si12C12, Zn12O12, and Ga12N12

The optimized configurations, electronic structures, charge transfers, band gaps, total energies, cohesive energies, electron density maps, infrared absorption spectra, Raman spectra, and relevant modes of natural acoustic vibrations for the semiconductor clusters C₂₄, B₁₂N₁₂, Si₁₂C₁₂, Zn₁₂O₁₂, and Ga₁₂N₁₂ are calculated using the ab initio Hartree-Fock method in the 6–31G basis set. Original Russian Text ? V.V. Pokropivny, L.I. Ovsyannikova, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 3, pp. 535–542.     

Influence of Si4+ substitution on the temperature-dependent characteristics of Y3Al5O12:Ce

A series of Y3Al5O12:Ce(YAG:Ce) phosphors doped with different Si 4+ concentrations is prepared by solid-state reaction.The temperature dependent characteristics of luminescent spectrum and decay time of Ce 3+ are investigated.With Si 4+ doped,the emission spectrum shows a blue shift due to a decrease of the splitting of 5d levels of Ce 3+ ion.The thermal stability is greatly improved by adding Si 4+ because the activation energy E increases from 0.1836 eV to 0.2401 eV.The study of the decay times against temperature for various doping concentrations of Si 4+ shows that the calculated nonradiative decay rate is affected by Si 4+ substitution.The results are explained by the configurational coordinate diagram.     

Proton Magnetic Resonance Studies of Al(III) and Ga(III) Hydration Numbers in Aqueous Solution

Schweitzer and Stephens have recently suggested that the hydration numbers of Al³⁺ and Ga³⁺ and Ga³⁺ in aqueous solutions containing a considerable excess of chloride ion are probably less than six. Hydration numbers as low as 4.64 (in 1.44 M AlCl₃+ 2.15 M CaCl₂) or 4.61 (in 0.645 M GaCl₃+ 3.32 M CaCl₂) were obtained.¹ That Ga³⁺ forms chloro-complexes under these conditions is well known though interaction between Al³⁺ and chloride is considered unlikely in aqueous solution.^2–4     

Theoretical explanation for the DNA cleavage by GO with cation: anti-cooperativity effect among the π⋯π, cation⋯π/σ and H-bonding interactions in cytosine⋯GO⋯Mn+ (Mn+ = Na+, Mg2+, Al3+)

In order to reveal the nature of DNA cleavage by inorganic intercalator GO (graphene oxide) with cation, the cooperativity effects among the π?π, cation?π/σ and H-bonding interactions were evaluated in the cytosine?GO?Mⁿ⁺ (Mⁿ⁺?=?Na⁺, Mg²⁺, Al³⁺) model systems using the M06-2X, MP2 and ω B97X-D methods with the 6-311++G(2d,p) and 6-311++G(3df,3pd) basis sets. The Mⁿ⁺?O (ether) and N–H?O interactions induce the formation of the π?π stacking between cytosine and GO, and the anti-cooperativity effect are dominant in controling of the aggregation process of cytosine, GO and Mⁿ⁺, which was confirmed by the AIM (atoms-in-molecules) and RDG (reduced density gradient) analyses. Furthermore, the solvent effects of H₂O weaken greatly the anti-cooperativity effects. Thus, a deduction on the DNA cleavage by GO?cation with the intercalation mode is put forward: due to the anti-cooperativity effect and solvent effect, the π?π stacking is weakened in the complexes with Na⁺ or broken in those with Mg²⁺ or Al³⁺. Then the GO?Mg²⁺ moiety is squeezed out from the intercalating sites, leading to an invalid cleavage of DNA, while Na⁺ or Al³⁺ is bound tightly to cytosine, with a notable DNA cleavage. This deduction was used to explain reasonably the previous experimental phenomena.     

