Aqueous base-developable negative-tone films based on functionalized norbornene polymers

Patent metadata

Field	Value
Publication number	US-8986923-B2
Application number	US-201314050563-A
Country	US
Kind code	B2
Filing date	Oct 10, 2013
Priority date	Sep 21, 2009
Publication date	Mar 24, 2015
Grant date	Mar 24, 2015

Abstract

Embodiments in accordance with the present invention encompass negative-tone, aqueous base developable, self-imagable polymer compositions useful for forming films that can be patterned to create structures for microelectronic devices, microelectronic packaging, microelectromechanical systems, optoelectronic devices and displays.

First claim

What is claimed is:

1. A method for forming structures disposed on a substrate, comprising:
casting a polymer composition onto the substrate to form a polymer film thereon, where said polymer composition comprising a polymer consisting of a first repeating unit and a second repeating unit represented by formula Ia:

where for said first repeating unit at least one of R 1 , R 2 , R 3 and R 4 is —R 5 COOH and each of the remaining R 1 , R 2 , R 3 or R 4 is hydrogen, and where for said second repeating unit at least one of R 1 , R 2 , R 3 and R 4 is a pendent hydrocarbyl group represented by one of formulae B, C or D:

where R 5 is a C 1 to C 6 alkyl moiety or —CH 2 CH 2 OCH 2 — and each of the remaining R 1 , R 2 , R 3 or R 4 is hydrogen; and
an optional third repeating unit represented by formula Ia where ate least one of R 1 , R 2 , R 3 and R 4 is selected from epoxyhexylnorbornene, epoxycyclohexanenorbornene, hexylnorbornene, trioxanonanenorbornene, tetraoxadodecanenorbornene, methylglycidylethernorbornene, [(3-ethyl-3-oxetanyl)methoxy]dimethylnorbornenylethylsilane and 5-norbornene-2-yl(methylene)-4,4′-bis-(2,6-di-tert-butylphenol);
a photoacid generator; and
a casting solvent selected from one or more of propyleneglycol monomethylether, propyleneglycol monomethylether acetate, gamma-butyrolactone, and cyclohexanone;

image-wise exposing the polymer film to actinic radiation to form exposed and unexposed patterned portions of the polymer film;
first heating the exposed polymer film to a first temperature to initiate a condensation or cross-linking reaction within the exposed portions;
removing the unexposed portions by contacting the polymer film with an aqueous base developer solution; and
second heating exposed portions to a second temperature, the second heating fixing the exposed patterned portions to the substrate to form structures thereon.

2. The method of claim 1 , where for said second repeating unit the pendent hydrocarbyl group is represented by formula B.

3. The method of claim 2 , where R 5 of said second repeating unit is —CH 2 CH 2 OCH 2 — or —CH 2 —.

4. The method of claim 1 , further comprising a photosensitizer.

5. The method of claim 1 , where the photoacid generator is (p-isopropylphenyl)(p-methylphenyl)-iodonium tetrakis(pentafluorophenyl)borate or (2-(4-methoxynaphthalen-1-yl)-2-oxoethyl)dimethylsulfonium tetrakis(perfluorophenyl)borate and the photosensitizer is 1-chloro-4-propoxy-9-H-thioxanthen-9-one.

6. The method of claim 1 , where for said first repeating unit R 5 is —CH 2 CH 2 —, the second repeating unit is represented by formula B where R 5 for said second repeating unit is —CH 2 —, the photoacid generator is (p-isopropylphenyl)(p-methylphenyl)-iodonium tetrakis(pentafluorophenyl)borate and further comprising a photosensitizer consisting of 1-chloro-4-propoxy-9-H-thioxanthen-9-one.

7. The method of claim 1 , further comprising an adhesion promoter selected from (3-glycidyloxypropyl)trimethoxy silane or 3-ethyl-(triethoxysilylpropoxy)methyl oxetane.

8. The method of claim 6 , further comprising an adhesion promoter selected from (3-glycidyloxypropyl)trimethoxy silane or 3-ethyl-(triethoxysilylpropoxy)methyl oxetane.

9. The method of claim 1 , further comprising one or more cross-linking moieties selected from poly(propylene glycol)diglycidyl ether, trimethylolpropane triglycidyl ether, 3,4-epoxycyclohexyl-3,4-epoxycyclohexane, 1,4-bis[(2-ethyl-3-oxetanylmethoxy)methyl]benzene or tetrakis(methoxymethyl)glycoluril.

10. The method of claim 9 , further comprising a photosensitizer and an adhesion promoter, where the photosensitizer is 1-chloro-4-propoxy-9-H-thioxanthen-9-one and the adhesion promoter is (3-glycidyloxypropyl)trimethoxy silane.

11. The method of claim 1 , where the polymer is selected from:
a terpolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, norbornenylpropanoic acid, and trioxanonanenorbornene;
a copolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and norbornenylpropanoic acid; and
a copolymer derived from exo-norbornene ethoxymethylhexafluoropropanol and norbornenylpropanoic acid.

12. The method of claim 11 , where the photoacid generator is (p-isopropylphenyl)(p-methylphenyl)-iodonium tetrakis(pentafluorophenyl)borate or (2-(4-methoxynaphthalen-1-yl)-2-oxoethyl)dimethylsulfonium tetrakis(perfluorophenyl)borate and the photosensitizer is 1-chloro-4-propoxy-9-H-thioxanthen-9-one.

13. The method of claim 11 , where the photoacid generator is (p-isopropylphenyl)(p-methylphenyl)-iodonium tetrakis(pentafluorophenyl)borate and the adhesion promoter is selected from (3-glycidyloxypropyl)trimethoxy silane or 3-ethyl-(triethoxysilylpropoxy)methyl oxetane.

14. The method of claim 1 , where the polymer is a terpolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, norbornenylpropanoic acid, and trioxanonanenorbornene.

15. The method of claim 1 , where the polymer is a copolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and norbornenylpropanoic acid.

16. The method of claim 1 , where the polymer is a copolymer derived from exo-norbornene ethoxymethylhexafluoropropanol and norbornenylpropanoic acid ethyl ester.

17. The method of claim 1 , where the casting forms a polymer film having a thickness from 1 to 200 μm.

18. The method of claim 1 , where the casting forms a polymer film having a thickness from 1 to 60 μm.

19. The method of claim 1 , where the first heating is performed at a temperature in the range of from 90° C. to 145° C.

20. The method of claim 1 , where the second heating is performed at a temperature in the range of from 120° C. to 300° C.

Assignees

• Promerus Llc

Inventors

• Knapp Brian
• Elce Edmund
• Ng Hendra
• Bell Andrew
• Burns Cheryl
• Kaiti Sridevi
• Kocher Brian
• Patel Yogesh
• Sakamoto Masanobu
• Wu Xiaoming
• Zhang Wei

Classifications

• C08F232/08 Primary

  having condensed rings (coumarone-indene polymers C08F244/00) · CPC title

• G03F7/0045

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

• Y10S430/106

  Binder containing · CPC title

• C08L45/00 Primary

  Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers (of cyclic anhydrides or imides C08L35/00; of cyclic esters of polyfunctional acids C08L31/00) · CPC title

• G03F7/0751

  used as adhesion-promoting additives or as means to improve adhesion · CPC title