Method for producing organic thin film by using film physical property improving process

• US 8,133,546 B2
• Filed: 07/31/2007
• Issued: 03/13/2012
• Est. Priority Date: 07/31/2006
• Status: Expired due to Fees

• Current Assignee: Nippon Soda Company Limited
• Original Assignee: Nippon Soda Company Limited
• Inventors: Kumazawa, Kazuhisa
• Primary Examiner(s): Ogden, Jr., Necholus
• Application Number:
  US12/309,801
• Publication Number:
  US 20090258160A1
• Time in Patent Office: 1,687 Days
• Field of Search: None
• US Class Current: 427/485
• CPC Class Codes: B01J 10/02 of the thin-film type
• CPC Class Codes: B05D 1/185 applying monomolecular layers B05D1/204 takes precedence
• CPC Class Codes: B05D 3/0254 After-treatment
• CPC Class Codes: B05D 3/0473 for heating, e.g. vapour heating
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures

Abstract

A method is provided for producing an organic thin film on a substrate surface comprising improved heat resistance or durability; said method comprising at least a step (B) of allowing the substrate to contact with an organic solvent solution comprising a metal surfactant having at least one or more hydrolysable group or hydroxyl group, and a catalyst that can interact with the metal surfactant, wherein the method further comprises after step (B), step (E1) of heating the substrate which has been in contact with the organic solvent solution at 100° C. to 150° C.; step (E2) of immersing the substrate which has been in contact with the organic solvent solution in a warm water of 40° C. or more and less than the boiling point; or step (E3) of allowing the substrate which has been in contact with the organic solvent solution to contact with a moisture vapor of 60° C. to 150° C.

Claims

1. A method for producing an organic thin film for forming an organic thin film on a substrate surface, comprising at least a step (B) of allowing the substrate to contact with an organic solvent solution comprising a metal surfactant having at least one or more hydrolysable group or hydroxyl group, and a catalyst that can interact with the metal surfactant, wherein the method further comprises after the step B, a step (E1) of heating the substrate which has been in contact with the organic solvent solution at 100°

C. to 150°

C.;

a step (E2) of immersing the substrate which has been in contact with the organic solvent solution in a warm water of 40°

C. or more and less than the boiling point;

or a step (E3) of allowing the substrate which has been in contact with the organic solvent solution to contact with a moisture vapor of 60°

C. to 150°

C.

2. The method for producing an organic thin film according to claim 1, wherein the range of 60°

C. to 150°

C. in the step (E3) is a range of 80°

C. to 130°

C.

3. The method for producing an organic thin film according to claim 1, wherein the method further comprises after the step (E2), a step (F2) of heating the substrate that has been immersed in a warm water at 80°

C. to 150°

C.

4. The method for producing an organic thin film according to claim 3, wherein the range of 80°

C. to 150°

C. in the step (F2) is a range of 100°

C. to 130°

C.

5. The method for producing an organic thin film according to claim 1, wherein the method further comprises prior to the step (B), a step (A) of performing UV ozone treatment to the substrate.

6. The method for producing an organic thin film according to claim 1, wherein the method further comprises after the step (B), and prior to the step (E1), (E2) or (E3), a step (C) of washing the substrate with a hydrocarbonic organic solvent.

7. The method for producing an organic thin film according to claim 6, wherein the method further comprises between the step (C) and the step (E1), (E2), or (E3), a step (D) of removing the hydrocarbonic organic solvent attached to the substrate.

8. The method for producing an organic thin film according to claim 1, wherein at least one catalyst selected from the group consisting of metal oxide;

metal hydroxide;

metal alkoxides, chelated or coordinated metal compound, partial hydrolyzed product of metal alkoxides, hydrolyzed product obtained by treating metal alkoxides with water in an amount equivalent to 2-fold or more of the metal alkoxides;

organic acids;

silanol condensation catalyst and acid catalyst;

is used as the catalyst that can interact with the metal surfactant.

9. The method for producing an organic thin film according to claim 8, wherein at least one or more metal selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, and lead;

is used as a metal of metal oxide, metal hydroxide, metal alkoxides, chelated or coordinated metal compounds, partial hydrolyzed product of metal alkoxides, or hydrolyzed product obtained by treating metal alkoxides with water in an amount equivalent to 2-fold or more of the metal alkoxides.

