Nanoparticulate encapsulation barrier stack

• US 9,493,348 B2
• Filed: 11/06/2006
• Issued: 11/15/2016
• Est. Priority Date: 11/06/2006
• Status: Active Grant

• Current Assignee: Agency For Science Technology and Research (Government of Singapore)
• Original Assignee: Agency For Science Technology and Research (Government of Singapore)
• Inventors: Ramadas, Senthil Kumar, Chua, Soo Jin
• Primary Examiner(s): Nguyen, Chau N
• Assistant Examiner(s): VARGHESE, ROSHN K
• Application Number:
  US12/513,569
• Publication Number:
  US 20100089636A1
• Time in Patent Office: 3,662 Days
• Field of Search: 174/521, 313/554
• US Class Current: 1/1
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 20/00 Nanooptics, e.g. quantum optics or photonic crystals
• CPC Class Codes: B82Y 25/00 Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: H10K 2102/331 Nanoparticles used in non-emissive layers, e.g. in packaging layer
• CPC Class Codes: H10K 50/8445 multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
• CPC Class Codes: H10K 50/846 comprising getter material or desiccants
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Abstract

A barrier stack for encapsulating a moisture and/or oxygen sensitive electronic device is provided. The barrier stack comprises a multilayer film having at least one barrier layer having low moisture and/or oxygen permeability, and at least one sealing layer arranged to be in contact with a surface of the barrier layer, wherein the sealing material comprises reactive nanoparticles capable of interacting with moisture and/or oxygen, thereby retarding the permeation of moisture and/or oxygen through defects present in the barrier layer.

Claims

1. An encapsulation barrier stack for encapsulating at least one of a moisture and oxygen sensitive article, comprising:

a multilayer film to be arranged on a substrate, the multilayer film having at least one barrier layer having at least one of low moisture and low oxygen permeability, and

at least one sealing layer arranged to be in contact with a surface of the at least one barrier layer, for plugging at least one defect present in the barrier layer, wherein the at least one sealing layer comprises reactive nanoparticles interacting by way of chemical reaction with at least one of moisture and oxygen to retard the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer, wherein the nanoparticles present in the at least one sealing layer plug the at least one defect present in the at least one barrier layer, wherein the nanoparticles have different at least one of shapes and sizes for controlling the sealing and plugging of the at least one defect, wherein the barrier layer comprises a material selected from indium tin oxide (ITO), TiAlN, SiO₂, SiC, Si₃N₄, TiO₂, HfO₂, Y₂O₃, Ta₂O₅, and Al₂O₃ and wherein a permeation rate of the barrier stack having the at least one sealing layer on the surface of the at least one barrier layer is 10<sup>−

3</sup> g/m²/day or less.

2. The barrier stack of claim 1, wherein the nanoparticles comprise a material selected from the group consisting of metals and metal oxides.

3. The barrier stack of claim 2, wherein the nanoparticles comprise a metal selected from the group consisting of Al, Ti, Mg, Ba and Ca.

4. The barrier stack of claim 2, wherein the nanoparticles comprise a metal oxide selected from the group consisting of TiO₂, Al₂O₃, ZrO₂, ZnO, BaO, SrO, CaO and MgO, VO₂, CrO₂, MoO₂, and LiMn₂O₄ or a transparent conductive oxide selected from the group consisting of cadmium stannate (Cd₂SnO₄), cadmium indate (CdIn₂O₄), zinc stannate (Zn₂SnO₄ and ZnSnO₃), and zinc indium oxide (Zn₂In₂O₅).

5. The barrier stack of claim 1, wherein the nanoparticles further comprise carbon nanotubes.

6. The barrier stack of claim 5, wherein the amount of carbon nanotubes present is about 0.01% to about 10% of the total weight of nanoparticles present in the sealing layer.

7. The barrier stack of claim 1, wherein the sealing layer comprises carbon nanotubes and metal oxide nanoparticles, the quantity of metal oxide nanoparticles present being between 500 to 15000 times (by weight) the quantity of carbon nanotubes present.

8. The barrier stack of claim 1, further comprising inert nanoparticles obstructing the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer.

9. The barrier stack of claim 8, wherein the inert nanoparticles comprise a material selected from the group consisting of gold, copper, silver, platinum, silica, wollastonite, mullite, monmorillonite, silicate glass, fluorosilicate glass, fluoroborosilicate glass, aluminosilicate glass, calcium silicate glass, calcium aluminum silicate glass, calcium aluminum fluorosilicate glass, titanium carbide, zirconium carbide, zirconium nitride, silicon carbide, or silicon nitride, metal sulfides, and a mixture or combination thereof.

