Paramagnetic defects in manganese-doped lead tungstate

In manganese-doped PbWO₄ crystals, low-intensity signals of triclinic clusters Mn⁴⁺-V _O and Fe³⁺-V _Pb have been revealed in addition to signals of Mn²⁺ tetragonal centers. The Mn⁴⁺-V _O cluster is formed by a Mn⁴⁺ ion in the W⁶⁺ position, which is associated with a vacancy of the nearest neighbor O^2?ion, and the Fe³⁺-V _Pb cluster consists of a Fe³⁺ ion substituting for Pb²⁺ with a local compensation of by a lead vacancy. It has been shown that, in PbWO₄: Mn, there is also a small amount of Mn⁴⁺ tetragonal centers located in the Pb²⁺ position with a nonlocal compensation of an excess charge.     

Photomagnetic effects and disaccommodation in Co-doped YIG

Y₃Fe₅O₁₂ (YIG) doped with ≦ 0.01 Co per molecule in combination with small dopes of V or (and) Mn show a decrease of the permeability in the dark (disaccommodation, DA) as well as when irradiated (photomagnetic effect, PE) with white light. All materials investigated exhibit DA and PE at 77 K, whereas in some cases effects occur at room temperature. The origin is attributed to domain wall pinning by magnetically anisotropic Co²⁺ ions that exchange electrons with Co³⁺ or other (V⁵⁺, Mn³⁺) ions. In view of the wide separation between the cobalt ions (?30 Å) the charge transport via iron ions is supposed to play an essential part.For a sample with higher cobalt dope the shape of the hysteresis loop at 77 K changes in the dark and the change can be hastened by irradiation. This phenomenon is attributed to the growth of a uniaxial anisotropy in the bulk of the material by Co²⁺, Co³⁺ ordering.From the electric resistivity of certain V and Si doped YIG materials it is concluded that V⁵⁺ ions oxidize Fe²⁺ ions according to V⁵⁺+Fe²⁺ → V⁴⁺+Fe³⁺.     

Xanes (X-ray absorption near edge structure) of V in vanadium-iron phosphate glasses

The X-ray Absorption Near-Edge Structure (XANES) of V in vanadium-iron glasses (50P₂O₅ + (50?x)FeO + xV₂O₅) have been measured. The effective charge of V ions in glasses has been determined. At low V₂O₅ concentration (x ～ 5) only V⁴⁺ with 6-fold coordination is present on the contrary a static mixed valence state (V⁴⁺, V⁵⁺) has been found at high concentrations 20?x?50. The results explain the electron hopping conductivity effects at high V₂O₅ concentration (x ～ 50) involving V⁴⁺ ? V⁵⁺ pairs and at low V₂O₅ concentration (x?10) involving V⁴⁺ ? Fe³⁺ pairs.     

Theoretical studies of the optical and EPR spectra for V in Y2O3 crystal

In this paper, we give an alternative suggestion that both the observed optical and electron paramagnetic resonance (EPR) spectra of Yttrium oxide (Y₂O₃):V³⁺ are attributed to V³⁺ ions at the S₆ site of Y₂O₃. This suggestion is different from the opinion in the previous paper that the optical and EPR spectra are attributed to V³⁺ ions at the C₂ and S₆ sites, respectively. From the suggestion, the optical band positions and spin-Hamiltonian parameters are calculated by diagonalizing the complete energy matrix for 3d² ions in trigonal symmetry. The results are in good agreement with the experimental values, suggesting that both the observed optical and EPR spectra in Y₂O₃:V³⁺ may be due to V³⁺ at S₆ site of Y₂O₃ crystal.     

Resonant cross-relaxation between Cr3+ and V3+ in Al2O3

Cross-relaxation, which occurs when a V³⁺ transition is resonant with a monitored Cr³⁺ transition, leads to a marked reduction of the spin-lattice relaxation time of Cr³⁺ in Al₂O₃. Measurements and an analysis of the temperature dependence of this effect give a value of 8.34 ± 0.49 cm^?1 for the zero-field splitting of V³⁺, an ion which is strongly coupled to the lattice.     

V centers in single crystal Al2O3

From optical and thermal bleaching experiments it is concluded that the 400 nm absorption band which appears in Al₂O₃ after γ-irradiation is a composite V band. One of its components is attributed to the V^-_OH center which also is responsible for a localized vibrational band at 3316 cm^-11 analogous to the one observed for the V_OH center in MgO. The irradiation also results in electron trapping at Cr³⁺ impurity ions to produce a band at 227 nm. Annealing at 170°C destroys the V^-_OH center by releasing holes which convert the Cr²⁺ to Cr³⁺ with an attendant thermoluminescence.     

