Absorption and luminescence of Nd3+:Y3Al5O12

In this paper there are briefly summarized the results of our experimental measurements of the fluorescence spectra, originating in levels of the⁴ F _3/2 term and terminating on the first two terms of the⁴I multipet, and the results of the absorption spectra at room temperature (RT) and at liquid-nitrogen temperature (NT) from which Nd³⁺: Y₃Al₅O₁₂ energy-level diagram was determined. Further, using the splitting of the⁴F_3/2,⁴F_5/2 and⁴F_7/2 terms the crystal-field parameters were calculated.     

Energy transfer and upconversion of Nd doped RbY2Cl7

Single crystals of Nd³⁺:RbY₂Cl₇ were grown by the Bridgman-Stockbarger method. The host crystal contains two slightly inequivalent Y³⁺ ions, each with an approximate C_2v site symmetry. Anti-Stokes emission from the ⁴G_7/2 and ⁴D_3/2 levels was observed after laser excitation of the ⁴F_3/2 and ⁴F_9/2 multiplets. Laser excitation at 413 cm⁻¹ or 453 cm⁻¹ above the ⁴F_3/2 multiplet resulted in emission from the ²P_1/2 level. Laser site-selective upconverted emission spectra have been measured, as well as their emission transients and power dependence. Possible excited state absorption and energy-transfer upconversion (ETU) mechanisms are proposed and discussed. Due to the smaller crystal field and a somewhat different energy level structure for the Nd³⁺ ions in RbY₂Cl₇ as compared with those observed for Nd³⁺ in fluoride or oxide hosts, the ⁴G_7/2 and ⁴D_3/2 multiplets are populated under ⁴F_3/2 excitation in a three and four step ETU process, respectively, instead of in a two and three step process as observed for the lighter hosts.     

Polarized spectroscopic properties of Nd-doped KGd(WO4)2 single crystal

The polarized absorption spectra, infrared fluorescence spectra, upconversion visible fluorescence spectra, and fluorescence decay curve of orientated Nd³⁺:KGd(WO₄)₂ crystal were measured at room-temperature. Some important spectroscopic parameters were investigated in detail in the framework of the Judd-Ofelt theory and the Fuchtbauer-Ladenburg formula. The effect of the crystal structure on the spectroscopic properties of the Nd³⁺ ions was analyzed. The relation among the spectroscopic parameters and the laser performances of the Nd³⁺:KGd(WO₄)₂ crystal was discussed.     

Inhomogeneous broadening of the dynamically split Kramers spectral line and up-conversion in the pair and quartet centers in CaF2:Nd

The site-selective and time-resolved fluorescence laser spectroscopy and kinetic measurements with high spectral and nanosecond temporal resolution was applied to analyze the high-energy wing of the M and N absorption bands of the ⁴I_9/2(1)→⁴G_5/2(1) crystal-field (CF) transition in a CaF₂:Nd³⁺ (0.6 wt%) crystal at 4.2 K. It was found that at helium temperatures the dynamically split spectral line assigned as the ⁴I_9/2(1)→⁴G_5/2(1) (CF) transition of coherently coupled Nd³⁺ ions in the pair M- and quartet N-centers of CaF₂:Nd³⁺ (0.6 wt%) is inhomogeneously broadened. It consists of the pair M- and quartet N-centers with at least 0.1 A variation of the positions of the fluorescence-excitation spectral lines registered at the ⁴F_3/2(1)→⁴I_9/2(1) CF transition. Small fluorescence-lifetimes variation of the ⁴F_3/2 and ⁴D_3/2 levels from the small variation of the distances R between Nd³⁺ ions in the pair is found. At least 2.7% variation of the value of the Nd-Nd distance R in the pair M-center was determined from the lifetime variation of the ⁴F_3/2 manifold with the assumption of a dipole-dipole interaction between the ions in the pair.The energy transfer up-conversion process responsible for the UV fluorescence observed when pumping the ⁴I_9/2(1)→⁴G_5/2(1) transition has been determined.     