Boron-, nitrogen-, aluminum-, and phosphorus-doped graphite electrodes for non-lithium ion batteries

Intercalation of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, and Al³⁺ ions into B-, N-, Al-, and P-doped graphite has been studied using density functional theory calculations. While the intercalation of Li⁺, K⁺, and Ca²⁺ ions into graphite is thermodynamically favorable, that of Na⁺, Mg²⁺, Zn²⁺, and Al³⁺ ions into graphite is unfavorable. When doped in the form of graphitic structure, B, Al, and P dopants significantly stabilize the ion-intercalated graphite compounds. As a result, Na⁺ ions that are unable to intercalate into graphite can intercalate into B-, Al-, and P-doped graphite. The electron transfer from B, Al, and P dopants to host C atoms reinforces the ion–graphene electrostatic interaction, enhancing the thermodynamic driving force for ion intercalation. The catalytic activity of the dopant to promote the ion intercalation increases in the order of N < B < P < Al, which is associated with the electronegativity of the dopant.     

Preparation and luminescence properties of SrTiO3:Pr,Al phosphor from the glycolate method

Spherical SrTiO₃:Pr³⁺,Al³⁺ phosphor with high crystallinity and uniform particle size distribution was formed from the glycolate precursor. The glycolate precursor was obtained by heating the mixed solution of metallic nitrates and titanium oxychloride in ethylene glycol up to 200 °C. The thermal decomposition of the glycolate precursor proceeded through three major stages, i.e., (i) evolution of glycols (∼200 °C), (ii) decomposition of glycolate precursor, and (iii) decomposition of strontium carbonate and crystallization of SrTiO₃:Pr³⁺,Al³⁺ phosphor.SrTiO₃:Pr³⁺,Al³⁺ phosphor exhibited a strong red emission, peaking at about 617 nm. SrTiO₃:Pr³⁺,Al³⁺ phosphor obtained from the glycolate complex has higher luminescent properties than the conventional solid state reaction and the Pechini method in terms of photoluminescence (PL) and cathodoluminescence (CL). High crystallinity, low residual carbon content and small grain size with uniform shape would enhance the luminescence intensity of phosphor by the glycolate method due to high surface area per unit volume and low organic content compared with the Pechini method. Also, Al³⁺ ion is more effective than Ga³⁺ ion to enhance PL intensity of SrTiO₃:Pr³⁺,Al³⁺ phosphor because of smaller Al³⁺ ion radius. Therefore, the glycolate method has been demonstrated to be a convenient and unique process for the production of muticomponent oxide with smaller grain size and higher crystallinity compared with the conventional mixed oxide reaction and the polymer precursor method.     

Electronic structural, elastic properties and thermodynamics of Mg17Al12, Mg2Si and Al2Y phases from first-principles calculations

Electronic structures, elastic properties and thermal stabilities of Mg₁₇Al₁₂, Mg₂Si and Al₂Y have been determined from first-principle calculations. The calculated heats of formation and cohesive energies show that Al₂Y has the strongest alloying ability and structural stability. The brittle behavior and structural stability mechanism is also explained through the electronic structures of these intermetallic compounds. The elastic constants are calculated, the bulk moduli, shear moduli, Young's moduli and Poisson ratio value are derived, the brittleness and plasticity of these phases are discussed. Gibbs free energy, Debye temperature and heat capacity are calculated and discussed.     

Electronic excitations in BeAl<Subscript>2</Subscript>O<Subscript>4</Subscript>, Be<Subscript>2</Subscript>SiO<Subscript>4</Subscript>, and Be<Subscript>3</Subscript>Al<Subscript>2</Subscript>Si<Subscript>6</Subscript>O<Subscript>18</Subscript> crystals

Low-temperature (T = 7 K) time-resolved selectively photoexcited luminescence spectra (2–6 eV) and luminescence excitation spectra (8–35 eV) of wide-bandgap chrysoberyl BeAl₂O₄, phenacite Be₂SiO₄, and beryl Be₃Al₂Si₆O₁₈ crystals have been studied using time-resolved VUV spectroscopy. Both the intrinsic luminescence of the crystals and the luminescence associated with structural defects were assigned. Energy transfer to impurity luminescence centers in alexandrite and emerald was investigated. Luminescence characteristics of stable crystal lattice defects were probed by 3.6-MeV accelerated helium ion beams.     

