Influence of barium substitution on the physical, thermal, optical and luminescence properties of Sm3+-doped metaphosphate glasses for reddish orange light applications.

Our present study focuses on examining the thermal, structural and luminescent characteristics of sodium barium metaphosphate glasses doped with Sm3+. Glass samples with molar compositions (100 - y)[(50P2O5)-(50-xNa2O)-(xBaO)]-ySm2O3, where x = 20, 25, 30, 35, 40 and y = 0.3 and 1% were first synthesized by conventional melt quenching and later dehydroxylated under a constant N2 flow to ensure final glasses with a very high degree of chemical and optical homogeneity and free of water. Upon the addition of BaO and Sm2O3, refractive index, molar mass, density, glass transition temperature and dilatometric softening temperature exhibited an increase, whereas the coefficient of thermal expansion showed a decrease. The FTIR spectra analysis reveals a network depolymerization that intensifies with rising BaO concentration, ultimately transitioning from a modifier oxide to a glass-forming element, at higher BaO concentrations. All doped samples exhibited prominent absorption bands in the visible (VIS) and near-infrared (NIR) regions, as revealed by the optical absorption spectra. The Na2O modifier demonstrated greater influence on Sm3+ emission compared to BaO, a phenomenon that can explained by the moderation of the local ligand field strength resulting from this substitution. With an increase in Sm2O3 concentration from 0.3 to 1 mol%, the experimental lifetimes of the 4G5/2 level decrease, primarily attributed to the presence of energy transfer mechanisms. A discussion of Judd-Ofelt parameter analysis and glass radiation properties will be presented.

Novel Sol-Gel Route to Prepare Eu3+-Doped 80SiO2-20NaGdF4 Oxyfluoride Glass-Ceramic for Photonic Device Applications.

Oxyfluoride glass-ceramics (OxGCs) with the molar composition 80SiO2-20(1.5Eu3+: NaGdF4) were prepared with sol-gel following the "pre-crystallised nanoparticles route" with promising optical results. The preparation of 1.5 mol % Eu3+-doped NaGdF4 nanoparticles, named 1.5Eu3+: NaGdF4, was optimised and characterised using XRD, FTIR and HRTEM. The structural characterisation of 80SiO2-20(1.5Eu3+: NaGdF4) OxGCs prepared from these nanoparticles' suspension was performed by XRD and FTIR revealing the presence of hexagonal and orthorhombic NaGdF4 crystalline phases. The optical properties of both nanoparticles' phases and the related OxGCs were studied by measuring the emission and excitation spectra together with the lifetimes of the 5D0 state. The emission spectra obtained by exciting the Eu3+-O2- charge transfer band showed similar features in both cases corresponding the higher emission intensity to the 5D0→7F2 transition that indicates a non-centrosymmetric site for Eu3+ ions. Moreover, time-resolved fluorescence line-narrowed emission spectra were performed at a low temperature in OxGCs to obtain information about the site symmetry of Eu3+ in this matrix. The results show that this processing method is promising for preparing transparent OxGCs coatings for photonic applications.

Role of Eu2+ and Dy3+ Concentration in the Persistent Luminescence of Sr2MgSi2O7 Glass-Ceramics.

In this study, glass-ceramics based on Sr2MgSi2O7 phosphor co-doped with Eu/Dy were obtained from the sintering and crystallisation of glass powders. The glasses were melted in a gas furnace to simulate an industrial process, and the dopant concentration was varied to optimise the luminescence persistence times. The doped parent glasses showed red emission under UV light excitation due to the doping of Eu3+ ions, while the corresponding glass-ceramics showed persistent blue emission corresponding to the presence of Eu2+ in the crystalline environment. The dopant concentration had a strong impact on the sintering/crystallisation kinetics affecting the final glass-ceramic microstructure. The microstructures and morphology of the crystals responsible for the blue emission were observed by scanning electron microscopy-cathodoluminescence. The composition of the crystallised phases and the distribution of rare-earth (RE) ions in the crystals and in the residual glassy phase were determined by X-ray diffraction and energy dispersive X-ray analysis. The emission and persistence of phosphorescence were studied by photoluminescence.

Non-Linear Optical Properties of Er3+-Yb3+-Doped NaGdF4 Nanostructured Glass-Ceramics.

