CHEMICALLY AMPLIFIED NEGATIVE RESIST COMPOSITION, PHOTO-CURABLE DRY FILM, MAKING METHOD, PATTERN FORMING PROCESS, AND ELECTRIC/ELECTRONIC PART PROTECTING FILM

• US 20130149645A1
• Filed: 12/05/2012
• Published: 06/13/2013
• Est. Priority Date: 12/09/2011
• Status: Active Grant

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Takemura, Katsuya, Miyazaki, Takashi, Urano, Hiroyuki
• Granted Patent: US 8,865,391 B2
• Time in Patent Office: Days
• US Class Current: 430/280.1
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: G03F 7/0382 the macromolecular compound being present in a chemically amplified negative photoresist composition
• CPC Class Codes: G03F 7/0757 Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: G03F 7/085 Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives G03F7/075 takes precedence
• CPC Class Codes: G03F 7/161 using a previously coated surface, e.g. by stamping or by transfer lamination
• CPC Class Codes: G03F 7/2002 with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
• CPC Class Codes: G03F 7/40 Treatment after imagewise removal, e.g. baking

Abstract

A chemically amplified negative resist composition is provided comprising (A) a resin having a crosslinking group, (B) a crosslinker, (C) a photoacid generator capable of generating an acid upon exposure to light of wavelength 190-500 nm, (D) a solvent, and (E) an isocyanuric acid. The resist composition overcomes the stripping problem that the film is stripped from metal wirings of Cu or Al, electrodes, and SiN substrates.

Claims

1. A chemically amplified negative resist composition comprising

(A) a resin having a crosslinking group or a reaction site susceptible to crosslinking reaction within the molecule,

(B) a crosslinker,

(C) a photoacid generator which is decomposed to generate an acid upon exposure to light of wavelength 190 to 500 nm,

(D) a solvent, and

(E) an isocyanuric acid of the structure having the general formula (1):

2. The resist composition of claim 1 wherein component (A) is a silicone structure-bearing polymer comprising recurring units of the general formula (2) and having a weight average molecular weight of 3,000 to 500,000,

3. The resist composition of claim 2 wherein 0.3≦

a≦

0.7, 0.2≦

b≦

0.5, 0<

c≦

0.2, and 0<

d≦

0.2 in formula (2).

4. The resist composition of claim 2 wherein 0.2≦

a≦

0.8, 0.2≦

b≦

0.8, c=0, and d=0 in formula (2).

5. The resist composition of claim 2 wherein b=1, and a, c and d are 0 in formula (2).

6. The resist composition of claim 1 wherein component (E) is an isocyanuric acid of the structure having formula (1) wherein at least one of R¹, R² and R³ is a crosslinking group selected from methylol, alkoxymethylol, glycidyl, and vinyloxy groups, or an organic group having a reaction site susceptible to crosslinking reaction, represented by the general formula (5) or (6):

7. The resist composition of claim 1 wherein the isocyanuric acid of component (E) is selected from the group consisting of compounds having the following formulae (I) to (V):

8. The resist composition of claim 1, further comprising a basic compound.

9. A pattern forming process comprising the steps of:

(1) coating the chemically amplified negative resist composition of claim 1 onto a substrate, and prebaking to form a resist film,

(2) exposing the resist film to high-energy radiation of wavelength 190 to 500 nm or electron beam through a photomask,

(3) baking and developing in a developer to pattern the resist film.

10. The process of claim 9, further comprising (4) post-curing the patterned resist film resulting from development step (3) at a temperature of 100 to 250°

C.

11. A photo-curable dry film comprising a photo-curable resin layer having a thickness of 10 to 100 μ

m sandwiched between a support film and a protective film,

the photo-curable resin layer being formed of a photo-curable resin composition which is the chemically amplified negative resist composition of claim 1.

12. A laminate comprising

a substrate provided with grooves and/or holes having an opening width of 10 to 100 μ

m and a depth of 10 to 120 μ

m, and

a layer lying on the substrate, the layer being a cured layer of the photo-curable resin composition extracted from the photo-curable dry film of claim 11.

13. A method of preparing a photo-curable dry film, comprising the steps of:

(i) continuously coating a photo-curable resin composition onto a support film, the photo-curable resin composition being the resist composition comprising components (A) to (E) as set forth in claim 1,

(ii) drying the photo-curable resin composition to form a photo-curable resin layer on the support film, and

(iii) applying a protective film onto the photo-curable resin layer.

14. A pattern forming process comprising the steps of:

(i) stripping the protective film from the photo-curable dry film of claim 11 and placing the bare photo-curable resin layer in close contact with a substrate,

(ii) exposing the photo-curable resin layer to radiation of wavelength 190 to 500 nm through a photomask and through the support film or with the support film stripped off,

(iii) post-exposure bake, and

(iv) developing in a developer to pattern the layer.

15. The process of claim 14, further comprising (v) post-curing the patterned layer resulting from development step (iv) at a temperature of 100 to 250°

C.

16. The process of claim 14 wherein the substrate is provided with grooves and/or holes having an opening width of 10 to 100 μ

m and a depth of 10 to 120 μ

m.

17. A film for the protection of electric and electronic parts, which is obtained from the photo-curable dry film of claim 11.