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m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e r

Getter composites for l i fetime

insurance in Organic ElectronicsP a o l o Va c c a

H e a d o f M a t e r i a l s C h e m i st r y L a b

A d v a n c e d C o u s e o n

O R G A N I C E L E C T R O N I C S

P r i n c i p l e s , d e v i c e s a n d a p p l i c a t i o n s

M i l a n o ( i t a l y ) , 2 6 - 2 9 N o v e m b e r, 2 0 1 3

m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013 ©SAES Group2

Outline

SAES Group

OLED degradation phenomena

Getter composites introduction

Organic electronics encapsulation

Configurations & GETTERs

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Core Business and Vision

Starting in 2004 the SAES® Group has expanded its business into knowledge-intensive materials markets, in particular the market of NiTiNOL, whose super elastic properties are applied to medical devices while shape memory properties

are applied in industrial and consumer electronics applications.

Pioneering the development of getter

technology, the SAES® Group is the

world leader in a variety of scientific

and industrial applications where

high/ultra-high vacuum conditions or

pure metal vapors or ultra-pure gases

are required

m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES Group11/21/2013Paolo Vacca ©SAES Group4

Global Presence

Worldwide-based sales and service network through Subsidiaries located inEurope, Asia, USA

Over 1000 employees

10 manufacturing facilities in 3 continents

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Our Research & Innovation idea

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SAES Core Technologies

SAES TECHNOLOGIES

VACUUM GETTER

TECHNOLOGY

METAL DISPENSING

GAS PURIFICATION

ADVANCED METALLURGY

HYBRID POLYMERS

SHAPE MEMORY ALLOYS

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Vacuum Metallurgy for Getters

Fine Powders Metallurgy

Thin Film Deposition

Metals Dispensing

Ultra-high vacuum science &

technology

UHP Gas Handling

In-house Core Competencies

Organic Chemistry

Hybrid Polymer Technology

Ultra High Porosity Sintering

Impregnated Sintered Metals

Nano Powder Technology

Shape Memory Alloys science

& technology

Vacuum Metallurgy for NiTi

Chemical and physical analysis

Materials science

m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES Group11/21/2013Paolo Vacca ©SAES Group8

SAES Core Competencies

SAES Group

CAPTURE (vapor and

gas impurities)

RELEASE (vapor, gas, electrons)

VACUUM

(a volume or a

chamber)

DISSIPATE (heat)

DRY & SEAL (moisture)

RECOVER

(shape)

ACTUATE (parts of

mechanicaldevices)

PURIFY

(gases)

SAES Group products are able to:

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A Customer-focused Approach

Nearly 2,000 active

customers in 5 continents,

spanning from blue chip

companies to business start-

ups, Universities and R&D

centers

70 years of expertise in

partnering with customers

for the engineering of fully

customized solutions

High flexibility in product

development, fine-tuning

and manufacturing, to foster

emerging and forefront

application technologies

Technical service network

and CRM structure

supporting customers’

innovation 24 hours a day

m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES Group11/21/2013Paolo Vacca ©SAES Group10

SAES Group Consolidated Sales

2000-2003 data compliant to Italian GAAP; 2004-2011 data compliant to IFRS

0

20

40

60

80

100

120

140

160

180

2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

172,6160,2

141,2

126,2

141,6138,6

166,7 167,2156,7

127,4140,6

148,6 142,5

M€

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Outline

SAES Group

OLED degradation

Getter composites introduction

Organic electronics encapsulation

Configurations

GETTER COMPOSITES

m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013

350 400 450 500 550 600 650

0,0

0,2

0,4

0,6

0,8

1,0 450

482

wavelength [nm]

Intensity [a.u.]

12V 11V 9V

420

OLED degradation

PhD Thesis “TECHNOLOGY AND ELECTRO-OPTICAL CHARACTERIZATION ON ORGANIC SEMICONDUCTOR DEVICES” P. Vacca

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m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013

Degradation phenomena

H2O, O2contamination

Extrinsic

External contamination

Intrinsic

Inter-diffusion

Material changes

Material blending

During shelf life During operation During operation

Dark spots Pixel shrinkage

Dark spots Short circuits

Luminance decrease

Anisotropic Anisotropic Isotropic

Evolution

Defects

Uniformity

Mechanism

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m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013

Degradation phenomena

In order to limit dark spot area growth and pixel shrinkage below values significantly affecting the display uniformity: maximum H2O pressure inside OLEDs ~ 1.1x10-4 Torr or ~ 0.1 ppm

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Outline

SAES Group

OLED degradation phenomena

Getter composites introduction

Organic electronics encapsulation

Configurations

GETTER COMPOSITES

m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013

Getter composites

A new class of getter materials:

Polymer-matrix (nano) composite chemistry enables the

design and the realization of multi-functional hybrid materials

featuring getter properties

Additional properties as well as optical, mechanical and

surface properties make these composites suitable for

exploitation in a variety of Organic Electronics devices such as

OLED displays, OLED light sources and Organic Photovoltaics.

