Method of manufacturing surface-modified polymer film and method of fabricating organic electronic device comprising the same

Patent metadata

Field	Value
Publication number	US-11050024-B2
Application number	US-201816168885-A
Country	US
Kind code	B2
Filing date	Oct 24, 2018
Priority date	Dec 12, 2017
Publication date	Jun 29, 2021
Grant date	Jun 29, 2021

Abstract

Disclosed is a method of manufacturing a surface-modified polymer film, including forming a hydroxyl group (—OH) on the surface of a polymer film by subjecting the polymer film to light irradiation and surface treatment with a photoacid generator. The polymer film can be introduced with a hydroxyl group (—OH) group using a photoacid generator, thereby modifying the surface of the polymer film without damage to the polymer film. Also, an organic electronic device including the surface-modified polymer film can be improved in electrical characteristics and stability.

First claim

What is claimed is:

1. A method of manufacturing a surface-modified polymer film, comprising:
(a) forming a hydroxyl group (—OH) on a surface of a polymer film by subjecting a solution comprising the polymer film and a photoacid generator to light irradiation;
wherein the photoacid generator includes at least one selected from among triphenylsulfonium triflate (TPS), (4-tert-butylphenyl) diphenylsulfonium triflate, (4-fluorophenyl)diphenylsulfonium triflate, N-hydroxynaphthalimide triflate (NHN), tris(4-tert-butylphenyl)sulfonium triflate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, and Boc-methoxyphenyldiphenylsulfonium triflate.

2. The method of claim 1 , further comprising (b) forming a self-assembled monolayer (SAM) on the surface of the polymer film having the hydroxyl group, after step (a).

3. The method of claim 2 , wherein the self-assembled monolayer (SAM) includes at least one selected from among aminopropyltriethoxysilane, hexamethyldisilazane, methyltrichlorosilane, octyltrichlorosilane (OTS), dodecyl trichlorosilane, octadecyltrichlorosilane, trichloro(1H,1H,2H,2H-perfluorooctyl)silane, pentafluorophenyl trichlorosilane, pentafluorophenyl propyl-trichlorosilane, 3-aminoisopropyltriethoxysilane, methoxysilane, chloromethyl (dimethyl)methoxysilane, (3-aminopropyl)trimethoxysilane, dimethyl (3-chloropropyl)methoxysilane, diethoxy(isobutyl)methoxysilane, methoxy(dimethyl)octadecylsilane, octylphosphonic acid, tetradecylphosphonic acid, decylphosphonic acid, octadecylphosphonic acid, 1-dodecanethiol, octanethiol, and caproic acid.

4. The method of claim 2 , wherein step (b) is performed at −30 to 60° C.

5. The method of claim 4 , wherein step (b) is performed at −20 to 30° C.

6. The method of claim 5 , wherein step (b) is performed at −10 to 10° C.

7. The method of claim 1 , further comprising (a′) subjecting the surface of the polymer film to irradiation with UV light and ozone treatment, before step (a).

8. The method of claim 1 , wherein the polymer film is manufactured through any one process of spin coating, dip coating, and spray coating, before step (a).

9. The method of claim 1 , wherein the polymer film includes at least one selected from among poly(vinyl alcohol), poly(4-vinyl phenol), poly(vinyl chloride), polyisoprene, poly(chloroprene) (PCP), poly(acrylonitrile butadiene), poly(styrene-ethylene-butadiene-styrene), poly(styrene butadiene), polyacrylamide, nylon, poly(vinyl acetate), poly(cis-butadiene), poly(1-vinyl naphthalate), polyethylene terephthalate, polyethylene, polyurethane, poly(hexamethylene adipamide), poly(methyl methacrylate), poly(styrene), poly(dimethylsiloxane), poly(vinylidene fluoride), poly(tert-butylstyrene) polyimide, benzocyclobutene (BCB), poly(acrylonitrile), poly(methylene oxide), poly(cyclohexyl methacrylate), and CYTOP (Cyclized Transparent Optical Polymer).

10. A method of fabricating an organic electronic device, comprising:
forming a gate insulating layer including a polymer film on a substrate; and
forming an active layer including an organic semiconductor, a source electrode and a drain electrode on the gate insulating layer,
wherein the forming the gate insulating layer including the polymer film comprises:
(a) forming a hydroxyl group (—OH) on a surface of the polymer film by subjecting a solution comprising the polymer film and a photoacid generator to light irradiation; and
(b) forming a self-assembled monolayer (SAM) on the surface of the polymer film having the hydroxyl group;
wherein the photoacid generator includes at least one selected from among triphenylsulfonium triflate (TPS), (4-tert-butylphenyl) diphenylsulfonium triflate, (4-fluorophenyl)diphenylsulfonium triflate, N-hydroxynaphthalimide triflate (NHN), tris(4-tert-butylphenyl)sulfonium triflate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, and Boc-methoxyphenyldiphenylsulfonium triflate.

11. The method of claim 10 , wherein the organic electronic device is any one selected from among an organic thin-film transistor, an organic solar cell, and an organic light-emitting diode.

12. The method of claim 11 , wherein the organic electronic device is an organic thin-film transistor.

13. The method of claim 10 , wherein the substrate is a flexible substrate.

14. The method of claim 13 , wherein the flexible substrate includes at least one selected from among polyimide, polyethylene naphthalate, Parylene, and polyethylene terephthalate.

15. The method of claim 10 , wherein the organic semiconductor includes at least one selected from among poly(3-hexyl)thiophene, poly(9,9-dioctylfluorene-co-bithiophene), poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene], polythiophene, diketopyrrolo-pyrrole-dithiophene-thienothiophene, tetracene, pentacene, fullerene, 6,13-bis(triisopropylsilylethynyl)pentacene (TIP S-pentacene), poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT), poly[(4,4-bis(2-ethylhexyl)cyclopenta[2,1-b:3,4-b0]dithiophene)-2,6-diyl-alt-[1,2,5]-thiadiazolo[3,4-c]pyridine] (PCDTPT), didodecyl[1]-benzothieno[3,2-b] [1] benzothiophene(C12-BTBT), diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (DPP-DTT), cyclopentadithiophene-benzothiadiazole (CDT-BTZ), phthalocyanine, rubrene, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene, and oligothiophene.

Assignees

• Ct Advanced Soft Electronics
• Postech Acad Ind Found
• Postech Academy—Industry Found

Inventors

• Cho Kilwon
• Kim Jinsung
• KANG Boseok

Classifications

• H10K71/12

  using liquid deposition, e.g. spin coating · CPC title

• C08J7/123 Primary

  Treatment by wave energy or particle radiation (C08J7/18 takes precedence) · CPC title

• C08J2311/00

  Characterised by the use of homopolymers or copolymers of chloroprene · CPC title

• C08J7/14

  with acids, their salts or anhydrides · CPC title

• B05D1/185

  applying monomolecular layers (B05D1/204 takes precedence) · CPC title