[PPT] - Aristotle University of Thessaloniki Thessaloniki Aristotle PowerPoint Presentation

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11th TAPPI European PLACE Conference

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Real Real-

time & in

time & in-

Line Optical Monitoring of Functional

Line Optical Monitoring of Functional Nanolayer Nanolayer Deposition on Flexible Polymeric Deposition on Flexible Polymeric Substrates Substrates

Lab for Thin Films Lab for Thin Films -

Nanosystems

Nanosystems & & Nanometrology Nanometrology (LTFN) (LTFN) Physics Department, Physics Department, AUTh AUTh

Aristotle University of Aristotle University of Thessaloniki Thessaloniki Physics Department Physics Department

GR GR-

54124 Thessaloniki, Greece

54124 Thessaloniki, Greece, http:// , http://ltfn.physics.auth.gr ltfn.physics.auth.gr

Prof. S.
Prof. S. Logothetidis

Logothetidis

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Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions

Outline Outline

Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

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Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

Outline Outline

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The interest on the Polymeric materials The interest on the Polymeric materials in in a wide range of a wide range of Scientific,Technological Scientific,Technological & Industrial Applications & Industrial Applications originates

riginates from the

from the Very Important Properties Very Important Properties they they exhibit and their exhibit and their Low Cost Low Cost & & Flexibility Flexibility in in Use Use in in Large Area Processes Large Area Processes. .

Barrier Films & Coatings for Barrier Films & Coatings for Encapsulation Encapsulation Protective Protective & Decorative & Decorative Coatings Coatings Corrosion Resistant Coatings Corrosion Resistant Coatings

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

Flexible Electronics Devices Flexible Electronics Devices Optoelectronic & Electronic Devices Optoelectronic & Electronic Devices Optical Optical & & Recording Devices Recording Devices Biocompatible Biocompatible -

Medical Implants

Medical Implants

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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 Film electronic modules (ITO layers, electron transport layers, organic emitters, etc.) Encapsulated FEDs FEDs roll roll Encapsulant (Flexible polymer layer) Functional Thin Film electronic modules (ITO layers, electron transport layers, organic emitters, etc.) Encapsulated FEDs FEDs roll roll roll roll

Encapsulation Concept Encapsulation Concept Large Large-

scale

scale roll roll-

to

to-

roll

roll (r (r2r) 2r) Encapsulation system Encapsulation system (roll length ~3000 m & 2 m width) (roll length ~3000 m & 2 m width)

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

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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 products Large Scale Production of novel products

Plasma Assisted Evaporation Sputtering

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Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

Outline Outline

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Determination of Determination of Thickness Thickness, , Bonding Bonding structure structure & & Configurations Configurations, , Vibrational Vibrational properties properties, , Electronic transitions Electronic transitions, , Stoichiometry Stoichiometry, , Optical anisotropy Optical anisotropy, , Deposition Rate Deposition Rate,

, Growth

Growth Mechanisn Mechanisn etc. etc.

Extensive spectral range: Extensive spectral range: Infra Infra-

Red region

Red region : : 900

900 -

4000 cm

4000 cm-

1

1

NIR NIR – – Vis Vis -

farUV

farUV region region: : 0.7

0.7 -

6.5

6.5 eV eV

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 Ellipsometry Ellipsometry in a wide in a wide spectral region (IR to spectral region (IR to Vis Vis-

fUV

fUV) )

Spectroscopic Spectroscopic Ellipsometry Ellipsometry – – SE SE … ….. ..

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

Optical Fiber Optical Fiber Sample Sample Polarizer Polarizer Photoelastic Photoelastic Modulator Modulator Analyzer Analyzer Detector Detector Monochromator Monochromator Data Acquisition Data Acquisition Computer Computer Xe Xe lamp lamp Shutter Shutter Optical Fiber Optical Fiber Sample Sample Polarizer Polarizer Photoelastic Photoelastic Modulator Modulator Polarizer Polarizer Photoelastic Photoelastic Modulator Modulator Analyzer Analyzer Detector Detector Monochromator Monochromator Data Acquisition Data Acquisition Computer Computer Xe Xe lamp lamp Shutter Shutter Xe Xe lamp lamp Xe Xe lamp lamp Shutter Shutter

3-6.5 eV 0.7- 6.5 eV EX-SITU CONFIGURATION IN-SITU CONFIGURATION

Near IR Near IR – – Visible Visible – – far UV far UV Phase Modulated Spectroscopic Phase Modulated Spectroscopic Ellipsometry Ellipsometry

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FTIRSE is a powerful & Sophisticated Optical technique for inves FTIRSE is a powerful & Sophisticated Optical technique for investigation of tigation of Vibrational Vibrational properties of properties of Bulk Materials, Thin films, Nanostructures, Bulk Materials, Thin films, Nanostructures, Multilayers Multilayers etc. etc.

Film Substrate Holder Ultra High Vacuum Chamber Photoelastic Modulator Polarizer IR source (SiC) Michelson Interferometer Focusing System BaF2 Windows Analyser Focusing System Focusing System BaF2 Windows

Acquisition & Analysis Software

Liquid Nitroge n Supply

Advantages Advantages

Non

Non-

destructive technique

destructive technique

Direct & Simultaneous Determination of Real

Direct & Simultaneous Determination of Real < <ε ε1

1(

(ω ω)> )> & Imaginary part & Imaginary part < <ε ε2

2(

(ω ω)> )> of

f <

<ε ε( (ω ω)>=< )>=<ε ε1

1(

(ω ω)>+ )>+i< i<ε ε2

2(

(ω ω)> )>

Identification of IR responses even at a Monolayer level

Identification of IR responses even at a Monolayer level

Can be used in a variety of Media

Can be used in a variety of Media ( (Vacuum Vacuum, , air air, , transparent liquids transparent liquids..) ..)

