Approche multimodale par spectroscopies IR, Raman et hyper-raman/hyper-rayleigh: Relation structure/propriétés dans les verres TeO2-TaO5/2-Zn0

Size: px

Start display at page:

Download "Approche multimodale par spectroscopies IR, Raman et hyper-raman/hyper-rayleigh: Relation structure/propriétés dans les verres TeO2-TaO5/2-Zn0"

Della Dickerson
6 years ago
Views:

1 Approche multimodale par spectroscopies IR, Raman et hyper-raman/hyper-rayleigh: Relation structure/propriétés dans les verres TeO-TaO5/-Zn0 Vincent Rodriguez University of Bordeaux / Department of Chemistry Institut des Sciences Moléculaires (ISM), UMR 555 CNRS FRANCE vincent.rodriguez@u-bordeaux.fr gsm.ism.u-bordeaux1.fr

2 Approche multimodale par spectroscopies IR, Raman et hyper-raman/hyper-rayleigh: Relation structure/propriétés dans les verres TeO-TaO5/-Zn0 G. Guéry (PhD work) K. Richardson CREOL, UCF, FL, USA T. Cardinal ICMCB, U Bordeaux, FR M. Dussauze, F. Adamietz, ISM, U Bordeaux, FR V. Rodriguez

3 Quadratic Nonlinear Optics P = µ + µ ( w ) + µ ( w ) + µ (3 w) +... (0) (1) () (3) i i i i i Molecular Dipolar electric response ( ) E ( ) µ () ( w) = b E w w i ijk j k ( ) ( ) ( ) µ (3) (3 w) = g E w E w E w i ijkl j k l g: second hyperpolarizability b: first hyperpolarizability ( ) µ (1) ( w) = a E w A D a: polarizability i ij j e T. Verbiest, K. Clays, V. Rodriguez, «Second-order nonlinear optical characterizations techniques : An Introduction», CRC Press, Francis & Taylor Group, Boca Raton, Verre Bordeaux 016, Nov 016, ICMCB, Pessac

4 Quadratic Nonlinear Optics ur uuur ur ur ur ur ur ur (0) P = µ + ae+ bee+ geee+... Symmetry rules Isotropic, quadrupolar Isotropic, quadrupolar, hexacadecapolar a: polarizability g: second hyperpolarizability Always active /even terms Dipolar, octupolar b: first hyperpolarizability 1-D/push-pull Octupolar noncentrosymmetric molecules /odd term NH NH p-nitroaniline (PNA) O N NO Triaminotrinitrobenzene (TATB) NH NH NO NO 4 Verre Bordeaux 016, Nov 016, ICMCB, Pessac

Multimodal techniques Extended vibrational

harmonic Light Scattering /hyper-rayleigh

i ijk j k V. Rodriguez, J. Raman Spectrosc.

5 Multimodal techniques Extended vibrational studies: multipolar activity IR: Infrared RS: Raman scattering (spontaneous) HRS: hyper-raman scattering (spontaneous) HLS: harmonic Light Scattering /hyper-rayleigh (spontaneous) ( ) E ( ) µ () ( w) = b E w w i ijk j k V. Rodriguez, J. Raman Spectrosc.,01, 43, Verre Bordeaux 016, Nov 016, ICMCB, Pessac

Hyper-Raman/hyper-Rayleigh and Raman setup Hyper-Raman/hyper-Rayleigh setup Z IwyV Y l/4 Polarization-resolved technique y/ l/ X -90 y 0 45 90 Laser Source : Nd:YVO4 @1064 nm, 65 ps, khz, E < 50 µj

6 Hyper-Raman/hyper-Rayleigh and Raman setup Hyper-Raman/hyper-Rayleigh setup Z IwyV Y l/4 Polarization-resolved technique y/ l/ X -90 y Laser Source : nm, 65 ps, khz, E < 50 µj Raman configuration (pulsed mode) Z An optimized setup for the study of liquids, solids IwyV Y X -45 Frequency doubling unit V. Rodriguez, J. Raman Spectrosc.,01, 43, Verre Bordeaux 016, Nov 016, ICMCB, Pessac

7 Extended vibrational studies: multipolar activity A simple example Combining the 3 techniques RS I VV +I HV (a.u.) e* RS A g (CCl scis) B 1g (CCl rock) A g (CCl s-str) B g (CCl a-str) B 1g (CCl a-str) A g (CC str) Pure liquid C Cl 4 Group symmetry D h : G IR = [B 1u Å B u Å B 3u ] G RS = [3 A g ]Å[ B 1g Å B g ] G HRS = [G IR ]Å[A u (silent mode)] IR HRS RS e hyper-rayleigh cm -1 1 (dipolar inactive) A (CCl twist) u B (CCl wag) 1u B (CCl s-str) 3u B (CCl a-str) u HRS cm -1 7 IR Transmittance IR B (CCl s-str) 3u B (CCl a-str) u cm -1 Verre Bordeaux 016, Nov 016, ICMCB, Pessac