Absorption spectra of Bi3+ and Fe3+ in Y3Ga5O12

The absorption spectra of Y₃Ga₅O₁₂:(Fe³⁺), Y₃Ga₅O₁₂:(Bi³⁺) and Y₃Ga₅O₁₂:(Bi³⁺, Fe³⁺) are presented to 40,000 cm^-1. Assignments are discussed and the transitions analysed in terms of their involvement in the large Faraday rotation observed in bismuth substituted iron garnets.     

Formation of the buffer layer of silicon suboxides SiOx in the Si/SiO2 low-dimensional heterosystem after Si+ ion implantation: Si L2, 3 X-ray emission spectra

Nanosized heterostructures n-Si/SiO₂ with different thicknesses of the oxide film (20, 500 nm) after implantation by Si⁺ ions with energies of 12 and 150 keV have been investigated using Si L _{2, 3} X-ray emission spectroscopy (the Si 3d3s → Si 2p _{1/2, 3/2} electronic transition). The ion-beam modification of the interface has been revealed and studied for the heterostructure with a silicon dioxide thickness of 20 nm. An analysis of the Si L _{2, 3} X-ray emission spectra has demonstrated that the Si⁺ ion implantation leads to the self-ordering of the structure of the initially amorphous SiO₂ film 20 nm thick due to the effect of high doses. A mechanism of ion-beam modification of the insulator-semiconductor interface has been proposed. No substantial transformation of the atomic and electronic structures of the heterostructure with a silicon dioxide thickness of 500 nm has been revealed after the ion implantation.     

化合物和合金中离子投影射程分布矩的计算(Ⅱ)——轻离子(Z1≤10)的射程分布矩

本文根据离子在固体材料中电子阻止截面的实验资料,给出了低能Li⁺,Be⁺,B⁺,C⁺,N⁺,O⁺,F⁺,Ne⁺等离子在固体中电子阻止截面S_e的经验公式。这些经验公式既能够很好地反映电子阻止本领的Z₁和Z₂振荡、又能正确地给出S_e随离子能量E的变化关系。用这种以实验为基础的S_e经验公式和符合于WHB势的核散射函数,计数了从H⁺到Ne⁺十种轻离子在非晶Al₂O₃,SiO₂,20/25/Nb不锈钢,LiNbO₃和UO₂等材料中的投影射程分布的一次至三次矩。将计算值与近几年的实验测量及其他人的计算结果进行了比较,在低能端,我们计算的平均投影射程R_p与实验符合得更好。 关键词：     

1MeV Si+衬底加温注入Al0.3Ga0.7As/GaAs超晶格和GaAs的晶格损伤研究

用卢瑟福背散射／沟道技术研究了１ＭｅＶＳｉ⁺在衬底加温和室温下以不同剂量注入Ａｌ_0.3Ｇ_0.7Ａｓ／ＧａＡｓ超晶格和ＧａＡｓ后的晶格损伤。在衬底加温下，观察到Ａｌ_0.3Ｇａ_0.7Ａｓ／ＧａＡｓ超晶格和ＧａＡｓ都存在一个动态退火速率与缺陷产生速率相平衡的剂量范围，以及两种速率失去平衡的临界剂量。超晶格比ＧａＡｓ更难以损伤，并且它的两种速率失去平衡的临界剂量也大于ＧａＡｓ中的相应临界剂量，用热尖峰与碰撞模型解释了晶格损伤积累与注入剂量和衬底温度的关系。用ＣＮＤＯ／２量子化学方法计算了ＧａＡｓ和Ａｌ_xＧａ_1-xＡｓ中化学键的相对强度，并根据计算结果解释了注入过程中Ａｌ_0.3Ｇａ_0.7Ａｓ／ＧａＡｓ超晶格和ＧａＡｓ中晶格损伤程度的差别。 关键词：     

