Gas barrier thin film, electronic device comprising the same, and method of preparing the gas barrier thin film

Patent metadata

Field	Value
Publication number	US-9368746-B2
Application number	US-50524509-A
Country	US
Kind code	B2
Filing date	Jul 17, 2009
Priority date	Dec 19, 2008
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

A gas barrier thin film having a substrate, an anchoring layer, and an inorganic oxide layer, the anchoring layer including a silicon-containing organic-inorganic composite copolymer comprising a repeating unit of the formula

—(SiO) n —,

a repeating unit of the formula

—(SiR 1 R 2 —NR 3 ) m —,

and at least one or a combination of repeating units of the formulas

wherein at least one of R 1 , R 2 , and R 3 is independently hydrogen, R 1 , R 2 , and R 3 are each independently C 1 -C 5 alkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl, C 1 -C 5 alkoxyl, or C 6 -C 15 aryl, R 4 , R 5 , R 6 , and R 7 are each independently hydrogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxyl, C 3 -C 10 cycloalkyl, or C 6 -C 15 aryl, R 4 and R 5 are not simultaneously hydrogen, R 6 and R 7 are not simultaneously hydrogen, n+m+r=1, 0<n<1, 0<m<1, and 0<r<1, ‘n’, ‘m’, and ‘r’ are each a molar ratio, ‘r’ is p, q, or p+q, and a degree of polymerization is about 1,000 to about 1,000,000.

First claim

What is claimed is:

1. A gas barrier film comprising:
a substrate;
an anchoring layer disposed on a surface of the substrate; and
an inorganic oxide layer disposed directly on a surface of the anchoring layer opposite the substrate, wherein the inorganic oxide layer comprises Al 2 O 3 , MgO, ZnO, or a mixture thereof;
wherein the anchoring layer comprises a coating of a silicon-containing organic-inorganic composite copolymer as a thermoset of a mixture of a polysilazane and a polysiloxane-based polymer,
wherein the copolymer comprises a repeating unit represented by Formula 1 below; a repeating unit represented by Formula 2 below; and at least one repeating unit selected from the group consisting of repeating units represented by Formulas 3 and 4 below, and a combination thereof:
—(SiO) n —  Formula 1

—(SiR 1 R 2 —NR 3 ) m —  Formula 2

wherein at least one of the group consisting of R 1 , R 2 , and R 3 is independently hydrogen, and the remaining R 1 , R 2 , and R 3 are each independently a C 1 -C 5 alkyl group, a C 2 -C 5 alkenyl group, a C 2 -C 5 alkynyl group, a C 1 -C 5 alkoxyl group, or a C 6 -C 15 aryl group,
R 4 , R 5 , R 6 , and R 7 are each independently hydrogen, a C 1 -C 3 alkyl group, a C 1 -C 3 alkoxyl group, a C 3 -C 10 cycloalkyl group or a C 6 -C 15 aryl group,
R 4 and R 5 are not simultaneously hydrogen,
R 6 and R 7 are not simultaneously hydrogen,
n+m+r=1, 0<n<1, 0<m<1, and 0<r<1,
‘n’, ‘m’, ‘p’, ‘q’, and ‘r’ are each a mole fraction of respective repeating units,
‘r’ is p, q, or p+q, and
a degree of polymerization is in the range of about 1,000 to about 1,000,000,
wherein the at least one repeating unit selected from the group consisting of repeating units represented by Formulas 3, 4, and a combination thereof of the silicon-containing organic-inorganic composite copolymer is randomly cross-linked with the repeating unit represented by Formula 2 of the silicon-containing organic-inorganic composite copolymer, wherein the crosslink results from removal of a hydroxyl group at an end group of the polysiloxane-based polymer,
wherein a mixing weight ratio of the polysilazane and the polysiloxane-based polymer of the mixture is in a range of about 9:1 to about 1:2, and
wherein a light transmittance of the gas barrier film is equal to or greater than about 70% in a visible light wavelength region.

2. The gas barrier film of claim 1 , wherein a visible light transmittance of the gas barrier thin film is about 70% or more.

3. The gas barrier film of claim 1 , further comprising a protecting layer disposed on the inorganic oxide layer.

4. The gas barrier film of claim 1 , wherein the silicon-containing organic-inorganic composite copolymer thermoset is from exposure of the mixture of a polysilazane and a polysiloxane-based polymer at a temperature equal to or less than about 150° C.

5. The gas barrier film of claim 1 , wherein the polysilazane comprises a repeating unit represented by Formula 5 below:
—(SiR 1 R 2 —NR 3 ) a —  Formula 5,

wherein at least one of the group consisting of R 1 , R 2 , and R 3 is independently hydrogen, R 1 , R 2 , and R 3 are each independently a C 1 -C 5 alkyl group, a C 2 -C 5 alkenyl group, a C 2 -C 5 alkynyl group, a C 1 -C 5 alkoxyl group, or a C 6 -C 15 aryl group, and
‘a’ is an integer in the range of about 100 to about 1,000,000.