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Getter materials

G + g G�g×

irreversible / reversible

Key properties of getter materials are: � kinetics of the capture process (adsorption, absorption, chemical

reaction)

� capacity (weight of specific chemical species captured by unit

weight of getter)

� partial pressure of a specific chemical species in equilibrium with

getter

Getter materials are (chemical nature):� pure metals (Ba, Ca, Ti): evaporated thin films

� metal alloys (ZrVFe, ZrCo, TiNi, etc.): bulk and thin coatings

� inorganic, non metal: bulk and thick coatings

� hybrid organic-inorganic: polymer-matrix composites

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Processes: L � L � S getter formulations

� surface properties� rheological properties

deposition processes

� functional properties

solidification processes

L L S

phase1 -> phase2 -> phase3

material characteristics -> processability -> functional properties

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Processability optimization

� Wettabilitymodulation

Increasingpaste polarity

� Rheologicalbehavior

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Getter composites: new systems

Polymer-matrix micro- and nano-composites based on

metal oxides

Polymer-matrix nano-composites based on nano-sized

zeolites

Liquid getters based on perfluoropolymers

Polymer-matrix solid solutions of inorganic hydrophilic

salts

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m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013 ©SAES Group21

Outline

SAES Group

OLED degradation phenomena

Getter composites introduction

Organic electronics encapsulation

Configurations

GETTER COMPOSITES

m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013

Getter composites in device encapsulation config.

� Getter (pattern)

Filler

Getter filmSe

ala

nt

Se

ala

nt

Organic electronic device

� Getter (film)

� Edge sealant

� Filler

� Frame

Fra

me

Fra

me

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Active

sea

lan

t

Active

sea

lan

t

In order to limit dark spot area growth and pixel shrinkage below values significantly affecting the

display uniformity: maximum H2O pressure inside OLEDs ~ 1.1x10-4 Torr or ~ 0.1 ppm

Paolo Vacca ©SAES Group

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m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013

Getter configuration

Getter (film or pattern)

quasi-stationary equilibrium with permeation

High Pumping Speed (high pearmeability) with

the required capacity (lifetime sorption)

PoliMI 2013Paolo Vacca 11/21/2013

glass

active layers

getter

glue

No direct contact with OLED stack

No overlapping with conductive structure

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Frame configuration

Edge sealant

Dryer

Dryer in frame configuration works like an active barrier

(transient regime)

High capacity

Low permeability

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glass

active layers

getter

glue

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Getter

Deposition

Getter

uncured film

Curing Getter film or frame

IN AIR OR

DRY GAS

Process Flow

Device sealing

IN GLOVE BOX

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Composites for getter & frame configuration

Polymer-matrix micro- and nano-composites based on metal oxides

Solventless formulations

Consolidation process (when available) is promoted trough a polymerization mechanism

No solvent evolution during heating treatment

Controlled particles size

Modulated sorption kinetics

Tunable viscosity

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Modified metal oxides: particle size control

0

10

20

30

40

50

60

70

80

90

100

Cu

mu

lativ

e di

strib

utio

n Q

3 /

%

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

Den

sity

dis

trib

utio

n q

3*

0.1 0.2 0.4 0.6 0.8 1.0 2 4 6 8 10 20 40particle size / µm

Particle size distribution after dissolution of paste matrix

raw materials

synthetic route

� micro / sub-micro

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Sorption kinetics modulation

Sorption kinetics

Kinetics modulation

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Tunable sorption kinetic

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Tunable viscosity

Strong increasing in

sorption capacity

Sorption capacity

viscosity

No significant modification

in shear viscosity

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m a k i n g i n n o v a t i o n h a p p e n , t o g e t h e rPaolo Vacca ©SAES GroupPaolo Vacca 11/21/2013

Encapsulation configurations

Getter & frame

Filler

Transparent filler

Active barrier (Sealant)

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Filler configuration - constraints

Chemical compatibility for the OLED stack

Curing conditions suitable for the encapsulation process

Particle size limitation

Outgassing properties

SealantDevice

Encapsulation sheet

FIller

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Dryer in fill configuration works like an active barrier (transient regime)

©SAES Group

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Liquid getters based on perfluoro polymers

Perfluoro polyether

Low volatility

Chemical inertness

Low surface

High oxidative and thermal stability

Wide temperature range stability

High volume resistivity

Non-curable formulation

One-component, low hygroscopic

active filler

Dispersion of SAES proprietary

engineered nano-zeolites

Active filler looks like a slightly

translucent liquid

Active filler shows liquid features

ZetaFill-F3/LV-N/

Organic matrix Perfluoro

Polyether

Average particle size (nm) 300

Viscosity @ 5s-1 (cP) 3.000

Density (g/cm3) 1,90

Curing conditions -

Moisture sorption

capacity (%wt)1,0

Organic matrix

optical T%n.a.