Does not require Special Conditions

Does not require Special Conditions for the measured materials for the measured materials

Acquisition time ~

Acquisition time ~ 2 2 sec, sec, for for in in-

situ

situ & & real real-

time

time Monitoring of Deposition & Treatment Monitoring of Deposition & Treatment of Materials & Systems

f Materials & Systems

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

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SE SE measures the dielectric function measures the dielectric function ε ε( (ω ω)= )=ε ε1

1(

(ω ω)+i )+iε ε2

2(

(ω ω) )

Probes

Probes the Electronic the Electronic-

Vibrational

Vibrational-

Structural

Structural-

Morphological material properties

Morphological material properties

Non

Non-

destructive

destructive, Surface sensitive ( , Surface sensitive (thickness of thickness of Å Å can be measured can be measured) )

Capability for i

Capability for in n-

situ

situ & & real real-

time

time monitoring monitoring of

f phenomena

phenomena & & mechanisms mechanisms

Ultra high speed

Ultra high speed of measurement

f measurement
A

Advanced dvanced modelling modelling procedures procedures

Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Basic Principles : Basic Principles

Bulk Materials Bulk Materials

ip

E r

is

E r

rs

E r

rp

E r

θ0 θ0

περιβάλλον (0)

μέσον (1)

n1 n0

θ1

Ēts Ētp

Medium (1) Medium (0) φ0 φ0 medium (0) film (1)

Ν Ν1

1 φ1 φ2 φ1 φ1

d

substrate (2)

Ν2 Ν Ν0

φ0 φ0 medium (0) film (1)

Ν Ν1

1 φ1 φ2 φ1 φ1

d

substrate (2)

Ν2 Ν Ν0

Film / Substrate Systems Film / Substrate Systems

⎥ ⎥ ⎦ ⎤ ⎢ ⎢ ⎣ ⎡ ⎟ ⎟ ⎠ ⎞ ⎜ ⎜ ⎝ ⎛ + − + =

2 2 2 2

tan ~ 1 ~ 1 1 sin ) ( ~ φ φ N ρ ρ ω ε

ο

Calculated Quantity Calculated Quantity

iΔ ) δ i(δ s p s p

tanΨe e r r r r ρ

s p

= = =

−

~ ~ ~ ~ ~

Complex Reflectance Ratio Complex Reflectance Ratio

θ sin n n λ d 2π β

2 2 2 1 −

⎟ ⎠ ⎞ ⎜ ⎝ ⎛ =

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SE obtains accurate results from the measured <ε(ω)> spectra, of the film/substrate system, with specific modeling procedures: 1.

1. Tauc

Tauc-

Lorentz

Lorentz 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 the Materials, we use the Effective Effective Medium Approximation Medium Approximation (BEMA) (BEMA)

ε ~ 2 ε ~ ε ~

ε

~ )

(1

ε ~ 2 1 ε ~

1

= + + +

eff eff eff eff

f f

eff

~ ε

ε

~

: optical response of top layer : optical response of bottom layer f : void volume fraction parameter

ω ω ω ω ω ω ω ε 1 2 2 2 ) 2 2 ( 2 ) ( ) ( 2 ⋅ + − − = C g ω C A

O O

, ω>ωg

ξ ω ξ ξ ξω π ε ε

ω

d P ω

g

∫

∞ ∞

− + =

2 2 2 1

) ( 2 ) (

Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Basic Principles : Basic Principles

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Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

Outline Outline

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PolyEthylene PolyEthylene Terephthalate Terephthalate (PET) (PET) PolyEthylene PolyEthylene Naphthalate Naphthalate (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 properties thermal, and barrier properties

Polymeric Substrates Polymeric Substrates… …

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c (MD) b (TD) a (ND)

θ

Ellipsometer system (x’,y’,z’)

y’ z’

Plane of Incidence

x’

Polymer film system (a,b,c)

c (MD) b (TD) a (ND)

θ

Ellipsometer system (x’,y’,z’)

y’ z’

Plane of Incidence

x’

Polymer film system (a,b,c)

Machine Direction

TD

MD

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 properties Optical properties

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

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PEN PEN Peak I: Peak I: ~ 3. ~ 3.5 5 eV eV Peak II: Peak II: ~ 3.6 ~ 3.6 eV eV Peak III: Peak III: ~ 4.4 ~ 4.4 eV eV Peak IV: Peak IV: ~ 5.1 ~ 5.1 eV eV

n n π π* * C=O C=O

1 1A

Ag

g 1 1B

Bu

u

Peak I: Peak I: ~ 4.1 ~ 4.1 eV eV Peak II: Peak II: ~ 4.3 ~ 4.3 eV eV Peak III: Peak III: ~ 5.1 ~ 5.1 eV eV Peak IV: Peak IV: ~ 6.5 ~ 6.5 eV eV

n n π π* * C=O C=O

1 1A

Ag

g 1 1B

Bu

u

PET PET I, II III, IV

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 1.5 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)

ε1(ω) ε2(ω)

ε2(ω) ε1(ω) IVa IVb IVc IIIc IIIb IIIa II

ε2(ω) ε1(ω)

Photon energy (eV) I PEN (25 μm) III PET (12 μm) II I IV

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

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

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4,0 4,5 5,0 5,5 6,0 6,5 2 3 4 5 6 7 1 2 3 4 5 6

30
60
90
120
150
ε2(ω)

ε1(ω) Photon Energy (eV)

IV III II

(a) PET

I

Angle θ

c (MD) b (TD) a (ND)

θ

Ellipsometer system (x’,y’,z’)

y’ z’

Plane of Incidence

x’

Polymer film system (a,b,c) 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5

1

1 2 3 4 5 6 7 8 9 10 2 4 6 8 10

Angle θ

IVc IVb IVa IIIc IIIb IIIa II

30
60
90
120
150
ε2(ω)

ε1(ω)

Photon Energy (eV)

(b) PEN

I

PET at various angles θ PEN at various angles θ

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

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

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* 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

2 4 6 8 10

30
60
90
120
150
1650

1345 1370 1490 1515 1720 1410

ε2(ω) Wavenumber (cm

1)

