Temperature and wavelength dependence of the thermo-optical properties of tellurite and chalcogenide glasses

The refractive index and the temperature coefficient of the optical path length change of tellurite (80TeO(2):20Li(2)O) and chalcogenide glasses (72.5Ga(2)S(3):27.5La(2)O(3)) were determined as a function of temperature (up to 150 degrees C) and wavelength (in the range between 454 and 632.8 nm). The tellurite glass exhibits the usual refractive index dispersion in the wavelength range analyzed, while anomalous refractive index dispersion was observed for the chalcogenide glass between 454 and 530 nm. The dispersion parameters were determined by means of the single-effective oscillator model. In addition, a strong dependence of the temperature coefficient of the optical path length on the photon energy and temperature was found for the chalcogenide glass. The latter was correlated to the shift of the optical band gap (or electronic edge) with temperature, which was interpreted by the electron-phonon interaction model. (C) 2007 American Institute of Physics.

Strong infrared spectral broadening in low-loss As-S chalcogenide suspended core microstructured optical fibers

We report the fabrication and characterization of the first guiding chalcogenide As(2)S(3) microstructured optical fibers (MOFs) with a suspended core. At 1.55 mu m, the measured losses are approximately 0.7 dB/m or 0.35 dB/m according to the MOF core size. The fibers have been designed to present a zero dispersion wavelength (ZDW) around 2 mu m. By pumping the fibers at 1.55 mu m, strong spectral broadenings are obtained in both 1.8 and 45-m-long fibers by using a picosecond fiber laser. (C) 2010 Optical Society of America

Frequency upconversion in a Pr(3+) doped chalcogenide glass containing silver nanoparticles

We report on orange-to-blue frequency upconversion (UC) in Pr(3+) doped chalcogenide glass (Ga(10)Ge(25)S(65)) doped with Ag(2)S and heat treated under different conditions to nucleate silver nanoparticles (NPs). The experiments were performed using 7 ns pulses from a dye laser that operates at similar to 590 nm, in resonance with the (3)H(4)->(1)D(2) transition of Pr(3+) ions. The enhancement observed in the UC emission at similar to 494 nm, ascribed as (3)P(0)->(3)H(4) transition of the Pr(3+) ion, is attributed to the large local field acting on the emitting ions due to the presence of the metallic NPs. (C) 2008 American Institute of Physics.

Microstructured chalcogenide optical fibers from As2S3 glass: towards new IR broadband sources

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

Nonlinear effects generation in suspended core chalcogenide fibre

In this work we report our achievements in the elaboration and optical characterizations of low-losses suspended core optical fibers elaborated from As2S3 glass. For preforms elaboration, alternatively to other processes like the stack and draw or extrusion, we use a process based on mechanical drilling. The drawing of these drilled performs into fibers allows reaching a suspended core geometry, in which a 2 μm diameter core is linked to the fiber clad region by three supporting struts. The different fibers that have been drawn show losses close to 0.9 dB/m at 1.55 μm. The suspended core waveguide geometry has also an efficient influence on the chromatic dispersion and allows its management. Indeed, the zero dispersion wavelength, which is around 5 μm in the bulk glass, is calculated to be shifted towards around 2μm in our suspended core fibers. In order to qualify their nonlinearity we have pumped them at 1.995 μm with the help of a fibered ns source. We have observed a strong non linear response with evidence of spontaneous Raman scattering and strong spectral broadening. © 2011 SPIE.

Recent developments in chalcogenide photonic crystal fibres

Elaboration of low-losses highly non linear chalcogenide optical fibers for the generation of efficient non linear effects in the infrared remains a challenge. In recent years, much work has been devoted to the study of microstructured optical fibers (MOFs) with different designs and various elaboration processes. Their background losses were typically of several dB/m. © 2011 IEEE.

Study of the glass transition temperature of as-s glasses for the fabrication of chalcogenide optical fibers

Values of glass transition temperature (Tg) and of linear expansion coefficient (α) for Asx S100-x glasses were measured in the range of concentrations 35 × 42. Because of the importance of the glass formation region 35 × 42 for the optical fibers elaboration, special attention was made on high-pure Asx S100-x glasses. For the glass in the range of 35 × 38, we measure Tg with the interval of x equal to 1 at.% of arsenic. We also measured the Tg values with the interval of x equal to 0.5 at.% of As. We obtained nonlinear behavior of Tg, reflecting the change in molecular composition of As-S glass in the glass composition range studied. The control of such parameters is important to produce optical fibers with specific numerical aperture. © 2013 The American Ceramic Society and Wiley Periodicals, Inc.

