The review of experimental results concerning improving the tuning and energy properties of UV lasers based on crystals with the scheelite-type (LiY1-xLuxF4) and colquiriite-type (LiCa1-x SrxAlF6) structures doped by Ce3+ and Cr3+ ions is presented. The negative effect of pump-induced photodynamic processes in active elements impact on the laser properties and approaches to minimize it are discussed.
It was demonstrated that the amount of Ce3+ ions in centers with luminescence in the shorter wavelength region decreases and with luminescence in the longer wavelength increases upon transition from LiSrAlF6 to the LiCaAlF6 matrix. In this case, the longer wavelength edge of the excitation band corresponds to the luminescence of longer wave centers in the LiCaAlF6 matrix, while the opposite is observed for the LiSrAlF6 matrix. The picture also changes with an increase in the concentration of Ce3+ ions, namely, an increase in the luminescence intensity of longer-wave centers is observed; It is shown that mixed crystals at a low concentration of Ce3+ ions are characterized by a higher gain. In this case, the effect of the formation of color centers and induced absorption appears for LiSrAlF6 crystals and mixed LiSrxCa1-xAlF6 with an increase in the concentration of Ce3+ ions.
In the present work prototype of laser gas analyzer of differential absorption technique on the basis of pulsed tunable Ce:LiCaAlF6 laser is discussed. By means of wavelength tuning concentrations of NO2, SO2 and O3 in the atmosphere of Kazan city were measured. The measured detection threshold appeared to be 2,52·10-6 g/m3 for NO2, 0,30·10-6 g/m3 for SO2, 0,03·10-6 g/m3 for O3.
The Bridgman technology details of growing up to 100 mm-length Cr3+:LiCaAlF6 crystals are reported. The spectral-kinetic luminescence and laser properties for the pulse lamp-pumped laser are discussed.
Melanogenesis disorder leads to several pathologies, including vitiligo. Tetrahydrobiopterin (H4Bip) as the phenylalanine 4-hydroxylase coenzyme catalyzes the oxidation of phenylalanine to tyrosine (a melanin precursor). H4Bip is easily oxidized by oxygen in vivo and in vitro. Vitiligo is accompanied by three-fivefold increased de-novo synthesis of H4Bip, its excess and its further oxidation are essential factors in the pathogenesis of vitiligo. We have demonstrated that pterin products of H4Bip autoxidation (dihydropterin (H2Ptr), dihydroxanthopterin and pterin) predominate over biopterin products (dihydrobiopterin (H2Bip) and biopterin). It was shown that ultraviolet (UV) irradiation accelerates the autoxidation while the products of oxidative degradation of H4Bip act as photosensitizers. Photosensitized oxidation of H4Bip can contribute to the pathogenesis of vitiligo. The main distinguishing feature of UV photooxidation of H4Bip from autoxidation was the formation of dihydropterin (Н2Ptr)2 and dihydrobiopterin (Н2Bip)2 dimers. Here we reported on the dependences of the photodimerization reaction on the wavelength and intensity of radiation using xenon lamps and UV tunable lasers as sources of UV radiation. It was shown that UV irradiation with a laser is more efficient than that with xenon lamp. It was established that the greatest number of dimers were formed by irradiating the H4Bip solution by radiation with a wavelength in the range 308-312 nm. The data obtained are discussed in the context of UVB narrowband vitiligo phototherapy.
Here laser studies of Ce3+:LiLuxMe1-x F4 (Me=Y3+,Yb3+) mixed crystals homologous to well-known Ce3+:LiYF4and Ce3+:LiLuF4 UV crystalline active media are reported. Optical spectroscopy and X-ray diffraction studies have
proved scheelite structure of the investigated mixture crystals. Advantages of LiLuYF4:Ce3++Yb3+ mixture crystals were
detected. Among them an opportunity to wider tuning range of laser oscillation in comparison to LiLuF4:Ce3++Yb3+
active medium by means of varying YF3/LuF3 content relation. As it was shown from laser experiments mutual shift of
5d-4f emitting transition of Ce3+ ions and color centers absorption band due to lattice parameter change gives an
optimum for YF3/LuF3 content relation corresponding to minimal overlap and maximal amplification band. EPR and
optical spectroscopy revealed the optimum ratio of Y3+ ions and Lu3+ in solid solutions of LiF-LuF3-YF3, where the
segregation coefficient Ce3+ of ions is increased 3-5 times compared with crystals LiYF4 and LiLuF4.
We have discovered that total intracavity losses, being dependent on color centers amount, go down for higher pump
energies for LiCaAlF6: Ce3+. This dependence is explained by the formation by the pump radiation and destruction of
color centers due to laser radiation. The more energy remains in the lasing cavity, the lower the color centers absorption.
Such dependencies were investigated for active medium crystals grown by different methods. Influence of growth
conditions on active media characteristics is discussed.
As a result we have shown for the first time that the crystal LiCaAlF6:Ce3+ internal losses depend on the pump energy.
