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.     

Endor for characterizing transition metal centres in LiNbO3

Abstract

ENDOR investigations show that in nearly stoichiometric LiNbO₃ Mn²⁺ substitutes for Li with a Li vacancy in the first Li shell for most centres. In heavily Mg codoped LiNbO₃ the Cr³⁺ dopant, characterized by a new isotropic ESR signal, is shown to substitute for Nb. Information on local disorder is obtained.     

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.     

Spectroscopic analysis of the interaction between chromium (III) and apoovotransferrin

Ovotransferrin (OTf) is a main member of the transferrin family that functions both as an iron transporter and an antibacterial agent. In this study, the thermodynamic property of the interaction between chromium (III) and ovotransferrin was investigated. The conditional binding constants for Cr³⁺ binding to the protein were determined by difference UV spectroscopy and were found to be log K_C=13.08±0.24 and log K_N=5.65±0.12. It was found that Cr³⁺ preferentially binds to the C-terminal site over the N-terminal site under these experimental conditions. The conformational changes in apoovotransferrin (apoOTf) during Cr³⁺ binding were studied by fluorescence spectroscopy using 2-p-toluidinylnaphthalene-6-sulfonate (TNS) as the fluorescence probe and by circular dichroism (CD) spectroscopy. The results show that a large conformational change in apoOTf can be attributed to binding of Cr³⁺ to the N-terminal site, instead of the C-terminal site. In addition, the binding of Cr³⁺ to apoOTf stabilizes the structure of OTf as determined by guanidine hydrochloride denaturation studies. These findings help advance our understanding of the biological effects of Cr³⁺.     

Cr<Superscript>3+</Superscript> spectroscopy study in ZnO-codoped and Zn-in-diffused congruent LiNbO<Subscript>3</Subscript>:Cr crystals

This paper reports on the spectroscopy properties, absorption and luminescence, of Cr³⁺ ions in singly doped, ZnO-codoped, and Zn in-diffused LiNbO₃:Cr crystals. In addition to the broad absorption, inter-ionic transitions ascribed to Cr³⁺ ions located in Li⁺ and Nb⁵⁺ sites; [Cr]_Li and [Cr]_Nb centres two absorption bands at higher energy are reported and ascribed to the charge transfer transitions of the Cr³⁺ ions of the two defect centres. The charge transfer transitions are used as optical probe to study the role of the Zn ions in the Zn in-diffused LiNbO₃:Cr samples. It has been observed that the Zn-in-diffused processes created [Cr]_Nb centres in the diffusion zone. The location of the diffused Zn²⁺ ions is considered to be in Li⁺ site, displacing the Cr³⁺ ions from the Li⁺ sites, [Cr]_Li, to the Nb⁵⁺ positions, [Cr]_Nb.     

Study of divalent and trivalent chromium in forsterite by high-frequency EPR spectroscopy

Divalent and trivalent chromium ions Cr²⁺ and Cr³⁺ replacing magnesium ions at octahedral positions in Mg₂SiO₄: Cr and Mg₂SiO₄: Cr: Li crystals are investigated by submillimeter EPR spectroscopy in the frequency range 65–230 GHz. The crystals are grown from the melt by the Czochralski method. The content of mixed-valence chromium species in forsterite is analyzed. It is demonstrated that, in crystals grown in argon (the oxygen partial pressure is \(P_{O_2 } \) = 0.01 kPa), approximately half of the chromium ions are in the divalent form. The Cr²⁺ ions are distributed over the M1 and M2 positions in a ratio of approximately 2: 1. A change in the oxygen partial pressure \(P_{O_2 } \) and the chromium concentration, as well as an additional doping with lithium, does not lead to substantial changes in the distribution of divalent chromium ions over the positions. It is shown that an increase in the oxygen partial pressure \(P_{O_2 } \) from 0.01 to 2.00 kPa results in a decrease in the coefficient of divalent chromium distribution between the crystal and the melt. Doping with lithium also decreases the concentration of Cr²⁺ centers. In crystals grown without lithium, approximately half of the trivalent chromium ions are associated with magnesium vacancies. The addition of lithium leads to the destruction of these associates, an increase in the concentration of individual Cr³⁺ centers, and the formation of lithium associates with trivalent chromium ions. The conditions for the formation of associates of trivalent chromium ions with lithium ions are optimum when the crystal contains approximately identical amounts of Cr³⁺ and Li⁺ ions. Doping with lithium increases the concentration of Cr³⁺ ions and, thus, decreases the fraction of Cr²⁺ and Cr⁴⁺ ions in the total content of chromium centers.     

