Radiation-sensitive resin composition and method for forming resist pattern

Patent metadata

Field	Value
Publication number	US-12422748-B2
Application number	US-202318215863-A
Country	US
Kind code	B2
Filing date	Jun 29, 2023
Priority date	Apr 17, 2017
Publication date	Sep 23, 2025
Grant date	Sep 23, 2025

Abstract

A radiation-sensitive resin composition includes: a base resin comprising a structure unit having an acid-dissociable group; and a radiation-sensitive acid generator which comprises compounds represented by formula (2) and formula (3), and optionally a compound represented by formula (1). R1-R3 are each independently a group having a cyclic structure; X11-X32 are each independently a hydrogen atom, a fluorine atom, or a fluorinated hydrocarbon group. At least one of X11 or X12, at least one of X21 or X22, and at least one of X31 or X32 are not a hydrogen atom, respectively. A11-A32 are each independently a hydrogen atom, or a hydrocarbon group having a carbon number of 1 to 20. The radiation-sensitive resin composition does not comprise a ketone-based solvent. The the radiation-sensitive resin composition does not comprise a monovalent onium cation other than an onium cation represented by formulas (X-1), (X-3), (X-4), or (X-5).

First claim

What is claimed is:

1. A radiation-sensitive resin composition, comprising:
a base resin comprising a structure unit having an acid-dissociable group;
a radiation-sensitive acid generator;
an acid diffusion controlling agent which is an onium salt compound capable of being degraded and losing acid diffusion controlling properties by an exposure; and
a solvent;
wherein the radiation-sensitive acid generator comprises a compound represented by formula (2), a compound represented by formula (3), and optionally a compound represented by formula (1), provided that the compound represented by the formula (1) and the compound represented by the formula (3) within the scope of the compound represented by the formula (2) are excluded:

wherein in the formulae (1) to (3),
R 1 and R 3 are each independently a group having a cyclic structure, and R 2 is an alicyclic hydrocarbon group or an alicyclic group in which a carbon ring atom of an alicyclic hydrocarbon group is replaced with a hetero atom;
X 11 , X 12 , X 21 , X 22 , X 31 and X 32 are each independently a hydrogen atom, a fluorine atom, or a fluorinated hydrocarbon group, provided that at least one of X 11 or X 12 is not a hydrogen atom, at least one of X 21 or X 22 is not a hydrogen atom, and at least one of X 31 or X 32 is not a hydrogen atom;
A 11 , A 12 , A 21 , A 22 , A 31 and A 32 are each independently a hydrogen atom, or a hydrocarbon group having a carbon number of 1 to 20;
m 1 , m 2 and m 3 are each independently an integer of 0 to 5;
n 1 , n 2 and n 3 are each independently an integer of 1 to 4;
G is a single bond, or a divalent linking group; and
Z 1 + , Z 2 + and Z 3 + are each independently a monovalent onium cation,
wherein the radiation-sensitive resin composition does not comprise a ketone-based solvent, and
the radiation-sensitive resin composition does not comprise a monovalent onium cation other than an onium cation represented by formula (X-1), an onium cation represented by formula (X-3), an onium cation represented by formula (X-4), or an onium cation represented by formula (X-5):

