Photoactive compounds
The present invention relates to novel photoacid generators.
1 . A compound having the formula
wherein R 1 and R 2 are each independently selected from C 1-20 straight or branched alkyl chain; each of R 30 , R 31 , R 32 , R 33 , and R 34 are independently selected from Z, hydrogen, C 1-20 straight or branched alkyl chain optionally containing one or more O atoms, C 5-50 monocyclic or polycyclic alkyl group, C 5-50 cyclic alkylcarbonyl group, C 6-50 aryl group, C 6-50 aralkyl group, arylcarbonylmethylene group, —OR 4 where R 4 is hydrogen, C 1-20 straight or branched alkyl group or C 5-50 monocyclic or polycyclic alkyl group; Z is —(O) k —(V) n —Y, where V is a linkage group selected from a divalent C 1-20 straight or branched alkyl group, divalent C 5-50 aryl group, divalent C 5-50 aralkyl group, or divalent C 5-50 monocyclic or polycyclic alkyl group; Y is selected from —C(═O)O—R 8 and —O—C(═O)—R 8 ; R 8 is a C 1-20 straight or branched alkyl chain optionally containing one or more O atoms, a C 5-50 monocyclic or polycyclic alkyl group, or a C 5-50 aryl group; k is 0 or 1, and n is 0 or 1; the C 1-20 straight or branched alkyl chain optionally containing one or more O atoms, C 1-20 straight or branched alkyl chain, C 5-50 monocyclic or polycyclic alkyl group, C 5-50 cyclic alkylcarbonyl group, C 5-50 aralkyl group, C 5-50 aryl group, or arylcarbonylmethylene group being unsubstituted or substituted by one or more groups selected from the group consisting of Z, halogen, C 1-20 alkyl, C 1-20 perfluoroalkyl C 3-20 cyclic alkyl, C 1-20 alkoxy, C 3-20 cyclic alkoxy, di C 1-20 alkylamino, dicyclic di C 1-20 alkylamino, hydroxyl, cyano, nitro, tresyl, oxo, aryl, aralkyl, oxygen atom, CF 3 SO 3 , aryloxy, arylthio, and groups of formulae (II) to (VI):
R 10 and R 11 each independently represent a hydrogen atom, a C 1-20 straight or branched alkyl chain optionally containing one or more O atoms, or a C 5-50 monocyclic or polycyclic alkyl group, or R 10 and R 11 together can represent an alkylene group to form a five- or six-membered ring,
R 12 represents a C 1-20 straight or branched alkyl chain optionally containing one or more O atoms, a C 5-50 monocyclic or polycyclic alkyl group, or a C 5-50 aralkyl group, or R 10 and R 12 together represent an alkylene group which forms a five- or six-membered ring together with the interposing —C—O— group, the carbon atom in the ring being optionally substituted by an oxygen atom,
R 13 represents a C 1-20 straight or branched alkyl chain optionally containing one or more O atoms or a C 5-50 monocyclic or polycyclic alkyl group,
R 14 and R 15 each independently represent a hydrogen atom, a C 1-20 straight or branched alkyl chain optionally containing one or more O atoms or a C 5-50 monocyclic or polycyclic alkyl group,
R 16 represents a C 1-20 straight or branched alkyl chain optionally containing one or more O atoms, a C 5-50 monocyclic or polycyclic alkyl group, a C 5-50 aryl group, or a C 5-50 aralkyl group, and
R 17 represents C 1-20 straight or branched alkyl chain optionally containing one or more O atoms, a C 5-50 monocyclic or polycyclic alkyl group, a C 5-50 aryl group, a C 5-50 aralkyl group, the group —Si(R 16 ) 2 R 17 , or the group —O—Si(R 16 ) 2 R 17 , the C 1-20 straight or branched alkyl chain optionally containing one or more O atoms, C 5-50 monocyclic, bicyclic, or tricyclic alkyl group, C 5-50 aryl group, and C 5-50 aralkyl group being unsubstituted or substituted as above; and
A − is an anion represented by the formula
Rg-O-Rf-SO 3 −
where Rf is selected from the group consisting of linear or branched (CF 2 ) j where j is an integer from 4 to 10 and C 3 -C 12 perfluorocycloalkyl divalent radical which is optionally perfluoroC 1-10 alkyl substituted,
Rg is selected from the group consisting of C 1 -C 20 linear, branched, monocyclic or polycyclic alkyl, C 1 -C 20 linear, branched, monocyclic or polycyclic alkenyl, C 5-50 aryl, and C 5-50 aralkyl, the alkyl, alkenyl, aralkyl and aryl groups being unsubstituted, substituted, partially fluorinated or perfluorinated.
