Two-photon excited red upconversion luminescence of thulium ions doped GeS2-In2S3-CsI glass

We report a novel phenomenon in GeS2-In2S3-CsI chalcohalide glass doped with Tm3+ ions. Under irradiation with an 808 nm laser diode, a bright red emission centered at 700 nm is observed for the first time in this glass. The log-log correlation between integrated emission intensity and pump power reveals that a two-photon absorption process is involved in the phenomenon, suggesting that the F-3(3,2) -> H-3(6) transition of Tm3+ ions is responsible for the appearance of the red emission. The results indicate that the indium (In) based chalcohalide glass containing Tm3+ ions is expected to find applications in visible lasers, high density optical storage and three-dimensional color displays. (C) 2009 Elsevier B.V. All rights reserved.

Mössbauer effect investigations of the hyperfine interactions and relaxation phenomena in salts of thulium

Two new phenomena have been observed in Mössbauer spectra: a temperature-dependent shift of the center of gravity of the spectrum, and an asymmetric broadening of the spectrum peaks. Both phenomena were observed in thulium salts. In the temperature range 1˚K ≤ T ≤ 5˚K the observed shift has an approximate inverse temperature dependence. We explain this on the basis of a Van Vleck type of interaction between the magnetic moment of two nearly degenerate electronic levels and the magnetic moment of the nucleus. From the size of the shift we are able to deduce an “effective magnetic field” H = (6.0 ± 0.1) x 10⁶ Gauss, which is proportional to ‹r^-3›_M‹G|J|E› where ‹r^-3›_M is an effective magnetic radial integral for the 4f electrons and |G› and |E› are the lowest 4f electronic states in Tm Cl₃·6H₂O. From the temperature dependence of the shift we have derived a preliminary value of 1 cm^-1 for the splitting of these two states. The observed asymmetric line broadening is independent of temperature in the range 1˚K ≤ T ≤ 5˚K, but is dependent on the concentration of thulium ions in the crystal. We explain this broadening on the basis of spin-spin interactions between thulium ions. From size and concentration dependence of the broadening we are able to deduce a spin-spin relaxation time for Tm Cl₃·6H₂O of the order of 10^-11 sec.

Sensitized thulium blue upconversion emission in Nd3+/Tm3+/Yb3+ triply doped lead and cadmium germanate glass excited around 800 nm

Bright blue upconversion emission by thulium ions in PbGeO3-PbF2-CdF2 glass triply doped with Nd3+-Tm3+-Yb3+ under diode laser excitation around 800 nm is reported. The results revealed that the Nd3+/Tm3+/Yb3+-codoped sample generated ten times more 475 nm blue upconversion fluorescence than the Yb3+-sensitized Tm3+-doped one, under the same excitation power. The upconversion process also showed a strong dependence upon the Yb3+ concentration. The results also indicated that the neodymium ions played a major role in the upconversion process by transfering the 800 nm excitation to thulium ions. The population of the Tm3+ ions (1)G(4) emitting level was accomplished through a multiion interaction involving ground-state absorption of pump photons around 800 nm by the Nd3+(I-4(9/2)-->H-2(9/2), F-4(5/2)) and Tm3+(H-3(6)-->F-3(4)) ions followed by energy-transfer processes involving the Nd3+-Yb3+(F-4(3/2), F-2(7/2)-->I-4(11/2), F-2(5/2)) and Yb3+-Tm3+(F-2(5/2), F-3(4)-->F-2(7/2), (1)G(4)) pairs. (C) 2003 American Institute of Physics.

