aristotle university of thessaloniki physics department · 2007-07-25 · 11th tappi european place...

11th TAPPI European PLACE Conference1

RealReal--time & intime & in--Line Optical Monitoring of Functional Line Optical Monitoring of Functional NanolayerNanolayer Deposition on Flexible Polymeric Deposition on Flexible Polymeric

SubstratesSubstrates

Lab for Thin Films Lab for Thin Films -- NanosystemsNanosystems & & NanometrologyNanometrology (LTFN)(LTFN)Physics Department, Physics Department, AUThAUTh

Aristotle University of Aristotle University of ThessalonikiThessalonikiPhysics DepartmentPhysics Department

GRGR--54124 Thessaloniki, Greece54124 Thessaloniki, Greece, http://, http://ltfn.physics.auth.grltfn.physics.auth.gr

Prof. S. Prof. S. LogothetidisLogothetidis


Polymeric Materials: New Emerging Technologies & ApplicationsPolymeric Materials: New Emerging Technologies & Applications

Optical Properties of Materials for the Production of Flexible Optical Properties of Materials for the Production of Flexible Electronic Devices (Electronic Devices (FEDsFEDs))

UpUp--scaling of Optical Sensing techniques from Lab scale to scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production ProcessesLarge scale r2r Production Processes

Summarising & ConclusionsSummarising & Conclusions

OutlineOutline

Spectroscopic Spectroscopic EllipsometryEllipsometry : Principles & Methodology: Principles & Methodology

Anisotropic Polymeric SubstratesAnisotropic Polymeric SubstratesBarrier Barrier NanoNano--layerslayersElectrodes & Transparent Conductive Oxides (Electrodes & Transparent Conductive Oxides (TCOsTCOs))Organic Conductive OxidesOrganic Conductive Oxides








OutlineOutline


The interest on the Polymeric materials The interest on the Polymeric materials in in a wide range of a wide range of Scientific,TechnologicalScientific,Technological& Industrial Applications & Industrial Applications originatesoriginates from the from the Very Important PropertiesVery Important Properties they they exhibit and their exhibit and their Low CostLow Cost & & FlexibilityFlexibility in in UseUse in in Large Area ProcessesLarge Area Processes..

Barrier Films & Coatings for Barrier Films & Coatings for EncapsulationEncapsulationProtectiveProtective & Decorative& Decorative CoatingsCoatingsCorrosion Resistant CoatingsCorrosion Resistant Coatings

Polymeric Materials: Polymeric Materials: New Emerging Technologies & ApplicationsNew Emerging Technologies & Applications

Final ApplicationsFinal ApplicationsFlexible Electronics DevicesFlexible Electronics DevicesOptoelectronic & Electronic DevicesOptoelectronic & Electronic DevicesOpticalOptical & & Recording DevicesRecording DevicesBiocompatibleBiocompatible -- Medical ImplantsMedical Implants


The Fabrication of the state-of-the-art Products includes their encapsulation into transparent Polymeric media to Protect them against atmospheric O2 &

H2O-moisture, which are harmful for their Performance & Long-term Stability.

Encapsulant (Flexible polymer layer)

Functional Thin Filmelectronic modules (ITO layers, electron transportlayers, organic emitters, etc.)

EncapsulatedFEDsFEDs

roll

roll




roll

roll

roll

roll

Encapsulation ConceptEncapsulation Concept LargeLarge--scale scale rollroll--toto--rollroll (r(r2r) 2r) Encapsulation systemEncapsulation system

(roll length ~3000 m & 2 m width)(roll length ~3000 m & 2 m width)

Polymeric Materials: Polymeric Materials: New Emerging Technologies & ApplicationsNew Emerging Technologies & Applications


Plasma Assisted Evaporation and Sputtering techniques for the deposition of functional nano-layers onto flexible polymeric

films by large scale r2r techniques

Polymeric Materials: Polymeric Materials: Large Scale Production of novel productsLarge Scale Production of novel products

Plasma Assisted Evaporation Sputtering








OutlineOutline


Determination of Determination of ThicknessThickness, , Bonding Bonding structurestructure & & ConfigurationsConfigurations, , VibrationalVibrational

propertiesproperties, , Electronic transitionsElectronic transitions, , StoichiometryStoichiometry, , Optical anisotropyOptical anisotropy, ,

Deposition RateDeposition Rate,, Growth Growth MechanisnMechanisn etc.etc.

Extensive spectral range:Extensive spectral range: InfraInfra--Red regionRed region : : 900 900 -- 4000 cm4000 cm--11

NIR NIR –– VisVis -- farUVfarUV regionregion: : 0.7 0.7 -- 6.5 6.5 eVeV

The optical monitoring of Polymeric The optical monitoring of Polymeric substrates & Deposition of transparent substrates & Deposition of transparent barrier layers is being performed by barrier layers is being performed by Spectroscopic Spectroscopic EllipsometryEllipsometry in a wide in a wide spectral region (IR to spectral region (IR to VisVis--fUVfUV))

Spectroscopic Spectroscopic EllipsometryEllipsometry –– SE SE ……....


Study of the Electronic Structure & Study of the Electronic Structure & Properties of the Polymeric materialsProperties of the Polymeric materials((Electronic transitionsElectronic transitions))

Optical FiberOptical Fiber

SampleSample

PolarizerPolarizerPhotoelasticPhotoelasticModulatorModulator

AnalyzerAnalyzer

DetectorDetector

MonochromatorMonochromatorData AcquisitionData AcquisitionComputerComputer

XeXe lamplamp

ShutterShutter


SampleSample



AnalyzerAnalyzer

DetectorDetector


XeXe lamplamp

ShutterShutter

XeXe lamplampXeXe lamplamp

ShutterShutter

3-6.5 eV

0.7- 6.5 eV

EX-SITU CONFIGURATION

IN-SITU CONFIGURATION

Near IR Near IR –– Visible Visible –– far UVfar UVPhase Modulated Spectroscopic Phase Modulated Spectroscopic EllipsometryEllipsometry


FTIRSE is a powerful & Sophisticated Optical technique for invesFTIRSE is a powerful & Sophisticated Optical technique for investigation of tigation of VibrationalVibrational properties of properties of Bulk Materials, Thin films, Nanostructures, Bulk Materials, Thin films, Nanostructures, MultilayersMultilayers etc.etc.