8 Extended vibrational studies: multipolar activity Symmetry rules in any isotropic media including glasses DP = DP RS RS a µ 1 a + a 3 15 a µ 1 + a 10 α α // J= 0 J= ^ J= ^ 3rRS aj = ; r RS = = r // RS aj = 0 RAMAN (, 3/4) : quadrupole DP HRS β µ β + β β µ β + β β + DP HRS = = β ë // J= 1 J= 3 ^ J= 1 J= 3 ^ 1 é7 1r ù HRS bj = 3 ; HRS 9 ê r 7+ r ú = // HRS bj = 1 û HYPER-RAMAN (, /3) : octupole (0, 1/9) : dipole I I VV HV = = I I^ Raman: sensible to density fluctuation P Hyper-Raman: sensible to orientational correlation (rotation) (0, 0) : isotropic r RS r HRS Verre Bordeaux 016, Nov 016, ICMCB, Pessac

9 Extended vibrational studies: multipolar activity Hyper-Raman/hyper-Rayleigh setup Z I w yv Polarization-resolved technique New additional TO-LO selection rules in hyper-raman X Y l/4 l/ Vibrational Multipolar Decomposition (with reduced RS and HRS intensities: at least corrected from Temperature) Isotropic J RS I I I // ^ ( = 0: ) l= 0 µ + 3 RS -4 RS 9 ( ) ( ) Dipolar TO J HRS I I I IR e n Abs n n TO VV HV " : ( = 1: ) l= 1 µ + HRS - 3 HRS ; ( ): µ / : LO ( J = 1: HRS) I µ+ I - I ; ( IR): -Im 1 LO VH CH l= 1 HRS HRS Quadrupolar ( J = : RS) I µ I l= Octupolar ( J = 3: HRS) I µ - I + 9I ^ RS VV HV l= 3 HRS HRS V. Rodriguez, J. Raman Spectrosc.,01, 43, 67. ( e ) Hyper-Raman intensity Verre Bordeaux 016, Nov 016, ICMCB, Pessac ZZZ Z(ZZ+YY+ZY+YZ) ZYY TO TO+LO TO HV: case 3 CV: case 6 VV: case wavenumber / cm -1 SiO SiO silica glass silica glass

10 Hyper-Rayleigh Scattering: a unique tool to elucidate the (Nano) Structure of materials Z I yv w Polarization-resolved technique y/ X Y l/4 l/ gives an indication of the dipolar /octupolar nature of the ESU: ESU: Elementary Structural Unit y ( DR = I I ) VV HV I VV I HV v-sio DR=3/ Octupolar Regular SiO tetrahedra I VV I HV v-na 0-SiO DR=.34 > 3/ Dipolar/octupolar Distorted SiO tetrahedra Verre Bordeaux 016, Nov 016, ICMCB, Pessac

Hyper-Rayleigh Scattering: a unique tool to elucidate the (Nano) Structure of materials sensible to the special extent of the ESU Structural Incoherent response Structural Coherent response

11 Hyper-Rayleigh Scattering: a unique tool to elucidate the (Nano) Structure of materials sensible to the special extent of the ESU Structural Incoherent response Structural Coherent response Interaction X X No interaction ~ dilution X X Sodium Niobium Borophosphate oxide glasses (BPNx) (1-x)[0,95NaPO 3 +0,05Na B 4 O 7 ]+xnb O 5 I µ [ N ] b w Incoherent X X I µ [ N ] b w coherent X X sensible to nonlocal response of sizable nanoclusters (d> ~15 nm) (Quadrupolar effective electric response) Coherent response from highly correlated nanoclusters of NbO 3 11 Verre Bordeaux 016, Nov 016, ICMCB, Pessac

12 Te-based Glasses for Raman gain P = µ + a E + b E E + g E E E +... (0) i i ij j ijk j k ijkl j k l Glass Families for nonlinear optical applications Measured at 1.5 µm Third-order nonlinear polarization (Stimulated Raman Gain-SRG) Sulfide, Selenide Oxide n /n SiO χ (3) ) χ (3) SiO 100 Chalcogenide 10 Tellurite ChG and Tellurite glasses offer: Good near/mid-infrared transparency, Modest melting temperatures and good glass stability, High linear and nonlinear refractive indices. d 0 ions (Ti 4+, Nb 5+, W 6+ ) in silicate, borate, phosphate matrices 1 Silicates, borates, phosphates Fluoride 0,1 Fluoride 1 Verre Bordeaux 016, Nov 016, ICMCB, Pessac

