Negative-type photosensitive polymer, polymer solution, negative-type photosensitive resin composition, cured film, and semiconductor device

Patent metadata

Field	Value
Publication number	US-2024272551-A1
Application number	US-202218566685-A
Country	US
Kind code	A1
Filing date	Jun 22, 2022
Priority date	Jun 25, 2021
Publication date	Aug 15, 2024
Grant date	—

Abstract

A negative-type photosensitive polymer of the present invention is a solvent-soluble negative-type photosensitive polymer which has a structural unit containing an imide ring and contains a group represented by General Formula (t) at at least one of both terminals, in which an average value of positive electric charges (δ+) of two carbonyl carbons of the imide ring is equal to or less than 0.095 as calculated by a charge equilibration method.

First claim

What is claim is:

1 . A solvent-soluble negative-type photosensitive polymer which has a structural unit containing an imide ring, the negative-type photosensitive polymer comprising, at at least one of both terminals,
a group represented by General Formula (t), wherein an average value of positive electric charges (δ+) of two carbonyl carbons of the imide ring is equal to or less than 0.095 as calculated by a charge equilibration method,

(in General Formula (t), R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, provided that at least one is an alkyl group having 1 to 3 carbon atoms; and * represents a bonding site).

2 . The negative-type photosensitive polymer according to claim 1 ,
wherein a fluorine atom is not contained in a molecular structure.

3 . The negative-type photosensitive polymer according to claim 1 ,
wherein the structural unit is represented by General Formula (1),

(in General Formula (1), X represents a divalent organic group including an aromatic group; A represents a ring structure having two carbons of the imide ring; and Q represents a divalent organic group).

4 . The negative-type photosensitive polymer according to claim 3 , further comprising
an asymmetrical electron-donating group at two ortho positions with respect to a carbon atom bonded to a nitrogen atom in General Formula (1), wherein the aromatic group included in the divalent organic group as X in General Formula (1) is bonded to the nitrogen atom.

5 . The negative-type photosensitive polymer according to claim 3 ,
wherein X in General Formula (1) is a divalent group represented by General Formula (1a) or General Formula (1 b),

(in General Formula (1a), R 1 to R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, provided that R 1 and R 2 are different groups, and R 3 and R 4 are different groups; X 1 represents a single bond, —SO 2 —, —C(═O)—, a linear or branched alkylene group having 1 to 5 carbon atoms, or a fluorenylene group; and * represents a bonding site, and
in General Formula (1 b), R a and R b each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, provided that a plurality of R a 's may be the same as or different from each other, and a plurality of R b 's may be the same as or different from each other; and * represents a bonding site).

6 . The negative-type photosensitive polymer according to claim 3 ,
wherein A in General Formula (1) is an aromatic ring.

7 . The negative-type photosensitive polymer according to claim 3 ,
wherein Q in General Formula (1) is a divalent group containing an imide ring.

8 . The negative-type photosensitive polymer according to claim 5 ,
wherein the structural unit represented by General Formula (1) includes a structural unit represented by General Formula (1-1),

(in General Formula (1-1), X is the divalent group represented by General Formula (1a) or General Formula (1 b); and Y is a divalent organic group).

9 . The negative-type photosensitive polymer according to claim 8 ,
wherein Y in General Formula (1-1) is a divalent organic group selected from General Formula (a1-1), General Formula (a1-2), General Formula (a1-3), and General Formula (a1-4),

(in General Formula (a1-1), R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, provided that a plurality of R 7 's may be the same as or different from each other, and a plurality of R 8 's may be the same as or different from each other; R 9 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, provided that a plurality of R 9 's may be the same as or different from each other; and * represents a bonding site,
in General Formula (a1-2), R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, provided that a plurality of R 10 's may be the same as or different from each other, and a plurality of R 11 's may be the same as or different from each other; and * represents a bonding site,
in General Formula (a1-3), Z 1 represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group; and * represents a bonding site, and
in General Formula (a1-4), Z 2 represents a divalent aromatic group; and * represents a bonding site).

10 . The negative-type photosensitive polymer according to claim 8 , further comprising, at at least one of both of the terminals,
a group represented by General Formula (t-1),

(in General Formula (t-1), R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, provided that at least one is an alkyl group having 1 to 3 carbon atoms; Q 2 represents a divalent organic group; and * represents a bonding site).

11 . The negative-type photosensitive polymer according to claim 1 ,
wherein equal to or more than 5% by mass of the negative-type photosensitive polymer is dissolved in a solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone (GBL), and cyclopentanone.

12 . The negative-type photosensitive polymer according to claim 1 ,
wherein equal to or more than 5% by mass of the negative-type photosensitive polymer is dissolved in cyclopentanone.

13 . The negative-type photosensitive polymer according to claim 1 ,
wherein a reduction rate of a weight-average molecular weight measured under the following condition is equal to or less than 15%, (condition) when 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water are added to 100 parts by mass of the negative-type photosensitive polymer to stir at 100° C. for 6 hours, calculation is carried out by the following expression,
expression: [(weight-average molecular weight before test−weight-average molecular weight after test)/weight-average molecular weight before test]×100.

14 . A polymer solution comprising
the negative-type photosensitive polymer according to claim 1 .

15 . A negative-type photosensitive resin composition comprising:
(A) the negative-type photosensitive polymer according to claim 1 ; (B) a crosslinking agent (B) (excluding the polyimide (A)) having a substituted or unsubstituted maleimide group; and (C) a photosensitizer.

16 . The negative-type photosensitive resin composition according to claim 15 ,
wherein the crosslinking agent (B) has a structural unit represented by General Formula (b),

(in General Formula (b), R 1 and R 2 each inde

Assignees

• Sumitomo Bakelite Co

Inventors

• Imai Keita
• Otoguro Akihiko

Classifications

• G03F7/039

  Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) · CPC title

• G03F7/0048

  characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents · CPC title

• G03F7/0045

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• G03F7/038 Primary

  Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) · CPC title

• G03F7/027

  Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence) · CPC title