Negative tone photosensitive compositions

1. A negative tone photoimagable composition comprising:

a) a polymer having a pendent acidic group, which is selected from the group consisting of:

i) a polymer of formula (Ia):

ii) a polymer comprising a repeating unit of formula (Ib) derived from a monomer of formula (IB):

wherein represents a position at which the bonding takes place with another repeat unit;

R 4 is selected front the group consisting of —(CH 2 ) y —CO 2 R 4a , —(CH 2 ) v —Ar—OH, —(CH 2 ) y —C(O)—Ar—OH, —(CH 2 ) y —OC(O)—Ar—OH, —(CH 2 ) y —C(O)O—Ar—OH and —C(O)O(CH 2 ) y —Ar—OH, where each v is Independently an integer from 4) to 4, and R 4a is hydrogen, Ar Is substituted or unsubstituted phenyl or napthenyl where substituents if present are selected from the group consisting of halogen, (C 1 -C 4 )alkyl, fluorinated or perfluorinated (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy and fluorinated or perfluorinated (C 1 -C 4 )alkoxy; and

iii) a polymer comprising one or more distinctive monomer repeating units of formula (Ic) derived from a monomer of formula (IC) and maleic anhydride-type repeating units of formulae (Id1) and (Id2) derived from a maleic anhydride monomer of formula (ID):

wherein:

represents a position at which the bonding takes place with another repeat unit;

g is 0;

R 5 , R 6 , R 7 and R 8 are the same or different and independently of each other selected from the group consisting of hydrogen, methyl, ethyl, a fluorinated or perflourinated methyl, ethyl and a linear or branched substituted or unsubstituted (C 3 -C 25 )hydrocarbyl group;

wherein:

represents a position at which the bonding takes place with another repeat unit;

R 9 is selected from the group consisting of methyl, ethyl, a fluorinated or perfluorinated methyl or ethyl a linear or branched (C 3 -C 9 ) hydrocarbyl and a linear or branched fluorinated or perfluorinated (C 3 -C 9 )hydrocarbyl group;

R 10 and R 11 are the same or different and are selected from hydrogen, methyl and ethyl;

b) one or more olefinic functional group containing compound selected from the group consisting of:

i) a compound of formula (IIa):

where

each b is independently an integer from 1 to 6;

K is CH 2 ; and

X is O;

ii) a compound of formula (IIb):

where

K is CH 2 ;

X is SiR 2 R 3 , —(CZ 2 ) b — where Z is hydrogen, —C(O)—, —CH═CH— or —C≡C— where R 2 and R 3 are each independently methyl or ethyl; and

each b is independently an integer from 1 to 8;

ii) a compound of formula (IIc):

where

b is an integer from 1 to 6; and

K is CH 2 or CH 2 —CH 2 ;

iv) a compound of formula (III) selected from the group consisting of:

1,3-di(bicyclo[2.2.1]hept-5-en-2-yl)propane;

5,5′-(2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)propane-1,3-diyl)bis(bicyclo[2.2.1]hept-2-ene);

bis(4-bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane; and

tris(4-bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane; and

v) a compound of formula (IV) selected from the group consisting of:

4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl acetate;

5-decylbicyclo[2.2.1]hept-2-ene;

5-undecylbicyclo[2.2.1]hept-2-ene;

5-dodecylbicyclo[2.2.1]hept-2-ene;

1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)benzene;

bis(bicyclo[2.2.1]hept-en-2-ylmethyl) carbonate; and

c) a photoacid generator.

2. The composition of claim 1 wherein the compound of formula (II) is selected from the group consisting of:

5,5′-(oxybis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

5,5′-(oxybis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);

bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methane;

1,2-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethane;

1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)propane;

1,4-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)butane;

1,6-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)hexane;

1,8-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)octane;

bicyclo[2.2.1]hept-5-em-2-ylmethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate; and

bicyclo[2.2.2]oct-5-en-2-ylmethyl bicyclo[2.2.2]oct-5-ene-2-carboxylate.

3. The composition of claim 1 wherein the compound of formula (III) is selected from the group consisting of:

1,3-di(bicyclo[2.2.1]]hept-5-en-2-yl)propane;

bis(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane; and

tris(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane.

4. The composition of claim 1 wherein the compound of formula (IV) is selected from the group consisting of:

4-(bicyclo[2.2.1]]hept-5-en-2-yl)phenyl acetate;

5-decylbicyclo[2.2.1]hept-2-ene; and

5-dodecylbicyclo[2.2.1]hept-2-ene.

5. The composition of claim 1 wherein the photoacid generator is selected from the group consisting of:

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tetrakis(perfluorophenyl)borate (Irgacure PAG 290);

(2-(4-methoxynapthalen-1-yl)-2-oxoethyl)dimethylsulfonium tetrakis(perflourophenyl)borate (TAG 382);

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tris((trifluoromethyl)sulfonyl)methanide;

(4-ethylphenyl)(4-isopropylphenyl)iodonium tetrakis(perfluorophenyl)borate;

di-(p-t-butylphenyl)iodonium tris(trifluoromethanesulfonyl)methanide and a mixture in any combination thereof.

6. The composition of claim 1 wherein said polymer is selected from the group consisting of:

polyhydroxystyrene;

a terpolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 3-(bicyclo[2.2.1]hept-2-en-2-yl)propanoic acid, and trioxanonanenorbornene;

a copolymer derived from maleic anhydride and norbornene which is ring opened with butanol; and

a copolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and bicyclo[2.2.1]hept-5-en-2-ylmethanol.

