1. Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014 Development of optical sensors for early stage diagnosis of pathologies Fourth Network-wide GlaCERCo workshop Rennes - October 22 nd – 23 rd, 2014 Yaroslav Shpotyuk CNRS, Glasses and Ceramics Team, University of Rennes 1

2. Outline o Introduction o Description of work o Results o Conclusions Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014

3. Introduction (I) Research and training activities Role in GlaCERco Project: ESR 9 Start date : 01 October 2012 End date: 31 March 2014 Work Package 3. Design, synthesis and characterisation of special glasses suitable for photonic devices. Secondment: Phosphate glasses doped with a rare-earth for medical applications Start date : October, 2013 Duration: 2 months

4. Work Package 3. Design, synthesis and characterisation of special glasses suitable for photonic devices. Topic: Optical sensor characterization. Main Objectives: to fabricate Se\Te-based glasses with extended optical windows towards far IR, which allows detect new vibration modes of targeted molecules as signatures of early stage pathologies; to develop rare-earth doped optical fibres pumped in visible or NIR and re-emitted in mid-IR as secondary remote sources for probing some biological liquids or tissues; Investigate the stability of this glasses against environment (oxidation etc.) and physical ageing; Improve the process of purification to avoid absorption in IR caused by H 2 O, CO 2, O-based bonds, etc. Introduction (I) Objectives: CNRS

5. Introduction (I) Objectives: Abo Academy Preparation of rare-earth doped glasses of B 2 O 3 -CaO/SrO-P 2 O 5 systems using different CaO/SrO ratios. Investigation of the effect of the glass composition on the structural, optical and thermal properties of the glasses as well as on the glass bioactivity response when in contact with simulated body fluid (SBF). Preparation of preforms with good quality for further fiber drawing. Investigation of the effect of the drawing on the structural, optical and thermal properties of the glasses as well as on the glass bioactivity response when in contact with SBF.

6. Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014 Introduction (I) Still looking for Postdoc position… Topic: Radiation induced effects on optical properties of As-Sb-S glasses. Faculty of Electronics Ivan Franko National University of Lviv Supervisor: Ihor Polovynko Topic: Development of optical sensors for early diagnosis of pathologies. Institute of Chemistry University of Rennes 1, CNRS Supervisors: Bruno Bureau and Catherine Boussard-Pledel 08.10.2014 Joint-supervision PhD defense: 08.10.2014

7. Outline o Introduction o Description of work o Results o Conclusions Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014

8. Description of work The field of research ChG – the unique disordered solids, being simultaneously: inorganic polymers, in terms of their chemical nature, semiconductors, in terms their electronic nature, glasses, in terms of their thermodynamic nature. Chalcogenide glass (ChG) – is a glass containing one or more chalcogen elements (S, Se or Te) with other elements from IV-th and V-th groups of the Periodic Table (typically As, Sb, Bi, Ge, etc.) obtained by conventional melt quenching.

9. Description of work ChG preparation

10. Description of work The aim of the activity The spectral range of IR spectroscopy allows to probe the vibrational fingerprint of biomolecules. Evanescent wave in optical fiber interacts with environment, allowing identification of molecules at the basis of spectrum analysis

11. To ensure high solubility of rare-earth ions, the ChVS matrix should contain Ga additions Description of work The aim of the activity transparent in IR up to 20 m; good mechanical and thermodynamic properties (T=T x –T g > 100 o C); well purified; Main requirements to the glass properties to be used in FEWS: transparent in visible or NIR (up to 1.5 m ); glass with low phonon energy. ability to introduce rare-earth ions; Additional task: active fibers As-Se based  Ga x Te 20 As 30-x Se 50 ;  Ga x (As 0.4 Se 0.6 ) 100-x-y Te y ; Studied glasses: Ge-Se-Te based  Ga 5 Ge 20 Sb 10 Se 65-x Te x  Ga 10 Ge 15 Te 75-x M x (M=Se, CsCl) Dopands  Pr 3+  Tb 3+