Film

Substrate Holder

Ultra High Vacuum Chamber

PhotoelasticModulator

Polarizer

IR source (SiC)

Michelson Interferometer

Focusing System

BaF2Windows

Analyser

Focusing System

Focusing System

BaF2 Windows

Acquisition & Analysis Software

Liquid Nitrogen Supply

AdvantagesAdvantages-- NonNon--destructive techniquedestructive technique-- Direct & Simultaneous Determination of Real Direct & Simultaneous Determination of Real <<εε11((ωω)>)> & Imaginary part & Imaginary part <<εε22((ωω)>)> of of <<εε((ωω)>=<)>=<εε11((ωω)>+)>+i<i<εε22((ωω)>)>-- Identification of IR responses even at a Monolayer levelIdentification of IR responses even at a Monolayer level-- Can be used in a variety of Media Can be used in a variety of Media ((VacuumVacuum, , airair, , transparent liquidstransparent liquids..) ..) -- Does not require Special Conditions Does not require Special Conditions for the measured materialsfor the measured materials-- Acquisition time ~ Acquisition time ~ 2 2 sec, sec, for for inin--situsitu & & realreal--timetime Monitoring of Deposition & Treatment Monitoring of Deposition & Treatment of Materials & Systemsof Materials & Systems

Fourier Transform IR Phase Modulated Fourier Transform IR Phase Modulated Spectroscopic Spectroscopic EllipsometryEllipsometry (FTIRSE)(FTIRSE)


SE SE measures the dielectric function measures the dielectric function εε((ωω)=)=εε11((ωω)+i)+iεε22((ωω))-- Probes Probes the Electronicthe Electronic--VibrationalVibrational-- StructuralStructural-- Morphological material propertiesMorphological material properties-- NonNon--destructivedestructive, Surface sensitive (, Surface sensitive (thickness of thickness of ÅÅ can be measuredcan be measured))-- Capability for iCapability for inn--situsitu && realreal--time time monitoring monitoring ofof phenomena phenomena & & mechanismsmechanisms-- Ultra high speedUltra high speed of measurement of measurement -- AAdvanceddvanced modellingmodelling proceduresprocedures

Spectroscopic Spectroscopic EllipsometryEllipsometry : Basic Principles: Basic Principles

Bulk MaterialsBulk MaterialsipEr

isEr rsE

r

rpEr

θ0 θ0περιβάλλον (0)

μέσον (1) n1

n0

θ1

ĒtsĒtp

Medium (1)

Medium (0)

φ0 φ0medium (0)

film (1) ΝΝ11φ1

φ2

φ1 φ1 d

substrate (2) Ν2

ΝΝ00φ0 φ0medium (0)

film (1) ΝΝ11φ1

φ2

φ1 φ1 d

substrate (2) Ν2

ΝΝ00

Film / Substrate SystemsFilm / Substrate Systems

⎥⎥⎦

⎤

⎢⎢⎣

⎡⎟⎟⎠

⎞⎜⎜⎝

⎛+−

+= 02

2

022 tan~1

~11sin)(~ φφNρρωε ο

Calculated Quantity Calculated Quantity

iΔ)δi(δ

s

p

s

p tanΨeerr

rr

ρ sp === −

~~

~~

~

Complex Reflectance RatioComplex Reflectance Ratio

θsinnnλd2πβ 22

021 −⎟

⎠

⎞⎜⎝

⎛=


SE obtains accurate results from the measured <ε(ω)> spectra, of the film/substrate system, with specific modeling procedures:

1.1. TaucTauc--LorentzLorentz Model*Model*

* S. Logothetidis, Diam. Relat. Mater. 12, 141 (2003).G.E. Jellison, Jr and F.A. Modine, Appl. Phys. Lett. 69, 371 (1996).

2.2. For the analysis of Composite For the analysis of Composite Materials, we use theMaterials, we use the Effective Effective

Medium Approximation Medium Approximation (BEMA)(BEMA)0

ε~2ε~ε~-ε~

)-(1ε~21ε~-1

=+

++ eff

eff

eff

eff ff

eff~ε ε~

: optical response of top layer : optical response of bottom layer

f : void volume fraction parameter

ωωωω

ωωωε 1

222)22(

2)()(2 ⋅

+−

−=

CgωCA

O

O

, ω>ωg

ξωξξξω

πεε

ωdPω

g∫∞

∞ −+=

222

1

)(2)(

Spectroscopic Spectroscopic EllipsometryEllipsometry : Basic Principles: Basic Principles








OutlineOutline


PolyEthylenePolyEthylene TerephthalateTerephthalate (PET)(PET)

PolyEthylenePolyEthylene NaphthalateNaphthalate (PEN)(PEN)

PEN is a relatively new polymeric material PEN is a relatively new polymeric material with enhanced mechanical, with enhanced mechanical,

thermal, and barrier propertiesthermal, and barrier properties

Polymeric SubstratesPolymeric Substrates……


c (MD)b (TD)

a (ND)

θ

Ellipsometersystem (x’,y’,z’)

y’

z’

Plane ofIncidence

x’

Polymer film system (a,b,c)

c (MD)b (TD)

a (ND)

θ


y’

z’

Plane ofIncidence

x’


Machine Direction

TDMD

a=4.50Å, b=5.90 Å, c=10.76 Å, α=100.3°, β=118.6°, γ=110.7°

(α-polymorphism)a=6.51Å, b=5.75 Å, c=13.20 Å,α=81.33°, β=144°, γ=100°

(β- polymorphism)a=9.26Å, b=15.59 Å, c=12.73 Å, α=121.6°, β=95.57° γ=122.52°

The study of the Optical & Electronic properties of the PET and PEN Polymeric materials involves a high degree of Complexity due to the Macromolecular Chains & Stretching during their fabrication…

Polymeric Substrates: Polymeric Substrates: Optical propertiesOptical properties

* A. Laskarakis, S. Logothetidis, J. Appl. Phys. 99, 066101-1 (2006).


PENPENPeak I:Peak I: ~ 3.~ 3.55 eVeV

Peak II:Peak II: ~ 3.6 ~ 3.6 eVeV

Peak III:Peak III: ~ 4.4 ~ 4.4 eVeVPeak IV:Peak IV: ~ 5.1 ~ 5.1 eVeV

n n ππ**C=OC=O

11AAgg11BBuu

Peak I:Peak I: ~ 4.1 ~ 4.1 eVeV

Peak II:Peak II: ~ 4.3 ~ 4.3 eVeV

Peak III:Peak III: ~ 5.1 ~ 5.1 eVeV

Peak IV:Peak IV: ~ 6.5 ~ 6.5 eVeV

n n ππ**C=OC=O

11AAgg11BBuu

PETPET

I, II

III, IV

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.50

1

2

3

4

5

6

7

8

0

1

2

3

4

5

6

7

81.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

ε2(ω)

ε1(ω)

ε 1(ω)

ε 2(ω)

ε2(ω)

ε1(ω)

IVaIVb

IVcIIIcIIIbIIIa

II

ε 2(ω)

ε 1(ω)

Photon energy (eV)

I

PEN (25 μm)

III

PET (12 μm)

III

IV


Polymeric Substrates: Polymeric Substrates: Optical & Dielectric propertiesOptical & Dielectric properties


4,0 4,5 5,0 5,5 6,0 6,5

2

3

4

5

6

7

0

1

2

3

4

5

6

0o

30o

60o

90o

120o

150o

ε 2(ω)

ε 1(ω)

Photon Energy (eV)

IVIII

II

(a) PET

I

Angle θ

c (MD)b (TD)

a (ND)

θ


y’

z’

