materials for photonic applications glasses, optical...
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Materials for Photonic Applications
Glasses, Optical Fibers and Sol-Gel Materials
www.sampaproject.com
Sidney J.L. Ribeiro, Edison Pecoraro, Marcelo Nalin, Younes Messaddeq
and collaborators
Project UNESP-PROPG-NEaD-TIC (UNESP Graduate Studies Office)
Graduate Robson R. Silva and Undergraduate Fernando E. Maturi
April-June- 2013
www.iq.unesp.br www.unesp.br
270 kM
from the
City of
São Paulo
ARARAQUARA
derived from “Aracoara”
“City of the Sunshine”
“World capital of oranges”
200.000 inhabitants
18th in number of
inhabitants in the
state of São Paulo
1st in quality of life
http://pt.wikipedia.org/wiki/Araraquara
University of the State of São Paulo
UNESP
32 schools / 23 cities
169 undergraduate programs
35,000 undergraduate students
10,000 graduate students
9,000 Diplomas per year
3,400 Academic staff (95% PhDs – 87% full
time)
7,000 Non academic staff
www.unesp.br
Undergraduate and Graduate Chemistry Studies 80 prof/res, 1000 undergraduate students, 500 graduate students (>1000 thesys)
Biomaterials
Photonics
Energy
Biofuels
Natural products
Biochemistry
Ceramics, glasses
Nanotechnology Biophotonics
Materials science
Catalysis
Our Institute.. www.iq.unesp.br
Laboratory of Photonic Materials
10 pos-docs, 10 grad- std, 10 undergrad. std
Sidney J.L. Ribeiro Younes Messaddeq
Development of novel photonic materials and biomaterials
Edison Pecoraro Marcelo Nalin
Health (luminescent markers for imaging and
diagnostics, temporary substitutes for the
skin. Templates for bones regeneration)
Education Science diffusion
Technology transfer
Spin-off companies
Agriculture (fiber optics sensors for
nutrients, encapsulation
of nutrients, slow delivery)
Environment (optical fibers sensors,
materials for solar energy)
Telecommunications
And Information (optical fibers, exhotic fibers, waveguides)
Materials for Photonic Applications
Glasses
Glass-ceramics
Waveguides
Optical fibers,thin films and channel waveguides
Spontaneous and Stimulated emission
Fundamental of Lanthanides Spectroscopy
Luminescent markers, luminophors
Lasers, Optical amplifiers
Sol-Gel Methodology (soft chemistry)
Organic-inorganic hybrids
the best of the organic and inorganic worlds
Nature as inspiring source- Biomimicking in
Photonics
2013 tentative program May vary following the specific
Interest of attendees
M.C.Escher
“Hand with reflecting sphere”- 1935
www.mcescher.com
electronics Opto-electronics Photonics
20th century 21th century
Photonics- photons as information carriers
A.Graham Bell
Photophone
1880
Lasers
Optical fibers
Efficient detectors
modulators
Optical fibers
Materials for Photonics
How new are the “state of the art materials” we are using?
Lycurgus cup
"the most spectacular glass of the period,
fittingly decorated, which we know to have existed"
Venetian
red glasses
Roman and Venetian Glasses
Au/Ag nanoparticles
Absorption and scattering effects
in the control of the colors we see
Beginning of PLASMONICS
Michael Faraday stated for the first time that the
colors of ruby gold were due to its finely divided
state (19th century).
Faraday’s sample of Au nanocrystals in the Royal Museum
Institution in London
Lubomir Spanhel- Rennes- France
Plasmons- collective oscillations of metal surface electrons
Considering nanoparticles, plasmons can be excited with visible light
The local electric field can lead to enhancement of intensities
in different spectroscopic techniques
Surface-enhanced spectroscopy
• Surface-enhanced Raman scattering (SERS)
• Surface-enhanced resonance Raman scattering (SERRS)
• Surface-enhanced fluorescence (SEF)
• Surface-enhanced infrared absorption (SEIRA)
Maya blue
8th to15th centuries
Can we enhance resistance to weathering of
organic devices (OLEDs, solar cells, etc??)
Materials for Photonics
How new are the “state of the art” materials we are using?
1st Organic-Inorganic Hybrid
(indigo blue dye + clays)
Amazing resistance to weathering
over more than 15 centuries!!!
We still don´t know how Maya artists prepared their blue pigment!!
Glasses and Photonics
What is a glass? How a glass is prepared?