(a) PET

1255 1200 1170 985 950 1025 1075 1125

Angle φ

900 1000 1100 1200 1300 1400 1500 1600 1700 1800

4
3
2
1

1 2 3 4 5 6 7

30
60
90
120
150
Wavenumber (cm
1)

(b) PEN

1635 1335 1374 1483 1549 1713 1450

ε2(ω)

1257 1184 980 957 1020 1096 1135

Angle θ Angle θ

Polymeric Substrates: Polymeric Substrates: Optical & Optical & Vibrational Vibrational Properties Properties PEN PEN PET PET

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PLASMA PLASMA Surface treatment of polymers Surface treatment of polymers using ion beams and plasma using ion beams and plasma Dramatic physical & chemical modifications Dramatic physical & chemical modifications that influence the surface that influence the surface nano nano-

topography,

topography,

ptical, mechanical and biological properties
ptical, mechanical and biological properties

Bond breaking, Cross Bond breaking, Cross-

linking,

linking, Formation of new chemical groups, Formation of new chemical groups, Emission of small molecular groups Emission of small molecular groups

Surface Modification Surface Modification & & Activation Activation Adhesion improvement, Sterilization Adhesion 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 overlayer

verlayer (thickness d)

(thickness d)

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

POLYMER SUBSTRATE POLYMER SUBSTRATE MODIFIED OVERLAYER MODIFIED OVERLAYER

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N2

Film Ion beam Substrate Holder Plasma

Ar O2

ULTRA HIGH VACUUM DEPOSITION CHAMBER Gas Inlet

End Hall Ion Source

Pulsed DC Supply PhotoElastic Modulator Polarizer IR Source (SiC) Michelson Interferometer Focusing System IR Windows BaF2 Analyser Detection System Focusing System IR Windows BaF2 Acquisition & Analysis System Liquid Ν2 Inlet

Kauffman Ion Source

Pulsed DC Plasma Treatment Pulsed DC Plasma Treatment

Ion Beam Bombardment Ion Beam Bombardment Ultra High Vacuum Deposition Chamber equipped with in-situ & real-time Optical sensing techniques

In In-

situ Optical Monitoring of Surface

situ Optical Monitoring of Surface Functionalization Functionalization

f Polymers by Plasma:
f Polymers by Plasma: Experimental Set

Experimental Set-

up

up

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Optical Investigation by Optical Investigation by FTIR SE FTIR SE of the N

f the N2

2 Plasma treatment on

Plasma treatment on PET Polymer Substrates PET Polymer Substrates

900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1 2 3 4 5 6 7 8

str. mode

CH2 C-H ε1(ω)

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

Dielectric Function ε(ω) Wavenumber (cm

1)

ε2(ω) C=O C-O C-H CH2 ester mode

Reduction 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 Torr P(N2)= 30 mTorr ΦΝ2= 40 sccm PDC Voltage = 300,500,700 Volt T=1200 sec

In In-

situ Optical Monitoring of Surface

situ Optical Monitoring of Surface Functionalization Functionalization

f Polymers by Plasma:
f Polymers by Plasma: IR region

IR region

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

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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

IV III II Untreated 200 V 300 V 500 V 700 V ε2(ω) Photon Energy (eV) I PET

The Surface Modification affects the Optical properties

f the PET film in a surface
verlayer due to…

Optical Investigation by Optical Investigation by Vis Vis-

fUV

fUV SE SE of the N

f the N2

2 Plasma treatment on

Plasma treatment on PET Polymer Substrates PET Polymer Substrates

In In-

situ Optical Monitoring of Surface

situ Optical Monitoring of Surface Functionalization Functionalization

f Polymers by Plasma:
f Polymers by Plasma: Vis

Vis-

fUV

fUV region region

…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 Modified Overlayer Depth (nm) Pulsed DC Bias Voltage (V) TRIM PET modified overlayer

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Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions

Outline Outline

Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

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G Gas transport pathways as transport pathways through through the the barrier barrier layer layer

Issues to Solve Issues to Solve … …. .

TARGET

The achievement of Ultra High Barrier Properties for the envisaged applications

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

water vapour permeability / g / m2 d

xygen permeability / cm3/ m2 d bar

OLE D displays, organic solar cells standard: 1 inorg. layer S ingle polymers s ens itive food products L C D / L E D dis plays , photovoltaic modules vac uum ins ulating panels P OLO: 2 inorg. layers P OL O: 1 inorg. layer

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

water vapour permeability / g / m2 d

xygen permeability / cm3/ m2 d bar

OLE D displays, organic solar cells standard: 1 inorg. layer S ingle polymers s ens itive food products L C D / L E D dis plays , photovoltaic modules vac uum ins ulating panels P OLO: 2 inorg. layers P OLO: 2 inorg. layers P OL O: 1 inorg. layer P OL O: 1 inorg. layer

PE PET

PA
PP

10-50 μm e.g. PET/SiOx/PE SiOx ~40nm

Permeability of Permeability of Atmospheric Gases ( Atmospheric Gases (O O2

2 και

και H H2

2O

O) )

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

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Optical Properties

Penn Gap ω0
Refractive Index n
Fundamental Gap ωg

Optical Properties Optical Properties

Penn Gap ω0
Refractive Index n
Fundamental Gap ωg

In order to In order to Integrate Optical Sensing Techniques Integrate 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 Correlations Correlations must be Established must be Established… … Intermediate Properties

Thickness
Stoichiometry
Composition
Density

Intermediate Properties Intermediate Properties

Thickness
Stoichiometry
Composition
Density

Functional Properties

O2 transmission
H2O transmission

Functional Properties Functional Properties

O2 transmission
H2O transmission

Towards the Determination & Optimization Towards the Determination & Optimization

f Barrier properties of Polymer materials
f Barrier properties of Polymer materials

PET

SiOx film

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 1.5 0.0

ε1(ω)

ε2(ω)

ε2(ω) IVa IVb IVc IIIc IIIb IIIa II

ε1(ω)

