Non-ionic aryl ketone based polymeric photo-acid generators

Patent metadata

Field	Value
Publication number	US-9951164-B2
Application number	US-201615235673-A
Country	US
Kind code	B2
Filing date	Aug 12, 2016
Priority date	Aug 12, 2016
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

Non-ionic photo-acid generating (PAG) polymerizable monomers were prepared that contain a side chain sulfonate ester of an alpha-hydroxy aryl ketone. The aryl ketone group has a perfluorinated substituent alpha to the ketone carbonyl. The sulfur of the sulfonate ester is also directly linked to a fluorinated group. PAG polymers prepared from the PAG monomers release a strong sulfonic acid when exposed to high energy radiation such as deep UV or extreme UV light. The photo-generated sulfonic acid has a low diffusion rate in an exposed resist layer subjected to a post-exposure bake (PEB) at 100° C. to 150° C., resulting in formation of good line patterns after development.

First claim

What is claimed is:

1. A compound of formula (1):

wherein
Ar is a monovalent radical comprising one or more aromatic rings,
L′ is a single bond or a divalent C 0 -C 10 linking group,
P′ is a C 2 -C 20 monovalent radical comprising a polymerizable carbon-carbon double bond,
R 1 is a monovalent perfluorinated C 1 -C 10 radical, wherein R 1 has a molecular formula consisting of elements carbon and fluorine, and
Z′ is a divalent C 1 -C 10 radical having a molecular formula consisting of elements carbon, fluorine, and optionally hydrogen.

2. The compound of claim 1 , wherein P′ is

wherein
R 2 is a monovalent radical selected from the group consisting of hydrogen, methyl, and trifluoromethyl,
Y′ is a divalent radical selected from the group consisting of

 and aromatic groups comprising one or more aromatic rings, and
Y′ is linked to L′.

3. The compound of claim 2 , wherein Y′ is

and the compound is a methacrylate ester.

4. The compound of claim 2 , wherein Y′ is benzene-1,4-diyl:

5. The compound of claim 1 , wherein P′ is selected from the group consisting of

wherein R 2 is selected from the group consisting of hydrogen, methyl, and trifluoromethyl.

6. The compound of claim 1 , wherein P′ is

wherein R 2 is selected from the group consisting of hydrogen, methyl, and trifluoromethyl.

7. The compound of claim 1 , wherein P′ is

wherein R 2 is selected from the group consisting of hydrogen, methyl, and trifluoromethyl.

8. The compound of claim 1 , wherein P′ is

9. The compound of claim 1 , wherein Z′ is selected from the group consisting of

10. The compound of claim 1 , wherein R 1 is selected from the group consisting of trifluoromethyl and perfluoroethyl.

11. The compound of claim 1 , wherein Ar is selected from the group consisting of

12. The compound of claim 9 , wherein the compound is selected from the group consisting of

13. A photo-acid generating polymer (PAG polymer), comprising a non-ionic PAG repeating unit of formula (8):

wherein
the PAG polymer has a polymer backbone,
A′ is a trivalent radical comprising a pair of covalently linked carbons which are carbons of the polymer backbone,
Ar is a monovalent aryl radical comprising one or more aromatic rings,
L′ is a single bond or a divalent C 0 -C 10 linking group,
R 1 is a monovalent perfluorinated C 1 -C 10 radical, wherein R 1 has a molecular formula consisting of elements carbon and fluorine, and
Z′ is a divalent C 1 -C 10 radical consisting of elements carbon, fluorine, and optionally hydrogen.

14. The PAG polymer of claim 13 , wherein A′ is

wherein
R 2 is a monovalent radical selected from the group consisting of hydrogen, methyl, and trifluoromethyl,
Y′ is a divalent radical selected from the group consisting of

 and aromatic groups comprising one or more aromatic rings, and
Y′ is linked to L′.

15. The PAG polymer of claim 14 , wherein Y′ is

wherein the oxygen is linked to L′.

16. The PAG polymer of claim 14 , wherein Y′ is benzene-1,4-diyl.

17. The PAG polymer of claim 14 , wherein the PAG polymer is thermally stable in a lithographic process up to at least 130° C.

18. The PAG polymer of claim 14 , wherein the PAG repeating unit is selected from the group consisting of:

and combinations thereof.

19. The PAG polymer of claim 14 , wherein the PAG polymer comprises a second repeating unit comprising an acid labile group, the acid labile group comprising a protected carboxylic acid group capable of being deprotected by an acid, and the PAG polymer is capable of chemical amplification in a lithographic process.

20. The PAG polymer of claim 19 , wherein the acid labile group of the protected carboxylic acid group is protected with an acid-labile functionality selected from the group consisting of tertiary esters, acetals, ketals, carbonates, and orthoesters.

21. A resist composition, comprising:
the PAG polymer of claim 13 ; and
an organic solvent, wherein the PAG polymer is dissolved in the organic solvent, and the resist composition is suitable for forming a resist pattern in a lithographic process.

22. A method, comprising:
providing a layered structure comprising a resist layer disposed on a surface of a substrate, the resist layer comprising the PAG polymer of claim 13 ;
pattern-wise exposing the resist layer to radiation, thereby forming an exposed resist layer;
baking the exposed resist layer at about 90° C. to about 130° C. for at least 1 second, thereby forming a treated resist layer; and
selectively removing a region of the treated resist layer using a developer, thereby forming a patterned resist layer.

23. The method of claim 22 , wherein the developer is an aqueous alkaline developer that selectively removes an exposed region of the treated resist layer, leaving a positive tone patterned resist layer.

24. The method of claim 22 , wherein the developer is an organic solvent developer that selectively removes a non-exposed region of the treated resist layer, leaving a negative tone patterned resist layer.

25. The method of claim 22 , wherein the radiation has a wavelength less than 300 nm.

Assignees

• IBM
• Central Glass Co Ltd

Inventors

• Ishimaru Takehisa
• Narizuka Satoru
• Sanders Daniel P
• Sooriyakumaran Ratnam
• Truong Hoa D
• Wojtecki Rudy J

Classifications

• G03F7/2004

  characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light · CPC title

• C07C309/68

  of a carbon skeleton substituted by singly-bound oxygen atoms · CPC title

• G03F7/38

  Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} · CPC title

• C07C309/70

  of a carbon skeleton substituted by carboxyl groups · CPC title

• C07C309/69

  of a carbon skeleton substituted by nitrogen atoms, not being part of nitro or nitroso groups · CPC title