Development of optical sensors
for early stage diagnosis of
pathologies
Fourth Network-wide GlaCERCo workshop
Rennes - October 22nd – 23rd, 2014
Yaroslav Shpotyuk
CNRS, Glasses and Ceramics Team,
University of Rennes 1
Fourth Network-wide GlaCERCo workshop
Rennes –October 22nd – 23rd, 2014
Outline
o Introduction
o Description of work
o Results
o Conclusions
Fourth Network-wide GlaCERCo workshop
Rennes –October 22nd – 23rd, 2014
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
Introduction (I)
Objectives: CNRS
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: 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…
Joint-supervision PhD defense: 08.10.2014
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
Fourth Network-wide GlaCERCo workshop
Rennes –October 22nd – 23rd, 2014
Outline
o Introduction
o Description of work
o Results
o Conclusions
Fourth Network-wide GlaCERCo workshop
Rennes –October 22nd – 23rd, 2014
Description of work
The field of research
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.
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.
Description of work
ChG preparation
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
Description of work
The aim of the activity
Main requirements to the glass properties to be used in FEWS:
• transparent in IR up to 20 m;
• good mechanical and thermodynamic properties (T=Tx–Tg > 100 oC);
• well purified;
Additional task: active fibers
• transparent in visible or NIR (up to 1.5 m );
• glass with low phonon energy.
• ability to introduce rare-earth ions;
To ensure high solubility of rare-earth ions,
the ChVS matrix should contain Ga additions
Studied glasses:
As-Se based
 GaxTe20As30-xSe50;
 Gax(As0.4Se0.6)100-x-yTey;
Ge-Se-Te based
 Ga5Ge20Sb10Se65-xTex
 Ga10Ge15Te75-xMx (M=Se, CsCl)
Dopands
 Pr3+
 Tb3+
Description of work
The aim of the activity
80
70
Se-based
60
Te-based
40
30
20
10
Transmission, %
Se-based
50
0
400
S-based
70
60
Transmission, %
80
S-based
Te-based
50
40
30
20
10
600
800
1000
1200
1400
1600
1800
Wavelength, nm
2000
2200
2400
2600
0
4
6
8
10
12
14
16
18
20
22
Wavelength, m
-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)
24
Description of work
The aim of the activity
Heat Flow, W/g
Tx
Tg
Tx – Tg > 100 oC
Temperature, oC
For the successful fiber drawing
difference between Tx and Tg should be at least 100 oC
Description of work
The aim of the activity
Why use RE?
Energy level diagrams of Pr3+
showing IR emission
• 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
Description of work
The aim of the activity
Effect of Ga-addition on solubility of RE
1% of Ga
Without Ga
80
80
As30Se50Te20
70
As30Se50Te20 + 500ppm Pr
Transmission, %
Transmission, %
Ga1As29Se50Te20 + 500ppm Pr
60
60
50
40
30
20
50
40
30
20
10
10
0
Ga1As29Se50Te20
70
2
4
6
8
10
12
14
16
Wavelength, m
18
20
22
24
0
2
4
6
8
10
12
14
16
Wavelength, m
18
20
22
24
Outline
o Overview
o Description of work
o Results
o Conclusions
Fourth Network-wide GlaCERCo workshop
Rennes –October 22nd – 23rd, 2014
Results
Gax(As0.4Se0.6)100-x system: Ga effects in glassy arsenic selenide
80
Tx,
C
T,
C
xGa
Sample
Composition
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
G0
G1
G2
G3
G4
G5
70
60
Transmission, %
Tg,
C
Density,
g/cm3
50
40
30
20
10
0
2
4
6
8
10
12
14
16
18
20
22
24
Wavelength, m
*
* - Ga2Se3 crystalline phase
*
*
Intensity, a.u.
*
*
*
*
*
G5
*
G4
G3
Restricted functionality at high Ga content
is caused by spontaneous crystallization.
G2
G1
G0
10
20
Ga2Se3 cubic phase, space group: F 4 3 m
Fourth Network-wide GlaCERCo workshop
Rennes –October 22nd – 23rd, 2014
30
40
50
2

60
70
80
90
Results
Ga2(As0.4Se0.6)98-yTey system: Te effects in Ga-based arsenic selenide
80
Composition
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
40
30
20
10
* - Ga2Se3 crystalline phase
Intensity, a.u.
T30
T20
Ga2Se3 cubic phase,
space group: F 4 3 m
T15
T10
G2
30
40
50
2