Photon energy (eV) I PEN (25 μm) PEN PEN

Polymer substrate

PEN PEN

Polymer substrate

900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1 2 3 4 5 6 7 8

str. mode

CH2 C-H ε1(ω) PET untreated treated V=300V treated V=500V treated V=700V Dielectric Function ε(ω) Wavenumber (cm

1)

ε2(ω) C=O C-O C-H CH2 ester mode

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1) Control unit of the UFMWE 2) Multi-wavelength unit 3) FUV Monochromator 4) Power supply of Xe lamp UFMWE provides UFMWE provides Measurements at ~100 ms Measurements at ~100 ms For the monitoring of the Optical properties of the deposited tr For the monitoring of the Optical properties of the deposited transparent ansparent barrier layers we use barrier layers we use real real-

time Ultra Fast Multi

time Ultra Fast Multi-

Wavelength

Wavelength Ellipsometer Ellipsometer (UFMWE) (UFMWE) of 32

f 32-
channels (in the energy range 3

channels (in the energy range 3-

6.5

6.5 eV eV) ) Set Set-

up

up that that involves: involves:

4 1 2 3

Lab Lab-

Scale Ultra

Scale Ultra-

High Vacuum deposition system

High Vacuum deposition system with Stationary substrates with Stationary substrates

SLIDE 27

11th TAPPI European PLACE Conference

27

<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 6.5 1 2 3 4 5 6

2
1

1 2 3 4 5

<ε2(ω)> <ε1(ω)> <ε2(ω)> <ε1(ω)> Photon Energy (eV) PET SiOx/PET

Deposition of Deposition of SiO SiOx

x Barrier

Barrier Layers onto PET by e Layers onto PET by e-

beam evaporation

beam evaporation

Geometrical Model Geometrical Model

PET

SiOx film

Optical Characterization of Optical Characterization of SiOx SiOx/PET /PET Evaluation of Method & Establishment of Correlation Evaluation of Method & Establishment of Correlation

The measured < The measured <ε ε( (ω ω)> )> of PET and the

f PET and the

SiOx SiOx/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 sophisti sophisti-

cated

cated theoretical models . . . theoretical models . . .

SLIDE 28

11th TAPPI European PLACE Conference

28

The Refractive Index n of the films depends on:

Stoichiometry

Stoichiometry

Composition

Composition

Microvoids

Microvoids

Optical Properties

(refractive index n)

Optical Optical Properties Properties

(refractive index n) (refractive index n)

Intermediate Properties

(Stoichiometry, Composition)

Intermediate Intermediate Properties Properties

( (Stoichiometry Stoichiometry, , Composition) Composition)

Correlation of n with intermediate properties Correlation of n with intermediate properties ( (stoichiometry stoichiometry) for ) for SiO SiOx

x films

films

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

Refractive Index n by SE Stoichiometry x by XPS

Sample #1 Sample #2

SLIDE 29

11th TAPPI European PLACE Conference

29

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating

coating Deposition on PET: an Example Deposition on PET: an Example…… ……. .

PET Substrate PET Substrate 1 1st

st Layer

Layer 2 2nd

nd Layer

Layer 3 3rd

rd Layer

Layer 4 4th

th Layer

Layer

Ultra Fast SE measurements at ~100 ms Ultra Fast SE measurements at ~100 ms SiOx SiOx / PET / PET < <ε ε( (ω ω)> of )> of SiOx SiOx / PET / PET < <ε ε( (ω ω)> of PET )> of PET The real The real-

time optical monitoring plays a major role in the monitoring & c

time optical monitoring plays a major role in the monitoring & control

ntrol

the growth mechanisms during the deposition of barrier the growth mechanisms during the deposition of barrier nano nano-

layers ..

layers ..

SLIDE 30

11th TAPPI European PLACE Conference

30

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

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating

coating Deposition on PET: an Example Deposition on PET: an Example…… ……. .

SLIDE 31

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31

Real Real-

time modeling and Analysis of

time modeling and Analysis of SiO SiOx

x

nano nano-

coating Deposition on PET

coating Deposition on PET

…… ……and Real Time Modeling and Real Time Modeling during Deposition during Deposition Kinetic Model Kinetic 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

ptical parameters during

deposition

Evaluation of thickness Evaluation of εr & εi with time

SLIDE 32

11th TAPPI European PLACE Conference

32

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating Deposition on

coating Deposition on PET: an Example PET: an Example…… ……. .

PET PET (substrate) (substrate) PET PET (substrate) (substrate)

PET

Total deposition time t=60 s SiOx film

SiO SiOx

x

SiO SiOx

x

SLIDE 33

11th TAPPI European PLACE Conference

33

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating Deposition on

coating Deposition on PEN: an Example PEN: an Example…… ……. .

Total deposition time t=60 s

P hoton E nergy (eV) 6 5 4 3 Ä _i 7.000 6.000 5.000 4.000 3.000 2.000 1.000

PEN PEN (substrate) (substrate)

PEN

SiOx SiOx

SiOx film

PEN PEN (substrate) (substrate) SiOx SiOx

SLIDE 34

11th TAPPI European PLACE Conference

34

10 20 30 40 50 60 50 100 150 200 250 300 350 400 1 2 3 4 5 6 10 20 30 40 50

Deposition Time (sec) Thickness (nm) Thickness (nm) Deposition Time (sec) Deposition Rate: 4.97 nm/s

Initial stages

f growth

10 20 30 40 50 60 2 3 4 5 6 7 8

dL/dt (nm/s) Time (sec)

PET Substrate

1 2 3 4 5 6 2 3 4 5 6 7 8 dL/dt (nm/s) Time (sec)

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating Deposition on

coating Deposition on PET PET

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

Electron Transition Energy (eV)

Time (sec) x x

ΙΙ ΙΙ ΙΙ Ι

PET Substrate

Ι Ι

PET Substrate PET 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 & Stoichiometry Stoichiometry with Time with Time

SLIDE 35

11th TAPPI European PLACE Conference

35

10 20 30 40 50 60 1 2 3 4 5 6

2 4 6 8 10 1 2 3 4 5 6 dL/dt (nm/s Time (s)

dL/dt (nm/s Time (s)