Ion beam mixing induced by electronic energy deposition in Fe-Si multilayers

Abstract

Spectroscopic properties of Ce³⁺ ions in GdAlO₃ crystal are presented. At least three Ce³⁺ nonequivalent centres (multisites) are present in this crystal. Energy transfer from the Ce³⁺ main in the UV emitting centres to the Ce³⁺ green emitting centres is observed. Ce³⁺ fluorescence decays are either fast (1.5–20 ns) or slower due to complicated processes of energy transfer and migration (Ce³⁺)_i → (Gd³⁺)_n-steps → (Ce³⁺)_j (energy transfer through Gd³⁺ sublattice).     

New aspects of the luminescence of magnesiumtitanate part I: Activation with chromium

Mg₂TiO₄:Cr³⁺ annealed at 560°C shows luminescence properties which differ considerably from those of the unannealed phosphor used so far. In both cases the regular Cr³⁺ ions only absorb the irradiated energy transferring it radiationless to the real luminescence centres, but the annealed phosphor reveals a new spectrum consisting of a few sharp lines. The radiance of the single lines can be influenced by powdering, which in connection with the annealing effect shows that the centres of both types of phosphors consist of clusters of lattice defects and octahedrally coordinated Cr³⁺ ions. These clusters or associates form themselves by thermal diffusion during the annealing process. Furthermore criteria have been found showing that the R lines do not come from only one but from two Cr³⁺ ions situated in non-equivalent lattice sites.     

PrS0→Cr energy transfer and ESR investigation in Pr and Cr activated SrAl12O19 quantum cutting phosphor

With the help of the Dexter's theory, the energy transfer mechanism from Pr³⁺¹S₀ to Cr³⁺ is investigated theoretically in SrAl₁₂O₁₉:Pr³⁺, Cr³⁺ quantum cutting phosphors. The electron spin resonance (ESR) spectra of Pr³⁺ and Cr³⁺-doped SrAl₁₂O₁₉ with magnetoplumbite structure have been studied. The Cr³⁺ ion is found to enter the Al4(4f) site, which is very close to the Sr(2d) site replaced by the Pr³⁺ ions in the host. The theoretical results indicate that the efficient Pr³⁺¹S₀→Cr³⁺ energy transfer can only take place in the intermediate mirror planes, in which for the nearest and next-nearest Pr³⁺-Cr³⁺ pairs, both dipole-dipole and dipole-quadrupole interactions can play their parts in the transfer. Finally, an overview is given about the research on the energy transfer from Pr³⁺¹S₀ to codopants in their co-doped materials.     

Electron paramagnetic resonance of Cr<Superscript>3+</Superscript>-Li<Superscript>+</Superscript> centers in (Cr,Li): Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> synthetic forsterite