Measurement of the F5/2 and H(2)9/2 manifold lifetime in Nd:YLiF4

We present direct measurements of the lifetime of the ⁴F_5/2 and ²H(2)_9/2 manifold in Nd³⁺:YLiF₄, using a fluorescence pump-probe technique. The technique populates the ⁴F_5/2 and ²H(2)_9/2 manifold directly with a pump pulse. Via excited state absorption from this excited manifold, the ²F(2)_5/2 manifold of Nd³⁺ is populated with a delayed probe pulse. The population in the ⁴F_5/2 and ²H(2)_9/2 manifold is monitored as a function of time by observing the change in integrated UV fluorescence from the ²F(2)_5/2 manifold for each time delay between pump and probe pulses. The pump and probe beams come from the fundamental and second harmonic wavelengths of a femtosecond Ti:sapphire regenerative amplifier. The measured lifetime agrees well with the energy gap law, based on other nonradiative lifetime measurements from the literature for Nd³⁺:YLiF₄.     

Spectral properties of Nd<Superscript>3+</Superscript> ions in samples of transparent Y<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics

The spectral and luminescent characteristics of samples of Y₂O₃:Nd³⁺ ceramics obtained from different precursors under different preparation conditions (the concentration of an HfO₂ compacting additive, the temperature and time of synthesis) are studied at 300 and 77 K. It is shown that the spectral positions of absorption and luminescence lines of ceramics correspond to those of a Y₂O₃:Nd³⁺ single crystal. At the same time, the absorption and luminescence spectra show an inhomogeneous broadening, characteristic of disordered crystals and glass. The energies of the ⁴ I _9/2 and ⁴ F _3/2 Stark states of the Nd³⁺ ion are calculated. The calculation results nearly coincide with the data from the literature for the Y₂O₃:Nd³⁺ single crystal and transparent ceramics. Samples containing the compacting additive show additional lines, whose intensities correlate with its concentration and the method of preparation of Y₂O₃:Nd³⁺ ultradispersed powders. It is assumed that these lines are related to the fact that either Nd³⁺ ions enter the composition of the HfO₂ compacting additive or Hf⁴⁺ ions are present in the nearest environment of Nd³⁺ ions at the boundaries of granules enriched with HfO₂.     

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.     

Laser spectroscopy of Nd and Dy ions in lead borate glasses

The spectroscopic and laser properties of Nd³⁺ and Dy³⁺ ions in lead borate glass were studied. Luminescence spectra recorded in the near-infrared and visible ranges correspond to ⁴F_3/2-⁴I_J/2 (J=9, 11, 13) transitions of Nd³⁺ and ⁴F_9/2-⁶H_J/2 (J=11, 13, 15) transitions of Dy³⁺, respectively. Luminescence decay curves were analyzed as a function of activator concentration. Luminescence quenching is observed, which is due to Ln-Ln interaction increasing. Several spectroscopic parameters relevant to laser potential of Ln³⁺ ions (Ln=Nd, Dy) in lead borate glass were determined. The relatively large values of the quantum efficiency and the room-temperature emission cross-section for the ⁴F_3/2-⁴I_11/2 transition of Nd³⁺ at 1061 nm and the ⁴F_9/2-⁶H_13/2 transition of Dy³⁺ at 573 nm imply that Ln-doped lead borate glasses can be considered as promising solid-state materials for laser applications.     

Spectra, energy levels, and symmetry assignments for Stark components of Eu(4f) in gadolinium gallium garnet (Gd3Ga5O12)

