Spectroscopic and Thermographic Qualities of Praseodymium-Doped Oxyfluorotellurite Glasses.

The thermal stability of oxyfluorotellurite glass systems, (65-x)TeO2-20ZnF2-12PbO-3Nb2O5-xPr2O3, doped with praseodymium was examined. The different concentrations of praseodymium oxide (x = 0.5 and 2 mol%) were applied to verify the thermal, optical and luminescence properties of the materials under study. The relatively high values of the Dietzel (ΔT) and Saad-Poulain (S or H') thermal stability factors determined using a differential thermal analysis (DTA) indicate the good thermal stability of the glass matrix, which gradually improves with the content of the active dopant. The temperature dependence of optical spectra in the temperature range 300-675 K for the VIS-NIR region was investigated. The involved Pr3+ optical transition intensities and relaxation dynamic of the praseodymium luminescent level were determined. The ultrashort femtosecond pulses were utilized to examine a dynamic relaxation of the praseodymium luminescent levels. Although the measured emission of the Pr3+ active ions in the studied glass encompasses the quite broad spectral region, the observed luminescence may only be attributed to 3PJ excited states. As a result, the observed decrease in the experimental lifetime for the 3P0 level along with the increasing activator content was identified as an intensification of the Pr-Pr interplay and the associated self-quenching process. The maximum relative sensitivities (Sr) estimated over a relatively wide temperature range are ~0.46% K-1 (at 300 K) for FIR (I530/I497) and 0.20% K-1 (at 600 K) for FIR (I630/I497), which seems to confirm the possibility of using investigated glasses in optical temperature sensors.

Ultrafast photoluminescence and multiscale light amplification in nanoplasmonic cavity glass.

Interactions between plasmons and exciton nanoemitters in plexcitonic systems lead to fast and intense luminescence, desirable in optoelectonic devices, ultrafast optical switches and quantum information science. While luminescence enhancement through exciton-plasmon coupling has thus far been mostly demonstrated in micro- and nanoscale structures, analogous demonstrations in bulk materials have been largely neglected. Here we present a bulk nanocomposite glass doped with cadmium telluride quantum dots (CdTe QDs) and silver nanoparticles, nAg, which act as exciton and plasmon sources, respectively. This glass exhibits ultranarrow, FWHM = 13 nm, and ultrafast, 90 ps, amplified photoluminescence (PL), λem≅503 nm, at room temperature under continuous-wave excitation, λexc = 405 nm. Numerical simulations confirm that the observed improvement in emission is a result of a multiscale light enhancement owing to the ensemble of QD-populated plasmonic nanocavities in the material. Power-dependent measurements indicate that >100 mW coherent light amplification occurs. These types of bulk plasmon-exciton composites could be designed comprising a plethora of components/functionalities, including emitters (QDs, rare earth and transition metal ions) and nanoplasmonic elements (Ag/Au/TCO, spherical/anisotropic/miscellaneous), to achieve targeted applications.

Exploring Structure-Sensitive Factors Relevant to Cryogenic Laser Operation in Oxide Crystals Doped with Er3+ Ions.

Crystals of Gd3Al2.5Ga2.5O12:Er3+, (Lu0.3Gd0.7)2SiO5:Er3+ and LiNbO3:Er3+ compounds differing in origin and the nature of their inherent structural disorder were crystalized. Optical absorption and luminescence spectra for transitions between the 4I15/2 and the 4I13/2 multiplets of Er3+ ions for the crystal samples were recorded versus temperatures in the region of 80-300 K. Gathered data were analyzed thoroughly providing the in-depth knowledge of the effects of temperature on intensities, wavelengths and bandwidths of Er3+ transitions. The information acquired together with the knowledge of significant structural dissimilarities of the host crystals chosen made it possible to propose an interpretation of the impact of a structural disorder in Er3+-doped crystals on their spectroscopic properties, and to determine their lasing ability at cryogenic temperatures upon resonant (in-band) optical pumping.

Examining the Spectroscopic and Thermographic Qualities of Er3+-doped Oxyfluoride Germanotellurite Glasses.

Novel ternary fluoro-germano-tellurite (GTS) glasses doped with Er3+ ions with 0.5 mol% and 1.0 mol% were fabricated by a conventional melt and quenching method and investigated using methods of optical spectroscopy. The room-temperature absorption spectrum was recorded and analyzed to determine radiative transition rates, radiative lifetimes, and branching ratios of Er3+ luminescence. Decay curves of Er3+ luminesccence were recorded and analyzed. Temperature dependences of emission spectra and absorption spectra in the region from RT (room-temperature) up to 675 K were studied in detail. The contribution of competing radiative and nonradiative processes to the relaxation of luminescent levels of Er3+ was assessed. Absolute and relative sensitivity were established utilizing the comprehensive model based on thermally coupled 2H11/2/4S3/2 excited states of erbium. The high quantum efficiency of the first erbium-excited state and value of gain coefficient indicate that GTS:Er glass system can be considered as conceivable NIR (near infrared) laser material as well.

