# US 2014/0151656 A1 · Gas and moisture permeation barriers

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- Number: US 2014/0151656 A1
- Document ID: US20140151656A1
- Status: Published application
- Kind: A1
- Application number: 14/073,809
- Filed: 2013-11-06
- Published: 2014-06-05
- Earliest claimed: 2012-12-03
- Assignees: Cheil Industries Inc.
- Applicants: Cheil Industries, Inc.
- Inventors: Xianghui Zeng; Lorenza Moro; Damien Boesch
- Web page: https://patentgrep.com/patent/US20140151656A1

## CPC

- C23C 14/081: {of aluminium, magnesium or beryllium}
- C23C 14/00: Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C 16/403: {of aluminium, magnesium or beryllium}
- C23C 16/45525: {Atomic layer deposition [ALD]}
- H10K 50/844: Encapsulations
- H10K 77/10: Substrates, e.g. flexible substrates
- Y02E 10/549: Organic PV cells
- Y10T 428/31504: Composite [nonstructural laminate]
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A gas and moisture permeation barrier stack deposited by both sputtering and atomic layer deposition techniques. In one embodiment, the barrier stack comprises a bottom barrier layer deposited on a substrate by sputtering and a top barrier layer deposited on the sputtered layer by atomic layer deposition. In one embodiment, the sputtered barrier layer has a water vapor transmission rate of about 10−5 gm/m2·day or lower, and the top barrier layer improves the water vapor transmission rate of the resulting two-layer barrier stack to about 10−6 gm/m2·day or lower.

## Claims

### Claim 1

A composite article comprising:
a substrate; and
a barrier stack for protecting a surface of the substrate, the barrier stack comprising:
a first barrier layer on the surface of the substrate, the first barrier layer being a sputtered barrier layer, and
a second barrier layer on a surface of the first barrier layer, the second barrier layer being an atomic layer-deposited barrier layer,
the first barrier layer being between the substrate and the second barrier layer,
wherein the first barrier layer, in the absence of the second barrier layer, has a water vapor transmission rate of about 10−5 gm/m2·day or lower, and
wherein the barrier stack has a water vapor transmission rate of about 10−6 gm/m2·day or lower.

### Claim 2 (depends on 1)

The article according to claim 1, wherein the second barrier layer is sufficiently thick to correct physical defects present on the exposed surface of the first barrier layer, but thin enough to flex without cracking.

### Claim 3 (depends on 1)

The article according to claim 1, wherein the second barrier layer is thinner than the first barrier layer.

### Claim 4 (depends on 1)

The article according to claim 1, wherein the substrate comprises an organic light-emitting device.

### Claim 5 (depends on 1)

The article according to claim 1, wherein the composite article comprises a laminate film.

### Claim 6 (depends on 1)

The article according to claim 1, wherein the first barrier layer comprises at least one of (a)-(c):
(a) a metal oxide;
(b) a layer thickness from about 20 to about 100 nm;
(c) a refractive index of about 1.6 or greater.

### Claim 7 (depends on 1)

The article according to claim 1, further comprising a planarization layer on the substrate between the substrate and the first barrier layer.

### Claim 8 (depends on 7)

The article according to claim 7, further including a tie layer on the substrate between the substrate and the planarization layer.

### Claim 9 (depends on 8)

The article according to claim 8, wherein the first and second barrier layers each comprise a monolayer, and the barrier stack forms the outer surface of the article.

### Claim 10

A method for protecting a substrate from the permeation of moisture and gases, the method comprising:
sputtering a first barrier layer on a substrate, wherein the sputtered first barrier layer has a water vapor transmission rate of about 10−5 gm/m2·day or lower, and
depositing a second barrier layer on the first barrier layer by atomic layer deposition, to form a barrier stack having a water vapor transmission rate of about 10−6 gm/m2·day or lower.

### Claim 11 (depends on 10)

The method according to claim 10, wherein the second barrier layer is sufficiently thick to correct physical defects present on the surface of the first barrier layer but thin enough to flex without cracking.

### Claim 12 (depends on 10)

The method according to claim 10, wherein the second barrier layer is thinner than the first barrier layer.

### Claim 13 (depends on 10)

The method according to claim 10, wherein the first barrier layer comprises at least one of (a)-(c):
(a) a metal oxide;
(b) a layer thickness from about 20 to about 100 nm;
(c) a refractive index of about 1.6 or greater.

### Claim 14 (depends on 10)

The method according to claim 10, further comprising depositing a planarization layer between the first barrier layer and the substrate.

### Claim 15 (depends on 14)

The method according to claim 14, further comprising depositing a tie layer between the planarization layer and the substrate.

### Claim 16 (depends on 11)

The method according to claim 11, wherein the substrate comprises an organic light emitting device.

### Claim 17 (depends on 16)

The method according to claim 16, wherein the first and second barrier layers each comprise a single layer, and the barrier stack forms an outer surface of the article.

### Claim 18 (depends on 1)

The method according to claim 1, wherein the sputtering of the first organic material comprises AC sputtering or pulsed DC sputtering.

### Claim 19

A composite article comprising:
a substrate; and
a two-layer barrier stack for protecting a surface of the substrate, the barrier stack comprising:
a bottom barrier layer on the surface of the substrate, the bottom barrier layer being a sputtered barrier layer having a water vapor transmission rate of about 10−5 gm/m2·day or lower, and
a top barrier layer on a surface of the bottom barrier layer, the top barrier layer being an atomic layer-deposited barrier layer, wherein the two-layer barrier stack has a water vapor transmission rate of about 10−6 gm/m2·day or lower,
wherein the bottom barrier layer has a film thickness of at least about 20 nm.

### Claim 20 (depends on 19)

The article according to claim 19, wherein the composite article comprises a laminate film.

### Claim 21 (depends on 19)

The article according to claim 19, wherein the substrate comprises an organic light-emitting device.

### Claim 22 (depends on 19)

The article according to claim 19, wherein the first and second barrier layers each comprise a single layer, and the barrier stack forms the outer surface of the article.

### Claim 23 (depends on 20)

The article according to claim 20, wherein the first barrier layer is formed by AC sputtering or pulsed DC sputtering.

### Claim 24 (depends on 20)

The article according to claim 20, wherein the first barrier layer comprises aluminum oxide.

### Claim 25

A multilayer composite article comprising:
a substrate;
a first two-layer barrier stack comprising a first barrier layer on a surface of the substrate, the first barrier layer being a sputtered barrier layer, and a second barrier layer on the first barrier layer and being an atomic layer-deposited barrier layer; and
a second two-layer barrier stack comprising a third barrier layer comprising a sputtered barrier layer, and a fourth barrier layer on the third barrier layer and comprising an atomic layer-deposited barrier layer;
wherein the second two-layer barrier stack is deposited on a surface of the first two-layer barrier stack.

### Claim 26 (depends on 25)

The multilayer article according to claim 25, further comprising a planarization layer between the first and second two-layer barrier stacks.

### Claim 27 (depends on 25)

The multilayer article according to claim 25, wherein the second barrier layer of one or both of the two-layer barrier stacks is thinner than the first barrier layer of the same two-layer barrier stack.

### Claim 28 (depends on 25)

The multi-layer article according to claim 25, wherein the first barrier stack has a water vapor transmission rate of 10−6 gm/m2 day or lower.