7. The composition of claim 1 wherein the compound of formula (II), (III) or (IV) is selected from the group consisting of:

5,5′-(oxybis(methylene))bis(bicyclo[2.2.1]]hept-2-ene);

5,5′-(oxybis(ethane-2,1-diyl))bis(bicyclo[2.2.1]]hept-2-ene);

bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methane;

4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl acetate; and

5-decylbicyclo[2.2.1]hept-2-ene.

8. The composition of claim 1 wherein the photoacid generator is selected from the group consisting of:

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium

tetrakis(perfluorophenyl)borate;

(4-ethylphenyl)(4-isopropylphenyl)iodonium

tetrakis(perfluorophenyl)borate; and

di-(p-t-butylphenyl)iodonium tris(trifluoromethanesulfonyl)methanide.

9. A negative tone photoimagable composition comprising:

a) a polymer having a pendent acidic group, which is selected from the group consisting of:

i) a polymer of formula (Ia):

ii) a polymer comprising a repeating unit of formula (Ib) derived from a monomer of formula (IB):

wherein represents a position at which the bonding takes place with another repeat unit;

R 4 is selected from the group consisting of —(CH 2 ) v —CO 2 R 4a , —(CH 2 ) v —Ar—OH, —(CH 2 ),—C(O)—Ar—OH, —(CH 2 ) v —OC(O)—Ar—OH, —(CH 2 ) v —C(O)O—Ar—OH, and —C(O)O(CH 2 ) v —Ar—OH,

where each v is independently an integer from 0 to 4, and R 4a is hydrogen, Ar is substituted or unsubstituted phenyl or naphthyl where substituents if present are selected from the group consisting of halogen, (C 1 -C 4 )alkyl, fluorinated or perfluorinated (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy and fluorinated or perfluorinated (C 1 -C 4 )alkoxy; and

iii) a polymer comprising one or more distinctive monomer repeating units of formula (Ic) derived from a monomer of formula (IC) and maleic anhydride-type repeating units of formulae (Id1) and (Id2) derived from a maleic anhydride monomer of formula (ID):

wherein:

represents a position at which the bonding takes place with another repeat unit;

g is 0;

R 5 , R 6 , R 7 and R 8 are the same or different and independently of each other selected from the group consisting of hydrogen, methyl, ethyl, a fluorinated or perfluorinated methyl, ethyl and a linear or branched substituted or unsubstituted (C 3 -C 25 )hydrocarbyl group;

wherein:

represents a position at which the bonding takes place with another repeat unit;

R 9 is selected from the group consisting of methyl, ethyl, a fluorinated or perfluorinated methyl or ethyl, a linear or branched (C 3 -C 9 )hydrocarbyl and a linear or branched fluorinated or perfluorinated (C 3 -C 9 )hydrocarbyl group;

R 10 and R 11 are the same or different and are selected from hydrogen, methyl and ethyl;

b) a compound selected from the group consisting of:

5,5′-(oxybis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

5,5′-(oxybis(ethane-2, l-diyl))bis(bicyclo[2.2.1]hept-2-ene);

bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methane;

4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl acetate; and

5-decylbicyclo[2.2.1]hept-2-ene; and

c) a photoacid generator selected from the group consisting of:

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium

tetrakis(perfluorophenyl)borate;

(2-(4-methoxynaphthalen-1-yl)-2-oxoethyl)dimethylsulfonium

tetrakis(perfluorophenyl)borate;

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium

tris((trifluoromethyl)sulfonyl)methanide;

(4-ethylphenyl)(4-isopropylphenyl)iodonium

tetrakis(perfluorophenyl)borate; and

di-(p-t-butylphenyl)iodonium tris(trifluoromethanesulfonyl)methanide.

10. The composition of claim 9 further comprising one or more solvent selected from the group consisting of: N-methyl-2-pyrrolidone,

γ-butyrolactone, N,N-dimethylacetamide, dimethylsulfoxide, diethyleneglycol dimethylether, diethyleneglycol diethylether, diethyleneglycol dibutylether, propyleneglycol monomethylether, dipropylene glycol monomethylether, propyleneglycol monomethylether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, tetrahydrofuran, methyl-1,3-butyleneglycolacetate, 1,3-butyleneglycol-3-monomethylether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate and a mixture in any combination thereof.

11. The composition of claim 9 further comprising one or more compounds selected from the group consisting of a phenolic resin, a leveling agent, an antioxidant, a flame retardant, a plasticizer, a silane coupling agent and a curing accelerator.

12. A semiconductor device comprising a laminated semiconductor element where said lamination consists of a composition according to claim 9 .

13. A semiconductor device comprising one or more of a redistribution layer structure, a chip stack structure and a complementary metal oxide semiconductor image sensor dam structure, where said structure comprises a composition according to claim 9 .

14. A film comprising the composition of claim 9 .

15. A microelectronic or optoelectronic device comprising one or more of a redistribution layer structure, a chip-stack structure or a complementary metal oxide semiconductor image sensor dam structure, where said structure comprises a composition according to claim 9 .

16. A method of forming a film for the fabrication of a microelectronic or optoelectronic device comprising:

coating a suitable substrate with a composition according to claim 9 to form a film;

patterning the film with a mask by exposing to a suitable radiation;

developing the film after exposure to form a photo-pattern; and

curing the film by heating to a suitable temperature.

17. The method of claim 16 , where said developing is performed by a solvent developer, which is propyleneglycol monomethylether acetate.

18. The method of claim 16 , where the substrate is first hardbaked before said curing at a temperature of from 130° C. to 160° C. for 20 minutes to 60 minutes.