Mid-infrared supercontinuum generation in a suspended-core As2S3 chalcogenide microstructured optical fiber

We demonstrate the supercontinuum (SC) generation in a suspended-core As2S3 chalcogenide microstructured optical fiber (MOF). The variation of SC is investigated by changing the fiber length, pump peak power and pump wavelength. In the case of long fibers (20 and 40 cm), the SC ranges are discontinuous and stop at the wavelengths shorter than 3500 nm, due to the absorption of fiber. In the case of short fibers (1.3 and 2.4 cm), the SC ranges are continuous and can extend to the wavelengths longer than 4 μm. The SC broadening is observed when the pump peak power increases from 0.24 to 1.32 kW at 2500 nm. The SC range increases with the pump wavelength changing from 2200 to 2600 nm, corresponding to the dispersion of As2S3 MOF from the normal to anomalous region. The SC generation is simulated by the generalized nonlinear Schrödinger equation. The simulation includes the SC difference between 1.3 and 2.4 cm long fiber by 2500 nm pumping, the variation of SC with pump peak power in 2.4 cm long fiber, and the variation of SC with pump wavelength in 1.3 cm long fiber. The simulation agrees well with the experiment.

IR-visible upconversion and thermal effects in Pr3+/Yb3+-codoped Ga2O3 : La2S3 chalcogenide glasses

IR-visible upconversion fluorescence spectroscopy and thermal effects in pr(3+)/Yb3+-codoped Ga2O3:La2S3 chalcogenide glasses excited at 1.064 mum is reported. Intense visible upconversion emission in the wavelength region of 480-680 nm peaked around 500, 550, 620 and 660 nm is observed. Upconversion excitation of the Pr3+ excited-state visible emitting levels is achieved by st combination of phonon-assisted absorption, energy-transfer and phonon-assisted excited-state absorption processes. A threefold upconversion emission enhancement induced by thermal effects when the codoped sample was heated in the temperature range of 20-200 degreesC is demonstrated. The thermal-induced enhancement is attributed to a multiphonon-assisted anti-Stokes process which takes place in the excitation of the ytterbium and excited-state absorption of the praseodymium. The thermal effect is modelled by conventional rate equations considering temperature-dependent effective absorption cross-sections for the F-2(7/2)-F-2(5/2) ytterbium transition and (1)G(4)-P-3(0) praseadymium excited-state absorption, and it is shown to agree very well with experimental results. Frequency upconversion in singly Pr3+-doped samples pumped at 836 nm and 1.064 mum in a two-beam configuration is also examined.

Structure and Ionic Conductivity in the Mixed-Network Former Chalcogenide Glass System [Na2S](2/3)[(B2S3)(x)(P2S5)(1-x)](1/3)

Glasses in the system [Na2S](2/3)[(B2S3)(x)(P2S5)(1-x)](1/3) (0.0 <= x <= 1.0) were prepared by the melt quenching technique, and their properties were characterized by thermal analysis and impedance spectroscopy. Their atomic-level structures were comprehensively characterized by Raman spectroscopy and B-11, P-31, and Na-23 high resolution solid state magic-angle spinning (MAS) NMR techniques. P-31 MAS NMR peak assignments were made by the presence or absence of homonuclear indirect P-31-P-31 spin-spin interactions as detected using homonuclear J-resolved and refocused INADEQUATE techniques. The extent of B-S-P connectivity in the glassy network was quantified by P-31{B-11} and B-11{P-31} rotational echo double resonance spectroscopy. The results clearly illustrate that the network modifier alkali sulfide, Na2S, is not proportionally shared between the two network former components, B and P. Rather, the thiophosphate (P) component tends to attract a larger concentration of network modifier species than predicted by the bulk composition, and this results in the conversion of P2S74-, pyrothiophosphate, Na/P = 2:1, units into PS43-, orthothiophosphate, Na/P = 3:1, groups. Charge balance is maintained by increasing the net degree of polymerization of the thioborate (B) units through the formation of covalent bridging sulfur (BS) units, B S B. Detailed inspection of the B-11 MAS NMR spectra reveals that multiple thioborate units are formed, ranging from neutral BS3/2 groups all the way to the fully depolymerized orthothioborate (BS33-) species. On the basis of these results, a comprehensive and quantitative structural model is developed for these glasses, on the basis of which the compositional trends in the glass transition temperatures (T-g) and ionic conductivities can be rationalized. Up to x = 0.4, the dominant process can be described in a simplified way by the net reaction equation P-1 + B-1 reversible arrow P-0 + B-4, where the superscripts denote the number of BS atoms for the respective network former species. Above x = 0.4, all of the thiophosphate units are of the P-0 type and both pyro-(B-1) and orthothioborate (B-0) species make increasing contributions to the network structure with increasing x. In sharp contrast to the situation in sodium borophosphate glasses, four-coordinated thioborate species are generally less abundant and heteroatomic B-S-P linkages appear to not exist. On the basis of this structural information, compositional trends in the ionic conductivities are discussed in relation to the nature of the charge-compensating anionic species and the spatial distribution of the charge carriers.