The role of glass modifiers in the solubility of Tm3+ ions in As2S3 glasses

Au cours des années une variété des compositions de verre chalcogénure a été étudiée en tant qu’une matrice hôte pour les ions Terres Rares (TR). Pourtant, l’obtention d’une matrice de verre avec une haute solubilité des ions TR et la fabrication d’une fibre chalcogénure dopée au TR avec une bonne qualité optique reste toujours un grand défi. La présente thèse de doctorat se concentre sur l’étude de nouveaux systèmes vitreux comme des matrices hôtes pour le dopage des ions TR, ce qui a permis d’obtenir des fibres optiques dopées au TR qui sont transparents dans l’IR proche et moyenne. Les systèmes vitreux étudiés ont été basés sur le verre de sulfure d’arsenic (As2S3) co-dopé aux ions de Tm3+ et aux différents modificateurs du verre. Premièrement, l’addition de Gallium (Ga), comme un co-dopant, a été examinée et son influence sur les propriétés d’émission des ions de Tm a été explorée. Avec l’incorporation de Ga, la matrice d’As2S3 dopée au Tm a montré trois bandes d’émission à 1.2 μm (1H5→3H6), 1.4 μm (3H4→3F4) et 1.8 μm (3F4→3H6), sous l’excitation des longueurs d’onde de 698 nm et 800 nm. Les concentrations de Tm et de Ga ont été optimisées afin d’obtenir le meilleur rendement possible de photoluminescence. À partir de la composition optimale, la fibre Ga-As-S dopée au Tm3+ a été étirée et ses propriétés de luminescence ont été étudiées. Un mécanisme de formation structurale a été proposé pour ce système vitreux par la caractérisation structurale des verres Ga-As-S dopés au Tm3+, en utilisant la spectroscopie Raman et l’analyse de spectrométrie d’absorption des rayons X (EXAFS) à seuil K d’As, seuil K de Ga et seuil L3 de Tm et il a été corrélé avec les caractéristiques de luminescence de Tm. Dans la deuxième partie, la modification des verres As2S3 dopés au Tm3+, avec l’incorporation d’halogénures (Iode (I2)), a été étudiée en tant qu’une méthode pour l’adaptation des paramètres du procédé de purification afin d’obtenir une matrice de verre de haute pureté par distillation chimique. Les trois bandes d’émission susmentionnées ont été aussi bien observées pour ce système sous l’excitation à 800 nm. Les propriétés optiques, thermiques et structurelles de ces systèmes vitreux ont été caractérisées expérimentalement en fonction de la concentration d’I2 et de Tm dans le verre, où l’attention a été concentrée sur deux aspects principaux: l’influence de la concentration d’I2 sur l’intensité d’émission de Tm et les mécanismes responsables pour l’augmentation de la solubilité des ions de Tm dans la matrice d’As2S3 avec l’addition I2.

利用窄得-奥菲特理论研究Tm:Lu_2SiO_5晶体的光谱特性

采用丘克拉斯基(Czochralski)技术生长了掺铥硅酸镥(Tm∶Lu2SiO5,Tm∶LSO)晶体;测量了LSO晶体在室温下的非偏振吸收光谱和非偏振荧光光谱;利用窄得-奥菲特(Judd-Ofelt)理论计算了Tm∶LSO晶体的窄得-奥菲特强度参数、振子强度、自发辐射概率、辐射寿命、积分吸收截面和积分发射截面.Tm∶LSO晶体的强度参数为Ω2=9.1355×10-20cm2,Ω4=8.4103×10-20cm2,Ω6=1.5908×10-20cm2;Tm∶LSO晶体在1.9μm附近有明显的发射峰(3F4→3H6跃迁),相应的辐射寿命为2.03 ms,积分发射截面为5.81×10-18cm2,半峰全宽(FWHM)为250 nm.用Tm∶LSO晶体在77 K温度下实现了激光运转.利用792 nm的激光二极管(LD)作为抽运源,获得中心波长为1960 nm的激光输出,抽运阈值为2.13 kW/cm2.

(Sr,Tm)ZrO3 powders prepared by the polymeric precursor method: Synthesis, optical properties and morphological characteristics

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Energy transfer rates and population inversion investigation of sup(1)Gsub(4) and sup(1)Dsub(2) excited states of Tmsup(3+) in Yb:Tm:Nd:KYsub(3)Fsub(10) crystals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Near-infrared luminescence from sol-gel materials doped with holmium(III) and thulium(III) complexes

A series of ternary Ln(tta)(3)L complexes (Ln = Ho, Tm; Htta = 2-thenoyltrifluoroacetone; L = 1,10-phenanthroline, 2,2'-bipyridine, or triphenyl phosphate oxide) and their corresponding sol-gel hybrid materials formed via the in situ synthesis process (designated as Ln-T-L gel) were reported. The complexes and the gels were studied in detail, which suggest the complexes have been successfully synthesized in the corresponding gels.

Structural and optical properties on thulium-doped LHPG-grown Ta(2)O(5) fibres

Structural, spectroscopic and dielectric properties of thulium-doped laser-heated pedestal Ta(2)O(5) as-grown fibres were studied. Undoped samples grow preferentially with a single crystalline monoclinic structure. The fibre with the lowest thulium content (0.1 at%) also shows predominantly a monoclinic phase and no intra-4f(12) Tm(3+) recombination was observed. For sample with the highest thulium amount (1.0 at%), the appearance of a dominant triclinic phase as well as intraionic optical activation was observed. The dependence of photoluminescence on excitation energy allows identification of different site locations of Tm(3+) ions in the lattice. The absence of recombination between the first and the ground-state multiplets as well as the temperature dependence of the observed transitions was justified by an efficient energy transfer between the Tm(3+) ions. Microwave dielectric properties were investigated using the small perturbation theory. At a frequency of 5 GHz, the undoped material exhibits a dielectric permittivity of 21 and for thulium-doped Ta(2)O(5) samples it decreases to 18 for the highest doping concentration. Nevertheless, the dielectric losses maintain a very low value. (C) 2008 Elsevier Ltd. All rights reserved.