12. Description of work The aim of the activity -Region of interest in the Vis/NIR for laser pumping (optical band gap more than 0.8 eV (less than 1500nm) -Region of interest in the IR for biosensing (up to 20m)

13. Description of work The aim of the activity For the successful fiber drawing difference between T x and T g should be at least 100 o C T x – T g > 100 o C

14. Description of work The aim of the activity Why use RE? To have secondary remote sources of light in the IR region from 1 to 10 m. In case of Pr 3+ the large numbers of bands in mid IR offers the promise of high-brightness sources for remote sensing. To ensure solubility of rare-earth elements, the glassy matrix should contain some additions like Ga Energy level diagrams of Pr 3+ showing IR emission

15. Description of work The aim of the activity 1% of Ga Effect of Ga-addition on solubility of RE Without Ga

16. Outline o Overview o Description of work o Results o Conclusions Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014

17. Results Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014 x Ga SampleComposition Density, g/cm 3 Tg,CTg,C Tx,CTx,C  T,  C 0G0As 40 Se 60 4.619184--- 1G1Ga 1 (As 0.4 Se 0.6 ) 99 4.629182--- 2G2Ga 2 (As 0.4 Se 0.6 ) 98 4.635182307125 3G3Ga 3 (As 0.4 Se 0.6 ) 97 4.631180283103 4G4Ga 4 (As 0.4 Se 0.6 ) 96 4.64218227795 5G5Ga 5 (As 0.4 Se 0.6 ) 95 4.66218027696 Ga x (As 0.4 Se 0.6 ) 100-x system: Ga effects in glassy arsenic selenide Restricted functionality at high Ga content is caused by spontaneous crystallization. Ga 2 Se 3 cubic phase, space group:

18. Results Ga 2 (As 0.4 Se 0.6 ) 98-y Te y system: Te effects in Ga-based arsenic selenide SampleComposition Density, g/cm 3 Tg,CTg,C Tx,CTx,C  T,  C G2Ga 2 (As 0.4 Se 0.6 ) 98 4.635182307125 T10Ga 2 (As 0.4 Se 0.6 ) 88 Te 10 4.791151267116 T15Ga 2 (As 0.4 Se 0.6 ) 83 Te 15 4.860149265116 T20Ga 2 (As 0.4 Se 0.6 ) 78 Te 20 4.940132239107 T30Ga 2 (As 0.4 Se 0.6 ) 68 Te 30 5.069115264149 Te effects: (1) decrease in the phonon energy of glassy matrix and stretching in the IR transmittance ; (2) covalent bonds delocalization – long-wave shift in the fundamental optical absorption edge (decrease in E g ). The restricted functionality at high Te content is connected with spontaneous crystallization: Ga 2 Se 3 cubic phase, space group:

19. Results Ga 2 (As 0.4-z Sb z Se 0.6 ) 98 system: As  Sb effects in Ga-based arsenic selenide glass SampleComposition Density, g/cm 3 Tg,CTg,C Tx,CTx,C  T,  C G2Ga 2 (As 0.4 Se 0.6 ) 98 4.635182307125 S1 Ga 2 (As 0.36 Sb 0.04 Se 0.60 ) 98 4.727187--- S2 Ga 2 (As 0.28 Sb 0.12 Se 0.60 ) 98 4.900191--- S3 Ga 2 (As 0.20 Sb 0.20 Se 0.60 ) 98 5.073196306110 S4 Ga 5 (As 0.28 Sb 0.12 Se 0.60 ) 95 4.873194--- Sb effects : (1) enhanced concentration limit (due to Ga) in phase separation and crystallization; (2) metallization of chemical bonds – small long-wave shift in optical absorption edge (decrease in E g ). Partial substitution of As by Sb in As 2 Se 3 -based glass allows to introduce more Ga without crystallization

