Te - USTV

VERRES EXOTIQUES
Jacques
q
LUCAS
Verres et Céramiques
Université de Rennes
Verres
e es base o
oxydes
ydes →
Énergies de phonon élevées
W 1100 -11 pour SiO2
Wp=1100cm
opaque dans le moyen Infrarouge
Chimie d’atomes lourds nécessaire →
HALOGENURES surtout fluorures
CHALCOGENURES S
CHALCOGENURES:
S,Se,
S T
Te
T
Transmis
sion (%)
Transmission of different
glasses
100
90
80
70
60
50
40
30
20
10
0
Chalcogenide
g
gglasses
Fluoride g
glasses
Silica
2
4
6
8
10
12
wavelength (µm)
14
16
18
Energy landscape
Glass
Energy of
crystallization
Crystal
Structure des Verres de Fluorures
VERRES DE FLUORURES POUR L’OPTIQUE GUIDÉE
Glass
Composition
Tg
((°C))
Tx
((°C))
Tm
((°C))
nd
ZBLAN
ZrF4 – BaF2 – LaF3 –AlF3 –
NaF
262
352
455
1.498
ZBLA
without NaF
307
392
548
1.516
PZG
39 PbF2 - 29 ZnF2 - 32 GaF3
266
304
543
1.574
Optical
fibers
Channel
waveguides
Fonction active
D
Dopage
terre rare L
Ln3+:
(Nd3+, Pr3+, Tm3+, Er3+)
FIBRE LASER - Principe
Laser de pompe (1)
Miroir réfléchissant à 2
Verre de cœur dopé terre rare
Verre de gaine
}
Fibre optique
monomode
d
Miroir semi-réfléchissant
semi réfléchissant à 2
Émission laser (
Pr
FIBRES
LASERS
Nd
Ho
Er
Fluoride
glass
Tm
Yb
Pr
Nd
Sm
Silica
glass
l
Ho
Er
Tm
Yb
0.2
0.6
1.0
1.4
1.8
2.2
2.6
W l
Wavelength
h (µm)
( )
3.0
3.4
3.8
AMPLIFICATEUR OPTIQUE
Line
Li
- silica -
Input signal
Optical
O
ti l amplifier
lifi
RE-doped fiber (Er, Tm, Pr)
Coupler
p
Pump laser
Coupler
p
Line
Li
- silica -
Amplified
output
COURBE D’ATTÉNUATION D’UNE FIBRE DE LIGNE EN
SILICE
ATTEN U AT
A
TI O N ( dB
B/ km)
1, 2
GEANT
1
0, 8
0, 6
Pr aséody
yme
Sulfure
Pr aséodyme
Fluoré
Néodyme
Fluoré
0, 4
Thulium
Fluoré
BANDES
EXP LOI TEES
Erbium
Silice
C
L
0,, 2
0
1000
1200
1400
LO N GU EUR D 'O N DE ( nm )
1600
1800
Chalcogenide glasses
Sb
S
As
Se
Ge
Te
Ga
CHALCOGENIDE GLASS SAMPLE
Se : a key atom in chalcogenide
glasses
• Good glass former
– low phonon characteristics
– technical g
glasses such as AMTIR ((Amorphous
p
materials Inc) and GASIR (Umicore IR
Glasses)) based on combination of Se, Ge, As,
Sb.
• Excellent local probes for NMR
spectroscopy
t
Se
s
p
Groupe VI

Localised (4e-)5p
Lone pairs
Se meltingg : 217°C


Viscous liquid
Se chains :
easy rotation
and bending
Crystal
Glass
Easy glass forming
Chalcogenide glasses structural models
1) 1D spaghetti-type, such as vitreous Se
2) 2D distorted planar glasses such as As2S3
As
S
3) 3D glasses
glasses, such as GeS4
Ge
Se
Energy landscape
Glass
Energy of
crystallization
Crystal
Se/As/Ge GLASS SAMPLE
Se NMR spectra of As/Se chains ramified glasses (1D/2D)
a
b
c
3 types of Se: (a) at 850 ppm , (b)
at 550 ppm and (c) at 380 ppm
Se
AsSe9
As-Se-As ((c))
Se Se Se (a)
Se-Se-Se
AsSe4.5
AsSe3.3
Se-Se-As (b)
As2Se3
1200
800
400
Chemical shift (ppm)
0
-400
Chalcogenide Glasses
IR transparency range of different
glasses
120
silica
trans
smission (%
%)
100
Fluorides
80
S lfid
Sulfide
selenide
60
telluride
40
20
0
1
3
5
7
9
11
13
15
17
wavelength (µm)
19
21
23
25
27
Spectral emission of black body
104
T=6000 °C
Em
mission
102
T=20 °C
1
10-2
10-44
10-6 0,1
01
1
10
wavelength (µm)
100
Transmission of atmosphere
Trransmis
ssion
1
H2O
0.8
CO22
CO
0.6
0.4
H2O
0.2
CO2
O3
0
0
2
4
6
8
10
wavelength (µm)
12
14
OPTICS MOULDING for
THERMAL IMAGING
IR CAMERAS
CHALCOGENIDE MOULDED LENSES
(left) DIFFRACTIVE
(right) ASPHERIC
THALES ELVIR INFRARED
CAMERA equiped
i d with
i h molded
ld d
chalcodenide glass optics
Détection infrarouge
de jour ou de nuit
d’une nappe
d’hydrocarbures
rejetés
j é par un
Pétrolier. L’émission
thermique de l’eau
estt différente
diffé t de
d celle
ll
du polluant
Detection of overheating
on elecrical lines
Night vision camera
For car driving assistance
Chalcogenide glass
optics
Image in the visible 
Thermal image in the
Infrared