Preparation and characterization
optical properties, colors, luminescence
Materials for Photonic Applications
Glasses, Optical Fibers and Sol-Gel Materials
Glasses
-1st material man learned how to prepare
-isotropic medium
-transparency, shining
-freedom for compositions (properties
tunning)
-freedom for shape (moldable)
-mechanical resistance
-chemical resistance, solubility may be tunned
-beauty
Photonics
architecture , biomaterials,
kitchenware, sensors
packaging, etc, etc and etc
on off smart windows
self-cleaning glasses
stoves cover panels
zero expansion materials
optical fibers
Optical fibers- How are they made?
http://www.youtube.com/watch?v=D4nGPI6DTLw
Some videos available at internet that you must see!!
Marbles- Everybody has already played with one of these. How are they made?
http://www.youtube.com/watch?feature=player_embedded&v=mAUAy8rlwHY#!
Corning vision- “A day made of glass” series- amazing!!
A day made of glass 1- http://www.youtube.com/watch?v=wk146eGRUtI
A day made of glasss 2- http://www.youtube.com/watch?v=v-Hd9kip1wA
A day made of glass 2 with additional comments- What exists already and what
is still to come- http://www.youtube.com/watch?v=X-GXO_urMow
400 450 500 550 600 650 700 750 800 850 9000
30
60
90
120
150
180
210
+3F
2,3
3H
4
3H
6
3H
6
3H
6
3F
4
1G
4
PP = 800 mW
P = 1.064 m
Room Temperature
1G
4
Upconvers
ion inte
nsity
(a.u
.)
Wavelength (nm)
Yb3+ Tm3+
2F7/2
2F5/2
3H6
3H5
3H4
3F4
3F2,3
1G4
1.0
64
m
655 n
m
485
nm
800
nm
655 n
m
Yb-Tm doped tellurite
Glasses, thin films and
optical fibers
IR excited
White light emission
Functionality in glasses
Examples
dos Santos et al., J.Appl.Phys. 90(12)6550(2001)
Photosensitive glasses
Photoexpansion in Ga10Ge25S65
laser-351nm
Holographic grating
n25%
Refrative index
profile
Messaddeq et al, Appl. Surf. Sci. 252(24)8738(2006)
Functionality in glasses
Examples
ionicsuperionic
transition
125oC
Transparent glass-ceramics
PbF2 nanocrystals
in PbGeO3-CdF2-PbF2 glasses Superionics TEM
50nm
IR emission- Er3+
Transparent GC “Crystal-like” spectra
Glass
nm
-Low dispersion of crystallite sizes
-no clustering
-reproducible
Functionality in glasses
Examples
Tambelli et al, J.Chem.Phys, 120, 9638(2004)
Ribeiro et al, Mat.Sci.Forum, 514-516, 1299(2006)
Tungsten glasses for optical devices
BaF2-NaPO3-WO3
0 400 800 1200
x=70
x=60
x=50
x=40
x=30
x=20
x=10
x=0
Wavenumber (cm1)
NaPO3
WO3
0 20 40 60 80 100
0,3
0,4
0,5
0,6
0,7
0,8
0,9
NBW50
NBW40
NBW30
Tra
nsm
ita
ncia
(I/
I 0)
Intensidade de entrada (MW/cm2)
2
5,6cm/GW
11cm/GW
Optical limiting
Optical fiber preform
WO3 clustering
Raman scattering
Functionality in glasses
Examples
Poirier et al, J.Appl.Phys., 91(12)10221(2002)
Incre
asin
g W
con
ten
t
X=
WO
3 c
on
ten
t
Photochromic properties
300 400 500 600 700 800 900
0
20
40
60
80
100
850nm
514nm
488nm
350nmTra
nsm
itância
(%
)
Comprimento de onda (nm)
Continuous
UV laser
Continuous
visible laser
Pulsed infrared
laser
(fentosecond)
Photochromism W6+W5+
reversible
Functionality in glasses
Examples
Poirier et al, J.Chem.Phys. 125(16)161101(2006)
Transmission spectrum
Glass ceramics
Ceramics obtained from glasses. Are they better than
classic ceramics?
Transparent glass-ceramics. They are made as glasses
but display crystal-like properties
Materials for Photonic Applications
Glasses, Optical Fibers and Sol-Gel Materials
Light guides
Optical fibers. How are they prepared?
Sensors, PBG (photonic band gap) fibers
Thin films, channel waveguides, Integrated optics
Stimulated and spontaneous emission
Fundamentals of lanthanides spectroscopy
Luminescent markers, luminophors,
Lasers andOptical amplifiers
Materials for Photonic Applications
Glasses, Optical Fibers and Sol-Gel Materials
{111}
450 500 550 600 650 700 750
Reflection (
u.a
.)