10. The method for producing an organic thin film according to claim 8, wherein a product having a property of being dispersed stably without being agglutinated in an organic solvent in the absence of acid, base and/or dispersion stabilizer, is used as a partial hydrolyzed product of metal alkoxides.

11. The method for producing an organic thin film according to claim 8, wherein a product obtained by hydrolyzing at a temperature range of −

100°

C. to the reflux temperature of the organic solvent, by using water in an amount of 0.5 to 2.0-fold mol relative to metal alkoxides in an organic solvent, is used as a partial hydrolyzed product of metal alkoxides.

12. The method for producing an organic thin film according to claim 8, wherein an organic acid having a pKa level of 1 to 6 is used as organic acid.

13. The method for producing an organic thin film according to claim 1, wherein a compound represented by formula (I) is used as a metal surfactant having at least one or more hydrolysable group or hydroxyl group,

R¹_nMX_m-n 

 

(I)

(wherein R¹ represents a hydrocarbon group optionally having a substituent, a halogenated hydrocarbon group optionally having a substituent, a hydrocarbon group comprising a linking group, or a halogenated hydrocarbon group comprising a linking group;

M represents at least one metal atom selected from the group consisting of silicon atom, germanium atom, tin atom, titanium atom and zirconium atom;

X represents a hydroxyl group or hydrolysable group;

n represents any integer of 1 to (m-1);

m represents an atomic valence of M;

when n is 2 or more, R1 may be the same or different;

when (m-n) is 2 or more, X may be the same or different;

with the proviso that at least one X among (m-n)×

X is a hydrolysable group or hydroxyl group.

14. The method for producing an organic thin film according to claim 1, wherein a compound represented by formula (II) is used as a metal surfactant having at least one or more hydrolysable group or hydroxyl group,

R²_3C—

(CR³₂)p-R⁴q-MY_rX_m-r-1 

 

(II)

(wherein M represents at least one metal atom selected from the group consisting of silicon atom, germanium atom, tin atom, titanium atom and zirconium atom;

X represents a hydroxyl group or hydrolysable group;

R² and R³ independently represent a hydrogen atom or fluorine atom;

R⁴ represents an alkylene group, vinylene group, ethynylene group, arylene group, or a divalent linking group comprising a silicon atom and/or oxygen atom;

Y represents a hydrogen atom, alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group;

p represents 0 or a positive integer;

q represents 0 or 1;

r represents an integer of 0 to (m-2);

when r is 2 or more, Y may be the same or different;

when (m-r-1) is 2 or more, X may be the same or different;

with the proviso that at least one X among (m-n-1)×

X is a hydrolysable group or hydroxyl group).

15. The method for producing an organic thin film according to claim 13 or 14, wherein X is a hydrolysable group consisting of a halogen atom, C1-C6 alkoxy group, or acyloxy group.

16. The method for producing an organic thin film according to claim 1, wherein a hydrocarbonic solvent solution or fluorocarbonic solvent solution is used as an organic solvent solution.

17. The method for producing an organic thin film according to claim 1, wherein the organic thin film is a crystalline organic thin film.

18. The method for producing an organic thin film according to claim 1, wherein the organic thin film is a monomolecular film.

19. The method for producing an organic thin film according to claim 1, wherein the organic thin film is a chemisorbed film.

20. The method for producing an organic thin film according to claim 1, wherein the organic thin film is a self-assembled film.

21. The method for producing an organic thin film according to claim 1, wherein a substrate comprising an active hydrogen on the surface is used as a substrate.

22. The method for producing an organic thin film according to claim 1, wherein a substrate consisting of at least one selected from the group consisting of metal, glass, silicon wafer, ceramics, and plastic is used as a substrate.

23. The method for producing an organic thin film according to claim 1, wherein the substrate is not crystalline, and the organic thin film is crystalline.

24. The method for producing an organic thin film according to claim 1, wherein the step (B) is a step (B′

) of applying an organic solvent solution comprising a metal surfactant having at least one or more hydrolysable group or hydroxyl group, and a catalyst that can interact with the metal surfactant on the substrate by at least one method selected from dipping method, spin coating method, rolling coating method, Mayer bar method, screen printing method, offset printing method, brush coating method, and spraying method.