Fluorine free photopatternable phenol functional group containing polymer compositions

Patent metadata

Field	Value
Publication number	US-10054854-B2
Application number	US-201615276997-A
Country	US
Kind code	B2
Filing date	Sep 27, 2016
Priority date	Oct 1, 2015
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

Various polycycloolefinic polymers containing phenolic pendent groups and compositions thereof useful for forming self-imageable films encompassing such polymers are disclosed. Such polymers encompass norbornene-type repeating units containing phenolic pendent groups which contain very low levels of fluorine containing monomers. The films formed from such polymer compositions provide self imageable, low-k, thermally stable layers for use in microelectronic and optoelectronic devices.

First claim

What is claimed is:

1. A polymer selected from the group consisting of:
a terpolymer of 2-(bicyclo[2.2.1]hept-5en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid;
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 4-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)butan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid;
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 5-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)pentan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid;
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3 -hexafluoropropan-2-ol and 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid;
a terpolymer of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)propan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol;
a terpolymer of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)propan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 4-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)butan-2-ol;
a terpolymer of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)propan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 5-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)pentan-2-ol; and
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene.

2. The polymer according to claim 1 , which is selected from the group consisting of:
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol and 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid; and
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene.

3. A layer forming polymer composition comprising:
a polymer selected from the group consisting of:
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid;
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 4-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)butan-2-ol and 2-bicyclo[2.2.1]hept-5-en-2-yl)acetic acid;
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 5-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1,-trifluoro-2-(trifluoromethyl)pentan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid;
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol and 3-(bicyclo[2.2.1]hept-5-en-2-propanoic acid;
a terpolymer of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)propan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol;
a terpolymer of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl propan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)Propanoic acid and 4-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)butan-2-ol;
a terpolymer of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)propan-l-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)Propanoic acid and 5-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)pentan-2-ol; and
a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-(4-hydroxyphenyl)ethan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene;

a photo active compound;
an epoxy resin; and
a solvent.

4. The composition according to claim 3 , wherein said photoactive compound comprises a 1,2-naphthoquinonediazide-5-sulfonyl moiety and/or a 1,2-naphthoquinonediazide-4-sulfonyl moiety as represented by structural formulae (IIIa) and (IIIb), respectively:

or a sulfonyl benzoquinone diazide group represented by structural formula (IIIc):

5. The composition according to claim 4 , wherein said photoactive compound is

wherein at least one of Q is a group of formula (VIIa) or (VIIb):

and the remaining Q is hydrogen.

6. The composition according to claim 3 , wherein said epoxy resin is selected from the group consisting of:
bisphenol A epoxy resin;
polypropylene glycol epoxy resin;
bis(4-(oxiran-2-ylmethoxy)phenyl)methane;
glycidyl ether of para-tertiary butyl phenol;
polyethylene glycol diglycidyl ether;
polypropylene glycol diglycidyl ether;
and a mixture in any combination thereof.

7. The composition according to claim 3 , wherein said solvent is propyleneglycol monomethylether acetate, gamma-butyrolactone or N-methylpyrrolidone.

8. The composition according to claim 3 , wherein said composition further comprises one or more additives selected from the group consisting of:
adhesion promoters;
antioxidants;
surfactants;
thermal acid generator;
thermal base generator; and
mixtures in any combination thereof.

9. A process for forming a cured product, comprising: (i) applying the layer forming polymer composition of claim 3 on a substrate to form a coating film, (ii) exposing the coating film to light through a desired pattern mask, (iii) dissolving and removing the exposed portions by developing with an alkaline developer to obtain the desired pattern, and (iv) heating the obtained desired pattern.

10. A cured product obtained by curing the layer forming polymer composition of claim 3 .

11. An optoelectronic or microelectronic device comprising the cured product of claim 10 , which is having a dielectric constant of 3.2 or less at 1 MHz.

Assignees

• Promerus Llc

Inventors

• Elce Edmund
• Groff Royce

Classifications

• G03F7/327

  Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts · CPC title

• G03F7/2002

  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 title

• G03F7/0395 Primary

  the macromolecular compound having a backbone with alicyclic moieties · CPC title

• C09D145/00

  Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers (based on polymers of cyclic esters of polyfunctional acids C09D131/00; based on polymers of cyclic anhydrides or imides C09D135/00) · CPC title

• C08L45/00

  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