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ALD ULTRA-BARRIERS FOR ELECTRONIC

APPLICATIONSSTRATEGIES AND
IMPLEMENTATION
P.F Carcia* , R.S. McLean, B.B Sauer, and M.H. Reilly
DuPont Research & Development, Experimental Station,
Wilmington, DE 19880-0400 USA
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Motivation
Enable flexible electronics on
polymer substrates:
-OLED Displays
-OLED Lighting
-Organic transistors and solar
cells
-CIGS solar cells
18.7%
efficiency
Motivation
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Need Moisture Barrier Coating
Most organic devices are extremely moisture sensitive and
need a packaging strategy to protect from moisture-driven
degradation.
However, flexible polymer substrates are highly permeable to
all atmospheric gases, whereas glass is impermeable.
What is needed is a barrier coating on flexible polymers that
essentially excludes atmospheric gases, comparable to glass.
This barrier coating must be pinhole-free, defect-free, and
dense.
A barrier coating grown by atomic layer deposition (ALD) is as
close to perfect as one can practically achieve.
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10
10
-1
10
-3
10
-5
WVTR/OTR
g or cc/m
2
/day
Thin Film PV (CIGS)
OLEDs
Polymer films
PET, PEN,
FEP
Traditional
packaging films
Range of Barrier Requirements
LCD
Need an Ultra-barrier technology to meet needs for OLEDs and
and CIGS solar.
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Ref. A. Dameron (NREL)
Most sensitive commercial instrument for WVTR
1-3 days measurement time
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WVTR measurement using Ca-test
L
i
g
h
t
PEN or PET
Barrier film
Epoxy
Ca (50 60 nm, semi-transparent)
Glass Substrate
14
16
18
0 1000 2000 3000
%
T
t(hr)
60 C/85% RH
38 C/85% RH
oxide barrier/HS-PEN-5mil
WVTR~1.7x10
-5
g/m
2
/day
WVTR~6.5x10
-5
g/m
2
/day
Ca + H
2
O CaO + H
2
or
Ca + 2 H
2
O Ca(OH)
2
+ H
2
Both CaO and Ca(OH)
2
are transparent
WVTR (CaO)

D(CaO)/t

m(H
2
O)/m(CaO)
%
T
ALD Al2O3 at ~120

C
10x more sensitive than MOCON
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How good is a single ALD barrier coating?
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Outline
How important is the temperature of the ALD process for
ultra-barrier properties.
Does pre-treatment/cleaning of the substrate affect ultra-
barrier properties
plasma etching
How does substrate surface chemistry affect ultra-barrier
properties.
Raw polymer side
Slip-side
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Effect of ALD Synthesis Temperature
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Leakage current density and breakdown voltage in ALD
Al2O3 depends of synthesis temperaturebarriers?
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Moisture permeation in ALD Al
2
O
3
depends on synthesis T and film
thickness; failure (pinholes) is abrupt, but prior changes track glass.
(1200 hr at 38 C/85% RH +500 hr at 60 C/85% RH)
Polymer PET surface
Films grown at higher T and
thicker are more stable.
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Permeation model*
Moisture permeation in ALD Al
2
O
3
is not due to
pinholes.
Permeation is attributed to diffusion of molecularly
dissolved H
2
O along defect clusters (-OH) in the Al
2
O
3
amorphous network. ([H]-content increases for low ALD synthesis)
Permeation breakthrough occurs when the defect
clusters percolate the ALD barrier film thickness.
(analogous to electrical breakdown)
Postulate the time-to-failure, t
f
=t
0
(H/kT-d
0
/d), where
H is ~ bonding energy between H
2
O and
oxide/hydroxide defect clusters, and d
0
~ threshold
barrier thickness.
*Carcia et al. Appl. Phys. Lett. 97, 221901 (2010)
Pfeffer and Ohring, J . Appl. Phys. 52, 777 (1981)
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Effect of plasma-etching PET surface
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contact angle,
c
=62.2

for PET
Etched PET surface is more hydrophillic

c
=23.6
Dark region (phase image) is
softer amorphous segment
between harder (light)
crystalline domains.
Etching preferentially removes
softer amorphous segment.
Ar-etching at -50 V(10 min)
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Lower moisture permeation for thinner Al2O3 on etched
PET.
Hydrophilic surface may
present a more reactive
surface for TMA
adsorption--improved
nucleation
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Effect of surface chemistryraw polymer versus
coated slip-side of PET polymer
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Coated slip-side of
PET is rougher and
absent the
crystalline fibril
features of raw
polymer surface.
Comparison of slip and raw polymer sides of PET
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Barrier performance is superior for ALD on raw polymer side.
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ALD Barrier Application to CIGS Solar Cells
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85

C/85% RH
Environmental Chamber
Measured at IEC (U. Delaware)
Encapsulated PV cell
2mil FEP
25 nm ALD
Al
2
O
3
on
uv-PET
encapsulant
CIGS cell
Glass
Change in efficiency of CIGS ~2% in 1032 hr at
85

C/85% RH +solar illumination
adhesive
8
9
10
11
12
13
14
0 10 20 30 40
85 C/85 % RH +ill umi nati on 1032 hr
E
f
f
i
c
i
e
n
c
y

(
%
)
t(days)
1xALD-uv-PET
2xALD-uv-PET
Damp Heat Test Results for CIGS
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Summary
For best barrier performance: thicker films and higher ALD
growth temperature are preferred.
Polymer surface pre-treatment, e.g. plasma etching, improves
barrier properties.
The two sides of a polymer film are more often chemically
different, and ALD growth may produce better barrier
properties on one side.
ALD barrier films are a promising candidate for a transparent,
flexible front sheet for CIGS solar cells.
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