Plane ofIncidence

x’


3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5

-1

0

1

2

3

4

5

6

7

8

9

10

0

2

4

6

8

10Angle θ

IVc

IVb

IVa

IIIcIIIbIIIa

II

0o

30o

60o

90o

120o

150o

ε 2(ω)

ε 1(ω)

Photon Energy (eV)

(b) PEN

I

PET at various angles θ PEN at various angles θ


Polymeric Substrates: Polymeric Substrates: Optical & Dielectric propertiesOptical & Dielectric properties

11th TAPPI European PLACE Conference18* A. Laskarakis, S. Logothetidis, Applied Surface Science (in press 2006)

Vibration Band PET (cm -1) Dichroic Ratio PEN (cm-1) Dichroic Ratio C-O stretch 940, 971 ~6.8,S ~4.66S 950, 980

C-O and C-H in plane def. 1025 1.51S 1020 - Ethylene glycol stretching & bend. + ring modes 1098 ~1.31A

CH2 stretch 1125 ~1.61A 1135 ~1.28A C-H in line bend. 1170 1.19S -

C-C bend & C-C stretching mode (naphthyl) - 1184 1.34S Ester modes 1255 ~1.53A 1257 1.32A

CH2 wagging mode (trans) 1342 ~2.29S 1335 1.29S CH2 wagging mode (gauge) 1370 1374 1.24S

C-H in plane def. (phenyl ring) 1410 1.93S - CH2 bending mode (gauge) - 1450 CH2 bending mode (trans) 1470 1483

C-H in plane def. 1505 - C=C stretching mode (aromatic ring) - 1635 1.48S

C=O stretch 1720 0.504A 1713 0.68A S: measured by the FTIRSE spectra; A: calculated by the ratio of peak area (see text).

900 1000 1100 1200 1300 1400 1500 1600 1700 1800

-8

-6

-4

-2

0

2

4

6

8

10

0o

30o

60o

90o

120o

150o

165013

4513

70 1490

1515

1720

1410

ε 2(ω)

Wavenumber (cm-1)

(a) PET 1255

120011

70

98595

0

1025

1075

1125

Angle φ

900 1000 1100 1200 1300 1400 1500 1600 1700 1800-4

-3

-2

-1

0

1

2

3

4

5

6

7

0o

30o

60o

90o

120o

150o

Wavenumber (cm-1)

(b) PEN

1635

1335

1374

1483

1549

1713

1450

ε 2(ω)

1257

1184

980

957 10

20

1096

1135

Angle θ

Angle θ

Polymeric Substrates: Polymeric Substrates: Optical & Optical & VibrationalVibrational PropertiesProperties

PENPENPETPET


PLASMAPLASMA

Surface treatment of polymers Surface treatment of polymers using ion beams and plasmausing ion beams and plasma

Dramatic physical & chemical modifications Dramatic physical & chemical modifications that influence the surface that influence the surface nanonano--topography, topography, optical, mechanical and biological properties optical, mechanical and biological properties

Bond breaking, CrossBond breaking, Cross--linking, linking, Formation of new chemical groups,Formation of new chemical groups,Emission of small molecular groupsEmission of small molecular groups

Surface ModificationSurface Modification && Activation Activation Adhesion improvement, SterilizationAdhesion improvement, Sterilization

For the modeling of the Surface Treatment of the For the modeling of the Surface Treatment of the polymers we use a polymers we use a two layer model consisted by two layer model consisted by a substrate (represented by untreated polymer a substrate (represented by untreated polymer film) and the modified film) and the modified overlayeroverlayer (thickness d)(thickness d)

Surface Reactions on Polymers: Surface Reactions on Polymers: Ion Beam & Plasma Treatment Ion Beam & Plasma Treatment

POLYMER SUBSTRATEPOLYMER SUBSTRATE

MODIFIED OVERLAYERMODIFIED OVERLAYER


N2

Film

Ion beam

Substrate Holder

Plasma

Ar

O2ULTRA HIGH VACUUMDEPOSITION CHAMBER

Gas Inlet

End Hall Ion Source

Pulsed DC Supply

PhotoElasticModulator

Polarizer

IR Source (SiC)

Michelson Interferometer

Focusing System

IR Windows BaF2

Analyser

Detection System

Focusing System

IR Windows BaF2

Acquisition & Analysis System

Liquid Ν2Inlet

Kauffman Ion Source

Pulsed DC Plasma TreatmentPulsed DC Plasma Treatment

Ion Beam BombardmentIon Beam Bombardment

Ultra High Vacuum DepositionChamber equipped with in-situ& real-time Optical sensing techniques

InIn--situ Optical Monitoring of Surface situ Optical Monitoring of Surface FunctionalizationFunctionalizationof Polymers by Plasma: of Polymers by Plasma: Experimental SetExperimental Set--upup


Optical Investigation by Optical Investigation by FTIR SEFTIR SE of the Nof the N22 Plasma treatment on Plasma treatment on PET Polymer SubstratesPET Polymer Substrates

900 1000 1100 1200 1300 1400 1500 1600 1700 18000

1

2

3

4

5

6

7

8

str. modeCH2

C-H

ε1(ω)

PET untreated treated V=300V treated V=500V treated V=700V

Die

lect

ric F

unct

ion ε(ω

)

Wavenumber (cm-1)

ε2(ω)

C=O

C-O

C-H

CH2

ester modeReduction of C-O bonding groups (~1234 cm-1)

Increase of C=O bonds in C-(C=O)-C & C-(C=O)-Ο-C)bonding groups (~1714 cm-1 & ~1741 cm-1)

Experimental Conditions:Pb= ~10-7 TorrP(N2)= 30 mTorrΦΝ2= 40 sccmPDC Voltage = 300,500,700 VoltT=1200 sec

InIn--situ Optical Monitoring of Surface situ Optical Monitoring of Surface FunctionalizationFunctionalizationof Polymers by Plasma: of Polymers by Plasma: IR regionIR region

A. Laskarakis, S. Logothetidis, S. Kassavetis, E. Papaioannou, Thin Solid Films (in press 2006).


3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5

-0,5

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

IVIII

II

Untreated 200 V 300 V 500 V 700 V

ε 2(ω)

Photon Energy (eV)

I

PET The Surface Modification affects the Optical properties of the PET film in a surface overlayer due to…

Optical Investigation by Optical Investigation by VisVis--fUVfUV SESE of the Nof the N22 Plasma treatment on Plasma treatment on PET Polymer SubstratesPET Polymer Substrates

InIn--situ Optical Monitoring of Surface situ Optical Monitoring of Surface FunctionalizationFunctionalizationof Polymers by Plasma: of Polymers by Plasma: VisVis--fUVfUV regionregion

…the Surface Modification is confined in surface layers from~15 to 40 nm, depending on the Ion Energy of plasma… 200 300 400 500 600 700

5

10

15

20

25

30

35

40

45

Tauc-Lorentz

Lorentz

Mod

ified

Ove

rlaye

r Dep

th (n

m)

Pulsed DC Bias Voltage (V)

TRIM

PET

modified overlayer






OutlineOutline




GGas transport pathways as transport pathways throughthrough the the barrierbarrier layerlayer

Issues to Solve Issues to Solve ……..