2 . The compound of claim 1 wherein R 30 and R 34 are hydrogen.
3 . The compound of claim 2 wherein R 1 and R 2 are each independently selected from C 1-20 straight or branched alkyl chain and each of R 31 , R 32 , and R 33 are independently selected from hydrogen, Z, —OR 4 , and C 1-20 straight or branched alkyl chain optionally containing one or more O atoms.
4 . The compound of claim 3 wherein each of R 31 and R 33 are C 1-20 straight or branched alkyl chain optionally containing one or more O atoms.
5 . The compound of claim 3 wherein R 32 is selected from —OR 4 and Z.
6 . The compound of claim 5 wherein R 32 is —OR 4 .
7 . The compound of claim 6 wherein R 4 is C 1-20 straight or branched alkyl group.
8 . The compound of claim 6 wherein R 4 is hydrogen.
9 . The compound of claim 6 wherein R 4 is C 5-50 monocyclic or polycyclic alkyl group.
10 . The compound of claim 3 wherein each of R 31 and R 33 are hydrogen.
11 . The compound of claim 10 wherein R 32 is —OR 4 .
12 . The compound of claim 11 wherein R 4 is C 1-20 straight or branched alkyl group.
13 . The compound of claim 6 wherein R 32 is Z.
14 . The compound of claim 13 wherein k is 0, n is 0 and Y is —O—C(═O)R 8 .
15 . The compound of claim 14 wherein R 8 is C 1-20 straight or branched alkyl chain optionally containing one or more O atoms.
16 . The compound of claim 13 wherein k is 1, n is 1, V is a divalent C 1-20 straight or branched alkyl group and Y is C(═O—R 8 .
17 . The compound of claim 16 wherein R 8 is C 1-20 straight or branched alkyl chain optionally containing one or more O atoms.
18 . The compound of claim 1 , wherein A − is selected from CF 3 CHFO(CF 2 ) 4 SO 3 − , CF 3 CH 2 O(CF 2 ) 4 SO 3 − , CH 3 CH 2 O(CF 2 ) 4 SO 3 − , and CH 3 CH 2 CH 2 O(CF 2 ) 4 SO 3 − .
19 . The compound of claim 1 ,
20 . The compound of claim 19 selected from the group consisting of
21 . The compound of claim 1 ,
22 . The compound of claim 21 selected from the group consisting of
23 . The compound of claim 1 ,
24 . The compound of claim 23 selected from the group consisting of
25 . The compound of claim 1
26 . The compound of claim 25 selected from the group consisting of
27 . The compound of claim 1 ,
28 . The compound of claim 27 selected from the group consisting of
29 . A photoresist composition useful for imaging in deep UV comprising;
a) a polymer containing an acid labile group; and,
b) a compound of claim 1 .
30 . The photoresist composition of claim 29 wherein a) the polymer comprises one or more monomers selected from maleic anhydride, t-butyl norbornene carboxylate, mevalonic lactone methacrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 3,5-dimethyl-7-hydroxy adamantyl methacrylate, 3-hydroxy-1-methacryloxyadamantane, 3-hydroxy-1-adamantyl acrylate, ethycyclopentylacrylate, tricyclo[5,2, 1,0 2,6 ]deca-8-yl methacrylate, 3,5-dihydroxy-1-methacryloxyadamantane, gamma-butyrolactone methacrylate, methacryloylxy norbornane methacrylate, and mixtures thereof.
