Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014 Development of optical...

Fourth Network-wide GlaCERCo workshopRennes –October 22nd – 23rd, 2014

Development of optical sensors for early stage diagnosis of

pathologies

Fourth Network-wide GlaCERCo workshopRennes - October 22nd – 23rd, 2014

Yaroslav Shpotyuk

CNRS, Glasses and Ceramics Team, University of Rennes 1

Outline

o Introduction

o Description of work

o Results

o Conclusions


Introduction (I)Research and training activities

Role in GlaCERco Project: ESR 9

Start date : 01 October 2012 End date: 31 March 2014Work 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

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 H2O, CO2, O-based bonds, etc.

Introduction (I)Objectives: CNRS

Introduction (I)Objectives: Abo Academy

• Preparation of rare-earth doped glasses of B2O3-CaO/SrO-P2O5 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.


Introduction (I)Still looking for Postdoc position…

Topic: Radiation induced effects on optical properties of As-Sb-S glasses.

Faculty of ElectronicsIvan Franko National University of LvivSupervisor: Ihor Polovynko

Topic: Development of optical sensors for early diagnosis of pathologies.

Institute of ChemistryUniversity of Rennes 1, CNRSSupervisors: Bruno Bureau and Catherine Boussard-Pledel

Joint-supervision PhD defense: 08.10.2014

Outline

o Introduction


o Results

o Conclusions


Description of workThe 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.

Description of workChG preparation

Description of workThe 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

To ensure high solubility of rare-earth ions, the ChVS matrix should contain Ga additions


• transparent in IR up to 20 m;• good mechanical and thermodynamic properties (T=Tx–Tg > 100 oC);• 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 GaxTe20As30-xSe50; Gax(As0.4Se0.6)100-x-yTey;

Studied glasses:

Ge-Se-Te based Ga5Ge20Sb10Se65-xTex

Ga10Ge15Te75-xMx (M=Se, CsCl)

Dopands Pr3+

Tb3+


400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 26000

10

20

30

40

50

60

70

80

Te-basedSe-based

S-based

Tra

nsm

issi

on, %

Wavelength, nm4 6 8 10 12 14 16 18 20 22 24

0

10

20

30

40

50

60

70

80

Te-based

Se-based

Tra

nsm

issi

on, %

Wavelength, m

S-based

- 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 20m)


For the successful fiber drawingdifference between Tx and Tg should be at least 100 oC

Tx

Hea

t Flo

w, W

/g

Temperature, oC

Tg

Tx – Tg > 100 oC


Why use RE?

• To have secondary remote sources of light in the IR region from 1 to 10 m.

• In case of Pr3+ 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 Pr3+ showing IR emission


2 4 6 8 10 12 14 16 18 20 22 240

10

20

30

40

50

60

70

80

Tra

nsm

issi

on, %

Wavelength, m

As30Se

50Te

20

As30Se

50Te

20 + 500ppm Pr

2 4 6 8 10 12 14 16 18 20 22 240

10

20

30

40

50

60

70

80

Tra

nsm

issi

on, %

Wavelength, m

Ga1As

29Se

50Te

20

Ga1As

29Se

50Te

20 + 500ppm Pr

1%

of G

a

Effect of Ga-addition on solubility of RE

With

ou

t Ga

Outline

o Overview


o Results

o Conclusions


Results


xGa Sample Composition Density, g/cm3

Tg,C

Tx,C

T,C

0 G0 As40Se60 4.619 184 --- ---

1 G1 Ga1(As0.4Se0.6)99 4.629 182 --- ---

2 G2 Ga2(As0.4Se0.6)98 4.635 182 307 125

3 G3 Ga3(As0.4Se0.6)97 4.631 180 283 103

4 G4 Ga4(As0.4Se0.6)96 4.642 182 277 95

5 G5 Ga5(As0.4Se0.6)95 4.662 180 276 96

Gax(As0.4Se0.6)100-x system: Ga effects in glassy arsenic selenide

Restricted functionality at high Ga content is caused by spontaneous crystallization.

Ga2Se3 cubic phase, space group: mF 34

2 4 6 8 10 12 14 16 18 20 22 240

10

20

30

40

50

60

70

80

G0 G1 G2 G3 G4 G5

Tra

nsm

issi

on, %

Wavelength, m

10 20 30 40 50 60 70 80 90

G4

G3

G2G1

G0

* - Ga2Se

3 crystalline phase

* * * **

*

*

*

Inte

nsi

ty, a

.u.