TARGETThe achievement of Ultra High Barrier

Properties for the envisaged applications

10 -6 10 -4 10 -2 10 0 10 210 -6

10 -4

10 -2

10 0

10 2

water vapour permeability / g / m2 d

oxyg

en p

erm

eabi

lity

/ cm

3 / m

2d

bar

OLED displays, organic solar cells

standard: 1 inorg. layer

Single polymers

sensitive foodproducts

LCD / LED displays,photovoltaicmodules

vacuum insulating

panels

POLO: 2 inorg. layers

POLO: 1 inorg. layer

10 -6 10 -4 10 -2 10 0 10 210 -6

10 -4

10 -2

10 0

10 2

water vapour permeability / g / m2 d

oxyg

en p

erm

eabi

lity

/ cm

3 / m

2d

bar

OLED displays, organic solar cells

standard: 1 inorg. layer

Single polymers

sensitive foodproducts

LCD / LED displays,photovoltaicmodules

vacuum insulating

panels

POLO: 2 inorg. layersPOLO: 2 inorg. layers

POLO: 1 inorg. layerPOLO: 1 inorg. layer

PEPEToPAoPP10-50 μm

e.g. PET/SiOx/PESiOx ~40nm

Permeability ofPermeability ofAtmospheric Gases (Atmospheric Gases (OO22 καικαι HH22OO))

The Atmospheric Gas permeation through the multilayer material sThe Atmospheric Gas permeation through the multilayer material structure tructure sets the limits for the operation and stability of the whole FEDsets the limits for the operation and stability of the whole FED structurestructure……


Optical Properties- Penn Gap ω0- Refractive Index n- Fundamental Gap ωg

Optical PropertiesOptical Properties- Penn Gap ω0- Refractive Index n- Fundamental Gap ωg

In order to In order to Integrate Optical Sensing TechniquesIntegrate Optical Sensing Techniques for the Determination for the Determination & Optimization of the & Optimization of the Functional properties of the Materials & Systems,Functional properties of the Materials & Systems,certain certain CorrelationsCorrelations must be Establishedmust be Established……

Intermediate Properties- Thickness- Stoichiometry - Composition- Density

Intermediate PropertiesIntermediate Properties- Thickness- Stoichiometry - Composition- Density

Functional Properties- O2 transmission- H2O transmission

Functional PropertiesFunctional Properties- O2 transmission- H2O transmission

Towards the Determination & OptimizationTowards the Determination & Optimizationof Barrier properties of Polymer materialsof Barrier properties of Polymer materials

PETSiOx film

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.50

1

2

3

4

5

6

7

8

0

1

2

3

4

5

6

7

81.5 0.0

ε1(ω)

ε 2(ω)

ε2(ω)

IVaIVb

IVcIIIcIIIbIIIa

II

ε 1(ω)

Photon energy (eV)

I

PEN (25 μm)

PENPENPolymer substrate

PENPENPolymer substrate

900 1000 1100 1200 1300 1400 1500 1600 1700 18000

1

2

3

4

5

6

7

8

str. modeCH2

C-H

ε1(ω)

PET untreated treated V=300V treated V=500V treated V=700V

Die

lect

ric F

unct

ion ε(ω

)

Wavenumber (cm-1)

ε2(ω)

C=O

C-O

C-H

CH2

ester mode


1) Control unit of the UFMWE2) Multi-wavelength unit3) FUV Monochromator4) Power supply of Xe lamp

UFMWE provides UFMWE provides Measurements at ~100 msMeasurements at ~100 ms

For the monitoring of the Optical properties of the deposited trFor the monitoring of the Optical properties of the deposited transparent ansparent barrier layers we use barrier layers we use realreal--time Ultra Fast Multitime Ultra Fast Multi--Wavelength Wavelength EllipsometerEllipsometer(UFMWE) (UFMWE) of 32of 32--channels (in the energy range 3channels (in the energy range 3--6.5 6.5 eVeV) ) SetSet--up up that that involves:involves:

4

1

2

3

LabLab--Scale UltraScale Ultra--High Vacuum deposition system High Vacuum deposition system with Stationary substrateswith Stationary substrates


<ε(ω)> of the PET substrate

<ε(ω)> of the SiOx/PET

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.50

1

2

3

4

5

6

-2

-1

0

1

2

3

4

5

<ε2(ω)>

<ε1(ω)>

<ε2(ω

)>

<ε1(ω

)>

Photon Energy (eV)

PET SiOx/PET

Deposition of Deposition of SiOSiOxx Barrier Barrier Layers onto PET by eLayers onto PET by e--beam evaporationbeam evaporation

Geometrical ModelGeometrical Model

PETSiOx film

Optical Characterization of Optical Characterization of SiOxSiOx/PET /PET Evaluation of Method & Establishment of CorrelationEvaluation of Method & Establishment of Correlation

The measured <The measured <εε((ωω)> )> of PET and the of PET and the SiOxSiOx/PET are used for the deduction of /PET are used for the deduction of quantitative results by the use of quantitative results by the use of sophistisophisti----catedcated theoretical models . . . theoretical models . . .


The Refractive Index n of the films depends on:• StoichiometryStoichiometry•• CompositionComposition•• MicrovoidsMicrovoids

Optical Properties

(refractive index n)

Optical Optical Properties Properties

(refractive index n)(refractive index n)

Intermediate Properties

(Stoichiometry,Composition)

Intermediate Intermediate PropertiesProperties

((StoichiometryStoichiometry,,Composition)Composition)

Correlation of n with intermediate properties Correlation of n with intermediate properties ((stoichiometrystoichiometry) for ) for SiOSiOxx filmsfilms

1,0 1,2 1,4 1,6 1,8 2,0 2,2

1,4

1,5

1,6

1,7

1,8

1,9

2,0 Reference APPLIED FILMS ALCAN

Ref

ract

ive

Inde

x n

by S

E

Stoichiometry x by XPS

Sample #1Sample #2


RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating coating Deposition on PET: an ExampleDeposition on PET: an Example…………..

PET SubstratePET Substrate

11stst LayerLayer

22ndnd LayerLayer

33rdrd LayerLayer44thth LayerLayer

Ultra Fast SE measurements at ~100 msUltra Fast SE measurements at ~100 ms

SiOxSiOx / PET / PET

<<εε((ωω)> of )> of SiOxSiOx / PET / PET

<<εε((ωω)> of PET )> of PET

The realThe real--time optical monitoring plays a major role in the monitoring & ctime optical monitoring plays a major role in the monitoring & control ontrol the growth mechanisms during the deposition of barrier the growth mechanisms during the deposition of barrier nanonano--layers .. layers ..