Broadband Near-Infrared Luminescence in Lead Germanate Glass Triply Doped with Yb3+/Er3+/Tm3.

This paper deals with broadband near-infrared luminescence properties of lead germanate glass triply doped with Yb3+/Er3+/Tm3+. Samples were excited at 800 nm and 975 nm. Their emission intensities and lifetimes depend significantly on Er3+ and Tm3+ concentrations. For samples excited at 800 nm, broadband emissions corresponding to the overlapped 3H4 → 3F4 (Tm3+) and 4I13/2 → 4I15/2 (Er3+) transitions centered at 1.45 µm and 1.5 µm was identified. Measurements of decay curves confirm reduction of 3H4 (Tm3+), 2F5/2 (Yb3+) and 4I13/2 (Er3+) luminescence lifetimes and the presence of energy-transfer processes. The maximal spectral bandwidth equal to 269 nm for the 3F4 → 3H6 transition of Tm3+ suggests that our glass co-doped with Yb3+/Er3+/Tm3+ is a good candidate for broadband near-infrared emission. The energy transfer from 4I13/2 (Er3+) to 3F4 (Tm3+) and cross-relaxation processes are responsible for the enhancement of broadband luminescence near 1.8 µm attributed to the 3F4 → 3H6 transition of thulium ions in lead germanate glass under excitation of Yb3+ ions at 975 nm.

Exploring the Impact of Structure-Sensitivity Factors on Thermographic Properties of Dy3+-Doped Oxide Crystals.

Optical absorption spectra and luminescence spectra were recorded as a function of temperature between 295 K and 800 K for single crystal samples of Gd2SiO5:Dy3+, Lu2SiO5:Dy3+, LiNbO3:Dy3+, and Gd3Ga3Al2O12:Dy3+ fabricated by the Czochralski method and of YAl3(BO3)4:Dy3+ fabricated by the top-seeded high temperature solution method. A thermally induced change of fluorescence intensity ratio (FIR) between the 4I15/2→ 6H15/2 and 4F9/2 → 6H15/2 emission bands of Dy3+ was inferred from experimental data. It was found that relative thermal sensitivities SR at 350 K are higher for YAl3(BO3)4:Dy3+ and Lu2SiO5:Dy3+than those for the remaining systems studied. Based on detailed examination of the structural peculiarities of the crystals it was ascertained that the observed difference between thermosensitive features cannot be attributed directly to the dissimilarity of structural factors consisting of the geometry and symmetry of Dy3+ sites, the number of non-equivalent Dy3+ sites, and the host anisotropy. Instead, it was found that a meaningful correlation between relative thermal sensitivity SR and rates of radiative transitions of Dy3+ inferred from the Judd-Ofelt treatment exists. It was concluded that generalization based on the Judd-Ofelt parameters and luminescence branching ratio analysis may be useful during a preliminary assessment of thermosensitive properties of new phosphor materials.

Phonon Sideband Analysis and Near-Infrared Emission in Heavy Metal Oxide Glasses.

In this work, spectroscopic properties of europium and erbium ions in heavy metal oxide glasses have been studied. The phonon energy of the glass host was determined based on Eu3+ excitation spectra measurements. Near-IR emission spectra at 1550 nm related to 4I13/2 → 4I15/2 transition of erbium in heavy metal glasses were examined with special regards to luminescence bandwidth and measured lifetime. In particular, correlation between phonon energy and the measured lifetime 4I13/2 (Er3+) was proposed. The luminescence lifetime for the 4I13/2 upper laser state of erbium decreases with increasing phonon energy in glass matrices. Completely different results were obtained glass samples with europium ions, where the 5D0 lifetime increases with increasing phonon energy. Our investigations suggest that the values of measured 5D0 lifetime equal to radiative lifetimes for all heavy metal oxide glasses.

Spectroscopy and calculations for 4f(N) → 4f(N-1)5d transitions of lanthanide ions in K3YF6.

