Diffusion barrier coatings having graded compositions and devices incorporating the same

• US 7,943,205 B2
• Filed: 03/16/2006
• Issued: 05/17/2011
• Est. Priority Date: 09/11/2002
• Status: Active Grant

• Current Assignee: BOE Technology Group Co., Ltd.
• Original Assignee: General Electric Company
• Inventors: Flanagan, Kevin Warner, Schaepkens, Marc
• Primary Examiner(s): Turocy; David
• Application Number:
  US11/376,325
• Publication Number:
  US 20060216410A1
• Time in Patent Office: 1,888 Days
• Field of Search: 427/569, 427/69
• US Class Current: 427/569
• CPC Class Codes: B82Y 20/00 Nanooptics, e.g. quantum optics or photonic crystals
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: G02F 1/133305 Flexible substrates, e.g. plastics, organic film
• CPC Class Codes: G02F 2201/50 Protective arrangements
• CPC Class Codes: H10K 2101/80 Composition varying spatially, e.g. having a spatial gradient
• CPC Class Codes: H10K 2102/311 Flexible OLED
• CPC Class Codes: H10K 2102/331 Nanoparticles used in non-emissive layers, e.g. in packaging layer
• CPC Class Codes: H10K 50/125 specially adapted for multicolour light emission, e.g. for emitting white light
• CPC Class Codes: H10K 50/844 Encapsulations
• CPC Class Codes: H10K 50/854 comprising scattering means
• CPC Class Codes: H10K 59/877 comprising scattering means
• CPC Class Codes: Y10T 428/12021 having composition or density gradient or differential porosity
• CPC Class Codes: Y10T 428/1321 Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/1352 Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/24802 Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/31667 Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Abstract

A composite article comprises a substrate having at least a substrate surface and a graded-composition coating disposed on a substrate surface. The composition of the coating material varies substantially continuously across its thickness. The coating reduces the transmission rates of oxygen, water vapor, and other chemical species through the substrate such that the composite article can be used effectively as a diffusion barrier to protect chemically sensitive devices or materials. An organic light-emitting device incorporates such a composite article to provide an extended life thereto.

Claims

1. A method for making a composite article, said method comprising the steps of:

providing a substrate having at least a substrate surface;

depositing a coating material on said substrate surface using plasma-enhanced chemical-vapor deposition, wherein said coating material comprises an inorganic and an organic material deposited substantially simultaneously, and

effecting a penetration of at least a portion of said coating material into said substrate to produce a diffuse region between said substrate and said coating;

said at least a portion of said coating material comprises an inorganic and an organic material.

2. The method according to claim 1 wherein said depositing is selected from the group consisting of:

radio-frequency plasma-enhanced chemical-vapor deposition, expanding thermal-plasma chemical-vapor deposition, electron-cyclotron-resonance plasma-enhanced chemical-vapor deposition, inductively-coupled plasma-enhanced chemical-vapor deposition, and combinations thereof.

3. The method according to claim 1 wherein said substrate comprises a polymeric material selected from the group consisting of:

polyethyleneterephthalate, polyacrylates, polycarbonate, silicone, epoxy resins, silicone-functionalized epoxy resins, polyester, polyimide, polyetherimide, polyethersulfone, polyethylenenapthalene, polynorbonene, and poly(cyclic olefins).

4. The method according to claim 1 wherein said coating material comprises material selected from the group consisting of:

organic, inorganic, ceramic materials, and combinations thereof.

5. The method according to claim 4 wherein said inorganic and ceramic materials are selected from the group consisting of oxide, nitride, carbide, boride, and combinations thereof of elements of Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, and IIB, metals of Groups IIIB, IVB, and VB, and rare-earth metals.

6. The method according to claim 1 wherein said diffuse region is produced by an energetic ion bombardment of a surface of said substrate to sputter a portion of a material of said substrate, and depositing a mixed material comprising sputtered substrate material and another material.

7. The method of claim 1 wherein said substrate is flexible.

8. The method of claim 1 wherein said substrate is substantially transparent.

9. The method of claim 1 wherein said substrate comprises a metal.

10. The method of claim 1 wherein said substrate comprises glass.

11. The method of claim 1 wherein said coating has an oxygen permeability rate of approximately 0.001 ml/m²-day or less.

12. The method of claim 1 wherein said coating has a water vapor permeability rate of approximately 0.000001 g/m²-day or less.

13. A method of making an assembly comprising a device, said method comprising the steps of:

providing a substrate having a first substrate surface and a second substrate surface;

depositing a coating material on said first substrate surface using plasma-enhanced chemical-vapor deposition;

disposing said device on said coated first substrate surface or on said second substrate surface, wherein said coating material comprises an inorganic and an organic material deposited substantially simultaneously, and

effecting a penetration of at least a portion of said coating material into said substrate to produce a diffuse region between said substrate and said coating, said at least a portion of said coating material comprises an inorganic and an organic material.

14. The method of claim 13 wherein said device is selected from the group consisting of:

liquid crystal displays, photovoltaic cells, integrated circuits, and components of medical diagnostic systems.

15. The method of claim 13 wherein said device is an organic electroluminescent (“

EL”

) member.

16. The method of claim 15 wherein said EL member is an organic light emitting diode.

17. The method of claim 15 wherein said EL member comprises an organic EL layer disposed between two electrodes.

18. The method of claim 17 wherein said EL member further comprises a reflective layer comprising material selected from the group consisting of:

metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and combinations thereof.

