Fluorine free photopatternable phenol functional group containing polymer compositions
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.
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.