Diode pumped Pr<Superscript>3+</Superscript>:LiYF<Subscript>4</Subscript>-BBO ultraviolet laser at 320 nm

A diode pumped Pr³⁺:LiYF₄ laser at 639.5 nm has been demonstrated. With an incident pump power of 920 mW, the maximum red output power was 272 mW. Moreover, intracavity second-harmonic generation (SHG) has also been achieved with a maximum ultraviolet power of 23 mW by using a β-BaB₂O₄ (BBO) nonlinear crystal. To the best of our knowledge, this is the first report on continuous-wave ultraviolet generation by intracavity frequency doubling Pr³⁺:LiYF₄ laser.     

Vacuum ultraviolet gain measurements in optically pumped LiYF4:Nd3+

 We present measurements of the net-induced gain on the 5d–4f transition at 186 nm in LiYF₄ : Nd³⁺ optically pumped by radiation from a molecular fluorine laser. It is found that for LiYF₄ : Nd³⁺, one of a series of potential continuously tunable VUV lasers, relatively strong excited-state absorption results in net-induced loss. The prospects for VUV laser operation being realised in other rare-earth-doped fluorides is discussed. Received: 4 March 1996/Revised version: 10 July 1996     

Orange,red and deep-red flashlamp-pumped Pr3+:LiYF4 laser with improved output energy and efficiency

Three laser transitions (607.2 nm, 639.5 nm, 720.9 nm) in a flashlamp-pumped Pr³⁺:LiYF₄ laser at room temperature are investigated. Cerium ions (Ce³⁺) doped into the fused-quartz envelope of the flashlamp efficiently transfer strong UV radiation from pumping light into the absorption region of Pr³⁺ ions ( = 420–480 nm), so that the slope efficiency of all three laser emissions could be increased by almost 100% compared to excitation with a pure quartz flashlamp. At a pump energy of 30 J the output energy of these three laser emissions reached 4.7 mJ, 87 mJ and 30 mJ.     

Crystal growth and luminescence properties of Pr-doped LuLiF4 single crystal

0.1, 1, and 3% Pr (with respect to Lu) doped LuLiF₄ (Pr:LuLiF₄) single crystals were grown by the micro-pulling-down (μ-PD) method. Transparency of the grown crystals was higher than 70% in the visible wavelength region with some absorption bands due to Pr³⁺ 4f-4f transitions. Intense absorption bands related with the Pr³⁺ 4f-5d transitions were observed at 190 and 215 nm. In radioluminescence spectra, Pr³⁺ 5d-4f emissions were observed at 220, 240, 340, and 405 nm. In the pulse height spectra recorded under ¹³⁷Cs γ-ray excitation, the Pr 3% doped sample showed the highest light yield of 2050 photons/MeV and the scintillation decay time of it exhibited 23 and 72 ns also excited by ¹³⁷Cs γ-ray.     

Comparative analysis of energy-level splitting of Pr3＋ doped in LiYF4 and LiBiF4 crystals： a complete energy matrix calculation

Based on the combination of Racah's group-theoretical consideration with Slater's wavefunction, a 91 × 91 complete energy matrix is established in tetragonal ligand field D_2d for Pr³⁺ ion. Thus, the Stark energy-levels of Pr³⁺ ions doped separately in LiYF₄ and LiBiF₄ crystals are calculated, and our calculations imply that the complete energy matrix method can be used as an effective tool to calculate the energy-levels of the systems doped by rare earth ions. Besides, the influence of Pr³⁺ on energy-level splitting is investigated, and the similarities and the differences between the two doped crystals are demonstrated in detail by comparing their several pairs of curves and crystal field strength quantities. We see that the energy splitting patterns are similar and the crystal field interaction of LiYF₄:Pr³⁺ is stronger than that of LiBiF₄:Pr³⁺.     