Real-Time monitoring of SiOx depositon onto PET Substrate

< >

< > < > < >< >

< >

Monitoring of <εr> & <εi> with time

Monitoring of n & k with time

Monitoring of <εr> & <εi> with energy

RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating coating Deposition on PET: an ExampleDeposition on PET: an Example…………..


RealReal--time modeling and Analysis of time modeling and Analysis of SiOSiOxxnanonano--coating Deposition on PETcoating Deposition on PET

…………and Real Time Modeling and Real Time Modeling during Depositionduring Deposition

Kinetic ModelKinetic Model…………

D. Georgiou, S. Logothetidis, C. Koidis, A. Laskarakis “In-Situ & Real-Time Monitoring of High Barrier Layers Growth onto Polymeric Substrates” (Submitted to ICSE-4)

Determination of thickness and optical parameters during

deposition

Evaluation of thickness

Evaluation of εr & εi with time


RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating Deposition on coating Deposition on PET: an ExamplePET: an Example…………..

PET PET (substrate)(substrate)

PET PET (substrate)(substrate)

PET

Total deposition time t=60 s

SiOx film

SiOSiOxx

SiOSiOxx


RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating Deposition on coating Deposition on PEN: an ExamplePEN: an Example…………..

Total deposition time t=60 s

Photon Energy (eV)6543

Ä_i

7.000

6.000

5.000

4.000

3.000

2.000

1.000PENPEN(substrate)(substrate)

PEN

SiOxSiOxSiOx film

PEN PEN (substrate)(substrate)

SiOxSiOx


0 10 20 30 40 50 600

50

100

150

200

250

300

350

4000 1 2 3 4 5 6

0

10

20

30

40

50

Deposition Time (sec)

Thickness (nm)

Thic

knes

s (n

m)


Deposition Rate: 4.97 nm/s

Initial stages of growth

0 10 20 30 40 50 602

3

4

5

6

7

8

dL/d

t (nm

/s)

Time (sec)

PET Substrate

0 1 2 3 4 5 62

3

4

5

6

7

8

dL/d

t (nm

/s)

Time (sec)

RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating Deposition on coating Deposition on PETPET

0 5 10 15 20 25 30 35 40 45 50 55 60

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

0.70

0.75

0.80

0.85

0.90

0.95

1.00

1.05

1.10

Eg Eo

Ele

ctro

n Tr

ansi

tion

Ene

rgy

(eV)

Time (sec)

x

x

ΙΙ ΙΙ ΙΙΙ

PET Substrate

ΙΙ

PET SubstratePET Substrate

D. Georgiou, N. Goktsis, C. Koidis, A. Laskarakis, S. Logothetidis (Submitted to E-MRS 2007-accepted for poster presentation)

Evaluation of Optical Properties & Evaluation of Optical Properties & StoichiometryStoichiometry with Timewith Time


0 10 20 30 40 50 600

1

2

3

4

5

6

0 2 4 6 8 100

1

2

3

4

5

6

dL/d

t (nm

/s

T im e (s)

dL/d

t (nm

/s

Time (s)

0 10 20 30 40 50 600

20

40

60

80

100

1200 2 4 6 8 10

0

5

10

15

20

25

30

Thickness (nm)

L

Thic

knes

s (n

m)

Time (sec)

Deposition Rate: 1.556nm/sec

PEN SubstratePEN SubstratePEN SubstratePEN Substrate

0 10 20 30 40 50 60

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

0.70

0.75

0.80

0.85

0.90

0.95

1.00

1.05

1.10

E

lect

ron

Tran

sitio

n En

ergy

(eV

) Eg Eo

Time (sec)

x

x

D. Georgiou, N. Goktsis, C. Koidis, A. Laskarakis, S. Logothetidis (Submitted to E-MRS 2007-accepted for poster presentation)

Evaluation of Optical Properties & Evaluation of Optical Properties & StoichiometryStoichiometry with Timewith Time

RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating Deposition on coating Deposition on PETPET


Fast kinetic measurements of <Fast kinetic measurements of <εε22((ωω)> )> during deposition of during deposition of SiOSiOxx nanonano--layers layers onto Hybrid (inorganiconto Hybrid (inorganic--organic) materials developed onto PET substratesorganic) materials developed onto PET substrates……

RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating Deposition on coating Deposition on Hybrid MaterialsHybrid Materials: an Example: an Example…………..

Hybrid #1 / PETHybrid #1 / PET

SiOxSiOx SiOxSiOx

Hybrid #2 / PETHybrid #2 / PET

PETPETHybridHybridSiOSiOxxThe realThe real--time optical monitoring & time optical monitoring & modellingmodelling leads to leads to

the understanding of the growth mechanisms and the the understanding of the growth mechanisms and the crosslinkingcrosslinking at the interfacesat the interfaces……


0 10 20 30 40 50 600

500

1000

1500

2000

2500

3000

3500

4000 SiOx/ Hybrid #1 / PET SiOx/ Hybrid #2 / PET SiOx/Hybrid #3 / PET

Thic

knes

s (A

)


RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating Deposition oncoating Deposition onHybrid MaterialsHybrid Materials: an Example: an Example…………..

The evolution of Thickness of The evolution of Thickness of SiOxSiOx nanonano--layers deposited onto the layers deposited onto the Hybrid MaterialsHybrid Materials

The different The different deposition rates of deposition rates of SiOSiOxx onto Hybrid onto Hybrid materials yields materials yields significant results on significant results on the the SiOxSiOx growth growth mechanismsmechanisms……

5.9 nm/s5.9 nm/s

3.9 nm/s3.9 nm/s

2.1 nm/s2.1 nm/s

S. Logothetidis, A. Laskarakis, D. Georgiou, N. Goktsis, S. Amberg-Schwab and U. Weber, “Investigation of the Optical Properties of Organic-Inorganic Hybrid Polymers by IR to Vis-fUV Spectroscopic Ellipsometry”, (Submitted to ICSE-4)


6 7 8 9 10 111E-3

0.01

0.1

1

10

WVTR (SiOx/PET)

OTR (SiOx/PET)OTR (AlOx/PET)

OTR of PET

WVTR of PET

WVTR (AlOx/PET)

Gas

Per

mea

bilit

y

Penn Gap E0 (eV)

WVTR (g/m2.d) (23oC, 85-0%) Hybrid #1 / SiOx /PET Hybrid #2 / SiOx/PET Hybrid #2 / AlOx/PET Hybrid #3 / AlOx/PET

OTR (cm3/m2.d.bar) (23oC, 50-0%) Hybrid #1 / SiOx /PET Hybrid #2 / SiOx/PET Hybrid #2 / AlOx/PET Hybrid #3 / AlOx/PET

Improvement of the Barrier properties of the Polymer substrates Improvement of the Barrier properties of the Polymer substrates by the by the sequential deposition of Inorganic and Organic sequential deposition of Inorganic and Organic nanonano--layers that increase layers that increase

the path of permeating gas moleculesthe path of permeating gas molecules

Hybrid (Organic/Inorganic)Hybrid (Organic/Inorganic)MaterialsMaterials

PEN

InorganicOrganicInorganicOrganicInorganicOrganicInorgani

PEN


Polymer substrate

PEN


PEN


Polymer substrate

~4 orders of magnitude Improvement of Barrier Properties

S. Logothetidis et al., to be submitted 2007

RealReal--time monitoring of time monitoring of SiOxSiOx nanonano--coating Deposition oncoating Deposition onHybrid MaterialsHybrid Materials: an Example: an Example…………..