WAVELENGTH (nm)
450 500 550 600 650 700 750
45o-603nm 110-673nm
Pseudo photonic band gap
Barros Filho et al, J. Coll. Interface Sci., 291(2005)448
2D photonic crystals
Sb2S3
Photoresist template Deposition of the active layer
Template removal Sb2S3 2D PBG
Sol-Gel Methodology
Colloids, nanotechnology
Organic-inorganic hybrids- better things from both worlds
Photonic Applications
Nature mimicking
Materials for Photonic Applications
Glasses, Optical Fibers and Sol-Gel Materials
Sol-Gel process-Preparation of glasses/ceramics from solutions
of organometalics or inorganics
Sol- stable dispersion of solid particles in a liquid
Gel- 3D stable solid particles interconnected and expanded in a liquid medium
Figure from http://www.chemat.com/chemattechnology/aboutus.aspx
cryogels
Hydrolysis
SN
Metal (and semimetal) oxide nanocolloids in sol-gel chemistry
solvent : alcohol
M
O R
RO OR
R O
O H
H
ROH + M
OR
RO OH
OR
M
OR
RO OR
OR
SN
Condensation
ROH + M
O R
RO O
OR
M
O R
OR
OR
“sol” “gel”
glasses
ceramics
TEOS
Tetraethoxysilane
Lubomir Spanhel- Rennes- France
Control of hydrolysis and condensation reactions -pH
-Catalyst (acid, base, NH4F, amines...)
-H2O/Si molar ratio
-aging time
Acid catalyzed Base catalyzed
Linear or randomly
branched polymer Highly branched clusters
Porosity at the nanometric scale
High optical quality
Preforms, thin films...
Dense Sub-micronic particles of
Silica (Stober process)
Controlled packingPhotonic
Crystals
Michael Faraday stated for the first time that the
colors of ruby gold were due to its finely divided
state (19th century).
Faraday’s sample of Au nanocrystals in the Royal Museum
Institution in London
Lubomir Spanhel- Rennes- France
Colloids and nanotechnology
molar mass [g/mol] 100 102 104 108 106 1010 1012
atoms
molecules
proteins
polymers
virus, DNA, vesícles
macroscopic
solids
size [nm] 2 20 200 2000
“Colloids”
clusters, nanoparticles microparticles
surface area [m2/g] 1000 100 10
Nanotechnology Lubomir Spanhel- Rennes- France
Nano-analytical methods
1 nm 10 nm 100 nm 1 µm colloidal limit
Ultracentrifugation
Electrophoresis
Nitrogen Adsorption
XPS, AFM, SEM, STM, HRTEM
SAXS, SANS, XRD
UV-vis, fluorescence, confocal opt. microscopy Pulse radiolysis, Laser photolysis
Mie scattering PCS
20 nm !
Particle size
Aggregate structures
Interface chemistry
Nanocrystallinity
Surface area
Particle size
Zeta potential
In situ monitoring of
colloid growth
Lubomir Spanhel- Rennes- France
Richard Feynman’s statement
in Berkeley in 1959:
“...there is plenty at the bottom”
initiated development of new thin film
technologies combined with “top-down”
approach to nanoparticles
(bottom limit: 10 nm)
Richard Feynman is considered the
precursor of nanotechnology
A. Efros et al: Ioffe Institut in St. Petersburg, 1978
L. Brus et al: Bell Labs in New Jersey, 1982
A. Henglein et al: Hahn-Meitner-Institut in Berlin, 1983:
chemical “bottom-up” approach to nanoparticles (bottom limit: 0.5 nm)
quantum theory of semiconductor particle size effects
Lubomir Spanhel- Rennes- France
Eu3+ doped SnO2 nanoparticles (in water!!)
Capped particles
Non-Capped
particles
2-5nm
Visible emission
Under UV excitation
Gonçalves et al, J.Nanosci.Nanotech. 11, 2433, 2011
L.D.Carlos et al-Adv.Functional Materials, 2001, 11(2),111
Silica cluster
POE fragment
Siloxane clusters and polyoxiethylene units linked by
urea bridges- UREASILS
siloxane clusters
polymer chains
Main characteristic- Photoluminescence is tuned by the
molecular local structure.
GPTS/MPTS water
pre-hydrolized
Zr(OPr)3
MMA
Photopolymerizable
SOL
water
MPTS
GPTS
Modified ZrO2 sol
Photopolymerizable sols
H.Krug et al- SPIE, 1758,448,1992
q
q
q
sample
mirror
Bragg gratings- Lloyd Interferometer
Ar laser
351nm
Interference
Pattern with
Period given by q
Lycurgus Cup (4th century )
Ag and Au nanoparticles (50-100nm) in the glass
British Museum, London transmited light reflected light
How to make a glass?
Recipe- Assirian Kingum vidro- Ashurbanipal- 669-616 b.C.
But, what is a glass?
-Amorphous solids
-under cooled liquids
-Amorphous solids displaying Tg
-”The vitreous state”-I.Gutzov- Any state,
thermodinamycally metastable,
with "frozen-in" properties
www.cmog.org- Corning Museum of Glass