13 Te-based Glasses for Raman gain Te 4+ : (Tellurite) TeO 4 trigonal bipyramidal units TeO 3+1 disphenoids TeO 3 trigonal pyramidal units TeO chain-like arrangement, observed in paratellurite α-teo V. Rodriguez et al., Hyper-Raman and Raman scattering in paratellurite TeO. Journal of Raman Spectroscopy 013, 44, Verre Bordeaux 016, Nov 016, ICMCB, Pessac

14 Te-based Glasses for Raman gain TeO -TaO 5/ -ZnO glass system (80+x)TeO -(0-x)TaO 5/ Glass modifier impact of the glass structure? Trade-off in the choice of the glass modifiers: ZnO helps for the fiber fabrication but what about the consequences? Raman gain response? NLO responses? 80TeO -(0-y)TaO 5/ -yzno Glass former Effect of the glass polymerization? V. Rodriguez et al., JPC C 016, 10, vibrational responses and signatures? G. Guéry et al., Int. J. of Applied Glass Science 014, 5(), 178 G. Guery et al., Chemical Physics Letters 01, 554, Verre Bordeaux 016, Nov 016, ICMCB, Pessac

IR Te-based Glasses for Raman gain IR Extended vibrational studies: RS RS-VV HRS-VV Dipolar Isotropic, Quadrupolar Dipolar, Octupolar 90TeO -10TaO 90TeO -10TaO 5/ 5/ HRS 90TeO -10TaO 5/ 85TeO -15TaO

15 IR Te-based Glasses for Raman gain IR Extended vibrational studies: RS RS-VV HRS-VV Dipolar Isotropic, Quadrupolar Dipolar, Octupolar 90TeO -10TaO 90TeO -10TaO 5/ 5/ HRS 90TeO -10TaO 5/ 85TeO -15TaO 5/ 80TeO -0TaO 5/ 85TeO -15TaO 5/ 80TeO -0TaO 5/ 85TeO -15TaO 5/ 80TeO -0TaO 5/ Binary TeO -TaO 5/ 80TeO -15TaO -5Zn0 5/ 80TeO -15TaO -5ZnO 5/ 80TeO -10TaO -10ZnO 5/ 80TeO -10TaO -10ZnO 5/ 80TeO -5TaO -15ZnO 5/ 80TeO -5TaO -15ZnO 5/ ternary TeO -TaO 5/ -ZnO 80TeO -15TaO 5/ -5ZnO 80TeO -10TaO 5/ -10ZnO 80TeO -5TaO 5/ -15ZnO Te-O-Te TeO 4 TeO 3+1 TaO 6 Wavenumber (cm-1) Wavenumber (cm-1) Verre Bordeaux 016, Nov 016, ICMCB, Pessac Wavenumber (cm-1) Vibrational spectra (IR, RS and HRS) are governed by the tellurite network à Need of spectrum deconvolution for obtaining the real species contributions. V. Rodriguez et al., JPC C 016, 10, 3144.

Te-based Glasses for Raman gain Extended vibrational studies: one model, five spectra e" n as 90TeO -10TaO 5/ e" n as 80TeO -5TaO 5/ -15ZnO Dipolar TeO 4 Isotropic, Quadrupolar RS: VV n s RS: HV RS:

16 Te-based Glasses for Raman gain Extended vibrational studies: one model, five spectra e" n as 90TeO -10TaO 5/ e" n as 80TeO -5TaO 5/ -15ZnO Dipolar TeO 4 Isotropic, Quadrupolar RS: VV n s RS: HV RS: VV n s RS: HV Dipolar, Octupolar HRS: VV n s n as HRS: HV HRS: VV n s n as HRS: HV TeO Wavenumber (cm -1 ) Wavenumber (cm -1 ) Wavenumber (cm -1 ) Wavenumber (cm -1 ) 16 Verre Bordeaux 016, Nov 016, ICMCB, Pessac

17 Te-based Glasses for Raman gain (80+x)TeO -(0-x)TaO 5/ Glass modifier impact of the glass structure? 80TeO -(0-y)TaO 5/ -yzno I VV I HV Glass former Effect of the glass polymerization? No change with composition DR ~ 3.8 (more dipolar) No change of ESU structure Structure insights from hyper-rayleigh scattering HLS intensity normalized to SiO I (80+x)TeO -(0-x)TaO 5/ µ [ N ] b w Incoherent X X 80TeO -(0-y)TaO 5/ -yzno [Te] x 10 7 (mol/m 3 ) Structural incoherent response: Behavior of «diluted-like ESU» TeO 4 TeO Verre Bordeaux 016, Nov 016, ICMCB, Pessac