Simulative Investigation on the Electronic, Vibrational and Optical Properties of the Ge2Sb2Te5 Chalcogenide

Chalcogenides are chemical compounds with at least one of the following three chemical elements: Sulfur (S), Selenium (Sn), and Tellurium (Te). As opposed to other materials, chalcogenide atomic arrangement can quickly and reversibly inter-change between crystalline, amorphous and liquid phases. Therefore they are also called phase change materials. As a results, chalcogenide thermal, optical, structural, electronic, electrical properties change pronouncedly and significantly with the phase they are in, leading to a host of different applications in different areas. The noticeable optical reflectivity difference between crystalline and amorphous phases has allowed optical storage devices to be made. Their very high thermal conductivity and heat fusion provided remarkable benefits in the frame of thermal energy storage for heating and cooling in residential and commercial buildings. The outstanding resistivity difference between crystalline and amorphous phases led to a significant improvement of solid state storage devices from the power consumption to the re-writability to say nothing of the shrinkability. This work focuses on a better understanding from a simulative stand point of the electronic, vibrational and optical properties for the crystalline phases (hexagonal and faced-centered cubic). The electronic properties are calculated implementing the density functional theory combined with pseudo-potentials, plane waves and the local density approximation. The phonon properties are computed using the density functional perturbation theory. The phonon dispersion and spectrum are calculated using the density functional perturbation theory. As it relates to the optical constants, the real part dielectric function is calculated through the Drude-Lorentz expression. The imaginary part results from the real part through the Kramers-Kronig transformation. The refractive index, the extinctive and absorption coefficients are analytically calculated from the dielectric function. The transmission and reflection coefficients are calculated using the Fresnel equations. All calculated optical constants compare well the experimental ones.

Synthesis and characterization of metal-chalcogenide MQ 2-Nanoparticles (M = Mo, W, Zr; Q = S, O)

Here, we present the adaptation and optimization of (i) the solvothermal and (ii) the metal-organic chemical vapor deposition (MOCVD) approach as simple methods for the high-yield synthesis of MQ2 (M=Mo, W, Zr; Q = O, S) nanoparticles. Extensive characterization was carried out using X-ray diffraction (XRD), scanning and transmission electron micros¬copy (SEM/TEM) combined with energy dispersive X-ray analysis (EDXA), Raman spectroscopy, thermal analyses (DTA/TG), small angle X-ray scattering (SAXS) and BET measurements. After a general introduction to the state of the art, a simple route to nanostructured MoS2 based on the decomposition of the cluster-based precursor (NH4)2Mo3S13∙xH2O under solvothermal conditions (toluene, 653 K) is presented. Solvothermal decomposition results in nanostructured material that is distinct from the material obtained by decomposition of the same precursor in sealed quartz tubes at the same temperature. When carried out in the presence of the surfactant cetyltrimethyl¬ammonium bromide (CTAB), the decomposition product exhibits highly disordered MoS2 lamellae with high surface areas. The synthesis of WS2 onion-like nanoparticles by means of a single-step MOCVD process is discussed. Furthermore, the results of the successful transfer of the two-step MO¬CVD based synthesis of MoQ2 nanoparticles (Q = S, Se), comprising the formation of amorphous precursor particles and followed by the formation of fullerene-like particles in a subsequent annealing step to the W-S system, are presented. Based on a study of the temperature dependence of the reactions a set of conditions for the formation of onion-like structures in a one-step reaction could be derived. The MOCVD approach allows a selective synthesis of open and filled fullerene-like chalcogenide nanoparticles. An in situ heating stage transmission electron microscopy (TEM) study was employed to comparatively investigate the growth mechanism of MoS2 and WS2 nanoparticles obtained from MOCVD upon annealing. Round, mainly amorphous particles in the pristine sample trans¬form to hollow onion-like particles upon annealing. A significant difference between both compounds could be demonstrated in their crystallization conduct. Finally, the results of the in situ hea¬ting experiments are compared to those obtained from an ex situ annealing process under Ar. Eventually, a low temperature synthesis of monodisperse ZrO2 nanoparticles with diameters of ~ 8 nm is introduced. Whereas the solvent could be omitted, the synthesis in an autoclave is crucial for gaining nano-sized (n) ZrO2 by thermal decomposition of Zr(C2O4)2. The n-ZrO2 particles exhibits high specific surface areas (up to 385 m2/g) which make them promising candidates as catalysts and catalyst supports. Co-existence of m- and t-ZrO2 nano-particles of 6-9 nm in diameter, i.e. above the critical particle size of 6 nm, demonstrates that the particle size is not the only factor for stabilization of the t-ZrO2 modification at room temperature. In conclusion, synthesis within an autoclave (with and without solvent) and the MOCVD process could be successfully adapted to the synthesis of MoS2, WS2 and ZrO2 nanoparticles. A comparative in situ heating stage TEM study elucidated the growth mechanism of MoS2 and WS2 fullerene-like particles. As the general processes are similar, a transfer of this synthesis approach to other layered transition metal chalcogenide systems is to be expected. Application of the obtained nanomaterials as lubricants (MoS2, WS2) or as dental filling materials (ZrO2) is currently under investigation.

