Local structure and the electron paramagnetic resonance parameters for the Cr3+ ions at K+-vacancy site in Cr3+:KZnF3 laser crystal

The quantitative relationship between the electron paramagnetic resonance (EPR) parameters D,g_∥,g_⊥ and the local structure parameters of Cr³⁺ ion in KZnF₃ crystals is established. The local structure for Cr³⁺ paramagnetic center in KZnF₃:Cr³⁺ crystal has been determined from EPR parameters of Cr³⁺ ion. This work shows that the trigonal crystal field of Cr³⁺ ion in KZnF₃ crystals comes from following two origins: (1) the nearest-neighbor K⁺ vacancy caused by the charge compensation in the [1 1 1]-axis direction; and (2) the lattice distortions of the nearest-neighbor fluorine coordination caused by the K⁺ vacancy and the differences in mass, charge, and radius between Cr³⁺ ion and Zn²⁺ ion. The unified calculation of the EPR zero-field splitting and g factors, taking into account the K⁺ vacancy and the lattice distortions, has been carried out on the basis of the complete diagonalization procedure and the superposition crystal-field model, all calculation results are in excellent agreement with the experimental data. Although the main source of the trigonal crystal field comes from the K⁺ vacancy caused by the charge compensation, the contribution of the lattice distortion cannot be neglected.     

Magnetic properties of paramagnetically doped crystals Fe3+, Nd3+ and Ho3+ in various compounds

In this work we calculate the energy levels, wave functions and transition probabilities for a number of compounds whose crystal field parameters have been determined. We introduce a convergence criterion in the diagonalization of the Hamilton matrices dependent upon a self consistency test on the eigenvectors. This assures us of numerically accurate wave functions.First we calculated energy level and susceptibility differences in (Nd³⁺)PbMoO₄ dependent on the multiplicative constants θ_n, used with the published A_l^m to determine the crystal field parameters B_l^m, (B_l^m = θ_nA_l^M). Calculated energy levels as a function of external magnetic field strength and orientation are compared with experimental results for three different sets of published crystal field parameters, B_l^m, for (Fe³⁺)TiO₂. The ground state energy levels, and wave functions, have been calculated for the non-Kramers Ho³⁺ ion in the crystals PbMoO₄, LaCl₃ and HoCl₃. Easily distinguishable variations in the temperature dependence of the X_zz component of the susceptibility are found as a function of the host crystal. It is pointed out that susceptibility calculations, based upon measured crystal field parameters, in conjunction with subsequent susceptibility measurements, provide a good check on the validity of the crystal field parameters.     

Intensity parameters of Tm3+ and Er3+ in borate,phosphate and germanate glasses

Intensity parameters τ_λ of the Judd-Ofelt expression were obtained from oscillator strengths of the electronic transitions of Tm³⁺ and Er³⁺ in the visible and infrared part of the spectra. The parameters are interpreted by means of static and dynamic crystal field expansion. The τ_λ 's of Tm³⁺, Er³⁺ and Eu³⁺ are expressed as a function of the h (covalency parameter) parameter of the glass. It is concluded that vibrational interaction plays a dominant role in the origin of the forced electric dipole transitions of Tm³⁺ and Er³⁺ in glasses.     

Optical properties of UV-induced color centers in a KY3F10:Ce3+ crystal

The evolution of color centers induced in a KY₃F₁₀:Ce³⁺ crystal by UV radiation has been observed and interpreted. It has been revealed that, initially, the UV irradiation of the KY₃F₁₀:Ce³⁺ crystal induces the formation of color centers predominantly of the F-type, which, in a short time period of about ten minutes, are transformed into complex color centers of the F ₂-type, as well as into impurity color centers. Based on the data obtained, a diagram of energy states of the crystal, dopant, and color centers has been constructed, on which most probable processes that are caused by electronic transitions occurring in the KYF:Ce³⁺ crystal after its UV irradiation have been indicated.     

The laser-diode-excited 5d-4f luminescence of Ce3+ and Pr3+ ions embedded into a BaR2F8 matrix

We show the possibility of obtaining UV luminescence from 5d-4f transitions of rare-earth ions in the BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) crystal under upconversion excitation by standard laser diodes with lasing wavelengths of 960, 808, and 840 nm. Various upconversion mechanisms of pumping for populating the higher-lying energy levels of the active ions, as well as methods of adaptation of the active medium BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) to these mechanisms, are considered.     