19. The method of claim 17 wherein said organic EL layer comprises a material selected from the group consisting of poly(n-vinylcarbazole), poly(alkylfluorene), poly(paraphenylene), polysilanes, derivatives thereof, mixtures thereof, and copolymers thereof.

20. The method of claim 17 wherein said organic EL layer comprises a material selected from the group consisting of 1,2,3-tris {n-(4-diphenylaminophenyl)phenylamino}benzene, phenylanthracene, tetraarylethene, coumarin, rubrene, tetraphenylbutadiene, anthracene, perylene, coronene, aluminum-(picolymethylketone)-bis {2,6-di(t-butyl)phenoxides}, scandium-(4-methoxy-picolymethylketone)-bis(acetylacetonate), aluminum-acetylacetonate, gallium-acetylacetonate, and indium-acetylacetonate.

21. The method of claim 17 further comprising a light-scattering layer, said layer comprising scattering particles dispersed in a substantially transparent matrix and being disposed on a surface of said substrate opposite to said organic EL member.

22. The method of claim 21 further comprising particles of a photoluminescent (“

PL”

) material mixed with scattering particles in said light-scattering layer, wherein said PL material is selected from the group consisting of (Y_1-xCE_x)₃Al₅O₁₂;

(Y_1-x-yGd_xCe_y)₃Al₅O₁₂;

(Y_1-xCe_x)₃(Al_1-yGa_y)O₁₂;

(Y_1-x-yGd_xCe_y)(Al_5-zGa_z)O₁₂;

(Gd_1-xCe_x)Sc₂Al₃O₁₂;

Ca₈Mg(SiO₄)₄Cl₂;

Eu²⁺, Mn²⁺;

GdBO₃;

Ce³⁺,Tb³⁺;

CeMgAl₁₁O₁₉;

Tb³⁺;

Y₂SiO₅;

Ce³⁺,Tb³⁺;

BaMg₂Al₁₆O₂₇;

Eu²⁺,Mn²⁺;

Y₂O₃;

Bi³⁺,Eu³⁺;

Sr₂P₂O₇;

Eu²⁺,Mn²⁺;

SrMgP₂O₇;

Eu²⁺,Mn²⁺;

(Y,Gd)(V,B)O₄;

Eu³⁺;

3.5MgO.0.5MgF₂GeO₂;

Mn⁴⁺ (magnesium fluorogemanate);

BaMg₂Al₁₆O₂₇;

Eu²⁺;

Sr₅(PO₄)₁₀Cl₂;

Eu²⁺;

(Ca,Ba,Sr)(Al,Ga)₂S₄;

Eu²⁺;

(Ba,Ca,Sr)₅(PO₄)₁₀(Cl,F)₂;

Eu²⁺,Mn²⁺;

Lu₃Al₅O₁₂;

Ce³⁺;

Tb₃Al₅O₁₂;

Ce³⁺; and

mixtures thereof;

wherein 0≦

x≦

1, 0≦

y≦

1, 0≦

z≦

5 and x+y≦

1.

23. The method of claim 21 further comprising at least an organic PL material dispersed in said scattering layer, said organic PL material being capable of absorbing at least a portion of electromagnetic (“

EM”

) radiation emitted by said organic EL material and emitting EM radiation in a visible spectrum.

24. The method of claim 17 wherein said organic EL member further comprises at least an additional layer disposed between one of said electrodes and said organic EL layer, said additional layer performing at least a function selected from the group consisting of electron injection enhancement, electron transport enhancement, hole injection enhancement, and hole transport enhancement.

25. The method of claim 13 wherein said depositing is selected from the group consisting of:

radio-frequency plasma-enhanced chemical-vapor deposition, expanding thermal-plasma chemical-vapor deposition, electron-cyclotron-resonance plasma-enhanced chemical-vapor deposition, inductively-coupled plasma-enhanced chemical-vapor deposition, and combinations thereof.

26. The method according to claim 13 wherein said substrate comprises a polymeric material selected from the group consisting of:

polyethyleneterephthalate, polyacrylates, polycarbonate, silicone, epoxy resins, silicone-functionalized epoxy resins, polyester, polyimide, polyetherimide, polyethersulfone, polyethylenenapthalene, polynorbonene, and poly(cyclic olefins).

27. The method according to claim 13 wherein said coating material further comprises material selected from the group consisting of:

organic, inorganic, ceramic materials, and combinations thereof.

28. The method according to claim 27 wherein said inorganic and ceramic materials are selected from the group consisting of oxide, nitride, carbide, boride, and combinations thereof of elements of Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, and IIB, metals of Groups IIIB, IVB, and VB, and rare-earth metals.

29. The method according to claim 13 wherein said diffuse region is produced by an energetic ion bombardment of a surface of said substrate to sputter a portion of a material of said substrate, and depositing a mixed material comprising sputtered substrate material and another material.

30. The method of claim 13 wherein said substrate is flexible.

31. The method of claim 13 wherein said substrate is substantially transparent.

32. The method of claim 13 wherein said substrate comprises a metal.

33. The method of claim 13 wherein said substrate comprises glass.

34. The method of claim 13 wherein said coating has an oxygen permeability rate of approximately 0.001 ml/m²-day or less.

35. The method of claim 13 wherein said coating has a water vapor permeability rate of approximately 0.000001 g/m²-day or less.

36. The method of claim 13 wherein said coating and said substrate encapsulate said device.

37. The method of claim 13 wherein said coating encapsulates said substrate and said device.