Transparent oxyfluoride glass-ceramics containing NaGdF4 nanocrystals were prepared by melt-quenching and doped with Er3+ (0.5 mol%) and different amounts of Yb3+ (0-2 mol%). The selected dopant concentration the crystallization thermal treatments were chosen to obtain the most efficient visible up-conversion emissions, together with near infrared emissions. The crystal size increased with dopant content and treatment time. NaGdF4 NCs with a size ranging 9-30 nm were obtained after heat treatments at Tg + 20-80 °C as confirmed by X-ray diffraction and high-resolution transmission electron microscopy. Energy dispersive X-ray analysis shows the incorporation of rare earth ions into the NaGdF4 nanocrystals. Near-infrared emission spectra, together with the up-conversion emissions were measured. The optical characterization of the glass-ceramics clearly shows that Er3+ and Yb3+ ions are incorporated in the crystalline phase. Moreover, visible up-conversion emissions could be tuned by controlling the nanocrystals size through appropriated heat treatment, making possible a correlation between structural and optical properties.

Transparent Sol-Gel Oxyfluoride Glass-Ceramics with High Crystalline Fraction and Study of RE Incorporation.

Transparent oxyfluoride glass-ceramic films and self-supported layers with composition 80SiO2-20LaF3 doped with Er3+ have been successfully synthesized by sol-gel process for the first time. Crack-free films and self-supported layer with a maximum thickness up to 1.4 µm were obtained after heat treatment at the low temperature of 550 °C for 1 min, resulting in a LaF3 crystal fraction of 18 wt%, as confirmed by quantitative Rietveld refinement. This is the highest value reported up to now for transparent oxyfluoride glass-ceramics prepared by sol-gel. This work provides a new synthesis strategy and opens the way to a wide range of potential applications of oxyfluoride glass-ceramics. The characterization by a wide range of techniques revealed the homogeneous precipitation of LaF3 nanocrystals into the glass matrix. X-ray absorption spectroscopy and electron paramagnetic resonance confirmed that the Er3+ ions are preferentially embedded in the low phonon-energy LaF3 nanocrystals. Moreover, photoluminescence (PL) measurements confirmed the incorporation of dopants in the LaF3 nanocrystals. The effective concentration of rare-earth ions in the LaF3 nanocrystals is also estimated by X-ray absorption spectroscopy.

Site symmetry and host sensitization-dependence of Eu3+ real time luminescence in tin dioxide nanoparticles.

The present work gives a detailed investigation of the dependence of the real time luminescence of Eu3+-doped tin dioxide nanopowder on rare earth (RE) site symmetry and host defects. Ultrafast time-resolved analysis of both RE-doped and undoped nanocrystal powder emissions, together with electronic paramagnetic resonance studies, show that host-excited RE emission is associated with RE-induced oxygen vacancies produced by the non-isoelectronic RE-tin site substitution that are decoupled from those producing the bandgap excited emission of the SnO2 matrix. A lower limit for the host-RE energy transfer rate and a model for the excitation mechanism are given.

Transparent Glass-Ceramics Produced by Sol-Gel: A Suitable Alternative for Photonic Materials.

Transparent glass-ceramics have shown interesting optical properties for several photonic applications. In particular, compositions based on oxide glass matrices with fluoride crystals embedded inside, known as oxyfluoride glass-ceramics, have gained increasing interest in the last few decades. Melt-quenching is still the most used method to prepare these materials but sol-gel has been indicated as a suitable alternative. Many papers have been published since the end of the 1990s, when these materials were prepared by sol-gel for the first time, thus a review of the achievements obtained so far is necessary. In the first part of this paper, a review of transparent sol-gel glass-ceramics is made focusing mainly on oxyfluoride compositions. Many interesting optical results have been obtained but very little innovation of synthesis and processing is found with respect to pioneering papers published 20 years ago. In the second part we describe the improvements in synthesis and processing obtained by the authors during the last five years. The main achievements are the preparation of oxyfluoride glass-ceramics with a much higher fluoride crystal fraction, at least double that reported up to now, and the first synthesis of NaGdF4 glass-ceramics. Moreover, a new SiO2 precursor was introduced in the synthesis, allowing for a reduction in the treatment temperature and favoring hydroxyl group removal. Interesting optical properties demonstrated the incorporation of dopant ions in the fluoride crystals, thus obtaining crystal-like spectra along with higher efficiencies with respect to xerogels, and hence demonstrating that these materials are a suitable alternative for photonic applications.

Influence of Upconversion Processes in the Optically-Induced Inhomogeneous Thermal Behavior of Erbium-Doped Lanthanum Oxysulfide Powders.