Method has been worked out to determine the intracavity losses of the laser, which allows evaluation of prospects of its
practical use in the most correct way.
Here we report on pump-probe studies of KY3F10 and CaF2 doped with Ce3+ and Yb3+ ions. The crystals
Ce3+:KY3F10 and Ce3+:CaF2 show attractive spectral characteristics for tunable UV lasers application but have poor
photochemical stability. Their properties under intense UV pumping are affected by excited state absorption and color
centers formation.
This work was aimed at dynamic processes investigation induced by laser radiation of UV spectral range in
KY3F10 and CaF2 doped with Ce3+ and Yb3+ ions.
Optical gain was observed on CaF2:3++Yb3+ in the range 325-335 nm for the first time. It proves Yb3+ ions
coactivation antisolarant effect elaborated by us earlier. It is shown that in investigated crystals under a pump radiation,
resonant to 4f-5d Ce3+ ions transitions several types of color centers (CC) are formed. Set of these CC types are
determine the absorption at expected stimulated emission spectral range and magnitude of the induced loses is dependent
on many factors. As a result of competition between CC formation, free charges recombination and CC photodestruction
this balance can be shifted towards either rising or dropping losses at 5d-4f Ce3+ ions luminescence spectral range.
Here spectral-kinetic properties of Ce3+ ions and UV pumping induced color centers in KY3FI0 (KYF) crystals are reported and discussed. The efficiency of crystal-chemical approach of UV pumping induced solarization processes inhibition in these crystals was shown. Laser oscillation was achieved on the Ce:KYF crystals which were considered earlier as unpromising as active medium due to its photochemical instability.
Here the photochemical properties of CaF2 crystal doped by Ce3+ and Yb3+ ions under pumping with ultraviolet (UV) irradiation resonant to the Ce3+ ion interconfigurational 5d-4f transitions were studied and significant codoping effect on the crystal solarization suppression was observed. The photodynamic processes model occurring in the active medium and which taking into account the color center formation and processes of enhanced free charges recombination via valence change of variety of impurity centers was proposed. This model allows to explain both electronic and hole types color centers suppression in Ce:CaF2 sampels codoped by Yb3+ ions. It was shown that Yb3+ ions in the crystal act as centers of electron and hole recombination with probability dependent on the extra charge compensation type. Therefore the proposed antisolarant mechanism of the coactivation effect satisfactorily describes photochemical properties of fluorite and other crystal hosts.
Opportunities of laser tests as a powerful and unique research tool of active medium fundamental properties directly in real laser operation conditions for variable intracavity losses are discussed. New technique of laser experimental data interpretation was developed and applied to the analysis of laser tests results for the series of Ce3+:LiYbxLu1-xF4 single crystals. Contribution coefficient into total pump-induced intracavity losses of ESA from upper laser level of Ce3+ ions and CC absorption at the laser wavelength was estimated. Basic parameters relevant to laser action performance were defined: Ce3+ ions ionization cross-section by pumping radiation and Ce3+ ion ESA at the laser wavelength, CC absorption (ionization) cross-section at the both pumping and laser radiation wavelength, life-times of transient and long-living color centers, stimulated emission cross-section and relative values of pump-induced free-charges trapping rate by host lattice defects and their corresponding recombination rate.
The spectral-kinetic characteristics of Ce3+ ions doped Na4Y6-xYbxF22 (x=0-0.05) single crystals were studied. Ce3+ ions 5d-4f interconfigurational fluorescence quantum yield versus Yb3+ ion codopant concentration was measured. Pump-induced color center absorption spectra were studied and the efficiency of Yb3+ ions codoping antisolarant crystal-chemical technique applied to Na4Y6F22:Ce3+ was demonstrated. The optimal Yb3+ ions content from the point of view of effective tunable laser action was estimated. The obtained results allow proposing Na4Y6-xYbxF22 as a new prospective photochemically stabilized material for UV/VUV application.
All known solid-state UV/VUV active media based on the interconfigurational 5d-4f transitions of trivalent rare earth ions in wide-band gap fluoride crystals are solarizable under intense UV/VUV pumping. Active media- specific pumping-induced color centers, on one hand, would absorb the laser radiation and reduce the laser efficiency. On the other hand they also get bleached by the pump laser radiation so that the current value of total intracavity losses is governed by dynamic equilibrium and depends on some active medium microparameters as well as the pump flux and is cavity specific. Presented here are the model of dynamic processes in a UV solarizable active medium under pumping conditions and the new technique of laser experimental data analysis for variable intracavity losses based on this model. It is shown that properly set laser experiment enables us to obtain the necessary active medium microparameters, including the pump excited state absorption and color center absorption of laser radiation cross- sections, photoelectron trapping rate by host lattice defects and their recombination rate. The results of this technique application to the laser experiment analysis for the series of Ce3+:LiYbxLu1-xF4 single crystals are presented.
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