Synthetic single crystals of chromium-and lithium-doped forsterite, namely, (Cr,Li): Mg₂SiO₄, are studied using electron paramagnetic resonance spectroscopy. It is revealed that, apart from the known centers Cr³⁺(M1) and Cr³⁺(M2) (with local symmetries C_i and C_s, respectively), these crystals involve two new types of centers with C₁ symmetry, namely, Cr³⁺(M1)′ and Cr³⁺(M2)′ centers. The standard parameters D and E in a zero magnetic field [zero-field splitting (ZFS) parameters expressed in GHz] and principal components of the g tensor are determined as follows: D=31.35, E=8.28, and g=(1.9797, 1.9801, 1.9759) for Cr³⁺(M1)′ centers and D=15.171, E=2.283, and g=(1.9747, 1.9769, 1.9710) for Cr³⁺(M2)′ centers. It is found that the lowsymmetric effect of misalignment of the principal axes of the ZFS and g tensors most clearly manifests itself (i.e., its magnitude reaches 19°) in the case of Cr³⁺(M2)′ centers. The structural models Cr³⁺(M1)-Li⁺(M2) and Cr³⁺(M2)-Li⁺(M1) are proposed for the Cr³⁺(M1)′ and Cr³⁺(M2)′ centers, respectively. The concentrations of both centers are determined. It is demonstrated that, upon the formation of Cr³⁺-Li⁺ ion pairs, the M1 position for chromium appears to be two times more preferable than the M2 position. Reasoning from the results obtained, the R₁ line (the ²E → ⁴A₂ transition) observed in the luminescence spectra of (Cr,Li): Mg₂SiO₄ crystals in the vicinity of 699.6 nm is assigned to the Cr³⁺(M1)′ center.     

In situ measurement of pressure and strain effects in corundum ceramics

Abstract

An Equipement has been built for the generation of uniaxial pressure and of bending stress respectivety directly in the cavity of an X-band ESR spectrometer. Changes of the structure of paramagnetic centres (Fe³⁺ on Al³⁺ sites) could be detected in materials with a high content of corundum under the innuence of pressure and bending stress. The objects of investigation are not only suitable model system but also have practical relevance. The Fe³⁺-ions, incorporated in the materials react very sensitive on mechanically or thermally induced changes of the state of the matrix. They give insight into the materials at a microscopic level The interpretation of the observed intensity and shift effects is possible on the basis of an adequate spin-hamiltonian.     

The optical properties and laser characteristics of Cr and Nd co-doped Y3Al5O12 ceramics

We have fabricated Cr³⁺ and Nd³⁺ co-doped YAG (Cr;Nd:YAG) ceramics, and investigated their optical properties and laser characteristics. The Cr;Nd:YAG has two broad absorption bands at around 440 nm (⁴A₂→⁴T₁) and 600 nm (⁴A₂→⁴T₂) respectively, caused by Cr³⁺ ions. In the case of pumping at 440 nm, the maximum effective lifetime of the Cr;Nd:YAG was 737 μs with a 0.1 at% Cr³⁺ and 1.0 at% Nd³⁺ co-doped YAG sample. Cr³⁺ ions take a role of an effective sensitizer to convert the UV light of flashlamp. For single-shot laser operation, a 10.4 J output energy at 1064 nm was obtained with 0.1 at% Cr³⁺ and 1.0 at% Nd³⁺ co-doped YAG ceramic rod with a laser efficiency of 4.9%. The laser efficiency was found to be more than twice that of a 1.0 at % Nd³⁺:YAG ceramic rod.     

Combustion synthesized MgAl2O4:Cr phosphors—An EPR and optical study

Magnesium aluminate (MgAl₂O₄) doped with trivalent chromium (Cr³⁺) was synthesized by the combustion method. The prepared sample was characterized by X-ray powder diffraction, Brunauer-Emmet-Teller (BET) adsorption isotherms and diffuse-reflectance UV-vis spectroscopy techniques. Electron paramagnetic resonance (EPR) and photoluminescence (PL) studies have been performed at room temperature and at 110 K. The EPR spectrum exhibit resonance signals at g=5.37, 4.53, 3.82, 2.26 and 1.96 characteristic of Cr³⁺ ions. The luminescence of Cr³⁺-activated MgAl₂O₄ exhibits a red emission peak around 686 nm from the synthesized phosphor particles upon 551 nm excitation. The luminescence is assigned to a transition from the upper ²E_g→⁴A_2g ground state of Cr³⁺ ions. By correlating EPR and optical data the crystal field splitting parameter (D_q), Racah inter-electronic repulsion parameter (B) and the bonding parameters have been evaluated and discussed. The bonding parameters suggests that the ionic nature of Cr³⁺ ions with the ligands and the Cr³⁺ ions are in distorted octrahedral environment.     