Optical absorption and emission of LiYF4:Pr3+

The optical absorption, emission and excitation spectra of Pr³⁺ ions in LiYF₄ have been measured. Energy transfer is observed and an estimate of the energy transfer rate is made. The temperature dependence of the emission lifetimes for Pr³⁺ and Er³⁺ and the Judd-Ofelt theory were used to make this determination. The energy levels responsible for the various transitions have been assigned previously by Esterowitz et al. and the polarized optical absorption and emission data presented in this paper are in agreement with their excellent work.     

VUV luminescence of Er<Superscript>3+</Superscript> ions in LiYF<Subscript>4</Subscript> and BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals

Vacuum ultraviolet luminescence of Er³⁺ ions in LiYF4 and BaY₂F₈ crystals has been investigated. It is revealed that under excitation by 193 nm radiation from an ArF excimer laser the interconfigurational 5d–4f radiative transitions in Er³⁺ ions are observed. It is shown that from the LiYF₄:Er crystal only the spin-forbidden luminescence (λ = 165 nm) is detected, whereas both the spin-forbidden (λ = 169 nm) and spin-allowed (λ = 160.5 nm) components are observed from the BaY₂F₈:Er crystal.     

Optical properties of some fluoride compounds and their application to dosimetry

Effects of β, X and VUV irradiation on the optical properties have been studied in various simple and complex fluoride crystals by using optical absorption, X- and UV-excited luminescence (XL and PL), thermoluminescence (TL) and photo-transferred TL (PTTL) techniques. In most tested crystals, the main TL peaks with the same thermal activation energies appear after VUV as well as after X or β irradiation, thus indicating that the same traps are induced by the different types of radiation. The TL excitation spectra generally show absorption maxima on the long wavelengths tail of the fundamental absorption. Within this study, various dosimetric properties, as well as the possible application of the crystals as sensitive radiation detectors and dosimeters for the VUV have also been investigated. The TL sensitivities of the various studied materials have been compared to that of the classic dosimeter TLD-100 (LiF:Mg,Ti). For example, the sensitivity of SrF₂:Pr³⁺ has been found to be the highest among the examined crystals and at a dose of 90 Gy its response is higher by a factor of ～3 than that of TLD-100. The sensitivity of CsGd₂F₇:Pr³⁺ and KYF₄:Pr³⁺ are slightly higher than that of TLD-100, whereas that of nanostructured CaF₂:ZnO crystals is about twice that of TLD-100, but the sensitivity of LiF:Eu is much lower. The SrF₂:Pr³⁺ crystals also showed some important dosimetric properties.     

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%.     

Optical transitions of Pr3+ and Er3+ ions in LiYF4

The optical absorption, emission, and excitation spectra of Pr³⁺ and Er³⁺ ions in LiYF₄ have been measured and energy level schemes established which agree with previous work. The temperature dependence of the emission lifetimes were investigated and analyzed using the Huang-Rhys and Struck-Fonger treatments of multiphonon decay. The non-radiative processes in LiYF₄: Er³⁺ were shown to follow the same “gap law” behavior as Er³⁺ in LaF₃ and MnF₂. Theoretical fits to the Huang-Rhys model allowed the construction of a configuration coordinate diagram for the Er³⁺ system. The non-exponential temperature dependence of the ¹D₂ lifetime in Pr³⁺ can be understood as a non-radiative transition from higher levels.     

Crystal fields of Pr in LiYF4 under pressure

Fluorescence spectra of LiYF₄:Pr³⁺ have been measured between 12,000 and 22,000 cm⁻¹ under pressures up to 10 GPa. In total, 25 crystal field energy levels were obtained and used for the determination of free-ion and crystal field parameters under pressure. According to the nephelauxetic effect, the free-ion parameters decrease with increasing pressure. The relative decrease is larger for the Slater than for the spin-orbit coupling parameter. This behavior is consistent with former studies on Pr³⁺ in different crystals and can be explained by a special covalency model. According to an effective D_2d symmetry, five crystal field parameters B₀²(f,f), B₀⁴(f,f), B₄⁴(f,f), B₀⁶(f,f), and B₄⁶(f,f) are non-zero. The pressure-induced changes of these parameters have been determined up to the maximum pressure of 10 GPa. In order to improve the calculation of the crystal field levels, the configuration interactions with the 4f¹6p¹ configuration have been taken into account. The effect of these interactions are also analyzed under pressure and distinct improvements of the energy level calculations have been obtained.     

