Pattern forming method and resist composition

Patent metadata

Field	Value
Publication number	US-9551935-B2
Application number	US-201113636965-A
Country	US
Kind code	B2
Filing date	Mar 25, 2011
Priority date	Mar 25, 2010
Publication date	Jan 24, 2017
Grant date	Jan 24, 2017

Abstract

Provided is a method of forming a pattern, ensuring excellent exposure latitude (EL) and focus latitude (depth of focus DOF). The method of forming a pattern includes (A) forming a film from a resist composition, the resist composition, (B) exposing the film to light, and (C) developing the exposed film using a developer containing an organic solvent, thereby forming a negative pattern. The resist composition contains (a) a resin that is configured to decompose when acted on by an acid and ΔSP thereof represented by formula (1) below is 2.5 (MPa) 1/2 or above, (b) a compound that is composed to generate an acid when exposed to actinic rays or radiation, and (c) a solvent.

ΔSP=SP F −SP I   (1)

First claim

The invention claimed is:

1. A method of forming a pattern, comprising:
(A) forming a film from a resist composition, the resist composition comprising:
(a) a resin that is configured to decompose when acted on by an acid and ASP thereof represented by formula (1) below is 2.5 (MPa) 1/2 or above,
(b) a compound that is composed to generate an acid when exposed to actinic rays or radiation, and
(c) a solvent;

(B) exposing the film to light; and
(C) developing the exposed film using a developer containing an organic solvent, thereby forming a negative pattern
ΔSP=SP F −SP I   (1)

in the formula (1),
SP I represents a solubility parameter of the resin before decomposition, and
SP F represents a solubility parameter of the resin after decomposition,
wherein the resin contains a repeating unit containing a group that is decomposed when acted on by an acid to thereby produce an alcoholic hydroxyl group.

2. The method of forming a pattern according to claim 1 , wherein SP F is 24.2 (MPa) 1/2 or above.

3. The method of forming a pattern according to claim 1 , wherein SP 1 is 23.0 (MPa) 1/2 or below.

4. The method of forming a pattern according to claim 1 , wherein a solubility parameter of the developer is equal to or more than 15.0 (MPa) 1/2 and less than 23.0 (MPa) 1/2 .

5. The method of forming a pattern according to claim 1 , wherein the resin contains a repeating unit represented by general formula (AI) below

in the formula (AI),
Xa 1 represents a hydrogen atom, a methyl group, or a group represented by —CH 2 R 9 in which R 9 represents a hydroxyl group or a monovalent organic group,
T represents a single bond or a bivalent connecting group,
each of Rx 1 to Rx 3 independently represents an alkyl group or a cycloalkyl group, and at least two of Rx 1 to Rx 3 may be bonded to each other to thereby form a cycloalkyl group.

6. The method of forming a pattern according to claim 5 , wherein the content of the repeating unit represented by general formula (AI) based on all the repeating units in the resin is 50 mol % or above.

7. The method of forming a pattern according to claim 5 , wherein the content of the repeating unit represented by general formula (AI) based on all the repeating units in the resin is 60 mol % or above.

8. The method of forming a pattern according to claim 5 , wherein the part corresponding to —C(Rx 1 )(Rx 2 )(Rx 3 ) in general formula (AI) has 4 to 8 carbon atoms.

9. The method of forming a pattern according to claim 5 , wherein the part corresponding to —C(Rx 1 )(Rx 2 )(Rx 3 ) in general formula (AI) has 4 to 7 carbon atoms.

10. The method of forming a pattern according to claim 1 , wherein the resist composition further comprises a hydrophobic resin.

11. The method of forming a pattern according to claim 10 , wherein the hydrophobic resin contains at least one of fluorine atom and silicon atom.

12. A method of manufacturing a semiconductor device, comprising the method of forming a pattern according to claim 1 .

13. The method of forming a pattern according to claim 1 , wherein the acid-decomposable resin contains a repeating unit (A) containing a polar group, in addition to the repeating unit containing a group that is decomposed when acted on by an acid to thereby produce an alcoholic hydroxyl group.