VOC (ppm) < 2 ,0

Low outgassing

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Encapsulation configurations

Getter & frame

Filler

Transparent filler

Active barrier (Sealant)

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Light outcoupling in OLED structureDifferent approaches can be adopted:

In bottom emission configuration:

thin film of a low-loss, high-refractive-index dielectric material on

glass substrate before ITO

Spherically shaped patterns on the back side of the glass substrate

ordered and disordered micro-lens arrays on the backside of

substrate surface

incorporation of well designed microcavities in OLEDs

In top emission configuration:

Introduction of organic layers with high refractive index in OLED

stack

Employment of mirror layers

Passive layers

Employment of organic filler with high optical transmittance and

matched refractive index

35Paolo Vacca 11/21/2013 ©SAES Group

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Transparent filler for light outcoupling

A transparent filler can solve two limitations in large

diffusion of organic light emitting devices

degradation phenomena

light outcoupling

Light

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Polymer-matrix solid solutions of inorganic hydrophilic salts

Liquid scavenger made of an active specie in a

polymer matrix.

It is designed to work as dryer film or as an active filler

Fluid and transparent liquid

It is a solvent free scavenger

Two versions: UV-curable

Thermally curable

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Optical Transmittance

Transmittance > 95% for a film 100um in thickness

Product 405nm 532nm 633nm

matrix 1,50 1,49 1,49

Composite getter 1,50 1,50 1,49

Composite getter

after moisture saturation1,49 1,49 1,49

A molecularly dispersed getter in a

polymeric matrix

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Curing conditions

UV curing conditions for 10-100

um thick layer:

100mW/cm2 for 15s (@365nm)

Volume shrinkage ~ 8% (z-axis)

No Thermal post-curing required

UV curing

Thermal curing

Thermal curing conditions:

80°C for 30 minutes

100°C for 15 minutes

glass PET Stainless

steel

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Getter Ink : rheological properties

Drop break-up is strongly related to the

polymer molecular weight.

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Encapsulation configurations

Getter & frame

Filler

Transparent filler

Active Sealant

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Active sealant

Requirements

Barrier properties

Adhesion properties

Thermodynamic stability

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Active barrier configuration

43Paolo Vacca 11/21/2013 PoliMI 2013

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Active sealant: nano-composites based on nano-

sized zeolites

Main properties

no phase segregation due to chemically tailored

particle surface (class-I materials from non-reactive

capping agents, class-II hybrid materials from reactive

capping agents)

no leaking pathways within the substrate/scavenger

interphase due to particles wetting

good sorption properties (capture rate, capacity,

energetics: low H2O vapour pressure)

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100 nm

SAES nano-zeolite

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SAES nano-zeolite integration

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Zeolite : surface modification

------- mod1

------- raw

------- mod2

------- raw

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Nano-zeolite in organic matrices

Raw nano-zeolite

Surface-modified nano-zeolite

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Active sealant diffusion kinetics

FTIR 3D map of moisture

diffusion front

(transmittance of OH

combination peak ~

stretching + bending)

TEST CONFIGURATION

glass-to-glass,

150 μm-thick,

at 85 °C / 85% RH

reactive edge sealantreactive edge sealantreactive edge sealantreactive edge sealant

glass substrate

glass sheet

d

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Materials Chemisty Lab.

Paolo Vacca, MS in Chemistry, PhD in Organic Electronics

Marco Visconti, MS in Chemistry, PhD in Chemical Science

Giorgio Macchi, MS in Materials Science, PhD in Materials Science

Jiabril Gigli, MS in Food Science, PhD in Food Biotechnology

Alessandra Colombo, MS in Applied and Environmental Chemistry

Marco Mudu, Diploma Degree in Industrial Chemistry

Emiliano Bertinotti, Diploma Degree in Industrial Chemistry

Katia Antico, Diploma Degree

Elisabetta Bossi, MS in Chemistry, PhD student in Materials Eng.

Miriam Riva, MS in Applied and Envir.Chemistry, PhD student

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w w w . s a e s g r o u p . c o m

Thank you for your attention