18 Te-based Glasses for Raman gain (80+x)TeO -(0-x)TaO 5/ Glass modifier impact of the glass structure? 80TeO -(0-y)TaO 5/ -yzno Glass former c (1) ( n ) = é -1 4pù ë nm Introduction of tantalum oxide slightly decreases the susceptibilities Effect of the glass polymerization? LO and NLO responses (HLS,Raman gain and Linear susceptibility) (3) nm (660 cm -1 ) 80TeO -0TaO 5/ Introduction of zinc oxide drastically decreases the susceptibilities 80TeO -5TaO 5/ -15ZnO 90TeO -10TaO 5/ Raman gain measured with spontaneous Raman (C. Rivero et al.) () nm [Te] 10 7 / mol/m 3 80TeO -0ZnO C. Vincent Rivero, Rodriguez, PhD thesis ISM, Université (005) de University Bordeaux of Central 18 Florida, Verre Bordeaux USA/University 016, Nov of 016, Bordeaux, ICMCB, Pessac France

19 Te-based Glasses for Raman gain Strong correlation of the decrease of the susceptibilities and the RS and HRS intensities of TeO 4 TeO 4 TeO 3+1 while RS and HRS intensities of TeO 3+1 increase. 19 Verre Bordeaux 016, Nov 016, ICMCB, Pessac

20 Te-based Glasses for Raman gain Strong correlation of the decrease of the susceptibilities and the RS and HRS intensities of TeO 4 TeO 4 TeO chain-like arrangement Discontinuity of Te-O-Te chains: change of the size of correlated chains TeO 3+1 while RS and HRS intensities of TeO 3+1 increase. 0 Verre Bordeaux 016, Nov 016, ICMCB, Pessac

Te-based Glasses for Raman gain Strong correlation of the decrease of the susceptibilities and the RS and HRS intensities of TeO 4 TeO 4 Relative Mol content of TeO 4 1.0 0.8 0.6 0.4 0.

21 Te-based Glasses for Raman gain Strong correlation of the decrease of the susceptibilities and the RS and HRS intensities of TeO 4 TeO 4 Relative Mol content of TeO TeO -0Zn0 80TeO -10Ta0-10Zn0 5/ 80TeO -15Ta0-5Zn0 5/ 80TeO -0Ta0 5/ 85TeO -15Ta0 5/ 90TeO -10Ta0 5/ Relative HLS Intensity TeO Verre Bordeaux 016, Nov 016, ICMCB, Pessac In good accordance with neutron diffraction results of 80TeO -0ZnO

22 Approche multimodale par spectroscopies IR, Raman et hyper-raman/hyper-rayleigh: Relation structure/propriétés dans les verres TeO-TaO5/-Zn0 Vincent Rodriguez University of Bordeaux / Department of Chemistry Institut des Sciences Moléculaires (ISM), UMR 555 CNRS FRANCE vincent.rodriguez@u-bordeaux.fr gsm.ism.u-bordeaux1.fr

Quadratic Nonlinear Optics Linear and nonlinear dielectric properties P( w ) = µ w = Nf a( w) E( w) = c ( w) E( w) The induced polarization of a medium is given by ( ) [ ] (1) w N: number density of

23 Quadratic Nonlinear Optics Linear and nonlinear dielectric properties P( w ) = µ w = Nf a( w) E( w) = c ( w) E( w) The induced polarization of a medium is given by ( ) [ ] (1) w N: number density of molecules, fw = : local field factor (Lorentz-Lorenz) c (1) : first-order susceptibility (or linear susceptibility) Optical constants: ( w) ( w) ( w) ˆn n ik n + 3 å i i w (1) n w = w = 1+ 4 ( ) e pc w = + Maxwell (homogeneous medium): ( ˆn = e = e ' + ie '' ) c () : second-order susceptibility Second Harmonic Generation (SFG, DFG, OR) c (3) : Third-order susceptibility A lot of processes. (Four waves mixing) Raman gain (stimulated Raman) 3 Verre Bordeaux 016, Nov 016, ICMCB, Pessac

Elaboration and optimization of tellurite-based materials for Raman gain application

Clemson University TigerPrints All Dissertations Dissertations 8-2013 Elaboration and optimization of tellurite-based materials for Raman gain application Guillaume Guery Clemson University, gguery@clemson.edu