V替代Mn对La_(0.45)Ca_(0.55)MnO_3电荷有序相及自旋玻璃态的影响

用固相反应法制备了La0.45Ca0.55Mn1-xVxO3(x=0.00,0.10)多晶样品.通过X射线衍射谱、质量磁化强度-温度曲线、电子自旋共振谱,研究了V5+替代Mn3+/Mn4+对La0.45Ca0.55MnO3电荷有序相和自旋玻璃态的影响.实验结果表明,当x=0.10时,不仅母体的电荷有序相基本破坏,而且母体在40K左右出现的自旋玻璃态也被融化.电荷有序相被破坏的主要原因是用V5+替代Mn3+/Mn4+后,增加了Mn3+与Mn4+的比例,使铁磁双交换作用优于反铁磁超交换作用;自旋玻璃态的融化是由于V替代Mn后破坏了反铁磁背景下有少量铁磁成分的自旋玻璃态的形成条件.     

V3+∶YAG晶体的生长、色心与光谱性能研究

采用石墨电阻加热的温梯法生长了V∶YAG晶体，晶体的不同部位呈现两种不同的颜色：浅绿色和黄褐色.通过对比分析不同颜色V∶YAG晶体的室温吸收光谱，推断出石墨发热体高温下扩散出来的C可以起到还原作用，提高晶体中V³⁺_tetra离子的浓度，同时诱导了F心的形成.在1300℃下，对不同颜色的V∶YAG晶体进行真空退火处理，发现处于八面体格位中的V³⁺离子在热激发作用下与近邻的四面体格位Al³⁺离子存在置换反应，由此产生一定浓度的四面体格位V³⁺离子.同时，F心在退火过程中被完全消除，释放出来的自由电子被高价态的V离子俘获，可以进一步提高晶体中四面体格位V³⁺离子的浓度. 关键词： V∶YAG晶体 四面体格位 碳还原 真空退火 F心     

Synthesis and Luminescent Properties of M<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu (M=Sr,Ba) Nanophosphors

A solution combustion route for the synthesis of Eu³⁺-activated M₂V₂O₇ (M = Sr, Ba) and their luminescent properties have been investigated. Structure and luminescent characteristics of Sr₂V₂O₇:Eu³⁺ and Ba₂V₂O₇:Eu³⁺ nanophosphors have been studied by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, fluorescence spectrometry and Fourier transform infra-red spectroscopy. The incorporation of Eu³⁺ activator in these nanoparticles has been checked by luminescence characteristics. These nanoparticles have displayed red color under a UV source which is due to characteristics transition of Eu³⁺ from ⁵D₀ → ⁷F₂ at 613 nm in both Sr₂V₂O₇:Eu³⁺ and Ba₂V₂O₇:Eu³⁺ nanophosphors. In addition, the optimal Eu³⁺ - doped contents of Sr_2(1-x)Eu_2xV₂O₇ and Ba_2(1-x)Eu_2xV₂O₇ nanophosphors for both were 4 mol%.     

Quadratic crystal field tensors and spin Hamiltonian tensors of Fe3+ in Li2Ge7O15 above and below the phase transition temperature

Dopant Fe³⁺ ions in tetrahedral and octahedral positions of Ge⁴⁺ in the crystal Li₂Ge₇O₁₅ were studied using EPR. Fe³⁺ substitutes for Ge⁴⁺ with a local charge compensation. The octahedral site and the tetrahedral sites significantly differ by the value of the invariant sumS(B ₄) of theB ₄ tensor of the spin Hamiltonian of Fe³⁺. The irreducible tensor products {V ₄ ? V ₄}₄ and {V ₄?V ₄}₂ theV ₄ tensor of the crystal field calculated using the point-charge model for octahedral and tetrahedral complexes provide the predominant contribution of the crystal field to theB ₄ andB ₂ tensors of the spin Hamiltonian of Fe³⁺, respectively. A comparison of the fourth-rank tensorsB ₄ of the spin Hamiltonian and {V ₄?V ₄}₄ of the crystal field determined at 300 K with those determined at 77 K supports the conclusion that the phase transition is accompanied by combined rotation of the [GeO₄] tetrahedra with the [Ge(1)O₆] octahedron almost unaltered. The spectrum lines are narrow and the variety of point defects in the vicinity of the paramagnetic impurity ions Fe³⁺, Cr³⁺ and Cu²⁺ is not detected. These facts are inconsistent with the statistically distributed model for the Li(2) atom. In specific cases at 300 K, when the wings of the two spectrum lines of theM→M+1 and theM+2 →M+3 transitions of Fe³⁺ ions belonging to one system of translationally equivalent positions overlap an extra line appears in the center between these lines. It is suggested that this effect is due to the soft phonon mode above the phase transition temperature.     