Dynamics of Tm-Ho energy transfer and deactivation of the F-3(4) low level of thulium in fluorozirconate glasses

The mechanism involved in the Tm3+ (F-3(4))-->Ho3+ (I-5(7)) energy transfer and Tm3+ (H-3(4), H-3(6))-->Tm3+ (F-3(4), F-3(4)) cross relaxation as a function of the donor and acceptor concentrations was investigated in Tm-Ho-codoped fluorozirconate glasses. The experimental transfer rates were determined for the Tm-->Ho energy transfer from the best fit of the acceptor luminescence decay using an expression which takes into account the Inokuti-Hirayama model and localized donor-to-acceptor interaction solution. The original acceptor solution derived from the Inokuti-Hirayama model fits well the acceptor luminescence transient only for low-concentrated systems. The results showed that a fast excitation diffusion that occurs in a very short time (t<ions before the energy transfer to acceptor already observed in Yb:Er:ZBLAN. The fast excitation diffusion effect was observed to dominate both the Tm-->Tm cross relaxation and Tm-->Ho energy transfer ions from H-3(4) and F-3(4) thulium states, respectively. (C) 2004 American Institute of Physics.

Application of standard and modified Judd-Ofelt theories to thulium doped fluoroindate glass

Fluoroindate glasses of the following compositions: (40-x)InF3-20ZnF(2)-16BaF(2)-20SrF(2)-2GdF(3)-2NaF-xTmF(3) with x = 1,3 mol% were prepared in a dry box under an argon atmosphere. The absorption spectra at room temperature in the spectral range 350-2200 nm were obtained. The spectra obtained for each sample had similar absorption and only the amplitude of the different bands changed as the concentration of Tm3+. The experimental oscillator strengths were determined from the areas under the absorption bands. Using the standard and modified Judd-Ofelt theory, intensity parameters Ohm(lambda) (lambda = 2,4,6) and (lambda = 2,3,4,5,6), respectively for f-f transitions of Tm3+ ions as well as transition probabilities, branching ratios and radiative lifetimes for each band were determined. The results are compared with those of other glasses described in the literature. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Blue upconversion enhancement by a factor of 200 in Tm 3+-doped tellurite glass by codoping with Nd 3+ ions

We investigated near-infrared-to-blue upconversion from thulium (Tm 3+) doped in tellurite glasses upon continuous wave excitation near 800 nm. We observed an enhancement of over two orders of magnitude of the upconverted emission at ∼480nm when neodymium (Nd 3+) ions were codoped with Tm 3+ ions. For comparison, using a Tm 3+:Nd 3+ codoped fluorozirconate glass as a reference material we observed a 40-fold enhancement of the blue emission. Analysis of the blue emission for samples with different doping levels of Nd 3+ ions showed that energy transfer between Nd 3+ and Tm 3+ is the mechanism responsible for the enhancement in upconversion. © 2002 American Institute of Physics. © 2002 American Institute of Physics.

Synchronous fluorescence and UV–vis spectroscopic studies of interactions between the tetracycline antibiotic, aluminium ions and DNA with the aid of the Methylene Blue dye probe

Synchronous fluorescence spectroscopy (SFS) was applied for the investigation of interactions of the antibiotic, tetracycline (TC), with DNA in the presence of aluminium ions (Al3+). The study was facilitated by the use of the Methylene Blue (MB) dye probe, and the interpretation of the spectral data with the aid of the chemometrics method, parallel factor analysis (PARAFAC). Three-way synchronous fluorescence analysis extracted the important optimum constant wavelength differences, Δλ, and showed that for the TC–Al3+–DNA, TC–Al3+ and MB dye systems, the associated Δλ values were different (Δλ = 80, 75 and 30 nm, respectively). Subsequent PARAFAC analysis demonstrated the extraction of the equilibrium concentration profiles for the TC–Al3+, TC–Al3+–DNA and MB probe systems. This information is unobtainable by conventional means of data interpretation. The results indicated that the MB dye interacted with the TC–Al3+–DNA surface complex, presumably via a reaction intermediate, TC–Al3+–DNA–MB, leading to the displacement of the TC–Al3+ by the incoming MB dye probe.