10. The barrier stack of claim 1, wherein the size of the nanoparticles is smaller than the average diameter of defects present in the at least one barrier layer.

11. The barrier stack of claim 1, wherein when the at least one of the oxygen and moisture sensitive article comprises an electroluminescent electronic component, the average size of the nanoparticles is less than one-half the characteristic wavelength of light produced by the electroluminescent electronic component.

12. The barrier stack of claim 1, wherein the sealing layer further comprises a polymeric binder.

13. The barrier stack of claim 1, further comprising a substrate for supporting the multilayer film.

14. The barrier stack of claim 13, wherein the multilayer film is orientated such that the sealing layer is arranged on the substrate.

15. The barrier stack of claim 13, wherein the substrate comprises a material selected from polyacetate, polypropylene, polyimide, cellophane, poly(l-trimethylsilyl-1-propyne, poly(4-methyl-2-pentyne), polyimide, polycarbonate, polyethylene, polyethersulfone, epoxy resins, polyethylene terepthalate, polystyrene, polyurethane, polyacrylate, and polydimethylphenylene oxide, styrene-divinylbenzene copolymers, polyvinylidene fluoride (PVDF), nylon, nitrocellulose, cellulose, glass, indium tin oxide, nano-clays, silicones, polydimethylsiloxanes, biscyclopentadienyl iron, and polyphosphazenes.

16. The barrier stack of claim 13, further comprising a planarising layer interposed between the substrate and the multilayer film.

17. The barrier stack of claim 1, wherein the multilayer film is arranged on one surface of the substrate or wherein each multilayer film is arranged on each opposing surface of the substrate.

18. The barrier stack of claim 1, further comprising a terminal layer for protecting the multilayer film.

19. The barrier stack of claim 18, wherein the terminal layer comprises an acrylic film.

20. The barrier stack of claim 19, wherein the acrylic film comprises distributed therein at least one of LiF and MgF₂ particles.

21. The encapsulation barrier stack of claim 1, wherein the chemical reaction is at least one of hydrolysis or oxidation.

22. An electronic device comprising:

an active component that is sensitive to at least one of moisture and oxygen, the active component being arranged within an encapsulation barrier stack for encapsulating at least one of a moisture and oxygen sensitive article, the encapsulation barrier stack comprising;

a multilayer film to be arranged on a substrate, the multilayer film having

at least one barrier layer having at least one of low moisture and low oxygen permeability, and

at least one sealing layer arranged to be in contact with a surface of the at least one barrier layer, for plugging at least one defect present in the barrier layer, wherein the at least one sealing layer comprises reactive nanoparticles interacting by way of a chemical reaction with at least one of moisture and oxygen to retard the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer, wherein the nanoparticles present in the at least one sealing layer plug the at least one defect present in the at least one barrier layer, wherein the nanoparticles have different at least one of shapes and sizes for controlling the sealing and plugging of the at least one defect, wherein the barrier layer comprises a material selected from indium tin oxide (ITO), TiAlN, SiO₂, SiC, Si₃N₄, TiO₂, HfO₂, Y₂O₃, Ta₂O₅, and Al₂O₃ and wherein a permeation rate of the barrier stack having the at least one sealing layer on the surface of the at least one barrier layer is 10<sup>−

3</sup> g/m²/day or less.

23. The electronic device of claim 22, wherein the encapsulation barrier stack forms a base substrate for supporting the reactive component.

24. The electronic device of claim 22, wherein the encapsulation barrier stack further comprises a covering layer arranged proximally over the active component to form a proximal encapsulation, the reactive component being sandwiched between the covering layer and the encapsulation barrier stack.

25. The electronic device of claim 24, wherein the shape of the covering layer conforms to the external shape of the reactive component.

26. The electronic device of claim 22, wherein the encapsulation further comprises a cover substrate attached to the base substrate by means of an adhesive layer, the adhesive layer being arranged at least substantially along the edge of the cover substrate for forming a rim-sealed enclosure around the reactive component.

27. The electronic device of claim 22, wherein the active component is arranged on a base substrate, and the encapsulation barrier stack forms an encapsulation layer over the reactive component that seals the reactive component against the base substrate.