Interaction of different types of nanocages (Al12N12, Al12P12, B12N12, Be12O12, Mg12O12, Si12C12 and C24) with HCN and ClCN: DFT,TD-DFT,QTAIM, and NBO calculations

In this work, the ability of different types of nanocages including Al₁₂N₁₂, Al₁₂P₁₂, Be₁₂O₁₂, B₁₂N₁₂, Si₁₂C₁₂, Mg₁₂O₁₂ and C₂₄ for the adsorption and detection of poisonous gases HCN and ClCN has been investigated, theoretically using the D3 dispersion corrected density functional theory (DFT-D3). The absorption spectra of HCN–nanocage and ClCN–nanocage complexes were calculated by the time-dependent density functional theory (TD-DFT) and compared with the calculated absorption spectrum of isolated nanocage to investigate the ability of nanocage for sensing of HCN and ClCN gases. It was found that the strongest interaction between HCN (ClCN) molecule and nanocage takes place when the molecule is adsorbed via its N atom on the surface of nanocage except for C₂₄. Also, it was shown that the Al₁₂N₁₂ is the best adsorbent for HCN and ClCN gases among the selected nanocages and Si₁₂C₁₂ is the best sensor for the detection of these gases using the electroconductivity and absorption spectroscopy techniques.     

Synthesis and Mössbauer study of new garnets Ln3Fe5−tGatO12 (Ln = Nd,Pr)

The range of existence of the garnet phase in Nd₃Fe_5?tGa_tO₁₂ and Pr₃Fe_5?tGa_tO₁₂ solid solutions was determined to be 1.25 ? t_Nd ? 5 and 22.25 ? t_Pr ? 5, respectively Mossbauer spectroscopy was used to study the Fe³⁺ and Ga³⁺ distribution over the octahedral and tetrahedral sites of the garnet and to give an estimate of the stabilization energies of cations at different sites The Néel temperatures were determined for compositions with t ? 2.5. Some specific features of the phase transition from the magnetically ordered state to the paramagnetic one are discussed.     

Sputtering and secondary ion emission of a two-phase system composed of small oxide precipitates dispersed in a copper matrix

This paper deals with the ion emission of a two-phase system composed of a copper single crystal matrix in which small precipitates of Al₂O₃ or BeO oxide of a few hundreds Å in diameter (from 60 to 470 Å) are included. It is observed that ions originate from three regions of the sample: region I. copper matrix: Cu⁺, Cu⁺₂, Cu⁺₃,…; region II. precipitates: Al⁺, Al⁺₂, AlO⁺ Al₂O⁺, …; respectively Be⁺, Be⁺₂, BeO⁺ Be₂O⁺,…; region III, matrix-precipitate interface: Cu⁺, CuAl⁺ or CuBe⁺,…. The presence of CuAl⁺ or CuBe⁺ ions and the enhancement of Cu⁺ emission at the periphery of precipitates in region III, makes the principle of the linear superposition of mass spectra of the two phases invalid. The interpretation of the results is based upon a simple model of sputtering which involves a coupling between the sputtering of precipitates and matrix. This model shows that, under steady state conditions, the surface density of precipitates is roughly proportional to the ratio S/S_p of the sputtering yields of the matrix and precipitates. We have taken advantage of the dependence of S on the crystal orientation of the sample with respect to the bombarding direction, to change the surface density of precipitates. Any change in S is followed by a time evolution of ion intensities originating from regions H and III. The average time of evolution allows one to characterize the size of precipitates. The sputtering process of a two-phase system (formation of cones) is discussed together with the ionization process.