Absorption and fluorescence spectra observed between 450 and 750 nm at 85 K and room temperature (300 K) are reported for Eu³⁺(4f⁶) in single-crystal Czochralski-grown garnet, Gd₃Ga₅O₁₂ (GGG). The spectra represent transitions between the ^2S+1L_J multiplets of the 4f⁶ electronic configuration of Eu³⁺ split by the crystal field of the garnet. In absorption, Eu³⁺ transitions are observed from the ground state, ⁷F₀, and the first excited multiplet, ⁷F₁, to multiplet manifolds ⁵D₀, ⁵D₁, and ⁵D₂. The Stark splitting of the ⁷F_J multiplets (J=0-6) was determined by analyzing the fluorescence transitions from ⁵D₀, ⁵D₁, and ⁵D₂ to ⁷F_J. The Eu³⁺ ions replace Gd³⁺ ions in sites of D₂ symmetry in the lattice during crystal growth. Associated with each multiplet manifold are 2J+1 non-degenerate Stark levels characterized by one of four possible irreducible representations (irreps) assigned by an algorithm based on the selection rules for electric-dipole (ED) and magnetic-dipole (MD) transitions between Stark levels in D₂ symmetry. The quasi-doublet in ⁵D₁ was characterized by an analysis of the magneto-optical spectra obtained from the transitions observed between ⁵D₁ and ⁷F₁. A parameterized Hamiltonian defined to operate within the entire 4f⁶ electronic configuration of Eu³⁺ was used to model the experimental Stark levels and their irreps. The crystal-field parameters were determined through use of a Monte-Carlo method in which nine independent crystal-field parameters, were given random starting values and optimized using standard least-squares fitting between calculated and experimental levels. The final fitting standard deviation between 57 calculated-to-experimental Stark levels is 5.9 cm⁻¹. The choice of coordinate system, in which the nine are real and the crystal-field z-axis is parallel to the [0 0 1] crystal axis and perpendicular to the xy plane, is identical to the choice we used previously in analyzing the spectra of Er³⁺ and Ho³⁺ garnets.     

Absorption of Dy3+ and Nd3+ ions in BaR 2F8 single crystals

The Dy³⁺ absorption and excitation spectra of BaY₂F₈ and BaYb₂F₈ single crystals are investigated in the ultraviolet, vacuum ultraviolet, and visible ranges at a temperature of 300 K. These crystals exhibit intense broad absorption bands due to the spin-allowed 4f-5d transitions in the range (56–78) × 10^?3 cm^?1 and less intense absorption bands that correspond to the spin-forbidden transitions in the range (50–56) × 10^?3 cm^?1. The Nd³⁺ absorption spectra of BaY₂F₈ single crystals are studied in the range (34–82) × 10^?3 cm^?1 at 300 K for different crystal orientations.     

Growth and spectral properties of Nd:GdVO4 laser crystal

In this paper, the Czochralski growth, absorption spectra, and photoluminescence spectra of Nd:GdVO₄ crystals are studied. From its absorption spectra, Nd:GdVO₄ is found to exhibit an anisotropic optical absorption effect, and its effective Judd-Ofelt parameters are calculated: Ω₂=10.281×10⁻²⁰ cm², Ω₄=5.426×10⁻²⁰ cm² and Ω₆=9.943×10⁻²⁰ cm². By these parameters, the absorption oscillator strengths, emission oscillator strengths, transition probabilities, fluorescence branch ratios, energy lifetimes, and integrated emission cross-sections are also derived. The photoluminescence spectra of Nd:GdVO₄ crystal consist of a wide emission band of host and the characteristic emission bands of Nd³⁺. Based on the excitation spectrum, both the two evident peaks locating at 345 and 371 nm are ascribed to the characteristic excitation of Nd³⁺, and an energy transfer from the host to its doping Nd³⁺ ions is indicated.     

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.     

Luminescence and excitation spectra of YAG:Nd excited by synchrotron radiation

The low-temperature 4f²5d→4f³ fast emission of Nd³⁺ from YAG:Nd³⁺ has been studied under excitation by synchrotron radiation. Additionally, 4f³→4f³ luminescence of Nd³⁺ has been observed and assigned to transitions from the ²F(2)_5/2 and ⁴F_3/2 multiplet terms. The observed experimental spectra of Nd³⁺ d-f emission and f-d excitation are well simulated by crystal-field calculations.     