Cascade fluorescent decay in Pr3+-doped fluorides: Achievement of a quantum yield greater than unity for emission of visible light

Studies of the fluorescence spectrum of Pr³⁺ under excitation with the 185 nm resonance line of Hg have been made in a number of fluoride host lattices. In some of these phosphors such as YF₃ and LaF₃ the radiative decay originates in the ¹S₀ level of Pr³⁺ and proceeds via a simple cascade process in which, for some of the decay paths, two visible photons are emitted. In other hosts such as LiYF₄ the fluorescence originates in the 4f5d levels and consists of four principal bands in the ultraviolet. A third type of host exhibits a mixture of these two types of emission. In one phosphor of the first type, YF₃ activated with 0.1 mol % Pr³⁺, an overall quantum yield of 1.4 ± 0.15 for visible light has been measured at room temperature.     

Spectroscopic characteristics of Pr<Superscript>3+</Superscript> in biaxial La<Subscript>2</Subscript>(WO<Subscript>4</Subscript>)<Subscript>3</Subscript> crystal

A Pr³⁺-doped La₂(WO₄)₃ crystal grown by the Czochralski method has been investigated as a promising laser material. The principal axes of the optical indicatrix and Pr³⁺ concentration of the crystal were determined. The polarized absorption, fluorescence spectra and fluorescence decay curves of the main emission multiplets of the crystal were measured at room temperature. The spectroscopic parameters were obtained by the modified Judd–Ofelt theory combined with the normalized method. The peak stimulated emission cross-sections of the major emission lines were estimated. The good spectroscopic properties imply that the Pr³⁺:La₂(WO₄)₃ crystal is a potential laser gain medium for solid-state laser and self-stimulated Raman laser applications. PACS 78.20.-e; 42.70.Hj     

Affinement d'une raie de fluorescence de Pr3+: LaAlO3 par excitation laser

A cw dye laser has been used for fluorescence line narrowing experiments by resonant excitation on Pr³⁺ ions in LaAlO₃. Scanning the excitation radiation through the absorption line width corresponding to the transition ³H₄ (0 cm^-1) → ¹D₂ (16 694 cm^-1) while fluorescence was observed, has put into evidence a deformation of the symmetry around Pr³⁺ ions, different for every site.This experiment shows the power of cw dye laser spectroscopy for investigating optical spectra in crystals.     

Luminescence characteristics of the Pr3+ ion in SrAlF5

The paper reports on a study of luminescence and excitation spectra of SrAlF₅:Pr³⁺ (0.5 mol %) polycrystals performed at 10 and 300 K with synchrotron radiation in the range from 5 to 25 eV. The Pr³⁺ ions in SrAlF₅ were shown to emit successively two photons in transitions from the ¹ S ₀ and ³ P ₀ levels. The main energy characteristics of the compound, namely, the position of the 4f → 5d excitation band (5.95–8.0 eV), the energy separation between the ¹ S ₀, 4f and the lowest 5d levels (～0.15 eV), and the SrAlF₅ band gap width (～12 eV), were determined. SrAlF₅:Pr³⁺ was found to possess a number of features not found in other Pr³⁺-activated fluorides.     

