Photoimageable compositions containing thermal base generators

Patent metadata

Field	Value
Publication number	US-9690196-B2
Application number	US-201514982672-A
Country	US
Kind code	B2
Filing date	Dec 29, 2015
Priority date	Dec 30, 2014
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

Embodiments in accordance with the present invention encompass positive-tone, aqueous developable, self-imageable 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 photoimageable aqueous developable positive tone composition comprising:
a) a polymer having one or more first repeating units represented by formula (IA), said first repeating unit is derived from a monomer of formula (I):

wherein:
m is an integer 0, 1 or 2;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, halogen, linear or branched (C 1 -C 12 )alkyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 6 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, —(CH 2 ) a —CO 2 R, a group of formula (A):
—(CH 2 ) b —(OCH 2 —CH 2 ) c —OR  (A);

and a group of formula (B):

wherein:
a is an integer from 0 to 4
b is an integer 0, 1, 2, 3 or 4;
c is an integer 0, 1, 2, 3 or 4; and

R is selected from the group consisting of hydrogen, linear or branched (C 1 -C 6 )alkyl, (C 5 -C 8 )cycloalkyl, (C 6 -C 10 )aryl and (C 7 -C 12 )aralkyl; and
a second repeating unit represented by formula (IIA) or (IIB), said second repeating unit is derived from a monomer of formula (II):

wherein:
R 5 , R 6 , R 7 and R 8 are each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl, fluorinated or perfluorinated (C 1 -C 9 )alkyl, (C 1 -C 12 )alkoxy(C 1 -C 12 )alkyl and (C 1 -C 12 )alkoxy(C 1 -C 12 )alkoxy(C 1 -C 12 )alkyl; and
wherein each of aforementioned groups, where valence is permissible, is optionally substituted with one or more groups selected from the group consisting of linear or branched (C 1 -C 6 )alkyl, (C 3 -C 7 )cycloalkyl, (C 1 -C 6 )perfluoroalkyl, (C 1 -C 6 )alkoxy, (C 3 -C 7 )cycloalkoxy, (C 1 -C 6 )perfluoroalkoxy, halogen, hydroxy, linear or branched hydroxy(C 1 -C 6 )alkyl, acetoxy, phenyl, hydroxyphenyl and acetoxyphenyl;

b) a thermal base generator selected from the group consisting of:
(i) a compound of formula (III):

(ii) a compound of formula (IV):

(iii) a compound of formula (V):

 and
(iv) a compound of formula (VI):

wherein
R 9 , R 10 and R 11 are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, cyano(C 1 -C 16 )alkyl, cyano(C 1 -C 16 )alkoxy(C 1 -C 16 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 1 -C 12 )alkoxy(C 1 -C 8 )alkyl, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy and (C 1 -C 6 )acyloxy;
R 12 is selected from the group consisting of (C 1 -C 6 )alkyloxycarbonyl, (C 6 -C 10 )aryl(C 1 -C 6 )alkyloxycarbonyl, (C 6 -C 10 )aryloxycarbonyl and cyano(C 1 -C 6 )alkyl;
R 13 , R 14 and R 17 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl, a linear, branched or cyclic (C 3 -C 12 )alkyl, a linear, branched or cyclic (C 3 -C 12 )heteroalkyl having from 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur, (C 6 -C 10 )aryl and (C 5 -C 10 )heteroaryl having from 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur;
R 15 and R 16 are the same or different and each independently of one another selected from the group consisting of hydrogen and (C 1 -C 6 )alkyl;
or where
R 16 taken together with the nitrogen atom to which it is attached to and one of R 13 or R 14 taken together with the nitrogen atom to which it is attached to and any intervening atoms form a cyclic heteroalkyl group;
R 17 taken together with the carbon atom to which it is attached to and one of R 13 or R 14 taken together with the nitrogen atom to which it is attached to and any intervening atoms form a cyclic heteroalkyl group;
one of R 13 or R 14 taken together with the nitrogen atom to which it is attached to and one of adjacent R 13 or R 14 taken together with the nitrogen atom to which it is attached to and any intervening atoms form a cyclic heteroalkyl group;
and
X Θ is selected from the group consisting of halide, sulfonate, methanesulfonate, trifluoromethanesulfonate and a carboxylate anion;

c) a photoactive compound; and
d) a carrier solvent.

2. The composition of claim 1 , wherein m is 0, R 1 is phenethyl, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen.

3. The composition of claim 1 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:
5-benzylbicyclo[2.2.1]hept-2-ene; and
5-phenethylbicyclo[2.2.1]hept-2-ene.

4. The composition of claim 1 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:
maleic anhydride; and
2-methyl-maleic anhydride.

5. The composition of claim 1 , wherein the polymer is selected from the group consisting of:
a copolymer containing repeating units derived from 5-phenethylbicyclo[2.2.1]hept-2-ene and repeat unit of formula (IIA) where R 5 , R 6 , R 7 and R 8 are hydrogen;
a copolymer containing repeating units derived from 5-phenethylbicyclo[2.2.1]hept-2-ene and repeat unit of formula (IIA) where R 5 , R 6 , R 7 are hydrogen and R 8 is methyl.

6. The composition of claim 1 , wherein the thermal base generator is of the formula (III):

wherein
R 12 is selected from the group consisting of tert-butoxycarbonyl, iso-butoxycarbonyl, iso-propoxycarbonyl, n-propoxycarbonyl, methoxycarbonyl, ethoxycarbonyl and cyanoethyl; and
R 9 , R 10 and R 11 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl, phenyl and cyanoethoxymethyl.

7. The composition of claim 6 , wherein the thermal base generator is selected from the group consisting of:
1-(tert-butoxycarbonyl)imidazole;
1-(iso-butoxycarbonyl)imidazole;
1-(iso-propoxycarbonyl)imidazole;
1-(n-propoxycarbonyl)imidazole;
1-(methoxycarbonyl)imidazole;

Assignees

• Promerus Llc

Inventors

• Ng Hendra
• Kaiti Sridevi

Classifications

• G03F7/0397

  the macromolecular compound having an alicyclic moiety in a side chain · CPC title

• G03F7/0751

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

• G03F7/0233 Primary

  characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides · CPC title

• G03F7/023

  Macromolecular quinonediazides; Macromolecular additives, e.g. binders {(G03F7/0226 takes precedence)} · CPC title

• G03F7/039 Primary

  Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) · CPC title