Multilayer film for encapsulating oxygen and/or moisture sensitive electronic devices

• US 10,103,359 B2
• Filed: 04/08/2009
• Issued: 10/16/2018
• Est. Priority Date: 04/09/2008
• 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, Ke, Lin Karen
• Primary Examiner(s): Jackson, Monique
• Application Number:
  US12/937,259
• Publication Number:
  US 20110132449A1
• Time in Patent Office: 3,478 Days
• Field of Search: 428323, 428324, 428328, 428329, 428330, 428331, 428508
• CPC Class Codes: B32B 2457/206 Organic displays, e.g. OLED
• CPC Class Codes: B32B 27/20 using fillers, pigments, thixotroping agents
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: H05B 33/04 Sealing arrangements , e.g. against humidity
• CPC Class Codes: H05B 33/10 Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
• CPC Class Codes: H10K 2102/331 Nanoparticles used in non-emissive layers, e.g. in packaging layer
• CPC Class Codes: H10K 30/88 Passivation; Containers; Encapsulations
• CPC Class Codes: H10K 50/841 Self-supporting sealing arrangements
• 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: H10K 50/865 comprising light absorbing layers, e.g. light-blocking layers
• CPC Class Codes: H10K 59/871 Self-supporting sealing arrangements
• CPC Class Codes: H10K 59/8731 multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
• CPC Class Codes: H10K 59/874 including getter material or desiccant
• CPC Class Codes: H10K 59/8792 comprising light absorbing layers, e.g. black layers
• CPC Class Codes: H10K 71/00 Manufacture or treatment specially adapted for the organic devices covered by this subclass
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y10T 428/24995 Two or more layers
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31511 : Of epoxy ether
• CPC Class Codes: Y10T 428/31533 : Of polythioether
• CPC Class Codes: Y10T 428/3154 : Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31678 : Of metal
• CPC Class Codes: Y10T 428/31721 : Of polyimide
• CPC Class Codes: Y10T 428/31725 : Of polyamide
• CPC Class Codes: Y10T 428/31931 : Polyene monomer-containing
• CPC Class Codes: Y10T 428/31935 : Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31938 : Polymer of monoethylenically unsaturated hydrocarbon

Abstract

The present invention refers to a multilayer barrier film capable of encapsulating a moisture and/or oxygen sensitive electronic or optoelectronic device, the barrier film comprises at least one nanostructured layer comprising reactive nanoparticles capable of interacting with moisture and/or oxygen, the reactive nanoparticles being distributed within a polymeric binder, and at least one ultraviolet light neutralizing layer comprising a material capable of absorbing ultraviolet light, thereby limiting the transmission of ultraviolet light through the barrier film.

Claims

1. A multilayer barrier film capable of encapsulating a moisture and/or oxygen sensitive electronic or optoelectronic device, said barrier film comprising:

at least one nanostructured layer comprising reactive nanoparticles capable of interacting with moisture and/or oxygen, and inert nanoparticles which do not interact with moisture and/or oxygen and which are adapted to obstruct the permeation of moisture and/or oxygen, said reactive nanoparticles and inert nanoparticles being distributed within a polymeric binder, and

at least one ultraviolet light neutralizing layer comprising a material capable of absorbing ultraviolet light selected from the group consisting of 4-methylbenzylidene camphor, isoamyl p-methoxycinnamate, 2-hydroxyphenyl benzotriazole, 2-hydroxy-benzophenone, 2-hydroxy-phenyltriazine and oxalanilide, thereby limiting the transmission of ultraviolet light through the barrier film,

wherein an ultraviolet light neutralizing layer of the at least one ultraviolet light neutralizing layer is formed on the electronic or optoelectronic device, and a nanostructured layer of the at least one nanostructured layer is formed on the ultraviolet light neutralizing layer, and

wherein the multilayer barrier film does not comprise an inorganic layer.