The efficient infrared-to-visible upconversion emission present in Er-doped lanthanum oxysulfide crystal powders is used as a fine thermal sensor to determine the influence of upconversion processes on the laser-induced thermal load produced by the pump laser and to assess the potentialities of this material in order to obtain anti-Stokes laser-induced cooling. The analysis of the upconversion emission and excitation spectra as well as the decay curves indicates that energy transfer upconversion is the main mechanism responsible for the green (4S3/2) and red (4F9/2) upconversion luminescence. The dependence on temperature of the intensity ratio of upconversion emission from thermally-coupled ²H11/2 and 4S3/2 levels of Er3+ in the 240-300 K temperature range has been used to estimate a relative sensitivity of 1.09 × 10-2 K-1. Thermal measurements performed on the powder samples by using a thermal infrared camera exhibit a very inhomogeneous heat distribution at the sample surface due to the random distribution of the pumping energy inside the sample as well as to the random properties of the thermal field. The analysis of both spectroscopic and thermal measurements show that after a transient heating induced by the background absorption, cooling of discrete regions by means of anti-Stokes processes can be observed.

Random Laser Action in Nd:YAG Crystal Powder.

This work explores the room temperature random stimulated emission at 1.064 µm of a Nd:YAG crystal powder (Neodymium-doped yttrium aluminum garnet) in a very simple pump configuration with no assistance from an internal mirror. The laser threshold energy as a function of pump beam area and pump wavelength has been measured, as well as the temporal dynamics of emission pulses. The absolute energy of stimulated emission and the absolute laser slope efficiency have been measured by using a method proposed by the authors. The results show a surprising high efficiency that takes the low Nd3+ ion concentration of the crystal powder into account.

Diffusive random laser modes under a spatiotemporal scope.

At present the prediction and characterization of the emission output of a diffusive random laser remains a challenge, despite the variety of investigated materials and theoretical interpretations given up to now. Here, a new mode selection method, based on spatial filtering and ultrafast detection, which allows to separate individual lasing modes and follow their temporal evolution is presented. In particular, the work explores the random laser behavior of a ground powder of an organic-inorganic hybrid compound based on Rhodamine B incorporated into a di-ureasil host. The experimental approach gives direct access to the mode structure and dynamics, shows clear modal relaxation oscillations, and illustrates the lasing modes stochastic behavior of this diffusive scattering system. The effect of the excitation energy on its modal density is also investigated. Finally, imaging measurements reveal the dominant role of diffusion over amplification processes in this kind of unconventional lasers.

Low temperature red luminescence of a fluorinated Mn-doped zinc selenite.

M2(SeO3)F2 (M = Zn (1), Mn (2)) stoichiometric phases together with the Zn2-xMnx(SeO3)F2 compound doped at various concentrations (x = 0.002-0.2) were synthesized by employing mild hydrothermal conditions. These compounds have been characterized by scanning electron microscopy (SEM), Rietveld refinement of the X-ray powder diffraction patterns, ICP-Q-MS, thermogravimetric and thermodiffractometric analyses, and IR, UV/vis and electron paramagnetic resonance (EPR) spectroscopies. Compounds 1 and 2 crystallize in the orthorhombic Pnma space group with lattice parameters: a = 7.27903(4), b = 10.05232(6) and c = 5.26954(3) Šfor the zinc species and a = 7.50848(9), b = 10.3501(12) and c = 5.47697(6) Šfor the manganese phase, with Z = 4. The crystal structures of these compounds are isotypic and are built up from a 3D framework constructed by (010) sheets of [MO3F3] octahedra linked up by [SeO3] building units. Luminescence measurements of Mn2(SeO3)F2 were performed at different temperatures between 10 and 150 K. At 10 K, the emission spectrum consists of a broad band peaked at around 660 nm related to the (4)T1g→(6)A1g transition in octahedrically coordinated Mn(2+). Moreover, the influence of temperatures up to 295 K and the Mn concentration on the luminescent properties of the Zn2-xMnx(SeO3)F2 system were systematically studied. Magnetic measurements of 2 show antiferromagnetic coupling as the major interactions exhibiting a spin canting at low temperature.

Laser action in Nd(3+)-doped lanthanum oxysulfide powders.

We have investigated the stimulated emission properties of Nd(3+) doped La(2)O(2)S powders at room temperature as a function of pumping energy density, excitation wavelength, and Nd(3+) ion concentration. The absolute stimulated emission energy has been measured. Expressions for the slope efficiencies and lasing thresholds as a function of rare earth concentration and pumping wavelengths, which qualitatively agree with experimental observations, are discussed.

Synthetic control to achieve lanthanide(III)/pyrimidine-4,6-dicarboxylate compounds by preventing oxalate formation: structural, magnetic, and luminescent properties.