Ferromagnetism induced by oxygen-vacancy complex in (Mn,in) codoped ZnO

Mn doped Zinc oxide (ZnO) thin films were prepared by metal organic chemical vapor deposition (MOCVD) technique. Structural characterizations by X-ray diffraction technique (XRD) and photoluminescence (PL) indicate the crystal quality of ZnO films. PL and Raman show a large fraction of oxygen vacancies (V_O²⁺) are generated by vacuum annealed the film. The enhancement of ferromagnetism in post-annealed (Mn, In) codoped ZnO could result from V_O²⁺ incorporation. The effect of V_O²⁺ on the magnetic properties of (Mn, In) codoped ZnO has been studied by first-principles calculations. It is found that only In donor cannot induce ferromagnetism (FM) in Mn-doped ZnO. Besides, the presence of V_O²⁺ makes the Mn empty 3d-t_2g minority state broadened, and a t_2g-V_O²⁺ hybrid level at the conduction band minimum forms. The presence of V_O²⁺ can lead to strong ferromagnetic coupling with the nearest neighboring Mn cation by BMP model based on defects reveal that the ferromagnetic exchange is mediated by the donor impurity state, which mainly consists of Mn 3d electrons trapped in oxygen vacancies.     

Electronic structure and term energy calculations for cubic and axial iron defects in SrTiO3

The spin-unrestricted Xα method is used to obtain the molecular orbital diagrams relevant to cubic Fe²⁺, Fe³⁺ and axial Fe⁺ ?V₀ to Fe³⁺ ?V₀ defects in SrTiO₃, where V₀ is an oxygen vacancy. The relative energies of the lower spin multiplets are determined through the transition-state model of Slater. The electronic structures and the term patterns allow to discuss the stability and the ground term of each center trapped in cubic SrTiO₃. The mechanisms of ligand-metal and intervalence charge transfers are examined and compared to the abundant experimental data provided by EPR and optical measurements. The different behaviours of ferroelectrics like BaTiO₃: Fe and LiNbO₃: Fe in regard to the mechanisms implied in the photorefractive effects are reviewed according to the theoretical electronic structures with a special emphasis to the Fe²⁺ ? Fe³⁺ charge transfer.     

Vanadium ions in zinc oxide

Trace amounts of trivalent vanadium in zinc oxide single crystals can be converted into divalent ions by heating the samples in an atmosphere of zinc vapor. The ESR spectra of V²⁺ have been investigated at low temperature and the parameters of the spin-Hamiltonian were determined by making use of a computer program. The parameter values for V³⁺ have been refined. The ions are assumed to be at substitutional Zn²⁺ sites.     

Jahn-teller effects in (3d)2 ions in Al2O3

APR experiments have been carried out on V³⁺ and Cr⁴⁺ ions in Al₂O₃ partly to remove discrepancies in earlier measurements, and partly to provide additional information necessary for the theoretical analysis which follows. We find |G_-| ～ 45± 10 cm^?1 and ～ 160±30 cm^?1 for V³⁺ and Cr⁴⁺ respectively. It is shown that all the data for both ions can only be explained satisfactorily if a moderately strong Jahn-Teller effect operates in the cubic ³T₁, ground state of the ion. Full details are given, γ is found to be 0.14 and 0.36 for V³⁺ and Cr⁴⁺ respectively and important contributions from second-order Jahn-Teller effects are also present. The results also show that it is necessary to use a multimode full-lattice model of the Jahn-Teller effect as the constraints of the cluster model are broken. The implications of the proposed model on thermal conductivity, phonon spectroscopy and optical measurements are also briefly discussed. It is also pointed out that some important errors exist in the literature concerning the interpretation of experimental data for these systems.     

