Photoimageable polyolefin compositions containing photobase generators
Embodiments in accordance with the present invention encompass self-imageable polymer compositions containing a variety of photobase generators which are useful for forming films that can be patterned to create structures for microelectronic devices, microelectronic packaging, microelectromechanical systems, optoelectronic devices and displays. The compositions of this invention can be tailored to form positive tone or negative tone images depending upon the intended application in aqueous developable medium. The images formed therefrom exhibit improved properties including low wafer stress and better thermo-mechanical properties, among other property enhancements.
1. A photoimageable composition consisting of:
a) a copolymer or terpolymer consisting of 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 0;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, hexyl, decyl, —(CH 2 ) 2 —C(CF 3 ) 2 OH, —(CH 2 ) 2 —CO 2 H, benzyl and phenethyl;
and
a third repeating unit selected from the group consisting of a repeat unit of formula (IIIA) and a repeat unit of formula (IIIB), said third repeating unit is derived from a monomer of formula (III):
wherein:
Z is O or N—R 12 wherein R 12 is selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl, (C 3 -C 7 )cycloalkyl and (C 6 -C 12 )aryl;
R 5 , R 6 and R 7 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 6 -C 12 )aryl and (C 6 -C 12 )aryl(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 photobase generator selected from the group consisting of:
a compound of formula (IV):
a compound of formula (V):
a compound of formula (VI):
a compound of formula (VIIA):
a compound of formula (VIIB):
a compound of formula (VIIC):
wherein
R 13 and R 14 each independently of each other selected from the group consisting of hydrogen, linear or branched (C 1 -C 8 )alkyl, cyclohexyl, and (C 6 -C 10 )aryl; or
R 13 and R 14 taken together with the nitrogen atom to which they are attached form a 5 to 7 membered monocyclic ring or 6 to 12 membered bicyclic ring, said rings optionally containing one or more heteroatoms selected from O and N, and said rings optionally substituted with a group selected from the group consisting of linear or branched (C 1 -C 8 )alkyl, (C 6 -C 10 )aryl, halogen, hydroxy, linear or branched (C 1 -C 8 )alkoxy and (C 6 -C 10 )aryloxy; and
R 15 , R 16 and R 17 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, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, hydroxy, halogen, linear or branched (C 1 -C 12 )alkoxy and (C 6 -C 10 )aryloxy; and
c) a carrier solvent.
2. The composition of claim 1 , wherein Z is O, R 5 and R 6 are hydrogen, and R 7 is hydrogen or linear or branched (C 1 -C 9 )alkyl.
3. The composition of claim 1 , wherein Z is N—R 12 , R 5 and R 6 are hydrogen, R 7 is hydrogen and R 12 is hydrogen or linear or branched (C 1 -C 9 )alkyl.
4. The composition of claim 1 , wherein m=0, R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, decyl, phenethyl, —(CH 2 ) 2 —C(CF 3 ) 2 OH and —(CH 2 ) 2 —CO 2 H.
5. The composition of claim 1 , wherein the polymer consisting of:
one or more first repeat units derived from the corresponding monomers selected from the group consisting of:
bicyclo[2.2.1]hept-2-ene;
5-decylbicyclo[2.2.1]hept-2-ene;
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol;
5-phenethylbicyclo[2.2.1]hept-2-ene; and
norbornenylpropanoic acid; and
one or more third repeat units derived from the corresponding monomers selected from the group consisting of:
maleic anhydride; and
2-methyl-maleic anhydride.
6. The composition of claim 1 , wherein the polymer is:
a copolymer containing repeating units derived from 5-phenethylbicyclo[2.2.1]hept-2-ene and ring opened maleic anhydride repeat units which is ring opened with methanol.
7. The composition of claim 1 , wherein the polymer is:
a copolymer containing repeating units derived from bicyclo[2.2.1]hept-2-ene and ring opened maleic anhydride repeat units which is ring opened with n-butanol.
8. The composition of claim 1 , wherein the polymer is:
a terpolymer containing repeating units derived from 5-phenethylbicyclo[2.2.1]hept-2-ene, 5-decylbicyclo[2.2.1]hept-2-ene and ring opened maleic anhydride repeat units which is ring opened with methanol.
9. The composition of claim 1 , wherein the photobase generator is a compound of formula (IV):
wherein
R 13 and R 14 each independently of each other selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl and phenyl;
and
R 15 , R 16 and R 17 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy and isopropoxy.
10. The composition of claim 1 , wherein the photobase generator is a compound of formula (V):
wherein
R 13 and R 14 each independently of each other selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl and phenyl; or
R 13 and R 14 taken together with the nitrogen atom to which they are attached form a five or six membered monocyclic ring, and said ring is optionally substituted with a group selected from the group consisting of methyl, ethyl and hydroxy;
and
R 15 , R 16 and R 17 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy and isopropoxy.
11. The composition of claim 1 , wherein the photobase generator is a compound of formula (VI):
wherein
R 13 and R 14 each independently of each other selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclohexyl and phenyl; or
R 13 and R 14 taken together with the nitrogen atom to which they are attached form a five or six membered monocyclic ring;
and
R 15 , R 16 and R 17 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy and isopropoxy.
12. The composition of claim 1 , wherein the photobase generator is selected from the group consisting of:
a compound of formula (VIIA):
a compound of formula (VIIB):
and
a compound of formula (VIIC):
13. The composition of claim 1 , wherein the photobase generator is selected from the group consisting of:
14. The composition of claim 1 , wherein the photobase generator is selected from the group consisting of:
15. The composition of claim 1 , wherein the photobase generator is selected from the group consisting of:
16. The composition of claim 1 , wherein the photobase generator is:
a compound of formula (VIIA):
17. The composition of claim 1 , wherein the photobase generator is:
a compound of formula (VIIB):
18. The composition of claim 1 , wherein the photobase generator is:
a compound of formula (VIIC):