Recent Improvements in PET film

for
Flexible Electronics and Photovoltaic Applications
Jan LaRiviere, Keith Rollins, Bill MacDonald,
and Bob Rustin
AIMCAL 2012

Melinex®and Mylar® are registered trademarks of DuPont Teijin Films U.S. Limited Partnership. Teijin ® Tetoron® is a registered trademarks of Teijin Limited and are licensed to DuPont Teijin Films US, Limited Partnership.
Teonex® is registered trademark of Teijin DuPont Films Japan Limited and licensed to DuPont Teijin Films U.S. Limited Partnership. Copyright © 2004-2009 DuPont Teijin Films (UK) Ltd. All rights reserved.
Scope

 Polyester film process

 Heat stabilized polyester film

 Latest film developments for flexible electronics

Low Bloom, Planarization, Refractive Index control

 Latest film developments for flexible PV

Weatherability, Adhesion

 Conclusion
Polyester Film Technology (1)

• PET and PEN polyester films Transverse Draw

• Biaxially oriented, semi-crystalline Forward Draw

• High stiffness
• Dimensional stability
• Optical transparency
• Solvent resistance
• Thickness = 0.6-500 µm

Melinex®, Mylar® and Teijin® Tetoron® Teonex®

Polyethylene terephthalate (PET) Polyethylene naphthalate (PEN)
O O
O O
O Tm = 255 °C O Tm = 263 °C
Tg = 78 °C Tg = 120 °C
O n O n
Polyester Film Technology (2)

• In-line Heat Stabilisation • Off-line Heat Stabilisation

• Oven

• Film can relax in TD but not in MD • Allows relaxation in MD

 Leads to shrinkage on subsequent processing  Minimum shrinkage on both directions
Heat-Stabilised PEN and PET Films
Upper temperature for processing
180-220 °C
Young’s Modulus
Shrinkage in MD after at 20 °C
30 min at 150 °C 0.05%
5 GPa
150 °C
Minimal shrinkage at 0.1% 4 GPa
temperatures > Tg
Young’s Modulus
20 ppm/°C at 150 °C
CTLE 25 ppm/°C 1 GPa
3 GPa

ST506 (PET)
78 °C
Q65FA (PEN)
Glass transition
1000 ppm temperature
1000 ppm 0.7% 120 °C
Moisture pick-up
at 200 °C, 40% RH 0.7%
Haze
Polyester Films for Flexible Electronics

• Red denotes new

• Melinex® -A diverse range of heat stabilised PET films
– Dimensionally stable up to 150C
– Thickness 50 micron to 250 micron
– UV stabilised
– Range of pretreats for enhanced adhesion to functional coatings
• Tetoron®-Low shrink, planarized PET films
– Ultrasmooth defect free surface for improved device performance
• Teonex® -Leading range of high performance PEN films
– Dimensionally stable up to 180-200C
– Thickness 25-200micron
– Pretreated for enhanced adhesion to functional coatings
– White film at 75 micron
• Teonex®- Low shrink, planarized PEN films
– High temperature performance with ultrasmooth defect free surface
– 50 and 125 micron film
– Protect film (one or two side) available
Polyester Films for Flexible Electronics

• To discuss specific requirements please contact

• Jan LaRiviere (US)

– Jan.S.LaRiviere@usa.dupont.com

• Thane Gough (Europe)

– Thane.C.Gough@gbr.dupont.com
Films for Touchscreen

• Rapid Touch Screen Market growth

• Requires continued optimization for PET

Touch Screen Revenue Forecast

Source:
DisplaySearch 2011 Touch Panel Market Analysis
Films for Touchscreen

• Projected Capacitive Touch is the primary driver for growth

– Many designs use PET film as the transparent conductor
substrate
– Manufacturing processes expose PET film to very high
temperatures for extended periods
• Heat stabilized film satisfies the shrinkage requirement
• But, PET will “haze-up” under these conditions
Cyclic Oligomers
Observed that if PET film is held at temperatures above 100C film starts to go hazy
due to migration of cyclic oligomers to the surface

<1% Haze Increased Haze

100o C for 10 min 120o C for 10 min 140o C for 10 min

PEN

PET

Polyhedral or hexagonal platelike oligomer crystals form, a few microns in size

Soluble in solvents (e.g. MEK)
Cyclic Trimer

Cyclic trimer Tm 318C present at ca 1.1 to 1.4wt%

O O

C C

O O

O O

O C C O

C O O C

O O

Other cyclics present but in lower amounts. Trimer is low strain relative
to other cyclics.
The Cyclic Oligomer Equilibrium
O O