2. The barrier film of claim 1, wherein the reactive nanoparticles are capable of interacting with moisture and/or oxygen through chemical reaction.

3. The barrier film of claim 2, wherein the reactive nanoparticles comprise a material selected from the group consisting of metals, metal oxides and mixtures thereof.

4. The barrier film of claim 3, wherein the reactive nanoparticles comprise a metal selected from the group consisting of Al, Ti, Mg, Ba Ca, and mixtures thereof.

5. The barrier film of claim 3, wherein the reactive nanoparticles comprise a metal oxide selected from the group consisting of TiO₂, Al₂O₃, ZrO₂, ZnO, BaO, SrO, CaO and MgO, VO₂, CrO₂, MoO₂, LiMn₂O₄, cadmium stannate (Cd₂SnO₄), cadmium indate (CdIn₂O₄), zinc stannate (Zn₂SnO₄ and ZnSnO₃), zinc indium oxide (Zn₂In₂O₅) and mixtures thereof.

6. The barrier film of claim 1, wherein the reactive nanoparticles are capable of interacting with moisture and/or oxygen through adsorption.

7. The barrier film of claim 6, wherein the reactive nanoparticles comprise carbon nanotubes.

8. The barrier film of claim 1, wherein the nanostructured layer comprises both carbon nanotubes and reactive metal oxide nanoparticles, the amount of metal oxide nanoparticles present being between 500 to 15000 times (by weight) the quantity of carbon nanotubes present.

9. The barrier film of claim 1, wherein when the oxygen and/or moisture sensitive electronic device comprises an organic light emitting device, the average size of the reactive nanoparticles is less than one-half the characteristic wavelength of light produced by the organic light emitting device.

10. The barrier film of claim 1, wherein the at least one nanostructured layer of the multilayer film comprises at least 2 types of reactive nanoparticles that are capable of interacting with moisture and/or oxygen.

11. The barrier film of claim 10, wherein the multilayer film comprises a first nanostructured layer comprising reactive metal nanoparticles, and a second nanostructured layer comprising reactive metal oxide nanoparticles.

12. The barrier film of claim 11, wherein the multilayer film comprises a plurality of said first and said second nanostructured layers arranged in alternating sequence in the multilayer film.

13. The barrier film of claim 10, wherein the multilayer film comprises one nanostructured layer having distributed therein reactive metal nanoparticles and reactive metal oxide nanoparticles.

14. The barrier film of claim 1, wherein the amount of reactive nanoparticles present in the nanostructured layer is between about 0.0000001% to about 50% by weight of monomers of the polymeric binder in the nanostructured layer.

15. The barrier film of claim 14, wherein the polymeric binder comprises a material selected from the group consisting of polyacrylate, polymethacrylate, polyacrylamide, polyepoxide, parylene, polysiloxanes and polyurethane.

16. The barrier film of claim 1, wherein the ultraviolet light neutralizing layer comprises reactive metal oxide nanoparticles distributed in a polymer layer.

17. The barrier film of claim 16, wherein the reactive metal oxide nanoparticles being selected from the group consisting of hafnium dioxide (HfO₂), magnesium oxide (MgO), barium oxide (BaO), silicone oxide (SiO₂) titanium dioxide (TiO₂), tantalum oxide (Ta₂O₅), cerium oxide (CeO₂), niobium oxide (Nb₂O₅), zirconium oxide (ZrO₂), zinc oxide (ZnO) and mixtures thereof.

18. The barrier film of claim 1, wherein the multilayer film further comprises an organic barrier layer.

19. The barrier film of claim 18, wherein the barrier layer comprises a material selected from the group consisting of parylene, polyimide, polyacrylamide, polyamide, polyacetate, polypropylene, polyimide, poly(l-trimethylsilyl-1-propyne, poly(4-methyl-2-pentyne), polyethylene, polyethersulfone, epoxy resins, polyethylene terepthalate, polystyrene, polyurethane, polyacrylate, polydimethylphenylene oxide, styrene-divinylbenzene, and polyvinylidene fluoride (PVDF).