14. The method of forming a pattern according to claim 13 , wherein the polar group contained in the repeating unit (A) is a functional group selected from functional groups (1)-(4), which are:
(1) a functional group containing a structure in which an oxygen atom is bonded through a single bond to an atom whose electronegativity exhibits a difference of 1.1 or greater from that of the oxygen atom;
(2) a functional group containing a structure in which a nitrogen atom is bonded through a single bond to an atom whose electronegativity exhibits a difference of 0.6 or greater from that of the nitrogen atom;
(3) a functional group containing a structure in which two atoms whose electronegativity value exhibit a difference of 0.5 or greater are bonded to each other through a double bond or triple bond; and
(4) a functional group containing an ionic moiety.

15. The method of forming a pattern according to claim 13 , wherein the polar group contained in the repeating unit (A) is at least one selected from the group consisting of (I) a hydroxyl group, (II) a cyano group, (III) a lactone group, (IV) a carboxylate group, (V) an amido group, a sulfonamide group or a group corresponding to a derivative thereof, (VI) an ammonium group or a sulfonium group, and a group formed of a combination of two or more thereof.

16. The method of forming a pattern according to claim 1 , wherein the group that is decomposed when acted on by an acid to thereby produce an alcoholic hydroxyl group is at least one selected from the group consisting of general formulae (II-1) to (II-4) below:

wherein in the formulae,
R 3 , or each of R 3 s independently, represents a hydrogen atom or a monovalent organic group, provided that R 3 s may be bonded to each other to thereby form a ring;
R 4 , or each of R 4 s independently, represents a monovalent organic group, provided that R 4 s may be bonded to each other to thereby form a ring and that R3 and R 4 may be bonded to each other to thereby form a ring; and
each of R 5 s independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group, provided that at least two R 5 s may be bonded to each other to thereby form a ring and that when one or two of three R 5 s are hydrogen atom, at least one of the rest of R 5 s represents an aryl group, an alkenyl group or an alkynyl group.

17. A method of forming a pattern, comprising:
(A) forming a film from a resist composition, the resist composition comprising:
(a) a resin that is configured to decompose when acted on by an acid and ASP thereof represented by formula (1) below is 2.5 (MPa) 1/2 or above,
(b) a compound that is composed to generate an acid when exposed to actinic rays or radiation, wherein said compound is selected from a compound having a sulfonate group, and a carboxylic acid onium salt, and
(c) a solvent;

(B) exposing the film to light; and
(C) developing the exposed film using a developer containing an organic solvent, thereby forming a negative pattern
ΔSP=SP F −SP I   (1)

in the formula (1),
SP I represents a solubility parameter of the resin before decomposition,
SP F represents a solubility parameter of the resin after decomposition, and
wherein the content ratio of the acid-decomposable resin based on the total solid content of the composition is 60 to 95 mass %,
wherein the resin component (a) consists of a single resin, and
wherein the resin contains a repeating unit represented by general formula (AI) below

in the formula (AI),
Xa 1 represents a hydrogen atom, a methyl group, or a group represented by —CH 2 —R 9 R 9 represents a hydroxyl group or a monovalent organic group,
T represents a single bond or a bivalent connecting group,
each of Rx 1 to Rx 3 independently represents an alkyl group or a cycloalkyl group, and at least two of Rx 1 to Rx 3

Assignees

• Kato Keita
• Tarutani Shinji
• Tsuchihashi Toru
• Kamimura Sou
• Enomoto Yuichiro
• Fujii Kana
• Iwato Kaoru
• Kataoka Shohei
• Mizutani Kazuyoshi
• Fujifilm Corp

Inventors

• Kato Keita
• Tarutani Shinji
• Tsuchihashi Toru
• Kamimura Sou
• Enomoto Yuichiro
• Fujii Kana
• Iwato Kaoru
• Kataoka Shohei
• Mizutani Kazuyoshi

Classifications

• G03F7/0397

  the macromolecular compound having an alicyclic moiety in a side chain · CPC title

• G03F7/2041

  in the presence of a fluid, e.g. immersion; using fluid cooling means · CPC title

• G03F7/0757

  Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence) · CPC title

• G03F7/0392 Primary

  the macromolecular compound being present in a chemically amplified positive photoresist composition · CPC title

• Y10T428/24

  Structurally defined web or sheet [e.g., overall dimension, etc.] · CPC title