Synthesis, Structure and Non-Linear Optical Properties of Tellurium Oxide Based Glasses and Glass-Ceramics

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 Hôtel à projets 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 TeO2 glass structure is closer to the γ-TeO2 structure than the traditionally used α-TeO2 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 of the structural units: - characteristic of the structural units linkage:

presence of TeO 3, TeO 3+1 and TeO 4 units chains not directed along one axis and presence of double bridges

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Modelling of the non-linear optical properties

What’s the origin of high 3rd-order NLO property ?

TeO + x%M O TeO 2 2 x y

TeO 4 disphenoid TeO 3+1 unit TeO 3 triangular pyramid

Decrease of polarisability and hyperpolarisability

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Modelling of the non-linear optical properties

What’s the origin of high 3rd-order NLO property ?

Ab initio (DFT) Molecular Orbital calculations on TeO 4 and TeO 3 structural units.

+ TeO 4H4 TeO 3H3

TeO4H4 TeO3H3 + Remark <γ Te lp> 470 203 >> <γ Te-Obp> 206 175 ~ <γ Olp> 71 60 ~ Te lp in the TeO 4 geometry is a key γ <γ O-Hbp> 39 17 Small values of high in TeO 2-based glasses <γ cluster > 2018 1134 ∑<γ bond >

S. SUEHARA, P. THOMAS, A.P. MIRGORODSKY and al. , Phys. Rev. B, (70), (2004), 205121-1 – 205121-7.

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Modelling of the non-linear optical properties

What’s the origin of high 3rd-order NLO property ?

Ab initio (DFT) Molecular approach

Geometry determination of a series of (TeO 2)p clusters Many more-or-less realistic stable clusters

1D « chain-like »; p=6 2D « circle »; p=6 3D « cage »; p=8

Nonlinear susceptibility χχχ3 . χ(3) linear chain-like structure ~ χ(3) (exp.) . The polymerization contributes strongly to the hyperpolarisability (Te lone pairs 5%!!): electronic delocalization within the chains.

A.P.Mirgorodsky, M.Smirnov, M.Soulis, P.Thomas, T.Merle-Méjean, Phys. Rev. B 73, 134206, 2006

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Modelling of the non-linear optical properties

What’s the origin of high 3rd-order NLO property ?

Periodic DFT approach Use of ab initio calculations with structural experimental data and a finite field approach (SIESTA 2.0, CRYSTAL 06) to obtain hyperpolarisab ility coefficients χ(2) and χ(3) .

γ -TeO 2 Lp: lone pair (Orthorhombic: P 2 1 21 21 )

XXXX 10,8 χ(3) YYYY 20,4 (10 -13 esu) ZZZZ 19,5

χ(3) : more important contribution along the b and c directions

- c direction: linear chains of corner-shared TeO 3 units with quasi-symmetric Te-OII-Te (1,95-2,02 Å) bridges / electronic delocalization within the chains. - b direction: succession of quasi-symmetric Te-OII-Te bridges and non-symmetric Te-OI---Te (1,86-2,19 Å) bridges / more “polarizable” lone pairs of Te atoms ?

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties

P = P0 + ε0 [ χ(1) E( ω) + χ(2) E2(ω) + χ(3) E3(ω) + …]

Waveguide

Second Harmonic Generation

frequency doubling

Optical fiber Third Harmonic Generation Kerr effect

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties χ(3)

χχχ(3) (time-resolved Mach-Zhender interferometer) ICMCB-CPMOH Bordeaux Measured at 1.5 µµµm 160

70TeO 2-30Tl 2O 140

SI) 120 90TeO 2-10Nb 2O5 -23 -23 90TeO -10WO 100 2 3 (10

(3) 90TeO 2-10Al 2O3

χ 80 90TeO 2-10Ga 2O3

90TeO -10Sb O SF 60 2 2 4 59

1 2 3 4 5 6 7

ns 2 >>d 0>>d 10 , ns 2np 6

- The non-linear properties of such glasses are higher than that of a lead-silica glass and clearly dependent of the nature of the modifier oxide.

- The third order nonlinearity increases with the linear polarizability of the adding cation .