Control over the synthetic conditions in many metal/diazinedicarboxylato systems is crucial to prevent oxalate formation, since dicarboxylato ligands easily undergo degradation in the presence of metal salts. We report here an efficient route to obtain oxalato-free compounds for the lanthanide/pyrimidine-4,6-dicarboxylato (pmdc) system on the basis of the reaction temperature and nonacidic pH or oxygen free atmosphere. Two different crystal architectures have been obtained: {[Ln(µ-pmdc)(1.5)(H(2)O)(3)]·xH(2)O}(n) (1-Ln) and {[Ln(2)(µ(4)-pmdc)(2)(µ-pmdc)(H(2)O)(2)]·H(2)O}(n) (2-Ln) with Ln(III) = La-Yb, except Pm. Both crystal structures are built from distorted two-dimensional honeycomb networks based on the recurrent double chelating mode established by the pmdc. In compounds 1-Ln, the tricapped trigonal prismatic coordination environment of the lanthanides is completed by three water molecules, precluding a further increase in the dimensionality. Crystallization water molecules are arranged in the interlamellar space, giving rise to highly flexible supramolecular clusters that are responsible for the modulation found in compound 1-Gd. Two of the coordinated water molecules are replaced by nonchelating carboxylate oxygen atoms of pmdc ligands in compounds 2-Ln, joining the metal-organic layers together and thus providing a compact three-dimensional network. The crystal structure of the compounds is governed by the competition between two opposing factors: the ionic size and the reaction temperature. The lanthanide contraction rejects the sterically hindered coordination geometries whereas high-temperature entropy driven desolvation pathway favors the release of solvent molecules leading to more compact frameworks. The characteristic luminescence of the Nd, Eu, and Tb centers is improved when moving from 1-Ln to 2-Ln compounds as a consequence of the decrease of the O-H oscillators. The magnetic properties of the compounds are dominated by the spin-orbit coupling and the ligand field perturbation, the exchange coupling being almost negligible.

Enhancement of the luminescent properties of a new red-emitting phosphor, Mn2(HPO3)F2, by Zn substitution.

The Mn(2)(HPO(3))F(2) phase has been synthesized as single crystals by using mild hydrothermal conditions. The compound crystallizes in the orthorhombic Pnma space group, with unit cell parameters of a = 7.5607(8), b = 10.2342(7), and c = 5.5156(4) Å, with Z = 4. The crystal structure consists of a three-dimensional framework formed by alternating (010) layers of [MnO(3)F(3)] octahedra linked up by three connected [HPO(3)] tetrahedra. Luminescence measurements were performed at different temperatures between 10 and 150 K. The 10 K emission spectrum of the octahedrally coordinated Mn(II) cation exhibits a broad band centered at around 615 nm corresponding to the (4)T(1) → (6)A(1) transition. In order to explore the effect of the Mn(II) concentration and the possibility of enhancing the luminescence properties of the Mn(II) cation in Mn(2)(HPO(3))F(2), different intermediate composition members of the finite solid solution with the general formula (Mn(x)Zn(1-x))(2)(HPO(3))F(2) were prepared and their luminescent properties studied. The magnetic and specific heat behavior of M(2)(HPO(3))F(2) (M = Mn, Fe) have also been investigated. The compounds exhibit a global antiferromagnetic ordering with a spin canting phenomenon detected at approximately 30 K. The specific heat measurements show sharp λ-type peaks at 29.7 and 33.5 K for manganese and iron compounds, respectively. The total magnetic entropy is consistent with spin S = 5/2 and S = 2 of Mn(II) and Fe(II) cations.

Lanthanide(III)/pyrimidine-4,6-dicarboxylate/oxalate extended frameworks: a detailed study based on the lanthanide contraction and temperature effects.