RealReal--time monitoring of time monitoring of AlOAlOxx nanonano--coatingcoating Deposition Deposition on PET : an Exampleon PET : an Example…………..

Time-Plot for 120nm AlOx on PETWeb speed: 0,2m/min Kinetic model & Real Time Analysis

100nm

110nm

120nm

130nm

140nm

0 100 200 300 400 500 600 700 800 900 1000 1100 1200

Time

Thic

knes

s

Thickness Evaluation Evaluation of the of the

uniformity uniformity of coating of coating

STREP Project NMP3-CT-2005-013883 “FLEXONICS”


Incorporation of SiOIncorporation of SiO22 NanoparticlesNanoparticles in Hybrid Materialin Hybrid Material-- Optical Optical PropertiesProperties……..

PETSiOx

SiO2

HybridHybrid #1 (3-4μm)-1%PSiO2/ SiOx/PET

Hybrid #1 (4-5μm)-5%PSiO2/ SiOx/PET




0% 1% 5% 10% 20% 30%2.2

2.4

2.6

7.0

7.2

7.4

7.6

5.0

5.5

7.0

7.5

8.0

8.5

Electron Transition E

nergy (eV)-SiO

2

Eg Hybrid#1 Eo Hybrid#1

Ele

ctro

n Tr

ansi

tion

Ener

gy (e

V)-

Hyb

rid

% SiO2

Eg SiO2

Eo SiO2

The increase of the SiO2 % leads to the reduction of the Penn gap values of the Hybrid#1, whereas the Eg is almost stable at ~2,45 eV…

0 5 10 15 20 25 30 350

5

10

15

20

25

30

35

% S

iO2 b

y S

pect

rosc

opic

Elli

psom

etry

Estimated % SiO2

The determined % of SiO2 nano-particles from SE analysis is higher than the initially estimated..






OutlineOutline




Transparent Conductive Oxides (Transparent Conductive Oxides (TCOsTCOs))

OLED StructureOLED Structure

Transparent Conductive Oxides (Transparent Conductive Oxides (TCOsTCOs)) are an essential part of the FED Technology since they exhibit both large-area electrical contact and optical access in the visible portion of the light spectrum.

High transparencyElectrical conductivity (103 Ω-1 cm-1)Environmental stability

TCO CharacteristicsTCO Characteristics

Tin-doped indium oxide (ITO), GdInOx, SnO2, F-doped In2O3, ZnOx, …

Common TCO materialsCommon TCO materials……

Drawbacks of the currently used Drawbacks of the currently used TCOsTCOs• Elevated deposition temperatures (>100°C), (incompatible to polymer substrates)• Increased roughness • Low elasticity• Very high cost, • Low abundance


ZnOZnO is a promising wide is a promising wide bandgapbandgap semiconductor material. semiconductor material. The The interest on interest on ZnOZnO originates from its poriginates from its potentialityotentiality for use in a for use in a wide range of Scientific, Technological & Industrial applicationwide range of Scientific, Technological & Industrial applications. s.

SOME APPLICATIONSSOME APPLICATIONS……Flexible electronic Devices (Flexible electronic Devices (FEDsFEDs))Gas sensorsGas sensorsUV light emitting devices & sensorsUV light emitting devices & sensorsBiosensorsBiosensors

PROPERTIES:PROPERTIES:Electrical conductivity Good ultraviolet absorption, PiezoelectricityBiocompatibility & Non-toxicity Easy manufacturing of nanostructuresLow cost & Abundance Easy fabricationCompatibility with large scale processes

ZnOZnO has a has a wurtzitewurtzite crystal structure and is a direct gap (IIcrystal structure and is a direct gap (II--VI) VI) semiconductor, with a fundamental absorption edge at 3.37 semiconductor, with a fundamental absorption edge at 3.37 eVeV. .

Transparent Conductive Oxides (Transparent Conductive Oxides (TCOsTCOs) : ) : Zinc Oxide (Zinc Oxide (ZnOZnO))


RealReal--time monitoring of time monitoring of ZnOZnO nanonano--coating coating Example: Deposition on Example: Deposition on cc--SiSi substratesubstrate

Ultra Fast SE measurements at ~100 msUltra Fast SE measurements at ~100 ms

<<εε((ωω)> of )> of ZnOZnO / / cc--SiSi

The realThe real--time optical monitoring plays a major role in the monitoring & ctime optical monitoring plays a major role in the monitoring & control ontrol the growth mechanisms during the deposition of the growth mechanisms during the deposition of ZnOZnO nanonano--layers .. layers ..

<<εε((ωω)> of )> of cc--SiSi

cc--SiSiZnO film



ModellingModelling of the measured of the measured pseudodielectricpseudodielectric function function <<εε((ωω))> > of of ZnOZnO films with films with the theoretical fit, the theoretical fit, by the analysis of the by the analysis of the <<εε((ωω))> > with the TL modelwith the TL model

0)(2

1222)22(

2)()(2

=

⋅+−

−=

ETL

EECEEgEECAE

ETLO

O

ε

ε

ξξ

ξξεπ

εεω

dE

PEg

TL ∫∞

∞ −+= 22

21

)(2)(

TaucTauc--LorentzLorentz (TL) Model*(TL) Model*

ModellingModelling of the Optical Properties of of the Optical Properties of ZnOZnO thin filmsthin filmsVisVis--fUVfUV spectral region (1.5spectral region (1.5--6.5 6.5 eVeV))

2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.50

1

2

3

4

5

6

7

8

-3

-2

-1

0

1

2

3

4

5

Pse

udod

iele

ctric

Fun

ctio

n <ε

2(ω)>

<ε2(ω)>

Pse

udod

iele

ctric

Fun

ctio

n <ε

1(ω)>

Experimental Data Theoretical Fit

Photon Energy (eV)

<ε1(ω)>

Measurement of <ε(ω)> and fit with appropriate models

polymerpolymerZnO film

0 1 2 3 4 5 6 7 8 91.5

2.0

2.5

3.0

3.5

4.0

4.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

ε2(ω)

Photon Energy (eV)

Die

lect

ric F

unct

ion ε 1(ω

)

Die

lect

ric F

unct

ion ε 2(ω

)

BULK DIELECTRICFUNCTION of ZnO layer

ε1(ω)

Εg = 3.28 ± 0.02 eVε∞ = 2.27 ± 0.04 eVΑ1 = 153.6 ± 8.9Ε1 = 3.37 ± 0.04 eVC1 = 1.21 ± 0.05Α2 = 50.2 ± 1.7Ε2 = 6.41 ± 0.25 eVC2 = 11.16 ± 0.53