The magnetic exchange interactions in chromium chalcogenide spinels

The chromium chalcogenide spinels, MCr2X4 (M = Zn, Cd, Hg; X = O, S, Se), have been the subject of considerable interest in recent years. In each case the crystal structure is that of a normal spinel with the chromium ions exclusively occupying the octahedral (B) sites, so that when diamagnetic ions are located at the tetrahedral (A) sites the only magnetic interactions present are those between B-site ions. Despite such apparently simple circumstances a rich variety of magnetic behaviour is exhibited. For the oxides the ground state spin configurations are antiferromagnetic whilst for the selenides ferromagnetic interactions dominate and several authors have drawn attention to the fact that the nature of the dominant interaction is a function of the nearest neighbour chromium - chromium separation. However, at least two of the compounds exhibit spiral structures and it has been proved difficult to account for the various spin configurations within a unified theory of the magnetic interactions involved. More recently, the possibility of formulating a simplified interpretation of the magnetic interactions has been provided by the discovery that the crystal struture of spinels does not always conform to the centrosymmetrical symmetry Fd3m that has been conventionally assumed. The deviation from this symmetry is associated with small < 111> displacements of the octahedrally coordinated metal ions and the structures so obtained are more correctly referred to the non-centrosymmetrical space group F43m. In the present study, therefore, extensive X-ray diffraction data have been collected from four chromium chalcogenide specimens and used to refine the corresponding structural parameters assuming F43m symmetry and also with conventional symmetry. The diffracted intensities from three of the compounds concerned cannot be satisfactorily accounted for on the basis of conventional symmetry and new locations have been found for the chromium ions in these cases. It is shown, however, that these displacements in chromium positions only partially resolve the difficulties in interpreting the magnetic behaviour. A re-examination of the magnetic data from different authors indicates much greater uncertainty in their measurements than they had claimed. By taking this into consideration it is shown that a unified theory of magnetic behaviour for the chromium chalcogenide spinels is a real possibility.

Dispersion engineering of highly nonlinear chalcogenide suspended-core fibers

Chalcogenide optical fibers are currently undergoing intensive investigation with the aim of exploiting the excellent glass transmission and nonlinear characteristics in the near- and mid-infrared for several applications. Further enhancement of these properties can be obtained, for a particular application, with optical fibers specifically designed that are capable of providing low effective area together with a properly tailored dispersion, matching the characteristics of the laser sources used to excite nonlinear effects. Suspended-core photonic crystal fibers are ideal candidates for nonlinear applications, providing small-core waveguides with large index contrast and tunable dispersion. In this paper, the dispersion properties of As2S3 suspended-core fibers are numerically analyzed, taking into account, for the first time, all the structural parameters, including the size and the number of the glass bridges. The results show that a proper design of the cladding struts can be exploited to significantly change the fiber properties, altering the maximum value of the dispersion parameter and shifting the zero-dispersion wavelengths over a range of 400 nm.