An EPR investigation of Fe and Mn in LiNbO3

EPR spectra of Fe³⁺ and Mn²⁺ in LiNbO₃ have been analyzed at 9.4 and 35.4 GHz.     

Unified calculations of the optical and electron paramagnetic resonance spectral data for Ce ion in Y3Ga5O12 crystal

Seven crystal field energy levels (obtained from the optical spectra) and three g factors g_x, g_y and g_z (obtained from electron paramagnetic resonance (EPR) spectra) for Ce³⁺ ion in Y₃Ga₅O₁₂ crystal are calculated together by diagonalizing a complete energy matrix. The Hamiltonian of this energy matrix includes all the interactions for 4f¹ ion Ce³⁺ in rhombic crystal field and under an external magnetic field, and so the optical and EPR data can be studied in a unified way. The calculated crystal field energy levels are in better agreement with the experimental values than the calculated values in the previous paper, and the g factors (which have not been calculated previously) are explained reasonably. The results are discussed.     

Temperature and pressure dependences of EPR spectra of Gd ion doped in the EuAl3(BO3)4 monocrystal

The ground state of Gd³⁺ ions substituting for trivalent europium in the EuAl₃(BO₃)₄ single crystal was studied by electron paramagnetic resonance (EPR) over the temperature range of 300-4.2 K and at pressures up to 9 kbar. The EPR spectra were analysed using the spin Hamiltonian of axial symmetry. The following parameters are reported: g=1.981±0.002, b₂⁰=280.18±0.12, b₄⁰=−12.95±0.08 and b₆⁰=0.61±0.12 (at Т=298 K). The distortions of the nearest environment of Gd³⁺ ion were analysed within the framework of the superposition model of crystal field.     

Spectroscopic studies on Pb3O4-ZnO-P2O5 glasses doped with transition metal ions

Optical absorption, Electron Paramagnetic Resonance (EPR) studies are carried out on lead zinc phosphate glass systems doped with Cr³⁺ and VO²⁺. From optical absorption investigations the crystal-field parameters Dq, B and C are evaluated. EPR measurements on Cr³⁺ systems indicate that Cr³⁺ ions are located at sites with low symmetry. EPR spectra of vanadyl doped system revealed the characteristic nature of vanadyl ion. Spin-Hamiltonian and hyperfine values are evaluated for both the systems. Optical absorption spectra of vanadyl doped system revealed three bands that are characteristic of VO(II) ion in tetragonally distorted octahedral site. By correlating both EPR and optical data, the dipolar coupling constant (P) and Fermi-constant coupling parameter (κ) and molecular orbital coefficients β^?2, e_π^?2 are evaluated. Electron Paramagnetic Resonance and optical absorption studies showed that the chemical bonds of Cr³⁺ ions and VO²⁺ ions with the ligands have more covalent nature. From these studies it is also observed that lead spinals are playing major key role in sustaining the covalent nature of bonding.     

Temperature dependence of the EPR lines in weakly doped LiNbO3:Yb—possible evidence of Yb ion pairs formation

The electron paramagnetic resonance (EPR) studies of LiNbO₃ single crystal doped with 1 wt% of Yb³⁺ are reported. To put the EPR results in perspective, a brief discussion of optical absorption spectroscopy investigations of LiNbO₃:Yb³⁺ is provided. The temperature behavior of the EPR lines intensity and linewidth for LiNbO₃:Yb³⁺ reveals antiferromagnetic coupling between Yb³⁺ ions. The deconvolution of the EPR lines indicates that EPR signals arise from both the isolated Yb³⁺ ions as well as the Yb³⁺-Yb³⁺ ion pairs; the latter signals dominate. Based on this indication, EPR spectra are interpreted using a spin Hamiltonian for the Yb³⁺ dissimilar ion pairs. The negative sign of the isotropic parameter J confirms the existence of the antiferromagnetic interactions within Yb³⁺-Yb³⁺ pairs. The value of J obtained based on the proposed pair model, assuming the dipole-dipole interactions, is used to identify the positions of the Yb³⁺-Yb³⁺ pairs in the unit cell. Our results suggest the ^evenYb³⁺-^evenYb³⁺ pairs are located at the neighboring Li⁺ and Nb⁵⁺ positions, whereas the pair axis is not parallel to the optical c-axis. Some alternative explanations of the observed EPR spectra are also considered.     

Investigation of quasi lateral-field-excitation on (yxl)-17° LiNbO3 single crystal

Quasi lateral-field-excitation (LFE) on LiNbO₃ crystal is investigated both theoretically and experimentally. It is found that when the driving electric field direction is parallel to the crystallographic X-axis of the piezoelectric substrate, (yxl)-17° LiNbO₃ LFE bulk acoustic wave devices work on quasi-LFE mode. The experimental results agreed with the theoretical prediction well. The results provide the cut of LiNbO₃ crystal for quasi-LFE bulk acoustic wave devices, which is important for designing high performance LFE sensors on LiNbO₃ substrates.     