10 20 30 40 50 60 20 40 60 80 100 120 2 4 6 8 10 5 10 15 20 25 30

Thickness (nm) L Thickness (nm) Time (sec) Deposition Rate: 1.556nm/sec PEN Substrate PEN Substrate PEN Substrate PEN Substrate

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

Electron Transition Energy (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 & Stoichiometry Stoichiometry with Time with Time

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating Deposition on

coating Deposition on PET PET

SLIDE 36

11th TAPPI European PLACE Conference

36

Fast kinetic measurements of < Fast kinetic measurements of <ε ε2

2(

(ω ω)> )> during deposition of during deposition of SiO SiOx

x nano

nano-

layers

layers

nto Hybrid (inorganic
nto Hybrid (inorganic-
organic) materials developed onto PET substrates
rganic) materials developed onto PET substrates…

…

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating Deposition on

coating Deposition on Hybrid Materials Hybrid Materials: an Example : an Example…… ……. .

Hybrid #1 / PET Hybrid #1 / PET

SiOx SiOx SiOx SiOx

Hybrid #2 / PET Hybrid #2 / PET

PET PET

Hybrid Hybrid SiO SiOx

x

The real The real-

time optical monitoring &

time optical monitoring & modelling modelling leads to leads to the understanding of the growth mechanisms and the the understanding of the growth mechanisms and the crosslinking crosslinking at the interfaces at the interfaces… …

SLIDE 37

11th TAPPI European PLACE Conference

37

10 20 30 40 50 60 500 1000 1500 2000 2500 3000 3500 4000

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

Thickness (A) Deposition Time (sec)

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating Deposition on

coating Deposition on Hybrid Materials Hybrid Materials: an Example : an Example…… ……. .

The evolution of Thickness of The evolution of Thickness of SiOx SiOx nano nano-

layers deposited onto the

layers deposited onto the Hybrid Materials Hybrid Materials The different The different deposition rates of deposition rates of SiO SiOx

x onto Hybrid

nto Hybrid

materials yields materials yields significant results on significant results on the the SiOx SiOx growth growth mechanisms mechanisms… …

5.9 nm/s 5.9 nm/s 3.9 nm/s 3.9 nm/s 2.1 nm/s 2.1 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)

SLIDE 38

11th TAPPI European PLACE Conference

38

6 7 8 9 10 11 1E-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 Permeability Penn Gap E0 (eV)

WVTR (g/m

2.d) (23

C, 85-0%)

Hybrid #1 / SiOx /PET Hybrid #2 / SiOx/PET Hybrid #2 / AlOx/PET Hybrid #3 / AlOx/PET OTR (cm

3/m 2.d.bar) (23

C, 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 nano nano-

layers that increase

layers that increase the path of permeating gas molecules the path of permeating gas molecules

Hybrid (Organic/Inorganic) Hybrid (Organic/Inorganic) Materials Materials

PEN

Inorganic Organic Inorganic Organic Inorganic Organic Inorgani

PEN

Inorganic Organic Inorganic Organic Inorganic Organic Inorgani

Polymer substrate

PEN

Inorganic Organic Inorganic Organic Inorganic Organic Inorgani

PEN

Inorganic Organic Inorganic Organic Inorganic Organic Inorgani

Polymer substrate

~4 orders of magnitude Improvement of Barrier Properties

S. Logothetidis et al., to be submitted 2007

Real Real-

time monitoring of

time monitoring of SiOx SiOx nano nano-

coating Deposition on

coating Deposition on Hybrid Materials Hybrid Materials: an Example : an Example…… ……. .

SLIDE 39

11th TAPPI European PLACE Conference

39

Real Real-

time monitoring of

time monitoring of AlO AlOx

x nano

nano-

coating

coating Deposition Deposition

n PET : an Example
n PET : an Example……

……. .

Time-Plot for 120nm AlOx on PET

Web speed: 0,2m/min Kinetic model & Real Time Analysis

100nm 110nm 120nm 130nm 140nm 100 200 300 400 500 600 700 800 900 1000 1100 1200

Time Thickness

Thickness

Evaluation Evaluation

f the
f the

uniformity uniformity

f coating
f coating

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

SLIDE 40

11th TAPPI European PLACE Conference

40

Incorporation of SiO Incorporation of SiO2

2 Nanoparticles

Nanoparticles in Hybrid Material in Hybrid Material-

Optical

Optical Properties Properties… …. .

PET

SiOx

SiO2 Hybrid

Hybrid #1 (3-4μm)-1%PSiO2/ SiOx/PET Hybrid #1 (4-5μm)-5%PSiO2/ SiOx/PET Hybrid #1 (5-6μm)-10%PSiO2/ SiOx/PET Hybrid #1 (6-7μm)-20%PSiO2/ SiOx/PET Hybrid #1 (7-8μm)-30%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 Energy (eV)-SiO2 Eg Hybrid#1 Eo Hybrid#1 Electron Transition Energy (eV)-Hybrid % 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…

5 10 15 20 25 30 35 5 10 15 20 25 30 35

% SiO2 by Spectroscopic Ellipsometry Estimated % SiO2

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

SLIDE 41

11th TAPPI European PLACE Conference

41

Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions

Outline Outline

Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

SLIDE 42

11th TAPPI European PLACE Conference

42

Transparent Conductive Oxides ( Transparent Conductive Oxides (TCOs TCOs) )

OLED Structure OLED Structure

Transparent Conductive Oxides ( Transparent Conductive Oxides (TCOs TCOs) ) 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 transparency Electrical conductivity (103 Ω-1 cm-1) Environmental stability

TCO Characteristics TCO Characteristics

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

Common TCO materials Common TCO materials… …

Drawbacks of the currently used Drawbacks of the currently used TCOs TCOs

Elevated deposition temperatures (>100°C),

(incompatible to polymer substrates)

Increased roughness
Low elasticity
Very high cost,
Low abundance

SLIDE 43

11th TAPPI European PLACE Conference

43 ZnO ZnO is a promising wide is a promising wide bandgap bandgap semiconductor material. semiconductor material. The The interest on interest on ZnO ZnO originates from its p

riginates from its potentiality
tentiality for use in a

for use in a wide range of Scientific, Technological & Industrial application wide range of Scientific, Technological & Industrial applications. s.

