Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agent

Patent metadata

Field	Value
Publication number	US-9023247-B2
Application number	US-97769310-A
Country	US
Kind code	B2
Filing date	Dec 23, 2010
Priority date	Sep 22, 2004
Publication date	May 5, 2015
Grant date	May 5, 2015

Abstract

The invention provides an antistatic treatment agent having an ability of preventing resist film thinning phenomenon in a chemically amplified resist, an antistatic film, a coated article and a pattern forming method using such antistatic treatment agent, in particular, the invention provides an antistatic treatment agent comprising an aqueous solvent-soluble electroconductive polymer, a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound and an anionic surfactant, an antistatic film, a coated article and a pattern forming method using such antistatic treatment agent. As the aqueous solvent-soluble electroconductive polymer, a π-conjugated electroconductive polymer having a Brönsted acid group is a sulfonic acid group is preferred and it is preferable that the amount of the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound be from 0.1 to 75 mol % based on the total number of moles of the basic compounds.

First claim

The invention claimed is:

1. A method of performing photolithography, comprising:
a step of forming an antistatic film by applying an antistatic treatment agent comprising (a) an aqueous solvent-soluble electroconductive polymer having a Brönsted acid group, (b) a diamine or polyamine aliphatic basic compound and (c) a volatile basic compound onto a resist sensitive to a charged-particle-beam, and
a step of drawing patterns by radiating a charged-particle-beam onto the resist having applied thereon the antistatic treatment agent,
wherein the molar ratio of diamine or polyamine aliphatic basic compound in the total mole number of all basic compounds present is within a range of 0.1 to 75 mol %, and the number of moles of the basic group contained in the diamine or polyamine aliphatic basic compound is within a range of 0.05 to 50 mol % based on the number of moles of the Brönsted acid group contained in the aqueous solvent-soluble electroconductive polymer, and
wherein the diamine or polyamine aliphatic basic compound consists of one or more kinds selected from the group consisting of diaminoalkane, triaminoalkane, polyaminoalkane and polyalkylimine.

2. The method according to claim 1 , wherein at least one kind of the diamine or polyamine aliphatic basic compounds has a boiling point of 80° C. or higher.

3. The method according to claim 1 , wherein the diamine or polyamine aliphatic basic compound consists of one or more kinds selected from the group consisting of ethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminooctane, diaminodecane and polyethyleneimine.

4. The method according to claim 1 , wherein the aqueous solvent-soluble electroconductive polymer is a π-conjugated electroconductive polymer.

5. The method according to claim 1 , wherein the Brönsted acid group is a sulfonic acid group.

6. The method according to claim 1 , wherein the antistatic treatment agent is an aqueous solution containing 0.1 to 10 mass % of an aqueous solvent-soluble electroconductive polymer, 0.1 to 20 mass % of a diamine or polyamine aliphatic basic compound and 0.1 to 20 mass % of a volatile basic compound, provided that the entire amount of the antistatic treatment agent is 100 mass %.

7. The method according to claim 1 , wherein the antistatic treatment agent further comprises a surfactant.

8. The method according to claim 7 , wherein the surfactant is an anionic surfactant, an amphoteric surfactant or a mixture thereof.

9. The method according to claim 7 , wherein the surfactant is an anionic surfactant.

10. The method according to claim 9 , wherein the antistatic treatment agent is an aqueous solution containing 0.1 to 10 mass % of an aqueous solvent-soluble electroconductive polymer, 0.1 to 20 mass % of a diamine or polyamine aliphatic basic compound, 0.1 to 20 mass % of a volatile basic compound and 0.001 to 1 mass % of an amphoteric surfactant provided that the entire amount of the antistatic treatment agent is 100 mass %.

11. The method according to claim 1 , wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (1):

in the formula, m and n each independently represents 0 or 1; X represents S, N—R 1 or O; A represents an alkylene group or an alkenylene group or that may have two more double bonds having 1 to 4 carbon atoms and having at least a substituent represented by —B—SO 3 − M + , wherein the alkylene and alkenylene group may be substituted with a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group or a substituted phenyl group; B represents —(CH 2 ) p —(O) q —(CH 2 ) r — in which p, q and r independently represents 0 or an integer of 1 to 3; and M + represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.

12. The method according to claim 1 , wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (2):

in the formula, R 2 to R 4 each independently represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a —B—SO 3 − M + group; B represents —(CH 2 ) p —(O) q —(CH 2 ) r — in which p, q and r independently represents 0 or an integer of 1 to 3; and M + represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion, and,
(b) a volatile basic compound selected from the group consisting of ammonia, methylamine, ethylamine and dimethylamine.

13. The method according to claim 12 , wherein the aqueous solvent-soluble electroconductive polymer is a polymer including 5-sulfonisothianaphthene-1,3-diyl as a chemical structure.

14. The method according to claim 1 , wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (3):

in the formula, R 5 represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a —B—SO 3 − M + group; B represents —(CH 2 ) p —(O) q —(CH 2 ) r — in which p, q and r independently represents 0 or an integer of 1 to 3; and M + represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.

15. The method according to claim 1 , wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (4):

in the formula, R 6 to R 8 each independently represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a —SO 3 − M + group; R 9 represents a hydrogen atom or a monovalent group selected from a group of linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group; B represents —(CH 2 ) p —(O) q —(CH 2 ) r — in which p, q and r independently represents 0 or an integer of 1 to 3; and M + represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.

16. The method according to claim 1 , wherein the volatile basic compound is selected from the group consisting of ammonia, methylamine, ethylamine and dimethylamine.

Assignees

• Ohkubo Takashi
• Saida Yoshihiro
• Showa Denko Kk

Inventors

• Ohkubo Takashi
• Saida Yoshihiro

Classifications

• C08G2261/312

  Non-condensed aromatic systems, e.g. benzene · CPC title

• C09K3/16 Primary

  Anti-static materials · CPC title

• G03F7/093

  characterised by antistatic means, e.g. for charge depletion · CPC title

• Y10T428/31855

  Of addition polymer from unsaturated monomers · CPC title

• B32B27/18

  characterised by the use of special additives · CPC title