Electron paramagnetic resonance in Y1−cH1.92:Erc

We have investigated the EPR of isotopically enriched ¹⁶⁸Er³⁺ in Y_1?cH_1.92:Er_c where c = 100 and 1400 ppm, at both 1.4 and 9 GHz and between 1.5 and 50 K. Resonance lines were observed from Er³⁺ ions in both sites of cubic symmetry and sites of axial symmetry. We determine the numbers of Er³⁺ in cubic, and C_4v axial symmetry to be in the ratio 2:1. The cubic site resonance line is at g = 6.85 ± 0.07 and is attributed to a Γ₇ doublet. The linewidth has a linear thermal broadening of 3.9 ± 0.05 gauss K^-1 below circa 7 K. From the nonlinear thermal broadening above this temperature we determine the first excited state, in the cubic crystal field scheme, to be a Γ₈ at 35 ± 10 K above the Γ₇ ground state. We have investigated the origins of the (T = 0) residual linewidth for the ions in cubic symmetry, and conclude there to be a small but significant contribution due to unresolved transferred hyperfine structure from the surrounding hydrogen nuclei.     

Electron paramagnetic resonance of Fe3+ in orthorhombic KNbO3

EPR spectra of KNbO₃:Fe single crystals are obtained in the - 10–110°C temperature range. The angular dependence of resonant lines is well reproduced by spin Hamiltonian parameters relevant to a Fe³⁺ impurity ion substituted to Nb ion in KNbO₃ crystal. The temperature behaviour of resonant lines is explained by a quadratic dependence of axial parameter D vs polarization P_s of the form D = βP²_s in the orthorhombic phase.     

Direct measurements of anticrossings of the electron-nuclear energy levels in LiYF4∶Ho3+ with submillimeter EPR spectroscopy

The electron paramagnetic resonance (EPR) spectra of impurity Ho³⁺ ions in monocrystals LiYF₄∶Ho³⁺ (0.1 and 1%) with the natural abundance of⁶Li (7.42%) and⁷Li (92.58%) isotopes, and in the sample⁷LiYF₄∶Ho³⁺ (0.1%) isotopically pure in⁷Li were taken at the temperature 4.2 K in the frequency range of 165–285 GHz. Resonance transitions between crystal field sublevels (the ground non-Kramers doublet and the nearest excited singlet) of the⁵I₈ term were detected. The refined set of crystal field parameters and the effective constant of the magnetic hyperfine interaction were determined from the detailed analysis of the recorded spectra at frequencies varied by 0.05 GHz. The fine structure of EPR lines with intervals of about 300 MHz observed in the sample LiYF₄∶Ho³⁺ (0.1%) can be interpreted as a result of the isotopic disorder in the Li sublattices. Direct information about energy gaps at the anticrossing points of the electron-nuclear sublevels of the ground doublet was obtained. These gaps are induced by the hyperfine interaction that mixes doublet and singlet states and by random crystal fields. Weak EPR signals from distorted single ion and pair centers of impurity Ho³⁺ ions were resolved. From a comparison of the measured and simulated spectra, estimates of spectral parameters of the dimer centers have been obtained.     

EPR spectra of Fe centers in layered TlGaSe2 single crystal

A single-crystal TlGaSe₂ doped by paramagnetic Fe ions has been studied at room temperature by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra were interpreted to correspond to the transitions among spin multiplet (S=5/2, L=0) of Fe³⁺ ion, which are splitted by the local ligand crystal field (CF) of orthorhombic symmetry. Four equivalent Fe³⁺ centers have been observed in the EPR spectra and the local symmetry of crystal field at the Fe³⁺ site and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of GaSe₄ tetrahedrons, and the rhombic distortion of the CF is caused by the Tl ions located in the trigonal cavities between the tetrahedral complexes.     

Absorption spectra of vanadyl ion doped in MgNH4PO4·6H2O (struvite) crystal

Results of Electron Paramagnetic Resonance (EPR) and optical absorption studies of VO²⁺ ion doped in struvite at room liquid nitrogen temperatures are reported. Three preferential V=O bond directions in the crystal have been identified. The optical and EPR data have shown the formation of NH₄(PO₄VO(H₂O)₅ complex in the crystal as a result of VO²⁺ doping. Correlating the optical and EPR data the molecular orbital coefficients are also obtained and discussed.     