SOME APPLICATIONS SOME APPLICATIONS… …

Flexible electronic Devices ( Flexible electronic Devices (FEDs FEDs) ) Gas sensors Gas sensors UV light emitting devices & sensors UV light emitting devices & sensors Biosensors Biosensors

PROPERTIES: PROPERTIES:

Electrical conductivity Good ultraviolet absorption, Piezoelectricity Biocompatibility & Non-toxicity Easy manufacturing of nanostructures Low cost & Abundance Easy fabrication Compatibility with large scale processes

ZnO ZnO has a has a wurtzite wurtzite crystal structure and is a direct gap (II crystal 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 eV eV. .

Transparent Conductive Oxides ( Transparent Conductive Oxides (TCOs TCOs) : ) : Zinc Oxide ( Zinc Oxide (ZnO ZnO) )

SLIDE 44

11th TAPPI European PLACE Conference

44

Real Real-

time monitoring of

time monitoring of ZnO ZnO nano nano-

coating

coating Example: Deposition on Example: Deposition on c c-

Si

Si substrate substrate

Ultra Fast SE measurements at ~100 ms Ultra Fast SE measurements at ~100 ms < <ε ε( (ω ω)> of )> of ZnO ZnO / / c c-

Si

Si The real The real-

time optical monitoring plays a major role in the monitoring & c

time optical monitoring plays a major role in the monitoring & control

ntrol

the growth mechanisms during the deposition of the growth mechanisms during the deposition of ZnO ZnO nano nano-

layers ..

layers .. < <ε ε( (ω ω)> of )> of c c-

Si

Si c c-

Si

Si

ZnO film

S. Logothetidis et al., to be submitted 2006

SLIDE 45

11th TAPPI European PLACE Conference

45

Modelling Modelling of the measured

f the measured pseudodielectric

pseudodielectric function function < <ε ε( (ω ω) )> > of

f ZnO

ZnO films with films with the theoretical fit, the theoretical fit, by the analysis of the by the analysis of the < <ε ε( (ω ω) )> > with the TL model with the TL model

) ( 2 1 2 2 2 ) 2 2 ( 2 ) ( ) ( 2 = ⋅ + − − = E TL E E C E E g E E C AE E TL

O O

ε ε

ξ ξ ξ ξε π ε ε

ω

d E P E

g

TL

∫

∞ ∞

− + =

2 2 2 1

) ( 2 ) (

Tauc Tauc-

Lorentz

Lorentz (TL) Model* (TL) Model*

Modelling Modelling of the Optical Properties of

f the Optical Properties of ZnO

ZnO thin films thin films Vis Vis-

fUV

fUV spectral region (1.5 spectral region (1.5-

6.5

6.5 eV eV) )

2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 1 2 3 4 5 6 7 8

3
2
1

1 2 3 4 5

Pseudodielectric Function <ε2(ω)> <ε2(ω)> Pseudodielectric Function <ε1(ω)> Experimental Data Theoretical Fit Photon Energy (eV) <ε1(ω)>

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

polymer polymer

ZnO film

1 2 3 4 5 6 7 8 9 1.5 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) Dielectric Function ε1(ω) Dielectric Function ε2(ω) BULK DIELECTRIC FUNCTION of ZnO layer ε1(ω)

Εg = 3.28 ± 0.02 eV ε∞ = 2.27 ± 0.04 eV Α1 = 153.6 ± 8.9 Ε1 = 3.37 ± 0.04 eV C1 = 1.21 ± 0.05 Α2 = 50.2 ± 1.7 Ε2 = 6.41 ± 0.25 eV C2 = 11.16 ± 0.53

Determined Determined Parameters Parameters

S. Logothetidis et al., to be submitted 2006

SLIDE 46

11th TAPPI European PLACE Conference

46

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 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 5.4 5.6 5.8 6.0 6.2

Fundamental Gap E0 E1 E2 Electron Transition Energy (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 6.5 2 4 6 8 10 12 14 16

Film Thickness (nm) Deposition Time (min)

Evolution of Evolution of E Eg

g gap and absorption

gap and absorption energies E energies E1

1 & E

& E2

2 determined by analysis of

determined by analysis of SE data during SE data during ZnO ZnO deposition deposition Thickness of the Thickness of the ZnO ZnOx

x thin film determined

thin film determined by analysis of SE data during deposition by analysis of SE data during deposition

Modelling Modelling of the Optical Properties of

f the Optical Properties of ZnO

ZnO thin films: thin films: Example: Example: Pulsed DC Magnetron Sputtering Deposition of Pulsed DC Magnetron Sputtering Deposition of ZnO ZnO

PET Substrate

Layer Layer-

by

by-

layer

layer Growth Mechanism Growth Mechanism

f
f ZnO

ZnO… … Homogeneous film Homogeneous film Growth Growth… …

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

SLIDE 47

11th TAPPI European PLACE Conference

47 Homogeneous film growth Nucleation layer

100 200 300 400 500 600 10 20 30 40 50 60 70 80 90 100 110 120 20 40 60 80 100

Voids (%) Thickness (nm) Deposition Time (sec) Top Layer Bottom Layer Total Film Thickness Voids of Top Layer

1. Nucleation
2. Coalescence
3. Homogeneous growth

Evolution of Evolution of E Eg

g gap and absorption

gap and absorption energies E energies E1

1 & E

& E2

2 determined by analysis of

determined by analysis of SE data during SE data during ZnO ZnO deposition deposition Thickness of the Thickness of the ZnO ZnOx

x thin film determined

thin film determined by analysis of SE data during deposition by analysis of SE data during deposition

Modelling Modelling of the Optical Properties of

f the Optical Properties of ZnO

ZnO thin films: thin films: Example: Example: DC Magnetron Sputtering Deposition of DC Magnetron Sputtering Deposition of ZnO ZnO