Spectroscopic properties of Nd—doped phosphate glass with a high emission cross section

Neodymium doped phosphate glasses have been prepared by the semi-continuous melting technique. Their absorption and emission spectra have been recorded at room temperature. The Judd－Ofelt theory has been applied to evaluate the stimulated emission cross sections of ⁴F_3/2→⁴I_11/2 transition for Nd³⁺. The higher stimulated emission cross section, 4.0×10^-20cm², is obtained. The fluorescence decays of the ⁴F_3/2→⁴I_11/2 transition of Nd³⁺ are measured for the samples doped (0.7－10) wt% of Nd₂O₃ at room temperature. The concentration quenching of Nd-doped phosphate glass is mainly attributed to cross-relaxation and energy migration. The site-dependent properties of fluorescence spectra and the fluorescence lifetime of the Nd³⁺-doped phosphate glass (with 2.2wt%Nd₂O₃) are studied using laser-induced fluorescence line narrowing techniques, and the site-to-site variations of optical properties are observed at low temperature.     

Synthesis and near-infrared luminescence properties of LaOCl:Nd3+/Yb3+

Near-infrared emitting phosphors LaOCl:Nd³⁺/Yb³⁺ were prepared by the solid-state method, and their structures and luminescent properties were investigated by using X-ray diffraction and photoluminescence analysis, respectively. The studies shows that tetragonal LaOCl:Nd³⁺/Yb³⁺ can be synthesized by the solid-state reaction at 600 °C for 3 h. Upon 353 nm UV excitation, LaOCl:Nd³⁺/Yb³⁺ sample shows strong near-infrared emission lines in the region of 1060–1150 nm (corresponding to ⁴F_3/2 → ⁴I_J′ transition of Nd³⁺, J′ = 9/2, 11/2, 13/2, 15/2) and 980–1050 nm (corresponding to ²F_5/2 → ²F_7/2 transition of Yb³⁺). The decreasing emission intensity of Nd³⁺ with increasing doping concentration of Yb³⁺ proved the energy transfer in LaOCl:Nd³⁺/Yb³⁺. The possible near-infrared emission and energy transfer mechanism between Nd³⁺ and Yb³⁺, as well as the energy transfer efficiency of LaOCl:Nd³⁺/Yb³⁺ were discussed.     

Energy transfer in YAlG:Nd codoped with Ce

Laser excited luminescence has been used to study an energy transfer between Ce³⁺ and Nd³⁺ ions in YAlG:Nd,Ce laser crystal with varying small Ce concentrations. Radiative Ce³⁺Nd³⁺ energy transfer dominates in the studied single crystal samples but this process can also be accompanied by multistep transfer mechanisms (for example by (Ce³⁺Ce³⁺)_n Nd³⁺ transfer mechanism). The Ce³⁺Nd³⁺ radiative energy transfer improves pumping of green and yellow excitation lines in YAlG:Nd,Ce laser rods because the contribution of the additional transfer pumping of Nd³⁺ ions from Ce³⁺ ions is more than three times greater than should be expected from concentration differences between Nd and Ce. This favourable behaviour is explained from high quantum efficiency of Ce³⁺ emission and higher Ce³⁺ absorption cross sections in comparison with the Nd³⁺ ones (more than one order of magnitude difference).This work was done in cooperation with Monokrystaly Turnov, Research Institute for Single Crystals. The author is grateful to Jos. Kvapil and J. Kubelka for supplying him with samples used in this work. He would like to acknowledge many fruitful discussions with J. Kvapil and K. Blaek of Monokrystaly Turnov.     