2

*

G5

ResultsGa2(As0.4Se0.6)98-yTey system: Te effects in Ga-based arsenic selenide

Sample Composition Density, g/cm3

Tg,C

Tx,C

T,C

G2 Ga2(As0.4Se0.6)98 4.635 182 307 125

T10 Ga2(As0.4Se0.6)88Te10 4.791 151 267 116

T15 Ga2(As0.4Se0.6)83Te15 4.860 149 265 116

T20 Ga2(As0.4Se0.6)78Te20 4.940 132 239 107

T30 Ga2(As0.4Se0.6)68Te30 5.069 115 264 149

2 4 6 8 10 12 14 16 18 20 22 240

10

20

30

40

50

60

70

80

G2 T10 T15 T20 T30

Tra

nsm

issi

on, %

Wavelength, m

10 20 30 40 50 60 70 80 90

*

* * - Ga2Se

3 crystalline phase

Inte

nsi

ty, a

.u.

2

T30

T20

T15

T10

G2

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 Eg).

The restricted functionality at high Te content is connected with spontaneous crystallization:

Ga2Se3 cubic phase, space group: mF 34

ResultsGa2(As0.4-zSbzSe0.6)98 system: AsSb effects in Ga-based arsenic selenide glass

600 800 1000 1200 1400 1600 1800 20000

10

20

30

40

50

60

70

80

G2 S1 S2 S3

Tra

nsm

issi

on, %

Wavelength, nm2 4 6 8 10 12 14 16 18 20 22 24

0

10

20

30

40

50

60

70

80

G2 S1 S2 S3

Tra

nsm

issi

on, %

Wavelength, m

Sample Composition Density, g/cm3

Tg,C

Tx,C

T,C

G2 Ga2(As0.4Se0.6)98 4.635 182 307 125

S1 Ga2(As0.36Sb0.04Se0.60)98 4.727 187 --- ---

S2 Ga2(As0.28Sb0.12Se0.60)98 4.900 191 --- ---

S3 Ga2(As0.20Sb0.20Se0.60)98 5.073 196 306 110

S4 Ga5(As0.28Sb0.12Se0.60)95 4.873 194 --- ---

10 20 30 40 50 60 70 80 90

Ga5(As

0.28Sb

0.12Se

0.60)95 (S4)

Ga5(As

0.40Se

0.60)95 (G5)

Inte

nsit

y, a

.u.

2Sb 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 Eg).

2 4 6 8 10 12 14 16 18 20 22 240

10

20

30

40

50

60

70

80

Ga5(As

0.28Sb

0.12Se

0.60)95 (S4)

Ga5(As

0.40Se

0.60)95 (G5)

Tra

nsm

issi

on, %

Wavelength, m

Partial substitution of As by Sb in As2Se3-based glass allows to introduce more Ga without crystallization

ResultsGaxTe20As30-xSe50 system (Ga-TAS-235): Ga effects in TAS-235

xGa Sample Composition Density, g/cm3

Tg,C

Tx,C

T,C

0 Ga0 As30Se50Te20 4.888 134 --- ---

1 Ga1 Ga1As29Se50Te20 4.912 131 --- ---

2 Ga2 Ga2As28Se50Te20 4.920 128 --- ---

5 Ga5 Ga5As25Se50Te20 4.940 126 223 97

10 Ga10 Ga10As20Se50Te20 4.899 118 231 113

2 4 6 8 10 12 14 16 18 20 22 240

10

20

30

40

50

60

70

80

Tra

nsm

issi

on, %

Wavelength, m

Ga0

Ga2

Ga1

Ga5

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 -Ga2Se3 cubic phase with 200–300 nm diameter) and Gа5 microcrystallites of - and - Ga2Se3 cubic phases with more than 10 m size).

Glass forming region:(a) glasses(b) tendency to phase separation

Ga2

Ga510 20 30 40 50 60 70 80 90

Ga10

Ga5

Ga2

Ga1

Ga0

Inte

nsi

ty, a

u

2

- dominant crystalline phase under small Ga content (3–5 %) is HT-modification of cubic -Ga2Se3. - additional extractions of cubic

-Ga2Se3 appear under higher Ga content (above 5 %).