28. The electronic device of claim 22, wherein the reactive component is selected from the group consisting of an Organic Light Emitting Device (OLED), charged-coupled device (CCD), and micro-electro-mechanical sensors (MEMS).

29. A method to manufacture an encapsulation barrier stack, comprising:

forming at least one barrier layer; and

forming at least one sealing layer on a surface of the at least one barrier layer, wherein forming the at least one sealing layer comprises conformal deposition of the at least one sealing layer over the at least one barrier layer under vacuum or in an inert gas environment, wherein the encapsulation barrier stack is for encapsulating at least one of a moisture and oxygen sensitive article, the at least one barrier layer having at least one of low moisture and low oxygen permeability, wherein the at least one sealing layer is arranged to be in contact with the surface of the at least one barrier layer to plug at least one defect present in the barrier layer, wherein the at least one sealing layer comprises reactive nanoparticles interacting by way of a chemical reaction with at least one of moisture and oxygen to retard the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer, wherein the nanoparticles present in the at least one sealing layer plug the at least one defect present in the at least one barrier layer and wherein the nanoparticles have different at least one of shapes and sizes for controlling the sealing and plugging of the at least one defect, wherein the barrier layer comprises a material selected from indium tin oxide (ITO), TiAlN, SiO₂, SiC, Si₃N₄, TiO₂, HfO₂, Y₂O₃, Ta₂O₅ and Al₂O₃ and wherein a permeation rate of the barrier stack having the at least one sealing layer on the surface of the at least one barrier layer is 10<sup>−

3</sup> g/m²/day or less.

30. The method of claim 29, further comprising providing a substrate for supporting the barrier stack, wherein the at least one sealing layer is first formed on the substrate.

31. The method of claim 30, wherein the substrate comprises at least one of a barrier layer and a polymer substrate.

32. The method of claim 29, wherein the conformal deposition comprises mixing a polymeric binding material with a nanoparticle dispersion comprising nanoparticles dispersed in a solvent for doping the nanoparticle dispersion with the polymeric binding material, to form a sealing mixture, and optionally polymerising the sealing mixture over the at least one barrier layer.

33. The method of claim 29, wherein the nanoparticles are distributed in a sealing solution with a concentration of the nanoparticles of at least 50% by weight of the sealing solution.

34. The method of claim 29, wherein the concentration of the nanoparticles is at least 50% and less than 70% by weight of the sealing solution.

35. An encapsulation barrier stack for encapsulating at least one of a moisture and oxygen sensitive article, comprising:

a multilayer film to be arranged on a substrate, the multilayer film comprising at least one barrier layer having at least one of low moisture and low oxygen permeability, and at least one sealing layer arranged to be in contact with a surface of the at least one barrier layer to plug at least one defect present in the barrier layer, wherein the at least one sealing layer comprises reactive nanoparticles interacting by way of a chemical reaction with at least one of moisture and oxygen to retard the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer, wherein the nanoparticles present in the at least one sealing layer plug the at least one defect present in the at least one barrier layer, wherein the sealing layer is formed by conformal deposition, wherein the conformal deposition is selected from the group consisting of chemical vapour deposition, spin coating, screen printing, WebFlight method, tip coating, atomic layer deposition, and pulsed laser deposition, wherein the barrier layer comprises a material selected from indium tin oxide (no), TiAlN, SiO₂, SiC, Si₃N₄, TiO₂, HfO₂, Y₂O₃, Ta₂O₅ and Al₂O₃ and wherein a permeation rate of the barrier stack having the at least one sealing layer on the surface of the at least one barrier layer is 10<sup>−

3</sup> g/m²/day or less.

36. The barrier stack of claim 35, wherein the amount by weight of the polymeric binder present in the sealing layer is less than the amount by weight of the nanoparticles present in the sealing layer.

37. The barrier stack of claim 36, wherein the polymeric binder is between 30% and 50% of the total weight of the sealing layer.