Upconverted VUV luminescence of Nd and Er doped into LiYF4 crystals under XeF-laser excitation

The upconverted VUV (185 nm) and UV (230 and 260 nm) luminescence due to 5d-4f radiative transitions in Nd³⁺ ions doped into a LiYF₄ crystal has been obtained under excitation by 351/353 nm radiation from a XeF excimer laser. The maximum upconversion efficiency, defined as the ratio of intensity for 5d-4f luminescence to overall intensity for 5d-4f and 4f-4f luminescence from the ⁴D_3/2 Nd³⁺ level, has been estimated to be about 70% under optimal focusing conditions for XeF laser radiation. A redistribution of intensity between three main components of 5d-4f Nd³⁺ luminescence is observed under changing the excitation power density, which favors the most long-wavelength band (260 nm) at higher excitation density level. The effect is interpreted as being due to excited state absorption of radiation emitted. The upconverted VUV and UV luminescence from the high-lying ²F(2)_7/2 4f level of Er³⁺ doped into a LiYF₄ crystal has also been obtained under XeF-laser excitation the most intense line being at 280 nm from the spin-allowed transition to the ²H(2)_11/2 4f level of Er³⁺, but the efficiency of upconversion for Er³⁺ emission is low, less than 5%.     

Spectral studies of Nd3+ and Er3+ ions in POCl3:SnCl4 laser liquid

The optical absorption spectra of triply ionized neodymium and erbium ions in POCl₃SnCl₄ laser liquid have been studied for the first time in the UV-VIS and NIR regions. Spectroscopic and Judd-Ofelt intensity parameters are evaluated from the observed band positions and their intensities. Radiative lifetimes and the luminescent branching ratios for the excited fluorescent levels of Nd³⁺ and Er³⁺ ions are theoretically estimated and the possible laser transitions are indicated. From the observed splittings of certain bands in the second-derivative spectrum of the Nd³⁺ ion, the crystal field (A ₂₀,A ₄₀) parameters are evaluated assumingC _3h symmetry for the ion.     

Low-temperature high-resolution VUV spectroscopy of Ce doped LiYF4, LiLuF4 and LuF3 crystals

For LiYF₄:Ce³⁺, LiLuF₄:Ce³⁺ and LuF₃:Ce³⁺ crystals UV/visible emission and time-resolved VUV/UV excitation spectra were recorded at liquid helium temperature with spectral resolution of 0.1 nm for excitation spectra and better than 0.3 nm for emission spectra. Well resolved fine structures due to zero-phonon lines were clearly observed in both excitation and emission spectra for LiYF₄:Ce³⁺ and LiLuF₄:Ce³⁺. For LuF₃:Ce³⁺ crystal no fine structure was detected in the spectra even at the highest spectral resolution. Under the host excitation, the fine structure for high-energy emission band of Ce³⁺ (5d-²F_5/2) in LiLuF₄:Ce³⁺ becomes well pronounced because of weaker reabsorption effect, as compared to Ce³⁺ 4f-5d absorption, due to small penetration depth for exciting radiation. As a result the crystal-field splitting for ²F_7/2 and ²F_5/2 levels of Ce³⁺ in LiLuF₄ crystal was measured. First observation of zero-phonon lines at ∼81,550 and ∼82,900 cm⁻¹ as well as vibronic side bands due to interconfigurational 4f¹⁴-4f¹³5d transitions in Lu³⁺ is reported for excitation spectrum of LiLuF₄:Ce³⁺.     

Stimulated emission and radiative properties of Nd ions in barium fluorophosphate glass containing sulphate

Spectroscopic properties of Nd³⁺ in barium fluorophosphate glassy matrix containing sulphate have been analysed by fitting the experimental data with the standard Judd-Ofelt theory. Various spectroscopic parameters viz. radiative transition probabilities, radiative decay time, fluorescence branching ratios, electric dipole line strengths, stimulated emission cross sections and optical gain of the principal fluorescence transition from the ⁴F_3/2 metastable level are obtained. Results show that addition of sulphate to the fluorophosphate matrix will enhance the fluorescence spectral properties of Nd³⁺ considerably. Quantum efficiency of the ⁴F_3/2 emission is found to be higher than that of fluorophosphate glasses and stimulated emission cross section of the ⁴F_3/2→⁴I_11/2 transition is the highest among all reported values. Quantitative estimation of the non-radiative processes such as multiphonon relaxation and quenching by water content was carried out and the results show that the water content is below the critical level for optimum laser performance.