100 200 300 400 500 600 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.8 6.0 6.2 6.4 6.6

Electronic Transition Energy (eV) Deposition Time (s) Eg E1 E2

PET Substrate PET Substrate PET Substrate PET Substrate PET Substrate

d1 d2

Two layer model Two layer model

S. Logothetidis et al., to be submitted 2006

SLIDE 48

11th TAPPI European PLACE Conference

48

Total deposition time t=20 min PET PET

PEN PEN (substrate) (substrate) ZnO ZnO/PET /PET

ZnO film

Real Real-

time monitoring of

time monitoring of ZnO ZnO nano nano-

coating

coating Example: Example: Deposition on PEN substrate Deposition on PEN substrate

Real Real-

Time Monitoring of

Time Monitoring of deposition Processes: deposition Processes: i) i) Thickness versus deposition Thickness versus deposition Time Time ii) ii) Optical Parameters Optical Parameters

C. Koidis, D. Georgiou, N. Goktsis, S. Lousinian, A. Laskarakis, S. Logothetidis,

(Submitted to E-MRS 2007-accepted for oral presentation)

SLIDE 49

11th TAPPI European PLACE Conference

49 Evolution of Evolution of E Eg

g gap and absorption

gap and absorption energies E energies E1

1 & E

& E2

2 determined by analysis of

determined by analysis of SE data during SE data during ZnO ZnO deposition deposition

2 4 6 8 10 12 14 16 18 20 2.9 3.0 3.1 3.2 3.3 3.4 4 6 8 10 12

ZnO on PEN

Electron Transition Energy (eV) Time (min)

Eg E1 E2

Thickness of the Thickness of the ZnO ZnOx

x thin film determined

thin film determined by analysis of SE data during deposition by 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)

Real Real-

time monitoring of

time monitoring of ZnO ZnO nano nano-

coating

coating Example: Example: Deposition on PEN substrate Deposition on PEN substrate

SLIDE 50

11th TAPPI European PLACE Conference

50

Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions

Outline Outline

Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

SLIDE 51

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51

In In-

situ & Real

situ & Real-

time measurements of Optical Properties

time measurements of Optical Properties

For the quality control of the deposited organic For the quality control of the deposited organic nano nano-

layers it is necessary the

layers it is necessary the real real-

time optical monitoring during the growth

time optical monitoring during the growth… …

Organic Conductive Oxides Organic Conductive Oxides

OLED Structure OLED Structure

Real Real-

time

time monitoring monitoring by SE by SE

PET, PEN, … Barrier nano-layers… TCO materials (ITO, ZnO, …) AlQ3, Pentacenes, P3HT, etc…

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

SLIDE 52

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52

Organic Conductive Oxides are increasingly used in the productio Organic Conductive Oxides are increasingly used in the production of n of FEDs FEDs, , such as the such as the Organic Organic PVs PVs… …

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

Acceptor materials Acceptor materials

BCP pentacene CuPC

Donor materials Donor materials

PFDTBT

Organic Conductive Oxides Organic Conductive Oxides

SLIDE 53

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53

Organic Conductive Oxides are increasingly used in the productio Organic Conductive Oxides are increasingly used in the production of n of FEDs FEDs, , such as the such as the OLEDs OLEDs… …

Emissive materials Emissive materials

PPP PPV

PFO PFE Blue Blue

PPV BCP

Green Green

PT CN-PPV DCM

Red Red

Organic Conductive Oxides Organic Conductive Oxides

SLIDE 54

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54

2 4 6 8 10 2 3 4

PEDOT:PSS 0

PEDOT:PSS 90
ε1 (ω)

Photon Energy(eV)

2 4 6 8 10 1 2

PEDOT:PSS 0

PEDOT:PSS 0
Photon Energy(eV)

ε2 (ω)

Dispersion Equation: 2 2-

TL oscillator

TL oscillator

Εg = 4.829 ±0.04 eV ε∞ = 2.537 ± 0.03 eV Α1 = 50.85 ± 2.45 Ε1 = 5.32 ± 0.019 eV C1 = 0.596 ± 0.012 Α2 = 16.36 ± 0.74 Ε2 = 6.37 ± 0.07 eV C2 = 0.62 ± 0.025

Determined Determined Parameters Parameters

PEDOT:PSS on PEN

Organic Conductive Oxides Organic Conductive Oxides

SLIDE 55

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55

Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions

Outline Outline

Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

SLIDE 56

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56

Deposition Process Technologies Deposition Process Technologies

Lab scale Ultra High Vacuum Chamber (LTFN) Pilot scale R2R Vacuum Coating Systems (Research Institutes) Large Scale R2R Vacuum Coater systems (Industry)

SLIDE 57

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57

Modulator & Polarizer Housing Xe lamp & Analyzer Housing

Adaptation of the Prototype UFMWE Adaptation of the Prototype UFMWE

n the deposition chamber at LTFN
n the deposition chamber at LTFN

SLIDE 58

11th TAPPI European PLACE Conference

58

From Research... From Research...

EC Growth Project TransMach

...and Industrial Scale ...and Industrial Scale ...to Pilot ... ...to Pilot ... Up Up-

scaling the integration of UFMWE from

scaling the integration of UFMWE from real real-

time Lab

time Lab to to in in-

line r2r Processes

line r2r Processes… …

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Large Scale r2r Production Sequence of Large Scale r2r Production Sequence of FEDs FEDs

Encapsulant (Flexible polymer layer) Functional Thin Film electronic modules (ITO layers, electron transport layers, organic emitters, etc.) Encapsulated FEDs FEDs roll roll Encapsulant (Flexible polymer layer) Functional Thin Film electronic modules (ITO layers, electron transport layers, organic emitters, etc.) Encapsulated FEDs FEDs roll roll roll roll

R2R Production Processes of R2R Production Processes of FEDs FEDs

Real time Optical Monitoring (SE)

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Up Up-

scaling the integration of UFMWE to All Steps of the

scaling the integration of UFMWE to All Steps of the Production of Production of FEDs FEDs

From Polymer Substrates From 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 nano nano-

layers it is necessary to integrate the real

layers it is necessary to integrate the real-

time

time control in all the production steps control in all the production steps … …. .