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties χ(3)

5 TeO 3 TeO 4 tp tbp 4 5TiO 2 5PbO 3 5BiO

(esu) 1.5 100

- 11 10GaO 90 1.5

×10 2 80 (3) 70 χ 10ZnO 1 60

Raman Intensity (a.u.) Raman 50 660 680 700 720 740 760 Raman shift / cm -1 0 760 740 720 700 680 660 Raman Shift / cm-1

Reχ (3) as a function of the peak Raman shift for various heavy-

metal oxide doped TlO 0.5 -TeO 2 glasses

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties

Second harmonic Generation (SHG) in glasses

The SHG corresponds to the generation of a double frequency 2 ωωω from a intense incident wave which is propagating through the considered nonlinear material ωωω ωωω POLARIZED GLASS NON-CENTROSYMMETRIC 2ω χχχ(2) ≠ 0

SHG in glass is forbidden because of its isotropy

Break the centrosymmetry of glasses:

Poling techniques: Glass-ceramics : - electric poling controlled crystallization - thermal poling of a non-centrosymmetric phase - e-beam poling inside a bulk glass - all-optical poling

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties SHG Optical poling

Optical poling is based on the creation of a persistent static electric field in a centrosymetric material which can be induced by two intense electric fields of laser lights (ω, 2ω) interacting with matter.

χ2 =0 ω χ2 χ2 > 0 ω ω 2ω Readout Optical Poling Readout

The applications of the technology are immense, up conversion frequency device, high speed optical-switch, and so forth.

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties SHG Optical poling SHG in 70 mol% TeO 2 - 30 mol% ZnO glass

20 Laser source: Nd/YAG 1064 nm Pulse duration: 70ps 15 Repetition rate: 10Hz (a)

(SH) (a) SHG evolution versus writing time (I I fJ 1064 = 2.9, I 532 = 0.70) 5

(b) (b) SHG evolution versus reading time (I

0 reading = 2 GW/cm²). 0 10 20 30 40

Time (minutes) Evolution of SH signal characteristic of the inscription and erasure of a χ(2) by all optical poling: - intensity increases and reaches saturation - the signal decays exponentially with a time constant of about 6 min (erasure of the photoinduced non-linearity by the reading beam)

G. VRILLET, P. THOMAS, V. COUDERC, A. BARTHELEMY, J.C. CHAMPARNAUD-MESJARD. J. Non Cryst. Solids, 345&346, (2004), 417-421 INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties SHG Optical poling Influence of the doping oxide

m/V) 25 50% TlO 0.5 -17 20 50% TlO 0.5 15 40% TlO 0.5 ( 10 ( 10 40% TlO 0.5

eff 10 30% TlO 0.5 d 25% TlO 0.5 5 25% TlO 0.5 0 0 5 10 15 20 Poling Time (min)

deff as a function of poling time for four TeO2-Tl2O glasses.

Higher nonlinearities: addition of ZnO and Tl 2O. Maximum for 35 mol% ZnO. χ Increasing % of Tl 2O ⇒ decrease of deff ⇒ decrease of (2).

Induction of nonlinearity in different glasses: adjustment of the poling

conditions (I 1064 ) : lower I 1064 with thallium doping: favourable for SHG.

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties SHG

d33 (pm/V)

100 LiNbO3 3030 Verre 10 Oxyde de niobium tellurite 1 11 SiO2 0,1 0,30,3

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS Non-linear optical properties Devices

- Development of micro-laser sources having a large emission spectrum (1-5 µm) :

new compositions of TeO 2-based glasses

waveguide

micro-laser

Scheme of a CARS system (Coherent Anti-Stokes Raman Spectroscopy)

-New TeO 2-based fibers (Powder technology, Coll. J.L Auguste and al. XLIM Limoges)

-New TeO 2-based fibers (Microstructured , Coll. F. Smektala Institut Carnot de Bourgogne, T. Cardinal ICMCB) INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS

I would like to thank our collaborators at:

V. Rodriguez (ISM, Bordeaux),

E Fargin (ICMCB, Bordeaux), T. Cardinal (ICMCB, Bordeaux),

V. Couderc, A. Crunteanu (XLIM, Limoges)

M. Nogami, T. Hayakawa (Nitech Nagoya, Japon),

M. Smirnov (Fock Institute of Physics, Saint-Pétersb ourg, Russie),

J. Junquera (CITIMAC, Université de Cantabria, Santander, Bilbao (Espagne)

INDO-FRENCH Workshop on Glasses and Glass-Ceramics University of Lille, France, June 6-8, 2012 SPC TS www. unilim.fr/spcts European Ceramic Centre, Limoges, France