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

sidney@iq.unesp.br

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

Typical Brazilian tree

IPÊ

IPÊ AMARELO

“YELLOW IPÊ”

IPÊ BRANCO

“WHITE IPÊ”

IPÊ ROSA

“PINK IPÊ”

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

Fiber optics for telecommunications Optimizing Graham Bell´s photophone

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

Glass ceramics Glass crystallization under control

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

Urbach tail

Optical Loss in Fibers

Photonic band gap materials

PBG fibers

Figure 7 from Benabid F.

Figure 1 from Poletti et al

Photonic band gap materials

PBG fibers 2D PBG materials

3D- inverse opals

{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 templates- double exposition Photoresists

Cubic crystals

90o

Hexagonal crystals

60o

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

Front face illumination

Rear illumination

1 m

Bragg diffraction of visible light

PHOTONIC CRYSTALS

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

Opals from Brazil

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

Questions to the next week...

What is a glass??

How do we make a glass??

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

Iguaçu Falls- Southwest Brazil Triple frontier- Brazil, Argentina, Paraguay