Spectroscopic Spectroscopic Ellipsometry Ellipsometry (SE) (SE)

Optical Fiber Optical Fiber Sample Sample Polarizer Polarizer Photoelastic Photoelastic Modulator Modulator Analyzer Analyzer Detector Detector Monochromator Monochromator Data Acquisition Data Acquisition Computer Computer Xe Xe lamp lamp Shutter Shutter Optical Fiber Optical Fiber Sample Sample Polarizer Polarizer Photoelastic Photoelastic Modulator Modulator Polarizer Polarizer Photoelastic Photoelastic Modulator Modulator Analyzer Analyzer Detector Detector Monochromator Monochromator Data Acquisition Data Acquisition Computer Computer Xe Xe lamp lamp Shutter Shutter Xe Xe lamp lamp Xe Xe lamp lamp Shutter Shutter

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From Batch to From Batch to … ….. .. In In-

line

line

R2R Production Processes of R2R Production Processes of FEDs FEDs

BATCH PRODUCTION

1000 m 1000 m2

2

SEMI-BATCH PRODUCTION

300 m 300 m2

2

IN-LINE PRODUCTION (OLEDs)

100 m 100 m2

2

IN-LINE PRODUCTION (OLEDs)

100 m 100 m2

2

SE SE SE SE Quality Control SE SE SE SE Quality Control

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

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 ] thickness [ nm ] / transmittance [ % ] 1 2 3 4 5 6 7 8 9 10

xygen transmittance [ cm³/m²/day ] / Eg

Thickness measured online Thickness set point Light transmittance at 356nm Oxygen transmittance Eg

here:

xygen inlet

here: posttreat- ment optimised

In In-

Line r2r Process Control by Real

Line r2r Process Control by Real-

Time

Time Optical monitoring with Spectroscopic Optical monitoring with Spectroscopic Ellipsometry Ellipsometry

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“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

xide 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 LTFN LTFN in the field of Plastic Electronics in the field of Plastic Electronics

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ISOTECH TRANSMACH

From the Lab to From the Lab to Industry & Society Industry & Society Activities of Activities of LTFN LTFN in the field of Plastic Electronics in the field of Plastic Electronics

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“ “Ultra Ultra-

high barrier films for r2r encapsulation of flexible electronics

high barrier films for r2r encapsulation of flexible electronics” ” FLEXONICS ( FLEXONICS (www.flexonics.org www.flexonics.org) )

STREP Project (2005 STREP Project (2005 -

2008)

2008) Project Coordinator : Prof. S. Project Coordinator : Prof. S. Logothetidis Logothetidis

Development of novel transparent & flexible material systems wit Development of novel transparent & flexible material systems with h ultra ultra-

high

high barrier properties barrier properties and the related processing technologies in order to be used for and the related processing technologies in order to be used for the the large large-

scale roll

scale roll-

to

to-

roll (r2r) encapsulation of future flexible

roll (r2r) encapsulation of future flexible opto

pto-
& 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

Activities of Activities of LTFN LTFN in the field of Plastic Electronics in the field of Plastic Electronics

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66

Polymeric Materials: New Emerging Technologies & Applications Polymeric 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 (FEDs FEDs) ) Up Up-

scaling of Optical Sensing techniques from Lab scale to

scaling of Optical Sensing techniques from Lab scale to Large scale r2r Production Processes Large scale r2r Production Processes Summarising & Conclusions Summarising & Conclusions

Outline Outline

Spectroscopic Spectroscopic Ellipsometry Ellipsometry : Principles & Methodology : Principles & Methodology Anisotropic Polymeric Substrates Anisotropic Polymeric Substrates Barrier Barrier Nano Nano-

layers

layers Electrodes & Transparent Conductive Oxides ( Electrodes & Transparent Conductive Oxides (TCOs TCOs) ) Organic Conductive Oxides Organic Conductive Oxides

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In In-

line SE will play a major role towards the Cost

line SE will play a major role towards the Cost-

effective

effective Large Large Scale r2r production Scale r2r production of transparent functional layers onto

f transparent functional layers onto

Polymeric substrates Polymeric substrates… … Real Real-

time SE in combination to

time SE in combination to Modelling Modelling & Analysis techniques & Analysis techniques provides accurate results on the provides accurate results on the Optical properties Optical properties, , Thickness Thickness, , Stoichiometry Stoichiometry, , Composition Composition, , Microstructure Microstructure & & Density Density of

f Polymeric

Polymeric Substrates, Substrates, Barrier Barrier layers layers, , TCOs TCOs and and Organic Organic Layers Layers… … The C The Correlation

rrelation of
f O

Optical ptical Properties Properties to to Intermediate Intermediate & & Functional properties Functional properties, leads to the Determination & Control the , leads to the Determination & Control the Quality Quality of transparent Functional layers (barrier, electrodes, etc.)

f transparent Functional layers (barrier, electrodes, etc.)

developed onto developed onto P Polymer

lymers

s for for Flexible Electronics Flexible Electronics applications applications… …

Summarizing & Conclusions Summarizing & Conclusions

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Our Partners

Staff of the Staff of the Lab Lab Thin Films Thin Films-

Nanosystems

Nanosystems & & Nanometrology Nanometrology (Aristotle University of (Aristotle University of Thessaloniki Thessaloniki) )

IVV

ACKNOWLEDGEMENTS ACKNOWLEDGEMENTS

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Nanosystems

Nanosystems & & Nanometrology Nanometrology (LTFN) (LTFN)

Aristotle University of Aristotle University of Thessaloniki Thessaloniki, Physics Department , Physics Department GR GR-

54124

54124 Thessaloniki Thessaloniki, Greece , Greece, http:// , http://ltfn.physics.auth.gr ltfn.physics.auth.gr