Insulator-metal transition in V3O5

The results of a study of the insulator-metal phase transition in V₃O₅ occuring at T = 450 K are presented. Conductivity, thermopower, magnetic, structural and optical data are reported. On a basis of the data obtained we conclude that the high-temperature phase is a poor metal with strong electron correlations and localized magnetic moments. The metal-non-metal transition is presumably driven by the spatial ordering of V³⁺ and V⁴⁺ ions.     

Heavy vector mesons and the anomalous eμ events in e+e− annihilation

As a possible explanation of the SLAC anomalous eμ events, we computed the cross section for e⁺ + e^? → V⁺ + V^? → μ^± + e^± + neutrinos, taking into account the spin correlations of V^±. If one assumes that the vector meson has an anomalous magnetic moment (κ ≈ 1), the spin effects are considerable. The V^± production hypothesis seems to be a viable alternative to that of the heavy lepton production.     

Optical properties of vanadium-doped bismuth borate glasses before and after gamma-ray irradiation

UV–visible, infrared and Raman spectra, together with thermal properties, were measured for glasses from the system Bi₂O₃–B₂O₃–V₂O₅ before and after successive gamma irradiations. The UV–visible spectrum of the undoped glass before irradiation reveals five UV bands at 210, 275, 310, 350 nm, an intense band at 380 nm and a visible band at 420 nm due to the possible combined presence of trace iron impurities and Bi³⁺ ions. The V-doped glasses reveal six UV bands and two visible bands, probably arising from vanadium ions in three possible valencies, V³⁺, V⁴⁺ and V⁵⁺, beside that due to trace iron impurity beside Bi³⁺ ions. The spectra reveal an obvious resistance of the glasses to successive gamma irradiation. The Raman and infrared spectra show characteristic absorption bands, which indicate the sharing of Bi³⁺ ions as glass-forming (BiO₆) octahedral units together with the presence of various groups of the borate network.     

Pulse compression in diode-pumped doubly Q-switched Nd:GdVO<Subscript>4</Subscript> laser with both V<Superscript>3+</Superscript>:YAG and Co<Superscript>2+</Superscript>:LMA saturable absorber

By simultaneously using both a V³⁺:YAG and a Co²⁺:LaMgAl₁₁O₁₉ saturable absorber in the cavity, for the first time to our knowledge, a diode-pumped doubly Q-switched Nd:GdVO₄ laser has been realized. The dependence of pulse width, pulse repetition rate, pulse energy and peak power on the incident pump power are measured. Under the absorbed pump power of 8.59 W, both the pulse temporal profile of the passive double-switching with the pulse width of 25.29 ns, and the passive single-switching just using V³⁺:YAG with pulse width of 30.46 ns are obtained. The pulse duration is partly compressed in contrast to the purely passively Q-switched laser with V³⁺:YAG.     

Synthesis and electrical properties of new perovskite-like <Emphasis Type="Italic">A</Emphasis>Mn<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript> (A = Ca,Ce, and Sm) compounds

AMn₃V₄O₁₂ (A = Ca, Ce, and Sm) compounds with a perovskite structure are synthesized at high pressures and temperatures. The crystalline structure of these compounds (space group \(Im\bar 3\)Z = 2) is determined via X-ray analysis. If ions in the A sublattice are changed in the order Ca²⁺–Sm³⁺–Ce³⁺, the valence is redistributed from Ca²⁺Mn₃²⁺V₄⁴⁺O₁₂ to Sm³⁺Mn₃²⁺V₄^3.75+O₁₂, and to Ce³⁺Mn₃²⁺V₄^3.75+O₁₂. The temperature dependences of the electrical resistivity are studied.     

Energy levels of vanadium ions in CdTe

In CdTe doped with vanadium the photoluminescence due to the ³ T ₂(F) ³ A ₂(F) transition of V³⁺(d ²) is detected. Its decay time is determined as (630±20) s, a result comparable to the analogous emissions in various host lattices. Further emissions around 5000 cm^–1 and 9000 cm^–1 are caused by charge-transfer transitions or bound-exciton decay. Excitation and sensitization spectra yield information on the positions of the energy levels within the gap, which are discussed using two different models. At T=4.2 K, the distance of the V²⁺/V³⁺ donor level is 7300 cm^–1 and 5700 cm^–1 referred to the valence and the conduction band edges, respectively. The absence of V²⁺(d ³) centres is tentatively ascribed to the existence of deeply bound excitons.