Absorption and EPR spectra of Cr3+ ions in a LaBeAl11O19 crystal

Electron spectra of optical absorption and EPR of Cr³⁺ ions in a LaBeAl₁₁O₁₉ crystal are investigated. It is shown that the Cr³⁺ ions occupy, three different octahedral positions of Al³⁺ in the LaBeAl₁₁O₁₉ structure, namely, 12k, 2a, and 4f₂; the ratio of their intensitites is 1∶2∶30, respectively. Parameters of the Cr³⁺ centers are determined and its is shown that the optical absorption spectra in the visible region are practically determined by the Cr³⁺ (III) occupying the 4f₂-positions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 275–277, March–April, 1999.     

Laser and absorption saturation measurements of Cr crystals, pumped by broadband pulsed 940 nm radiation

The characteristics of a 940 nm pumped Cr⁴⁺:forsterite laser have been investigated using a pulsed colour centre laser as the excitation source. Laser threshold, slope efficiency and temporal behaviour have been determined for high and low Cr⁴⁺ doped material. 940 nm pumping is found to be more efficient than 532 and 730–770 nm excitation. Discrepancies with 1064 nm pumping are attributed to excited state absorption. Absorption saturation measurements have been used to assess the potential applications of Cr⁴⁺:forsterite, Cr⁴⁺:YAG and Cr⁴⁺: Lu₃A1₅O₁₂ (LuAG) as passive Q-switches for Nd lasers in the 940 nm region.     

Spectroscopy of multisites Cr3+ and Nd3+ in yttrium aluminium garnet

Cr³⁺ and Nd³⁺ non-equivalent crystal field sites were observed. By use of a high-resolution dye laser,²E and⁴A₂ splittings, zero-phonon⁴A₂ →²E,²T₁,⁴T₂ transitions and vibronic levels of²E doublets of Cr³⁺ non-equivalent centres were recorded. Energy transfers from Cr³⁺ multisites to Nd³⁺ were studied by site-selective spectroscopy and fluorescence decays.     

Local structure of the trigonal defect center for Cr3+ ions in KMgF3 crystals

Abstract

The zero-field splitting D, the anisotropic g-factors g _∥, Δg(=g _∥ ? g _⊥) and the first excited state splitting Δ(² E) for the trigonal Cr³⁺–V_K center in KMgF₃: Cr³⁺ crystals have been studied from Macfarlane's high-order perturbation formulas. From the studies, the local structure of the trigonal center is obtained. The local lattice distortions (i.e., the displacement directions of the ions in the center) are consistent with the expectation based on the electrostatic interaction.     

High pressure spectroscopy of chromium doped LiTaO3 crystals

Abstract

The effect of pressure on the luminescence spectrum of the weak field system Cr³⁺ : LiTaO₃ is presented. By using pressure to induce a low to high crystal field strength transition, we demonstrate the ability of pressure to identify distinct dopant bonding environments in luminescent materials.     

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.     

An NMR Analysis of Transitions in FexNbxV2-2xO4

The first order semiconductor - metall phase transition with the lattice symmetry change from monoclinic to tetragonal and the conductivity jump of several orders of magnitude is observed in pure vanadium dioxide and the dioxide doped by varios impurities [I]. Transition temperature T_t for pure VO₂ is 68°C and depends on the impurity. For example, the impurities which enter the insulating phase as pentavalent ions Nb⁵⁺ [2] give rise to a decrease in metal-semiconductor transition temperature at low concentrations and the trivalent ions Cr³⁺, Fe³⁺ [3,4] lead to an increase in T_t. In the latter case three different monoclinic phases are stabilized at a temperature below T_t. It has been already shown [5] that for double doping of vanadium dioxide by pentavalent Nb⁵⁺ and trivalent Fe³⁺ or Cr³⁺ ions three semiconductor phases exist (M_I, M₂, M₃) but the transition temperature decreases as the impurity concentration increases.