20. Results Ga x Te 20 As 30-x Se 50 system (Ga-TAS-235): Ga effects in TAS-235 x Ga SampleComposition Density, g/cm 3 Tg,CTg,C Tx,CTx,C  T,  C 0Ga0As 30 Se 50 Te 20 4.888134--- 1Ga1Ga 1 As 29 Se 50 Te 20 4.912131--- 2Ga2Ga 2 As 28 Se 50 Te 20 4.920128--- 5Ga5Ga 5 As 25 Se 50 Te 20 4.94012622397 10Ga10Ga 10 As 20 Se 50 Te 20 4.899118231113 Restricted functionality at high Ga content is caused by spontaneous crystallization: Gа2 – the Rayleigh scattering on crystallites with character sizes of 200-300 nm; Gа5 – the Rayleigh scattering + the Mie scattering on intrinsic microscopic inhomogeneities. Micrographs of Gа1 surface (homogeneous glass), Gа2 (droplets of homogeneous nano- inclusions of  -Ga 2 Se 3 cubic phase with  200– 300 nm diameter) and Gа5 microcrystallites of  - and  - Ga 2 Se 3 cubic phases with more than 10  m size). Glass forming region: (a) glasses (b) tendency to phase separation Ga2 Ga5 - dominant crystalline phase under small Ga content (3–5 %) is HT-modification of cubic  -Ga 2 Se 3. - additional extractions of cubic  -Ga 2 Se 3 appear under higher Ga content (above 5 %).

21. Results Ga 5 Ge 20 Sb 10 Se 65-x Te x system : Te effects x Te Composition Density, g/cm 3 Tg,  C Tx,  C  T,  C 0Ga 5 Ge 20 Sb 10 Se 65 4.629279--- 5Ga 5 Ge 20 Sb 10 Se 60 Te 5 4.724267--- 10Ga 5 Ge 20 Sb 10 Se 55 Te 10 4.824253408155 20Ga 5 Ge 20 Sb 10 Se 45 Te 20 4.983233387154 30Ga 5 Ge 20 Sb 10 Se 35 Te 30 5.129221335114 40Ga 5 Ge 20 Sb 10 Se 25 Te 40 5.438Crystallized 50Ga 5 Ge 20 Sb 10 Se 15 Te 50 5.733Crystallized

22. Results RE doping and fiber drawing of Ga 2 (As 0.4 Se 0.6 ) 88 Te 10 glass Optical loss spectra in fiber drawn from glassy Ga 2 (As 0.40 Se 0.60 ) 88 Te 10 alloy, purified via single-step (black line) and three-step distillation (red line). Optical transmission spectra of glassy samples RE1 and RE2 as compared with Ga 2 (As 0.4 Se 0.6 ) 88 Te 10. Optical loss spectra in fiber drawn from glassy Ga 2 (As 0.4 Se 0.6 ) 88 Te 10 alloy, doped with 500 ppm Pr 3+ (insert – micrograph of fiber cross section). SampleComposition Density, g/cm 3 Tg,CTg,C Tx,CTx,C  T,  C RE1 Ga 2 (As 0.4 Se 0.6 ) 88 Te 10 + 500ppm Pr 4.778160273113 RE2 Ga 2 (As 0.4 Se 0.6 ) 88 Te 10 + 1000ppm Pr 4.787160279119

23. Outline o Overview o Description of work o Results o Conclusions Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014

24. Glass forming ability of Ga-doped chalcogenides of ~100 compositions, such as o Ga x As 30-x Se 50 Te 20 o Ga x (As 0.4 Se 0.6 ) 100-x-y Te y o Ga 5 Ge 25 Se 70-x Te x o Ga 5 Ge 20 Sb 10 Se 65-x Te x o Ga 10 Ge 15 Te 75-x Se x o Ga 10 Ge 15 Te 75 -CsCl was studied; It was established that Ga 2 Se 3 crystalline phase is destroying covalent- bonding network arrangement of the most glassy systems which were studied; Selected compositions were successfully doped with rare-earth elements and drawn into fibers. Conclusions (I)