In the present work, we report on the combined experimental and theoretical studies of the 4f-5d spectra of Ce(3+), Pr(3+), Nd(3+), Eu(3+), Gd(3+), Tb(3+), Dy(3+), and Er(3+) ions in a newly synthesized K3YF6 matrix. The low temperature experimental 4f-5d excitation spectra have been analyzed and compared with the results of the energy-level and intensity calculations. For this theoretical analysis, the extended phenomenological crystal-field model for the 4f(N-1)5d configuration (i.e., the extended f-shell programs, developed by Prof. M. F. Reid) and exchange charge model (developed by Prof. B. Z. Malkin) have been used together to estimate the crystal field parameters and implement the spectral simulations. On the basis of the results of the performed theoretical analysis, we suggest the most probable positions occupied by optically active ions. Although the spectra of only eight lanthanide ions have been studied, the Hamiltonian parameters of the 4f(N-1)5d configuration have been evaluated for the whole lanthanide series and reported here for the first time, to give a complete and unified description of the spectroscopic properties of the trivalent rare earth ions in the chosen host. In addition to the studies of the 4f-5d transitions, various possible competitive excitation channels overlapping with 4f-5d ones have also been discussed, where a theoretical scheme giving rudiments to understand 4f-6s spectra are proposed for the first time. An excellent agreement between the calculated and measured excitation spectra shapes confirms validity of the performed analysis. The obtained parameters of the crystal field Hamiltonians for different ions and various electron configurations can be used in a straightforward way to generate the energy level positions and calculate the particular transition intensities for any rare earth ion in any particular spectral region. With the aid of the obtained parameters, the positions of the lowest energy levels of the 4f(N), 4f(N-1)5d ,and 4f(N-1)6s configurations of rare earth ions and 4f(N+1)(np)(5) configuration of rare earth ions and ligands (corresponding to the ligand-impurity ion charge transfer transitions) in the band gap of K3YF6 have all been estimated. The obtained Hamiltonian parameters and energy levels diagrams, which include the electronic structure of a host material, can be used as a starting point for analysis of spectroscopic properties of trivalent lanthanides in similar fluorides.

Near-infrared ultrabroadband luminescence spectra properties of subvalent bismuth in CsI halide crystals.

We observed two ultrabroadband near-infrared (NIR) luminescence bands around 1.2 and 1.5 µm in as-grown bismuth-doped CsI halide crystals, without additional aftertreatment. Dependence of the NIR emission properties on the excitation wavelength and measurement temperature was studied. Two kinds of NIR active centers of subvalent bismuth and color centers were demonstrated to coexist in Bi:CsI crystal. The eye-safe 1.5 µm emission band with an FWHM of 140 nm and lifetime of 213 µs at room temperature makes Bi:CsI crystal promising in the applications of the ultrafast laser and ultrabroadband amplifier.

Effect of temperature on spectroscopic features relevant to laser performance of YVO4:Tm3+, GdVO4:Tm3+, and LuVO4:Tm3+ crystals.

Optical spectra and luminescence decay curves were measured for thulium-doped YVO(4), GdVO(4), and LuVO(4) single crystals as a function of temperature in the 300-670 K temperature region. In spite of structural similarity, the three systems studied display significantly different transition intensities and nonradiative relaxation rates. It was found, in particular, that the peak value of the pump band absorption intensity diminishes by about 30% for Tm:YVO(4) and Tm:GdVO(4), and the effective emission cross section for the laser transition of Tm(3+) diminishes by a factor of 2 roughly when temperature increases from 300 to 500 K. An unusually small quantum efficiency of the upper laser level in Tm:LuVO(4) has been derived from the analysis of luminescence decay curves.

Spectral characterization and laser performance of a mixed crystal Nd:(LuxY1-x)3Al5O12.

An Nd-doped Lu(1.5)Y(1.5)Al(5)O(12) (Nd:LuYAG) crystal was obtained by Czochralski method. Absorption and emission spectra were recorded at low and room temperature. Continuous wave (CW) and passively Q-switched laser operations of Nd:LuYAG crystal were, to our knowledge, demonstrated for the first time. A CW output power of 1.67 W with slope efficiency of 39.8% was obtained. In the passively Q-switched operation, the shortest pulse width, largest pulse energy, and highest peak power were achieved to be 9.6 ns, 61.7µJ, and 6.4 kW, respectively, with Cr(4+):YAG crystals as the saturable absorbers.

Estimation of low-temperature spectra behavior in Nd-doped Sc2SiO5 single crystal.

High optical quality Nd-doped Sc(2)SiO(5) crystal with size of diameter 27 mm x 60 mm was obtained by Czochralski method. An x-ray diffraction pattern of Nd:SSO crystal confirmed that the as-grown crystal was isostructual with the SSO crystal. Absorption and emission spectra were recorded at 10 K. The Judd-Ofelt theory was applied to obtain standard parameters Omega t(t=2,4,6) and the fitting result of experimental absorption line strengths, which provided the F3/24 radiative lifetime (tau(rad)) of 219 micros and the luminescence branching ratio beta of 0.57 for the (4)F(3/2)-(4)I(9/2) laser transition. The stimulated emission cross section of 1.04 x 10(-19) cm(2) at 1074 nm was calculated using the Füchtbauer-Ladenburg equation. The (4)F(3/2) luminescence lifetimes with 215 micros at 10 K and 198 micros at 300 K were determined from luminescence decay curves, indicating high quantum efficiency in the Nd:SSO crystal. All these results showed that Nd:SSO would be a promising gain media in solid-state lasers.

