Synthesis, Structure and Non-Linear Optical Properties of Tellurium Oxide Based Glasses and Glass-Ceramics
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SPC TS Synthesis, structure and non-linear optical properties of tellurium oxide based glasses and glass-ceramics. David HAMANI, Olivier MASSON, Maggy COLAS, Jean-René DUCLERE, Abid BERGHOUT, Gaëlle DELAIZIR, Olivier NOGUERA, Andreï MIRGORODSKY, Philippe THOMAS. Science of Ceramic Processes and of Surface Treatments laboratory, UMR 7315 CNRS, European Ceramic Center, 12 rue Atlantis, 87068 Limoges Cedex, France INDO-FRENCH Workshop on Glasses and Glass-Ceramics. INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Science of Ceramic Processes and of Surface Treatments UMR CNRS 7315 University of Limoges – ENSCI- CNRS www.unilim.fr/spcts Director : T. Chartier . Paris Limoges European Ceramic Center STAFF 154 people - 84 permanents 47 Professors and Associate Professors 13 CNRS researchers 24 Engineers and Technicians 70 Ph.D. Students and Post-docs INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS SPCTS is a research laboratory Involving in key domains such as: - micro/nanotechnologies ex : «nanostructured materials», MEMs - materials for electronic and optoelectronic (TIC) ex : glass with high factor of non-linearity - new technologies of energy ex : Solid oxide fuel cells (SOFC) Syngaz - Nuclear - biomaterials ex : apatites, carbonates, implants - environment ex : matrix for trapping heavy metals filtration INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Σ-LIM: LABEX : Ceramic materials and components specific to integrated, secure and intelligent communication systems 7 Complementary themes 4 themes 3 themes «heart of competences» « interfaces » National Research ENERGY and Innovation - New sources Material and ceramic Chair - New generations of processes Strategy (SNRI) nuclear reactors - Energy saving Chair Axe 3 Information, communication GEMH Hôtel à projets à Hôtel Electronic and photonic and nanotechnologies components and circuits HEALTH Axe 1 - Autonomy Moddeling Health, quality of life, alimentation - Treatment/prevention And biotechnologies Chair Chair - Tissue engineering Axe 2 Electronic and photonic Environnemental emergency secure fonctions and ecotechnologies CHU and systems SAFETY Challenge of multidisciplinary knowledge: Innovative science and technology on - Property Mater and materials - Place - People INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Synthesis, structure and non-linear optical properties of tellurium oxide based glasses and glass-ceramics. David HAMANI, Olivier MASSON, Maggy COLAS, Jean-René DUCLERE, Abid BERGHOUT, Gaëlle DELAIZIR, Olivier NOGUERA, Andreï MIRGORODSKY, Philippe THOMAS. Science of Ceramic Processes and of Surface Treatments laboratory, UMR 7315 CNRS, European Ceramic Center, 12 rue Atlantis, 87068 Limoges Cedex, France INDO-FRENCH Workshop on Glasses and Glass-Ceramics. INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Outline I. TeO2-based glasses interest II. Synthesis III. Structural characterization IV. Modelling of the non-linear optical properties V. Non-linear optical properties (3rd -order and second harmonic generation) INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Background Strong Demands on All optical network; very reliable and ultra-fast, optical devices Investigations on transparent glasses with very high third-order non-linear properties ・Optical switching, Four-wave mixing frequency converter Higher third-order optical susceptibility, χ(3) ・Raman Amplification Higher Raman Intensity TeO2-based glasses are promising INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS TeO 2-based glasses interest ・ Good visible and infrared light transmittance (up to 6 µm) ・ Adjustable composition, low melting point, good chemical and thermal stability χ(3) ・ High refractive linear (n 0) and non-linear ( n 2, ) indices ・ Low linear ( α) and nonlinear ( β) absorption coefficients ・ Second harmonic generation (frequency doubling) by thermal or optical poling ・ High Raman gain coefficients (60 times as large as silicate glass) INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS TeO 2-based glasses interest n /n SiO Measured at 1.5 µm Non-linear Index 2 2 2 Sulfide Selenide 100 Chalcogenide glasses Tellurite glasses 10 Oxide d 0ions(Ti 4+, Nb5+ , W6+ ) Silicates, Borates, Phosphates glasses Silicate, Borate, 1 Phosphate glasses Fluoride Fluoride glasses 