60
70
80
18
The restricted functionality at high Te content
is connected with spontaneous crystallization:
*
20
T20
T30
50
0
10
T10
T15
60
2
4
6
8
10 12 14 16
Te effects:
(1) decrease in the phonon energy of glassy matrix and stretching in the IR transmittance ;
Wavelength, m
(2) covalent bonds delocalization – long-wave shift in the fundamental optical absorption edge (decrease in Eg).
*
G2
70
Transmission, %
Sample
Density,
g/cm3
90
20
22
24
Results
Ga2(As0.4-zSbzSe0.6)98 system: AsSb effects in Ga-based arsenic selenide glass
80
Tx,
C
T,
C
Sample
Composition
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
---
---
50
40
30
20
10
70
60
60
50
40
30
G2
20
S1
S2
10
S3
0
600
800
1000
1200
1400
1600
Wavelength, nm
Sb effects:
1800
6
8
10
14
16
18
20
22
24
Ga5(As0.28Sb0.12Se0.60)95 (S4)
Ga5(As0.40Se0.60)95 (G5)
S3
40
12
Wavelength, m
S1
S2
50
30
20
0
4
G2
10
2000
2
Intensity, a.u.
Transmission, %
Transmission, %
80
70
Ga5(As0.40Se0.60)95 (G5)
60
0
80
Ga5(As0.28Sb0.12Se0.60)95 (S4)
70
Transmission, %
Tg,
C
Density,
g/cm3
2
4
6
8
10
12
14
16
Wavelength, m
18
20
22
24
10
20
30
40
50
2
60

(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).
Partial substitution of As by Sb in As2Se3-based glass allows to introduce more Ga without crystallization
70
80
90
Results
GaxTe20As30-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
Glass forming region:
(a) glasses
(b) tendency to
phase separation
Restricted functionality at high Ga content is caused by spontaneous crystallization:
Gа2
Gа5
– the Rayleigh scattering on crystallites with character sizes of 200-300 nm;
– the Rayleigh scattering + the Mie scattering on intrinsic microscopic inhomogeneities.
80
Ga1
70
Ga2
Ga0
50
40
30
Ga2
20
Ga10
Intensity, au
Transmission, %
60
Ga5
Ga5
Ga2
10
0
Ga1
2
4
6
8
10
12
14
16
Wavelength, m
18
20
22
24
Ga5
- 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 %).
Ga0
10
20
30
40
50
2
60
70
80
90

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).
Results
Ga5Ge20Sb10Se65-xTex system : Te effects
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
Crystallized
Ga5Ge20Sb10Se35Te30
Ga5Ge20Sb10Se25Te40
Counts
xTe
10
20
30
40
50
60
Position 2
80
80
70
70
60
50
40
Ga5Ge20Sb10Se65
30
Ga5Ge20Sb10Se60Te5
20
Ga5Ge20Sb10Se55Te10
Ga5Ge20Sb10Se45Te20
10
0
600
Transmission, %
Transmission, %
60
Ga5Ge20Sb10Se35Te30
900
1200
1500
1800
2100
Wavelength, nm
2400
2700
3000
50
Ga5Ge20Sb10Se65
40
Ga5Ge20Sb10Se60Te5
30
Ga5Ge20Sb10Se55Te10
20
Ga5Ge20Sb10Se45Te20
10
Ga5Ge20Sb10Se35Te30
0
2
4
6
8
10
12
14
16
Wavelength, m
18
20
22
24
70
80
90
Results
RE doping and fiber drawing of Ga2(As0.4Se0.6)88Te10 glass
Density,
g/cm3
Composition
RE2
T,
C
Tx,
C
24
4.778
160
273
113
4.787
160
279
119
Ga2(As0.40Se0.60)88Te10 (3-step distillation)
Attenuation, dB/m
8,00E-020
RE2
3
2
40
F3
30
20
10
3
F2
6,00E-020
3
F4
4,00E-020
2,00E-020
3
H6
0,00E+000
1200
1500
1800
2100
Wavelength, nm
900
1200
1500
1800
2100
2400
16
12
Optical transmission spectra
of glassy samples RE1 and RE2 as compared
with Ga2(As0.4Se0.6)88Te10.
RE1
-
12
As-O
8
H2O
2
3
4
5
6
7
8
9
10
11
12
Wavelength, m
As-O
8
H2 O
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).
2700
Wavelength, nm
OH
0
4
2400
16
4
Se-H
50
0
600
Ga2(As0.40Se0.60)88Te10 (1-step distillation)
20
Absorption cross section, cm
Transmission, %
60
24
T10
RE1
RE2
3
Pr : H4- H5
Se-H
20
80
70
3+ 3
Se-H
Ga2(As0.4Se0.6)88Te10
+ 500ppm Pr
Ga2(As0.4Se0.6)88Te10
+ 1000ppm Pr
RE1
Tg,
C
Attenuation, dB/m
Sample
0
2
3
4
5
6
7
8
9
10
Wavelength, m
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).
11
12
Outline
o Overview
o Description of work
o Results
o Conclusions
Fourth Network-wide GlaCERCo workshop
Rennes –October 22nd – 23rd, 2014
Conclusions (I)
• 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 covalentbonding network arrangement of the most glassy systems which were
studied;
• Selected compositions were successfully doped with rare-earth elements
and drawn into fibers.