Determined Determined ParametersParameters



0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

3.03.23.43.63.84.04.24.44.6

5.4

5.6

5.8

6.0

6.2 Fundamental Gap E0

E1

E2

Elec

tron

Tran

sitio

n En

ergy

(eV)

Deposition Time (min)

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.50

2

4

6

8

10

12

14

16

Film

Thi

ckne

ss (n

m)

Deposition Time (min)

Evolution of Evolution of EEgg gap and absorption gap and absorption energies Eenergies E11 & E& E22 determined by analysis of determined by analysis of

SE data during SE data during ZnOZnO depositiondepositionThickness of the Thickness of the ZnOZnOxx thin film determined thin film determined by analysis of SE data during depositionby analysis of SE data during deposition

ModellingModelling of the Optical Properties of of the Optical Properties of ZnOZnO thin films:thin films:Example: Example: Pulsed DC Magnetron Sputtering Deposition of Pulsed DC Magnetron Sputtering Deposition of ZnOZnO

PET Substrate

LayerLayer--byby--layer layer Growth MechanismGrowth Mechanism

of of ZnOZnO……

Homogeneous filmHomogeneous filmGrowthGrowth……

S. Logothetidis et al., to be submitted 2006S. Logothetidis et al., to be submitted 2006


Homogeneous film growth

Nucleation layer

0 100 200 300 400 500 6000

10

20

30

40

50

60

70

80

90

100

110

120

0

20

40

60

80

100

Voi

ds (%

)

Thic

knes

s (n

m)


Top Layer Bottom Layer Total Film Thickness Voids of Top Layer

1. Nucleation

2. Coalescence

3. Homogeneous growth


SE data during SE data during ZnOZnO depositiondepositionThickness of the Thickness of the ZnOZnOxx thin film determined thin film determined by analysis of SE data during depositionby analysis of SE data during deposition

ModellingModelling of the Optical Properties of of the Optical Properties of ZnOZnO thin films:thin films:Example: Example: DC Magnetron Sputtering Deposition of DC Magnetron Sputtering Deposition of ZnOZnO

0 100 200 300 400 500 6003.03.23.43.63.84.04.24.44.64.85.8

6.0

6.2

6.4

6.6

Ele

ctro

nic

Tran

sitio

n E

nerg

y (e

V)

Deposition Time (s)

Eg

E1

E2

PET SubstratePET SubstratePET SubstratePET SubstratePET Substrate

d1

d2

Two layer modelTwo layer model



Total deposition time t=20 min

PETPET

PEN PEN (substrate)(substrate)

ZnOZnO/PET/PET

ZnO film

RealReal--time monitoring of time monitoring of ZnOZnO nanonano--coating coating Example:Example: Deposition on PEN substrateDeposition on PEN substrate

RealReal--Time Monitoring of Time Monitoring of

deposition Processes:deposition Processes:

i)i) Thickness versus deposition Thickness versus deposition TimeTime

ii)ii) Optical ParametersOptical Parameters

C. Koidis, D. Georgiou, N. Goktsis, S. Lousinian, A. Laskarakis, S. Logothetidis, (Submitted to E-MRS 2007-accepted for oral presentation)



SE data during SE data during ZnOZnO depositiondeposition

0 2 4 6 8 10 12 14 16 18 202.9

3.0

3.1

3.2

3.3

3.4

4

6

8

10

12ZnO on PEN

Elec

tron

Tra

nsiti

on E

nerg

y (e

V)

Time (min)

Eg E1 E2

Thickness of the Thickness of the ZnOZnOxx thin film determined thin film determined by analysis of SE data during depositionby analysis of SE data during deposition

C. Koidis, D. Georgiou, N. Goktsis, S. Lousinian, A. Laskarakis, S. Logothetidis, (Submitted to E-MRS 2007-accepted for oral presentation)

RealReal--time monitoring of time monitoring of ZnOZnO nanonano--coating coating Example:Example: Deposition on PEN substrateDeposition on PEN substrate






OutlineOutline




InIn--situ & Realsitu & Real--time measurements of Optical Propertiestime measurements of Optical Properties

For the quality control of the deposited organic For the quality control of the deposited organic nanonano--layers it is necessary the layers it is necessary the realreal--time optical monitoring during the growthtime optical monitoring during the growth……

Organic Conductive OxidesOrganic Conductive Oxides

OLED StructureOLED Structure

RealReal--time time monitoringmonitoring

by SEby SEPET, PEN, …Barrier nano-layers…TCO materials (ITO, ZnO, …)

AlQ3, Pentacenes, P3HT, etc…

The integration of SE optical technique in the various productioThe integration of SE optical technique in the various production steps of the n steps of the FED structure will optimize the production process and the finalFED structure will optimize the production process and the final product product characteristics (operation, stability, efficiency, ..) characteristics (operation, stability, efficiency, ..)


Organic Conductive Oxides are increasingly used in the productioOrganic Conductive Oxides are increasingly used in the production of n of FEDsFEDs, , such as the such as the Organic Organic PVsPVs……

Niyazi Serdar Sariciftci Materials Today, Volume 7, Issue 9, September 2004, Pages 36-40

Acceptor materialsAcceptor materials

BCPpentacene

CuPC

Donor materialsDonor materials

PFDTBT



Organic Conductive Oxides are increasingly used in the productioOrganic Conductive Oxides are increasingly used in the production of n of FEDsFEDs, , such as the such as the OLEDsOLEDs……

Emissive materialsEmissive materials

PPPPPV PFO

PFE

BlueBlue

PPV

BCP

GreenGreen

PT CN-PPV DCM

RedRed



0 2 4 6 8 10

2

3

4

PEDOT:PSS 0o

PEDOT:PSS 90o

ε 1 (ω)

Photon Energy(eV)

0 2 4 6 8 100

1

2

PEDOT:PSS 0o

PEDOT:PSS 0o

Photon Energy(eV)

ε 2 (ω

)

Dispersion Equation:

22--TL oscillatorTL oscillator

Εg = 4.829 ±0.04 eVε∞ = 2.537 ± 0.03 eVΑ1 = 50.85 ± 2.45Ε1 = 5.32 ± 0.019 eVC1 = 0.596 ± 0.012Α2 = 16.36 ± 0.74Ε2 = 6.37 ± 0.07 eVC2 = 0.62 ± 0.025

Determined Determined ParametersParameters

PEDOT:PSS on PEN







OutlineOutline




Deposition Process TechnologiesDeposition Process Technologies

Lab scale Ultra High Vacuum Chamber (LTFN)

Pilot scale R2R Vacuum Coating Systems (Research Institutes)

Large Scale R2R Vacuum Coater systems (Industry)


Modulator &PolarizerHousing

Xe lamp &AnalyzerHousing

Adaptation of the Prototype UFMWE Adaptation of the Prototype UFMWE on the deposition chamber at LTFNon the deposition chamber at LTFN


From Research...From Research...