38. The barrier stack of claim 35, wherein the sealing layer is a nanoparticle sealing layer.

39. A method to manufacture an encapsulation barrier stack, comprising:

providing at least one barrier layer; and

forming at least one sealing layer on a surface of the at least one barrier layer, wherein forming the at least one sealing layer comprises conformal deposition of the at least one sealing layer over the at least one barrier layer under vacuum or in an inert gas environment, the at least one barrier layer having at least one of low moisture and low oxygen permeability, wherein the at least one sealing layer is arranged to be in contact with the surface of the at least one barrier layer to plug at least one defect present in the barrier layer, wherein the at least one sealing layer comprises reactive nanoparticles interacting by way of a chemical reaction with at least one of moisture and oxygen to retard the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer, wherein the nanoparticles present in the at least one sealing layer plug the at least one defect present in the at least one barrier layer, wherein the conformal deposition is selected from the group consisting of chemical vapour deposition, screen printing, WebFlight method, tip coating, atomic layer deposition, and pulsed laser deposition, wherein the barrier layer comprises a material selected from indium tin oxide (ITO), TiAlN, SiO₂, SiC, Si₃N₄, TiO₂, HfO₂, Y₂O₃, Ta₂O₅, and Al₂O₃ and wherein a permeation rate of the barrier stack having the at least one sealing layer on the surface of the at least one barrier layer is 10<sup>−

3</sup> g/m²/day or less.

40. An encapsulation barrier stack for encapsulating at least one of a moisture and oxygen sensitive article, comprising:

a multilayer film to be arranged on a substrate, the multilayer film comprising at least one barrier layer having at least one of low moisture and low oxygen permeability, and at least one sealing layer arranged to be in contact with a surface of the at least one barrier layer, for plugging at least one defect present in the barrier layer, wherein the at least one sealing layer comprises reactive nanoparticles interacting by way of a chemical reaction with at least one of moisture and oxygen to retard the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer, wherein the nanoparticles present in the at least one sealing layer plug the at least one defect present in the at least one barrier layer, wherein a shape of the nanoparticles is used to control sealing of defects in the at least one barrier layer, wherein the defects are structural defects including at least one of pinholes and cracks, wherein the barrier layer comprises a material selected from indium tin oxide (ITO), TiAlN, SiO₂, SiC, Si₃N₄, TiO₂, HfO₂, Y₂O₃, Ta₂O₅ and Al₂O₃ and wherein a permeation rate of the barrier stack having at least one sealing layer on the surface of the at least one barrier layer is 10<sup>−

3</sup> g/m²/day or less.

41. A method to manufacture an encapsulation barrier stack, comprising:

forming at least one barrier layer; and

forming at least one sealing layer on a surface of the at least one barrier layer, wherein forming the at least one sealing layer comprises conformal deposition of the at least one sealing layer over the at least one barrier layer under vacuum or in an inert gas environment, the at least one barrier layer having at least one of low moisture and low oxygen permeability, wherein the at least one sealing layer is arranged to be in contact with the surface of the at least one barrier layer, to plug at least one defect present in the barrier layer, wherein the at least one sealing layer comprises reactive nanoparticles interacting by way of a chemical reaction with at least one of moisture and oxygen to retard the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer, wherein the nanoparticles present in the at least one sealing layer plug the at least one defect present in the at least one barrier layer, wherein the forming the at least one sealing layer comprises adding the nanoparticles to an organic solvent, and curing the sealing layer, wherein the barrier layer comprises a material selected from indium tin oxide (ITO), TiAlN, SiO₂, SiC, Si₃N₄, TiO₂, HfO₂, Y₂O₃, Ta₂O₅ and Al₂O₃ and wherein a permeation rate of the barrier stack having the at least one sealing layer on the surface of the at least one barrier layer is 10<sup>−

3</sup> g/m²/day or less.

42. An encapsulation barrier stack for encapsulating at least one of a moisture and oxygen sensitive article, comprising:

a multilayer film to be arranged on a substrate, the multilayer film comprising at least one barrier layer having at least one of low moisture and low oxygen permeability, and at least one sealing layer arranged to be in contact with a surface of the at least one barrier layer, for entirely plugging at least one defect present in the barrier layer, wherein the at least one sealing layer comprises reactive nanoparticles interacting by way of a chemical reaction with at least one of moisture and oxygen to retard the permeation of the at least one of moisture and oxygen through the at least one defect present in the barrier layer, wherein the nanoparticles present in the at least one sealing layer are distributed in a sealing solution to entirely plug the at least one defect present in the at least one barrier layer, wherein the barrier layer comprises a material selected from indium tin oxide (no), TiAlN, SiO₂, SiC, Si₃N₄, TiO₂, HfO₂, Y₂O₃, Ta₂O₅ and Al₂O₃ and wherein a permeation rate of the barrier stack having the at least one sealing layer on the surface of the at least one barrier layer is 10<sup>−

3</sup> g/m²/day or less.