0.1 INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Synthesis TeO 2-based materials: new glass forming domains Processing Melting in platinum crucibles Glassy domains at 800°C Shaping: air-quenching of the melt by flattening between two brass blocks separated by a brass ring 10mm Annealing / Polishing INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Synthesis TeO 2-based glass ceramics - Improvement of the non-linear optical properties - Strengthen the mechanical properties of the glass - Keep the optical transparency . Conventional annealing in a classical furnace . Spark Plasma Sintering (SPS) - Non conventional synthesis method for glass-ceramic preparation - Many opportunities (research projects in progress including the understanding of the mechanisms involved in the sintering of glass) - Partial devitrification and shaping in 1 step - Higher crystallization kinetics rate in comparison with a heat treatment in a conventional furnace (×100) INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Structural characterization TeO 2 based glasses: promising materials for optoelectronics applications Origin of these properties • Te(IV) electronic lone pair (Te 4+ : [Kr] 4d 10 5s 2) • influence of the structure (short and medium range order) → need of a better understanding of the actual structure of glasses Raman spectra of glasses in the system x Tl 2O - (100-x) TeO 2 - Raman and IR spectroscopies 725 TeO 3 trigonal pyramid - Modeling: lattice Dynamics (Lady) 295 660 450 5s 2 loned x=50 active pair x=33 - EXAFS, XANES x=29 x=25 Intensity (a.u.) (a.u.) (a.u.) IntensityIntensityIntensity x=21 x=18 - X-ray and neutron diffraction x=14 x=11 5s 2 loned x= 8 active pair - X-ray and neutron Total Scattering x= 0 200 300 400 500 600 700 800 -1 TeO disphenoid - Atomic scale Modelling Frequency (cm ) 4 INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Structural characterization X-ray and neutron Total Scattering : pair distribution function analysis G(r) (Pair distribution function) : • Peak position -> interatomic distance • Peak area -> coordination number • Peak width -> disorder Direct space X-ray total scattering PDF neutron total scattering PDF Total scattering diffractometer at SPCTS INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Structural characterization Structure of tellurite glasses: use of Reverse Monte Carlo method Local order in the TeO 2-based crystallized phases The local environment of the tellurium (IV) atom is asymmetric due to the steric effect of its lone pair TeO 4 The structural units vary with the addition of a modifier oxide M xOy (contrary to silicates) TeO 3 TeO TeO 3+1 5 3/18 INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Structural characterization use of RMC method The starting structural configuration : comparative study of the TeO 2 glass with TeO 2 polymorphs α -TeO 2 (calculated) β -TeO 2 (calculated) γ -TeO 2 (calculated) TeO 2 glass (experimental) • 1.9 Å: common peak for the 4 compounds (structural units) γ • at medium range order: similitude between the TeO 2 glass and the -TeO 2 polymorph The TeO 2 glass structure is closer to the γ-TeO 2 structure than the traditionally used α-TeO 2 structure 14/18 INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Structural characterization RMC: Our short range structural model Optimized parameters = − c j C1 ∑∑ Vkj V j j k Ajj’ rjj’ cj = 1 ()− ρ O-O 711.0 0.324 1.0 C2 ∑∑∑∑ Ajj ' exp Rkk ' / jj ' 2 j k j'' k O-LP 637.1 0.307 1.0 Te-O 3929.0 0.236 1.0 • Bond valence constraints • + Lone-pair steric effect constraints The obtained parameters were tested by reproducing known structural units => Application to RMC study of TeO 2 glass INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Structural characterization RMC modelling of TeO 2 glass γ • starting structural configuration: -TeO 2 structure • constraints of our structural model • fit performed against the experimental data RMC simulation box S(Q) Q (Å -1) Q (Å -1) The experimental and calculated data match number of mean valence mean valence satisfaction of atom type γ atoms ( -TeO 2) (TeO 2 glass) the constraint Te 876 3.9 3.8 92 % O 1792 -1.9 -1.9 90 % 16/18 INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Structural characterization RMC modelling of TeO 2 glass Partial Pair Distribution Functions Angular distributions γ TeO 2 Single bridges β TeO 2 Density Density ofprobability Doubles bridges Density Density ofprobability - characteristic