ResultsGa5Ge20Sb10Se65-xTex system : Te effects

2 4 6 8 10 12 14 16 18 20 22 240

10

20

30

40

50

60

70

80

Tra

nsm

issi

on, %

Wavelength, m

Ga5Ge

20Sb

10Se

65

Ga5Ge

20Sb

10Se

60Te

5

Ga5Ge

20Sb

10Se

55Te

10

Ga5Ge

20Sb

10Se

45Te

20

Ga5Ge

20Sb

10Se

35Te

30

600 900 1200 1500 1800 2100 2400 2700 30000

10

20

30

40

50

60

70

80

Tra

nsm

issi

on, %

Wavelength, nm

Ga5Ge

20Sb

10Se

65

Ga5Ge

20Sb

10Se

60Te

5

Ga5Ge

20Sb

10Se

55Te

10

Ga5Ge

20Sb

10Se

45Te

20

Ga5Ge

20Sb

10Se

35Te

30

xTe Composition Density, g/cm3

Tg,C

Tx,C

T,C

0 Ga5Ge20Sb10Se65 4.629 279 --- ---

5 Ga5Ge20Sb10Se60Te5 4.724 267 --- ---

10 Ga5Ge20Sb10Se55Te10 4.824 253 408 155

20 Ga5Ge20Sb10Se45Te20 4.983 233 387 154

30 Ga5Ge20Sb10Se35Te30 5.129 221 335 114

40 Ga5Ge20Sb10Se25Te40 5.438 Crystallized

50 Ga5Ge20Sb10Se15Te50 5.733 Crystallized10 20 30 40 50 60 70 80 90

Counts

Position 2

Ga5Ge

20Sb

10Se

35Te

30

Ga5Ge

20Sb

10Se

25Te

40

ResultsRE doping and fiber drawing of Ga2(As0.4Se0.6)88Te10 glass

2 3 4 5 6 7 8 9 10 11 120

4

8

12

16

20

24

H2O

As-O

Se-H

Att

enua

tion

, dB

/m

Wavelength, m

Ga2(As

0.40Se

0.60)

88Te

10 (1-step distillation)

Ga2(As

0.40Se

0.60)

88Te

10 (3-step distillation)

Optical loss spectra in fiber drawn from glassy Ga2(As0.40Se0.60)88Te10 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 Ga2(As0.4Se0.6)88Te10.

Optical loss spectra in fiber drawn from glassy Ga2(As0.4Se0.6)88Te10

alloy, doped with 500 ppm Pr3+ (insert – micrograph of fiber cross section).

2 3 4 5 6 7 8 9 10 11 120

4

8

12

16

20

24

As-O

Pr3+: 3H4-3H

5Se-HSe-H

600 900 1200 1500 1800 2100 2400 27000

10

20

30

40

50

60

70

80

1200 1500 1800 2100 24000,00E+000

2,00E-020

4,00E-020

6,00E-020

8,00E-020

3F4

3H6

3F2

3F3

RE2

Abs

orpt

ion

cros

s se

ctio

n, c

m2

Wavelength, nm

T10 RE1 RE2

Tran

smis

sion

, %

Wavelength, nm

Sample CompositionDensity,

g/cm3

Tg,C

Tx,C

T,C

RE1Ga2(As0.4Se0.6)88Te10

+ 500ppm Pr4.778 160 273 113

RE2Ga2(As0.4Se0.6)88Te10

+ 1000ppm Pr4.787 160 279 119

Outline

o Overview


o Results

o Conclusions


• Glass forming ability of Ga-doped chalcogenides of ~100 compositions, such as

o GaxAs30-xSe50Te20

o Gax(As0.4Se0.6)100-x-yTey

o Ga5Ge25Se70-xTex

o Ga5Ge20Sb10Se65-xTex

o Ga10Ge15Te75-xSex

o Ga10Ge15Te75-CsCl

was studied;

• It was established that Ga2Se3 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)

Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014 Development of optical...

Documents

Transcript of Fourth Network-wide GlaCERCo workshop Rennes –October 22 nd – 23 rd, 2014 Development of optical...