Photoresist compositions and pattern formation methods

Patent metadata

Field	Value
Publication number	US-2022229366-A1
Application number	US-202117565019-A
Country	US
Kind code	A1
Filing date	Dec 29, 2021
Priority date	Dec 31, 2020
Publication date	Jul 21, 2022
Grant date	—

Abstract

Disclosed herein is a pattern formation method, comprising (a) applying a layer of a photoresist composition over a semiconductor substrate, (b) pattern-wise exposing the photoresist composition layer to i-line radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image; wherein the photoresist composition comprises a non-ionic photoacid generator; a solvent; a first polymer and a second polymer; and wherein the first polymer comprises a polymeric dye.

First claim

What is claimed is:

1 . A pattern formation method, comprising:
(a) applying a layer of a photoresist composition over a substrate, (b) pattern-wise exposing the photoresist composition layer to i-line radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image; wherein the photoresist composition comprises:
a non-ionic photoacid generator;
a solvent;
a first polymer comprising first polymerized units of formula (1), second polymerized units of formula (2); and third polymerized units of formula (3):

wherein a is an integer from 1 to 5 and Z 3 is a hydrogen or an alkyl group having 1 to 5 carbon atoms, Z and R5 are independently selected from a hydrogen atom, C 1 -C 4 alkyl, C 1 -C 4 fluoroalkyl, or cyano; Zi is a non-hydrogen substituent comprising an acid-labile group, the cleavage of which forms a carboxylic acid on the polymer; L is a divalent linking group; An is a substituted or unsubstituted anthracene group; wherein the first polymer is present in the photoresist composition in an amount of from 0.1 to 10 wt %, based on total solids of the photoresist composition; and
a second polymer comprising first polymerized units of formula (4)

wherein b is an integer from 1 to 5 and Z 4 is a hydrogen or an alkyl group having 1 to 5 carbon atoms; and second polymerized units of a monomer comprising an acid-labile group; and wherein the second polymer is free of polymerized units of formula (3): present in the photoresist composition in an amount of 10 to 99 wt %, based on total solids of the photoresist composition.

2 . The method of claim 1 , wherein the acid-labile group of the second polymerized unit of formula (2) is a tertiary ester group or an acetal group.

3 . The method of claim 1 , wherein the third polymerized units of the first polymer are represented by formula (3a)

wherein each R 4 is selected from a hydrogen, a halogen, a substituted or unsubstituted alkyl having 1 to about 12 carbon atoms; a substituted or unsubstituted alkoxy having 1 to about 12 carbon atoms; a substituted or unsubstituted alkenyl having 2 to about 12 carbon atoms; a substituted or unsubstituted alkynyl having 2 to about 12 carbon atoms; a substituted or unsubstituted alkylthio having 1 to about 12 carbon atoms; a cyano; a nitro; an amino; or a hydroxyl; m is an integer of from 0 to 9 and wherein R 5 is selected from a hydrogen atom, C 1 -C 4 alkyl, C 1 -C 4 fluoroalkyl and a cyano group; and wherein L is a divalent linking group.

4 . The method of claim 3 , wherein the first polymerized unit of formula (1) comprises polyhydroxystyrene and wherein the second polymerized unit of formula (2) comprises a tertiary alkyl ester.

5 . The method of claim 1 , where the second polymer has a higher average molecular weight than the first polymer and wherein the second polymer has a weight average molecular weight of 5,000 g/mole to 50,000 g/mole.

6 . The method of claim 1 , where the first polymer comprises polyhydroxystyrene, a polymer derived from an ethylenically unsaturated acrylic ester that has an acid labile group and a polymer having the structure:

wherein R 5 is hydrogen.

7 . The method of claim 1 , where the first polymer has the structure of formula (4)

wherein 1 is 40 to 75 mol %, m is 8 to 16 mol % and n is 5 to 30 mol %, based on total moles of the copolymer; and wherein the weight average molecular weight of the first polymer is 5,000 to 15,000 grams per mole.

8 . The method of claim 1 , wherein the second polymer is a copolymer having the structure of formula (8), (9), (10), (11) or (12)

wherein in formula (8) o is 40 to 90 mol % and p is 10 to 60 mol %;

wherein in formulas (9) through (12), o is 50 to 85 mol %, p is 5 to 30 mol %, and q is 10 to 25 mol %; and wherein all mole percentages are based on the total molar content of the second polymer.

9 . The photoresist composition of claim 1 , where the photoacid generator has the structure shown in formula (13)

wherein in formula (13), R 4 is a substituted or unsubstituted, linear or branched Ci to C14 alkyl group, a substituted heterocyclic group, or a halogen atom; and wherein R 5 is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms; a halogen atom, or an aryl group having 6 to 20 unsubstituted carbon atoms; and x is an integer from 0 to 6.

10 . The method of claim 1 , wherein the photoresist composition further comprises a base quencher and wherein the base quencher is selected from N,N-diethyldodecanamide, 2,8-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine and 1,1-dimethylethyl 4-hydroxypiperidine-l-carboxylate.

11 . The method of claim 1 , wherein the acid-labile group of the second polymer is a tertiary alkyl ester group or an acetal group.

12 . The method of claim 1 , wherein the acid-labile group containing monomer of the second polymer has the structure of formula (7)

wherein in formula (7), R b is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl; each A is independently a halogen, a hydroxy, a carboxylic acid or ester, a thiol, a straight chain or branched C 1-20 alkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, a monocyclic or polycyclic C 3-20 fluorocycloalkenyl, a monocyclic or polycyclic C 3-20 heterocycloalkyl, a monocyclic or polycyclic C 6-20 aryl, or a monocyclic or polycyclic C 4-20 heteroaryl, each of which is substituted or unsubstituted; and m is independently an integer of 0 to 4;
wherein in formula (7), R 11 , R 10 , and R 8 are each independently hydrogen, a straight chain or branched C 1-20 alkyl, a straight chain or branched C 1-20 heteroalkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, a monocyclic or polycyclic C 3-20 heterocycloalkyl, a monocyclic or polycyclic C 6-20 aryl, a C 7-20 aryloxyalkyl, or a monocyclic or polycyclic C 4-20 heteroaryl, each of which is substituted or unsubstituted and wherein any two of R 11 , R 10 , and R 8 together optionally may form a ring;
wherein in formula (7), R 7 is hydrogen, a substituted or unsubstituted straight chain or branched C 1-20 alkyl, a substituted or unsubstituted monocyclic or polycyclic C 3-20 cycloalkyl, a substituted or unsubstituted monocyclic or polycyclic C 3-20 heterocycloalkyl, a substituted or unsubstituted C 6-14 aryl, a substituted or unsubstituted C 3-14 heteroaryl, a substituted or unsubstituted C 7-18 arylalkyl, a substituted or unsubstituted C 4-18 heteroarylalkyl, or a substituted or unsubstituted C 1-12 heteroalkyl; and wherein in formula (7), R 9 is hydrogen, a substituted or unsubstituted straight chain or branched C 1-20 alkyl, a substituted or

Assignees

• Rohm & Haas Elect Mat

Inventors

• Haga Mitsuru
• Li Mingqi

Classifications

• G03F7/004 Primary

  Photosensitive materials (G03F7/12, G03F7/14 take precedence) · CPC title

• G03F7/0045 Primary

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

• G03F7/20

  Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00) · CPC title

• C08F220/18

  with acrylic or methacrylic acids · CPC title

• G03F7/16

  Coating processes; Apparatus therefor (applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74) · CPC title