Spectroscopic characteristics of Yb3+-doped Li3Ba2Y3(WO4)8 crystal

This paper reports the spectroscopic properties of Yb³⁺:Li₃Ba₂Y₃(WO₄)₈ crystal. The polarized spectral properties of Yb³⁺:Li₃Ba₂Y₃(WO₄)₈ crystal were investigated. The laser performance parameters β_min, I_sat and I_min of Yb³⁺:Li₃Ba₂Y₃(WO₄)₈ crystals have been also established. Yb³⁺:Li₃Ba₂Y₃(WO₄)₈ crystal has a broad FWHM of the gain cross-section and larger absorption and emission cross-sections. These results may regard the Yb³⁺:Li₃Ba₂Y₃(WO₄)₈ crystal as a tunable laser material.     

Nonradiative energy transfer from Mn2+ to Eu3+ in K2CaP2O7:Mn2+,Eu3+ phosphor

A series of color tunable phosphors K₂Ca_1?x?yP₂O₇:xMn²⁺, yEu³⁺ are synthesized by solid state reaction method. The energy transfer phenomenon from Mn²⁺ to Eu³⁺ has been observed in the Mn²⁺/Eu³⁺ codoped non-magnetic K₂CaP₂O₇ host, which was confirmed by PL spectra and decay curves. The Mn²⁺→Eu³⁺ energy transfer is controlled by quadrupole–quadrupole interaction between sensitizer and activator. The maximum efficiency of energy transfer is estimated to be 33% with x=0.125 and y=0.03 in K₂Ca_1?x?yP₂O₇:xMn²⁺, yEu³⁺ phosphor. The phosphors can emit light from green to yellow and eventually to orange under 400 nm excitation by changing the Mn²⁺/Eu³⁺ content ratio, indicating that K₂CaP₂O₇: Mn²⁺, Eu³⁺ would be potential candidates for use in lighting and displays applications.     

Neutron diffraction study of a single crystal of lutetium-aluminum garnet activated with chromium, Lu3Al5O12:Cr3+

For the purpose of comparative analysis, the structure of a garnet crystal activated by 1 at % of chromium, Lu₃Al₅O₁₂:Cr³⁺, (sp. gr. Ia $\bar 3$ d, a = 11.910 Å, R _w = 5.5%) and a pure garnet crystal (R _w = 4.0%) is studied by neutron diffraction. It is found according to an increase in the volume of the octahedron that the Cr³⁺ cation is located at an octahedral position upon isomorphous substitution of the smaller Al³⁺ cation. Structural imperfection increases in the chromium-activated garnet, which is manifested in numerous reflections, forbidden in the space group of garnet, and the increasing divergence of refinement R _w of the structure.     

EPR,ENDOR and optical spectroscopy of Yb3+ ion in KZnF3 single crystals

The paramagnetic center of tetragonal symmetry formed by the Yb³⁺ ion in the KZnF₃ crystal has been studied using methods of EPR, ENDOR and optical spectroscopy. The location of the impurity ion and the structural model of the complex differing from the model of the Yb³⁺ center in KMgF₃ have been established. The empirical scheme of the energy levels of the Yb³⁺ ion has been found. The parameters of its interaction with the crystal electrostatic field and the hyperfine interaction with ligands of the nearest environment have been determined. The parameters of the crystal field were used for the analysis of the distortions of the crystal lattice in the vicinity of Yb³⁺. The parameters of the transferred hyperfine interaction have been calculated for the distances between Yb³⁺ and F⁻ ions of the nearest environment obtained taking into account the found distortions. They are in good agreement with the experimental values.     

Wide-band EPR spectroscopy of YAlO3: Tm3+ single crystals

The YAlO₃: Tm³⁺ single crystal has been studied on a wide-band EPR spectrometer. The EPR spectra of Tm³⁺ ions in the frequency range of 90–160 GHz have been detected for the first time. It has been confirmed that thulium ions substitute the position of Y³⁺ in the crystal lattice. The detected spectra have been described with the use of a spin Hamiltonian with the effective spin S = 1/2. A comparative analysis of the orientation of the magnetic axes of the Tm³⁺ paramagnetic center with earlier data on other rare-earth ions has been performed.     