EC Growth Project TransMach

...and Industrial Scale...and Industrial Scale

...to Pilot ......to Pilot ...

UpUp--scaling the integration of UFMWE from scaling the integration of UFMWE from realreal--time Labtime Lab to to inin--line r2r Processesline r2r Processes……


Large Scale r2r Production Sequence of Large Scale r2r Production Sequence of FEDsFEDs




roll

roll




roll

roll

roll

roll

R2R Production Processes of R2R Production Processes of FEDsFEDs

Real time Optical Monitoring (SE)


UpUp--scaling the integration of UFMWE to All Steps of the scaling the integration of UFMWE to All Steps of the Production of Production of FEDsFEDs

From Polymer SubstratesFrom Polymer Substrates……

.. to the final FED product!!.. to the final FED product!!

For the quality control of the deposited For the quality control of the deposited nanonano--layers it is necessary to integrate the reallayers it is necessary to integrate the real--time time control in all the production steps control in all the production steps ……..

Spectroscopic Spectroscopic EllipsometryEllipsometry (SE)(SE)


SampleSample


AnalyzerAnalyzer

DetectorDetector


XeXe lamplamp

ShutterShutter


SampleSample



AnalyzerAnalyzer

DetectorDetector


XeXe lamplamp

ShutterShutter

XeXe lamplampXeXe lamplamp

ShutterShutter


From Batch to From Batch to …….. .. InIn--lineline

R2R Production Processes of R2R Production Processes of FEDsFEDs

BATCH PRODUCTION1000 m1000 m22

SEMI-BATCH PRODUCTION300 m300 m22

IN-LINE PRODUCTION (OLEDs)100 m100 m22

IN-LINE PRODUCTION (OLEDs)100 m100 m22

SESESESE

Quality Control

SESESESE

Quality Control


In-line thickness by UFMWE, Compared to:Set thickness values, in-line Transmittance Correlated to: off-line OTR results, in-line measured Eg

0

10

20

30

40

50

60

70

80

90

100

8000 9000 10000 11000 12000 13000 14000 15000 16000 17000 18000 19000 20000 21000 22000

running length [ m ]

thic

knes

s [ n

m ]

/ tra

nsm

ittan

ce [

% ]

0

1

2

3

4

5

6

7

8

9

10

oxyg

en tr

ansm

ittan

ce [

cm³/m

²/day

] /

Eg

Thickness measured onlineThickness set pointLight transmittance at 356nmOxygen transmittanceEg

here: oxygen inlet

here: posttreat- ment optimised

InIn--Line r2r Process Control by RealLine r2r Process Control by Real--Time Time Optical monitoring with Spectroscopic Optical monitoring with Spectroscopic EllipsometryEllipsometry


“Transparent Films Vacuum Coatings Machine with Integrated In-line Monitoring and Control (TransMach)''

GROWTH Project (2001- 2004)Project Coordinator : Prof. S. Logothetidis

Development of a new generation ultra-fast Spectroscopic Ellipsometry(SE) units for in-line Monitoring & Production control of TRANSPARENT oxide nanolayers on large area and flexible substrates.

Adaptation and optimization of the new SE units on large-scale industrial coaters

IVV

From From Research...Research...

...to Industrial scale...to Industrial scale

Rated from the European Commission as Rated from the European Commission as OUTSTANDING OUTSTANDING

Activities of Activities of LTFNLTFN in the field of Plastic Electronicsin the field of Plastic Electronics

http://www.cordis.lu/fp5/home.html


ISOTECH

TRANSMACH

From the Lab to From the Lab to Industry & Society Industry & Society



““UltraUltra--high barrier films for r2r encapsulation of flexible electronicshigh barrier films for r2r encapsulation of flexible electronics””FLEXONICS (FLEXONICS (www.flexonics.orgwww.flexonics.org))

STREP Project (2005 STREP Project (2005 -- 2008)2008)Project Coordinator : Prof. S. Project Coordinator : Prof. S. LogothetidisLogothetidis

Development of novel transparent & flexible material systems witDevelopment of novel transparent & flexible material systems with h ultraultra--highhighbarrier propertiesbarrier properties and the related processing technologies in order to be used forand the related processing technologies in order to be used for thethelargelarge--scale rollscale roll--toto--roll (r2r) encapsulation of future flexible roll (r2r) encapsulation of future flexible optoopto-- & electronic devices.& electronic devices.

1. Aristotle University of Thessaloniki – LTFN (Coordinator) (Greece)2. Fraunhofer-Gesellschaft POLO Alliance (Germany)3. Horiba Jobin Yvon (France)4. Applied Materials (Germany)5. Isovolta AG (Austria)6. Alcan Packaging Services Ltd. (Switzerland)7. Siemens Aktiengesellschaft (Germany)8. Technical University Graz (Austria)9. Konarka (Austria)

Project Consortium: 9 partners from 5 EU countries

IVV







OutlineOutline




InIn--line SE will play a major role towards the Costline SE will play a major role towards the Cost--effective effective Large Large Scale r2r productionScale r2r production of transparent functional layers onto of transparent functional layers onto Polymeric substratesPolymeric substrates……

RealReal--time SE in combination to time SE in combination to ModellingModelling & Analysis techniques & Analysis techniques provides accurate results on the provides accurate results on the Optical propertiesOptical properties, , ThicknessThickness, , StoichiometryStoichiometry, , CompositionComposition, , MicrostructureMicrostructure & & DensityDensity of of PolymericPolymericSubstrates,Substrates, BarrierBarrier layerslayers, , TCOsTCOs and and OrganicOrganic LayersLayers……

The CThe Correlationorrelation of of OOpticalptical PropertiesProperties to to IntermediateIntermediate & & Functional propertiesFunctional properties, leads to the Determination & Control the , leads to the Determination & Control the QualityQuality of transparent Functional layers (barrier, electrodes, etc.) of transparent Functional layers (barrier, electrodes, etc.) developed onto developed onto PPolymerolymerss for for Flexible Electronics Flexible Electronics applicationsapplications……

Summarizing & ConclusionsSummarizing & Conclusions


Our Partners

Staff of the Staff of the Lab Lab Thin FilmsThin Films--NanosystemsNanosystems & & NanometrologyNanometrology(Aristotle University of (Aristotle University of ThessalonikiThessaloniki))

IVV

ACKNOWLEDGEMENTSACKNOWLEDGEMENTS


Laboratory for Thin Films Laboratory for Thin Films -- NanosystemsNanosystems & & NanometrologyNanometrology (LTFN)(LTFN)Aristotle University of Aristotle University of ThessalonikiThessaloniki, Physics Department, Physics DepartmentGRGR--54124 54124 ThessalonikiThessaloniki, Greece, Greece, http://, http://ltfn.physics.auth.grltfn.physics.auth.gr

THANK YOU THANK YOU FOR YOUR ATTENTIONFOR YOUR ATTENTION !!!!!!

aristotle university of thessaloniki physics department · 2007-07-25 · 11th tappi european place...

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