Broadening of the lines due to the 4f n -4f n − 15d transitions of Ce3+, Pr3+, and Tb3+ ions in the absorption spectra of CdF2 crystals

The structure of the absorption spectra of Ce³⁺, Pr³⁺, and Tb³⁺ ions in the vicinity of 4f-5d transitions has been investigated. At low temperatures the absorption spectra exhibit a weakly pronounced fine structure, in contrast to narrow-line spectra in crystals of Ca, Sr, and Ba fluorides. The spectra of Ce³⁺, Pr³⁺, and Tb³⁺ ions in CdF₂ can be considered as the absorption spectra of these ions in alkali-earth fluorides, broadened by 60–75 cm^?1. The broadening is related to the autoionization of electron from the local 5d(e _g ) level to the energy-degenerate states of the conduction band of CdF₂ crystal.     

Optical spectroscopy and diode-pumped laser characteristics of codoped Tm-Ho : YLF and Tm-Ho : BaYF : a comparative analysis

Single crystals of monoclinic BaY₂F₈ and tetragonal LiYF₄ codoped with the same Tm³⁺ and Ho³⁺ concentrations were successfully grown by the Czochralski method. Here we present a comparative analysis of the two hosts including spectroscopic characterization and cw diode-pumped laser experiments in the 2-μm wavelength region at room temperature. The main differences between the two hosts are a lower slope efficiency associated with a much wider tuning range (2005–2094 nm) of BaY₂F₈ with respect to LiYF₄. Received: 29 July 2002 / Published online: 11 December 2002 RID="*" ID="*"Corresponding author. Fax: +39-050/2214-333, E-mail: toncelli@df.unipi.it     

Luminescence of La3F3[Si3O9]:Ce

The luminescence properties of Ce³⁺ in La₃F₃[Si₃O₉] are reported. Excitation and emission bands corresponding to 4f¹→5d¹ transitions of Ce³⁺ were identified. The center of gravity of the 5d states lies at remarkable high energy (43.2×10³ cm⁻¹) for Ce³⁺ in a silicate compound. This high value is attributed to the combined oxygen/fluoride coordination of the Ce³⁺ ion. Emission from the lowest 4f5d level to the ²F_5/2 and ²F_7/2 levels was found at 32.4×10³ and 30.4×10³ cm⁻¹. These results are compared with literature data on silicates and fluorides. From the values found for Ce³⁺, predictions are made for the positions of the 4f5d bands of Pr³⁺ and Er³⁺ in La₃F₃[Si₃O₉]. For both ions, it is concluded that in this host lattice emission is expected from high lying 4fⁿ energy levels.     

Stmmry talk on evaluation and theory

Abstract

Single crystal samples of Ce³⁺-doped fluorides CaNaYF₆ and BaMgF₄ have been grown in a reducing atmosphere, with the intent of studying the effects of symmetry and ligand coordination on the dopant energy levels. The optical absorption spectra of Ce³⁺ in these crystals consist, at most, of five overlapping bands. The luminescence is also a broad band due to strong electron—phonon interaction in the 5d excited state. The energies of the lowest absorption band and the luminescence band are shifted to low energy compared to those in LiCaAlF₆ and LiYF₄. This trend may be explained by lowering symmetry of the anion-coordinate polyhedra of Ce³⁺ in these crystals.     

Monochromatic blue-green and red emission of rare-earth ions in MgGa2O4 spinel

Pr³⁺-activated blue-green phosphor and Eu³⁺-activated red phosphor hosted in MgGa₂O₄ spinel have been prepared by a gel-assisted high-temperature calcination process, respectively. Both anion and cation vacancies in the host were formed by decreasing the Mg concentration in the reaction source. The induced vacancies provide possibility of the accommodation of the doped rare-earth ions with larger atomic size in the highly symmetrical spinel structure. Due to the efficient energy transfer from the spinel host to the sole 4f sub-level of the doped rare earths, monochromatic emissions with high efficiency can be obtained to allow the phosphors to find applications in solid-state laser device and other phosphors excited under low energy. The corresponding spectroscopic transition mechanism has been proposed in this work.