Luminescence kinetics of LiNbO3:Yb3+-Er3+, LiNbO3:Er3+, and LiNbO3:Yb3+ crystals under selective excitations in the impurity subsystem

The results of investigations of luminescent radiations’ kinetic characteristics for LiNbO₃:Yb³⁺-Er³⁺, LiNbO₃:Er³⁺, and LiNbO₃:Yb³⁺ crystals under optical excitations at 532 nm and 1064 nm wavelengths are presented. The shapes and times of rise and damping of luminescent signals at 550 nm, 980 nm and 1555 nm wavelengths under selective excitations in the impurity subsystem of the investigated materials are determined. Comparison of the temporal characteristics of luminescent responses of LiNbO₃ crystals doped separately with Yb³⁺ and Er³⁺ ions with those of the LiNbO₃:Yb³⁺-Er³⁺ crystal allows identifying the contributions from different energy transfer processes of optical excitation taking place in the impurity subsystem of the material.     

Luminescence and energy transfer of white-light emitting CaAl2SiO6:Ce3+, Tb3+ phosphors

A novel white-light emitting CaAl₂SiO₆: Ce³⁺, Tb³⁺ phosphor has been prepared by a sol–gel method. X-ray diffractometry and spectrofluorometry were used to characterize structural and optical properties of the samples. The results indicate that the crystal structure of the phosphor is a single phase of CaAl₂SiO₆. The excitation band of the phosphor covers a wide region from 240 nm to 380 nm. CaAl₂SiO₆: Ce³⁺, Tb³⁺ phosphors show four emission bands: one at 400 nm for Ce³⁺ and three at 487 nm, 543 nm and 585 nm for Tb³⁺. With appropriate tuning of Tb³⁺ content, white light with different hues can be achieved under UV radiation. The energy transfer mechanism from Ce³⁺ to Tb³⁺ in CaAl₂SiO₆ host was demonstrated to be dipole–dipole interaction.     

Site-selective laser spectroscopy of BaF2:Eu3+

The selective laser excitation of the flourescence of Eu³⁺ ions is used to investigate the defect sites in BaF₂:Eu³⁺ for Eu³⁺ concentrations ranging from 0.03 to 2.43 mol%. We identified the fluorescence lines arising from the (Eu³⁺, F^-_i) dipole of C_3v symmetry and established its energy level diagram. The compensating ion is an interstitial F^-_i ion located in the next-nearest-neighbour site, with respect to the Eu³⁺ ion. This (Eu³⁺, F^-_i) dipole dominates in BaF₂. Fluorescence lines assignable to next-nearest-neighbour pairs of (Eu³⁺, F^-_i) dipoles have been found above 0.1 mol% dopant concentration.     

Selective laser spectroscopy of Mn4+-Mn4+ pair centers in SrTiO3 crystal

Zero-phonon lines of a pair center of Mn⁴⁺ ions are observed in the luminescence and luminescence-excitation spectra of SrTiO₃:Mn crystal. Based on the experimental data, the energy-level structure of the ground state ∣⁴ A _2g ,⁴ A _2g 〉 and excited state ∣⁴ A _2g ,² E _g 〉 of the Mn⁴⁺-Mn⁴⁺ pair center is constructed. It is shown that the exchange interaction in the ground state of the Mn⁴⁺-Mn⁴⁺ pair is antiferromagnetic. Energies of the levels are calculated assuming that the pair is formed by Mn⁴⁺ ions occupying neighboring octahedral positions of Ti⁴⁺ ions along the [110] axis. Experimental values of the exchange integral in the ground state ∣⁴ A _2g ,⁴ A _2g 〉 and energies of spin multiplets in the excited state ∣⁴ A _2g ,² E _g 〉 agree well with calculation of the exchange interaction carried out within the framework of the channel model with the parameters J _ξη = 32 cm^4-1 and J _ζζ = ?45.5 cm^4-1. Experimental data and calculations unambiguously demonstrate that zero-phonon lines in the luminescence and luminescence-excitation spectra have magnetic-dipole nature.     

Racah and Judd-Ofelt parameters for Pr3+, Nd3+, and Er3+ ions in a laser liquid

The values of the Slater-Condon (F₂, F₄, F₆), Racah (E¹, E², E³) and Lande ξ₄f coefficients the nephelauxetic ratio (β), the bonding parameter (σ), and the Judd-Ofelt intensity (T_λ) parameters have been calculated from the reported absorption spectra of Pr³⁺, Nd³⁺, and Er³⁺ ions in an aprotic solvent SeOCl₂ acidified with antimony pentachloride. The nature of the bonding is suggested to be covalent for praseodymium, neodymium and erbium ions in the laser liquid in view of the magnitude of the respective bonding parameters.     