31 . The photoresist composition of claim 29 wherein a) the polymer is selected from the group poly(2-methyl-2-adamantyl methacrylate-co-2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-α-gamma-butyrolactone methacrylate); poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-β-gamma-butyrolactone methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-α-gamma-butyrolactone methacrylate); poly(t-butyl norbornene carboxylate-co-maleic anhydride-co-2-methyl-2-adamantyl methacrylate-co-β-gamma-butyrolactone methacrylate-co-methacryloyloxy norbornane methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-β-gamma-butyrolactone methacrylate-co-tricyclo[5,2,1,0 2,6 ]deca-8-yl methacrylate); poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl acrylate-co-β-gamma-butyrolactone methacrylate); poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl acrylate-co-α-gamma-butyrolactone methacrylate-co-tricyclo[5,2,1,0 2,6 ]deca-8-yl methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3,5-dihydroxy-1-methacryloxyadamantane-co-α-gamma-butyrolactone methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3,5-dimethyl-7-hydroxy adamantyl methacrylate-co-α-gamma-butyrolactone methacrylate); poly(2-methyl-2-adamantyl acrylate-co-3-hydroxy-1-methacryloxyadamantane-co-α-gamma-butyrolactone methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-β-gamma-butyrolactone methacrylate-co-tricyclo[5,2,1,0 2,6 ]deca-8-yl methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-β-gamma-butyrolactone methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-ethylcyclopentylacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl acrylate-co-α-gamma-butyrolactone methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-α-gamma-butyrolactone methacrylate-co-2-ethyl-2-adamantyl methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-β-gamma-butyrolactone methacrylate-co-tricyclo[5,2,1,0 2,6 ]deca-8-yl methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-2-ethyl-2-adamantyl methacrylate-co-β-gamma-butyrolactone methacrylate-co-3-hydroxy-1-methacryloxyadamantane); and poly(2-methyl-2-adamantyl methacrylate-co-2-ethyl-2-adamantyl methacrylate-co-α-gamma-butyrolactone methacrylate-co-3-hydroxy-1-methacryloxyadamantane).
32 . The photoresist composition of claim 29 wherein a) the polymer is selected from poly(2-methyl-2-adamantyl methacrylate-co-2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-α-gamma-butyrolactone methacrylate); poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-β-gamma-butyrolactone methacrylate); poly(t-butyl norbornene carboxylate-co-maleic anhydride-co-2-methyl-2-adamantyl methacrylate-co-β-gamma-butyrolactone methacrylate-co-methacryloyloxy norbornane methacrylate); poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-β-gamma-butyrolactone methacrylate-co-tricyclo[5,2,1,0 2,6 ]deca-8-yl methacrylate); poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl acrylate-co-β-gamma-butyrolactone methacrylate); poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl acrylate-co-α-gamma-butyrolactone methacrylate-co-tricyclo[5,2,1,0 2,6 ]deca-8-yl methacrylate); and poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-β-gamma-butyrolactone methacrylate-co-tricyclo[5,2,1,0 2,6 ]deca-8-yl methacrylate).
33 . A process for imaging a photoresist comprising the steps of:
a) coating a substrate with the composition of claim 29;
b) baking the substrate to substantially remove the solvent;
c) image-wise exposing the photoresist coating;
d) post-exposure baking the photoresist coating; and
e) developing the photoresist coating with an aqueous alkaline solution.
34 . The process of claim 33 , where the image-wise exposure wavelength is below 200 nm.
35 . The process according to claim 33 , where the aqueous alkaline solution comprises tetramethylammonium hydroxide.
36 . The process according to claim 33 , where the aqueous alkaline solution further comprises a surfactant.
37 . The process according to claim 33 , where the substrate is selected from a microelectronic device and a liquid crystal display substrate.
38 . A method for producing a semiconductor device by producing a photo-image on a substrate by coating a suitable substrate with a photoresist composition comprising:
a) coating a suitable substrate with the composition of claim 29;
b) heat treating the coated substrate of step a) until substantially all of the photoresist solvent is removed; image-wise exposing the composition and removing the image-wise exposed areas of such composition with a suitable developer.