Camera IR
Pour assistance
a la conduite de
nuit.
nuit
Infrared transmitting glass ceramics
(Zhang Laurent Calvez Uof Rennes)
(Zhang,
The basic glass is :GeS2/Sb2S3/CsCl. By heating  nucléation
then growth of CsCl particles.
GeS2
0
Compositions vitreuses
Compositions cristallisées
10
100
90
20
80
30
70
40
60
50
50
60
40
70
30
80
20
90
10
100
Sb2S3
0
0
10
20
30
40
50
60
70
80
90
100
CsCl
T
Transm
mission
n (%)
100
90
80
70
60
50
40
30
20
10
0
sample A
sample B
sample A
0
1
2
3
4
5
6
sample B
7
8
Wavelength (µm)
9
10
11
12
Verres et vitrocéramiques à base de séléniures: Système Ge-Ga-Se
Ge23Ga12Se63
G 23Ga
Ge
G 12Se
S 63
Tg = 370°C
Tx = 460°C
λgap= 690 nm
Verre de
d base
b
M. Rozé, L. Calvez, Y. Ledemi, X.H Zhang
Vitrocéramique
Advantages of glass ceramics
Glass ceramic
Glass
Resistance to fracture propagation
Collaboration with LARMAUR, Rennes
Tellurium based glasses for
biosensors and space
Optical
O
ti l fib
fibers needed
d d
stable glass candidate
TAS g
glass: Te/As/Se
TAS glass properties
As
(a) : No tendency to
crystallization
20
70
(b) : Tendency to
crystallization 40
60
60
(a)
40
(b)
80
Se
Te2As3Se5
80
20
40
60
20
80
Te
T
Transmiss
sion (%)
Glassy areas :
60
50
40
30
20
10
0
0
2
4
6
8
10
12
14
16
Wavelength (µm)
• Large optical window lying from 2 to 18 µm
• Excellent resistance to devitrification during the fibering process
• Good durability towards water and solvent corrosion
• High refractive index (ex. Te2As3Se5 : n ~ 2.8)
•Good candidate for the first window: 4 to 12µm
18
20
Optical fiber preparation
Preform
translation
• Glass temperatures Tg ~ 135 °C
C
• Fibering temperature Tf ~ 270 °C
He g
gas
Preform
Furnace
Diameter
system
control
Polymer
coating
equipment
Pulley coupled with
tension-meter
Drum
Drawing tower
Fiber Evanescent Wave Spectroscopy Principle
nair = 1
Wave 

c
nglass = 2,8
 = incident angle
of the wave
c = critical
i i angle
Medium which does not absorb 
evanescent field without
energy loss
Total Internal Reflection
Medium which absorb 
wave attenuation by absorption
Attenuated Total Reflection : ATR
Tapered fibers (2)
Transportation
section
Sensing
zone
about 10cm
Two routes for tapering locally the fibre :
Strong increase of the fibering speed during the drawing process
Chemical etching using H2SO4 + H2O2 solutions