Effect of temperature on spectroscopic features relevant to laser performance of YVO4:Er(3+) and GdVO4:Er(3+) crystals.

Optical spectra and luminescence decay curves were measured for erbium-doped YVO(4) and GdVO(4) single crystals as a function of temperature in the 300 K-670 K temperature region. In spite of structural similarity the two systems studied display significantly different transition intensities and nonradiative relaxation rates. It was found in particular that the intensity of parasitic upconverted emission excited at 978 nm depends weakly on temperature for YVO(4):Er(3+), whereas it decreases monotonously with increasing temperature for GdVO(4):Er(3+) and becomes negligibly small at 670 K. It was concluded that GdVO(4):Er(3+) may be a promising laser active material operating at high thermal loading conditions encountered in high-power diode-pumped IR lasers.

Unusual behavior of Tb3+ in K3YF6 green-emitting phosphor.

We report on photoluminescence studies of Tb3+ in a polycrystalline cryolite type K3YF6 host. The location of the Tb3+ in the center of inversion forbids the electric-dipole transitions of terbium ions in this material. As a consequence almost the entire luminescence intensity is related to the 5D4-(7)F5 magnetic-dipole transition, and it is contained in the extremely narrow spectral bandwidth amounting to 1.7 nm at 8K and to 18 nm at room temperature. The phosphor under study can be efficiently excited making use of intense f-d transitions of Tb3+ in the UV-vacuum-UV region and may be of interest for applications requiring high spectral purity of the emission.

Er-doped lead borate glasses and transparent glass ceramics for near-infrared luminescence and up-conversion applications.

Lead borate based glasses have been analyzed using Raman and infrared spectroscopy. The formation of different borate groups and the direction of BO3 <--> BO4 conversion strongly depends on the PbO- and/or PbF2-to-B2O3 ratio in chemical composition. PbF2-PbO-B2O3 based glasses containing Er3+ ions have been studied after annealing. The orthorhombic PbF2 crystallites are formed during thermal treatment, which was evidenced by X-ray diffraction analysis. Near-infrared luminescence at 1530 nm and green up-conversion at 545 nm have been registered for samples before and after annealing. The luminescence bands correspond to 4I13/2-4I15/2 and 4S3/2-4I15/2 transitions of Er3+ ions, respectively. In comparison to the precursor glasses, the luminescence intensities are higher in the studied transparent oxyfluoride glass ceramics. Simultaneously, the half-width of the luminescence lines slightly decreases. It can be the evidence that a small amount of the Er3+ ions is incorporated into the orthorhombic PbF2 phase.

Electronic structure of U3+ in Cs3Lu2Cl9 and Cs3Y2I9 single crystals.

Low-temperature emission and polarized absorption spectra have been recorded for U(3+) ions diluted in Cs(3)Lu(2)Cl(9) and Cs(3)Y(2)I(9) host crystals. The experimental crystal-field levels were fitted to 13 parameters of a semiempirical Hamiltonian representing the combined atomic, one-electron crystal field (CF) as well as two-particle correlation crystal-field (CCF) operators. The red shift of the first f-d transitions from approximately 14,800 cm(-1) in the spectrum of U(3+):Cs(3)Lu(2)Cl(9) to as low as 11,790 cm(-1) in that of U(3+):Cs(3)Y(2)I(9) has been attributed to an increase in the covalence of the U(3+)-X(-) bonds. Comparison of the differences in the Coulomb repulsion strength between U(3+) and Er(3+) ions in Cs(3)Lu(2)Cl(9) and Cs(3)Y(2)I(9) crystals suggests that the 5f electrons of U(3+) ions are more 3d-like than 4f. The CF splitting of the (2)H(9/2) and (4)F(5/2) multiplets is unexpectedly larger for U(3+):Cs(3)Y(2)I(9) than for U(3+):Cs(3)Lu(2)Cl(9), which may be viewed as a result of the proximity of f-d states. For a correct description of the energy level structure of the (2)H(9/)(2) and (4)F(5/2) multiplets, the inclusion of CCF terms in the parametric Hamiltonian has proved to be essential. The larger f-f transition intensities for U(3+):Cs(3)Y(2)I(9) were also considered to be a consequence of the red shift of the first f-d states. The inadequacy in determination of the minor atomic parameters (other than parameters for Coulomb and spin-orbit interactions) and the insufficient inclusion of the influence of excited configuration in the applied CF Hamiltonian are assumed to be the main deficiencies preventing a better agreement between the experimental and calculated energies of CF levels.