PET C C O CH2CH2 O H

Mol Wt =x

Driven by
Driven by Process control
-time at temperature
in melt
-amount of work in
extrusion system
OC COOCH2CH2O

PET

Mol Wt =x-3

n=3
Cycylic Oligomer Crystals

• Perovic, J Mat Sci, 20, 1985, 1370

• 130C –hexagonal crystals up to 5-
6 micron initially but can grow
larger with time
Traditional Strategy

• Traditional strategy used is to coat the surface with a coating

that acts as a barrier to oligomers migrating to surface

• ITO blocks to an extent but blooming becomes more of an

issue with other approaches to conductive films eg printed
silver grids etc
Strategies for Control -Block

• Presence of planarizing coatings significantly reduces bloom

• Coatings acting as a barrier

Non planarized PET : 30mins / 120 C planarized PET : 30mins / 120 C

Features of planarized films

50

planarizer
40
Increase in haze %

30 Two side planarised

Q65WA
20 Uncoated Q65FWA

10
Uncoated PEN
0
0 5 10 15 20 25 30 35
-10
Time / hours

Time dependence of oligomer migration (measured by haze

increase) of PEN and two side planarized PEN at 200C
New Strategy for Control -Process Control

• Through process control at PET polymerisation stage and

during film processing it is possible to
– Significantly reduce the cyclic content in the PET polymer
– Minimise the reformation of the cyclic oligomers during subsequent
filming process
New Developments

• New development grade, 1% haze on ageing at 150oC /30

mins
• Now in qualification with customers
• Able to tailor with respect to surface treatments for specific
applications
• DTF is investigating further strategies to minimise the impact
of blooming on subsequent processing
• For more information contact Nicole Williamson
– Nicole.M.Williamson@USA.dupont.com
Refractive index control

• Controlling refraction and reflection effects in optical stacks

An example:
Reduced iridescence in hard coats

• Typically, hard coated PET films exhibit iridescence or rainbow

which is objectionable in display and touch applications
• Rainbow results from interference fringes stemming from
reflections in the optical stack
• Through optical modelling we can model the effect and
design the stack to minimize fringing
– Monitor the effect of changing specific layer parameters,
e.g. refractive index and thickness
– Look for ‘fringing’ in visible spectrum as an indication of
rainbow effect
• For more information contact Nori Mandokoro
– Nori.Mandokoro@USA.dupont.com
Modeling the transmission spectrum
shows the fringing effect

1.68
Refractive Index of Film Layer, n

1.66
1.64
1.62
Modeled Transmission Spectrum
1.6
1.58
1.56
1.54
1.52
1.5
0 5 10 15 20 25 30 35
Frame No.

Substrate refractive index is cycled between

1.67 and 1.51 to show effect on fringing (right),
Fringing occurs at higher RI values.

Hard Coat (RI=1.5)

Substrate (RI varied)

In the real world, it’s a bit more complex

Hard Coat (RI=1.5)

Note: most top layers require an
Adhesion Primer (RI = X) adhesion priming layer

PET Film (RI=1.67)

• Manipulation and control of the adhesion primer can optically

bridge the gap from substrate to top layer
DTF primer technology can reduce
hard coat fringing
ACTUAL DATA
Transmission spectra of new trial films + hardcoat, compared to standard film control
93
Reduced Iridescence
92

91

Optimized Iridescence
90
Reduced Iridescence

89
%T

88

87

No index matching, high iridescence

86

85

84

83
400 450 500 550 600 650 700
Wavelength (nm)
Visual of the new film’s effect

New Product

Standard PET Competitor X Competitor Y

Each sample is hard coated PET and photographed under a

monochromatic light source
Latest Film Developments for PV
Substrates for PV Cells – Gen. 2 & 3

Gen I Gen II Gen III

Thin Films

c-Si CdTe CIGS a-Si DSSC OPV

Encapsulation Encapsulation / Cell

Front Sheet
Superstrate
 A complex film development agenda!!
Cell Active Layer Stack Module
Substrate
Back Sheet
Functionalities

Surface Quality
Dimensional Stability Barrier

Front Sheet
Heat Stability Weatherability
Superstrate
Active Layer
Substrate

Back Sheet

Conductivity Adhesion
Light Management
 Surface Quality
Dimensional Stability Barrier

Front Sheet
Heat Stability Weatherability
Superstrate
Active Layer
Substrate

Back Sheet

Conductivity Adhesion
Light Management
Photo-oxidative Degradation

This pathway OC COOCH2CH2O This pathway

to colour
to chain breaking
n=ca 100
hv + O2 hv + O2

.
CO COOCH2CH2O OC
.
COOCHCH 2O

hv + O2
n=ca 100 n=ca 100
OH
hv + O2

CO COOCH2CH2O
OC .
HO
O
P-H
n=ca 100
CO COOCH2CH2O

OC +P .
O
n=ca 100
Upon UV light-induced degradation:

• Yellowness increases
– formation of new light-absorbing chemical species
• Haze increases (clear films)
– bulk + surface scattering
• Gloss decreases
– surface roughens
• Light transmittance decreases
– more absorption and scattering
• Mechanical properties i.e. %ETB, UTS decrease
– chains break down
UV Stabilisers

• UV stabilizers work by:

– Energy dissipation ie radiation is absorbed and then dissipated (heat ,
fluorescence)
– Radical deactivation and retardation of propagation of degradation
reactions
– Singlet oxygen quenching
– Peroxide decomposition
• Efficacy of a UV stabilizer depends on:
– How its optimum absorption wavelength(s) fits with the optimum
degradation wavelength(s) of the polymer
– Its efficiency at converting UV radiation into less harmful energy
(heat)
– Its intrinsic UV stability
– Its thermal stability to survive PET processing temperatures
 Weatherability – UV Resistance

• Lifetime perception: “Polyester films degrade rapidly under UV light exposure”

→ In reality, only non-UV stabilised films will!

• Polyester films can be modified to have improved resistance to UV light

• Typical results from Weather-Ometer® ageing of a DTF UV stabilised film

1) Mechanical properties:

% Retention of Elongation to Break % Retention of Ultimate Strength

120% 120%

100% 100%

80% 80%

60% 60%

` `
40% 40%
UV stabilised PET film UV stabilised PET film
20% Standard PET film 20% Standard PET film

0% 0%
0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000
Hours in the Weatherometer Hours in the Weatherometer
Method: ASTM 4892-2
Weatherability – UV Resistance

• Typical results from Weather-Ometer® ageing of a DTF UV stabilised film

2) Optical properties:

% Retention of Light Transmittance % Increase of Yellowness Index

105% 300%

250%
100%

200%
95%
150%
90% ` `
100%
Standard PET film Standard PET film
85%
UV stabilised PET film 50% UV stabilised PET film

80% 0%
0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000
Hours in the Weatherometer Hours in the Weatherometer

• 10,000 hours in Weather-Ometer® – Equivalent irradiation = 5 (Florida) to 11

years (Northern Europe)
This is not a lifetime guarantee
Weatherability – Hydrolysis Resistance

• Lifetime perception: “Polyester films hydrolyse rapidly”

→ This is very slow under normal atmospheric (T,P) conditions !

• Polyester films can be modified to pass the standard “Damp Heat” test –
Retention of 10% ETB after 1000 h at 85 °C / 85% RH

• Some industry interest in higher performance PET films for extended testing
times (2000+ hours in Damp Heat test)
% Elongation at Break (Melinex® 238)
200

150
 DTF's filled Melinex® 238
at 50 µm reaches 2000 h at
ETB (%)

100
85 °C / 85% RH
 DTF can also apply this
50 technology to optically clear
films
0
0 500 1000 1500 2000
Damp Heat Test (hours)
Hydrolysis of PET

• Catalysed by COOH end groups in PET

Strategies for Improving Hydrolysis
Resistance

• Raising Mol Wt of film

• Chemically modifying end groups
• Affecting film crystallinity
 Surface Quality
Dimensional Stability Barrier

Front Sheet
Heat Stability Weatherability
Sun-facing Substrate
PV Active Layer
Non Sun-facing Substrate
Back Sheet

Conductivity Adhesion
Light Management
Adhesion

• Multi-layer adhesion is appearing as one of the most challenging technical areas

and is key to optimise device/module lifetime and lab certification

• DTF has designed Melinex® films with enhanced adhesion to EVA (a typical cell
backside encapsulant)
- Received positive market feedback

• Similarly films with excellent adhesion to DuPont™ Surlyn® have also been
developed
Adhesion to Glass

• Industry-standard bonding interlayer eg

– polyvinyl butyral (PVB)
– “ionoplast” systems such as DuPont’s SentryGlas® 48
• These do not show good adhesion to many standard PET film
pretreatments, but specialist systems are available.
• The key parameter in this respect is the bonding or laminating
temperature required to give good adhesion and whether this
is in excess of what can be tolerated by the completed o-PV
cell.
• This remains an area of active research.
Conclusion

• Recent improvements in PET film support emerging flexible

electronics and flexible PV markets
• Active continuing innovation to meet future needs
• Underlying science that affect processing on polyester films
being researched
• Knowhow on how to get the most out of the handling and
processing on polyester film available to users
• Please contact us with any questions you may have

• THANK YOU !