Transportation
section
Experimental set-up
FTIR
spectrometer
MCT detector
Sample to analyze
optical fiber
A lifi
Amplifier
0,90
0,85
0,80
0,75
0,70
0,65
0,60
Absorbance
0,55
0,50
0,45
0,40
0 35
0,35
0,30
0,25
0,20
0,15
0,10
0,05
0,00
4
6
8
10
Wavelength (micrometers)
Signal
g
treatment
A unique chalcogenide glass fiber aimed at transmittting the beam and at probing the sample.
sample
Alcoholic fermentation
0.7
Ethanol
-1
1045 cm
t
transmission
n signal
0.65
Fructose
-1
1063 cm
Ethanol
-1
1085 cm
Glucose
-1
1033 cm
0.6
0.55
0.5
o day
25 days
60 days
0.45
0.4
940
990
1040
1090
1140
1190
wavenumbers (cm-1)
Cider fabrication process from apple juice fermentation,
in situ control of the transformation of glucose and fructose
i t ethanol
into
th l
Study of a biological tissue : mouse liver (1)
OBJECTIVE :
PRINCIPLE :
Following the effect of a starvation in the liver cells
IR
Spectrometer
Liver biopsy (10 µm)
The tissues were merely deposited on the tapered
part of the fibre to ensure an optimal contact
between the fibre and the tissue
Study of a biological tissue : the liver
Diminution of
glucose rate
IR spectra of mice liver samples :
0,50
Lipids
accumulation
0,45
0,40
0,35
Abso
orbance
0,30
0,25
0,20
Normal fed
0,15
0,10
0,05
0,00
-0,05
-0,10
-0,15
-0,20
0,20
Not fed for 12H
-0,25
-0,30
-0,35
-0,40
3500
3000
2500
2000
1500
1000
Wavenumber (cm-1)
Possibility to detect metabolic variations in the liver.
Study of a bacterial biofilm : Proteus mirabilis (1)
 Opportunist pathogen agent of the human urany tract
 Presents
P
t two
t phenotypes
h
t
: swarming
i
and
d vegetative
t ti
 Their spreading from innoculum exhibit some terraces
IR source
MCT
detector
spectra
p
recorded in situ every
y 15 min.
during the migration process
IR spectrometer
in the Petri plate.
heating
e
g plate
p e
maintain at 37°C
Gelose as
substrate
Study of a bacterial biofilm : Proteus mirabilis (2)
0,30
Amide I et II
0,25
Abso
orbance
0,20
Polysaccharides
0,15
0,10
1076 cm-1
0,05
0,00
1800
1600
1400
1200
1000
-1
Nombre
d'onde
(cm
-1) )
wavenumber
(cm
1086 cm-1
wavenumber (cm-1)
Nombre d ’onde (cm-1)
• Increase of the absorbencyy in
• Shift of the ppolysaccharides
y
absorption
p
bands
agreement with the bio-mass growth
Detection in real time of the bacteria
bacteria-sensor
sensor contact
IR signatures of the both phenotypes
Te structure and bonding, seven order of
magnitude in conductivity between Se and Te
b
Crystalline structure of metallic Te
a
d1
 metallic bonding
d1
d2
d2
Te
RIGIDITY
• Pure Te → no glass
l
• Te is not a glass former
c
a
• Tm = 450°C, fluid melt
Hexagonal structure
d1: 2.83 Å
d2: 3.49 Å
New optical Tellurium based
glasses: Ga
Ga-Ge-Te
Ge Te
Strategy: suppress the possibility of metallic bond to allow flexibility
Ga
0
Glass formation region in
the Ga-Ge-Te system
10
Structural model:
100
connection of
tetrahedra and
triangles building
blocks
90
20
80
30
70
40
Te
Te
G
Ge
Te
Te
Te
Te
Tetrahedra
60
50
Te
Te
50
60
40
Te
Te
Te
70
30
T
Te
Ga
80
20
90
Te
10
100
Te
0
0
10
20
30
Ge20Te80
40
50
60
70
80
90
100
Ge
 bulk glasses with 70% to 80% of Te
Te
Triangle
Glass formation domain in the Ge/Te/I system
The glass to crystal competition is strong
Tg= 150°C Tx= 274°C
I
55
45
60
Glass
Ceramic
40
65
35
70
30
75
25
80
20
85
15
90
10
95
5
Te
5
10
15
20
25
30
35
40
45
Ge
( )
(a)
Optical transmission of a Te glass compared to an equivalent
Se based glass
The 15µm CO2 absorption band is in the middle of the
transparency window
DARWIN
MISSION
ESA, European
Space Agency
Target: detection of
bi l i l off
biological
biological life on
exoplanets out of
exoplanets,
the solar system
markers are H20, O3
and CO2 having their
signature in the IR:
6
6µm,
10
10µm, 15µm
15
Two windows: 6-10 µm for water (vibration) and ozone detection
10-20µm for carbon dioxide and water (rotation) detection.
Infrared single mode fibre for
wavelength filtering
1
0.8
0.6
0.4
0.2
0
150
100
50
0
Planet emitting IR light
0
50
100
Gaussian IR light output
150
200
Rod in tube vacuum method
(RTVM)
Preparation of a core glass rod
Reducing the diameter of the core glass by fiber drawing
 = 10 mm
 = 1.97 mm
intmm
int
mm
extmm
P
Preparation
ti off a cladding
l ddi tube
t b off 10 mm
 = 1.96 mm
Fixation of the core rod inside the cladding tube
Drawing an intermediate core-cladding rod of 2 mm
Space between core glass rod and cladding
tube evacuated by a vacuum pump
Preparation
ep
o of
o a cladding
c dd g tube
ube oof 10
0 mm
Fixation of the core-cladding rod in the cladding tube
Final fibering process leading to the final fiber : TAS#2
intmm
 t  
extmm
cladµm
coreµm
Single mode fibre at 10µm (CO2 laser)