wherein in the formula (X-1),
k1, k2 and k3 are each independently an integer of 0 to 5, and
R a1 , R a2 and R a3 are each independently, at each occurrence, a substituted or unsubstituted, straight or branched chain alkyl group, alkoxy group or alkoxy carbonyloxy group having a carbon number of 1 to 12; a substituted or unsubstituted, monocyclic or polycyclic cycloalkyl group having a carbon number of 3 to 12; a substituted or unsubstituted aromatic hydrocarbon group having a carbon number of 6 to 12; a hydroxy group, —OSO 2 —R P , —SO 2 —R Q or —S—R T ; or a ring structure obtained by combining two or more thereof, wherein R P , R Q and R T are each independently, at each occurrence, a substituted or unsubstituted, straight or branched chain alkyl group having a carbon number of 1 to 12; a substituted or unsubstituted alicyclic hydrocarbon group having a carbon number of 5 to 25; and a substituted or unsubstituted aromatic hydrocarbon group having a carbon number of 6 to 12,
in the formula (X-3),
R c1 , R c2 and R c3 are each independently a substituted or unsubstituted, straight or branched chain alkyl group having a carbon number of 1 to 12; or a substituted or unsubstituted aromatic hydrocarbon group having a carbon number of 6 to 12,
in the above formula (X-4),
k6 and k7 are each independently an integer of 0 to 5, and
R d1 and R d2 are each independently, at each occurrence, a substituted or unsubstituted, straight or branched chain alkyl group, alkoxy group or alkoxycarbonyl group having a carbon number of 1 to 12; a substituted or unsubstituted aromatic hydrocarbon group having a carbon number of 6 to 12; a halogen atom; a halogenated alkyl group having a carbon number of 1 to 4; a nitro group; or a ring structure obtained by combining two or more thereof, and
in the above formula (X-5),
k8 and k9 are each independently an integer of 0 to 4, and
R e1 and R e2 are each independently, at each occurrence, a halogen atom; a substituted or unsubstituted straight or branched chain alkyl group having a carbon number of 1 to 12; or
a substituted or unsubstituted aromatic hydrocarbon group having a carbon number of 6 to 12,
wherein a CDU property of the radiation-sensitive resin composition is 3.1 nm or less,
wherein the CDU property is obtained by:
forming a hole resist pattern by exposing to an electron beam in an amount of an optimum exposed amount (Eop);
measuring hole diameters of the hole resist pattern at 16 points within a square 400 nm;
calculating an average value of the hole diameters; and
measuring the average values at five hundred of arbitrary points and determining a 3σ value from a distribution of the average values as the CDU properties (nm), and

wherein the Eop is obtained by:
applying the radiation-sensitive resin composition to a substrate conducting a heating at 90° C. for 60 seconds, and then conducting a cooling at 23° C. for 30 seconds to form a resist film having a film thickness of 50 nm;
exposing the resist film to an electron beam through a mask for forming a pattern having 40 nm line and space;
conducting heating at 120° C. for 60 seconds:
developing with 2.38% by mass of aqueous TMAH solution at 23° C. for 30 seconds; and
determining an amount of the exposure as the Eop, when width of the formed line was 40 nm.

2. The radiation-sensitive resin composition according to claim 1 , wherein each of a molecular weight of an anionic moiety in the radiation-sensitive acid generator is 230 or more.

3. The radiation-sensitive resin composition according to claim 1 , wherein the onium salt compound is triphenylsulfonium salicylate or triphenylsulfonium 10-camphorsulfonate.

4. The radiation-sensitive resin composition according to claim 1 , wherein the radiation-sensitive acid generator comprises the compound represented by the formula (1), and a total content of the compound represented by the formula (1) is not less than 1 part by mass and not more than 45 parts by mass based on 100 parts by mass of the base resin.

5. The radiation-sensitive resin composition according to claim 1 , wherein a content of the structural unit having the acid-dissociable group in the base resin is 30-75 mol %.

6. A method of forming a resist pattern, comprising:
forming a resist film from the radiation-sensitive resin composition according to claim 1 ;
exposing the resist film; and
developing the exposed resist film.

7. The method according to claim 6 , wherein each of a molecular weight of an anionic moiety in the radiation-sensitive acid generator is 230 or more.

8. The method according to claim 6 , wherein the onium salt compound is triphenylsulfonium salicylate or triphenylsulfonium 10-camphorsulfonate.

9. The method according to claim 6 , wherein the radiation-sensitive acid generator comprises the compound represented by the formula (1), and a total content of the compound represented by the formula (1) is not less than 1 part by mass and not more than 45 parts by mass based on 100 parts by mass of the base resin.

10. The method according to claim 6 , wherein a content of the structural unit having the acid-dissociable group in the base resin is 30-75 mol %.

11. A radiation-

Assignees

• Jsr Corp

Inventors

• Maruyama Ken

Classifications

• G03F7/30

  Imagewise removal using liquid means · CPC title

• C07C303/32

  of salts of sulfonic acids · CPC title

• C07C309/19

  of a saturated carbon skeleton containing rings · CPC title

• C07C309/12

  containing esterified hydroxy groups bound to the carbon skeleton · CPC title

• C07C381/12

  Sulfonium compounds · CPC title