20. The barrier film of claim 19, further comprising a substrate for supporting the electronic device to be encapsulated, wherein the barrier film is formed on a surface of the substrate.

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

22. The barrier film of claim 21, wherein the terminal layer comprises a material selected from the group consisting of polypropylene and polycarbonate.

23. The barrier film of claim 22, wherein the terminal layer has distributed therein particles comprising a material selected from the group consisting of BaF₂, MgF₂ and CaF₂.

24. The barrier film of claim 1, wherein the inert nanoparticles are made of a material selected from the group consisting of copper, platinum, gold, silver;

minerals, clays, wollastonite, mullite, montmorillonite;

rare earth elements, silicate glass, fluorosilicate glass, fluoroborosilicate glass, aluminosilicate glass, calcium silicate glass, calcium aluminium silicate glass, calcium aluminium fluorosilicate glass, titanium carbide, zirconium carbide, zirconium nitride, silicon carbide, or silicon nitride, metal sulfides, mixtures and combinations thereof.

25. An encapsulated electronic device, comprising a base substrate having arranged thereon an electronic device, said electronic device being covered by an encapsulation for protecting the electronic device from moisture and/or oxygen, wherein the encapsulation comprises a barrier film of claim 1.

26. The device of claim 25, further comprising a secondary encapsulation comprising an adhesive layer arranged on the multilayer barrier film, and a cover substrate arranged on the adhesive layer.

27. The device of claim 26, wherein the adhesive layer is selected from the group consisting of ethylene vinyl acetate resins, epoxy resins, polysulfide, silicone and polyurethane.

28. The device of claim 27, wherein the cover substrate is selected from the group consisting of glass, indium tin oxide, nanocomposites laminated with an inorganic barrier film, and transparent plastics.

29. The device of claim 1, wherein the electronic device is selected from the group consisting of an Organic Light Emitting Device (OLED), charged-coupled device (CCD), micro-electro-mechanical sensors (MEMS), and an organic or inorganic photovoltaic device which is based on a thin-film solar cell.

30. An organic electroluminescent (EL) panel comprising a plurality of encapsulated organic light emitting devices (OLEDs), said panel comprising:

a substrate having arranged thereon said plurality of encapsulated OLEDs, each encapsulated OLED comprising;

a base substrate having arranged thereon an OLED including a first electrode layer, an organic layer, and a second electrode layer;

said OLED being enclosed within a multilayer film according to claim 1 for protecting the OLED from moisture and/or oxygen.

31. An encapsulated photovoltaic device comprising:

a moisture and/or oxygen sensitive photovoltaic device being sandwiched between two multilayer barrier films, each of the multilayer barrier films comprising;

at least one nanostructured layer comprising reactive nanoparticles capable of interacting with moisture and/or oxygen, and inert nanoparticles which do not interact with moisture and/or oxygen and which are adapted to obstruct the permeation of moisture and/or oxygen, said reactive nanoparticles and inert nanoparticles being distributed within a polymeric binder, and

at least one ultraviolet light neutralizing layer comprising a material capable of absorbing ultraviolet light selected from the group consisting of 4-methylbenzylidene camphor, isoamyl p-methoxycinnamate, 2-hydroxyphenyl benzotriazole, 2-hydroxy-benzophenone, 2-hydroxy-phenyltriazine and oxalanilide, thereby limiting the transmission of ultraviolet light through the barrier film, for protecting said photovoltaic device from moisture and/or oxygen;

wherein an ultraviolet light neutralizing layer of the at least one ultraviolet light neutralizing layer in each of said multilayer barrier films is formed on and attached to the photovoltaic device, and a nanostructured layer of the at least one nanostructured layer in each of said multilayer barrier films is formed on and attached to the ultraviolet light neutralizing layer, and

wherein the multilayer barrier films do not comprise an inorganic layer.