Investigation of gain characteristics in mixed crystals LiMeF4 (Me = Y,Lu, Yb) doped by Ce3+ ions

Differential gain spectra in the range 295–335 nm were measured in crystals of scheelite structure LiY_{1 ? x} Lu _x F₄ (x = 0–1), doped by Ce³⁺ ions. It is shown that variation of Lu³⁺ and Y³⁺ ions relative content in LiY_{1 ? x} Lu _x F₄ crystals allows to manipulate the spectral width of the amplification band. Cross-sections of excited-state absorption at the wavelengths of Ce³⁺ luminescence, probability ratios of formation and thermal destruction of color centers depending on the Y³⁺ ions content in LiY_{1 ? x} Lu _x F₄ crystals were estimated. Even better gain characteristics have been demonstrated by LiLuF₄:Ce³⁺, doped by Yb³⁺ ions. The highest optical gain coefficient with a wide amplification band among studied samples was observed in LiLuF₄:Ce³⁺ crystal, codoped by Yb³⁺ ions.     

White-light generation through Ce3+/Mn2+-codoped and Eu2+-doped Ba1.2Ca0.8SiO4 T-phase phosphors

Hexagonal Ba_1.20Ca_0.8?2x?ySiO₄:xCe³⁺,xLi⁺,yMn²⁺ phosphors exhibit two emission bands peaking near 400 and 600 nm from the allowed f–d transition of Ce³⁺ ions and the forbidden ⁴T₁–⁶A₁ transition of Mn²⁺ ions, respectively. The strong interaction between Ce³⁺/Mn²⁺ ions is investigated in terms of energy transfer, crystal field effect, and microstructure by varying their concentrations. They show a higher quenching temperature of 250 °C than that of a commercially used (Ba,Sr)₂SiO₄:Eu²⁺ phosphor (150 °C). Finally, mixtures of these phosphors with green-emissive Ba_1.20Ca_0.70SiO₄:0.10Eu²⁺ are tested and yielded correlated color temperatures from 3500 to 7000 K, and color rendering indices up to 95%.     

Narrow pulse width and high power passively Q-switched Nd3+:Gd3Ga5O12 laser with Cr4+:YAG saturable absorber

A compact, diode-pumped passively Q-switched Nd³⁺:Gd₃Ga₅O₁₂ (Nd:GGG) laser with Cr⁴⁺:YAG saturable absorber has been successfully demonstrated. Stable Q-switched pulses with pulse energy of 100 ??J and high peak power of 14 kW have been obtained. The pulse width was as short as 7 ns with low repetition rate of 10 kHz. The dependence of pulse width, pulse repetition rate, pulse energy and pulse peak power on pump power have been measured respectively. Experimental results reveal that the Nd:GGG crystal with Cr⁴⁺:YAG saturable absorber is suitable for narrow pulse width and high power passively Q-switched lasers.     

Growth, spectroscopic characteristics and laser potential of Yb3+:Ca3La2(BO3)4 crystal

Crystal of Yb³⁺-doped Ca₃La₂(BO₃)₄ has been grown by the Czochralski technique. The room temperature absorption and fluorescence spectra of the crystal have been investigated. The result showed that this crystal exhibits broad absorption and emission with the FWHM of 11 nm at 978 nm and 66 nm FWHM at 1025 nm, respectively. The stimulated emission cross-section of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg method, respectively. The room temperature fluorescence decay curves of ² F _5/2 manifold of Yb³⁺ ions were recorded for both crystal and powder samples. The effect of radiation tapping on the spectroscopic properties is discussed. The result that the lifetime of the powder sample is shorter than that of the bulk sample demonstrates the existence of radiation trapping effect. The laser potentiality was also evaluated and the results show that this crystal is a good candidate for tunable and ultrashort pulse lasers.     

Optische Absorptionsspektren und Kristallfeldaufspaltungen des Er3+-Ions in YPO4 und YVO4

The optical absorption spectra of trivalent erbium in isostructural single crystals of YPO₄ and YVO₄ have been obtained between 14000 and 29000 cm^?1. The observed crystal field splittings are interpreted in terms of crystal potentials of symmetryD _2d. From the positions of 33 Stark components the five crystal field parametersB ₀ ² , B ₀ ⁴ , B ₀ ⁶ , B ₄ ⁴ andB ₄ ⁶ have been determined. The values of the parameters for Er³⁺:YPO₄ are significantly different from those of Er³⁺:YVO₄.