6. The gas barrier film of claim 1 , wherein the polysilazane comprises at least one repeating unit represented by Formulas 8, 9, and 10 below:

wherein ‘d’ is an integer in the range of about 500 to about 1,000,000, and ‘e’ and ‘f’ are each independently an integer in the range of about 250 to about 500,000.

7. The gas barrier film of claim 1 , wherein the polysiloxane-based polymer comprises at least one repeating unit selected from the group consisting of repeating units represented by Formulas 6 and 7 below, and a combination thereof, and wherein the polysiloxane-based polymer further comprises about 5 mol % or more of a hydroxyl group as an end group of the polysiloxane-based polymer:

wherein R 4 , R 5 , R 6 , and R 7 are each independently hydrogen, a C 1 -C 3 alkyl group, a C 1 -C 3 alkoxyl group, a C 3 -C 10 cycloalkyl group, or a C 6 -C 15 aryl group,
R 4 , and R 5 are not simultaneously hydrogen,
R 6 , and R 7 are not simultaneously hydrogen, and
‘b’ and ‘c’ are each independently an integer in the range of about 200 to about 200,000.

8. The gas barrier film of claim 1 , further comprising at least one layer selected from the group consisting of a second anchoring layer, a second inorganic oxide layer, and any combination thereof, wherein the layers are alternately stacked on another surface of the substrate.

9. The gas barrier film of claim 1 , further comprising at least one layer selected from the group consisting of a second anchoring layer, a second inorganic oxide layer, and any combination thereof, wherein the layers are alternately stacked on the inorganic oxide layer.

10. The gas barrier film of claim 1 , wherein the substrate comprises a plastic or a metal.

11. The gas barrier film of claim 10 , wherein the plastic and the metal are flexible.

12. An electronic device comprising a gas barrier film, wherein the gas barrier thin film comprises:
a substrate;
an anchoring layer disposed on a surface of the substrate; and
an inorganic oxide layer disposed directly on the anchoring layer, wherein the inorganic oxide layer comprises Al 2 O 3 , MgO, ZnO, or a mixture thereof;
wherein the anchoring layer comprises a coating of a silicon-containing organic-inorganic composite copolymer as a thermoset of a mixture of a polysilazane and a polysiloxane-based polymer,
wherein the copolymer comprises a repeating unit represented by Formula 1 below; a repeating unit represented by Formula 2 below; and at least one repeating unit selected from the group consisting of the repeating units represented by Formulas 3 and 4 below, and a combination thereof:
—(SiO) n —  Formula 1

—(SiR 1 R 2 —NR 3 ) m —  Formula 2

wherein at least one of the group consisting of R 1 , R 2 , and R 3 is independently hydrogen, and the remaining R 1 , R 2 , and R 3 are each independently a C 1 -C 5 alkyl group, a C 2 -C 5 alkenyl group, a C 2 -C 5 alkynyl group, a C 1 -C 5 alkoxyl group, or a C 6 -C 15 aryl group,
R 4 , R 5 , R 6 , and R 7 are each independently hydrogen, a C 1 -C 3 alkyl group, a C 1 -C 3 alkoxyl group, a C 3 -C 10 cycloalkyl group, or a C 6 -C 15 aryl group,
R 4 and R 5 are not simultaneously hydrogen,
R 6 and R 7 are not simultaneously hydrogen,
n+m+r=1, 0<n<1, 0<m<1, and 0<r<1,
‘n’, ‘m’, ‘p’, ‘q’ and ‘r’ are each a mole fraction of respective repeating units of the silicon-containing organic-inorganic composite copolymer,
‘r’ is p, q, or p+q, and
a degree of polymerization is in the range of about 1,000 to about 1,000,000,
wherein the at least one repeating unit selected from the group consisting of repeating units represented by Formulas 3, 4, and a combination thereof of the silicon-containing organic-inorganic composite copolymer is randomly cross-linked with the repeating unit represented by Formula 2 of the silicon-containing organic-inorganic composite

Assignees

• Lee Kwang-Hee
• Park Jong-Jin
• Bulliard Xavier
• Choi Yun-Hyuk
• Samsung Electronics Co Ltd

Inventors

• Lee Kwang-Hee
• Park Jong-Jin
• Bulliard Xavier
• Choi Yun-Hyuk

Classifications

• H10P14/6922

  the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC · CPC title

• H10P14/6322

  Formation by thermal treatments (formation by plasma treatment H10P14/6319) · CPC title

• H10P14/6506 Primary

  Formation of intermediate materials · CPC title

• H10K50/8445

  multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers · CPC title

• H10F77/169

  Thin semiconductor films on metallic or insulating substrates · CPC title