Detailed structural, magnetic, and luminescence studies of six different crystalline phases obtained in the lanthanide/pyrimidine-4,6-dicarboxylate/oxalate system have been afforded: {[Ln(µ-pmdc)(µ-ox)(0.5)(H(2)O)(2)]·3H(2)O}(n) (1-Ln), {[Ln(µ-pmdc)(µ-ox)(0.5)(H(2)O)(3)]·2H(2)O}(n) (2-Ln), {[Ln(µ(3)-pmdc)(µ-ox)(0.5)(H(2)O)(2)]·~2.33H(2)O}(n) (3-Ln), {[Ln(2)(µ(3)-pmdc)(µ(4)-pmdc)(µ-ox)(H(2)O)(3)]·5H(2)O}(n) (4-Ln), {[Ln(µ(3)-pmdc)(µ-ox)(0.5)(H(2)O)(2)]·H(2)O}(n) (5-Ln), and [Ln(pmdc)(1.5)(H(2)O)(2.5)] (6-Ln). The slow generation of the oxalate (ox) anion, obtained from the in situ partial hydrothermal decomposition of the pyrimidine-4,6-dicarboxylate (pmdc) ligand, allows us to obtain good shaped single crystals, while direct addition of potassium oxalate provides the same compounds but as polycrystalline samples. The crystal structures of all compounds are based on the double chelation established by the pmdc and ox ligands to provide distorted 2D honeycomb layers that, in some cases, are fused together, leading to 3D systems, by replacing some of the coordinated water molecules that complete the coordination sphere of the lanthanide by uncoordinated carboxylate oxygen atoms of the pmdc. The presence of channels occupied by crystallization water molecules is also a common feature with the exception of compounds 5-Ln. It is worth noting that compounds 3-Ln present a commensurate crystal structure related to the partial occupancy of the crystallization water molecules placed within the channels. Topological analyses have been carried out, showing a previously nonregistered topology for compounds 4-Ln, named as jcr1. The crystal structures are strongly dependent on the lanthanide ion size and the temperature employed during the hydrothermal synthesis. The lanthanide contraction favors crystal structures involving sterically less hindranced coordination environments for the final members of the lanthanide series. Additionally, reinforcement of the entropic effects at high temperatures directs the crystallization process toward less hydrated crystal structures. The magnetic data of these compounds indicate that the exchange coupling between the lanthanide atoms is almost negligible, so the magnetic behavior is dominated by the spin-orbit coupling and the ligand field perturbation. The luminescence properties that exhibit the compounds containing Nd(III), Eu(III), and Tb(III) have been also characterized.

Novel approach towards cross-relaxation energy transfer calculation applied on highly thulium doped tellurite glasses.

In this paper we calculated, for the first time to the best of our knowledge, the cross relaxation parameter of Tm(3+) ions in tellurite glasses over a wide range of concentrations: from 0.36 mol% up to 10 mol%. A new measurement approach based on emission spectra monitoring is proposed. This method is very simple and allows to measure even very highly doped samples. The obtained values of cross-relaxation parameter show a linear dependence with respect to dopant concentration over the full investigated interval, suggesting a dipole-dipole interaction process. The measured slope is 1.81x10(-17) cm(3) s(-1) mol%(-1).

Efficient Nd(3+)-->Yb(3+) energy transfer in 0.8CaSiO(3)-0.2Ca(3)(PO(4))(2) eutectic glass.

In this work we report the study of energy transfer between Nd(3+) and Yb(3+) ions in glasses with the 0.8CaSiO(3)-0.2Ca(3)(PO(4))(2) eutectic composition at room temperature by using steady-state and time-resolved laser spectroscopy. The Nd(3+)?Yb(3+) transfer efficiency obtained from the Nd(3+) lifetimes in the single doped and codoped samples reaches 73% for the highest Nd(3+) concentration. The donor decay curves obtained under pulsed excitation have been used to establish the multipolar nature of the Nd(3+)-->Yb(3+) transfer process and the energy transfer microparameter. The nonradiative energy transfer is consistent with an electric dipole-dipole interaction mechanism assisted by energy migration among donors. Back transfer from Yb(3+) to Nd(3+) is also observed.

Real time random laser properties of Rhodamine-doped di-ureasil hybrids.

This investigation explores, for the first time, the random laser behavior of ground powder obtained from organic-inorganic hybrid materials based on Rhodamine 6G incorporated into a di-ureasil matrix. The experimental results, both in the spectral and temporal domains, obtained by pumping with picosecond laser pulses, show the existence of efficient random laser emission in this system. Finally, the random laser performance is compared with the one of other Rhodamine-doped solid state silica compounds.

1Low threshold random lasing in dye-doped silica nano powders.

Random laser action is demonstrated in two kinds of powder samples containing rhodamine 6G (Rh6G) doped SiO2 nanoparticles which are either directly dispersed within pure silica particles or embedded in a silica gel matrix which is subsequently ground. Both organic-inorganic hybrid materials present different laser thresholds and emission features which are systematically studied and compared. The dependence of the emission kinetics, emission spectrum, random laser threshold and slope efficiency on the dye doped nanoparticles concentration is investigated in both cases. We also explore if the incorporation of additional TiO2 scatterers could enhance the random laser operation of the studied systems.