Theoretical study of EPR spectra and local structure for (NiO6) cluster in LiNbO3:Ni and Al2O3:Ni systems

For a d⁸ configuration ion, the 45×45 complete energy matrix, which contains the electron-electron repulsion interaction, the ligand-field interaction, the spin-orbit coupling interaction as well as the Zeeman interaction, has been established. By diagonalizing the complete energy matrix, the local lattice structure, EPR parameters (D, g_//, g_⊥) and optical absorption spectra for Ni²⁺ ions doped in LiNbO₃ and Al₂O₃ have been investigated. The local structure distortion parameters ΔR, Δθ₁ and Δθ₂ are determined for LiNbO₃:Ni²⁺ and Al₂O₃:Ni²⁺ systems, simultaneously. These results show that local structure of (NiO₆)¹⁰⁻ cluster exhibits an elongation distortion in both LiNbO₃:Ni²⁺ and Al₂O₃:Ni²⁺ systems, in spite of the different reasons of the elongation in both systems. In addition, we have found that the orbit reduction effect is very important to understand the anisotropic g-factors for Ni²⁺ ions doped in LiNbO₃ and Al₂O₃ crystals.     

Spectroscopic analysis of Er transition in Mg/Er-codoped LiNbO3 crystal

We present a Judd-Ofelt spectroscopic analysis on the Mg/Er-codoped congruent lithium niobate (LiNbO₃) crystals. The Judd-Ofelt model is applied to the room temperature unpolarized absorption intensities of Er³⁺ ions on eleven transition bands to determine their intensity parameters: Ω₂=2.36×10⁻²⁰ cm², Ω₄=0.76×10⁻²⁰ cm², Ω₆=0.30×10⁻²⁰ cm² in Er:LiNbO₃ crystal heavily codoped with MgO. The radiative lifetime of ²H_9/2 becomes longer when MgO is added into Er:LiNbO₃ crystal. The experimental lifetimes are obtained using microsecond time-resolved spectra at 400 nm femtosecond pulse excitation to predict radiative quantum efficiency. Combining higher radiative quantum efficiency with longer radiative lifetime, we conclude that Mg/Er-codoped LiNbO₃ crystals are more suitable than Er: LiNbO₃ ones in laser materials.     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

EPR and optical absorption studies of VO doped l-alanine (C3H7NO2) single crystals

VO²⁺ doped l-alanine (C₃H₇NO₂) single crystals and powders are examined by electron paramagnetic resonance (EPR) and optical absorption spectroscopy. Three magnetically different sites are resolved from angular variations of l-alanine single crystal EPR spectra. In some specific orientations each VO²⁺ line splits into three superhyperfine lines with intensities of 1:2:1 and maximum splitting value of 2.23 mT. The local symmetries of VO²⁺ complex sites are nearly axial. The optical absorption spectra show three bands. Spin Hamiltonian parameters are measured and molecular orbital coefficients are calculated by correlating EPR and optical absorption data for the central vanadyl ion.     

Theoretical interpretation of optical and EPR spectra and the substitutional site of ferroelectric LiNbO3:Ni crystal

The optical absorption spectrum, zero-field splitting (ZFS) and EPR g factor of LiNbO₃:Ni²⁺ are explained uniformly on the basis of complete energy matrix diagonalization procedure (CDP) and Zhao's self-consistent field (SCF) d-orbit of free Ni²⁺ ions. The agreement between the calculated results and the experimental data shows quantitatively that impurities Ni²⁺ replace the Nb⁵⁺ rather than Li⁺ sites in LiNbO₃:Ni²⁺.     

The Fe3+-O2- pair in the diamagnetic AMF3 perovskites: A sensitive probe for EPR investigations of structural phase changes

In AMF₃ cubic crystals, the EPR spectrum, at X band, of the Fe³⁺-O^2- n.n. pair, is characterized by an anisotropic line, due to a strong axial crystal field. This property is used to evidence the rotation of the ligand octahedra in the tetragonal phase, below 124 K, in RbCdF₃. Moreover the pair constitutes a sensitive probe to particularise the transition.     

Antiferromagnetic resonance in ferroborate NdFe3(BO3)4

The AFMR spectra of the NdFe₃(BO₃)₄ crystal are measured in a wide range of frequencies and temperatures. It is found that by the type of its magnetic anisotropy the compound is an “easy-plane” antiferromagnet with a weak anisotropy in the basal plane. The effective magnetic parameters are determined: anisotropy fields H_a1=1.14 kOe and H_a2=60 kOe and magnetic excitation gaps Δν₁=101.9 GHz and Δν₂=23.8 GHz. It is shown that commensurate-incommensurate phase transition causes a shift in resonance field and a considerable change in absorption line width.At temperatures below 4.2 K nonlinear regimes of AFMR excitation at low microwave power levels are observed.     

The effect of In doping on optical properties of Fe:LiNBO3 crystals

Fe:LiNbO₃ and In:Fe:LiNbO₃ crystals were grown by Czochralski method. The absorption spectra were measured to investigate their defect structure. The photo damage resistance and photorefractive properties were measured. The photo damage resistance of the In:Fe:LiNbO₃ crystal in which the In concentration is above the threshold value is one order of magnitude higher than that of the Fe:LiNbO₃ crystal. The mechanisms of the violet shift of the absorption edge and the enhancement of the photorefractive effect of In:Fe:LiNbO₃ crystals were investigated.     

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.